£EPA
United States
Environmental Protection
Agency
Environmental Monitoring and Support EPA-600/7-78-085
Laboratory May 1978
Cincinnati OH 45268
Research and Development
Investigation of
Matrix Interferences
for AAS Trace
Metal Analyses of
Sediments
nteragency
Energy/Environment
R&D Program
Report
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from the
effort funded under the 17-agency Federal Energy/Environment Research and
Development Program. These studies relate to EPA's mission to protect the public
health and welfare from adverse effects of pollutants associated with energy sys-
tems. The goal of the Program is to assure the rapid development of domestic
energy supplies in an environmentally-compatible manner by providing the nec-
essary environmental data and control technology. Investigations include analy-
ses of the transport of energy-related pollutants and their health and ecological
effects; assessments of, and development of, control technologies for energy
systems; and integrated assessments of a wide range of energy-related environ-
mental issues.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/7-78-085
May 1978
INVESTIGATION OF MATRIX INTERFERENCES
FOR AAS TRACE METAL ANALYSES OF SEDIMENTS
by
Mary M. McKown
Charles R. Tschrin
Patty P.F. Lee
Gulf South Research Institute
New Orleans, Louisiana 70186
EPA Grant No. R 804317-01
Project Officer
John F. Kopp
Physics and Chemistry Methods Branch
Environmental Monitoring and Support Laboratory
Cincinnati, Ohio 45268
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Environmental Monitoring and Support
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recommendation for use.
11
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FOREWORD
Environmental measurements are required to determine the quality of am-
bient waters and the character of waste effluents. The Environmental Moni-
toring and Support Laboratory-Cincinnati conducts research to:
°Develop and evaluate techniques to measure the presence and
concentration of physical, chemical, and radiological solid
waste.
""Investigate methods for the concentration, recovery, and
identification of viruses, bacteria, and other microbio-
logical organisms in water. Conduct studies to determine
the responses of aquatic organisms to water quality.
"Conduct an Agency-wide quality assurance program to
assure standardization and quality control of systems
for monitoring water and wastewater.
The standard methods for analysis of water and waste samples are under
continual review to assure that the most accurate results possible are ob-
tained. If a chemical interference in an important analytical procedure is
discovered it must be evaluated and, if necessary, a procedural modification
made to circumvent the interference. This report investigates the inter-
ference of sediment matrices on trace metal analyses by atomic absorption
spectrophotometry.
Dwight G. Ballinger
Director
Environmental Monitoring and Support
Laboratory
iii
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ABSTRACT
This research program was initiated with the overall objective of devel-
oping reliable, cost-effective methods utilizing flame atomic absorption
spectrophotometry (AAS) for the trace elemental analysis of soil and sediment
samples containing complex matrices. The soil sample matrix studied con-
sisted of more than 0.1 percent aluminum and iron; the sediment sample
matrix contained more than 0.1 percent aluminum and iron plus lesser
quantities of calcium, magnesium, manganese, phosphate, and potassium.
Conventional flame AAS methods were found to produce accurate results
for the analyses of cobalt, copper, lead, manganese, nickel, and zinc in these
matrices. The barium, calcium, strontium, and vanadium content of these
samples could not be accurately determined by conventional flame AAS tech-
niques. However, reliable results were obtained using appropriate flame types
with the addition of lanthanum and/or an easily ionizable alkali salt to all
samples and standards. Interferences present in the analyses of beryllium,
chromium, and titanium were difficult to correct in samples containing large
concentrations of interfering matrix constituents. The use of matrix-matched
standards was recommended for samples of this type. The analysis of selenium
was performed using a nitrous oxide-acetylene flame. However, the detection
limit obtained wj.th this technique may not be sufficient for many applications
because small concentrations of selenium are very toxic. Direct AAS analysis
of selenium using lower-temperature flame types was affected by interferences
that were not corrected by those techniques chosen for investigation. Cor-
rection of these interferences was therefore beyond the scope of this research
effort.
Procedures used in this research should be applicable to all environmen-
tal samples containing similar matrices. Information provided in this report
will permit adaptation of these techniques to samples other than those examined
here.
This report is submitted in fulfillment of Grant No. R 804317-01 by
Gulf South Research Institute under the sponsorship of the U.S. Environmen-
tal Protection Agency. This report covers the period April 1, 1976, to
November 30, 1977; work was completed on September 30, 1977.
iv
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CONTENTS
Foreword ill
Abstract iv
1. Introduction 1
2. Conclusions and Recommendations 2
3. Sample Collection 4
Site selection 4
Collection of samples 6
4. Experimental Procedures 7
Glassware cleaning 7
Reagents and standards 7
Apparatus 7
Sample preparation 7
Quality control 8
5. Results and Discussion 9
Initial analyses 9
Interference study 10
Final analyses 21
Quality control procedures 21
6. Figures and Tables 24
References 129
v
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SECTION 1
INTRODUCTION
The emphasis of this research was to develop accurate, cost-effective
flame atomic absorption spectrophotometric (AAS) methods for the analysis of
trace metals in complex matrices. Bottom sediment subjected to acid mine
drainage and soil receiving fallout from a coal-fired power plant were
employed for this investigation.
Because the production and usage of energy from coal, gas, and oil
are major sources of trace metal pollution, the current energy crisis
has meant increased emphasis on environmental monitoring. Trace metal
concentrations in environmental samples must be accurately determined to
assess the toxic effects of these contaminants. The speed with which
these analyses can be performed is an important factor in the selection
of analytical methods since the effectiveness of environmental monitoring
is lessened by elaborate, time-consuming analytical protocols.
Flame AAS has been widely employed for the analysis of trace metals in
environmental samples. Despite the speed and accuracy of this method, signif-
icant errors result when AAS is applied to the analysis of samples such as
sediment and soil that involve complicated matrices. This report presents
methods for the detection and treatment of interferences resulting from
matrix constituents in soil and sediment affected by the production and
use of coal.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
Reliable, cost-effective methods utilizing flame atomic absorption
spectrophotometry (AAS) were developed for the trace elemental analysis of
soil and sediment samples containing complex matrices. One matrix studied
included aluminum and iron; the second matrix contained large concen-
trations of aluminum and iron plus lesser quantities of calcium, mag-
nesium, manganese, phosphate, and potassium.
Conventional flame AAS methods produced accurate results for the anal-
yses of cobalt, copper, lead, manganese, nickel, and zinc in these matrices.
The barium, calcium, strontium, and vanadium content of these samples could
not be accurately determined by conventional flame AAS techniques; however,
reliable results were obtained using appropriate flame types with the addition
of lanthanum and/or an easily ionizable alkali salt to all samples and
standards. Interferences present in the analyses of beryllium, chromium, and
titanium were difficult to correct for samples containing large concentrations
of interfering matrix constituents. The use of matrix-matched standards was
recommended for samples of this type. The analysis of selenium is common-
ly performed using a nitrous oxide-acetylene flame. However, the detection
limit obtained using this technique may not be sufficient for most applications
since small concentrations of selenium are very toxic, Direct AAS analy-
sis of selenium using alternate flame types involved interferences that
were not corrected by those techniques selected for investigation and were
therefore beyond the scope of this research effort.
Procedures used in this research should be applicable to all environ-
mental samples containing similar matrices. Information provided in this
report will permit adaptation of these AAS techniques to samples other
than those examined here.
Trace metal contamination is a major concern in many areas of environ-
mental control other than coal production and consumption. Because environ-
mental samples usually contain complicated matrices that vary widely in
composition, the analysis of samples containing a large variety of matrix
components should be investigated for a diverse number of trace elements. A
broad knowledge of the control of interferences involved in the analysis of
trace metals by AAS is essential for the accurate assessment of environmen-
tal abuse.
The analysis of arsenic and selenium in environmental samples is of
particular importance; the extreme toxicity of these elements makes accurate
detection of small concentrations imperative. Reliable methods of sufficient
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sensitivity are not presently available for the analysis of arsenic and
selenium by direct flame AAS. Alternative methods with adequate sensitivi-
ties are time consuming. More sensitive, time-saving methods should be
sought for these analyses.
Investigation of methods of trace element extraction from soil and
sediment samples was not within the scope of this research. However,
the efficiency and reproducibility of the sample preparation procedure
is essential to the reliability of the final result. Research in this
area should be continued.
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SECTION 3
SAMPLE COLLECTION
The samples acquired for this research were selected from two different
environmental situations. One sample set consisted of bottom sediment
affected by acid drainage from coal mines. The second group was soil sam-
ples subjected to exposure to fallout from a coal-fired power plant.
Background samples were collected for each sampling site to assist in
evaluation of the results.
SITE SELECTION
Sediment Affected by Acid Mine Drainage
Selection of a sampling site influenced by acid mine drainage was
accomplished with the aid of the Region III Wheeling Field Office of the U.S.
Environmental Protection Agency, Wheeling, West Virginia. The sampling
operation was supervised by Roland W. Schrecongost, Director, and Scott C.
McPhilliamy, Environmentalist.
The sampling program outlined in the proposal was modified to reduce the
cost and effort required to obtain the samples. The Kiskiminetas was recom-
mended as a potential primary river, with the Allegheny serving as a secondary
stream. Mr. Schrecongost and his staff of the Wheeling Field Office evaluated
this system and others applicable to the study. The Kiskiminetas River is a
primary stream receiving nearly 26,000 kg (58,000 Ib) of acid per day from
coal mining activities. The Allegheny is of good water quality upstream of
the Kiskiminetas and would serve as a suitable background area.
The second area evaluated for sampling was Toby Creek and the main
stream Clarion River in Pennsylvania. Toby Creek qualifies as a primary stream
since this stream is mineralized and acidic under all conditions. The quality
of the Clarion River has deteriorated due to the influx of acid mine drainage
from Toby Creek. The background sampling area for this system is the
Clarion River above Toby Creek, which is only slightly affected by acid mine
drainage. The Wheeling Field Office recommended selection of the Toby
Creek/Clarion River water system since samples could be procured easily.
Highway bridges, footbridges, and ponds exist along the waterways and would
facilitate sampling at several points.
A total of 17 sample collection points was selected for the Toby
figures and tables mentioned in the text are included in Section 6.
4
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Creek/Clarion River system. The map in Figure 1* specifies the location of
these sites, which were sampled the week of June 14, 1976. A left bank
sample, a right bank sample, and a midstream sample were taken at each site.
The background samples are numbered 1 through 5, the primary stream samples
are numbered 6 through 10, and the secondary stream samples, 11 through 17.
The samples taken at site 13 did not include a midstream location since the
bottom was solid rock. A list of sample designations and sampling locations
is given in Table 1. The prefix "PA" (Pennsylvania) was added to each site
number to simplify identification. U.S. Geological Survey topological maps
showing the exact location of each sampling site were forwarded to Gulf
South Research Institute by the EPA Wheeling Office. Specific locations
for each of the 17 sampling sites are shown in Figures 2 through 8.
Soil Samples Affected by Coal Combustion
The second group of samples acquired represented soil exposed to the
effects of coal combustion. Plant Jack Watson in Gulfport, Mississippi, is
one of the few power plants in proximity to New Orleans that use coal as an
energy source. GSRI contacted Southern Services Company, the parent company
of the Mississippi Power Company, for permission to obtain the required
number of soil samples. These efforts were aided by Larry D. McNair,
the resident environmentalist for Southern Services, who was conducting a
study at Plant Jack Watson. Mr. McNair offered to act as intermediary for
GSRI and accompanied the GSRI sampling team to Plant Jack Watson.
The emission stack at the plant is 93 m (305 ft) high and is equipped
with an electrostatic precipitator which, according to Mr. McNair, is very
efficient. However, the dispersion pattern of fallout from the stack has
not been determined, and the current study is not of sufficient magnitude to
obtain information of this type.
A good indication of the geography of the land surrounding this power
plant can be obtained from Figure 9, which is a reproduction of an infrared
photograph.* The area on the eastern side of the plant is primarily marsh-
land and would present the greatest sampling difficulty. In addition, the
presence of a small number of housing developments on the east side indicates
that the area has been disturbed and therefore is unsuitable for sampling.
The area west of the plant is both industrialized and residential. Several
industries, including a creosote plant, a weld-fabricating facility, and a
chemical plant, are located in this vicinity. Because the soil samples
preferred for this study are those that have not been affected by other in-
dustrial concerns, this area was also avoided.
Farmland and residences are located directly north of Plant Jack Watson.
Interstate 1Q lies approximately one-half mile north of the plant. The
sampling site was chosen north of the interstate since this area is in
proximity to the coal combustion process, is easily accessible to the sampling
team, and is removed from the close-range effects of other industrial
effluents. A topographic map illustrating the 14 selected sample sites and
*Maps and photograph supplied to GSRI through the courtesy of Mr. McNair of
Southern Services Company.
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Plant Jack Watson is presented as Figure 10.
Six additional samples of the same soil type were collected to provide
background measurements for these 14 samples. Areas along Interstate 10
between Gulfport, Mississippi, and the Mississippi state line that were
removed from industrial activity were selected as collection sites and are
indicated on the map in Figure 11. The areas immediately adjacent to the
interstate were not sampled since these areas are disturbed land masses. A
complete list of the sampling locations for these 20 samples is given in
Table 2. The prefix GP was used to indicate the samples were from the
Gulfport sampling site.
COLLECTION OF SAMPLES
One-liter polyethylene wide-mouth jars with linerless caps were prepared
for sample collection. The bottles were washed with detergent, thoroughly
rinsed, and washed in 1:1 nitric acid and 1:1 hot hydrochloric acid. Each
acid wash was followed by thorough rinsing with deionized, distilled water.
A total of 51 empty sample containers and 2 shipping blanks was
sent to the Wheeling Field Office for the sediment (PA) sample collection. The
shipping blanks were returned intact with the samples. The GSRI sampling
team collected 20 soil samples from the Gulfport, Mississippi, area in
identically cleaned containers and carried a designated shipping blank
throughout the entire procedure.
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SECTION 4
EXPERIMENTAL PROCEDURES
GLASSWARE CLEANING
All glassware used in sample preparation and analysis was washed with
detergent, a solution of 1:1 nitric acid, and a hot solution of 1:1 hydrochloric
acid. Each item was thoroughly rinsed between washings with deionized,
distilled water. This rigorous cleaning procedure eliminated significant
contamination from the glassware.
REAGENTS AND STANDARDS
All chemicals and reagents employed were of reagent grade or better.
Standards used in AAS analyses were prepared daily from standard stock solu-
tions (1000 ppm metal) purchased from Ventron Corporation, Beverly, Massachu-
setts. Sodium chloride and potassium chloride used throughout the study were
recrystallized to remove trace metal contamination. Aluminum, calcium, magne-
sium, manganese, lanthanum, and phosphate used in the study of matrix inter-
ferences were obtained as the following compounds: A1C1,, CaCl -2H-0, MgCl9,
MnCl2, La(N03)3-6H20, and H3P04<
APPARATUS
Atomic absorption spectrophometric analyses were performed using a
Perkin-Elmer model 306 AAS instrument equipped with a Perkin-Elmer model 56
recorder. A 3-slot, 10-cm (4-inch) burner was employed for all analyses
requiring an air-acetylene flame, except that for nickel analysis. A single-
slot, 10-cm (4-inch) burner head was used for the nickel analysis. Those
analyses utilizing a nitrous oxide-acetylene flame were performed with a
conventional 5-cm (2-inch) nitrous oxide burner head. Flame conditions
employed for the initial analyses of the sediment and soil samples were
selected from the Perkin-Elmer AAS manual.
SAMPLE PREPARATION
Preparation of the soils and sediments was initiated immediately upon
receipt of the samples. All samples were thoroughly mixed to insure homo-
geneity. After mixing, the samples were dried to a constant weight in a
1Q5°C oven so that results could be reported on a dry-weight basis. The
samples were then ground in mortars, mixed again, and redried. These ground
samples were transferred to sterile Whirlpack bags and refrigerated until
needed for further sample preparation.
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The partial digestion procedure recommended by EPA for analysis of
sediments was selected for these analyses. Details of the procedure are
provided in the Appendix. Experience with the analysis of soil and sediment
led to the adoption of some modifications with the consent of EPA. During
previous studies it was determined that 1 to 2 g of sample is insufficient
to detect metals at very low levels. Thus, a 4-g sample aliquot was employed,
along with a final dilution volume of 50 ml to obtain lower detection limits.
In order to effect efficient extraction of all metals, the aliquots of HC1
and HNO were increased to 10 and 1.0 ml, respectively, for use with 4-g
aliquots. The digestion period was increased to approximately 3 hours (the
time required to reduce the volume to 10 to 15 ml). Past research has shown
this procedure to provide increased recovery of copper, chromium, iron,
nickel, and vanadium.
Trace metal concentrations in the acid extracts obtained by the above
procedure are stable for approximately 6 months. Consequently, aliquots of
each sample had to be digested at three intervals during the contract
period to provide sufficient sample extracts for accurate research. For
convenience, a group of samples prepared at the same time will be referred
to as a "set." A totaPof four sample sets was analyzed at appropriate
times throughout the study. Sets I and II each contained extracts of both
the soil and sediment samples. Set III contained only extracts of the soil
samples, and Set IV included only extracts of the sediment samples.
QUALITY CONTROL
A reagent/glassware blank was included with each of the four analysis
sets. A single shipping blank for the soil samples and two shipping blanks
for the bottom sediment samples were carried throughout the sampling pro-
cedures and were analyzed for contamination along with the analysis of Set
I. Three duplicates and three spiked soil and sediment samples were in-
cluded in analysis Set III. Four duplicates and three spiked sediment
samples were in analysis Set IV.
Because standard reference materials for soil and sediment analysis
were not available from the National Bureau of Standards, two sediment pools
were used in this study for in-house reference sediments. These two sediment
pools were referred to as reference sediments B and C. Replicates and
spiked aliquots of each of these sediments were included in analysis Sets
II, III, and IV.
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SECTION 5
RESULTS AND DISCUSSION
The analyses of trace elements and major inorganic constituents in soil
and sediment samples were initially performed by flame AAS using analytical
conditions recommended in the Perkin-Elmer AAS analytical manual. The
objective of this research was to develop interference-free flame AAS
techniques for the analyses of the trace elements detected. These initial
analyses were therefore investigated for possible interferences and for ways
to eliminate the interferences. The analyses of the detectable trace
elements in the soil and sediment samples were finally performed again by
AAS using the analytical conditions subject to the least interference. The
flow chart in Figure 12 outlines the scheme of this research. The research
is detailed below in four sections: initial analyses, interference study,
final analyses, and quality control procedures.
INITIAL ANALYSES
A list of trace elements of environmental interest and major constitu-
ents for each sample set was compiled with the aid of published literature
and past experience in the study of these interferences. The major inorganic
elements for both sets of samples were aluminum, calcium, iron, magnesium,
potassium, phosphate, and sodium. The trace metals examined differed for
the soil (GP) and bottom sediment (PA) samples. The soil samples were
examined for trace constituents present in fallout from coal-fired power
plants. The bottom sediment samples were analyzed for trace metal contami-
nants arising from acid mine drainage. The trace elements studied in the
soil samples include antimony, arsenic, beryllium, bismuth, cadmium, chromium,
cobalt, copper, lead, nickel, selenium, silver, tin, titanium, and zinc.
The bottom sediments were analyzed for barium, beryllium, cadmium, chromium,
cobalt, copper, lead, manganese, molybdenum, nickel, silver, strontium,
vanadium, and zinc.
All constituents except phosphate were analyzed by flame AAS and cali-
brated using aqueous standards. The conditions employed for each of these
analyses are detailed in Table 3. Phosphate was analyzed by the phosphomolyb-
dovanadate-colorimetric method measuring the intensity of the yellow color
at 470 nm. The interference from ferric ion was corrected for by using an
aliquot of the sample solution as a blank.
Soil Samples
The results of the analysis of the suspected major constituents in soil
samples are displayed in Table 4. The matrix of the soil samples was less
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complicated than that for the bottom sediment samples. Calcium, magnesium,
sodium, and potassium were present in trace quantities; only aluminum,
iron, and phosphate were considered as possible interferences for this
sample set.
The trace metals analyzed are listed in Table 5. Of the 15 elements
examined, the following nine were present in less than detectable con-
centrations: antimony, arsenic, beryllium, bismuth, cadmium, cobalt, lead,
nickel, and tin. Those elements that were examined for the presence of inter-
ferences in the AAS analysis were calcium, chromium, copper, lead, magnesium,
selenium, titanium, and zinc.
Bottom Sediment Samples
The concentrations of major inorganic constituents found in the bottom
sediment samples (Table 6) varied greatly from sample to sample. However,
aluminum, calcium, iron, potassium, magnesium, and phosphate were present in
concentrations large enough to exert interferences in the analysis of trace
elements. Calcium levels as low as 3.0 ppm were also observed. Calcium
analysis was known to be subject to various interferences, especially to
phosphate interference, and was investigated further in the study.
Table 7 contains lists of the concentrations of the suspected trace
elements in the bottom sediment samples. Manganese was present in large
enough concentrations to be considered a matrix element but was also examined
for possible interferences. Cadmium, molybdenum, and silver were not detected
in these samples. The hydrochloric acid used in the digestion procedure
should have precipitated silver (if any) as silver chloride in the digestate.
Those elements in the sediment samples that were selected to be examined
for the presence of interferences are barium, beryllium, calcium, chromium,
cobalt, copper, lead, manganese, nickel, strontium, vanadium, and zinc.
INTERFERENCE STUDY
The interferences in AAS analysis are typically of four types: chemical,
ionization, spectral, and matrix. Except for the spectral interferences,
these interferences can be detected using the method of standard additions
(MSA) and/or extensive synthetic sample study. To minimize spectral interfer-
ences, a single-element lamp was used for all the analyses; deuterium back-
ground correction was employed for all applicable analyses.
Analysis by MSA involves preparation of a series of solutions, each
containing an aliquot of a sample digestate. One of the solutions contains
only the diluted digestate, whereas the remaining solutions also contain
increasing concentrations of the trace element of interest. The solutions
are analyzed by flame AAS along with a series of aqueous standards. The
peak heights obtained from the analysis are plotted on the y-axis of a graph
(using linear regression analysis), and the known additions are plotted on
the x-axis. The x-intercept of the MSA plot is used to calculate the
unknown concentration in the sample as shown in Equation 1.
in sam le = ICx~:i-ntercept)|X(MSA dilution factor)X(initial dilution vol.)
weight of sample used (g)
10
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Only the solutions or standards that produced absorbances in the linear
range of an analysis were used in order to maintain the validity of the
aqueous or MSA results. Any curve having a correlation coefficient of less
than 0.999, if suspected to be due to experimental error, was discarded and
the experiment repeated.
Sample digestates analyzed by MSA are diluted during the process of an
MSA experiment. This dilution reduces the concentrations of the matrix
constituents and thereby reduces possible interferences. An effort was made
to minimize the sample dilutions while maintaining all the MSA solutions in
the linear range.
Because MSA alone does not identify the interferences in AAS analyses,
synthetic sample studies were performed. The synthetic samples are solutions
containing specific concentrations of one or more matrix constituents along
with the trace element of interest. The concentration of that trace element
in these solutions represents the average concentration in the sediment or
soil sample extracts. Deionized, distilled water was used to prepare a
reference solution that contained only the trace element. The effect of
the added constituent is indicated by the percent net change in peak height
calculated as;
„ , _ peak ht(with interference)-peak ht(without interference) ..-.,, ,„,.
ange peak ht (without interference)
Interference studies -for trace elements of interest are detailed below
in alphabetical order.
Arsenic
Direct AAS analysis of soil sample extracts for arsenic using a nitrous
oxide-acetylene flame yielded a detection limit of 37 ppm. No arsenic was
detected in any of the GP samples using this method of analysis. Each
sample was reanalyzed for arsenic using an argon-hydrogen flame with a
wavelength of 193.7 nm and a spectral band width of 0.7 nm. The results
indicated that all samples contained less than the detection limit of 6 ppm
arsenic (on a dry-weight basis); therefore, analysis for arsenic was not
pursued.
Later research efforts focused on the analysis of selenium showed that
serious interferences were inherent in the use of argon-hydrogen flame,
mostly due to its relatively low temperature. Alternate analysis methods
capable of detection of low arsenic concentrations, i.e., hydride generation
and flameless AAS, are beyond the scope of this research (p. 17).
Barium
Barium was determined using a wavelength of 553.6 nm, a spectral band
width of 0.4 nm, and a nitrous oxide-acetylene flame. A concentration of
Q.2 percent potassium or sodium salt (recrystallized from reagent grade KC1
or NaCl) was added to all test solutions. Calcium has been reported to
elevate the barium result in AAS analysis because theundissociated CaOH in
the flame absorbs at the barium wavelength (554 nm). Figure 13 shows the
11
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MSA curves of 3 samples containing different amounts of calcium in the
digestate: PA-3 (28 ppm Ca),* PA-6 (127 ppm Ca), and PA-12 (1236 ppm Ca).
The graph suggests additional interferences that cannot be assigned to the
presence of calcium since the aqueous calibrated results were less than the
MSA results. An examination of the sources of this depression can be made
from the synthetic sample study in Table 8. Aluminum, at a concentration of
500 ppm, depressed the absorbance of barium by 36 percent. A 10 percent
depression was caused by the presence of iron at a concentration of 5000
ppm. The remaining constituents, when added at the same high level, showed
only slight effects at the concentrations present in the sediment sample
digestates.
In an attempt to control interferences from aluminum and iron, a
second set of synthetic samples containing 0.2 percent lanthanum (as L^O^)
was analyzed. The results shown in Table 9 indicate that lanthanum is very
effective in controlling these interferences when used in conjunction with
an alkali metal salt. A concentration of 500 ppm aluminum depressed the
absorbance of 5 ppm barium by 5 percent under these conditions. The barium
peak height was suppressed only 5 percent by a concentration of 5000 ppm
iron. A concentration of 50 ppm calcium, magnesium, or manganese produced
insignificant effects. The effect of phosphate was also studied under these
conditions and was determined to be inconsequential.
The ability of lanthanum to reduce interferences effectively was sub-
stantiated by the following experiments. Digestates of sample PA-3 and PA-
12 were each subjected to two analyses by MSA. With the addition of only
potassium to the samples and standards in the first MSA analysis (Figure
14), the barium absorbances were depressed. The analysis was repeated with
a concentration of 0.2 percent lanthanum also added. The interferences were
minimal with both potassium and lanthanum added, as shown in Figure 15.
It was concluded that the barium analysis of soil and sediment sample
digestates was most accurate when performed using a nitrous oxide-acetylene
flame with a concentration of 0.2 percent lanthanum and potassium (or
sodium) added to all samples and standards.
Beryllium
Beryllium was analyzed with a nitrous oxide-acetylene flame, using a
wavelength of 234.9_ nm and a spectral band width of 0-7 nm. The MSA analysis
of sample PA-16, as shown in Figure 16, exhibited a depressed beryllium
absorbance. A set of synthetic samples was analyzed to determine the source
of the depression. The data in Table 10 indicate a severe interference from
aluminum. The effects of iron, magnesium, and manganese were insignificant
a,t concentrations present in the sediment samples.
Fleet et al. reported that 2.5 percent oxine (8-hydroxyquinoline) was
effective in controlling the interference of 4000 ppm aluminum on 4 ppm
beryllium. Table 11 contains the data from a brief study of the potential
*Concentration of calcium in sample digestate.
12
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for oxine (at less than 2.5 percent) to reduce the interference of 400 ppm
aluminum. The amount of oxine added did not significantly alter the effect
of aluminum. To attain 2.5 percent oxine in a given test solution, it is
necessary to dilute the acid digestates by a factor of 2 since 5 percent
oxine* was used for the addition. The beryllium concentrations in these
digestates were very near the detection limit of the instrument; therefore,
dilution of these digestates was not possible.
Table 12 contains additional data for the analysis of beryllium.
Calcium and phosphate had no significant effect on the absorbance of beryl-
lium, and the addition of 0.1 percent lanthanum did not correct the inter-
ference caused by the presence of aluminum.
An attempt was made to analyze the sediment sample digestates for
beryllium using matrix-matched standards. The average concentration of
each PA matrix constituent determined was added to the standard solutions.
However, because less than 0.2 ppm beryllium was present in the sample
digestates, the difference in the beryllium results obtained from the
matrix-matched standards compared to those of the aqueous standards was no
more than 0.02 ppm in the digestates. The present study was unable to
treat such a small variation adequately. The use of matrix-matched standards
would be necessary to analyze samples containing larger beryllium concen-
trations. Alternate methods of controlling the interference due to aluminum
should also be investigated.
Calcium
A wavelength of 422.7 nm and a spectral band width of 1.4 nm were used
for the analysis of calcium. An air-acetylene flame with 0.2 percent sodium
(as NaCl) added to the test solutions was used to analyze samples PA-7 and
GP-1 by MSA. Extreme depression was indicated by the resultant MSA graphs,
as displayed in Figures 17 and 18.
Lanthanum concentrations of 0.1 to 1 percent were reported to provide
effective control.of the interferences of the calcium analysis in the air-
acetylene flame. The following experiment was designed to determine the
optimum amount of lanthanum needed for controlling the interferences.
Aliquots of the digestate from sample PA-1, diluted by a factor of 25, were
treated with increasing concentrations of lanthanum. The AAS results are
illustrated in Figure 19.. The enhancement in absorbance was maximized by
the addition of 0.2 percent lanthanum; however, the enhancement was decreased
with the, addition of more than 0.2 percent lanthanum.
The capability of 0.2 percent lanthanum to reduce interferences in the
air-acetylene flame was tested with the use of synthetic samples. Table 13
shows the individual effects, of aluminum, iron, magnesium, manganese, and
phospate on the absorbance of 5 ppm calcium. A concentration of 0.2
*Five percent oxine dissolved in hydrochloric acid was prepared; precipitation
resulted when more oxine was added, although Fleet et al. reported the dis-
solution of 10 percent oxine.
13
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percent lanthanum and 0.2 percent sodium was added to all solutions. The
effect of aluminum on the absorbance of calcium was drastically reduced, and
the effects of iron, magnesium, manganese, and phosphate were minimal.
Because most AAS analyses using a nitrous oxide-acetylene (hotter) flame
are subject to fewer interferences than those using an air-acetylene flame,
calcium analysis using nitrous oxide-acetylene was also investigated. However,
even with 0. 2 percent sodium added to all solutions, strong depression of the
calcium absorbance was indicated by the MSA graphs for digestates of samples
GP-7 and PA-1, shown in Figures 20 and 21. The depression was not as serious
as that initially encountered using the air-acetylene flame.
A synthetic study was devised to identify the sources of the interfer-
ence under the nitrous oxide-acetylene flame conditions. Table 14 presents
a list of the individual effects of aluminum, iron, magnesium, manganese,
and phosphate on the absorbance of calcium. Aluminum created the most serious
interference; the remaining elements had little or no effect on the analysis
of calcium.
The addition of lanthanum along with sodium to the digestate of sample
PA-1 was used to investigate the interferences in the nitrous oxide-acetylene
flame. The results of this study, shown in Figure 22, indicate that the
addition of lanthanum enhanced the calcium absorbance, and that any addition
of lanthanum in concentrations between 0.2 and 2.0 percent produced compara-
ble results. This phenomenon is especially significant since the calcium
absorbance with the air-acetylene flame was more critically dependent on the
concentration of lanthanum added.
Another synthetic sample study was performed with a nitrous oxide-
acetylene flame with a concentration of 0.2 percent lanthanum and 0.2
percent sodium added to all solutions. The results shown in Table 15
indicate that none of the added constituents had any significant effect on
the absorbance of 5 ppm calcium.
Calcium results of MSA analyses for four samples, with and without
lanthanum, using both air-acetylene and nitrous oxide-acetylene flame are
provided in Table 16. With both sodium and lanthanum added, each of the
flame types yielded similar MSA and aqueous (aq.) calibrated results, as
shown in Figures 23 through 26. However, the nitrous oxide-acetylene flame
was used for the final analysis since it is subject to less interference, as
shown by the synthetic sample study.
Chromium
The wavelength used for chromium determinations was 357.4 nm with a
spectral band width of 0.7 nm. A nitrous oxide-acetylene flame was used
since the chromium analysis with an air-acetylene flame is subject to inter-
ferences from iron and nickel. The existence of interferences in the
chromium analysis with a nitrous oxide-acetylene flame was indicated by the
nonparallel relationship of the aqueous and MSA curves for sample GP-10
shown in Figure 27. Very slight interference was indicated by the MSA for
sample PA-13, as shown in Figure 28. This interference was substantiated by
14
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the synthetic sample study summarized in Table 17, which represents the effects
of aluminum, calcium, iron, potassium, magnesium, manganese, and phosphate
on chromium absorbance. Nickel, a known interference for chromium analysis,
was no.t included since it was present only in trace quantities. The results
of the synthetic sample study had been corrected for the chromium absorbance
exhibited by the iron solutions used for making up the synthetic samples.
The significant increases in the chromium absorbance observed for each of
the constituents added suggested an ionization interference.
To control the ionization interferences, a concentration of 0.2
percent sodium (as NaCl) was added to the same set of synthetic samples.
The results, listed in Table 18, showed considerably fewer interferences.
The only added constituent that still produced any significant effect was
iron. The average iron concentration in the bottom sediment digestates was
5000 ppm; this concentration decreased the absorbance of 3 ppm chromium by
6 percent. To remove the iron interference from the chromium analysis, 1
percent lanthanum (as LaCl_«6H_0), along with 0.2 percent sodium (as NaCl),
was added to all solutions. Tne results of the synthetic sample study thus
obtained were identical to those of the previous study (Table 18) without
the addition of lanthanum. Moreover, the MSA graphs for the digestate of
sample PA-17 with and without lanthanum added were nearly identical, as
shown in Figure 29, whereas both were parallel with the aqueous standard curve.
This study indicated that the addition of 1 percent lanthanum did not affect
the analysis of chromium in the presence of 0.2 percent alkali metal salt.
Background absorbance was suspected both in the synthetic solutions
and in samples containing high iron concentrations since the solution of 1
percent FeCl, used for the preparation of synthetic samples showed an absorb-
ance equivalent to that of 1.3 ppm chromium. This suspicion was tested
using a uranium lamp, since the principal resonance line of uranium (358.5
run) is close to that of chromium (357.9 ran) and serves as a non-absorbing
wavelength. No significant background absorbance was detected either in the
1 percent iron solution or any of the soil or sediment sample digestates.
This study indicated that the chromium analyses of the soil and sediment
samples are not subject to any serious interferences using a nitrous oxide-
acetylene flame with 0.2 percent sodium added to all solutions. However,
samples containing greater concentrations of iron may require matrix-matched
standards or other techniques for controlling the interference caused by
iron.
During the final performance of this research, an article about chromium
analysis submitted by9Rawa and Henn appeared in the August 1977 issue of
American Laboratory. This article reported that a nitrous oxide-acetylene
flame was preferred to the air-acetylene flame for chromium analysis, and
that the chromium analysis using an air-acetylene flame is subject to certain
interferences even with 1 percent oxine added to all test solutions. However,
the present study shows that chromium analysis with nitrous oxide-acetylene
is not entirely interference free, and that the ionization of chromium in
'the flame is sufficiently serious to require corrective measures.
15
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Cobalt
The analysis of cobalt was performed with an air-acetylene flame using
a wavelength of 240.7 nm with a spectral band width of 0.2 nm. The MSA plot
in Figure 30 indicates a very slight depression of the aqueous calibrated
results. Two sets of synthetic samples were prepared to examine possible
sources of interference in the cobalt analysis. The first set (Table 19)
indicated no interference from aluminum, iron, potassium, magnesium, or
manganese; the second set (Table 20) indicated no interference from calcium
or phosphate. Because this interference was insignificant, further research
was not performed for cobalt.
Copper
Copper was analyzed with an air-acetylene flame at a wavelength of
324.8 nm with a spectral band width of 0.7 nm. The MSA plots for samples
GP-4 and PA-5, as shown in Figures 31 and 32, were nearly parallel with
the aqueous standard curve. Because past studies by GSRI (Table 21) have
shown that copper is relatively free from iron and aluminum interferences
in the soil and sediment matrices, no further studies were conducted.
Lead
The AAS analysis of lead was performed using an air-acetylene flame, a
wavelength of 283.3 nm, and a spectral band width of 0.7 nm. A graph of the
MSA and aqueous curves for digestates of sample GP-5 (Figure 33) indicate a
slight elevation of the lead absorbances in the sample. The same effect is
apparent for sample PA-14 (Figure 34). Although the interferences are
slight, the analysis of lead was investigated further using synthetic
samples. The data obtained from the synthetic sample study are displayed in
Table 22. None of the added constituents produced an appreciable effect on
the analysis of 5 ppm lead. A combination of excessive amounts of all these
constituents proved to produce insignificant changes in the lead absorbance.
The use of synthetic samples showed that the analysis of lead in these soil
and sediment samples was not subject to significant interferences.
Magnesium
The magnesium analyses were performed with a nitrous oxide-acetylene
flame, using a wavelength of 285.2 nm and a spectral band width of 0.7 nm.
Magnesium concentrations in the soil samples were large enough to permit the
dilution of the GP-5 digestate by a factor of 1QO for analysis by MSA. The
graph in Figure 35 displays excellent correlation between the MSA and aqueous
standard curves for sample GP-5. The analysis of magnesium was not affected
by the aluminum and iron concentrations present in the soil and sediment
digestates.
Manganese
An air-acetylene flame, a wavelength of 279.5 nm, and a spectral band
width of 0.2 nm were the conditions used for manganese analyses. Figure 36
illustrates the MSA plot for PA-14 (diluted by a factor of 100). The near-
16
-------
parallel lines in the graph represent the minimal interference encountered
in this analysis. The content of manganese obtained for sample PA-4 by MSA
was 502 ppm; the value obtained by aqueous calibration was 498 ppm. No
further study was deemed necessary for manganese.
Nickel
An air-acetylene flame was used for nickel analysis; a wavelength of
232.0 nm with a spectral band width of 0.2 nm was selected. The digestate
of sample PA-2 was analyzed by MSA and was diluted by a factor of 3. The
resultant MSA plot in Figure 37 indicates no significant interference for
the nickel analysis. Therefore, the AAS conditions used here were used for
the final analysis of nickel in these digestates.
Selenium
The wavelength for selenium analyses was 196.0 nm with a spectral
band width of 0.7 nm. An argon-hydrogen flame was selected for the initial
analysis of selenium because the low selenium concentration in the soil
sample digestates could not be detected by direct AAS analysis,using either
an air-acetylene flame or a nitrous oxide-acetylene flame. ' However,
Figure 38 depicts the severe depression of selenium absorbance exhibited by
an MSA study of sample GP-9. The value obtained by MSA (14.1 ppm) was
significantly greater than that obtained by aqueous calibration of the
undiluted digestate (5.1 ppm).
The sources of the interferences were studied using synthetic samples
containing aluminum, calcium, iron, potassium, and magnesium. The severe
depressive effects of these constituents (except potassium) are readily ob-
served in Table 23. Aluminum produced the strongest effect by depressing
the selenium peak height by more than 90 percent. A concentration of 25 ppm
aluminum produced approximately the same effect as 1000 ppm aluminum. The
iron concentrations tested ranged from 50 to 1000 ppm, and the resulting
depressions ranged from 50 to 76 percent. The presence of potassium in
concentrations ranging from 50 to 500 ppm produced negative effects ranging
from 1 to 7 percent.
Methods employed to alleviate the aluminum interferences, including
various additions of EDTA, disodium EDTA, sodium, or lanthanum, are outlined
in Table 24. None of the additives resulted in effective removal of the
interference; addition of lanthanum caused major depression of the selenium
absorbance.
Three spiked soil samples were examined using three flame types:
argon-hydrogen, air-acetylene, and nitrous oxide-acetylene. These soil
samples., ea,ch containing less than 14 ppm selenium, were spiked with 50 ppm
selenium. The results for the analyses of these spiked samples are listed
in Table 25. The concentration of selenium in all three spiked samples
should he in the range of 50 to 64 ppm. However, the values obtained were
less than 30 ppm selenium with an argon-hydrogen flame, more than 64 ppm
selenium with a air-acetylene flame, and 55 ppm for all three samples with a
nitrous oxide-acetylene flame.
17
-------
The experiment described above showed that although the selenium analysis
with the argon-hydrogen flame was subject to negative interferences because
of the relatively cool flame temperature, the analysis with the air-acetylene
flame is subject to positive interferences. The analysis using a nitrous
oxide-acetylene flame appears to be the most accurate of the three; however,
this method has a minimum detection limit of 25 ppm. Neither the use of an
air-acetylene flame nor that of a nitrous oxide-acetylene flame was investi-
gated further since selenium in these soil samples was not detectable in
either flame system.
The method most often used for the analysis of low selenium concentra-
tions is either the flameless AAS or the hydride-generation method using
an argon-hydrogen flame atomization. These methods were not within the
scope of work and were not investigated further. However, it has been reported
by Pierce and Brown that interferences are present for selenium analysis by
these two methods, and that an automated hydride generation methodgUsing a
quartz tube for atomization is subject to the least interference.
Strontium
A wavelength of 460.7 nm and a spectral band width of 1.4 nm were used
for all strontium analyses. In the initial analyses of strontium, a nitrous
oxide-acetylene flame was used and 0.2 percent potassium (as KC1) was added
to all test solutions to control interferences from ionization in the flame.
The MSA experiment for sample PA-7, as shown by the nonparallel lines in
Figure 39, indicates the presence of interferences. The strontium content
in sample PA-7 was determined to be 15.0 ppm from aqueous calibration and
20.7 ppm from MSA.
Synthetic samples were used to investigate interferences encountered in
the initial analysis of strontium with 0.2 percent potassium added to all
samples and standards. The results are listed in Table 26. The only added
constituent that caused severe interference was aluminum; a concentration
of 500 ppm aluminum depressed the strontium absorbance by 25 percent.
To minimize the interference due to aluminum, a concentration of 1
percent lanthanum as La(NO,) -6H 0 was added to the set of synthetic samples
containing 0.2 percent potassium as KC1. The results in Table 27 reveal a
considerable improvement. At concentrations present in the sediment matrix,
aluminum, iron, manganese, and phosphate have only minimal effects on the
absorbance of strontium. In this study, phosphate concentrations of 200 ppm
and 500 ppm caused considerable baseline noise and a depressive effect for
the strontium absorbance. These effects were due to the aspiration of the
precipitate of lanthanum phosphate into the flame. Filtration should
remove the precipitate and thus the interference; it.has been reported that
strontium was not removed by the filtration process.
The accuracy of the analysis using a nitrous oxide-acetylene flame with
1 percent lanthanum and 0.2 percent sodium in all solutions was substan-
tiated with analysis by MSA. Figure 40 and Figure 41 show the MSA plots for
digestates of samples PA-14-sp (sample PA-14 spiked with 50 ppm strontium)
and PA-15, with and without lanthanum added. The interference observed
18
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without lanthanum added (Figure 40) disappeared when lanthanum was added
(Figure 41).
The strontium analysis using an air-acetylene flame with addition of
both lanthanum and sodium to all test solutions was also investigated, since
this method was suggested in the Perkin-Elmer MS Users Manual. The MSA
analyses of digestates of samples PA-14-sp and PA-15 utilizing these condi-
tions are shown in Figure 42. Both MSA plots revealed interferences in the
analysis of strontium.
Synthetic samples were used to study the sources of the interference in
the air-acetylene flame including both sodium and lanthanum addition. The
data in Table 28 indicate that iron and magnesium have a significant negative
effect on the absorbance of 2 ppm strontium. This technique is not suitable
for analysis of these soil and sediment samples.
The strontium concentrations in samples PA-14-sp and PA-15 as obtained
by aqueous calibration and MSA utilizing different flame types and conditions
are listed in Table 29. Only the strontium analysis performed in a nitrous
oxide-acetylene flame with both sodium and lanthanum added yielded aqueous
calibrated results similar to the MSA results, and this method was used for
the final analyses.
Titanium
The analysis of titanium was performed with a nitrous oxide-acetylene
flame; a concentration of 0.2 percent sodium (as NaCl) was added to all
test solutions. A wavelength of 365.3 nm with a spectral band width of
0.2 nm was selected for this determination.
The MSA experiment for the sample GP-10 digestate (dilution factor of
2), shows a very slight interference in the titanium analysis (Figure 43).
The concentration of titanium in sample GP-10 was 118 ppm by the aqueous
standard calibration curve and 122 ppm by MSA.
A synthetic sample study was performed to search for interferences not
readily observable in the MSA study. As listed in Table 30, the presence of
calcium, iron, and phosphate all produce slightly negative effects on the
absorbance of 30 ppm titanium in the presence of sodium. A concentration of
500 ppm aluminum produced a 7 percent increase of the titanium peak height.
A solution containing average quantities of matrix constituents present in
soil digestates showed a 7 percent elevation of the titanium results.
In an effort to eliminate the interferences produced by aluminum,
calcium, and iron, a second synthetic sample study was performed with 1
percent lanthanum as La(NO_) «6H20 added to all solutions. Rather than
lessening the degree of interference, the negative interferences were
enhanced, as shown in Table 31. This effect was also observed in the MSA
plot of GP-10 (Figure 44). With both lanthanum and sodium added, the
calculated titanium content in sample GP-10 was 52 ppm using the aqueous
calibration curve and 130 ppm as determined by MSA experiments. The addition
of lanthanum is detrimental rather than helpful for the analysis of titanium.
19
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Because the analysis of titanium using a nitrous oxide-acetylene flame with a
concentration of 0.2 percent sodium added to all solutions was subject to
some interferences, matrix-matched standards were used for the final analyses
of titanium in the soil samples.
Vanad ium
For all the vanadium analyses, a nitrous oxide-acetylene flame was
employed, using a wavelength of 318.4 nm with a spectral band width of 0.7
nm. Interference in the vanadium analysis was obvious from the MSA plot for
sample PA-15 shown in Figure 45. The concentration of vanadium in PA-15 was
33 ppm from the aqueous standard curve and 24 ppm from the MSA experiment.
The synthetic sample study, shown in Table 32, represents the effects
of aluminum, calcium, iron, potassium, magnesium, manganese, and phosphate
on the absorbance of 6 ppm vanadium. At the average concentrations present
in the sediment sample digestates, only manganese did not exhibit a substan-
tial effect on the vanadium absorbance. The most surprising effect was that
a concentration of 50 ppm potassium elevated the vanadium absorbance by 24
percent, and concentrations of 500 ppm potassium caused an increase of 36
percent in the vanadium peak height. This phenomenon indicated that vanadium
may have been ionized in the flame and that the addition of potassium chloride
(or any other alkali metal salt) should alleviate this interference.
A second analysis using synthetic samples with sodium added confirmed
this suspicion. A concentration of 0.2 percent sodium (as NaCl) was added
to all solutions listed in Table 33. As a result, all interferences were
minimized except those due to iron. A 5000 ppm iron concentration, in the
presence of sodium, decreased the vanadium absorbance by 17 percent.
However, the effect of a combination of the six constituents was only 4
percent.
The experimental attempt for eliminating the interference caused by
iron led to a vanadium study using the addition of I percent lanthanum along
with 0.2 percent sodium. The results displayed in Table 34 show that the
interferences, due to aluminum, calcium, and even iron disappeared.
The MSA plots for sample PA-17 in the presence of sodium, with and
without lanthanum added, were almost parallel with the aqueous standard curve
as shown in Figure 46 and Figure 47. Results obtained for vanadium in the
sample are similar and are listed in Table 35.
It has been reported by Zander that iron has a resonance line at 318.3
nm, wtyich is very close to the wavelength used for vanadium analysis (318.4
nm). The fact that no absorbance was observed for a 1 percent iron
solution in the vanadium analysis at 318.4 nm indicates that the 318.3 nm is
a very weak resonance line of iron. However, this spectral interference
should be investigated if larger iron concentrations are present in the
sample digestates.
20
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Zinc
The analysis of zinc was studied using an air-acetylene flame, a wave-
length of 213.9 nm, and a spectral band width of 0.7 nm. The MSA plot for
soil sample GP-7, as displayed in Figure 48, shows a parallel relationship
between the MSA and aqueous standard curves. The MSA analysis of sediment
sample PA-7 is represented in Figure 49. The sample digestate was diluted
by a factor of 50, and insignificant interferences were indicated by the
results. Because zinc was not a trace metal of interest for these samples,
and no significant interferences were observed, it was concluded that the
zinc analysis with the air-acetylene flame was interference free.
FINAL ANALYSES
From the information gathered in the interference study, a list of the
methods recommended for each element studied was compiled. This list is
presented in Table 36. In the initial analyses of soil and sediment samples,
the elements subject to interferences were: barium, beryllium, calcium,
chromium, selenium, strontium, titanium, and vanadium. These and other
elements were analyzed again using the methods given in Table 36 for the
soil and sediment samples. Results of calcium analysis employing the
recommended method listed in Table 36 yielded values different from those
of the initial analysis. The calcium results for soil and sediment samples
are listed in Table 37.
The results of trace elements for this final analysis are listed in
Table 38 for soil samples and in Table 39 for bottom sediment samples. The
following elements were present in concentrations less than the detection
limit and were not included in the table: antimony, arsenic, bismuth,
cadmium, selenium, and tin. All these results except that for titanium were
calibrated against aqueous standards. Because the titanium analysis was
subject to interferences, matrix-matched standards containing the average
matrix concentration of the soil digestates were used for calibration. The
aqeuous calibrated titanium results were also listed for comparison.
Although the interferences persist for the beryllium analysis, only the
aqueous calibrated values were listed in the table because the low beryllium
concentration in these samples (<2 ppm beryllium, dry-weight basis) resulted
in a very slight difference (_<0.2 ppm beryllium, dry-weight basis) between
the values calibrated against aqueous and matrix-matched standard curves.
Because partial digestion procedures were used for this study, the
resultant elemental contents in the soil and sediment samples represent only
the hot acid extractable amount rather than the total amount of the element in
the sample.
QUALITY CONTROL PROCEDURES
Quality assurance measures were employed throughout the project to
ensure the validity of all data. The quality control procedures involved
the analysis of shipping and reagent/glassware blanks to account for possible
contamination during handling or preparation. Duplicate and spiked
21
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samples and in-house reference sediments were included to confirm the
accuracy and precision of the digestions and analyses.
Shipping Blanks
Designated shipping blanks accompanied the soil and sediment sample
containers throughout the sampling process. The blanks were treated identi-
cally to the sample bottles except that these containers were returned empty
and intact. The single shipping blank that accompanied the soil samples
and the two shipping blanks for the sediment samples were tested for contami-
nation by rinsing the containers with nitric acid and analyzing the extract
by AAS. Results of these analyses are given in Table 40 as micrograms of the
element of interest extracted from inside the sample container. Of the 24
elements tested, 15 were not detectable in the blanks. The remaining nine
elements were detectable in the containers but could not contribute signifi-
cantly to the elemental concentration in the sample since a minimum of 500 g
of sample was collected in every bottle.
Soil and Sediment Samples
Duplicate Samples—
The results of duplicate analyses of the sediment and soil samples are
an indication of both the homogeneity of the sample and the reproducibility
of the digestions and analyses. Homogenization of the sediment samples was
hindered by the presence of many small pebbles and rocks. The average value
and standard deviation for each pair of duplicate samples displayed in Table
41 indicate good reproducibility. The methods of analysis used for sets III
and IV are the same as those employed for the .final analysis of the samples
(Table 36).
Spiked Samples—
The metal concentrations selected for spiking the samples varied for
each metal and were tailored to the metal concentrations present in the
sample. The percent recovery for each of these spikes is listed in Table
42. Very good accuracy for this digestion procedure is generally indicated
by these results. The AAS analysis procedures for each of these deter-
minations are the same as those used for the analysis of the duplicate
samples.
In-House Reference Sediments
Two sediments pools, reference sediments B and C, which had been
prepared and analyzed previously by GSRI for seven of the trace metals of
interest were used as in-house reference sediments. Replicate and spiked
aliquots of each of these sediments were digested and analyzed along with
sets II, III, and IV. Set II was analyzed using the AAS conditions for
initial analysis (Table 3). Sets III and IV were analyzed using the AAS
conditions for final analysis (Table 36) .
22
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Replicate Samples—
Lists of the replicate values obtained for reference sediments B and C
are summarized in Tables 43 and 44. The mean and standard deviation for
these analyses were not calculated since improved methods of analysis were
used for Sets III and IV. Reproducibility in Sets III and IV was excellent
for most metals except titanium. The results for titanium in reference
sediment C range from 15 to 122 ppm. Although the analysis method used for
the titanium determination does suffer some interference, such a big discrep-
ancy in the replicate results is probably the result of anomalies not defined
in these experiments.
Quality control charts for reference sediments B and C are contained in
Figures 50-62 for the following metals: barium, chromium, copper, lead, nickel,
vanadium, and zinc. The values obtained during this research project are
indicated by circles. The means and standard deviations from the previous
project are indicated by the solid and dashed horizontal lines. Results
obtained for the analysis of barium, chromium, and vanadium in Sets III and
IV were not necessarily expected to be comparable with the results from the
previous project, since more accurate methods were used for the analysis of
Sets III and IV. This difference is especially noticeable for the chromium
analysis in reference sediment B (Figure 51). Using the same analysis
method as that for the previous project, similar values were obtained (Set
II); using the improved analysis method, lower values were obtained (Sets
III and IV). The overall'comparisons for most metals are favorable, except
that for copper in reference sediment C (Figure 58). The present study
showed a better precision than the previous one. Quality control charts to
be used in the future based on these data will be modified to include the
average and standard deviation values calculated using methods developed
for this study.
Spiked Samples—
The percent recovery data are listed in Tables 45 and 46 for reference
sediments B and C. Recoveries for most metals were very good, except for
chromium, strontium, and vanadium in Set II, where improved analysis methods
were used and earlier values were probably inaccurate. Percent recoveries
for titanium were not calculated because the replicate samples gave inconsis-
tent results.
23
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SECTION 6
FIGURES AND TABLES
-------
stream or ,
plre Tunnel
stream of
iss Run
COOKSBURG
Figure 1. Sampling scheme for the Toby Creek - Clarion River system.
-------
Figure 2. Sampling locations from Ridgway Quadrangle, Pennsylvania.
26
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Figure 3. Sampling locations from Portland Mills Quadrangle, Pennsylvania.
27
-------
Figure 4. Sampling locations from Carman Quadrangle, Pennsylvania.
28
-------
Figure 5. Sampling location from Falls Creek Quadrangle, Pennsylvania.
29
-------
Figure 6. Sampling locations from Sigel Quadrangle, Pennsylvania.
30
-------
[PA13
v>
Figure 7. Sampling locations from Hallton Quadrangle, Pennsylvania.
31
-------
Figure 8, Sampling locations from Cooksburg Quadrangle, Pennsylvania.
32
-------
Plant Jack Watson
Figure 9. Aerial photograph of Gulfport, Mississippi, area in the vicinity
of Plant Jack Watson.
33
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30'30" I*.
J/4S
(MC HENRY 1:02300)
'75
3 3
Figure J,0. Sampling locations from Gulf port North
Quadrangle, Mississippi.
-------
u>
Mississippi
Louisiana
Mississippi
Louisiana
Figure 11. Background sampling locations for soil samples.
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SEDIMENT
SOIL SAMPLE
|SAMPLE PREPARATION]
I
ACID EXTRACTION
OF METALS
CONSTANT
VOLUME ADJUSTMENT
DILUTION j
ANALYSIS (AAS) OF
MAJOR CONSTITUENTS
Fe Al Ca Mg Na K
I
1
BOTTOM SEDIMENT
I
ANALYSIS (AAS) OF
TRACE CONSTITUENTS
ANALYSIS (AAS) OF
TRACE CONSTITUENTS
Cd Cr Ag Ni Ti Se Sn Be
Sb Bi Cu Zn Pb As Co
Be V Pb Zn Mn Sr Ni
Ba Cd Cu Cr Mo Ag Co
IDENTIFICATION OF MATRIX INTERFERENCES
ANALYSIS BY METHOD OF
STANDARD ADDITIONS
DATA
INTERPRETATION
ANALYSIS WITH MATRIX
MATCHED STANDARDS
1
1
ANALYSIS USING
NONAS SORB ING WAVELENGTH
ANALYSIS C
SYNTHETIC
1
DATA
INTERPRETATION
RECOMMENTATION OF AAS
PROCEDURE FOR EACH TRACE
METAL FOR EACH SAMPLE TYPE
ANALYSIS OF
SYNTHETIC SAMPLES
I FINAL REPORT]
Figure 12. Schematic of experimental approach.
36
-------
Experiment 1
u>
Flame type: N 0-C H
Additive: 0.2% K
-10
ppm Ba added
Figure 13. MSA plot for barium - Experiment 1.
-------
oo
J.O-
Experiment 2
Flame type: N^O-C^H^
Additive: 0.2% K
-e 14-
o
4-)
^3 19
•H
0)
,£
3 10-
0)
FM
OH
\f
' S
8- -
Standard curve
MSA (PA-3)
MSA (PA-12)
-202
ppm Ba added
Figure 14. MSA plot for barium - Experiment 2.
-------
Experiment 3
Flame type: N20-C2H2
Additives: 0.2% La
0.2% Na
-| Standard curve
MSA (PA-3)
X MSA (PA-12)
-10 -8
-6 -4-202
ppm Ba added
Figure 15. MSA plot for barium - Experiment 3.
-------
Conditions
Flame type: N2
Additive: None
— Standard curve
MSA (PA-16)
-0.6 -0.4 -0.2 0.0 0.2 0/4 0.6 0.8 1.0 1.2 1.4 1.6
ppm Be added
Figure 16. MSA plot for beryllium.
-------
Experiment 1
Flame type: Air-C-H
Additive: 0.2% Na
-2
18T
164-
141
12
w
•a
•H
0)
tfl
0)
PM
—. — — • Standard curve
/
s
X
, — J
L ^ o • • — u
*- 1 — 1 1 1 1_- I
-1 01234
ppm Ca added
Figure 17. MSA plot for calcium - Experiment 1.
-------
B
a
60
•H
CL)
cfl
o;
18 T
16--
14. .
12. .
10. .
8
ppm Ca added
Standard curve
MSA(PA-l)
4.
2.
c
-1 C
X* ^^
X-^
v^ 1 1 1
III
) 1 2 3
Experiment 2
Flame type: Air-C2H2
Additive: 0.2% Na
1 i
1 1
4 5
Figure 18. MSA plot for calcium - Experiment 2,
-------
CJ
60
•H
0)
a
01
PH
Flame type: Air-C H
Additive: 0.2% Na
Figure 19.
I
0.4
0.8 1.2
Percent La added
1.6
2.0
Calcium absorbance of sample PA-1 in the presence of
lanthanum - Experiment 3.
43
-------
18-r
Experiment 4
Flame type: N 0-C2H
Additives: 0.2% Na
— — — Standard curve
MSA (GP-7)
-2 0
ppm Ca added
Figure 20. MSA plot for calcium - Experiment 4.
-------
Experiment 5
Flame type: N20-C HU
Additive: 0.2% Na
-2
16.
14.
12.
— _ Standard curve
MSA (PA-1)
-101
ppm Ca added
Figure 21. MSA plot .for calcium - Experiment 5.
-------
20
6
o
n)
0)
PM
12
1 1 I
Experiment 6
Flame type: N^-C^
Additive: 0.2% Na
1 1
0 0.4 0.8 1.2 1.6 2.0
Percent La added
Figure 22- Calcium absorbance of sample PA-1 in the presence of
lanthanum - Experiment 6.
46
-------
Experiment 7
Flame type: Air-C2H2
Additives: 0.2% La
0.2% K
16-
14.
10..
— — Standard curve
MSA (GP-2)
ppm Ca added
Figure 23. MSA plot" for calcium - Experiment 7.
-------
Experiment 8
Flame type: ^O-CoH,,
Additives: 0.2% La
0.2% K
20.
18.
16.
CO
-2
-1
14..
12
a 10
— — —H— — — Standard curve
Q MSA (GP-2)
ppm Ca added
Figure 24. MSA plot for calcium - Experiment
-------
e
o
•a
•H
cS
-------
22 -•
20 -.
18 ..
16
14
12
•a
"Si 10 ..
*
Standard curve
MSA (PA-5)
o
4 _
, X
//
/
*
/
Experiment 10
Flame type: N20-C2H2
Additives: 0.2% La
0.2% Na
-2-10123456
ppm Ca added
Figure 26. MSA plot for calcium - Experiment 10.
-------
Experiment 1
Flame type: N^O-C^HU
Additive: None
J.U -
9 -
8 .
7
g 4
-a
•rl
01
43
^!
c
-------
Experiment 2
Flame type: N 0-C2H
Additive: None
-2
20
18
16 . .
12
10
— Standard curve
MSA (PA-13)
-1 0
ppm Cr added
Figure 28. MSA plot for chromium - Experiment 2.
-------
Experiment 3
Flame type: N O-C
Additive: 0.2% Na
Ui
-2
20__
18. .
16..
14--
12..
8
u
oo
•H
OJ
f
10- -
8--
_ •— — —_ Standard curve
s ^
U/ A I. — MSA (PA-1
Si 1 1 1 J
(PA-17 with La also added)
10123
ppm Cr added
Figure 29. MSA plot for chromium - Experiment 3.
-------
10 T
Conditions
Flame type: Air-C
Additive: None
Ul
-2
-1
Standard curve
MSA (PA-2)
ppm Co added
Figure 30. MSA plot for cobalt.
-------
Experiment 1
Flame type: Air-C2H2
Additive: None
-2
-1
20--
18-.
__ __ Standard curve
MSA (GP-4)
ppm Cu added
Figure 31. MSA plot for copper - Experiment 1,
-------
22 -r
Experiment 2
Flame type: -^^
Additive: None
— Standard curve
-2
-1
012 3
ppm Cu added
Figure 32. MSA plot for copper - Experiment 2.
-------
16..
14..
12
•a 101
•H *
Experiment 1
Flame type: Air-C2H
Additive: None
_/
— — —-U — Standard curve
L .
1. 1 1 1 ^
X 1 1-
O,_
, 1 ,
,. MSA Cr,P_S^
— 1 1 1 1 1
-4 -3 -2-1 0 1
ppm Pb added
10
Figure 33. MSA plot for lead - Experiment 1.
-------
00
20 T
18--
16..
14..
e
CJ
^ 10
jj
•a
•rl
J8 8
4..
2..
Experiment 2
Flame type:
Additive: None
/
— Standard curve
MSA (PA-14)
-4 -3
r /
-2-10 1
2
I 1
3 4
5
6
7
8
9 1C
ppm Pb added
Figure 34.
MSA plot for lead - Experiment 2.
-------
18-r-
Conditions
Flame type:
Additive: None
-0.2
__ __—f— _— Standard curve
MSA (GP-5)
i S 1
JE. 1 1 1 1
-0.1 0 0.1
ppm Mg added
0.2
0.3
0.4
Figure 35. MSA plot for magnesium.
-------
h
-1
20-r
18--
16-.
14..
12..
Conditions
Flame type: Air-C2H2
Additive: None
Standard curve
MSA (PA-4)
ppm Mn added
Figure 36.
MSA plot for manganese.
-------
18.
16.
14.
12
10. .
Conditions
Flame type:
Additive: None
— Standard curve
MSA (PA-2)
-2
-1
ppm Ni added
Figure 37. MSA plot for nickel.
-------
-2
00
•H
-------
Standard curve
MSA (PA-7)
Experiment 1
Flame type: N20-C2H2
Additive: 0.2% K
-2
-1
ppm Sr added
Figure 39. MSA plot for strontium - Experiment 1.
-------
22 T
Experiment 2
Flame type: ^O-
Additive: 0.2% K
Standard curve
MSA (PA-14-sp)
A MSA (PA-15)
/
-3
-2
-1
0
ppm Sr added
Figure 40. MSA plot for strontium - Experiment 2.
-------
11-1-
Ul
/
/
/
/
/
/
Additives: 1% La
0.2% K
— _• Standard curve
MSA (PA-14-sp)
MSA (PA-15)
23
ppm Sr added
Figure 41. MSA plot for strontium - Experiment 3.
-------
Experiment A
Flame type: Air-C2H2
Additives: 1% La
0.2% K
-3
Standard curve
, X ,X
s A ' ^
^ an' A
[ 1 1
MSA (PA-15)
1 — 1
-2-10 1 2
ppm Sr added
Figure 42. MSA plot for strontium - Experiment 4.
-------
20-r-
-20
-10
16..
S 12.
v_^
4J
* 10.
-------
OS
00
-20
+
20-j-
18- -
16- -
14..
Experiment 2
Flame type: N-O-C^H
Additives: 1% La
0.2% Na
__ — Standard curve
MSA (GP-10)
-10 0 10 20 30
ppm Ti added
Figure 44. MSA plot for titanium - Experiment 2.
40
-------
Experiment 1
Flame type: N20-C2H
Additive: None
20 _
18.
16.
14.
12
10
8. .
•u
•a 6
•H
0)
— — Standard curve
MSA (PA-15)
| 1 ,__£
-6 -4-2 0 2
ppm V added
-I
h
46 8 10 12 14
Figure 45. MSA plot for vanadium - Experiment I.
16 18
20
-------
22-r-
Experiment 2
Flame type: N2
Additive: 0.2% Na
Standard curve
MSA (PA-17)
6
-2-1012345
ppm V added
Figure 46. MSA plot for vanadium - Experiment 2.
8
-------
Experiment 3
Flame type: N20-C2H2
Additives: 1% La
0.2% Na
22 - •
20 - •
18 _ .
16 . .
14 _ .
12 . .
g
a
•H
0)
n)
01
10 _.
8 . .
6 __
4 . .
___-•__— Standard curve
2 $
1 \l
/ /
I /"
/
"\J
— 1 1 1 1 1 1
2 -1 0
ppm V added
Figure 47. MSA plot for vanadium - Experiment 3.
-------
Experiment 1
Flame type: Air-CJl
Additive: None
— — —— — — Standard curve
Q MSA (GP-7)
0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
ppm Zn added
Figure 48. MSA plot for zinc - Experiment 1.
-------
14-.-
12- -
10- -
|— — — Standard curve
MSA (PA-7)
Experiment 2
Flame type: Air-
Additive: None
-0.3
-0.2
0.0
ppm Zn added
0.1
0.2
0.3
0.4
Figure 49. MSA plot for zinc - Experiment 2.
0.5
-------
20
15
PQ
P*
10
I
II II IV IV
Analysis set number
Figure 50. Quality control chart for barium in reference sediment B.
70
50
u
I
30
O
I
I
I
II
II III
Analysis set number
IV
IV
Figure 51. Quality control chart for chromium in reference sediment B.
74
-------
10 r-
3
u
B
a.
o.
o
o
II II III IV IV
Analysis set number
Figure 52. Quality control chart for copper in reference sediment B.
10
.1
n
II II III IV
Analysis set number
Figure 53. Quality control chart for lead in reference sediment B.
IV
75
-------
e
D-
CX
5.0
4.0
3.0
2.0
1.0
o.o
I
I
J
II II III III IV
Analysis set number
Figure 54. Quality control chart for nickel in reference sediment B.
>
0
15 r
10
O
II II IV IV
Analysis set number
Figure 55. Quality control chart for vanadium in reference sediment B
76
-------
30
25
20
e
OH , R
cx 15
O
O O -D °
I
I
II II II II IV IV
Analysis set number
Figure 56. Quality control chart for barium in reference sediment C,
400
300
u
6
P.
a,
200
0
?
1
I
I
1
III III
IV
IV
II II II II III
Analysis get number
Figure 57. Quality control chart for chromium in reference sediment C.
77
-------
40 i-
30
d
u
B
o.
ex
o o
o o
o o o
20
f
I
J I
II II II II III III III IV IV
Analysis set number
/
Figure 58. Quality control chart for copper in reference sediment C.
30
20
D.
O,
10
0
Q ¥
_ -o- - o— D - -0—D—-o—o
I I I I I I
II II II II III HI III IV IV
Analysis set number
Figure 59. Quality control chart for lead in reference sediment C.
78
-------
3
&
a,
0
—o--o--o--o----- o--o
I
I
I
II
IV
II II II III III III IV
Analysis set number
Figure 60. Quality control chart for nickel in reference sediment C.
15
10
>
e
a
0
r>
n
I
j
L
II
III
IV IV
II II II III III
Analysis set number
Figure 61. Quality control chart for vanadium in reference sediment C.
79
-------
a
N
6
CX
P.
60
50
40
30
20
10
0
O
O
o o o ~° °
o
o
••
-
,
II II II II III III III IV IV
Analysis set number
Figure 62. Quality control chart for zinc in reference sediment C.
80
-------
TABLE 1. SAMPLE LOG FOR SEDIMENT (PA) SAMPLES
GSRI Sample I.D. Sample Description
PA-1 West Branch Clarion River
PA-2 East Branch Clarion River
PA-3 Clarion River at Johnsonburg, Pa.
PA-4 Clarion River at Ridgway, Pa.
PA-5 Clarion River below Ridgway, Pa.
PA-6 Toby Creek at mouth
PA-7 Toby Creek 1-1/2 miles above mouth
PA-8 Toby Creek 2 miles upstream of Empire Tunnel
PA-9 Toby Creek upstream of Bliss Run
PA-10 Toby Creek at Brockway at 219 Highway Bridge
PA-11 Clarion River at Callen Run Footbridge
PA-12 Clarion River at Belltown Highway Bridge
PA-13 Clarion River upstream of Church Run and Footbridge
PA-14 Clarion River at Maxwell Run Ford
PA-15 Clarion River at Arroyo Ford Bridge
PA-16 Clarion River at Route 899 Bridge
PA-17 Clarion River at Route 36 Bridge at Cooksburg, Pa.
81
-------
TABLE 2. SAMPLE LOG FOR SOIL (GP) SAMPLES
GSRI Sample I.D.
Sample Description
GP-1
GP-2
GP-3
GP-4
GP-5
GP-6
GP-7
GP-8
GP-9
GP-10
GP-11
GP-12
GP-13
GP-14
GP-15
GP-16
GP-17
GP-13
GP-19
GP-20
Latitude 30027'01"N.
Latitude 30°27'22"N.
Latitude 30°27'31"N.
Latitude 30°27'48"N.
Latitude 30028'23"N.
Latitude 30°28'40"N.
Latitude 30°28'57"N.
Latitude 30°29'06"N.
Latitude 30°29T14"N.
Latitude 30°29'15"N.
Latitude 30°28'52"N.
Latitude 30°28'32"N.
Latitude 30°27"42"N.
Latitude 30°27'21"N.
Longitude 89°02'13"W.
Longitude 89°02'21"W.
Longitude 89°02'26"W.
Longitude 89°02'30"W.
Longitude 89°02'45"W.
Longitude 89°02'53"W.
Longitude 89°02'51"W.
Longitude 80°03'02"W.
Longitude 89°Q3'07"W.
Longitude 89"03"36"W.
Longitude 89"04'07"W.
Longitude 89004'06"W.
Longitude 89°04'05"W.
Longitude 89°04'17"W.
One mile north of 1-10 near Pass Christian,
Long Beach exit.
One mile north of 1-10 near Pass Christian,
Long Beach exit.
Between Kiln and 1-10 near 1-10 Kiln exit.
One hundred yards north of 1-10 and one mile
east of NASA 1-10 exit.
One mile north of 1-10 NASA exit, east side
of road.
One mile south of 1-10 NASA exit.
82
-------
TABLE 3. CONDITIONS USED FOR INITIAL ANALYSIS OF SOIL (GP) AND SEDIMENT (PA) SAMPLES
oo
Element
Ag
Al
As
Ba
Be
Bi
Ca
Cd
Co
Cr
Cu
Fe
K
Mg
Mn
Mo
Na*
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Wavelength
(nm)
328.1
309-3
193.7
553.6
234.9
223.1
422.7
228.3
240.7
357.9
324.8
248.3
766.5
285.2
279.5
313.3
589.0
232.0
283.3
217.6
196.0
286.3
460.7
365.3
318.4
213.9
Spectral Band
(nm)
0.7
0.7
0.7
0.4
0.7
0.7
1.4
0.7
0.2
0.7
0.7
0.2
1.4
0.7
0.2
0.7
1.4
0.2
0.7
0.2
0.7
0.7
1.4
0.2
0.7
0.7
Flame
Type
Air-C_H_
„ ,-l^TT^
.2 ~ 2^2
Argon-tL
-„ N90-C9H0
2. L 2.
N-O-C.H-
2 22
Air-ClC
2 2
Air-qin
Air-C H
Air-CiTHlT
N 0-C H
2 22
Air-C H
Air-C^H^
Ai-r~C2H2
N20-C2H2
Air-C9H
N D-C^lC
Air-C9H0
(Air-C2H
Air-C_H
Air-C.H
Argon-H
Air-C?H
N2°~C2H2
N20-C H
N20-C2H2
Air-C2H2
Detection Limit
Comments (ppm)
1.3
5
6
Add 0.2% potassium or 6
sodium to all solutions
0.4
6
2
0.3
3.0
2
0.6
2
1.5
0.3
0.5
6.3
0.2
Use 4-inch single slot burner 6
head
4.0
25
2.5
25
Add 0.2% potassium or 1.5
sodium to all solutions
Add 0.2% potassium or 25
sodium to all solutions
6.0
0.7
AAnalysis was done by atomic emission
-------
TABLE 4. AAS ANALYSIS OF MATRIX CONSTITUENTS
IN SOIL (GP) SAMPLES
Sample
CP-1
GP-2
GP-3
GP-4
GP-5
GP-6
GP-7
GP-8
GP-9
GP-10
GP-11
GP-12
GP-13
GP-14
GP-15
GP-16
GP-17
GP-13
GP-19
GP-20
% Al
0.141
0.500
0.304
0.427
0.534
0.595
0.519
0.595
1.080
0.830
0.633
0.472
0.589
0.534
0.469
0.215
0.397
0.455
0.658
0.828
ppm Ca
<2.0
<2.0
4.1
3.5
<2.0
<2.0
<2.0
<2.0
3.5
22.0
<2.0
<2.0
31.9
<2.0
<2.0
<2.0
<2.0
4.8
7.9
9.8
% Fe
0.105
0.444
0.490
0.352
0.380
0.347
0.408
0.493
0.657
0.876
0.437
0.284
0.448
0.383
0.307
0.184
0.264
0.263
0.201
0.789
ppm K
102
144
103
139
143
106
173
131
212
152
836
97
166
70
73
60
99
104
241
263
ppm Mg
163
143
103
174
137
111
155
L64
270
184
119
133
275
95
76
84
148
155
255
288
ppm Na
23.1
13.8
18.1
15.1
23.2
12.6
20.0
28.5
32.1
30.3
36.0
17.1
22.5
0.3
14.0
20.9
18.5
19.6
180
26.0
% P04
0.032
0.037
0.043
0.043
0.031
0.017
0.026
0.048
0.034
0.045
0.016
0.030
0.22
0.017
0.018
0.018
0.019
0.022
0.069
0.030
84
-------
TABLE 5. AAS ANALYSIS OF TRACE METAL CONCENTRATIONS
IN SOIL (GP) SAMPLES
Sample ppm Ag
GP-1 <1.3
GP-2 <1.3
GP-3 <1.3
GP-4 <1.3
GP-5 <1.3
GP-6 <1.3
GP-7 <1.3
GP-8 <1.3
GP-9 <1.3
GP-10 <1.3
GP-11 <1.3
GP-12 <1.3
GP-13 <1.3
GP-14 <1.3
GP-15 <1.3
GP-16 <1.3
GP-17 <1.3
GP-18 <1.3
GP-19 <1.3
GP-20 <1.3
ppm As
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
ppm
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
Be
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
ppm Bi
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
<6.0
ppm
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
Cd
.3
.3
.3
.3
.3
.3
.3
.3
.3
.3
.3
.3
. 3
. 3
. 3
, 3
. 3
. 3
. 3
. 3
ppm
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
<3.
Co
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
ppm
4.
4.
4.
5.
6.
6.
5.
6.
10.
18.
6.
4.
9.
4.
2.
2.
6.
10.
6.
15.
Cr
1
7
3
4
4
8
8
6
7
9
9
1
4
1
0
5
6
9
6
0
ppm Cu
1.6
1.7
1.9
2.2
2.1
1.8
2.2
2.1
1.9
4.0
1.3
0.7
2.9
2.7
1.2
0.6
0.7
0.7
1.6
2.9
(continued)
85
-------
TABLE 5 (continued).
Sample
GP-1
GP-2
GP-3
GP-4
GP-5
GP-6
GP-7
GP-8
GP-9
GP-10
GP-11
GP-12
GP-13
GP-1 4
GP-1 5
GP-16
GP-17
GP-18
GP-19
GP-20
ppm Ni
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
<6
c6
ppm Pb
7.3
6.6
11.9
9.3
12.7
6.7
8.1
10.1
12.7
12.4
4.1
6.8
7.2
7.0
7.9
8.0
8.0
4.3
15.0
15.3
ppm Sb
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
ppm Se
<2.5
8.9
7.2
7.7
9.9
4.5
9.9
<2.5
9.0
10.8
10.0
<2.5
6.2
9.9
<2.5
9.9
8.9
6.3
6.3
9.0
ppm Sn
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25
ppm Ti
211
98
57
72
162
163
195
201
243
129
147
175
71
111
87
61
98
149
65
242
ppm Zn
9.3
11.6
9.4
22.3
10.4
8.4
11.1
9.5
11.6
11.6
5.7
5.7
149
6.3
5.1
5.0
5.8
5.7
9.7
9.9
86
-------
TABLE 6. AAS ANALYSIS OF MATRIX CONSTITUENTS
IN SEDIMENT (PA) SAMPLES
Sample
PA-1
PA- 2
PA- 3
PA-4
PA-5
PA-6
PA- 7
PA-8
PA-9
PA-10
PA- 11
PA-12
PA-13
PA-14
PA-15
PA-16
PA-17
% Al
0.477
0.686
0.321
0.630
0.356
0.496
0.500
0.369
0.420
0.544
0.381
0.927
1.03
0.396
0.840
0.924
0.926
ppm Ca
70.5
57.4
10.4
122
5.0
288
254
12.3
3.6
502
38.0
5830
51.3
25.7
3.1
22.9
4.1
% Fe
2.68
2.95
5.31
3.81
7.83
3.96
3.89
3.06
5.25
6.90
2.41
7.60
5.60
2.45
10.6
6.17
5.30
ppm K
685
642
303
541
376
481
461
362
330
513
494
696
753
343
605
889
622
ppm Mg
440
483
282
462
206
632
608
267
348
447
286
1780
1380
308
854
997
1260
ppm Na
112
82.0
87.9
132
129
122
123
209
51.5
76.5
205
70.9
50.0
64.9
67.0
88.4
68.7
°/ "PO
/[
0.10
5'C
0.10
0.11
0.19
0.11
0.11
0.09
0.14
0.18
0.23
0.23
0.16
0.11
0.34
0.34
0.17
*Sample size insufficient for analysis
87
-------
TABLE 7. AAS ANALYSIS OF TRACE CONSTITUENTS
IN SEDIMENT (PA) SAMPLES
Sample ppm Ag
PA-1 <1.3
PA-2 <1.3
PA-3 <1.3
PA-4 <1.3
PA-5 <1 . 3
PA-6 <1.3
PA-7 <1.3
PA-8 <1.3
PA-9 <1.3
PA-10 <1.3
PA-11 <1.3
PA-12 <1.3
PA-13 <1.3
PA-14 <1.3
PA-15 <1.3
PA-16 <1.3
PA-17 <1.3
ppm Ba
68
44
35
56
30
54
72
31
28
117
44
177
32
55
29
29
28
ppm Be
0.7
0.8
1.2
1.0
1.7
1.0
1.0
1.2
1.2
1.1
0.9
1.2
1.2
1.0
1.9
1.8
1.7
ppm Cd
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0.3
<0. 3
<0. 3
<0. 3
<0. 3
ppm Co
8.9
20.9
12.2
12.0
18.3
15.3
15.8
14.9
15.7
16.8
13.0
17.3
15.5
11.8
20.5
16.6
14.2
ppm Cr
8.6
11.0
13.6
7.2
10.4
9.3
13.1
7.3
12.8
19.7
1.3
27.4
21-. 5
5.8
25.8
27.6
12.7
ppm Cu
10.5
10.9
8.5
32.7
12.9
57.6
48.0
10.2
16.2
17.8
9.0
25.3
21.9
28.8
25.9
26.2
29.3
(continued)
88
-------
TABLE 7 (continued).
Sample
PA-1
PA-2
PA-3
PA-4
PA-5
PA-6
PA-7
PA-8
PA-9
PA-10
PA-11
PA-12
PA-13
PA-14
PA- 15
PA-16
PA-17
ppm Mn
571
1890
931
562
990
787
850
991
1050
2040
1020
593
702
864
1100
798
627
ppm Mo
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
<6.3
ppm Nl
15.8
24.8
22.4
21.2
27.6
18.1
20.1
25.6
19.4
23.1
26.5
61.1
20.8
16.8
25.0
25.2
22.3
ppm Pb
28.8
19.2
22.3
26.3
17.8
30.4
31.0
15.0
17.3
28.0
13.9
28.7
22.1
24.4
23.9
21.7
21.8
ppm Sr
5.3
3.4
2.7
8.8
4.3
15.8
11.5
3.3
4.7
11.6
3.4
26.7
7.7
8.5
5.0
13.7
6.2
ppm V
12
13
12
15
19
15
13
8.6
18
24
6.5
27
30
12
32
33
<6-0
ppm Zn
128
181
163
194
184
155
150
199
199
175
192
192
140
183
171
160
159
89
-------
TABLE 8. FIRST INTERFERENCE STUDY FOR THE ANALYSIS OF BARIUM*
ppm Metal Added
ppm Ba
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
Al
0
10
50
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
250
500
Fe
0
0
0
0
0
0
1000
5000
10000
0
0
0
0
0
0
0
0
0
500
5000
Ca
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
Mn
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
Peak
Height
(cm)
11.3
10.2
8.5
8.0
7.3
6.3
11.2
10.2
10.2
11.5
12.0
12.3
11.5
11.9
11.9
11.7
11.7
11.5
6.8
6.1
Net
Change
Absorbance (%)
0.049
0.045
0.038
0.035
0.032
0.027
0.051
0.046
0.045
0.052
0.054
0.054
0.051
0.053
0.053
0.053
0.052
0.051
0.031
0.027
0
-10
-25
-29
-36
-45
- 1
-10
-10
+ 2
+ 6
+ 8
+ 1
+ 5
+ 5
+ 3
+ 3
+ 1
-40
-47
*0.2% K added; N 0-C H flame
90
-------
TABLE 9. SECOND INTERFERENCE STUDY FOR
ppm Major Constituents Added
ppm Ba
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
Al
0
50
100
500
1000
0
0
0
0
b
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
500
Ca
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
250
Fe
0
0
0
0
0
0
0
0
,0
0
1000
5000
10000
0
0
0
0
0
0
0
0
0
0
0
0
0
5000
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
250
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
250
P04
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
250
Peak
Height
(cm)
16.4
16.0
15.9
15.5
15.5
15.4
15.6
15.4
15.2
15.4
14.9
14.6
14.1
15.3
15.5
15.0
14.8
14.7
14.7
14.5
14.5
14.6
14.6
14 .'6
14.5
14.6
14.2
Net
Change
Absorbance (%)
0.067
0.061
0.064
0.064
0.064
0.064
0.064
0.064
0.064
0.064
0.061
0.061
0.058
0.064
0.064
0.064
0.061
0.061
0.061
0.058
0.058
0.059
0.059
0.059
0.059
0.059
0.059
0
-2
-3
-5
-5
0
+1
0
-1
0
-3
-5
-8
0
+1
-2
-3
0
0
-1
-1
0
0
0
0
0
-3
*0.2% La and 0.2% Na added;
flame
91
-------
TABLE 10. INTERFERENCE STUDY FOR THE ANALYSIS OF BERYLLIUM*
ppm Be
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
ppm
Al
0
100
500
1000
0
0
0
0
0
0
0
0
0
500
500
250
Ma j or
Fe
0
0
0
0
1000
5000
10000
0
0
0
0
0
0
500
5000
5000
Constituents
Mg
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
Added
Mn
0
0
0
0
0
0
0
0
0
0
50
200 -
500
0
0
0
Peak
Height
(cm)
15.7
14.9
13.0
11.8
16.5
16.1
16.0
15.9
15.9
16.0
16.0
15.8
15.9
13.0
13.7
14.2
Absorbance
0.134
0.127
0 . 110
0.099
0.142
0.138
0.136
0.135
0.134
0.138
0.138
0.135
0.136
0.109v
0.115
0.120
Net
Change
(%)
0
- 5
-17
-25
+ 5
+ 3
+ 2
+ 2
+ 2
+ 2
+ 2
+ 1
+ 2
-16
-13
_ Q
*N 0-C2H flame
92
-------
TABLE 11. THE USE OF OXINE TO CONTROL INTERFERENCES
ppm Be
1
1
1
1
1
1
1
*N
ppm Al
Added
0
0
0
500
500
500
500
20-C2H2 flame
TABLE 12. ALUMINUM,
%
CALCIUM,
Oxine
Added
0
0.15
0.25
0
0.10
0.20
0.40
_-- i
Peak Height
(cm)
6.1
6.1
6.1
5.3
5.3
5.4
5.5
AND PHOSPHATE INTERFERENCE
FOR THE ANALYSIS OF
BERYLLIUM*
Net Change
0
0
0
-13
-13
-11
-10
STUDY
ppm Major Constituents
ppm Be
1
1
1
1
1
1
1
1
1
Al Ca
0 0
500 0
0 50
0 200
0 500
0 0
0 0
0 0
500 0
P°4
0
0
0
0
0
50
200
500
0
Added
La
0
0
0
0
0
0
0
0
1000
Peak Net
Height Change
(cm) Absorbance (%)
19.0 0.171
13.7 0.124
18.2 0.163
18.5 0.166
19-0 0.169
19.1 0.170
19.0 0.167
19.3 0.169
14.1 0.127
0
-28
- 4
- 3
0
0
0
+ 2
-26
flame
93
-------
TABLE 13. FIRST INTERFERENCE STUDY FOR THE ANALYSIS OF CALCIUM*
ppm Major Constituents Added
ppm Ca Al
5 0
5 50
5 100
5 500
5 1000
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 ' 0
5 0
5 1000
Fe
0
0
0
0
0
50
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
1000
Mg
0
0
0
0
0
0
0
0
0
50
100
200
500
0
0
0
0
0
0
0
0
0
500
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
50
100
200
500
0
0
0
0
0
500
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
10
70
130
200
850
200
Peak
Height
(cm)
13.7
13.5
13.6
12.2
9.8
13.5
13.0
12.7
12.8
13.4
13.4
12.8
12.9
13.8
13.3
13.0
11.7
13.5
13.4
13.1
13.0
8.6
6.9
Absorbance
0.251
0.250
0.250
0.232
0.200
0.248
0.238
0.230
0.237
0.250
0.248
0.233
0.238
0.256
0.242
0.240
0.214
0.245
0.246
0.242
0.242
0.167
0.124
Net
Change
(%)
0
-1
-1
-11
-28
-1
-5
-7
-6
-2
-2
-6
-5
+1
-3
-5
-14
-1
-1
-4
-5
-37
-50
*0.2% La and 0.2% Na added; Air-C H flame
94
-------
TABLE 14. SECOND INTERFERENCE STUDY FOR THE ANALYSIS OF CALCIUM*
ppm
ppm Ca Al
5 0
5 50
5 100
5 500
5 1000
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 1000
Major
Fe
0
0
0
0
0
50
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
1000
Constituent
Mg
0
0
0
0
0
0
0
0
0
50
100
200
500
0
0
0
0
0
0
0
0
0
500
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
50
100
200
500
0
0
0
0
0
500
Added
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
10
70
130
200
850
200
Peak
Height
(cm)
12
10
9
6
6
12
12
11
11
11
12
12
12
12
12
12
12
12
12
12
12
12
7
.2
.2
.2
.7
.9
.0
.1
.9
.9
.9
.1
.0
.0
.0
.1
.1
.0
.2
.2
.3
.0
.1
.6
Absorbance
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
456
378
341
249
258
443
450
445
441
441
451
447
445
445
450
450
447
450
450
459
445
446
250
Net
Change
(%)
0
-16
-24
-45
-43
-1
0
-2
-2
-2
0
-1
-1
-1
0
0
-1
0
0
+1
-1
0
-37
*0.2% Na added;
flame
95
-------
TABLE 15. THIRD INTERFERENCE STUDY FOR THE ANALYSIS OF CALCIUM*
ppm Ca
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
ppm
Al
0
50
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1000
Major Constituents Added
Fe
0
0
0
0
0
50
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
1000
Mg
0
0
0
0
0
0
0
0
0
50
100
200
500
0
0
0
0
0
0
0
0
0
500
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
50
100
200
500
0
0
0
0
0
200
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
10
70
130
200
850
200
Peak
Height
(cm)
12.0
12.2
12.4
11.8
10.8
12.1
11.7
11.7
12.4
12.0
11.8
11.9
11.9
12.1
12.1
11.7
11.4
11.8
11.7
12.1
12.1
11.6
10.5
Absorbance
0,445
0.450
0.463
0.442
0.402
0.451
0.438
0.430
0.462
0.444
0.444
0.443
0.440
0.450
0.450
0.437
0.424
0.444
0.438
0.462
0.445
0.427
0.390
Net
Change
(%)
0
+2
+3
-2
-10
+1
-3
-3
+3
0
-2
-1
-1
+1
+1
_o
-5
-2
-3
+1
+1
-3
-13
*0.2% La and 0.2% Na added; N 0-C H flame
96
-------
TABLE 16. COMPARISON OF CALCIUM RESULTS FROM MSA AND AQUEOUS CALIBRATED
IN TWO FLAMES. WITH AND WITHOUT LANTHANUM
. ,.i —»•!..._. ... - -- -- - - _ - - . I I _ _ -n -.--_-_.. _ . - - -- __ , „-.„ ^ - -. . - . I
Sample
GP-7
GP-7
PA-1
PA-1
GP-2
GP-2
PA- 5
PA-5
Additives
0.2% Na
0.2% Na
0.2% Na
0.2% Na
0.2% Na + 0.2% La
0.2% Na + 0.2% La
0.2% Na + 0.2% La
0.2% Na + 0.2% La
Flame Type Figure
Air-C2H2 17
N20-C2H2 20
A -T -v f~* U T Q
Air— (_.~n_ J.O
Nn— r H 71
ou ^-")"") *-
A -IT— f H 9T
AJ.T L.~n_ £.j
N20-C2H2 24
Air— C~H_ 25
Nr\ r* u o £.
0U— Ij_n0 ZD
ppm Ca in
Aqueous
2.7
62
1.6
1106
162
170
283
254
Sample % Deviation between
MSA Aqueous
11.9
122
5.0
1369
163
178
275
262
and MSA values
-77
-49
-68
-19
0
-4
+3
-4
-------
TABLE 17. FIRST INTERFERENCE STUDY FOR THE ANALYSIS OF CHROMIUM*
ppm Major Constituents Added
ppm Cr
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Al
0
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
250
Ca
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2500
Fe
0
0
0
0
0
0
0
0
0
100
1000
5000
10000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
25
K
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
0
0
25
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
25
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
25
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
25
Peak
Height
(cm)
11.0
12.1
12.4
12.4
11.0
12.2
12.7
13.1
11.2
12.1
12.7
12.7
12.4
11.1
12.7
13.2
13.5
11.2
12.3
12.5
12.6
11.2
11.8
12.1
12.5
il.3
12.3
13.2
13.7
11.2
11.4
Absorbance
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
049
054
055
055
049
053
057
060
048
052
057
057
057
050
057
062
062
052
055
059
059
053
055
059
059
054
059
062
064
054
054
Net
Change
(%)
0
+10
+13
+13
0
+11
+15
+19
0
+8
+17
+17
+11
0
+14
+19
+22
0
+10
+11
+13
0
+5
+8
+12
0
+9
+17
+21
0
+2
*N_0-C2H flame
98
-------
TABLE 18. SECOND INTERFERENCE STUDY FOR THE ANALYSIS OF CHROMIUM*
ppm Major Constituents
ppm Cr
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Al
0
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
250
Ca
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
25
Fe
0
0
0
0
0
0
0
0
0
100
1000
5000
10000
0
0
0
0
0
0
0
0
0
0
0
0
0
2500
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
25
Added
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
25
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
25
Peak
Height
(cm)
13.5
13.5
13.5
13.4
13.4
13.5
13.7
13.6
13.5
13.6
13.4
12.7
12.1
13.9
13.8
13.5
13.5
13.2
13.3
13.3
13.4
13.5
13.5
13.5
13.8
13.5
13.8
Absorbance
0.067
0.066
0.066
0.066
0.066
0.066
0.067
0.067
0.062
0.061
0.060
0.058
0.056
0.070
0.070
0.061
0.061
0.061
0.061
0.061
0.064
0.064
0.064
0.064
0.067
0.064
0.061
Net
Change
(%)
0
0
0
-1
0
+1
+2
+1
0
+1
-1
-6
-11
0
-1
-3
-3
0
0
+2
+2
0
0
0
+2
0
-2
*0.2% Na added; N-C flame
99
-------
TABLE 19. INTERFERENCE STUDY FOR THE ANALYSIS OF COBALT*
ppm Major
pm Co
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Al
0
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
Fe
0
0
0
0
1000
5000
10000
0
0
0
0
0
0
0
0
0
Constituents Added
K
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
Mg
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
Peak
Height
(cm)
6.4
6.2
6.3
6.3
6.2
6.3
6.1
6.6
6.5
6.5
6.2
6.3
6.3
6.3
6.4
6.4
Net
Change
Absorbance (%)
0.055
0.054
0.054
0.054
0.053
0.054
0.053
0.056
0.057
0.057
0.053
0.053
0.055
0.055
0.055
0.055
0
-3
-2
-2
-3
-2
-5
+3
+2
+2
_0
-2
_2
-2
0
0
*Air-C H2 flame
100
-------
TABLE 20. CALCIUM AND PHOSPHATE INTERFERENCE STUDY
FOR THE ANALYSIS OF COBALT*
ppm Co
2
2
2
2
2
2
2
2
ppm Major
Ca
0
50
200
500
0
0
0
500
Constituents
P°4
0
0
0
0
50
200
500
500
Added Peak
Heieht
(cm) Absorbance
6.3 0.053
6.3 0.053
6.3 0.053
6.4 0.053
6.5 0.054
6.5 0.054
6.5 0.054
6.5 0.054
Net
Change
(%)
0
0
0
+2
+3
+3
+3
+3
*Air-C
H flame
TABLE 21.
INTERFERENCE
STUDY FOR COPPER ANALYSIS
Added Constituents
ppm Cu
3.00
3.00
3.00
3.00
3.00
ppm Fe
0
200
0
200
200
ppm Al
0
0
500
200
500
Apparent Concentration
of Cu (ppm)
3.00
3.07
2.85
3.02
3.02
% Net
Change
0
+2.4
-4.9
+0.8
+0.8
101
-------
TABLE 22. INTERFERENCE STUDY FOR THE ANALYSIS OF LEAD*
ppm Metal Added
ppb Pb Al
5 0
5 100
5 500
5 1000
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 0
5 1000
Ca
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
500
Fe
0
0
0
0
0
0
0
100
500
1000
5000
10000
0
0
0
0
0
0
0
0
0
0
0
0
0
10000
K
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
500
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
500
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
500
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
1000
500
Peak
Height
(cm)
16.
16.
16.
15.
16.
16.
16.
16.
16.
16.
15.
15.
16.
16.
16.
16.
16.
16.
16.
16.
16.
16.
17.
16.
17.
15.
0
1
1
9
6
7
7
3
1
2
9
6
5
4
4
4
6
6
6
6
7
6
0
8
0
6
Net
Change
Absorbance (%)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.022
.022
.022
.021
.023
.023
.023
.022
.022
.022
.022
.022
.023
.023
.023
.023
.023
.023
.022
.022
.022
.023
.023
.023
.023
.021
0
+1
+1
-1
+4
+5
+5
+2
+1
+1
-1
-2
+3
+2
+2
+2
+4
+4
+4
+4
+4
+4
+6
+5
+6
-3
*Air-C H flame
102
-------
TABLE 23. INTERFERENCE STUDY FOR THE ANALYSIS OF SELENIUM*
ppm Metal Added
ppm Se
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
Al
0
25
50
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Fe
0
0
0
0
0
0
50
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
Ca
0
0
0
0
0
0
0
0
0
0
50
100
200
500
0
0
0
0
0
0
0
0
K
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
100
200
500
0
0
0
0
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
100
200
500
Peak
Height
(cm)
14.7
0.5
0.6
0.8
1.7
1.2
7.4
6.3
4.2
3.6
5.6
5.2
5.7
5.1
13.7
14.1
14.6
14.1
5.6
5.6
5.1
4.8
Absorbance
0.098
0.000
0.001
0.001
0.005
0.004
0.047
0.040
0.020
0.023
0.034
0.033
0.033
0.033
0.091
0.096
0.098
0.094
0.035
0.035
0.032
0.030
Net
Change
(°/\
\'°)
0
-96
-96
-95
-88
-92
-50
-57
-72
-76
-62
-65
-61
-65
-7
-4
-1
-4
-62
-65
-65
-67
*Ar-H2 flame
103
-------
TABLE 24. USE OF ADDITIVES TO CONTROL INTERFERENCES
IN THE ANALYSIS OF SELENIUM*
ppm Se ppm Al EDTA
5
5
5
5
5
5
5
5
5
0 0
100 0
0 0
50 0
0 0
100 0
0 2000
100 2000
0 0
ppm Additive
Peak
Height
La Na Na2~EDTA (cm)
0 0
0 0
0 2000
0 2000
1000 0
100 0
0 0
0 0
0 0
0 8.8
0 1.1
0 7.7
0 5.9
0 1.3
0 2.2
0 8.7
0 1.9
2000 4.7
Absorbance
0.113
0.007
0.099
0.076
0.015
0.027
0.112
0.245
0.061
Net
Change
0
-88
-13
-33
-85
-75
-1
-78
-46
*Ar-H2 flame
TABLE 25.
COMPARISON OF
BY THREE AAS
RESULTS OF SELENIUM
FLAME METHODS
ANALYSIS
Sample
GP-10-SP*
GP-12-SP*
GP-20-SP*
Ar-H_ flame
20
14
17
ppm Selenium
Air-C2H2 Flame N
66
64
82
20-C2H2 Flame
55
55
55
*Sample spiked with 50 ppm selenium on a dry weight basis.
104
-------
TABLE 26. FIRST INTERFERENCE STUDY FOR THE ANALYSIS OF STRONTIUM*
ppm Major Constituents Added
ppm Sr
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
Al
0
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
Fe
0
0
0
0
0
500
1000
9000
0
0
0
0
0
0
0
0
Mn
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
Peak
Height
(cm)
19.4
*
17.2
14.6
13.5
19.4
19.2
19.4
18.6
19.5
19.7
19-7
19.8
19.5
19.8
19.8
19.8
Absorbance
0.248
0.238
0.194
0.180
0.248
0.250
0.251
0.245
0.252
0.260
0.260
0.260
0.252
0.260
0.260
0.260
Net
Change
0
-11
-25
-30
0
-1
0
-4
0
+1
+1
+1
0
+2
+2
+2
*0.2% K added;
flame
105
-------
TABLE 27. SECOND INTERFERENCE STUDY FOR THE ANALYSIS OF STRONTIUM*
ppm Major Constituents Added
ppm Sr Al
4 0
4 100
4 500
4 1000
4 0
4 0
4 0
4 0
4 0
4 0
4 0
4 0
4 0
4 0
4 0
4 0
Fe
0
0
0
0
0
500
1000
9000
0
0
0
0
0
0
0
0
Mn
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
Peak
Height
(cm)
19.4
20.2
20.2
19.6
19.5
19.2
19.4
18.4
19.4
20.0
20.0
19.8
19.1
19.3
17.6
16.0
Absorbance
0.260
0.270
0.270
0.255
0.260
0.255
0.255
0.241
0.260
0.266
0.266
0.266
0.260
0.267
0.237
0.220
Net
Change
0
+4
+4
+1
0
-2
0
-5
0
+3
+3
+2
0
+1
-8
-16
*1.0% La and 0.2% K added; N-O-C^H- flame
106
-------
TABLE 28. THIRD INTERFERENCE STUDY FOR THE ANALYSIS OF STRONTIUM*
ppm Major Constituents Added
ppm Sr
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
Al
0
10
30
50
70
100
500
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Ca
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
0
0
Fe
0
0
0
0
0
0
0
0
0
0
0
500
1000
5000
10000
0
0
0
0
0
0
0
0
0
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
Peak
Height
(cm)
18.2
17.1
17.5
17.4
17.4
17.5
16.9
16.0
17.7
17.3
17.3
17.0
16.6
14.7
12.6
16.8
16.2
16.0
16.9
17.4
17.0
17.1
17.7
16.0
Net
Change
Absorbance (%)
0.078
0.074
0.075
0.076
0.076
0.076
0.073
0.070
0.071
0.073
0.073
0.072
0.071
0.062
0.052
0.072
0.071
0.070
0.072
0.078
0.077
0.076
0.079
0.070
0
-6
-4
-4
-4
-4
-7
-12
-3
-4
-4
-6
-8
-19
-31
-8
-11
-11
-7
-3
-7
-6
-3
-11
*1% La and 0.2% K added; air-C^ flame
107
-------
TABLE 29. THE COMPARISON OF STRONTIUM ANALYSES USING VARIOUS METHODS
o
00
ppm Sr in Sample
Sample Flame
PA-14-SP Air-C H
PA-14-SP N20-C2H2
PA-14-SP N20-C2H2
PA-15 Air-C 2H2
PA-15 N20-C2H2
PA-15 N00-C0H0
Additives
0.2% Na +
0.2% Na
0.2% Na +
0.2% Na +
0.2% Na
0.2% Na +
1 % La
1% La
1% La
1% La
Figure
42
40
41
42
40
41
Aqueous
38
47
60
10
9.4
12
MSA
68
65
60
14
14
13
% Deviation between
Aqueous and MSA values
-44
-28
0
-29
-33
-8
-------
TABLE 30. FIRST INTERFERENCE STUDY FOR THE ANALYSIS OF TITANIUM*
ppm Major Constituents Added
ppm Ti
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
Al
0
20
60
100
500
1000
2000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
500
Ca
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
50
Fe
0
0
0
0
0
0
0
0
0
0
0
0
100
500
1000
5000
10000
0
0
0
0
0
5000
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
Peak
Height
(cm)
12.2
13.0
13.4
13.3
13.0
12.5
12.1
12.1
11.3
11.3
11.8
12.0
11.6
11.2
11.1
10.9
10.0
11.4
11.2
11.6
10.9
11.4
12.2
Absorbance
0.084
0.089
0.091
0.090
0.089
0.086
0.082
0.083
0.077
0.078
0.076
0.082
0.080
0.076
0.076
0.076
0.069
0.075
0.075
0.075
0.076
0.075
0.083
Net
Change
0
+7
+10
+9
+7
+3
-1
0
-7
-7
-3
0
-3
-6
-4
-9
-17
0
-2
+2
-4
0
+7
*0.2% Na added; N2°~C2H2 flame
109
-------
TABLE 31. SECOND INTERFERENCE STUDY FOR THE ANALYSIS OF TITANIUM*
ppm Major Constituents Addec
ppm Ti
30
30
30
30
30
30
30
30
30
30
30
30
30
30
Al
0
100
500
1000
0
0
0
0
0
0
0
0
0
430
Ca
0
0
0
0
0
50
200
500
0
0
0
0
0
0
Fe
0
0
0
0
0
0
0
0
0
1000
5000
9000
0
325
1 Peak
Height
(cm)
16.1
5.7
6.0
5.6
16.1
17.5
17.5
17.5
16.1
14.4
13.2
13.3
16.1
6.4
Absorbance
0.113
0.040
0.044
0.040
0.113
0.122
0.122
0.122
0.113
0.099
0.093
0.093
0.113
0.046
Net
Change
0
-65
-63
-65
0
+9
+9
+9
0
-11
-18
-18
0
-60
*1% La and 0.2% Na added; N 0-C H flame
110
-------
TABLE 32. FIRST INTERFERENCE STUDY FOR THE ANALYSIS OF VANADIUM*
ppm Major Constituents
ppm V
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Al
0
20
60
100
500
1000
2000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Ca
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Fe
0
0
0
0
0
0
0
0
0
0
0
0
500
1000
5000
10000
0
0
0
0
0
0
0
0
0
0
0
0
K
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
Added
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Peak
Height
(cm)
5.8
7.0
7.0
7.6
7.6
7-6
7.4
5.5
6.1
7.3
7.5
5.6
5.1
4.9
4.5
4.1
5.5
6.8
7.2
7.5
5.6
6.7
6.8
6.8
5.6
5.7
6.0
6.5
Absorbance
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
015
019
019
019
019
019
019
015
017
020
021
015
013
012
010
009
015
019
020
021
015
019
019
019
,015
0.015
0.016
0.018
Net
Change
("/)
\'°)
0
+21
+21
+31
+31
+31
+29
0
+11
+33
+36
0
-9
-13
-20
-27
0
+24
+31
+36
0
+20
+21
+21
0
+2
+7
+16
flame
(continued)
111
-------
TABLE 32 (continued)
ppm V
6
6
6
6
ppm Major Constituents
Al
0
0
0
0
Ca
0
0
0
0
Fe
0
0
0
0
K
0
0
0
0
Mg
0
0
0
0
Added
Mn
0
0
0
0
P°4
0
50
200
500
Peak
Height
(cm)
5.5
6.5
7.2
7.2
Absorbance
0.015
0.018
0.020
0.020
Net
Change
(%)
0
+18
+31
+31
112
-------
TABLE 33. SECOND INTERFERENCE STUDY FOR THE ANALYSIS OF VANADIUM*
ppm Major Constituents Added
ppm V
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Al
0
20
60
100
500
1000
2000
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Ca
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Fe
0
0
0
0
0
0
0
0
0
0
0
0
100
500
1000
5000
1000
0
0
0
0
0
0
0
0
0
0
0
0
Mg
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
0
0
0
0
Mn
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
0
0
0
0
P°4
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
50
200
500
Peak
Height
(cm)
8
8
8
8
8
8
8
8
8
8
8
8
7
7
7
6
6
7
8
7
7
7
7
7
7
7
7
7
7
.2
.4
.5
.4
.5
.4
.2
.1
.0
.2
.5
.1
.8
.4
.3
.7
.5
.9
.0
.8
.9
.9
.8
.8
.9
.9
.9
.9
.9
Absorbance
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.022
.022
.023
.022
.022
.022
.022
.021
.020
.022
.022
.021
.018
.018
.018
.018
.017
.020
.020
.020
.020
.020
.020
.020
.020
.020
.020
.020
.020
Net
Change
(%)
0
+2
+4
+2
+4
+2
0
0
-1
+1
+5
0
-4
-9
-10
-17
-20
0
+1
-1
0
0
-1
-1
0
0
0
0
0
*0.2% Na added; N20-C2H2 flame (continued)
113
-------
TABLE 33 (continued)
ppm V
6
6
6
ppm
Al
0
500
500
Major Constituents Added
Ca
0
50
50
Fe
0
1000
5000
Mg
0
50
50
Mn
0
50
50
P°4
0
50
50
Peak
Height
(cm)
7.8
8.1
8.1
Absorbance
0.020
0.020
0.020
Net
Change
(%)
0
+4
+4
114
-------
TABLE 34. THIRD INTERFERENCE STUDY FOR THE ANALYSIS OF VANADIUM*
pj>m Major Constituents Added
ppm V
6
6
6
6
6
6
6
6
6
6
6
6
Al
0
100
500
1000
0
0
0
0
0
0
0
0
Ca
0
0
0
0
0
50
200
500
0
0
0
0
Fe
0
0
0
0
0
0
0
0
0
100
5000
9000
Peak
Height
(cm)
15.3
15.4
15.3
15.3
15.5
15.5
15.7
15.7
15.3
15.2
15.1
15.4
Absorbance
0.026
0.026
0.026
0.026
0.026
0.027
0.027
0.027
0.026
0.025
0.025
0.025
Net
Change
(%)
0
0
0
0
0
0
+3
+3
0
-1
-1
+1
*1% La and 0.2% Na added; N20-C H flame.
TABLE 35. THE ANALYSIS OF VANADIUM IN PA-17
ppm V in PA-17
Flame Type Figure # Additives Aqueous MSA
N2°~C2H2 46 °'2% Na 25 24
N 0-C H 47 0.2% Na + 1% La 24 23
115
-------
TABLE 36. CONDITIONS USED FOR THE FINAL ANALYSIS OF SOIL (GP) AND SEDIMENT (PA) SAMPLES
Spectral Band
Wavelength Width Flame
Element (nm) (nm) Type
Interferences
Corrective Measures
Detection Limit
(ppm)
Ba
Be
Ca
Co
Cr
Cu
Mn
553.6
234.9
422.7
240.7
357.9
324.8
279.5
0.4
0.7
1.4
0.2
0.7
0.7
0.2
N 0-C H
Air-C2H2
lonization effect
Al, Fe
Al
lonization effect
Al
None
Addition of 0.2% potassium 6
or sodium to all solutions
Addition of 0.2% of lanthanum
to all solutions
Use of matrix-matched standards 0.4
Addition of oxine
Addition of 0.2% potassium 2
or sodium to all solutions
Addition of 0.2% lanthanum
and sodium to all solutions
No corrective measures required 3.0
lonization effect Addition of 0.2% potassium
Fe
None
None
or sodium to all solutions
Use of matrix-matched standards 2
for samples containing >500 ppm
Fe
No corrective measures required 0.6
No corrective measures required 0.5
-------
TABLE 36. (Continued)
Spectral Band
Wavelength Width Flame Detection Limit
Element (nm) (nm) Type Interferences Corrective Measures (ppm)
Ni
Pb
Se
Sr
232.0 0.2 Air-C_H? None No corrective measures required
283.3 0.7 Air-C_H9 None No corrective measures required
196.0 0.7 N20-C2H2 To be defined To be defined
460.7 1.4 N 0-C2H2 lonization effect Addition of 0.2% potassium or
sodium to all solutions
Al Addition of 0.2% lanthanum to
all solutions
2
4.0
25
1.5
Ti
V
365.3
318.4
0.2
0.7
N20-C2H2 lonization effect
N 0-C H lonization effect
Fe
Addition of 0.2% potassium to 25
all solutions
Use of matrix-matched standards
for samples containing >5000
ppm Fe
Addition of 0.2% potassium or 6.0
sodium to all solutions
Addition of 0.2% lanthanum to
all solutions
Zn
213.9
0.7
Air-C2H2 None
No corrective measures required 0.7
-------
TABLE 37. CALCIUM CONCENTRATIONS IN SOIL (GP) SAMPLES
AND SEDIMENT (PA) SAMPLES *
Sample
GP-1
GP-2
GP-3
GP-4
GP-5
GP-6
GP-7
GP-8
GP-9
GP-10
GP-11
GP-12
GP-13
GP-14
GP-15
GP-16
GP-17
GP-18
GP-19
GP-20
ppm Ca
90.7
177
180
386
204
111
97.0
89.5
48.3
206
45.9
38.6
584
70.3
37.4
70.1
75.1
135
408
78.9
Sample
PA-1
PA-2
PA-3
PA-4
PA-5
PA-6
PA- 7
PA-8
PA-9
PA-10
PA-11
PA-12
PA-13
PA-14
PA-15
PA-16
PA-17
ppm Ca
933
273
341
1780
205
1590
246
147
247
1650
280
15400
322
129
252
28.4
239
0.2% Na and 0.2% La added; N20 -
flame.
118
-------
TABLE 38. FINAL ANALYSIS OF TRACE ELEMENTS IN SOIL (GP) SAMPLES
ppm Constituent
Sample
GP-1
GP-2
GP-3
GP-4
GP-5
GP-6
GP-7
GP-8
GP-9
GP-10
GP-11
GP-12
GP-13
GP-14
GP-15
GP-16
GP-17
GP-18
GP-19
GP-20
Be
<0.4
<0.4
<0.4
<0.4
<0.4
O.4
<0.4
<0.4
<0.4
<;0.4
<0.4
<0.4
<0.4
<0.4
<0.4
<0.4
<0.4
<0.4
<0.4
<;0.4
Co
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
<3.0
3.0
Cr
5.2
5.5
3.8
4.5
6.9
4.8
5.2
5.9
8.6
21.3
6.8
4.8
8.6
4.1
3.8
2.4
5.3
5.5
5.2
12.4
Cu
0.8
1.7
1.2
1.7
2.1
1.7
1.7
1.7
1.7
4.1
1.7
0.8
2.5
1.2
0.8
1.2
1.2
0.8
1.7
2.7
Ni
3.0
3.0
2.5
3.8
3.8
3.4
3.6
3.8
3.8
6.8
4.5
2.7
4.5
3.0
<2.0
2.3
2.5
4.9
3.4
3.8
Pb
8.9
8.9
9.4
8.9
8.9
7.1
8.9
8.9
9.8
8.9
7.1
<4.0
<4.0
8.9
4.5
6.2
8.9
7.1
11.6
8.9
Ti
Aqueous
101
98
77
50
169
133
163
169
100
158
148
56
44
80
124
50
89
33
33
62
MM
87
84
66
43
145
115
141
145
94
136
128
48
38
69
107
43
77
28
28
54
Zn
6.7
8.6
7.9
19.3
7.3
7.2
10.6
8.3
7.8
10.9
4.7
3.1
11.6
5.0
4.3
5.2
7.8
4.2
8.4
6.4
-------
TABLE 39. FINAL ANALYSIS OF TRACE ELEMENTS IN SEDIMENT (PA) SAMPLES
ppm Constituent
Sample
PA-1
PA- 2
PA- 3
PA- 4
PA- 5
PA- 6
PA- 7
PA- 8
PA-9
PA-10
PA-11
PA-12
PA- 13
PA-14
PA-15
PA-16
PA-1 7
Ba
43
47
43
50
33
49
26
36
53
41
39
134
39
51
74
33
33
Be
0.8
1.5
1.4
1.4
1.9
1.2
1.5
1.5
1.5
1.0
1.0
1.4
1.5
1.0
2.2
1.9
1.9
Co
7.5
19.5
11.8
10.6
16.5
12.2
13.4
14.4
17.3
12.2
13.8
13.8
13.4
15.4
16.9
12.6
13.8
Cr
8.8
10.3
8.8
12.2
11.7
12.9
9.8
9.3
12.9
13.6
7.8
31.1
19.0
9.4
27.5
21.0
22.1
Cu
12.0
12.0
9.8
28.5
12.0
62.6
13.2
10.8
16.5
12.4
10.0
27.3
20.7
18.1
27.3
24.1
26.1
Mn
693
2010
985
500
1260
806
701
1060
1280
922
1570
532
657
504
1300
693
693
Ni
16.4
30.2
29.3
25.8
36.7
25.1
28.0
30.4
30.2
23.6
31.6
31.6
26.2
26.2
33.1
27.3
28.7
Pb
31.2
17.9
21.4
28.6
14.3
33.0
17.0
13.4
17.0
19.6
15.2
28.6
19.6
21.4
21.4
16.1
18.7
Sr
7.9
8.6
5.7
19.7
5.0
19.2
7.9
7.1
10.2
8.7
10.0
31.5
23.6
7.9
11.6
15.0
13.4
V
12
13
12
13
15
14
9.5
11
12
14
9.0
24
20
11
27
19
22
Zn
90
127
122
121
156
102
121
124
133
112
135
116
112
60
154
118
118
-------
TABLE 40. AAS ANALYSIS OF ELEMENTS IN SHIPPING BLANKS
Shipping
pg Element Present
Blank Al Ag As Ba Be Bi Ca Cd Co Cr Cu Fe K
GP <20 <5 <300 * <0.2 <25 77
PA-a <20 <5 * <25 <0.2 * 175
PA-b 76 <5 * <25 <0.2 * 100
-------
TABLE 41. AVERAGES AND STANDARD DEVIATIONS OF DUPLICATE SOIL (GP) AMD SEDIMENT (PA) SAMPLES
Sample
GP-3
GP-7
GP-17
PA- 2
PA-3
PA-8
PA-13
Set
III
III
III
IV
IV
IV
IV
Ba
*
*
A
47+3
43 + 5
36 + 2
39 + 1
Average ppm
Be
•
t
t
t
1.6 + 0.0
1.4 + 0.1
1.6 + 0.0
1.6 + 0.0
Trace Constituent and Standard Deviation
Co
t
t
t
19.5 + 0.2
11.8 + 0.8
14.4 + 0.6
13.4 + 0.0
3.
5.
5.
10.
8.
9.
19.
8
2
3
7
9
5
6
Cr
+ 0.0
+ 0.0
+ 0.2
+ 0.5
+ 0.0
+ 0.5
+ 0.2
1.2
1.7
1.2
12.0
9.8
10.8
20.7
Cu
+ 0.0
+ 0.0
+ 0.0
+ 0.0
+ 1.0
+ 0.0
+ 0.2
Mn
*
5V
A
2010 +
985 +
1060 +
657 +
21
156
220
12
-continued-
*Analysis not required.
Average and standard deviation not applicable since element not detectable in sample.
-------
TABLE 41 (continued)
OO
Sample
GP-3
GP~7
GP-17
PA-2
PA- 3
PA-8
PA- 13
Set
III
III
III
IV
IV
IV
IV
Ni
2.5 + 0.2
3.6 + 0.2
2.5 + 0.2
30.2 + 0.0
29.3 + 0.5
30.4 ± 0.2
26.2 + 0.0
Average ppm
Pb
9.4 + 0.4
8.9 + 0.0
8.9 + 0.0
17.9 + 0.0
21.4 + 0.0
13.4 + 0.0
19.6 + 0.0
Trace Constituent and Standard Deviation
Sr
A
*
j.
8.6 + 0.2
5.7 + 0.6
7.1 + 0.8
23.6 + 3.4
Ti(Aq)
77 + 6
163 + 15
89 + 9
ft
A
*
ft
Ti(MM)
66 + 5
141 + 13
77 + 7
ft
*
ft
ft
V
ft
ft
ft
13 + 1
12 + 1
11 + 1
20 + 0
Zn
7.9 + 0.2
10.6 + 1.1
7.8 + 2.9
127 + 6
122 + 10
124 + 1
112 + 0
*Analysis not required.
-------
TABLE 42. PERCENT RECOVERY OF SPIKED SOIL (GP) AND SEDIMENT (PA) SAMPLES
Sample
GP-4
GP-8
GP-19
PA-9
PA- 14
PA- 12
Set
III
III
III
IV
IV
IV
Recovery
Ba Be Co Cr
* t # 100
t # 101
* t # 105
61 96 88 94
44 95 88 101
96 87 84 99
Cu
84
80
88
89
88
90
Mn
ft
ft
ft
t
t
t
TABLE 42 (continued).
Sample
GP-4
GP-8
GP-19
PA-9
PA-14
PA-17
Set
III
III
III
IV
IV
IV
% Recovery
Ni Pb Sr Ti(Aq) Ti(MM)
102 74 * 107 92
102 75 * 1" f
109 89 * 86 74
94 94 90 ft ft
95 90 98 * *
91 84 94 * *
V
ft
ft
*
86
90
104
Zn
87
95
100
114
t
130
*Analysis not required.
Spike omitted
Percent recovery not applicable since element not detectable in sample.
124
-------
TABLE 43. T_RACEJELEMENT CONCENTRATIONS IN REFERENCE SEDIMENT B
Reference
Sediment Set
B II
B II
B III
B IV
B IV
ppm Trace Constituent
Ba Be Cd Co Cr Cu
12 <0.4 * <3.0 59.7 8.9
13 <0.4 * <3.0 63.3 8.9
* <0.4 0.9 <3.0 49-8 8.3
14 <0.4 1.0 <3.0 48.4 8.0
14 0.4 1.0 <3.0 50.5 8.8
Mn
8.3
7.2
ft
6.0
6.5
TABLE 43 (continued)
Reference
Sediment Set
B II
B II
B III
B IV
B IV
ppm Trace Constituent
Ni Pb Sr Ti V
2.3 8.7 2.3 87 9.2
2.3 7.9 2.3 82 10
2.3 8.2 * 41 *
2.4 8.0 2.0 * 8.6
2.4 8.0 2.0 * 8.6
Zn
12.4
13.0
12.1
11.9
13.5
*Analysis not required.
125
-------
TABLE 44. TRACE ELEMENT CONCENTRATIONS IN REFERENCE SEDIMENT C
Reference
Sediment
C
C
C
C
C
C
C
C
Set
II
II
II
II
III
III
IV
IV
Ba Be
26 <0.4
20 <0.4
20 <0.4
20 <0.4
* <0.4
* <0.4
21 <0.4
21 <0.4
ppm Trace Constituent
Cd Co Cr
* <3.0 297
* <3.0 320
* <3.0 295
* <3.0 286
4.3 <3.0 241
4.4 <3.0 245
5.0 <3.0 276
4.9 <3.0 268
Cu
24.5
26.8
24.7
24.2
23.8
23.8
24.1
24.1
Mn
11.6
15.6
11.4
13.2
*
*
14.0
12.0
Reference
Sediment
C
C
C
C
C
C
C
C
C
Set
II
II
II
II
III
III
III
IV
TV
TABLE 44
Ni
2.4
2.4
2.4
2.4
2.5
2.5
2.7
2.4
2.4
(continued) .
ppm Trace Constituent
Pb Sr Ti
18.0 5.3 70
19.0 5.3 122
18.0 4.6 46
18.0 4.6 82
17.0 * 65
16.9 * 15
16.9 * 71
18.0 5.3 *
18.0 4.2 *
V
12
12
12
13
*
*
*
10
9.2
Zn
28.0
37.4
52.0
37.0
37.0
38.4
41.0
38.6
33.2
*Analysis not required.
126
-------
TABLE 45. PERCENT RECOVERY OF SPIKED SAMPLES FOR REFERENCE SEDIMENT B
Sample Set
B II
B III
B IV
% Recovery
Ba
A
*
76
Be
94
102
104
Cd
*
97
94
Co
t
f
t
Cr
95
97
105
Cu
83
87
95
Mn
*
A
106
TABLE 45 (continued)
Reference
Sediment
B
B
B
% Recovery
Set
II
III
IV
Ni
87
107
95
Pb
93
89
94
Sr
81
A
100
Ti
#
#
A
V
117
t
97
Zn
60
100
92
*Analysis not required.
'Percent recovery not applicable since element not detectable in sample,
Spike omitted.
127
-------
TABLE 46. PERCENT RECOVERY OF SPIKED SAMPLES FOR REFERENCE SEDIMENT C
Reference
Sediment
C
C
C
C
Set
II
II
III
III
Ba Be
* 83
* 85
ft 97
80 101
% Recovery
Cd Co
ft
ft
87 f
93 t
Cr
#
104
94
112
Cu
91
90
91
97
Mn
ft
ft
ft
100
TABLE 46 (continued).
Reference
Sediment
C
C
C
C
% Recovery
Set
II
II
III
III
Ni
86
86
82
98
Pb
94
94
83
88
Sr
72
79
*
95
Ti
#
#
#
j.
V
118
118
*
105
Zn
90
101
94
80
"'Analysis not required.
4.
'Percent recovery not applicable since element not detectable in sample.
#Spike omitted.
128
-------
REFERENCES
1. The Perkin-Elmer Corporation. Analytical Methods for Atomic-Absorption
Spectrophotometry. Norwalk, Connecticut, September 1976.
2. McKown, M.M., J.G. Montalvo, and D.V. Brady, BLM Progress Report I,
MAFLA Baseline Environmental Survey. BLM Project No. 08550-CT-4-15,
Bureau of Land Management, Washington, B.C., December 20, 1974.
3. Davison, R.L., D.F.S. Natusch, J.R. Wallace, and C.A. Evans, Jr.
Trace Elements in Fly Ash: Dependence of Concentration on Particle
Size. Env. Sci. Tech. 8(13):1107-11113, 1974.
4. Barnes, H.L., and S.B. Romberger, Chemical Aspects of Acid Mine Drainage.
J. Water Pollution Control Fed. 40:371-384, 1968.
5. Snell, F.D., editor. Encyclopedia of Industrial Chemical Analysis.
Vol. 17, Wiley Inter-Science, Somerset, N.J., 1973. pp. 66-67.
6. Klein, R., Jr., and C. Hack, Standard Additions: Uses and Limitations
in Spectrophotometric Analysis. Amer. Lab. 9(7):21-27, 1977.
7. Koirtyohann, S.R., and E.E. Pickett, Spectral Interferences in Atomic
Absorption Spectrometry. Anal. Chem. 38:585-587, 1966.
8. Bano, F.J. The Determination of Trace Amounts of Barium in Calcium
Carbonate by Atomic-Absorption Spectrophotometry. Analyst 98:655-658,
1973.
9. Cioni, R., A. Mazzucotelli, and G. Ottonello, Interference Effects in
the Determination of Barium in Silicates by Flame Atomic-Absorption
Spectrophotometry. Analyst 101:956-960, 1976.
10. Fleet, B., V. Liberty, and T.S. West, A Study of Some Matrix Effects
in the Determination of Beryllium by Atomic Absorption Spectroscopy in
the Nitrous Oxide Acetylene Flame. Talanta 17^:203-210, 1970.
11. Sirdiropoulos, N, The Determination of Calcium in Chrome Refractories
by Atomic Absorption Spectroscopy. Analyst ^4_:389, 1969.
12. Rawa, J.A., and E.L. Henn, Interference effects in the determination
of Chromium by Atomic Absorption. Amer. Lab. 9(8):31-34, 36, 38, 1977.
13. Chakrabarti, C.L., The Atomic Absorption Spectroscopy of Selenium. Anal.
Chim. Acta 42:379-387, 1968.
129
-------
14. Kirkbright, G.F., and L. Ranson, Use of the Nitrous Oxide-Acetylene
Flame for Determination of Arsenic and Selenium by Atomic Absorption
Spectrometry. Anal. Chem. 43:1238-1241, 1971.
15. Martin, T.D., and J.F. Kopp, Determining Selenium in Water, Wastewater,
Sediment, and Sludge by Flameless Atomic Absorption Spectroscopy. At.
Absorp. Newsl. 14:109-116, 1975.
16. Fernandez, F.J., and D.C. Manning, The Determination of Arsenic at Sub-
Microgram Levels by Atomic Absorption Spectrophotometry. At. Absorp.
Newsl. 10:86-88, 1971.
17. Pierce, F.D., T.C., Lamoreaux, H.R. Brown, and R.S. Fraser, An Automated
Technique for the Submicrogram Determination of Selenium and Arsenic
in Surface Water by Atomic Absorption Spectroscopy. Appl. Spectroscopy
3_0:38-42, 1976.
18. Pierce, F.D., and H.R. Brown, Comparison of Inorganic Interferences in
Atomic Absorption Spectrometric Determination of Arsenic and Selenium.
Anal. Chem. 4jh 1417-1422, 1977.
19. Yore1, J., R. Avni, and M. Stiller, Elimination of Phosphate Interference
in Flame Photometric Determination of Strontium and Barium. Anal.
Chim. Acta 28_: 331-335, 1263.
20. Zander, A.T., Factors Influencing Accuracy in Background-Correcter
AAS. Amer. Lab. 8(11): 11-22, 19_76.
21. McKown, M.M., and J.G. Montalvo, The Quality Control of Trace Metal
Analysis for the MAFLA Environmental Survey BLM Contract #08550-CT-4-15
Bureau of Land Management, Washington, D.C., August 1, 1975.
130
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PROCEDURE FOR METAL ANALYSIS OF SEDIMENTS
Environmental Protection Agency
Region IV, Surveillance and Analysis Division
Chemical Services Branch
Tentative Digestion of Sediments for Metal Analysis
June 28, 1973
1. Weigh 1 to 2 g of dry (103°C) sediment into a 250 ml Erlenmeyer flask.
2. Add 50 ml water, 0.5 ml cone HNO and 5 ml cone HC1.
3. Heat at 95°C for 15 min.
4. Cool and clarify sample by filtering or centrifuging.
5. Dilute to 100 ml.
6. Proceed with atomic absorption analyses for Pb, Zn, Mn, Cd, Cu, Ni,
and Cr.
GSRI ALTERATIONS*
1. 4 g of dry sediment was used.
2. 75 ml of water, 1.0 ml cone. HNO,., and 10 ml cone. HC1 were added.
3. Heating at 95°C was continued until volume was reduced to 10 to 15 ml
(approximately 3 hr).
4. Filtration rather than centrifugation was performed.
5. The final dilution volume was 50 ml.
*Changes described were effected in order to improve accuracy and
detection limits.
131
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/7-78-085
3. RECIPIENT'S ACCESSIOI*NO.
4. TITLE AND SUBTITLE
Investigation of Matrix Interferences for AAS Trace
Metal Analyses of Sediments
5. REPORT DATE
May ]978 issuing date
6. PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
Mary M. McKown, Charles R. Tschirn and Patty P.F. Lee
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Gulf South Research Institute
P.O. Box 26518
New Orleans, LA 7-186
10. PROGRAM ELEMENT NO.
EHE 625
11. CONTRACT/GRANT NO.
R 804317-01
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Monitoring and Support Lab.
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
-Cin., OH
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/06
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This research program was initiated with the overall objective of•developing
reliable, cost-effective methods utilizing flame atomic absorption spectrophotometry
for the trace elemental analysis of soil and sediment samples containing complex
matrices. The soil sample matrix studied consisted of more than 0.1 percent
aluminum and iron; the sediment sample matrix contained more than 0.1 percent
aluminum and iron plus lesser quantities of calcium, magnesium, manganese, phosphate
and potassium.
Conventional flame AAS methods were found to produce accurate results for the
analyses of cobalt, copper, lead, manganese, nickel and zinc in these matrices.
The barium, calcium, strontium and vanadium content of these samples could not
be accurately determined by conventional flame AAS techniques. However, reliable
results were obtained using appropriate flame types with the addition of lanthanum
and/or an easily ionizable alkali salt to all samples and standards.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COS AT I Field/Group
Cobalt, copper, lead, manganese, nickel,
zinc, barium, calcium, strontium,
vanadium .
Sediment Analysis
Trace Metals
Atomic Absorption
99A
99E
13. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS
URITY CLASS (ThisReport)
UNCLASSIFIED
20. SECURITY CLASS (This page)
UNCLASSIFIED
21. NO. OF PAGES
138
22. PRICE
EPA Form 2220-1 (9-73)
132
ft U.S. GOVERNMENT PRINTING OFFICE 1978- 757- 140/685Z
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