[Federal Register Volume 64, Number 113 (Monday, June 14, 1999)]
[Rules and Regulations]
[Pages 31898-31962]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 99-12893]
[[Page 31897]]
_______________________________________________________________________
Part II
Environmental Protection Agency
_______________________________________________________________________
40 CFR Part 63
National Emission Standards for Hazardous Air Pollutants for Source
Categories; Portland Cement Manufacturing Industry; Final Rule
Federal Register / Vol. 64, No. 113 / Monday, June 14, 1999 / Rules
and Regulations
[[Page 31898]]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 63
[FRL-6347-2]
RIN 2060-AE78
National Emission Standards for Hazardous Air Pollutants for
Source Categories; Portland Cement Manufacturing Industry
AGENCY: Environmental Protection Agency (EPA).
ACTION: Final rule.
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SUMMARY: This action promulgates national emission standards for
hazardous air pollutants (NESHAP) for new and existing sources in the
portland cement manufacturing industry. This action also adds Method
320 for the measurement of vapor phase organic and inorganic emissions
by extractive Fourier Transform Infrared (FTIR) spectroscopy and Method
321 for the measurement of gaseous hydrogen chloride emissions from
portland cement kilns by FTIR spectroscopy to appendix A of part 63.
Some of the hazardous air pollutants (HAPs) released from portland
cement manufacturing facilities include, but are not limited to,
acetaldehyde, arsenic, benzene, cadmium, chromium, chlorobenzene,
dibenzofurans, formaldehyde, hexane, hydrogen chloride, lead,
manganese, mercury, naphthalene, nickel, phenol, polycyclic organic
matter, selenium, styrene, 2,3,7,8-tetrachlorodibenzo-p-dioxin,
toluene, and xylenes. Exposure to these HAPs can cause reversible or
irreversible health effects including carcinogenic, respiratory,
nervous system, developmental, reproductive and/or dermal health
effects. The EPA estimates that this final rule will reduce nationwide
emissions of HAPs from portland cement manufacturing facilities by
approximately 82 megagrams per year (Mg/yr) [90 tons per year (tpy)],
and particulate matter (PM) by approximately 4,700 Mg/yr (5,200 tpy).
These standards implement section 112(d) of the Clean Air Act (CAA)
and are based on the Administrator's determination that portland cement
manufacturing facilities may reasonably be anticipated to emit several
of the 188 HAPs listed in section 112(b) of the CAA from the various
process operations found within the industry. The final rule provides
protection to the public by requiring portland cement manufacturing
plants to meet emission standards reflecting the application of the
maximum achievable control technology (MACT).
EFFECTIVE DATE: June 14, 1999. See the SUPPLEMENTARY INFORMATION
section concerning judicial review.
ADDRESSES: Docket. Docket No. A-92-53, containing information
considered by the EPA in development of the promulgated standards, is
available for public inspection between 8:00 a.m. to 5:30 p.m., Monday
through Friday, except Federal holidays, at the following address: U.S.
Environmental Protection Agency, Air and Radiation Docket and
Information Center (6102), 401 M Street S.W., Washington, DC 20460,
telephone number (202) 260-7548. The docket is located at the above
address in room M-1500, Waterside Mall (ground floor). A reasonable fee
may be charged for copying docket materials.
FOR FURTHER INFORMATION CONTACT: For further information concerning
applicability and rule determinations, contact the appropriate State or
local agency representative. If no State or local representative is
available, contact the EPA Regional Office staff listed in the
Supplementary Information section of this preamble. For information
concerning the analyses performed in developing this rule, contact Mr.
Joseph Wood, P. E., Minerals and Inorganic Chemicals Group, Emission
Standards Division (MD-13), Office of Air Quality Planning and
Standards, U.S. EPA, Research Triangle Park, North Carolina 27711,
telephone number (919) 541-5446, facsimile number (919) 541-5600,
electronic mail address wood.joe@epamail.epa.gov''. For information
regarding Methods 320 and 321 contact Ms. Rima Dishakjian, Emission
Measurement Center, Emissions, Monitoring and Analysis Division (MD-
19), U.S. Environmental Protection Agency, Research Triangle Park, NC
27711, telephone number (919) 541-0443.
SUPPLEMENTARY INFORMATION:
Regulated entities. Entities potentially regulated by this action
are those that manufacture portland cement. Regulated categories and
entities shown in Table 1.
Table 1.--Regulated Entities
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Examples of Regulated
Category NAICS Code SIC Code Entities
----------------------------------------------------------------------------------------------------------------
Industry............................................... 32731 3241 Owners or operators of
portland cement
manufacturing plants.
State.................................................. 32731 3241 Owners or operators of
portland cement
manufacturing plants.
Tribal associations.................................... 32731 3241 Owners or operators of
portland cement
manufacturing plants.
Federal agencies....................................... (\1\) (\1\) None.
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\1\ None.
This table is not intended to be exhaustive, but rather provides a
guide for readers regarding entities likely to be regulated by this
action. This table lists the types of entities that the EPA is now
aware could potentially be regulated by this action. To determine
whether your facility, company, business organization, etc. is
regulated by this action, you should carefully examine the
applicability criteria in Sec. 63.1340 of the rule. If you have
questions regarding the applicability of this action to a particular
entity, consult the appropriate regional representative:
Region 1--Janet Bowen, Office of Ecosystem Protection, U.S. EPA,
Region I, CAP, JFK Federal Building, Boston, MA 02203, (617) 565-3595.
Region II--Kenneth Eng, Air Compliance Branch Chief, U.S. EPA,
Region II, 290 Broadway, New York, NY 10007-1866 (212) 637-4000.
Region III--Bernard Turlinski, Air Enforcement Branch Chief, U.S.
EPA, Region III (3AT10), 841 Chestnut Building, Philadelphia, PA 19107,
(215) 566-2110.
Region IV--Lee Page, Air Enforcement Branch, U.S. EPA, Region IV,
Atlanta Federal Center, 61 Forsyth Street, Atlanta, GA 30303-3104,
(404) 562-9131.
Region V--George T. Czerniak, Jr., Air Enforcement Branch Chief,
U.S. EPA, Region V (5AE-26), 77 West Jackson Street, Chicago, IL 60604,
(312) 353-2088.
Region VI--John R. Hepola, Air Enforcement Branch Chief, U.S. EPA,
[[Page 31899]]
Region VI, 1445 Ross Avenue, Suite 1200, Dallas, TX 75202-2733, (214)
665-7220.
Region VII--Donald Toensing, Chief, Air Permitting and Compliance
Branch, U.S. EPA, Region VII, 726 Minnesota Avenue, Kansas City, KS
66101, (913) 551-7446.
Region VIII--Douglas M. Skie, Air and Technical Operations Branch
Chief, U.S. EPA, Region VIII, 999 18th Street, Suite 500, Denver, CO
80202-2466, (303) 312-6432.
Region IX--Barbara Gross, Air Compliance Branch Chief, U.S. EPA,
Region IX, 75 Hawthorne Street, San Francisco, CA 94105, (415) 744-
1138.
Region X--Anita Frankel, Air and Radiation Branch Chief, U.S. EPA,
Region X (AT-092), 1200 Sixth Avenue, Seattle, WA 98101-1128, (206)
553-1757.
Judicial Review. The NESHAP for portland cement manufacturing was
proposed on March 24, 1998 (63 FR 14182). Today's Federal Register
action announces the EPA's final decision on the rule. Under section
307(b)(1) of the Act, judicial review of the final rule is available by
filing a petition for review in the U.S. Court of Appeals for the
District of Columbia Circuit within 60 days of today's publication of
this final rule. Under section 307(b)(2) of the Act, the requirements
that are the subject of today's notice may not be challenged later in
civil or criminal proceedings brought by the EPA to enforce these
requirements.
Technology Transfer Network. In addition to being available in the
docket, an electronic copy of today's document, which includes the
regulatory text, is available through the Technology Transfer Network
(TTN) at the Office of Air and Radiation Policy and Guidance website.
Following promulgation, a copy of the rule will be posted at the TTN's
policy and guidance page for newly proposed or promulgated rules
(http://www.epa.gov/ttn/oarpg/t3pfpr.html). A copy of the Response to
Comments document for this rule will be posted on the TTN at http://
www.epa.gov/ttn/oarpg/t3bid.html. The TTN provides information from EPA
in various areas of air pollution technology or policy. If more
information on the TTN is needed, call the TTN help line at (919) 541-
5384.
Outline. The following outline is provided to aid in reading this
preamble to the final rule.
I. Statutory Authority
II. Background and Public Participation
III. Summary of Final Rule
A. Applicability
B. Emission Limits and Operating Limits
C. Performance Test Provisions
D. Monitoring Requirements
E. Notification, Recordkeeping, and Reporting Requirements
IV. Summary of Changes Since Proposal
A. Designation of Affected Sources
B. Definitions
C. Emission Standards and Operating Limits
D. Performance Test Requirements
E. Monitoring Requirements
F. Additional Test Methods
G. Reporting
H. Exemption from New Source Performance Standards
I. Delegation of Authority
J. Test Methods 320, 321, and 322
V. Summary of Impacts
A. Air Quality Impacts
B. Water Impacts
C. Solid Waste Impacts
D. Energy Impacts
E. Nonair Health and Environmental Impacts
F. Cost Impacts
G. Economic Impacts
VI. Summary of Responses to Major Comments
VII. Administrative Requirements
A. Docket
B. Executive Order 12866
C. Executive Order 12875: Enhancing Intergovernmental
Partnerships
D. Unfunded Mandates Reform Act
E. Regulatory Flexibility Act
F. Submission to Congress and the General Accounting Office
G. Paperwork Reduction Act
H. Pollution Prevention Act
I. National Technology Transfer and Advancement Act
J. Executive Order 13045
K. Executive Order 13084: Consultation and Coordination with
Indian Tribal Governments
I. Statutory Authority
The statutory authority for this rule is provided by sections 101,
112, 113, 114, 116, and 301 of the Clean Air Act, as amended (42 U.S.C.
7401, 7412, 7413, 7414, 7416, and 7601). This rule is also subject to
section 307(d) of the CAA (42 U.S.C. 7407(d)).
II. Background and Public Participation
The Clean Air Act was created in part ``to protect and enhance the
quality of the Nation's air resources so as to promote the public
health and welfare and the productive capacity of its population.''
(Clean Air Act, section 101(b)(1)) Section 112(b), as revised in 61 FR
30816 (June 18, 1996), lists 188 HAPs believed to cause adverse health
or environmental effects. Section 112(d) requires that emission
standards be promulgated for all categories and subcategories of
``major'' sources of these HAP and for ``area'' sources listed for
regulation, pursuant to section 112(c). Major sources are defined as
those that emit or have the potential to emit (from all emission points
in all source categories within the facility) at least 10 tons per year
of any single HAP or 25 tons per year of any combination of HAP. Area
sources are stationary sources of HAP that are not major sources.
On July 16, 1992 (57 FR 31576), the EPA published a list of
categories of sources slated for regulation. This list included the
portland cement source category regulated by the standards being
promulgated today. The statute requires emissions standards for the
listed source categories to be promulgated between November 1992 and
November 2000. On June 4, 1996, the EPA published a schedule for
promulgating these standards (61 FR 28197). Standards for the portland
cement manufacturing source category covered by this rule were proposed
on March 24, 1998 (63 FR 14182).
As in the proposal, the final standards give existing sources 3
years from the date of promulgation to comply. New sources are required
to comply with the standard upon initial startup. The EPA believes
these standards to be achievable for affected sources within the time
provided.
Operating limits, methods for determining initial compliance, as
well as monitoring, recordkeeping, and reporting requirements are
included in the final rule. All of these components are necessary to
ensure that sources will comply with the standards both initially and
over time. However, the EPA has made every effort to simplify the
requirements in the rule.
The amended Clean Air Act requires the EPA to promulgate national
emission standards for sources of HAPs. Section 112(d) provides that
these standards must reflect:
``* * * the maximum degree of reduction in emissions of the HAP * *
* that the Administrator, taking into consideration the cost of
achieving such emission reduction, and any nonair quality health and
environmental impacts and energy requirements, determines is achievable
for new or existing sources in the category or subcategory to which
such emission standard applies * * *'' [42 U.S.C. 7412(d)(2)].
This level of control is referred to as MACT. The Clean Air Act
goes on to establish the least stringent level of control for MACT;
this level is termed the ``MACT floor.''
For new sources, the standards for a source category or subcategory
``shall not be less stringent than the emission control that is
achieved in practice by the best controlled similar source, as
determined by the Administrator'' [section 112(d)(3)]. Existing source
[[Page 31900]]
standards shall be no less stringent than the average emission
limitation achieved by the best performing 12 percent of the existing
sources for source categories and subcategories with 30 or more
sources, or the average emission limitation achieved by the best
performing 5 sources for sources or subcategories with fewer than 30
sources [section 112(d)(3)]. These two minimum levels of control define
the MACT floor for new and existing sources.
The standards were proposed in the Federal Register on March 24,
1998 (63 FR 14182). The preamble for the proposed standards described
the rationale for the proposed standards. Public comments were
solicited at the time of proposal. To provide interested individuals
the opportunity for oral presentation of data, views, or arguments
concerning the proposed standards, a public hearing was offered at
proposal. However, the public did not request a hearing and, therefore,
one was not held. The public comment period, which was extended by
thirty days in response to requests from commenters, was from March 24,
1998 to June 26, 1998. A total of 28 comment letters were received.
Commenters included industry representatives, State and local agencies,
and environmental groups. Today's final rule reflects the EPA's full
consideration of all of the comments. These public comments along with
the EPA's responses to comments on the proposed rule are summarized in
this preamble. A more detailed discussion of public comments and the
EPA's responses can be found in the Response to Comment Document
(Docket No. A-92-53, Item V-C-1).
III. Summary of Final Rule
A. Applicability
The standards apply to each portland cement manufacturing plant at
any facility which is a major source or an area source, with the
following exception. Some portland cement plants fire hazardous wastes
in the kiln to provide part or all of the fuel requirement for clinker
production. Portland cement kilns and in-line kiln/raw mills subject to
the NESHAP for hazardous waste combustors (HWC), 40 CFR 63, subpart
EEE, are not subject to this standard; however other affected sources
at portland cement plants where hazardous waste is burned in the kiln
are subject to this standard. HW kilns and HW in-line kiln/raw mills
that temporarily or permanently stop burning hazardous waste may be
subject to the emission standards, notification, testing, and
monitoring requirements of today's rule, as provided by subpart EEE of
this part.
Except for hazardous waste burning (HW) cement kilns and HW in-line
kiln/raw mills, these standards apply to all cement kilns and in-line
kiln/raw mills regardless of the material being combusted in the kiln.
Currently, cement kilns which combust municipal solid waste, medical
waste, or other waste materials (other than HW) are subject to today's
rule. Since these devices currently are not subject to section 129
standards, EPA is including them in this rule to avoid a situation
where they aren't regulated at all. This measure, however, is
potentially an interim step. EPA could determine that cement kilns
combusting solid waste materials should be regulated under section 129
of the Clean Air Act, 42 U.S.C. Sec. 7429, and if so, EPA would revise
the applicability section of these regulations accordingly at the time
section 129 regulations applicable to cement kilns are promulgated.
EPA also considered but rejected the possibility of subcategorizing
cement kilns based on the nature of feed preparation for the kiln. As
discussed in the proposal preamble, there are two types of portland
cement manufacturing processes differentiated on the basis of feed
preparation: wet process, and dry process (which includes the long kiln
dry process, preheater process, and preheater/precalciner process). The
wet process kilns and all variations of the dry process kilns use the
same raw materials and use the same types of air pollution controls.
Therefore, if subcategories were defined based on process type, the
MACT floor technology would be identical (docket item II-B-73). For
this reason, the EPA is not promulgating separate rules based on
process (kiln) type.
For portland cement plants with on-site non-metallic minerals
processing facilities, the first affected source in the sequence of
materials handling operations subject to this NESHAP is the raw
material storage, which is just prior to the raw mill. The primary and
secondary crushers and any other equipment in the non-metallic minerals
processing plant, which precede the raw material storage are not
affected sources under this NESHAP. The first conveyor system transfer
point subject to this NESHAP is the transfer point associated with the
conveyor transferring material from the raw material storage to the raw
mill.
This regulation does not apply to the emissions from cement kiln
dust (CKD) storage facilities (e.g., CKD piles or landfills). A
separate rulemaking will be forthcoming utilizing RCRA authority that
will apply to air emissions associated with CKD management and disposal
facilities.
B. Emission Limits and Operating Limits
In today's notice, the EPA is establishing emission limitations for
particulate matter (as a surrogate for HAP metals), dioxins/furans (D/
F), and total hydrocarbons (as a surrogate for organic HAPs, including
polycyclic organic matter). The NESHAP for portland cement
manufacturing applies to both major and area sources of HAPs. The
affected sources for which emission limits are established include the
non-hazardous waste (NHW) kiln, NHW in-line kiln/raw mill, clinker
cooler, raw material dryer, and materials handling processes that
include the raw mill, finish mill, raw material storage, clinker
storage, finished product storage, conveyor transfer points, bagging
and bulk loading and unloading systems (hereafter referred to as
materials handling processes).
The NESHAP limits PM (surrogate for HAP metals) emissions, as well
as opacity, from new and existing NHW kilns, NHW in-line kiln/raw
mills, and clinker coolers, and limits opacity from raw material dryers
and materials handling processes, at portland cement plants which are
major sources. The rule also limits D/F emissions from new and existing
NHW kilns and NHW in-line kiln/raw mills located at portland cement
plants which are major or area sources of HAPs. In addition, the rule
limits total hydrocarbon (THC) as a surrogate for organic HAP emissions
from new greenfield NHW kilns, new greenfield NHW in-line kiln/raw
mills, and new greenfield raw material dryers at portland cement plants
which are major or area sources. Tables 2 and 3 present a summary of
the emission limits for new and existing portland cement affected
sources.
[[Page 31901]]
Table 2.--Summary of Emission Limits a,\b for Affected Sources at Portland Cement Plants
(Metric units)
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Emission limit for existing Emission limit for new
Affected source and pollutant sources sources
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NHW kiln and NHW in-line kiln/raw mill c PM.......... 0.15 kg/Mg dry feed e and 0.15 kg/Mg dry feed e and
opacity level cc no greater opacity level cc no
than 20 percent greater than 20 percent
NHW kiln and NHW in-line kiln/raw mill D/F c,\d...... 0.2 ng TEQ/dscm or 0.4 ng 0.2 ng TEQ/dscm or 0.4 ng
TEQ/dscm with PM control TEQ/dscm with PM control
device operated at 204 deg.C g eq>204 deg.C g
NHW kiln and NHW in-line kiln/raw mill THC d......... none........................ 50 ppmvd f (as propane)
Clinker cooler PM.................................... 0.05 kg/Mg dry feed and 0.05 kg/Mg dry feed and
opacity level no greater opacity level no greater
than 10 percent than 10 percent
Raw material dryer and materials handling processes 10 percent opacity 10 percent opacity
(raw mill system, finish mill system, raw material
storage, clinker storage, finished product storage,
conveyor transfer points, bagging, and bulk loading
and unloading systems) PM.
Raw material dryer THC d............................. none........................ 50 ppmvd f (as propane)
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a All concentration limits at 7 percent oxygen.
b Applies to major sources only, except as noted.
c Includes main and alkali bypass stacks.
d Applies to both major and area source portland cement plants.
e If there is an alkali bypass stack associated with the kiln or in-line kiln/raw mill, the combined PM emission
from the kiln or in-line kiln/raw mill and the alkali bypass must be less than 0.15 kg/Mg dry feed.
f Applies only to new greenfield affected sources.
g The average temperature of the test run averages during performance test must be less than or equal to 204
degrees C.
Table 3.--Summary of Emission Limits a,\b for Affected Sources at Portland Cement Plants
(English units)
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Emission limit for existing Emission limit for new
Affected source and pollutant sources sources
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NHW kiln and NHW in-line kiln/raw mill c PM.......... 0.30 lb/ton dry feed e and 0.30 lb/ton dry feed e and
opacity level c no greater opacity level c no greater
than 20 percent than 20 percent
NHW kiln and NHW in-line kiln/raw mill D/F c,\d...... 8.7 x 10 -11 gr TEQ/dscf or 8.7 x 10 -11 gr TEQ/dscf or
1.7 x 10 -10 gr TEQ/dscf 1.7 x 10 -10 gr TEQ/dscf
with PM control device with PM control device
operated at 400 operated at 400
deg.F g deg.F g
NHW kiln and NHW in-line kiln/raw mill THC d......... none........................ 50 ppmvd f (as propane)
Clinker cooler PM.................................... 0.10 lb/ton dry feed and 0.10 lb/ton dry feed and
opacity level no greater opacity level no greater
than 10 percent than 10 percent
Raw material dryer and materials handling processes 10 percent opacity 10 percent opacity
(raw mill system, finish mill system, raw material
storage, clinker storage, finished product storage,
conveyor transfer points, bagging, and bulk loading
and unloading systems) PM.
Raw material dryer THC d............................. none........................ 50 ppmvd f (as propane)
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a All concentration limits at 7 percent oxygen.
b Applies to major sources only, except as noted.
c Includes main and alkali bypass stacks.
d Applies to both major and area source portland cement plants.
e If there is an alkali bypass stack associated with the kiln or in-line kiln/raw mill, the combined PM emission
from the kiln or in-line kiln/raw mill and the alkali bypass must be less than 0.30 lb/ton dry feed.
f Applies only to new greenfield affected sources.
g The average temperature of the test run averages during performance test must be less than or equal to 400
degrees F.
The NESHAP imposes operating limits on affected sources that are
subject to D/F emission limits. These operating limits are summarized
in Table 4.
[[Page 31902]]
Table 4.--Summary of Operating Limits for Affected Sources at Portland
Cement Plants
------------------------------------------------------------------------
Affected Source/Pollutant Pollutant Operating Limits
------------------------------------------------------------------------
All kilns and in-line kiln D/F Operate such that the 3-hour
raw mills at major and area rolling average particulate
sources (including alkali matter control device (PMCD)
bypasses). inlet temperature is no
greater than temperature
established at performance
test.
.......... Operate such that the three-
hour rolling average
activated carbon injection
rate is no less than the
rate established at
performance test (if
applicable).
.......... Operate such that the three-
hour rolling average
activated carbon injection
nozzle pressure drop or
carrier fluid flow rate is
no less than that specified
by manufacturer (if
applicable).
------------------------------------------------------------------------
The rule requires the owner or operator to operate such that the
temperature at the inlet to the kiln or in-line kiln raw mill
particulate matter control device (PMCD) is at a level no greater than
the level established during the successful Method 23 performance test.
The three-hour rolling average temperature limit is established by
taking the average of the one-minute average temperatures for each test
run conducted during the successful Method 23 performance test, then
averaging each test run average. Further, sources may petition the
Administrator for an alternate averaging period or method for
establishing operating parameter limits.
Owners or operators of in-line kiln/raw mills are required to
establish separate PMCD inlet temperatures applicable to periods when
the raw mill is operating and periods when the raw mill is not
operating. The appropriate ``raw mill operating status dependent'' PMCD
inlet temperature shall not be exceeded. Owners or operators of kilns
or in-line kiln/raw mills equipped with alkali bypasses are required to
establish a separate temperatures for the inlet to the kiln or in-line
kiln raw mill PMCD and the kiln or in-line kiln/raw mill alkali bypass
PMCD. The applicable temperature limit for the alkali bypass is
established during the performance test in which the raw mill is
operating.
After a transition period in which the status of the raw mill was
changed from ``off'' to ``on'' or from ``on'' to ``off'', compliance
with the operating limits for the new mode of operation begins, and the
three-hour rolling average is established anew, i.e., without
considering previous recordings.
If carbon injection is used for D/F control, the carbon injection
system must be operated such that the carbon injection rate shall be
maintained at a level equaling or exceeding the rate which existed
during the successful Method 23 performance test. The three-hour
rolling average carbon injection rate limit is established in the same
way as the temperature limit, as described above. The injection nozzle
pressure drop or carrier fluid flow rate must also be monitored, and
the minimum levels for these parameters are established based on
manufacturers specifications. The nozzle pressure drop or carrier fluid
flow rate is monitored with a 3-hour rolling averaging period.
C. Performance Test Provisions
A performance test is required to demonstrate initial compliance
with each applicable numerical limit. The rule requires the owner or
operator to use EPA Method 5, ``Determination of Particulate Emissions
from Stationary Sources'' to measure PM emissions from kilns, in-line
kiln/raw mills and clinker coolers. These tests will be repeated every
5 years. Kilns and in-line kiln/raw mills equipped with alkali bypasses
are required to meet the particulate standard based on combined
emissions from the kiln exhaust and the alkali bypass. Owners or
operators of in-line kiln/raw mills are required to conduct a Method 5
performance test while the raw mill is operating and a separate Method
5 performance test while the raw mill is not operating. In conducting
the Method 5 tests, a determination of the particulate matter collected
in the impingers (``back half'') of the particulate sampling train is
not required to demonstrate initial compliance with the standard,
however the permitting authority may require a ``back half'' for
permitting, determination of emission fees, particulate matter
monitoring or other purposes. Owners or operators are also required to
determine the kiln or in-line kiln/raw mill dry feed rate, because the
PM emission standards for kilns, in-line kiln/raw mills and clinker
coolers are expressed as lb PM/ton (kg PM/Mg) dry feed.
The opacity exhibited during the period of the initial Method 5
performance test shall be determined, if feasible, through the use of a
continuous opacity monitor (COM). Where the control device exhausts
through a monovent or where the use of a COM in accordance with the
installation specifications of EPA Performance Specification (PS)-1 of
appendix B to 40 CFR part 60, is not feasible, EPA Method 9, ``Visual
Determination of the Opacity of Emissions from Stationary Sources''
shall be used. Where the control device discharges through a fabric
filter (FF) with multiple stacks or an electrostatic precipitator (ESP)
with multiple stacks, the owner or operator has the option of
conducting an opacity test in accordance with Method 9, in lieu of
installing a COM.
The rule requires the owner or operator to use EPA Method 23,
``Determination of Polychlorinated Dibenzo-p-dioxins and
Polychlorinated Dibenzofurans from Stationary Sources'' to measure D/F
emissions from kilns and in-line kiln/raw mills. These D/F tests shall
be repeated every 2 and one-half years. The temperature at the inlet to
the particulate matter control device (PMCD) during the period of the
Method 23 performance test shall be continuously recorded. One minute
average temperatures must be calculated for each minute of each run of
the test. The average of the one-minute averages must be calculated for
each test run and included in the performance test report. The average
of one-minute averages for each test run is averaged for all test runs,
and this is the operating temperature limit not-to-be-exceeded by any
3-hour rolling average temperature during subsequent operations of the
affected source. If carbon injection is used for D/F control, the
carbon injection rate and other associated operating parameters must be
measured during the period of each run of the Method 23 performance
tests. The average carbon injection rate and other associated operating
parameters measured for the three runs must be determined and included
in the test report.
Owners or operators of in-line kiln/raw mills are required to
conduct a Method 23 performance test, and record the temperature at the
inlet to the PMCD
[[Page 31903]]
while the raw mill is operating, and a separate Method 23 performance
test with PMCD inlet temperature recording while the raw mill is not
operating. If applicable, the carbon injection rate shall be determined
during both performance tests. Where applicable, the exhausts from both
the kiln or in-line kiln/raw mill and the alkali bypass are required to
meet the D/F standard.
The owner or operator is required to repeat the performance tests
for opacity, PM, and D/F emissions from kilns and in-line kiln/raw
mills within 90 days of any significant change in the raw material
components or fuels fed to the kiln (e.g, when there is an increase in
the input rate of municipal solid waste, tire-derived fuel, medical
waste, or other solid wastes to the kiln or in-line kiln/raw mill,
above the rate used in the previous performance test.) Under the
standard, the owner or operator shall use a THC continuous emission
monitor (CEM) to conduct a performance test of THC emissions from new
greenfield kilns, new greenfield in-line kiln/raw mills, and new
greenfield raw material dryers. Owners or operators of new greenfield
in-line kiln/raw mills are required to demonstrate initial compliance
by measuring THC emissions while the raw mill is operating and while
the raw mill is not operating. The standard for THC does not apply to
the exhaust from the alkali bypass of kilns or the alkali bypass of in-
line kiln/raw mills, and these streams are not subject to a performance
test for THC. Each THC CEM is required to be designed, installed, and
operated in accordance with EPA Performance Specification (PS)-8A of 40
CFR part 60, appendix B.
Under the standard, the owner or operator shall use EPA Method 9,
``Visual Determination of the Opacity of Emissions from Stationary
Sources'' to measure the opacity of gases discharged from raw mills,
finish mills, raw material dryers and materials handling processes.
These tests would be repeated every five years. A summary of
performance test requirements is given in Table 5.
Table 5.--Summary of Performance Test Requirements
------------------------------------------------------------------------
Affected source and pollutant Performance Test
------------------------------------------------------------------------
New and existing NHW kiln and NHW in-line kiln/ EPA Method 5 a
raw mill b c PM.
New and existing NHW kiln and NHW in-line kiln/ COM if feasible d e or
raw mill b c Opacity. EPA Method 9 visual
opacity readings.
New and existing NHW kiln and NHW in-line kiln/ EPA Method 23 j
raw mill b c f g D/F.
New greenfield NHW kiln and NHW in-line kiln/raw THC CEM (EPA PS-8A) h
mill THC.
New and existing clinker cooler PM.............. EPA Method 5 a
New and existing clinker cooler opacity......... COM d i or EPA Method
9 visual opacity
readings
New and existing raw and finish mill PM......... EPA Method 9 a i
New and existing raw material dryer and EPA Method 9 a i
materials handling processes (raw material
storage, clinker storage, finished product
storage, conveyor transfer points, bagging, and
bulk loading and unloading systems) PM.
New greenfield raw material dryer THC........... THC CEM (EPA PS-8A) h
------------------------------------------------------------------------
a Required initially and every 5 years thereafter.
b Includes main exhaust and alkali bypass.
c In-line kiln/raw mill to be tested with and without raw mill in
operation.
d Must meet COM performance specification criteria. If the fabric filter
or electrostatic precipitator has multiple stacks, daily EPA Method 9
visual opacity readings may be taken instead of using a COM.
e Opacity limit is 20 percent.
f Alkali bypass is tested with the raw mill on.
g Temperature parameters determined separately with and without the raw
mill operating.
h EPA Performance Specification (PS)-8A of appendix B to 40 CFR part 60.
i Opacity limit is 10 percent.
j Required initially and every 2.5 years thereafter.
D. Monitoring Requirements
The owner or operator of each portland cement manufacturing plant
shall prepare for each affected source subject to the rule, a written
operations and maintenance plan. The plan shall be submitted to the
Administrator for review and approval as part of the application for a
part 70 permit. The operations and maintenance plan shall include
procedures for proper operation and maintenance of the affected source
and air pollution control devices in order to meet the emission limits
of the rule. The operations and maintenance plan shall also include
procedures to be used during an inspection of the components of the
combustion system of each kiln and each in-line kiln/raw mill. This
inspection must be conducted at least once per year. Additionally, the
operations and maintenance plan shall include corrective action
procedures for the raw mill and finish mill, and associated particulate
matter control devices (PMCDs), which must be implemented when required
by the rule. The operations and maintenance plan shall also include
provisions for monitoring opacity from materials handling sources, and
to conduct M. 9 tests if visible emissions are observed. (Further
details of this are discussed in the preamble section ``Summary of
Changes Since Proposal''.) Finally, failure to implement procedures
consistent with the operations and maintenance plan will be a violation
of this subpart.
The rule requires owners or operators to monitor the opacity of
gases discharged from kilns, in-line kiln/raw mills, alkali bypasses
and clinker coolers using a COM, if a COM can be feasibly installed in
accordance with PS-1 of appendix B to 40 CFR part 60. Where it is not
feasible to install a COM, e.g. where the control device discharges
through a monovent, the owner or operator is required to monitor
emissions by conducting daily Method 9 tests. Where the control device
discharges through a FF with multiple stacks or an ESP with multiple
stacks, the owner or operator has the option of conducting daily tests
in accordance with Method 9, in lieu of installing a COM. The duration
of the Method 9 tests is 30 minutes.
The rule requires that kilns and in-line kiln raw mills subject to
the particulate matter (PM) standards must install, correlate, and
operate PM continuous emission monitors (CEMs). However, the compliance
date for
[[Page 31904]]
installing PM CEMs is deferred pending further rulemaking. Further
discussion of this issue is found in the preamble sections ``Summary of
Changes Since Proposal'' and ``Summary of Responses to Major
Comments.''
The owner or operator of a kiln or in-line kiln raw mill must
install, calibrate, maintain and continuously operate a device to
monitor and record the temperature of the exhaust gases from the kiln,
in-line kiln/raw mill, and/or alkali bypass (if applicable), at the
inlet to or upstream of the kiln, in-line kiln/raw mill, and alkali
bypass PMCD. The calibration of the thermocouple or other temperature
sensor must be verified at least once every three months.
If activated carbon injection is used for D/F control, the owner or
operator must install, operate, calibrate and maintain a device to
continuously monitor and record the weight of activated carbon injected
and record the weight in 1 minute rolling averages. The accuracy of the
weight measurement device must be 1 percent of the weight
being measured. The calibration of the device must be verified at least
once every three months. The owner or operator must record the feeder
setting at least once per day and determine the mass of carbon injected
for every three-hour rolling average period. In addition, the carbon
injection nozzle pressure drop or activated carbon carrier fluid flow
rate must be monitored and recorded. Further, the activated carbon
specifications must be the same as or better than the specifications of
the carbon used during the previous performance test.
To clarify how the three-hour rolling average is calculated at
initial start-up, operating parameter limits will not become effective
on the compliance date until enough data have been accumulated to
calculate the rolling average for the limit. For example, given that
compliance with the standards begins nominally at 12:01 am on the
compliance date, the three-hour rolling average temperature limit does
not become effective as a practical matter until 3:01 am on the
compliance date. This approach is adopted for all continuous monitoring
systems, including CEMs.
During intermittent operations, however, periods of time when
operating parameters are not recorded for any reason (e.g., source
shutdown) are to be ignored when calculating rolling averages. For
example, consider how the three-hour rolling average for a parameter
would be calculated if a source shuts down for yearly maintenance for a
three week period. The first one-minute average value recorded for the
parameter for the first minute of renewed operations is added to the
last 179 one-minute averages before the source shut down, to calculate
the three-hour rolling average. This approach is adopted for all
continuous monitoring systems, including CEMs. This approach would
inhibit a source from intentionally interrupting the monitoring system
to avoid unwanted parameter values.
The rule requires the owner or operator to monitor THC emissions
from the main exhaust of greenfield kilns; the main exhaust of
greenfield in-line kiln/raw mills; and greenfield raw material dryers
using a CEM installed in accordance with PS-8A in 40 CFR part 60,
appendix B.
The rule requires the owner or operator to monitor the opacity from
raw mills and finish mills by conducting a daily six-minute test in
accordance with Method 22, ``Visual Determination of Fugitive Emissions
from Material Sources and Smoke Emissions from Flares.''
Owners or operators of raw mills and finish mills are required to
initiate corrective action within one hour of a Method 22 test during
which visible emissions are observed. A 30-minute Method 9 opacity test
must be started within 24 hours of observing visible emissions.
A summary of monitoring requirements is given in Table 6.
Table 6.--Summary of Monitoring Requirements
------------------------------------------------------------------------
Affected source and pollutant Monitor/Type/ Monitoring
or opacity Operation/Process requirement
------------------------------------------------------------------------
All affected sources.......... Operations and Prepare written plan
maintenance plan. for all affected
sources and control
devices.
All kilns and in-line kiln raw COM, if Install, calibrate,
mills at major sources applicable. maintain and operate
(including alkali bypass)/ in accordance with
opacity. general provisions
and with PS-1.
Method 9 opacity Daily test of at
test, if least 30-minutes,
applicable. while kiln is at
highest load or
capacity level.
All kilns and in-line kiln raw PM CEM........... The compliance date
mills at major sources is deferred until a
(including alkali bypass)/PM. future rulemaking,
at which time EPA
will consider what
performance
specification
requirements should
be established.
All kilns and in-line kiln raw Combustion system Conduct annual
mills at major and area inspection. inspection of
sources (including alkali components of
bypass)/D/F. combustion system.
Continuous Install, operate,
temperature calibrate and
monitoring at maintain continuous
PMCD inlet. temperature
monitoring and
recording system;
calculate 3-hour
rolling average;
verify temperature
sensor calibration
at least quarterly.
Activated carbon Install, operate,
injection rate, calibrate and
nozzle pressure maintain continuous
drop or carrier activated carbon
fluid flow rate, injection rate
and carbon type/ monitor; verify
brand, if calibration at least
applicable. quarterly; record
feeder setting
daily; calculate
average injection
rate for each 3-hour
rolling average.
Monitor nozzle
pressure drop or
carrier fluid flow
rate according to
manufacturers
specifications, and
calculate rolling 3-
hour averages.
New greenfield kilns and in- THC CEM.......... Install, operate, and
line raw mills at major and maintain THC CEM in
area sources/THC. accordance with PS-
8A; calculate 30-day
block average THC
concentration.
All clinker coolers at major COM, if Install, calibrate,
sources/opacity. applicable. maintain and operate
in accordance with
general provisions
and with PS-1.
Method 9 opacity Daily test of at
test, if least 30-minutes,
applicable. while kiln is at
highest load or
capacity level.
[[Page 31905]]
All materials handling M. 22 visible For each MHO, conduct
operations (MHO) at major emissions test monthly 1-minute
sources/opacity. as part of Method 22 visible
operations and emissions test; if
maintenance plan. visible emissions
are observed,
initiate corrective
action within one
hour and conduct 30-
minute Method 9 test
within 10 minutes.
For each MHO, if no
visible emissions
are observed after
first 6 months,
reduce monitoring to
semi-annual. If no
VE are observed
thereafter, reduce
monitoring to annual
basis. If VE are
observed for a MHO,
revert back to
conducting VE tests
on a monthly basis.
All raw mills and finish mills Method 22 visible Conduct daily 6-
at major sources/opacity. emissions test. minute Method 22
visible emissions
test while mill is
operating at highest
load or capacity
level; if visible
emissions are
observed, initiate
corrective action
within one hour and
conduct 30-minute
Method 9 test within
24 hours.
New greenfield raw material THC CEM.......... Install, operate, and
dryers at major and area maintain THC CEM in
sources/THC. accordance with PS-
8A; calculate 30-day
block average THC
concentration.
------------------------------------------------------------------------
E. Notification, Recordkeeping, and Reporting Requirements
All notification, recordkeeping, and reporting requirements in the
general provisions (40 CFR part 63, subpart A) apply to portland cement
manufacturing plants. These include: (1) Initial notification(s) of
applicability, notification of performance test, and notification of
compliance status; (2) a report of performance test results; (3) a
startup, shutdown, and malfunction plan with semiannual reports of
reportable events (if they occur); and (4) semiannual reports of excess
emissions. If excess emissions are reported, the owner or operator
shall report quarterly until a request to return the reporting
frequency to semiannual is approved.
The NESHAP general provisions (40 CFR part 63, subpart A) require
that records be maintained for at least 5 years from the date of each
record. The owner or operator must retain the records onsite for at
least 2 years but may retain the records offsite the remaining 3 years.
The files may be retained on microfilm, microfiche, on a computer disk,
or on magnetic tape. Reports may be made on paper or on a labeled
computer disk using commonly available and compatible computer
software.
IV. Summary of Changes Since Proposal
In response to comments received on the proposed standards, changes
have been made to the final standards. These changes include
clarifications designed to make the EPA's intent clearer as well as
changes to the requirements of the proposed standards. A summary of the
substantive changes made since the proposal is given in the following
sections, along with the rationales for these changes. Further details
on the rationales for these changes can be found in Section VI of the
preamble: Summary of Responses to Major Comments.
A. Designation of Affected Sources
The section of the rule on designated affected sources is being
clarified to include new greenfield raw material dryers that are
located at facilities that are area sources. The EPA is clarifying
today that these affected sources are subject to limitations on THC.
The preamble for the proposed rule stated that polycyclic organic
matter (POM) emissions (using THC as a surrogate) from portland cement
NHW kiln area sources would be subject to MACT standards under EPA's
interpretation of section 112(c)(6). The EPA proposed to use THC as a
surrogate for organic HAPs, and today it is clarifying that POM is an
organic HAP for which THC is a surrogate. Since POM was a listed HAP
from portland cement NHW cement kilns (at both area and major source
portland cement plants) in the section 112(c)(6) listing (63 FR 17838,
April 10, 1998), the EPA is clarifying that the limitation of emissions
of THC applies to new greenfield cement kilns, in-line kiln raw mills
and raw material dryers at major and area source cement plants in the
portland cement industry. Further discussion of this change is found
below in the discussion of standards.
B. Definitions
The definitions of ``alkali bypass'' and ``feed'' have been
expanded to reflect cement industry practices. Definitions of
``greenfield'' and new ``brownfield'' affected sources have been added
to the final rule to clarify the applicability of the final THC
standards to specific affected sources. A definition of ``one-minute
average'' has been added to clarify the monitoring provisions of the
final rule. A definition of rolling average has been added to clarify
and maintain consistency with the requirements for HW kilns.
C. Emission Standards and Operating Limits
Based on comments received, the EPA is clarifying today that the
THC limitation applicable to new kilns, new in-line kiln/raw mills, and
new raw material dryers is restricted to greenfield sources, in
recognition of the difficulty that owners or operators of reconstructed
and new brownfield affected sources might have in obtaining suitable
kiln feed materials while remaining competitive. The selection of a
site tied to feed materials with relatively low levels of naturally
occurring organic matter is the basis for the MACT standard and is an
option only available to greenfield sources. Further, as discussed
above, the EPA is clarifying that this THC limitation applies to new
greenfield kilns, new greenfield in-line kiln/raw mills, and greenfield
raw material dryers located at facilities that are area, as well as
major, sources.
The requirements in the proposal for initiating a site-specific
operating and maintenance plan, and implementation of a quality
improvement plan, due to stipulated exceedences of a 15 percent kiln
opacity limit, have been removed. The EPA agrees with commenters who
questioned this tiered approach, and so the final rule will retain only
a 20 percent opacity limit for the kiln and in-line kiln/raw mill.
In response to a comment, the EPA is clarifying that the opacity
limitation on gases discharged from raw mills and finish mills is
restricted to the mill sweep and air separator air pollution control
devices. This is consistent with the MACT floor technology for control
of gases from these affected sources.
The final rule has been reformatted to provide a separate section
for operating
[[Page 31906]]
limits. Control of temperature at the inlet to kiln and in-line kiln/
raw mill PMCDs and control of the activated carbon injection parameters
(if applied as a D/F control technique) are provisions promulgated as
operating limits.
The averaging period for the operating limit for the inlet kiln and
in-line kiln/raw mill PM control device temperature (to demonstrate
compliance with the D/F emission limits) has been changed from a 9-hour
block average period to a three-hour rolling average period. Comments
were received that the averaging period should be shorter. In addition,
the rule has been clarified to include data reduction procedures to be
followed to demonstrate compliance. Furthermore, sources may petition
the Administrator for an alternate averaging period or method for
establishing operating parameter limits.
The provisions for establishing the PM control device inlet
temperature limit based on the D/F performance test have been changed
to correct an error in drafting the proposal. A commenter pointed out
that the proposal would allow a source to conduct its D/F performance
test with an inlet PM control device temperature below 400 degrees F,
but after the performance test, the source would be allowed to operate
its PM control device with an inlet temperature up to 400 degrees F. In
drafting the proposal, the EPA did not intend to allow a source to
operate its PM control device at a temperature higher than the
temperature during the performance test, and so the EPA is clarifying
today that the inlet temperature limit is established as and capped at
the average temperature during the D/F performance test. To further
achieve consistency with the D/F temperature requirements for HW kilns
and to better assure that the standard reflects MACT, the EPA is
dropping the proposed provision which would have allowed the
temperature limit to be established as the average temperature during
the performance test plus 25 degrees F if the D/F level was below 0.15
ng/dscm. To clarify and maintain consistency with the requirements for
HW kilns (and to best implement standards representing MACT), if the
source complies with the O.4 ng TEQ/dscm D/F limit, the average
temperature of the test run averages during the performance test must
be below 400 degrees F. To further achieve consistency with the
requirements for HW kilns, additional operating parameter limits
associated with the use of activated carbon injection must be
established and these parameters must be monitored continuously. The
averaging period for the activated carbon injection rate and other
operating parameters has been changed from a 9-hour period to a 3-hour
rolling average period. Further details on the establishment of the
temperature and other operating parameter limits are discussed in
section VI. of this preamble.
D. Performance Test Requirements
In response to comment, the EPA is clarifying that both during the
performance test and to demonstrate continuous compliance, opacity
limitations for the kiln and clinker cooler must be met for each 6-
minute block period. (The proposal incorrectly required a 30-minute
averaging time.) This is consistent with the requirements of the NSPS,
which is the basis for the MACT floor for PM/metals and opacity.
Based on comments received that there should be consistency with
the requirements for HW kilns, the performance tests for D/F must be
conducted every 2 and one-half years. (The proposal would have required
that the D/F emissions tests be conducted every 5 years.) To further
achieve consistency, and to assure that the kiln continues to achieve
the requisite emissions reductions reflected in the standard, the EPA
is also clarifying today that in addition to repeating performance
tests every five years (or 2.5 years for the D/F performance tests),
performance tests for kilns or in-line kiln/raw mills must be repeated
within 90 days of initiating any significant change in the feed
materials or fuels fed to the kilns (e.g., an increase in the input
rate of municipal solid waste, tire-derived fuel, or medical waste to
the kiln or in-line kiln/raw mill above the rate used in the previous
performance test; or a switch from burning natural gas to coal). Such
changes in fuel or feeds could result in changes to emissions.
E. Monitoring Requirements
In response to a comment, clarification has been added to the final
rule to establish that any required Method 9 and Method 22 tests must
be conducted while the affected source is operating at the highest load
or capacity level reasonably expected to occur within the day that the
test is performed.
The option for use of triboelectric bag leak detection systems for
monitoring raw mill and finish mill fabric filter performance is not
being promulgated at this time. Numerous commenters expressed concern
regarding installation, operation, calibration and maintenance, and
that the lack of clear-cut specifications would lead to open-ended
liability for owners/operators. Those owners or operators who want to
use bag leak detection systems may petition the Administrator for
approval of alternative monitoring requirements under the General
Provisions.
Requirements for temperature monitoring devices (including range
and reference standard) have been added to the final rule. In response
to a comment, monitoring requirements for activated carbon injection
system accuracy, calibration frequency, and data recording and
reduction have also been added to the final rule. To achieve
consistency with the requirements for HW kilns, activated carbon
injection nozzle pressure drop or carrier fluid flow rate, and carbon
specifications, must also be monitored and recorded.
An explicit monitoring requirement for an inspection of the
components of the combustion system of each kiln or in-line kiln/raw
mill has been added to the rule. This inspection must be conducted at
least once per year, in accordance with the procedures specified in the
operation and maintenance plan for the affected source. This change was
made in response to several comments that were received suggesting that
provisions (such as limitations on and monitoring of carbon monoxide)
be added to the final rule to ensure good combustion and thus minimize
formation of D/F.
The operations and maintenance plan requirement has been changed to
explain that the plan must also include provisions for observing
opacity from materials handling sources, and for conducting a M. 9 test
if visible emissions (VE) are observed. Specifically, materials
handling sources' VE shall be monitored via M. 22 once per month. After
6 months without VE for each individual source, the monitoring
frequency would be reduced to a semi-annual basis. If there are no VE
in the next 6 month period for a particular source, the monitoring
frequency would be reduced to an annual basis. If VE occurs during the
annual inspection, the frequency would revert back to once per month.
If VE are observed during one of these inspections, a Method 9 test is
required. This change was made to provide greater assurance that these
units are in compliance with the opacity limit and to meet the Agency's
commitment to incorporate enhanced monitoring in all MACT standards.
Finally, the final rule is being clarified that failure to
implement procedures consistent with the operations and maintenance
plan will be a violation of this subpart.
[[Page 31907]]
In the preamble to the proposal, the EPA noted its intent to
include a requirement for PM continuous emission monitors (CEMs) in the
final rule, unless the analyses of new information and data showed that
it is not appropriate. (See 63 FR at 14205). Based on successful
testing on an incinerator, as well as extensive use of these monitors
in Europe, EPA believes there is sound evidence the PM CEMs should work
at cement kilns. Accordingly, the final rule contains a requirement to
install PM CEMs. However, we are deferring the effective date of this
requirement pending further testing and additional rulemaking. Please
see the preamble section ``Summary of Responses to Major Comments'' for
further details on this issue.
F. Additional Test Methods
The final rule has been changed to permit the use of either Method
320 or Method 321 for the determination of hydrogen chloride (HCl) for
the purpose of making an applicability determination. These methods are
being promulgated as part of this rulemaking.
Since proposal of Method 322 for the measurement of HCl along with
the portland cement NESHAP, the EPA attempted to utilize Method 322 to
gather data from lime kilns (which have a matrix similar to portland
cement sources) and encountered technical problems with the gas filter
correlation infrared spectroscopy (GFCIR). Many of these problems were
adequately identified by the data quality indicators in the method.
However, as a backup option, the Agency collected data sets at lime
kilns using both GFCIR and Fourier transform infrared spectroscopy
(FTIR). These paired data sets provide unexpected contradictory
results.
The dynamic spiking results of the GFCIR would indicate that Method
322 results should be biased by overpredicting the true value (the
spike recovery consistently showed greater than 100 percent recovery).
However, FTIR data collected nearly simultaneously with the GFCIR data
show that the GFCIR results were significantly lower than FTIR results.
Since the Agency applied statistical methods to analyze the FTIR data
and concluded that the FTIR method did not have a significant bias, the
Agency is confident in the values reported by the FTIR instrument.
Therefore, this leads to a paradox with the GFCIR data; the results are
contradictory for the GFCIR. At this point, the Agency has not
determined the cause of the paradox, which has led to the decision to
postpone promulgation of Method 322 as an alternative method for
measurement of HCl from portland cement kilns.
The EPA will continue to investigate the reasons for the
differences in the two methods, and if a satisfactory solution is found
to correct the problem, may consider further action on this method if
additional evaluation data are available. For this reason proposed
Method 322 is not being promulgated at this time and may not be used in
applicability determinations for portland cement plants. (A more
detailed discussion of this can be found in comment 2.5.1 in the
Response to Comment Document.)
In the proposal, we stated that Methods 26 and 26A may be used in
applicability determinations provided that these methods are validated
concurrently using M. 321 or 322. Several comments were received
stating that EPA is restricting M. 26 and M. 26A use by requiring that
they be validated each time they are used, and that Method 26 has long
been an approved EPA test method. Based on these comments, this
requirement has been changed such that Methods 26 and 26A may be used
to confirm a source is a major source without concurrent validation
with M. 321 or M. 322. However, M. 26 or 26A may not be used to make
the assertion that the source is an area source. Only the FTIR methods
may be used for the measurement of HCl if the source wishes to claim it
is not a major source. See the preamble section ``Summary of Responses
to Major Comments'' for further discussion of this issue about how a
source should determine whether it is a major or area source.
G. Reporting
A provision has been added to the final rule requiring that the
semi-annual summary report for the period in which the annual
combustion system component inspection was conducted include the
results of the inspection.
H. Exemption from New Source Performance Standards
To eliminate overlap or duplicate coverage of NSPS and MACT
standards for portland cement facilities, affected sources subject to
requirements under this NESHAP are exempted from requirements under 40
CFR 60, subpart F, the New Source Performance Standards. However, there
are two exceptions to this: kiln and in-line kiln/raw mills, and
greenfield raw material dryers, that are new or reconstructed sources
under the definition in Subpart F, and are located at area source
cement plants, would still be subject to applicable PM limits, opacity
limits, and recordkeeping and reporting requirements of the NSPS. The
reason for this is that these ``NSPS'' kilns and in-line kiln/raw
mills, and greenfield raw material dryers that are located at area
source cement plants would be subject to the NESHAP's D/F and/or THC
limits, but would not be subject to the NESHAP's PM limits, because
they are located at area source cement plants.
I. Delegation of Authority
The final rule reserves authority for approval of alternate
emission standards, major alternatives to test methods, major
alternatives to monitoring procedures and waivers of recordkeeping.
J. Test Methods 320, 321, and 322
Test Methods 320 and 321 are being promulgated with minor
corrections to clarify and improve test procedures, and correct
equations incorrectly stated in the proposal notice. Proposed Test
Method 322 is not being promulgated at this time as noted in Section F
above.
V. Summary of Impacts
A. Air Quality Impacts
The air quality impacts of the final rule are identical to those of
the proposed rule. Nationwide baseline HAP emissions from portland
cement manufacturing plants are estimated to be 260 Mg/yr (290 tpy) at
the current level of control. This rule will reduce emissions of HAPs
by 82 Mg/yr (90 tpy) from baseline levels. Estimates of annual
emissions of HAPs and expected reductions from implementation of this
rule are given in metric and English units in Tables 7 and 8. The
following text reviews the information provided in Tables 7 and 8.
[[Page 31908]]
Table 7.--Nationwide Annual Emission Reductions of HAPS and Other Pollutants From Portland Cement Manufacturing
Plants
(Metric units)
----------------------------------------------------------------------------------------------------------------
Baseline emissions (Mg/ Emission reduction [Mg/
Source Pollutant yr) yr]
----------------------------------------------------------------------------------------------------------------
Kilns, in-line kiln/raw HAP Metals a.............. 150....................... 35
mills, and alkali bypasses. PM a...................... 14,000.................... 3,400
D/F (TEQ) b............... 44 g/yr................... 16 g/yr
Organic HAPs c............ 120....................... 47
THC c..................... 530....................... 200
Clinker coolers............. HAP Metals a.............. 1.1....................... 0.18
PM a...................... 8,100..................... 1,300
----------------------------------------------------------------------------------------------------------------
a These numbers pertain to existing sources only.
b These numbers pertain to both new and existing NHW kilns.
c These numbers pertain to new greenfield NHW kilns only.
Table 8.--Nationwide Annual Emission Reductions of HAPS and Other Pollutants From Portland Cement Manufacturing
Plants
[English units]
----------------------------------------------------------------------------------------------------------------
Source Pollutant Baseline emissions (tpy) Emission reduction (tpy)
----------------------------------------------------------------------------------------------------------------
Kilns, in-line kiln/raw HAP Metals a.............. 160....................... 38
mills, and alkali bypasses. PM a...................... 16,000.................... 3,800
D/F (TEQ) b............... 0.096 lbs/yr.............. 0.035 lbs/yr
Organic HAPs c............ 130....................... 52
THC c..................... 580....................... 220
Clinker coolers............. HAP Metals a.............. 1.2....................... 0.2
PM a...................... 8,800..................... 1,400
----------------------------------------------------------------------------------------------------------------
a These numbers pertain to existing sources only.
b These numbers pertain to both new and existing NHW kilns.
c These numbers pertain to new greenfield NHW kilns only.
This rule will reduce PM emissions from the existing NHW cement
kilns and in-line kiln/raw mills by 3,400 Mg/yr (3,800 tpy) from the
baseline level, a reduction of 24 percent. Emissions of HAP metals from
the affected existing NHW cement kilns and in-line kiln/raw mills will
be reduced by 35 Mg/yr (38 tpy), a reduction of 24 percent from the
baseline level. Emissions of D/F TEQ will be reduced by 15 grams (g)/yr
(0.033 lb/yr), a reduction of 36 percent from the baseline level, at
existing NHW cement kilns and in-line kiln/raw mills located at major
source and area source facilities.
For new NHW cement kilns and in-line kiln/raw mills, the MACT
standards are projected to reduce emissions of D/F TEQ by an average of
0.6 g/yr (0.001 lb/yr) over the next 5 years (from major and area
sources), a 36 percent reduction from projected baseline emissions. For
new kilns, the MACT standards will also reduce projected emissions of
THC by an average of 200 Mg/yr (220 tpy) and organic HAPs by an average
of 47 Mg/yr (52 tpy) over the next 5 years, an emissions reduction for
each of 39 percent from corresponding estimated nationwide baseline
emissions.
The MACT standards will reduce PM emissions from 35 percent of the
existing clinker coolers by 1,300 Mg/yr (1,400 tpy) from the baseline
level, a reduction of 16 percent. Emissions of HAP metals from affected
existing clinker coolers will be decreased by 0.18 Mg/yr (0.2 tpy), a
reduction of 16 percent from the baseline level.
Additional reductions of THC and organic HAPs will result from the
MACT standards for new greenfield raw material dryers. However,
information on THC emission rates from raw material dryers and a
projection of the number of such affected sources is not currently
available, so nationwide reductions cannot be estimated.
B. Water Impacts
The impacts of the final rule are identical to those of the
proposed rule. Control of D/F emissions using water injection for
temperature reduction will result in an estimated increased water
consumption (evaporated into the kiln exhaust gas for cooling) of 190
million gallons per year for existing NHW kilns and NHW in-line kiln/
raw mills and 8 million gallons per year for new NHW kilns and NHW in-
line kiln/raw mills.
C. Solid Waste Impacts
The impacts of the final rule are identical to those of the
proposed rule. The amount of solid waste from existing NHW kilns, in-
line kiln/raw mills, and clinker coolers (located at major sources)
will increase by an estimated 4,700 Mg/yr (5,200 tpy) due to the
requirements for PM control in the final rule.
D. Energy Impacts
The impacts of the final rule are identical to those of the
proposed rule. For existing NHW kilns and NHW in-line kiln/raw mills
the MACT standards for PM and D/F will increase energy consumption by
an estimated 11 million kilowatt hours (KWh)/yr [38 billion British
thermal units (Btu)/yr]. For new NHW kilns and NHW in-line kiln/raw
mills the MACT standards for D/F will increase energy consumption by an
estimated 10,600 KWh/yr (36 million Btu/yr).
E. Nonair Health and Environmental Impacts
The reduction in HAP emissions will have a beneficial effect on
nonair health and environment impacts. Dioxin/furan and HAP metals have
been found in the Great Lakes and other water bodies and
[[Page 31909]]
have been listed as pollutants of concern due to their persistence in
the environment, potential to bioaccumulate, and toxicity to humans and
the environment. Implementation of the NESHAP will aid in reducing
aerial deposition of these emissions.
Occupational exposure limits under 29 CFR part 1910 are in place
for some of the regulated HAPs (and surrogates) not including D/F. The
National Institute for Occupational Safety and Health recommends an
exposure level for D/F at the lowest feasible concentration. The final
rule will reduce emissions, and consequently, occupational exposure
levels for plant employees.
F. Cost Impacts
For new and existing NHW kilns, NHW in-line kilns/raw mills,
clinker coolers, raw and finish mills, and materials handling
facilities, the projected overall total capital costs of the final rule
for controlling and monitoring emissions of D/F, PM (includes opacity),
and THC are $108 million. The overall projected annual costs of the
rule, for controlling and monitoring for D/F, PM (includes opacity),
and THC, are $37 million. For new and existing NHW kilns and NHW in-
line kiln/raw mills, the projected total capital and annual costs of
complying with the MACT standard for D/F (includes controls and
monitoring) are $15 million and $3.6 million, respectively. For new and
existing sources subject to PM and/or opacity limits, the projected
total capital and annual costs of complying with the MACT standards for
PM and opacity (including PM controls, PM CEMs, and continuous opacity
monitors) are $92 million and $33 million, respectively. With respect
to PM CEMs costs only, the projected total capital and annual costs of
PM CEMs are $15 million and 7.6 million, respectively. The THC
emissions limit for new greenfield NHW kilns, NHW in-line kiln/raw
mills and raw material dryers can be met by processing materials with
typical levels of organic content, without installing and operating
add-on pollution control systems that would be relatively costly. Feed
materials that have sufficiently low levels of organic matter are
widespread across the U.S., and the siting of new greenfield kilns is
not expected to be significantly limited by the emission limit. The
projected fifth-year national capital and annual costs of monitoring
THC with a continuous emission monitor for new greenfield NHW kilns,
in-line kiln/raw mills and raw material dryers are $0.75 million and
$0.45 million, respectively (based on an estimated four new affected
sources).
G. Economic Impacts
EPA conducted an economic analysis of the proposed NESHAP, and has
reconducted its analysis to include the costs of PM CEMs and the
monitoring of materials handling sources. The economic impacts of the
final rule are slightly greater than those of the rule as proposed.
Because the final standards may potentially include costs associated
with PM CEMs and the monitoring of materials handling sources, EPA
reconducted its economic analysis. This revised analysis evaluates a
regulatory option that is more stringent than the final standards.
Analyzing this more stringent option, which overstates the expected
compliance costs, causes the economic impacts presented here to over
estimate the expected impacts of the final standards. However, these
economic impacts are only slightly greater than those of the proposal
analysis.
The EPA estimates that regional market price increases of portland
cement will be between 0.3 and 2.6 percent. The national average price
increase is estimated to be 1.1 percent. The related decreases in
quantity demanded of portland cement are estimated to range from 0.3 to
2.3 percent, with a national average of 1.0 percent. Domestic
production of portland cement is estimated to decrease more than
consumption (2.2 percent compared to 1.0 percent nationally because
imports are estimated to increase by 5.5 percent). The decreases in
domestic production may lead to the loss of approximately 334 jobs in
the United States. No plants are expected to close; four kilns are
expected to cease operating.
VI. Summary of Responses to Major Comments
A complete summary of all of the public comments on the proposal,
and responses to these comments is provided in the ``Response to
Comments'' document available in the docket and from EPA's Technology
Transfer Network. The responses to major comments are given in this
section.
Portland Cement Source Category
Comment: Commenters raised objections to splitting the portland
cement category for cement kilns by the type of fuel (hazardous waste
vs. fossil fuels) burned in the kiln. The commenters stated that
splitting the industry by fuel type deviates from EPA's original source
category list (July 16, 1992 FR) which included only a portland cement
manufacturing category, and that no distinction is made regarding fuel
type under the New Source Performance Standards (NSPS) for portland
cement plants. The commenters were concerned that EPA's decision not to
use the NSPS category will result in what Congress hoped to avoid
(through section 112(c)(1)) by causing unnecessary costs and
dislocations in the cement industry.
Response: Section 112(d)(1) of the Clean Air Act specifically
provides that ``the Administrator may distinguish among classes, types
and sizes of sources within a category or subcategory in establishing
standards. . . .''. With regard to having separate categories/
subcategories, the EPA believes that there can be significant
differences in emissions due to hazardous waste burning that warrant
separate classes for these devices. The types of HAPs found in
emissions from hazardous waste-burning kilns are different from, and
more numerous than, those from NHW kilns. Hazardous wastes can contain
virtually any HAP, which in turn can be in stack emissions. The fact
that hazardous waste-burning kilns are dealt with separately under a
different statute (RCRA section 3004(q)(special standards for
industrial furnaces which burn hazardous waste fuels)) likewise
indicates that hazardous waste-burning cement kilns can be dealt with
legitimately as a separate class. Indeed, this existing RCRA regulatory
regime has created a different data base, and system of existing
controls, which can result in different analyses, different floor
controls and standards under the section 112 MACT process, again
indicating that these sources can reasonably be classified as a
distinct class. To summarize, this NESHAP for portland cement
manufacturing covers NHW kilns and NHW in-line kiln raw mills; it does
not apply to HW cement kilns which are subject to subpart EEE of this
part. This NESHAP also covers affected sources located at portland
cement manufacturing plants (such as clinker coolers, raw material
dryers, and materials handling processes), regardless of whether the
plant operates HW kilns.
Comment: Two commenters stated that EPA has not met its legal
burden to be consistent when regulating HW and NHW cement kilns. The
commenters stated that the EPA has not used consistent rationales and
approaches to develop emission limitations for the same pollutants.
Response: There are a number of differences between kilns that burn
hazardous waste and those that do not
[[Page 31910]]
in terms of process feed/fuel, process operation, pollutants and
pollutant quantities generated, existing regulations that impact MACT
floor determinations, and the economics of their operations. These
differences provide the bases for differences in determinations of MACT
floors, emission limits, and other regulatory requirements. When there
is no rational reason for differences between the two standards, EPA
has changed the two sets of rules (see section IV. of this preamble for
a discussion of changes made to this rule since proposal) to make them
more consistent.
Regulation of Cement Kilns Under Section 129
Comment: According to one commenter, the EPA is required to
regulate any facility that combusts any solid waste under section 129
of the Clean Air Act. However, EPA's current section 129 regulations
either: (1) Exempt portland cement kilns that burn any amount of
hospital waste, medical waste, and infectious waste from the medical
waste incinerator (MWI) rule, (2) exempt cement kilns that burn less
than thirty percent waste from the municipal waste combustor (MWC)
rule, or (3) have yet to be promulgated as the commercial and
industrial waste rule. The commenter asserts that the EPA cannot fail
to promulgate section 129 regulations for cement kilns that burn non-
hazardous solid waste by suggesting that it may promulgate section 129
regulations in the future. Cement kilns would then be permitted to
combust any of these wastes without complying with section 129, despite
the fact that the Clean Air Act expressly mandates that any unit
burning any solid waste must comply with section 129. Therefore, the
commenter asserts that the EPA must promulgate section 129 standards
for cement kilns that burn any solid waste now. If EPA cannot
promulgate section 129 standards immediately, the commenter asserts
that EPA must, at a minimum, include numerical emission standards for
the pollutants listed in section 129 (including mercury, cadmium, and
lead) in its proposed regulations under section 112.
Response: EPA does not read section 129 as precluding EPA from
promulgating an interim section 112 (d) standard for portland cement
kilns which burn non-hazardous solid waste. The interim alternative is
to have no regulation at all for HAP emissions. This is because the
only rules implementing section 129 explicitly do not apply to waste-
burning cement kilns (see 40 CFR sections 60.50b(p), 60.32b(m),
60.50c(g) and 60.32e(g)) and the explanation for these provisions in 62
FR at 45117 (Aug. 25, 1997) and 62 FR at 48538 (Sept. 15, 1997)).
Neither the commenter or any other person challenged these provisions,
and EPA is not reopening the section 129 rules for consideration here.
EPA does not regard interim non-regulation of non-hazardous waste
burning cement kilns as a reasonable alternative to including them
within the scope of these portland cement MACT regulations. Indeed,
were the Agency to exempt waste burning cement kilns from these MACT
standards, it would create a strong incentive for cement kilns to burn
waste to escape MACT regulation. EPA emphasizes, however, as we did at
proposal, that the standards in today's rule do not represent EPA's
final determination that only section 112 (d) standards are appropriate
or required for solid non-hazardous waste-burning cement kilns. Today's
action does not in any way foreclose an eventual section 129
standard.1
---------------------------------------------------------------------------
\1\ Any waste burning cement kiln subject to a section 129
standard would no longer be subject to these section 112 (d) MACT
standards. See CAA section 129 (h) (2).
---------------------------------------------------------------------------
With regard to the commenter's suggestion that EPA adopt specific
emission limits in this MACT rule for mercury, lead, and cadmium--which
are pollutants identified in Section 129 for regulation--as EPA
discussed at proposal, emission limits were considered in the MACT rule
for these pollutants. As discussed at proposal, EPA was unable to
identify a MACT floor for mercury. As a result, there is no mercury
emission limit which can be associated with a MACT floor. The use of
activated carbon injection (ACI) was considered by EPA as a ``beyond
the floor'' alternative. However, as also discussed at proposal, based
on the relatively low levels of existing mercury emissions from
individual NHW cement kilns and the costs of reducing these emissions
by ACI, EPA does not consider this beyond the floor alternative
justified. Thus, no mercury emission limit is included in the final
MACT rule, and thus would not be included even if this was a section
129 rule. Finally, as also discussed at proposal, EPA considers PM a
surrogate for semi-volatile metals (e.g., lead, cadmium, etc.). The
proposed rule and the final rule include a PM emission limit based on
the use of MACT. As a result, the final rule achieves reductions in
emissions of these pollutants consistent with MACT. Furthermore,
sufficient data do not exist to identify emission limits for lead and/
or cadmium associated with MACT and EPA is unable to establish emission
limits for these pollutants in this rule. See Sierra Club v. EPA, no.
97-1686 (D.C. Cir. 1999) slip op. at 15 (EPA is not obliged to
establish a MACT standard for HAPs for which the Agency is unable to
quantify emission reductions). Even if such emission limits could be
developed, however, they would not result in any further reduction in
emissions beyond that achieved by the MACT rule, given the PM standard.
Comment: Other commenters believe that cement kilns, irrespective
of their fuel or raw material mix, should be regulated under the
portland cement NESHAP and not under section 129 of the Clean Air Act.
Commenters stated that the EPA's discussion of its authority under
section 129 is irrelevant to, and inappropriate in, the proposed
portland cement NESHAP. They said that if EPA intends to regulate
cement kilns that burn solid waste materials under section 129, the
proper venue would be in a proposal pursuant to section 129. Commenters
stated that, based on the discussion of section 129, EPA has apparently
already determined how it intends to treat solid waste burning cement
kilns in the section 129 rulemaking. Ten commenters were concerned that
cement kilns could be subject to different regulations from year-to-
year (or day-to-day) depending on whether they trigger the section 129
applicability thresholds. The commenters believe that such a regulatory
structure is confusing, burdensome, inappropriate, and raises serious
legal issues. Commenters noted that the EPA's proposed regulation of
solid waste burning cement kilns under section 129 could lead to
increased fuel consumption and emissions of greenhouse gases as cement
kilns try to avoid triggering section 129 regulation by not burning
alternative fuels like solid waste.
Response: The EPA acknowledges all the comments dealing with the
potential future regulation under section 129 of the CAA of air
emissions from cement kilns that burn solid waste (other than hazardous
waste). Both the proposed and final promulgated portland cement NESHAP
apply to cement kilns which burn solid waste (other than hazardous
waste). If the EPA decides in the future that emission standards
developed under the authority of section 129 of the CAA are warranted
for cement kilns that burn solid waste, a separate rule will be
proposed to allow for public comment. The commenters' concerns
regarding duplicative regulations are misplaced, however. See CAA
section 129(h)(2)
[[Page 31911]]
(units can't be regulated simultaneously under both sections 129 and
112(d)(2)).
Regulation Under 112(c)(6)
Comment: Commenters stated that the EPA should not exercise its
authority under section 112(c)(6) to regulate dioxin/furan emissions
from area sources since the area sources have de minimis dioxin/furan
emissions and regulating them under section 112 will impose significant
burdens (for reporting, recordkeeping, monitoring, and control
technology) while providing negligible environmental benefits. These
commenters further state that EPA's own estimates indicate D/F
emissions from NHW kilns contribute only 0.8 percent of total
nationwide D/F emissions. The commenters do not believe that Congress
intended such a result in drafting section 112(c)(6).
Response: Regarding the above comments about regulation of D/F
under section 112(c)(6), the EPA is required by section 112(c)(6) to
``list categories and subcategories of sources assuring that sources
accounting for not less than 90 per centum of the aggregate emissions
of each such pollutant are subject to standards under subsection (d)(2)
or (d)(4) of this section.'' The method for identifying and selecting
sources for listing and regulation under these subsections was
discussed at length in Federal Register notices published on June 20,
1997 (62 FR 33625) and April 10, 1998 (63 FR 17838). Section 112(c)(6)
does not provide for de minimis exemptions for source categories, but
rather directs EPA to make findings on the basis of what is necessary
to meet the requirement to assure that sources accounting for 90
percent of the emissions of these pollutants are subject to standards.
Moreover, because the pollutants addressed by section 112(c)(6) are
persistent, that is, they remain in the environment for extremely long
periods of time without breaking down, the EPA believes that any claims
of de minimis contributions should be considered with great caution,
and granted in only very exceptional circumstances. Consequently, the
EPA believes that its decisions in response to section 112(c)(6)
represent a reasonable exercise of its discretion within the
constraints of that subsection.
Comment: Several commenters stated that EPA's proposed action to
regulate cement kiln ``area sources'' under CAA section 112(c)(6)
violates the CAA and is arbitrary and capricious. They stated that the
EPA has improperly proposed to apply the MACT standards to area source
cement kilns and other HWCs before deciding upon listing criteria and
preparing the overall list or lists of sources required by that
provision. In referring to EPA's proposal to regulate area sources of
112(c)(6) pollutants, they stated their view that only those 112(c)(6)
pollutants for which a source category is listed under 112(c)(6) should
be regulated.
Response: Regarding the initial portion of the above comment, the
notice of the final source category listing for section 112(d)(2)
rulemaking pursuant section 112(c)(6) requirements was published April
10, 1998, in 63 FR 17838-17855. The referenced notice provides the
required listing of area sources, and therefore the commenter's point
is moot.
The proposed rules for NHW kiln portland cement manufacturing would
only have regulated area sources for
D/F emissions, which is one of the pollutants for which these plants
are listed as area sources. The pollutants for which portland cement
NHW kilns were listed under 112(c)(6) are polycyclic organic matter
(POM), D/F, and mercury. At proposal, the EPA had conducted an analysis
under section 112(d)(2) for D/F and mercury with respect to
establishing emission standards, and concluded that area sources of D/F
should be regulated. The analysis for mercury showed that the MACT
floor for new and existing sources was no control. The BTF technology,
use of activated carbon injection, was determined not to be cost-
effective. Therefore, no emission standard was proposed for mercury.
The preamble for the proposed rule stated that POM emissions (using
THC as a surrogate) from portland cement NHW kiln area sources would be
subject to MACT standards under EPA's interpretation of section
112(c)(6). A THC emission standard was proposed for new raw material
dryers and new NHW in-line kiln/raw mill main exhausts at cement plants
that are major sources. At proposal, THC was identified as a surrogate
for organic HAP emissions, which would include POM. The final rule's
limits on THC emissions are applicable only to new greenfield kilns,
in-line kiln raw mills, and raw material dryers, for reasons discussed
in section IV.C. of this preamble. EPA is clarifying today that since
THC is a surrogate for POM, the THC emission limits are applicable to
new greenfield kilns and raw material dryers at cement plants that are
major and area sources.
Comment: Several commenters stated their support for an alternative
interpretation of regulating area sources emitting HAPs listed under
112(c)(6). They stated that section 112(d)(5) does not exclude area
source categories listed pursuant to section 112(c)(6) from the
Agency's discretionary authority to apply GACT standards nor does
section 112(c)(6) prohibit EPA from exercising its discretionary
authority under section 112(d)(5). According to the commenters, section
112(d)(5) grants the Administrator authority to establish GACT
standards for any area sources listed pursuant to section 112(c),
whether such sources are listed pursuant to section 112(c)(3) or
(c)(6). They contended that had Congress intended to exclude section
112(c)(6) area sources from the GACT standards under section 112(d)(5),
Congress would have stated this exclusion in section 112(d)(5).
Another commenter argued against the alternative interpretation
owing to the bioaccumulation potential of the 112(c)(6) pollutants and
the fact that the GACT approach would include no floor analysis or
residual risk assessment.
Response: Section 112(c)(6) specifically states that EPA is to
assure that sources of the pollutants to which this subsection applies
be subject to standards under subsections (d)(2) or (d)(4). These
subsections refer, respectively, to MACT and standards for pollutants
for which a health threshold has been established (a null set of
purposes for this rule). The natural reading of the provision (and at
the least, a permissible one) is to say that MACT standards apply to
emissions of 112(c)(6) HAPs from all sources. The alternative reading,
that GACT requirements could apply because GACT requirements apply in
lieu of section 112d(2) MACT requirements reads language into section
112c(6) not apparent on its face. Moreover, where Congress wished to
reference subsection (d) without limitation, it omitted references to
specific paragraphs. Compare the language of section 112(c)(6), which
refers to standards under subsection (d)(2) or (d)(4), with the
language of section 112(k)(3)(B)(ii), which refers to standards under
subsection (d). In addition, the reading suggested by the industry
commenters goes against the natural purpose of section 112c(6), namely,
to assure that the maximum available control technology is applied to
control the emission of the most dangerous HAPs. (This is also the
thrust of the comment summarized above criticizing the reading
suggested by industry commenters. EPA agrees with this comment.) The
Agency has therefore concluded that none of the comments provided
compelling facts or arguments to overcome the interpretation that
section 112(d)(2) specifically refers to MACT standards.
[[Page 31912]]
Regulatory Flexibility Act and the Small Business Regulatory
Enforcement Fairness Act
Comment: Several commenters stated or supported the belief that the
proposed rulemaking was incorrectly certified, contending that no
factual basis was provided for the Agency's certification of no
significant impact on a substantial number of small entities, and thus,
EPA is not in compliance with provisions of the Regulatory Flexibility
Act (RFA), 5 U.S.C. 601 et seq. They stated that EPA needs to review
its certification and provide a factual basis for it or complete an
initial regulatory flexibility analysis, as required by the RFA.
The commenters contended the certification was deficient in that
the Agency's guidance allows regulators to bypass a regulatory
flexibility analysis if the industry has fewer than 100 firms.
Furthermore, the seven small companies, representing 16 percent of the
total number of affected companies, constitutes a ``substantial
number.'' Some commenters also stated their concern that even at a less
than one percent cost-to-sales ratio effect on small businesses there
could be a significant economic impact. Another commenter stated that
EPA had not evaluated ``reasonable worst case'' impacts for any single
plant. Several commenters requested more information regarding EPA's
assessment of small business impacts and steps taken to minimize the
impacts.
Response: The following discussion responds to the small business
impact issues raised by the commenters. In accordance with the RFA, the
Agency conducted a small business assessment and based its finding of
``no significant impact on a substantial number of small entities'' on
the reported impacts of the proposed NESHAP on small businesses within
the cement industry (Docket Item II-A-46, Table 4-7; Docket Item IV-C-
15). The Agency did not intend to suggest that this certification was
based solely upon the number of small businesses potentially affected
by the rule, nor that the Agency sets thresholds for determining
whether a particular number of businesses is a substantial number or a
particular impact is a significant impact. The EPA did not certify that
the rule would have no significant impact on a substantial number of
small firms based solely on there being less than 100 firms subject to
the rulemaking (Docket Item II-C-14). To clarify the factual basis of
EPA's determination and address subsequent comments, a summary of the
Agency's small business assessment is provided below.
Based on SBA-defined small business criteria, the Agency originally
identified nine of the 44 companies within the U.S. cement industry as
small businesses, or roughly 20 percent of total. However, based on
updated information and changes in ownership since 1993, the Agency
determined that four of these companies should not be considered small
businesses. The APCA indicated that there are currently seven small
businesses within this industry. This list includes the remaining five
identified by the Agency plus Dacotah Cement and Royal Cement Company.
Dacotah Cement is owned by the State of South Dakota and, thus, was not
considered a small business by the Agency. Royal Cement Company began
operations in 1995 after the Agency had completed its small business
assessment and, thus, was not included in the Agency's small business
assessment because EPA's engineering and economic data base did not
contain information on this relatively new facility.
The Agency typically uses the cost-to-sales ratio as a measure of
impact on small businesses. This ratio refers to the change in the
annual control cost divided by the annual revenue generated from sales
of the particular good or goods being produced in the process for which
additional pollution control is required. It can be estimated for
either individual firms or as an average for some set of firms such as
affected small companies. While it has different significance for
different market situations, it is a good rough gage of potential
impact. In this case, to develop the cost-to-sales ratios, the Agency
used the estimated control costs specific to the kilns operating at
each manufacturing plant owned by a small business divided by their
baseline cement sales. Contrary to industry's comments, the cost-to-
sales measure of impact used by the Agency is a conservative approach
and may, in fact, overstate the regulatory burden on small businesses
for two reasons: (1) The Agency's sales estimate understates company
sales because it only reflects cement operations and most companies
have other vertical or horizontal business lines; and (2) this measure
does not account for the expected market adjustments, i.e., increase in
market prices that can potentially offset a portion of the regulatory
costs.
For the economic impact analyses, the regulatory control costs were
input to an economic model to predict outcomes at the market and plant
level, including the impacts for markets served by manufacturing plants
owned by small businesses. As shown in Table 4-7 of the EIA report
(Docket Item II-A-46), the Agency did not project any plants or kilns
owned by the original nine small businesses to close as a result of the
proposed NESHAP.
As summarized in the Agency's June 10, 1998, letter to industry
(Docket Item IV-C-15), a second small business assessment was conducted
for the small businesses identified by the APCA. The weighted average
cost-to-sales ratio for these small businesses was 0.93 percent with no
plants or kilns projected to cease operations (Docket Item IV-B-5).
A third small business assessment was conducted to include the cost
of PM CEMs and the monitoring of materials handling operations. (The
promulgated rule requires the installation of PM CEMs, and more
frequent monitoring of materials handling operations than included in
the proposed rule. See Section IV and this section for further
discussion of these requirements). The new weighted average cost-to-
sales ratio for the small businesses was 1.4 percent with no plants or
kilns projected to cease operations. See Docket Item IV-B-11 for the
resulting company-specific cost-to-sales ratios for this third
analysis. Further, to measure the relative regulatory burden on small
businesses, these impacts at small businesses can be compared to those
for the whole industry. See Docket Item IV-A-4 for this comparison.
As discussed above, based on the Agency's revised small business
impacts assessments, which now include the cost of PM CEMs and other
monitoring costs not considered at proposal, the Agency concludes that
this NESHAP as promulgated today will not have a significant impact on
a substantial number of small businesses. Nevertheless, EPA will
reassess, as appropriate, small business impacts in the future proposed
rulemaking that will establish the date that PM CEMs must be installed
on NHW cement kilns.
Comment: One commenter stated that EPA must have objective,
reasonable certainty that there will be no pertinent impacts on small
entities or it cannot validly certify. The EPA must create a testable
record against which the validity of certifications could be judicially
reviewed. 5 U.S.C. 611(a) and (b). The commenter further claimed that
EPA's SBREFA Guidance states that when EPA ``cannot or does not certify
that a proposed rule will not have a significant impact on a
substantial number of small entities, it must prepare a regulatory
flexibility analysis for the proposed rule.'' The commenter
[[Page 31913]]
does not believe EPA has met this burden for the proposed rule.
Response: Section 605(b) provides an exemption from the
requirements in sections 603 and 604 to conduct a regulatory
flexibility analysis when the Agency ``certifies that the rule will
not, if promulgated, have a significant economic impact on a
substantial number of small entities.'' The EPA has made this
certification for the rulemaking. The EPA believes its interpretation
of the requirements of the RFA is reasonable and that its factual basis
for certification is also reasonable.
To the extent that the commenter is suggesting that the RFA
requires more than a reasonable basis for its decision to certify, the
EPA disagrees. Courts review compliance with the RFA in accordance with
Chapter 7 of the Administrative Procedure Act (APA), 5 U.S.C. 701, et
seq. See 5 U.S.C. 611(a)(1) and (2). Under the APA, courts generally
provide substantial deference to agency decisionmaking and will only
set aside administrative actions or findings if the court concludes
that the agency's action or finding was arbitrary, capricious, or
otherwise contrary to law. 5 U.S.C. 706(2)(A). The Supreme Court has
explained, ``To make this finding the court must consider whether the
decision was based on consideration of the relevant factors and whether
there has been a clear error of judgement.'' Citizens to Preserve
Overton Park v. Volpe, 401 U.S. 415 (1971). The EPA believes that its
detailed economic analysis more than adequately supports its conclusion
that the rule will not result in a significant impact on a substantial
number of small entities.
Comment: The same commenter believes SBREFA can only be interpreted
to allow numerical cutoffs based on the percentage of all small
entities in the regulated universe that experience any impact. The
commenter contends that when a rule impacts all the small entities in
an industry, the statute a fortiori requires an analysis of whether
those impacts are significant, and precludes a certification based
solely on any absolute number of small entities impacted. By the same
token, if the percentage of small entities experiencing any impact is
more than de minimis, a similar analysis appears required. The
commenter contends that this concept has been repeatedly recognized by
EPA findings that impacts on more than 20 percent of the small entities
within a universe proposed to be regulated constitute a ``significant
number.'' 61 FR 48206, 48228 (September 12, 1996); 59 FR 62585, 62588
(December 6, 1994). It also lies at the heart of the ``impacts'' matrix
in EPA's SBREFA Guidance. The commenter notes that under that matrix,
greater ``impact'' priority is assigned to rules that will impact a
larger percentage of small entities, even if the impacts are relatively
low.
Response: Other than small entities, the RFA does not define the
term, or any part of the term, ``significant impact on a substantial
number of small entities.'' Thus, the statute does not specify whether
an agency may properly certify a rule either because there is not a
significant impact on small entities, or because, even if the impact is
significant, there are not a substantial number of small entities
affected. In any event, the EPA has chosen not to establish any
mechanistic approach for determining when an impact is significant or
when the number of small entities is substantial. Instead the EPA
considers a variety of approaches depending on the particular
circumstances of the rulemaking. In general, the EPA looks at both the
extent of the potential impact and the number of small entities
impacted to decide whether a more detailed regulatory flexibility
analysis pursuant to sections 603 and 604 of the RFA is warranted. The
EPA's Guidance repeatedly explains that the criteria offered in the
Guidance cannot be applied mechanistically and that rule writers should
consider other relevant information in deciding whether or not to
certify a rule.
EPA's analysis of both the number of small entities impacted and
the extent of that impact are described in previous responses in this
section of this preamble, and as indicated above, the EPA has not
certified this rulemaking based solely on the number (or percentage) of
small entities.
Economic Impact Analysis
Comment: Several commenters believe that the final EPA economic
analysis at proposal was inaccurate and should be either revised to
reflect industry's comments (in Attachment G to docket item IV-D-26) or
withdrawn. Another commenter stated that EPA's model economic impacts
data are seriously flawed because:
1. The model would not detect company-level impacts.
2. The economic analysis is not based on any estimate or analysis
of actual small-entity impacts but is based on an aggregated industry
wide economic model based on theoretically constructed model kilns.
3. The model predicts that older smaller dry kilns will close,
which is counterintuitive because wet kilns are substantially more
costly to operate per unit of product.
4. Flaws in the market-specific part of the model which lead
directly to the modeled conclusion that profits will increase with more
stringent control.
Response: The EPA disagrees with the preceding comments suggesting
the analysis is inaccurate and should be withdrawn. The Agency
developed its economic analysis based on the best available information
using an accepted approach firmly rooted in economic theory to provide
the necessary impact results to satisfy legislative and administrative
requirements. Furthermore, the Agency conducted a revised economic
impact analysis in response to the additional monitoring requirements
for cement kilns and materials handling operations at major source
cement plants (as fully described in Appendix G recently added to the
July 1996 EIA report, Docket Item II-A-46). In conducting this revised
analysis, the Agency also updated the original 1993 baseline
information that supported the economic analysis for proposal to 1995
and is thereby consistent with the baseline used by the Agency for the
Cement Kiln Dust (CKD) rulemaking and Hazardous Waste Combustion MACT
Standards. This adjustment to the baseline characterization results in
some differences in the projected economic impacts from the proposal
analysis. In particular, under 1995 baseline conditions, the model
predicts an aggregate loss in industry profits because of the sharp
reduction in excess U.S. cement capacity from 1993 to 1995. This
increase in capacity utilization to roughly 94 percent in 1995 severely
limits the ability of unaffected (and slightly affected) domestic
producers to offset production declines at affected cement plants. As a
result, the potential profit gains to these producers from offsetting
these reductions is no longer present in 1995 as in 1993 and the
economic model predicts an aggregate loss in pre-tax earning of the
U.S. industry, which is consistent with the expectations of the
commenter. However, this occurs through the difference in baseline
characterization rather than flaws in the Agency economic model and
approach.
The following responses address the above comments that are
specific to the economic analysis conducted for the regulation as
originally proposed. First, the comments are specific to a draft
version of the EIA report that has been revised. Comments were
addressed in changes to the analysis prior to proposal as follows:
[[Page 31914]]
1. As the commenter suggested, the economic model incorporated a
more realistic assumption for the elasticity of supply from foreign
imports.
2. According to the commenter the draft EIA report did not
adequately describe the basis for defining the regional markets used in
the economic analysis and led to some confusion and/or
misinterpretation by the industry as reflected in its comments.
Contrary to assertions, the Agency's economic model does not omit any
market areas as all U.S. production and consumption of cement is
accounted for within the 20 regional markets as defined by the Agency.
The Agency utilized the best available information in defining regional
markets to better account for the regional competition within the
industry.
3. The commenter claimed the draft EIA report did not adequately
describe the basis for selecting the imperfectly competitive market
structure for the cement industry and the implications of this
selection of the economic impact results. The Agency's selection of
market structure was not an attempt to distort the economic impact
results or to infer that the industry is collusive and lacks any
competition. Rather it was selected to provide better estimates given
well-known characteristics of the industry. The Agency has
appropriately modeled the competitive interaction between domestic
producers of cement as well as foreign imports (where applicable)
within each regional market in a manner that is consistent with the
empirical evidence for cement markets and economic theory.
In regard to the statement that the economic impact data are flawed
and accompanying reasons, the Agency responds as follows:
1. The economic impact analysis does allow the Agency to detect
company-level impacts by aggregating the estimated control costs and
related economic impacts at all manufacturing plants owned by each
company, both large and small. Although the issue of capital
availability is an important consideration for small businesses, it is
not typically addressed in EPA economic analyses of regulatory actions
as it requires company-specific information not available to the Agency
and, moreover, there is not a generally accepted method with which to
model and analyze this complex issue in the context of environmental
regulation.
2. The Agency's characterization of costs at individual kilns was
based on the econometric estimation of cost functions for cement kilns
by Das (1991 and 1992). Using the best information available, the EPA
made adjustments to these cost functions to better reflect the
operating costs of kilns by process type and capacity (as fully
described in Appendix C, Docket Item II-A-46). However, in accounting
for size or economies of scale in estimating baseline operating costs,
the Agency was limited by the two capacity size classifications of less
than and greater than 500,000 short tons per year for which labor
productivity and fuel consumption were reported by the Portland Cement
Association. This data limitation prevents the EPA from developing
baseline cost functions for very small kilns and, effectively, ``lumps
smaller kilns in with mid-size kilns into a larger class'' of all kilns
as stated by industry. Therefore, it is possible that the EPA's
economic model understates the baseline operating costs at very small
kilns. However, the Agency is able to estimate the incremental
compliance costs for many categories of kiln capacity below 500,000
short tons per year ranging from 55,000 to 450,000 short tons per year.
This more detailed classification scheme for estimating the regulatory
compliance costs reduces the uncertainty related to the Agency's
estimates of kiln closures.
3. The Agency agrees with the industry comment that wet kilns are
generally more costly to operate, which has contributed to their use of
hazardous waste to reduce their fuel costs and remain competitive with
the dry process kilns, especially those using precalciner and/or
preheater technologies. However, the economic impacts of the proposed
NESHAP depend not only on the baseline costs of cement production but
also on the incremental costs of compliance for each kiln. The proposed
NESHAP largely impacts non-hazardous waste burning kilns as opposed to
hazardous waste kilns that are most often wet process kilns. As stated
in the EIA report, it is the higher relative incremental cost impact
compared to that for its competitors that causes the Agency's model to
project closure for two dry process kilns under the proposed NESHAP.
Furthermore, the baseline costs of cement production were high for
these kilns because they were each older and smaller than average.
Thus, the projected closures are actually consistent with the
commenter's statement that older and smaller kilns are more vulnerable
to closure with regulation. Moreover, in the final EIA report, the
Agency provides closure estimates for additional regulatory
alternatives and, for more stringent ``above-the-floor'' alternatives,
the economic model projects up to 10 kilns to close including 5 wet
process kilns. Thus, the Agency believes that its economic model
produces closure estimates that are consistent with the commenter's
characterizations.
4. Although the Agency projects a net increase in profits for the
cement industry as a whole in response to regulation, there is a
``social cost'' to reducing hazardous air emissions from the
manufacture of cement. As shown in the final report, the Agency
estimates that society must give up $34.5 million per year for the
expected environmental benefits (as compared to the $28.8 million in
regulatory compliance costs incurred by industry after market
adjustments). Furthermore, factors cited by industry are not the reason
for the model's prediction of a net increase in profits for the
industry as a whole. The Agency believes that it has appropriately
modeled the competitive interaction between domestic producers of
cement as well as foreign imports (where applicable) within each
regional market in a manner that is consistent with the empirical
evidence for cement markets and economic theory.
Related to the net increase in profits for the industry as a whole,
several commenters were surprised that the economic analysis predicts
an increase in cement plants' pretax earnings. They interpreted this as
applying to individual plants, which is a misinterpretation. The
economic analysis projects a net increase in the U.S. cement industry's
pre-tax earnings, which reflects profit gains at unaffected or
relatively less affected cement plants and profit losses at affected
plants that incur higher relative compliance costs. Thus, the
commenter's statement that each cement plant's pre-tax earnings will
increase by X dollars for every dollar spent on compliance is incorrect
as these impacts are distributed across different plants. Also, the
estimated price increase applies to all cement produced by U.S.
manufacturing plants whereas the MACT compliance costs apply only to
cement produced at affected plants. Therefore, the commenter's
calculation of the projected price increase as a share of MACT
compliance costs is also incorrect as the commenter is understating the
relevant change in cost by dividing the MACT compliance costs by all
cement produced rather than only the affected share of cement
production. The projected increase in pre-tax earnings is a net result
for the industry that results from losses at some cement plants that
are offset by gains at other cement plants.
[[Page 31915]]
PM CEMs
Comment: Numerous comments were received stating that the EPA has
not fully considered the impacts of a potential requirement for PM CEMS
applied to NHW kilns, and that PM CEMs have not been adequately
demonstrated on cement kilns.
Response: In the preamble to the proposal, EPA noted its intent to
include a requirement for PM continuous emission monitoring system
(CEMS) in the final rule, unless the analysis of existing or newly
acquired data and information showed that it is not appropriate (see 63
FR at 14205). Based on successful testing on an incinerator conducted
in the interim, as well as extensive use of these monitors in Europe,
EPA believes there is sound evidence that PM CEMS should work at cement
kilns. In addition, preliminary analyses of the cost of PM CEMS applied
to cement kilns (docket items IV-C-1 and IV-C-21) and hazardous waste
combustors (HWC) suggest that these costs are reasonable. Accordingly,
the final rule contains a requirement to install PM CEMS. However, we
agree with comments that indicate a need to develop cement kiln-
specific performance requirements for CEMS and to resolve other
outstanding technical issues. These issues include all questions
related to implementation of the CEM requirement (i.e. relation to all
other testing, monitoring, notification, and recordkeeping), relation
of the CEM requirement to the PM emission standard, as well as
technical issues involving performance, maintenance and correlation of
the CEM itself. These issues will be addressed in a subsequent
rulemaking. Therefore, we are deferring the effective date of this
requirement pending further testing and additional rulemaking. As a
result, in today's final rule, EPA is requiring that particulate matter
continuous emission monitoring systems (PM CEMS) be installed at cement
kilns. However, since the Agency has not finalized the performance
specifications for the use of these instruments at cement kilns or
resolved some of the technical issues noted above, we are deferring the
effective date of the requirement to install, correlate, maintain and
operate PM CEMS until these actions can be completed. The PM CEMS
installation deadline will be established through future rulemaking,
along with other pertinent requirements, such as final Performance
Specification 11, Appendix F Procedure 2. It should finally be noted
that EPA has a concurrent rulemaking process underway for hazardous
waste combustors (HWC) and plans to adopt the same approach in that
rule.
EPA also is taking action now to avoid facilities being in
violation of the PM standard during CEM correlation testing. Commenters
properly observed that CEM correlation testing would require sources to
manipulate their PM control device during correlation tests to obtain
higher PM emissions levels than the emission limit. It is necessary to
do so because a good PM CEMS correlation must include CEMS and manual
method data above the stated emission standard in order to have a wide
enough range of data to meet the correlation coefficiency statistical
requirement and to assure that calibrated readings above the level of
the emission standard can be properly interpreted. Such data, however,
could be misconstrued by state or local enforcement authorities or
citizens as violations of the PM standard. It is important to address
this issue now to encourage the development of additional PM CEMS data,
and not to discourage facilities from choosing to install a CEM before
the deferred effective date.
We are addressing this concern here in the same manner we plan to
address it in the HWC MACT rule by providing that the particulate
matter and opacity standards of parts 60, 61, 63 (i.e., all applicable
Parts of Title 40) do not apply during particulate matter CEMS
correlation testing, provided that you comply with certain provisions
discussed below that ensure that the provision is not abused. EPA is
also making this provision effective immediately, so that sources need
not wait for the compliance date to take advantage of this particulate
matter CEMS correlation test provision. We believe this approach
adequately addresses commenters' concerns.
The temporary exemption from particulate matter and opacity
standards is conditioned on several requirements. Sources are required
to develop and submit to permitting officials a PM CEMS correlation
test plan along with a statement of when and how any excess emissions
will occur during the correlation tests (i.e., how you will modify
operating conditions to ensure a wide range of particulate emissions,
and thus a valid correlation test). If the permitting officials fail to
respond to the test plan in 30 days, the source may proceed with the
tests as described in the test plan. If the permitting officials
comment on the plan, the source must address those comments and
resubmit the plan for approval. In addition, runs that exceed any PM or
opacity emission standard are limited to no more than a total of 96
hours per correlation test. This 96 hours is sufficient time for a
source to increase emissions to the desired level and reach system
equilibrium, conduct testing at the equilibrium condition followed by a
return to normal settings indicative of compliance with emissions
standard(s) after those higher emissions data have been obtained, and
return to equilibrium at normal conditions. Finally, to ensure these
periods of high emissions are due to the bona fide need described here,
a manual method test crew must be on-site and making measurements (or
in the event some unforeseen problem develops, prepared to make
measurements) at least 24 hours after you make equipment or workplace
modifications to increase PM emissions to levels of the high
correlation runs.
Selection of Emission Limits in General
Comment: One commenter stated that according to section 112(d) EPA
may not base the floors of its emission standards on a particular
technology. Instead, emission standards for existing sources must be no
less stringent than ``the average emission limitation achieved by the
best performing twelve percent of the existing sources'' (for which EPA
has data). The commenter further stated that for new sources, standards
must be based on the emission control that is achieved in practice by
the best controlled similar source. Thus, the standards proposed for
emissions of dioxins, mercury, total hydrocarbons, and hydrogen
chloride are not valid.
Response: First, it should be noted most of the commenter's points
were recently rejected by the DC Circuit in Sierra Club v. EPA (March
2, 1999). That case holds that because MACT standards must be
achievable in practice, EPA must assure that the standards are
achievable ``under most adverse circumstances which can reasonably be
expected to recur'' (assuming proper design and operation of control
technology). Slip op. p. 13. The case further holds that EPA can
reasonably interpret the MACT floor methodology language so long as the
Agency's methodology in a particular rule allows it to ``make a
reasonable estimate of the performance of the top 12 percent of
units'', slip op. p. 7; that evaluating how a given MACT technology
performs is a permissible means estimating this performance, id. at 13;
and that new source standards need not be based on performance of a
single source, id.
Second, the commenter provided no additional emissions data for any
pollutant. The EPA has selected emission limits at the floor level of
[[Page 31916]]
control. Section 112(d) requires EPA to promulgate emission standards
based on what is determined to be achievable through the application of
techniques, methods, etc. The rule does not require the use of any
specific technology to meet the emission standard. The emission
standards are based on the emissions levels achieved through the
application of MACT floor technologies and account for variation in the
process and in the air pollution control device effectiveness.
Although the commenter did not specifically mention PM, the
following discussion using PM as an example will help clarify EPA's
approach in setting MACT standards for this source category. The EPA
evaluated the PM MACT floor technology for both existing and new
sources at proposal and determined that the MACT floor technology is
properly designed and operated FFs and ESPs. Commenters provided no
data to suggest that a particular design or operating mode, or an
alternative technology could achieve a lower level of PM emissions on a
consistent basis. Nor did EPA identify other technologies for existing
or new kilns or in-line kiln/raw mills that would consistently achieve
lower emission levels of PM than the NSPS limit.
As discussed in docket item number IV-B-10, the data upon which the
MACT floor was based were obtained from EPA Method 5 compliance tests
on kilns subject to the NSPS and represent performance of PMCDs
associated with new kilns over a relatively short period (typically
three 1-hour test runs). These test data were obtained at kilns
equipped with well designed and operated ESPs and FFs representative of
the MACT floor, which is also represented by the NSPS emission level.
Method 5 testing of these cement kilns equipped with MACT floor
technology showed a range of emissions up to the NSPS level. Additional
Method 5 tests performed on some of the same kilns included in the MACT
floor analysis showed PM variations after control as plotted in docket
item IV-B-10. EPA believes that the data base--which shows cement kilns
with properly designed and operated fabric filters and electrostatic
precipitators achieving levels up to and including the NSPS level--
adequately accounts for the variability inherent in the air pollution
control technologies, and indicates what PM levels are consistently
achievable in practice. See Sierra Club, slip op. p. 13. In summary,
the PM emission limit reflects an emission level consistently
achievable with the use of well designed and operated MACT floor
technology.
The emission standard for dioxin is based on the emission level
achievable through the application of the MACT floor control
technology, which is exhaust gas temperature control at the inlet to
the PM control device to less than 400 deg. F, and efficient
combustion. Based on data evaluated at proposal, the technology can be
represented by the dual standard of 0.2 ng TEQ/dscm or 0.4 ng TEQ/dscm
with a PM control device inlet temperature of 400 deg. F or less. Since
the commenter provided no additional data, the EPA has reviewed, in
response to this comment, the existing test data and literature on D/F
formation and concluded that the selected emission limits are
consistently achievable and represent the MACT floor. Similar to the
discussion above regarding the PM data, the D/F performance test data
are based on short-term tests of facilities using the MACT floor
technology. Thus the proposed emission limits are retained and account
for normal, inherent process and air pollution control operating
variability, including the use of various fuels.
As discussed in the proposal preamble, there are no standards for
THC emissions from existing sources because the MACT floor for control
of THC for existing sources is no control. Further, the BTF control
technique for existing sources, and a floor control for new sources,
would be based on the performance of precalciner/no preheater
technology. However, as discussed in the proposal, EPA rejected this
technology as a basis for setting THC emission limits because of the
technology's negative environmental and energy impacts. The basis for
the THC limit for new greenfield kilns is site selection to ensure low
hydrocarbon content in feed materials. (In the proposal, the THC limit
applied to all new kilns, but based on comments received, the rule has
been changed such that the THC limit will only apply to new greenfield
kilns. See comment responses regarding this issue for more detail.) As
discussed in the proposal, this option is not available to existing
(and new brownfield) kilns, in that facilities are generally tied to
existing raw material sources in close proximity to the facility, so
that raw material proximity (i.e., transportation cost) is usually a
major (indeed, critical) factor in plant site selection.
As discussed in the proposal preamble, no standards are being
adopted for Hg and HCl because the MACT floor has been determined to be
no control and the BTF controls were not cost effective (docket item
II-B-67).
This standard was developed under section 112, not section 129, so
there is no statutory requirement to establish standards for individual
HAP metals. However, control of cadmium, lead, and other non-volatile
and semi-volatile metal HAPs is achieved via the floor level-based
emission limit for PM, which serves as a surrogate for the non-volatile
and semi-volatile metals. This is supported by data from coal-fired
electric utility boilers which show relatively high HAP metals (except
mercury) removal with fabric filters and electrostatic precipitators.
(Study of Hazardous Air Pollutant Emissions from Electric Utility Steam
Generating Units--Final Report to Congress, volume 1, 453/R-98-004a,
February 1998, p. 13-23 and 13-26).
PM Limits
Comment: Numerous commenters supported the use of PM as a surrogate
for non-volatile HAP metals. One commenter questioned the use of PM as
a surrogate for HAP metals, and suggested that the EPA require stack
testing for specific metal content.
Response: The final rule retains the use of PM as a surrogate for
HAP metals because the MACT floor equipment and level of control for
HAP metals, i.e., properly designed and operated fabric filters (FFs)
and electrostatic precipitators (ESPs), is identical to that for PM.
Using PM as a surrogate for specific HAP metals eliminates the cost of
performance testing to comply with numerous standards for individual
metals, and achieves exactly the same level of HAP metal emissions
limitation.
Comment: Although many commenters were in favor of the MACT floor
determination and associated emission limit for PM (see docket item,
number to be assigned), several other commenters suggested that more
stringent PM standards were required in recognition of the performance
test data presented in the preamble showing that many affected sources
achieved lower levels of PM emissions than the proposed standard.
Response: The proposed PM standards have been retained in the final
rule. EPA evaluated the MACT floor technology for both existing and new
sources at proposal and determined that the MACT floor technology is
properly designed and operated FFs and ESPs. Commenters provided no
data to support that an alternative design or technology represents a
floor that could achieve a lower level of PM emissions on a consistent
basis. The EPA did not identify other technologies for existing or new
kilns or in-line kiln/raw mills that would consistently achieve lower
emission levels of PM than the NSPS limit.
[[Page 31917]]
As discussed in the proposal preamble, the data upon which the MACT
floor was based were obtained from EPA Method 5 compliance tests on
kilns subject to the NSPS and represent performance of PMCDs associated
with new kilns over a relatively short period (typically three 1-hour
test runs). These test data were obtained at kilns equipped with well
designed and operated ESPs and FFs representative of the MACT floor,
which is also represented by the NSPS emission level. Method 5 testing
of these cement kilns equipped with MACT floor technology showed a
range of emissions up to the NSPS level. Additional Method 5 tests
performed on some of the same kilns included in the MACT floor analysis
showed PM variations after control as plotted in the reference,
confirming that some operating variability is inherent. EPA believes
that these data reasonably represent levels achievable in practice by
the average of the best performing 12 percent of sources, and by
accounting adequately for variability, further assure that the standard
will be achievable under the worst forseeable circumstances consistent
with proper design and operation. Sierra Club, slip. op. p. 13. In
summary, the PM emission limit reflects an emission level consistently
achievable with the use of well designed and operated MACT floor
technology.
Comment: One commenter stated that it is feasible, both technically
and economically, for portland cement kilns to use fuels and raw
materials with low metals content. Because feed limits are an
achievable measure that would further reduce emissions, EPA must
require them.
Response: Feed and/or fossil-fuel switching has not been undertaken
by any NHW kilns to reduce metals emissions, and therefore this is not
a MACT floor option.
The use of feed material selection and feed material blending to
achieve lower metals emissions thus is a potential beyond-the-floor
technology. Cost is a consideration in the decision to go beyond-the-
floor. The ability of a facility to remain cost competitive typically
depends on the use of raw materials mined in close proximity to the
facility. Several commenters described the economic difficulties in
locating, purchasing, and transporting feed materials to existing
sites; the comment to the contrary stated the opposite categorically,
but provided no supporting cost, economic or technical data. See Sierra
Club, slip op. p. 13 (rejecting argument that pollution prevention
measures had to be included as part of a standard where costs were not
adequately quantified). EPA disagrees with this comment. Cement kilns
require enormous amounts of raw material, and the costs of transporting
the raw material are enormous, given the volumes involved. Finding a
new source of raw material will often (if not invariably) entail more
costs because the source of the raw materials will be further from the
facility. The Agency believes that in many cases a facility could not
even remain economically viable were existing sources of raw material
to become unavailable. In many cases, costs of the change in raw
material would exceed air pollution benefits.2
---------------------------------------------------------------------------
\2\ As discussed above, EPA considered control of feed materials
as a potential beyond the floor technology. EPA is aware of the
Conference Report to the 1990 amendments which state that controls
on feed materials are not to be part of MACT for mineral processing
facilities. H.R. Rep. No. 952, 101st Cong., 2d sess. 339.
However, the text of the statute does not reflect this legislative
history, stating unambiguously that MACT for all sources includes
eliminating HAP emissions through ``substitution of materials''.
Section 112 (d) (2) (A). EPA is following the explicit statutory
text in considering (albeit rejecting) feed control as a potential
beyond the floor technology in this rule. At the very least, this is
a permissible interpretation of the statute, given the statutory
goal of protecting and enhancing of the Nation's air resources.
Section 101 (b)(1).
---------------------------------------------------------------------------
In the case of NHW kilns, fuel switching is not a demonstrated
metals control technology. There are no data available to EPA that
indicate that this technology can or has achieved metals emission
reductions from NHW kilns. A HW kiln operator can control metals via
the hazardous waste fuel, but this is not an option available to NHW
kiln operations.
D/F Limits
Comment: Several comments were received regarding the D/F limits in
the proposed rule, which were based on the MACT floor. Some commenters
suggested that a lower D/F emission limit was appropriate for both new
and existing sources, based on the performance test data reported in
the proposal preamble. Other commenters felt that the proposed emission
limit was too stringent and unjustified, and was not representative of
the MACT floor technology. Many other commenters supported the proposed
standards.
Response: In response to these comments, the EPA has reviewed the
existing test data and literature on D/F formation and concluded that
the selected emissions limits represent the MACT floor and are
consistently achievable. Again, EPA is influenced by the fact that
cement kilns using the floor control technology achieved different D/F
levels in their performance tests--indicating that different levels
reflect normal variability of the process and control technology.
Consequently, EPA is retaining the proposed standard for D/F emissions
from kilns and in-line kiln/raw mills in the final rule.
In order to establish a more stringent emission limit for new
kilns, it is necessary to identify a different technology to which
better performance is attributable. Since EPA could not identify a
different technology for new kilns, the standard is based on the range
of available data, considering process and control variability.
The EPA determined that the MACT floor technology for both existing
and new sources was inlet PM control device temperature control to
400 deg. F accompanied by good combustion and process control. Based on
data evaluated at proposal, the technology can be represented by the
dual standard of 0.2 ng TEQ/dscm or 0.4 ng TEQ/dscm with a PM control
device inlet temperature of 400 deg. F or less. The performance test
data are based on short-term tests but do indicate that all kilns will
achieve the numerical emission limit of 0.4 ng TEQ/dscm with the
application of the floor technology. Thus the 0.4 ng TEQ/dscm emission
limit is retained to account for normal inherent process and air
pollution control operating variability, including the use of various
fuels, such as tires.
THC Limit
Comment: Several comments were received questioning the
specification of a THC standard for reconstructed kilns or new kilns
built at existing sites. Commenters asserted that these facilities
could not economically locate, purchase and transport suitable feed
materials to meet this standard.
Response: In recognition of these comments, the final rule has been
changed to make the THC limitation applicable only to greenfield kilns,
greenfield in-line kiln/raw mills and greenfield raw material dryers.
EPA agrees that only greenfield sources would be able to apply MACT,
which is the site selection of feed materials with low levels of
naturally occurring organic material. The EPA considered the use of
precalciner/no preheater kilns for THC control, (docket items II-B-47,
II-B-48, II-B-67, and II-B-76), but concluded that because of negative
energy impacts and increased emissions of criteria pollutants these did
not provide the maximum achievable control technology for either
existing or new sources. Further discussion of this technology is
provided in the response to the next comment.
[[Page 31918]]
Comment: Commenters stated that the proposed rulemaking provides no
justification or insufficient support for the selection of 50 ppmvd as
the total hydrocarbon (THC) standard for new or modified kilns. Another
commenter noted that EPA has recognized that portland cement kilns use
a variety of methods and technologies to control their THC emissions,
including precalciner/no preheater technology and a combination of feed
material selection, site location, and feed material blending. All of
these methods and technologies are reflected in existing sources'
actual performance, on which EPA must base the floors for its THC
standard. That commenter stated that under section 112(d) the THC
emission standard would be much lower than 50 ppmvd.
Response: First, with regard to the methods and technologies
determined to be the MACT floor, the ``precalciner, no preheater'' kiln
is not considered maximum achievable control technology when other
considerations such as energy impacts and NOX emissions are
taken into account. As explained in the preamble to the proposed rule,
EPA believes that use of these technologies would not be MACT for new
or existing sources because of the adverse environmental impacts
associated with these technologies' use, in particular increased
emissions of certain criteria pollutants. See Portland Cement Assn v.
Ruckelshaus, 486 F. 2d 375, 385-96 (D.C. Cir. 1973) (if use of a
particular technology results in other, adverse environmental
consequences, that technology need not be considered the ``best''). The
proposal preamble also addressed consideration of feed material
selection for existing sources as a MACT floor technology and concluded
that this option is not available to existing (and new brownfield)
kilns, in that facilities are generally tied to existing raw material
sources in close proximity to the facility, and that raw material
proximity (i.e., transportation cost) is usually a major factor in
plant site selection. This conclusion was supported by several
commenters. The commenters described the economic difficulties in
locating, purchasing, and transporting low organic feed materials to
existing sites. However, for new ``greenfield'' kilns, feed material
selection as achieved through appropriate site selection and feed
material blending is considered new source MACT.
With regard to the level of standard, it is based upon data
available to the Administrator and no data were provided after proposal
which would justify a different standard. Based on a review of
available information (docket item II-B-62, docket item II-B-75, docket
item II-D-195) the EPA believes that a THC concentration of 50 ppmvd
represents a level that is achievable nationwide across a broad
spectrum of feed materials. This level has been retained in the final
rule.
Comment: Comments were received concerning the suitability of THC
as a surrogate for organic HAP, in light of the high variability in the
ratio of organic HAP to THC in cement kiln exhaust gas.
Response: The EPA recognizes the variability of the data but
concludes that when speciated analyses of THC were undertaken organic
HAPs were found to be present. No attempt was made to correlate organic
HAP emissions with THC emissions. Because of the cost savings to
industry in conducting performance tests to establish compliance with a
THC standard, EPA has chosen not to set standards for individual
speciated organic HAPs. Further, since the source of organic HAPs is
the same source as for THC (feed materials), using MACT will also
control organic HAP emissions. Adopting THC as a surrogate will result
in cost savings to the cement industry and to the EPA during compliance
testing and monitoring.
The EPA notes further that the same issue was presented when EPA
adopted standards for boilers and industrial furnaces burning hazardous
waste, and in the course of that rulemaking, not only the Agency but
the Science Advisory Board concluded that THC was indeed a reasonable
surrogate for toxic organic emissions from cement kilns. [See 56 FR at
7153-54 (Feb. 21, 1991).]
The proposal preamble stated that POM, one of the seven pollutants
listed in section 112(c)(6), would be regulated using THC as a
surrogate. The final source category listing notice for section 112(d)
rulemaking pursuant to section 112(c)(6) requirements shows the NHW
kiln facilities portion of the portland cement source category to be a
significant source of POM (63 FR 17838, April 10,1998). For this
reason, and to control other THC HAPs, the final rule limits emissions
of THC from new greenfield raw material dryers and new greenfield kilns
and greenfield in-line kiln/raw mills at area sources as well as major
sources.
Mercury Limit
Comment: Comments were received concerning the need for an emission
standard to limit the emissions of mercury from NHW cement kilns. Other
commenters suggested that a mercury standard be established based on a
presumed floor or beyond the floor basis of fuel and/or feed material
control, referring to the proposed Hazardous Waste Combustor rules and
research on clean coal to reduce mercury emissions in the electric
utility industry. Other commenters agreed with EPA's determination for
no mercury emission limit.
Response: The EPA determined, at proposal, that the MACT floor for
both new and existing sources was no control. The EPA evaluated
activated carbon injection as a beyond the floor alternative for
control of mercury emission from NHW kilns and in-line kiln/raw mills,
and this technology was not found to be cost effective. Feed and/or
fossil-fuel switching or cleaning has not been undertaken by any NHW
kilns in order to reduce mercury emissions, and therefore these are not
MACT floor options. For this reason feed and/or fossil-fuel switching
or cleaning would be considered a beyond the MACT floor option but the
EPA does not have data, nor did commenters provide data, that show that
this option would consistently decrease mercury emissions. Moreover, as
noted earlier, raw material feed control is prohibitively costly for
this industry.
The proposed rule for Hazardous Waste Combustors included a
standard of mercury. However, control of mercury in that rule would be
based on controlling the amount of mercury in the hazardous waste fuel,
not controlling raw material or fossil fuel. This approach is thus not
available to NHW kilns. In addition, based on the Electric Utility
Report to Congress on HAP emissions, EPA believes that fuel switching
among different coals and from coal to oil would not consistently
reduce HAP metal emissions from cement manufacturing plants. (Study of
Hazardous Air Pollutant Emissions from Electric Utility Steam
Generating Units--Final Report to Congress, volume 1, 453/R-98-004a,
February 1998, pp. 13-1 through 13-5.) Therefore, this final rule
establishes MACT for mercury as no control. However, EPA will be
performing research and development work with the objective of finding
more cost effective methods to reduce mercury air emissions from
fossil-fuel fired electric utilities, and EPA will in the future
consider whether any more cost effective methods may be appropriate as
a basis for reducing mercury emissions from NHW cement kilns.
Hydrogen Chloride Limit
Comment: Comments were received stating the need for an emission
standard for HCl emissions from kilns
[[Page 31919]]
because EPA did not provide data to show that HCl emissions pose no
threat to public health and that HCl is emitted in large quantities
from new and existing NHW kilns. Other commenters stated that EPA
appropriately concluded that there is no basis for a MACT standard for
HCl.
Response: With regard to the threat to public health comment, the
EPA is conducting this rulemaking under section 112(d)(2) and therefore
the decision on an emission standard is not based on health risk.
Impacts to public health will be studied and addressed later under
section 112(f) of the Act. The EPA determined, at proposal, that the
MACT floor for both new and existing sources was no control. Further,
no cost effective beyond the floor alternatives were identified. The
commenters provided no new information on the use of any control
technologies to limit emissions of HCl from NHW kilns. For this reason
no emission standard is being established for HCl.
Opacity Limit
Comment: One commenter requested that EPA clarify the duration of
both the performance test and continuous compliance demonstrations for
opacity emissions.
Response: The opacity requirements in the final rule have been
changed to provide for compliance on the basis of average opacity for
each and every 6-minute block of operating time. This is consistent
with the NSPS which is the MACT floor level of PM control upon which
the standard is based. (The proposed rule incorrectly required a
thirty-minute averaging time for demonstrating continuous compliance.)
Comment: Commenters expressed concern regarding the requirement to
initiate a Quality Improvement Plan (QIP) and the need to track and
statistically analyze opacities at levels below the standards. One
commenter stated that a violation triggered by not initiating a QIP
when the source was not violating an emission standard was extreme.
Response: The requirements for developing and implementing a QIP in
response to a 15 percent kiln and in-line kiln/raw mill opacity trigger
have been removed from the final rule. The final rule retains the
opacity limit of 20 percent which if exceeded during any 6-minute
period is a violation.
Comment: One commenter requested that EPA specify the scope of
monitoring opacity from raw and finish mills.
Response: The EPA has clarified that the opacity limitation on
gases discharged from raw mills and finish mills is restricted to the
mill sweep and air separator air pollution control devices. This is
consistent with the MACT floor technology for control of gases from
these affected sources.
Comment: A commenter noted that the proposed rule did not specify
under what conditions visual opacity monitoring should be conducted.
Response: The final rule clarifies that Method 9 (and Method 22)
tests must be conducted under the highest load or capacity level
reasonably expected to occur.
Comment: Numerous commenters expressed concern regarding
installation, operation, calibration and maintenance of triboelectric
bag leak detection systems, and that the lack of clear-cut
specifications would lead to open-ended liability for owners/operators.
Response: The option for use of triboelectric bag leak detection
systems for monitoring fabric filter performance is not being
promulgated at this time. The EPA is presently considering this issue
and may propose revised bag leak detector requirements for some source
categories. Those owners or operators who want to use bag leak
detection systems may petition the Administrator for approval of
alternative monitoring requirements under the General Provisions.
The rule requires the owner or operator to monitor the opacity from
raw mills and finish mills by conducting a daily six-minute test in
accordance with Method 22, ``Visual Determination of Fugitive Emissions
from Material Sources and Smoke Emissions from Flares.''
Owners or operators of raw mills and finish mills are required to
initiate corrective action within one hour of a Method 22 test during
which visible emissions are observed. A 30-minute Method 9 opacity test
must be started within 24 hours of observing visible emissions.
D/F Monitoring
Comment: Several commenters suggested averaging periods for
temperature limits shorter than 9 hours as proposed. One commenter
preferred one-hour rolling averages. Two commenters preferred ten-
minute averages as rationalized in the proposed Hazardous Waste
Combustor Rule.
Response: As noted in section IV. Summary of Changes Since
Proposal, the final rule, in response to these comments, has been
changed to a shorter averaging period. The nine-hour block average
period used for the monitoring of temperature (as well as the activated
carbon injection rate, if applicable) has been changed to a three-hour
rolling average period. The three-hour averaging time will help to
limit disproportionate increases in D/F emissions that could be caused
by very short periods of higher temperatures. A three-hour averaging
time is reasonable because it is within the range of values the Agency
could have selected, ranging from an instantaneous limit (i.e., no
averaging period) up to a nine-hour averaging period.
The enforceable operating limit for gas stream temperature is
derived from the temperature measured during 3 three-hour measurements
of D/F emission. The three-hour rolling average temperature limit is
established by taking the average of the one-minute average
temperatures for each test run conducted during the successful Method
23 performance test, then averaging each test run average. Further,
sources may petition the Administrator for an alternative averaging
period or an alternative method for establishing operating parameter
limits.
Comment: A commenter pointed out that the proposal would allow a
source to conduct its D/F performance test with an inlet PM control
device temperature below 400 degrees F, but after the performance test,
the source would be allowed to operate its PM control device with an
inlet temperature up to 400 degrees F.
Response: In drafting the proposal, the EPA did not intend to allow
a source to operate its PM control device at a temperature higher than
the temperature during the performance test, and so the EPA has
clarified that the inlet temperature limit is established as and capped
at the average temperature during the D/F performance test.
Comment: One commenter stated that the D/F standard should be
coordinated with the rule for hazardous waste combustors.
Response: As was previously noted, the EPA has adopted a shorter
temperature averaging time. To further achieve consistency with the D/F
temperature requirements for HW kilns, the EPA is dropping the proposed
provision which would have allowed the temperature limit to be
established as the average temperature during the performance test plus
25 degrees F if the D/F level (during compliance testing) was below
0.15 ng/dscm. Further, new activated carbon injection operating
parameters (nozzle pressure drop or carrier fluid flow rate) and
averaging time have been added and changed, respectively, to be
consistent with the requirements for the HW kilns.
Comment: A comment was received requesting a clarification of the
[[Page 31920]]
procedure for demonstrating compliance for in-line kiln/raw mills
during time periods which span a change in raw mill operating status.
Response: After a transition period in which the status of the raw
mill was changed from ``off'' to ``on'' or from ``on'' to ``off'',
compliance with the operating limits for the new mode of operation
begins, and the three-hour rolling average is established anew, i.e.,
without considering previous recordings.
Comment: Comments were received suggesting that combustion
parameters (e.g., CO and THC) should be monitored to demonstrate
compliance with the
D/F standard.
Response: The final rule does not require monitoring of these
parameters as a means of monitoring combustion because the EPA believes
that THC and CO emissions from NHW cement kilns are largely due to
formation outside of the combustion zone, i.e., due to the feed
materials. Therefore THC and carbon monoxide emissions might not
accurately reflect combustion conditions, therefore the EPA has not
included CO monitoring requirements to ensure good combustion. However,
the final rule has been changed to include a monitoring requirement for
an inspection of combustion system components to be conducted at least
annually.
THC Monitoring
Comment: The EPA received comments related to the use of THC
monitoring as a means of controlling combustion related pollutants and,
therefore, organic HAPs (see comment 6.4.1 in the Response to Comments
Document).
Response: Stack THC emissions from kilns, in-line kiln raw mills,
and raw material dryers result mainly from organic material within the
feed and not from incomplete combustion. As a result, the suggested
combustion monitoring alternatives are not relevant.
Performance Testing Frequency
Comment: The EPA received a comment requesting that performance
tests be required more frequently than once every five years, citing
other rules with more frequent testing requirements.
Response: The EPA selected the five year testing interval to
synchronize the testing schedule with Title V permit renewals. The
testing frequency for NHW cement kilns and other affected sources at
portland cement manufacturing facilities has not been changed. The
exception to this is the
D/F performance tests. To maintain consistency with the requirements
for HW kilns, the D/F performance testing frequency has been changed to
every 2 and one half years.
Definitions
Comment: Commenters requested various changes to the definitions,
including those of ``alkali bypass'' and ``feed'' to reflect cement
industry practices.
Response: The final rule expands the definition of ``alkali
bypass'', and defines ``kiln exhaust gas bypass'' as a synonym for
alkali bypass. The final rule clarifies the definition of ``feed'' to
include recycled cement kiln dust, consistent with past practice in
enforcement of the NSPS.
Major Source Determination
Comment: Numerous comments were received regarding the use of
emissions test data and emission factors (based on data provided in the
proposal docket) in determining whether a source is major for hazardous
air pollutants.
Response: The need for HAP-specific test methods and the validity
of data obtained by various means to determine major source status are
closely related. Hence this discussion covers both aspects under the
overall title of major source determination.
Although emission standards are being promulgated for PM as a
surrogate for semi-volatile and non-volatile HAP metals; THC as a
surrogate for organic HAPs; and D/F, each facility owner/operator must
make a major source determination that requires an estimate of the
facility's potential to emit all HAPs from all emission sources. HCl
and organic HAP emissions such as (but not limited to) benzene,
toluene, hexane, formaldehyde, hexane, naphthalene, phenol, styrene,
and xylenes are the main HAPs from the kiln that may cause facilities
to be major sources, but HAPs emitted from all sources at the plant
site should be accounted for in making a major source determination.
Comment: Some commenters questioned the need for accurate HCl
measurements, since there is no HCl emission standard. Others stated
that EPA should provide industry the choice of conducting testing for
HCl with either Method 26, 321, or 322. They objected to the
restriction that Method 26 could be used only if validated by Method
321 or 322. They also stated their belief that the Agency's decision
regarding the negative bias of Method 26 was based on a limited set of
test results and an insufficient investigation of the potential cause.
Additional comments noted that Method 26 may actually give false
positives due to inclusion of chloride salts in the calculation of
measured results.
Response: As discussed above, HCl and organic HAPs emissions are
the main HAPs from the kiln that will cause a source to be a major
source, but HAPs emitted from all sources at the plant site, including
metals emissions (discussed below) should be accounted for in making a
major source determination. Accurate measurements of HCl in the kiln
exhaust gases are necessary for major source determination. The EPA
agrees with commenters that Method 26 may have positive biases
attributable to chloride salts rather than to HCl; and negative biases
due to condensation and/or removal of HCl on the filter and/or in the
sampling probe. Therefore, the Agency has decided that Method 26 and
26A use without concurrent validation with M. 321 or M. 322 will only
be acceptable for measuring HCl from NHW kilns to confirm that the
portland cement plant is a major source. M. 26 or 26A may not be used
to measure HCl in the determination that the source is an area source.
Only the FTIR methods may be used in the measurement of HCl if the
source claims it is not a major source.
Further, as a result of technical problems encountered by the
Agency with the use of draft Method 322 (based on gas filter
correlation/infrared technology) in the emission testing of lime kilns
(which have a matrix similar to portland cement sources) [See Section
IV.F. on Additional Test Methods for a description of the technical
problems], and in response to concerns expressed by the commenters, the
EPA is modifying its position regarding HCl measurements using this
method in promulgating the final rule.
For the above reasons, the Agency has decided that only Methods 320
and 321 will be acceptable for measuring HCl from NHW kilns if the
owner/operator wishes to claim its portland cement facility is not a
major source. These methods are being promulgated as part of this
rulemaking.
Comment: Commenters also requested that EPA allow cement
manufacturers the option of using Method 25 (in addition to Method 18
or Method 320) for testing emissions of organic HAPs. The commenters
suggest that the relatively inexpensive Method 25 could be used by
cement plants that have low concentrations of organic matter in the raw
material mix to verify that the plant's THC emissions are less than 10
tons/year.
Response: The focus of these commenters' point is alternatives to
[[Page 31921]]
measurement of organic HAPs in the process of making a major source
determination. However, all HAPs (organic, HCl, metals, etc.) from all
sources must be included in that determination, so it is necessary to
obtain data that will allow summation of all HAP emissions to compare
to the 10/25 ton per year thresholds specified in section 112 of the
Clean Air Act. Depending on site-specific circumstances, EPA Method 25
may not provide sufficient information to make an accurate summation.
For example, a source's determination that its THC emissions based on
Method 25 or 25A are less than 10 tons per year does not necessarily
signify that it is an area source; the source may be a major source
based on the 25 ton per year criterion when all other HAP emissions are
summed with the THC. If the source's THC emissions are over 10 tons per
year, the source may choose to conduct emissions tests using EPA Method
320 to make a determination of actual organic HAP emissions. However,
in lieu of conducting Method 320 emissions tests, the source could use
Method 25A, but the source would have to assume that the mass emission
rate (as propane) from all combustion sources combined at the site is
attributed to one organic HAP. This amount would then have to be
compared to the 10 ton per year threshold for one HAP. To summarize, in
addition to accounting for organic HAPs (either through Method 320
testing or assuming all THC is one organic HAP), accurate measurements
of HCl in the kiln exhaust gases would be necessary for major source
determination, as well as measurements of HAP metals (see below), to
obtain data that will allow summation of all HAP emissions to compare
to the 10/25 ton per year thresholds.
Comment: Another commenter requested that EPA allow the use of an
alternative to what they perceived as an EPA-suggested emission factor
for metal emissions, of one percent of PM emissions, to determine major
source status.
Response: If after the source determines that it is not major
because it does not meet either the 10/25 ton per year thresholds based
on the summation of HCl and organic HAP emissions from all sources at
the plant, the source would need to determine its HAP metals emissions
from all sources at the facility as well, to make a determination that
it is not a major source. The use of a ``one percent HAP metals in PM''
emission factor assumption will not provide definitive evidence that
the source is an area source. However, the Agency would allow sources
to forego the speciated HAP metals emission tests (through the use of
Method 29) if it is assumed that 1 percent of the total PM emissions
from all sources at the site are metal HAPs. This assumed amount of
metal HAPs emissions would be added to the amount of HCl and organic
HAPs emitted (determined as described above), and this total amount
would then be compared to the 25 ton per year threshold for all HAPs
combined. To reiterate, each facility owner/operator must make a major
source determination that requires an estimate of the facility's
potential to emit all HAPs from all emission sources, accounting for
HCl, organic HAPs (either through speciation of organic HAPs or
assuming all THC is one organic HAP), and metals (either through
speciation of metal HAPs or assuming 1 percent of PM is metal HAP), to
allow summation of all HAP emissions to compare to the 10/25 ton per
year thresholds.
Voluntary Consensus Standards
Comment: One commenter (IV-D-17) stated that EPA's actions (in
developing and proposing the precursor to EPA Fourier Transform
Infrared Spectroscopy [FTIR] test method 320) directly conflict with
the guidance of and directives of the 1995 National Technology Transfer
and Advancement Act and the Office of Management and Budget (OMB)
Circular A-119 because: (1) the American Society of Testing and
Materials (ASTM) FTIR consensus based test method is available, and (2)
the EPA Emission Measurement Center (EMC) representatives were made
aware of the development of the ASTM method and chose duplicative
measures in developing and proposing the precursor to EPA FTIR test
method 320. (The OMB Circular states specifically that ``If a voluntary
consensus standards body is in the process of developing or adopting a
voluntary consensus standard that would likely be lawful and practical
for an agency to use, and would be developed on a timely basis, an
agency should not be developing its own government unique standard and
instead should be participating in the activities of the voluntary
consensus standards body.'')
Response: The Agency has been actively developing extractive FTIR-
based methods for HAPs since 1992. Methods 320 and 321 are direct
products of this long-term effort to apply an innovative approach to
emissions measurement in the form of extractive FTIR. The Agency has
tested these methods in the laboratory and in the field extensively
(conducting testing at two portland cement facilities), and has
conducted multiple validation tests of these methods. The Portland
Cement Association (PCA), in representing various members of the
regulated industry, has conducted its own series of validation tests of
these methods. Actually, Method 321 was developed and validated by PCA,
and has been adopted by the Agency as Method 321. Agency personnel
informed ASTM in 1996 that the Agency methods were in active
development, and an ASTM standard seemed redundant. Additionally, the
ASTM standard has not undergone field validation, which is essential in
establishing the precision and accuracy of any test method.
The Agency has conducted a review of the ASTM method. While the
ASTM method is in some ways similar to Method 320, the ASTM method is
not sufficiently detailed to document proper application, and does not
contain the quality assurance procedures the Agency requires in
compliance methods. Specifically, the ASTM method does not address
specific calibration transfer standards, nor does it address the
preparation of reference spectra. Therefore, EPA has determined that it
is impractical to adopt the ASTM method at this time and is
promulgating Method 320.
Pollution Prevention
Comment: Comments were received stating that the proposed rule did
not contain measures that prevent pollution or reduce energy
requirements, and suggested specific pollution prevention measures,
including process modifications, taken by specific facilities.
Response: The NESHAP is written in terms of emissions standards
based on MACT floor technologies and allows pollution prevention
techniques to achieve compliance. The EPA considered pollution
prevention options available and the basis for the standard for THC for
new greenfield sites, feed material selection, is a pollution
prevention measure. In addition, the final standard includes a
monitoring requirement for inspection of the combustion system
components of kilns and in-line kiln raw mills (an energy efficiency
and pollution prevention measure) and standards for PM from product
handling affected sources (which leads to improved recovery of salable
product and pollution prevention). Furthermore, the final standard
clarifies that recovered cement kiln dust can be included in the
calculation of kiln feed (encouraging recycling, improved PM control
and pollution prevention).
[[Page 31922]]
Control Cost Impacts and Data Evaluation
Comment: Comments were received concerning the EPA's control cost
estimates, including the assumptions regarding the number of sources
requiring upgrades to meet the standards for PM and D/F, and the
capital expenditures necessary to meet the standard. In particular one
commenter projected that capital costs would exceed the threshold which
triggers Executive Order 12866. Another commenter questioned the lack
of cost data on upgrades to PMCDs for material handling affected
sources.
Response: The costs to achieve compliance are expected to be highly
site-specific and vary significantly. The commenters did not provide
any details regarding their estimates of the cost to comply, so the EPA
is unable to determine whether the commenters' cost estimates were
limited to those costs necessary to comply with the provisions of the
NESHAP.
The EPA has reviewed cost data provided by the Portland Cement
Association prior to proposal. The foundation for the cost estimates,
and initial point of criticism of EPA's cost estimates, is the model
plant characteristics. For example, the APCA report provided a review
of the model plant characteristics and suggested that the design
characteristics for each model be 20 to 25 percent higher than the
annual average production rate basis for the model. In particular, the
APCA report stated that the EPA model plant gas flows for wet process
and long dry kilns were 25 to 30 percent too low, based on their
consultant's design practice.
The EPA developed design characteristics for the model plants based
on data provided to the Agency in ICRs and test reports (docket items
II-B-24 and II-B-37). For a kiln with a given nominal production rate
that might be found in several different plants, variations in gas flow
rates would be expected. The EPA used the flow rate and production data
from actual installations to develop production rate versus gas flow
graphs to establish the model plant characteristics. Owners may elect
to design their upgrades or new equipment to accommodate higher
production rates, but those costs and other impacts are not
attributable to compliance with the MACT standards. EPA did not include
costs associated with upgrading equipment used to control emissions
from materials handling affected sources, as these affected sources
have been subject to the NSPS for many years (a longer period than the
expected life of these affected sources), and compliance with the
NESHAP, which is equivalent to the NSPS for these affected sources
would not impose additional costs.
The basis of the control costs for model plants estimated in the
docket memoranda and proposal preamble is the Office of Air Quality
Planning and Standards Cost Manual. The cost algorithms in the manual
were derived from control equipment vendor quotes, standard cost
estimating factors, and contractor experience. Installation costs,
utilities, maintenance, and other operating costs were estimated and
included for impact estimation. The EPA maintains that the costs
provided in the proposal preamble are a reasonable basis for projecting
the national impacts of the these rules.
VII. Administrative Requirements
A. Docket
A record has been established for this rulemaking under docket
number A-92-53. This record includes information considered by the EPA
in the development of the promulgated standards. A public version of
this record, which does not include any information included as
confidential business information, is available for inspection from
8:00 a.m. to 5:30 p.m. Monday-Friday, excluding legal holidays. The
public record is located in the Air & Radiation Docket & Information
Center, Room M1500, 401 M Street S.W., Washington, D.C. 20460.
Response-to-Comment Document
The response-to-comment document for the promulgated standards
contains a summary of all public comments received following proposal
of the rule and the EPA's response to these comments. This document is
located in the docket (Docket Item No. V-C-1) and is available for
downloading from the Technology Transfer Network (TTN). The TTN is one
of the EPA's electronic bulletin boards. The TTN provides information
from EPA in various areas of air pollution technology or policy. The
service is free except for the cost of a phone call. Dial (919) 541-
5742 for up to a 14,400 bps modem, or connect through the internet to
the following address: ``www.epa.gov/ttn/oarpg''. If more information
on the Technology Transfer Network is needed, call the HELP line at
(919) 541-5384.
B. Executive Order 12866
Under Executive Order 12866 (58 FR 5173, October 4, 1993), the EPA
must determine whether the regulatory action is ``significant'' and
therefore subject to Office of Management and Budget (OMB) review and
the requirements of the Executive Order. The Executive Order defines
``significant regulatory action'' as one that is likely to result in
standards that may:
(1) Have an annual effect on the economy of $100 million or more or
adversely affect, in a material way, the economy, a sector of the
economy, productivity, competition, jobs, the environment, public
health or safety, or State, local, or tribal governments or
communities;
(2) Create a serious inconsistency or otherwise interfere with an
action taken or planned by another agency;
(3) Materially alter the budgetary impact of entitlement, grants,
user fees, or loan programs or the rights and obligations of recipients
thereof; or
(4) Raise novel legal or policy issues arising out of legal
mandates, the President's priorities, or the principles set forth in
the Executive Order.
Because the projected annual costs (including monitoring) for this
NESHAP are $37 million, a regulatory impact analysis has not been
prepared. However this action is considered a ``significant regulatory
action'' within the meaning of Executive Order 12866 (primarily due to
this action's overlap with the Hazardous Waste Combustor MACT
standard), and the promulgated regulation presented in this notice was
submitted to the OMB for review. Any written comments are included in
the docket listed at the beginning of today's notice under ADDRESSESS.
The docket is available for public inspection at the EPA's Air Docket
Section, which is listed in the ADDRESSES section of this preamble.
C. Executive Order 12875: Enhancing Intergovernmental Partnerships
Under Executive Order 12875, the EPA may not issue a regulation
that is not required by statute and that creates a mandate upon a
State, local or tribal government, unless the Federal government
provides the funds necessary to pay the direct compliance costs
incurred by those governments, or EPA consults with those governments.
If EPA complies by consulting, Executive Order 12875 requires EPA to
provide to the Office of Management and Budget a description of the
extent of EPA's prior consultation with representatives of affected
State, local and tribal governments, the nature of their concerns,
copies of any written communications from the governments, and a
statement supporting the need to issue the regulation. In addition,
Executive Order 12875 requires EPA to
[[Page 31923]]
develop an effective process permitting elected officials and other
representatives of State, local and tribal governments ``to provide
meaningful and timely input in the development of regulatory proposals
containing significant unfunded mandates.''
Today's rule does not create a mandate on State, local or tribal
governments. The rule does not impose any enforceable duties on these
entities. Accordingly, the requirements of section 1(a) of Executive
Order 12875 do not apply to this rule.
D. Unfunded Mandates Reform Act
Title II of the Unfunded Mandates Reform Act of 1995 (UMRA), Public
Law 104-4, establishes requirements for Federal agencies to assess the
effects of their regulatory actions on State, local, and tribal
governments and the private sector. Under section 202 of the UMRA, the
EPA generally must prepare a written statement, including a cost-
benefit analysis, for proposed and final rules with ``Federal
mandates'' that may result in expenditures to State, local, and tribal
governments, in the aggregate, or to the private sector, of $100
million or more in any one year. Before promulgating an EPA rule for
which a written statement is needed, section 205 of the UMRA generally
requires the EPA to identify and consider a reasonable number of
regulatory alternatives and adopt the least costly, most cost-effective
or least burdensome alternative that achieves the objectives of the
rule. The provisions of section 205 do not apply when they are
inconsistent with applicable law. Moreover, section 205 allows the EPA
to adopt an alternative other than the least costly, most cost-
effective, or least burdensome alternative if the Administrator
publishes with the final rule an explanation why that alternative was
not adopted. Before the EPA establishes any regulatory requirements
that may significantly or uniquely affect small governments, including
tribal governments, it must have developed under section 203 of the
UMRA a small government agency plan. The plan must provide for
notifying potentially affected small governments, enabling officials of
affected small governments to have meaningful and timely input in the
development of EPA regulatory proposals with significant Federal
intergovernmental mandates, and informing, educating, and advising
small governments on compliance with the regulatory requirements.
The EPA has determined that this rule does not contain a Federal
mandate that may result in expenditures of $100 million or more for
State, local, and tribal governments, in aggregate, or the private
sector in any one year, nor does the rule significantly or uniquely
impact small governments, because it contains no requirements that
apply to such governments or impose obligations upon them. Thus, the
requirements of the UMRA do not apply to this rule.
E. Regulatory Flexibility Act
The EPA has determined that it is not necessary to prepare a
regulatory flexibility analysis in connection with this final rule. As
discussed earlier in the response to comments section of the preamble,
the EPA has determined that this rule will not have a significant
economic impact on a substantial number of small entities.
Although the rule will not have a significant impact on a
substantial number of small entities, the EPA worked with portland
cement small entities throughout the rulemaking process. Meetings were
held on a regular basis with the Portland Cement Association (PCA) and
industry representatives, including both small and large firms, to
discuss the development of the rule, exchange information and data,
solicit comments on draft rule requirements, and provide a list of the
small firms. In addition, some cement industry representatives formed a
group called the ``Small Cement Company MACT Coalition'', which
designated the PCA as its representative in meetings with the EPA
concerning the rulemaking for the portland cement industry.
The promulgated emission standards are representative of the floor
level of emision control, which is the minimum level of control allowed
under the Act. Further, the costs of required performance testing and
monitoring have been minimized by specifying emission limits and
monitoring parameters in terms of surrogates for HAP emissions, which
are less costly to measure. The Agency has also tried to make the rule
``user friendly,'' with language that is easy to understand by all of
the regulated community. EPA is also allowing affected firms up to 3
years from the effective date of the final rule to comply, which could
lessen capital availability concerns. An extra year may be granted by
the Administrator or delegated regulatory authority if necessary to
install controls. Further, EPA has deferred the compliance date for
installing PM CEMs pending a future proposed rulemaking.
F. Submission to Congress and the General Accounting Office
The Congressional Review Act, 5 U.S.C. 801 et seq., as added by the
Small Business Regulatory Enforcement Fairness Act of 1996, generally
provides that before a rule may take effect, the agency promulgating
the rule must submit a rule report, which includes a copy of the rule,
to each House of the Congress and to the Comptroller General of the
United States. The EPA will submit a report containing this rule and
other required information to the U.S. Senate, the U.S. House of
Representatives, and the Comptroller General of the United States prior
to publication of the rule in the Federal Register. This rule is not a
``major rule'' as defined by 5 U.S.C. Sec. 804(2).
G. Paperwork Reduction Act
The information collection requirements in this rule are being
submitted for approval to the Office of Management and Budget (OMB)
under the Paperwork Reduction Act, 44 U.S.C. 3501 et seq. An
Information Collection Request (ICR) document has been prepared by EPA
(ICR No. 1801.02) and a copy may be obtained from Sandy Farmer by mail
at OP Regulatory Information Division; U.S. Environmental Protection
Agency (2137); 401 M St., S.W.; Washington, DC 20460, by email at
farmer.sandy@epamail.epa.gov, or by calling (202) 260-2740. A copy may
also be downloaded off the internet at http://www.epa.gov/icr. The
information requirements are not effective until OMB approves them.
The EPA is required under section 112 (d) of the Clean Air Act to
regulate emissions of HAPs listed in section 112 (b). The requested
information is needed as part of the overall compliance and enforcement
program. The ICR requires that portland cement manufacturing plants
retain records of parameter and emissions monitoring data at facilities
for a period of 5 years, which is consistent with the General
Provisions to 40 CFR part 63 and the permit requirements under 40 CFR
part 70. All sources subject to this rule will be required to obtain
operating permits either through the State-approved permitting program
or, if one does not exist, in accordance with the provisions of 40 CFR
part 71, when promulgated.
The public reporting burden for this collection of information is
estimated to average 2148 hours per respondent per year for an
estimated 36 respondents. This estimate includes performance tests and
reports (with repeat tests where needed); one-time preparation of an
operation and maintenance plan with semiannual reports of any event
where the procedures in the plan were not followed; semiannual excess
emissions reports; notifications; and
[[Page 31924]]
recordkeeping. The total annualized capital costs associated with
monitoring requirements over the three-year period of the ICR is
estimated at $750,000. This estimate includes the capital and startup
costs associated with installation of required continuous monitoring
equipment for those affected sources subject to the standard. The total
operation and maintenance cost is estimated at $682,000 per year.
Burden means the total time, effort, or financial resources expended by
persons to generate, maintain, retain, or disclose or provide
information to or for a Federal agency. This includes the time needed
to review instructions; develop, acquire, install, and utilize
technology and systems for the purposes of collecting, validating, and
verifying information, processing and maintaining information, and
disclosing and providing information; adjust the existing ways to
comply with any previously applicable instructions and requirements;
train personnel to be able to respond to a collection of information;
search data sources; complete and review the collection of information;
and transmit or otherwise disclose the information.
An Agency may not conduct or sponsor, and a person is not required
to respond to a collection of information unless it displays a
currently valid OMB control number. The OMB control numbers for EPA's
regulations are listed in 40 CFR Part 9 and 48 CFR Chapter 15.
H. Pollution Prevention Act
During the development of this rule, the EPA explored opportunities
to eliminate or reduce emissions through the application of new
processes or work practices. This NESHAP includes a monitoring
requirement for an inspection of the components of the combustion
system of each kiln and in-line kiln raw mill to be conducted at least
once per year. Such an inspection will promote fuel efficiency and
decrease the formation of combustion related pollutants.
I. National Technology Transfer and Advancement Act
Section 12(d) of the National Technology Transfer and Advancement
Act (NTTAA) directs all Federal agencies to use voluntary consensus
standards in regulatory and procurement activities unless to do so
would be inconsistent with applicable law or otherwise impracticable.
Voluntary consensus standards are technical standards (e.g., materials
specifications, test methods, sampling procedures, and business
practices) developed or adopted by one or more voluntary consensus
bodies. The NTTAA requires Federal agencies to provide Congress,
through annual reports to OMB, with explanations when an agency does
not use available and applicable voluntary consensus standards.
Consistent with the NTTAA, the EPA conducted a search to identify
voluntary consensus standards. The search identified 21 voluntary
consensus standards that appeared to have possible use in lieu of EPA
standard reference methods. However, after reviewing available
standards, EPA determined that 14 of the candidate consensus standards
identified for measuring emissions of the HAPs or surrogates subject to
emission standards in the rule would not be practical due to lack of
equivalency, documentation, validation data and other important
technical and policy considerations. Six of the remaining candidate
consensus standards are new standards under development that EPA plans
to follow, review and consider adopting at a later date.
One consensus standard, ASTM D6216-98, appears to be practical for
EPA use in lieu of EPA Performance Specification 1 (See 40 CFR Part 60,
Appendix B). On September 23, 1998, EPA proposed incorporating by
reference ASTM D6216-98 under a separate rulemaking (63 FR 50824) that
would allow broader use and application of this consensus standard. EPA
plans to complete this action in the near future. For these reasons,
EPA defers taking action in this rulemaking that would adopt D6216-98
in lieu of PS-1 requirements as it would be impractical for EPA to act
independently from other rulemaking activity already undergoing notice
and comment.
Additionally, EPA received comments that ASTM FTIR Standard D6348
should be used in lieu of EPA's proposed Fourier transform infrared
spectroscopy (FTIR) emission test methods. EPA has determined for a
number of reasons that the ASTM Standard D6348 is one of the 14
standards determined to be impractical to adopt for the purposes of
this rulemaking. EPA review comments on ASTM Standard D6348 are
included in the docket for this rulemaking and summarized in the
response to comments section of this preamble. ASTM has also been
advised of the reasons for impracticality and ASTM Subcommittee D22-03
is now undertaking a revision of the ASTM standard. Upon demonstration
of technical equivalency with the EPA FTIR methods, the revised ASTM
standard could be incorporated by reference for EPA regulatory
applicability at a later date.
This rule requires standard EPA methods known to the industry and
States. Approved alternative methods also may be used with prior EPA
approval.
J. Executive Order 13045
Executive Order 13045 applies to any rule that EPA determines (1)
is ``economically significant'' as defined under Executive Order 12866,
and (2) the environmental health or safety risk addressed by the rule
has a disproportionate effect on children. If the regulatory action
meets both criteria, the Agency must evaluate the environmental health
or safety effects of the planned rule on children and explain why the
planned regulation is preferable to other potentially effective and
reasonably feasible alternatives considered by the Agency.
This final rule is not subject to E.O. 13045, entitled ``Protection
of Children from Environmental Health Risks and Safety Risks'' (62 FR
19885, April 23, 1997), because it is not an economically significant
regulatory action as defined by Executive Order 12866, and it does not
address an environmental health or safety risk that would have a
disproportionate effect on children.
K. Executive Order 13084: Consultation and Coordination With Indian
Tribal Governments
Under Executive Order 13084, EPA may not issue a regulation that is
not required by statute, that significantly or uniquely affects the
communities of Indian tribal governments, and that imposes substantial
direct compliance costs on those communities, unless the Federal
government provides the funds necessary to pay the direct compliance
costs incurred by the tribal governments, or EPA consults with those
governments. If EPA complies by consulting, Executive Order 13084
requires EPA to provide to the Office of Management and Budget, in a
separately identified section of the preamble to the rule, a
description of the extent of EPA's prior consultation with
representatives of affected tribal governments, a summary of the nature
of their concerns, and a statement supporting the need to issue the
regulation. In addition, Executive Order 13084 requires EPA to develop
an effective process permitting elected officials and other
representatives of Indian tribal governments ``to provide meaningful
and timely input in the development of regulatory policies on matters
that
[[Page 31925]]
significantly or uniquely affect their communities.''
Today's rule does not significantly or uniquely affect the
communities of Indian tribal governments. Accordingly, the requirements
of section 3(b) of Executive Order 13084 do not apply to this rule.
List of Subjects in 40 CFR Part 63
Environmental protection, Air pollution control, Hazardous
substances, Portland cement manufacturing, Reporting and recordkeeping
requirements.
Dated: May 14, 1999.
Carol M. Browner,
Administrator.
For the reasons set out in the preamble, part 63 of title 40,
chapter 1 of the Code of Federal Regulations is amended as follows:
PART 63--NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS
FOR SOURCE CATEGORIES
1. The authority citation for part 63 continues to read as follows:
Authority: 42 U.S.C. 7401, et seq.
2. Part 63 is amended by adding a new subpart LLL, consisting of
Secs. 63.1340 through 63.1359 to read as follows:
Subpart LLL--National Emission Standards for Hazardous Air Pollutants
From the Portland Cement Manufacturing Industry
General
Sec.
63.1340 Applicability and designation of affected sources.
63.1341 Definitions.
Emission Standards and Operating Limits
63.1342 Standards: General.
63.1343 Standards for kilns and in-line kiln/raw mills.
63.1344 Operating limits for kilns and in-line kiln/raw mills.
63.1345 Standards for clinker coolers.
63.1346 Standards for new and reconstructed raw material dryers.
63.1347 Standards for raw and finish mills.
63.1348 Standards for affected sources other than kilns; in-line
kiln raw mills; clinker coolers; new and reconstructed raw material
dryers; and raw and finish mills.
Monitoring and Compliance Provisions
63.1349 Performance testing requirements.
63.1350 Monitoring requirements.
63.1351 Compliance dates.
63.1352 Additional test methods.
Notification, Reporting and Recordkeeping
63.1353 Notification requirements.
63.1354 Reporting requirements.
63.1355 Recordkeeping requirements.
Other
63.1356 Exemption from new source performance standards.
63.1357 Temporary, conditioned exemption from particulate and
opacity standards.
63.1358 Delegation of authority.
63.1359 [Reserved]
Table 1 to Subpart LLL of Part 63--Applicability of General Provisions
Subpart LLL--National Emission Standards for Hazardous Air
Pollutants From the Portland Cement Manufacturing Industry
General
Sec. 63.1340 Applicability and designation of affected sources.
(a) Except as specified in paragraphs (b) and (c) of this section,
the provisions of this subpart apply to each new and existing portland
cement plant which is a major source or an area source as defined in
Sec. 63.2.
(b) The affected sources subject to this subpart are:
(1) Each kiln and each in-line kiln/raw mill at any major or area
source, including alkali bypasses, except for kilns and in-line kiln/
raw mills that burn hazardous waste and are subject to and regulated
under subpart EEE of this part;
(2) Each clinker cooler at any portland cement plant which is a
major source;
(3) Each raw mill at any portland cement plant which is a major
source;
(4) Each finish mill at any portland cement plant which is a major
source;
(5) Each raw material dryer at any portland cement plant which is a
major source and each greenfield raw material dryer at any portland
cement plant which is a major or area source;
(6) Each raw material, clinker, or finished product storage bin at
any portland cement plant which is a major source;
(7) Each conveying system transfer point at any portland cement
plant which is a major source;
(8) Each bagging system at any portland cement plant which is a
major source; and
(9) Each bulk loading or unloading system at any portland cement
plant which is a major source.
(c) For portland cement plants with on-site nonmetallic mineral
processing facilities, the first affected source in the sequence of
materials handling operations subject to this subpart is the raw
material storage, which is just prior to the raw mill. The primary and
secondary crushers and any other equipment of the on-site nonmetallic
mineral processing plant which precedes the raw material storage are
not subject to this subpart. Furthermore, the first conveyor transfer
point subject to this subpart is the transfer point associated with the
conveyor transferring material from the raw material storage to the raw
mill.
(d) The owner or operator of any affected source subject to the
provisions of this subpart is subject to title V permitting
requirements.
Sec. 63.1341 Definitions.
All terms used in this subpart that are not defined in this section
have the meaning given to them in the CAA and in subpart A of this
part.
Alkali bypass means a duct between the feed end of the kiln and the
preheater tower through which a portion of the kiln exit gas stream is
withdrawn and quickly cooled by air or water to avoid excessive buildup
of alkali, chloride and/or sulfur on the raw feed. This may also be
referred to as the ``kiln exhaust gas bypass''.
Bagging system means the equipment which fills bags with portland
cement.
Clinker cooler means equipment into which clinker product leaving
the kiln is placed to be cooled by air supplied by a forced draft or
natural draft supply system.
Continuous monitor means a device which continuously samples the
regulated parameter specified in Sec. 63.1350 of this subpart without
interruption, evaluates the detector response at least once every 15
seconds, and computes and records the average value at least every 60
seconds, except during allowable periods of calibration and except as
defined otherwise by the continuous emission monitoring system
performance specifications in appendix B to part 60 of this chapter.
Conveying system means a device for transporting materials from one
piece of equipment or location to another location within a facility.
Conveying systems include but are not limited to the following:
feeders, belt conveyors, bucket elevators and pneumatic systems.
Conveying system transfer point means a point where any material
including but not limited to feed material, fuel, clinker or product,
is transferred to or from a conveying system, or between separate parts
of a conveying system.
Dioxins and furans (D/F) means tetra-, penta-, hexa-, hepta-, and
octa-chlorinated dibenzo dioxins and furans.
Facility means all contiguous or adjoining property that is under
common ownership or control, including properties that are separated
only by a road or other public right-of-way.
[[Page 31926]]
Feed means the prepared and mixed materials, which include but are
not limited to materials such as limestone, clay, shale, sand, iron
ore, mill scale, cement kiln dust and flyash, that are fed to the kiln.
Feed does not include the fuels used in the kiln to produce heat to
form the clinker product.
Finish mill means a roll crusher, ball and tube mill or other size
reduction equipment used to grind clinker to a fine powder. Gypsum and
other materials may be added to and blended with clinker in a finish
mill. The finish mill also includes the air separator associated with
the finish mill.
Greenfield kiln, in-line kiln/raw mill, or raw material dryer means
a kiln, in-line kiln/raw mill, or raw material dryer for which
construction is commenced at a plant site (where no kilns and no in-
line kiln/raw mills were in operation at any time prior to March 24,
1998) after March 24, 1998.
Hazardous waste is defined in Sec. 261.3 of this chapter.
In-line kiln/raw mill means a system in a portland cement
production process where a dry kiln system is integrated with the raw
mill so that all or a portion of the kiln exhaust gases are used to
perform the drying operation of the raw mill, with no auxiliary heat
source used. In this system the kiln is capable of operating without
the raw mill operating, but the raw mill cannot operate without the
kiln gases, and consequently, the raw mill does not generate a separate
exhaust gas stream.
Kiln means a device, including any associated preheater or
precalciner devices, that produces clinker by heating limestone and
other materials for subsequent production of portland cement.
Kiln exhaust gas bypass means alkali bypass.
Monovent means an exhaust configuration of a building or emission
control device (e. g. positive pressure fabric filter) that extends the
length of the structure and has a width very small in relation to its
length (i. e., length to width ratio is typically greater than 5:1).
The exhaust may be an open vent with or without a roof, louvered vents,
or a combination of such features.
New brownfield kiln, in-line kiln raw mill, or raw material dryer
means a kiln, in-line kiln/raw mill or raw material dryer for which
construction is commenced at a plant site (where kilns and/or in-line
kiln/raw mills were in operation prior to March 24, 1998) after March
24, 1998.
One-minute average means the average of thermocouple or other
sensor responses calculated at least every 60 seconds from responses
obtained at least once during each consecutive 15 second period.
Portland cement plant means any facility manufacturing portland
cement.
Raw material dryer means an impact dryer, drum dryer, paddle-
equipped rapid dryer, air separator, or other equipment used to reduce
the moisture content of feed materials.
Raw mill means a ball and tube mill, vertical roller mill or other
size reduction equipment, that is not part of an in-line kiln/raw mill,
used to grind feed to the appropriate size. Moisture may be added or
removed from the feed during the grinding operation. If the raw mill is
used to remove moisture from feed materials, it is also, by definition,
a raw material dryer. The raw mill also includes the air separator
associated with the raw mill.
Rolling average means the average of all one-minute averages over
the averaging period.
Run average means the average of the one-minute parameter values
for a run.
TEQ means the international method of expressing toxicity
equivalents for dioxins and furans as defined in U.S. EPA, Interim
Procedures for Estimating Risks Associated with Exposures to Mixtures
of Chlorinated Dibenzo-p-dioxins and -dibenzofurans (CDDs and CDFs) and
1989 Update, March 1989.
Emission Standards and Operating Limits
Sec. 63.1342 Standards: General.
(a) Table 1 to this subpart provides cross references to the 40 CFR
part 63, subpart A, general provisions, indicating the applicability of
the general provisions requirements to subpart LLL.
(b) Table 1 of this section provides a summary of emission limits
and operating limits of this subpart.
Table 1 to Sec. 63.1342.--Emission Limits and Operating Limits
----------------------------------------------------------------------------------------------------------------
Affected source Pollutant or opacity Emission and operating limit
----------------------------------------------------------------------------------------------------------------
All kilns and in-line kiln/raw mills at PM..................................... 0.15 kg/Mg of feed (dry
major sources (including alkali Opacity................................ basis).
bypass). 20 percent.
All kilns and in-line kiln/raw mills at D/F.................................... 0.20 ng TEQ/dscm
major and area sources (including or
alkali bypass). 0.40 ng TEQ/dscm when the
average of the performance
test run average particulate
matter control device (PMCD)
inlet temperatures is 204
deg. C or less. [Corrected to
7 percent oxygen]
Operate such that the three-
hour rolling average PMCD
inlet temperature is no
greater than the temperature
established at performance
test.
If activated carbon injection
is used: Operate such that
the three-hour rolling
average activated carbon
injection rate is no less
than rate established at
performance test. Operate
such that either the carrier
gas flow rate or carrier gas
pressure drop exceeds the
value established at
performance test. Inject
carbon of equivalent
specifications to that used
at performance test.
New greenfield kilns and in-line kiln/ THC.................................... 50 ppmvd, as propane,
raw mills at major and area sources. corrected to 7 percent
oxygen.
All clinker coolers at major sources... PM..................................... 0.050 kg/Mg of feed (dry
Opacity................................ basis)
10 percent.
All raw mills and finish mills at major Opacity................................ 10 percent.
sources.
New greenfield raw material dryers at THC.................................... 50 ppmvd, as propane,
major and area sources. corrected to 7 percent
oxygen.
All raw material dryers and material Opacity................................ 10 percent.
handling points at major sources.
----------------------------------------------------------------------------------------------------------------
[[Page 31927]]
Sec. 63.1343 Standards for kilns and in-line kiln/raw mills.
(a) General. The provisions in this section apply to each kiln,
each in-line kiln/raw mill, and any alkali bypass associated with that
kiln or in-line kiln/raw mill.
(b) Existing, reconstructed, or new brownfield/major sources. No
owner or operator of an existing, reconstructed or new brownfield kiln
or an existing, reconstructed or new brownfield in-line kiln/raw mill
at a facility that is a major source subject to the provisions of this
subpart shall cause to be discharged into the atmosphere from these
affected sources, any gases which:
(1) Contain particulate matter (PM) in excess of 0.15 kg per Mg
(0.30 lb per ton) of feed (dry basis) to the kiln. When there is an
alkali bypass associated with a kiln or in-line kiln/raw mill, the
combined particulate matter emissions from the kiln or in-line kiln/raw
mill and the alkali bypass are subject to this emission limit.
(2) Exhibit opacity greater than 20 percent.
(3) Contain D/F in excess of:
(i) 0.20 ng per dscm (8.7 x 10-11 gr per dscf) (TEQ)
corrected to seven percent oxygen; or
(ii) 0.40 ng per dscm (1.7 x 10-10 gr per dscf) (TEQ)
corrected to seven percent oxygen, when the average of the performance
test run average temperatures at the inlet to the particulate matter
control device is 204 deg.C (400 deg.F) or less.
(c) Greenfield/major sources. No owner or operator that commences
construction of a greenfield kiln or greenfield inline kiln/raw mill at
a facility which is a major source subject to the provisions of this
subpart shall cause to be discharged into the atmosphere from these
affected sources any gases which:
(1) Contain particulate matter in excess of 0.15 kg per Mg (0.30 lb
per ton) of feed (dry basis) to the kiln. When there is an alkali
bypass associated with a kiln or in-line kiln/raw mill, the combined
particulate matter emissions from the kiln or in-line kiln/raw mill and
the bypass stack are subject to this emission limit.
(2) Exhibit opacity greater than 20 percent.
(3) Contain D/F in excess of:
(i) 0.20 ng per dscm (8.7 x 10-11 gr per dscf) (TEQ)
corrected to seven percent oxygen; or
(ii) 0.40 ng per dscm (1.7 x 10-10 gr per dscf) (TEQ)
corrected to seven percent oxygen, when the average of the performance
test run average temperatures at the inlet to the particulate matter
control device is 204 deg.C (400 deg.F) or less.
(4) Contain total hydrocarbon (THC), from the main exhaust of the
kiln or in-line kiln/raw mill, in excess of 50 ppmvd as propane,
corrected to seven percent oxygen.
(d) Existing, reconstructed, or new brownfield/area sources. No
owner or operator of an existing, reconstructed, or new brownfield kiln
or an existing, reconstructed or new brownfield in-line kiln/raw mill
at a facility that is an area source subject to the provisions of this
subpart shall cause to be discharged into the atmosphere from these
affected sources any gases which contain D/F in excess of:
(1) 0.20 ng per dscm (8.7 x 10-11 gr per dscf) (TEQ)
corrected to seven percent oxygen; or
(2) 0.40 ng per dscm (1.7 x 10-10 gr per dscf) (TEQ)
corrected to seven percent oxygen, when the average of the performance
test run average temperatures at the inlet to the particulate matter
control device is 204 deg.C (400 deg.F) or less.
(e) Greenfield/area sources. No owner or operator of a greenfield
kiln or a greenfield in-line kiln/raw mill at a facility that is an
area source subject to the provisions of this subpart shall cause to be
discharged into the atmosphere from these affected sources any gases
which:
(1) Contain D/F in excess of:
(i) 0.20 ng per dscm (8.7 x 10-11 gr per dscf) (TEQ)
corrected to seven percent oxygen; or
(ii) 0.40 ng per dscm (1.7 x 10-11 gr per dscf) (TEQ)
corrected to seven percent oxygen, when the average of the performance
test run average temperatures at the inlet to the particulate matter
control device is 204 deg.C (400 deg.F) or less.
(2) Contain THC, from the main exhaust of the kiln or in-line kiln/
raw mill, in excess of 50 ppmvd as propane, corrected to seven percent
oxygen.
Sec. 63.1344 Operating limits for kilns and in-line kiln/raw mills.
(a) The owner or operator of a kiln subject to a D/F emission
limitation under Sec. 63.1343 must operate the kiln such that the
temperature of the gas at the inlet to the kiln particulate matter
control device (PMCD) and alkali bypass PMCD, if applicable, does not
exceed the applicable temperature limit specified in paragraph (b) of
this section. The owner or operator of an in-line kiln/raw mill subject
to a D/F emission limitation under Sec. 63.1343 must operate the in-
line kiln/raw mill, such that:
(1) When the raw mill of the in-line kiln/raw mill is operating,
the applicable temperature limit for the main in-line kiln/raw mill
exhaust, specified in paragraph (b) of this section and established
during the performance test when the raw mill was operating is not
exceeded.
(2) When the raw mill of the in-line kiln/raw mill is not
operating, the applicable temperature limit for the main in-line kiln/
raw mill exhaust, specified in paragraph (b) of this section and
established during the performance test when the raw mill was not
operating, is not exceeded.
(3) If the in-line kiln/raw mill is equipped with an alkali bypass,
the applicable temperature limit for the alkali bypass, specified in
paragraph (b) of this section and established during the performance
test when the raw mill was operating, is not exceeded.
(b) The temperature limit for affected sources meeting the limits
of paragraph (a) of this section or paragraphs (a)(1) through (a)(3) of
this section is determined in accordance with Sec. 63.1349(b)(3)(iv).
(c) The owner or operator of an affected source subject to a D/F
emission limitation under Sec. 63.1343 that employs carbon injection as
an emission control technique must operate the carbon injection system
in accordance with paragraphs (c)(1) and (c)(2) of this section.
(1) The three-hour rolling average activated carbon injection rate
shall be equal to or greater than the activated carbon injection rate
determined in accordance with Sec. 63.1349(b)(3)(vi).
(2) The owner or operator shall either:
(i) Maintain the minimum activated carbon injection carrier gas
flow rate, as a three-hour rolling average, based on the manufacturer's
specifications. These specifications must be documented in the test
plan developed in accordance with Sec. 63.7(c), or
(ii) Maintain the minimum activated carbon injection carrier gas
pressure drop, as a three-hour rolling average, based on the
manufacturer's specifications. These specifications must be documented
in the test plan developed in accordance with Sec. 63.7(c).
(d) Except as provided in paragraph (e) of this section, the owner
or operator of an affected source subject to a D/F emission limitation
under Sec. 63.1343 that employs carbon injection as an emission control
technique must specify and use the brand and type of activated carbon
used during the performance test until a subsequent performance test is
conducted, unless the site-specific performance test plan contains
documentation of key parameters that
[[Page 31928]]
affect adsorption and the owner or operator establishes limits based on
those parameters, and the limits on these parameters are maintained.
(e) The owner or operator of an affected source subject to a D/F
emission limitation under Sec. 63.1343 that employs carbon injection as
an emission control technique may substitute, at any time, a different
brand or type of activated carbon provided that the replacement has
equivalent or improved properties compared to the activated carbon
specified in the site-specific performance test plan and used in the
performance test. The owner or operator must maintain documentation
that the substitute activated carbon will provide the same or better
level of control as the original activated carbon.
Sec. 63.1345 Standards for clinker coolers.
(a) No owner or operator of a new or existing clinker cooler at a
facility which is a major source subject to the provisions of this
subpart shall cause to be discharged into the atmosphere from the
clinker cooler any gases which:
(1) Contain particulate matter in excess of 0.050 kg per Mg (0.10
lb per ton) of feed (dry basis) to the kiln.
(2) Exhibit opacity greater than ten percent.
(b) [Reserved].
Sec. 63.1346 Standards for new and reconstructed raw material dryers.
(a) Brownfield/major sources. No owner or operator of a new or
reconstructed brownfield raw material dryer at a facility which is a
major source subject to this subpart shall cause to be discharged into
the atmosphere from the new or reconstructed raw material dryer any
gases which exhibit opacity greater than ten percent.
(b) Greenfield/area sources. No owner or operator of a greenfield
raw material dryer at a facility which is an area source subject to
this subpart shall cause to be discharged into the atmosphere from the
greenfield raw material dryer any gases which contain THC in excess of
50 ppmvd, reported as propane, corrected to seven percent oxygen.
(c) Greenfield/major sources. No owner or operator of a greenfield
raw material dryer at a facility which is a major source subject to
this subpart shall cause to be discharged into the atmosphere from the
greenfield raw material dryer any gases which:
(1) Contain THC in excess of 50 ppmvd, reported as propane,
corrected to seven percent oxygen.
(2) Exhibit opacity greater than ten percent.
Sec. 63.1347 Standards for raw and finish mills.
The owner or operator of each new or existing raw mill or finish
mill at a facility which is a major source subject to the provisions of
this subpart shall not cause to be discharged from the mill sweep or
air separator air pollution control devices of these affected sources
any gases which exhibit opacity in excess of ten percent.
Sec. 63.1348 Standards for affected sources other than kilns; in-line
kiln/raw mills; clinker coolers; new and reconstructed raw material
dryers; and raw and finish mills.
The owner or operator of each new or existing raw material,
clinker, or finished product storage bin; conveying system transfer
point; bagging system; and bulk loading or unloading system; and each
existing raw material dryer, at a facility which is a major source
subject to the provisions of this subpart shall not cause to be
discharged any gases from these affected sources which exhibit opacity
in excess of ten percent.
Monitoring and Compliance Provisions
Sec. 63.1349 Performance testing requirements.
(a) The owner or operator of an affected source subject to this
subpart shall demonstrate initial compliance with the emission limits
of Sec. 63.1343 and Secs. 63.1345 through 63.1348 using the test
methods and procedures in paragraph (b) of this section and Sec. 63.7.
Performance test results shall be documented in complete test reports
that contain the information required by paragraphs (a)(1) through
(a)(10) of this section, as well as all other relevant information. The
plan to be followed during testing shall be made available to the
Administrator prior to testing, if requested.
(1) A brief description of the process and the air pollution
control system;
(2) Sampling location description(s);
(3) A description of sampling and analytical procedures and any
modifications to standard procedures;
(4) Test results;
(5) Quality assurance procedures and results;
(6) Records of operating conditions during the test, preparation of
standards, and calibration procedures;
(7) Raw data sheets for field sampling and field and laboratory
analyses;
(8) Documentation of calculations;
(9) All data recorded and used to establish parameters for
compliance monitoring; and
(10) Any other information required by the test method.
(b) Performance tests to demonstrate initial compliance with this
subpart shall be conducted as specified in paragraphs (b)(1) through
(b)(4) of this section.
(1) The owner or operator of a kiln subject to limitations on
particulate matter emissions shall demonstrate initial compliance by
conducting a performance test as specified in paragraphs (b)(1)(i)
through (b)(1)(iv) of this section. The owner or operator of an in-line
kiln/raw mill subject to limitations on particulate matter emissions
shall demonstrate initial compliance by conducting separate performance
tests as specified in paragraphs (b)(1)(i) through (b)(1)(iv) of this
section while the raw mill of the in-line kiln/raw mill is under normal
operating conditions and while the raw mill of the in-line kiln/raw
mill is not operating. The owner or operator of a clinker cooler
subject to limitations on particulate matter emissions shall
demonstrate initial compliance by conducting a performance test as
specified in paragraphs (b)(1)(i) through (b)(1)(iii) of this section.
The opacity exhibited during the period of the Method 5 of Appendix A
to part 60 of this chapter performance tests required by paragraph
(b)(1)(i) of this section shall be determined as required in paragraphs
(b)(1)(v) through (vi) of this section.
(i) EPA Method 5 of appendix A to part 60 of this chapter shall be
used to determine PM emissions. Each performance test shall consist of
three separate runs under the conditions that exist when the affected
source is operating at the highest load or capacity level reasonably
expected to occur. Each run shall be conducted for at least one hour,
and the minimum sample volume shall be 0.85 dscm (30 dscf). The average
of the three runs shall be used to determine compliance. A
determination of the particulate matter collected in the impingers
(``back half'') of the Method 5 particulate sampling train is not
required to demonstrate initial compliance with the PM standards of
this subpart. However this shall not preclude the permitting authority
from requiring a determination of the ``back half'' for other purposes.
(ii) Suitable methods shall be used to determine the kiln or inline
kiln/raw mill feed rate, except for fuels, for each run.
(iii) The emission rate, E, of PM shall be computed for each run
using equation 1:
[GRAPHIC] [TIFF OMITTED] TR14JN99.001
Where:
[[Page 31929]]
E = emission rate of particulate matter, kg/Mg of kiln feed.
cs = concentration of PM, kg/dscm.
Qsd = volumetric flow rate of effluent gas, dscm/hr.
P = total kiln feed (dry basis), Mg/hr.
(iv) When there is an alkali bypass associated with a kiln or in-
line kiln/raw mill, the main exhaust and alkali bypass of the kiln or
in-line kiln/raw mill shall be tested simultaneously and the combined
emission rate of particulate matter from the kiln or in-line kiln/raw
mill and alkali bypass shall be computed for each run using equation 2,
[GRAPHIC] [TIFF OMITTED] TR14JN99.002
Where:
Ec = the combined emission rate of particulate matter from
the kiln or in-line kiln/raw mill and bypass stack, kg/Mg of kiln feed.
csk = concentration of particulate matter in the kiln or in-
line kiln/raw mill effluent, kg/dscm.
Qsdk = volumetric flow rate of kiln or in-line kiln/raw
mill effluent, dscm/hr.
csb = concentration of particulate matter in the alkali
bypass gas, kg/dscm.
Qsdb = volumetric flow rate of alkali bypass gas, dscm/hr.
P=total kiln feed (dry basis), Mg/hr.
(v) Except as provided in paragraph (b)(1)(vi) of this section the
opacity exhibited during the period of the Method 5 performance tests
required by paragraph (b)(1)(i) of this section shall be determined
through the use of a continuous opacity monitor (COM). The maximum six-
minute average opacity during the three Method 5 test runs shall be
determined during each Method 5 test run, and used to demonstrate
initial compliance with the applicable opacity limits of
Sec. 63.1343(b)(2), Sec. 63.1343(c)(2), or Sec. 63.1345(a)(2).
(vi) Each owner or operator of a kiln, in-line kiln/raw mill, or
clinker cooler subject to the provisions of this subpart using a fabric
filter with multiple stacks or an electrostatic precipitator with
multiple stacks may, in lieu of installing the continuous opacity
monitoring system required by paragraph (b)(1)(v) of this section,
conduct an opacity test in accordance with Method 9 of appendix A to
part 60 of this chapter during each Method 5 performance test required
by paragraph (b)(1)(i) of this section. If the control device exhausts
through a monovent, or if the use of a COM in accordance with the
installation specifications of Performance Specification 1 (PS-1) of
appendix B to part 60 of this chapter is not feasible, a test shall be
conducted in accordance with Method 9 of appendix A to part 60 of this
chapter during each Method 5 performance test required by paragraph
(b)(1)(i) of this section. The maximum six-minute average opacity shall
be determined during the three Method 5 test runs, and used to
demonstrate initial compliance with the applicable opacity limits of
Sec. 63.1343(b)(2), Sec. 63.1343(c)(2), or Sec. 63.1345(a)(2).
(2) The owner or operator of any affected source subject to
limitations on opacity under this subpart that is not subject to
paragraph (b)(1) of this section shall demonstrate initial compliance
with the affected source opacity limit by conducting a test in
accordance with Method 9 of appendix A to part 60 of this chapter. The
performance test shall be conducted under the conditions that exist
when the affected source is operating at the highest load or capacity
level reasonably expected to occur. The maximum six-minute average
opacity exhibited during the test period shall be used to determine
whether the affected source is in initial compliance with the standard.
The duration of the Method 9 performance test shall be 3-hours (30 6-
minute averages), except that the duration of the Method 9 performance
test may be reduced to 1-hour if the conditions of paragraphs (b)(2)(i)
through (ii) of the section apply:
(i) There are no individual readings greater than 10 percent
opacity;
(ii) There are no more than three readings of 10 percent for the
first 1-hour period.
(3) The owner or operator of an affected source subject to
limitations on D/F emissions shall demonstrate initial compliance with
the D/F emission limit by conducting a performance test using Method 23
of appendix A to part 60 of this chapter. The owner or operator of an
in-line kiln/raw mill shall demonstrate initial compliance by
conducting separate performance tests while the raw mill of the in-line
kiln/raw mill is under normal operating conditions and while the raw
mill of the in-line kiln/raw mill is not operating. The owner or
operator of a kiln or in-line kiln/raw mill equipped with an alkali
bypass shall conduct simultaneous performance tests of the kiln or in-
line kiln/raw mill exhaust and the alkali bypass, however the owner or
operator of an in-line kiln/raw mill is not required to conduct a
performance test of the alkali bypass exhaust when the raw mill of the
in-line kiln/raw mill is not operating.
(i) Each performance test shall consist of three separate runs;
each run shall be conducted under the conditions that exist when the
affected source is operating at the highest load or capacity level
reasonably expected to occur. The duration of each run shall be at
least three hours and the sample volume for each run shall be at least
2.5 dscm (90 dscf). The concentration shall be determined for each run
and the arithmetic average of the concentrations measured for the three
runs shall be calculated and used to determine compliance.
(ii) The temperature at the inlet to the kiln or in-line kiln/raw
mill PMCD, and where applicable, the temperature at the inlet to the
alkali bypass PMCD, must be continuously recorded during the period of
the Method 23 test, and the continuous temperature record(s) must be
included in the performance test report.
(iii) One-minute average temperatures must be calculated for each
minute of each run of the test.
(iv) The run average temperature must be calculated for each run,
and the average of the run average temperatures must be determined and
included in the performance test report and will determine the
applicable temperature limit in accordance with Sec. 63.1344(b).
(v) If activated carbon injection is used for D/F control, the rate
of activated carbon injection to the kiln or in-line kiln/raw mill
exhaust, and where applicable, the rate of activated carbon injection
to the alkali bypass exhaust, must be continuously recorded during the
period of the Method 23 test, and the continuous injection rate
record(s) must be included in the performance test report. In addition,
the performance test report must include the brand and type of
activated carbon used during the performance test and a continuous
record of either the carrier gas flow rate or the carrier gas pressure
drop for the duration of the test. Activated carbon injection rate
parameters must be determined in accordance with paragraphs (b)(3)(vi)
of this section.
(vi) The run average injection rate must be calculated for each
run, and the average of the run average injection rates must be
determined and included in the performance test report and will
determine the applicable injection rate limit in accordance with
Sec. 63.1344(c)(1).
(4) The owner or operator of an affected source subject to
limitations on emissions of THC shall demonstrate initial compliance
with the THC limit by operating a continuous emission monitor in
accordance with Performance Specification 8A of appendix B to part 60
of this chapter. The duration of the performance test shall be three
hours, and the average THC concentration (as calculated from the one-
minute averages) during the three hour performance test shall be
[[Page 31930]]
calculated. The owner or operator of an in-line kiln/raw mill shall
demonstrate initial compliance by conducting separate performance tests
while the raw mill of the in-line kiln/raw mill is under normal
operating conditions and while the raw mill of the in-line kiln/raw
mill is not operating.
(c) Except as provided in paragraph (e) of this section,
performance tests required under paragraphs (b)(1) and (b)(2) of this
section shall be repeated every five years, except that the owner or
operator of a kiln, in-line kiln/raw mill or clinker cooler is not
required to repeat the initial performance test of opacity for the
kiln, in-line kiln/raw mill or clinker cooler.
(d) Performance tests required under paragraph (b)(3) of this
section shall be repeated every 30 months.
(e) The owner or operator is required to repeat the performance
tests for kilns or in-line kiln/raw mills as specified in paragraphs
(b)(1) and (b)(3) of this section within 90 days of initiating any
significant change in the feed or fuel from that used in the previous
performance test.
(f) Table 1 of this section provides a summary of the performance
test requirements of this subpart.
Table 1 to Sec. 63.1349.--Summary of Performance Test Requirements
------------------------------------------------------------------------
Affected source and pollutant Performance test
------------------------------------------------------------------------
New and existing kiln and in-line EPA Method 5.a
kiln/raw mill b c PM.
New and existing kiln and in-line COM if feasible d e or EPA Method 9
kiln/raw mill b c Opacity. visual opacity readings.
New and existing kiln and in-line EPA Method 23h.
kiln/raw mill b c f gD/F.
New greenfield kiln and in-line THC CEM (EPA PS-8A) i.
kiln/raw mill c THC.
New and existing clinker cooler EPA Method 5 a.
PM.
New and existing clinker cooler COM d,j or EPA Method 9 visual
opacity. opacity readings.
New and existing raw and finish EPA Method 9.a j
mill opacity.
New and existing raw material EPA Method 9.a j
dryer and materials handling
processes (raw material storage,
clinker storage, finished
product storage, conveyor
transfer points, bagging, and
bulk loading and unloading
systems) opacity.
New greenfield raw material dryer THC CEM (EPA PS-8A).i
THC.
------------------------------------------------------------------------
a Required initially and every 5 years thereafter.
b Includes main exhaust and alkali bypass.
c In-line kiln/raw mill to be tested with and without raw mill in
operation.
d Must meet COM performance specification criteria. If the fabric
filter or electrostatic precipitator has multiple stacks, daily EPA
Method 9 visual opacity readings may be taken instead of using a COM.
e Opacity limit is 20 percent.
f Alkali bypass is tested with the raw mill on.
g Temperature and (if applicable) activated carbon injection parameters
determined separately with and without the raw mill operating.
h Required initially and every 30 months thereafter.
i EPA Performance Specification (PS)-8A of appendix B to 40 CFR part 60.
j Opacity limit is 10 percent.
Sec. 63.1350 Monitoring requirements.
(a) The owner or operator of each portland cement plant shall
prepare for each affected source subject to the provisions of this
subpart, a written operations and maintenance plan. The plan shall be
submitted to the Administrator for review and approval as part of the
application for a part 70 permit and shall include the following
information:
(1) Procedures for proper operation and maintenance of the affected
source and air pollution control devices in order to meet the emission
limits and operating limits of Secs. 63.1343 through 63.1348;
(2) Corrective actions to be taken when required by paragraph (e)
of this section;
(3) Procedures to be used during an inspection of the components of
the combustion system of each kiln and each in-line kiln raw mill
located at the facility at least once per year; and
(4) Procedures to be used to periodically monitor affected sources
subject to opacity standards under Secs. 63.1346 and 63.1348. Such
procedures must include the provisions of paragraphs (a)(4)(i) through
(a)(4)(iv) of this section.
(i) The owner or operator must conduct a monthly 1-minute visible
emissions test of each affected source in accordance with Method 22 of
Appendix A to part 60 of this chapter. The test must be conducted while
the affected source is in operation.
(ii) If no visible emissions are observed in six consecutive
monthly tests for any affected source, the owner or operator may
decrease the frequency of testing from monthly to semi-annually for
that affected source. If visible emissions are observed during any
semi-annual test, the owner or operator must resume testing of that
affected source on a monthly basis and maintain that schedule until no
visible emissions are observed in six consecutive monthly tests.
(iii) If no visible emissions are observed during the semi-annual
test for any affected source, the owner or operator may decrease the
frequency of testing from semi-annually to annually for that affected
source. If visible emissions are observed during any annual test, the
owner or operator must resume testing of that affected source on a
monthly basis and maintain that schedule until no visible emissions are
observed in six consecutive monthly tests.
(iv) If visible emissions are observed during any Method 22 test,
the owner or operator must conduct a 6-minute test of opacity in
accordance with Method 9 of appendix A to part 60 of this chapter. The
Method 9 test must begin within one hour of any observation of visible
emissions.
(b) Failure to comply with any provision of the operations and
maintenance plan developed in accordance with paragraph (a) of this
section shall be a violation of the standard.
(c) The owner or operator of a kiln or in-line kiln/raw mill shall
monitor opacity at each point where emissions are vented from these
affected sources including alkali bypasses in accordance with
paragraphs (c)(1) through (c)(3) of this section.
(1) Except as provided in paragraph (c)(2) of this section, the
owner or operator shall install, calibrate, maintain, and continuously
operate a
[[Page 31931]]
continuous opacity monitor (COM) located at the outlet of the PM
control device to continuously monitor the opacity. The COM shall be
installed, maintained, calibrated, and operated as required by subpart
A, general provisions of this part, and according to PS-1 of appendix B
to part 60 of this chapter.
(2) The owner or operator of a kiln or in-line kiln/raw mill
subject to the provisions of this subpart using a fabric filter with
multiple stacks or an electrostatic precipitator with multiple stacks
may, in lieu of installing the continuous opacity monitoring system
required by paragraph (c)(1) of this section, monitor opacity in
accordance with paragraphs (c)(2)(i) through (ii) of this section. If
the control device exhausts through a monovent, or if the use of a COM
in accordance with the installation specifications of PS-1 of appendix
B to part 60 of this chapter is not feasible, the owner or operator
must monitor opacity in accordance with paragraphs (c)(2)(i) through
(ii) of this section.
(i) Perform daily visual opacity observations of each stack in
accordance with the procedures of Method 9 of appendix A of part 60 of
this chapter. The Method 9 test shall be conducted while the affected
source is operating at the highest load or capacity level reasonably
expected to occur within the day. The duration of the Method 9 test
shall be at least 30 minutes each day.
(ii) Use the Method 9 procedures to monitor and record the average
opacity for each six-minute period during the test.
(3) To remain in compliance, the opacity must be maintained such
that the 6-minute average opacity for any 6-minute block period does
not exceed 20 percent. If the average opacity for any 6-minute block
period exceeds 20 percent, this shall constitute a violation of the
standard.
(d) The owner or operator of a clinker cooler shall monitor opacity
at each point where emissions are vented from the clinker cooler in
accordance with paragraphs (d)(1) through (d)(3) of this section.
(1) Except as provided in paragraph (d)(2) of this section, the
owner or operator shall install, calibrate, maintain, and continuously
operate a COM located at the outlet of the clinker cooler PM control
device to continuously monitor the opacity. The COM shall be installed,
maintained, calibrated, and operated as required by subpart A, general
provisions of this part, and according to PS-1 of appendix B to part 60
of this chapter.
(2) The owner or operator of a clinker cooler subject to the
provisions of this subpart using a fabric filter with multiple stacks
or an electrostatic precipitator with multiple stacks may, in lieu of
installing the continuous opacity monitoring system required by
paragraph (d)(1) of this section, monitor opacity in accordance with
paragraphs (d)(2)(i) through (ii) of this section. If the control
device exhausts through a monovent, or if the use of a COM in
accordance with the installation specifications of PS-1 of appendix B
to part 60 of this chapter is not feasible, the owner or operator must
monitor opacity in accordance with paragraphs (d)(2)(i) through (ii) of
this section.
(i) Perform daily visual opacity observations of each stack in
accordance with the procedures of Method 9 of appendix A of part 60 of
this chapter. The Method 9 test shall be conducted while the affected
source is operating at the highest load or capacity level reasonably
expected to occur within the day. The duration of the Method 9 test
shall be at least 30 minutes each day.
(ii) Use the Method 9 procedures to monitor and record the average
opacity for each six-minute period during the test.
(3) To remain in compliance, the opacity must be maintained such
that the 6-minute average opacity for any 6-minute block period does
not exceed 10 percent. If the average opacity for any 6-minute block
period exceeds 10 percent, this shall constitute a violation of the
standard.
(e) The owner or operator of a raw mill or finish mill shall
monitor opacity by conducting daily visual emissions observations of
the mill sweep and air separator PMCDs of these affected sources, in
accordance with the procedures of Method 22 of appendix A of part 60 of
this chapter. The Method 22 test shall be conducted while the affected
source is operating at the highest load or capacity level reasonably
expected to occur within the day. The duration of the Method 22 test
shall be six minutes. If visible emissions are observed during any
Method 22 visible emissions test, the owner or operator must:
(1) Initiate, within one-hour, the corrective actions specified in
the site specific operating and maintenance plan developed in
accordance with paragraphs (a)(1) and (a)(2) of this section; and
(2) Within 24 hours of the end of the Method 22 test in which
visible emissions were observed, conduct a visual opacity test of each
stack from which visible emissions were observed in accordance with
Method 9 of appendix A of part 60 of this chapter. The duration of the
Method 9 test shall be thirty minutes.
(f) The owner or operator of an affected source subject to a
limitation on D/F emissions shall monitor D/F emissions in accordance
with paragraphs (f)(1) through (f)(6) of this section.
(1) The owner or operator shall install, calibrate, maintain, and
continuously operate a continuous monitor to record the temperature of
the exhaust gases from the kiln, in-line kiln/raw mill and alkali
bypass, if applicable, at the inlet to, or upstream of, the kiln, in-
line kiln/raw mill and/or alkali bypass PM control devices.
(i) The recorder response range must include zero and 1.5 times
either of the average temperatures established according to the
requirements in Sec. 63.1349(b)(3)(iv).
(ii) The reference method must be a National Institute of Standards
and Technology calibrated reference thermocouple-potentiometer system
or alternate reference, subject to approval by the Administrator.
(2) The owner or operator shall monitor and continuously record the
temperature of the exhaust gases from the kiln, in-line kiln/raw mill
and alkali bypass, if applicable, at the inlet to the kiln, in-line
kiln/raw mill and/or alkali bypass PMCD.
(3) The three-hour rolling average temperature shall be calculated
as the average of 180 successive one-minute average temperatures.
(4) Periods of time when one-minute averages are not available
shall be ignored when calculating three-hour rolling averages. When
one-minute averages become available, the first one-minute average is
added to the previous 179 values to calculate the three-hour rolling
average.
(5) When the operating status of the raw mill of the in-line kiln/
raw mill is changed from off to on, or from on to off the calculation
of the three-hour rolling average temperature must begin anew, without
considering previous recordings.
(6) The calibration of all thermocouples and other temperature
sensors shall be verified at least once every three months.
(g) The owner or operator of an affected source subject to a
limitation on D/F emissions that employs carbon injection as an
emission control technique shall comply with the monitoring
requirements of paragraphs (f)(1) through (f)(6) and (g)(1) through
(g)(6) of this section to demonstrate continuous compliance with the D/
F emission standard.
[[Page 31932]]
(1) Install, operate, calibrate and maintain a continuous monitor
to record the rate of activated carbon injection. The accuracy of the
rate measurement device must be 1 percent of the rate being
measured.
(2) Verify the calibration of the device at least once every three
months.
(3) The three-hour rolling average activated carbon injection rate
shall be calculated as the average of 180 successive one-minute average
activated carbon injection rates.
(4) Periods of time when one-minute averages are not available
shall be ignored when calculating three-hour rolling averages. When
one-minute averages become available, the first one-minute average is
added to the previous 179 values to calculate the three-hour rolling
average.
(5) When the operating status of the raw mill of the in-line kiln/
raw mill is changed from off to on, or from on to off the calculation
of the three-hour rolling average activated carbon injection rate must
begin anew, without considering previous recordings.
(6) The owner or operator must install, operate, calibrate and
maintain a continuous monitor to record the activated carbon injection
system carrier gas parameter (either the carrier gas flow rate or the
carrier gas pressure drop) established during the D/F performance test
in accordance with paragraphs (g)(6)(i) through (g)(6)(iii) of this
section.
(i) The owner or operator shall install, calibrate, operate and
maintain a device to continuously monitor and record the parameter
value.
(ii) The owner or operator must calculate and record three-hour
rolling averages of the parameter value.
(iii) Periods of time when one-minute averages are not available
shall be ignored when calculating three-hour rolling averages. When
one-minute averages become available, the first one-minute average
shall be added to the previous 179 values to calculate the three-hour
rolling average.
(h) The owner or operator of an affected source subject to a
limitation on THC emissions under this subpart shall comply with the
monitoring requirements of paragraphs (h)(1) through (h)(3) of this
section to demonstrate continuous compliance with the THC emission
standard:
(1) The owner or operator shall install, operate and maintain a THC
continuous emission monitoring system in accordance with Performance
Specification 8A, of appendix B to part 60 of this chapter and comply
with all of the requirements for continuous monitoring systems found in
the general provisions, subpart A of this part.
(2) The owner or operator is not required to calculate hourly
rolling averages in accordance with section 4.9 of Performance
Specification 8A.
(3) Any thirty-day block average THC concentration in any gas
discharged from a greenfield raw material dryer, the main exhaust of a
greenfield kiln, or the main exhaust of a greenfield in-line kiln/raw
mill, exceeding 50 ppmvd, reported as propane, corrected to seven
percent oxygen, is a violation of the standard.
(i) The owner or operator of any kiln or in-line kiln/raw mill
subject to a D/F emission limit under this subpart shall conduct an
inspection of the components of the combustion system of each kiln or
in-line kiln raw mill at least once per year.
(j) The owner or operator of an affected source subject to a
limitation on opacity under Sec. 63.1346 or Sec. 63.1348 shall monitor
opacity in accordance with the operation and maintenance plan developed
in accordance with paragraph (a) of this section.
(k) The owner or operator of an affected source subject to a
particulate matter standard under Sec. 63.1343 shall install,
calibrate, maintain and operate a particulate matter continuous
emission monitoring system (PM CEMS) to measure the particulate matter
discharged to the atmosphere. The compliance deadline for installing
the PM CEMS and all requirements relating to performance of the PM CEMS
and implementation of the PM CEMS requirement is deferred pending
further rulemaking.
(l) An owner or operator may submit an application to the
Administrator for approval of alternate monitoring requirements to
demonstrate compliance with the emission standards of this subpart,
except for emission standards for THC, subject to the provisions of
paragraphs (l)(1) through (l)(6) of this section.
(1) The Administrator will not approve averaging periods other than
those specified in this section, unless the owner or operator
documents, using data or information, that the longer averaging period
will ensure that emissions do not exceed levels achieved during the
performance test over any increment of time equivalent to the time
required to conduct three runs of the performance test.
(2) If the application to use an alternate monitoring requirement
is approved, the owner or operator must continue to use the original
monitoring requirement until approval is received to use another
monitoring requirement.
(3) The owner or operator shall submit the application for approval
of alternate monitoring requirements no later than the notification of
performance test. The application must contain the information
specified in paragraphs (l)(3)(i) through (l)(3)(iii) of this section:
(i) Data or information justifying the request, such as the
technical or economic infeasibility, or the impracticality of using the
required approach;
(ii) A description of the proposed alternative monitoring
requirement, including the operating parameter to be monitored, the
monitoring approach and technique, the averaging period for the limit,
and how the limit is to be calculated; and
(iii) Data or information documenting that the alternative
monitoring requirement would provide equivalent or better assurance of
compliance with the relevant emission standard.
(4) The Administrator will notify the owner or operator of the
approval or denial of the application within 90 calendar days after
receipt of the original request, or within 60 calendar days of the
receipt of any supplementary information, whichever is later. The
Administrator will not approve an alternate monitoring application
unless it would provide equivalent or better assurance of compliance
with the relevant emission standard. Before disapproving any alternate
monitoring application, the Administrator will provide:
(i) Notice of the information and findings upon which the intended
disapproval is based; and
(ii) Notice of opportunity for the owner or operator to present
additional supporting information before final action is taken on the
application. This notice will specify how much additional time is
allowed for the owner or operator to provide additional supporting
information.
(5) The owner or operator is responsible for submitting any
supporting information in a timely manner to enable the Administrator
to consider the application prior to the performance test. Neither
submittal of an application, nor the Administrator's failure to approve
or disapprove the application relieves the owner or operator of the
responsibility to comply with any provision of this subpart.
(6) The Administrator may decide at any time, on a case-by-case
basis that additional or alternative operating limits, or alternative
approaches to establishing operating limits, are necessary to
demonstrate compliance with the emission standards of this subpart.
[[Page 31933]]
(m) A summary of the monitoring requirements of this subpart is
given in Table 1 to this section.
Table 1 to Sec. 63.1350.--Monitoring Requirements
------------------------------------------------------------------------
Affected source/pollutant or Monitor type/ Monitoring
opacity operation/process requirements
------------------------------------------------------------------------
All affected sources........ Operations and Prepare written plan
maintenance plan. for all affected
sources and control
devices.
All kilns and in-line kiln Continuous opacity Install, calibrate,
raw mills at major sources monitor, if maintain and
(including alkali bypass)/ applicable. operate in
opacity. accordance with
general provisions
and with PS-1.
Method 9 opacity Daily test of at
test, if applicable. least 30-minutes,
while kiln is at
highest load or
capacity level.
Kilns and in-line kiln raw Particulate matter Deferred.
mills at major sources continuous emission
(including alkali bypass)/ monitoring system.
particulate matter.
Kilns and in-line kiln raw Combustion system Conduct annual
mills at major and area inspection. inspection of
sources (including alkali components of
bypass)/ D/F. combustion system.
Continuous Install, operate,
temperature calibrate and
monitoring at PMCD maintain continuous
inlet. temperature
monitoring and
recording system;
calculate three-
hour rolling
averages; verify
temperature sensor
calibration at
least quarterly.
Kilns and in-line kiln raw Activated carbon Install, operate,
mills at major and area injection rate calibrate and
sources (including alkali monitor, if maintain continuous
bypass)/ D/F (continued). applicable. activated carbon
injection rate
monitor; calculate
three-hour rolling
averages; verify
calibration at
least quarterly;
install, operate,
calibrate and
maintain carrier
gas flow rate
monitor or carrier
gas pressure drop
monitor; calculate
three-hour rolling
averages; document
carbon
specifications.
New greenfield kilns and in- Total hydrocarbon Install, operate,
line kiln raw mills at continuous emission and maintain THC
major and area sources/THC. monitor. CEM in accordance
with PS-8A;
calculate 30-day
block average THC
concentration.
Clinker coolers at major Continuous opacity Install, calibrate,
sources/opacity. monitor, if maintain and
applicable. operate in
accordance with
general provisions
and with PS-1.
Method 9 opacity Daily test of at
test, if applicable. least 30-minutes,
while kiln is at
highest load or
capacity level.
Raw mills and finish mills Method 22 visible Conduct daily 6-
at major sources/opacity. emissions test. minute Method 22
visible emissions
test while mill is
operating at
highest load or
capacity level; if
visible emissions
are observed,
initiate corrective
action within one
hour and conduct 30-
minute Method 9
test within 24
hours.
New greenfield raw material Total hydrocarbon Install, operate,
dryers at major and area continuous emission and maintain THC
sources/THC. monitor. CEM in accordance
with PS-8A;
calculate 30-day
block average THC
concentration.
Raw material dryers; raw Method 22 visible As specified in
material, clinker, finished emissions test. operation and
product storage bins; maintenance plan.
conveying system transfer
points; bagging systems;
and bulk loading and
unloading systems at major
sources/opacity.
------------------------------------------------------------------------
Sec. 63.1351 Compliance dates.
(a) The compliance date for an owner or operator of an existing
affected source subject to the provisions of this subpart is June 10,
2002.
(b) The compliance date for an owner or operator of an affected
source subject to the provisions of this subpart that commences new
construction or reconstruction after March 24, 1998 is June 9, 1999 or
immediately upon startup of operations, whichever is later.
6Sec. 3.1352 Additional test methods.
(a) Owners or operators conducting tests to determine the rates of
emission of hydrogen chloride (HCl) from kilns, in-line kiln/raw mills
and associated bypass stacks at portland cement manufacturing
facilities, for use in applicability determinations under Sec. 63.1340
are permitted to use Method 320 or Method 321 of appendix A of this
part.
(b) Owners or operators conducting tests to determine the rates of
emission of hydrogen chloride (HCl) from kilns, in-line kiln/raw mills
and associated bypass stacks at portland cement manufacturing
facilities, for use in applicability determinations under Sec. 63.1340
are permitted to use Methods 26 or 26A of appendix A to part 60 of this
chapter, except that the results of these tests shall not be used to
establish status as an area source.
(c) Owners or operators conducting tests to determine the rates of
emission of specific organic HAP from raw material dryers, kilns and
in-line kiln/raw mills at portland cement manufacturing facilities, for
use in applicability determinations under Sec. 63.1340 of this subpart
are permitted to use Method 320 of appendix A to this part, or Method
18 of appendix A to part 60 of this chapter.
[[Page 31934]]
Notification, Reporting and Recordkeeping
Sec. 63.1353 Notification requirements.
(a) The notification provisions of 40 CFR part 63, subpart A that
apply and those that do not apply to owners and operators of affected
sources subject to this subpart are listed in Table 1 of this subpart.
If any State requires a notice that contains all of the information
required in a notification listed in this section, the owner or
operator may send the Administrator a copy of the notice sent to the
State to satisfy the requirements of this section for that
notification.
(b) Each owner or operator subject to the requirements of this
subpart shall comply with the notification requirements in Sec. 63.9 as
follows:
(1) Initial notifications as required by Sec. 63.9(b) through (d).
For the purposes of this subpart, a Title V or 40 CFR part 70 permit
application may be used in lieu of the initial notification required
under Sec. 63.9(b), provided the same information is contained in the
permit application as required by Sec. 63.9(b), and the State to which
the permit application has been submitted has an approved operating
permit program under part 70 of this chapter and has received
delegation of authority from the EPA. Permit applications shall be
submitted by the same due dates as those specified for the initial
notification.
(2) Notification of performance tests, as required by Secs. 63.7
and 63.9(e).
(3) Notification of opacity and visible emission observations
required by Sec. 63.1349 in accordance with Secs. 63.6(h)(5) and
63.9(f).
(4) Notification, as required by Sec. 63.9(g), of the date that the
continuous emission monitor performance evaluation required by
Sec. 63.8(e) is scheduled to begin.
(5) Notification of compliance status, as required by Sec. 63.9(h).
Sec. 63.1354 Reporting requirements.
(a) The reporting provisions of subpart A of this part that apply
and those that do not apply to owners or operators of affected sources
subject to this subpart are listed in Table 1 of this subpart. If any
State requires a report that contains all of the information required
in a report listed in this section, the owner or operator may send the
Administrator a copy of the report sent to the State to satisfy the
requirements of this section for that report.
(b) The owner or operator of an affected source shall comply with
the reporting requirements specified in Sec. 63.10 of the general
provisions of this part 63, subpart A as follows:
(1) As required by Sec. 63.10(d)(2), the owner or operator shall
report the results of performance tests as part of the notification of
compliance status.
(2) As required by Sec. 63.10(d)(3), the owner or operator of an
affected source shall report the opacity results from tests required by
Sec. 63.1349.
(3) As required by Sec. 63.10(d)(4), the owner or operator of an
affected source who is required to submit progress reports as a
condition of receiving an extension of compliance under Sec. 63.6(i)
shall submit such reports by the dates specified in the written
extension of compliance.
(4) As required by Sec. 63.10(d)(5), if actions taken by an owner
or operator during a startup, shutdown, or malfunction of an affected
source (including actions taken to correct a malfunction) are
consistent with the procedures specified in the source's startup,
shutdown, and malfunction plan specified in Sec. 63.6(e)(3), the owner
or operator shall state such information in a semiannual report.
Reports shall only be required if a startup, shutdown, or malfunction
occurred during the reporting period. The startup, shutdown, and
malfunction report may be submitted simultaneously with the excess
emissions and continuous monitoring system performance reports; and
(5) Any time an action taken by an owner or operator during a
startup, shutdown, or malfunction (including actions taken to correct a
malfunction) is not consistent with the procedures in the startup,
shutdown, and malfunction plan, the owner or operator shall make an
immediate report of the actions taken for that event within 2 working
days, by telephone call or facsimile (FAX) transmission. The immediate
report shall be followed by a letter, certified by the owner or
operator or other responsible official, explaining the circumstances of
the event, the reasons for not following the startup, shutdown, and
malfunction plan, and whether any excess emissions and/or parameter
monitoring exceedances are believed to have occurred.
(6) As required by Sec. 63.10(e)(2), the owner or operator shall
submit a written report of the results of the performance evaluation
for the continuous monitoring system required by Sec. 63.8(e). The
owner or operator shall submit the report simultaneously with the
results of the performance test.
(7) As required by Sec. 63.10(e)(2), the owner or operator of an
affected source using a continuous opacity monitoring system to
determine opacity compliance during any performance test required under
Sec. 63.7 and described in Sec. 63.6(d)(6) shall report the results of
the continuous opacity monitoring system performance evaluation
conducted under Sec. 63.8(e).
(8) As required by Sec. 63.10(e)(3), the owner or operator of an
affected source equipped with a continuous emission monitor shall
submit an excess emissions and continuous monitoring system performance
report for any event when the continuous monitoring system data
indicate the source is not in compliance with the applicable emission
limitation or operating parameter limit.
(9) The owner or operator shall submit a summary report
semiannually which contains the information specified in
Sec. 63.10(e)(3)(vi). In addition, the summary report shall include:
(i) All exceedences of maximum control device inlet gas temperature
limits specified in Sec. 63.1344(a) and (b);
(ii) All failures to calibrate thermocouples and other temperature
sensors as required under Sec. 63.1350(f)(7) of this subpart; and
(iii) All failures to maintain the activated carbon injection rate,
and the activated carbon injection carrier gas flow rate or pressure
drop, as applicable, as required under Sec. 63.1344(c).
(iv) The results of any combustion system component inspections
conducted within the reporting period as required under
Sec. 63.1350(i).
(v) All failures to comply with any provision of the operation and
maintenance plan developed in accordance with Sec. 63.1350(a).
(10) If the total continuous monitoring system downtime for any CEM
or any continuous monitoring system (CMS) for the reporting period is
ten percent or greater of the total operating time for the reporting
period, the owner or operator shall submit an excess emissions and
continuous monitoring system performance report along with the summary
report.
Sec. 63.1355 Recordkeeping requirements.
(a) The owner or operator shall maintain files of all information
(including all reports and notifications) required by this section
recorded in a form suitable and readily available for inspection and
review as required by Sec. 63.10(b)(1). The files shall be retained for
at least five years following the date of each occurrence, measurement,
maintenance, corrective action, report, or record. At a minimum, the
most recent two years of data shall be retained on site. The remaining
three
[[Page 31935]]
years of data may be retained off site. The files may be maintained on
microfilm, on a computer, on floppy disks, on magnetic tape, or on
microfiche.
(b) The owner or operator shall maintain records for each affected
source as required by Sec. 63.10(b)(2) and (b)(3) of this part; and
(1) All documentation supporting initial notifications and
notifications of compliance status under Sec. 63.9;
(2) All records of applicability determination, including
supporting analyses; and
(3) If the owner or operator has been granted a waiver under
Sec. 63.8(f)(6), any information demonstrating whether a source is
meeting the requirements for a waiver of recordkeeping or reporting
requirements.
(c) In addition to the recordkeeping requirements in paragraph (b)
of this section, the owner or operator of an affected source equipped
with a continuous monitoring system shall maintain all records required
by Sec. 63.10(c).
Other
Sec. 63.1356 Exemption from new source performance standards.
(a) Except as provided in paragraphs (a)(1) and (a)(2) of this
section, any affected source subject to the provisions of this subpart
is exempted from any otherwise applicable new source performance
standard contained in 40 CFR part 60, subpart F.
(1) Kilns and in-line kiln/raw mills, as applicable under 40 CFR
60.60(b), located at area sources are subject to PM and opacity limits
and associated reporting and recordkeeping, under 40 CFR part 60,
subpart F.
(2) Greenfield raw material dryers, as applicable under 40 CFR
60.60(b), located at area sources are subject to opacity limits and
associated reporting and recordkeeping under 40 CFR part 60, subpart F.
Sec. 63.1357 Temporary, conditioned exemption from particulate matter
and opacity standards.
(a) Subject to the limitations of paragraphs (b) through (f) of
this section, an owner or operator conducting PM CEMS correlation tests
(that is, correlation with manual stack methods) is exempt from:
(1) Any particulate matter and opacity standards of part 60 or part
63 of this chapter that are applicable to cement kilns and in-line
kiln/raw mills.
(2) Any permit or other emissions or operating parameter or other
limitation on workplace practices that are applicable to cement kilns
and in-line kiln raw mills to ensure compliance with any particulate
matter and opacity standards of this part or part 60 of this chapter.
(b) The owner or operator must develop a PM CEMS correlation test
plan. The plan must be submitted to the Administrator for approval at
least 90 days before the correlation test is scheduled to be conducted.
The plan must include:
(1) The number of test conditions and the number of runs for each
test condition;
(2) The target particulate matter emission level for each test
condition;
(3) How the operation of the affected source will be modified to
attain the desired particulate matter emission rate; and
(4) The anticipated normal particulate matter emission level.
(c) The Administrator will review and approve or disapprove the
correlation test plan in accordance with Sec. 63.7(c)(3)(i) and (iii).
If the Administrator fails to approve or disapprove the correlation
test plan within the time period specified in Sec. 63.7(c)(3)(iii), the
plan shall be considered approved, unless the Administrator has
requested additional information.
(d) The stack sampling team must be on-site and prepared to perform
correlation testing no later than 24 hours after operations are
modified to attain the desired particulate matter emissions
concentrations, unless the correlation test plan documents that a
longer period is appropriate.
(e) The particulate matter and opacity standards and associated
operating limits and conditions will not be waived for more than 96
hours, in the aggregate, for a correlation test, including all runs and
conditions.
(f) The owner or operator must return the affected source to
operating conditions indicative of compliance with the applicable
particulate matter and opacity standards as soon as possible after
correlation testing is completed.
Sec. 63.1358 Delegation of authority.
(a) In delegating implementation and enforcement authority to a
State under subpart E of this part, the authorities contained in
paragraph (b) of this section shall be retained by the Administrator
and not transferred to a State.
(b) Authority which will not be delegated to States:
(1) Approval of alternative non-opacity emission standards under
Sec. 63.6(g).
(2) Approval of alternative opacity standards under
Sec. 63.6(h)(9).
(3) Approval of major changes to test methods under
Secs. 63.7(e)(2)(ii) and 63.7(f). A major change to a test method is a
modification to a federally enforceable test method that uses unproven
technology or procedures or is an entirely new method (sometimes
necessary when the required test method is unsuitable).
(4) Approval of major changes to monitoring under Sec. 63.8(f). A
major change to monitoring is a modification to federally enforceable
monitoring that uses unproven technology or procedures, is an entirely
new method (sometimes necessary when the required monitoring is
unsuitable), or is a change in the averaging period.
(5) Waiver of recordkeeping under Sec. 63.10(f).
Sec. 63.1359 [Reserved]
Table 1 to Subpart LLL.--Applicability of General Provisions
----------------------------------------------------------------------------------------------------------------
General Provisions 40 CFR Citation Requirement Applies to Subpart LLL Comment
----------------------------------------------------------------------------------------------------------------
63.1(a)(1) through (4).............. Applicability.......... Yes. .......................
63.1(a)(5).......................... No...................... [Reserved].
63.1(a)(6) through (a)(8)........... Applicability.......... Yes. .......................
63.1(a)(9).......................... No...................... [Reserved].
63.1(a)(10) through (14)............ Applicability.......... Yes. .......................
63.1(b)(1).......................... Initial Applicability No...................... Sec. 63.1340 specifies
Determination. applicability.
63.1(b)(2) and (3).................. Initial Applicability Yes. .......................
Determination.
63.1(c)(1).......................... Applicability After Yes. .......................
Standard Established.
63.1(c)(2).......................... Permit Requirements.... Yes..................... Area sources must
obtain Title V
permits.
[[Page 31936]]
63.1(c)(3).......................... No...................... [Reserved].
63.1(c)(4) and (5).................. Extensions, Yes. .......................
Notifications.
63.1(d)............................. No...................... [Reserved].
63.1(e)............................. Applicability of Permit Yes. .......................
Program.
63.2................................ Definitions............ Yes. Additional definitions
in Sec. 63.1341.
63.3(a) through (c)................. Units and Abbreviations Yes. .......................
63.4(a)(1) through (a)(3)........... Prohibited Activities.. Yes. .......................
63.4(a)(4).......................... No...................... [Reserved].
63.4(a)(5).......................... Compliance date........ Yes. .......................
63.4(b) and (c)..................... Circumvention, Yes. .......................
Severability.
63.5(a)(1) and (2).................. Construction/ Yes. .......................
Reconstruction.
63.5(b)(1).......................... Compliance Dates....... Yes. .......................
63.5(b)(2).......................... No...................... [Reserved].
63.5(b)(3) through (6).............. Construction Approval, Yes. .......................
Applicability.
63.5(c)............................. No...................... [Reserved].
63.5(d)(1) through (4).............. Approval of Yes. .......................
Construction/
Reconstruction.
63.5(e)............................. Approval of Yes. .......................
Construction/
Reconstruction.
63.5(f)(1) and (2).................. Approval of Yes. .......................
Construction/
Reconstruction.
63.6(a)............................. Compliance for Yes. .......................
Standards and
Maintenance.
63.6(b)(1) through (5).............. Compliance Dates....... Yes. .......................
63.6(b)(6).......................... No...................... [Reserved].
63.6(b)(7).......................... Compliance Dates....... Yes.
63.6(c)(1) and (2).................. Compliance Dates....... Yes.
63.6(c)(3) and (c)(4)............... ....................... No...................... [Reserved].
63.6(c)(5).......................... Compliance Dates....... Yes.
63.6(d)............................. No...................... [Reserved].
63.6(e)(1) and (e)(2)............... Operation & Maintenance Yes.
63.6(e)(3).......................... Startup, Shutdown Yes.
Malfunction Plan.
63.6(f)(1) through (3).............. Compliance with Yes.
Emission Standards.
63.6(g)(1) through (g)(3)........... Alternative Standard... Yes.
63.6(h)(1) and (2).................. Opacity/VE Standards... Yes.
63.6(h)(3).......................... No...................... Reserved
63.6(h)(4) and (h)(5)(i)............ Opacity/VE Standards... Yes.
63.6(h)(5)(ii) through (iv)......... Opacity/VE Standards... No...................... Test duration specified
in Subpart LLL.
63.6(h)(6).......................... Opacity/VE Standards... Yes.
63.6(i)(1) through (i)(14).......... Extension of Compliance Yes.
63.6(i)(15)......................... No...................... [Reserved].
63.6(i)(16)......................... Extension of Compliance Yes.
63.6(j)............................. Exemption from Yes.
Compliance.
63.7(a)(1) through (a)(3)........... Performance Testing Yes..................... Sec. 63.1349 has
Requirements. specific requirements.
63.7(b)............................. Notification........... Yes.
63.7(c)............................. Quality Assurance/Test Yes.
Plan.
63.7(d)............................. Testing Facilities..... Yes.
63.7(e)(1) through (4).............. Conduct of Tests....... Yes.
63.7(f)............................. Alternative Test Method Yes.
63.7(g)............................. Data Analysis.......... Yes.
63.7(h)............................. Waiver of Tests........ Yes.
63.8(a)(1).......................... Monitoring Requirements Yes.
63.8(a)(2).......................... Monitoring............. No...................... Sec. 63.1350 includes
CEM requirements.
63.8(a)(3).......................... No...................... [Reserved].
63.8(a)(4).......................... Monitoring............. No...................... Flares not applicable.
63.8(b)(1) through (3).............. Conduct of Monitoring.. Yes.
63.8(c)(1) through (8).............. CMS Operation/ Yes. Performance
Maintenance. specification
supersedes
requirements for THC
CEM. Temperature and
activated carbon
injection monitoring
data reduction
requirements given in
subpart LLL.
63.8(d)............................. Quality Control........ Yes.
63.8(e)............................. Performance Evaluation Yes..................... Performance
for CMS. specification
supersedes
requirements for THC
CEM.
63.8(f)(1) through (f)(5)........... Alternative Monitoring Yes..................... Additional requirements
Method. in Sec. 1350(l).
63.8(f)(6).......................... Alternative to RATA Yes.
Test.
63.8(g)............................. Data Reduction......... Yes.
63.9(a)............................. Notification Yes.
Requirements.
63.9(b)(1) through (5).............. Initial Notifications.. Yes.
63.9(c)............................. Request for Compliance Yes.
Extension.
63.9(d)............................. New Source Notification Yes.
for Special Compliance
Requirements.
63.9(e)............................. Notification of Yes.
Performance Test.
63.9(f)............................. Notification of VE/ Yes Notification not
Opacity Test. required for VE/
opacity test under
Sec. 63.1350(e) and
(j).
[[Page 31937]]
63.9(g)............................. Additional CMS Yes.
Notifications.
63.9(h)(1) through (h)(3)........... Notification of Yes.
Compliance Status.
63.9(h)(4).......................... No...................... [Reserved].
63.9(h)(5) and (h)(6)............... Notification of Yes.
Compliance Status.
63.9(i)............................. Adjustment of Deadlines Yes.
63.9(j)............................. Change in Previous Yes.
Information.
63.10(a)............................ Recordkeeping/Reporting Yes Yes.
63.10(b)............................ General Requirements... Yes.
63.10(c)(1)......................... Additional CMS Yes..................... PS-8A applies.
Recordkeeping.
63.10(c)(2) through (c)(4).......... No...................... Reserved]
63.10(c)(5) through (c)(8).......... Additional CMS Yes..................... PS-8A applies instead
Recordkeeping. of requirements for
THC CEM.
63.10(c)(9)......................... No...................... [Reserved]
63.10(c)(10) through (15)........... Additional CMS Yes..................... PS-8A applies instead
Recordkeeping. of requirements for
THC CEM.
63.10(d)(1)......................... General Reporting Yes.
Requirements.
63.10(d)(2)......................... Performance Test Yes.
Results.
63.10(d)(3)......................... Opacity or VE Yes.
Observations.
63.10(d)(4)......................... Progress Reports....... Yes.
63.10(d)(5)......................... Startup, Shutdown, Yes.
Malfunction Reports.
63.10(e)(1) and (e)(2).............. Additional CMS Reports. Yes.
63.10(e)(3)......................... Excess Emissions and Yes..................... Exceedences are defined
CMS Performance in subpart LLL.
Reports.
63.10(f)............................ Waiver for Yes.
Recordkeeping/
Reporting.
63.11(a) and (b).................... Control Device No...................... Flares not applicable.
Requirements.
63.12(a)-(c......................... )State Authority and Yes.
Delegations.
63.13(a)-(c)........................ State/Regional Yes.
Addresses.
63.14(a) and (b).................... Incorporation by Yes.
Reference.
63.15(a) and (b).................... Availability of Yes.
Information.
----------------------------------------------------------------------------------------------------------------
3. Appendix A of part 63 is amended by adding, in numerical
order, Methods 320 and 321 to read as follows:
Appendix A to Part 63--Test Methods
* * * * *
Test Method 320--Measurement of Vapor Phase Organic and Inorganic
Emissions by Extractive Fourier Transform Infrared (FTIR) Spectroscopy
1.0 Introduction.
Persons unfamiliar with basic elements of FTIR spectroscopy
should not attempt to use this method. This method describes
sampling and analytical procedures for extractive emission
measurements using Fourier transform infrared (FTIR) spectroscopy.
Detailed analytical procedures for interpreting infrared spectra are
described in the ``Protocol for the Use of Extractive Fourier
Transform Infrared (FTIR) Spectrometry in Analyses of Gaseous
Emissions from Stationary Sources,'' hereafter referred to as the
``Protocol.'' Definitions not given in this method are given in
appendix A of the Protocol. References to specific sections in the
Protocol are made throughout this Method. For additional information
refer to references 1 and 2, and other EPA reports, which describe
the use of FTIR spectrometry in specific field measurement
applications and validation tests. The sampling procedure described
here is extractive. Flue gas is extracted through a heated gas
transport and handling system. For some sources, sample conditioning
systems may be applicable. Some examples are given in this method.
Note: sample conditioning systems may be used providing the
method validation requirements in Sections 9.2 and 13.0 of this
method are met.
1.1 Scope and Applicability.
1.1.1 Analytes. Analytes include hazardous air pollutants
(HAPs) for which EPA reference spectra have been developed. Other
compounds can also be measured with this method if reference spectra
are prepared according to section 4.6 of the protocol.
1.1.2 Applicability. This method applies to the analysis of
vapor phase organic or inorganic compounds which absorb energy in
the mid-infrared spectral region, about 400 to 4000 cm-1
(25 to 2.5 m). This method is used to determine compound-
specific concentrations in a multi-component vapor phase sample,
which is contained in a closed-path gas cell. Spectra of samples are
collected using double beam infrared absorption spectroscopy. A
computer program is used to analyze spectra and report compound
concentrations.
1.2 Method Range and Sensitivity. Analytical range and
sensitivity depend on the frequency-dependent analyte absorptivity,
instrument configuration, data collection parameters, and gas stream
composition. Instrument factors include: (a) spectral resolution,
(b) interferometer signal averaging time, (c) detector sensitivity
and response, and (d) absorption path length.
1.2.1 For any optical configuration the analytical range is
between the absorbance values of about .01 (infrared transmittance
relative to the background = 0.98) and 1.0
(T = 0.1). (For absorbance > 1.0 the relation between absorbance and
concentration may not be linear.)
1.2.2 The concentrations associated with this absorbance range
depend primarily on the cell path length and the sample temperature.
An analyte absorbance greater than 1.0, can be lowered by decreasing
the optical path length. Analyte absorbance increases with a longer
path length. Analyte detection also depends on the presence of other
species exhibiting absorbance in the same analytical region.
Additionally, the estimated lower absorbance (A) limit
(A = 0.01) depends on the root mean square deviation (RMSD) noise in
the analytical region.
1.2.3 The concentration range of this method is determined by
the choice of optical configuration.
1.2.3.1 The absorbance for a given concentration can be
decreased by decreasing the path length or by diluting the sample.
There is no practical upper limit to the measurement range.
1.2.3.2 The analyte absorbance for a given concentration may be
increased by increasing the cell path length or (to some extent)
using a higher resolution. Both modifications also cause a
corresponding increased absorbance for all compounds in the sample,
and a decrease in the signal throughput. For this reason the
practical lower detection range (quantitation limit) usually depends
on sample characteristics such as moisture content of the gas, the
presence of other interferants, and losses in the sampling system.
[[Page 31938]]
1.3 Sensitivity. The limit of sensitivity for an optical
configuration and integration time is determined using appendix D of
the Protocol: Minimum Analyte Uncertainty, (MAU). The MAU depends on
the RMSD noise in an analytical region, and on the absorptivity of
the analyte in the same region.
1.4 Data Quality. Data quality shall be determined by executing
Protocol pre-test procedures in appendices B to H of the protocol
and post-test procedures in appendices I and J of the protocol.
1.4.1 Measurement objectives shall be established by the choice
of detection limit (DLi) and analytical uncertainty
(AUi) for each analyte.
1.4.2 An instrumental configuration shall be selected. An
estimate of gas composition shall be made based on previous test
data, data from a similar source or information gathered in a pre-
test site survey. Spectral interferants shall be identified using
the selected DLi and AUi and band areas from
reference spectra and interferant spectra. The baseline noise of the
system shall be measured in each analytical region to determine the
MAU of the instrument configuration for each analyte and interferant
(MIUi).
1.4.3 Data quality for the application shall be determined, in
part, by measuring the RMS (root mean square) noise level in each
analytical spectral region (appendix C of the Protocol). The RMS
noise is defined as the RMSD of the absorbance values in an
analytical region from the mean absorbance value in the region.
1.4.4 The MAU is the minimum analyte concentration for which
the AUi can be maintained; if the measured analyte
concentration is less than MAUi, then data quality are
unacceptable.
2.0 Summary of Method
2.1 Principle. References 4 through 7 provide background
material on infrared spectroscopy and quantitative analysis. A
summary is given in this section.
2.1.1 Infrared absorption spectroscopy is performed by
directing an infrared beam through a sample to a detector. The
frequency-dependent infrared absorbance of the sample is measured by
comparing this detector signal (single beam spectrum) to a signal
obtained without a sample in the beam path (background).
2.1.2 Most molecules absorb infrared radiation and the
absorbance occurs in a characteristic and reproducible pattern. The
infrared spectrum measures fundamental molecular properties and a
compound can be identified from its infrared spectrum alone.
2.1.3 Within constraints, there is a linear relationship
between infrared absorption and compound concentration. If this
frequency dependent relationship (absorptivity) is known (measured),
it can be used to determine compound concentration in a sample
mixture.
2.1.4 Absorptivity is measured by preparing, in the laboratory,
standard samples of compounds at known concentrations and measuring
the FTIR ``reference spectra'' of these standard samples. These
``reference spectra'' are then used in sample analysis: (1)
Compounds are detected by matching sample absorbance bands with
bands in reference spectra, and (2) concentrations are measured by
comparing sample band intensities with reference band intensities.
2.1.5 This method is self-validating provided that the results
meet the performance requirement of the QA spike in sections 8.6.2
and 9.0 of this method, and results from a previous method
validation study support the use of this method in the application.
2.2 Sampling and Analysis. In extractive sampling a probe
assembly and pump are used to extract gas from the exhaust of the
affected source and transport the sample to the FTIR gas cell.
Typically, the sampling apparatus is similar to that used for
single-component continuous emission monitor (CEM) measurements.
2.2.1 The digitized infrared spectrum of the sample in the FTIR
gas cell is measured and stored on a computer. Absorbance band
intensities in the spectrum are related to sample concentrations by
what is commonly referred to as Beer's Law.
[GRAPHIC] [TIFF OMITTED] TR14JN99.003
Where:
Ai = absorbance at a given frequency of the ith sample
component.
ai = absorption coefficient (absorptivity) of the ith
sample component.
b = path length of the cell.
ci = concentration of the ith sample component.
2.2.2 Analyte spiking is used for quality assurance (QA). In
this procedure (section 8.6.2 of this method) an analyte is spiked
into the gas stream at the back end of the sample probe. Analyte
concentrations in the spiked samples are compared to analyte
concentrations in unspiked samples. Since the concentration of the
spike is known, this procedure can be used to determine if the
sampling system is removing the spiked analyte(s) from the sample
stream.
2.3 Reference Spectra Availability. Reference spectra of over
100 HAPs are available in the EPA FTIR spectral library on the EMTIC
(Emission Measurement Technical Information Center) computer
bulletin board service and at internet address http://
info.arnold.af.mil/epa/welcome.htm. Reference spectra for HAPs, or
other analytes, may also be prepared according to section 4.6 of the
Protocol.
2.4 Operator Requirements. The FTIR analyst shall be trained in
setting up the instrumentation, verifying the instrument is
functioning properly, and performing routine maintenance. The
analyst must evaluate the initial sample spectra to determine if the
sample matrix is consistent with pre-test assumptions and if the
instrument configuration is suitable. The analyst must be able to
modify the instrument configuration, if necessary.
2.4.1 The spectral analysis shall be supervised by someone
familiar with EPA FTIR Protocol procedures.
2.4.2 A technician trained in instrumental test methods is
qualified to install and operate the sampling system. This includes
installing the probe and heated line assembly, operating the analyte
spike system, and performing moisture and flow measurements.
3.0 Definitions
See appendix A of the Protocol for definitions relating to
infrared spectroscopy. Additional definitions are given in sections
3.1 through 3.29.
3.1 Analyte. A compound that this method is used to measure.
The term ``target analyte'' is also used. This method is multi-
component and a number of analytes can be targeted for a test.
3.2 Reference Spectrum. Infrared spectrum of an analyte
prepared under controlled, documented, and reproducible laboratory
conditions according to procedures in section 4.6 of the Protocol. A
library of reference spectra is used to measure analytes in gas
samples.
3.3 Standard Spectrum. A spectrum that has been prepared from a
reference spectrum through a (documented) mathematical operation. A
common example is de-resolving of reference spectra to lower-
resolution standard spectra (Protocol, appendix K to the addendum of
this method). Standard spectra, prepared by approved, and
documented, procedures can be used as reference spectra for
analysis.
3.4 Concentration. In this method concentration is expressed as
a molar concentration, in ppm-meters, or in (ppm-meters)/K, where K
is the absolute temperature (Kelvin). The latter units allow the
direct comparison of concentrations from systems using different
optical configurations or sampling temperatures.
3.5 Interferant. A compound in the sample matrix whose infrared
spectrum overlaps with part of an analyte spectrum. The most
accurate analyte measurements are achieved when reference spectra of
interferants are used in the quantitative analysis with the analyte
reference spectra. The presence of an interferant can increase the
analytical uncertainty in the measured analyte concentration.
3.6 Gas Cell. A gas containment cell that can be evacuated. It
is equipped with the optical components to pass the infrared beam
through the sample to the detector. Important cell features include:
path length (or range if variable), temperature range, materials of
construction, and total gas volume.
3.7 Sampling System. Equipment used to extract the sample from
the test location and transport the sample gas to the FTIR analyzer.
This includes sample conditioning systems.
3.8 Sample Analysis. The process of interpreting the infrared
spectra to obtain sample analyte concentrations. This process is
usually automated using a software routine employing a classical
least squares (cls), partial least squares (pls), or K- or P-matrix
method.
3.9 One hundred percent line. A double beam transmittance
spectrum obtained by combining two background single beam spectra.
Ideally, this line is equal to 100 percent transmittance (or zero
absorbance) at every frequency in the spectrum. Practically, a zero
absorbance line is used to measure the baseline noise in the
spectrum.
3.10 Background Deviation. A deviation from 100 percent
transmittance in any region
[[Page 31939]]
of the 100 percent line. Deviations greater than 5
percent in an analytical region are unacceptable (absorbance of
0.021 to -0.022). Such deviations indicate a change in the
instrument throughput relative to the background single beam.
3.11 Batch Sampling. A procedure where spectra of discreet,
static samples are collected. The gas cell is filled with sample and
the cell is isolated. The spectrum is collected. Finally, the cell
is evacuated to prepare for the next sample.
3.12 Continuous Sampling. A procedure where spectra are
collected while sample gas is flowing through the cell at a measured
rate.
3.13 Sampling resolution. The spectral resolution used to
collect sample spectra.
3.14 Truncation. Limiting the number of interferogram data
points by deleting points farthest from the center burst (zero path
difference, ZPD).
3.15 Zero filling. The addition of points to the interferogram.
The position of each added point is interpolated from neighboring
real data points. Zero filling adds no information to the
interferogram, but affects line shapes in the absorbance spectrum
(and possibly analytical results).
3.16 Reference CTS. Calibration Transfer Standard spectra that
were collected with reference spectra.
3.17 CTS Standard. CTS spectrum produced by applying a de-
resolution procedure to a reference CTS.
3.18 Test CTS. CTS spectra collected at the sampling resolution
using the same optical configuration as for sample spectra. Test
spectra help verify the resolution, temperature and path length of
the FTIR system.
3.19 RMSD. Root Mean Square Difference, defined in EPA FTIR
Protocol, appendix A.
3.20 Sensitivity. The noise-limited compound-dependent
detection limit for the FTIR system configuration. This is estimated
by the MAU. It depends on the RMSD in an analytical region of a zero
absorbance line.
3.21 Quantitation Limit. The lower limit of detection for the
FTIR system configuration in the sample spectra. This is estimated
by mathematically subtracting scaled reference spectra of analytes
and interferences from sample spectra, then measuring the RMSD in an
analytical region of the subtracted spectrum. Since the noise in
subtracted sample spectra may be much greater than in a zero
absorbance spectrum, the quantitation limit is generally much higher
than the sensitivity. Removing spectral interferences from the
sample or improving the spectral subtraction can lower the
quantitation limit toward (but not below) the sensitivity.
3.22 Independent Sample. A unique volume of sample gas; there
is no mixing of gas between two consecutive independent samples. In
continuous sampling two independent samples are separated by at
least 5 cell volumes. The interval between independent measurements
depends on the cell volume and the sample flow rate (through the
cell).
3.23 Measurement. A single spectrum of flue gas contained in
the FTIR cell.
3.24 Run. A run consists of a series of measurements. At a
minimum a run includes 8 independent measurements spaced over 1
hour.
3.25 Validation. Validation of FTIR measurements is described
in sections 13.0 through 13.4 of this method. Validation is used to
verify the test procedures for measuring specific analytes at a
source. Validation provides proof that the method works under
certain test conditions.
3.26 Validation Run. A validation run consists of at least 24
measurements of independent samples. Half of the samples are spiked
and half are not spiked. The length of the run is determined by the
interval between independent samples.
3.27 Screening. Screening is used when there is little or no
available information about a source. The purpose of screening is to
determine what analytes are emitted and to obtain information about
important sample characteristics such as moisture, temperature, and
interferences. Screening results are semi-quantitative (estimated
concentrations) or qualitative (identification only). Various
optical and sampling configurations may be used. Sample conditioning
systems may be evaluated for their effectiveness in removing
interferences. It is unnecessary to perform a complete run under any
set of sampling conditions. Spiking is not necessary, but spiking
can be a useful screening tool for evaluating the sampling system,
especially if a reactive or soluble analyte is used for the spike.
3.28 Emissions Test. An FTIR emissions test is performed
according specific sampling and analytical procedures. These
procedures, for the target analytes and the source, are based on
previous screening and validation results. Emission results are
quantitative. A QA spike (sections 8.6.2 and 9.2 of this method) is
performed under each set of sampling conditions using a
representative analyte. Flow, gas temperature and diluent data are
recorded concurrently with the FTIR measurements to provide mass
emission rates for detected compounds.
3.29 Surrogate. A surrogate is a compound that is used in a QA
spike procedure (section 8.6.2 of this method) to represent other
compounds. The chemical and physical properties of a surrogate shall
be similar to the compounds it is chosen to represent. Under given
sampling conditions, usually a single sampling factor is of primary
concern for measuring the target analytes: for example, the
surrogate spike results can be representative for analytes that are
more reactive, more soluble, have a lower absorptivity, or have a
lower vapor pressure than the surrogate itself.
4.0 Interferences
Interferences are divided into two classifications: analytical
and sampling.
4.1 Analytical Interferences. An analytical interference is a
spectral feature that complicates (in extreme cases may prevent) the
analysis of an analyte. Analytical interferences are classified as
background or spectral interference.
4.1.1 Background Interference. This results from a change in
throughput relative to the single beam background. It is corrected
by collecting a new background and proceeding with the test. In
severe instances the cause must be identified and corrected.
Potential causes include: (1) Deposits on reflective surfaces or
transmitting windows, (2) changes in detector sensitivity, (3) a
change in the infrared source output, or (4) failure in the
instrument electronics. In routine sampling throughput may degrade
over several hours. Periodically a new background must be collected,
but no other corrective action will be required.
4.1.2 Spectral Interference. This results from the presence of
interfering compound(s) (interferant) in the sample. Interferant
spectral features overlap analyte spectral features. Any compound
with an infrared spectrum, including analytes, can potentially be an
interferant. The Protocol measures absorbance band overlap in each
analytical region to determine if potential interferants shall be
classified as known interferants (FTIR Protocol, section 4.9 and
appendix B). Water vapor and CO2 are common spectral
interferants. Both of these compounds have strong infrared spectra
and are present in many sample matrices at high concentrations
relative to analytes. The extent of interference depends on the (1)
interferant concentration, (2) analyte concentration, and (3) the
degree of band overlap. Choosing an alternate analytical region can
minimize or avoid the spectral interference. For example,
CO2 interferes with the analysis of the 670
cm-1 benzene band. However, benzene can also be measured
near 3000 cm-1 (with less sensitivity).
4.2 Sampling System Interferences. These prevent analytes from
reaching the instrument. The analyte spike procedure is designed to
measure sampling system interference, if any.
4.2.1 Temperature. A temperature that is too low causes
condensation of analytes or water vapor. The materials of the
sampling system and the FTIR gas cell usually set the upper limit of
temperature.
4.2.2 Reactive Species. Anything that reacts with analytes.
Some analytes, like formaldehyde, polymerize at lower temperatures.
4.2.3 Materials. Poor choice of material for probe, or sampling
line may remove some analytes. For example, HF reacts with glass
components.
4.2.4 Moisture. In addition to being a spectral interferant,
condensed moisture removes soluble compounds.
5.0 Safety
The hazards of performing this method are those associated with
any stack sampling method and the same precautions shall be
followed. Many HAPs are suspected carcinogens or present other
serious health risks. Exposure to these compounds should be avoided
in all circumstances. For instructions on the safe handling of any
particular compound, refer to its material safety data sheet. When
using analyte standards, always ensure that gases are properly
vented and that the gas handling system is leak free. (Always
perform a leak check with the system under maximum vacuum and,
again, with the system at greater than ambient pressure.) Refer to
section 8.2 of this method for leak check procedures. This method
does not address all of the potential safety risks associated with
its use. Anyone performing this method must follow
[[Page 31940]]
safety and health practices consistent with applicable legal
requirements and with prudent practice for each application.
6.0 Equipment and Supplies
Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.
The equipment and supplies are based on the schematic of a
sampling system shown in Figure 1. Either the batch or continuous
sampling procedures may be used with this sampling system.
Alternative sampling configurations may also be used, provided that
the data quality objectives are met as determined in the post-
analysis evaluation. Other equipment or supplies may be necessary,
depending on the design of the sampling system or the specific
target analytes.
6.1 Sampling Probe. Glass, stainless steel, or other
appropriate material of sufficient length and physical integrity to
sustain heating, prevent adsorption of analytes, and to transport
analytes to the infrared gas cell. Special materials or
configurations may be required in some applications. For instance,
high stack sample temperatures may require special steel or cooling
the probe. For very high moisture sources it may be desirable to use
a dilution probe.
6.2 Particulate Filters. A glass wool plug (optional) inserted
at the probe tip (for large particulate removal) and a filter
(required) rated for 99 percent removal efficiency at 1-micron
(e.g., Balston'') connected at the outlet of the heated probe.
6.3 Sampling Line/Heating System. Heated (sufficient to prevent
condensation) stainless steel, polytetrafluoroethane, or other
material inert to the analytes.
6.4 Gas Distribution Manifold. A heated manifold allowing the
operator to control flows of gas standards and samples directly to
the FTIR system or through sample conditioning systems. Usually
includes heated flow meter, heated valve for selecting and sending
sample to the analyzer, and a by-pass vent. This is typically
constructed of stainless steel tubing and fittings, and high-
temperature valves.
6.5 Stainless Steel Tubing. Type 316, appropriate diameter
(e.g., 3/8 in.) and length for heated connections. Higher grade
stainless may be desirable in some applications.
6.6 Calibration/Analyte Spike Assembly. A three way valve
assembly (or equivalent) to introduce analyte or surrogate spikes
into the sampling system at the outlet of the probe upstream of the
out-of-stack particulate filter and the FTIR analytical system.
6.7 Mass Flow Meter (MFM). These are used for measuring analyte
spike flow. The MFM shall be calibrated in the range of 0 to 5 L/min
and be accurate to 2 percent (or better) of the flow
meter span.
6.8 Gas Regulators. Appropriate for individual gas standards.
6.9 Polytetrafluoroethane Tubing. Diameter (e.g., \3/8\ in.)
and length suitable to connect cylinder regulators to gas standard
manifold.
6.10 Sample Pump. A leak-free pump (e.g., KNFTM),
with by-pass valve, capable of producing a sample flow rate of at
least 10 L/min through 100 ft of sample line. If the pump is
positioned upstream of the distribution manifold and FTIR system,
use a heated pump that is constructed from materials non-reactive to
the analytes. If the pump is located downstream of the FTIR system,
the gas cell sample pressure will be lower than ambient pressure and
it must be recorded at regular intervals.
6.11 Gas Sample Manifold. Secondary manifold to control sample
flow at the inlet to the FTIR manifold. This is optional, but
includes a by-pass vent and heated rotameter.
6.12 Rotameter. A 0 to 20 L/min rotameter. This meter need not
be calibrated.
6.13 FTIR Analytical System. Spectrometer and detector, capable
of measuring the analytes to the chosen detection limit. The system
shall include a personal computer with compatible software allowing
automated collection of spectra.
6.14 FTIR Cell Pump. Required for the batch sampling technique,
capable of evacuating the FTIR cell volume within 2 minutes. The
pumping speed shall allow the operator to obtain 8 sample spectra in
1 hour.
6.15 Absolute Pressure Gauge. Capable of measuring pressure
from 0 to 1000 mmHg to within 2.5 mmHg (e.g.,
BaratronTM).
6.16 Temperature Gauge. Capable of measuring the cell
temperature to within 2 deg.C.
6.17 Sample Conditioning. One option is a condenser system,
which is used for moisture removal. This can be helpful in the
measurement of some analytes. Other sample conditioning procedures
may be devised for the removal of moisture or other interfering
species.
6.17.1 The analyte spike procedure of section 9.2 of this
method, the QA spike procedure of section 8.6.2 of this method, and
the validation procedure of section 13 of this method demonstrate
whether the sample conditioning affects analyte concentrations.
Alternatively, measurements can be made with two parallel FTIR
systems; one measuring conditioned sample, the other measuring
unconditioned sample.
6.17.2 Another option is sample dilution. The dilution factor
measurement must be documented and accounted for in the reported
concentrations. An alternative to dilution is to lower the
sensitivity of the FTIR system by decreasing the cell path length,
or to use a short-path cell in conjunction with a long path cell to
measure more than one concentration range.
7.0 Reagents and Standards
7.1 Analyte(s) and Tracer Gas. Obtain a certified gas cylinder
mixture containing all of the analyte(s) at concentrations
within 2 percent of the emission source levels
(expressed in ppm-meter/K). If practical, the analyte standard
cylinder shall also contain the tracer gas at a concentration which
gives a measurable absorbance at a dilution factor of at least 10:1.
Two ppm SF6 is sufficient for a path length of 22 meters
at 250 deg.F.
7.2 Calibration Transfer Standard(s). Select the calibration
transfer standards (CTS) according to section 4.5 of the FTIR
Protocol. Obtain a National Institute of Standards and Technology
(NIST) traceable gravimetric standard of the CTS ( 2
percent).
7.3 Reference Spectra. Obtain reference spectra for each
analyte, interferant, surrogate, CTS, and tracer. If EPA reference
spectra are not available, use reference spectra prepared according
to procedures in section 4.6 of the EPA FTIR Protocol.
8.0 Sampling and Analysis Procedure
Three types of testing can be performed: (1) Screening, (2)
emissions test, and (3) validation. Each is defined in section 3 of
this method. Determine the purpose(s) of the FTIR test. Test
requirements include: (a) AUi, DLi, overall
fractional uncertainty, OFUi, maximum expected
concentration (CMAXi), and tAN for each, (b)
potential interferants, (c) sampling system factors, e.g., minimum
absolute cell pressure, (Pmin), FTIR cell volume
(VSS), estimated sample absorption pathlength,
LS', estimated sample pressure, PS',
TS', signal integration time (tSS), minimum
instrumental linewidth, MIL, fractional error, and (d) analytical
regions, e.g., m = 1 to M, lower wavenumber position, FLm, center
wavenumber position, FCm, and upper wavenumber position,
FUm, plus interferants, upper wavenumber position of the
CTS absorption band, FFUm, lower wavenumber position of
the CTS absorption band, FFLm, wavenumber range FNU to
FNL. If necessary, sample and acquire an initial spectrum. From
analysis of this preliminary spectrum determine a suitable
operational path length. Set up the sampling train as shown in
Figure 1 or use an appropriate alternative configuration. Sections
8.1 through 8.11 of this method provide guidance on pre-test
calculations in the EPA protocol, sampling and analytical
procedures, and post-test protocol calculations.
8.1 Pretest Preparations and Evaluations. Using the procedure
in section 4.0 of the FTIR Protocol, determine the optimum sampling
system configuration for measuring the target analytes. Use
available information to make reasonable assumptions about moisture
content and other interferences.
8.1.1 Analytes. Select the required detection limit
(DLi) and the maximum permissible analytical uncertainty
(AUi) for each analyte (labeled from 1 to i). Estimate,
if possible, the maximum expected concentration for each analyte,
CMAXi. The expected measurement range is fixed by
DLi and CMAXi for each analyte (i).
8.1.2 Potential Interferants. List the potential interferants.
This usually includes water vapor and CO2, but may also
include some analytes and other compounds.
8.1.3. Optical Configuration. Choose an optical configuration
that can measure all of the analytes within the absorbance range of
.01 to 1.0 (this may require more than one path length). Use
Protocol sections 4.3 to 4.8 for guidance in choosing a
configuration and measuring CTS.
8.1.4 Fractional Reproducibility Uncertainty (FRUi).
The FRU is determined for each analyte by comparing CTS spectra
taken before and after the reference spectra were measured. The EPA
para-xylene reference spectra were collected on 10/31/91 and 11/01/
91 with corresponding CTS spectra ``cts1031a,'' and
[[Page 31941]]
``cts1101b.'' The CTS spectra are used to estimate the
reproducibility (FRU) in the system that was used to collect the
references. The FRU must be < au.="" appendix="" e="" of="" the="" protocol="" is="" used="" to="" calculate="" the="" fru="" from="" cts="" spectra.="" figure="" 2="" plots="" results="" for="" 0.25="">-1 CTS spectra in EPA reference library:
S3 (cts1101b-cts1031a), and S4
[(cts1101b+cts1031a)/2]. The RMSD (SRMS) is calculated in the
subtracted baseline, S3, in the corresponding CTS region
from 850 to 1065 cm-1. The area (BAV) is calculated in
the same region of the averaged CTS spectrum, S4.
8.1.5 Known Interferants. Use appendix B of the EPA FTIR
Protocol.
8.1.6 Calculate the Minimum Analyte Uncertainty, MAU (section
1.3 of this method discusses MAU and protocol appendix D gives the
MAU procedure). The MAU for each analyte, i, and each analytical
region, m, depends on the RMS noise.
8.1.7 Analytical Program. See FTIR Protocol, section 4.10.
Prepare computer program based on the chosen analytical technique.
Use as input reference spectra of all target analytes and expected
interferants. Reference spectra of additional compounds shall also
be included in the program if their presence (even if transient) in
the samples is considered possible. The program output shall be in
ppm (or ppb) and shall be corrected for differences between the
reference path length, LR, temperature, TR,
and pressure, PR, and the conditions used for collecting
the sample spectra. If sampling is performed at ambient pressure,
then any pressure correction is usually small relative to
corrections for path length and temperature, and may be neglected.
8.2 Leak-Check
8.2.1 Sampling System. A typical FTIR extractive sampling train
is shown in Figure 1. Leak check from the probe tip to pump outlet
as follows: Connect a 0-to 250-mL/min rate meter (rotameter or
bubble meter) to the outlet of the pump. Close off the inlet to the
probe, and record the leak rate. The leak rate shall be
200 mL/min.
8.2.2 Analytical System Leak check. Leak check the FTIR cell
under vacuum and under pressure (greater than ambient). Leak check
connecting tubing and inlet manifold under pressure.
8.2.2.1 For the evacuated sample technique, close the valve to
the FTIR cell, and evacuate the absorption cell to the minimum
absolute pressure Pmin. Close the valve to the pump, and
determine the change in pressure Pv after 2
minutes.
8.2.2.2 For both the evacuated sample and purging techniques,
pressurize the system to about 100 mmHg above atmospheric pressure.
Isolate the pump and determine the change in pressure
Pp after 2 minutes.
8.2.2.3 Measure the barometric pressure, Pb in mmHg.
8.2.2.4 Determine the percent leak volume %VL for
the signal integration time tSS and for
Pmax, i.e., the larger of
Pv or Pp, as follows:
[GRAPHIC] [TIFF OMITTED] TR14JN99.004
where 50 = 100% divided by the leak-check time of 2 minutes. 8.2.2.5
Leak volumes in excess of 4 percent of the FTIR system volume
VSS are unacceptable.
8.3 Detector Linearity. Once an optical configuration is
chosen, use one of the procedures of sections 8.3.1 through 8.3.3 to
verify that the detector response is linear. If the detector
response is not linear, decrease the aperture, or attenuate the
infrared beam. After a change in the instrument configuration
perform a linearity check until it is demonstrated that the detector
response is linear.
8.3.1 Vary the power incident on the detector by modifying the
aperture setting. Measure the background and CTS at three instrument
aperture settings: (1) at the aperture setting to be used in the
testing, (2) at one half this aperture and (3) at twice the proposed
testing aperture. Compare the three CTS spectra. CTS band areas
shall agree to within the uncertainty of the cylinder standard and
the RMSD noise in the system. If test aperture is the maximum
aperture, collect CTS spectrum at maximum aperture, then close the
aperture to reduce the IR throughput by half. Collect a second
background and CTS at the smaller aperture setting and compare the
spectra again.
8.3.2 Use neutral density filters to attenuate the infrared
beam. Set up the FTIR system as it will be used in the test
measurements. Collect a CTS spectrum. Use a neutral density filter
to attenuate the infrared beam (either immediately after the source
or the interferometer) to approximately \1/2\ its original
intensity. Collect a second CTS spectrum. Use another filter to
attenuate the infrared beam to approximately \1/4\ its original
intensity. Collect a third background and CTS spectrum. Compare the
CTS spectra. CTS band areas shall agree to within the uncertainty of
the cylinder standard and the RMSD noise in the system.
8.3.3 Observe the single beam instrument response in a
frequency region where the detector response is known to be zero.
Verify that the detector response is ``flat'' and equal to zero in
these regions.
8.4 Data Storage Requirements. All field test spectra shall be
stored on a computer disk and a second backup copy must stored on a
separate disk. The stored information includes sample
interferograms, processed absorbance spectra, background
interferograms, CTS sample interferograms and CTS absorbance
spectra. Additionally, documentation of all sample conditions,
instrument settings, and test records must be recorded on hard copy
or on computer medium. Table 1 gives a sample presentation of
documentation.
8.5 Background Spectrum. Evacuate the gas cell to 5
mmHg, and fill with dry nitrogen gas to ambient pressure (or purge
the cell with 10 volumes of dry nitrogen). Verify that no
significant amounts of absorbing species (for example water vapor
and CO2) are present. Collect a background spectrum,
using a signal averaging period equal to or greater than the
averaging period for the sample spectra. Assign a unique file name
to the background spectrum. Store two copies of the background
interferogram and processed single-beam spectrum on separate
computer disks (one copy is the back-up).
8.5.1 Interference Spectra. If possible, collect spectra of
known and suspected major interferences using the same optical
system that will be used in the field measurements. This can be done
on-site or earlier. A number of gases, e.g. CO2,
SO2, CO, NH3, are readily available from
cylinder gas suppliers.
8.5.2 Water vapor spectra can be prepared by the following
procedure. Fill a sample tube with distilled water. Evacuate above
the sample and remove dissolved gasses by alternately freezing and
thawing the water while evacuating. Allow water vapor into the FTIR
cell, then dilute to atmospheric pressure with nitrogen or dry air.
If quantitative water spectra are required, follow the reference
spectrum procedure for neat samples (protocol, section 4.6). Often,
interference spectra need not be quantitative, but for best results
the absorbance must be comparable to the interference absorbance in
the sample spectra.
8.6 Pre-Test Calibrations.
8.6.1 Calibration Transfer Standard. Evacuate the gas cell to
5 mmHg absolute pressure, and fill the FTIR cell to
atmospheric pressure with the CTS gas. Alternatively, purge the cell
with 10 cell volumes of CTS gas. (If purge is used, verify that the
CTS concentration in the cell is stable by collecting two spectra 2
minutes apart as the CTS gas continues to flow. If the absorbance in
the second spectrum is no greater than in the first, within the
uncertainty of the gas standard, then this can be used as the CTS
spectrum.) Record the spectrum.
8.6.2 QA Spike. This procedure assumes that the method has been
validated for at least some of the target analytes at the source.
For emissions testing perform a QA spike. Use a certified standard,
if possible, of an analyte, which has been validated at the source.
One analyte standard can serve as a QA surrogate for other analytes
which are less reactive or less soluble than the standard. Perform
the spike procedure of section 9.2 of this method. Record spectra of
at least three independent (section 3.22 of this method) spiked
samples. Calculate the spiked component of the analyte
concentration. If the average spiked concentration is within 0.7 to
1.3 times the expected concentration, then proceed with the testing.
If applicable, apply the correction factor from the Method 301 of
this appendix validation test (not the result from the QA spike).
8.7 Sampling. If analyte concentrations vary rapidly with time,
continuous sampling is preferable using the smallest cell volume,
fastest sampling rate and fastest spectra collection rate possible.
Continuous sampling requires the least operator intervention even
without an automated sampling system. For continuous monitoring at
one location over long periods, Continuous sampling is preferred.
Batch sampling and continuous static sampling are used for screening
and performing test runs of finite duration. Either technique is
preferred for sampling several
[[Page 31942]]
locations in a matter of days. Batch sampling gives reasonably good
time resolution and ensures that each spectrum measures a discreet
(and unique) sample volume. Continuous static (and continuous)
sampling provide a very stable background over long periods. Like
batch sampling, continuous static sampling also ensures that each
spectrum measures a unique sample volume. It is essential that the
leak check procedure under vacuum (section 8.2 of this method) is
passed if the batch sampling procedure is used. It is essential that
the leak check procedure under positive pressure is passed if the
continuous static or continuous sampling procedures are used. The
sampling techniques are described in sections 8.7.1 through 8.7.2 of
this method.
8.7.1 Batch Sampling. Evacuate the absorbance cell to
5 mmHg absolute pressure. Fill the cell with exhaust gas
to ambient pressure, isolate the cell, and record the spectrum.
Before taking the next sample, evacuate the cell until no spectral
evidence of sample absorption remains. Repeat this procedure to
collect eight spectra of separate samples in 1 hour.
8.7.2 Continuous Static Sampling. Purge the FTIR cell with 10
cell volumes of sample gas. Isolate the cell, collect the spectrum
of the static sample and record the pressure. Before measuring the
next sample, purge the cell with 10 more cell volumes of sample gas.
8.8 Sampling QA and Reporting
8.8.1 Sample integration times shall be sufficient to achieve
the required signal-to-noise ratio. Obtain an absorbance spectrum by
filling the cell with N2. Measure the RMSD in each analytical region
in this absorbance spectrum. Verify that the number of scans used is
sufficient to achieve the target MAU.
8.8.2 Assign a unique file name to each spectrum.
8.8.3 Store two copies of sample interferograms and processed
spectra on separate computer disks.
8.8.4 For each sample spectrum, document the sampling
conditions, the sampling time (while the cell was being filled), the
time the spectrum was recorded, the instrumental conditions (path
length, temperature, pressure, resolution, signal integration time),
and the spectral file name. Keep a hard copy of these data sheets.
8.9 Signal Transmittance. While sampling, monitor the signal
transmittance. If signal transmittance (relative to the background)
changes by 5 percent or more (absorbance = -.02 to .02) in any
analytical spectral region, obtain a new background spectrum.
8.10 Post-test CTS. After the sampling run, record another CTS
spectrum.
8.11 Post-test QA
8.11.1 Inspect the sample spectra immediately after the run to
verify that the gas matrix composition was close to the expected
(assumed) gas matrix.
8.11.2 Verify that the sampling and instrumental parameters
were appropriate for the conditions encountered. For example, if the
moisture is much greater than anticipated, it may be necessary to
use a shorter path length or dilute the sample.
8.11.3 Compare the pre- and post-test CTS spectra. The peak
absorbance in pre- and post-test CTS must be 5
.
.
9.0 Quality Control.
Use analyte spiking (sections 8.6.2, 9.2 and 13.0 of this
method) to verify that the sampling system can transport the
analytes from the probe to the FTIR system.
9.1 Spike Materials. Use a certified standard (accurate to
2 percent) of the target analyte, if one can be
obtained. If a certified standard cannot be obtained, follow the
procedures in section 4.6.2.2 of the FTIR Protocol.
9.2 Spiking Procedure. QA spiking (section 8.6.2 of this
method) is a calibration procedure used before testing. QA spiking
involves following the spike procedure of sections 9.2.1 through
9.2.3 of this method to obtain at least three spiked samples. The
analyte concentrations in the spiked samples shall be compared to
the expected spike concentration to verify that the sampling/
analytical system is working properly. Usually, when QA spiking is
used, the method has already been validated at a similar source for
the analyte in question. The QA spike demonstrates that the
validated sampling/analytical conditions are being duplicated. If
the QA spike fails then the sampling/analytical system shall be
repaired before testing proceeds. The method validation procedure
(section 13.0 of this method) involves a more extensive use of the
analyte spike procedure of sections 9.2.1 through 9.2.3 of this
method. Spectra of at least 12 independent spiked and 12 independent
unspiked samples are recorded. The concentration results are
analyzed statistically to determine if there is a systematic bias in
the method for measuring a particular analyte. If there is a
systematic bias, within the limits allowed by Method 301 of this
appendix, then a correction factor shall be applied to the
analytical results. If the systematic bias is greater than the
allowed limits, this method is not valid and cannot be used.
9.2.1 Introduce the spike/tracer gas at a constant flow rate of
10 percent of the total sample flow, when possible.
Note: Use the rotameter at the end of the sampling train to
estimate the required spike/tracer gas flow rate.
Use a flow device, e.g., mass flow meter (# 2
percent), to monitor the spike flow rate. Record the spike flow rate
every 10 minutes.
9.2.2 Determine the response time (RT) of the system by
continuously collecting spectra of the spiked effluent until the
spectrum of the spiked component is constant for 5 minutes. The RT
is the interval from the first measurement until the spike becomes
constant. Wait for twice the duration of the RT, then collect
spectra of two independent spiked gas samples. Duplicate analyses of
the spiked concentration shall be within 5 percent of the mean of
the two measurements.
9.2.3 Calculate the dilution ratio using the tracer gas as
follows: where:
[GRAPHIC] [TIFF OMITTED] TR14JN99.005
Where:
[GRAPHIC] [TIFF OMITTED] TR14JN99.006
DF=Dilution factor of the spike gas; this value shall be
10.
SF6(dir)=SF6 (or tracer gas) concentration
measured directly in undiluted spike gas.
SF6(spk)=Diluted SF6 (or tracer gas)
concentration measured in a spiked sample.
Spikedir=Concentration of the analyte in the spike
standard measured by filling the FTIR cell directly.
CS=Expected concentration of the spiked samples.
Unspike=Native concentration of analytes in unspiked samples.
10.0 Calibration and Standardization
10.1 Signal-to-Noise Ratio (S/N). The RMSD in the noise must be
less than one tenth of the minimum analyte peak absorbance in each
analytical region. For example if the minimum peak absorbance is
0.01 at the required DL, then RMSD measured over the entire
analytical region must be 0.001.
10.2 Absorbance Path length. Verify the absorbance path length
by comparing reference CTS spectra to test CTS spectra. See appendix
E of the FTIR Protocol.
10.3 Instrument Resolution. Measure the line width of
appropriate test CTS band(s) to verify instrument resolution.
Alternatively, compare CTS spectra to a reference CTS spectrum, if
available, measured at the nominal resolution.
10.4 Apodization Function.In transforming the sample
interferograms to absorbance spectra use the same apodization
function that was used in transforming the reference spectra.
10.5 FTIR Cell Volume. Evacuate the cell to 5 mmHg.
Measure the initial absolute temperature (Ti) and
absolute pressure (Pi). Connect a wet test meter (or a
calibrated dry gas meter), and slowly draw room air into the cell.
Measure the meter volume (Vm), meter absolute temperature
(Tm), and meter absolute pressure (Pm); and
the cell final absolute temperature (Tf) and absolute
pressure (Pf). Calculate the FTIR cell volume VSS,
including that of the connecting tubing, as follows:
[[Page 31943]]
[GRAPHIC] [TIFF OMITTED] TR14JN99.007
11.0 Data Analysis and Calculations
Analyte concentrations shall be measured using reference spectra
from the EPA FTIR spectral library. When EPA library spectra are not
available, the procedures in section 4.6 of the Protocol shall be
followed to prepare reference spectra of all the target analytes.
11.1 Spectral De-resolution. Reference spectra can be converted
to lower resolution standard spectra (section 3.3 of this method) by
truncating the original reference sample and background
interferograms. Appendix K of the FTIR Protocol gives specific
deresolution procedures. Deresolved spectra shall be transformed
using the same apodization function and level of zero filling as the
sample spectra. Additionally, pre-test FTIR protocol calculations
(e.g., FRU, MAU, FCU) shall be performed using the de-resolved
standard spectra.
11.2 Data Analysis. Various analytical programs are available
for relating sample absorbance to a concentration standard.
Calculated concentrations shall be verified by analyzing residual
baselines after mathematically subtracting scaled reference spectra
from the sample spectra. A full description of the data analysis and
calculations is contained in the FTIR Protocol (sections 4.0, 5.0,
6.0 and appendices). Correct the calculated concentrations in the
sample spectra for differences in absorption path length and
temperature between the reference and sample spectra using equation
6,
[GRAPHIC] [TIFF OMITTED] TR14JN99.008
Where:
Ccorr=Concentration, corrected for path length.
Ccalc=Concentration, initial calculation (output of the
analytical program designed for the compound).
Lr=Reference spectra path length.
Ls=Sample spectra path length.
Ts=Absolute temperature of the sample gas, K.
Tr=Absolute gas temperature of reference spectra, K.
Ps=Sample cell pressure.
Pr=Reference spectrum sample pressure.
12.0 Method Performance
12.1 Spectral Quality. Refer to the FTIR Protocol appendices
for analytical requirements, evaluation of data quality, and
analysis of uncertainty.
12.2 Sampling QA/QC. The analyte spike procedure of section 9
of this method, the QA spike of section 8.6.2 of this method, and
the validation procedure of section 13 of this method are used to
evaluate the performance of the sampling system and to quantify
sampling system effects, if any, on the measured concentrations.
This method is self-validating provided that the results meet the
performance requirement of the QA spike in sections 9.0 and 8.6.2 of
this method and results from a previous method validation study
support the use of this method in the application. Several factors
can contribute to uncertainty in the measurement of spiked samples.
Factors which can be controlled to provide better accuracy in the
spiking procedure are listed in sections 12.2.1 through 12.2.4 of
this method.
12.2.1 Flow meter. An accurate mass flow meter is accurate to
1 percent of its span. If a flow of 1 L/min is monitored
with such a MFM, which is calibrated in the range of 0-5 L/min, the
flow measurement has an uncertainty of 5 percent. This may be
improved by re-calibrating the meter at the specific flow rate to be
used.
12.2.2 Calibration gas. Usually the calibration standard is
certified to within 2 percent. With reactive analytes,
such as HCl, the certified accuracy in a commercially available
standard may be no better than 5 percent.
12.2.3 Temperature. Temperature measurements of the cell shall
be quite accurate. If practical, it is preferable to measure sample
temperature directly, by inserting a thermocouple into the cell
chamber instead of monitoring the cell outer wall temperature.
12.2.4 Pressure. Accuracy depends on the accuracy of the
barometer, but fluctuations in pressure throughout a day may be as
much as 2.5 percent due to weather variations.
13.0 Method Validation Procedure
This validation procedure, which is based on EPA Method 301 (40
CFR part 63, appendix (A), may be used to validate this method for
the analytes in a gas matrix. Validation at one source may also
apply to another type of source, if it can be shown that the exhaust
gas characteristics are similar at both sources.
13.1 Section 5.3 of Method 301 (40 CFR part 63, appendix A),
the Analyte Spike procedure, is used with these modifications. The
statistical analysis of the results follows section 6.3 of EPA
Method 301. Section 3 of this method defines terms that are not
defined in Method 301.
13.1.1 The analyte spike is performed dynamically. This means
the spike flow is continuous and constant as spiked samples are
measured.
13.1.2 The spike gas is introduced at the back of the sample
probe.
13.1.3 Spiked effluent is carried through all sampling
components downstream of the probe.
13.1.4 A single FTIR system (or more) may be used to collect
and analyze spectra (not quadruplicate integrated sampling trains).
13.1.5 All of the validation measurements are performed
sequentially in a single ``run'' (section 3.26 of this method).
13.1.6 The measurements analyzed statistically are each
independent (section 3.22 of this method).
13.1.7 A validation data set can consist of more than 12 spiked
and 12 unspiked measurements.
13.2 Batch Sampling. The procedure in sections 13.2.1 through
13.2.2 may be used for stable processes. If process emissions are
highly variable, the procedure in section 13.2.3 shall be used.
13.2.1 With a single FTIR instrument and sampling system, begin
by collecting spectra of two unspiked samples. Introduce the spike
flow into the sampling system and allow 10 cell volumes to purge the
sampling system and FTIR cell. Collect spectra of two spiked
samples. Turn off the spike and allow 10 cell volumes of unspiked
sample to purge the FTIR cell. Repeat this procedure until the 24
(or more) samples are collected.
13.2.2 In batch sampling, collect spectra of 24 distinct
samples. (Each distinct sample consists of filling the cell to
ambient pressure after the cell has been evacuated.)
13.2.3 Alternatively, a separate probe assembly, line, and
sample pump can be used for spiked sample. Verify and document that
sampling conditions are the same in both the spiked and the unspiked
sampling systems. This can be done by wrapping both sample lines in
the same heated bundle. Keep the same flow rate in both sample
lines. Measure samples in sequence in pairs. After two spiked
samples are measured, evacuate the FTIR cell, and turn the manifold
valve so that spiked sample flows to the FTIR cell. Allow the
connecting line from the manifold to the FTIR cell to purge
thoroughly (the time depends on the line length and flow rate).
Collect a pair of spiked samples. Repeat the procedure until at
least 24 measurements are completed.
13.3 Simultaneous Measurements With Two FTIR Systems. If
unspiked effluent concentrations of the target analyte(s) vary
significantly with time, it may be desirable to perform synchronized
measurements of spiked and unspiked sample. Use two FTIR systems,
each with its own cell and sampling system to perform simultaneous
spiked and unspiked measurements. The optical configurations shall
be similar, if possible. The sampling configurations shall be the
same. One sampling system and FTIR analyzer shall be used to measure
spiked effluent. The other sampling system and FTIR analyzer shall
be used to measure unspiked flue gas. Both systems shall use the
same sampling procedure (i.e., batch or continuous).
13.3.1 If batch sampling is used, synchronize the cell
evacuation, cell filling, and collection of spectra. Fill both cells
at the same rate (in cell volumes per unit time).
13.3.2 If continuous sampling is used, adjust the sample flow
through each gas cell so that the same number of cell volumes pass
through each cell in a given time (i.e. TC1 =
TC2).
13.4 Statistical Treatment. The statistical procedure of EPA
Method 301 of this appendix, section 6.3 is used to evaluate the
bias and precision. For FTIR testing a validation ``run'' is defined
as spectra of 24 independent samples, 12 of which are spiked with
the analyte(s) and 12 of which are not spiked.
13.4.1 Bias. Determine the bias (defined by EPA Method 301 of
this appendix, section 6.3.2) using equation 7:
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[GRAPHIC] [TIFF OMITTED] TR14JN99.009
Where:
B = Bias at spike level.
Sm = Mean concentration of the analyte spiked samples.
CS = Expected concentration of the spiked samples.
13.4.2 Correction Factor. Use section 6.3.2.2 of Method 301 of
this appendix to evaluate the statistical significance of the bias.
If it is determined that the bias is significant, then use section
6.3.3 of Method 301 to calculate a correction factor (CF).
Analytical results of the test method are multiplied by the
correction factor, if 0.7 CF 1.3. If is
determined that the bias is significant and CF > 30
percent, then the test method is considered to ``not valid.''
13.4.3 If measurements do not pass validation, evaluate the
sampling system, instrument configuration, and analytical system to
determine if improper set-up or a malfunction was the cause. If so,
repair the system and repeat the validation.
14.0 Pollution Prevention.
The extracted sample gas is vented outside the enclosure
containing the FTIR system and gas manifold after the analysis. In
typical method applications the vented sample volume is a small
fraction of the source volumetric flow and its composition is
identical to that emitted from the source. When analyte spiking is
used, spiked pollutants are vented with the extracted sample gas.
Approximately 1.6 x 10-\4\ to 3.2 x 10-\4\ lbs of a single HAP
may be vented to the atmosphere in a typical validation run of 3
hours. (This assumes a molar mass of 50 to 100 g, spike rate of 1.0
L/min, and a standard concentration of 100 ppm). Minimize emissions
by keeping the spike flow off when not in use.
15.0 Waste Management.
Small volumes of laboratory gas standards can be vented through
a laboratory hood. Neat samples must be packed and disposed
according to applicable regulations. Surplus materials may be
returned to supplier for disposal.
16.0 References.
1. ``Field Validation Test Using Fourier Transform Infrared
(FTIR) Spectrometry To Measure Formaldehyde, Phenol and Methanol at
a Wool Fiberglass Production Facility.'' Draft. U.S. Environmental
Protection Agency Report, EPA Contract No. 68D20163, Work Assignment
I-32, September 1994.
2. ``FTIR Method Validation at a Coal-Fired Boiler''. Prepared
for U.S. Environmental Protection Agency, Research Triangle Park,
NC. Publication No.: EPA-454/R95-004, NTIS No.: PB95-193199. July,
1993.
3. ``Method 301--Field Validation of Pollutant Measurement
Methods from Various Waste Media,'' 40 CFR part 63, appendix A.
4. ``Molecular Vibrations; The Theory of Infrared and Raman
Vibrational Spectra,'' E. Bright Wilson, J. C. Decius, and P. C.
Cross, Dover Publications, Inc., 1980. For a less intensive
treatment of molecular rotational-vibrational spectra see, for
example, ``Physical Chemistry,'' G. M. Barrow, chapters 12, 13, and
14, McGraw Hill, Inc., 1979.
5. ``Fourier Transform Infrared Spectrometry,'' Peter R.
Griffiths and James de Haseth, Chemical Analysis, 83, 16-25,(1986),
P. J. Elving, J. D. Winefordner and I. M. Kolthoff (ed.), John Wiley
and Sons.
6. ``Computer-Assisted Quantitative Infrared Spectroscopy,''
Gregory L. McClure (ed.), ASTM Special Publication 934 (ASTM), 1987.
7. ``Multivariate Least-Squares Methods Applied to the
Quantitative Spectral Analysis of Multicomponent Mixtures,'' Applied
Spectroscopy, 39(10), 73-84, 1985.
Table 1.--Example Presentation of Sampling Documentation.
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Sample time Spectrum file name Background file name Sample conditioning Process condition
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Sample time Spectrum file Interferogram Resolution Scans Apodization Gain CTS Spectrum
--------------------------------------------------------------------------------------------------------------------------------------------------------
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BILLING CODE 6560-50-P
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[GRAPHIC] [TIFF OMITTED] TR14JN99.010
[[Page 31946]]
[GRAPHIC] [TIFF OMITTED] TR14JN99.011
BILLING CODE 6560-50-O
Addendum to Test Method 320--Protocol for the Use of Extractive Fourier
Transform Infrared (FTIR) Spectrometry for the Analyses of Gaseous
Emissions from Stationary Sources
1.0 Introduction
The purpose of this addendum is to set general guidelines for
the use of modern FTIR spectroscopic methods for the analysis of gas
samples extracted from the effluent of stationary emission sources.
This addendum outlines techniques for developing and evaluating such
methods and sets basic requirements for reporting and quality
assurance procedures.
1.1 Nomenclature
1.1.1 Appendix A to this addendum lists definitions of the
symbols and terms used in this Protocol, many of which have been
taken directly from American Society for Testing and Materials
(ASTM) publication E 131-90a, entitled ``Terminology Relating to
Molecular Spectroscopy.''
1.1.2 Except in the case of background spectra or where
otherwise noted, the term ``spectrum'' refers to a double-beam
spectrum in units of absorbance vs. wavenumber (cm-1).
1.1.3 The term ``Study'' in this addendum refers to a
publication that has been subjected to EPA- or peer-review.
2.0 Applicability and Analytical Principle
2.1 Applicability. This Protocol applies to the determination
of compound-specific concentrations in single- and multiple-
component gas phase samples using double-beam absorption
spectroscopy in the mid-infrared band. It does not specifically
address other FTIR applications, such as single-beam spectroscopy,
analysis of open-path (non-enclosed) samples, and continuous
measurement techniques. If multiple spectrometers, absorption cells,
or instrumental linewidths are used in such analyses, each distinct
operational configuration of the system must be evaluated separately
according to this Protocol.
2.2 Analytical Principle
2.2.1 In the mid-infrared band, most molecules exhibit
characteristic gas phase absorption spectra that may be recorded by
FTIR systems. Such systems consist of a source of mid-infrared
radiation, an interferometer, an enclosed sample cell of known
absorption pathlength, an infrared detector, optical elements for
the transfer of infrared radiation between components, and gas flow
control and measurement components. Adjunct and integral computer
systems are used for controlling the instrument, processing the
signal, and for performing both Fourier transforms and quantitative
analyses of spectral data.
2.2.2 The absorption spectra of pure gases and of mixtures of
gases are described by a linear absorbance theory referred to as
Beer's Law. Using this law, modern FTIR systems use computerized
analytical programs to quantify compounds by comparing the
absorption spectra of known (reference) gas samples to the
absorption spectrum of the sample gas. Some standard mathematical
techniques used for comparisons are classical least squares, inverse
least squares, cross-correlation, factor analysis, and partial least
squares. Reference A describes several of these techniques, as well
as additional techniques, such as differentiation methods, linear
baseline corrections, and non-linear absorbance corrections.
3.0 General Principles of Protocol Requirements
The characteristics that distinguish FTIR systems from gas
analyzers used in instrumental gas analysis methods (e.g., Methods
6C and 7E of appendix A to part 60 of this chapter) are: (1)
Computers are necessary to obtain and analyze data; (2) chemical
concentrations can be quantified using previously recorded infrared
reference
[[Page 31947]]
spectra; and (3) analytical assumptions and results, including
possible effects of interfering compounds, can be evaluated after
the quantitative analysis. The following general principles and
requirements of this Protocol are based on these characteristics.
3.1 Verifiability and Reproducibility of Results. Store all
data and document data analysis techniques sufficient to allow an
independent agent to reproduce the analytical results from the raw
interferometric data.
3.2 Transfer of Reference Spectra. To determine whether
reference spectra recorded under one set of conditions (e.g.,
optical bench, instrumental linewidth, absorption pathlength,
detector performance, pressure, and temperature) can be used to
analyze sample spectra taken under a different set of conditions,
quantitatively compare ``calibration transfer standards'' (CTS) and
reference spectra as described in this Protocol. (Note: The CTS may,
but need not, include analytes of interest). To effect this, record
the absorption spectra of the CTS (a) immediately before and
immediately after recording reference spectra and (b) immediately
after recording sample spectra.
3.3 Evaluation of FTIR Analyses. The applicability, accuracy,
and precision of FTIR measurements are influenced by a number of
interrelated factors, which may be divided into two classes:
3.3.1 Sample-Independent Factors. Examples are system
configuration and performance (e.g., detector sensitivity and
infrared source output), quality and applicability of reference
absorption spectra, and type of mathematical analyses of the
spectra. These factors define the fundamental limitations of FTIR
measurements for a given system configuration. These limitations may
be estimated from evaluations of the system before samples are
available. For example, the detection limit for the absorbing
compound under a given set of conditions may be estimated from the
system noise level and the strength of a particular absorption band.
Similarly, the accuracy of measurements may be estimated from the
analysis of the reference spectra.
3.3.2 Sample-Dependent Factors. Examples are spectral
interferants (e.g., water vapor and CO2) or the overlap
of spectral features of different compounds and contamination
deposits on reflective surfaces or transmitting windows. To maximize
the effectiveness of the mathematical techniques used in spectral
analysis, identification of interferants (a standard initial step)
and analysis of samples (includes effect of other analytical errors)
are necessary. Thus, the Protocol requires post-analysis calculation
of measurement concentration uncertainties for the detection of
these potential sources of measurement error.
4.0 Pre-Test Preparations and Evaluations
Before testing, demonstrate the suitability of FTIR spectrometry
for the desired application according to the procedures of this
section.
4.1 Identify Test Requirements. Identify and record the test
requirements described in sections 4.1.1 through 4.1.4 of this
addendum. These values set the desired or required goals of the
proposed analysis; the description of methods for determining
whether these goals are actually met during the analysis comprises
the majority of this Protocol.
4.1.1 Analytes (specific chemical species) of interest. Label
the analytes from i = 1 to I.
4.1.2 Analytical uncertainty limit (AUi). The
AUi is the maximum permissible fractional uncertainty of
analysis for the ith analyte concentration, expressed as
a fraction of the analyte concentration in the sample.
4.1.3 Required detection limit for each analyte
(DLi, ppm). The detection limit is the lowest
concentration of an analyte for which its overall fractional
uncertainty (OFUi) is required to be less than its
analytical uncertainty limit (AUi).
4.1.4 Maximum expected concentration of each analyte
(CMAXi, ppm).
4.2 Identify Potential Interferants. Considering the chemistry
of the process or results of previous studies, identify potential
interferants, i.e., the major effluent constituents and any
relatively minor effluent constituents that possess either strong
absorption characteristics or strong structural similarities to any
analyte of interest. Label them 1 through Nj, where the
subscript ``j'' pertains to potential interferants. Estimate the
concentrations of these compounds in the effluent (CPOTj,
ppm).
4.3 Select and Evaluate the Sampling System. Considering the
source, e.g., temperature and pressure profiles, moisture content,
analyte characteristics, and particulate concentration), select the
equipment for extracting gas samples. Recommended are a particulate
filter, heating system to maintain sample temperature above the dew
point for all sample constituents at all points within the sampling
system (including the filter), and sample conditioning system (e.g.,
coolers, water-permeable membranes that remove water or other
compounds from the sample, and dilution devices) to remove spectral
interferants or to protect the sampling and analytical components.
Determine the minimum absolute sample system pressure
(Pmin, mmHg) and the infrared absorption cell volume
(VSS, liter). Select the techniques and/or equipment for
the measurement of sample pressures and temperatures.
4.4 Select Spectroscopic System. Select a spectroscopic
configuration for the application. Approximate the absorption
pathlength (LS', meter), sample pressure (PS',
kPa), absolute sample temperature TS', and signal
integration period (tSS, seconds) for the analysis.
Specify the nominal minimum instrumental linewidth (MIL) of the
system. Verify that the fractional error at the approximate values
PS' and TS' is less than one half the smallest
value AUi (see section 4.1.2 of this addendum).
4.5 Select Calibration Transfer Standards (CTS's). Select CTS's
that meet the criteria listed in sections 4.5.1, 4.5.2, and 4.5.3 of
this addendum.
Note: It may be necessary to choose preliminary analytical
regions (see section 4.7 of this addendum), identify the minimum
analyte linewidths, or estimate the system noise level (see section
4.12 of this addendum) before selecting the CTS. More than one
compound may be needed to meet the criteria; if so, obtain separate
cylinders for each compound.
4.5.1 The central wavenumber position of each analytical region
shall lie within 25 percent of the wavenumber position of at least
one CTS absorption band.
4.5.2 The absorption bands in section 4.5.1 of this addendum
shall exhibit peak absorbances greater than ten times the value
RMSEST (see section 4.12 of this addendum) but less than
1.5 absorbance units.
4.5.3 At least one absorption CTS band within the operating
range of the FTIR instrument shall have an instrument-independent
linewidth no greater than the narrowest analyte absorption band.
Perform and document measurements or cite Studies to determine
analyte and CTS compound linewidths.
4.5.4 For each analytical region, specify the upper and lower
wavenumber positions (FFUm and FFLm,
respectively) that bracket the CTS absorption band or bands for the
associated analytical region. Specify the wavenumber range, FNU to
FNL, containing the absorption band that meets the criterion of
section 4.5.3 of this addendum.
4.5.5 Associate, whenever possible, a single set of CTS gas
cylinders with a set of reference spectra. Replacement CTS gas
cylinders shall contain the same compounds at concentrations within
5 percent of that of the original CTS cylinders; the entire
absorption spectra (not individual spectral segments) of the
replacement gas shall be scaled by a factor between 0.95 and 1.05 to
match the original CTS spectra.
4.6 Prepare Reference Spectra
Note: Reference spectra are available in a permanent soft copy
from the EPA spectral library on the EMTIC (Emission Measurement
Technical Information Center) computer bulletin board; they may be
used if applicable.
4.6.1 Select the reference absorption pathlength
(LR) of the cell.
4.6.2 Obtain or prepare a set of chemical standards for each
analyte, potential and known spectral interferants, and CTS. Select
the concentrations of the chemical standards to correspond to the
top of the desired range.
4.6.2.1 Commercially-Prepared Chemical Standards. Chemical
standards for many compounds may be obtained from independent
sources, such as a specialty gas manufacturer, chemical company, or
commercial laboratory. These standards (accurate to within
2 percent) shall be prepared according to EPA
Traceability Protocol (see Reference D) or shall be traceable to
NIST standards. Obtain from the supplier an estimate of the
stability of the analyte concentration. Obtain and follow all of the
supplier's recommendations for recertifying the analyte
concentration.
4.6.2.2 Self-Prepared Chemical Standards. Chemical standards
may be prepared by diluting certified commercially prepared chemical
gases or pure analytes with ultra-pure carrier (UPC) grade nitrogen
according to the barometric and volumetric techniques generally
described in Reference A, section A4.6.
[[Page 31948]]
4.6.3 Record a set of the absorption spectra of the CTS {R1},
then a set of the reference spectra at two or more concentrations in
duplicate over the desired range (the top of the range must be less
than 10 times that of the bottom), followed by a second set of CTS
spectra {R2}. (If self-prepared standards are used, see section
4.6.5 of this addendum before disposing of any of the standards.)
The maximum accepted standard concentration-pathlength product
(ASCPP) for each compound shall be higher than the maximum estimated
concentration-pathlength products for both analytes and known
interferants in the effluent gas. For each analyte, the minimum
ASCPP shall be no greater than ten times the concentration-
pathlength product of that analyte at its required detection limit.
4.6.4 Permanently store the background and interferograms in
digitized form. Document details of the mathematical process for
generating the spectra from these interferograms. Record the sample
pressure (PR), sample temperature (TR),
reference absorption pathlength (LR), and interferogram
signal integration period (tSR). Signal integration
periods for the background interferograms shall be
tSR. Values of PR, LR,
and tSR shall not deviate by more than 1
percent from the time of recording {R1} to that of recording {R2}.
4.6.5 If self-prepared chemical standards are employed and
spectra of only two concentrations are recorded for one or more
compounds, verify the accuracy of the dilution technique by
analyzing the prepared standards for those compounds with a
secondary (non-FTIR) technique in accordance with sections 4.6.5.1
through 4.6.5.4 of this addendum.
4.6.5.1 Record the response of the secondary technique to each
of the four standards prepared.
4.6.5.2 Perform a linear regression of the response values
(dependant variable) versus the accepted standard concentration
(ASC) values (independent variable), with the regression constrained
to pass through the zero-response, zero ASC point.
4.6.5.3 Calculate the average fractional difference between the
actual response values and the regression-predicted values (those
calculated from the regression line using the four ASC values as the
independent variable).
4.6.5.4 If the average fractional difference value calculated
in section 4.6.5.3 of this addendum is larger for any compound than
the corresponding AUi, the dilution technique is not
sufficiently accurate and the reference spectra prepared are not
valid for the analysis.
4.7 Select Analytical Regions. Using the general considerations
in section 7 of Reference A and the spectral characteristics of the
analytes and interferants, select the analytical regions for the
application. Label them m = 1 to M. Specify the lower, center and
upper wavenumber positions of each analytical region
(FLm, FCm, and FUm, respectively).
Specify the analytes and interferants which exhibit absorption in
each region.
4.8 Determine Fractional Reproducibility Uncertainties. Using
appendix E of this addendum, calculate the fractional
reproducibility uncertainty for each analyte (FRUi) from
a comparison of {R1} and {R2}. If FRUi > AUi
for any analyte, the reference spectra generated in accordance with
section 4.6 of this addendum are not valid for the application.
4.9 Identify Known Interferants. Using appendix B of this
addendum, determine which potential interferants affect the analyte
concentration determinations. Relabel these potential interferant as
``known'' interferants, and designate these compounds from k = 1 to
K. Appendix B to this addendum also provides criteria for
determining whether the selected analytical regions are suitable.
4.10 Prepare Computerized Analytical Programs
4.10.1 Choose or devise mathematical techniques (e.g, classical
least squares, inverse least squares, cross-correlation, and factor
analysis) based on equation 4 of Reference A that are appropriate
for analyzing spectral data by comparison with reference spectra.
4.10.2 Following the general recommendations of Reference A,
prepare a computer program or set of programs that analyzes all of
the analytes and known interferants, based on the selected
analytical regions (section 4.7 of this addendum) and the prepared
reference spectra (section 4.6 of this addendum). Specify the
baseline correction technique (e.g., determining the slope and
intercept of a linear baseline contribution in each analytical
region) for each analytical region, including all relevant
wavenumber positions.
4.10.3 Use programs that provide as output [at the reference
absorption pathlength (LR), reference gas temperature
(TR), and reference gas pressure (PR)] the
analyte concentrations, the known interferant concentrations, and
the baseline slope and intercept values. If the sample absorption
pathlength (LS), sample gas temperature (TS),
or sample gas pressure (PS) during the actual sample
analyses differ from LR, TR, and
PR, use a program or set of programs that applies
multiplicative corrections to the derived concentrations to account
for these variations, and that provides as output both the corrected
and uncorrected values. Include in the report of the analysis (see
section 7.0 of this addendum) the details of any transformations
applied to the original reference spectra (e.g., differentiation),
in such a fashion that all analytical results may be verified by an
independent agent from the reference spectra and data spectra alone.
4.11 Determine the Fractional Calibration Uncertainty.
Calculate the fractional calibration uncertainty for each analyte
(FCUi) according to appendix F of this addendum, and compare these
values to the fractional uncertainty limits (AUi; see
section 4.1.2 of this addendum). If FCUi >AUi,
either the reference spectra or analytical programs for that analyte
are unsuitable.
4.12 Verify System Configuration Suitability. Using appendix C
of this addendum, measure or obtain estimates of the noise level
(RMSEST, absorbance) of the FTIR system. Alternatively,
construct the complete spectrometer system and determine the values
RMSSm using appendix G of this addendum. Estimate the
minimum measurement uncertainty for each analyte (MAUi,
ppm) and known interferant (MIUk, ppm) using appendix D
of this addendum. Verify that (a) MAUi <>i)(DLi), FRUi <>i, and FCUi <>i for each analyte and that (b) the CTS chosen meets
the requirements listed in sections 4.5.1 through 4.5.5 of this
addendum.
5.0 Sampling and Analysis Procedure
5.1 Analysis System Assembly and Leak-Test. Assemble the
analysis system. Allow sufficient time for all system components to
reach the desired temperature. Then, determine the leak-rate
(LR) and leak volume (VL), where
VL=LR tSS. Leak volumes shall be
4 percent of VSS.
5.2 Verify Instrumental Performance. Measure the noise level of
the system in each analytical region using the procedure of appendix
G of this addendum. If any noise level is higher than that estimated
for the system in section 4.12 of this addendum, repeat the
calculations of appendix D of this addendum and verify that the
requirements of section 4.12 of this addendum are met; if they are
not, adjust or repair the instrument and repeat this section.
5.3 Determine the Sample Absorption Pathlength
Record a background spectrum. Then, fill the absorption cell
with CTS at the pressure PR and record a set of CTS
spectra {R3}. Store the background and unscaled CTS single beam
interferograms and spectra. Using appendix H of this addendum,
calculate the sample absorption pathlength (LS) for each
analytical region. The values LS shall not differ from
the approximated sample pathlength LS' (see section 4.4
of this addendum) by more than 5 percent.
5.4 Record Sample Spectrum. Connect the sample line to the
source. Either evacuate the absorption cell to an absolute pressure
below 5 mmHg before extracting a sample from the effluent stream
into the absorption cell, or pump at least ten cell volumes of
sample through the cell before obtaining a sample. Record the sample
pressure PS. Generate the absorbance spectrum of the
sample. Store the background and sample single beam interferograms,
and document the process by which the absorbance spectra are
generated from these data. (If necessary, apply the spectral
transformations developed in section 5.6.2 of this addendum). The
resulting sample spectrum is referred to below as SS.
Note: Multiple sample spectra may be recorded according to the
procedures of section 5.4 of this addendum before performing
sections 5.5 and 5.6 of this addendum.
5.5 Quantify Analyte Concentrations. Calculate the unscaled
analyte concentrations RUAi and unscaled interferant
concentrations RUIK using the programs developed in
section 4 of this addendum. To correct for pathlength and pressure
variations between the reference and sample spectra, calculate the
scaling factor, RLPS using equation A.1,
[GRAPHIC] [TIFF OMITTED] TR14JN99.012
[[Page 31949]]
Calculate the final analyte and interferant concentrations
RSAi and RSIk using equations A.2 and A.3,
[GRAPHIC] [TIFF OMITTED] TR14JN99.013
[GRAPHIC] [TIFF OMITTED] TR14JN99.014
5.6 Determine Fractional Analysis Uncertainty. Fill the
absorption cell with CTS at the pressure PS. Record a set
of CTS spectra {R4}. Store the background and CTS single beam
interferograms. Using appendix H of this addendum, calculate the
fractional analysis uncertainty (FAU) for each analytical region. If
the FAU indicated for any analytical region is greater than the
required accuracy requirements determined in sections 4.1.1 through
4.1.4 of this addendum, then comparisons to previously recorded
reference spectra are invalid in that analytical region, and the
analyst shall perform one or both of the procedures of sections
5.6.1 through 5.6.2 of this addendum.
5.6.1 Perform instrumental checks and adjust the instrument to
restore its performance to acceptable levels. If adjustments are
made, repeat sections 5.3, 5.4 (except for the recording of a sample
spectrum), and 5.5 of this addendum to demonstrate that acceptable
uncertainties are obtained in all analytical regions.
5.6.2 Apply appropriate mathematical transformations (e.g.,
frequency shifting, zero-filling, apodization, smoothing) to the
spectra (or to the interferograms upon which the spectra are based)
generated during the performance of the procedures of section 5.3 of
this addendum. Document these transformations and their
reproducibility. Do not apply multiplicative scaling of the spectra,
or any set of transformations that is mathematically equivalent to
multiplicative scaling. Different transformations may be applied to
different analytical regions. Frequency shifts shall be less than
one-half the minimum instrumental linewidth, and must be applied to
all spectral data points in an analytical region. The mathematical
transformations may be retained for the analysis if they are also
applied to the appropriate analytical regions of all sample spectra
recorded, and if all original sample spectra are digitally stored.
Repeat sections 5.3, 5.4 (except the recording of a sample
spectrum), and 5.5 of this addendum to demonstrate that these
transformations lead to acceptable calculated concentration
uncertainties in all analytical regions.
6.0 Post-Analysis Evaluations
Estimate the overall accuracy of the analyses performed in
accordance with sections 5.1 through 5.6 of this addendum using the
procedures of sections 6.1 through 6.3 of this addendum.
6.1 Qualitatively Confirm the Assumed Matrix. Examine each
analytical region of the sample spectrum for spectral evidence of
unexpected or unidentified interferants. If found, identify the
interfering compounds (see Reference C for guidance) and add them to
the list of known interferants. Repeat the procedures of section 4
of this addendum to include the interferants in the uncertainty
calculations and analysis procedures. Verify that the MAU and FCU
values do not increase beyond acceptable levels for the application
requirements. Re-calculate the analyte concentrations (section 5.5
of this addendum) in the affected analytical regions.
6.2 Quantitatively Evaluate Fractional Model Uncertainty (FMU).
Perform the procedures of either section 6.2.1 or 6.2.2 of this
addendum:
6.2.1 Using appendix I of this addendum, determine the
fractional model error (FMU) for each analyte.
6.2.2 Provide statistically determined uncertainties FMU for
each analyte which are equivalent to two standard deviations at the
95 percent confidence level. Such determinations, if employed, must
be based on mathematical examinations of the pertinent sample
spectra (not the reference spectra alone). Include in the report of
the analysis (see section 7.0 of this addendum) a complete
description of the determination of the concentration uncertainties.
6.3 Estimate Overall Concentration Uncertainty (OCU). Using
appendix J of this addendum, determine the overall concentration
uncertainty (OCU) for each analyte. If the OCU is larger than the
required accuracy for any analyte, repeat sections 4 and 6 of this
addendum.
7.0 Reporting Requirements
[Documentation pertaining to virtually all the procedures of
sections 4, 5, and 6 will be required. Software copies of reference
spectra and sample spectra will be retained for some minimum time
following the actual testing.]
8.0 References
(A) Standard Practices for General Techniques of Infrared
Quantitative Analysis (American Society for Testing and Materials,
Designation E 168-88).
(B) The Coblentz Society Specifications for Evaluation of
Research Quality Analytical Infrared Reference Spectra (Class II);
Anal. Chemistry 47, 945A (1975); Appl. Spectroscopy 444, pp. 211-
215, 1990.
(C) Standard Practices for General Techniques for Qualitative
Infrared Analysis, American Society for Testing and Materials,
Designation E 1252-88.
(D) ``EPA Traceability Protocol for Assay and Certification of
Gaseous Calibration Standards,'' U.S. Environmental Protection
Agency Publication No. EPA/600/R-93/224, December 1993.
Appendix A to Addendum to Method 320--Definitions of Terms and Symbols
A.1 Definitions of Terms. All terms used in this method that
are not defined below have the meaning given to them in the CAA and
in subpart A of this part.
Absorption band means a contiguous wavenumber region of a
spectrum (equivalently, a contiguous set of absorbance spectrum data
points) in which the absorbance passes through a maximum or a series
of maxima.
Absorption pathlength means the distance in a spectrophotometer,
measured in the direction of propagation of the beam of radiant
energy, between the surface of the specimen on which the radiant
energy is incident and the surface of the specimen from which it is
emergent.
Analytical region means a contiguous wavenumber region
(equivalently, a contiguous set of absorbance spectrum data points)
used in the quantitative analysis for one or more analytes.
Note: The quantitative result for a single analyte may be based
on data from more than one analytical region.
Apodization means modification of the ILS function by
multiplying the interferogram by a weighing function whose magnitude
varies with retardation.
Background spectrum means the single beam spectrum obtained with
all system components without sample present.
Baseline means any line drawn on an absorption spectrum to
establish a reference point that represents a function of the
radiant power incident on a sample at a given wavelength.
Beers's law means the direct proportionality of the absorbance
of a compound in a homogeneous sample to its concentration.
Calibration transfer standard (CTS) gas means a gas standard of
a compound used to achieve and/or demonstrate suitable quantitative
agreement between sample spectra and the reference spectra; see
section 4.5.1 of this addendum.
Compound means a substance possessing a distinct, unique
molecular structure.
Concentration (c) means the quantity of a compound contained in
a unit quantity of sample. The unit ``ppm'' (number, or mole, basis)
is recommended.
Concentration-pathlength product means the mathematical product
of concentration of the species and absorption pathlength. For
reference spectra, this is a known quantity; for sample spectra, it
is the quantity directly determined from Beer's law. The units
``centimeters-ppm'' or ``meters-ppm'' are recommended.
Derivative absorption spectrum means a plot of rate of change of
absorbance or of any function of absorbance with respect to
wavelength or any function of wavelength.
Double beam spectrum means a transmission or absorbance spectrum
derived by dividing the sample single beam spectrum by the
background spectrum.
Note: The term ``double-beam'' is used elsewhere to denote a
spectrum in which the sample and background interferograms are
collected simultaneously along physically distinct absorption paths.
Here, the term denotes a spectrum in which the sample and background
interferograms are collected at different times along the same
absorption path.
Fast Fourier transform (FFT) means a method of speeding up the
computation of a discrete FT by factoring the data into sparse
matrices containing mostly zeros.
Flyback means interferometer motion during which no data are
recorded.
Fourier transform (FT) means the mathematical process for
converting an amplitude-time spectrum to an amplitude-frequency
spectrum, or vice versa.
Fourier transform infrared (FTIR) spectrometer means an
analytical system that
[[Page 31950]]
employs a source of mid-infrared radiation, an interferometer, an
enclosed sample cell of known absorption pathlength, an infrared
detector, optical elements that transfer infrared radiation between
components, and a computer system. The time-domain detector response
(interferogram) is processed by a Fourier transform to yield a
representation of the detector response vs. infrared frequency.
Note: When FTIR spectrometers are interfaced with other
instruments, a slash should be used to denote the interface; e.g.,
GC/FTIR; HPCL/FTIR, and the use of FTIR should be explicit; i.e.,
FTIR not IR.
Frequency, v means the number of cycles per unit time.
Infrared means the portion of the electromagnetic spectrum
containing wavelengths from approximately 0.78 to 800 microns.
Interferogram, I() means record of the modulated
component of the interference signal measured as a function of
retardation by the detector.
Interferometer means device that divides a beam of radiant
energy into two or more paths, generates an optical path difference
between the beams, and recombines them in order to produce
repetitive interference maxima and minima as the optical retardation
is varied.
Linewidth means the full width at half maximum of an absorption
band in units of wavenumbers (cm-1).
Mid-infrared means the region of the electromagnetic spectrum
from approximately 400 to 5000 cm-1.
Reference spectra means absorption spectra of gases with known
chemical compositions, recorded at a known absorption pathlength,
which are used in the quantitative analysis of gas samples.
Retardation, means optical path difference between two
beams in an interferometer; also known as ``optical path
difference'' or ``optical retardation.''
Scan means digital representation of the detector output
obtained during one complete motion of the interferometer's moving
assembly or assemblies.
Scaling means application of a multiplicative factor to the
absorbance values in a spectrum.
Single beam spectrum means Fourier-transformed interferogram,
representing the detector response vs. wavenumber.
Note: The term ``single-beam'' is used elsewhere to denote any
spectrum in which the sample and background interferograms are
recorded on the same physical absorption path; such usage
differentiates such spectra from those generated using
interferograms recorded along two physically distinct absorption
paths (see ``double-beam spectrum'' above). Here, the term applies
(for example) to the two spectra used directly in the calculation of
transmission and absorbance spectra of a sample.
Standard reference material means a reference material, the
composition or properties of which are certified by a recognized
standardizing agency or group.
Note: The equivalent ISO term is ``certified reference
material.''
Transmittance, T means the ratio of radiant power transmitted by
the sample to the radiant power incident on the sample. Estimated in
FTIR spectroscopy by forming the ratio of the single-beam sample and
background spectra.
Wavenumber, v means the number of waves per unit length.
Note: The usual unit of wavenumber is the reciprocal centimeter,
cm-1. The wavenumber is the reciprocal of the wavelength,
, when is expressed in centimeters.
Zero-filling means the addition of zero-valued points to the end
of a measured interferogram.
Note: Performing the FT of a zero-filled interferogram results
in correctly interpolated points in the computed spectrum.
A.2 Definitions of Mathematical Symbols. The symbols used in
equations in this protocol are defined as follows:
(1) A, absorbance = the logarithm to the base 10 of the
reciprocal of the transmittance (T).
[GRAPHIC] [TIFF OMITTED] TR14JN99.015
(2) AAIim = band area of the ith analyte
in the mth analytical region, at the concentration
(CLi) corresponding to the product of its required
detection limit (DLi) and analytical uncertainty limit
(AUi) .
(3) AAVim = average absorbance of the ith
analyte in the mth analytical region, at the
concentration (CLi) corresponding to the product of its
required detection limit (DLi) and analytical uncertainty
limit (AUi) .
(4) ASC, accepted standard concentration = the concentration
value assigned to a chemical standard.
(5) ASCPP, accepted standard concentration-pathlength product =
for a chemical standard, the product of the ASC and the sample
absorption pathlength. The units ``centimeters-ppm'' or ``meters-
ppm'' are recommended.
(6) AUi, analytical uncertainty limit = the maximum
permissible fractional uncertainty of analysis for the
ith analyte concentration, expressed as a fraction of the
analyte concentration determined in the analysis.
(7) AVTm = average estimated total absorbance in the
mth analytical region.
(8) CKWNk = estimated concentration of the
kth known interferant.
(9) CMAXi = estimated maximum concentration of the
ith analyte.
(10) CPOTj = estimated concentration of the
jth potential interferant.
(11) DLi, required detection limit = for the
ith analyte, the lowest concentration of the analyte for
which its overall fractional uncertainty (OFUi) is
required to be less than the analytical uncertainty limit
(AUi).
(12) FCm = center wavenumber position of the
mth analytical region.
(13) FAUi, fractional analytical uncertainty =
calculated uncertainty in the measured concentration of the
ith analyte because of errors in the mathematical
comparison of reference and sample spectra.
(14) FCUi, fractional calibration uncertainty =
calculated uncertainty in the measured concentration of the
ith analyte because of errors in Beer's law modeling of
the reference spectra concentrations.
(15) FFLm = lower wavenumber position of the CTS
absorption band associated with the mth analytical
region.
(16) FFUm = upper wavenumber position of the CTS
absorption band associated with the mth analytical
region.
(17) FLm = lower wavenumber position of the
mth analytical region.
(18) FMUi, fractional model uncertainty = calculated
uncertainty in the measured concentration of the ith
analyte because of errors in the absorption model employed.
(19) FNL = lower wavenumber position of the CTS
spectrum containing an absorption band at least as narrow as the
analyte absorption bands.
(20) FNU = upper wavenumber position of the CTS
spectrum containing an absorption band at least as narrow as the
analyte absorption bands.
(21) FRUi, fractional reproducibility uncertainty =
calculated uncertainty in the measured concentration of the
ith analyte because of errors in the reproducibility of
spectra from the FTIR system.
(22) FUm = upper wavenumber position of the
mth analytical region.
(23) IAIjm = band area of the jth
potential interferant in the mth analytical region, at
its expected concentration (CPOTj).
(24) IAVim = average absorbance of the ith
analyte in the mth analytical region, at its expected
concentration (CPOTj).
(25) ISCi or k, indicated standard concentration =
the concentration from the computerized analytical program for a
single-compound reference spectrum for the ith analyte or
kth known interferant.
(26) kPa = kilo-Pascal (see Pascal).
(27) LS' = estimated sample absorption pathlength.
(28) LR = reference absorption pathlength.
(29) LS = actual sample absorption pathlength.
(30) MAUi = mean of the MAUim over the
appropriate analytical regions.
(31) MAUim, minimum analyte uncertainty = the
calculated minimum concentration for which the analytical
uncertainty limit (AUi) in the measurement of the
ith analyte, based on spectral data in the mth
analytical region, can be maintained.
(32) MIUj = mean of the MIUjm over the
appropriate analytical regions.
(33) MIUjm, minimum interferant uncertainty = the
calculated minimum concentration for which the analytical
uncertainty limit CPOTj/20 in the measurement of the
jth interferant, based on spectral data in the
mth analytical region, can be maintained.
(34) MIL, minimum instrumental linewidth = the minimum linewidth
from the FTIR system, in wavenumbers.
Note: The MIL of a system may be determined by observing an
absorption band known (through higher resolution examinations) to be
narrower than indicated by the system. The MIL is fundamentally
limited by the retardation of the interferometer, but is also
affected by other operational parameters (e.g., the choice of
apodization).
[[Page 31951]]
(35) Ni = number of analytes.
(36) Nj = number of potential interferants.
(37) Nk = number of known interferants.
(38) Nscan = the number of scans averaged to obtain
an interferogram.
(39) OFUi = the overall fractional uncertainty in an
analyte concentration determined in the analysis (OFUi =
MAX{FRUi, FCUi, FAUi,
FMUi}).
(40) Pascal (Pa) = metric unit of static pressure, equal to one
Newton per square meter; one atmosphere is equal to 101,325 Pa; 1/
760 atmosphere (one Torr, or one millimeter Hg) is equal to 133.322
Pa.
(41) Pmin = minimum pressure of the sampling system
during the sampling procedure.
(42) PS' = estimated sample pressure.
(43) PR = reference pressure.
(44) PS = actual sample pressure.
(45) RMSSm = measured noise level of the FTIR system
in the mth analytical region.
(46) RMSD, root mean square difference = a measure of accuracy
determined by the following equation:
[GRAPHIC] [TIFF OMITTED] TR14JN99.016
Where:
n = the number of observations for which the accuracy is determined.
ei = the difference between a measured value of a
property and its mean value over the n observations.
Note: The RMSD value ``between a set of n contiguous absorbance
values (Ai) and the mean of the values'' (AM)
is defined as
[GRAPHIC] [TIFF OMITTED] TR14JN99.017
(47) RSAi = the (calculated) final concentration of
the ith analyte.
(48) RSIk = the (calculated) final concentration of
the kth known interferant.
(49) tscan, scan time = time used to acquire a single
scan, not including flyback.
(50) tS, signal integration period = the period of
time over which an interferogram is averaged by addition and scaling
of individual scans. In terms of the number of scans
Nscan and scan time tscan, tS =
Nscantscan.
(51) tSR = signal integration period used in
recording reference spectra.
(52) tSS = signal integration period used in
recording sample spectra.
(53) TR = absolute temperature of gases used in
recording reference spectra.
(54) TS = absolute temperature of sample gas as
sample spectra are recorded.
(55) TP, Throughput = manufacturer's estimate of the fraction of
the total infrared power transmitted by the absorption cell and
transfer optics from the interferometer to the detector.
(56) VSS = volume of the infrared absorption cell,
including parts of attached tubing.
(57) Wik = weight used to average over analytical
regions k for quantities related to the analyte i; see appendix D of
this addendum.
Appendix B to Addendum to Method 320--Identifying Spectral Interferants
B.1 General
B.1.1 Assume a fixed absorption pathlength equal to the value
LS'.
B.1.2 Use band area calculations to compare the relative
absorption strengths of the analytes and potential interferants. In
the mth analytical region (FLm to
FUm), use either rectangular or trapezoidal
approximations to determine the band areas described below (see
Reference A, sections A.3.1 through A.3.3). Document any baseline
corrections applied to the spectra.
B.1.3 Use the average total absorbance of the analytes and
potential interferants in each analytical region to determine
whether the analytical region is suitable for analyte concentration
determinations.
Note: The average absorbance in an analytical region is the band
area divided by the width of the analytical region in wavenumbers.
The average total absorbance in an analytical region is the sum of
the average absorbances of all analytes and potential interferants.
B.2 Calculations
B.2.1 Prepare spectral representations of each analyte at the
concentration CLi = (DLi)(AUi),
where DLi is the required detection limit and
AUi is the maximum permissible analytical uncertainty.
For the mth analytical region, calculate the band area
(AAIim) and average absorbance (AAVim) from
these scaled analyte spectra.
B.2.2 Prepare spectral representations of each potential
interferant at its expected concentration (CPOTj). For
the mth analytical region, calculate the band area
(IAIjm) and average absorbance (IAVjm) from
these scaled potential interferant spectra.
B.2.3 Repeat the calculation for each analytical region, and
record the band area results in matrix form as indicated in Figure
B.1.
B.2.4 If the band area of any potential interferant in an
analytical region is greater than the one-half the band area of any
analyte (i.e., IAIjm > 0.5 AAIim for any pair
ij and any m), classify the potential interferant as a known
interferant. Label the known interferants k = 1 to K. Record the
results in matrix form as indicated in Figure B.2.
B.2.5 Calculate the average total absorbance (AVTm)
for each analytical region and record the values in the last row of
the matrix described in Figure B.2. Any analytical region where
AVTm > 2.0 is unsuitable.
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BILLING CODE 6560-50-C
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Appendix C to Addendum to Method 320--Estimating Noise Levels
C.1 General
C.1.1 The root-mean-square (RMS) noise level is the standard
measure of noise in this addendum. The RMS noise level of a
contiguous segment of a spectrum is defined as the RMS difference
(RMSD) between the absorbance values which form the segment and the
mean value of that segment (see appendix A of this addendum).
C.1.2 The RMS noise value in double-beam absorbance spectra is
assumed to be inversely proportional to: (a) the square root of the
signal integration period of the sample single beam spectra from
which it is formed, and (b) the total infrared power transmitted
through the interferometer and absorption cell.
C.1.3 Practically, the assumption of C.1.2 allows the RMS noise
level of a complete system to be estimated from the quantities
described in sections C.1.3.1 through C.1.3.4:
C.1.3.1 RMSMAN, the noise level of the system (in
absorbance units), without the absorption cell and transfer optics,
under those conditions necessary to yield the specified minimum
instrumental linewidth, e.g., Jacquinot stop size.
C.1.3.2 tMAN, the manufacturer's signal integration
time used to determine RMSMAN.
C.1.3.3 tSS, the signal integration time for the
analyses.
C.1.3.4 TP, the manufacturer's estimate of the fraction of the
total infrared power transmitted by the absorption cell and transfer
optics from the interferometer to the detector.
C.2 Calculations
C.2.1 Obtain the values of RMSMAN, tMAN,
and TP from the manufacturers of the equipment, or determine the
noise level by direct measurements with the completely constructed
system proposed in section 4 of this addendum.
C.2.2 Calculate the noise value of the system
(RMSEST) using equation C.1.
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Appendix D to Addendum to Method 320--Estimating Minimum Concentration
Measurement Uncertainties (MAU and MIU)
D.1 General
Estimate the minimum concentration measurement uncertainties for
the ith analyte (MAUi) and jth
interferant (MIUj) based on the spectral data in the
mth analytical region by comparing the analyte band area
in the analytical region (AAIim) and estimating or
measuring the noise level of the system (RMSEST or
RMSSM).
Note: For a single analytical region, the MAU or MIU value is
the concentration of the analyte or interferant for which the band
area is equal to the product of the analytical region width (in
wavenumbers) and the noise level of the system (in absorbance
units). If data from more than one analytical region are used in the
determination of an analyte concentration, the MAU or MIU is the
mean of the separate MAU or MIU values calculated for each
analytical region.
D.2 Calculations
D.2.1 For each analytical region, set
RMS = RMSSM if measured (appendix G of this addendum), or
set RMS = RMSEST
if estimated (appendix C of this addendum).
D.2.2 For each analyte associated with the analytical region,
calculate MAUim using equation D.1,
[GRAPHIC] [TIFF OMITTED] TR14JN99.020
D.2.3 If only the mth analytical region is used to
calculate the concentration of the ith analyte, set
MAUi = MAUim.
D.2.4 If more than one analytical region is used to calculate
the concentration of the ith analyte, set MAUi
equal to the weighted mean of the appropriate MAUim
values calculated above; the weight for each term in the mean is
equal to the fraction of the total wavenumber range used for the
calculation represented by each analytical region. Mathematically,
if the set of analytical regions employed is {m'}, then the MAU for
each analytical region is given by equation D.2.
[GRAPHIC] [TIFF OMITTED] TR14JN99.021
where the weight Wik is defined for each term in the sum
as
[GRAPHIC] [TIFF OMITTED] TR14JN99.022
D.2.5 Repeat sections D.2.1 through D.2.4 of this appendix to
calculate the analogous values MIUj for the interferants
j = 1 to J. Replace the value (AUi) (DLi) in
equation D.1 with CPOTj/20; replace the value
AAIim in equation D.1 with IAIjm.
Appendix E to Addendum to Method 320--Determining Fractional
Reproducibility Uncertainties (FRU)
E.1 General
To estimate the reproducibility of the spectroscopic results of
the system, compare the CTS spectra recorded before and after
preparing the reference spectra. Compare the difference between the
spectra to their average band area. Perform the calculation for each
analytical region on the portions of the CTS spectra associated with
that analytical region.
E.2 Calculations
E.2.1 The CTS spectra {R1} consist of N spectra, denoted by
S1i, i=1, N. Similarly, the CTS spectra {R2} consist of N
spectra, denoted by S2i, i=1, N. Each Ski is
the spectrum of a single compound, where i denotes the compound and
k denotes the set {Rk} of which Ski is a member. Form the
spectra S3 according to S3i =
S2i-S1i for each i. Form the spectra
S4 according to S4i =
[S2i+S1i]/2 for each i.
E.2.2 Each analytical region m is associated with a portion of
the CTS spectra S2i and S1i, for a particular
i, with lower and upper wavenumber limits FFLm and
FFUm, respectively.
E.2.3 For each m and the associated i, calculate the band area
of S4i in the wavenumber range FFUm to
FFLm. Follow the guidelines of section B.1.2 of this
addendum for this band area calculation. Denote the result by
BAVm.
E.2.4 For each m and the associated i, calculate the RMSD of
S3i between the absorbance values and their mean in the
wavenumber range FFUm to FFLm. Denote the
result by SRMSm.
E.2.5 For each analytical region m, calculate FMm
using equation E.1,
[[Page 31954]]
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E.2.6 If only the mth analytical region is used to
calculate the concentration of the ith analyte, set
FRUi = FMm.
E.2.7 If a number pi of analytical regions are used
to calculate the concentration of the ith analyte, set
FRUi equal to the weighted mean of the appropriate
FMm values calculated according to section E.2.5.
Mathematically, if the set of analytical regions employed is {m'},
then FRUi is given by equation E.2,
[GRAPHIC] [TIFF OMITTED] TR14JN99.024
where the Wik are calculated as described in appendix D
of this addendum.
Appendix F of Addendum to Method 320--Determining Fractional
Calibration Uncertainties (FCU)
F.1 General
F.1.1 The concentrations yielded by the computerized analytical
program applied to each single-compound reference spectrum are
defined as the indicated standard concentrations (ISC's). The ISC
values for a single compound spectrum should ideally equal the
accepted standard concentration (ASC) for one analyte or
interferant, and should ideally be zero for all other compounds.
Variations from these results are caused by errors in the ASC
values, variations from the Beer's law (or modified Beer's law)
model used to determine the concentrations, and noise in the
spectra. When the first two effects dominate, the systematic nature
of the errors is often apparent and the analyst shall take steps to
correct them.
F.1.2 When the calibration error appears non-systematic, apply
the procedures of sections F.2.1 through F.2.3 of this appendix to
estimate the fractional calibration uncertainty (FCU) for each
compound. The FCU is defined as the mean fractional error between
the ASC and the ISC for all reference spectra with non-zero ASC for
that compound. The FCU for each compound shall be less than the
required fractional uncertainty specified in section 4.1 of this
addendum.
F.1.3 The computerized analytical programs shall also be
required to yield acceptably low concentrations for compounds with
ISC = 0 when applied to the reference spectra. The ISC of each
reference spectrum for each analyte or interferant shall not exceed
that compound's minimum measurement uncertainty (MAU or MIU).
F.2 Calculations
F.2.1 Apply each analytical program to each reference spectrum.
Prepare a similar table to that in Figure F.1 to present the ISC and
ASC values for each analyte and interferant in each reference
spectrum. Maintain the order of reference file names and compounds
employed in preparing Figure F.1.
F.2.2 For all reference spectra in Figure F.1, verify that the
absolute values of the ISC's are less than the compound's MAU (for
analytes) or MIU (for interferants).
F.2.3 For each analyte reference spectrum, calculate the
quantity (ASC-ISC)/ASC. For each analyte, calculate the mean of
these values (the FCUi for the ith analyte)
over all reference spectra. Prepare a similar table to that in
Figure F.2 to present the FCUi and analytical uncertainty
limit (AUi) for each analyte.
Figure F.1.--Presentation of Accepted Standard Concentrations (ASC's) and Indicated Standard Concentrations (ISC's)
--------------------------------------------------------------------------------------------------------------------------------------------------------
--------------------------------------------------------------------------------------------------------------------------------------------------------
Compound name Reference spectrum file ASC (ppm) ISC (ppm)
name
Analytes Interferants
i=1 I
j=1 J
--------------------------------------------------------------------------------------------------------------------------------------------------------
--------------------------------------------------------------------------------------------------------------------------------------------------------
Figure F.2--Presentation of Fractional Calibration Uncertainties (FCU's) and Analytical Uncertainties (AU's)
----------------------------------------------------------------------------------------------------------------
Analyte name FCU (%) AU (%)
----------------------------------------------------------------------------------------------------------------
----------------------------------------------------------------------------------------------------------------
Appendix G to Addendum to Method 320--Measuring Noise Levels
G.1 General
The root-mean-square (RMS) noise level is the standard measure
of noise. The RMS noise level of a contiguous segment of a spectrum
is the RMSD between the absorbance values that form the segment and
the mean value of the segment (see appendix A of this addendum).
G.2 Calculations
G.2.1 Evacuate the absorption cell or fill it with UPC grade
nitrogen at approximately one atmosphere total pressure.
G.2.2 Record two single beam spectra of signal integration
period tSS.
G.2.3 Form the double beam absorption spectrum from these two
single beam spectra, and calculate the noise level RMSSm
in the M analytical regions.
Appendix H of Addendum to Method 320--Determining Sample Absorption
Pathlength (LS) and Fractional Analytical Uncertainty (FAU)
H.1 General
Reference spectra recorded at absorption pathlength
(LR), gas pressure (PR), and gas absolute
temperature (TR) may be used to determine analyte
concentrations in samples whose spectra are recorded at conditions
[[Page 31955]]
different from that of the reference spectra, i.e., at absorption
pathlength (LS), absolute temperature (TS),
and pressure (PS). This appendix describes the
calculations for estimating the fractional uncertainty (FAU) of this
practice. It also describes the calculations for determining the
sample absorption pathlength from comparison of CTS spectra, and for
preparing spectra for further instrumental and procedural checks.
H.1.1 Before sampling, determine the sample absorption
pathlength using least squares analysis. Determine the ratio
LS/LR by comparing the spectral sets {R1} and
{R3}, which are recorded using the same CTS at LS and
LR, and TS and TR, but both at
PR.
H.1.2 Determine the fractional analysis uncertainty (FAU) for
each analyte by comparing a scaled CTS spectral set, recorded at
LS, TS, and PS, to the CTS
reference spectra of the same gas, recorded at LR,
TR, and PR. Perform the quantitative
comparison after recording the sample spectra, based on band areas
of the spectra in the CTS absorbance band associated with each
analyte.
H.2 Calculations
H.2.1 Absorption Pathlength Determination. Perform and document
separate linear baseline corrections to each analytical region in
the spectral sets {R1} and {R3}. Form a one-dimensional array
AR containing the absorbance values from all segments of
{R1} that are associated with the analytical regions; the members of
the array are ARi, i = 1, n. Form a similar one-
dimensional array AS from the absorbance values in the
spectral set {R3}; the members of the array are ASi, i =
1, n. Based on the model AS = rAR + E,
determine the least-squares estimate of r', the value of r which
minimizes the square error E2. Calculate the sample
absorption pathlength, LS, using equation H.1,
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H.2.2 Fractional Analysis Uncertainty. Perform and document
separate linear baseline corrections to each analytical region in
the spectral sets {R1} and {R4}. Form the arrays AS and
AR as described in section H.2.1 of this appendix, using
values from {R1} to form AR, and values from {R4} to form
AS. Calculate NRMSE and IAAV using
equations H.2 and H.3,
[GRAPHIC] [TIFF OMITTED] TR14JN99.026
[GRAPHIC] [TIFF OMITTED] TR14JN99.027
The fractional analytical uncertainty, FAU, is given by equation
H.4,
[GRAPHIC] [TIFF OMITTED] TR14JN99.028
Appendix I to Addendum to Method 320--Determining Fractional Model
Uncertainties (FMU)
I.1 General
To prepare analytical programs for FTIR analyses, the sample
constituents must first be assumed. The calculations in this
appendix, based upon a simulation of the sample spectrum, shall be
used to verify the appropriateness of these assumptions. The
simulated spectra consist of the sum of single compound reference
spectra scaled to represent their contributions to the sample
absorbance spectrum; scaling factors are based on the indicated
standard concentrations (ISC) and measured (sample) analyte and
interferant concentrations, the sample and reference absorption
pathlengths, and the sample and reference gas pressures. No band-
shape correction for differences in the temperature of the sample
and reference spectra gases is made; such errors are included in the
FMU estimate. The actual and simulated sample spectra are
quantitatively compared to determine the fractional model
uncertainty; this comparison uses the reference spectra band areas
and residuals in the difference spectrum formed from the actual and
simulated sample spectra.
I.2 Calculations
I.2.1 For each analyte (with scaled concentration
RSAi), select a reference spectrum SAi with
indicated standard concentration ISCi. Calculate the
scaling factors, RAi, using equation I.1,
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Form the spectra SACi by scaling each SAi by
the factor RAi.
I.2.2 For each interferant, select a reference spectrum
SIk with indicated standard concentration
ISCk. Calculate the scaling factors, RIk,
using equation I.2,
[GRAPHIC] [TIFF OMITTED] TR14JN99.030
Form the spectra SICk by scaling each SIk by
the factor RIk.
I.2.3 For each analytical region, determine by visual
inspection which of the spectra SACi and SICk
exhibit absorbance bands within the analytical region. Subtract each
spectrum SACi and SICk exhibiting absorbance
from the sample spectrum SS to form the spectrum
SUBS. To save analysis time and to avoid the introduction
of unwanted noise into the subtracted spectrum, it is recommended
that the calculation be made (1) only for those spectral data points
within the analytical regions, and (2) for each analytical region
separately using the original spectrum SS.
I.2.4 For each analytical region m, calculate the RMSD of
SUBS between the absorbance values and their mean in the
region FFUm to FFLm. Denote the result by
RMSSm.
I.2.5 For each analyte i, calculate FMm, using
equation I.3,
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for each analytical region associated with the analyte.
I.2.6 If only the mth analytical region is used to
calculate the concentration of the ith analyte, set
FMUi=FMm.
I.2.7 If a number of analytical regions are used to calculate
the concentration of the ith analyte, set FMi
equal to the weighted mean of the appropriate FMm values
calculated using equation I-3. Mathematically, if the set of
analytical regions employed is {m'}, then the fractional model
uncertainty, FMU, is given by equation I.4,
[GRAPHIC] [TIFF OMITTED] TR14JN99.032
where Wik is calculated as described in appendix D of
this addendum.
[[Page 31956]]
Appendix J of Addendum to Method 320--Determining Overall Concentration
Uncertainties (OCU)
The calculations in this addendum estimate the measurement
uncertainties for various FTIR measurements. The lowest possible
overall concentration uncertainty (OCU) for an analyte is its MAU
value, which is an estimate of the absolute concentration
uncertainty when spectral noise dominates the measurement error.
However, if the product of the largest fractional concentration
uncertainty (FRU, FCU, FAU, or FMU) and the measured concentration
of an analyte exceeds the MAU for the analyte, then the OCU is this
product. In mathematical terms, set OFUi =
MAX{FRUi, FCUi, FAUi,
FMUi} and OCUi =
MAX{RSAi*OFUi, MAUi}.
Test Method 321--Measurement of Gaseous Hydrogen Chloride Emissions At
Portland Cement Kilns by Fourier Transform Infrared (FTIR) Spectroscopy
1.0 Introduction
This method should be performed by those persons familiar with
the operation of Fourier Transform Infrared (FTIR) instrumentation
in the application to source sampling. This document describes the
sampling procedures for use in the application of FTIR spectrometry
for the determination of vapor phase hydrogen chloride (HCl)
concentrations both before and after particulate matter control
devices installed at portland cement kilns. A procedure for analyte
spiking is included for quality assurance. This method is considered
to be self validating provided that the requirements listed in
section 9 of this method are followed. The analytical procedures for
interpreting infrared spectra from emission measurements are
described in the ``Protocol For The Use of Extractive Fourier
Transform Infrared (FTIR) Spectrometry in Analyses of Gaseous
Emissions From Stationary Industrial Sources'', included as an
addendum to proposed Method 320 of this appendix (hereafter referred
to as the ``FTIR Protocol)''. References 1 and 2 describe the use of
FTIR spectrometry in field measurements. Sample transport presents
the principal difficulty in directly measuring HCl emissions. This
identical problem must be overcome by any extractive measurement
method. HCl is reactive and water soluble. The sampling system must
be adequately designed to prevent sample condensation in the system.
1.1 Scope and Application
This method is specifically designed for the application of FTIR
Spectrometry in extractive measurements of gaseous HCl
concentrations in portland cement kiln emissions.
1.2 Applicability
This method applies to the measurement of HCl [CAS No. 7647-01-
0]. This method can be applied to the determination of HCl
concentrations both before and after particulate matter control
devices installed at portland cement manufacturing facilities. This
method applies to either continuous flow through measurement (with
isolated sample analysis) or grab sampling (batch analysis). HCl is
measured using the mid-infrared spectral region for analysis (about
400 to 4000 cm-1 or 25 to 2.5 m). Table 1 lists
the suggested analytical region for quantification of HCl taking the
interference from water vapor into consideration.
Table 1.--Example Analytical Region for HCl
------------------------------------------------------------------------
Analytical Potential
Compound region (cm-1) interferants
------------------------------------------------------------------------
Hydrogen chloride............. 2679-2840 Water.
------------------------------------------------------------------------
1.3 Method Range and Sensitivity
1.3.1 The analytical range is determined by the instrumental
design and the composition of the gas stream. For practical purposes
there is no upper limit to the range because the pathlength may be
reduced or the sample may be diluted. The lower detection range
depends on (1) the absorption coefficient of the compound in the
analytical frequency region, (2) the spectral resolution, (3) the
interferometer sampling time, (4) the detector sensitivity and
response, and (5) the absorption pathlength.
1.3.2 The practical lower quantification range is usually
higher than the instrument sensitivity allows and is dependent upon
(1) the presence of interfering species in the exhaust gas including
H2O, CO2, and SO2, (2) analyte
losses in the sampling system, (3) the optical alignment of the gas
cell and transfer optics, and (4) the quality of the reflective
surfaces in the cell (cell throughput). Under typical test
conditions (moisture content of up to 30% and CO2
concentrations from 1 to 15 percent), a 22 meter path length cell
with a suitable sampling system may achieve a lower quantification
range of from 1 to 5 ppm for HCl.
1.4 Data Quality Objectives
1.4.1 In designing or configuring the analytical system, data
quality is determined by measuring of the root mean square deviation
(RMSD) of the absorbance values within a chosen spectral
(analytical) region. The RMSD provides an indication of the signal-
to-noise ratio (S/N) of the spectral baseline. Appendix D of the
FTIR Protocol (the addendum to Method 320 of this appendix) presents
a discussion of the relationship between the RMSD, lower detection
limit, DLi, and analytical uncertainty, AUi.
It is important to consider the target analyte quantification limit
when performing testing with FTIR instrumentation, and to optimize
the system to achieve the desired detection limit.
1.4.2 Data quality is determined by measuring the root mean
square (RMS) noise level in each analytical spectral region
(appendix C of the FTIR Protocol). The RMS noise is defined as the
root mean square deviation (RMSD) of the absorbance values in an
analytical region from the mean absorbance value in the same region.
Appendix D of the FTIR Protocol defines the minimum analyte
uncertainty (MAU), and how the RMSD is used to calculate the MAU.
The MAUim is the minimum concentration of the ith analyte
in the mth analytical region for which the analytical uncertainty
limit can be maintained. Table 2 presents example values of AU and
MAU using the analytical region presented in Table 1.
Table 2.--Example Pre-Test Protocol Calculations for Hydrogen Chloride
------------------------------------------------------------------------
HCl
------------------------------------------------------------------------
Reference concentration (ppm-meters)/K..................... 11.2
Reference Band area........................................ 2.881
DL (ppm-meters)/K.......................................... 0.1117
AU......................................................... 0.2
CL (DL x AU)............................................. 0.02234
FL (cm-1).................................................. 2679.83
FU (cm-1).................................................. 2840.93
FC (cm-1).................................................. 2760.38
AAI (ppm-meters)/K......................................... 0.06435
RMSD....................................................... 2.28E-03
MAU (ppm-meters)/K......................................... 1.28E-01
MAU ppm at 22 meters and 250 deg.F........................ .0.2284
------------------------------------------------------------------------
2.0 Summary of Method
2.1 Principle
See Method 320 of this appendix. HCl can also undergo rotation
transitions by absorbing energy in the far-infrared spectral region.
The rotational transitions are superimposed on the vibrational
fundamental to give a series of lines centered at the fundamental
vibrational frequency, 2885 cm-\1\. The frequencies of absorbance
and the pattern of rotational/vibrational lines are unique to HCl.
When this distinct pattern is observed in an infrared spectrum of an
unknown sample, it unequivocally identifies HCl as a component of
the mixture. The infrared spectrum of HCl is very distinctive and
cannot be confused with the spectrum of any other compound. See
Reference 6.
[[Page 31957]]
2.2 Sampling and Analysis. See Method 320 of this appendix.
2.3 Operator Requirements. The analyst must have knowledge of
spectral patterns to choose an appropriate absorption path length or
determine if sample dilution is necessary. The analyst should also
understand FTIR instrument operation well enough to choose
instrument settings that are consistent with the objectives of the
analysis.
3.0 Definitions
See appendix A of the FTIR Protocol.
4.0 Interferences
This method will not measure HCl under conditions: (1) where the
sample gas stream can condense in the sampling system or the
instrumentation, or (2) where a high moisture content sample
relative to the analyte concentrations imparts spectral interference
due to the water vapor absorbance bands. For measuring HCl the first
(sampling) consideration is more critical. Spectral interference
from water vapor is not a significant problem except at very high
moisture levels and low HCl concentrations.
4.1 Analytical Interferences. See Method 320 of this appendix.
4.1.1 Background Interferences. See Method 320 of this
appendix.
4.1.2 Spectral interferences. Water vapor can present spectral
interference for FTIR gas analysis of HCl. Therefore, the water
vapor in the spectra of kiln gas samples must be accounted for. This
means preparing at least one spectrum of a water vapor sample where
the moisture concentration is close to that in the kiln gas.
4.2 Sampling System Interferences. The principal sampling
system interferant for measuring HCl is water vapor. Steps must be
taken to ensure that no condensation forms anywhere in the probe
assembly, sample lines, or analytical instrumentation. Cold spots
anywhere in the sampling system must be avoided. The extent of
sampling system bias in the FTIR analysis of HCl depends on
concentrations of potential interferants, moisture content of the
gas stream, temperature of the gas stream, temperature of sampling
system components, sample flow rate, and reactivity of HCl with
other species in the gas stream (e.g., ammonia). For measuring HCl
in a wet gas stream the temperatures of the gas stream, sampling
components, and the sample flow rate are of primary importance.
Analyte spiking with HCl is performed to demonstrate the integrity
of the sampling system for transporting HCl vapor in the flue gas to
the FTIR instrument. See section 9 of this method for a complete
description of analyte spiking.
5.0 Safety
5.1 Hydrogen chloride vapor is corrosive and can cause
irritation or severe damage to respiratory system, eyes and skin.
Exposure to this compound should be avoided.
5.2 This method may involve sampling at locations having high
positive or negative pressures, or high concentrations of hazardous
or toxic pollutants, and can not address all safety problems
encountered under these diverse sampling conditions. It is the
responsibility of the tester(s) to ensure proper safety and health
practices, and to determine the applicability of regulatory
limitations before performing this test method. Leak-check
procedures are outlined in section 8.2 of Method 320 of this
appendix.
6.0 Equipment and Supplies
Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.
6.1 FTIR Spectrometer and Detector. An FTIR Spectrometer system
(interferometer, transfer optics, gas cell and detector) having the
capability of measuring HCl to the predetermined minimum detectable
level required (see section 4.1.3 of the FTIR Protocol). The system
must also include an accurate means to control and/or measure the
temperature of the FTIR gas analysis cell, and a personal computer
with compatible software that provides real-time updates of the
spectral profile during sample and spectral collection.
6.2 Pump. Capable of evacuating the FTIR cell volume to 1 Torr
(133.3 Pascals) within two minutes (for batch sample analysis).
6.3 Mass Flow Meters/Controllers. To accurately measure analyte
spike flow rate, having the appropriate calibrated range and a
stated accuracy of 2 percent of the absolute measurement
value. This device must be calibrated with the major component of
the calibration/spike gas (e.g., nitrogen) using an NIST traceable
bubble meter or equivalent. Single point calibration checks should
be performed daily in the field. When spiking HCl, the mass flow
meter/controller should be thoroughly purged before and after
introduction of the gas to prevent corrosion of the interior parts.
6.4 Polytetrafluoroethane tubing. Diameter and length suitable
to connect cylinder regulators.
6.5 Stainless Steel tubing. Type 316 of appropriate length and
diameter for heated connections.
6.6 Gas Regulators. Purgeable HCl regulator.
6.7 Pressure Gauge. Capable of measuring pressure from 0 to
1000 Torr (133.3 Pa=1 Torr) within 5 percent.
6.8 Sampling Probe. Glass, stainless steel or other appropriate
material of sufficient length and physical integrity to sustain
heating, prevent adsorption of analytes and capable of reaching gas
sampling point.
6.9 Sampling Line. Heated 180 deg.C (360 deg.F) and
fabricated of either stainless steel, polytetrafluoroethane or other
material that prevents adsorption of HCl and transports effluent to
analytical instrumentation. The extractive sample line must have the
capability to transport sample gas to the analytical components as
well as direct heated calibration spike gas to the calibration
assembly located at the sample probe. It is important to minimize
the length of heated sample line.
6.10 Particulate Filters. A sintered stainless steel filter
rated at 20 microns or greater may be placed at the inlet of the
probe (for removal of large particulate matter). A heated filter
(Balston or equivalent) rated at 1 micron is necessary
for primary particulate matter removal, and shall be placed
immediately after the heated probe. The filter/filter holder
temperature should be maintained at 180 deg.C (360 deg.F).
6.11 Calibration/Analyte Spike Assembly. A heated three-way
valve assembly (or equivalent) to introduce surrogate spikes into
the sampling system at the outlet of the probe before the primary
particulate filter.
6.12 Sample Extraction Pump. A leak-free heated head pump
(KNF Neuberger or equivalent) capable of extracting sample
effluent through entire sampling system at a rate which prevents
analyte losses and minimizes analyzer response time. The pump should
have a heated by-pass and may be placed either before the FTIR
instrument or after. If the sample pump is located upstream of the
FTIR instrument, it must be fabricated from materials non-reactive
to HCl. The sampling system and FTIR measurement system shall allow
the operator to obtain at least six sample spectra during a one-hour
period.
6.13 Barometer. For measurement of barometric pressure.
6.14 Gas Sample Manifold. A distribution manifold having the
capabilities listed in sections 6.14.1 through 6.14.4;
6.14.1 Delivery of calibration gas directly to the analytical
instrumentation;
6.14.2 Delivery of calibration gas to the sample probe (system
calibration or analyte spike) via a heated traced sample line;
6.14.3 Delivery of sample gas (kiln gas, spiked kiln gas, or
system calibrations) to the analytical instrumentation;
6.14.4 Delivery (optional) of a humidified nitrogen sample
stream.
6.15 Flow Measurement Device. Type S Pitot tube (or equivalent)
and Magnahelic set for measurement of volumetric flow
rate.
7.0 Reagents and Standards
HCl can be purchased in a standard compressed gas cylinder. The
most stable HCl cylinder mixture available has a concentration
certified at 5 percent. Such a cylinder is suitable for
performing analyte spiking because it will provide reproducible
samples. The stability of the cylinder can be monitored over time by
periodically performing direct FTIR analysis of cylinder samples. It
is recommended that a 10-50 ppm cylinder of HCl be prepared having
from 2-5 ppm SF6 as a tracer compound. (See sections 7.1 through 7.3
of Method 320 of this appendix for a complete description of the use
of existing HCl reference spectra. See section 9.1 of Method 320 of
this appendix for a complete discussion of standard concentration
selection.)
8.0 Sample Collection, Preservation and Storage
See also Method 320 of this appendix.
8.1 Pretest. A screening test is ideal for obtaining proper
data that can be used for preparing analytical program files.
Information from literature surveys and source personnel is also
acceptable. Information about the sampling location and gas stream
composition is required to determine the optimum sampling system
configuration for measuring HCl. Determine the percent moisture of
the kiln gas by Method 4 of appendix A to part 60 of this chapter or
by performing a wet bulb/dry bulb measurement. Perform a preliminary
traverse
[[Page 31958]]
of the sample duct or stack and select the sampling point(s).
Acquire an initial spectrum and determine the optimum operational
pathlength of the instrument.
8.2 Leak-Check. See Method 320 of this appendix, section 8.2
for direction on performing leak-checks.
8.3 Background Spectrum. See Method 320 of this appendix,
section 8.5 for direction in background spectral acquisition.
8.4 Pre-Test Calibration Transfer Standard (Direct Instrument
Calibration). See Method 320 of this appendix, section 8.3 for
direction in CTS spectral acquisition.
8.5 Pre-Test System Calibration. See Method 320 of this
appendix, sections 8.6.1 through 8.6.2 for direction in performing
system calibration.
8.6 Sampling
8.6.1 Extractive System. An extractive system maintained at 180
deg.C (360 deg.F) or higher which is capable of directing a total
flow of at least 12 L/min to the sample cell is required (References
1 and 2). Insert the probe into the duct or stack at a point
representing the average volumetric flow rate and 25 percent of the
cross sectional area. Co-locate an appropriate flow monitoring
device with the sample probe so that the flow rate is recorded at
specified time intervals during emission testing (e.g., differential
pressure measurements taken every 10 minutes during each run).
8.6.2 Batch Samples. Evacuate the absorbance cell to 5 Torr (or
less) absolute pressure before taking first sample. Fill the cell
with kiln gas to ambient pressure and record the infrared spectrum,
then evacuate the cell until there is no further evidence of
infrared absorption. Repeat this procedure, collecting a total of
six separate sample spectra within a 1-hour period.
8.6.3 Continuous Flow Through Sampling. Purge the FTIR cell
with kiln gas for a time period sufficient to equilibrate the entire
sampling system and FTIR gas cell. The time required is a function
of the mechanical response time of the system (determined by
performing the system calibration with the CTS gas or equivalent),
and by the chemical reactivity of the target analytes. If the
effluent target analyte concentration is not variable, observation
of the spectral up-date of the flowing gas sample should be
performed until equilibration of the sample is achieved. Isolate the
gas cell from the sample flow by directing the purge flow to vent.
Record the spectrum and pressure of the sample gas. After spectral
acquisition, allow the sample gas to purge the cell with at least
three volumes of kiln gas. The time required to adequately purge the
cell with the required volume of gas is a function of (1) cell
volume, (2) flow rate through the cell, and (3) cell design. It is
important that the gas introduction and vent for the FTIR cell
provides a complete purge through the cell.
8.6.4 Continuous Sampling. In some cases it is possible to
collect spectra continuously while the FTIR cell is purged with
sample gas. The sample integration time, tss, the sample
flow rate through the gas cell, and the sample integration time must
be chosen so that the collected data consist of at least 10 spectra
with each spectrum being of a separate cell volume of flue gas.
Sampling in this manner may only be performed if the native source
analyte concentrations do not affect the test results.
8.7 Sample Conditioning
8.7.1 High Moisture Sampling. Kiln gas emitted from wet process
cement kilns may contain 3- to 40 percent moisture. Zinc selenide
windows or the equivalent should be used when attempting to analyze
hot/wet kiln gas under these conditions to prevent dissolution of
water soluble window materials (e.g., KBr).
8.7.2 Sample Dilution. The sample may be diluted using an in-
stack dilution probe, or an external dilution device provided that
the sample is not diluted below the instrument's quantification
range. As an alternative to using a dilution probe, nitrogen may be
dynamically spiked into the effluent stream in the same manner as
analyte spiking. A constant dilution rate shall be maintained
throughout the measurement process. It is critical to measure and
verify the exact dilution ratio when using a dilution probe or the
nitrogen spiking approach. Calibrating the system with a calibration
gas containing an appropriate tracer compound will allow
determination of the dilution ratio for most measurement systems.
The tester shall specify the procedures used to determine the
dilution ratio, and include these calibration results in the report.
8.8 Sampling QA, Data Storage and Reporting. See the FTIR
Protocol. Sample integration times shall be sufficient to achieve
the required signal-to-noise ratio, and all sample spectra should
have unique file names. Two copies of sample interferograms and
processed spectra will be stored on separate computer media. For
each sample spectrum the analyst must document the sampling
conditions, the sampling time (while the cell was being filled), the
time the spectrum was recorded, the instrumental conditions (path
length, temperature, pressure, resolution, integration time), and
the spectral file name. A hard copy of these data must be maintained
until the test results are accepted.
8.9 Signal Transmittance. Monitor the signal transmittance
through the instrumental system. If signal transmittance (relative
to the background) drops below 95 percent in any spectral region
where the sample does not absorb infrared energy, then a new
background spectrum must be obtained.
8.10 Post-test CTS. After the sampling run completion, record
the CTS spectrum. Analysis of the spectral band area used for
quantification from pre- and post-test CTS spectra should agree to
within 5 percent or corrective action must be taken.
8.11 Post-test QA. The sample spectra shall be inspected
immediately after the run to verify that the gas matrix composition
was close to the assumed gas matrix, (this is necessary to account
for the concentrations of the interferants for use in the analytical
analysis programs), and to confirm that the sampling and
instrumental parameters were appropriate for the conditions
encountered.
9.0 Quality Control
Use analyte spiking to verify the effectiveness of the sampling
system for the target compounds in the actual kiln gas matrix. QA
spiking shall be performed before and after each sample run. QA
spiking shall be performed after the pre- and post-test CTS direct
and system calibrations. The system biases calculated from the pre-
and post-test dynamic analyte spiking shall be within 30
percent for the spiked surrogate analytes for the measurements to be
considered valid. See sections 9.3.1 through 9.3.2 for the requisite
calculations. Measurement of the undiluted spike (direct-to-cell
measurement) involves sending dry, spike gas to the FTIR cell,
filling the cell to 1 atmosphere and obtaining the spectrum of this
sample. The direct-to-cell measurement should be performed before
each analyte spike so that the recovery of the dynamically spiked
analytes may be calculated. Analyte spiking is only effective for
assessing the integrity of the sampling system when the
concentration of HCl in the source does not vary substantially. Any
attempt to quantify an analyte recovery in a variable concentration
matrix will result in errors in the expected concentration of the
spiked sample. If the kiln gas target analyte concentrations vary by
more than 5 percent (or 5 ppm, whichever is greater) in
the time required to acquire a sample spectrum, it may be necessary
to: (1) Use a dual sample probe approach, (2) use two independent
FTIR measurement systems, (3) use alternate QA/QC procedures, or (4)
postpone testing until stable emission concentrations are achieved.
(See section 9.2.3 of this method). It is recommended that a
laboratory evaluation be performed before attempting to employ this
method under actual field conditions. The laboratory evaluation
shall include (1) performance of all applicable calculations in
section 4 of the FTIR Protocol; (2) simulated analyte spiking
experiments in dry (ambient) and humidified sample matrices using
HCl; and (3) performance of bias (recovery) calculations from
analyte spiking experiments. It is not necessary to perform a
laboratory evaluation before every field test. The purpose of the
laboratory study is to demonstrate that the actual instrument and
sampling system configuration used in field testing meets the
requirements set forth in this method.
9.1 Spike Materials. Perform analyte spiking with an HCl
standard to demonstrate the integrity of the sampling system.
9.1.1 An HCl standard of approximately 50 ppm in a balance of
ultra pure nitrogen is recommended. The SF6 (tracer)
concentration shall be 2 to 5 ppm depending upon the measurement
pathlength. The spike ratio (spike flow/total flow) shall be no
greater than 1:10, and an ideal spike concentration should
approximate the native effluent concentration.
9.1.2 The ideal spike concentration may not be achieved because
the target concentration cannot be accurately predicted prior to the
field test, and limited calibration standards will be available
during testing. Therefore, practical constraints must be applied
that allow the tester to spike at an anticipated concentration. For
these tests, the analyte concentration contributed by the HCl
standard spike should be 1 to 5 ppm or should more closely
approximate the native concentration if it is greater.
[[Page 31959]]
9.2 Spike Procedure
9.2.1 A spiking/sampling apparatus is shown in Figure 2.
Introduce the spike/tracer gas mixture at a constant flow
(2 percent) rate at approximately 10 percent of the
total sample flow. (For example, introduce the surrogate spike at 1
L/min 20 cc/min, into a total sample flow rate of 10 L/min). The
spike must be pre-heated before introduction into the sample matrix
to prevent a localized condensation of the gas stream at the spike
introduction point. A heated sample transport line(s) containing
multiple transport tubes within the heated bundle may be used to
spike gas up through the sampling system to the spike introduction
point. Use a calibrated flow device (e.g., mass flow meter/
controller), to monitor the spike flow as indicated by a calibrated
flow meter or controller, or alternately, the SF6 tracer
ratio may be calculated from the direct measurement and the diluted
measurement. It is often desirable to use the tracer approach in
calculating the spike/total flow ratio because of the difficulty in
accurately measuring hot/wet total flow. The tracer technique has
been successfully used in past validation efforts (Reference 1).
9.2.2 Perform a direct-to-cell measurement of the dry,
undiluted spike gas. Introduce the spike directly to the FTIR cell,
bypassing the sampling system. Fill cell to 1 atmosphere and collect
the spectrum of this sample. Ensure that the spike gas has
equilibrated to the temperature of the measurement cell before
acquisition of the spectra. Inspect the spectrum and verify that the
gas is dry and contains negligible CO2. Repeat the
process to obtain a second direct-to-cell measurement. Analysis of
spectral band areas for HCl from these duplicate measurements should
agree to within 5 percent of the mean.
9.2.3 Analyte Spiking. Determine whether the kiln gas contains
native concentrations of HCl by examination of preliminary spectra.
Determine whether the concentration varies significantly with time
by observing a continuously up-dated spectrum of sample gas in the
flow-through sampling mode. If the concentration varies by more than
5 percent during the period of time required to acquire
a spectra, then an alternate approach should be used. One alternate
approach uses two sampling lines to convey sample to the gas
distribution manifold. One of the sample lines is used to
continuously extract unspiked kiln gas from the source. The other
sample line serves as the analyte spike line. One FTIR system can be
used in this arrangement. Spiked or unspiked sample gas may be
directed to the FTIR system from the gas distribution manifold, with
the need to purge only the components between the manifold and the
FTIR system. This approach minimizes the time required to acquire an
equilibrated sample of spiked or unspiked kiln gas. If the source
varies by more than 5 percent (or 5 ppm, whichever is
greater) in the time it takes to switch from the unspiked sample
line to the spiked sample line, then analyte spiking may not be a
feasible means to determine the effectiveness of the sampling system
for the HCl in the sample matrix. A second alternative is to use two
completely independent FTIR measurement systems. One system would
measure unspiked samples while the other system would measure the
spiked samples. As a last option, (where no other alternatives can
be used) a humidified nitrogen stream may be generated in the field
which approximates the moisture content of the kiln gas. Analyte
spiking into this humidified stream can be employed to assure that
the sampling system is adequate for transporting the HCl to the FTIR
instrumentation.
9.2.3.1 Adjust the spike flow rate to approximately 10 percent
of the total flow by metering spike gas through a calibrated mass
flowmeter or controller. Allow spike flow to equilibrate within the
sampling system before analyzing the first spiked kiln gas samples.
A minimum of two consecutive spikes are required. Analysis of the
spectral band area used for quantification should agree to within
5 percent or corrective action must be taken.
9.2.3.2 After QA spiking is completed, the sampling system
components shall be purged with nitrogen or dry air to eliminate
traces of the HCl compound from the sampling system components.
Acquire a sample spectra of the nitrogen purge to verify the absence
of the calibration mixture.
9.2.3.3 Analyte spiking procedures must be carefully executed
to ensure that meaningful measurements are achieved. The
requirements of sections 9.2.3.3.1 through 9.2.3.3.4 shall be met.
9.2.3.3.1 The spike must be in the vapor phase, dry, and heated
to (or above) the kiln gas temperature before it is introduced to
the kiln gas stream.
9.2.3.3.2 The spike flow rate must be constant and accurately
measured.
9.2.3.3.3 The total flow must also be measured continuously and
reliably or the dilution ratio must otherwise be verified before and
after a run by introducing a spike of a non-reactive, stable
compound (i.e., tracer).
9.2.3.3.4 The tracer must be inert to the sampling system
components, not contained in the effluent gas, and readily detected
by the analytical instrumentation. Sulfur hexafluoride
(SF6) has been used successfully (References 1 and 2) for
this purpose.
9.3 Calculations
9.3.1 Recovery. Calculate the percent recovery of the spiked
analytes using equations 1 and 2.
[GRAPHIC] [TIFF OMITTED] TR14JN99.033
Sm = Mean concentration of the analyte spiked effluent
samples (observed).
[GRAPHIC] [TIFF OMITTED] TR14JN99.034
Ce = Expected concentration of the spiked samples
(theoretical).
Df = dilution Factor (Total flow/Spike flow). total flow
= spike flow plus effluent flow.
Cs = cylinder concentration of spike gas.
Su = native concentration of analytes in unspiked
samples.
The spike dilution factor may be confirmed by measuring the total
flow and the spike flow directly. Alternately, the spike dilution
can be verified by comparing the concentration of the tracer
compound in the spiked samples (diluted) to the tracer concentration
in the direct (undiluted) measurement of the spike gas.
If SF6 is the tracer gas, then
[GRAPHIC] [TIFF OMITTED] TR14JN99.035
[SF6]spike = the diluted SF6
concentration measured in a spiked sample.
[SF6]direct = the SF6 concentration
measured directly.
9.3.2 Bias. The bias may be determined by the difference
between the observed spike value and the expected response (i.e.,
the equivalent concentration of the spiked material plus the analyte
concentration adjusted for spike dilution). Bias is defined by
section 6.3.1 of EPA Method 301 of this appendix (Reference 8) as,
[GRAPHIC] [TIFF OMITTED] TR14JN99.036
Where:
B = Bias at spike level.
Sm = Mean concentration of the analyte spiked samples.
Ce = Expected concentration of the analyte in spiked
samples.
Acceptable recoveries for analyte spiking are 30
percent. Application of correction factors to the data based upon
bias and recovery calculations is subject to the approval of the
Administrator.
10.0 Calibration and Standardization
10.1 Calibration transfer standards (CTS). The EPA Traceability
Protocol gases or NIST traceable standards, with a minimum accuracy
of 2 percent shall be used. For other requirements of
the CTS, see the FTIR Protocol section 4.5.
10.2 Signal-to-Noise Ratio (S/N). The S/N shall be less than
the minimum acceptable measurement uncertainty in the analytical
regions to be used for measuring HCl.
10.3 Absorbance Pathlength. Verify the absorbance path length
by comparing CTS spectra to reference spectra of the calibration
gas(es).
10.4 Instrument Resolution. Measure the line width of
appropriate CTS band(s) to verify instrumental resolution.
10.5 Apodization Function. Choose the appropriate apodization
function. Determine any appropriate mathematical transformations
that are required to correct instrumental errors by measuring the
CTS. Any mathematical transformations must be documented and
reproducible. Reference 9 provides additional information about FTIR
instrumentation.
11.0 Analytical Procedure
A full description of the analytical procedures is given in
sections 4.6-4.11, sections 5, 6, and 7, and the appendices of the
FTIR Protocol. Additional description of quantitative spectral
analysis is provided in References 10 and 11.
[[Page 31960]]
12.0 Data Analysis and Calculations
Data analysis is performed using appropriate reference spectra
whose concentrations can be verified using CTS spectra. Various
analytical programs (References 10 and 11) are available to relate
sample absorbance to a concentration standard. Calculated
concentrations should be verified by analyzing spectral baselines
after mathematically subtracting scaled reference spectra from the
sample spectra. A full description of the data analysis and
calculations may be found in the FTIR Protocol (sections 4.0, 5.0,
6.0 and appendices).
12.1 Calculated concentrations in sample spectra are corrected
for differences in absorption pathlength between the reference and
sample spectra by
[GRAPHIC] [TIFF OMITTED] TR14JN99.037
Where:
Ccorr = The pathlength corrected concentration.
Ccalc = The initial calculated concentration (output of
the multicomponent analysis program designed for the compound).
Lr = The pathlength associated with the reference
spectra.
Ls = The pathlength associated with the sample spectra.
Ts = The absolute temperature (K) of the sample gas.
Tr = The absolute temperature (K) at which reference
spectra were recorded.
12.2 The temperature correction in equation 5 is a volumetric
correction. It does not account for temperature dependence of
rotational-vibrational relative line intensities. Whenever possible,
the reference spectra used in the analysis should be collected at a
temperature near the temperature of the FTIR cell used in the test
to minimize the calculated error in the measurement (FTIR Protocol,
appendix D). Additionally, the analytical region chosen for the
analysis should be sufficiently broad to minimize errors caused by
small differences in relative line intensities between reference
spectra and the sample spectra.
13.0 Method Performance
A description of the method performance may be found in the FTIR
Protocol. This method is self validating provided the results meet
the performance specification of the QA spike in sections 9.0
through 9.3 of this method.
14.0 Pollution Prevention
This is a gas phase measurement. Gas is extracted from the
source, analyzed by the instrumentation, and discharged through the
instrument vent.
15.0 Waste Management
Gas standards of HCl are handled according to the instructions
enclosed with the material safety data sheet.
16.0 References
1. ``Laboratory and Field Evaluation of a Methodology for
Determination of Hydrogen Chloride Emissions From Municipal and
Hazardous Waste Incinerators,'' S.C. Steinsberger and J.H. Margeson.
Prepared for U.S. Environmental Protection Agency, Research Triangle
Park, NC. NTIS Report No. PB89-220586. (1989).
2. ``Evaluation of HCl Measurement Techniques at Municipal and
Hazardous Waste Incinerators,'' S.A. Shanklin, S.C. Steinsberger,
and L. Cone, Entropy, Inc. Prepared for U.S. Environmental
Protection Agency, Research Triangle Park, NC. NTIS Report No. PB90-
221896. (1989).
3. ``Fourier Transform Infrared (FTIR) Method Validation at a
Coal Fired-Boiler,'' Entropy, Inc. Prepared for U.S. Environmental
Protection Agency, Research Triangle Park, NC. EPA Publication No.
EPA-454/R95-004. NTIS Report No. PB95-193199. (1993).
4. ``Field Validation Test Using Fourier Transform Infrared
(FTIR) Spectrometry To Measure Formaldehyde, Phenol and Methanol at
a Wool Fiberglass Production Facility.'' Draft. U.S. Environmental
Protection Agency Report, Entropy, Inc., EPA Contract No. 68D20163,
Work Assignment I-32.
5. Kinner, L.L., Geyer, T.G., Plummer, G.W., Dunder, T.A.,
Entropy, Inc. ``Application of FTIR as a Continuous Emission
Monitoring System.'' Presentation at 1994 International Incineration
Conference, Houston, TX. May 10, 1994.
6. ``Molecular Vibrations; The Theory of Infrared and Raman
Vibrational Spectra,'' E. Bright Wilson, J.C. Decius, and P.C.
Cross, Dover Publications, Inc., 1980. For a less intensive
treatment of molecular rotational-vibrational spectra see, for
example, ``Physical Chemistry,'' G.M. Barrow, chapters 12, 13, and
14, McGraw Hill, Inc., 1979.
7. ``Laboratory and Field Evaluations of Ammonium Chloride
Interference in Method 26,'' U.S. Environmental Protection Agency
Report, Entropy, Inc., EPA Contract No. 68D20163, Work Assignment
No. I-45.
8. 40 CFR 63, appendix A. Method 301--Field Validation of
Pollutant Measurement Methods from Various Waste Media.
9. ``Fourier Transform Infrared Spectrometry,'' Peter R.
Griffiths and James de Haseth, Chemical Analysis, 83, 16-25, (1986),
P.J. Elving, J.D. Winefordner and I.M. Kolthoff (ed.), John Wiley
and Sons.
10. ``Computer-Assisted Quantitative Infrared Spectroscopy,''
Gregory L. McClure (ed.), ASTM Special Publication 934 (ASTM), 1987.
11. ``Multivariate Least-Squares Methods Applied to the
Quantitative Spectral Analysis of Multicomponent Mixtures,'' Applied
Spectroscopy, 39(10), 73-84, 1985.
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[GRAPHIC] [TIFF OMITTED] TR14JN99.039
[FR Doc. 99-12893 Filed 6-11-99; 8:45 am]
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