VARIAN

INSTRUMENTS
AT WORK
ATOMIC ABSORPTION

Determination of the Priority Pollutant Number AA-34

September 1983
Metals — Regulations and Methodology
Lucinda M. Voth,
Varian AA Resource Center, Park Ridge, IL. U.S.A.

Introduction TABLE I
With the realization that industrial man introduces
potentially hazardous substances into the
environment, there has been increasing concern over
the potentially detrimental effects of man-generated
pollution. Metals are a unique environmental and
industrial pollutant in that they are found naturally
distributed in all phases of the environment. They are
not created by man, but through industrial processes
they are transported, concentrated, and transformed
into various products. Often this results in human
exposure to much higher concentrations or different
chemical forms than those naturally present in the
environment. The Primary Drinking Water Regulations were
Various federal and state agencies, and private sector established to protect public health, but secondary
industrial and academic research participants have regulations were proposed to control such qualities as
co-operated in studies describing the source, taste, color, and odor. The Secondary Drinking Water
magnitude, distribution, and environmental and Standards include the regulation of four other metals,
toxicological impact of trace metal pollutants, as well listed with maximum allowable concentrations in
as consideration of natural sources of trace metal Table II1.
concentrations. These agencies, one being the U.S.
Environmental Protection Agency (EPA), have been TABLE II
legislatively assigned the difficult task of designating
maximum allowable concentration levels as well as the
regulation of industrial pollution at those levels.

Drinking Water Regulations

A main area of concern was the safety of public
drinking water. Under the directives of the Safe
Drinking Water Act of 1974, the EPA initiated the
National Interim Primary Drinking Water Regulations Though the Primary and Secondary Drinking Water
(NIPDWR) in 1975. Primary Drinking Water Standards Standards do not include regulation of sodium at this
were established for the regulation of eight metals, as time, the EPA has recommended that states voluntarily
listed with maximum allowable concentrations in establish programs for regular monitoring of sodium
Table I1. levels in public drinking water. Proposed amendments
to the Safe Drinking Water Act establish guidelines for
sodium concentrations. With this information,
consumers who must restrict dietary consumption of
sodium could if necessary make adjustments to their
diets or seek alternate sources of drinking water when
certain levels are exceeded. With evidences that pollutant limitations. Under the NPDES program each
excessive intake of sodium contributes to increased state then has the authority to issue permits for
blood pressure and to hypertension in susceptible “point-source”* discharges provided that the
people, the EPA has recommended a maximum level discharger meets the established federal effluent
of 20 mg/L for public drinking water2. limitations and toxic pollutant limitations1.
The EPA was unable to promulgate many of the
Effluent Regulations regulations set forth in the FWPCA Amendments of
A second area of concern was control of water 1972 in the time specified. Subsequently, in 1976, four
pollution through the regulation of industrial effluents. suits, brought against the EPA by various
Legislative concerns over water pollution resulted in environmental groups, were filed to force the agency to
the passage of the original Federal Water Pollution establish regulations that would assure that water
Control Act (FWPCA) in 1948. This act and its quality goals would be met. According to the
numerous more recent amendments are often referred court-upheld “Consent Decree” Settlement
to as the Clean Water Act (CWA). Originally, regulatory Agreement, the EPA agreed to develop and adhere to
responsibility for pollution control belonged to the a scheduled program to establish and enforce BAT
Department of Health, Education and Welfare (HEW), effluent limitations, pre-treatment standards,** and
but was transferred to the Department of the Interior in new source performance standards (NSPS)*** for 65
1966. The EPA was formed in 1970, at which time it “priority” pollutants and classes of pollutants. Thirteen
took on the responsibilities for water pollution control of these are metals and their compounds3. In
previously held by the Department of Interior. Since accordance with the Settlement Agreement, 21
that time, with subsequent amendments to the industries (or point source categories) would be
FWPCA, additional federal programs have been addressed by these standards.
created to meet water quality goals1.
The Federal Water Pollution Control Act Amendments
of 1972 established a comprehensive program to
restore the quality of the nation’s waterways. Its goals
were to make U.S. waterways fishable and swimmable
by 1983 and to eliminate the discharge of all toxic and
harmful pollutants by 1985. The task of the EPA was to
develop regulations to meet the provisions of this act
and then monitor and enforce those regulations. In
order to meet established effluent limitations, industry
would be required to apply various levels of water
pollution control technology. By July 1, 1977, existing
dischargers were to achieve established effluent
limitations requiring the application of the best practical
pollution control technology (BPT). By July 1, 1983,
dischargers were to achieve established effluent
limitations requiring the application of the best
available technology economically achievable (BAT) to
progress reasonably to the national goal of zero
discharge of pollutants..
In addition to establishing guidelines for effluent
reductions attainable by various levels of technology
(BPT and BAT), the EPA also established effluent * There are over forty point-source categories addressed by effluent
limitations for toxic pollutants applicable to all standards. A few include — electroplating, inorganic chemicals
manufacturing, petroleum refining, iron and steel manufacturing,
dischargers3. Nine compounds were designated as paint formulation, plastics and synthetics, grain mills, et al. Among
toxic pollutants including 2 metals — cadmium and the effluent pollutant regulated, up to 35 different metal pollutants
mercury1. may be addressed by NPDES permits for various industries.
Additional industries are regulated at this time by various other
The regulations for direct dischargers were federal regulations1 .
incorporated into the National Pollutant Discharge ** Pretreatment standards for existing sources and new sources
Elimination System (NPDES) which was established (PSES and PSNS) were established to protect publicly owned
as the main regulatory system for water pollution treatment works (POTW). They apply to waste streams sent to
control. The EPA has required each state to establish POTW for final treatment and provide protections from materials that
might harm the treatment facilities or remain untreated1.
water quality standards that meet or exceed federal *** NSPS — New Source performance standards apply to effluent
water quality standards. These standards provide the sources where construction began after promulgation of regulations
basis for source-specific effluent limitations and toxic setting standards for that point source category.

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The Clean Water Act of 1977 incorporated several of decentralization of rigid federal regulations of
the components of the “Consent Decree” Settlement treatment facilities5. Meanwhile the EPA’s Effluent
Agreement. This act required that, by July 1, 1984, Guidelines Division in Washington D.C. continues to
effluent limitations requiring the application of BAT be propose effluent regulations and has established dates
achieved for toxic pollutants, including 65 “priority” for final promulgations of BAT standards for various
pollutants and classes of pollutants3. Other provisions industries. Within a specified period NPDES permits
of the act include a provision that if a POTW removes will reflect the new BAT standards.
all or some of a toxic pollutant, the owner of the POTW
may adjust the standards applied to the discharger to Hazardous Waste Regulations
reflect the final treatment of the POTW. Also in A third area of concern was the regulation of pollution
accordance with this act the EPA is required to from liquid and solid waste. The Resource
establish, by July 1, 1984, limitations for conventional Conservation and Recovery Act (RCRA) of 1978 is the
pollutant control technology available (BCT)*. it is legislative basis for guidelines for the regulation of
intended that BCT guidelines replace the more pollution of groundwater, surface water, and ambient
stringent and often more costly BAT guidelines for air from solid waste. For nonhazardous waste, the EPA
conventional pollutants after cost and benefit studies, has established that waste disposal is primarily a local
but that BAT guidelines would remain in effect for toxic problem and has established guidelines to assist the
pollutants. Essentially, with the Clean Water Act of states in making regulations to protect groundwater
1977, BAT has become the main source of and surface water from pollution by liquid and sold
establishing effluent pollution limitations. waste. The guidelines include consideration of
It considers both industrial process controls as well as environmentally sensitive areas, air quality, food chain
end line treatment techniques applied by separate crops, diseases, and safety. Through a series of steps
treatment facilities. It is meant to establish criteria over several years the states are required to survey
based on the application of the highest degree of and evaluate existing disposal sites, and while
technological pollution control that is feasible and following federal criteria, develop and periodically
affordable to the industry4. review solid waste regulation plans within a specific
In summary, the EPA has required industry to control period following the final promulgation of federal
effluent pollution through various regulations. Industry criteria. Federal guidelines will include criteria for
must monitor effluent discharges and not exceed design and operation of landfills, leachate control, gas
specified pollutant levels set by NPDES permits. migration control, and groundwater monitoring as well
NPDES permit levels are established on the basis of as guidelines for landspreading and surface
BPT, BAT, and NSPS guidelines. Pretreatment impoundment of solid wastes4.
standards apply for effluents to be treated at separate The EPA’s main concern is the disposal of hazardous
treatment facilities (POTW). For some point-source waste, and extensive regulations have been
dischargers the NPDES permits are in the process of promulgated to control the disposal of hazardous
review, as BAT guidelines replace the earlier BPT waste. They include control from the point of
guidelines. Originally, the EPA was to promulgate all generation through transportation, storage, and final
major BAT standards by March 1984. Recently the disposal. The regulations apply to specific substances
EPA has proposed to extend the deadline for final that are not related to any particular industry. At this
industrial compliance of BAT standards to July 1, 1988, time, wastes that are corrosive, reactive, ignitable, or
considering the current July 1, 1984 deadline toxic are considered hazardous. But the EPA has
unobtainable. Other proposals include changes in proposed that other criteria such as radioactivity,
pretreatment plant regulations, specifically less infectiousness and mutagenicity, also be used to
stringent federal control if local governments have the determine what constitutes a hazardous waste1.
ability to regulate well run local waste treatment plants.
A series of test procedures is being developed to
Industry would like to see provisions for modifying the
define a hazardous waste. One such test is the
stringent BAT requirements if current controls or Extraction Procedure Toxicity Test. The EP Toxicity
modified BAT controls meet water quality criteria.
test was designed to simulate the leaching process in
These controversial proposals have been strongly an improperly designed sanitary landfill. It considers
objected to by environmental groups, particularly the toxic constituents that under these conditions would
NRDC (National Resources Defense Council). It tend to migrate. This test involves an acid extraction
remains to be seen whether there will be any procedure in which the representative waste sample is
modification in the regulations of BAT standards or any extracted with distilled water maintained at a pH of 5
with acetic acid. If a representative sample contains
greater than 0.5% solids it is filtered. The filtrate is
saved for later analysis and the solid portion is
* Does not apply to metals but to pH, suspended solids, BOD, COD,
fecal coliform, oil and grease. subjected to the acetic acid extraction. If the sample

3
contains less than 0.5% filterable solids the filtrate is At this time, these values are 100 times the National
acidifed with acetic acid and analyzed. The solids Interim Drinking Water Standards, but will change with
portion is discarded. A more detailed flow chart is revisions of the drinking water standards1. Also,
shown in Figure 1. This flow chart and instructions for proposals have been presented for a distinction to be
made between the different valence states of
chromium, specifically Cr+6 and Cr+3, due to differing
toxicities and different migration potentials. There is
substantial evidence that hexavalent chromium
compounds are carcinogenic in man. Studies with
trivalent chromium did not show serious mutagenic
potential, in fact trivalent chromium has been shown to
have a nutritional function. Also, trivalent chromium
salts are virtually insoluble as well as strongly
absorbed by inorganic and organic soil materials and
therefore have significantly lower migration potentials
from a waste disposal area. This is not true for highly
soluble hexavalent chromium which can leach out into
groundwater. Though this information was known
when the present regulations were promulgated there
was concern that trivalent chromium would oxidize to
the hexavalent form under waste management
conditions. Studies indicate that this is unlikely to occur
under most waste management systems. But the
chlorination treatment of public drinking water may
result in the oxidation of trivalent chromium. This is
already reflected in the drinking water level. Chromium
will remain a toxic pollutant and no changes will be
made in drinking water levels7.
The proposal to amend the characteristic of EP toxicity
to include just hexavalent chromium rather than total
chromium requires that there be an analytical method
to distinguish between the two oxidation states. A
Figure 1. method has been developed and is based on the
Extraction Procedure Flowchart separation of hexavalent chromium from solution by
coprecipitation of lead ch.romate with lead sulphate
the extraction procedure and methods of analysis can under a controlled pH of 3.5. The precipitate is
be obtained in the US EPA Office of Water and Waste resolubilized in nitric acid and analyzed by atomic
Management publication “Test Methods for Evaluating absorption methods. Trivalent chromium does not
Solid Waste”6. The EP toxicity test included analysis of precipitate under these conditions. This method is
specific trace elements, pesticides and herbicides. being evaluated in various industrial wastes and EP
Considering just trace elements, if the values listed in extracts. It is expected that the proposal to amend the
Table III are exceeded, the waste exhibits a characteristic of EP Toxicity for hexavalent chromium
characteristic of EP toxicity and is considered will be promulgated after adequate supportive data is
hazardous6. obtained7.
In summary, it is the responsibility of the waste
TABLE III generator to determine whether the waste produced is
hazardous. If sufficient quantities of hazardous waste
are produced he is responsible for proper disposal
according to strict regulatory requirements*. A permit is
required for both on-site waste management and

* At this time low-volume waste procedures, those generating less

than one ton of hazardous waste per month, are not required to
comply with the full RCRA regulations. They are allowed to treat or
dispose of their wastes on site or send them to an EPA-approved
treatment facility. Recently, it has been proposed that this
exemption be lowered or eliminated.

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transportation to another site for disposal. Proposed TABLE IV — SUMMARY OF AA METHODS
regulations contain strict requirements for operation of
hazardous waste facilities and long-term monitoring of
ground and surface water for contamination. It has
been suggested that hazardous waste permits be
integrated into the NPDES system. The NPDES
system, operated at the state level, would be required
to promulgate regulations to meet federal
requirements. These regulations would have to be
approved by the EPA, but if the states were unable to
enforce the regulations, control of hazardous waste
would revert back to the EPA1.

Summary of AA Analysis Methods

Atomic absorption methods are recommended for the
determination of metal concentrations, being relatively
simple, rapid, and applicable to various types of water
and waste samples from drinking water to industrial
sludges. Drinking water can usually be analyzed
directly, waste water may require pretreatment to
solubilize suspended material, and sludges or samples
with solid portions may require some type of acid
digestion or acid extraction prior to analysis.
Most of the concentrations used to determine
“Characteristic of EP Toxicity” (listed in Table III) can
be determined by flame atomic absorption techniques,
but analysis at the very low concentrations
encountered in the determination of drinking water
levels and NPDES permit levels may be difficult if not
impossible by flame atomic absorption. Therefore, the
more sensitive graphite furnace techniques are part of
approved EPA methodology. Other approved methods
of analysis include pre-concentration by
chelation-extraction procedures, the gaseous hydride
method for arsenic and selenium, and the cold vapor
technique for mercury. Colorimetric methods have also
been approved for some elements. Other instrumental
techniques such as emission spectroscopy*, x-ray
fluorescence, and anodic stripping are considered as be preferable to determine the arsenic and selenium by
alternate test procedures and must be approved prior the more sensitive hydride generation method or
to their use8. Table IV summarizes atomic absorption furnace techniques. If concentrations lower than the
methods for the determination of pollutant metal maximum allowable need to be accurately quantitated
concentrations at levels established by the National the more sensitive furnace techniques may also be
Interim Primary and Secondary Drinking Water needed for the other elements.
Standards. Up to 35 different metals may be regulated at various
For hazardous waste regulations the maximum levels according to individual NPDES permits. Thirteen
concentrations for “Characteristic of EP Toxicity” listed of these are designed as “priority pollutants” (Sb, As,
in Table III can be determined by flame atomic Be, Cd, Cr, Cu, Pb, Hg, Ni, Se, Ag, Tl, and Zn). The
absorption except for mercury which would be NPDES permit levels are based on the federal BAT
determined by the cold vapor technique. Depending on pollution standards. These standards were established
the sensitivity of the AA spectrophotometer used it may with consideration of the pollutant toxicity, persistence
or degradability, effect on organisms in the receiving
body of water, the importance of the particular
organism, and a reasonable safety margin. The federal
* ICP methods of analysis are currently awaiting formal approval for
water criteria vary by the water type (domestic water
NPDES monitoring. At that time alternate analytical test data supply, irrigation water, freshwater aquatic, marine
showing comparability of results to a currently approved method aquatic, etc.), but the maximum allowable effluent
will not be required9. levels can be as stringent as the drinking water

5
standards, particularly since the total pollutant furnace can also be a source of contamination. They
discharge over long periods of time is considered. can be cleaned by soaking in 1:5 HNO3 followed by
Therefore, determinations of the 13 priority pollutants thorough rinsing with deionized water. The analyst
required to meet NPDES permit levels are often in the should protect the sample from laboratory dust,
µg/L range requiring the most sensitive AA techniques. another source of contamination. A reagent blank
should always be prepared and treated to the same
Sample Collection and Storage procedures as the sample. Reagent blank
concentrations should be subtracted from sample
Prior to sampling the analyst should determine the type
concentration results8.
of data required — dissolved metals, suspended
metals, total concentration or extractable metals.
(NPDES permits usually require total metal Analysis Requirements
concentration). Before developing an atomic absorption analysis
1. Dissolved Metals — Sample is filtered through a method the analyst should decide on the degree of
0.45 µ membrane filter as soon as possible accuracy and precision required. If the analysis is to
following collection. The filtrate is acidified with 1:1 satisfy a regulatory requirement, must he only show
NHO3 to a pH of 2 and analyzed. that the concentration is below a fixed level or must he
quantitate lower levels of the analyte?
2. Suspended Metals — Sample is filtered through a
0.45 µ membrane filter. The volume is recorded The degree of precision required must also be
and the suspended metal concentration is determined—plus or minus 100% or plus or minus
calculated from the determination of the metal 0.1%. The maximum precision obtainable will depend
concentration on the membrane filter following an on the method of analysis and the concentration level
acid digestion. of the determination. The concentration range of the
samples will determine the instrumental techniques as
3. Total Metals — The entire, unfiltered sample is
well as measurement methods. The determinations of
acidified at time of collection to a pH of 2 with 1:1
high concentrations often require a reduction of
NHO3 acid. A representative aliquot is taken and
instrument sensitivity, but determinations near the
treated to an acid digest prior to analysis.
detection limit require careful instrument optimization
4. Extractable Metals — The entire sample is heated and the calculated mean of numerous readings.
with HCl and HNO3 acid and after a specified time Alternately, a more sensitive technique may be used.
and temperature the sample is filtered and
To help the analyst maintain analytical accuracy, the
analyzed.
EPA has established quality control guidelines. The
Detailed instructions for these procedures can be minimum quality control requirements for the analysis
obtained from the US EPA publications “Methods for of drinking water (NIPDWR) by atomic absorption
Chemical Analysis of Water and Wastes”8. include:8
Solutions to be analyzed for trace metals can be 1. All quality control data must be recorded and easily
collected and stored in glass or hard plastic. All liquid available for inspection.
samples should be acidified to a pH of 2 with 1:1
2. Once a year a performance standard must be
HNO3. The acidified samples can be stored for up to 6
months, except for Hg which should be analyzed within analyzed and the results must be within a control
38 days if stored in glass or within 13 days if stored in limit. If not, corrective action must be taken and a
plastic8. follow-up performance standard must be analyzed.
For the determination of trace metals, contamination is The following requirements must be met daily:
a major source of analytical error. There is potential 1. Calibration curves must be prepared for a reagent
contamination from trace metal impurities in reagents blank and a minimum of three standards.
and from laboratory glassware and containers which Subsequent calibrations must be verified by at
come in contact with the sample. As well as positive least a reagent blank and a standard at or near the
error due to contamination, containers can introduce maximum allowable concentration level. The
negative errors by adsorption of metal cations onto the standard check must be within ± 10% of the
surface of the container. Thus the proper treatment of original calibration,
all apparatus and glassware used in the collection and 2. If more than 20 samples are analyzed per day the
treatment of the sample is of the utmost importance. calibration curve must be verified by running an
Sample containers should be thoroughly washed with additional standard at or near the maximum
a laboratory detergent and tap water, rinsed with nitric allowable concentration level every 20 samples.
acid, and thoroughly rinsed with deionized-distilled The standard check must be within ± 10% of the
water. Any glassware used during the analysis should original calibration.
be cleaned in the same manner. Pipette tips used in Based on knowledge of the regulatory requirements for
manual dispensement of samples in the graphite his particular industry, the analyst can select the proper

6
instrumental method. With the skilful applications of
laboratory and instrumental techniques and quality
control procedures he can obtain accurate and precise
answers satisfying federal and state requirements for
regulated pollutant metals.

References
1. U.S. EPA, A Handbook of Key Federal
Regulations and Criteria for Multimedia
Environmental Control, EPA-600/7-79-175 (1979).
2. U.S. EPA, “Drinking Water
Regulations-Amendments”, Federal Register, 44
(140), 42250 (1979).
3. U.S. EPA, Federal Register, 44 (247), 75927
(1979).
4. Cross, Frank, “Update: Effluent Limitations
Guidelines”, Pollution Engineering, p. 41 (Sept.
1980).
5. Hanson, David, “Proposed Changes to Clean
Water Act Debated”, Chemical and Engineering
News, 60 (32), 14 (1982).
6. U.S. EPA, Test Methods for Evaluation of Solid
Waste, Physical/Chemical Methods, SW-646
(1980).
7. U.S. EPA, “Hazardous Waste Management
Systems”, Federal Register, 45 (212), 72029
(1979).
8. U.S. EPA, Methods for Chemical Analysis of Water
and Wastes, EPA-600/4-79-020 (1979).
9. Kopp, J., Martin, T., “Trace
Elements-Methodology, and Legislation”, ASTM
Standardization News, p. 18 (Feb. 1983).
This publication is intended as a general reference
source only. Although it was compiled from sources
believed to be reliable and the most current, Varian
Associates, Incorporated disclaims any and all
expressed or implied representation as to the absolute
correctness of sufficiency of the information contained
herein. Those using this information do so at their own
risk and assume any and all liability resulting
therefrom.