[Federal Register Volume 60, Number 201 (Wednesday, October 18, 1995)]
[Proposed Rules]
[Pages 53988-54006]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 95-25775]
[[Page 53987]]
_______________________________________________________________________
Part III
Environmental Protection Agency
_______________________________________________________________________
40 CFR Part 136
Guidelines Establishing Test Procedures for the Analysis of Pollutants:
New Methods; Proposed Rule
Federal Register / Vol. 60, No. 201 / Wednesday, October 18, 1995 /
Proposed Rules
[[Page 53988]]
ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 136
[FRL-5308-4]
Guidelines Establishing Test Procedures for the Analysis of
Pollutants: New Methods
AGENCY: Environmental Protection Agency (EPA).
ACTION: Proposed rule and request for comment.
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SUMMARY: Under the Clean Water Act, Section 304(h), EPA proposes to
amend its list of approved analytical techniques by adding new or
revised test procedures for certain metal and inorganic chemical
pollutants, by adding method citations to Table IB and by amending the
incorporation by reference section of the regulation accordingly.
EPA is also proposing to substitute reagents that are more
environmentally friendly for certain hazardous and toxic chemical
reagents currently used in certain approved methods.
In addition, EPA is proposing to withdraw approval of certain
outdated or little used analytical methods, as well as, certain methods
that require the use of hazardous or toxic reagents. For each method
that is proposed for withdrawal, one or more commonly used methods have
been previously approved.
Comments are requested on this proposed rulemaking. After
considering comments received in response to this proposal, EPA will
promulgate a final rule.
This action amends guidelines establishing test procedures for the
analysis of pollutants by adding clarifying notes to lists of approved
test procedures, by adding and updating certain method citations in
Tables IB and IC, and by amending the incorporation by reference
section of the regulation accordingly.
DATES: Comments on the proposed amendments will be accepted until
December 18, 1995.
ADDRESSES: Send written comments to the 304(h) Docket Clerk (Ben
Honaker), Water Docket (MC-4101), U.S. Environmental Protection Agency,
401 M Street, SW., Washington, DC 20460. Please submit any references
cited in your comments. EPA would appreciate an original and three
copies of your comments and enclosures (including references).
Commenters who want EPA to acknowledge receipt of their comments should
enclose a self-addressed, stamped envelope. No facsimiles (faxes) will
be accepted because EPA cannot assure that they will be submitted to
the Water Docket.
The supporting materials are available for review at the Water
Docket at the address above. For access to Docket Materials, call (202)
260-3027 between 9 am and 3:30 pm for an appointment.
FOR FURTHER INFORMATION CONTACT: Mr. James E. Longbottom, Aquatic
Research Division, National Exposure Research Laboratory, Office of
Research and Development, U.S. Environmental Protection Agency,
Cincinnati, Ohio 45268. Telephone number: (513) 569-7308.
SUPPLEMENTARY INFORMATION:
Materials in the public docket include:
``Methods for the Determination of Metals in Environmental
Samples'' Supplement I, EPA-600/R-94/111, May 1994.
``Methods for the Determination of Inorganic Substances in
Environmental Samples'', EPA-600/R-93/100, August 1993.
``Determination of Trace Elements in Water by Inductively
Coupled Plasma-Mass Spectrometry: Collaborative Study'', Journal of
AOAC-International, 77, pp. 1004-1023, 1994.
``Determination of Inorganic Anions in Water by Ion
Chromatography: Collaborative Study'', Journal of AOAC-International,
77, pp. 1253-1263, 1994.
``Ion Chromatographic Method for Dissolved Hexavalent
Chromium in Drinking Water, Ground Water, and Industrial Wastewater
Effluents: Collaborative Study'', Journal of AOAC-International, 77,
pp. 994-1004, 1994.
``Low-level Chlorine Analysis by Amperometric Titration'',
Journal of the Water Pollution Control Federation, 51, pp. 2636-2640,
1979.
A copy of the first two items can also be obtained from EPA through
a facsimile request to the Chemistry Research Branch, Aquatic Research
Division, Cincinnati, Ohio, on (513) 569-7757.
I. Authority
This regulation is proposed under authority of sections 301, 304(h)
and 501(a) of the Clean Water Act, 33 U.S.C. 1251 et seq. (the Federal
Water Pollution Control Act Amendments of 1972 as amended) (the
``Act''). Section 301 prohibits the discharge of any pollutant into
navigable waters unless the discharge complies with a NPDES permit,
issued under Section 402 of the Act. Section 304(h) of the Act requires
the Administrator of the EPA to ``promulgate guidelines establishing
test procedures for the analysis of pollutants that shall include the
factors which must be provided in any certification pursuant to section
401 of this Act or permit application pursuant to section 402 of this
Act''. Section 501(a) of the Act authorizes the Administrator to
``prescribe such regulations as are necessary to carry out his
functions under this Act''.
The use of approved test procedures or approved alternate
procedures is required whenever the waste constituent specified is
required to be measured for: an NPDES permit application; discharge
monitoring reports; state certification; and other requests from the
permitting authority for quantitative or qualitative effluent data. Use
of approved test procedures is also required for the expression of
pollutant amounts, characteristics, or properties in effluent
limitations guidelines and standards of performance and pretreatment
standards, unless otherwise specifically noted or defined.
II. Regulatory Background
The CWA establishes two principal bases for effluent limitations.
First, existing discharges are required to meet technology-based
effluent limitations. New source discharges must meet new source
performance standards based on the best demonstrated technology-based
controls. Second, where necessary, additional requirements are imposed
to assure attainment and maintenance of water quality standards
established by the States under Section 303 of the CWA. In establishing
or reviewing NPDES permit limits, EPA must ensure that permitted
discharges will not cause or contribute to a violation of water quality
standards, including designated water uses.
For use in permit applications, discharge monitoring reports, and
state certification and to ensure compliance with effluent limitations,
standards of performance, and pretreatment standards, EPA has
promulgated regulations providing nationally-approved testing
procedures at 40 CFR Part 136. Test procedures have previously been
approved for 262 different parameters. Those procedures apply to the
analysis of inorganic (metal, non-metal, mineral) and organic chemical
(including pesticides), radiological, biological, nutrient, demand,
residue, and physical parameters.
Additionally, some particular industries may discharge pollutants
for which test procedures have not been proposed and approved under 40
CFR Part 136. Under 40 CFR 122.41 permit writers may impose monitoring
[[Page 53989]]
requirements and establish test methods for pollutants for which no
approved Part 136 method exists. 40 CFR 122.41(j) (4). EPA may also
approve additional test procedures when establishing industry-wide
technology-based effluent limitations guidelines and standards as
described at 40 CFR 401.13.
The procedures for approval of alternate test procedures (ATPs) are
described at 40 CFR 136.4 and 136.5. Under these procedures the
Administrator may approve alternate test procedures for nationwide use
which are developed and proposed by any person. 40 CFR 136.4 (a).
Persons wishing to use such alternate procedures, must apply to the
State or Regional EPA permitting office [for limited approval under
136.4 (b)], and to the Director of the Environmental Monitoring Systems
Laboratory in Cincinnati [for nationwide approval under 136.4 (d)]. As
specified below, today's proposed rule would approve additional
nationwide test procedures for certain metals, anions, Cr(VI) and VOCs
in wastewater and related samples.
III. Summary of Proposed Methods
The proposed methods have been reviewed by appropriate members of
and written in the EPA Environmental Monitoring Management Council
Format.
The methods proposed for addition include new methods for:
preparation of samples for metals analysis, inductively coupled plasma/
mass spectrometry (ICP/MS), a stabilized temperature graphite furnace
atomic absorption (STGFAA) method for metals, and ion chromatography
(IC) methods for anions and for hexavalent chromium [Cr(VI)]. A revised
EPA inductively coupled plasma atomic emission spectrometry (ICP-AES)
method for metals to replace the currently approved method, and a low-
level extension of the approved method for the determination of low
level total residual chlorine are also being proposed.
Methods 200.7, 200.8, and 200.9 were approved for use in EPA's
drinking water programs at 40 CFR Part 141.23(k)(1) on December 5, 1994
(59 FR 62466). When the methods proposed today are promulgated at 40
CFR Part 136 for use in EPA's wastewater programs, these three methods
will be conformed for the two programs.
Although not part of today's proposal, the Agency's Environmental
Monitoring Management Council (EMMC) will soon propose integrated
methods for citation in several regulations, including those at Part
136. The methods include a graphite furnace atomic absorption
spectrometry method for certain metals and an inductively coupled
plasma atomic emissions spectrometry method for metals. These methods
may be included in the final rule for today's proposal.
In the interest of pollution prevention, EPA is proposing to
replace mercuric sulfate with copper sulfate in the total Kjeldahl
nitrogen methods and to permit the substitution of the AMCO-AEPA-1
Standard for the formazin standard in the turbidity method. Replacement
of these two reagents would remove hazardous or potentially
carcinogenic chemicals from use in EPA approved methods.
A. Sample Preparation for Total Recoverable Elements
EPA is proposing a new broad-purpose digestion procedure for total
recoverable elements. It has the advantage of being compatable with
several of the approved measurement techniques, which will allow
laboratories to achieve some cost savings by reducing preparations and
increasing flexibility in choosing approved analytical techniques after
digestion. This preparation procedure is a variation of the procedures
given in the previously approved EPA 200 Series Methods for ``total
recoverable'' metals published in ``Methods for Chemical Analysis of
Water and Wastes''. It utilizes the same acid combination (nitric +
hydrochloric) as the previous ``total recoverable'' procedures, but the
acid concentration has been modified by lowering the amount of
hydrochloric acid.
This sample preparation procedure has been incorporated into three
EPA Methods proposed today, including, a May 1994 revision of the
approved ICP/AES Method 200.7, a new measurement technology ICP/MS
Method 200.8, and a stabilized temperature graphite furnace automatic
absorption (GFAA) method (Method 200.9). In addition, EPA has prepared
a stand-alone version of the digestion procedure: Method 200.2 ``Sample
Preparation Procedure for Spectrochemical Determination of Total
Recoverable Elements''. EPA proposes to permit the substitution of
Method 200.2 for the digestion procedure in certain non-EPA approved
direct aspiration flame atomic absorption procedures. The digestion
procedure has been tested on various matrices using determinative
methods 200.7, 200.8 and 200.9 and has been found comparable to
previously approved NPDES preparation procedures. Method 200.2 was also
validated through interlaboratory testing in the joint EPA/AOAC
International study of Method 200.8. Each of the new EPA procedures
includes: a list of elements to which it applies, sample preservation
practices, and preparation conditions.
EPA proposes to withdraw the EPA AA direct aspiration and AA
furnace methods contained in ``Methods for Chemical Analysis of Water
and Wastes''. The methods are out of date and lack many of the
necessary instructions included in more recently produced EPA methods.
The remaining approved non-EPA methods for AA direct aspiration are
sufficiently identical to the withdrawn methods as to result in no
impact on the regulated community. The EPA furnace methods are being
replaced by EPA Method 200.9. Appendix D to this regulation, which
contains the interlaboratory measures of precision and accuracy for the
EPA methods that are being withdrawn, would also be removed by this
proposal.
B. Elemental Analysis by ICP/AES
The EPA proposes to approve the May 1994 revision of Method 200.7,
``Determination of Metals and Trace Elements in Water and Wastes by
Inductively Coupled Plasma-Atomic Emission Spectrometry'' and to cite
the revised method by reference. Accordingly, Appendix C to 40 CFR Part
136 would be deleted. The May 1994 edition of the method has been
demonstrated to produce precision and recovery for the applicable
elements that is equal to or better than that achieved by the currently
approved edition and published in Table 4 of Appendix C. The procedure
includes: A list of elements to which it applies, sample collection
practices, preparation conditions, and quality control practices. The
EMMC inductively coupled plasma-atomic emission spectrometry method
being proposed elsewhere is proposed to be interchangeable with Method
200.7 for the purposes of this regulation.
C. Elemental Analysis by ICP/MS
The Agency is proposing a new multielement test procedure, ICP/MS,
Method 200.8 ``Determination of Trace Elements in Waters and Wastes by
Inductively Coupled Plasma-Mass Spectrometry'' for the detection and
quantification of 20 metals in aqueous samples. Sample material in
solution is introduced by pneumatic nebulization into a radio-frequency
plasma where energy transfer processes cause desolvation, atomization
and ionization. The ions are extracted from the plasma through a
differentially pumped vacuum interface and separated on the basis of
their mass-to-charge ratio by a
[[Page 53990]]
quadrupole mass spectrometer having a minimum resolution capability of
1 amu peak width at 5% peak height. The ions transmitted through the
quadrupole are registered by an electron multiplier or Faraday detector
and the ion information processed by a data handling system.
Interferences relating to the technique must be identified and results
must be corrected accordingly. Such corrections must include
compensation for isobaric elemental interferences and interferences
from polyatomic ions derived from the plasma gas, reagents or sample
matrix. Instrumental drift, as well as suppressions or enhancements of
instrument response caused by the sample matrix, must be corrected by
the use of internal standardization.
The Agency developed ICP/MS Method 200.8 under a contract and in
cooperation with AOAC International jointly conducted an
interlaboratory validation study of the method. This method (May 1994)
represents the current state-of-the-art for the determination of metals
in wastewater and water related media. The method description includes
a list of the elements to which the method applies, sample collection
practices, recommended analytical conditions, quality control
practices, instrumental and method detection limits, and performance
criteria based on the interlaboratory study data.
AOAC-International has approved and published this ICP/MS method
along with the study results as AOAC-International Method 993.14. The
same method is in the final stages of the ASTM consensus process. EPA
proposes to approve the AOAC-International method, as well as, consider
approval of the ASTM ICP/MS Method if full ASTM Society acceptance is
achieved prior to final EPA rulemaking.
D. Elemental Analysis by Stabilized Temperature Platform GFAA
The May 1994 Revision of Method 200.9 ``Determination of Trace
Metals by Stabilized Temperature Graphite Furnace Atomic Absorption''
is being proposed as a replacement for the currently approved EPA
furnace methods. Method 200.9 determines elements by stabilized
temperature graphite furnace atomic absorption (STGFAA). In STGFAA, the
sample and required matrix modifier are first pipetted onto the
platform or a device which provides delayed atomization. The sample is
then dried at a relatively low temperature (120 deg.C) to
avoid spattering. Once dried, the sample is normally pretreated in a
char or ashing step which is designed to minimize the interference
effects caused by the concomitant sample matrix. After the char step,
the furnace is allowed to cool prior to atomization. The atomization
cycle is characterized by rapid heating of the furnace to a temperature
where the metal (analyte) is atomized from the pyrolytic graphite
surface. The resulting atomic cloud absorbs the element specific atomic
emission produced by a hollow cathode lamp or a electrodeless discharge
lamp.
Because the resulting absorbance usually has a nonspecific
component associated with the actual analyte absorbance, an
instrumental background correction device is necessary to subtract from
the total signal the component which is nonspecific to the analyte. In
the absence of interferences, the background corrected absorbance is
directly related to the concentration of the analyte. Interferences
relating to suppression or enhancement of instrument response caused by
the sample matrix, must be corrected by the method of standard
addition.
The method description includes a list of elements to which the
method applies, sample collection practices, recommended analytical
conditions, quality control practices, method detection limits and
performance criteria based on single laboratory study data. The EMMC
furnace atomic absorption method being proposed elsewhere is proposed
to be interchangeable with Method 200.9 for the purposes of this
regulation.
E. Anions by Ion Chromatography
EPA developed IC Method 300.0 for the following anions: Bromide,
chloride, fluoride, nitrate-N, nitrite-N, ortho-phosphate, and sulfate.
Using IC, a water sample is injected into a stream of carbonate-
bicarbonate eluent and passed through a series of ion exchangers. The
anions of interest are separated on the basis of their relative
affinities for a low capacity, strongly basic anion exchanger (guard
and separator columns). The separated anions are directed through a
hollow fiber cation exchanger membrane (fiber suppressor) or
micromembrane suppressor bathed in continuously flowing strongly acid
solution (regenerant solution). In the suppressor the separated anions
are converted to their highly conductive acid forms and the carbonate-
bicarbonate eluent is converted to weakly conductive carbonic acid. The
separated anions in their acid forms are measured by conductivity. They
are identified on the basis of retention time as compared to reference
standards. Quantitation is by measurement of peak area or peak height.
EPA, in cooperation with ASTM Committee D-19 on Water, has
conducted an interlaboratory validation study of EPA method 300.0 ``The
Determination of Inorganic Anions in Water by Ion Chromatography'',
August 1993. The method represents current state-of-the-art for
determination of the anions listed above. The method description
includes: Sample collection practices, recommended analytical
conditions, quality control practices and estimated detection limits
for the applicable analytes and performance criteria based on the
interlaboratory study data. ASTM, Standard Methods, and AOAC-
International have approved the method under their consensus systems
and have published the method in their Books of Standards. EPA also
proposes to approve the ASTM Method D-4327, as well as, Method 4110 B
published in the 18th edition of ``Standard Methods for the Examination
of Water and Wastewater'' (SMEWW) and AOAC-International Method 993.30
all of which were derived from EPA Method 300.0.
F. Cr (VI) by Ion Chromatography
Using the IC Cr(VI) Method (Method 218.6), an aqueous sample is
filtered through a 0.45 m filter and the filtrate is adjusted
to a pH of 9 to 9.5 with a buffer solution. A measured volume of sample
(50-250 l) is introduced into the ion chromatograph. A guard
column is employed to remove organics from the sample prior to
separation of Cr(VI) as CrO4-2 on an anion exchange separator
column. Cr(VI) is determined by post column derivatization with
diphenylcarbazide and passing through a low-volume flow-through cell
and detection of the colored complex with a visible lamp detector at
530 nm.
EPA, in cooperation with ASTM Committee D-19 on Water, has
conducted an interlaboratory validation study of EPA Method 218.6
``Determination of Dissolved Hexavalent Chromium in Drinking Water,
Ground Water, and Industrial Wastewater Effluents by Ion
Chromatography''. The method description includes: Sample collection
practices, recommended analytical conditions, quality control practices
and method detection limits for Cr(VI), as well as performance criteria
based on the interlaboratory study data.
ASTM, Standard Methods, and AOAC-International have approved this
method as a standard test method under their consensus systems and have
published it in their manuals of methods. EPA also proposes to approve
the ASTM Method D-5257, Standard Methods Method 3500-Cr E, and
[[Page 53991]]
Method 993.23 from the AOAC-International Official Methods of Analysis,
16th Edition. All three of these methods were derived from EPA Method
218.6.
G. Method for Determination of Low Level Residual Chlorine
EPA is proposing to additionally approve SMEWW, Method 4500-Cl E
for the detection and quantification of low levels of chlorine in
water. This method is a minor modification of the approved amperometric
Method 4500-Cl D and is capable of measuring down to 10 g/L
chlorine. Federal and State permitting authorities have requested such
a method in order to assess compliance with effluent limits based on
EPA and State water quality criteria for chlorine. Supporting
performance data for the method can be found at Journal of the Water
Pollution Control Federation, Vol. 51, pages 2636-2640 (1979), a copy
of which is included in the docket for this proposal.
H. Replacement of Mercury Catalyst in Total Kjeldahl Nitrogen Methods
Due to demonstrated toxic hazards of mercuric sulfate, and
difficulty of disposal of laboratory wastes, EPA is proposing to
replace this chemical with copper sulfate in the total Kjeldahl
Nitrogen Methods. Copper sulfate exhibits significantly less toxicity
than mercuric sulfate. The European community has already eliminated
mercuric chloride from their total nitrogen methods in favor of less
toxic catalysts.
I. EPA is proposing to amend EPA Method 180.1--Turbidity by
accepting the use of styrene divinylbenzene beads (AMCO-AEPA-1
Standard) as a substitute for the presently used formazine standard,
which is prepared from hydrazine sulfate. The AEPA-1 Standard is an
alternate to formazine in the previously approved Standard Methods,
Method 2130 B. This substitution will eliminate the need to use
hydrazine sulfate, a known carcinogen.
J. EPA is proposing to delete liquid-liquid extraction (LLE)
methods, including EPA Methods 611 and 625 and Standard Methods Method
6410 B, as approved procedures for 1,2-dichlorobenzene, 1,3-
dichlorobenzene, and 1,4-dichlorobenzene. While these compounds can be
determined by these LLE methods, due to their volatility, significant
losses can occur when using the prescribed sample collection procedures
in the LLE methods resulting in low recovery of these compounds. These
compounds are more properly analyzed by EPA Method 624 or Method 1625
(an isotope-dilution method that compensates for any evaporation
losses).
K. EPA proposes to delete extraneous method citations, including
those EPA methods that reference another source for method details and
certain older EPA methods that are readily available from another
source. Some measurement technologies are proposed for removal because
they are no longer supported by the group that authored them or they
use toxic reagents. EPA plans to provide an 18-month transition period
after final rule to permit continued use of these methods following the
practice of the drinking water program (see 59 FR 62456). These
deletions include: colorimetric methods for cadmium, lead and zinc
(dithizone), copper (neocuprione), nickel (heptoxime), nitrate-nitrite
(automated hydrazine), potassium (cobaltinitrite), vanadium (gallic
acid); AA furnace methods for gold, iridium, platinum, rhodium,
ruthenium, titanium, and zinc; flame phometric methods for potassium
and sodium; voltametry for cadmium and lead; titration (mercuric
nitrate) for chloride; and the AA chelation-extraction for total
chromium. Table IB of Part 136(a) would be further revised to reorder
and clarify footnotes and method citations.
IV. Request for Comments
The Agency requests general comments on its policy to remove or
reject methods from this regulation on the basis of pollution
prevention when comparable approved methods are available. Comments on
the specific methods removed today are also solicited, as well as,
comments on other pollution prevention changes that should be
considered by the Agency. EPA considered the elimination of the Nessler
method for Total Kjeldahl because the Nessler reagent contains 10%
mercuric iodide. However, an assessment of the data submitted by
participants in recent Water Pollution (WP) performance evaluation
studies indicated that the Nessler method is broadly used and produces
above-average data compared to the other approved methods. Further, the
Nessler method may be necessary to this regulation because it is more
sensitive than the other methods. The Agency requests comments on
whether the Nessler methods should be removed from Part 136.
V. Regulatory Requirements
A. Executive Order 12866
Under Executive Order 12866, EPA must determine whether a
regulation is ``significant'' and, therefore subject to OMB review and
the requirements of the Executive Order. EPA has determined that this
regulation is not a ``significant regulatory action'' under the terms
of Executive Order 12866 and is therefore not subject to OMB review.
This rule will not result in an effect on the economy of $100 million
or more, a significant increase in cost or prices, or any of the
effects described in the Executive Order. This proposed rule simply
specifies analytical techniques which may be used by laboratories in
measuring concentrations of certain metals and, therefore, has no
adverse economic impacts.
B. Regulatory Flexibility Act
This proposed amendment is consistent with the objectives of the
Regulatory Flexibility Act (5 U.S.C. 601 et seq.) because it will not
have a significant economic impact on a substantial number of small
entities. The procedures proposed in this rule give all laboratories
the flexibility to use the new proposed procedures or already approved
alternate procedures.
C. Paperwork Reduction Act
This proposed rule contains no requests for information activities
and, therefore, no information collection request (ICR) was submitted
to the Office of Management and Budget (OMB) for review in compliance
with the Paperwork Reduction Act, 44 U.S.C. 3501 et seq.
D. Unfunded Mandates
Under Section 202 of the Unfunded Mandates Reform Act of 1995,
signed into law on March 22, 1995, EPA must prepare a written statement
to accompany rules where the estimated costs to State, local, or tribal
governments, or to the private sector will be $100 million or more in
any one year. Under Section 205, EPA must select the most cost-
effective and least burdensome alternative that achieves the objective
of such a rule and that is consistent with statutory requirements.
Section 203 requires EPA to establish a plan for informing and advising
any small governments that may be significantly and uniquely affected
by the rule.
EPA estimates that the costs to State, local or tribal governments,
or the private sector, from this proposed rule will be far less than
$100 million. This proposed rule should have minimal impact, if any, on
the existing regulatory burden imposed on NPDES permittees required to
monitor for regulated pollutants because the proposed rule would merely
make additional options
[[Page 53992]]
available to the laboratory analyst conducting an existing approved
test method. EPA has determined that an unfunded mandates statement
therefore is unnecessary. Similarly, the methods proposed today do not
establish any regulatory requirements that might significantly or
uniquely affect small governments.
List of Subjects in 40 CFR Part 136
Environmental protection, Incorporation by reference, Water
pollution control.
Dated: October 10, 1995.
Carol M. Browner,
Administrator.
In consideration of the preceding, EPA proposes to amend part 136
of title 40 of the Code of Federal Regulations as follows:
PART 136--[AMENDED]
1. The authority citation for part 136 continues to read as
follows:
Authority: Secs. 301, 304(h), 307, and 501(a) Public Law 95-217,
Stat. 1566, et seq. (33 U.S.C. 1251 et seq. (the Federal Water
Pollution Control Act Amendments of 1972 as amended by the Clean
Water Act of 1977).
2. Section 136.3(a) is proposed to be amended by revising Table IB
to read as follows:
Sec. 136.3 Identification of test procedures.
* * * * *
[[Page 53993]]
Table IB.--List of Approved Inorganic Test Procedures
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Reference (Method No. or Page)
--------------------------------------------------------------------------------------------------------------------------------------
Parameter, Units and Method EPA\1\ AOAC-international\3\ and
Std. Methods 18th Ed. ASTM USGS\2\ others
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
1. Acidity, as CaCO3, mg/L:
Electrometric or .................... 2310 B(4a) D1067-92 ........................................ .........................
phenolphthalein endpoint.
2. Alkalinity, as CaCo3, mg/L:
Electrometric or colorimetric .................... 2320 B D1067-92 I-1030-85 973.43
titration to pH 4.5, Manual,
or.
Automated...................... \15\310.215 ............................... ............................... I-2030-85 .........................
3. Aluminum--Total\4\, mg/L:
Digestion 5,6 followed by:
AA direct aspiration....... .................... 3111 D ............................... I-3051-85 .........................
AA graphite furnace........ 200.9 3113 B ............................... ........................................ .........................
Inductively Coupled Plasma/ 200.7 3120 B ............................... ........................................ .........................
Atomic Emission
Spectrometry (ICP/AES).
Inductively Coupled Plasma/ 200.8 ............................... ............................... ........................................ 993.14
Mass Spectrometry (ICP/MS).
Direct Current Plasma .................... ............................... D4190-82(88) ........................................ Note 16
(DCP), or.
Colorimetric (Eriochrome .................... 3500-Al D ............................... ........................................ .........................
cyanine R).
4. Ammonia (as N), mg/L:
Manual, distillation (at pH 350.1 4500-NH3 B ............................... ........................................ 973.49
9.5)\7\, followed by:.
Nesslerization............. .................... 4500-NH3 C D1426-93(A) I-3520-85............................... 973.49
Titration.................. .................... 4500-NH3 E ............................... ........................................ .........................
Electrode.................. .................... 4500-NH3 F or G D1426-93(B).................... ........................................ .........................
Automated phenate, or...... 350.1 4500-NH3 H ............................... I-4523-85 .........................
Automated electrode........ .................... ............................... ............................... ........................................ Note 17
5. Antimony-Total\4\, mg/L:
Digestion5 6 followed by:
AA direct aspiration....... .................... 3111 B ............................... ........................................ .........................
AA graphite furnace........ 200.9 3113 B ............................... ........................................ .........................
ICP/AES, or................ 200.7 3120 B ............................... ........................................ .........................
ICP/MS..................... 200.8 ............................... ............................... ........................................ 993.14
6. Arsenic-Total\4\, mg/L:
Digestion5 6 followed by:
AA gaseous hydride......... .................... 3114 B 4.d D2972-93(B) I-3062-85 .........................
AA graphite furnace........ 200.9 3113 B D2972-93(C) ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
Colorimetric (SDDC)........ .................... ............................... D2972-93(A) I-3060-85 .........................
7. Barium--Total\4\ mg/L:
Digestion5 6 followed by:
AA direct aspiration....... .................... 3111 D ............................... I-3084-85 .........................
AA graphite furnace........ .................... 3113 B D4382-91 ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... ............................... ........................................ Note 16
8. Beryllium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 D D3645-93(A) I-3095-85 .........................
AA graphite furnace........ 200.9 3113 B D3645-93(B) ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS..................... 200.8 ............................... ............................... ........................................ 993.14
DCP, or.................... .................... ............................... D4190-82(88) ........................................ Note 16
Colorimetric (aluminon).... .................... 3500-Be D ............................... ........................................ .........................
9. Biochemical oxygen demand
(BOD5), mg/L:
Dissolved Oxygen Depletion..... .................... 5210 B ............................... ........................................ 973.44, p.17\18\
[[Page 53994]]
10. Boron\8\--Total, mg/L:
Colorimetric (curcumin)........ .................... 4500-B B ............................... I-3112-85............................... .........................
ICP/AES, or.................... 200.7 3120 B ............................... ........................................ .........................
DCP............................ .................... ............................... D4190-82(88) ........................................ Note 16
11. Bromide, mg/L;
Titrimetric, or................ .................... ............................... D1246-82(88)(C) I-1125-85 p. S44\19\
Ion Chromatography............. 300.0 4110 B D4327-91....................... ........................................ 993.30
12. Cadmium--Total\4\, mg/L:
Digestion\5\,\6\ followed by:
AA direct aspiration....... .................... 3111 B or C D3557-90(A or B) I-3135-85 or I-3136-85 974.2 p. 37\18\
AA graphite furnace........ 200.9 3113 B D3557-90(D) ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... D4190-82(88) ........................................ Note 16
13. Calcium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 B D511-93(B) I-3152-85 .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
DCP, or.................... .................... ............................... ............................... ........................................ Note 16
Titrimetric (EDTA)......... .................... 3500-Ca D D511-93(A) ........................................ .........................
14. Carbonaceous biochemical oxygen .................... 5210 B ............................... ........................................ .........................
demand (CBOD\5\), mg/L\9\.
Dissolved Oxygen Depletion with
nitrification inhibitor
15. Chemical oxygen demand (COD),
mg/L:
Titrimetric, or................ 410.3\15\ 5220 B D1252-88(A) I-3560-85, I-3562-85 973.46, p. 17\18\
Spectrophotometric, manual or 410.4 5220 D D1252-88(B) I-3561-85 Notes 20, 21
automated.
16. Chloride, mg/L:
Titrimetric (silver nitrate)... 4500-Cl B D512-89(B) I-1183-85 .........................
Colorimetric, Manual, or....... .................... ............................... ............................... I-1187-85............................... .........................
Automated (Ferricyanide), .................... 4500-Cl-E ............................... I-2187-85............................... .........................
or.
Ion Chromatography............. 300.0 4110 B D4327-91 ........................................ 993.30
17. Chlorine--Total residual, mg/L:
Titrimetric: Amperometric .................... 4500-Cl D or E D1253-86(92) ........................................ .........................
direct.
Iodometric direct.......... .................... 4500-Cl B ............................... ........................................ .........................
Back titration either end- 4500-Cl C ............................... ........................................ .........................
point\10\.
DPD-FAS.................... .................... 4500-Cl F ............................... ........................................ .........................
Spectrophotometric (DPD), or... .................... 4500-Cl G ............................... ........................................ .........................
Electrode...................... .................... ............................... ............................... ........................................ Note 22
18. Chromium VI dissolved, mg/L:
0.45 micron filtration followed
by:
AA chelation-extraction.... .................... 3111 C ............................... I-1232-85 .........................
Ion Chromatography, or..... 218.6 3500-Cr E\23\ D5257-93 ........................................ 993.23
Colorimetric .................... 3500-Cr D D1687-92(A) I-1230-85 .........................
(Diphenylcarbazide).
19. Chromium--Total\4\, mg/L:
Digestion\5\,\66\ followed by:
AA direct aspiration....... .................... D1687-92(B) I-3236-85 974.27
AA graphite furnace........ 200.9 3113 B D1687-92(C) ........................................ .........................
ICP/AES.................... 200.7 3120 B......................... ............................... ........................................ .........................
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... D4190-82(88) ........................................ Note 16
Colorimetric .................... 3500-Cr D ............................... ........................................ .........................
(Diphenylcarbazide).
20. Cobalt--Total\4\, mg/L:
[[Page 53995]]
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 B or C D3558-90(A or B) I-3239-85 p.37\18\
AA graphite furnace........ 200.9 3113 B D3558-90(C) ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... D4190-82(88) ........................................ Note 16
21. Color, platinum cobalt units or
dominant wavelength, hue,
luminance purity:
Colorimetric (ADMI)............ .................... 2120 E ............................... ........................................ Note 24
Colorimetric (Platinum cobalt), .................... 2120B ............................... I-1250-85............................... .........................
or.
Spectrophotometric............. .................... 2120 C ............................... ........................................ .........................
22. Copper--Total\4\, mg/L:
Digestion5,6 followed by:
AA direct aspiration....... .................... 3111 B or C D1688-90(A or B) I-3270-85 or I-3271-85 974.27p.37\18\
AA graphite furnace........ 200.9 3113 B D1688-90(C)
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS..................... 200.8 ............................... ............................... ........................................ 993.14
DCP, or.................... .................... ............................... D4190-82(88) ........................................ Note 16
Colorimetric .................... ............................... ............................... ........................................ Note 25
(Bicinchoninate).
23. Cyanide--Total, mg/L:
Manual distillation\11\ with 335.4 4500-CN C D2036-91(A) ........................................ .........................
MgCl2 followed by:
Titrimetric................ .................... 4500-CN D ............................... ........................................ p.22\19\
Spectrophotometric, manual .................... 4500-CN E D2036-91(A) I-3300-85 .........................
or.
Spectrophotometric, 335.4 ............................... ............................... ........................................ .........................
automated.
24. Cyanide amenable to
chlorination, mg/L:
Manual distillation with MgCl2, .................... 4500-CN G D2036-91(B).................... ........................................ .........................
followed by titrimetric or
spectrophotometric.
25. Fluoride--Total, mg/L:
Manual distillation\7\, .................... 4500-F B ............................... ........................................ .........................
followed by:
Electrode, Manual.......... .................... 4500-F C D1179-93(B).................... ........................................ .........................
Electrode, Automated....... .................... ............................... ............................... I-4327-85 .........................
Colorimetric (SPADNS)...... .................... 4500-F D D1179-93(A) ........................................ .........................
Colorimetric (Auto .................... 4500-F-E ............................... ........................................ .........................
complexone), or.
Ion Chromatography......... 300.0 4110 B D4327-91 ........................................ 993.30
26. Gold--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration, or... .................... 3111 B ............................... ........................................ .........................
DCP........................ .................... ............................... ............................... ........................................ Note 16
27. Hardness--Total, as CaCO\3\, mg/
L:
Automated colorimetric......... 130.1\15\ ............................... ............................... ........................................ .........................
Titrimetric (EDTA), or......... .................... 2340 B or C D1126-86(92) I-1338-85 973.52B
Ca plus Mg as their carbonates,
by ICP/AES, AA direct
aspiration, or DCP.
(Parameters 13 and 33).
28. Hydrogen ion (pH), pH units:
Electrometric measurement, or.. .................... 4500-H+ B D1293-84(90) (A or B) I-1586-85 973.41
Automated electrode............ 150.2\15\ ............................... ............................... ........................................ Note 26
29. Iridium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 B ............................... ........................................ .........................
30. Iron--Total\4\, mg/L:
Digestion5,6 followed by:
AA direct aspiration....... .................... 3111 B D D1068-90(A or B) I-3381-85 974.27
AA graphite furnace........ 200.9 3113 B D1068-90(C) ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
DCP, or.................... .................... ............................... D4190-82(88) ........................................ Note 16
Colorimetric .................... ............................... ............................... ........................................ Note 27
(Phenanthroline).
31. Kjeldahl nitrogen--Total, (as
N), mg/L:
Digestion\12\ and distillation.
[[Page 53996]]
followed by: .................... 4500-Norg B or C............... D3590-89(A) ........................................ .........................
Titration.................. .................... 4500-NH3 E D3590-89(A) ........................................ 973.48
Nesslerization, or......... .................... 4500-NH3 C D3590-89(A) ........................................ .........................
Electrode.................. .................... 4500-NH3 F or G ............................... ........................................
Colorimetric (Automated l351.1\15\ ............................... ............................... ........................................ .........................
phenate)\12\.
Semi-automated block 351.2 ............................... D3590-89(B) ........................................ .........................
digestor\12\ colorimetric, or.
Manual or block digestor\12\ .................... ............................... D3590-89(A) ........................................ .........................
potentiometric.
Block digestor, followed by: .................... ............................... ............................... ........................................ Note 28
Auto distillation and
Titration, or
Nesslerization or.............. .................... ............................... ............................... ........................................ Note 29
Flow injection gas diffusion... .................... ............................... ............................... ........................................ Note 30
32. Lead--Total\4\, mg/L:
Digestion\5\ \6\ followed by:
AA direct aspiration....... .................... 3111 B or C D3559-90(A or B) I-3399-85 974.27
AA graphite furnace........ 200.9 3113 B D3559-90(D) ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... D4190-82(88) ........................................ Note 16
33. Magnesium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 B D511-93(B) I-3447-85 974.27
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
DCP........................ .................... ............................... ............................... ........................................ Note 16
Gravimetric................ .................... 3500-Mg D ............................... ........................................ .........................
34. Manganese--Total\4\, mg/L:
Digestion5,6 followed by:
AA direct aspiration....... .................... 3111 B D858-90(A or B) I-3454-85 974.27
AA graphite furnace........ 200.9 3113 B D858-90(C) ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS..................... 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... D4190-82(88) ........................................ Note 16
Colorimetric (Persulfate), .................... ............................... ............................... ........................................ 920.203
or.
Colorimetric (Periodate)... .................... ............................... ............................... ........................................ Note 31
35. Mercury--Total\4\, mg/L
Cold vapor, manual, or......... 245.1 3112 B D3223-91 I-3462-85 977.22
Cold vapor, automated.......... 245.2 ............................... ............................... ........................................ .........................
36. Molybdenum--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 D ............................... I-3490-85 .........................
AA graphite furnace........ .................... 3113 B ............................... ........................................ .........................
ICP/AES.................... 200.7 3120B ............................... ........................................ .........................
ICP/MS, OR................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... ............................... ........................................ Note 16
37. Nickel--Total \4\, mg/L:
Digestion\5\ \6\ followed by:
AA direct aspiration....... .................... 3111 B or C D1886-90(A or B) I-3499-85 .........................
AA graphite furnace........ 200.9 3113 B D1886-90(C) ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... D4190-82(88) ........................................ Note 16
38. Nitrate (as N), mg/L:
Colorimetric (Brucine sulfate). \15\352.1 ............................... ............................... ........................................ 973.50, p.28\18\
[[Page 53997]]
Ion Chromatography, or......... 300.0 4110 B D4327-91 ........................................ 993.30
Nitrate-nitrite N minus Nitrite
N (See parameters 39 and 40)
39. Nitrate-nitrite (sum as N), mg/
L:
Cadmium reduction, Manual...... .................... 4500-NO3 E D3867-90(B) ........................................ .........................
Cadmium reduction, Automated, 353.2 4500-NO3 F D3867-90(A) I-4545-85 .........................
or.
Ion Chromatography............. 300.0 4110 B D4327-91 ........................................ 993.30
40. Nitrite (as N), mg/L:
Spectrophotometric, Manual, or. .................... 4500-NO2 B ............................... ........................................ Note 32
Automated (Diazotization).. .................... ............................... ............................... I-4540-85 .........................
Cadmium reduction, Manual...... .................... 4500-NO3 E..................... D3867-90(B) ........................................ .........................
Cadmium reduction, Automated, 353.2 4500-NO3 F D3867-90(A) I-4545-85 .........................
or.
Ion Chromatography............. 300.0 4110 B D4327-91 ........................................ 993.30
41. Oil and grease--Total
recoverable, mg/L:
Gravimetric (extraction)....... 413.1 5520-B\33\ ............................... ........................................ .........................
42. Organic carbon--Total (TOC), mg/
L:
Combustion or oxidation........ .................... 5310-B,C or D D2579-93(A or B) ........................................ 973.47, p.14\35\
43. Organic nitrogen (as N), mg/L:
Total Kjeldahl N (Parameter 31)
minus ammonia N (Parameter 4)
44. Orthophosphate (as P), mg/L:
Ascorbic acid method:
Automated, or.............. 365.1 4500-P F ............................... I-4601-85 973.56
Manual single reagent...... .................... 4500-P E D515-88(A) ........................................ 973.55
Manual two reagent, or..... 365.3\15\ ............................... ............................... ........................................ .........................
Ion Chromatography............. 300.0 4110 B D4327-91 ........................................ 993.30
45. Osmium--Total,\4\ mg/L:
Digestion\5\ followed by:
AA direct aspiration, or... .................... 3111 D ............................... ........................................ .........................
AA graphite furnace........ .................... ............................... ............................... ........................................ .........................
46. Oxygen dissolved, mg/L:
Winkler (Azide modification), .................... 4500-O C D888-92(A) ........................................ 973.45B
or.
Electrode...................... .................... 4500-O G D888-92(B) ........................................ .........................
47. Palladium--Total,\4\ mg/L:
Digestion\5\ followed by:
AA direct aspiration, .................... 3111 B ............................... ........................................ p.S27\19\
AA graphite furnace, or.... .................... ............................... ............................... p.S28\19\...............................
DCP........................ .................... ............................... ............................... ........................................ Note 16
48. (Reserved)
49. Phenols, mg/L:
Manual distillation,\13\
followed by
Colorimetric (4AAP) manual, \15\420.1 ............................... ............................... ........................................ Note 35
or.
Colorimetric (4AAP) 420.4 ............................... ............................... ........................................ .........................
Automated.
50. Phosphorus (elemental), mg/L .................... ............................... ............................... ........................................ Note 36
Gas-liquid chromatography.
51. Phosphorus--Total, mg/L:
Persulfate digestion followed .................... 4500-P B,5 ............................... ........................................ 973.55
by:.
Ascorbic acid reduction, 365.3\15\ 4500-P E D515-88(A) ........................................ .........................
Manual, or.
Automated.................. 365.1 4500-P F ............................... I-4600-85............................... 973.56
Semi-automated block digestor.. .................... ............................... D515-88(B) ........................................ .........................
52. Platinum--Total\4\, mg/L;
Digestion\5\ followed by:
AA direct aspiration, or... .................... 3111 B ............................... ........................................ .........................
DCP........................ .................... ............................... ............................... ........................................ Note 16
53. Potassium--Total\4\, mg/L;
Digestion\5\ followed by:
AA direct aspiration, or... .................... 3111 B ............................... I-3630-85 973.53
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
54. Residue--Total, mg/L:
Gravimetric, 103-105 deg....... .................... 2540 B ............................... I-3750-85 .........................
55. Residue--filterable, mg/L;
Gravimetric, 180 deg........... .................... 2540 C ............................... I-1750-85 .........................
[[Page 53998]]
56. Residue--nonfilterable (TSS),
mg/L:
Gravimetric, 103-105 deg. post .................... 2540 D ............................... I-3765-85 .........................
washing of residue.
57. Residue--settleable, mg/L:
Volumetric (Imhoff cone), or .................... 2540 F ............................... ........................................ .........................
Gravimetric.
58. Residue--Volatile, mg/L:
Gravimetric, 550 deg. C........ 160.4\15\ ............................... ............................... I-3753-85 .........................
59. Rhodium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 B ............................... ........................................ .........................
60. Ruthenium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 B ............................... ........................................ .........................
61. Selenium--Total\4\, mg/L:
Digestion5,6 followed by:
AA graphite furnace........ 200.9 3113 B D3859-93(B) ........................................ .........................
AA gaseous hydride......... .................... 3114 B 3859-93(A) I-3667-85 .........................
ICP/AES, or................ 200.7 3120 B ............................... ........................................ .........................
ICP/MS..................... 200.8 ............................... ............................... ........................................ 993.14
62. Silica\8\ Dissolved, mg/L:
0.45 micron filtration followed
by:
Colorimetric , Manual, or.. .................... 4500-Si D D859-88 I-1700-85 .........................
Automated .................... ............................... ............................... I-2700-85 .........................
(Molybdosilicate), or.
ICP........................ 200.7 3120 B ............................... ........................................ .........................
63. Silver--Total\4\, mg/L:
Digestion5,14 followed by:
AA direct aspiration....... .................... 3111 B or C ............................... ........................................ 974.27, p.37\18\
AA graphite furnace........ 200.9 3113 B ............................... ........................................ .........................
ICP/AES.................... 200.7 3120 B ............................... ........................................ .........................
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... ............................... ........................................ Note 16
64. Sodium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 B ............................... I-3735-85 973.54
ICP/AES, or................ 200.7 3120 B ............................... ........................................ .........................
DCP........................ .................... ............................... ............................... ........................................ Note 16
65. Specific conductance, micromhos/
cm at 25 deg.C:
Wheatstone bridge.............. .................... 2510 B D1125-91(A) I-1780-85 973.40
66. Sulfate (as SO4), mg/L:
Colorimetric, Automated (Barium 375.1\15\ ............................... ............................... ........................................ .........................
chloranilate).
Gravimetric.................... .................... 4500-SO4-2 C or D ............................... ........................................ 925.54
Turbidimetric, or.............. .................... 4500-SO4-2 E D516-90........................ ........................................ .........................
Ion Chromatography............. 300.0 4110 B D4327-91 ........................................ 993.30
67. Sulfide (as S), mg/L:
Titrimetric (iodine), or....... .................... 4500-S-2 E ............................... I-3840-85 .........................
Colorimetric (methylene blue).. .................... 4500-S-2 D ............................... ........................................ .........................
68. Sulfite (as SO3), mg/L:
Titrimetric (iodine-iodate).... .................... 4500-SO3-2 B ............................... ........................................ .........................
69. Surfactants, mg/L:
Colorimetric (methylene blue).. .................... 5540 C D2330-88....................... ........................................ .........................
70. Temperature, deg.C:
[[Page 53999]]
Thermometric................... .................... 2550 B ............................... ........................................ Note 37
71. Thallium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 B ............................... ........................................ .........................
AA graphite furnace........ 200.9 ............................... ............................... ........................................ .........................
ICP/AES, or................ 200.7 3120 B ............................... ........................................ .........................
ICP/MS..................... 200.8 ............................... ............................... ........................................ 993.14
72. Tin--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration,...... .................... 3111 B
AA graphite furnace, or.... 200.9 3113 B.........................
ICP/AES.................... 200.7 ...............................
73. Titanium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 D
ICP/AES, or................ 200.7
DCP........................ .................... ............................... ............................... ........................................ Note 16
74. Turbidity, NTU:
Nephelometric.................. 180.1 2130 B D1889-88(A) I-3860-85
75. Vanadium--Total\4\, mg/L:
Digestion\5\ followed by:
AA direct aspiration....... .................... 3111 D
AA graphite furnace........ .................... ............................... D3373-93
ICP/AES.................... 200.7 3120 B
ICP/MS, or................. 200.8 ............................... ............................... ........................................ 993.14
DCP........................ .................... ............................... ............................... D4190-82(88)............................ Note 16
76. Zinc--Total\4\, mg/L:
Digestion\5\,\6\ followed by:
AA direct aspiration....... .................... 3111 (B or C) D1691-90 (A or B) I-3900-85 974.27, p. 37\18\
ICP/AES.................... 200.7 3120 B
ICP/MS..................... 200.8 ............................... ............................... ........................................ 993.14
DCP, or.................... .................... ............................... D4190-82(88)................... ........................................ Note 16
Colorimetric (zincon)...... .................... 3500-Zn F ............................... ........................................ Note 38
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Table IB--Notes
\1\``Methods for the Determination of Metals in Environmental Samples'', Supplement I, EMSL-CI, EPA/600/R-94/111, May 1994; and ``Methods for the Determination of Inorganic Substances in
Environmental Samples'', EMSL-CI, EPA/600/R-93/100, August, 1993.
\2\Fishman, M. J., et al., ``Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments'', U.S. Department of the Interior, Techniques of Water--Resource Investigations of the
U.S. Geological Survey (USGS), Denver, CO, Revised 1989.
\3\``Official Methods of Analysis of the Association of Official Analytical Chemists'', methods manual, 16th ed (1995).
\4\For the determination of total metals the sample is not filtered before processing and a digestion procedure is required a) to solubilize analytes in the suspended material and b) to render
the analyte available for analysis when colorimetric methods are used.
\5\For non-platform graphite furnace atomic absorption determinations a digestion using nitric acid is reguired prior to analysis. The procedure used should subject the sample to gentle, acid
refluxing and at no time should the sample be taken to dryness. For direct aspiration flame atomic absorption determinations (FLAA) a combination acid (nitric and hydrochloric acids)
digestion is preferred prior to analysis. Such a digestion is described as Method 200.2 in Supplement I of ``Methods for the Determination of Metals in Environmental Samples'' EPA-600/R-94/
111 May, 1994. However, when using the gaseous hydride technique or for the determination of certain elements such as antimony, arsenic, selenium, silver, and tin by non-EPA graphite furnace
atomic absorption methods, mercury by cold vapor atomic absorption, the noble metals and titanium by FLAA, a specific or modified sample digestion procedure may be required and in all cases
the referenced method write-up should be consulted for specific instruction and/or cautions. For analyses using inductively coupled plasma-atomic emission spectrometry (ICP-AES), the direct
current plasma (DCP) technique or the EPA spectrochemical techniques (platform furnace AA, ICP-AES, and ICP-MS) the appropriate sample digestion procedure to be used is included in the
referenced Standard Methods, ASTM, Fisons, or EPA methods, respectively.
\6\The digestion procedure ``Closed Vessel Microwave Digestion of Wastewater Samples for Determination of Metals'', CEM Corporation, P.O. Box 200, Matthews, NC 28106-0200, April 16, 1992, is
acceptable for use with any AA direct aspiration, ICP/AES, or DCP measurement system listed for this parameter. Available from the CEM Corporation.
\7\Manual distillation is not required if comparability data on representative effluent samples are on company file to show that this preliminary distillation step is not necessary; however,
manual distillation will be required to resolve any controversies.
\8\When determining boron and silica, only plastic, PFTE, or quartz labware may be used from start until completion of the analysis.
\9\Carbonaceous biochemical oxygen demand (CBOD5) must not be confused with the traditional BOD5 test which measures ``total BOD''. The addition of the nitrification inhibitor is not a
procedural option, but must be included to report the CBOD5 parameter. A discharger whose permit requires reporting the traditional BOD5 may not use a nitrification inhibitor in the
procedure for reporting the results. Only when a discharger's permit specifically states CBOD5 is required can the permittee report data using the nitrification inhibitor.
\10\The back titration method will be used to resolve controversy.
\11\When using EPA digestion procedure, must use EPA determinative procedure. When using Standard Methods digestion procedure, must use Standard Methods determinative procedure.
\12\Copper sulfate or other mercury-free catalyst shown to be effective must be used in place of mercuric sulfate in the digestion step.
[[Page 54000]]
\13\Just prior to distillation, adjust the sulfuric-acid-preserved sample to pH 4 with 1 + 9 NaOH.
\14\The digestion procedures in the approved Standard Methods direct aspiration flame atomic absorption and inductively coupled plasma-atomic emission spectrometry methods are useful for the
analysis of silver up to concentrations of 1 mg/l. However, where silver concentrations > 1 mg/L exist as an inorganic halide the referenced methods sample preparation procedures are
inadequate. For sample preparation in these situations a well-mixed representative 20 ml sample aliquot should be diluted to 100 mL by adding 40 mL each of 2 M Na2S2O3 and NaOH prior to
analysis by direct aspiration flame atomic absorption. Calibration standards should be prepared in the same manner. The approved EPA methods are useful for the analysis of silver up to
concentrations of 0.1 mg/L.
\15\``Methods for Chemical Analysis of Water and Wastes'', U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-CI), Cincinnati, OH, EPA-600/4-79-
020, Revised March 1983 and 1979 where applicable.
\16\``Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes, Method AE50029'', 1986--Revised 1991, Fison Instruments, Inc., 32
Commerce Center, Cherry Hill Drive, Danvers, MA 01923.
\17\Ammonia, Automated Electrode Method, Industrial Method Number 379-75 WE, dated February 19, 1976, Bran & Luebbe (Technicon) Auto Analyzer II, Bran & Luebbe Analyzing Technologies, Inc.,
Elmsford, NY 10523.
\18\American National Standard on Photographic Processing Effluents, Apr. 2, 1975. Available from ANSI, 1430 Broadway, New York, NY 10018.
\19\``Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency'', Supplement to the Fifteenth Edition of Standard Methods for the Examination of
Water and Wastewater (1981).
\20\OIC Chemical Oxygen Demand Method Oceanography International Corporation, 512 West Loop, P.O. Box 2980, College Station, TX 77840.
\21\Chemical Oxygen Demand, Method 8000, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.
\22\Orion Research Instruction Manual, Residual Chlorine Electrode Model 97-70, 1977, Orion Research Incorporated, 840 Memorial Drive, Cambridge, MA 02138.
\23\``Standard Method for the Examination of Water and Wastewater--Supplement to the 18th Edition'', 1994.
\24\National Council of the Paper Industry for Air and Stream Improvement (Inc.), Technical Bulletin 253, December 1971.
\25\Copper, Biocinchoninate Method, Method 8506, Hach Handbook of Water Analysis, 1979, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.
\26\Hydrogen ion (pH) Automated Electrode Method, Industrial Method Number 378-75WA, October 1976, Technicon AutoAnalyzer II, Technicon Industrial Systems, Tarrytown, NY 10591.
\27\Iron, 1,10-Phenanthroline Method, Method 8008, 1980, Hach Chemical Company, P.O.Box 389, Loveland, CO 80537.
\28\Nitrogen, Total Kjeldahl, Method PAI-DK01 (Block Digestion, Steam Distillation, Titrimetric Detection), revised 12/22/94, Perstop Analytical.
\29\Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block Digestion, Steam Distillation, Colorimetric Detection), revised 12/22/94, Perstop Analytical.
\30\Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block Digestion, Automated FIA Gas Diffusion), revised 12/22/94, Perstop Analytical.
\31\Manganese, Periodate Oxidation Method, Method 8034, Hach Handbook of Wastewater Analysis, 1979, pages 2-113 and 2-117, Hach Chemical Company, Loveland, CO 80537.
\32\Nitrogen, Nitrite, Method 8507, Hach Chemical Company, P.O. Box 389, Loveland, CO 80537.
\33\Only the trichlorotrifluoroethane extraction solvent option is approved.
\34\Wershaw, R.L., et al, ``Methods for Analysis of Organic Substances in Water'', Techniques of Water-Resources Investigation of the U.S. Geological Survey, Book 5, Chapter A3 (1972 Revised
1987), p.14.
\35\The approved method is cited in Standard Methods for the Examination of Water and Wastewater, 14th Edition. The colorimetric reaction is conducted at a pH of 10.00.2. The
approved methods are given on pp 576-81 of the 14th Edition: Method 510A for distillation, Method 510B for the manual colorimetric procedure, or Method 510C for the manual spectrophotometric
procedure.
\36\R. F. Addison and R. G. Ackman, ``Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography'', Journal of Chromatography, vol. 47, No. 3, pp. 421-426, 1970.
\37\Stevens, H. H., Ficke, J. F., and Smoot, G. F., ``Water Temperature--Influential Factors, Field Measurement and Data Presentation'', U.S. Geological Survey, Techniques of Water Resources
Investigations, Book 1, Chapter D1, 1975.
\38\Zinc, Zincon Method, Method 8009, Hach Handbook of Water Analysis, 1979, pages 2-231 and 2-333, Hach Chemical Company, Loveland, CO 80537.
[[Page 54001]]
3. Section 136.3(a) is proposed to be amended by revising entries
35-37 of Table IC to read:
136.3 Identification of Test Procedures.
* * * * *
Table 1C.--List of Approved Test Procedures For Non-Pesticide Organic Compounds
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
EPA Method Number2,7
Parameter\1\ ------------------------------------------------------------------- Standard methods 18th Ed. ASTM Other
GC GC/MS HPLC
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
* * * * * * *
35. 1,2-Dichlorobenzene............ 601,602 624, 1625................. --........................ 6220 B, 6230 B..................
36. 1,3-Dichlorobenzene............ 601,602 624, 1625................. --........................ 6220 B, 6230 B..................
37. 1,4-Dichlorobenzene............ 601,602 624, 1625................. --........................ 6220 B, 6230 B..................
* * * * * * *
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Table 1C Notes
\1\All parameters are expressed in micrograms per liter (g/L).
\2\The full text of Methods 601-613, 624, 625, 1624, and 1625, are given at Appendix A, ``Test Procedures for Analysis of Organic Pollutants,'' of this Part 136. The standardized test
procedure to be used to determine the method detection limit (MDL) for these test procedures is given at Appendix B, ``Definition and Procedure for the Determination of the Method Detection
Limit'' of this Part 136.
* * * * * * *
\7\Each Analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601-603, 624, 625, 1624, and 1625 (See Appendix A of
this Part 136) in accordance with procedures in section 8.2 of each of these Methods. Additionally, each laboratory, on an on-going basis must spike and analyze 10% (5% for Methods 624 and
625 and 100% for Methods 1624 and 1625) of all samples to monitor and evaluate laboratory data quality in accordance with sections 8.3 and 8.4 of these Methods. When the recovery of any
parameter falls outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect and cannot be reported to demonstrate regulatory compliance. Note:
These warning limits are promulgated as an ``interim final action with a request for comments.''
* * * * * * *
4. Section 136.3(b) is proposed to be amended by revising
references 1 through 38 and adding references 39 and 40 to read as
follows:
Sec. 136.3 Identification of test procedures.
* * * * *
(b) * * *
References, Sources, Costs, and Table Citations
(1) The full text of Methods 601-613, 624, 625, 1624, and 1625 are
printed in appendix A of this part 136. The full text for determining
the method detection limit when using the test procedures is given in
appendix B of this part 136. Table IC, Note 7; and Table ID, Note 2.
(2) ``Microbiological Methods for Monitoring the Environment, Water
and Wastes,'' U.S. Environmental Protection Agency, EPA-600/8-78-017,
1978. Available from: ORD Publications, CERI, U.S. Environmental
Protection Agency, Cincinnati, Ohio 45268. Table IA. Note 2.
(3) ``Methods for Chemical Analysis of Water and Wastes,'' U.S.
Environmental Protection Agency, EPA 600/4-79-020, March 1979, or
``Methods for Chemical Analysis of Water and Wastes, U.S. Environmental
Protection Agency, EPA-600/4-79-020, Revised March 1983. Available
from: ORD Publications, CERI, U.S. Environmental Protection Agency,
Cincinnati, Ohio 45268. Table IB, Note 15.
(4) ``Methods for Benzidine, Chlorinated Organic Compounds,
Pentachlorophenol and Pesticides in Water and Wastewater,'' U.S.
Environmental Protection Agency, 1978. Available from: ORD
Publications, CERI, U.S. Environmental Protection Agency, Cincinnati,
Ohio 45268, Table IC, Note 3; Table D, Note 3.
(5) ``Prescribed Procedures for Measurement of Radioactivity in
Drinking Water,'' U.S. Environmental Protection Agency, EPA-600/4-80-
032, 1980. Available from: ORD Publications, CERI, U.S. Environmental
Protection Agency, Cincinnati, Ohio 45268, Table IE, Note 1.
(6) ``Standard Methods for the Examination of Water and
Wastewater'', Joint Editorial Board, American Public Health
Association, American Water Works Association, and Water Environment
Federation, 18th Edition, 1992. Available from: American Public Health
Association, 1015 Fifteenth Street, NW., Washington, DC 20005, Cost
$160.00. Table IA, IB, IC, ID and IE.
(7) (Reserved)
(8) Ibid, 14th Edition, 1975. Table IB, Note 35.
(9) ``Selected Analytical Methods Approved and Cited by the United
States Environmental Protection Agency Supplement to the 15th Edition
of Standard Methods for the Examination of Water and Wastewater, 1981.
Available from: American Public Health Association, 1015 Fifteenth
Street NW., Washington, DC 20036. Cost available from publisher. Table
IB, Note 19; Table IC, Note 6; Table ID, Note 6.
(10) ``Annual Book of Standards--Water and Environmental
Technology'', Section 11, Parts 11.01 Water (I) and 11.02 Water (II),
American Society for Testing and Materials, 1994. 1916 Race Street,
Philadelphia, PA 19103. Cost available from publisher. Tables IB, IC,
ID, and IE.
(11) ``Methods for Collection and Analysis of Aquatic Biological
and Microbiological Samples,'' edited by Britton, L.J. and P.E.
Greason, Techniques of Water Resources Investigations, of the U.S.
Geological Survey, Book 5, Chapter A4 (1989). Available from: U.S.
Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225.
Cost: $9.25 (subject to change). Table IA.
(12) ``Methods for Determination of Inorganic Substances in Water
and Fluvial Sediments,'' by M.J. Fishman and Linda C. Friedman,
Techniques of Water-Resources Investigations of the U.S. Geological
Survey, Book 5 Chapter A1 (1989). Available from: U.S. Geological
Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Cost
$108.75 (subject to change). Table IB, Note 2.
(13) (Reserved)
(14) ``Methods for the Determination of Organic Substances in Water
and Fluvial Sediments, Wershaw, R.L., et al., Techniques of Water-
Resources
[[Page 54002]]
Investigations of the U.S. Geological Survey, Book 5, Chapter A3
(1987). Available from: U.S. Geological Survey, Denver Federal Center,
Box 25425. Cost: $0.90 (subject to change). Table IB, Note 34, Table
ID, Note 4.
(15) ``Water Temperature-Influential Factors, Field Measurement and
Data Presentation,'' by H.H. Stevens, Jr., J. Ficke, and G.F. Smoot,
Techniques of Water Resources Investigations of the U.S. Geological
Survey, Book 1, Chapter D1, 1975. Available from: U.S. Geological
Survey, Denver Federal Center, Box 25425, Denver, CO 80225, Cost: $1.60
(subject to change). Table IB, Note 37.
(16) ``Selected Methods of the U.S. Geological Survey of Analysis
of Wastewaters, by M.J. Fishman and Eugene Brown; U.S. Geological
Survey Open File Report 76-77 (1976). Available from: U.S. Geological
Survey, Branch of Distribution, 1200 South Eads Street, Arlington, VA
22202. Cost: $13.50 (subject to change). Table IE, Note 2.
(17) ``Official Methods of Analysis of AOAC-International'', 16th
Edition (1995). Price: $359.00. Available from: AOAC-International,
1970 Chain Bridge Rd., Dept. 0742, McLean, VA 22109-0742. Table IB,
Note 3.
(18) ``American National Standard on Photographic Processing
Effluents,'' April 2, 1975. Available from: American National Standards
Institute, 1430 Broadway, New York, New York 10018. Table IB, Note 18.
(19) ``An Investigation of Improved Procedures for Measurement of
Mill Effluent and Receiving Water Color, NCASI Technical Bulletin No.
253, December 1971. Available from: National Council of the Paper
Industry for Air and Stream Improvements, Inc., 260 Madison Avenue, New
York, NY 10016. Cost available from publisher. Table IB, Note 24.
(20) Ammonia, Automated Electrode Method, Industrial Method Number
379-75WE, dated February 19, 1976. Technicon Auto Analyzer II. Method
and price available from Technicon Industrial Systems, Tarrytown, New
York 10591. Table IB, Note 17.
(21) Chemical Oxygen Demand, Method 8000, Hach Handbook of Water
Analysis, 1979. Method price available from Hach Chemical Company, P.O.
Box 389, Loveland, Colorado 80537. Table IB, Note 21.
(22) OIC Chemical Oxygen Demand Method, 1978. Method and price
available from Oceanography International Corporation, 512 West Loop,
P.O. Box 2980, College Station, Texas 77840. Table IB, Note 20.
(23) ORION Research Instruction Manual, Residual Chlorine Electrode
Model 97-70, 1977. Method and price available from ORION Research
Incorporation, 840 Memorial Drive, Cambridge, Massachusetts 02138.
Table IB, Note 22.
(24) Bicinchoninate Method for Copper. Method 8506, Hach Handbook
of Water Analysis, 1979. Method and price available from Hach Chemical
Company, P.O. Box 300, Loveland, Colorado 80537. Table IB, Note 25.
(25) Hydrogen Ion (pH) Automated Electrode Method, Industrial
Method Number 378-75WA. October 1976. Bran & Luebbe (Technicon) Auto
Analyzer II. Method and price available from Bran & Luebbe Analyzing
Technologies, Inc. Elmsford, N.Y. 10523. Table IB, Note 26.
(26) 1,10-Phenanthroline Method using FerroVer Iron Reagent for
Water, Hach Method 8008, 1980. Method and price available from Hach
Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table IB,
Note 27.
(27) Periodate Oxidation Method for Manganese, Method 8034, Hach
Handbook for Water Analysis, 1979. Method and price available from Hach
Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table IB,
Note 31.
(28) Nitrogen, Nitrite-Low Range, Diazotization Method for Water
and Wastewater, Hach Method 8507, 1979. Method and price available from
Hach Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table
IB, Note 32.
(29) Zincon Method for Zinc, Method 8009, Hach Handbook for Water
Analysis, 1979. Method and price available from Hach Chemical Company,
P.O. Box 389, Loveland, Colorado 80537. Table IB, Note 38.
(30) ``Direct Determination of Elemental Phosphorus by Gas-Liquid
Chromatography,'' by R.F. Addison and R.G. Ackman, Journal of
Chromatography, Volume 47, No. 3, pp. 421-426, 1970. Available in most
public libraries. Back volumes of the Journal of Chromatography are
available from Elsevier/North-Holland,Inc., Journal Information Center,
52 Vanderbilt Avenue, New York, NY 10164. Cost available from
publisher, Table IB, Note 36.
(31) ``Direct Current Plasma (DCP) Optical Emission Spectrometric
Method for Trace Elemental Analysis of Water and Wastes'', Method AES
0029, 1986-Revised 1991. Fison Instruments, Inc., 32 Commerce Center,
Cherry Hill Drive, Danvers, MA 01923. Table IB, Note 16.
(32) ``Closed Vessel Microwave Digestion of Wastewater Samples for
Determination of Metals, CEM Corporation, P.O. Box 200, Matthews, North
Carolina 28106-0200, April 16, 1992. Available from the CEM
Corporation. Table IB, Note 6.
(33) Reserved.
(34) ``Organochlorine Pesticides and PCB's in Wastewater Using
EmporeTM Disk'', Test Method 3M 0222, Revised 10/28/94. 3M
Corporation, 3M Center Building 220-9E-10, St. Paul, MN 55144-1000.
Method available from 3M Corporation. Tables IC and ID, Note 9.
(35) ``Nitrogen, Total Kjeldahl, Method PAI-DK01 (Block Digestion,
Steam Distillation, Titrimetric Detection)'', revised 12/22/94, Perstop
Analytical. Method available from Perstorp Analytical Corporation, P.O.
Box 648, Wilsonville, OR 97070. Table IB, Note 28.
(36) ``Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block Digestion,
Steam Distillation, Colorimetric Detection)'', revised 12/22/94,
Perstop Analytical. Method available from Perstorp Analytical
Corporation, P.O. Box 648, Wilsonville, OR 97070. Table IB, Note 29.
(37) ``Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block Digestion,
Automated FIA Gas Diffusion)'', revised 12/22/94, Perstop Analytical.
Method available from Perstorp Analytical Corporation, P.O. Box 648,
Wilsonville, OR 97070. Table IB, Note 30.
(38) Methods for the Determination of Metals in Environmental
Samples, Environmental Monitoring Systems Laboratory, Office of
Research and Development, U.S. Environmental Protection Agency,
Cincinnati, OH 45268, EPA 600 R-94/111, May 1994. Table IB, Notes 1 and
5.
(39) ``Methods for the Determination of Inorganic Substances in
Environmental Samples'', Environmental Monitoring Systems Laboratory,
Office of Research and Development, U.S. Environmental Protection
Agency, Cincinnati, OH 45268, Revised EPA 600 R-93/100 August 1993.
Table IB, Note 1.
(40) ``Standard Methods for the Examination of Water and
Wastewater'', American Public Health Association, American Water Works
Association, Water Environment Federation, 18th Edition Supplement,
1994. Table IB, Note 23.
5. Section 136.3 (e) is proposed to be amended by revising Table II
to read as follows:
136.3 Identification of test procedures.
* * * * *
(e) * * *
[[Page 54003]]
Table II.--Required Containers, Preservation Techniques, and Holding Times
----------------------------------------------------------------------------------------------------------------
Test procedure table parameter Maximum holding
number/name Container\1\ Preservation procedure\2\-\4\ time\5\
----------------------------------------------------------------------------------------------------------------
Table IA--Biological Tests
----------------------------------------------------------------------------------------------------------------
1. Coliform (fecal)............. P,G a,b\6\ 6 hours.
2. Coliform (fecal), Pres. of P,G a,b\6\ 6 hours.
chlorine.
3. Coliform (total)............. P,G a,b\6\ 6 hours.
4. Coliform (total), Pres. of P,G a,b\6\ 6 hours.
chlorine.
5. Fecal streptococci........... P,G a,b\6\ 6 hours.
----------------------------------------------------------------------------------------------------------------
Table IB--Inorganic Tests
----------------------------------------------------------------------------------------------------------------
1. Acidity...................... P,G a 14 days.
2. Alkalinity................... P,G a 14 days.
3. Aluminum\7\.................. P,G c 6 months.
4. Ammonia...................... P,G a,d 28 days.
5. Antimony\7\.................. P,G c 6 months.
6. Arsenic\7\................... P,G c 6 months.
7. Barium\7\.................... P,G c 6 months.
8. Beryllium\7\................. P,G c 6 months.
9. Biochemical oxygen demand P,G a 48 hours.
(BOD).
10. Boron\7\.................... P,G c 6 months.
11. Bromide..................... P,G e 28 days.
12. Cadmium\7\.................. P,G c 6 months.
13. Calcium\7\.................. P,G c 6 months.
14. Carbonaceous biochemical P,G a 48 hours.
oxygen demand (CBOD).
15. Chemical oxygen demand (COD) P,G a,d 28 days.
16. Chloride.................... P,G e 28 days.
17. Chlorine.................... P,G e Immediate.
18. Chromium VI (dissolved)..... P,G a 24 hours.
19. Chromium\7\................. P,G c 6 months.
20. Cobalt\7\................... P,G c 6 months.
21. Color....................... P,G a 48 hours.
22. Copper\7\................... P,G c 6 months.
23. Cyanide..................... P,G a,f\6\,g 14 days.\8\
24. Cyanide amenable............ P,G a,f\6\,g 14 days.\8\
25. Fluoride.................... P e 28 days.
26. Gold\7\..................... P,G c 6 months.
27. Hardness.................... P,G c or d 6 months.
28. Hydrogen ion (pH)........... P,G e Immediate.
29. Iridium\7\.................. P,G c 6 months.
30. Iron\7\..................... P,G c 6 months.
31. Kjeldahl nitrogen........... P,G a,d 28 days.
32. Lead\7\..................... P,G c 6 months.
33. Magnesium\7\................ P,G c 6 months.
34. Manganese\7\................ P,G c 6 months.
35. Mercury..................... P,G c 28 days.
36. Molybdenum\7\............... P,G c 6 months.
37. Nickel\7\................... P,G c 6 months.
38. Nitrate..................... P,G a 48 hours.
39. Nitrate-nitrite............. P,G a,d 28 days.
40. Nitrite..................... P,G a 48 hours.
41. Oil and grease.............. G a; d or h 28 days.
42. Organic carbon.............. P,G a; d or h or i 28 days.
43. Organic nitrogen............ P,G a,d 28 days.
44. Orthophosphate.............. P,G a,j 48 hours.
45. Osmium\7\................... P,G c 6 months.
46. Oxygen, dissolved:
By probe.................... G e Immediate.
By winkler.................. G bottle and top k 8 hours. 4
47. Palladium\7\................ P,G c 6 months.
48. (Reserved).................. ........................ .............................. ....................
49. Phenols..................... G a,d 28 days.
50. Phosphorus (elemental)...... G a 48 hours.
51. Phosphorus.................. P,G a,d 28 days.
52. Platinum\7\................. P,G c 6 months.
53. Potassium\7\................ P,G c 6 months.
54. Residue, total.............. P,G a 7 days.
55. Residue, filterable......... P,G a 7 days.
56. Residue, nonfilterable (TSS) P,G a 7 days.
57. Residue, settleable......... P,G a 48 hours.
58. Residue, Volatile........... P,G a 7 days.
[[Page 54004]]
59. Rhodium\7\.................. P,G c 6 months.
60. Ruthenium\7\................ P,G c 6 months.
61. Selenium\7\................. P,G c 6 months.
62. Silica\7\................... P a 28 days.
63. Silver\7\................... P,G c 6 months.
64. Sodium\7\................... P,G c 6 months.
65. Specific conductance........ P,G a 28 days.
66. Sulfate..................... P,G a 28 days.
67. Sulfide..................... P,G a,l,m 7 days.
68. Sulfite..................... P,G e Immediate.
69. Surfactants................. P,G a 48 hours.
70. Temperature................. P,G e Immediate.
71. Thallium\7\................. P,G c 6 months.
72. Tin\7\...................... P,G c 6 months.
73. Titanium\7\................. P,G c 6 months.
74. Turbidity................... P,G a 48 hours.
75. Vanadium\7\................. P,G c 6 months.
76. Zinc\7\..................... P,G c 6 months.
----------------------------------------------------------------------------------------------------------------
Table IC--Non-Pesticide Organic Compounds\9\,\10\
----------------------------------------------------------------------------------------------------------------
1. Acenaphthene................. G,T a,b\6\,n 7 days.\11\
2. Acenaphthylene............... G,T a,b\6\,n 7 days.\11\
3. Acrolein..................... G,T a,o\6\,p 14 days.\12\
4. Acrylonitrile................ G,T a,o\6\ 14 days.
5. Anthracene................... G,T a,b\6\,n 7 days.\11\
6. Benzene...................... G,T a,h,o\6\ 14 days.
7. Benzidine.................... G,T a,b\6\,\13\ 7 days.\14\
8. Benzo(a)anthracene........... G,T a,b\6\,n 7 days.\11\
9. Benzo(a)pyrene............... G,T a,b\6\,n 7 days.\11\
10. Benzo(b)fluoranthene........ G,T a,b\6\,n 7 days.\11\
11. Benzo(g,h,i)perylene........ G,T a,b\6\,n 7 days.\11\
12. Benzo(k)fluoranthene........ G,T a,b\6\,n 7 days.\11\
13. Benzyl chloride............. G,T a,o\6\ 14 days.
14. Benzyl butyl phthalate...... G,T a 7 days.\11\
15. Bis(2-chloroethoxy) methane. G,T a,b\6\ 7 days.\11\
16. Bis(2-chloroethyl) ether.... G,T a,b\6\ 7 days.\11\
17. Bis(2-ethylhexyl) phthalate. G,T a 7 days.\11\
18. Bromodichloromethane........ G,T a,o\6\ 14 days.
19. Bromoform................... G,T a,o\6\ 14 days.
20. Bromomethane................ G,T a,o\6\ 14 days.
21. 4-Bromophenylphenyl ether... G,T a,b\6\ 7 days.\11\
22. Carbon tetrachloride........ G,T a,o\6\ 14 days.
23. 4-Chloro-3-methylphenol..... G,T a,b\6\ 7 days.\11\
24. Chlorobenzene............... G,T a,o\6\ 14 days.
25. Chloroethane................ G,T a,o\6\ 14 days.
26. 2-Chloroethylvinyl ether.... G,T a,o\6\ 14 days.
27. Chloroform.................. G,T a,o\6\ 14 days.
28. Chloromethane............... G,T a,o\6\ 14 days.
29. 2-Chloronaphthalene......... G,T a 7 days.\11\
30. 2-Chlorophenol.............. G,T a,b\6\ 7 days.\11\
31. 4-Chlorophenylphenyl ether.. G,T a,b\6\ 7 days.\11\
32. Chrysene.................... G,T a,b\6\,n 7 days.\11\
33. Dibenzo(a,h)anthracene...... G,T a,b\6\,n 7 days.\11\
34. Dibromochloromethane........ G,T a,o\6\ 14 days.
35. 1,2-Dichlorobenzene......... G,T a,o\6\ 14 days.
36. 1,3-Dichlorobenzene......... G,T a,o\6\ 14 days.
37. 1,4-Dichlorobenzene......... G,T a,h,o\6\ 14 days.
38. 3,3-Dichlorobenzidine....... G,T a,b\6\ 7 days.\13\
39. Dichlorodifluoromethane..... G,T a,o\6\ 14 days.
40. 1,1-Dichloroethane.......... G,T a,o\6\ 14 days.
41. 1,2-Dichloroethane.......... G,T a,o\6\ 14 days.
42. 1,1-Dichloroethene.......... G,T a,o\6\ 14 days.
43. trans-1,2-Dichloroethene.... G,T a,o\6\ 14 days.
44. 2,4-Dichlorophenol.......... G,T a,b\6\ 7 days.\11\
45. 1,2-Dichloropropane......... G,T a,o\6\ 14 days.
46. cis-1,3-Dichloropropene..... G,T a,o\6\ 14 days.
47. trans-1,3-Dichloropropene... G,T a,o\6\ 14 days.
48. Diethyl phthalate........... G,T a 7 days.\11\
49. 2,4-Dimethylphenol.......... G,T a,b\6\ 7 days.\11\
50. Dimethyl phthalate.......... G,T a 7 days.\11\
[[Page 54005]]
51. Di-n-butyl phthalate........ G,T a 7 days.\11\
52. Di-n-octyl phthalate........ G,T a 7 days.\11\
53. 2,4-Dinitrophenol........... G,T a,b\6\ 7 days.\11\
54. 2,4-Dinitrotoluene.......... G,T a,b\6\,n 7 days.\11\
55. 2,6-Dinitrotoluene.......... G,T a,b\6\,n 7 days.\11\
56. Epichlorohydrin............. G,T a,o\6\ 14 days.
57. Ethylbenzene................ G,T a,h,o\6\ 14 days.
58. Fluoranthene................ G,T a,b\6\,n 7 days.\11\
59. Fluorene.................... G,T a,b\6\,n 7 days.\11\
60. Hexachlorobenzene........... G,T a 7 days.\11\
61. Hexachlorobutadiene......... G,T a 7 days.\11\
62. Hexachlorocyclopentadiene... G,T a,b\6\ 7 days.\11\
63. Hexachloroethane............ G,T a,b\6\ 7 days.\11\
64. Ideno(1,2,3-cd)pyrene....... G,T a,b\6\,n 7 days.\11\
65. Isophorone.................. G,T a,b\6\,n 7 days.\11\
66. Methylene chloride.......... G,T a,o\6\ 14 days.
67. 2-Methyl-4,6-dinitrophenol.. G,T a,b\6\ 7 days,\11\
68. Naphthalene................. G,T a,b\6\,n 7 days.\11\
69. Nitrobenzene................ G,T a,b\6\,n 7 days.\11\
70. 2-Nitrophenol............... G,T a,b\6\ 7 days.\11\
71. 4-Nitrophenol............... G,T a,b\6\ 7 days.\11\
72. N-Nitrosodimethylamine...... G,T a,b\6\,n 7 days.\11\
73. N-Nitrosodi-n-propylamine... G,T a,b\6\,n 7 days.\11\
74. N-Nitrosodiphenylamine...... G,T a,b\6\,n\15\ 7 days.\11\
75. 2,2-Oxybis(1-chloropropane). G,T a,b\6\ 7 days.\11\
76. PCB-1016.................... G,T a,b\6\ 7 days.\11\
77. PCB-1221.................... G,T a,b\6\ 7 days.\11\
78. PCB-1232.................... G,T a,b\6\ 7 days.\11\
79. PCB-1242.................... G,T a,b\6\ 7 days.\11\
80. PCB-1248.................... G,T a,b\6\ 7 days.\11\
81. PCB-1254.................... G,T a,b\6\ 7 days.\11\
82. PCB-1260.................... G,T a,b\6\ 7 days.\11\
83. Pentachlorophenol........... G,T a,b\6\ 7 days.\11\
84. Phenanthrene................ G,T a,b\6\,n 7 days.\11\
85. Phenol...................... G,T a,b\6\ 7 days.\11\
86. Pyrene...................... G,T a,b\6\,n 7 days.\11\
87. 2,3,7,8-Tetrachlorodibenzo-p- G,T a,b\6\ 7 days.\11\
dioxin.
88. 1,1,2,2-Tetrachloroethane... G,T a,o\6\ 14 days.
89. Tetrachloroethene........... G,T a,o\6\ 14 days.
90. Toluene..................... G,T a,h,o\6\ 14 days.
91. 1,2,4-Trichlorobenzene...... G,T a,o\6\ 14 days.
92. 1,1,1-Trichloroethane....... G,T a,o\6\ 14 days.
93. 1,1,2-Trichloroethane....... G,T a,o\6\ 14 days.
94. Trichloroethene............. G,T a,o\6\ 14 days.
95. Trichlorofluoromethane...... G,T a,o\6\ 14 days.
96. 2,4,6-Trichlorophenol....... G,T a,b\6\ 7 days.\11\
97. Vinyl chloride.............. G,T a,o\6\ 14 days.
----------------------------------------------------------------------------------------------------------------
Table ID--Pesticides\9\,\10\
----------------------------------------------------------------------------------------------------------------
1-70. Pesticides................ G,T a,q\16\ 7 days.\11\
----------------------------------------------------------------------------------------------------------------
Table IE--Radiologic Tests
----------------------------------------------------------------------------------------------------------------
1-5. Alpha, beta and radium..... P,G c 6 months.
----------------------------------------------------------------------------------------------------------------
Table II Notes
\1\Container abbreviations: P = Polyethylene, G = Glass and T = PTFE-lined cap or septum.
\2\Sample preservation should be performed immediately upon sample collection. For composite chemical samples
each aliquot should be preserved at the time of collection. When use of an automated sampler makes it
impossible to preserve each aliquot, then chemical samples may be preserved by maintaining at 4 deg.C until
compositing and sample splitting is completed.
\3\Procedure abbreviations:
a: Cool 4 deg.C
b: 0.008% Na2S2O3\6\
c: HNO3 to pH<2 d:="">2SO4 to pH<2 e:="" none="" required="" f:="" 0.6="" g="" ascorbic="" acid\6\="" g:="" naoh="" to="" ph="">12
h: HCl to pH<2 i:="">3PO4 to pH <2 j:="" filter="" immediately="" [[page="" 54006]]="" k:="" fix="" on="" site="" and="" store="" in="" dark="" l:="" add="" zinc="" acetate="" m:="" naoh="" to="" ph="">9
n: Store in dark
o: 0.025 g ascorbic acid\6\
p: Adjust pH to 4-5\10\
q: Adjust pH to 5-9
\4\When any sample is to be shipped by common carrier or sent through the United States Mails, it must comply
with the Department of Transportation Hazardous Materials Regulations (49 CFR part 172). The person offering
such material for transportation is responsible for ensuring such compliance. For the preservation
requirements of Table II, the Office of Hazardous Materials, Materials Transportation Bureau, Department of
Transportation has determined that the Hazardous Materials Regulations do not apply to the following
materials: Hydrochloric acid (HCl) in water solutions at concentrations of 0.04% by weight or less (pH about
1.96 or greater); Nitric acid (HNO3) in water solutions at concentrations of 0.15% by weight or less (pH about
1.62 or greater); Sulfuric acid (H2SO4) in water solutions at concentrations of 0.35% by weight or less (pH
about 1.15 or greater); and Sodium hydroxide (NaOH) in water solutions at concentrations of 0.080% by weight
or less (pH about 12.30 or less).
\5\Samples should be analyzed as soon as possible after collection. The times listed are the maximum times that
samples may be held before analysis and still be considered valid. Samples may be held for longer periods only
if the permittee, or monitoring laboratory, has data on file to show that for the specific types of samples
under study, the analytes are stable for the longer time, and has received a variance from the Regional
Administrator under Sec. 136.3(e). Some samples may not be stable for the maximum time period given in the
table. A permittee, or monitoring laboratory, is obligated to hold the sample for a shorter time if knowledge
exists to show that this is necessary to maintain sample stability. See Sec. 136.3(e) for details. The term
``analyze immediately'' usually means within 15 minutes or less of sample collection.
\6\Should only be used in the presence of residual chlorine.
\7\Samples should be filtered immediately on-site before adding preservative for dissolved metals.
\8\Maximum holding time is 24 hours when sulfide is present. Optionally all samples may be tested with lead
acetate paper before pH adjustments in order to determine if sulfide is present. If sulfide is present, it can
be removed by the addition of cadmium nitrate powder until a negative spot test is obtained. The sample is
filtered and then NaOH is added to pH 12.
\9\Guidance applies to samples to be analyzed by GC, LC, or GC/MS for specific compounds.
\10\When samples are to be extracted and analyzed for multiple analytes, the most stringent preservation
procedures and shortest maximum holding times should be observed for optimum safeguard of sample integrity.
Samples extracted for a wide range of analytes may be preserved by cooling to 4 deg.C, reducing residual
chlorine with 0.008% sodium thiosulfate, storing in the dark, and adjusting the pH to 6-9; samples preserved
in this manner may be held for seven days before extraction and for forty days after extraction. Exceptions to
this optional preservation and holding time procedure are noted in footnotes 6,13, and 14.
\11\Samples must be extracted within seven days of collection. The extract must be analyzed within 40 days of
extraction.
\12\Samples for acrolein receiving no pH adjustment must be analyzed within 3 days of sampling.
\13\If 1,2-diphenylhydrazine is likely to be present, adjust the pH of the sample to 4.0 0.2 to
prevent rearrangement to benzidine.
\14\Extracts may be stored up to 7 days before analysis if storage is conducted under an inert (oxidant-free)
atmosphere.
\15\Adjust pH to 7-10 with NaOH within 24 hours of sampling.
\16\The pH adjustment may be performed upon receipt at the laboratory and may be omitted if the samples are
extracted within 72 hours of collection. For the analysis of aldrin, add 0.008% N2S2O3.
Appendices C and D--[Removed]
6. In Part 136, Appendices C and D are proposed to be removed.
[FR Doc. 95-25775 Filed 10-17-95; 8:45 am]
BILLING CODE 6560-50-P
