PARAMETER HANDBOOK
FOR THE
NATIONWIDE URBAN RUNOFF PROGRAM
\
ul
C3
October 1979
Water Planning Division
U.S. Environmental Protection Agency
Washington, D.C. 20460
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PARAMETER HANDBOOK
by
Philip E. Shelley, Ph.D.
EG&G Washington Analytical Services Center, Inc.
Rockville, Maryland 20850
Reprinted from the
AREAWIDE ASSESSMENT PROCEDURES MANUAL
EPA 600/9-76-014
for the
NATIONWIDE URBAN RUNOFF PROGRAM
Water Planning Division
U.S. Environmental Protection Agency
Washington, D.C. 20460
October 1979
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APPENDIX D, PART II
PARAMETER HANDBOOK
This Parameter Handbook has been written as a part of the
Areawide Assessment Procedures Manual to aid 208 planning agencies
in the establishment and conduct of water quality monitoring pro-
grams. The material presented summarizes existing work rather
than representing new research results. The intent is to present,
on one sheet of paper, enough salient information about a partic-
ular water quality parameter to allow decisions to be made as to
the likelihood of the constituent's presence in a particular stream
or discharge, its effects upon water quality or use, and factors
pertaining to sampling and analysis of the constituent that should
be considered in determining the ramifications of including the
parameter in a water quality monitoring program. The information
presented on analytical methodology, including sample quantity and
preservation and handling considerations, was largely taken from
one of three widely available sources:
fax. Chemical. Ana£t/^^A o^ WateA and floated, 1974
(commonly called "EPA Methods Manual"). Available from
USEPA Environmental Research Information Center,
Cincinnati, OH 45268.
• Standard Mvtkod& fan, the. Exo/naiation o£ WcvteA and
Woutzn., 14th Edition, 1976 (commonly called "Standard
Methods"). Available from the American Public Health
Association, 1015 18th Street, N.W., Washington,
D.C. 20036.
• Annual Book o£ StandaAd&, V
-------
regard, the USEPA has published, pursuant to section 304(g) of the
Water Pollution Control Act Amendments (PL 92-500), "Guidelines
Establishing Test Procedures for the Analysis of Pollutants" in
the Wednesday, December 1, 1976 issue of the Federal Register
(40 CFR 136), a- copy of which is attached at the end of this
Parameter Handbook. Some minor corrections to these Guidelines
were published in the Federal Register on Tuesday, January 18, 1977.
The synoptic presentations in this Parameter Handbook are
written for a reader without extensive training or experience in
water and wastewater analysis. A common format, depicted in
Figure 1, has been used for each parameter. The entries will be
discussed in turn.
Parameter Name: This is the most common name by which the param-
eter is most frequently known, not necessarily its proper chemical
name. Where other names are commonly used or the chemical for-
mula might be helpful, they are indicated in the general discus-
sion.
A number of parameters are part of the USEPA water quality
data storage and retrieval system (STORET) at the present time,
and more will be added in the future. Where a parameter is a
part of the STORET System as of March 1977, the following two
entries are filled in; otherwise they are left blank.
Parameter Group: Each parameter is assigned to a designated group
(e.g., metals, general organic, pesticides) in the STORET System,
and this entry indicates the group to which the parameter belongs.
STORET Units: The units that must be used for entry of the concen-
tration of the parameter into the STORET System are given here;
e.g., micrograms per liter (yg/£).
General: This is a brief summary of salient parameter character-
istics. Typically covered are such things as what the parameter
is; any common alternate name or chemical formula where possibly
helpful; natural sources; uses of the substance and possible
sources related thereto; indications of the persistence of the
parameter in water, including its solubility where appropriate;
effects of the parameter on water use, including toxicity data
where appropriate; and, since many of these parameters are
actually toxic substances or surrogate measures for toxic sub-
stances, the level of regulation that has been imposed upon them
(such as the two technologically feasible control oriented stand-
ards of "best practicable control technology currently available"
(BPT) or "best available control technology economically achiev-
able" (BAT) or "toxicity effluent limitations") has been noted
in accordance with the regulation (40 CFR 136), BAT parameters
under the Consent Decree, or toxicity guidelines under the Consent
Decree or other regulatory mandates.
D-144
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PARAMETER NAME
Parameter Group: STORET Units:
General:
Criterion:
Preservation Method:
Maximum Holding Time:
Container Type:
Sample Volume Required:
Measurement:
Precision and Accuracy:
Cost of Analysis:
Figure 1. Format for Parameter Information
D-145
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Criteria: If the USEPA has issued water quality criteria for the
parameter, they are g-iven here along with the beneficial use to be
protected by the criterion established.
Preservation Method: Physical and chemical preservatives to be
used to help maintain sample integrity are indicated here along
with any special sample handling considerations, e.g., keep sealed
until analyzed.
Maximum Holding Time: The maximum holding time between gathering
and preserving the sample and its analysis in the laboratory is
given here. It is a function not only of the physical and chemical
characteristics of the substance involved but also of the other
constituents in the sample. The holding times given are con-
servative in some instances and, if data indicate that longer
holding times do not significantly affect analytical results, they
may be used.
Container Type; Acceptable sample container materials are indi-
cated here. Although not addressed here, sample equipment cleaning
is very important, and special cleaning protocols will be required
for some parameters, e.g., pesticides, as will other special con-
siderations such as the use of TFE fluorocarbon cap liners, etc.
Sample Volume Required; An estimate of the quantity of sample
necessary to allow analysis for the parameter is given here. No
allowance for replication, sample splitting, spillage, etc., is
made. The exact sample quantity required will depend upon the
strength of the constituent, the need for concentration or dilu-
tion, removal of interferences, etc., and is best established after
preliminary laboratory work, but the given volumes can be used as
a first cut.
Measurement; Descriptions of common methods for making the deter-
mination are given here, primarily to indicate any special lab-
oratory equipment that might be required (e.g., AA, GC).
Applicable concentration ranges are given, and possible inter-
ferences and precautions are indicated in many cases. Where a
measurement is mandated by regulation, the regulation is cited.
Precision and Accuracy: Method sensitivity and detection limits are
provided where generally agreed to. Precision and accuracy data are
given where known.
Cost of Analysis: The information provided here is intended to
give an appreciation of the relative magnitude of cost for per-
forming the analysis. The data are typically presented as a range
that represents differences in cost among laboratories and (some-
times) methods for a given parameter. Cost information was ob-
tained from various laboratories across the United States and
D-146
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representative values were selected for the range. Extremely low
or high costs for a particular parameter from a given laboratory
were discarded as atypical. Costs are also influenced by sample
preparation procedures necessary to remove interferences. This is
especially true for pesticide analyses and is represented by large
ranges in many instances, with the lower end of the range being
more typical in most cases. Finally, although not indicated in
the cost data presented herein, many laboratories offer quantity
discounts that may be quite substantial, and local laboratories
should be consulted if firm budget numbers are desired.
There are many water quality parameters that might be of
interest to some 208 agencies. Those that were selected for in-
clusion in this first edition of the Parameter Handbook are the
ones that were considered to have the broadest appeal. They rep-
resent a compilation of those found in the newly issued EPA
Water Quality Criteria, the EPA Methods Manual, and the majority
of the substances listed in the Consent Decree. It is contemplated
that the parameter coverage will be increased in future editions of
this handbook. For many parameters, preferred analytical methods,
preservation techniques, maximum holding times, etc., have not
been established or are tentative. Considerable advancement is
expected in the near term time frame, and future editions will be
updated to disseminate this information.
To assist the reader in locating parameters of interest, a
number of tables are provided. In Table 1, all the parameters
in the handbook are listed in alphabetical order. The parameters
are alphabetically listed within each STORET parameter group in
Table 2. Those parameters for which the USEPA has issued water
quality criteria are alphabetically listed in Table 3. Finally,
those parameters designated by the Consent Decree are listed
alphabetically in Table 4. The parameter sheets in the handbook
are in alphabetical order. A copy of the 1 December 1976
Federal Register is attached at the end.
D-147
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TABLE 1. ALPHABETICAL LISTING OF PARAMETERS
Acidity
Acrolein
Acrylonitrile
Aldrin
Alkalinity
Aluminum
Antimony
Arsenic
Asbestos
Atrazine
Barium
enzene
Benzene Hexachloride (BHC)
Benzidine
Beryllium
Biochemical Oxygen Demand
Boron
Bromide
Cadmium
Calcium
Captan
Carbaryl
Carbon Tetrachloride
Chemical Oxygen Demand
Chlordane
Chloride
Chlorinated Benzenes
Chlorinated Ethanes
Chlorinated Naphthalene
Chlorinated Phenols (Other
Chlorine Demand
Chlorine Dioxide
Chlorine, Residual
Chloroalkyl Ethers
Chloroform
2-Chlorophenol
Chromium
Cobalt
Color
Copper
Cyanide
2, 4-D
DD
DDE
DDT
Demeton
Diazinon
Dichlorobenzenes
Dichlorobenzidine
Dichloroethylenes
2, 4-Dichlorophenol
Dichloropropane
Dichloropropene
Dieldrin
2, 4-Dimethylphenol
Dissolved Oxygen
Disyston
(BOD) Diuron
Endosulfan
Endrin
;% Ethylbenzene
Fecal Coliform
Fecal Streptococci
Fluoride
Guthion
Haloethers
* Halomethanes
Hardness, Total
) Heptachlor
Iodine
Iron
Lead
Lindane
Lithium
Magnesium
Malathion
Manganese
D-148
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TABLE 1. ALPHABETICAL LISTING OF PARAMETERS (Cont'd)
Residue, Total
Residue, Total Filterable
Residue, Total Nonfilterable
Residue, Volatile
Selenium
Silica
Silicon
Silver
Silvex (2, 4, 5-TP)
Sodium
Specific Conductance
Strontium
Sulfate
Sulfide
Sulfite
2, 4, 5-T
Temperature
Thallium
Threshold Odor
Tin
Titanium
^Toluene
Total Coliform
Toxaphene
Trichloroethylene
Turbidity
Uranium
Vandaium
Vinyl Chloride
Xylene
Zinc
Mercury
Methane
Methoxychlor
Methyl Parathion
Methylene Blue Active
Substances (MBAS)
Mi rex
Molybdenum
Naphthalene
Nickel
Nitrilotriacetic Acid (NTA)
Nitrobenzene
Nitrogen-Ammonia
Nitrogen, Kjeldahl
Nitrogen, Nitrate
Nitrogen, Nitrate-Nitrite
Nitrogen, Nitrite
Nitrophenols
Oil and Grease
Organic Carbon
Parathion
PCNB
Pentachlorophenol
PH
Phenolics
Phosphorous (all forms)
Phthalate Esters
Polychlorinated Biphenyls
Polynuclear Aromatic
Hydrocarbons
Potassium
Radioactivity (alpha and beta)
Radium
Residue, Settleable
D-149
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TABLE 2. LISTING OF PARAMETERS ACCORDING TO
STORET GROUP
Bacteriologic
Fecal Coliform
Fecal Streptococci
Total Coliform
Dissolved Oxygen
Dissolved Oxygen
General Organic
Benzene
Methylene Blue Active
Substances (MBAS)
Nitrilotriacetic Acid (NTA)
Oil and Grease
Organic Carbon
Phenolics
Phthalate Esters
Polychlorinated Biphenyls
Toluene
Xylene
General Inorganic
Acidity
Alkalinity
Asbestos
Bromide
Chloride
Chlorine Demand
Cyanide
Fluoride
Hardness, Total
Iodide
Sulfate
Sulfide
Sulfite
Metals
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Tin
Titanium
Uranium
Vanadium
Zinc
Miscellaneous
Chlorine, Residual
D-150
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TABLE 2. LISTING OF PARAMETERS ACCORDING TO
STORET GROUP (Cont'd)
Nitrogen
Nitrogen-Ammonia
Nitrogen, Kjeldahl
Nitrogen, Nitrate
Nitrogen, Nitrate-Nitrite
Nitrogen, Nitrite
Oxygen Demand
Biochemical Oxygen Demand
(BOD)
Chemical Oxygen Demand
Pesticides
Aldrin
Atrazine
Benzene Hexachloride (BHC)
Benzidine
Captan
Carbaryl
Carbon Tetrachloride
Chlordane
Chloroform
2, 4-D
ODD
DDE
DDT
Demeton
Diazinon
Dieldrin
Disyston
Diuron
Endosulfan
Endrin
Guthion
Heptachlor
Lindane
Malathion
Methoxychlor
Methyl Parathion
Mirex
Parathion
Pentachlorophenol
Silvex (-2, 4, 5-TP)
2, 4, 5-T
Toxaphene
Phosphorous
Phosphorus (all forms)
Physical
Color
PH
Specific Conductance
Threshold Odor
Turbidity
Radiological
Radioactivity (alpha and beta)
Strontium
Solids
Residue, Settleable
Residue, Total
Residue, Total Filterable
Residue, Total Nonfilterable
Residue, Volatile
Silica
Silicon
Temperature
Temperature
D-151
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TABLE 3. PARAMETERS FOR WHICH THE USEPA
HAS ISSUED WATER QUALITY CRITERIA
Aldrin
Alkalinity
Arsenic
Barium
Beryllium
Boron
Cadmium
Chlordane
Chlorine, Residual
Chromium
Color
Copper
Cyanide
2,4-D
DDT
Demeton
Dieldrin
Dissolved Oxygen
Endosulfan
Endrin
Guthion
Heptachlor
Iron
Lead
Lindane
Malathion
Manganese
Mercury
Methoxychlor
Mirex
Nickel
Oil and Grease
Parathion
pH
Phenolics
Phosphorus (all forms)
Phthalate Esters
Polychlorinated Biphenyls
Residue, Total Filterable
Residue, Total Nonfilterable
Selenium
Silver
Si1vex
Temperature
Toxaphene
Zinc
D-152
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TABLE 4. CHEMICAL CLASSES AND COMPOUNDS DESIGNATED
AS PRIORITY POLLUTANTS IN THE TOXICS SETTLEMENT AGREEMENT
Acenaphthene
Acrolein
Acrylonitrile
Aldrin
Antimony (total)
Arsenic (total)
Asbestos
Benzene
Benzidine
Beryllium (total)
Cadmium (total)
Carbon Tetrachloride
(tetrachloromethane)
Chlordane (technical mixture
and metabolites)
Chlorinated Benzenes (other
than dichlorobenzenes)
Chlorinated Ethanes (including
1, 2-trichloroethane and
hexachloroethane)
Chlorinated Naphthalene
Chlorinated Phenols, (other
than those listed else-
where; includes trichloro-
phenols and chlorinated
cresols)
Chloroalkyl Ethers (chloro-
methyl, chloroethyl, and
mixed ethers)
Chloroform (trichloromethane)
2-Chlorophenol
Chromium (total)
Copper (total)
Cyanide (total)
DDT and Metabolites
Dichlorobenzenes
Dichlorobenzidine
Dichloroethylenes (1,
1-dichloroethylene and
1, 2-dichloroethylene)
2, 4-Dichlorophenol
Dichloropropane and Dichloro-
propene
2, 4-Dimethylphenol
2, 4-Dinitrophenol
Dinitrotoluene
1, 2-Diphenlhydrazine
Endosulfan and Metabolites
Endrin and Metabolites
Ethylbenzene
Fluroanthene
Haloethers (other than those
listed elsewhere)
Halomethanes (other than those
listed elsewhere)
Heptachlor and Metabolites
Hexachlorobutadiene
Hexachlorocyclohexane (all
isomers)
Hexachlorocyclopentadiene
Isophorone
Lead (total)
Mercury
Naphthalene
Nickel (total)
Nitrobenzene
Nitrophenols (including 2,
4-dinitrophenol and dinitro-
cresol)
Nitrosamines
Pent ach1oropheno1
Phenol
Phthalate Esters
Polychlorinated Biphenyls (PCB's)
Polynuclear Aromatic Hydrocarbons
Selenium (total)
Silver (total)
2, 3, 7, 8-Tetrachlorodibenzo-
P-Dioxin (TCDD)
Tetrachloroethylene
Thallium (total)
Toluene
Toxaphene
Trichloroethylene
Vinyl Chloride (chloroethylene)
Zinc (total)
D-153
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ACIDITY
Parameter Group: General STORET Units: mg/£ as CaCO.
Inorganic
General; Acidity is a measure of a gross property of water, its
quantitative ability to neutralize a strong base to a designated
pH. It can be interpreted in terms of specific substances only
when the chemical composition of the sample is known. Acids con-
tribute to corrosiveness and influence certain chemical and bio-
logical processes; therefore, the acidity of water is important.
This is a parameter which is regulated by BPT guidelines prescribed
by the NPDES permits program.
Criterion: Not established
Preservation Method; Analyze as soon as practicable. Fill sample
bottles completely and cap tightly. The sample should not be agi-
tated or exposed to air for a prolonged period of time. Cool to
4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 100 mi
Measurement: The pH of the sample is determined and a measured
amount of standard acid is added, as needed, to lower the pH to
4 or less. Hydrogen peroxide is added, the solution boiled for
several minutes, cooled, and titrated electrometrically with
standard alkali to pH 8.2. Suspended matter present in the sam-
ple, or precipitates formed during the titration may cause a slug-
gish electrode response. This may be offset by allowing a 15-
20 second pause between additions of titrant or by slow dropping
addition of titrant as the endpoint pH is approached. For BPT
NPDES purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: On a round robin conducted by ASTM on
4 acid mine waters, including concentrations up to 2,000 mg/£, the
precision was found to be ±10 mg/£.
Cost of Analysis: $4 - $5
D-154
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ACROLEIN
Parameter Group: STORET Units:
General: Acrolein (also known as acrylic aldehyde or 2-propenol)
is a clear, colorless liquid at ordinary temperatures with a pun-
gent irritating odor. It is extremely irritating to the skin
and mucous membranes and is readily soluble in water. Its main
use is as an aquatic weed killer. This parameter will be regu-
lated by BAT guidelines prescribed by the NPDES permits program.
It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against separation. Fill the sample bottle completely and seal
until analysis is performed. Do not refrigerate.
Maximum Holding Time; Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement: No standard procedures for acrolein have been de-
veloped. It may require special treatment to extract from water
prior to gas chromatographic analysis. A BAT NPDES method will be
prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Precision and accuracy data are not
available.
Cost of Analysis: Expensive; must be quoted based on sample
composition.
D-155
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ACRYLONITRILE
Parameter Group: STORET Units:
General: Acrylonitrile is a flammable liquid used in the manu-
facture of synthetic rubber and plastics and as a pesticide fumi-
gant for stored grain. It is moderately soluble in water and does
not disassociate markedly. Upon disassociation it can form HCN,
the toxic cyanide principle. Concentrations of 20 mg/£ are dele-
terious for many fish. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. It is one of
the Consent Decree pollutants.
Criterion: Not established
Preservation Method; Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis .is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement: No preferred method has been established. Acrylon-
itrile has been determined in wastewater by azeotropic distilla-
tion with methanol followed by measurement of NH_ liberated by
alkali saponification, but the method may not be practicable for
many wastewaters. Detection limits are around 2,000 yg/£. A BAT
NPDES method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Precision and accuracy data are not
available.
Cost of Analysis: Expensive; must be quoted based on sample
composition.
D-156
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ALDRIN
Parameter Group: Pesticides STORET Units: \ig/l
General: Aldrin, the common name of an organochlorine insecticide,
is metabolically converted to dieldrin by aquatic organisms. Be-
cause of this metabolic conversion and because of evidence that
dieldrin is as toxic or slightly more toxic than aldrin to aquatic
organisms, an acceptable water concentration is based on the
presence of either aldrin or dieldrin or the sum of both. Aldrin
is used agriculturally at rates varying from 2 oz to 6 Ib per
acre, usually as a dust or emulsifiable concentrate; it is vir-
tually insoluble in water. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. "It is one of
the Consent Decree pollutants. A toxic effluent limitation has
been prescribed for this parameter by the NPDES permits program.
Criteria
• 003 yg/£ for freshwater and marine aquatic life
• The persistence, bioaccumulation potential, and carcino-
genicity of aldrin cautions human exposure to a minimum.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric or
electrolytic conductivity gas chromatography is recommended for
aldrin. Many interferences exist, especially PCB's, phthalate
esters, and organophosphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration. For
example, at the 0.015 and 0.110 yg/£ concentrations, recoveries
were around 69% and 72% and precisions were 47% and 41%,
respectively.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-157
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ALKALINITY
Parameter Group: General STORET Units: mg/£ as CaCO_
Inorganic
General: Alkalinity is a measure of a gross property of water,
its quantitative ability to neutralize a strong acid to a desig-
nated pH. It can be interpreted in terms of specific substances
only when the chemical composition of the sample is known. Alka-
linity, therefore, is a measure of the buffering capacity of the
water, and since pH has a direct effect on organisms as well as
an indirect effect on the toxicity of certain other pollutants in
the water, the buffering capacity is important to water quality.
This is a parameter which is regulated by BPT guidelines pre-
scribed by the NPDES permits program.
Criterion: 20 mg/£ or more as CaCO_ for freshwater aquatic life
except where natural concentrations are less.
Preservation Method: Analyze as soon as practicable. Fill sample
bottles completely and cap tightly. The sample should not be agi-
tated or exposed to air for a prolonged period of time. Cool to
4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 100 m£
Measurement: An unaltered sample is titrated to an electrometri-
cally determined end point of pH 4.5. The sample must not be
filtered, diluted, concentrated, or otherwise altered in any way.
Substances such as salts of weak organic and inorganic acids pres-
ent in large amounts may cause interference in the electrometric
pH measurements. Oil and grease may interfere by coating the
electrode, thereby causing sluggish response. For BPT NPDES pur-
poses the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy; No general statement can be made about
precision due to the great variation in sample characteristics.
Forty analysts in seventeen laboratories analyzed synthetic water
samples containing increments of bicarbonate equivalent to around
9 and 116 rag/£ CaCCL. The bias was approximately +16% and -8%
and relative standard deviation was approximately 14% and 5%,
respectively.
Cost of Analysis: $4 - $5
D-158
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ALUMINUM
Parameter Group: Metals STORET Units: yg/£ as Al
General: Aluminum, being the third most abundant element in the
earth's crust, occurs in minerals, rocks, and clays. Aluminum is
found as a soluble salt, a colloid, or an insoluble compound in
natural waters. Aluminum in wastewaters occurs from primary alu-
minum production and from secondary aluminum processes such as in-
got cooling and shot quenching, scrubbing of furnance fumes during
demagging, and wet milling of residues. Washwater from water
treatment plants is another likely source, as are discharges from
dyeing and cloth printing operation, paper mills, disinfectant op-
eration, tanneries, viscose rayon plants, and many other industrial
operations. Very little ingested aluminum is absorbed in the
alimentary canal, so its presence does not normally pose a public
health problem. Conflicting literature abounds on crop effects.
An average daily dose of 2 mg aluminum has not harmed rats. This
is a parameter which is regulated by BPT guidelines prescribed by
the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNCL to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 309.2 nm. Aluminum is partially ionized in
the nitrous oxide-acetylene flame. This problem may be con-
trolled by the addition of an alkali metal (potassium, 1,000 yg/
m£) to both sample and standard solutions. For BPT NPDES pur-
poses the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 1,000 yg/£;
its detection limit is 100 yg/£. The optimum concentration range
is 5,000-100,000 yg/£. At a concentration of 300 yg/£, the rela-
tive standard deviation is 22.2%, and the relative error is 0.7%.
Precision and accuracy decrease markedly for decreasing concen-
trations. For example, in an interlaboratory study on trace metals
analysis, at true values of 35 and 15 yg/£, the relative standard
deviations were 309% and 1,120%, respectively, while the relative
errors were 175% and 627%, respectively.
Cost of Analysis: $10 - $20
D-159
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ANTIMONY
Parameter Group: Metals STORET Units: yg/£ as Sb
General: Natural antimony occurs chiefly as the sulfide or in
oxide forms. Antimony is used in various industrial operations,
especially in alloying as, for example, with lead for storage
battery plates, with lead and tin in type metals, and with tin
and copper as a bearing or antifriction material, and may be
introduced into wastewaters from such sources, as well as the
rubber, textile, explosives, paint, ceramic, and glass industries.
Antimony has been reported to cause dermatitus and gastroin-
testinal disturbances in humans (it has long been used as an
emetic) and has been found to shorten the life span of rats.
This is a parameter which is regulated by BPT guidelines pre-
scribed by the NPDES permits program. This parameter will be
regulated by BAT guidelines prescribed by the NPDES permits pro-
gram. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO, to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 217.6 nm. In the presence of lead
(1,000 mg/£), a spectral interference may occur at the 217.6 nm
resonance line. In this case, the 231.1 nm antimony line should
be used. Increasing acid concentrations decrease antimony ab-
sorption. To avoid this effect, the acid concentration in the
samples and in the standards should be matched. For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 500 yg/£;
its detection limit is 200 yg/£. The optimum concentration range
is 1,000-40,000 yg/£. In a single laboratory, using a mixed
industrial-domestic waste effluent at concentrations of 5,000 yg
and 15,000 yg Sb/£, the relative standard deviations were 1.6% and
.66%, respectively. Recoveries at these levels were 96% and 97%,
respectively.
Cost of Analysis: $10 - $20
D-160
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ARSENIC
Parameter Group: Metals STORET Units: yg/£ as As
General: Mineral dissolution, industrial discharges, or the ap-
plication of pesticides may lead to the occurrence of arsenic in
water. Though most forms of arsenic are toxic to humans, arsen-
icals have been used in the medical treatment of spirochaetal in-
fections, blood dyscrasias and dermatitis. Arsenic and arsenicals
have many diversified industrial uses such as hardening of copper
and lead alloys, tannery operations, pigmentation in paints and
fireworks, and the manufacture of glass and ceramics, cloth, elec-
trical semiconductors, and petroleum products. Arsenicals are
used in the formulation of herbicides for forest management and
agriculture. This is a parameter which is regulated by BPT guide-
lines prescribed by the NPDES permits program. This parameter will
be regulated by BAT guidelines prescribed by the NPDES permits pro-
gram. It is one of the Consent Decree pollutants.
Criteria:
50 yg/£ for domestic water supplies (health)
100 yg/£ for irrigation of crops
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO, to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric gaseous hydride method is
recommended for determining total arsenic, using a wavelength of
193.7 nm. The method is applicable to most fresh and saline
waters in the absence of high concentrations of chromium, copper,
cobalt, mercury, molybdenum, nickel, and silver. A BAT NPDES
method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is approximately
2.5 yg/£; its detection limit is 2.0 yg/£. The working range of
the method is 2.0-20 yg/£. At a concentration of 10 yg/£, the
relative standard deviation is 6% and the relative error is 1%.
Ten replicate solutions of o-arsenilic acid at the 5, 10, and
20 yg/£ level were analyzed by a single laboratory. Relative
standard deviations were 6%, 9%, and 5.5% with recoveries of
94, 93, and 85%, respectively.
Cost of Analysis: $15 - $20
D-161
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ASBESTOS
Parameter Group: General STORET Units: Count/liter
Inorganic with length/
width >1
General: Asbestos is primarily an air pollutant which has been
shown to produce asbestosis, lung cancer, and mesothelioma in as-
bestos workers. However, the problems of asbestos in water have
been recognized. It was discovered in 1973 that the drinking
water of Duluth, Minnesota, and other cities on Lake Superior was
heavily contaminated with asbestos. Sources of asbestos contami-
nation include: asbestos mining, pulpmills, asbestos products,
installation of asbestos construction material, spray-on steel
fireproofing, and insulating cement application. This parameter
will be regulated by BAT guidelines prescribed by the NPDES per-
mits program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible
Maximum Holding Time: Unknown
Container Type: Glass or plastic
Sample Volume Required: Approximately 1,000 rut
Measurement: The present procedure is the microscopic count-
ing of fibers in water. Asbestos probably cannot be routinely
determined in effluents in the absence of gross contamination.
A BAT NPDES method will be prescribed for this parameter in
40 CFR 136.
Precision and Accuracy: Precision and accuracy data are not
available at this time.
Cost of Analysis: No standard pricing due to impracticability of
analysis.
D-162
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ATRAZINE
Parameter Group: Pesticides STORET Units:
General: Atrazine, 2-chloro-4-ethylamino-6-isopropylamino-S-
triazine,-is a triazine pesticide. It is used as a selective
herbicide. It has an oral LD_Q in rats of 3.08 g/kg. This is a
parameter which is regulated by BPT guide-lines prescribed by the
NPDES permits program.
Criterion: Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 1,000 nv£
Measurement: The recommended method covers the determination of
various symmetrical triazine pesticides. It involves an efficient
sample extraction procedure and provides, through use of column
chromatography, a method for the elimination of non-pesticide in-
terferences and the pre-separation of pesticide mixtures. Identi-
fication is made by selective gas chromatographic separation, and
measurement is accomplished by the use of an electrolytic conduc-
tivity detector (CCD). Solvents, reagents, glassware, and other
sample processing hardware may yield discrete artifacts and/or
elevated baselines causing misinterpretation of gas chromatograms.
The interferences in industrial effluents are high and varied.
Nitrogen containing compounds other than the triazines may
interfere. For BPT NPDES purposes the measurement of this param-
eter is prescribed by 40 CFR 136.
Precision and Accuracy: Atrazine can be determined by this method
with a sensitivity of 1 yg/£. Precision and accuracy data are not
available at this time.
Cost of Analysis: $30 to $150, depending upon preparation
required.
D-163
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BARIUM
Parameter Group: Metals STORET Units: yg/£ as Ba
General : Barium compounds are used in a variety of industrial ap-
plications including the metallurgical, paint and dye, glass,
ceramic, and electronics industries, as well as for medicinal
purposes, the vulcanizing of rubber, and explosives, manufacturing.
Barium naturally occurs only in trace amounts in water. Therefore,
appreciable amounts of barium indicates undesirable industrial dis-
charges. A barium dose of 550,000 to 600,000 yg is considered
fatal to human beings. This is a parameter which is regulated by
BPT guidelines prescribed by the NPDES permits program.
Criterion: 1 mg/£ for domestic water supply (health)
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO, to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 553.6 nm. The use of a nitrous oxide-
acetylene flame virtually eliminates chemical interference; how-
ever, barium is easily ionized in this flame and potassium must
be added (1,000,000 yg/£) to standards and samples alike to con-
trol this effect. If the nitrous oxide flame is not available and
acetylene-air is used, phosphate, silicon and aluminum will
severely depress the barium absorbance. This may be overcome by
the addition of 2,000,000 yg/£ lanthanum. For BPT NPDES purposes
the measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 400
its detection limit is 30 yg/£. The optimum concentration range
is 1000-20,000 pg/£. At a concentration of 500 yg/£, the relative
standard deviation is 10%, and the relative error is 8.6%. In a
single laboratory, using a mixed industrial-domestic waste efflu-
ent at concentrations of 400 and 2,000 pg Ba/£, the relative stand
ard deviations were 10.8% and 6.5%, respectively. Recoveries at
these levels were 94% and 113%, respectively.
. Cost of Analysis : $10 - $15
D-164
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BENZENE
Parameter Group: General STORET Units: yg/£
Organic
General: Benzene (C,Hfi) is the simplest of the aromatic compounds
and is used extensively as a commercial solvent and for the syn-
thesis of other organic substances. At normal temperatures it is
a volatile, flammable, colorless liquid with an ethereal odor. It
is moderately soluble in water, 820 mg/£ at 22°C. It occurs in
wastes from chemical plants, dyeing and other textile operations,
and many other industrial processes. The oral LD^ for rats is
around 5,600 mg/kg of body weight. The toxicity of benzene toward
fish has been reported from 5,000 yg/£ up to 395,000 yg/£ depend-
ing upon age and species. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. It is one of
the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 200-1,000 m£
Measurement: Hexadecone extraction followed by a gas chromato-
graphic and mass spectrometric analysis is often used. A BAT NPDES
method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Detection limits should be around
2-10 yg/£.Precision and accuracy data are not available at this
time.
Cost of Analysis: $15 - $30
D-165
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BENZENE HEXACHLORIDE (BHC)
Parameter Group: Pesticides STORET Units: pg/£
General: Benzene hexachloride (BHC), the common name of hexa-
chlorocyclohexane, is an organochlorine pesticide. It has five
known stereoisomers, the gamma isomer (lindane) being the most
powerful insecticidal principle. BHC has a residual life in
soil approaching that of DDT. Elevated concentrations of BHC
reduce treatment plant efficiency, cause stream organisms to
disappear, and produce disagreeable odors. It can impart a
musty odor and taste to crops. This parameter will be regulated
by BAT guidelines prescribed by the NPDES permits program. It
is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric or
electrolytic conductivity gas chromatography is recommended for
BHC. Many interferences exist, especially PCB's, phthalate esters,
and organophosphorus pesticides, and the method is only recommended
for use by a skilled, experienced pesticide analyst (or under
close supervision of such a person). A BAT NPDES method will be
prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors but usually falls in the 0.001 to 1 yg/£ range. Increased
sensitivity is likely to increase interference. Typically, the
percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-166
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BENZIDINE
Parameter Group: Pesticides STORET Units: yg/£
General: Benzidine (4, 4'-diaminobiphenyl, ci7H12N2^ *s
nuclear organic pesticide. A crystalline substance, it is only
slightly soluble in water. It possesses carcinogenic properties
and must be handled with great care. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits
program. This parameter will be regulated by BAT guidelines pre-
scribed by the NPDES permits program. It is one of the Consent
Decree pollutants. A toxic effluent limitation has been pre-
scribed for this parameter by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 1 week
Container Type: Borosilicate glass
Sample Volume Required: 1,000-4,000 mi, depending on concentration
and instrument used.
Measurement: Benzidines are separated and concentrated by multiple
extractions and then oxidized by chloramine T. The oxidation prod-
uct is extracted and measured spectrophotometrically. For BPT
NPDES purposes the measurement of this parameter is prescribed by
40 CFR 136. A BAT NPDES method will be prescribed for this param-
eter in 40 CFR 136.
Precision and Accuracy; The detection limit is approximately
0.2 yg/£.Precision and accuracy data are not available at this
time.
Cost of Analysis: $20 - $40; because of its carcinogenic proper-
ties, special facilities may be required at greatly increased cost.
D-167
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BERYLLIUM
Parameter Group: Metals STORET Units: yg/£ as Be
General: Beryllium is not likely to occur at significantly toxic
levels in ambient natural waters. Beryllium could enter waters in
effluents from certain metallurgical plants and discharges from
industries dealing with atomic reactors, X-ray diffraction tubes,
neon signs, aircraft and rockets, and missile fuel. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. It is one of
the Consent Decree pollutants.
Criteria:
11 \ig/t for the protection of aquatic life in soft fresh
water
1,100 pg/£ for the protection of aquatic life in hard
fresh water
100 yg/£ for continuous irrigation on all soils; except
500 ug/£ for irrigation on neutral to alkaline fine-
textured soils
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO_ to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement; The AA spectrophotometric or aluminum colorimetric
methods are suitable. The latter requires either a spectro-
photometer for use at 515 nm or a filter photometer equipped with
a green filter having maximum transmittance near 515 nm; either
must provide a light path of 5 cm. Sodium and silicon at concen-
trations in excess of 1,000,000 pg/£ have been found to severely
depress the beryllium absorbance. Bicarbonate ion is reported to
interfere; however, its effect is eliminated when samples are
acidified to a pH of 1.5. Aluminum at concentrations of >500 yg/£
is reported to depress the sensitivity of beryllium. For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136. A BAT NPDES method will be prescribed for this param-
eter in 40 CFR 136.
D-168
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Precision and Accuracy: The AA method sensitivity is 25 yg/£; its
detection limit is 5 pg/£. The optimum concentration range is
50-2,000 yg/£. In a single laboratory, using a mixed industrial-
domestic waste effluent at concentrations of 10, 50, and 250 yg/£,
the relative standard deviations were 10%, 2%, and 1%, respec-
tively. Recoveries at these levels were 100%, 98%, and 97%, re-
spectively. In 32 laboratories using a known sample containing
250 pg/£, the beryllium was determined •colorimetrically with a
relative standard deviation of 7% and a relative error of 12%.
Cost of Analysis: $10 - $20
D-169
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BIOCHEMICAL OXYGEN DEMAND (BOD) .
Parameter Group: Oxygen Demand STORET Units: mg/£
General: The biochemical oxygen demand (BOD) determination is an
empirical test used to obtain a measure of the relative oxygen de-
mand of water, especially treatment plant loadings and removal ef-
ficiencies. It is important to realize that BOD results cannot be
compared unless the results have been obtained under identical test
conditions and that the test is of limited value in determining the
actual oxygen demand of surface waters. Complete stabilization of
a given sample may require a period of incubation too long for prac-
ticable purposes, so the 5-day test is most commonly reported. As
an indicator parameter, BOD is not a pollutant and exercises no di-
rect harm. Its indirect effect is to depress dissolved oxygen
levels. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 6 hours
Container Type: Plastic or glass
Sample Volume Required: 1000 m£
Measurement: The recommended method is an empirical bioassay type
procedure which measures the dissolved oxygen consumed by microbial
life while assimilating and oxidizing the organic matter present.
The standard test conditions include dark incubation at 20°C for
5 days. The determination of dissolved oxygen may be made by use
of either the modified Winkler or the electrode method. Many sam-
ples will require seeding due to low microbal populations. For
BPT NPDES purposes the measurement of this parameter is prescribed
by 40 CFR 136.
Precision and Accuracy: Eighty-six analysts in fifty-eight labora-
tories analyzed natural water samples plus an exact increment of
biodegradable organic compounds. At mean values of 2.1 and
175 mg/£ BOD, the standard deviations were ±0.7 and ±26 mg/£,
respectively. There is no acceptable procedure for determining
the accuracy of the BOD test.
Cost of Analysis; $10 - $17
D-170
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BORON
Parameter Group: Metals STORET Units: yg/£ as B
General: Boron is usually found in nature as a sodium or calcium
borate salt. A major source of boron in domestic wastewater is
sodium perborate, used as a bleach in household washing powders.
Fluoroborate solutions are used for plating of cadmium, copper, lead,
nickel, tin, and zinc. Boron salts are used in fire retardants, the
production of glass, leather tanning and finishing industries,
cosmetics, photographic materials, metallurgy, and for high energy
rocket fuels. The ingestion of excessive doses of borates may
cause nausea, cramps, convulsions, coma, or other symptoms of
distress. It appears to pose a greater hazard to plants than
humans, however. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program.
Criterion: 750 ug/£ for long-term irrigation on sensitive crops
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO_ to pH <2.
Maximum Holding Time: 6 months
i
Container Type: Polyethylene bottles or alkali-resistant, boron-
free glassware.
Sample Volume Required: 50-200 m£
Measurement: The curcumin method using colorimetric equipment is
recommended for concentrations in the 100 to 1,000 yg/£ range.
When a sample of water containing boron is acidified and evaporated
in the presence of curcumin, a red-colored product called rosocya-
nine is formed. The rosocyanine is taken up in a suitable solvent,
and the red color is compared with standards either visually or
photometrically. One of the following equipments will be required:
(a) spectrophotometer for use at 540 nm with a light path of 1 cm,
or (b) a filter photometer equipped with a green filter having a
maximum transmittance near 540 nm with a minimum light path of
1 cm. Nitrate nitrogen concentrations above 20,000 yg/£ interfere.
Significantly high results are possible when the total of calcium
and magnesium hardness exceeds 100,000 jag/£ as CaCO_. Passing the
sample through a cation exchange resin eliminates this problem.
Close control of such variables as volumes and concentrations of
reagents, as well as time and temperature of drying, must be ex-
ercised for maximum accuracy. For BPT NPDES purposes the measure-
ment of this parameter is prescribed by 40 CFR 136.
D-171
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Precision and Accuracy: The minimum detectable quantity is
0.2 pg/£ B.A synthetic sample, containing 240 yg/£ B, 40 yg/£
As, 250 ug/£ Be, 20 ug/£ Se, and 6 yg/£ V in distilled water, was
analyzed by the curcumin method in 30 laboratories with a relative
standard deviation of 22.8% and a relative error of 0%.
Cost of Analysis: $5 - $20
D-172
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BROMIDE
Parameter Group: General STORET Units: mg/£ as Br
Inorganic
General: Naturally occurring bromide in water is negligible, out-
side of coastal areas, the major sources being chemical industry
and saltworks effluents. It is used for medicinal compounds,
dyestuffs, gasoline additives, and swimming pool water steriliza-
tion. Like other halogens it is antiseptic and disinfectant and,
hence, may possibly interfere with bacterial and other natural
purification processes. This is a parameter which is regulated by
BPT guidelines prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 100 m£
Measurement: The titrimetric method is recommended. The concen-
tration range for this method is 2-20 mg bromide/^. After pre-
treatment to remove interferences, the sample is divided into two
aliquots. One aliquot is analyzed for iodide. The other aliquot
is analyzed for iodide plus bromide. Bromide is then calculated
by difference. Iron manganese and organic matter can interfere;
however, the calcium oxide pretreatment removes or reduces these
to insignificant concentrations. Color interferes with the ob-
servation of indicator and bromine - water color changes. This
interference is eliminated by the use of a pH meter instead of a
pH indicator and the use of standardized amounts of oxidant and
oxidant quencher. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: In a single laboratory, using a mixed
domestic and industrial waste effluent, at concentrations of 0.3,
2.8, 5.3, 10.3, and 20.3 mg/£ of bromide, the relative standard
deviations were 43%, 13%, 7.2%, 4.3%, and 2.1%, respectively. At
concentrations of 2.8, 5.3, 10.3, and 20.3 mg/£ of bromide, re-
coveries were 96%, 83%, 97%, and 99%, respectively.
Cost of Analysis: $15 - $20
D-173
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CADMIUM
Parameter Group: Metals STORET Units: yg/£ as Cd
General: Cadmium occurs in nature chiefly as a sulfide salt, fre-
quently in association with zinc and lead ores. The salts of the
metal also may occur in wastes from electroplating plants, pigment
works, textile and chemical industries. Cadmium is also used in
everyday items such as paint, some pottery pigments, plastics, and
automobile tires. Cadmium is present as an impurity in the more
common galvanized coatings. Biologically, cadmium is a nonessen-
tial, nonbeneficial element recognized to be of high toxic po-
tential. The concentration and not the absolute amount determines
the acute toxicity of cadmium. Cadmium and cadmium compounds
produce acute or chronic symptoms varying in intensity from irri-
tations to extensive disturbances resulting in death. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. It is one of
the Consent Decree pollutants.
Criteria:
10 ]ig/t for domestic water supply (health)
• Aquatic Life:
Fresh Water
Soft Water Hard Water
0.4 yg/£ 1.2 yg/£ for cladocerans
and salmonid
fishes
4.0 yg/£ 12.0 yg/£ for other, less
sensitive, aquatic
life
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HMO. to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 mi
D-174
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Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 228.8 nm. For levels of cadmium below
20 pg/£, the extraction procedure is recommended. The dithizone
procedure may also be used. It requires either a spectrophotom-
eter for use at 518 nm or a filter pho.tometer equipped with a
green filter having a maximum light transmittance near 518 nm;
either must provide a light path of at least 1 cm. For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136. A BAT NPDES method will be prescribed for this
parameter in 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 250 yg/£; its
detection limit is 2 ug/£. The optimum concentration range is 50-
2,000 yg/£. At a concentration of 50 yg/£, for the AA method the
relative standard deviation is 21.6% and the relative error is
8.2%, while for the dithizone method they are 24.6% and 6.0%,
respectively.
Cost of Analysis: $10 - $15
D-175
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CALCIUM
Parameter Group: Metals STORET Units: mg/£ as Ca
General: Calcium enters water supplies through passage over de-
posits of limestone, daloraite, gypsum, and gypsiferous shale.
Calcium salts and ions are among the most commonly encountered
substances in water. Calcium salts breakdown on heating to form
scale in boilers, pipes, and cooking utensils. Calcium adds to
the total hardness of water. Calcium salts used on unpaved road-
ways and in innumerable industrial discharges represent other
sources. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO_ to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 422.7 nm. Phosphate, sulfate and aluminum
interfere but are masked by the addition of lanthanum. The nitrous
oxide-acetylene flame will provide two to five times greater sensi-
tivity and freedom from chemical interferences. lonization in-
terferences should be controlled by adding a large amount of
alkali to the sample and standards. For general use, the EDTA
titrimetric method is the method of choice due to its simplicity
and rapidity. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 0.08 mg/£;
its detection limit is 0.003 mg/£. The optimum concentration
range is 0.2-20 mg/£. In a single laboratory, using distilled
water at concentrations of 9.0 and 36 mg/£, the relative standard
deviations were 3.3% and 1.6%, respectively. Recoveries at both
these levels were 99%. In a 44-laboratory test, synthetic un-
known samples containing 108 mg/£ Ca (with other metals) were
analyzed with a relative standard deviation of 9.2% and a relative
error of 1.9%.
Cost of Analysis: $5 - $15
D-176
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CAPTAN
Parameter Group: Pesticides STORET Units: yg/£
General: Captan is an approved name for the organochlorine fungi-
cide CqH8Cl,NO_S. It is the active ingredient in the proprietary
product Captan 50-W and was also known as SR-406, Vancide 89, and
Orthocide. It is insoluble in water but partially soluble in some
organic solvents. Captan has a very low toxicity to mammals (e.g.,
the LD5Q for rats is over 9 g/kg of body weight) and is readily
hydrolyzed, the effective residual life being on the order of two
weeks. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric or
electrolytic conductivity gas chromatography is recommended for
captan. Many interferences exist, especially PCB's, phthalate
esters, and organophosphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors but usually falls in the 0.001 to 1 pg/£ range. Increased
sensitivity is likely to increase interference. Typically, the
percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-177
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CARBARYL
Parameter Group: Pesticides STORET Units: yg/£
General: Carbaryl, commonly known as Sevin, is an 0-ARYL
carbamate insecticide. It is commonly used on lawns as well as
for other purposes. It is slightly soluble in water, sparingly
soluble in most organic solvents, but freely soluble in amides.
It has low mammalian toxicity, the acute oral LD_n to rats being
reported from 500,000 to 2,190,000 vg/kg of body weight. Although
persistent, its toxicity to aquatic life appears to be low also.
This is a parameter which is regulated by BPT guidelines pre-
scribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 1,000 mi
Measurement; In the recommended method, a measured volume of water
is extracted with methylene chloride, and the concentrated extract
is cleaned up with a Florisil column. Appropriate fractions from
the column are concentrated and portions are separated by thin-
layer chromatography. The carbamates are hydrolyzed on the layer
and the hydrolysis products are reacted to yield specific colored
products. Quantitative measurement is achieved by visually com-
paring the responses of sample extracts to the responses of
standards on the same thin layer. Identifications are confirmed by
changing the pH of the layer and observing color changes of the
reaction products. Phenols interfere directly, and indirect inter-
ferences may be encountered from naturally colored materials whose
presence masks the carbamate reaction. The method is recommended
for use only by an experienced pesticide analyst (or under close
supervision of such a person). For BPT NPDES purposes the measure-
ment of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Carbaryl can be determined with a
sensitivity of 1 yg/£. Precision and accuracy data are not
available at this time.
Cost of Analysis: $30 - $60
D-178
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CARBON TETRACHLORIDE
Parameter Group: Pesticides STORET Units: yg/£
General: Carbon tetrachloride, CC1., is used in industry as an
organic solvent, fire extinguisher, and for dry cleaning of cloth-
ing. In human and veterinary medicine, it is used as an anti-
helminthic. Carbon tetrachloride is colorless nonflammable liquid
with a strong odor. Death has occurred from ingestion of 5 m£,
about 8 grams. Repeated skin contact will result in dermatitis.
This parameter will be regulated by BAT guidelines prescribed by
the NPDES permits program. It is one of the Consent Decree
pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect the
sample from phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement: The recommended method for carbon tetrachloride is a
direct aqueous-injection procedure for the determination of gas
chromatographable chlorinated hydrocarbons. A 3-10 y£ aliquot of
the sample is injected into the gas chromatograph equipped with a
halogen specific detector. Compounds containing bromine or iodine
will interfere with the determination. A BAT NPDES method will be
prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is approxi-
mately 1,000 pg/£.Detection limits of 0.2-3 yg/£ may be achieved.
Precision and accuracy data are not available at this time.
Cost of Analysis: Around $60.
D-179
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CHEMICAL OXYGEN DEMAND
Parameter Group: Oxygen Demand STORET Units: mg/£
General: The chemical oxygen demand (COD) test determines the
quantity of oxygen required to oxidize a portion of organic matter
in a waste sample, under specific conditions of oxidizing agent,
temperature, and time. It is an important parameter for stream
and industrial waste studies and control of waste treatment plants
and can be rapidly determined. Exactly the same technique must be
used each time, since the results depend upon the chemical oxidant
used, the structure of the organic compounds, and the manipulative
procedures. Although empirical correlations with other oxygen de-
mand indicators may be made for a given waste stream, there is no
uniform theoretical basis for association. COD is not a pollutant
in and of itself and exercises no direct harm. Its indirect
effect is to depress dissolved oxygen levels. This is a parameter
which is regulated by BPT guidelines prescribed by the NPDES per-
mits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add H_SO. to pH <2.
Maximum Holding Time: 7 .days
Container Type: Plastic or glass
Sample Volume Required: 50 m£
Measurement: The dichromate reflux method is recommended. The
method is applicable to domestic and industrial waste samples
having an organic carbon concentration greater than 15 mg/£. For
lower concentrations of carbon such as in surface water samples,
the low level modification should be used. When the chloride con-
centration of the sample exceeds 2,000 mg/£, the modification for
saline waters is required. To reduce loss of volatile organics,
the flask should be cooled during addition of the sulfuric acid
solution. For BPT NPDES purposes the measurement of this param-
eter is prescribed by 40 CFR 136.
Precision and Accuracy; Eighty-six analysts in fifty-eight labo-
ratories analyzed a distilled water solution containing oxidizable
organic material equivalent to 270 mg/£ COD. The relative standard
deviation was 6.6% and relative error was 4.7%. A set of synthetic
unknowns analyzed by 74 laboratories resulted in a relative stand-
ard deviation of 6.5% at the 200 mg/£ COD level. At 160 mg/£ COD
and 100 mg/£ chloride, the relative standard deviation was 10.8%.
Cost of Analysis: $10 - $17
D-180
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CHLORDANE
Parameter Group: Pesticides STORET Units: yg/£
General: Chlordane, the common name of an organochlorine insecti-
cide, is a highly persistent chemical which bioaccumulates in
aquatic organisms used for human food. Technical grade chlordane
is a mixture of toxic compounds that have not been separated in
manufacture. There is an extremely wide range for the acute
toxicity of chlordane to various species of freshwater fishes.
Fishes can concentrate chlordane directly from water by a factor
of 1,000 to 3,000 times, and invertebrates may concentrate to twice
this magnitude. Chlordane is stable in the soil and is fungi-
cidal. It could be contained in irrigation return flows. This is
a parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. It is one of
the Consent Decree pollutants.
Criteria:
0.01 yg/£ for freshwater aquatic life
0.004 \ig/t for marine aquatic life
The persistence, bioaccumulation potential, and carcino-
genicity of chlordane cautions human exposure to a minimum.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time; Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
chlordane under favorable conditions. Many interferences exist,
especially PCB's, phthalate esters, and organophosphorus pesti-
cides, and the method is only recommended for use by a skilled,
experienced pesticide analyst (or under close supervision of such
a person). For BPT NPDES purposes the measurement of this param-
eter is prescribed by 40 CFR 136. A BAT NPDES method will be
prescribed for this parameter in 40 CFR 136.
D-181
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Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. Increased
sensitivity is likely to increase interference. Typically, the
percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-182
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CHLORIDE
Parameter Group: General STORET Units: mg/£ as Cl
Inorganic
General: Chloride is one of the major inorganic anions in water
arising from natural mineral origin, seawater intrusion, salts
used for agricultural purposes, sewage, industrial effluents (in-
cluding paperworks, galvanizing plants, water softening plants,
oil wells, and petroleum refineries), roadway deicing, and other
sources. Chlorides in drinking water are not normally harmful at
palatable concentrations. It is generally the cation associated
with the chloride that produces a harmful effect. Chloride ions
exert a significant effect on the corrosion rate of metals (e.g.,
steel and aluminum) and are considered to be among the most
troublesome anions in irrigation water. Injury to livestock seldom
occurs below the 4,000 mg/£ level, but injury to fish has been re-
ported at 400 mg/£. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: None required
Maximum Holding Time; 7 days
Container Type: Plastic or glass
Sample Volume Required: 50 ro£
Measurement: The mercuric nitrate method is recommended wherein
a dilute mercuric nitrate solution is added to an acidified sample
in the presence of mixed diphenylcarbazone-bromophenol blue indi-
cator. The method is suitable for all concentration ranges, but
to avoid large titration volumes, the sample aliquot should not
contain more than 10 to 20 mg Cl per 50 m£. Sulfites interfere
and, if their presence is suspected, oxidize by treating 50 m£ of
sample with 0.5 to 1.0 m£ if K2Q2' Bromide and iodide are
titrated in the same manner as chloride. For BPT NPDES purposes
the measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy; A synthetic unknown sample containing
241 mg/£ Cl was analyzed in 10 laboratories with a relative
standard deviation of 3.3% and a relative error of 2.9%.
Cost of Analysis; $3 - $4
D-183
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CHLORINATED BENZENES
Parameter Group: STORE! Units:
General: Chlorinated benzenes (other than dichlorobenzenes) in-
clude chlorobenzene, 1, 2, 4-trichlorobenzene, and hexachloroben-
zene. They are heavy liquids and settle to the bottom in quiescent
water unless emulsified. Their chief use is as aquatic herbicides
to control weeds in lakes and ditches. They have pungent odors and
therefore are unlikely to cause serious harm to humans through di-
rect ingestion. Mild symptoms of poisoning of sheep and cattle
have been reported at concentrations in excess of 2,700 mg/£. This
parameter will be regulated by BAT guidelines prescribed by the
NPDES permits program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time; Unknown
Container Type: Borosilicate glass
Sample Volume Required; 200-1,000 m£
Measurement: No standard procedures have been developed. The
methodology generally requires extraction, concentration, and gas
chromatographic analysis. A BAT NPDES method will be prescribed
for this parameter in 40 CFR 136.
Precision and Accuracy: Detection limits of 0.1 to 10 yg/£ should
be achievable. Precision and accuracy data are not available at
this time.
Cost of Analysis: $25 - $40
D-184
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CHLORINATED ETHANES
Parameter Group: STORET Units:
General: Chlorinated ethanes are volatile halocompounds including:
1, 2-trichloroethane; hexachloroethane; 1, 2-dichloroethane; 1, 1,
1-trichloroethane; hexachloroethane; 1, 1-dichloroethane; 1, 1,
2-trichloroethane; 1, 1, 2, 2-tetrachloroetharie; and chloroethane.
Widely used in various industries and processes, their character-
istics vary from compound to compound. For example, 1,
2-dichloroethane (also called ethylene dichloride, C^H.Cl-) is a
heavy liquid with a pleasant odor and sweet taste and is highly
soluble in water. It is used as an industrial solvent and in the
manufacture of tobacco extract. Its oral LDr0 for rats is
770 mg/kg of body weight. By contrast, 1, 1, 1-trichloroethane
(also called methyl chloroform) is insoluble in water. It is used
as a solvent for fats, waxes, resins, and alkaloids, and for
cleaning metal and plastic molds. Its toxicity towards the
marine pinperch is twice that of 1, 1, 2-trichloroethane (i.e.,
75-100 mg/£ versus 150-175 mg/£). This parameter will be regu-
lated by BAT guidelines prescribed by the NPDES permits program.
It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement; In the recommended Bellar procedure the sample is
stripped with an inert gas; volatiles are captured on an ad-
sorbent trap and desorbed into a modified gas chromatograph
equipped with a halogen-specific detector. Methodology should be
checked for interferences, e.g., from bromine or iodine. A BAT
NPDES method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy; Sensitivity of 'the method is approximately
1,000 yg/£.Detection* limits of 0.2-3 pg/£ may be achieved. Pre-
cision and accuracy data are not available at this time.
Cost of Analysis: Around $60
D-185
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CHLORINATED NAPHTHALENE
Parameter Group: STORET Units:
General: 2-chloronaphthalene (C,0H_C1) is a solid (at normal tem-
peratures) polynuclear organic compound. It is insoluble in water,
but moderately soluble in other media such as alcohol, benzene, and
ether. This parameter will be regulated by BAT guidelines pre-
scribed by the NPDES permits program. It is one of the Consent
Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly. Cool to
4*CT
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 mi
Measurement: The general procedure involves extraction and meas-
urement with a gas chromatograph. Various cleanup techniques to
remove interferences may be required depending upon other con-
stituents in the sample. A skilled chemist or specialist will be
required. A BAT NPDES method will be prescribed for this param-
eter in 40 CFR 136.
Precision and Accuracy: Detection limits in the 1-10 yg/£ range
should be achievable. Precision and accuracy data are not avail-
able at this time.
Cost of Analysis: $40 - $60
D-186
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CHLORINATED PHENOLS (OTHER)
Parameter Group: STORET Units:
General: Other chlorinated phenols (C,H_C1_0) include the tri- .
chlorophenols and chlorinated cresols (C_H_C10). Although their
specific properties vary from compound to compound, they are gen-
erally only slightly soluble in water but fairly soluble in other
media such as alcohol, benzene, and ethers. Their main aesthetic
problem stems from their organoleptic properties in water and
fish. For example, the threshold odor level in water for 2, 4,
6-trichlorophenol is 3 vg/£. They tend to be persistent in water
and are capable of being transported long distances. They are not
efficiently removed by conventional water treatment processes and
can cause odor problems in distribution systems. This parameter
will be regulated by BAT guidelines prescribed by the NPDES permits
program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Acidify to a
pH of 4 with H3P04> Add l.Og CuS04•5H20/£ to inhibit biodegrada-
tion of phenols. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 mg/£ or more depending upon
initial concentration.
Measurement: The recommended method involves direct aqueous in-
jection for the gas-liquid chromatographic determination of con-
centrates containing more than 1 mg/£ phenolic compounds. A
flame-ionization detector is used for their individual measure-
ment. Suspended matter may interfere by plugging the microsyringe.
Interfering nonphenolic organic compounds may be removed by dis-
tillation. Steps should be taken to minimize or eliminate
ghosting. A BAT NPDES method will be prescribed for this param-
eter in 40 CFR 136.
Precision and Accuracy: Few precision and accuracy data are
available. Precision is very operator dependent. For example,
total precision may be 2 to 5 times single operator precision
values.
Cost of Analysis: $40 - $60
D-187
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CHLORINE DEMAND
Parameter Group: General Inorganic STORET Units: mg/£
General: The chlorine demand of water is caused by inorganic re-
ductants and others and varies with the amount of chlorine applied,
contact time, pH, and temperature. It is the difference between
the amount of chlorine applied at the amount of free, combined, or
total available chlorine remaining at the end of the contact pe-
riod. The usual purpose of a chlorine demand test is to determine
the amount of chlorine that must be applied to produce a specific
residual after a selected period of contact, rather than as an in-
dicator of pollution. It should not be confused with chlorine
requirement.
Criterion: Not designated
Preservation Method: Analyze as soon as possible. Cool to 48C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 200-500 m£; 5,000 m£ may be required to
develop a breakpoint curve.
Measurement; A laboratory method is recommended which involves
the addition of chlorine to the sample until the "breakpoint" is
reached. At the end of the contact period the free and/or combined
available residual chlorine is determined by a suitable technique,
e.g., the amperometric titration method.
Precision and Accuracy: Precision and accuracy will depend upon
the method chosen to measure free and/or combined available resid-
ual chlorine.
Cost of Analysis: $50 - $80 with breakpoint curve
D-188
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CHLORINE DIOXIDE
Parameter Group: STORET Units:
General: Chlorine dioxide is added to water supplies to combat
tastes and odors due to phenolic-type wastes, actinomycetes, and
algae as well as to oxidize soluble iron and manganese to a more
easily removable form. Chlorine dioxide acts as a disinfectant.
See also the residual chlorine discussion.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Avoid exposing
the sample to sunlight or agitation that aerates the sample
excessively.
Maximum Holding Time: No holding. Analyze on site if possible.
Container Type: Plastic or glass
Sample Volume Required: 200 m£
Measurement: The amperometric titration method is recommended.
It is an extension of the method for residual chlorine.
Precision and Accuracy: Precision and accuracy data are not
available.
Cost of Analysis: $30 - $40
D-189
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CHLORINE, RESIDUAL
Parameter Group: Miscellaneous STORET Units: mg/£
General: The toxicity of chlorine to aquatic life will depend upon
the concentration of total residual chlorine, which is the amount
of free chlorine plus chloramines. The persistence of chloramines
is dependent on the availability of material with a lower
oxidation-reduction potential. Free available chlorine (HOC1 and
OC1 ) and combined available chlorine (mono- and di-chloramines)
appear transiently in surface or ground waters as a result of dis-
infection of domestic sewage or from industrial processes that use
chlorine for bleaching operations or to control organisms that grow
in cooling water systems. This is a parameter which is regulated
by BPT guidelines prescribed by the NPDES permits program.
Criteria: Total residual chlorine:
• 2.0 pg/£ for salmonid fish
• 10.0 yg/£ for other freshwater and marine organisms
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Chlorine determinations should be started immediately after sam-
pling, avoiding excessive light and agitation.
Maximum Holding Time: 24 hours
Container Type; Plastic or glass
Sample Volume Required: 50 mi
Measurement: The amperometric titration method is recommended. It
is applicable to all types of waters and wastes that do not contain
a substantial amount of organic matter. This method cannot be used
for samples containing above 5 mg/£ total residual chlorine. Sam-
ples containing significant amounts of organic matter interfere with
the amperometric titration and the iodometric method must be used.
The amperometric titration is not subject to interference from
color, turbidity, iron, manganese, or nitrite nitrogen. For BPT
NPDES purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy; A sample containing a concentration of
.8 mg/£ was analyzed by 23 laboratories using the amperometric
method. The relative standard deviation was 42.3% with a rela-
tive error of 25.0%.
Cost of Analysis: $30 - $40
D-190
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CHLOROALKYL ETHERS
Parameter Group: STORET Units:
General: Chloroalkyl ethers are volatile halocompounds including
bis Cchl°romethyl) ether, bis C2-chloroethyl) ether, and
2-chloroethyl vinyl ether (mixed). This parameter will be regu-
lated by BAT guidelines prescribed by the NPDES permits program.
It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time; Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement: No standard procedure has been established. Method-
ology may require extraction, concentration, gas chromatography,
and mass spectrometry. Detection limits of 60 vg/t or less should
be achievable if procedure is optimized for sample composition.
A BAT NPDES method will be prescribed for this parameter in
40 CFR 136.
Precision and Accuracy: Precision and accuracy data are not
available.
Cost of Analysis: $20 - $30 each
D-191
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CHLOROFORM
Parameter Group: Pesticides STORET Units: yg/£
General: Chloroform is used as an anesthetic, counterirritant,
solvent, cleansing agent, and antiseptic. It is a colorless
and volatile .liquid with an ethereal odor and sweetish taste.
Stickleback will avoid solutions of 100,000 to 200,000 yg/£ of
chloroform in tap water. At 500,000 yg/£, they become anes-
thetized. This parameter will be regulated by BAT guidelines
prescribed by the NPDES permits program. It is one of the Consent
Decree pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect the
sample from phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement: The recommended method for chloroform is a direct
aqueous-injection procedure for the determination of gas chromato-
graphable chlorinated hydrocarbons. A 3-10 y£ aliquot of the sam-
ple is injected into the gas chromatograph equipped with a halogen
specific detector. Compounds containing bromine or iodine will
interfere with the determination. A BAT NPDES method will be pre-
scribed for this parameter in 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is approximately
1,000 ug/£.Detection limits of 0.2-3 yg/£ may be achieved. Pre-
cision and accuracy data are not available at this time.
Cost of Analysis: Around $60.
D-192
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2-CHLOROPHENOL
Parameter Group: STORET Units:
General: 2-chlorophenol (CJ-LC10) is a liquid only slightly
soluble in water but fairly soluble in other media such as alco-
hol. Its major aesthetic problem stems from its organoleptic
properties in water and fish. Threshold odor levels for
2-chlorophenol are around 2 yg/£. It is a persistent substance,
capable of being transported long distances in water and is not
removed efficiently by conventional water treatment. This
parameter will be regulated by BAT guidelines prescribed by the
NPDES permits program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Acidify to a
pH of 4 with H3P04. Add l.Og CuS04«5H20/£ to inhibit biodegrada-
tion of phenols. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 mg/£ or more depending upon
initial concentration.
Measurement: The recommended method involves direct aqueous in-
jection for the gas-liquid chromatographic determination of con-
centrates containing more than 1 mg/£ phenolic compounds. A
flame-ionization detector is used for their individual measurement.
Suspended matter may interfere by plugging the microsyringe. In-
terfering nonphenolic organic compounds may be removed by distil-
lation. Steps should be taken to minimize or eliminate ghosting.
A BAT NPDES method will be prescribed for this parameter in
40 CFR 136.
Precision and Accuracy: Few precision and accuracy data are
available. Precision is very operator dependent. For example,
total precision may be 2 to 5 times single operator precision
values.
Cost of Analysis; $40 - $60
D-193
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CHROMIUM
Parameter Group; Metals STORET Units: yg/£ as Cr
General: The primary source of chromium is industrial discharges.
Chromium compounds are used in cooling water to inhibit corrosion
and are employed in the manufacture of paint pigments, in chrome
tanning, aluminum anodizing, and other metal cleaning, plating,
and electroplating operations. Chromium in industrial wastes
occurs predominately as the hexavalent form, but the trivalent
form is also present, either as a result of partial wastewater
treatment or from its direct use. Industries that use trivalent
chromium directly in manufacturing processes include glass,
ceramics, photography, and textile dyeing. It is not clear if
chromium is an essential element to man. Hexavalent chromium has
been considered a toxic metal for years. Trivalent chromium is
less toxic, no reports of oral toxicity are known. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. It is one of
the Consent Decree pollutants.
Criteria:
50 ug/£ for domestic water supply (health)
100 pg/£ for freshwater aquatic life
Preservation Method; Acidify all samples at the time of collec-
tion to keep the metal in solution and prevent plating out on the
container wall; therefore, analyze as soon as possible. If stor-
age is necessary, add HNO_ to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required; 100-200 m£
Measurement: The AA spectrophotometric method is recommended for
the determination of total chromium in water and wastewater samples.
The colorimetric method may be used for the determination of hex-
avalent chromium in potable water. Use a wavelength of 357.9 nm
with the AA spectrophotometric method. The absorption of chromium
is suppressed by iron and nickel. If the analysis is performed in
a lean flame the interference can be lessened but the sensitivity
will also be reduced. The interference does not exist in nitrous
oxide-acetylene flame. For BPT NPDES purposes the measurement of
this parameter is prescribed by 40 CFR 136. A BAT NPDES method
will be prescribed for this parameter in 40 CFR 136.
D-194
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Precision and Accuracy; The AA method sensitivity is 100 pg/£; its
detection limit is 20 ug/£. The optimum concentration range is
200-10,000 yg/£. At a concentration of 50 yg/£, the relative
standard deviation is 26.4%, and the relative error is 2.3%. These
decrease with concentration; at 15.0 vg/£ they are 60% and 6.8%
respectively, while at 7.4 pg/£ they are 105% and 38%, respectively.
Cost of Analysis: $10 - $15
D-195
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COBALT
Parameter Group: Metals STORET Units: pg/£ as Co
General : Cobalt naturally occurs primarily as arsenide and sul-
fide, generally associated with iron, nickel, copper, and silver
minerals. Cobalt is used in alloys for magnets, high hardness
steels, cutting tools, heat resistant jet engine parts, etc., and
may appear in discharges from these and other industrial sources,
including nuclear technology, china and glass, ink, galvanoplating,
and as a feed supplement in salt licks. Ingestion of cobalt salts
may cause nausea or vomiting due to irritation, but it has a
relatively low toxicity to man. This is a parameter which is regu-
lated by BPT guidelines prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO, to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 mi
Measurement : The AA spectrophotometric method is recommended,
using a wavelength of 240.7 nm. For levels of cobalt below
50 mg/£, the extraction procedure is recommended. For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 200
its detection limit is 30 pg/£. The optimum concentration range is
500-10,000 yg/£. In a single laboratory, using a mixed industrial-
domestic waste effluent at concentrations of 200, 1,000 and
5,000 pg Co/£, the relative standard deviations were 6.5%, 1.0%,
and 1.0%, respectively. Recoveries at these levels were
and 97%, respectively.
Cost of Analysis; $10 - $15
D-196
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COLOR
Parameter Group: Physical STORET Units: Platinum-
Cobalt Units
General: The most common causes of color in natural water are
minerals and complex organic compounds originating from the de-
composition of naturally-occurring organic matter. Sources of
organic material include humic materials from the soil such as
tannins, humic acid and humates; decaying plankton; and other
decaying aquatic plants. Virtually all industrial discharges and
irrigation return flows also contain color to varying extents.
The effects of color on public water supplies are aesthetic. The
effects of color in water on aquatic life are to reduce light pen-
etration, and thereby generally reduce photosynthesis by phyto-
plankton and to restrict the zone for aquatic vascular plant
growth. Color is undesirable in waters for a number of industrial
uses also. Color values are extremely pH dependent. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criteria:
• Waters shall be virtually free from substances producing
objectionable color for aesthetic purposes;
• The source of supply should not exceed 75 color units on
the platinum-cobalt scale for domestic water supplies;
Increased color (in combination with turbidity) should not
reduce the depth of the compensation point for photo-
synthetic activity by more than 10 percent from the
seasonally established norm for aquatic life.
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 50 mi
Measurement: The platinum-cobalt visual comparison method is
acceptable for measuring the color of potable water. The method
is not applicable to color measurement on waters containing highly
colored industrial wastes, in which case the spectrophotometric or
tristimulus methods are useful. In the platinum-cobalt method,
color is measured by visual comparison of the sample with
platinum-cobalt standards. One unit of color is that produced by
D-197
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1 mg/£ platinum in the form of the chloroplatinate ion. Slight
amounts of turbidity interfere with the determination; therefore,
samples showing visible turibidity should be clarified by cen-
trifugation. For BPT NPDES purposes the measurement of this param-
eter is prescribed by 40 CFR 136.
Precision and Accuracy: Precision and accuracy data are not
available at this time.
Cost of Analysis: $3 - $5 for visual
$10 - $15 for tristimulus
$30 - $40 for spectrophotometric (10 ordinates)
$70 - $80 for spectrophotometric (30 ordinates)
D-198
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COPPER
Parameter Group: Metals STORET Units: yg/£ as Cu
General: Oxides and sulfates of copper are used for pesticides,
algicides, and fungicides. Copper is frequently incorporated into
paints and wood preservatives to inhibit growth of algae and
invertebrate organisms. Copper salts are'used in water supply
systems for controlling biological growths and for catalyzing the
oxidation of manganese. Primary sources of copper in industrial
wastewater are metal process pickling and plating baths; other
sources involve mine drainage, pulp and paper mills, fertilizer
manufacturing, petroleum refining, and certain rayon processes.
This is a parameter which is regulated by BPT guidelines pre-
scribed by the NPDES permits program. This parameter will be
regulated by BAT guidelines prescribed by the NPDES permits pro-
gram. It is one of the Consent Decree pollutants.
Criteria:
1.0 mg/£ for domestic water supplies (welfare).
• For freshwater and marine aquatic life, 0.1 times a
96-hour LC as determined through nonaerated bio-
assay using a sensitive aquatic resident species.
Preservation Method: Copper ion tends to be adsorbed on the
surface of the sample container; therefore, analyze as soon as
possible. If storage is necessary, use 0.5 m£ 1 + 1 HC1 per
100 mi of sample to prevent plating out. Alternatively, add HNO,
to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 50 to 200 mi
Measurement: The AA spectrophotometric and neocupreine methods are
recommended because of their high degree of freedom from interfer-
ences. The latter requires either a spectrophotometer for use at
457 nm or a filter photometer equipped with a narrow-band violet
filter having maximum transmittance in the 450- to 460-nm range;
either must provide a light path of at least 1 cm. For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136. A BAT NPDES method will be prescribed for this param-
eter in 40 CFR 136.
D-199
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Precision and Accuracy: The AA method sensitivity is 100
its detection limit is 100 pg/£. Precision and accuracy decrease
with concentration. At 1,000 yg/£, the relative standard devia-
tion is around 11% and the relative error, 3%. At 300 yg/£, the
relative standard deviation has increased to nearly 18%, at
70 pg/£ it is over 30%, and approaching 10 yg/£ it exceeds 80%.
Relative error has increased to nearly 16% at the last concentra-
tion.
Cost of Analysis: $5 - $10
D-200
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CYANIDE
Parameter Group: General STORET Units: mg/£ as CN
Inorganic
General: All of the CN groups in cyanide compounds that can be
determined as the cyanide ion, CN", whether in simple, e.g.,
A(CN)x, or complex, AyM(CN)x, form. In the first expression, A
may be an alkali or a metal; in the second, A is an alkali and M a
heavy metal. In such latter alkali-metallic cyanides, the anion
is not the CN group but the radical M(CN)x. Sources of cyanide in
waste streams include ore mining and extracting, photographic
processing, coke furnaces, synthetic manufacturing, case hardening
and pickling of steel, electroplating, and industrial gas scrub-
bing. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion: 5.0 vg/t for freshwater and marine aquatic life and
wildlife.
Preservation Method: Most cyanides are very reactive and unsta-
ble. Analyze as soon as possible. If oxidizing agents are pres-
ent, reduce with ascorbic acid. Add NaOH to raise sample pH to
12 or above and cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 500 m£
Measurement: For total cyanides, both dissociable and nondisso-
ciable forms of cyanide are being measured. Cyanides amenable to
chlorination represent only the former. Standard methods for de-
termination of total cyanide make use of a reflux-distillation pro-
cedure for concentrating and removing cyanides. The liberated
hydrogen cyanide is collected in sodium hydroxide, and its concen-
tration determined by using a titration method (above 1 mg/£), a
colorimetric method (below 1 mg/£), or an ion selective electrode
method (0.05 to 10 mg/£). Although the distillation procedure
eliminates or reduces many interferences, sulfides will distill
over and adversely affect the colorimetric and titrimetric proce-
dures, fatty acids will distill and form soaps under the alkaline
titration procedures obscuring the end point, thiocyanates may
interfere when distillation is carried out with the cuprous
chloride reagent, and aldehydes will convert cyanide to nitrile
under the distillation conditions. Special precautions are re-
quired when any of these are present. The colorimetric method re-
quires either a spectrophotometer for use at 578 nm or a filter
photometer equipped with a red filter having maximum transmittance
D-201
-------
in the 570 to 580 nm range; either must provide a light path of
1 cm. The ion selective electrode method requires a suitable
meter, a cyanide-ion selective electrode, and a double junction
reference electrode. For BPT NPDES purposes the measurement of
this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The titrimetric method yields a relative
standard deviation of 2% for samples containing more than
1 mg/£ CN without significant, interferences, increasing with de-
creasing concentration down to the limit of sensitivity, which is
around 0.1 mg/£, e.g., at 0.4 mg/£ the relative standard deviation
is 8%. The colorimetric method is sensitive to about 0.02 mg/£.
Within its designated range, its overall precision is given as
0.115X + 0.031, where X is the CN concentration in mg/£. Using
mixed domestic and industrial waste samples at concentrations of
0.28 and 0.62 mg/£ CN, relative standard deviations of 11% and
15% and recoveries of 85% and 102%, respectively, were observed
in a single laboratory. The overall precision of the ion selective
electrode method is given as 0.113X + 0.024, where X is the con-
centration in mg/£ CN.
Cost of Analysis: $10 - $30
CAUTION! Exercise care in the manipulation of cyanide samples be-
cause of their toxicity. Avoid contact, inhalation, or ingestion.
D-202
-------
2, 4-D
Parameter Group; Pesticides STORET Units:
General: 2, 4-D (2,^4-dichlorophenoxyacetic acid) is the widely
used chlorophenoxy herbicide CghLCKCL. This compound is formu-
lated in a variety of salts and esters that may have a marked
difference in herbicidal properties, but all are hydrolyzed rap-
idly to the corresponding acid in the body. 2, 4-D herbicide is
used for weed control on land, and as an aquatic herbicide in
lakes, streams, and irrigation canals. It is a plant hormone
that stimulates excessive growth, causing the plant to destroy
itself. 2, 4-D is of low toxicity to mammals, the acute oral
LD_0 for rats being 500,000 yg/kg of body weight, but may give
water an unpleasant taste. Fish toxicity levels are in the
hundreds of mg/£. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program.
Criterion: 100 yg/£ for domestic water supply (health).
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required; 100-1,000 mi, depending upon measurement
method used.
Measurement: In the recommended method, chlorinated phenoxy acids
and their esters are extracted from the acidified water sample with
ethyl ether. The esters are hydrolyzed to acids and extraneous
organic material is removed by a solvent wash. The acids are con-
verted to methyl esters which are extracted from the aqueous phase.
The extract is cleaned up by passing it through a micro-adsorption
column. Detection and measurement are accomplished by electron
capture, microcoulometric or electrolytic conductivity gas chroma-
tography. Interferences may be high and varied and often pose
great difficulty in obtaining accurate and precise measurement of
chlorinated phenoxy acid herbicides. Organic acids, especially
chlorinated acids, cause the most direct interference with the
determination. Phenols including chlorophenols will also inter-
fere with this procedure. The method is recommended for use only
by an experienced pesticide analyst (or under the close supervision
of such a person)-. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
D-203
-------
Precision and Accuracy: Sensitivity of the method is 1 yg/£. De-
tection limits of 0.05 yg/£ or so may be achieved. Precision and
accuracy data are not available at this time.
Cost of Analysis: $45 - $150, depending upon preparation required.
D-204
-------
ODD
Parameter Group: Pesticides STORET Units: yg/£
General: DDD, a metabolite of DDT, is an organochlorine insecti-
cide. It is the same as IDE and is also known as Rhothane. DDD
has much the same properties and is used similarly to DDT. Its
insecticidal activity approaches that 'of DDT, but its mammolian
toxicity is only about 20% of that of DDT. This is a parameter
which is regulated by BPT guidelines prescribed by the NPDES
permits program. This parameter will be regulated by BAT guide-
lines prescribed by the NPDES permits program. It is one of the
Consent Decree pollutants. A toxic effluent limitation has been
prescribed for this parameter by the NPDES permits program.
Criterion; Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
DDD. Many interferences exist, especially PCB's, phthalate esters,
and organophosphorus pesticides, and the method is only recommended
for use by a skilled, experienced pesticide analyst (or under close
supervision of such a person). For BPT NPDES purposes the measure-
ment of this parameter is prescribed by 40 CFR 136. A BAT NPDES
method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-205
-------
DDE
Parameter Group; Pesticides STORET Units: vg/t
General: DDE, a metabolite of DDT, is an organochlorine insecti-
cide. It is the same as DDX. DDE has much the same properties
and is used similarly to DDT. This is a parameter which is regu-
lated by BPT guidelines prescribed by the NPDES permits program.
This parameter will be regulated by BAT guidelines prescribed by
the NPDES permits program. It is one of the Consent Decree pol-
lutants. A toxic effluent limitation has been prescribed for this
parameter by the NPDES permits program.
Criterion: Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 nv£ or more
Measurement; The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
DDE. Many interferences exist, especially PCB's, phthalate esters,
and organophosphorus pesticides, and the method is only recommended
for use by a skilled, experienced pesticide analyst (or under close
supervision of such a person). For BPT NPDES purposes the measure-
ment of this parameter is prescribed by 40 CFR 136. A BAT NPDES
method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-206
-------
DDT
Parameter Group: Pesticides STORET Units: yg/£
General: DDT (1, 1, 1-trichloro -2, 2-bis (p-chlorophenyl)
ethane) is an organochlorine insecticide. Acute toxicity to
mammals generally is low. DDT is a highly persistent chemical
which bioaccumulates in aquatic organisms used for human food and
also is considered a potential human carcinogen. DDT will accum-
ulate in the food chain. A residue accumulation of up to two
million times for fish can occur. Application of DDT in agri-
culture and forest areas contributes to the presence of this toxic
material in surface and ground waters. Practically insoluble in
water, dilute acids, and alkalies, it is readily soluble in many
organic solvents. The vehicle is very important in determining
the toxicity of DDT. It has been found in river waters at con-
centrations to 20 yg/£. This is a parameter which is regulated
by BPT guidelines prescribed by the NPDES permits program. This
parameter will be regulated by BAT guidelines prescribed by the
NPDES permits program. It is one of the Consent Decree pollutants.
A toxic effluent limitation has been prescribed for this parameter
by the NPDES permits program.
Criterion:
0.001 yg/£ for freshwater and marine aquatic life
• The persistence, bioaccumulation potential, and carcino-
genicity of DDT cautions human exposure to a minimum.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 mi or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric or
electrolytic conductivity gas chromatography is recommended for DDT.
Many interferences exist, especially PCB's, phthalate esters, and
organophosphorus pesticides, and the method is only recommended for
use by a skilled, experienced pesticide analyst (or under close
supervision of such a person). For BPT NPDES purposes the measure-
ment of this parameter is prescribed by 40 CFR 136. A BAT NPDES
method will be prescribed for this parameter in 40 CFR 136.
D-207
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Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 ug/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration. For
example, at the 0.040 and 0.200 pg/£ concentrations, recoveries
were around 101% and 77% and precisions were 40% and 19%,
respectively.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-208
-------
DEMETON
Parameter Group: Pesticides STORET Units; \ig/l
General: Deraeton (also known as Systox) is the organophosphorus
insecticide CQH,00_PS0. Commercial demeton is a mixture of
o iy o t.
isomers of varying toxicities. It is insoluble in water but solu-
ble in alcohol. The estimated fatal dose to a 70-kg man is
0.1 gram. The acute oral LD,-n for stock and wildlife is re-
ported between 2,500 to 40,000 pg/kg of body weight. Toxicity to
aquatic life varies widely with age and species. Demeton is
unique in that the persistence of its ACHE enzyme inhibiting abil-
ity is greater than that of ten other common organophosphates,
even though its acute toxicity is apparently less. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criterion: 0.1 pg/£ for freshwater and marine acquatic life.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100 m£ or more
Measurement: The use of co-solvent extraction, column chromatog-
raphy, and liquid-liquid partition, and detection and measurement
accomplished by flame photometric gas chromatography using a
phosphorus specific filter is recommended for demeton. Great care
must be exercised in the selection and use of methods to minimize
interferences, and the method is only recommended for use by a
skilled, experienced pesticide analyst (or under close supervision
of such a person). For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors but is usually 0.010 yg/£ or higher. Sensitivity is typi-
cally 1 yg/£. Precision and accuracy data are not available at
this time.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-209
-------
DIAZINON
Parameter Group: Pesticides STORET Units: yg/£
General: Diazinon is the registered trade name of an organophos-
phorus insecticide. It is a liquid with a faint ester-like odor
and is miscible with a number of hydrocarbon solvents. Diazinon
has very high insecticidal and acaricidal properties. The esti-
mated fatal dose for a 70-kg man is 25 grams. The oral LD,-n to
o u
rats ranges from 100,000 to 435,000 yg/kg of body weight. Toxicity
data for aquatic life are limited. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits
program.
Criterion; Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100 mi or more
Measurement: The use of co-solvent extraction, column chromatog-
raphy, and liquid-liquid partition, and detection and measurement
accomplished by flame photometric gas chromatography using a phos-
phorus specific filter is recommended for diazinon. Great care
must be exercised in the selection and use of methods to minimize
interferences, and the method is only recommended for use by a
skilled, experienced pesticide analyst (or under close supervision
of such a person). For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but is usually 0.010 yg/£ or higher. Sensitivity is
typically 1 yg/£. Precision and accuracy data are not available
at this time.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-210
-------
DICHLOROBENZENES
Parameter Group: STORET Units:
General: Dichlorobenzenes (C,H.C1_) include 1, 2-dichlorobenzene,
««.«^«— D T1 A
1, 3-dichlorobenzene, and 1, 4-dichlorobenzene. Metadichloroben-
zene is a colorless liquid, insoluble in.water, and seldom used
commercially. Othodichlorobenzene is also a liquid and insoluble
in water and is used as a solvent for waxes, for preserving plants,
and for destroying insects such as termites. Paradichlorobenzene
is a white crystallic solid with a characteristic odor used chiefly
for killing moths, their larvae, and other insects. It is slightly
soluble in water, 70 mg/£ at 25°C. This parameter will be regu-
lated by BAT guidelines prescribed by the NPDES permits program.
It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 200-1,000 nv£
Measurement: No standard procedures have been developed. The
methodology generally requires extraction, concentration, and gas
chromatographic analysis. A BAT NPDES method will be prescribed
for this parameter in 40 CFR 136.
Precision and Accuracy: Detection limits of 0.1 to 10 yg/£ should
be achievable. Precision and accuracy data are not available at
this time.
Cost of Analysis: $25 - $40
D-211
-------
DICHLOROBENZIDINE
Parameter Group: STORET Units:
General: Dichlorobenzidine (3, 3'-dichlorobenzidine) is a poly-
nuclear organic compound. Due to its suspected carcinogenic
properties, it must be handled with great care. This parameter
will be regulated by BAT guidelines prescribed by the NPDES
permits program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 1 week
Container Type: Borosilicate glass
Sample Volume Required: 1,000-4,000 mi depending on concentration
and instrument used.
Measurement: Dichlorobenzidine is separated and concentrated by
multiple extractions and then oxidized by chloramine T. The
oxidation product is extracted and measured spectrophotometrically.
A BAT NPDES method will be prescribed for this parameter in
40 CFR 136.
Precision and Accuracy: The detection limit is approximately
0.2 pg/£.Precision and accuracy data are not available at this
time.
Cost of Analysis: $20 - $40; because of its carcinogenic proper-
ties, special facilities may be required at greatly increased
cost.
D-212
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DICHLOROETHYLENES
Parameter Group: STORET Units:
General: Dichloroethylenes are volatile halocorapounds including
1, 1-dichloroethylene and 1, 2-dichloroethylene. This parameter
will be regulated by BAT guidelines prescribed by the NPDES permits
program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement: In the recommended Bellar procedure the sample is
stripped with an inert gas; volatiles are captured on an ad-
sorbent trap and desorbed into a modified gas chromatograph
equipped with a halogen-specific detector. Methodology should be
checked for interferences, e.g., from bromine and iodine. A BAT
NPDES method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is approximately
1,000 vg/t.Detection limits of 0.2-3 vg/t may be achieved. Pre-
cision and accuracy data are not available at this. time.
Cost of Analysis: Around $60
D-213
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2, 4-DICHLOROPHENOL
Parameter Group: STORET Units:
General: 2, 4-dichlorophenol CCfiH.Cl-0) is a colorless, crystal-
line substance only slightly soluble in water but fairly soluble
in other media such as alcohol. It is used in the manufacture of
the herbicide 2, 4-D as well as for other purposes. It is per-
sistent and, since it is not efficiently removed by conventional
water treatment processes, can cause odor problems in distribution
systems. Fish flesh tainting concentrations range from 1 to
5 yg/£, levels that do not appear to adversely affect the fish.
The threshold odor level in water is as low as 1 pg/£. This
parameter will be regulated by BAT guidelines prescribed by the
NPDES permits program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Acidify to a
pH of 4 with H3P04. Add l.Og CuS04'5H20/£ to inhibit biodegrada-
tion of phenols. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 mg/£ or more depending upon
initial concentration.
Measurement; The recommended method involves direct aqueous in-
jection for the gas-liquid chromatographic determination of con-
centrates containing more than 1 mg/£ phenolic compounds. A
flame-ionization detector is used for their individual measurement.
Suspended matter may interfere by plugging the microsyringe. In-
terfering nonphenolic organic compounds may be removed by distil-
lation. Steps should be taken to minimize or eliminate ghosting.
A BAT NPDES method will be prescribed for this parameter in
40 CFR 136.
Precision and Accuracy: Few precision and accuracy data are
available. Precision is very operator dependent. For example,
total precision may be 2 to 5 times single operator precision
values.
Cost of Analysis; $40 - $60
D-214
-------
DICHLOROPROPANE
Parameter Group: STORET Units:
General: 1, 2-dichloropropane (also called propylene chloride,
C,H,C1~) is a heavy liquid that is slightly soluble in water.
This parameter will be regulated by BAT guidelines prescribed by
the NPDES permits program. It is one of the Consent Decree
pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement: In the recommended Bellar procedure the sample is
stripped with an inert gas; volatiles are captured on an ad-
sorbent trap and desorbed into a modified gas chromatograph
equipped with a halogen-specific detector. Methodology should be
checked for interferences, e.g., from bromine or iodine. Confir-
mation should be made for dichloropropane. A BAT NPDES method
will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is approximately
1,000 yg/£.Detection limits of 0.2-3 yg/£ may be achieved. Pre-
cision and accuracy data are not available at this time.
Cost of Analysis: Around $60
D-215
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DICHLOROPROPENE
Parameter Group: STORET Units:
General: 1, 3-dichloropropene (C,H.C12) is a heavy liquid, in-
soluble in water, and with a chloroform-like odor. It is used as
a soil fumigant for the control of nematodes. This parameter will
be regulated by BAT guidelines prescribed by the NPDES permits
program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 m£
Measurement: In the recommended Bellar procedure the sample is
stripped with an inert gas; volatiles are captured on an ad-
sorbent trap and desorbed into a modified gas chromatograph
equipped with a halogen-specific detector. Methodology should be
checked for interferences, e.g., from bromine or iodine. Con-
firmation should be made for dichloropropene. A BAT NPDES method
will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is approximately
1,000 ug/£.Detection limits of 0.2-3 yg/£ may be achieved. Precision
and accuracy data are not available at this time.
Cost of Analysis: Around $60
D-216
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DIELDRIN
Parameter Group: Pesticides STORET Units:
General: Dieldrin, the common name for an organochlorine insecti-
cide, is a highly persistent chemical which bioaccumulates in
aquatic organisms used for human food and is also considered a
potential human carcinogen. The USEPA has suspended the produc-
tion and use of dieldrin. This should result in a gradual decrease
in concentration in the environment. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits pro-
gram. This parameter will be regulated by BAT guidelines pre-
scribed by the NPDES permits program. It is one of the Consent
Decree pollutants. A toxic effluent limitation has been pre-
scribed for this parameter by the NPDES permits program.
Criteria:
.003 yg/£ for freshwater and marine aquatic life
The persistence, bioaccumulation potential, and carcino-
gencity of dieldrin cautions human exposure to a minimum.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
dieldrin. Many interferences exist, especially PCB's, phthalate
esters, and organophosphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 pg/£ range. Increased
sensitivity is likely to increase interference. Typically, the
percent .recovery decreases with increasing concentration. For
example, at the 0.02 and 0.125 ug/£ concentration, recoveries were
around 108% and 85% and precisions were 91% and 24%, respectively.
Cost of Analysis: $30 - $150 depending upon preparation required.
D-217
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2, 4-DIMETHYLPHENOL
Parameter Group: STORET Units:
General; 2, 4-dimethylphenol (2, 4-dimethyl-l-hydroxybenzene) is
only slightly soluble in water but highly soluble in other media
such as alcohol. It has a higher odor threshold concentration
than many other phenolic compounds, up to 75 vg/L. It is a per-
sistent substance, capable of being transported long distances in
water and is not removed efficiently by conventional water treat-
ment processes. This parameter will be regulated by BAT guidelines
prescribed by the NPDES permits program. It is one of the Consent
Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Acidify to a
pH of 4 with H3P04. Add l.Og CuS04«5H20/£ to inhibit biodegrada-
tion of phenols.
Maximum Holding Time: 24 hours
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 mg/£ or more depending upon
initial concentration.
Measurement^ The recommended method involves direct aqueous in-
jection for the gas-liquid chromatographic determination of con-
centrates containing more than 1 mg/£ phenolic compounds. A
flame-ionization detector is used for their individual measurement.
Suspended matter may interfere by plugging the microsyringe. In-
terfering nonphenolic organic compounds may be removed by distil-
lation. Steps should be taken to minimize or eliminate ghosting.
A BAT NPDES method will be prescribed for this parameter in
40 CFR 136.
Precision and Accuracy: Few precision and accuracy data are
available. Precision is very operator dependent. For example,
total precision may be 2 to 5 times single operator precision
values.
Cost of Analysis^ $40 - $60
D-218
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DISSOLVED OXYGEN
Parameter Group: Dissolved Oxygen STORET Units: mg/£
General: Dissolved oxygen (DO) levels in water, an important gage
of its overall quality, depend upon its physical, chemical, and
biological activities. Although excessive DO may be detrimental
to certain uses (e.g., it increases metallic corrosion), the main
concern is with DO deficiencies. Insufficient DO in the water
column may be detrimental to aquatic fauna, causes anaerobic de-
composition of any organic materials present, and generally de-
grades the aesthetic quality of the water body, this is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criteria:
• Aesthetics: Water should contain sufficient dissolved
oxygen to maintain aerobic conditions in the water column
and, except as affected by natural phenomena, at the
sediment-water interface.
• Freshwater aquatic life: A minimum concentration of dis-
solved oxygen to maintain good fish populations is 5.0 mg/£.
The criterion for salmonid spawning beds is a minimum of
5.0 mg/£ in the interstitial water of the gravel.
Preservation Method: Electrode: determine on site; Winkler: fix
on site.
Maximum Holding Time: No holding
Container Type: Glass only
Sample Volume Required: 300 mi
Measurement: The electrode method is recommended for a variety of
reasons, including freedom from interferences and, when used in
situ, from sampling effects that are otherwise difficult to account
for. Modified Winkler methods may be used, but great care in sam-
pling and accounting for interferences must be exercised. For BPT
NPDES purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: With most commercially available membrane
electrode systems an accuracy of ±0.1 mg/£ and a precision of
±0.05 mg/£. should be obtainable. No meaningful precision and accu-
racy data are available for the modified Winkler method.
Cost of Analysis: $3 - $6
D-219
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DISYSTON
Parameter Group: Pesticides STORET Units: yg/£
General: Disyston, an organophosphorus insecticide, is a clear,
oily liquid that is slightly soluble in water and quite soluble
in most organic solvents. Its acute oral LD-0 to rats has been
reported from 2,600 to 12,500 yg/kg of body weight. Toxicity
data for aquatic life are sparse but indicate a wide variability
with age and species. This is a parameter which is regulated by
BPT guidelines prescribed by the NPDES permits program.
Criterion; Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100 mi or more
Measurement: The use of co-solvent extraction, column chromatog-
raphy, and liquid-liquid partition, and detection and measurement
accomplished by flame photometric gas chromatography using a
phosphorus specific filter is recommended for disyston. Great
care must be exercised in the selection and use of methods to
minimize interferences, and the method is only recommended for
use by a skilled, experienced pesticide analyst (or under close
supervision of such a person). For BPT NPDES purposes the meas-
urement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but is usually 0.010 yg/£ or higher. Sensitivity is
typically 1 yg/£.- Precision and accuracy data are not available
at this time.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-220
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DIURON
Parameter Group: Pesticides STORET Units: yg/£
General: Diuron is the urea pesticide CgH-j-Cl-N-O. It is a
crystalline compound only slightly soluble in water and oils.
Its acute oral LD5Q to rats is 3,400 yg/£ of body weight. Its
toxicity to fish varies widely with age and species, but lethal
doses are measured in mg/£ concentrations. Apparently, aeration
slightly reduces the toxicity of diuron to aquatic life. This is
a parameter which is regulated by BPT guidelines prescribed by
the NPDES permits program.
Criterion; Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 1,000 m£
Measurement: The recommended method involves an extraction process
with methylene chloride and the concentrated extract is cleaned up
with a Florisil column. A thin-layer chromatography process is
then used. The layer is sprayed with 1-naphthol and the products
appear as colored spots. The measurement is achieved visually.
Direct interferences may be encountered from aromatic amines that
may be present in the sample. Indirect interferences may be en-
countered from naturally colored materials whose presence masks
the chromogenic reaction. For BPT NPDES purposes the measurement
of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The determination can be made with a
sensitivity of 1 yg/£. Precision and accuracy data are not avail-
able at this time.
Cost of Analysis: $30 - $60
D-221
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ENDOSULFAN
Parameter Group: Pesticides STORET Units: yg/£
General: The acute toxicity of endosulfan, an organochlorine
insecticide, to different fish species varies widely. No data are
available on the levels to which endosulfan could be expected to
accumulate in tissues of aquatic organisms at various water con-
centrations. Residues in fish are not anticipated to pose a haz-
ard to fish-eating predators because of endosulfan's low oral
toxicity to birds and mammals. Application of endosulfan in
agriculture and forest areas contributes to the presence of this
toxic material in surface and ground waters. This is a parameter
which is regulated by BPT guidelines prescribed by the NPDES
permits program. This parameter will be regulated by BAT guide-
lines prescribed by the NPDES permits program. It is one of the
Consent Decree pollutants.
Criteria:
• 0.003 yg/£ for freshwater aquatic life
0.001 yg/£ for marine aquatic life
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
endosulfan. Many interferences exist, especially PCB's, phthalate
esters, and organophosphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136. A BAT NPDES method will be prescribed for this param-
eter in 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-222
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ENDRIN
Parameter Group: Pesticides STORET Units:
General: Application of endrin, an organochlorine insecticide, in
agriculture and forest areas contributes to the presence of this
toxic material in surface and ground waters. It is possible that
some fish would accumulate endrin to 30,000 times water concentra-
tion. Although it has strong residual toxicity as does its closely
related compound dieldrin, endrin has been found to be eliminated
quickly after termination of exposure and to disappear relatively
quickly. Thus, it does not appear to cause an accumulation prob-
lem. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program. This parameter will be
regulated by BAT guidelines prescribed by the NPDES permits pro-
gram. It is one of the Consent Decree pollutants. A toxic efflu-
ent limitation has been prescribed for this parameter by the NPDES
permits program.
Criteria:
• 0.2 yg/£ for domestic water supply (health)
• 0.004 yg/£ for freshwater and marine aquatic life
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
endrin. Many interferences exist, especially PCB's, phthalate
esters, and organophosphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136. A BAT NPDES method will be prescribed for this param-
eter in 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-223
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ETHYLBENZENE
Parameter Group: STORET Units:
General: Ethylbenzene CCoH,n) is a volatile, flammable liquid with
an ethereal odor. It is insoluble in water at normal temperatures.
It is used commercially as a solvent and in the synthesis of other
organic compounds. Its toxicity to fish varies with water tempera-
ture, age, and species. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. It is one of
the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 200-1,000 m£
Measurement: Hexadecone extraction followed by gas chromatographic
and mass spectrometric analysis is often used. A BAT NPDES method
will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Detection limits should be around
2-10 pg/£.Precision and accuracy data are not available at this
time.
Cost of Analysis: $15 - $30
D-224
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FECAL COLIFORM
Parameter Group: Bacteriologic STORET Units: MPN
General: Pollution of aquatic systems by the excreta of warm-
blooded animals creates public health problems for man and
animals and potential disease problems for aquatic life. It is
known that enteric microbial pathogens may inhabit the gut of
most warmblooded animals and are shed in feces. The presence of
bacterial, viral, protozoan, and possibly fungal species is in-
dicated by the presence of the fecal coliform group of bacteria.
The number of fecal coliforms present is indicative of the degree
of health risk associated with using the water for drinking,
swimming, or shellfish harvesting. The fecal coliform bacteria,
which comprise a portion of the total coliform group, are able to
grow at 44.5°C and ferment lactose, producing acid and gas. This
is a parameter which is regulated by BPT guidelines prescribed by
the NPDES permits program.
Criteria:
Bathing Waters
Based on a minimum of not less than five samples taken over a
30-day period, the fecal coliform bacterial level should not ex-
ceed a log mean of 200 per 100 m£, nor should more than 10 percent
of the total samples taken during any 30 day period exceed
400 per 100 m£.
Shellfish Harvesting Waters
Not to exceed a median fecal coliform bacterial concentra-
tion of 14 MPN per 100 mi with not more than 10 percent of samples
exceeding 43 MPN per 100 m£ for the taking of shellfish.
Preservation Method: Cool to 4°C. Add a dechlorinating agent
(e.g., sodium thiosulfate) if residual chlorine is present. Sam-
ples high in heavy metals should have a chelating agent (e.g.,
EDTA) added to reduce metal toxicity.
Maximum Holding Time: 6 hours (30 hours absolute maximum for po-
table water samples).
Container Type: Plastic or glass
Sample Volume Required: 100 ra£
Measurement: The multiple tube fermentation technique may be
used if a determination of the total coliform group is also being
made. Otherwise, the simpler membrane filter technique is
D-225
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recommended. Results of the former are expressed statistically as
the Most Probable Number CMPN), while the latter are expressed as
number of colonies per 100 m£. For BPT NPDES purposes the measure-
ment of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy; The accuracy of the membrane filter
technique for differentiating between coliforms from warm-blooded
animals and coliforms from other sources is approximately 93%.
Cost of Analysis: $10 - $12 MFT
$15 - $20 MPN
D-226
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FECAL STREPTOCOCCI
Parameter Group: Bacteriologic STORET Units: Unspecified
General: The normal habitat of the fecal streptococcus group of
bacteria is the intestines of man and other warm-blooded animals
and, thus, these organisms are indicators of fecal pollution.
Because of their survival characteristics, it is not recommended
that.fecal streptococci be used as the sole fecal indicator. Since
certain fecal streptococci are host-specific, they may provide val-
uable additional information about the source of pollution; e.g.,
a predominance of S. bovis and S. equinus would indicate excrement
from nonhuman, warm-blooded animals as, for example, from feedlot
and farmland runoff, dairy wastes, and meat processing plants.
S. faecalis var liquefaciens is not restricted to the intestines of
warm-blooded animals, being also associated with vegetation, in-
sects, and certain types of soils. Biochemical characterization
is required to eliminate the possibility of a preponderance of this
latter type, thus avoiding misinterpretation of results. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criterion: Not established
Preservation Method: Cool to 4°C. Add a dechlorinating agent
(e.g., sodium thiosulfate) if residual chlorine is present. Sam-
ples high in heavy metals should have a chelating agent (e.g.,
EDTA) added to reduce metal toxicity.
Maximum Holding Time: 6 hours (30 hours absolute maximum for po-
table water samples).
Container Type: Plastic or glass
Sample Volume Required: 100 m£
Measurement: The multiple tube fermentation technique and the
simpler membrane filter technique are both recommended, especially
for nondrinking water tests. Results of the former are expressed
statistically as the Most Probable Number (MPN), while the latter
are expressed as number of colonies per 100 m£. The fecal strepto-
coccal plate count method may also be used. For BPT NPDES purposes
the measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Not applicable
Cost of Analysis: $10 - $12 MFT
$15 - $20 MPN
D-227
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FLUORIDE
Parameter Group: General STORET Units: mg/£ as F
Inorganic
General: The most reactive nonmetal, flourine is never found free
in nature, but it is a constitute of a number of minerals.
Fluorides in high concentrations are not common in natural surface
waters. They are used as insecticides, as disinfectants, as a
flux in steelmaking, for preserving wood and mucilages, for the
manufacture of glass and enamels, in chemical industries, tooth-
paste manufacture, for water treatment, and a host of minor ap-
plications. They are not normally found in industrial wastes
(other than traces) except as a result of spillage. In sufficient
quantities (over 200 mg), fluorides can be toxic to humans. Up to
5 mg/£ the only bad effect seems to be tooth discoloration. Under
100 mg/£ produces little adverse effects on plants. Toxic ef-
fects on aquatic life are observed starting at concentrations
above 2 mg/£. This is a parameter which is regulated by BPT guide-
lines prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 7 days
Container Type: Plastic or glass
Sample Volume Required: 300 mi
Measurement: The SPADNS method with Bellack distillation is rec-
ommended. A spectrophotometer for use at 570 nm or a filter
photometer equipped with a greenish yellow filter having maximum
transmittance at 550-580 nm is required; either must have a light
path of at least 1 cm. The method covers the range from 0.1 to
about 2.5 mg/£ F. Following distillation to remove interferences,
the sample is treated with the SPADNS reagent. The loss of color
resulting from the reaction of fluoride with the zirconyl-SPADNS
dye is a function of the fluoride concentration. The SPADNS rea-
gent is more tolerant of interfering materials than other accepted
fluoride reagents. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: On a sample containing 0.83 mg/£ F with
no interferences, the results of 53 analysts using the SPADNS
method had a relative standard deviation of 8% and a relative
error of 1.2%. After direct distillation, the relative standard
deviation was 11.0% and the relative error 2.4%. On a sample con-
taining 0.57 mg/£ F (with 200 mg/£ S04 and 10 mg/£ Al as
D-228
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interferences) results from the 53 analysts had relative standard
deviations and errors of 16.2% and 7.0% without distillation and
17.2 and 5.3 with distillation.
Cost of Analysis: $3 - $5 without distillation
$15 - $20 with distillation
D-229
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GUTHION
Parameter Group: Pesticides STORET Units: pg/£
General: Guthion is the organophosphorus insecticide
C.-jH.-N-O-PS-. It is a brown waxy solid that is insoluble in
water but soluble in most organic solvents. The half-life of
guthion spray and dust on cotton leaves has been reported as
2-4 days and 1-2 days for pondwater. An investigation of the
persistence of guthion in fish revealed that 50% of the
chemical was lost in less than one week. The estimated fatal
dose for a 70-kg man is 0.2 grams. The acute oral LD5_ to rats
ranges from 11,000 to 80,000 yg/kg of body weight. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criterion: 0.01 yg/£ for freshwater and marine aquatic life.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time; Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100 mi or more
Measurement: The use of co-solvent extraction, column chromatog-
raphy, and liquid-liquid partition, and detection and measurement
accomplished by flame photometric gas chromatography using a phos-
phorus specific filter is recommended for guthion. Great care
must be exercised in the selection and use of methods to minimize
interferences, and the method is only recommended for use by a
skilled, experienced pesticide analyst (or under close supervision
of such a person). For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but is usually 0.010 ug/£ or higher. Sensitivity is
typically 1 yg/£. Precision and accuracy data are not available
at this time.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-230
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HALOETHERS
Parameter Group: STORET Units:
General: Haloethers as used here comprise 4-chlorophenyl phenyl
ether; 4-bromophenyl phenyl ether, bis (2-chloroisopropyl) ether;
and bis (2-chloroethoxy) methane. This parameter will be regulated
by BAT guidelines prescribed by the NPDES permits program. It is
one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 200-1,000 ra£
Measurement: No standard procedures have been developed. The
methodology generally requires extraction, concentration, and gas
chromatographic analysis. A BAT NPDES method will be prescribed
for this parameter in 40 CFR 136.
Precision and Accuracy: Detection limits of 1 to 10 yg/£ should be
achievable. Precision and accuracy data are not available at this
time.
Cost of Analysis: $40 - $60
D-231
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HALOMETHANES
Parameter Group: STORET Units:
General: The halomethanes include dichloromethane (methylene
chloride), chloromethane (methyl chloride), bromomethane (methyl
bromide), tribromomethane (bromoform), dichlorobromomethane, tri-
chlorofluoromethane (Freon 11), dichlorodifluoromethane (Freon 12),
and chlorodibromomethane. These volatile halocompounds are mostly
gaseous at surface water temperatures and atmospheric pressure.
They range from soluble to insoluble in water; e.g., methyl chlo-
ride is soluble to about 4,000 mg/£ at 20°C. Chief uses are as
refrigerants, aerosol propellents, and certain industrial opera-
tions. Taste of water containing halomethanes in appreciable con-
centrations is sharp, sickening, and sweetish when first taken
into the mouth, followed by a burning sensation. It is unlikely
that humans would voluntarily drink such water. This parameter
will be regulated by BAT guidelines prescribed by the NPDES
permits program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 mi
Measurement: In the recommended Bellar procedure the sample is
stripped with an inert gas; volatiles are captured on an ad-
sorbent trap and desorbed into a modified gas chromatograph
equipped with a halogen specific detector. Methodology should be
checked for interferences, e.g., from bromine or iodine. A BAT
NPDES method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is approximately
1,000 ug/£.Detection limits of 0.2-3 yg/£ may be achieved. Pre-
cision and accuracy data are not available at this time.
Cost of Analysis: Around $60
D-232
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HARDNESS, TOTAL
Parameter Group; General STORET Units: mg/£ as CaC03
Inorganic
t
General: Water hardness is caused by the polyvalent metallic ions
dissolved in water. Principally, these are calcium and magnesium.
Other metals such as iron, strontium, and manganese contribute to
the extent that appreciable concentrations are present. Natural
sources of hardness are soil and geological formations (e.g.,
limestone) with which the water may have come in contact. In-
dustrial sources include the inorganic chemical industry and dis-
charges from operating and abandoned mines. Irrigation return
flows also increase hardness. The detrimental effects of hardness
include excessive soap consumption, the formation of scums and
curds in laundries and textile mills, the toughening of vegetables
cooked in hard water, and the formation of scabs in boilers, hot
water heaters, pipes, and utensils. Hence, they are principally
economic in nature. The hardness of "good" water should not exceed
250 mg/£. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion; Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time; 7 days
Container Type; Plastic or glass
Sample Volume Required: 100 m£
Measurement: The EDTA method, recommended when a complete mineral
analysis is not performed, is applicable to drinking, surface, and
saline waters, domestic and industrial wastes. Calcium and mag-
nesium ions in the sample are sequestered upon the addition of
disodium ethylenediamine tetraacetate (Na-EDTA). The end point of
the reaction is detected by means of Calmagite Indicator, which has
a red color in the presence of calcium and magnesium and a blue
color when the cations are sequestered. Excessive amounts of heavy
metals can interfere. This is usually overcome by complexing the
metals with cyanide. Routine addition of sodium cyanide solution
to prevent potential metallic interference is recommended. For
BPT NPDES purposes the measurement of this parameter is prescribed
by 40 CFR 136.
Precision and Accuracy: A synthetic unknown containing 610 mg/£
total hardness as CaCO. was analyzed in 56 laboratories with a
relative standard deviation of 2.9% and a relative error of 0.8%.
Cost of Analysis: $5 - $15
D-233
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HEPTACHLOR
Parameter Group: Pesticides STORET Units:
General: The acute toxicity of heptachlor, a refined ingredient
of the well-known organochlorine insecticide chlordane, is gener-
ally low to mammals; however, aquatic organisms exhibit sensitivity
to this pesticide at microgram-per-liter levels. Heptachlor will
accumulate in the food chain. Heptachlor is a highly persistent
chemical which bioaccumulates in aquatic organisms used for human
food and also is considered a potential human carcinogen. In
July 1975, the USEPA suspended the production and use of heptachlor.
This should result in a gradual decrease in concentrations in the
environment. Any addition of heptachlor to water should be con-
sidered potentially hazardous to humans. This is a parameter
which is regulated by BPT guidelines prescribed by the NPDES
permits program. This parameter will be regulated by BAT guide-
lines prescribed by the NPDES permits program. It is one of the
Consent Decree pollutants.
Criterion:
001 yg/£ for freshwater and marine aquatic life
The persistence,•bioaccumulation potential, and carcino-
genicity of heptachlor cautions human exposure to a minimum.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
heptachlor. Many interferences exist, especially PCB's, phthalate
esters, and organophosphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136. A BAT NPDES method will be prescribed for this
parameter in 40 CFR 136.
D-234
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Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-235
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IODIDE
Parameter Group: General STORET Units: mg/£ as I
Inorganic
General: Only trace concentrations of iodides are found in natural
fresh water; seawater is somewhat higher. Higher concentrations
may also be found in natural brines, waters treated with iodine as
the disinfectant, and a limited number of industrial wastes. It is
used sparingly in industry, e.g., for medicines, germicides, ana-
lytical chemistry, and as a table salt additive. All waterborne
pathogens are destroyed by 8 mg/£ of iodine; no adverse effects
were reported when water containing over twice this concentration
was consumed in the tropics. This is a parameter which is regu-
lated by BPT guidelines prescribed by the NPDES permits program.
Criterion; Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 100 m£
Measurement: The titrimetric method is recommended. After pre-
treatment to remove interferences, the sample is analyzed for
iodide by converting the iodide to iodate with bromine water and
titrating with phenylarsine oxide (PAU) or sodium thiosulfate.
Iron, manganese and organic matter can interfere; however, the
calcium oxide pretreatment removes or reduces these to insignif-
icant concentrations. Color interferes with the observation of
indicator and bromine-water color changes. This interference can
be eliminated by the use of a pH meter instead of a pH indicator
and the use of standardized amounts of bromine water and sodium
formate solution instead of observing the light yellow color
changes. For BPT NPDES purposes the measurement of this parameter
is prescribed by 40 CFR 136.
Precision and Accuracy: In a single laboratory, using a mixed
domestic and industrial waste effluent, at concentrations of
1.6, 4.1, 6.6, 11.6, and 21.6 rag/I of iodide, the relative stand-
ard deviations were 14.4%, 4.1%, 1.4%, .5%, and 2.3%, respectively.
At concentrations of 4.1, 6.6, 11.6 and 21.6 mg/£ of iodide,
recoveries were 80%, 97%, 97%, and 92%, respectively.
Cost of Analysis: $15 - $20
D-236
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IRON
Parameter Group: Metals STORET Units: yg/£ as Fe
General: Iron is an essential trace element required by both
plants and animals. The ferrous, or bivalent (Fe ), and the fer-
ric, or trivalent (Fe ) irons, are the primary forms of concern
in the aquatic environment. The ferrous (Fe ) form can persist in
waters void of dissolved oxygen and originates from groundwaters
or mines when these are pumped or drained. The ferric (Fe ) form
is insoluble. Potential sources of dissolved iron species include
discharges from mining operations, ore milling, chemical indus-
tries (organic, inorganic, petrochemical), dye industries, metal
processing industries, textile mills, food canneries, tanneries,
titanium dioxide production, petroleum refining, and fertilizers.
Limitations in drinking water arise primarily from taste
consideration. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program.
Criteria:
• 0.3 mg/£ for domestic water supplies (welfare)
1.0 mg/£ for freshwater aguatic life
Preservation Method; Analyze as soon as possible. If storage is
necessary, add HNCL to pH <2. For precise determinations of total
iron, use a separate container for sample collection and treat
with acid immediately to place the iron in solution and prevent
adsorption or desposition on the container walls.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 248.3 nm. The orthophenanthroline method
may be used for natural and treated waters. It requires either a
spectrophotometer for use at 510 nm or a filter photometer
equipped with a green filter having maximum transmittance near
510 nm; either must have a light path of at least 1 cm. In the
presence of excessive amounts of organic constituents, the sample
should first be digested to ensure complete dissolution of the
iron. For BPT NPDES purposes the measurement of this parameter
is prescribed by 40 CFR 136.
D-237
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Precision and Accuracy: The AA method sensitivity is 120
its detection limit is 20 pg/£. The optimum concentration range
is 300-10,000 ug/£. At a concentration of 300 pg/£, the relative
standard deviation is 16.5%, and the relative error is 0.6%. For
the colorimetric method at 300 pg/£ Fe, the values were 25.5% and
13.3%, respectively, from a 44-laboratory test. Serious diver-
gences have been found in reports of different laboratories be-
cause of variations in methods of collecting and treating samples.
Cost of Analysis: $3 - $15
D-238
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LEAD
Parameter Group: Metals STORET Units: yg/£ as Pb
General: Natural lead concentrations in surface waters may range
up to 40 pg/£. Lead and its compounds may also enter water at any
stage during mining, smelting, and processing. Lead is used in
the manufacture of storage batteries, television tubes, printing,
pigments, fuels, photographic materials, pesticides, and explo-
sives. The dissolution of lead plumbing is another source. This
is a parameter which is regulated by BPT guidelines prescribed by
the NPDES permits program. This parameter will be regulated by
BAT guidelines prescribed by the NPDES permits program. It is one
of the Consent Decree pollutants.
Criteria:
• 50 pg/£ for domestic water supply (health)
• 0.01 times the 96-hour LC5Q value, using the receiving
or comparable water as the diluent and soluble lead
measurements (nonfilterable lead using a 0.45 micron
filter), for sensitive freshwater resident species.
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO, to pH <2.
Maximum Holding Time. 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 283.3 nm. The analysis of this metal is ex-
ceptionally sensitive to turbulence and absorption bands in the
flame. Therefore, care should be taken to position the light beam
in the most stable, center portion of the flame. The dithizone
colorimetric method may also be used. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 500 vg/t;
its detection limit is 50 pg/£. The optimum concentration range
is 1,000-20,000 yg/£. At a concentration of 50 yg/£, the relative
standard deviation'is 23.5%, and the relative error is 19.0%. At
25 yg/£, the relative error was 25.7% in a 60-laboratory test.
Cost of Analysis: $10 - $15
D-239
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LINDANE
Parameter Group: Pesticides STORET Units; yg/£
General: Lindane, the common name of the gamma isomer of benzene
hexachloride (BHC), is an organochlorine insecticide. Application
of lindane in agriculture and forest areas contributes to the
presence of this toxic material in surface and ground waters. The
highest level of lindane found to have minimal or no long-term
effects in the most sensitive mammal tested, the dog, is 15.0 mg/
kg in the diet or 0.3 mg/kg of body weight/day. An increased re-
sistance to lindane toxicity among fish and invertebrates ex-
periencing previous exposure to the chemical has been observed.
This is a parameter which is regulated by BPT guidelines prescribed
by the NPDES permits program. This parameter will be regulated by
BAT guidelines prescribed by the NPDES permits program. It is one
of the Consent Decree pollutants.
Criteria:
4.0 yg/£ for domestic water supply (health)
0.01 yg/£ foT freshwater aquatic life
0.004 yg/£ for marine aquatic life
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
lindane. Many interferences exist, especially PCB's, phthalate
esters, and organophosphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration. For
D-240
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example, at the 0.010 and 0.100 yg/£ concentrations, recoveries
were around 97% and 73% and precisions were 53% and 26%, respectively.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-241
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LITHIUM
Parameter Group: Metals STORET Units: yg/£ as Li
General; Lithium is present in fresh waters in concentrations be-
low 10,000 yg/£; brines and thermal waters may be higher. Lithium
and its salts are used in dehumidifying units, as a deoxidizer and
degasser for nonferrous castings, to form a protective atmosphere
in furnaces, in medicinal waters, in metallurgical processes, in
the manufacture of some types of glass and storage batteries, and
as the hydride for many controlled organic reductions. In addi-
tion to these sources, lithium hypochlorite is used as a source of
chlorine in some swimming pools. Lithium may have a toxic effect
on plants and some forms of aquatic life, but little data exist
documenting toxicity to man.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO_ to pH <2.
Maximum Holding Time: 6 months
Container Type: Pyrex bottle
Sample Volume Required: 100-200 mi
Measurement: The flame photometric method is often used, using a
wavelength of 671 nm. Interferences in the photometric determina-
tion include barium, strontium, and calcium. These can be removed
by the addition of a sodium sulfate-sodium carbonate solution.
Digestion will be necessary if considerable organic matter is
present.
Precision and Accuracy: The minimum detectable lithium concentra-
tion is approximately 100 ug/£. In a lithium range of 700 to
1,200 vg/t, an accuracy of ±0.1 to 200 yg/£ can be obtained in the
determination of the lithium concentration.
Cost of Analysis: $12 - $18
D-242
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MAGNESIUM
Parameter Group: Metals STORET Units: mg/£ as Mg
General: Magnesium salts are important contributors of hardness
to water. Sources of magnesium include mining and ore processing,
oxide production, metallurgy, refractories, iron and steel produc-
tion, and its use in flash and incendiary products, signal flares,
as a deoxidizer in the casting of metals, as a reagent in organic
chemistry, and a host of other applications. Magnesium is an es-
sential element to humans, the daily requirement being about
700 mg. Taste considerations, rather than toxicity, are para-
mount for magnesium in drinking water. This is a parameter which
is regulated by BPT guidelines prescribed by the NPDES permits
program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNOj to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 mt
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 285.2 ran. The interference caused by
aluminum at concentrations greater than 2 mg/£ is masked by the
addition of lanthanum. For BPT NPDES purposes the measurement
of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 0.007 mg/£;
its detection limit is 0.0005 mg/£. The optimum concentration
range is 0.02-2 mg/£. At a concentration of .2 mg/£, the relative
standard deviation is 10.5%, and the relative error is 6.3%. In
a single laboratory, using a distilled water sample at concentra-
tions of 2.1 and 8.2 mg/£, the relative standard deviations were
4.7% and 2.4%, respectively. Recoveries at both of these levels
were 100%.
Cost of Analysis: $10
D-243
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MALATHION
Parameter Group: Pesticides STORE! Units: ug/£
General: Malathion, the organophosphorus pesticide C,0H1906PS2,
enters the aquatic environment primarily as a result of its appli-
cation as an insecticide. Because it degrades quite rapidly in
most waters, depending on pH, its occurrence is sporadic rather
than continuous. It is soluble in water to 145,000 yg/£. -The
freshwater fish most sensitive to malathion appear to be the
salmonids and centrarchids. Many aquatic invertebrates appear
to be more sensitive than fish to malathion. It appears to be
about 100 times less toxic to warm-blooded animals than parathion,
but only 2 to 4 times less toxic to insects. The estimated fatal
dose for a 70-kg man is 60 grams. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits
program.
Criterion: 0.1 yg/£ for freshwater and marine aquatic life.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100 m£ or more
Measurement; The use of co-solvent extraction, column chromatog-
raphy and liquid-liquid partition, and detection and measurement
accomplished by flame photometric gas chromatography using a phos-
phorus specific filter is recommended for malathion. Great care
must be exercised in the selection and use of methods to minimize
interferences, and the method is only recommended for use by a
skilled, experienced pesticide analyst (or under close supervision
of such a person). For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but is usually 0.010 yg/£ or higher. Sensitivity is
typically 1 yg/£. Precision and accuracy data are not available
at this time.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-244
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MANGANESE
Parameter Group: Metals STORET Units: yg/£ as Mn
General: Manganese and its salts are used in manufacturing steel
alloys, dry cell batteries, glass and ceramics, paint and varnish,
ink and dye, and matches and fireworks. Manganese is normally in-
gested as a trace nutrient in food. Very large doses of ingested
manganese can cause some diseases and liver damage. Inadequate
quantities of manganese in domestic animal food results in reduced
reproductive capabilities and deformed or poorly maturing young.
Manganese imparts objectionable and stubborn stains to laundry and
plumbing fixtures. Low limits on domestic water supplies stem
from these, rather than toxicological, considerations. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criteria;
• 50 yg/£ for domestic water supplies (welfare)
100 yg/£ for protection of consumers of marine mollusks
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO_ to pH <2.
Maximum Holding Time: 6 months
Container Type; Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 279.5 nm. For levels of manganese below
25 yg/£, the extraction procedure is recommended. Analytical
sensitivity is dependent on lamp current. For BPT NPDES purposes
the measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 50 yg/£; its
detection limit is 10 yg/£. The optimum concentration range is
100-10,000 yg/£. At a concentration of 50 yg/£, the relative
standard deviation is 13.5%, and the relative error is 6.0%.
These increase at decreasing concentrations. In a 55-laboratory
test, at concentrations of 17 and 11 yg/£ the relative standard
deviations were 118% and 245%, respectively, and the relative
errors were 22% arid 93%, respectively.
Cost of Analysis: $10
D-245
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MERCURY
Parameter Group: Metals STORET Units: pg/£ as Hg
General: Mercury is widely distributed in the environment, and
biologically is a nonessential or nonbeneficial element. Dis-
charged mercury does not remain localized. Mercury can enter the
environment by seeping up through layers of earth to the surface,
outgassing of mercury from rock and soil, and transport by natural
cycles. Most industrial mercury is eventually lost as waste into
streams or the atmosphere. Uses of mercury include the electrical
industry, chlor-alkali industry, industrial control equipment,
paints, agriculture, dental preparations, pulp and paper industry,
catalysts in chemical manufacturing processes, and general labor-
atory uses. The toxicity of mercury is attributed to its high
affinity for sulfur-containing compounds. Toxic effects vary with
the form of mercury and its mode of entry into the organism. This
is a parameter which is regulated by BPT guidelines prescribed by
the NPDES permits program. This parameter will be regulated by
BAT guidelines prescribed by the NPDES permits program. It is one
of the Consent Decree pollutants.
Criteria:
2.0 yg/£ for domestic water supply (health)
• 0.05 yg/£ for freshwater aquatic life and wildlife
0.10 yg/£ for marine aquatic life
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO- to pH <2.
Maximum Holding Time: 38 days (glass), 13 days (hard plastic)
Container Type: Glass or hard plastic
Sample Volume Required: 100 m£
Measurement: The flameless AA spectrophotometric method is recom-
mended. It is a physical method based on the absorption of radia-
tion at 253.7 nm by mercury vapor. The mercury is reduced to the
elemental state and aerated from solution in a closed system. The
mercury vapor passes through a cell positioned in the light path
of an atomic absorption spectrophotometer. Absorbance is measured
as a function of mercury concentrations. Possible interference
from sulfide is eliminated by the addition of potassium per-
manganate. Copper has also been reported to interfere. Inter-
ference from certain volatile organic materials which will absorb
at this wavelength is also possible. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
D-246
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Precision and Accuracy: At a concentration of 0.4 yg/£, the rela-
tive standard deviation is 21.2%, and the relative error is 2.4%.
In a single laboratory, using an Ohio River composite sample with
a background mercury concentration of 0.35 vg/t, spiked with con-
centrations of 1, 3, and 4 vg/t, the standard deviations were
±0.14, ±0.10, and ±0.08, respectively. Standard deviation at the
0.35 level was ±0.16. Percent recoveries at the three levels were
89%, 87%, and 87%, respectively.
Cost of Analysis: $15 - $25
D-247
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METHANE
Parameter Group: STORET Units:
General: Methane is a gaseous saturated (paraffin) hydrocarbon.
It is colorless, odorless, tasteless, and flammable. Methane
sources include the anaerobic decomposition of organic matter
(e.g., some marshes, mines, treatment plants, etc.) and natural
gas and petroleum plants. Concern about methane arises from its
explosion hazard rather than its negligible toxicity. For ex-
ample, an explosive limit of methane in air could be reached in a
poorly ventilated space sprayed with hot (68°C) water having a
methane concentration of only 0.7 mg/£.
Criterion: Not established
Preservation Method: Analyze as soon as possible. When collect-
ing the sample, ensure that the sample is under sufficient pressure
to ensure that no gas escapes from the water.
Maximum Holding Time: Unknown, but short
Container Type: Glass
Sample Volume Required: 3,000 m£
Measurement: The combustible-gas indicator method is often used.
The procedure is based on the catalytic oxidation of a combustible
gas or a heated platinum filament that is made a part of a wheat-
stone bridge. Small amounts of ethane, hydrogen gas, and hydrogen
sulfide may interfere. For greater accuracy, a gas chromatograph
should be used.
Precision and Accuracy; The sensitivity of the method is approx-
imately 0.2 mg/£.The accuracy of the determination is limited by
the accuracy of the instrument employed; errors of around 10% may
be expected.
Cost of Analysis: $15 - $20
D-248
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METHOXYCHLOR
Parameter Group: Pesticides STORET Units: yg/£
General; Application of methoxychlor, an organochlorine insecti-
cide, in agriculture and forest areas contributes to the presence
of this material in surface and ground waters. It is slightly
soluble in water but very soluble in alcohol. Sodium and
dimethylamine salts are freely soluble in water. The concentra-
tion of methoxychlor has been found to be degraded in a few weeks
or less in natural waters. The highest level of methoxychlor
found to have minimal or no long-term effects in man is 2.0 mg/kg
of body weight/day. Few data are available on acute and chronic
effects of methoxychlor on freshwater fish. Methoxychlor appears
to be considerably less bioaccumulative in aquatic organisms than
some of the other organochlorine pesticides. Methoxychlor has a
very low accumulation rate in birds and mammals. This is a param-
eter which is regulated by BPT guidelines prescribed by the NPDES
permits program.
Criteria:
100 ug/£ for domestic water supply (health)
• 0.03 pg/£ for freshwater and marine aquatic life
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
methoxychlor. Many interferences exist, especially PCB's,
phthalate esters, and organophosphorus pesticides, and the method
is only recommended for use by a skilled, experienced pesticide
analyst (or under close supervision of such a person). For BPT
NPDES purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 pg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis; $30 - $150, depending upon preparation required.
D-249
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METHYL PARATHION
Parameter Group: Pesticides STORET Units: jig/£
General: Methyl parathion is an organophosphorus insecticide
similar in action to parathion, Phosdrin, and TEPP. Its toxicity
is also similar. The half-life of methyl parathion on cotton
leaves is less than one hour. The estimated fatal dose for a
70-kg man is 0.15 gram. The acute oral LD5~ for rats ranges
from 9,000 to 25,000 pg/kg of body weight. Toxicity data for
aquatic life are sparse but appear to range widely with age and
species. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Cool to 48C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: 'Borosilicate glass
Sample Volume Required: 100 m£ or more
Measurement: The use of co-solvent extraction, column chromatog-
raphy and liquid-liquid partition, and detection and measurement
accomplished by flame photometric gas chromatography using a phos-
phorus specific filter is recommended for methyl parathion. Great
care must be exercised in the selection and use of methods to
minimize interferences, and the method is only recommended for use
by a skilled, experienced pesticide analyst (or under close super-
vision of such a person). For BPT NPDES purposes the measurement
of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but is usually 0.010 ng/£ or higher. Sensitivity is
typically 1 yg/£. Precision and accuracy data are not available
at this time.
Cost of Analysis; $30 - $150, depending upon preparation required.
D-250
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METHYLENE BLUE ACTIVE SUBSTANCES (MBAS)
Parameter Group: General STORET Units: mg/£
Organic
General; Certain solutes, even at low concentrations, have the
property of lowering the surface tension or other interfacial prop-
erties of their solvents. Such solutes are known as surfactants
or surface-active agents. They are found in soaps, detergents,
emulsifiers, wetting agents, and penetrants, with the most common
use, by far, being in synthetic detergents where they may account
for 20% - 40% of the product in active form alone. The specific
surfactant most widely used until recently is the group of alkyl
benzene sulfonates (ABS), which persist in sewage and streams in
biologically active solution without appreciable decomposition
from either treatment processes or natural purification, being
largely immune to biological degradation. Today, the more .biode-
gradable linear alkyl sulfonate (LAS) has essentially replaced ABS
on the surfactant market so that measurable surface-active agents
will probably be LAS type materials. In addition to foaming prob-
lems, anionic surfactants may enhance slime growth, inhibit the
growth of nitrifying bacteria, delay gas exchange with the atmos-
phere, and interfere with the uptake of oxygen. This is a parame^
ter which is regulated by BPT guidelines prescribed by the NPDES
permits program.
Criterion: Not established
Preservation Method; Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 250 m£
Measurement: Anionic-type surfactants react with methylene blue dye
in aqueous solution to form a blue colored salt which is extracta-
ble with chloroform, its color intensity being proportional to the
concentration of MBAS. The more complicated, time consuming, and
expensive tests for specific substances (e.g., LAS) are not usually
warranted. The method is recommended for determination in drinking
waters, surface waters, domestic and industrial wastes. It is not
applicable to measurement of surfactant-type materials in saline
waters. Chlorides at concentration of about 1,000 mg/£ show a pos-
itive interference, but the degree of interference has not been
quantified. For BPT NPDES purposes the measurement of this parame-
ter is prescribed by 40 CFR 136.
D-251
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Precision and Accuracy: A sample of filtered river water, spiked
with 2.94 mg LAS/t was analyzed in 110 laboratories with a relative
standard deviation of 9.1% and a relative error of 1.4%. In
similar analyses with a sample of tap water spiked with 0.48 mg
LAS/£, relative standard deviations and errors of 9.9% and 1.3%
were obtained, and for a sample of distilled water spiked with
0.27 mg lAS/t, the respective values were 14.8% and 10.6%.
Cost of Analysis: $10 - $15
D-252
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MIREX
Parameter Group: Pesticides STORET Units: yg/£
General; Mirex, an organochlorine insecticide, is largely used to
control the imported fire ant in the southeastern United States.
Crayfish and channel catfish survival is affected by mirex in the
water or by ingestion of the bait particles. Bioaccumulation is
well established for a wide variety of organisms but the effect of
this bioaccumulation on the aquatic ecosystem is unknown. There
is evidence that mirex is very persistent in bird tissue. Con-
sidering the extreme toxicity and potential for bioaccumulation,
every effort should be made to keep mirex bait particles out of
water containing aquatic organisms. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits
program.
Criterion: 0.001 yg/£. for freshwater and marine aquatic life.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type; Borosilicate glass
Sample Volume Required: 50 to 100 mi or more
Measurement; The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric or
electrolytic conductivity gas chromatography is recommended for
mirex. Many interferences exist, especially PCB's, phthalate
esters, and organophosphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 yg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required.
D-253
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MOLYBDENUM
Parameter Group: Metals STORET Unit: pg/£ as Mo
General: Molybdenum occurs naturally as molybdenum sulfide and
lead molybdate. Its chief use is in the production of alloy steels
(especially corrosion-resistant stainless steels) where advantage
is made of its marked passivity. Other possible sources include
mining and ore processing operations, chemical production, some
fertilizers, and metallurgical operations. Molybdenum has a rela-
tively low order of toxicity. This is a parameter which is regu-
lated by BPT guidelines prescribed by the NPDES permits program.
Criterion; Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO, to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 mi
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 313.3 nm. With the nitrous oxide-acetylene
flame, interferences of calcium and other ions may be controlled
by adding 1,000,000 yg/£ of a refractory metal such as aluminum.
This should be done to both the samples and standards. For BPT
NPDES purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 300 vg/t;
its detection limit is 100 yg/£. The optimum concentration range
is 500-20,000 yg/£. In a single laboratory, using a mixed
industrial-domestic waste effluent at concentrations of 300,
1,500, and 7,500 yg Mo/£, the relative standard deviations were
2.3%, 1.3%, and .93%, respectively. Recoveries at these levels
were 100%, 96%, and 95%, respectively.
Cost of Analysis: $10 - $15
D-254
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NAPHTHALENE
Parameter Group: STORET Units:
General: Naphthalene (C10Ho) is the most abundant single consti-
tuent of coal tar. It is a white solid with the odor of moth
balls. It is soluble in water at 20°C to the extent of about
30 mg/£. The use of naphthalene in organic syntheses and dye man-
ufacture is extensive, and hence it may occur in wastes from re-
fineries, coal-tar plants, textile mills, and chemical industries.
Lethal concentrations to fish are around 5-20 mg/£. Fish tainting
can occur at 1 mg/£.. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permits program. It is one of
the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly. Cool to
4°C.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 m£
Measurement: The general procedure involves extraction and meas-
urement with a gas chromatograph. Various cleanup techniques to
remove interferences may be required depending upon other con-
stituents in the sample. A skilled chemist or specialist will be
required. A BAT NPDES method will be prescribed for this parame-
ter in 40 CFR 136.
Precision and Accuracy: Detection limits in the 1-10 ug/£ range
should be achievable. Precision and accuracy data are not avail-
able at this time.
Cost of Analysis; $40 - $60
D-255
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NICKEL
Parameter Group: Metals STORET Units; yg/£ as Ni
General: Nickel principally occurs in nature as sulfide. Its
main industrial use is in electroplating, alloying, coin making,
and in alkaline storage batteries. Other potential sources include
silver refineries, basic steel works and foundaries, motor vehi-
cle and aircraft industries, and printing operations. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program. This parameter will be regulated by BAT
guidelines prescribed by the NPDES permit program. It is one of
the Consent Decree pollutants.
Criterion: 0.01 of the 96-hour LC™ for freshwater and marine
aquatic life.
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO- to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 mi
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 232.0 nm. The 352.4 nm wavelength is
less susceptible to nonatomic absorbance and may also be used.
The calibration curve is more linear at this wavelength; however,
there is some loss of sensitivity. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 150 yg/£;
its detection limit is 20 yg/£. The optimum concentration range
is 300-10,000 yg/£. In a single laboratory, using a mixed
industrial-domestic waste effluent at concentrations of 200,
1,000, and 5,000 yg Ni/£, the standard deviations were ±0.011,
±0.02, and ±0.04, respectively. Recoveries at these levels were
100%, 97%, and 93%, respectively.
Cost of Analysis: $10 - $15
D-256
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NITRILOTRIACETIC ACID (NTA)
Parameter Group: General STORET Units: mg/£
Organic
General: Nitrilotriacetic acid (NTA) is insoluble in water, but
its tribasic salt is quite soluble. NTA has a strong affinity
for iron, calcium, magnesium, and zinc, but its relative affinity
for toxic metals such as cadmium and mercury is riot known, nor
have its chelating properties in complex ionic solutions been
characterized. It has a potential large-scale use as a substitute
for phosphates in detergents. No cases of acute human poisoning
by NTA have been reported. It is biodegraded in the natural en-
vironment within 4 to 5 days; degradation is accelerated by bio-
logical waste treatment.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time; 24 hours
Container Type: Plastic or glass
Sample Volume Required: 50 m£
Measurement: The zinc-zircon method is often used. In this
method, NTA refers to the tri-sodium salt of nitrilotriacetic
acid. It is applicable to surface waters in the range of 0.5-
10.0 mg/i NTA. Cations, such as calcium, magnesium, zinc, cop-
per, iron, and manganese, complex with NTA and give a negative
interference. These ions are removed by batch treating samples
'with, ion-exchange resin. At concentrations higher than expected
in typical river waters, only zinc, copper, and iron were not
completely removed with ion-exchange treatment.
Precision and Accuracy: In a single laboratory, using spiked
surface water samples at concentrations of 0.5, 2, 6, and
10 mg/£ NTA, relative standard deviations were 3.4%, 7%, 1.7%,
and 1.6%, respectively. In a single laboratory, using spiked
surface water samples at concentrations of 1.0 and 7.5 mg/£ NTA,
recoveries were 120% and 103%, respectively.
Cost of Analysis: $10 - $12
D-257
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NITROBENZENE
Parameter Group: STORET Units:
General: Nitrobenzene (C6H5N02) is moderately soluble in water.
It is used in the manufacture of analine, soaps, and shoe polishes.
Nitrobenzene is an oily liquid and has an almond odor. A concen-
tration of 0.03 mg/£ in water will produce a faint odor. The oral
LD5Q for rabbits is 700 mg/kg of body weight. This parameter will
be regulated by BAT guidelines prescribed by the NPDES permits
program. It is one of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required; 200-1,000 mt
Measurement: No standard procedures have been developed. The
methodology generally requires extraction, concentration, and gas
chromatographic analysis. A BAT NPDES method will be prescribed
for this parameter in 40 CFR 136.
Precision and Accuracy: Detection limits of 1 to 10 jag/£ should be
achievable. Precision and accuracy data are not available at this
time.
Cost of Analysis: $40 - $60
D-2S8
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NITROGEN-AMMONIA
Parameter Group; Nitrogen STORET Units: mg/£ as N
General: Ammonia, one of the chemically interconvertible compo-
nents of the nitrogen cycle, is naturally present in surface and
ground water in concentrations from less than 0.01 to around
0.2 mg/£ as N in the absence of pollution. It is produced largely
by the deamination of nitrogenous organic matter and the hydrolysis
of urea. It may also result from the reduction of nitrate under
anaerobic conditions. Other sources include the discharge of indus-
trial wastes from chemical and gas plants, from ice plants, and
where it is used in scouring and cleaning operations. There ap-
pears little physiological risk in palatable concentrations, the
odor threshold being 0.037 mg/£. Because it changes rapidly to
nitrites and nitrates, ammonia is actually a fertilizer for most
crops; ammonium salts constitute a major source of nitrogen fer-
tilization. The toxicity of ammonia to fish is highly pH dependent.
This is a parameter which is regulated by BPT guidelines prescribed
by the NPDES permits program.
Criterion: Not established
Preservation Method; Analyze as soon as possible. Add 2 m£ of
concentrated H2S04 or 40 mg HgCl_/£ and store at 4°C. The use of
mercuric chloride is discouraged whenever possible, however.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 400 m£
Measurement: The distillation procedure is recommended for the
determination of ammonia-nitrogen. The method covers the range
from about 0.05 to 1.0 mg/£ NH_-N/£ for the colorimetric proce-
dures, from 1.0 to 25 mg/£ for the titrimetric procedure, and
from 0.05 to 1,400 mg/£ for the electrode method. A number of
aromatic and aliphatic amines will cause turbidity upon the ad-
dition of Nessler reagent. Cyanate will hydrolyze to some extent.
Volatile alkaline compounds may cause an off-color upon Nessleri-
zation. For BPT NPDES purposes the measurement of this parameter
is prescribed by 40 CFR 136.
Precision and Accuracy; Precision and accuracy are highly depend-
ent upon concentration, other constituents present, and the finish
method. Relative standard deviations may range from around 4% to
40% and relative errors from under 1% to over 15%.
Cost of Analysis: $10 - $12
D-259
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NITROGEN, KJELDAHL
Parameter Group: Nitrogen STORET Units: mg/£ as N
General : Kjeldahl nitrogen is defined as the sum of free-ammonia
and organic nitrogen compounds which are converted to ammonium
sulfate (NH.^SO. under conditions of digestion. Organic nitrogen
includes natural materials such as proteins and peptides, nucleic
acids and urea, and numerous synthetic organic substances. The
organic nitrogen concentrations of water and wastewater may vary
from less than 0.01 mg/£ for the former to over 10 mg/£ for the
latter. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion : Not established
Preservation Method: Analyze as soon as possible. Add 2 m£ of
concentrated I^SO. to pH <2 or 40 mg HgCl2/£ and store at 4°C.
The use of mercuric chloride is discouraged whenever possible,
however .
i Holding Time; 24 hours
Container Type; Plastic or glass
Sample Volume Required; 500 mi
Measurement: In the Kjeldahl nitrogen determination the sample is
heated in the presence of concentrated sulfuric acid, K^SO., and
HgSO. and evaporated until S0_ fumes are obtained and the solution
becomes colorless or pale yellow. The residue is cooled, diluted,
and is treated and made alkaline with a hydroxide-thiosulfate
solution. The ammonia is distilled and determined by either the
titrimetric method, the Nesslerization method, or the potenti-
ometric method. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Thirty-one analysts in twenty laboratories
analyzed natural water samples containing exact increments of
organic nitrogen. At the 0.2-0.3 mg/£ as N concentration level the
relative standard deviation and error were around 90% and 10%,
respectively. At around 4 mg/£ as N they were about 25% and 1%,
respectively.
Cost of Analysis: $15 - $20
D-260
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NITROGEN, NITRATE
Parameter Group: Nitrogen STORET Units; mg/£ as N
General; Nitrate, one of the chemically interconvertible compounds
of the nitrogen cycle, occurs in trace quantities in surface
water and in small amounts in fresh domestic wastewater. It is
seldom abundant, since it serves as an essential nutrient for all
types of plants. Some ground water may contain high levels of
nitrate (as a result of leachings from cesspools or excess appli-
cations of fertilizers, etc.) due to the lack of photosynthetic
action. There has been no reporting of physiological harm at
concentrations of less than 10 mg/£ as N. Nitrates are injurious
for certain industrial uses (e.g., fabric dyeing, fermentative
processes). High nitrate concentrations stimulate the growth of
plankton and aquatic weeds and accelerate eutrophication. This is
a parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criterion; Not established
Preservation Method: Analyze as soon as possible. Add 2 m£ con-
centrated H2S04/£ to ph <2 or 40 mg HgCl2/£ and store at 4°C.
The use of mercuric chloride is discouraged whenever possible,
however.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required; 100 mi
Measurement: The brucine method is recommended in the range from
0.1 to 2 mg NO_-N/£ for determination in drinking, surface, and
saline waters, domestic and industrial wastes. Dissolved or-
ganic matter will cause an off color. The effect of salinity is
eliminated by the addition of sodium chloride to the blanks, stand-
ards, and samples. All strong oxidizing or reducing agents
interfere. Residual chlorine interference is eliminated by the
addition of sodium arsenite. Ferrous and ferric iron and quadri-
valent manganese give slight positive interferences. Uneven heat-
ing of the samples and standards during the reaction time will
result in erratic values. The cadmium reduction method may also
be used; see discussion under Nitrogen, Nitrate-Nitrite. For BPT
NPDES purposes the measurement of this parameter is prescribed by
40 CFR 136.
D-261
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Precision and Accuracy: Five synthetic samples containing nitrate
and other constituents were analyzed in 50 laboratories at con-
centrations of 0.05, 0.5, and 5 mg/£ as N; relative standard
deviations were 66.7%, 14.4%, and 15.4% and relative errors were
7.6%, 0.6%, and 4.5%, respectively.
Cost of Analysis: $10 - $12
D-262
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NITROGEN, NITRATE-NITRITE
Parameter Group: Nitrogen STORET Units: mg/£ as N
General: See discussions under nitrate and nitrite. The combined
test is less expensive than making individual determinations and
provides a determination of total oxidized nitrogen. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Store at 4°C.
Maximum Holding Time; 24 hours
Container Type: Plastic or glass
Sample Volume Required: 100 m£
Measurement: The cadmium reduction method is recommended for the
determination of nitrite and nitrate combined in drinking, surface,
and saline waters, domestic and industrial wastes. Buildup of
suspended matter in the reduction column will restrict sample
flow. Low results might be obtained for samples that contain high
concentrations of iron, copper, or other metals. EDTA is added to
the samples to eliminate this interference. Samples that contain
large concentrations of oil and grease will coat the surface of
the cadmium. This interference is eliminated by pre-extracting
the sample with an organic solvent. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The applicable range of this method is
0.01 to 1.0 mg/£ nitrate-nitrite nitrogen. In a single laboratory,
using sewage samples at concentrations of 0.04, 0.24, 0.55, and
1.04 mg N03 + N02-N/£, the relative standard deviations were 12.5%,
1.6%, .9%, and .9%, respectively, while recoveries were 100%, 102%,
and 100%, respectively.
Cost of Analysis; $10 - $15
D-263
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NITROGEN, NITRITE
Parameter Group: Nitrogen STORET Units: mg/£ as N
General: Nitrite, one of the chemically interconvertible compounds
of the nitrogen cycle, occurs in the oxidation of ammonia to
nitrate and in the reduction of nitrate. This oxidation and reduc-
tion may occur in wastewater treatment plants, water distribution
systems, and natural waters. In conjunction with ammonia and
nitrate, nitrites are often indicative of water pollution. They
exhibit the same deleterious effects as nitrates except at lower
concentrations, e.g., no physiological harm under 2 mg/£ as N.
This is a parameter which is regulated by BPT guidelines prescribed
by the NPDES permits program.
/
Criterion: Not established
Preservation Method: Analyze as soon as possible. Store at 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 50 m£
Measurement: The diazotization method is recommended for the de-
termination of nitrite nitrogen in the range from 0.01 to
1.0 mg NCL-N/£. The diazonium compound formed by diazotation of
sulfanilamide by nitrite in water under acid conditions is coupled
with N-(l-naphthyl)-ethylenediamine to produce a reddish-purple
color which is read in a spectrophotometer at 540 nm. The presence
of strong oxidants or reductants to the samples will affect the
nitrite concentrations. High alkalinity (>600 mg/£) will give
low results due to a shift in pH. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Precision and accuracy data are not
available.
Cost of Analysis: $5 - $12
D-264
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NITROPHENOLS
Parameter Group: STORET Units:
General: Nitrophenols include 2, 4-dinitrophenol; dinitrocresol,
2-nitrophenol, 4-nitrophenol, and 4., 6-dinitro-o-cresol. Metani-
trophenol is highly soluble in cold water, p-nitrophenoi moderately
so, and o-nitrophenol only sparingly soluble. The ortho isomer is
used in chemical manufacturing. Minimum lethal doses to fish vary
with isomer, species, and other water constituents (e.g., hard
water concentrations may be 10 times greater than those of dis-
tilled water). This parameter will be regulated by BAT guidelines
prescribed by the NPDES permits program. It is one of the Consent
Decree pollutants.
Criterion: Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required; 200-1,000 m£
Measurement: No standard procedures have been developed. The
methodology generally requires extraction, concentration, and gas
chromatographic analysis. A BAT NPDES method will be prescribed
for this parameter in 40 CFR 136.
Precision and Accuracy: Detection limits of 1 to 10 pg/£ should be
achievable. Precision and accuracy data are not available at this
time.
Cost of Analysis: $40 - $60
D-265
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OIL AND GREASE
Parameter Group: General STORET Units: mg/£
Organic
General: Oils and grease are not definitive chemical categories
but include thousands of organic compounds with varying physical,
chemical, and toxicological properties. Grease and oil include
hydrocarbons, fatty acids, soaps, fats, waxes, and oils. The
three major industrial sources of oily waste are the petroleum
industry, metals manufacture and machining, and food processors.
Field and laboratory evidence have demonstrated both acute lethal
toxicity and long-term sublethal toxicity of oils to aquatic
organisms. Bioaccumulation of petroleum products presents two
especially important public health problems: (1) the tainting of
edible, aquatic species, and (2) the possibility of edible marine
organisms incorporating the high boiling, carcinogenic polycyclic
aromatics in their tissues. The direct effects of aquatic oil
pollution on man are minimal. This is a parameter which is regu-
lated by BPT guidelines prescribed by the NPDES permits program.
Criteria: For domestic water supply: Virtually free from oil
and grease, particularly from the tastes and odors that emanate
from petroleum products.
For aquatic life:
0.01 of the lowest continuous flow 96-hour LC5Q to several
important freshwater and marine species, each having a
demonstrated high susceptibility to oils and petrochemicals.
• Levels of oils or petrochemicals in the sediment which
cause deleterious effects to the biota should not be
allowed.
• Surface waters shall be virtually free from floating non-
petroleum oils of vegetable or animal origin, as well as
petroleum-derived oils.
Preservation Method: Analyze as soon as possible. If storage is
required, cool to 4°C, add H2S04 to pH <2.
Maximum Holding Time: 24 hours
Container Type: Glass
Sample Volume Required: 1,000 m£
D-266
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Measurement: The Soxhlet extraction method is recommended when
relatively polar, heavy petroleum fractions are present. The
method is applicable to the determination of relatively non-
volatile hydrocarbons, vegetable oils, animal fats, waxes, soaps,
and greases. The separatory funnel extraction method can also
be used. The infrared method is applicable for measurement of
most light petroleum fuels. The Soxhlet extraction and separatory
funnel extraction methods are not applicable to the light hydro-
carbons that volatize at temperatures below 70°C. For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: The three oil and grease methods were
tested by a single laboratory on a sewage. The Soxhlet extrac-
tion method determined the oil and grease level in the sewage
to be 14.8 mg/£. When 1-liter portions of the sewage were dosed
with 14.0 mg of a mixture of #2 fuel oil and Wesson oil, the
recovery was 88% with a standard deviation of 1.1 mg. The
separatory funnel extraction method determined the oil and grease
level in the sewage to be 12.6 mg/£. When 1-liter portions of the
sewage were dosed with 14.0 mg of a mixture of #2 fuel oil and
Wesson oil, the recovery was 93% with a standard deviation of
0.9 mg. The infrared method determined the oil and grease level
in the sewage to be 17.5 mg/£. When 1-liter portions of the
sewage were dosed with 14.0 mg of a mixture of #2 fuel oil and
Wesson oil, the recovery was 99% with a standard deviation of
1.4 mg.
Cost of Analysis: $15 - $30
D-267
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ORGANIC CARBON
Parameter Group: General STORET Units: mg/£ as C
Organic
General: Organic carbon is the carbon oxidized by dichromate or
other strong oxidizing agents, the most common measurement being
total organic carbon CTOC). As in the case of BOD, TOC is a
measure of a significant aspect of the strength of a discharge
but is not a pollutant per se. The value of TOC usually falls
below the true concentration of organic contaminants because
other constituent elements are excluded. TOC is a more direct
expression of the organic chemical content of water than either
the BOD or COD tests and is faster and more convenient. It is
often used, after an empirical relationship has been established,
to estimate BOD or COD. This is a parameter which is regulated
by BPT guidelines prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Add H2S04 to pH <2.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass (brown glass preferred)
Sample Volume Required: 25 mi
Measurement: The combustion-infrared method is recommended. The
method is applicable to measurement of organic carbon above
1 mg/£. Carbonate and bicarbonate carbon represent an interfer-
ence under the terms of this test and must be removed or accounted
for in the final calculation. Instrument manufacturer's direc-
tions must be followed. For BPT NPDES purposes the measurement
of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The difficulty of sampling particulates
limits the precision to approximately 5 to 10% or higher. On
clear or filtered samples, the precision may approach 1 to 2%.
A distilled water solution containing 107 mg/£ of oxidizable
organic compounds was analyzed by 28 analysts in 21 laboratories
with a relative standard deviation of 7.6% and a relative error of
1.01%.
Cost of Analysis: $12 - $15
D-268
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PARATHION
Parameter Group: Pesticides STORET Units: yg/£
General: Parathion is the organophosphorus insecticide C.-H .
It is a yellow liquid that is insoluble in water or kerosene but
freely soluble in alcohols and aromatic hydrocarbons. It is most
commonly applied to row and orchard crops. Few chronic exposure
data are available for aquatic organisms. At high concentrations
of parathion, deformities, tremors, convulsions, hypersensitivity,
hemorrhages were evident in bullheads. Inhibition of cholinester-
ase enzymes is the established mode of physiological action of
parathion. Parathion has been found acutely toxic to aquatic
invertebrates. The half-life of parathion in river water
(pH 7.3-8.0) is one week. The estimated fatal dose for a 70-kg
man is 0.1 gram. The acute oral LC,-n for rats ranges from 3,000
DU
to 15,000 yg/kg of body weight. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits
program.
Criterion: 0.04 yg/£ for freshwater and marine aquatic life.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100 rat or more
Measurement: The use of co-solvent extraction, column chromatog-
raphy and liquid-liquid partition, and detection and measurement
accomplished by flame photometric gas chromatography using a phos-
phorus specific filter is recommended for parathion. Great care
must be exercised in the selection and use of methods to minimize
interferences, and the method is only recommended for use by a
skilled, experienced pesticide analyst (or under close supervision
of such a person). For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The detection limit is affected by many
factors, but is usually 0.010 yg/£ or higher. Sensitivity is
typically 1 yg/£. Precision and accuracy data are not available
at this time.
Cost of Analysis: -$30 - $150, depending upon preparation required.
D-269
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PCNB
Parameter Group: STORET Units:
General: Pentachloronitrobenzene (PCNB) is an organochlorine in-
secticide. It is used as an agricultural fungicide. It is
soluble in carbon disulfide, benzene, and chloroform. It is
practically insoluble in water and cold alcohol.
Criterion: Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended
for PCNB. Many interferences exist, especially PCB's, phthalate
esters, and organophpsphorus pesticides, and the method is only
recommended for use by a skilled, experienced pesticide analyst
(or under close supervision of such a person).
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 pg/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis: $30 - $150, depending upon preparation required
D-270
-------
PENTACHLOROPHENOL
Paramater Group: Pesticides STORET Units: yg/£
General: Pentachlorophenol (C,HC150) is a crystalline material
only slightly soluble in water but freely soluble in alcohol,
ether, and benzene. However, its sodium salt is highly soluble
in water. Pentachlorophenol possesses bactericidal, herbicidal,
insecticidal, fungicidal, and molluscicidal properties. In con-
centrated doses, it causes lung, liver, and kidney damage to
humans. In sea water, a concentration of 1.0 mg/£ of soidum
Pentachlorophenol prevents the attachment of marine fouling or-
ganisms in pipe and conduit. Its toxicity is highly dependent
upon the vehicle in which it is administered. This is a param-
eter which is regulated by BPT guidelines prescribed by the NPDES
permits program. This parameter will be regulated by BAT guide-
lines prescribed by the NPDES permits program. It is one of the
Consent Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Acidify to a
pH of 4 with H3P04. Add l.Og CuS04'5H20/£ to inhibit biodegrada-
tion of phenols. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 mg/£ or more depending upon
initial concentration.
Measurement: The recommended method involves direct aqueous in-
jection for the gas-liquid chromatographic determination of con-
centrates containing more than 1 mg/£ phenolic compounds. A
flame-ionization detector is used for their individual measurement.
Suspended matter may interfere by plugging the microsyringe. In-
terfering nonphenolic organic compounds may be removed by distil-
lation. Steps should be taken to minimize or eliminate ghosting.
For BPT NPDES purposes the measurement of this parameter is pre-
scribed by 40 CFR 136. A BAT NPDES method will be prescribed for
this parameter in 40 CFR 136.
Precision and Accuracy: Few precision and accuracy data are
available. Precision is very operator dependent. For example,
total precision may be 2 to 5 times single operator precision
values.
Cost of Analysis: $40 - $60
D-271
-------
PH
Parameter Group: Physical STORET Units: Standard Units
General: The pH of a solution is expressed as the logarithm of
the reciprocal of the hydrogen ion activity in moles per liter
at a given temperature. The practical scale extends from 0 (very
acidic) to 14 (very alkaline) with 7 corresponding to exact neu-
trality at 25°C. Whereas alkalinity and acidity are measures of
the total resistance to pH change or buffering capacity of a
sample, pH represents the free hydrogen ion activity not bound by
carbonate or other bases. The pH of most natural waters falls in
the range of 4 to 9 with the majority being slightly basic.
Changes in the normal pH for a given water may indicate the dis-
charge of alkaline or acidic wastes. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits program.
Criteria:
5-9, domestic water supplies (welfare).
6.5 - 9.0, freshwater aquatic life.
6.5 - 8.5, marine aquatic life (within this range, pH should
not be more than 0.2 unit outside the normally occurring
range).
Preservation Methods: Analyze on site if at all possible. Other-
wise, seal the sample container and cool to 4°C. Sample bottle
should not be opened before analysis.
Maximum Holding Time: Any holding time beyond 6 hours should be
reported with the measurement.
Container Type: Plastic or glass
Sample Volume Required: 25 to 100 m£
Measurement: Although pH can be measured colorimetrically, the
method suffers from numerous interferences, deterioration of
indicators and color standards, and limited indicator range. The
glass electrode method is the standard technique, employing ei-
ther a glass electrode in conjunction with a separate reference
(constant potential) electrode, e.g., calomel, silver-silver
chloride, or a combination electrode (glass and reference). The
measurement is temperature-dependent. Oil and grease may coat the
pH electrode and cause a sluggish response. For BPT NPDES purposes
the measurement of this parameter is prescribed by 40 CFR 136.
D-272
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Precision and Accuracy: The precision and accuracy attainable
will depend upon the type and condition of the water and the care
used in standardization and operation. Precisions of ±0.02 pH
and accuracies of ±0.05 pH are achievable, but ±0.1 pH represents
the accuracy limit under normal conditions. Typical standard
deviations are from 0.1 to 0.2 pH.
Cost of Analysis: $3
D-273
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PHENOLICS
Parameter Group: General STORET Units: jjg/£
Organic
General: Phenols are hydroxy derivatives of benzene and its con-
densed nuclei. Phenolic compounds include a wide variety of or-
ganic chemicals and may arise from the distillation of coal and
wood; from oil refineries; chemical plants; livestock dips; human
and other organic wastes; hydrolysis, chemical oxidation, and
microbial degradation of pesticides; and from naturally occurring
sources and substances. Despite the fact that it is used as a
bactericide, weak phenol solutions are decomposed by bacteria and
biological action, rates typically exceeding 2,000 ug/£ per day
in natural streams. Chlorination of water containing phenolic
compounds produces odoriferous and objectionable tasting chloro-
phenols. The ingestion of concentrated solutions of phenol will
result in severe pain, renal irritation, shock, and possibly
death. A 1.5-gram dose may be fatal. Many of the phenolic
compounds are more toxic than pure phenol, especially to lower
life forms. This is a parameter which is regulated by BPT guide-
lines prescribed by the NPDES permits program.
Criterion: 1 vg/£ for domestic water supply (welfare), and to
protect against fish flesh tainting.
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Add H3P04 to pH <4 and l.Og CuS04/£.
Maximum Holding Time: 24 hours
Container Type; Glass only
Sample Volume Required: 500 m£
Measurement: The 4-aminoantipyrine (4-AAP) method with distilla-
tion is recommended and is applicable to the analysis of drinking,
surface, and saline waters, domestic and industrial wastes. Pheno-
lic materials react with 4-aminoantipyrine in the presence of
potassium ferricyanide at a pH of 10 to form a stable reddish-
' brown colored antipyrine dye. The amount of color produced is a
function of the concentration of the phenolic material. For most
samples, a preliminary distillation is required to remove inter-
fering materials. Gas chromatograph tests can be used to isolate
specific compounds. For BPT NPDES purposes the measurement of
this parameter is prescribed by 40 CFR 136.
D-274
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Precision and Accuracy: Using the extraction procedure for con-
centration of color, six laboratories analyzed samples at concen-
trations of 9.6, 48.3, and 93.5 vg/t. Relative standard deviations
were 10.3%, 6.4%, and 4.5%, respectively. The method must be re-
garded as an approximation representing the minimum amount of
phenols present because the phenolic value varies with the types of
phenols within a given sample. It is therefore impossible to
express the accuracy of the method.
Cost of Analysis: $15 - $25
D-275
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PHOSPHORUS CALL FORMS)
Parameter Group: Phosphorus STORET Units: mg/£ P
Generals. Phosphorus in its elemental form (yellow phosphorus) does
not occur free in nature and is particularly toxic to animal life',
being subject to bioaccumulation in much the same way as mercury.
Phosphorus as phosphate is abundant in nature and also from the
activities of man. Phosphates occur as a result of leaching from
minerals and ores in natural processes of degradation, from agri-
cultural drainage as one of the stabilized products of decomposi-
tion of organic matter, as a result of innumerable industrial
discharges, from some treated cooling waters, and as a major ele-
ment of municipal sewage. It is an essential nutrient for plant
and animal growth. Major uses include fertilizers, detergents,
and industrial chemicals. Organic phosphates are used extensively
in pesticides. The chief deleterious effect of high concentrations
is accelerated eutrophication. They also interfere with coagula-
tion and removal of turbidity. This is a parameter which is regu-
lated by BPT guidelines prescribed by the NPDES permits program.
Definitions of the various phosphorus forms are given below.
Total Phosphorus - all of the phosphorus present in the sam-
ple, regardless of form, as measured by the persulfate diges-
tion procedure.
Total Orthophosphate - inorganic phosphorus in the sample as
measured by the direct colorimetric analysis procedure.
Total Hydrolyzable Phosphorus - phosphorus in the sample
as measured by the sulfuric acid hydrolysis procedure, and
minus pre-determined orthophosphates. This hydrolyzable
phosphorus includes polyphosphorus plus some organic
phosphorus.
Total Organic Phosphorus - phosphorus (inorganic +
oxidizable organic) in the sample measured by the persulfate
digestion procedure, and minus hydrolyzable phosphorus and
orthopho sphat e.
Dissolved Phosphorus - all of the phosphorus present in the
filtrate of a sample filtered through a phosphorus-free
filter of 0.45 micron pore size and measured by the persul-
fate digestion procedure.
Dissolved Orthophosphate - as measured by the direct
colorimetric analysis procedure.
D-276
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Dissolved Hydrolyzable Phosphorus - as measured by the sul-
furic acid hydrolysis procedure and minus pre-determined
dissolved orthophosphates.
Dissolved Organic Phosphorus - as measured by the persulfate
digestion procedure, and minus dissolved hydrolyzable phos-
phorus and orthophosphate.
When sufficient amounts of phosphorus are present in the sample to
warrant such consideration, the insoluble forms may be calculated
as the total minus the dissolved fraction and reported as Insoluble
Phosphorus, Insoluble Orthophosphate, Insoluble Hydrolyzable
Phosphorus, or Insoluble Organic Phosphorus.
Criterion: 0.10 yg/£ yellow (elemental) phosphorus for marine or
estuarine waters.
Preservation Method: Filter on site if dissolved determination is
desired. Cool to 4°C. Analyze as soon as possible. Add 40 mg/£
mercuric chloride as a preservative if absolutely necessary, but
its use is discouraged whenever possible.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 50 m£
Measurement: The persulfate digestion method is recommended.
After digestion, determine the total orthophosphate in the
sample by the direct colorimetric analysis procedure. High iron
concentrations can cause precipitation of and subsequent loss of
phosphorus. Mercury chloride interferes when the chloride level
of the sample is low, <50 mg Cl/£. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Natural water samples with an exact
increment of organic phosphate were analyzed by 33 analysts in
19 laboratories. At around 0.1 and 0.8 mg/£ P, relative standard
deviations were around 35% and 15%, respectively, and relative
error ranges were 3-12% and 1-3%, respectively. Natural water
samples with an exact increment of orthophosphate were analyzed
by 26 analysts in 16 laboratories. At around 0.01 and 0.02 mg/£ P,
relative standard deviations were around 28% and 6% respectively,
and relative errors were around 5.5% and 2.3%, respectively.
Cost of Analysis: $10 - $15
D-277
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PHTHALATE ESTERS
Parameter Group: General STORET Units: yg/£
Organic
General: Phthalate esters include bis (2-ethylhexyl) phthalate,
butyl benzyl phthalate, di-n-butyl phthalate, diethyl phthalate,
and dimethyl phthalate and are organic compounds used as plasti-
cizers, particularly in polyvinyl chloride plastics. The di-2-
ethylhexyl and di-n-butyl phthalates are used as an orchard
acaricide and insect repellent. Phthalate esters can be detri-
mental to aquatic organisms at low water concentrations. Ability
to concentrate high levels from water and reproductive impair-
ment in certain species are suggestive of potential environmental
damage. This parameter will be regulated by BAT guidelines pre-
scribed by the NPDES permits program. It is one of the Consent
Decree pollutants.
Criterion: 3 pg/£ for freshwater aquatic life.
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 200-1,000 m£
Measurement: No standard procedures have been developed. The
methodology generally requires extraction, concentration, and
gas chromatographic analysis. A BAT NPDES method will be pre-
scribed for this parameter in 40 CFR 136.
Precision and Accuracy; Detection limits of 0.1 to 10 ug/£ should
be achievable. Precision and accuracy data are not available at
this time.
Cost of Analysis: $25 - $40
D-278
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POLYCHLORINATED BIPHENYLS
Parameter Group: General STORET Units: yg/£
Organic
General: Pol/chlorinated biphenyls (PCB's) are a class of compounds
produced by the chlorination of biphenyls and are registered in the
fRI
United States under the trade name Aroclor^ }. PCS compounds are
slightly soluble in water (25 to 200 yg/£), soluble in lipids,
oils, and organic solvents, and resistant to both heat and biolog-
ical degradation. PCB's are relatively nonflammable, have useful
exchange and dielectric properties, and were used principally in
the electrical industry in capacitors and transformers. The acute
and chronic effects of PCB's have been determined on a number of
aquatic organisms. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program. This parameter
will be regulated by BAT guidelines prescribed by the NPDES permits
program. It is one of the Consent Decree pollutants. A toxic
effluent limitation has been prescribed for this parameter by the
NPDES permits program.
Criterion;
.001 yg/£ for freshwater and marine aquatic life and for
consumers thereof
• Every reasonable effort should be made to minimize human
exposure.
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 mi
Measurement: The recommended gas chromatograph method covers the
following PCB mixtures: Aroclors 1221, 1232, 1242, 1248, 1254,
1260, and 1016. It is an extension of the method for organochlorine
pesticides - both the PCB's and the organochlorine pesticides may be
determined on the same sample. They are co-extracted by liquid-
liquid extraction and separated from one another prior to gas
chromatographic determination. A combination of the standard
Florisil column cleanup procedure and a silica gel microcolumn sepa-
ration procedure are employed. Identification is made from gas
chromatographic patterns obtained through the use of two or more
unlike columns. Detection and measurement is accomplished using an
electron capture, microcoulometric, or electrolytic conductivity
D-279
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detector. Solvents, reagents, glassware, and other sample process-
ing hardware may yield discrete artifacts and/or elevated baselines
causing misinterpretation of gas chromatograms. All of these
materials must be demonstrated to be free from interferences under
the conditions of the analysis. For BPT NPDES purposes the measure-
ment of this parameter is prescribed by 40 CFR 136. A BAT NPDES
method will be prescribed for this parameter in 40 CFR 136.
Precision and Analysis: The detection limit is approximately
1 yg/£.Precision and accuracy data are not available at this
time.
Cost of Analysis: $45 to $50 for a scan and one compound
$95 to $100 for total PCB's
D-280
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POLYNUCLEAR AROMATIC HYDROCARBONS
Parameter Group: STORET Units:
General: Polynuclear aromatic hydrocarbons include 1,
2-benzanthracene, 3, 4-benzopyrene, 3, 4-benzo£luoranthene, 11,
12-benzofluoranthene, chrysene, acenapthylene, anthracene, 1,
12-benzoperylene, fluoroethane, phenanthrene, 1, 2:5,
6-dibenanthracene, indeno Cl» 2, 3-C, D) pyrene, and pyrene.
This parameter will be regulated by BAT guidelines prescribed by
the NPDES permits program. It is one of the Consent Decree
pollutants.
Criterion: Not established
Preservation Method; Not determined. Analyze promptly. Cool to
4*c~;
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 1,000-4,000 mi
Measurement: Procedures for determination of polynuclear aromatic
hydrocarbons involve extraction, thin layer chromatography, and
fluorescence or UV absorption spectra. They require confirmation
on wastewater. A BAT NPDES method will be prescribed for this
parameter in 40 CFR 136.
Precision and Accuracy: Detection limits range from around 0.2
to 20 pg/£.Precision and accuracy data are not available at this
time.
Cost of Analysis: $300 - $600
D-281
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POTASSIUM
Parameter Group: Metals STORET Units: mg/£ as K
General: Potassium occurs in nature as chloride or sulfate in
certain salt deposits, in common rocks (average of the solid
earth shell is 2.6%) and minerals (e.g., feldspar, greensand,
alunite, leucite), and is present in vegetation. It is one of the
most active metals and, hence, is only found in the ionized or
molecular form. Its salts are indispensable for fertilizers, some
varieties of glass, and certain other purposes. All are highly
soluble and uses include baking powders, effervescent antiacids,
as a flux for silver solders, treating coal to prevent slag for-
mation, tanning, soap manufacturing, in matches and explosives,
pesticides, in wood industries, dyeing and bleaching cotton, paint
and varnish removers, electroplating, photoengraving, lithography,
photographic emulsions, table salt, disinfectants, and a host of
other uses. Potassium is an essential nutritional element, but in
excessive doses it acts as a cathartic. Its level of toxicity to
fish and other aquatic life depends upon its form and the age and
species involved. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO_ to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or Pyrex
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 766.5 nm. Sodium may interfere if present
at much higher levels than the potassium. This effect can be
compensated by approximately matching the sodium content of the
potassium standards with that of the sample. The flame photo-
metric method is rapid, sensitive, and accurate but requires a
special instrument and much preliminary work before samples can
be run routinely. The colorimetric method is usually inadvisable
for potassium levels below 10 mg/£. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 0.04 mg/£;
its detection limit is 0.005 mg/£. The optimum concentration
range is 0.1-2 mg/£. In a single laboratory, using distilled
D-282
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water samples at concentrations of 1.6 and 6.3 mg/£, the relative
standard deviations were 13% and 8%, respectively. Recoveries at
these levels were 103% and 102%. In a 33-laboratory test using a
synthetic unknown at 3.1 mg/£ K, results from the flame photo-
metric method yielded a relative standard deviation of 15.5% and
a relative error of 2.3%.
Cost of Analysis: $5 - $10
D-283
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RADIOACTIVITY (ALPHA AND BETA)
Parameter Group: Radiological STORET Units: Unspecified
General: Naturally occurring radioactivity in water is due to
contact with mineral deposits; many springs and deep wells have
high levels of radioactivity. Uranium, thorium, and radium and
their long series of daughter products are the chief naturally
occurring emitters of alpha and beta radiation. With the advent
of nuclear science, man has produced a long series of radioactive
products, including almost all of the elements in the periodic
table. In addition to mining and separation operations, other
manmade sources include the manufacture of nuclear weapons,
nuclear reactors, the production of isotopes, and their use in
medical therapy, research, and industrial processes and instru-
mentation. Radioactivity may be considered as an indestructable
property from the viewpoint of man's inability to cancel or
neutralize it by chemical or physical means. Gross alpha and beta
activity measurements represent the best overall indicator of the
presence of radioactive contamination in waters and the need for
more specific determinations of the more hazardous radionuclides.
The radioactivity of natural waters is usually in the 1 to
1,000 pCi/l range but may reach 100,000 pCi/l, and the radon
(short-lived) content of some mineral springs has been found to
be as high as 750,000 pCi/£. This is a parameter which is regu-
lated by BPT guidelines prescribed by'the NPDES permits program.
Criterion: Not established
Preservation Method: Preservatives may alter the distribution of
radioactivity in a sample and should not be used until the sample
is separated into suspended and dissolved fractions.
Maximum Holding Time: Unstated. Adsorption onto container surfaces
represents the greatest problem.
Container Type: Plastic or glass
Sample Volume Required: 1,000 m£
Measurement: The internal proportional counter is the recommended
instrument for counting gross beta radioactivity. With a Geiger
counter, the alpha activity cannot be determined separately. Alpha
counting efficiency in end-window counters may be very low. For
BPT NPDES purposes the measurement of this parameter is prescribed
by 40 CFR 136.
D-284
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Precision and Accuracy: In a study of two sets of paired water
samples containing known additions of radionuclides, 15 labora-
tories determined the gross alpha activity and 16 analyzed the
gross beta activity. The average recoveries of added gross alpha
activity were 86%, 87%, 84%, and 82%. The average recoveries of
added gross beta activity were 99%, 100%, 100%, and 100%.
Cost of Analysis: $9 - $15
D-285
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RADIUM
Parameter Group; STORET Units:
General: There are four naturally occurring radium isotopes:
radium 223, radium 224, radium 226, and radium 228. Radium 226
has a half life of 1600 years. Ra-228 is a beta emitter; the
others are alpha emitters. Although alpha particles cannot pene-
trate the skin, they are particularly dangerous when ingested and
deposited within the body. The determination of radium by precip-
itation is a screening technique applicable in particular to drink-
ing water. It includes all alpha emitting isotopes, and as long
as concentrations are within standards for Ra-226, the need for
examination by a more specific method is minimal. This is a param-
eter which is regulated by BPT guidelines prescribed by the NPDES
permits program.
Criterion: Not established
Preservation Method: None
Maximum Holding Time: Unknown, but prompt analysis is recommended.
Container Type: Plastic or glass
Sample Volume Required: 1,000 m£
Measurement: The recommended method is the determination of
radium by precipitation. It involves the alpha counting of a
borium-radium sulfate precipitate that has been isolated from the
sample and purified. The method is also applicable to sewage and
industrial wastes, provided that steps are taken to destroy organic
matter and eliminate other interfering ions. A counting instru-
ment is required. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: In a 20-laboratory study involving the
analysis of four samples for total radium, all four results from
two laboratories and two results from a third had to be rejected
as outliers. Of the remainder, recoveries averaged higher than
95%. At the 95% confidence level, the precision was around 30%.
Cost of Analysis: $40 - $50
D-286
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RESIDUE, SETTLEABLE
Parameter Group: Solids STORET Units: mi/I
General: Settleable residue (solids) which blankets the bottom of
water bodies damage the invertebrate populations, block gravel
spawning beds, and if organic, remove dissolved oxygen from over-
lying waters. They can interfere with recreation, navigation,
fish and shellfish production, and destroy aesthetic values of
water. They may decompose to produce putrefactive odors and may
exude products of decomposition to overlying waters. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required; 1000 m£
Measurement: Settleable matter is measured volumetrically with an
Imhoff cone. The practical lower limit of the determination is
about 1 m£/£/hr. For some samples, a separation of Settleable and
floating materials will occur. In such cases, the floating materi-
als are not measured. For BPT NPDES purposes the measurement of
this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Precision and accuracy data are not avail-
able at this time.
Cost of Analysis: $3 - $5
D-287
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RESIDUE, TOTAL
Parameter Group: Solids STORET Units: mg/£
General: Total residue (total solids) refers to all the solid mat-
ter (suspended and dissolved) in water or wastewater and is the ma-
terial left in a vessel after evaporation of a sample and its
subsequent drying in an oven. Thus it is the sum of filterable and
nonfilterable residue. Waters with high residue are generally of
inferior palatability and may induce adverse reaction to transient
consumers. Also see discussions of filterable and nonfilterable
residue. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 7 days
Container Type: Plastic or resistant glass
Sample Volume Required: 100 mi
Measurement: A well mixed aliquot of the test sample is quantita-
tively transferred to a pre-weighed evaporating dish and evaporated
to dryness at 103-105°C. The practical range of the determination
is from 10 mg/£ to 20,000 mg/£. Large, floating particles or sub-
merged agglomerates (non-homogeneous materials) should be excluded
from the test sample. Floating oil and grease, if present, should
be included in the sample and dispersed by a blender device before
aliquoting. For BPT NPDES purposes the measurement of this param-
eter is prescribed by 40 CFR 136.
Precision and Accuracy: The practical upper limit for this deter-
mination is 20,000 mg/£. Precision and accuracy data are not
available at this time.
Cost of Analysis: $3 - $15
D-288
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RESIDUE, TOTAL FILTERABLE
Parameter Group: Solids STORET Units: mg/£
General: Total filterable residue (total dissolved solids) consists
of inorganic salts, small amounts of organic matter, and dissolved
materials. The principal inorganic anions dissolved in water in-
clude the carbonates, chlorides, sulfates and nitrates (principally
in ground waters); the principal cations are sodium, potassium,
calcium, and magnesium. Excess dissolved solids are objectionable
in drinking water because of possible physiological effects, un-
palatable mineral tastes, and higher costs because of corrosion or
the necessity for additional treatment. Some communities use water
containing up to 4,000 mg/£ for drinking purposes. There is no
proof of beneficial or therapeutic value to mineral waters. This
is a parameter which is regulated by BPT guidelines prescribed by
the NPDES permits program.
Criterion: 250 mg/£ for chlorides and sulfates in domestic water
supplies (welfare).
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 7 days
Container Type: Plastic or resistant glass
Sample Volume Required: 100 nv£
Measurement: The recommended method is applicable to drinking,
surface, and saline waters, domestic and industrial wastes. A well
mixed sample is filtered through a standard glass fiber filter.
The filtrate is evaporated and dried to constant weight at 180°C.
Highly mineralized waters containing significant concentrations of
calcium, magnesium, chloride and/or sulfate may be hygroscopic and
will require prolonged drying, desiccation and rapid weighing.
Samples containing high concentrations of bicarbonate will require
careful and prolonged drying at 180°C to insure that all the bicar-
bonate is converted to carbonate. Too much residue in the evapo-
rating dish will crust over and entrap water that will not be
driven off during drying. Total residue should be limited to about
200 mg. For BPT NPDES purposes the measurement of this parameter.
is prescribed by 40 CFR 136.
Precision and Accuracy: The practical range of the determination
is 10 mg/£ to 20,000 mg/£. Precision and accuracy data are not
available at this time.
Cost of Analysis: $3 - $15
D-289
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RESIDUE, TOTAL NONFILTERABLE
Parameter Group: Solids STORET Units: mg/£
General: Total nonfilterable residue (suspended solids) is the
material retained on a standard glass fiber filter disk after fil-
tration of a well mixed sample. In natural waters it consi-sts of
erosion silt, organic detritus, and plankton. The discharge of
wastewater presents virtually unlimited possibilities. Total non-
filterable residue includes all settleable solids. It has varying
effects upon water uses (apart from individual effects of the sub-
stances constituting the suspended solids). It is the most diffi-
cult parameter in terms of obtaining a representative sample from
the bulk source and is used as a measure of treatment plant
efficiency. This is a parameter which is regulated by BPT guide-
lines prescribed by the NPDES permits program.
Criterion: Should not reduce the depth of the compensation point
for photosynthetic activity by more than 10% from the established
norm - for aquatic life.
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 7 days
Container Type: Plastic or resistant glass
Sample Volume Required: 100 m£
Measurement: The recommended method involves filtering a well
mixed sample through a standard glass fiber filter, and the residue
retained on the filter is dried to constant weight at 103-105°C.
Too much residue on the filter will entrap water and may require
prolonged drying. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The practical range of the determination
is 10 mg/£ to 20,000 mg/£. Precision and accuracy data are not
available at this time.
Cost of Analysis: $3 - $15
D-290
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RESIDUE, VOLATILE
Parameter Group: Solids STORET Units: mg/L
General: The volatile components in the residue represent a rough
indication of the amount of organic matter present. Since the re-
sult may reflect loss of water of crystallization, loss of volatile
organic matter before combustion, incomplete oxidation of certain
complex organics, and decomposition of mineral salts during combus-
tion, it may not yield an accurate measure of organic carbon.
This is a parameter which is regulated by BPT guidelines prescribed
by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 7 days
Container Type: Plastic or resistant glass
Sample Volume. Required: 100 m£
Measurement: The recommended method determines the weight of solid
material combustible at 550°C. The residue obtained from the de-
termination of total, filterable, or nonfilterable residue is ig-
nited at 550°C in a muffle furnace. The loss of weight on ignition
is reported as mg/£ volatile residue. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
Freei s ion and Ac curacy: A -collaborative study involving three lab-
oratories examining four samples by means of ten replicates showed
a standard deviation of ±11 mg/£ at 170 mg/£ volatile residue
concentration.
Cost of Analysis: $10 - $15
D-291
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SELENIUM
Parameter Group: Metals STORET Units: yg/£ as Se
General: Selenium appears in the soil as basic ferric selenite,
calcium selenate, and as elemental selenium. Selenium salts are
used in many industries, including paint, pigment and dye pro-
ducers, electronics, glass manufacture, insecticide sprays,
electrical apparatus (rectifiers, semiconductors, photoelectric
cells, etc.), rubber, and alloying. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits pro-
gram. This parameter will be regulated by BAT guidelines pre-
scribed by the NPDES permits program. It is one of the Consent
Decree pollutants.
Criteria:
10 pg/£ for domestic water supply (health)
For marine and freshwater aquatic life; 0.01 of the
96-hour LC50 as determined through bioassay using
a sensitive resident species
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO- to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 50 m£
Measurement; The AA spectrophotometric gaseous hydride method is
recommended using a wavelength of 196.0 nm. The method is ap-
plicable to most fresh and saline waters, in the absence of high
concentrations of chromium, cobalt, copper, mercury, molybdenum,
nickel and silver. The diaminobenzidine colorimetric method may
also be used. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy; The AA method sensitivity is approximately
2.5 ug/£; its detection limit is 2 yg/£. The working range of the
method is 2-20 pg/£. At a concentration of 10 pg/£, the relative
standard deviation is 11% and the relative error is 0.0%. Ten
replicate solutions of selenium oxide at the 5, 10 and 15 yg/£
level were analyzed by a single laboratory. Relative standard
deviations were 12%, 11%, and 19% with recoveries of 100%, 100%,
and 101%.
Cost of Analysis: $15 - $40
D-292
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SILICA
Parameter Group: Solids STORET Units: mg/£ as SiO-
General: Silica is abundant in the earth's crust. It appears as
an oxide in many rocks. The degradation of the rocks results in
the presence of silica in natural waters. Silica is also widely
used in industry and in water treatment. Silica in water forms
silica and silicate scales in various equipments, particularly on
high pressure steam turbine blades. In normally occurring concen-
trations it does not appear to cause adverse physiological effects.
This is a parameter which is regulated by BPT guidelines prescribed
by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 7 days
Container Type: Plastic or hard rubber
Sample Volume Required: 50-1000 mi
Measurement: Total silica is determined by a gravimetric method
wherein silica acids are formed and precipitated, ignited, and the
final determination made as the loss on volatilization. The rec-
ommended method for dissolved silica involves filtering a well-
mixed sample through a 0.45p membrane filter. The filtrate, upon
the addition of molybdate ion in acidic solution, forms a greenish-
yellow color complex proportional to the dissolved silica in the
sample. The color complex is then measured spectrophotometrically.
Excessive color and/or turbidity interfere. For BPT NPDES purposes
the measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Precision of the gravimetric method is
approximately ±0.2 mg SiO-. Photometric evaluations by the amino-
naphthal-sulfuric acid procedure have an estimated precision of
±0.10 mg/£ in the range from 0 to 2 mg/£. Photometric evaluations
of the silica-molybdate color in the range from 2 to 50 mg/t have
an estimated precision of approximately 4% of the quantity of
silica measured.
Cost of Analysis: $5 - $15
D-293
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SILICON
Parameter Group: Solids STORET Units: yg/£ as Si
General: Silicon, the second most abundant element making up
26% of the earth's crust, is not found free in nature but occurs
chiefly as the oxide (silica) in sand, quartz, agate, opal, etc.,
and as silicates in granite, feldspar, kaolinite, and other
minerals. Silicon is one of man's most useful elements, with ap-
plications ranging from metallurgy to solid state electronics and
the production of silicones, polymeric products ranging from liq-
uids to hard glass-like solids with many beneficial properties.
Silicon is also important in plant and animal life.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO- to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is often used,
with a wavelength of 251.6 nm. Avoid any prolonged contact with
glass.
Precision and Accuracy: The AA method sensitivity is 2,000 yg/£;
its detection limit is 300 pg/£. Precision and accuracy data are
not available at this time.
Cost of Analysis: $10 - $20
D-294
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SILVER
Parameter Group: Metals STORET Units: yg/£ as Ag
General: Silver ions cannot be expected to occur in significant
concentrations in natural waters. As a solid metal, silver is
used in the jewelry, silverware, metal alloy, and food processing
industries. The solid metal produces very little soluble waste.
Silver nitrate, which is soluble, is used in the porcelain, photo-
graphic, electroplating and ink manufacturing industries, and as
an antiseptic. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program. This param-
eter will be regulated by BAT guidelines prescribed by the NPDES
permits program. It is one of the Consent Decree pollutants.
Criteria:
• 50 yg/£ for domestic water supply (health)
• For marine and freshwater aquatic life, 0.01 of the
96-hour LC,-n as determined through bioassay using a
sensitive resident species
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO_ to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 mi
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 328.1 nm. For BPT NPDES purposes the mea-
surement of this parameter is prescribed by 40 CFR 136. A BAT
NPDES method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 60 yg/£; its
detection limit is 10 yg/£. The optimum concentration range is
100-4,000 Mg/t. At a concentration of 550 yg/£, the relative
standard deviation is 17.5%, and the relative error is 10.6%.
Cost of Analysis: $10 - $15
D-295
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SILVEX (2, 4, 5-TP)
Parameter Group: Pesticides STORET Units: yg/£
General: Silvex, 2 (2, 4, 5-trichlorophenoxy) propionic acid, is
a chlorinated phenoxy acid herbicide. It is used for weed con-
trol on land, and its esters and salts have been used as an
aquatic herbicide in lakes, streams, and irrigation canals. It
is slightly soluble in water and freely soluble in acetone and
methyl alcohol. Silvex is reported to be slightly less toxic than
2, 4-D and 2, 4, 5-T type materials. Its acute oral LD_0 to rats
is 650,000 mg/kg of body weight. At a level of 2,000 yg/£ it has
temporarily (e.g., 2 weeks) reduced the number of plankton in
lakes, but fish are unaffected. Apparently the threshold of
toxicity for fish is around 5,000 yg/£. In some instances, how-
ever, fish have acquired an unpleasant, oily taste following ex-
posure to Silvex. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program.
Criterion: 10 yg/£ for domestic water supply (health).
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100 - 1,000 m£, depending on measurement
method used.
Measurement: In the recommended method, chlorinated phenoxy acids
and their esters are extracted from the acidified water sample
with ethyl ether. The esters are hydrolyzed to acids, and extra-
neous organic material is removed by a solvent wash. The acids
are converted to methyl esters which are extracted from the
aqueous phase. The extract is cleaned up by passing it through
a micro-adsorption column. Detection and measurement are accom-
plished by electron capture, microcoulometric or electrolytic
conductivity gas chromatography. Interferences may be high and
varied and often pose great difficulty in obtaining accurate and
precise measurement of chlorinated phenoxy acid herbicides. Or-
ganic acids, especially chlorinated acids, cause the most direct
interference with the determination. Phenols including chloro-
phenols will also interfere with this procedure. The method is
recommended for use only by an experienced pesticide analyst (or
under the close supervision of such a person). For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
D-296
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Precision and Accuracy: Sensitivity of the method is 1 vg/t. De-
tection limits of 0.01 pg/£ or so may be achieved. Precision and
accuracy data are not available at this time.
Cost of Analysis: $45 - $150, depending upon preparation required.
D-297
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SODIUM
Parameter Group: Metals STORET Units: mg/£ as Na
General: Sodium is present in most natural waters and, as the
cation of many salts used in industry, is one of the most common
ions in industrial waters. A high sodium ratio has harmed soil
permeability. Humans with certain diseases (cardiac, renal, and
circulatory) require water with a low sodium concentration.
Otherwise, taste considerations prevail as far as human ingestion
is concerned. This is a parameter which is regulated by BPT guide-
lines prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Add HNO, to
pH of 2.
Maximum Holding Time: 6 months
Container Type: Polyethylene bottles
Sample Volume Required: 100-200 mi
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 589.6 nm. Low-temperature flames increase
sensitivity by reducing the extent of ionization of this easily
ionized metal. Ionization may also be controlled by adding
potassium (1,000 mg/£) to both standards and samples. The flame
photometric method may also be used. For BPT NPDES purposes the
measurement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy; The AA method sensitivity is 0.015 mg/£;
its detection limit is 0.002 mg/£. The optimum concentration
range is 0.03-1.0 mg/£. In a single laboratory, using distilled
water samples at levels of 8.2 and 52 mg/£, the relative standard
deviations were 1.2% and 1.5%, respectively. Recoveries at these
levels were 102% and 100%. In a 35-laboratory test using the
flame photometric method on a synthetic unknown at 19.9 mg/£ Na,
a relative standard deviation of 17.3% and a relative error of
4.0% were reported.
Cost of Analysis: $5 - $10
D-298
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SPECIFIC CONDUCTANCE
Parameter Group: Physical STORET Units: ymhos/cm @ 25°C
General: The determination of conductivity (specific electrical
conductance) is a quick method for determining the ion concentra-
tion of water. The mobility of each of the various ions, their
valences, and their actual and relative concentrations affect
conductivity. The specific conductance of potable waters generally
ranges from 50 to 1,500 ymhos/cm; for wastewaters it is highly
variable and may be well in excess of 10,000 ymhos/cm. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 100 mi
Measurement: The specific conductance of a sample is measured by
use of a self-contained conductivity meter, Wheatstone bridge-type
or equivalent. Samples are preferably analyzed at 25°C. If not,
temperature corrections are made and results reported at 25°C.
For BPT NPDES purposes the measurement of this parameter is pre-
scribed by 40 CFR 136.
Precision and Accuracy: Typically, relative standard deviations
of around 7 to 9% and relative errors from 2 to 5% are experienced.
/
Cost of Analysis: $-3 - $5
D-299
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STRONTIUM
Parameter Group: Radiological STORET Units: Unspecified
General: The radioactive nuclides of strontium produced in
nuclear fission are Sr-89 and Sr-90. Strontium 90 is one of the
most hazardous of all fission products. It has a half-life of
28 years. Strontium is concentrated in the bones if it is
ingested. Ten percent of the occupational maximum concentration
for Sr-90 in water is 100 pCi/£. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits
program.
Criterion: Not established.
Preservation Method: None
Maximum Holding Time: Unknown, but prompt analysis is recommended.
Container Type: Plastic or glass
Sample Volume Required: Not determined
Measurement: The recommended method involves the use of a "car-
rier" which is inactive strontium ions in the form of strontium
nitrate. Precipitation is used to obtain strontium carbonate
from the strontium carrier and the radionuclide of strontium. It
is dried to determine recovery of the carrier and then measured
for radioactivity. Radioactive barium interferes in the determina-
tion of radioactive strontium. A counting instrument is required.
For BPT NPDES purposes the measurement of this parameter is pre-
scribed by 40 CFR 136.
Precision and Accuracy: In a study of two sets of paired water
samples containing known additions of radionuclides, 12 labora-
tories determined the total radiostrontium and 10 laboratories
determined Sr-90. The average recoveries of total radiostrontium
from the four samples were 99%, 99%, 96%, and 93%. The average
recoveries of added Sr-90 from the four samples were 90%, 96%,
80%, and 94%.
Cost of Analysis: $40 - $50
D-300
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SULFATE
Parameter Group: General STORET Units: mg/£ as S
Inorganic
General: Sulfates occur naturally in waters as a result of leach-
ings from gypsum and other common minerals or as the final oxi-
dized stage of sulfides, sulfites, and-thiosulfates having both
mineral and organic origins. They may also be found in the wastes
from numerous industries, including tanneries, sulfate pulp mills,
textile mills, and other plants using sulfates or sulfuric acid.
Excessive sulfates may exert a laxative action toward new users
and cause taste problems, but such effects are not observed below
500 mg/£. Limits for industrial users (especially sugar making)
are much lower. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum HoIding Time: 7 days
Container Type: Plastic or glass
Sample Volume Required: 50 m£
Measurement: The turbidimetric method using a nephelometer is
normally acceptable. The method is suitable for all concentra-
tion ranges of sulfate; however, in order to obtain reliable
readings, use a sample aliquot containing not more than 40 mg/£
SO.. Suspended matter and color interfere. Correct by running
blanks from which the barium chloride has been omitted. The
gravimetric method is recommended when results of the greatest
accuracy are required. It is most accurate for sulfate concentra-
tions above 10 mg/£. For BPT NPDES purposes the measurement of
this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: A synthetic unknown sample containing
259 mg/£ sulfate, 108 mg/£ Ca, 82 mg/£ Mg, 3.1 mg/£ K, 19.9 mg/£
Na, 241 mg/£ chloride, 250 yg/£ nitrite N, 1.1 mg/£ nitrate N and
42.5 mg/£ total alkalinity (contributed by NaHCO,) was analysed
by the gravimetric method, with a relative standard deviation of
4.7% and a relative error of 1.9% in 32 laboratories. Using the
turbidimetric method in 19 laboratories, the relative standard
deviation was 9.1% and the relative error, 1.2°
Cost of Analysis: $4 - $12
•>?.
D-301
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SULFIDE
Parameter Group: General STORET Units: mg/£ as S
Inorganic
General: Sulfide is often present in groundwater and is common in
some natural waters and sewage, coming in part from the anaerobic
decomposition of organic matter. Sulfides are constituents of
many industrial wastes, e.g., tanneries, paper mills, chemical
plants, and gas works. It also occurs due to bacterial reduction
of sulfates. The highly unpleasant taste and odor that results
when sulfides occur in water make it unlikely that humans or ani-
mals will consume a harmful dose. Small traces of sulfide may
be detrimental to some industrial uses. Sulfides are of little
importance in irrigation waters. The sulfide ion readily reacts
with free hydrogen ions in water to form hydrogen sulfide, which
is very toxic, attacks metals directly, and indirectly causes
serious corrosion to concrete sewers. This is a parameter which
is regulated by BPT guidelines prescribed by the NPDES permits
program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Add 2 mi zinc
acetate, fill bottle completely, and stopper.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 50 m£
Measurement: The titrimetric iodine method is recommended. It is
applicable to the measurement of total and dissolved sulfides.
Acid insoluble sulfides are not measured by this test. Reduced
sulfur compounds, such as sulfite, thiosulfate and hydrosulfite,
which decompose in acid may yield erratic results. Volatile
iodine consuming substances will give high results. For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy: Precision and accuracy data have not been
determined.
Cost of Analysis: $5 - $12
D-302
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SULFITE
Parameter Group: General STORET Units: mg/£ as SCL
Inorganic
General: Sulfite may occur in certain industrial wastes but is
most commonly found in boilers and boiler feedwater to which
sodium sulfite has been added to reduce dissolved oxygen to a
minimum and prevent corrosion. It is thought that a high concen-
tration of sulfite in water may cause exema. This is a parameter
which is regulated by BPT guidelines prescribed by the NPDES
permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 50 m£
Measurement: The recommended method has a minimum detectable
limit of 2-3 mg/£ SO.. An acidified sample containing an indica-
tor is titrated with a standard potassium iodide-iodate titrant to
a faint permanent blue end point. The temperature of the sample
must be below 50°C. Oxidizable substances, such as organic com-
pounds, ferrous, iron and sulfide are positive interferences.
Nitrite gives a negative interference by oxidizing sulfite when
the sample is acidified. Copper and possibly other metals cata-
lyze the oxidation of sulfite. For BPT NPDES purposes the meas-
urement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Precision and accuracy data are not
available.
Cost of Analysis: $5 - $12
D-303
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2, 4, 5-T
Parameter Group: Pesticides STORET Units: yg/£
General: 2, 4, 5-T (2, 4, 5-trichlorophenoxyacetic acid) is the
chlorinated phenoxy acid herbicide CQHCC1,0_. It is a crystal-
o o o o
line substance, almost insoluble in water, but soluble in alco-
hol. It is a plant hormone. The estimated lethal dose for a
90-kg man is 54 grams. The acute oral ID-- to rats is 300,000 mg/
kg of body weight. 2, 4, 5-T forms phenol as a breakdown product.
Toxicity data for aquatic life are sparse. This is a parameter
which is regulated by BPT guidelines prescribed by the NPDES
permits program.
Criterion: Not established
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 100-1,000 m£, depending on measurement
method used.
Measurement: In the recommended method, chlorinated phenoxy acids
and their esters are extracted from the acidified water sample
with ethyl ether. The esters are hydrolyzed to acids and ex-
traneous organic material is removed by a solvent wash. The acids
are converted to methyl esters which are extracted from the aque-
ous phase. The extract is cleaned up by passing it through a
micro-adsorption column. Detection and measurement are accomplished
by electron capture, microcoulometric or electrolytic conductivity
gas chromatography. Interferences may be high and varied and often
pose great difficulty in obtaining accurate and precise measurement
of chlorinated phenoxy acid herbicides. Organic acids, especially
chlorinated acids, cause the most direct interference with the de-
termination. Phenols including chlorophenols will also interfere
with this procedure. The method is recommended for use only by an
experienced pesticide analyst (or under the close supervision of
such a person). For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is 1 ug/£.
Detection limits of 0.002 pg/£ or so may be achieved. Precision
and accuracy data are not available at this time.
Cost of Analysis: $45 - $150, depending upon preparation required.
D-304
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TEMPERATURE
Parameter Group: Temperature STORET Units: °C
General: Temperature changes in waters are due to natural climatic
phenomena or the discharge of irrigation return flows and wastes,
such as distilling effluents and cooling waters. The elevation of
stream temperatures may contribute to decreased oxygen capacity,
increased oxygen demand, anaerobic zones, and putrefaction of
sludge deposits. Temperature is a significant factor for water
treatment and many industrial uses, e.g., pulp and paper. Tem-
perature also affects the value of numerous other water quality
parameters. This is a parameter which is regulated by BPT guide-
lines prescribed by the NPDES permits program.
Criteria:
Freshwater Aquatic Life
For any time of year, there are two upper limiting tempera-
tures for a location (based on the important sensitive species
found there at that time):
1. One limit consists of a maximum temperature for short
exposures that is time dependent and is given by the species-
specific equation:
Temperature^ = (1/b) (log10 [time(min)]-a) -2'C
where: login = logarithm to base 10 (common logarithm)
a = intercept on the "y" or logarithmic axis of
the line fitted to experimental data and
which is available from Appendix II-C, NAS,
1974 for some species.
b = slope of the line fitted to experimental
data and available from Appendix II-C, NAS,
1974 for some species.
and
2. The second value is a limit on the weekly average tem-
perature that:
a. In the cooler months (mid-October to mid-April in
the north and December to February in the south)
will protect against mortality of important species
D-305
-------
or
or
if the elevated plume temperature is suddenly dropped
to the ambient temperature, with the limit being the
acclimation temperature minus 2°C when the lower lethal
threshold temperature equals the ambient water tempera-
ture (in some regions this limitation may also be
applicable in summer).
In the warmer months (April through October in the
north and March through November in the south) is
determined by adding to the physiological optimum
temperature (usually for growth) a factor calculated
as one-third of the difference between the ultimate
upper incipient lethal temperature and the optimum
temperature for the most sensitive important species
(and appropriate life state) that normally is found
at that location and time.
c. During reproductive seasons (generally April through
June and September through October in the north and
March through May and October through November in
the south) the limit is that temperature that meets
site-specific requirements for successful migration,
spawning, egg incubation, fry rearing, and other
reproductive functions of important species. These
local requirements should supersede all other re-
quirements when they are applicable.
d. There is a site-specific limit that is found neces-
sary to preserve normal species diversity or prevent
appearance of nuisance organisms.
Marine Aquatic Life
In order to ensure protection of the characteristic indig-
enous marine community of a water body segment from adverse
thermal effects:
a. The maximum acceptable increase in the weekly average
temperature due to artificial sources is 1°C (1.88F)
during all seasons of the year, providing the summer
maxima are not exceeded; and
or
D-306
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b. Daily temperature cycles characteristic of the
water body segment should not be altered in
either amplitude or frequency.
Summer thermal maxima, which define the upper thermal limits
for the communities of the discharge area, should be established
on a site-specific basis. Existing studies suggest the following
regional limits:
Short-term Maximum True
Maximum Daily Mean*
Sub-tropical Regions (south 32.2°C (90°F) 29.4°C (85°F)
of Cape Canaveral and Tampa
Bay, Florida, and Hawaii
Cape Hatteras, N.C., to 32.2°C (90°F) 29.4°C (85°F)
Cape Canaveral, Florida
Long Island (south shore) 30.6°C (87°F) 27.8°C (82°F)
to Cape Hatterras, N.C.
* (True Daily Mean = average of 24 hourly temperature
readings.)
Baseline thermal conditions should be measured at a site where
there is no unnatural thermal addition from any source, which is
in reasonable proximity to the thermal discharge (within 5 miles)
and which has similar hydrography to that of the receiving waters
at the discharge.
Preservation Method: Determination on site
Maximum Holding Time: No holding
Container Type: Plastic or glass
Sample Volume Required: 1000 m£
Measurement: Temperature measurements may be made with any good
grade of mercury-filled or dial type Celsius thermometer, or a
thermistor. The measurement device should be checked against a
precision thermometer certified by the National Bureau of Standards.
For BPT NPDES purposes the measurement of this parameter is pre-
scribed by 40 CFR 136.
Precision and Accuracy: Precision and accuracy will depend upon
instrument used.
Cost of Analysis: Not immediately determinable.
D-307
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THALLIUM
Parameter Group: Metals STORET Units: yg/£ as Tl
General: Thallium salts are used as rodenticides and ant bait,
dyes and pigments in fireworks, in optical glass, and as a
dipilatory. They are highly soluble in water and discharges are
not likely to form precipitates. It is a cumulative poison, four
times as toxic as arsenious oxide and affects the nervous system,
causes muscular pain, endocrine disorders, and loss of hair. This
is a parameter which is regulated by BPT guidelines prescribed by
the NPDES permits program. This parameter will be regulated by
BAT guidelines prescribed by the NPDES permits program. It is one
of the Consent Decree pollutants.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO, to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 ra£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 276.8 nm. For BPT NPDES purposes the meas-
urement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 500 ug/£;
its detection limit is 100 ug/£. The optimum concentration range
is 1,000-20,000 ug/£. In a single laboratory, using a mixed
industrial-domestic waste effluent at concentrations of 600, 3,000,
and 15,000 pg/£ Tl, the relative standard deviations were 3%,
1.7%, and 1.3%, respectively. Recoveries at these levels were
100%, 98%, and 98%, respectively.
Cost of Analysis: $15 - $20
D-308
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THRESHOLD ODOR
Parameter Group: Physical STORET Units: Threshold
Number
General: Odor is a quality factor that affects water in several
ways including the acceptability of drinking water, tainting of
fish, and the aesthetics of recreational waters. Odor can origi-
nate from industrial and municipal waste discharges and from natu-
ral sources such as decomposition of vegetable matter and living
microscopic organisms. Odorous substances in water must be vapor-
izable in order to be smelled.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Glass
Sample Volume Required: 200 to 500 mt
Measurement: The consistent series method, in which the sample is
divided to the point of the least definitely perceptible odor to
each tester, is often used. Highly odorous samples are reduced in
concentration proportionately before being tested. The method
is applicable to samples ranging from nearly odorless natural
waters to industrial wastes with threshold odor numbers in the
thousands. Most tap waters and some waste waters are chlorinated.
Dechlorination is achieved using sodium thiosulfate in exact
stoichiometric quantity.
Precision and Accuracy: Precision and accuracy data are not
available at this time.
Cost of Analysis: $5 - $10
D-309
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TIN
Parameter Group: Metals STORET Units: pg/£ as Sn
General: Tin does not occur in natural waters. • It is used in
dyeing of fabrics, decorating porcelain, glassworks, fingernail
polishes, some lacquers and varnishes, fungicides, insecticides,
antihelminthics, antifoulant marine coatings and, of course, the
tinning of vessels, especially foodstuff containers. Other sources
include iron and steel production and power plant and industrial
boilers. Tin is not believed to be toxic to man or other life
forms. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO- to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 286.3 nm. For BPT NPDES purposes the meas-
urement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 4 mg/£; its
detection limit is 800 yg/£. The optimum concentration range is
16,000-200,000 yg/£. In a single laboratory, using a mixed
industrial-domestic waste effluent at concentrations of 4,000,
20,000, and 60,000 yg/£ Sn, the relative standard deviations were
6.2%, 2.5%, and .8%, respectively. Recoveries at these levels
were 96%, 101%, and 101%, respectively.
Cost of Analysis: $15 - $20
D-310
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TITANIUM
Parameter Group: Metals STORET Units: yg/£ as Ti
General: Titanium ores and salts are abundantly distributed in
the earth's crust, constituting from 0.5% to 10% of soils. The
metal is used chiefly in alloying, and its salts are used in
paint, paper, and dyeing industries, in the manufacture of elec-
tronic components, and in glass and ceramic production. There is
little evidence of harm to life forms from titanium. This is a
parameter which is regulated by BPT guidelines prescribed by the
NPDES permits program.
Criterion; Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HN03 to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 365.3 nm. A number of elements increase
the sensitivity of titanium. To control this problem, potassium
(1,000 mg/£) must be added to the standards and samples. For BPT
NPDES purposes the measurement of this parameter is prescribed by
40 CFR 136.
Precision and Accuracy; The AA method sensitivity is 2,000 Mg/£;
its detection limit is 300 yg/£. The optimum concentration range
is 5,000-100,000 vg/t. In a single laboratory, using a mixed
industrial-domestic waste effluent at concentrations of 2,000,
10,000, and 50,000 vg/t Ti, the relative standard deviations were
3.5%, 1.0%, and .8%, respectively. Recoveries at these levels
were 97%, 91%, and 88%, respectively.
Cost of Analysis: $10 - $20
D-311
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TOLUENE
Parameter Group: General STORET Units: yg/£
Organic
General: Toluene (C,H,-CH,), a flammable liquid with an odor of
benzene, is a constituent of coal tar. It is used in the manu-
facture of organic substances and as a solvent in the extraction
of various principles from plants. Toluene is modestly soluble in
water at normal temperatures. Its LD,.-. for rats is 7,000 mg/kg of
ou
body weight. Lethal concentrations to fish in clean water range
from 10,000 to over 90,000 pg/£ depending upon temperature and
species. This parameter will be regulated by BAT guidelines pre-
scribed by the NPDES permits program. It is one of the Consent
Decree pollutants.
Criterion; Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 200-1,000 mi
Measurement: Hexadecone extraction followed by gas chromatographic
and mass spectrometric analysis is often used. A BAT NPDES method
will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Detection limits should be around
2-10 yg/£.Precision and accuracy data are not available at this
time.
Cost of Analysis: $15 - $30
D-312
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TOTAL COLIFORM
Parameter Group: Bacteriologic STORET Units: See below
General: The coliform bacteria group as defined by the tests de-
scribed herein includes organisms of diverse origins, including
intermediate and Aerobactor aerogenes strains, which are usually of
soil, vegetable, or other non-fecal origin; E. coli, which is usu-
ally but not always of fecal origin; and fecal coliform, which is a
positive indication of the excrement of warm-blooded animals. The
direct examination for the presence of a specific pathogen in water
is not usually practicable for control purposes, and total coli-
form has been widely used as a microbiological indicator organism.
The more specific fecal coliform indicator is gaining in popularity,
however. This is a parameter which is regulated by BPT guidelines
prescribed by the NPDES permits program.
Criterion: Not established
Preservation Method: Cool to 4°C. Add a dechlorinating agent
(e.g., sodium thiosulfate) if residual chlorine is present. Sam-
ples high in heavy metals should have a chelating agent (e.g.,
EDTA) added to reduce metal toxicity.
Maximum Holding Time: 6 hours (30 hours absolute maximum for po-
table water sample).
Container Type: Plastic or glass
Sample Volume Required: 100 m£
Measurement: The multiple tube fermentation technique, which de-
fines the coliform group as all aerobic and facultative anaerobic,
gram negative, rod-shaped, nonspore-forming bacteria that ferment
lactose with gas formations within 48 hours at 35°C, is recom-
mended. The simpler membrane filter technique, which defines the
coliform group as the above bacteria that produce a dark colony
with a metallic sheen within 24 hours on an Endo-type medium con-
taining lactose, is also recommended, especially for nondrinking
water tests. Results of the former are expressed statistically as
the Most Probable Number (MPN), while the latter are expressed as
number of colonies per 100 m£. For BPT NPDES purposes the measure-
ment of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: Not applicable
Cost of Analysis: $10 - $12 MFT
$15 - $20 MPN
D-313
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TOXAPHENE
Parameter Group: Pesticides STORET Units: yg/£
General: Toxaphene is a chlorinated camphene insecticide. It is
insoluble in water but highly soluble in organic solvents and oils.
It has been reported that lakes treated with toxaphene concentra-
tions ranging from 40 to 150 vg/t remained toxic to fish for per-
iods of a few months to five years. Bioconcentration accumulations
of toxaphene of 5,000 to 21,000 times water concentrations have
been observed in brook trout exposed only through water. Accumu-
lation factors of 3,400 to 17,000 from aqueous solution have been
reported for bacteria, algae, and fungi. Owing to the turpentine
odor, it is not likely that toxic concentrations will be consumed
by man or animals. This is a parameter which is regulated by BPT
guidelines prescribed by the NPDES permits program. This parameter
will be regulated by BAT guidelines prescribed by the NPDES permits
program. It is one of the Consent Decree pollutants. A toxic
effluent limitation has been prescribed for this parameter by the
NPDES permits program.
Criteria:
• 5 yg/£ for domestic supply (health)
• 0.005 pg/£ for freshwater and marine aquatic life
Preservation Method: Cool to 4°C; analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required: 50-100 m£ or more
Measurement: The use of co-solvent extraction and detection and
measurement accomplished by electron capture, microcoulometric
or electrolytic conductivity gas chromatography is recommended for
toxaphene under favorable conditions. Many interferences exist,
especially PCB's, phthalate esters, and organophosphorus pesti-
cides, and the method is only recommended for use by a skilled,
experienced pesticide analyst (or under close supervision of such
a person). For BPT NPDES purposes the measurement of this parame-
ter is prescribed by 40 CFR 136.
D-314
-------
Precision and Accuracy: The detection limit is affected by many
factors, but usually falls in the 0.001 to 1 ug/£ range. In-
creased sensitivity is likely to increase interference. Typically,
the percent recovery decreases with increasing concentration.
Cost of Analysis; $30 - $150, depending upon preparation required.
D-315
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TRICHLOROETHYLENE
Parameter Group: STORET Units:
General: Trichloroethylene, a nonflammable liquid with a
chloroform-like odor, is practically insoluble in water. It is
used as a solvent and in solvent extraction by several industries,
in degreasing, in the manufacture of chemicals and Pharmaceuticals,
and in dry cleaning. The oral LD5Q for dogs is 5.86 g/kg of body
weight. Concentrations of 55 mg/£ will stupify fish within
10 minutes. This parameter will be regulated by BAT guidelines
prescribed by the NPDES permits program. It is one of the Consent
Decree pollutants.
Criterion: Not established
Preservation Method: Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum jto].ding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample VolumeRequired: In excess of 200 mt
Measurement: In the recommended Bellar procedure the sample is
stripped with an inert gas; volatiles are captured on an ad-
sorbent trap and desorbed into a modified gas chromatograph
equipped with a halogen-specific detector. Methodology should be
checked for interferences, e.g., from bromine or iodine. A BAT
NPDES method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is approximately
1,000 yg/£.Detection limits of 0.2-3 pg/£ may be achieved. Pre-
cision and accuracy data are not available at this time.
Cost of Analysis: Around $60
D-316
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TURBIDITY
Parameter Group: Physical STORET Units: Formazin
Turbidity
Units
General: Turbidity is an optical property of water, reflecting
its propensity for scattering light. From chlorination considera-
tions, finished drinking waters typically have a maximum limit of
1 turbidity unit where the water enters the distribution system.
Turbid water interferes with recreational use and aesthetic en-
joyment of water. The less turbid the water, the more desirable
it becomes for swimming and other water contact sports. See
discussion for suspended solids. This is a parameter which is
regulated by BPT guidelines prescribed by the NPDES permits
program.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Cool to 4°C.
Maximum Holding Time: 24 hours
Container Type: Plastic or glass
Sample Volume Required: 100 m£
Measurement: The recommended method is applicable to drinking,
surface, and saline waters in the range of turbidity from 0 to
40 nephelometric turbidity units (MTU). The method is based upon
a comparison of the intensity of light scattered by the sample
under defined conditions with the intensity of light scattered by
a standard reference suspension. The presence of floating debris
and course sediments which settle out rapidly will give low read-
ings. Finely divided air bubbles will affect the results in a
positive manner. For BPT NPDES purposes the measurement of this
parameter is prescribed by 40 CFR 136.
Precision and Accuracy: In a single laboratory, using surface
water samples at levels of 26, 41, 75 and 180 NTU, the relative
standard deviations were 2.3%, 2.3%, 1.6%, and 2.6%, respectively.
Cost of Analysis: $3 - $5
D-317
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URANIUM
Parameter Group: Metals STORET Units: mg/£
General: In addition to atomic energy applications, uranium is
used in photography, glazing and painting porcelain, and in chemi-
cal processes. Many uranium salts are soluble in water. It has
been reported that uranium and many of its salts are toxic; how-
ever, limited studies indicate that natural uranium, absorbed by
people through the water and foodstuffs grown on land, may be a
limiting factor in the incidence of leukemia. There is generally
greater concern about the radiological hazards of uranium than
about its chemical effects, however.
Criterion: Not established
Preservation Method: Analyze as soon as possible. Add HNO to
pH«2 and cool to 4°C.
Maximum Holding Time: Unknown
Container Type: Plastic or glass
Sample Volume Required; 50 m£
Measurement; The direct fluorometric method is often used. The
concentration range is from 0.005 to 2.0 mg/£. For higher con-
centrations, the extraction method may be used. The method in-
volves the measurement of the fluorescence of a fused disk of so-
dium fluoride, lithium fluoride, and uranium compound exposed to
ultraviolet light. The intensity of the fluorescence is propor-
tional to the uranium concentration. Small quantities of cadmium,
chromium, cobalt, copper, iron, magnesium, manganese, nickel, lead,
platinum, silicon, thorium, and zinc interfere by quenching the
uranium fluorescence and a purification or spiking method must be
used. The AA method may also be used.
Precision and Accuracy: The single operator precision (S) at a
uranium concentration of X mg/£ may be estimated from
log (S-0.0016) = log 0.129 + 120 log X.
Cost of Analysis: $30 - $40
D-318
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VANADIUM
Parameter Group: Metals STORET Units: vg/t as V
General: Minerals containing vanadium are widespread in nature.
In addition to its metallurgical uses, principally in steel
alloying, its salts are used in the manufacture of glass, ce-
ramics, ink, in photography, and in the dyeing and printing of
fabrics. It is not considered toxic and, in fact, may play a
beneficial role in reducing cholesterol, preventing heart disease
and dental caries, and lowering the phospholipid content of the
liver. Small quantities of vanadium may stimulate plant growth.
This is a parameter which is regulated by BPT guidelines pre-
scribed by the NPDES permits program.
Criterion; Not established
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO, to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required; 100-200 mi
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 318.4 nm. High concentrations of aluminum
and titanium increase the sensitivity of vanadium. This inter-
ference can be controlled by adding excess aluminum (1,000 mg/£)
to both samples and standards. For BPT NPDES purposes the meas-
urement of this parameter is prescribed by 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 800 yg/£;
its detection limit is 200 yg/£. The optimum concentration range
is 1,000-100,000 Mg/£. In a single laboratory, using a mixed
industrial-domestic waste effluent at concentrations of 2,000,
10,000, and 50,000 ug/£ V, the relative standard deviations were
5%, 1%, and .4%, respectively. Recoveries at these levels were
100%, 95%, and 97%, respectively.
Cost of Analysis: $10 - $20
D-319
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VINYL CHLORIDE
Parameter Group: STORET Units:
General: Vinyl chloride (chloroethene, CH-.'CHCl), a flammable gas
with an ethereal odor, is only slightly soluble in water. It is
prepared by catalytic addition of hydrogen chloride to acetylene or
by pyrolysis of ethylene dichloride and is used chiefly for making
vinyl resins. U.S. production exceeds 3 billion pounds annually.
This parameter will be regulated by BAT guidelines prescribed by
the NPDES permits program. It is one of the Consent Decree
pollutants.
Criterion: Not established
Preservation Method; Sample history must be known before any chem-
ical or physical preservation steps can be applied to protect
against phase separation. Fill the sample bottle completely and
seal until analysis is performed. Do not refrigerate.
Maximum Holding Time: Unknown; preferably analyze within 1 hour.
Container Type: Borosilicate glass
Sample Volume Required: In excess of 200 mi
Measurement: In the recommended Bellar procedure the sample is
stripped with an inert gas; volatiles are captured on an ad-
sorbent trap and desorbed into a modified gas chromatograph
equipped with a halogen-specific detector. Methodology should be
checked for interferences, e.g., from bromine or iodine. A BAT
NPDES method will be prescribed for this parameter in 40 CFR 136.
Precision and Accuracy: Sensitivity of the method is approximately
1,000 ug/£.Detection limits of 0.2-3 yg/£ may be achieved. Pre-
cision and accuracy data are not available at this time.
Cost of Analysis: Around $60
D-320
-------
XYLENE
Parameter Group: General STORET Units: yg/£
Organic
General: Xylene (C6H.(CH_)2), a flammable liquid, is a constitu-
ent of coal tar. It is used in the manufacture of dyes and or-
ganic substances, as a solvent, and as a cleaning agent. Xylene is
insoluble in water. Its LD,. for white rats is 4.3g/kg of body
^ \J.
weight. Lethal concentrations to fish range from 10,000 to
90,000 yg/£ depending upon temperature and species.
Criterion; Not established
Preservation Method: Not determined. Analyze promptly.
Maximum Holding Time: Unknown
Container Type: Borosilicate glass
Sample Volume Required; 200-1,000 tat
Measurement^ Hexadecone extraction followed by gas chromatographic
and mass spectrometric analysis is often used.
Precision and Accuracy: Detection limits should be around
2-10 yg/£.Precision and accuracy data are not available at this
time.
Cost of Analysis: $15 - $30
D-321
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ZINC
Parameter Group; Metals STORET Units: yg/£ as Zn
General: Zinc is usually found in nature as the sulfide. Zinc is
used in galvanizing and in the preparation of alloys for dye cast-
ing. Zinc is also used in brass and bronze alloys, slush castings,
photoengraving, printing plates, silver and stainless steel table-
ware, viscose rayon yarn, wood pulp, and newsprint paper. Other
sources include mining areas, paint pigments, cosmetics, pharmaceu-
tics, insecticides, and many more. Zinc is an essential and bene-
ficial element in human metabolism. Excessive amounts of zinc
affect growth rates and decrease both the weight and fat content
of the liver. This is a parameter which is regulated by BPT guide-
lines prescribed by the NPDES permits program. This parameter will
be regulated by BAT guidelines prescribed by the NPDES permits pro-
gram. It is one of the Consent Decree pollutants.
Zinc is a
Criteria:
• 5,000 Mg/t for domestic water supplies (welfare).
• For freshwater aquatic life, 0.01 of the 96-hour LC5Q as
determined through bioassay using a sensitive resident
species.
Preservation Method: Analyze as soon as possible. If storage is
necessary, add HNO- to pH <2.
Maximum Holding Time: 6 months
Container Type: Plastic or glass
Sample Volume Required: 100-200 m£
Measurement: The AA spectrophotometric method is recommended,
using a wavelength of 213.9 nm. The air-acetylene flame absorbs
about 25% of the energy at the 213.9-nm line. The sensitivity may
be increased by the use of low-temperature flames. For BPT NPDES
purposes the measurement of this parameter is prescribed by
40 CFR 136. A BPT NPDES method will be prescribed for this param-
eter in 40 CFR 136.
Precision and Accuracy: The AA method sensitivity is 20 yg/£; its
detection limit is 5 yg/£. The optimum concentration range is 50-
2,000 yg/£. At a concentration of 500 vg/L, the relative standard
deviation is 8.2%, and the relative error is 0.4%.
Cost of Analysis: $10 - $15
D-322
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TUESDAY, OCTOBER 16, 1973
WASHINGTON, D.C.
Volume 38 • Number 199
PART II
ENVIRONMENTAL
PROTECTION
AGENCY
WATER PROGRAMS
Guidelines Establishing Test Procedures
for Analysis of Pollutants
No. 199—Pt. H 1
D-323
-------
28758
RULES AND REGULATIONS
Title 40—Protection of Environment
CHAPTER I—ENVIRONMENTAL
PROTECTION AUENCY
SUBCHAPTER D—WATER PROGRAMS
PART 135—GUIDELINES ESTABLISHING
TEST PROCEDURES FOR THE ANALY-
SIS OF POLLUTANTS
Notice was pubished In the FEDERAL
REGISTER Issue of June 29, 1973 (38 FR
17318) at 40 CFR 130, that the Environ-
mental Protection Agency (EPA) was
giving consideration to the testing pro-
cedures required pursuant to section
304 (g) of the Federal Water Pollution
Control Act Amendments of 1972 (86
Stat. 816, et seq., Pub. L. 92-500 (1972))
hereinafter referred to as the Act. These
considerations were given in the form of
proposed guidelines establishing test
procedures.
Section 304(g) of the Act requires that
the Administrator shall promulgate
guidelines establishing test procedures
for 'the analysis of pollutants that shall
'include factors which must be provided
in: 1, any certification pursuant to sec-
tion 401 of the Act, or 2, any permit ap-
plication pursuant to section 402 of the
Act. Such test procedures are to be used
by permit applicants to demonstrate that
effluent discharges meet applicable pol-
lutant discharge limitations, and by the
States and other enforcement activities
in routine or random monitoring of ef-
fluents to verify effectiveness of pollu-
tion control measures.
These guidelines require that discharge
measurements, including but not limited
to the pollutants and parameters listed
in Table I, be performed by the test
procedures indicated; or under certain
circumstances by other test procedures
for analysis that may be more advan-
tageous to use. when such other test
procedures have the approval of the Re-
gional Administrator of the Region
where such discharge will occur, and
when the Director of an approved State
National Pollutant Discharge Elimina-
tion System (NPDES) Program (here-
inafter referred to as the Director) for
the State in which such discharge will
occur has no objection to such approval.
The list of test procedures in Table I
is published herein as final rulemaking
and represents major departures from
the list of proposed test procedures which
was published in 38 FR 17318, dated
June 29, 1973. These revisions were made
after carefully considering all written
comments which were received pertain-
ing to the proposed test procedures. All
written comments are on file and avail-
able for public review with the Quality
Assurance Division, Office of Research
and Development, EPA, Washington, D.C.
The principal revisions to the proposed
test procedures are as follows:
1. Where several reliable test proce-
dures for analysis are available from
the given references for a given pollutant
or parameter, each such test procedure
has been approved for use for making
the measurements required by sections
401 and 402 and related sections of the
Act. Approved test procedures have been
selected to assure an acceptable level or
intercomparabillty of pollutants dis-
charge data. For several pollutants and
parameters it has still been necessary to
approve only a single test procedure to
assure this level of acceptability. This is
a major departure from the proposed
test procedures which would have re-
quired the use of a single reference
method for each pollutant or parameter.
2. Under certain circumstances a test
procedure not shown on the approved
list may be considered by an applicant
to be more advantageous to use. Under
guidelines in §§ 136.4 and 136.5 it may be
approved by the Regional Administrator
of the Region where the discharge will
occur, providing t'ne Director has no ob-
jections. Inasmuch as there is no longer
a single approved reference method
against which a comparison can be made.
the procedures for establishing such
comparisons that were required by the
proposed test procedures in § 130.4(b)
have been deleted from this final guide-
line for test procedures for the analysis
of pollutants.
3. A mechanism is also provided to
assure national uniformity of such ap-
provals of alternate test procedures for
the analysis of pollutants. This is
achieved through a centralized, internal
review within the EPA of all applications
for the use of alternate testing proce-
dures. These will be reviewed and ap-
proved or disapproved on the basis of
submitted information and other avail-
able information and laboratory tests
which may be required by the Regional
Administrator.
As deemed necessary, the Administra-
tor will expand or revise these guide-
lines to provide the most responsive and
appropriate list of test procedures to
meet the requirements of sections 304(g),
401 and 402 of the Act, as amended.
These final guidelines establishing test
procedures for the analysis of pollutants
supersede the interim list of test proce-
dures published in the FEDERAL REGISTER
on April 19. 1973 (38 FR 9740) at 40 CFR
Part 126 and subsequent procedures pub-
lished on July 24, 1973 (38 FR 19894)
at 40 CFR Part 124. Those regulations
established interim test procedures for
the submittal of applications under sec-
tion 402 of the Act. Because of the im-
portance of these guidelines for test
procedures for the analysis of pollutants
to the National Pollution Discharge Elim-
ination System (NPDES), the Adminis-
trator finds good cause to declare that
these guidelines shall be effective Octo-
ber 16,1973.
JOHN QUARLES,
Acting Administrator.
OCTOBER 3. 1973.
PART 136—TEST PROCEDURES FOR THE
ANALYSIS OF POLLUTANTS
Sec.
136.1 Applicability.
136.2 Definitions.
136.3 Identification of test procedures.
136.4 Application for alternate test proce<
duxes.
136:5 Approval of alternate test procedures.
AUTHOKITT: Sec. 304(g) of Federal Water
Pollution Control Act Amendments of 1672
86 Stat. 816, et seq., Pub. L. 92-600).
§ 136.1 Applicability.
The procedures prescribed herein
shall, except as noted in 8136.5, be used
to perform the measurements indicated
whenever the waste constituent specified
is required to be measured for:
(a) An application submitted to the
Administrator, or to a State having an
approved NPDES program, for a permit
under section 402 of the Federal Water
Pollution Control Act as amended
(FWPCA), and,
(b) Reports required to be submitted
by dischargers under the NPDES
established by Parts 124 and 125 of this
chapter, and,
(c) Certifications issued by States pur-
suant to section 401 of the FWPCA, as
amended.
§ 136.2 Definitions.
As used in this part, the term:
(a) "Act" means the Federal Water
Pollution Control Act, as amended. 33
U.S.C. 1314, et seq.
(b) "Administrator" means the Ad-
ministrator of the U.S. Environmental
Protection Agency.
(c) "Regional Administrator" means
one of the EPA Regional Administrators.
(d) "Director" means the Director of
the State Agency authorized to carry
out an approved National Pollutant Dis-
charge Elimination System Program
under section 402 of the Act.
• (e) "National Pollutant Discnarge
Elimination System (NPDES)" means
the national system for the issuance ol
permits under section 402 of the Act and
includes any State or interstate program
which has been approved by the Admin-
istrator, in whole or in part, pursuant to
section 402 of the Act.
(f) "Standard Methods" means Stand-
ard Methods for the Examination of
Water and Waste Water, 13th Edition,
1971. This publication is available from
the American Public Health Association,
1015 10th St. NW., Washington, D.C.
20036.
(g) "ASTM" means Annual Book of
Standards, Part T3, Water, Atmospheric
Analysis, 1972. This publication is avail-
able from the American Society for
Testing and Materials, 1916 Race St.,
Philadelphia, Pennsylvania 19103.
(h) "EPA Methods" means Methods
lor Chemical Analysis of Water and
Wastes, 1971, Environmental Protection
Agency. Analytical Quality Control Lab-
oratory, Cincinnati, Ohio. This publica-
tion is available from the Super-
intendent of Documents, U.S. Govern-
ment Printing Office, Washington, D.C.
20402 (Stock Number 5501-0067).
§ 136.3 Identification of test proce-
dure*.
Every parameter or pollutant for
which an effluent limitation is now spec-
ified pursuant to sections 401 and 402
of the Act is named together with test
descriptions and references in Table I.
The discharge parameter values for
which reports are required must be de-
FEDERAL REGISTER, VOL. 38, NO. 199—TUESDAY, OCTOBER 16, 1973
D-324
-------
termlned by one of the standard ana- glonal Administrator or the Director In
lytlcal methods cited and described the Region or State where the discharge
in Table I, or under certain clrcum- will occur may determine for a par-
stances by other methods that may be tlcular discharge that additional param-
more advantageous to use when such eters .or pollutants must be reported.
other methods have been previously ap- Under such circumstances, additional
proved by the Regional Administrator of test procedures for analysis of pollutants
the Region in which the discharge will may be speclfled by the Regional Ad-
occur and orovldlnf? that the Director . i *. *. T^I L n_
o^ut , <4»iu Curium!, v •.** ""^ «»wv.w ministrator or Director upon the recom-
01 the State In which such discharge ...
will occur does not object to the use of mendatlon of the Director of the
such alternate test procedures. Methods Development and Quality As-
Under certain circumstances the Re- surance Research Laboratory.
TABLE I— LIST or APPROVED TEST PROCEDURES
References
Standard A8TM EPA
methods methods
General analytical methods:
1. Alkalinity as CoCOimft Tllrallon- cleclronvtrlc. manual or auto- p. 370 p. 143 p. 6.
CoCO'/llter. mated method— methyl orange. p. 8.
2. B.O.D.nvedaymg/lller. Modified wlnkleror probe method p. 489
3. Chemical oxygen de- Dlchromate reflux p. 498 p. 219 p. 17.
mond (C.O.D.) mg/
, Illnr.
4. Total solids mg/lller Oravlmolrtr 103-106° C p. 634 p. 280.
6. Tolnl dissolved (niter- Glass liber miration 1RO° C p. 278.
able) solids mg/liter.
O Illtprublo) solids mg/
I lltor.
W 7. Total volatile solids rag/ Oravlmflrlc 650° C p. 636 p 282.
fxj liter.
C/i fl. Ammonia (as N) mg/ Distillation— nrsslcriiationor tllrallonau- . p 134
liter. tomatod phrnolrtto. p 141.
1). Klcldahl nitrogen (as N) Digestion + distillation— nos^ertiallon or p. 489 p. 149.
niR/llter. Utratlon ulomaud digestion phenolate. p. 167.
10. Nllrale (as N) mg/lller. Cadmium reduction; bruclne sulfate; au- p. 468 p. 124 p. 170.
tlon. p. 186.
11. Total phosphorus (as D Persulfato digestion and single reagent p. 626 p. 42 .. . p. 238.
mg/llter. (ascorbic acid), or manual digestion, p. 632 p. 246.
and autonmtod single roagont or atan- D. 269.
nous chloride.
12. Acidity mgCaCOiAUcr Elcclromnlrlc end polnl or phenolphlhal- p. 148
rln end iiolnt.
13. Total organic carbou Combustion— Infrared method ' p. 267 .... p. 702 n. 221.
(TOO mp/lller.
14. Hardness— total mg EDTA Utratlon; automated Colorlmetric p. 179 p. 170 ...p. 76.
CaCOi/llter. atomic abwrpllon. " p 78.
IS. Nllrlle (as N) mg/llUr. Manual or automated colorlmelrlc dlaiotl- p. 188.
tat Ion. p. 196.
Analytical methods for trace
metals:
10. Aluminum— total' me/ Atomic absorption p. 210 . D. 98.
liter. " v
lltor.
18. Arsenic-total rag/tiler. Digestion plus silver dlethyldlthlocarba- p. 68 p. 13.
mate; atomic absorption.' p. 62
1'J. Barium— total ' me/liter. Atomic absorption ' p. 210 .
'M. licrylllum— total ' mg/ Alumlnon; atomic absorption . u 67
liter. p. 210 ....
21. Horon-total me/liter... Curcumln p. 69
22. Cadmium— total ' rag/ Atomic absorption; colorimetrte p. 210 p. 692 . p. 101.
Illor- p. 422 .
23. Calcium-total ' mR/lller. EDTA tltraUon: atomic absorption p. 84 p. 6«2 p. 102.
24. Chromium VI mg/lllor. Extraction and atomic absorption; colort- p. 4'."J p. 94.
metric.
Parameter and units
28. Chromium— total ' mg/
liter.
26. Cobalt— total ' mg/llter.
27. Copper— total ' mg/llter.
28. Iron— total ' mg/Uler
30. Magnesium — lotal'mg/
liter.
31. Manganese— total' mg/
liter.
32. Mercury— total mg/llter.
33. Molybdenum— total >
mg/llter.
34. Nickel— total ' mil/liter.
Iller.
36. Selenium— total mg/lltor.
37. Silver-total'
38. Bodlum-lolal' mg/lller.
39. Thallium-total' mg/llter.
41. Titanium— lotal mg/
liter.
42. Vanadium— total ' mg/
liter.
43. Zinc— total ' mg/llter...
Analytical methods for nu-
Irlents, anlons, and organlcs:
44. Organic nitrogen (as N)
mg/llter.
46. Ortho-phosphate (as P)
mg/llter.
46. Sulfale (as SO,) mg/
Iller.
47. Buinde (as S) mg/lltcr..
48. SulRte (as SO,) mg/
liter.
49. Bromide mg/llter
60. Chloride mg/lller
61. Cyanide— total mg/llter.
62 Fluoride mg/llter
63. Chlorine— tyJlal residual
mg/lller.
64. Oil and grease mu/llter..
66. Surfactants mit/llter
69. Benildlne me/liter
69. Chlorinated organic
compounds (except
pesticides) mg/llter.
60. Pesticides mg/lfter
Analytical methods for
physical and biological
parameters:
61. Color platinum-cobalt
unl Is or dominant
n-ave-lenglh, hue,
luminance, purity.
62. Specific conductance
mho/cm at 24° C.
63. Turbidity Jackson
units.
See Note at end of Table I
Method
Atomic absorption; colorlmetrlc
do . .
Atomic absorption: Colorlmetric '
Atomic absorption; Colorlmetric; flame
photometric.
Atomic absorption '
do
do
Klcldahl nitrogen minus ammonia
nitrogen.
Direct single reagent; automaled single
reagent or slannous chloride.
Oravlmelrlc; turbldlmetric; automated
Colorlmetric— barium chloranllate.
Tllrimelric— Iodine
Titrimetric; lodlde-lodale
do
Silver nitrate; mercuric nitrate; automated
colorimelric-ferricyanlde.
Distillation— silver nitrate Utratlon or
pyridlne pyretolone colorlmetrlc.
Distillation— SPADNS
Liquid-Liquid extraction with trichloro-
Irlfluoroelhaue.
Colorlmelric, 4 AAP
Melhylene blue colorlmelrlc
Oas chromatography '
Colorlmetric; spectrophotometric
Wheatstone bridge..
Turbldlnuter
Standard
melhods
p. 210
p. 426
p. 210
p. 430
p. 210
p 433
p. 210
p 436
p. 210
p. 418
p. 201
p. 210
p. 443
•p. 283
p. 284
. p. 210
p. 210
p. 444
p. 468
p 632
p. 331
p. 334
. p. 661
. p. 337
p. 06
p. 97
p. 3U7
p. 171
p. 174
p 382
p 284
. p. 602
. p. 339
. p. 160....
. p. 323
. p. 350
References
A8TM
. p. 692
. p. 403
p. 692
. p. 692
. p. 410
. p. 692
p 162
. p. 693
p. 692
. p. 692
. p. 692
. p. 328
.. p. 692
.. p. 61. ,
.. p. 62
'.'. P'.'MI.".""""
.. p. 216
-P. 23
- P. 21
.. p. 666
.. p. 191
.. p. 448
.. p. 619
.. p. 163
.. p. 467
EPA
method!
p. 104.
p. 108.
p. 110.
p. 112.
p. 114.
pi'iTsV""
"p'TfisV
p. 120.
p. 149.
p. 238.
p. 248.
p. 269.
p. 288.
p. 288.
p. 294.
p. 29.
p. 31.
p. 41.
p. 64.
p. 232.
p. lit.
p. 38.
p. Mi.
p. 308.
JO
O
90
m
O
O
FEDERAL REGISTER, VOL. 38, NO. 199—TUESDAY, OCTOBER 16, 1973
en
to
-------
28760
RULES AND REGULATIONS
Parameter and units
Method
Reference]
Standard
methods
ASTM
EPA
methods
84. Fecal itreptocoed UPN; membrane alter, plate count .
bacteria numberAOO p. 690
ml. P- m
«. Courorm bacteria MPN: Membrane filter p. 669
(local) number/100 p. 684
ml.
66. Coliform bacteria do p. 664
(total) number/100 p. 679
ml.
Radiological parameters:
67. Alpha—total pCi/llter.. Proportional counter, scintillation counter p. 598 p. 609
68. Alpha—counting error do p. S9S p. 412
pCIAlter.
69. Deta—total pCIAlter... Proportional counter! p. 698 p. 478
70. Beta—counting error do p. 598 p. 478
pCI/liler.
71. Radium—total pCl/ Proportional counter; scintillation counter., p. 611 p. 674
liter. p. 617
1 A number of such systems manufactured by various companies are considered to be c--nparable in their per-
formance. In addition, another technique, based on Combustion-Methane Detection, Is also 'icceptable.
> For the determination of total metals the sample is not filtered before processing. Choose a volume of sample
appropriate for theeipected level of metals. If much suspended material is present, as little as 60-100 ml of well-mixed
sample will most probably be sufficient. (The sample volume required may also vary proportionally with the number
of metals to be determined.)
Transfer a representative aliquot of the well-mixed sample to a Qriffin beaker and add 3 ml of concentrated disti lied
HNOs. Place the beaker on a hotplate and evaporate to dryness making certain that the sample does not boil. Cool
the beaker and add another 3 ml portion of distilled concentrated HNOi. Cover the beaker with a watch glass and
return to the hotplate. Increase the temperature of the hotplate so that a gentle reflui action occurs. Continue heating,
adding additional acid as necessary until the digestion is complete, generally indicated by a light colored residue.
Add (1:1 with distilled water) distilled concentrated HC1 In an amount sufficient to dissolve the residue upon warm-
Ing. Wash down the beaker walls and the watch glass with distilled water and filter the sample to remove silicates
and other insoluble material that could clog the atomizer. Adjust the volume to some predetermined value based
on the expected metal concentrations. The sample Is now ready for analysis. Concentrations so determined shall be
reported as "total".
> See D. C. Manning, "Technical Notes", Atomic Absorption Newsletter, Vol. 10, No. 6 p. 123, 1971. Available
from Perkin-Elmer Corporation. Main Avenue, Norwalk, Connecticut 06S52.
• Atomic absorption method available from Methods Development and Quality Assurance Research Laboratory,
National Environmental Research Center, USEPA. Cincinnati, Ohio 46268.
> For updated method, see: Journal of the American Water Works Association 64. No. 1, pp. 20-25 (Jan. 1972) or
ASTM Method D 3223-73, American Society (or Testing and Materials Headquarters, 1916 Race St., Philadelphia,
Pa. 19103.
> Interim procedures for algid des, chlorinated organic compounds, and pesticides can be obtained from the Methods
Development and Quality Assurance Research Laboratory, National Environmental Research Center, USEPA,
Cincinnati. Ohio 46268.
' Bentidine may be estimated by the method of M.A. El-Dlb, "Colorimetric Determination of Aniline Derivatives
in Natural Waters", El-Dib, M.A., Journal of the Association of Official Analytical Chemists, Vol. 54, No. 6, Nov.,
1971, pp. 1383-1387.
t As a prescreening measurement.
§ 136.4 Application for alternate test
procedures.
(a) Any person may apply to the Re-
gional Administrator In the Region
where the discharge occurs for approval
of an alternative test procedure.
(b) When the discharge for which an
alternative test procedure, is proposed
occurs within a State having a permit
program approved pursuant to section
402 of the Act, the applicant shall sub-
mit his application to the Regional Ad-
ministrator through the Director of the
State agency having responsibility for
Issuance of NPDES permits within such
State.
(c) Unless and until printed applica-
tion forms are made available, an appli-
cation for an alternate test procedure
may be made by letter in triplicate. Any
application for an alternate test proce-
dure under this subchapter shall:
(1) Provide the name and address of
the responsible person or firm making
the discharge (if not the applicant) and
the applicable ID number of the existing
or .pending permit, issuing agency, and
type of permit for which the alternate
test procedure is requested, and the dis-
charge serial number.
(2) Identify the pollutant or parame-
ter for which approval of an alternate
testing procedure is being requested.
(3) Provide justification for using
testing procedures other than those
specified in Table I.
(4) Provide a detailed description of
the proposed alternate test procedure.
together with references to published
studies of the applicability of the alter-
nate test procedure to the effluents in
question.
§ 136.5 Approval of alternate lest pro-
cedures.
(a) The Regional Administrator of
the region in which the discharge will
occur has final responsibility for ap-
proval of any alternate test procedure.
(b) Within thirty days of receipt of
an application, the Director will forward
such application, together with his rec-
ommendations, to the Regional Admin-
istrator. Where the Director recommends
rejection of the. application for scien-
tific and technical reasons which he pro-
vides, the Regional Administrator shall
deny the application, and shall forward
a copy of the rejected application and
his decision to the Director of the State
Permit Program and to the Director of
the Methods Development and Quality
Assurance Research Laboratory.
(c) Before approving any application
for an alternate test procedure, the Re-
gional Administrator shall forward a
copy of the application to the Director
of the Methods Development and Qual-
ity Assurance Laboratory for review and
recommendation.
(d) Within ninety days of receipt by
the. Regional Administrator of an appli-
cation for an alternate test procedure,
the Regional Administrator shall notify
the applicant and the appropriate State
agency of approval or rejection, or shall
specify the additional information which
is required to determine whether to ap-
prove the proposed test procedure. Prior
to the expiration of such ninety day pe-
riod, a recommendation providing the
scientific and other technical basis for
acceptance or rejection will be forwarded
to the Regional Administrator by the Di-
rector of the Methods Development and
Quality Assurance Research Laboratory.
A copy of all approval and rejection
notifications will be forwarded to the
Director, Methods Development and
Quality Assurance Research Laboratory,
for the purposes of national coordination.
[FR Doc.73-21466 Filed 10-15-73:8:45 am]
FEDERAL REGISTER, VOL. 38. NO. 199—TUESDAY, OCTOBER 16, 1973
D-326
-------
WEDNESDAY, DECEMBER 1, 1976
PART II:
ENVIRONMENTAL
PROTECTION
AGENCY
WATER PROGRAMS
Guidelines Establishing Test Procedures
for the Analysis of Pollutants
Amendments
D-327
-------
52780
RULES AND REGULATIONS
Title 40—Protection of Environment
CHAPTER I—ENVIRONMENTAL
PROTECTION AGENCY
SUBCHAPTER D—WATER PROGRAMS
[FRL 630-4]
PART 136—GUIDELINES ESTABLISHING
TEST PROCEDURES FOR THE ANALYSIS
OF POLLUTANTS
Amendment of Regulations
On June 9,1975, proposed amendments
to the Guidelines Establishing Test Pro-
cedures for the Analysis of Pollutants
(40 CPB 136) were published in the FED-
ERAL REGISTER (40 PR 24535) as required
by section 304 (g) of the Federal Water
Pollution Control Act Amendments of
1972 (86 Stat. 816, et seq., Pub. L. 92-500,
1972) hereinafter referred to as the Act.
Section 304(g) of the Act requires that
the Administrator shall promulgate
guidelines establishing test procedures
for the analysis of pollutants that shall
include factors which must be provided
in: (1) any certification pursuant to sec-
tion 401 of the Act, or (2) any permit ap-
plication pursuant to section 402 of the
Act. Such test procedures are to be used
by permit applicants to demonstrate that
effluent discharges meet applicable pol-
lutant discharge limitations and by the
States and other enforcement activities
in routine or random monitoring of ef-
fluents to verify compliance with pollu-
tion control measures.
Interested persons were requested to
submit written comments, suggestions, or
objections to the proposed amendments
by September 7, 1975. One hundred and
thirty-five letters were received from
commenters. The following categories of
organizations were represented by the
commenters: Federal agencies accounted
for twenty-four responses: State agen-
cies accounted for twenty-six responses;
local agencies accounted for seventeen
responses; regulated major dischargers
accounted for forty-seven responses;
trade and professional organizations ac-
counted for eight responses; analytical
instrument manufacturers and vendors
accounted for seven responses; and an-
alytical service laboratories accounted
for six responses.
All comments were carefully evaluated
by a technical review committee. Based
upon the review of comments, the follow-
ing principal changes to the proposed
amendments were made:
(A) Definitions. Section 136.2 has been
amended to update references: Twenty
commenters, representing the entire
spectrum of responding groups pointed
out that the references cited in §§ 136.2
(f), 136.2(g), and 136.2(h) were out-of-
date; §§ 136.2(f), 136.2(g), and 136.2(h),
respectively, have been amended to show
the following editions of the standard
references: "14th Edition of Standard
Methods for the Examination of Water
and Waste Water;" "1974 EPA Manual
of Methods for the Analysis of Water and
Waste;" and "Part 31,1975 Annual Book
of ASTM Standards."
(B) Identification of Test Procedures.
Both the content and format of § 136.3.
"Table I, List of Approved Test Proce-
dures" have been revised in response to
twenty-one comments received from
State and local governments, major regu-
lated dischargers, professional and trade
associations, and analytical laboratories.
Table I has been revised by:
(1) The addition of a fourth column
of references which includes procedures
of the United States Geological Survey
which are equivalent to previously ap-
proved methods.
(2) The addition of a fifth column of
miscellaneous references to procedures
which are equivalent to previously ap-
proved methods.
(3) Listing generically related param-
eters alphabetically within four subcate-
gories: bacteria, metals, radiological and
residue, and by listing these subcategory
headings in alphabetic sequence rel-
ative to the remaining parameters.
(4) Deleting the parameter "Algicides"
and by entering the single relevant algi-
cide, "Pentachlorophenol" by its chemi-
cal name.
(C) Clarification of Test Parameters.
The conditions for analysis of several
parameters have been more specifically
defined as a result of comments received
by the Agency:
(1) In response to five commenters
representing State or local governments,
major dischargers, or analytical instru-
ment manufacturers, the end-point for
the alkalinity determination is specifi-
cally designated as pH 4.5.
(2) Manual digestion and distillation
are still required as necessary prelimi-
nary steps for the Kjeldahl nitrogen pro-
cedure. Analysis after such distillation
may be by Nessler color comparison,
titration, electrode, or automated pheno-
late procedures.
(3) In response to eight commenters
representative of Federal and State gov-
ernments, major dischargers, and ana-
lytical instrument manufacturers, man-
ual distillation at pH 9.5 is now specified
for ammonia measurement.
(D) New Parameters and Analytical
Procedures. Forty-four new parameters
have been added to Table I. In addition
to the designation of analytical proce-
dures for these new parameters, the fol-
lowing modifications have been made in
analytical procedures designated in re-
sponse to comments.
(1) The ortho-tolidine procedure was
not approved for the measurement of
residual chlorine because of its poor ac-
curacy and precision. Its approval had
been requested by seven commenters rep-
resenting major dischargers, State, or
local governments, and analytical instru-
ment manufacturers. Instead, the N,N-
diethyl-p-phenylenediamine (DPD)
method is approved as an interim pro-
cedure pending more intensive laboratory
testing. It has many of the advantages
of the ortho-tolidine procedure such as
low cost, ease of operation, and also is of
acceptable precision and accuracy.
(2) The Environmental Protection
Agency concurred with the American Dye
Manufacturers' request to approve its
procedure for measurement of color, and
copies of the procedure are now available
at the Environmental Monitoring and
Support Laboratory, Cincinnati (KMSL-
CI).
O) In response to three requests from
Federal, State governments, and dis-
chargers, "hardness," may be measured
as the sum of calcium and magnesium,
analyzed by atomic absorption and ex-
pressed as their carbonates.
(4) The proposal to limit measure-
ment of fecal coliform bacteria in the
presence of chlorine to only the "Most
Probable Number" (MPN) procedure has
been withdrawn in response to requests
from forty-five commenters including
State pollution control agencies, permit
holders, analysts, treatment plant op-
erators, and a manufacturer of analyt-
ical supplies. The membrane filter (MF)
procedure will continue to be an ap-
proved technique for the routine meas-
urement of fecal coliflorm in the pre-
sence of chlorine. However, the MPN
procedure must be used to resolve con-
troversial situations. The technique
selected by the analyst must be reported
with the data.
(5) A total of fifteen objections, re-
presenting the entire spectrum of com-
menters, addressed the drying tempera-
tures used for measurement of residues.
The use of different temperatures in dry-
ing of total residue, dissolved residue and
suspended residue was cited as not allow-
ing direct intercomparability between
these measurements. Because the intent
of designating the three separate residue
parameters is to measure separate waste
characteristics (low drying temperatures
to measure volatile substances, high dry-
ing temperatures to measure anhydrous
inorganic substances), the difference in
drying temperatures for these residue
parameters must be preserved.
(E) Deletion of Measurement Tech-
niques. Some measurement techniques
that had been proposed have been de-
leted in response to objections raised
during the public comment period.
(1) The proposed infrared spec-
trophotometric analysis for oil and
grease has been withdrawn. Eleven com-
menters representing Federal or State
agencies and major dischargers claimed
that this parameter is defined by the
measurement procedure. Any alteration
in the procedure would change the def-
inition of the parameter. The Environ-
mental Protection Agency agreed.
(2) The proposed separate parameter
for sulflde at concentrations below 1
mg/1, has been withdrawn. Methylene
blue spectrophotometry is now included
In Table I as an approved procedure for
sulflde analysis. The titrimetric iodine
procedure for sulfide analysis may only
be used for analysis of sulfide at concen-
trations in excess of one milligram per
liter.
(F) Sample Preservation and Holding
Times. Criteria for sample preservation
and sample holding times were requested
by several commenters. The reference for
sample preservation and holding time
criteria applicable to the Table I param-
eters is given in footnote (1) of Table I.
(G) Alternate Test Procedures. Com-
ments pertaining to § 136.4, Application
for Alternate Test Procedures, included
objections to various obstacles within
FEDERAL REGISTER, VO1. 41, NO. 232—WEDNESDAY, DECEMBER 1, 1976
D-328
-------
RULES AND REGULATIONS
52781
these procedures for expeditious ap-
proval of alternate test procedures. Four
analytical instrument manufacturers
commented that by limiting of applica-
tion for review and/or approval of alter-
nate test procedures to NPDES permit
holders, § 136.4 became an impediment to
the commercial development of new or
improved measurement devices based on
new measurement principles. Applica-
tions for such review and/or approval
will now be accepted from any person.
The intent of the alternate test pro-
cedure is to allow the use of measure-
ment systems which are known to be
equivalent to the approved test proce-
dures in waste water discharges.
Applications for approval of alternate
test procedures applicable to specific dis-
charges will continue to be made only by
NPDES permit holders, and approval of
such applications will be made on a
case-by-case basis by the Regional Ad-
ministrator in whose Region the dis-
charge is made.
Applications for approval of alternate
test procedures which are Intended for
nationwide use can now be submitted by
any person directly to the Director of the
Environmental Monitoring and Support
Laboratory in Cincinnati. Such applica-
tions should include a complete methods
write-up, any literature references, com-
parability data between the proposed al-
ternate test procedure and those already
approved by the Administrator. The ap-
plication should include precision and
accuracy data of the proposed alternate
test procedure and data confirming the
general applicability of the test proce-
dure to the industrial categories of waste
water for which it is intended. The Di-
rector of the Environmental Monitoring
and Support Laboratory, after review of
submitted information, will recommend
approval or rejection ot the application
to the Administrator, or he will return
the application to the applicant for more
information. Approval or rejection of ap-
plications for test procedures Intended
for nationwide use will be made by the
Administrator, after considering the rec-
ommendation made by the Director of
the Environmental Monitoring and Sup-
port Laboratory, Cincinnati. Since the
Agency considers these procedures for
approval of alternate test procedures for
nationwide use to be interim procedures,
we will welcome suggestions for criteria
for approval of alternate test procedures
for nationwide use. Interested persons
should submit their written comments in
triplicate on or before June 1, 1977 to:
Dr. Robert B. Medz, Environmental Pro-
tection Technologist, Monitoring Quality
Assurance Standardization, Office of
Monitoring and Technical Support (RD-
680), Environmental. Protection Agency,
Washington, D.C. 20460.
(H) Freedom of Information. A copy
of all public comments, an analysis by
parameter of those comments, and docu-
ments providing further information on
the rationale for the changes made in
the final regulation are available for
inspection and copying at the Environ-
mental Protection Agency Public Infor-
mation Reference Unit, Room 2922,
Waterside Mall, 401 M Street, SW.,
Washington, D.C. 20460, during normal
business hours. The EPA Information
regulation 40 CFR 2 provides that a rea-
sonable fee may be charged for copying
such documents.
Effective date: These amendments be-
come effective on April 1, 1977.
Dated: November 19,1976.
JOHN QUARLES,
Acting Administrator,
Environmental Protection Agency.
Chapter I, Subchapter D, of Title 40,
Code of Federal Regulations is amended
as follows:
1. In § 136.2, paragraphs (f), (g), and
(h) are amended to read as follows:
§ 136.2 Definitions.
(f) "Standard Methods" means Stand-
ard Methods for the Examination of
Water and Waste Water, 14th Edition,
1976. This publication is available from
the American Public Health Association,
1015 18th Street, N.W., Washington, D.C.
20036.
(g) "ASTM" means Annual Boofc of
Standards, Part 31, Water, 1975. This
publication is available from the Ameri-
can Society for Testing and Materials,
1916 Race Street, Philadelphia, Pennsyl-
vania 19103.
(h) "EPA Methods" means Methods
for Chemical Analysis of Water and
Waste, 1974. Methods Development and
Quality Assurance Research Laboratory,
National Environmental Research Cen-
ter, Cincinnati, Ohio 45268; U.S. Envi-
ronmental Protection Agency, Office of
Technology Transfer, Industrial Envi-
ronmental Research Laboratory, Cincin-
nati, Ohio 45268. This publication is
available from the Office of Technology
Transfer.
2. In § 136.3, the second sentence of
paragraph In presence
. of chlorine, number per 100
ml.
8. Feeal streptococci,1 number
per 100 nil.
9. Benildlne, milligrams per liter.
10. Biochemical oiygen demand,
9-d (BODi), milligrams per
liter.
11. Bromide, milligrams per liter..
12. Chemical oiygen demand
(COD), milligrams per liter.
13. Chloride, milligrams per liter..
So* footnotes at end of tabl«.
MPN;' nu-inbrane filter
do."
do.'
MPN;' membrane filter
with enrlcluueut.
MPN;' membraiio filter;
plate count.
Oxidation— colorimetric •
Winkler (Aiide modifica-
tion) or electrode method.
Titrimetrlc, io
-------
52782
RULES AND REGULATIONS
Parameter and units
14. Chlorinated organic com-
pounds (eicept pesticides),
milligrams per liter.
15. Chlorine— total residual, milli-
grams per liter.
16. Color, platinum cobalt units
or dominant wave length,
hue. luminance, purity.
17. Cyanide, total," milligrams
per liter.
IS. Cyanide amenable to chlorin-
•tlon, milligrams per liter.
19. Dissolved oxygen, milligrams
per liter.
JO. Fluoride, milligrams per liter..
Jl. Hardness— Total, as CaCOi,
milligrams per liter.
H. Hydrogen ion (pH), pH units.
». KJeldahl nitrogen (ai N),
milligrams per liter.
HITAIA
14. Aluminum— Total, milligrams
per liter.
IS. Aluminum— Dissolved, milli-
grams per liter.
M. Antimony— Total, milligrams
per liter.
ST. Antimony— Dissolved, milli-
grams per liter.
IS. Arsenic— Total, milligrams
per liter.
». Arsenic— Dissolved, milli-
grams per liter.
30. Barium— Total, milligrams
per liter.
11. Barium— Dissolved, milli-
grams per liter.
32 Beryllium — Total milligrams
per liter.
33. Beryllium— Dissolved, milli-
grams per liter.
34. Boron— Total,' milligrams per
liter.
35. Boron— Dissolved, milligrams
per liter.
36. Cadmium— Total, milligrams
per liter.
37. Cadmium— Dissolved, milli-
grams per liter.
38. Calcium— Total, milligrams
per liter.
39. Calcium— Dissolved, milli-
grams per liter.
40. Chromium VI, milligrams per
liter.
41. Chromium VI— Dissolved,
milligrams per liter.
42. Chromium— Total, milligrams
per liter.
43. Chromium— Dissolved, milli-
grams per liter.
1074 1
Method SPA *
methods a
Clas chromatography »
lodometric titrarton. am per-
ometric or starch-iodine
end-point: DPD colori- ..
metric or Titrimetric --
methods (these last 2 are
interim methods pending
laboratory testing).
Colorimetric: spectrophoto-
metric; or A DM1 pro-
cedure.13
Distillation followed by
silver nitrate titration or
pyridine pyrazolone (or
barbituric acid) colori-
metric.
. ..do. ...
Winkler (Aiide modifica-
tion) or electrode method.
Distillation* followed by ..
ion electrode; SPADN8;
or automated comple *one.
EDTA titration; auto-
mated colorimetric: or
atomic absorption (sum ..
of Ca and Mg as their
respective carbonates).
Electrometric measurement.
Digestion and distillation
followed by nessleritation.
titration, or electrode;
automated digestion auto-
mated pheaolate.
Digestion " followed by
atomic absorption '• or by ..
colorimetric (Eriochrome
Cyanine R).
0.45 micron nitration " fol- ..
lowed by referenced meth-
ods for total aluminum.
Digestion " followed by
atomic absorption. >•
0.45 micron nitration 1T fol-
lowed by referenced
method for total antimony.
Digestion followed by silver ..
cfiethyldithiocarbamate:
or atomic absorption. » »
0.45 micron filtration » fol- ..
lowed by referenced
method for total arsenic.
Digestion <> followed by
atomic absorption.'*
0.45 micron filtration " fol- ..
lowed by referenced
method for total barium.
Digestion " followed by
atomic absorption '• or by ..
colorimetric (Aluminon).
0.45 micron filtration " fol-
lowed by referenced
method for total beryllium.
Colorimetric (Curcumin) —
0 45 micron filtration >T fol-
lowed by referenced meth-
od for total boron.
Digestion » followed by
colorimetric (Dithiume).
0.45 micron filtration " fol- ._
lowed by referenced metn-
od for total cadmium.
Digestion >' followed by
EDTA titration.
0.45 micron filtration » fol- ..
lowed by referenced meth-
od for total calcium.
Extraction and atomic ab-
phenylcarbatide).
0.45 micron filtration " fol-
lowed by referenced meth-
od for chromium VI.
Digestion » followed by
colorimetric (Diphenyl-
carbaxide).
045 micron filtration" fol-
lowed bv referenced meth-
od for total chromium.
33
30
39
40
49
51
56
65
59
ei
68
70 ...
239
175
165 ..
182 ...
«
M ...
»
9*
97
99
13
101
103
89, 105 ...
105
References
tth ed. (page nos.) Other
letuods Ft. 31 US OS Methods
1975 methods'
ASTM
318
322 278 ..
332
329
64 . .
66 ..
301 503
376 505
443 368
450 ...
389
391 307
393 306 .
614
202 161
460 178
437
15»
171
tss .
wa
isa
152
152
177
187
148 345
182
148 145
189
192
14S 345
191 188
85 i«C-'2>
12G 1(609)
93
94 »(617)
129 >(«0f»
122 "(6121
11(19)
"(31)
«(»>
52
53
62 1 (61») » (37)
66
7« '.
75
78 • (619)
77
See footnotes at end o( table.
FEDERAL REGISTER, VOL. 41, NO. 232—WEDNESDAY, DECEMBER 1, 197*
D-330
-------
RULES AND. REGULATIONS
5278.1
44. Cobalt— Total, milligrams per
liter.
45. Cobalt- -Dissolved, milli-
grams per liter.
40. Popper— Toiul. milligrams
per liter.
grams per liter.
liter.
49. Iridlum— Total milligrams
per liter.
50. Iron — Total, milligrams per
liter.
ill. Iron — Dissolved, milligrams
per liter.
52. Lead— Total, milligrams per
liter.
53. Lead— Dissolved, milligrams
per liter.
51. Magnesium— Total, milli-
55. Magnesium — Dissolved milli-
grams per liter.
5G. Manganese- -Total milligrams
57. -Manganese — Dissolved milli-
grams per liter.
58. Mercnrv— Total. . milligrams
per liter.
50. Mei-curv— Dissolved, milli-
grams per liter.
60. Molybdenum— Total, milli-
grams per liter.
61. Molvbdenum— Dissolved,
milligrams i*r liter.
62. Nickel— Total, milligrams
per liter.
03. Nickel— Dissolved, milli-
grams per liter.
64. Osmium — Total, milligrams
per liter.
65. Palladium— Total, milligrams
per liter.
66. Platinum— Total, milligrams
per liter.
67. Potassium — Total, milligrams
per liter.
68. Potassium— Dissolved, milli-
grams per liter.
60. Rhodium — Total, milligrams
per liter.
70. Ruthenium— Total. milli-
grams per liter.
71. Selenium— Total, milligrams
per liter.
72. Selenium— Dissolved, milli-
grams per liter.
73. Silica— Dissolved, milligrams
per liter.
74. Silver— Total,* milligrams
per liter.
75. Silver— Dissolved." milli-
grams per liter.
76. Sodium— Total, milligrams
per liter.
77. Sodium— Dissolved, milli-
grams per liter.
Digestion " followed by
atomic absorption.1*
0.4") micron filtration 1T fol-
lowed by referenced melh-
oil for total cobalt.
Digestion 1J followed by
atomic absorption u or U\-
colorimiMm: (Neocu-
proint-i.
lowed by referenced meth-
od for total copper.
Digestion is followed In'
atomic absorption.1*
Digestion 1S followed bv
atomic absorption.1*
Digestion " followed by
atomic absorption N or by
colorimetric U'henantliru-
linei.
0.45 micron filtration 1: fol-
lowed by referenced meth-
od for total iron.
Digestion « followed by
atomic absorption « ur by
colorimetric (Dithizone't.
0.45 micron nitration " fol-
lowed by referenced meth-
od for total lead.
Digestion " followed by
gravimetric.
0.15 micron littvation i: dol-
lowed by referenced
method for total magne-
sium.
Digestion vi followed by
atomic absorption if or bv
oolorlmetric U'erstllfate or
periodate.i.
0.45 micron filtration » fol-
lowed hv referenced
method for total manga-
nese.
Flameless atomic absorp-
tion.
0.45 micron filtration " fol-
lowed by referenced
method for total murcury.
Digestion " followed by
atomic absorption."
0.45 micron nitration » fol-
lowed by referenced
method for total molybde-
num.
Digestion » followed bv
atomic absorption " or by
colorimetric (Heptoiime).
0.45 micron nitration " fol-
lowed by referenced
method for total nickel.
Digestion u followed bv
atomic absorption."
Digestion " followed by
atomic absorption."
Digestion » followed by
atomic absorption."
Digestion " followed bv
atomic absorption, colori-
metric (Cobaltinitrite), or
by flame photometric.
0.45 micron nitration a fol-
lowed by referenced metli-
of for total potassium.
Digestion u followed bv
atomic absorption."
Digestion " followed bv
atomic absorption."
Digestion " followed by
atomic absorption." "
0.45 micron filtration " fol-
lowed by referenced meth-
od for total selenium.
0.45 micron filtration « fol-
lowed by colorimetric
(Moiybdosilicate).
Digestion " followed by
atomic absorption >• or by .
colorimetric (Ditm>.oue).
0.45 micron nitration " fol- .
lowed by referenced meth-
od for total silver.
Digestion " followed by
atomic absorption or by
flame photometric.
0.45 micron filtration " (id- .
lowed by referenced meth-
od for total sodium.
1074 uth ed.
methods methods
107 118
108 148
IJKj
no us
208
112 148
215
114 148
221
116 148
OOJJ OO'
118 156
13il
HI 148
Ii3
235
234
143 159
274 487
1-M 148
243 .
UT
250
References
(page nos.i Other
Pt. 31 rSGS methods
1975 methods -
ASTM
34-. no •'(a;.
34.-, S3 * («l!i) i- (37)
'?.'$
345 102 1 (810)
326
34.5 105 ' (619;
315 109 > (6191
345 111 > (619)
338 "(51)
350
345 115 .
134 1 (820)
403
198 139
142 '(619) ['(37)
141 1 (021)
401
See footnotes at end of tnbl*.
KOERAt IECISTER, VOL. 41, NO. 232—WEDNESDAY, DECEMIEI 1, 1974
D-331
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52784
RULES AND REGULATIONS
Panineter and units
Method
1974 14th ed.
EPA standard
methods methods Pt. 31
References
(page nos.)
1975 methods'
ASTM
Other
approved
US OS methods
7S. Thallium—Total, milligrams Digestion '• followed by 149
pej- liter. atomic absorption."
79. Thallium—Dissolved, milli- 0.45 micron nitration" fol-
grams per liter. lowed by referenced meth-
od for total thallium.
80. Tin—Total, milligrams per Digestion" followed by 160.... "(64)
liter. atomic absorption.18
81. Tin—Dissolved, milligrams 0.45 micron nitration " to!-
per liter. lowed by referenced meth-
od for total tin.
82. Titanium—Total, imlligrams Digestion" followed by 161
per liter. atomic absorption.11
83. Titanium—Dissolved, milli- 0.45 micron nitration" fol-
grams per liter. lowed by referenced meth-
od for total titanium.
84. Vanadium—Total, milligrams Digestion" followed by 143 152
rxrliter. atomic absorption >'or by 260 441 "(67)
eolorimetric (Gallic acid).
85. Vanadium—Dissolved, niilli- 0.45 micron lilt ration " fol-
grams per liter. lowed by referenced meth-
od for total vanadium.
86. Zliw—Total, milligrams |X-r Digestion» followed by 145 148 344 149 '(619)»(37)
liter. atomic absorption»or by 284
colorimetric: (Dithizoue).
87. /.1m:—))issolv>'i 1, milligrams 0.4S micron nitration " fol-
per liter, lowed by referenced meth-
od for total zinc.
88. Nitrate •:\f .V'., Milligrams i*'r Cadmium reduction; brn- 201 423
liti-r. ' cine sultote; automated 1'.I7 427 348 11'J H014) i»i28)
cadmium or hydrazine re- 207 620
dnelion.-1
89. Nitrate .as.V'.1. milligrams |>>" Manual or automated colori- 215 434 121..
liter. metric (Diazotitation).
1)0. Oil and gr«-:tse. milligrams |>*-i Liquid-liquid extraction 2'JO M5
liter. ' ' with trichloro-trifluor*
et hane-gravimetrie.
91. Organic carbon; total (TOC;, Combustion—Infrared 23U 632 487 » (4)
milligrams per liter. method."
92. Organic nitrogen ias N), milli- KJeldahl nitrogen minus 175,16'J 437 122 '(612,814)
grains per liter. ammonia nitrogen.
93. Orthophosphate (.as P), milli- Manual or automated ascor- 249 481 384 131 ' (621)
grams per liter. bic acid reduction. 256 8J1
94. Pentachlorophenol, milli- Gas chromatography »
grams per liter.
05. Pesticides, milligrams per do." 445 529 » C24)..;
liter.
96. Phenols, milligrams per liter., rolorimetrie, \4AAP) 241 682 545
97. Phosphorus (elemental), milli- Gas chromatography "
grams per liter.
08. Phosphorus; total (as P), Pe.rsulfate digestion fol- 249 476,481 384 133 »(«21)
milligrams per liter. lowe.d'by manual or'auto 246 624...
mated ascorbic acid reduc-
tion.
RADtOI.O'SH'At.
•J!). Alpha—-Total, pCi per liter.. Proportional or scintillation 648 51Jin«i.7i-r7»)
counter.
100. Alpha—Counting error, pOl do 648 594 » (79)
per liter. v
101. Beta—Total. pCi per liter Proportional counter 648 601 >'•'» 1754-78)
102. Beta—Counting error, pCt per do 648 606 n (78)
liter.
10*. (a) Kadium—Total, pCi per do _ 661 661
liter.
(bj '"•' Ra, pCi per liter Scintillation counter b "f WHNT and xv.vieK, 107V' I.'.,*. K.nvireiiiiieniai I'lotevii-ni Ayiiey, table 2, pp.
viii >ii.
FEDERAL REGISTER. VOL. 41, NO. 232—WEDNESDAY, DECEMBER 1, 1976
D-332
-------
RULES AND REGULATIONS
52785
• \ll page references for USliS methods, unless otherwise noted, arc lo Brown, E., Skougstad, M. W.. and Fish-
man, M. J., "Methods (or Collection and Analysis of Water Samples for Dissolved Minerals and Gases," U.S. Geologi-
cal Survey Techniques of Water-Resources Inv., books, oh. Al, (19701. ,,,,,.,.,.,, . . ,
' EPA comparable method may be found on indicated page of "Oiucial .Methods of Analysis of the Association of
Official Analytical Chemists'' methods manual, 12th cd. (1975).
1 Manual distillation is not required if comparability data on representative effluent samples are on company file
toshow that this preliminary distillation step is not necessary; however, manual distillat ion will be. required lo resolve
any controversies.
- The method used must be specified.
« The 5 tube MPX is used.
7 Slack K. V. and others, "Methods fur Collection and Analysis of Aquatic Biological and Jlirco'uologieal samples:
L'.S. Geological Survey Techniques of Water- Resources inv. book 5, ch. AK1973)."
' Since the membrane filter technicruc usually yields low and variable recovery frc
MPN method will bo required to resolve, any controversies.
f from chlorinated woslcwalers, the
. .. - ngai
cinnati, Ohio 45268.
1° American National Standard on Photographic Processing Effluents, Apr. 2, U'75. Available from ANSI, U3Q
Broadway, New York, N.Y. 10018.
» Fishmaii. M. J. and Brown. Eugene, "Selected Methods of the U.S. Geological survey for Analysis of Waste-
waters," (1970) open-file report 76-177.
" Procedures for pentachloroplienol. chlorinated organic compounds ,and pesticides can be. obtained from the En-
vironmental Monitoring and Support Lbaoratory, U.S. Environmental Protection Agency, Cincinnati, Ohio-lo^GS.
"Color method (ADMI procedure) available from Environmental Monitoring and Support Lbaoratory, L'.S.
Environmental Protection Agency, Cincinnati, Ohio 45268.
11 For samples suspected of having thiocyanatc interference, nuignesium chloride is used as the digestion catalyst.
In the approved test procedure for cyanides, the recommended catalysts sire replaced with 20 ml of a solution of 510 syl
magnesium chloride (MgCU-OHjO). This substitution will eliminate tliiocyanate interference for both total cyanide
and cyanide amendable to chlorination measurements.
11 For the determination of total metals the sample is not filtered before processing. Because vigorous digestion
procedures may result in a loss of certain metals through preciptation. a less vigorous treatment is recommended as
given on p. 83 (4.1.-H ot "Methods lor Chemical Analysis o( Water and Wastes" (1974). In those instances where a
more vigorous digestion is desired the procedure on p. 82 (4.1.3) should be followed. For the measurement of the noble
metal series (gold, iridium, osmium, palladium, platimum, rhodium and ruthenium), an aqua regia digest ion is to be
substituted as follows: Transfer a representitive aliquot of the well-mixed sample to a Griffin beaker and add 3 ml
of concentrated redistilled IINOS. Place the beaker on a steam bath and evaporate to dryness. Cool the beaker and
cautiously add a 5 ml portion of aqua regia. (Aqua regia is prepared immediately before use by carefully adding 3
volumes of concent rated IICI to one volume of concentrated HNOj.) Cover the beaker with a watch glass and return
to the steam baUi. Continue heating the covered beaker for 50 mm. Remove cover and evaporate to dvyness. Cool
and take up the residue in a small quantity of 1:11IC1. Wash down the beaker walls and watch glass with distilled
water and tiller the sample to remove silicates and other insoluble material that could elog the atomizer. Adjust the
volm o to some predetermined value based on the expected metal concentration. The sample, is now ready for analysis.
lfl As the various furnace devices (nameless AA) are essentially atomic absorption techniques, they are considered
to be approved test methods. Methods of standard addition are to be followed as noted in p. 78 of "Methods for Chem-
ical Analysis of Water and Wastes," 1074.
17 Dissolved metals are defined as those eonstltutents which will pass though a 0.45 ^m membrane filter. A prc-
filtration is permissible to free the sample from larger suspended solids. Filter the sample as soon as practical
after collection using the first 50 to 100 ml to rinse the filter flask. (Gloss or plastic filtering apparatus are recommended
to avoid possible contamination.) Discard tho portion used to rinse the flask and collect the required volume of
nitrate. Acidify the filtrate with 1:1 redistilled HNOj to o pH of 2. Normally, 3 ml of (1:1) acid per liter should l>e
sufficient to preserve the samples.
" See "Atomic Absorption Newsletter," vol. 13,75 (1974). Available from Perkin-Elmor Corp., Main Ave., Nurvalk.
Conn. 06852.
'• Method available from Environmental Monitoring and Support Laboratory, U.S. Environmental Protection
Agency, Cincinnati, Ohio 45268.
!0 Recommended methods for the analysis of silver in industrial woslewaters at concentrations of 1 ing/1 ami
above are inadequate where silver exists as an inorganic halide. Silver halides such as the bromide and chloride
are relatively insoluble in reagents such as nitric acid but are readily soluble in an aqueous buffer of sodium thio-
sulfate and sodium hydroxide to a pH of 12. Therefore, for levels of silver above 1 mg/1 20 ml of sample should be
diluted to 100 ml by adding 40 ml each of 2M Na-SjOj and 2M NaOH. Standards should be prepared in the same
manner. For levels "of silver below 1 mg/1 the recommended method is satisfactory.
« An automated hydrazine reduction method is available from the Environmental Monitoring and Support
Laboratory. U.S. Environmental Protection Agency. Cincinnati, Ohio 45268.
" A number of such systems manufactured by various companies are considered to be comparable in their per-
formance. In addition, another technique, based on combustion-methane detection is also acceptable.
» Goerlitz. D., Brown, E., "Methods for Analysis of Organic Substances in Water": U.S. Geological Survey Tech-
niques of Water-Resources tnv., book o, eh. A3 (1972).
«' R. F. Addison and R. G. Ackman, "Direct Determination of Elemental Phosphorus by Gas-Liquid Chroma-
tography," "Journal of Chromatography," vol. 47, No. 3, pp. 421-426, 1070.
» Tlie method found on p. 75 measures only the dissolved portion while the method on p. 7S measures only sus-
pended. Therefore, the 2 results must be added together to obtain "total."
M 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 Inv.. book 1 (1075)."
4. In § 136.4, the second sentence of
paragraph (c) is amended by deleting
the word "subchapter" immediately fol-
lowing the phrase "procedure under this"
and immediately preceding the word
"shall" and replaced with the phrase
"paragraph c;" and § 136.4 is amended
by adding a new paragraph (d> to read
as follows:
136.4 Application
procedures.
for- alternate test
(c) * * * Any application for an alter-
nate test procedure under this paragraph
(c) shall: ' * *
(d) An application for approval of an
alternate test procedure for nationwide
use may be made by letter in triplicate
to the Director, Environmental Monitor-
Ing and Support Laboratory, Cincinnati,
Ohio 45268. Any application for an alter-
nate test procedure under this paragraph
(d) shall:
(1) Provide the name and address of
the responsible person or firm making
the application.
(2) Identify the pollutant(s) or pa-
rameter (s) for which nationwide ap-
proval of an alternate testing procedure
is being requested.
(3) Provide a detailed description of
the proposed alternate procedure, to-
gether with references to published or
other studies confirming the general ap-
plicability of the alternate test procedure
to the pollutant(s) or parameter(s) in
waste water discharges from representa-
tive and specified industrial or other
categories.
(4) Provide comparability data for the
performance of the proposed alternate
test procedure compared to the perform-
ance of the approved test procedures.
§ 136.5 [Amended]
5. In § 136.5, paragraph (a) is amended
by inserting the phrase "proposed by the
responsible person or firm making the
discharge" immediately after the words
"test procedure" and before the period
that ends the paragraph.
6. In § 136.5, paragraph (b) is amended
by inserting in the 'first sentence the
phrase "proposed by the responsible per-
son or firm making the discharge" im-
mediately after the words "such applica-
tion" and immediately before the comma.
The second sentence of paragraph (b>
is amended by deleting the phrase
"Methods Development and Quality As-
surance Research Laboratory" immedi-
ately after the phrase "State Permit
Program and to the Director of the" at
the end of the sentence, and inserting in
its place the phrase "Environmental
Monitoring and Support Laboratory,
Cincinnati."
7. In § 136.5, paragraph (c) is amended
by inserting the phrase "proposed by the
responsible person or firm making the
discharge1' immediately after the phrase
"application for an alternate test pro-
cedure" and immediately before the
.comma; and by deleting the phrase
"Methods Development and Quality As-
surance Laboratory" immediately after
the phrase "application to the Director
of the" and immediately before the
phrase "for review and recommenda-
tion" and inserting in its place the phrase
"Environmental Monitoring and Support
Laboratory, Cincinnati."
8. In § 136.5, the first sentence of para-
graph (d) is amended by inserting the
phrase, "proposed by the responsible
person or firm making the discharge,"
immediately after the phrase, "applica-
tion for an alternate test procedure,"
and immediately before the comma.
The second sentence of paragraph
-------
52786 RULES AND REGULATIONS
§ 136.5 Approval of alternate text pro-
te> Within ninety days of the receipt
by the Director of the Environmental
Monitoring and Support Laboratory,
Cincinnati of an application for an
alternate test procedure for nationwide
use, the Director of the Environmental
Monitoring and Support Laboratory,
Cincinnati shall notify the applicant of
his recommendation to the Adminis-
trator to approve or reject the applica-
tion, or shall specify additional informa-
tion which is required to determine
whether to approve the proposed test
procedure. After such notification, an
alternate method determined by the Ad-
ministrator to satisfy the applicable re-
quirements of this part shall be approved
for nationwide use to satisfy the require-
ments of this subchapter; alternate test
procedures determined by the Adminis-
trator not to meet the applicable require-
ments of 'this part shall be rejected.
Notice of these determinations shall be
submitted for publication in the FEDERAL
REGISTER not later than 15 days after
such notification and determination is
made.
[FR Doc.76-35032 Filed 11-30-76:8:45 am]
FEDERAL REGISTER, VOL 41, NO. 232—WEDNESDAY. DECEMBE1 1, 1976
D-334
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3306 RULES AND REGULATIONS
Title 40—Protection of Environment
CHAPTER I—ENVIRONMENTAL
PROTECTION AGENCY
SUBCHAPTER O—WATER PROGRAMS
PART 136—GUIDELINES ESTABLISHING
TEST PROCEDURES FOR THE ANAL-
YSIS OF POLLUTANTS
Amendment of Regulations; Corrections
In FR Doc. 76-35032 appearing at
pages 52780 to 52786 in the FEDERAL REG-
ISTER of Wednesday, December 1. 1976,
the following chances should be made1
§ 1.1S.3 IAmondo.il
I. On Page 52783. for parameter num-
ber 62. Nickel—Total, add "232" to the
page references in the column under the
14th edition of Standard Methods op-
posite the colortmetrlc method designa-
tion.
2. On page 52784, for parameter num-
ber 89. change the parameter designa-
tion from "Nitrate" to "Nitrite."
3. On page 52784, for parameter num-
ber 96. Phenols, delete the present meth-
od designation, "Colorimetric, <4AAP>."
and replace it with the method designa-
tion. "Distillation followed by colorimet-
rlc, (4AAP)"; delete the page reference
In the column under the 14th edition of
Standard Methods, "582," and replace
it with page number "574".
Dated. January 10.1977.
WILSON K. TALLEY.
Assistant Administrator for
Research and Development.
(FR Doc.77-1463 Filed 1-17-77:8:45 am)
FEDERAL REGISTER. VOL 4J, NO. 17—TUESDAY. JANUARY 18, 1977
I)-335
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