«- *
908R80015
SIMULTANEOUS MULTIELEMENT ANALYSIS OF LIQUID SAMPLES
BY
INDUCTIVELY COUPLED ARGON PLASMA ATOMIC-EMISSION SPECTROSCOPY
AT
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
REGION V
CENTRAL REGIONAL LABORATORY
1819 W. PERSHING ROAD
CHICAGO, ILLINOIS 60609
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The mention of trade names or commercial products does not imply endorsement
by the Environmental Protection Agency or the Central Regional Laboratory.
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1.0 Scope and Application
1.1 This method is applicable to fresh water samples including drinking
v/aters, surface waters, domestic and industrial waste effluents for the analyses
of total and dissolved metals of the twenty elements listed in Table 1.
1.2 The detection limits for the 20 elements are listed in Table 2. These
data represent the mean values determined on 5 days, over a 3 month period. Each
individual detection limit was determined by averaging 10 consecutive 10 second
exposures of each element. The numerical values are in yg/1 and each is the con-
centration of that element necessary to produce a signal twice the standard devia-
tion of the background noise.
The two sigma detection limit, defined above, is in common use and pro-
duces a figure of merit by which various analytical appproaches may be compared,
but, like most detection limits, are almost never at a level that can be accurately
reported. A more useful approach, which is similar to the Lower Optimum Concen-
tration Range (LOCR) reported for atomic absorption use , is the Lowest Quantitative
9
Determinable Concentration (LQO)~. The LQD is defined as the amount of material
necessary to produce a signal that is 10X the standard deviation of the noise
(i.e. 5X detection limit). The LQD for the 20 elements are also reported in Table 2
1.3 The relative standard deviation (RSD) of a 1 mg/1 standard for all ele-
ments is of the order of 1* over 5-10 minute periods and 2-4* over the course of
an 8 hour day. A typical set of RSDs is presented in Table 3 and demonstrates
variations for 10 consecutive 10 second integration periods.
1.4 The working ranges for all twenty elements are from the LQO to above
100 ppm. An illustration of these ranges are presented in Table 4, the value re-
ported is the average of four measurements made on the same day over an 3 hour
period. In the case of calcium two elemental lines sre simultaneously employed
and the linear dynamic range is increased to at least 1000 mg/1. For all elements
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the TOO mg/I upper limit doesn't represent the actual upper limit of linear instru- -
mental response for any element. Instead the limiting value indicates to an oper-
ator the need for careful judgement to insure that overlapping effects from other
elements are absent. (See Section 4) But this working range does define sample
concentration values normally reported in day-to-day operation.
1.5 For those procedures and applications described in this manuscript the
degree of operator skill necessary to perform analysis using an ICAP-AES is similar
to that required for operation of an atomic absorption spectrometer (AAS). However,
the initial set up of an installation, reviewing of data and routine instrumental
problem evaluation would probably still require ready access to an experienced
spectroscop-ist.
1.6 Approximately 50 digested or otherwise prepared samples and 10 quality
control samples can be run per hour. At this sample run rate a realistic analysis
output of between 5CQQ and 8000 analysis per man day can be expected. These huge
numbers assume all twenty elements are requested by the sample originator. This
is almost never the case. Furthermore, thousands of analysis per day assume no
sample pretreatment. In fact the majority of sample handling time is associated
with sample digestion. This situation /nil not change with the implementation of
the ICAP-AES. Lastly, the transfer of completed analyses from the teletype s,lieet
to the report form currently being used will be no faster with tne plasma system
than it is now and constitutes a significant fraction of the operator's time.
2.0 Summary of the Method
Liquid samples are aspirated into a high temperature argon plasma produced
by inductively coupling radio-frequency electromagnetic radiation to the argon
34 n
gas. The high temperature' of the plasma (-10,000 K) causes desolvation, molecu-
lar breakdown, atomization, and/or ionization and excitation of the metals in
solution. The resultant radiation produced as the excited atoms relax is oassed
-2-
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through the entrance slit of a dispersive device where it is separated into discrete
wavelengths. The intensity of each of the characteristic wavelengths is associated
with a metal and is measured by a photornul tipl ier tube. The photocurrent is trans-
formed, by reference to standards, to concentration values which are recorded.
3.0 Sample Handling and Preservation
3.1 General
Samples are collected, filtered (for dissolved metals), preserved and
digested according to approved EPA procedures.1
3.2 Sample Hand!ing
Samples are collected in polyethylene containers, preserved with "Cm!
of 50% HNOo/1 and sealed with plastic caps, containing a polyethylene insert.
O
3.3 Sample Digestion
For total metal analysis- samples are digested by the addition of 3 ml
of cone. HN03 to 100 ml of representative sample in a Griffin beaker. The beaker
is covered with a ribbed watch glass and carefully heated to dryness on a hot plate.
After cooling, 3 ,ml of cone. HN03 is added and the beaker is heated until the acid
mixture is brought to a gentle boil. At this point, to improve sample disolution,
5 ml of 1:1 HC1 is added to the warm HN03 mix-ure an^ -ns volumn is brought to
100 ml with distilled deionized water.
4.0 Interferences
4.1 Introduction
The ICAP is in many ways an ideal excitation source. The 10,000°'K
operating temperature is twice as hot as any chemical flame and therefore produces
significantly larger numbers of excited atoms. Further the plasma gas, a^gon, is
chemically inert and spectroscopica!ly simple. The combination of these character-
istics afford the ICAP an interference rree existence when compared with flames,
9
arcs and sparks". Still there are some concerns that must be considered in the
installation and operation of ."CAP spectrometer system. These are discussed below.
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4.2 Chemical Interferences
5 6
The ICAP is virtually free of the classical chemical interferences ' assoc
ciated with both flame AAS and flame atomic emission spectroscopy (AES). Molecular
formation among solution or gaseous atoms exposed to 10,000°t( is not likely and
has not been observed. Carrier gas induced chemical reactions are also very small
because argon is inert.
4.3 lonization Interferences
Changes in emission intensities due to the presence or absence of easily
ionized material (i.e. Na, K, La) has not been reported"*' nor does this work indi-
cate such problems exist.
4.4 Positional stability of radiation source
The positional stability of tne plasma is a very important consideration
because very small changes in plasma location can easily cause significant changes
in analytical results. A partial list of variables which would cause the position
or the area of the plasma to change is as follows:
1. Movement of plasma torcri
2. .Movement of coupling coils
3. Geometry of annular sample channel
4. Variations in either forward or reflected RF power
5. Gas pressure
6. Gas flow
7. Gas purity
8. Changes in inductance coupling
9. Solution viscosity changes
10. Changes in sample uptake rate
11. Unknown sources
In the thousands of analyses so far performed, none of these problems
have proved to be significant. However, because these problems can be present,
and can appear at any time, a comprehensive quality assurance audit orocedure is
included as a part of this method. The audits run to date show excellent long
term precision and daily precision of a 1.0 mg/1 solution for all elements to be
less than 5;^ with no restancaraization c ." a 10 hour period.
-4-
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4.5 Unwanted Light Interferences
There are two classes of light interferences which may affect each
channel of the instrument. They are:
1. Direct spectral overlaps.
2. Indirect and/or stray light additions.
In emission spectroscopy the possibility of two or more elements having
overlapping lines is an important consideration. In a direct reader this spectral
type of interference is predictable and can be empirically identified by measuring
the highest reported concentration of a particular element in the absence of all
other elements. The effect on all other elements is thus rec:rded. If problems
are observed these data can then be factored into the calculations.
A more uncommon type of direct spectral interference happens when two
lines are extremely close but do not normally overlap unless one of the elements
is extremely concentrated. The line broadening or reversal problem is identified
in the same manner as a direct spectral interference and can be controlled by a
careful specification of linear dynamic ranges.
The second class of light interference addresses itself to the observation
that any extraneous light introduced into the system may create poor results.
The most serious problems are associated with the introduction of unwanted lignt
which is unique to the sample and not the blank. For example an emission resulting
from a concentrated sample might reflect from some shiny surface within the direct
reader and cause an error. Any photcmultiplier tube which detects any of this
"stray" light will read that intensity as element intensity and therefore concen-
tration. Stray problems of this nature stem from three principle sources:
1. An imperfection in grating.
2. A reflective surface is exposed inside the spectrometer.
3. A mech?,^'cal breakdown or lack of some internal light shielding.
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In those cases where it has been determined that spectral corrections of the type
stated above are needed, they have been made. Generally speaking these corrections
are small, apply to only a few elements, and are easily verified.
5.0 Apparatus
5.1 Direct Reader
The Jarrell-Ash Plasma Atom Comp 750 equipped with exit slits listed
in Table 1 comprises the basic direct reader. Each slit is observed by a photo-
multiplier (PM) with associated power supply and picoampmeter. The details of
the spectrometer are included in J-A Manual Model 75 Atom Ccmp section Al and 01.
5,2 Plasma As sanely
The plasma assembly is composed of a nebulizer , spray chamber , torch1',
coupling box and power supply. The power supply and coupling box are supplied
by the CCA Corporation and Henry Radio Corporation, respectively, through Jarrell-
Ash Division of Fisher Scientific Company. The nebulizer is a right angle pneumatic
aerosol generator constructed of teflon and glass (with external brass fittings).
The plasma torch is all quartz and of standard design which separates coolant argon.
plasma argon and accepts nebulized solution. The spray chamber is modeled after
the conical chamber described by Fassel:
5.3 Argon Gas
Argon is supplied from a liquid t;ank (Linda GP45). The use of liquid
is preferable because it is cheaper, less labor is involved in moving tanks and
the quality of argon is superior to that from low grade gaseous tanks.
6.0 Reagents
6.1 Water and Acids
Distilled deionized water is used in all cases. All acids are analytical
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6.2 Standards
Standards are prepared monthly (or as needed) by the addition of O.SCCml
of 1000 tng/1 stock solutions of all metals in Table 1 (except Ag which is handled
separately) to a 500 ml volumetric flask. The solutions (except Ag) are acidified
with 25 ml of 1:1 HC1. Silver is prepared daily in 5% HN03. A blank is prepared
and run with reference to distilled water. Generally, no differences between the
prepared blank and distilled water have been observed and therefore samples are
run by reference to distilled water.
7.0 Procedure
7-1 Turn en argon gas
7-2 Turn on cooling water
7-3 Turn on R-F power supply (10 min. warm up)
7-4 Ignite plasma using Tesla coil
7-5 Adjust forward power to 1.0 KW
7-6 Adjust reflected power to less than one W.
7-7 Turn on teletype
7-8 Adjust entrance refractor plate such that Hg-?13 reads a maximum on
profile meter.
7-9 Choose a Basic Data Set ro be used and set time and date.
7-10 With plasma light blocked measure the dark currents of all channels to
be used.
7-11 With plasma lighi blocked measure the white light response of system.
7-12 Uncover plasma, redo 7-5 and record in intensity units blank water being
aspirated.
7-13 Use the two point standardization procedure.
a. List standards needed - command L
b. Clear computer memory - command J
c. Run each standard in duolica^e - command EGG
d. Record each standard - command N
-7-
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e. Standardize spectrometer for all standards - command S
f. Record gains and offsets of standard curves - command VI
g. Run (EGC) and record the 1000yg/l standard. This standard
should read 1000 - 2% for all elements. If any element does
not read within the specified range repeat sequence 7-13.
7-14 Create the operating commands for the days work (i.e. QEGIGIAC will run
a sample twice and print both runs in raw intensity and average both
runs and print the average in concentration units).
7-15 Run the 1000ug/l standard using the operating command for that day.
7-16 Run the blank used. Check against distilled water.
7-17 Run a sample - allow at least a 50 second wash.
7-18 Every 1/2 hour or 30 samples rerun 1000 ug/1 standard.
Every 1 hour or 50 samcles rerun 1CCO '_g/l standard a^c blank.
7-19 During every day of operation collect in addition to the da:;a called
for above:
a. A complete 10 x 10 sec. evaluation of dark current.
b. A complete 10 x 10 sec. evaluation of white light.
c. A complete 10 x 10 sec. evaluation of detection limits.
d. Compile and update the data collected in 7-18.
8.0 Calculations
8.1 Basic Approach
Intensity data for the blank and the mixed lOOO'-g/l standard are stored
in the computer after being entered by procedures outlined in section 7. A value
of "zero" is assigned to the intensity associated with the blank and a value of
TOOOug/l for the intensity corresponding to that solution. 3y reference to these
data the computer then assigns concentration values to unknown intensities. The
linear range and validity of this approach can be seen in Table 4. Background
corrections are made by reference to the standard Dynamic Background Correction
package supplied by the vendor. The use of an Internal Standard(s) is also a
possibility but none were used in these comparisons because no improvements in
results have been observed.
-8-
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8.2 Readout of Computation
The photocurrent output is frequently sampled (60/sec) and digitized
by a PDP8M computer. The computer can print intensity (I), ratioed intensity (R)
baseline corrected intensity (3) or concentration (C) using a standard SR33
teletype. The format of the output and other details are defined by a Basic
Data Set. All pertinent details necessary for the creation and use of the Basic
Data Set are defined in Operation Instructions for 8K Mark II System (CQ1-08P-S001 ,
08T, 080, C8B).
9.0 Comparability Data
3.1 Accuracy
The accuracy for 15 of the 20 elements has been verified b> reference
to "standard" water samples supplied to cur laboratory by the U.S. EPA, the L'.S.
Geological Survey (U.S.GS) and the National Bureau of Standards ('IBS). The U.S.
EPA comparisons for 13 metals in 5 -different solutions are presented in Tables
5, 6, 7, 3 and 9. No problems from ":he LQC to trie upper concentrations cresent
were observed. Note that any value below the LQD is presented here only for
comparison and would not normally be reported. A similar conclusion can be
drawn from the summary of data on two U.S.GS samples for 15 elements presented
in Table 10 and the 5 elements in the NBS material presented in Table ~. The
U.S.GS material was certified by a round robin evaluation and precision measure-
ments are reported with the mean value. The U.S. EPA and 'IBS reference materials
do not have such precision values available at this time. A fc.'rth material
analyzed is the AQC spike or reference sample used by the Petals Section of -he
CRL to ascertain daily performance. These data are presented in Table 12. Again
the comparison between referee and proposed analytical method results is acceptable
for all metals analyzed.
-9-
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9.2 Comparability to Reference Method
The reference materials used in the accuracy studies were prepared in
relatively pure waters and might not properly reflect problems associated with
real samples. Direct comparison to AAS was accomplished by two studies called
Study I and II. In the first study to compare the results of ICAP to the AAS
reference methods 18 elements were investigated. (No reference method exists
1
for Yttrium and Boron was referenced to the Curcumin Method.) In this approach
four different water matrices (laboratory, lake, river and effluent water) were
spiked with the 18 metals at two concentration levels. Concentrations were
cnosen to fall into tne optimum range for AAS analyses. The samolas -ve^e closer,
to cover a broad spectrum of sample types to approximate samples encountered
in our ''iPOES work. The samples were digested following EPA procedures and
soiked at two concentration levels. After standing for -8 hours the samples
were filtered to insure that homogenous aliquots could be taken. A set of 3
aliquots were analyzed by AAS for each element o, 3 different days ove1" approxi-
mately 5 weeks. An equivalent set was analyzed by an ICAP on 5 dirfarent days
over the same period. The results of this study are presented in Tables 13
through 32. Two total study summaries are also presented in Tables 33 ana 3^.
The average recovery data in the latcer Table would clearly indicate no problems
with these data. The linear correlation presented in Table 33 is the linear slope
of a plot of results by AAS (y) vs. ICAP (x). An ideal match would result in
a slope of l.OQ and have an intercept of 0. The data docurent a satisfactory
comparison of the two methods.
In the second study of comparability 22 pair; of samples which were part of
the normal laboratory AQC program were reanalyzed by an ICAP. Each :amp'e pair
is a sample and that sample spiked with the routine AAS spike solution. This
-in-
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spike solution contains Al, Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn. The results
reported in Tables 35 to 57 represent a comparison of ICAP to AAS for all metals
in the AQC spike requested by the sample originator for that sample. All sample
and spike pairs investigated are included. The total Study II comparison in
terms of percent recovery is given in Table 57. As is the case in the previous
studies, the methods are comparable.
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REFERENCES
1. Methods for Chemical Analysis of Water and Pastes, Methods Development and
Quality Assurance Research Laboratory, Cincinnati, Ohio 45258, EPA-62516-
74-003.
2. C. C. Butler, R. N. Kniseley and V. A. Fassel , Anal. Chem. . 47_, 825 (1975).
3. V. A. Fassel and R. N. Kniseley, Anaj. Chem. , 46_, 1110A, (1974).
4. 0. 0. Kalnicky, R. N. Kniseley and V. A. Fassel, in press (1975).
5. S. Greenfield, I. L. Jones and C. T. Berry, Analyst (London), 39_, 713 (1964!
5. G. F. Larson, V. A. Fassel, R. H. Scott and R. N. Kniseley, Anal. Cherr. ,
47, 238 (1975).
7. G. F. Larson and '/. A. "assel, in press (1975).
8. G. F. Larson, V. ,:,. Fassel, P. ,K. ,-<'inge and R. ,','. Xr.iseley presented at
1975 FACSS rr.eetir.g Indianapolis, Indiana.
9. R. 'i. 'Kniseley, H. Amenson, C. C. Butler and V. A. Fassel, Apol. Spectrosc.
28_, 235 (19/i}. ~* ~"
10. R. H. Scott, V. A. Fassal, R. N. Kniseley and 0. E. Nixon, Anal. Chs^. , -1-5,
75 (1974). ~
II. V. A. Fassel , ?rcc. 15th Col I._ Soectr\_ In_t. , Heidelberg, 1971, Adam Hilger,
London, ;972, p. 53.
-12-
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LIST OF TABLES
Table No.
General
Accuracy
Study
1
2
3
4
5
6
7
8
3
i o
i J
11
12
omparison
13
14
1 5
16
17
18
19
20
21
22
23
24
25
26
27
23
29
30
31
32
33
34
Element List and Analytical Lines
Mean Detection Limits and Lowest Quantitative!
Determinable Concentration
Typical Relative Standard Deviations at 1 rug/1
Demonstration of Linear Range
U.S. EPA Reference Material 1171 =1
U.S. EPA Reference Material 1171 =2
U.S. ERA Reference Material 1171 =3
U.S. EPA Reference Material ^75 =1
U.S. EPA Reference "ateria" -75 ~:2
, , r* -\ (- ^ .- * I j_ '""""I ' ' "7
U . -< . Ow i \ C i ~ ' , i v- ~ C. L^ " i I Z ' T ^ i «_i /
NBS Reference Materia^ ' Prel irninarv)
In House Check Standard Comparison
of all Elements in r.g/'l Range
Low Concentration in Distilled Water
Precision Study (LC) in Distilled Water
H i ^ h L. u 1 1 v- e i i i a '- . 3 n in _M ^ _ i ! i e G K a _ r
Precision Study (HC) in Distilled Water
Relative Recovery ir. Distilled Water
Low Concentration : n Lake Michigan Water
Precision Study (LC) in Lake '-'iciiigan Wat£r
High Ccncentraticn in Lake Michigan Water
Precision Study in Lake Michigan Water
Relative Recovery in Lake Michigan Water
Low Concentration in STP
Precision Study (LC) in STD
High Concentration in A STP
Precision Study (HC) in A ST?
Relative Recovery in A ST?
Low Concentration in the Calumet River
Precision Study (LC) in the Calumet River
High Concentration in the Calumet River
Precision Study (HC) in the Calumet River
Relative Recovery in "he ralume4" R"iv°r
Total Stucy I Comparison - Linear Correlation
Total Study I Comparison of Relative Recovery
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Table No.
Study II - Samples and Spiked Samples
35 STP #1070
36 STP =3392
37 STP #01142
38 STP =01172
39 ST? #1298
40 STP =13757
41 STP #21361
42 STP #21324
43 STP #3443
44 Electric Power Generating #1227
45 Electric Power Generating =12-3
46 Dirty River =21507
47 Military Arsenal =1346
A3 Drinking V.'ater =1130
49 General Industrial =1190
50 General Industrial = 132-
51 Automotive Industry =7134
52 General Industrial -1249
53 Tire Company #3-45
54 Paper Industry =7007
55 Communications Industry =0013
56 Conmunications Incus try =3^94
57 Summary of % Reco/ery in Study ]
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Ag
A1
B
3a
Ca(l)
Ca(2)
Cd
Co
Cr
Cu
Fe
Name X in nm
Silver 328.1
Aluminum 396.2
Boron 249.7
Barium 233.5
Calcium 393.4
Calcium 364.4
Cadmium 225.5
Cobalt 238.9
Chromium 267.7
Copper 324,3
o r* o ~*
iron 2o9,o
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
y
Zn
Name X in nm
Magnesium 279.6
Manganese 257.5
Molybdenum 203.8
Nickel 341.5
Lead 220.3
Tin 190.0
Titanium 334.7
Vanadium 309.3
Yttrium 417.8
Zinc 213.9
ELEMENT LIST AND ANALYTICAL LINES
TABLE I
A list of the eleven's currently analyzed by z'
?-AhS ins~ru,r,e°.u a;
the emission line chosen for each element.
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Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
O.L. LQD
ug/1 ug/l
4 20
7 35
3 15
1 5
<0.5 1
2 10
4 20
1 5
1 5
2 10
Mg
Hn
Mo
Hi
Pb
Sn
Ti
V
Y
Zn
D.L. LQD
ug/l ng/i
<0.5 1
1 5
5 25
15 75
12 60
12 60
1 5
1 5
1 5
1 5
:ive Runs over :hree Months
MEAN DE'
AND LOWEST QUANTITATIVE!.
> M ,~ r- > i n -\ -r T ~ >! C ,' I .
i-iL^.i i , -H i j. ,.; li v L v
TABLE 2
The detection lirr.it (D.L.) is the amount of material cha~ will produce
a signal chat is twice as large as the standard dev'ation of tr.e noise.
The lowest quantitative deteminable concentration (LCD) is 5 simes ti'.i
O.L. and is the lowest concentration one can exoect to rsoort.
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
-/
RSO
1.8
0.8
0.8
0.9
0.5
0.9
1.0
0.3
1.2
1.0
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Y
Zn
v
RSO
1.1
1.1
1.0
0.5
0.4
1.2
1.1
1.1
1.0
0.3
'YPICAL RELATIVE STANDARD DEVIATION
AT 1 mg/i
TABLE 3
These RSDs are typ.cal variations for 10 consecutive intergration
periods. Data of this type is recorded at the beginning and end
of each day's operation.
-------
Ag
Al
B
Ba
CaO)
Ca(2)
Cd
Co
Cr
Cu
Fe
100 rng/1
i
96 ± 1
95 ± 1
TOO = 1
105 ± 3
Q7 ± 1
989 - 2 *
105 i 4
97 + 3
QF.2 i 0.4
95 ± 7
94 ± 2
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Y
Zn
ino mg/l
106 ± 2
00^3
in? ± 2
inn ± i
IOA - i
105 ± d
inn ± i
9^ ± 5
100 ± 2
°6 ± 2
f?; at
^ i.. y \_i Lt
Average of 4 rur.s over 5 hours
Overall Average 100 = 4 ppm
n,TT\>! .^ ^
'
TABLE 4
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
USEPA
vg/i
25
1.8
9.2
9.0
18
I CAP
yg/1
16
<2
4.2
5
16.0
Mq
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
USEPA
vgn
13
28
in
I CAP
yg/l
12
39
Q.9
TABLE 5
Ag
3
8a
Ca
Cd
Co
Cr
Cu
Fe
USEPA
'-g/1
575
i 6
83
57
402
T p H 0
iLr-,i
ug/1
520
14
3?
55
435
M.g
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
USEPA
96
Q2
79
I CAP
^ / i
96
i
i
81
U.S. EPA R
[ABLE 5
Al
AAl
is a single blind experimen
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
USEPA
ug/l
1100
73
406
3M
759
I CAP
ug/1
1030
75
400
313
P£?
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
USEPA
ua/1
449
350
3?7
1
I CAP
ug/1
465
350
371
U.S. EPA REFERENCE MATERIAL
TABLE 7
All reference material run as a single blind experiment.
-------
I ICAP ; A.A.S. j US Ec
j.g/1 i Region V vg/1
Ag
Al 649 ' 650 700
3
3a
Ca ' 36.4* 37.5* 36. 7
i
Cd 54 49 i 50
Co : 522 510 500
Cr 157 150 150
Cu 1 252 ' 250 ; 250
re ; 575 610 ' 500
A I | ICAP : A.A.S. US
ug/1 Region V
1 , **"
i
Mg ' 12.3* 11.9*
Mn ' 358 350 3
! Mo ' :
Ni 273 ,260 2
Pb 254 260 2
) '
\ Sn :
1 Ti
W "7 Q *> ~ ~ P ~~
i / / o i / 0 u
Zn 205 190 2
EPA !
9/"i i
i
12 i
50
50
50
,
50
OP
J'J
I! s
EPA RE
TERIAL -175-1
Ag
Al
: 3
! Sa
Ca
t QQ
Co
Cr
I p_
Fe
i
t
i
ICAP
-g/i
75
7.3*
3
19
14
l_ 3 1 0 II .
/ ~".
-y / i
<200
i 7.2*
: <2G
1 <40
| <-0
: <20
<50
, US EPA
-g/i .
0 vj
7. 2
12.5
! 20
; 10
: 11
: 20 '
TCAP ' A.A.S. JS EPA ;
; -g/1 ' Reg^cn '/ uc/1
i : ^g/-
Mg 2.7* 2.5* 2.5
Mn 17 <20 15
"0
;ii 52 C50 30
3b '5 --0 7i
>-> ^ -, -_< W _
Sn i
Ti j i :
V ' 59 ' s-GC 70
i i
Zn | 13 ' <20 15
~D-\
RErERi:iCE MATERIAL ^75-2
i r1. 01_ Z ?
N'utr^e.i' Samp la -:-'
Cone, are "n r,c/l
reference -material r^n as
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
USGS
ug/i
6.4 ± 0.9
71 ± 35
92 - 29*
69.5±2.5*
4.7 ±1.4
5.1 = 0.6
16.5 ± 6
391 ± 24
37 - 15
i
i
I CAP
ug/1
d 7
^ « /
66. £
113
65.7
6.9
<4
19.7
379
sn
1
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
usns
yg/i
18.3 ± 0.9*
15o ± ,i
56.6 r i.6
9.3 ± 6
23 ± 11
347 ± 2S
i
,
I CAP
ug/1
13.7
160
62.5
<15
15.5
3^6
!
3' Z 1
Fhe USGS value represents :na average and stancard oevlaticn of al
v.'ho part;cv
i h e Ana 1 ' z
Water Samples 49 and -7 through May,
r Scandara
All reference material run as a sinal= blind exoer^nent.
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu<
Fe
NBS
yg/i
14
47
807
I CAP
ug/1
12
49
343
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
NBS
ug/1
42
*7
4392
I CAP
vg/1
44
ao
^77G
NBS REFERENCE -A7ERIAL 'PRELIMINARY-
FABLE i
The NBS values are preliminary and represent uncertified uheori t"'cal
supplied by NBS for thai" first Tiixed he" --'- '
reference "atarial.
All reference aiaterial run as a single blind experiment.
-------
1
Ag
A1
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
I CAP
Ave.
'VI
2257
1257
5C6
462
1312
AAS
Ave.
_. Q j 1
2610
1210
492
470
1 2C5
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
ICAP
Ave.
-a/1
50?
1229
1298
-"33
AAS
Ave .
/194
1242
1281
:-3,'
** Average 1 yea
***Average 2 mcnths i-
IN-HOUSE CHECK STA'''DA°D
OF AAS
-------
STUDY I
COMPARISON OF ICAP AND AAS AT
mg/1 CONCENTRATIONS
IN
DISTILLED WATER (Digested as Any Sample)
LAKE MICHIGAN (A Clean Lake)
?.
Residential V.'astss.
CALUMET RIVER ;A Dirty River)
FOR
r\ ^ i ,\ i-i'c. E ,\ r- c. R i 0 J ,(j - n u iv P R i. ^. 3 . C ri
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
I CAP
mg/1
0.260
10.0
0,50
9.4
25.8
0.252
0.97
1.04
1.00
1.18
i
AAS
mg/1
0.254
10.0
0.51*
9.1
25.4
0.249
1.03
1.02
1.02
1.05
f'g
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
i
I CAP
mg/1
o.q
l'.02
25.7
5.1
5.25 _
10.0
10.0
Q .0
0.55
i
- "'' - i
AAS
mn/1
°.8
0.99
26
4.96
5.0
10.
10.fi
9.5
0.50
i
LOV! CONCENTRATION IN DISTILLED WATER
TABLE 13
1
' 1
Aq
Al
B
Ba
Ca
Cd
Co
Cr
Cu
I Fe
i n
"~
ICA?
r a mg/1
0.007
0.3
0.02
0.2
0.5
0.006
0.02
0.01
0.02
0.03
5 ,..__
A AS
- 3 mg/1
0.002
0.1
0.02*
0.3
o.-i
0.002
0.02
0.01
0.06
0.02
3
r *
i-.
Mg
Mn
Mo
. iu
Ni
Pb
Sn
Ti
V
Zn
t_Jl_
- :
I CAP
± a mg/1
1
0 2
0.02
0.8
0.1
0.08
0.2
0.3
0.2
0.01
1
AAS
Mb
-n /I
- cr > i
0.2
0.02
-i
0.03
0.2
1
0.8
0.2
0.01
__i
3 V a r> n W P O <^ *
PRECISION STUDY - LOW CONCENTRATE
IN D IS" ILL ED V
-------
I CAP
mg/1
AAS
mg/1
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
0.52
15.3
1.00
14.1
49.8
0.512
1.94
2.07
2.00
2.25
0.52
14.4
0.99 *
13.7
52.9
0.50
2.02
Zn
15.0
2.05
52.1
10.3
10.4
19.6
19.6
1.06
20.6
?0.1
18.5
0.99
HIGH CONCENTRATION IN DISTILLED WATER
TABLE 15
_
AQ
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
n
I CAP
_ / n
* <* FIG/
_ sJ ll* 5 / '
1
0.02
n.2
0.04
0.1
0.4
0.006
0.02
0.05
0.01
0.04
/"
0
AAS
j. ma/I '
±0uiy/ i
. .
"
0.004 i
0.1
0.01"
0.8
0.8
0.01
0.05
a. 03
o.n
0.02
1 3
1 3
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
I CAP !
± c mg/1
AAS j
± cr ma /I i
.
I
j
0.3
0.02
0.7
0.2
0.2
0.5
0.2
0.05
0.01
6
0.2
0.03
2
n.l
0.1
0.2
0.1
n.A
i
l
i 0.02
i
3
PRECISION STUDY - HIGH CONCENTRATION
IN DISTILLED WATER
(over 6 ,'/esk:
*Curcumin Methcd
TABLE 15
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
I CAP
%
105
106
100
94.6
96
104
97
103
100
108
AAS
if
JO
108
88
96 *
93
106
100
101
105
103
97
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
I CAP
%
102
103
105
102
10?
97
96
°7
102
AAS
%
ion
%
103
98
97
113
95
90
98
* Curcumin Method
RELATIVE RECOVERY STUDY
IN
DISTILLED WATER
TABLE 17
Relative Recovery = High Cone. - Low Cone.
Spike Cone.
x 100
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
ICAP
mg/1
0.262
10.6
0.54
9.5
62.3
0.258
0.97
1.05
1.02
1.37
AAS
mg/1
0.258
10.3
0.55*
9.1
64.1
0.252
1.02
1.03
1.04
1.20
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
ICAP
mg/1
21.2
1.02
26.3
5.2
5.40
10.3
9.9
10.1
0.56
AA5
mg/1
20.9
0.98
21
5.02
5.1
10.4
10.6
9.5
0.50
LOW CONCENTRATION IN LAKE MICHIGAN WATER
TABLE 18
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
n
I CAP
±omg/l
0.009
0.3
0.04
0.2
0.4
0.008
0.03
0.02
0.03
0.02
6
AAS
tomg/1 '
0.005
0.1
0.04 *
0.3
0.4
0.003
0.02
0.01
0.09
0.01
3
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
n
ICAP
±°Vng/l
0.4
0.03
0.9
0.1
0.09
0.3
0.3
0.3
0.01
6
AAS 1
±tfmg/l |
I
0.3
0.02
1
0.07
0.1
1
0.8
0.2
0.0?
3
_
over 6 week'
PRECISION STUDY - LOW CONCENTRATION - LAKE MICHIGAN
TABLE 19
Curcumin Method
-------
Ag
AT
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
1CAP
mg/1
0.52
15.6
1.01
13.9
83.3
0.51
1.90
2.06
1.98
2.28
AAS
mg/1
0.52
14.4
1.03*
13.7
83.8
0.51
2.02
2.01
2. 05
2.07
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
ICAP
mg/1
25.6
2.02
51
10.2
10.3
19.6
19.5
19.4
1.05
AAS
mg/1
25.7
1.95
52
9.83
9.9
21. 8
20.1
18.5
0.98
HIGH CONCENTRATION IN LAKE MICHIGAN WATER
TABLE 20
Ag
Al
B
Ca
Cd
Co
Cr
Cu
V M
Fe
n
ICAP
ia'sng/l
0.02
0.3
0.07
0.2
0.5
0.01
0.04
0.05
0.05
0.06
6
AAS
±ama/l j
0.01
0.1
0.03*
0.3
0.5
0.01
0.05
0.07
0.08
0.03
3
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
n
ICAP
± a mg/1
0.4
0.04
1
0.2
0.2
0.6
0.4
0.4
0.02
6
AAS
±amg/l
n.2
0.02
2
n.ns
0.2
0.2
0.1
0.4
0.02
3
(over 5 wee-
PRECISION STUDY - HIGH CONCENTRATION - LAKE MICHIGAN
TABLE 21
*Curcumin Method
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
I CAP
%
103
100
94
90
104
100
93
101
96
91
AAS
%
104
88
96*
93
98
104
100
98
101
87
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
I CAP
%
88
100
101
99
98
' Q3
96
93
98
AAS
w
/a
°6
Q7
103
96
96
113
95
90
9£
* Curcumin Method
RELATIVE RECOVERY
IN
LAKE MICHIGAN WATER
TABLE 22
Relative Recovery = High Cone. - Low Cone. x 1Q(}
Spike Cone.
-------
I CAP
AAS
mg/1 mg/1
0.26
13.5
1.15
9.3
80.0
0.284
0.98
1.30
1.18
7.55
0.274
12.6
1.2 *
9.2
82.6
0.279
1.04
1.29
1.22
7.1
Zn
I CAP
mg/1
1.19
AAS
mg/1
LOW CONCENTRATION IN A STP
(Industrial & Residential Wastes)
TABLE 23
' ' 'T
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
1 "
I CAP
±amg/l
-
0.01
0.1
0.06
0.1
0.4
0.004
0.01
0.04
0.01
0.05
i
AAS
±~vng/l I
.
0.007
0.3
0.1 *
0.4
0.6
0.001
0.02
0.01
0.08
0.1
3
__ r
Mg
Mn 1
Mo
Ni
Pb
Sn
Ti
V
Zn
n
I CAP
-'omg/l
_ L
0.8
0.01
0.4
0.06
0.07
0.2
0.1
0.1
0.05
6
i
AAS
±o«ig/l
0.«
0.0?
1
0.02
n.2
0.3
0.4
0.2
0.05
1
3 j
PRECISION STUDY - LOW CONCENTRATION - ST?
TABLE 24
over 6 wee!
* Cur-cumin Method
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
L/ «
Fe
I CAP
mg/1
0.52
17. 6
1.65
13.7
84.7
0.52
1.90
2.27
2.09
8.9
AAS
mg/1
0.529
16.2
1.73*
13.7
83.7
0.53
2.04
2.29
2.19
8.5
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
I CAP
mg/1
46
2.13
49.6
10.2
10.0
18.9
18.9
28.5
1.67
AAS
mg/1
47.6
2.10
51
9.66
9.7
22
19.1
27.9
1.64
HIGH CONCENTRATIONS IN A STP
( Industrial & Residential Wastes }
TABLE 25
PRECISION STUDY - HIGH CONCENTRATION - STP
TABLE 25
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
\f W
Fe
n
I CAP
±a mg/1
0.02
0.4
0.09
0.3
0.5
0.01
0.04
0.08
0.04
n.l
6
AAS
±,cmg/l
0.004
0.4
0.05*
0.7
0.4
0.02
0.06
0..08
0.08
0.2
3
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
m
I CAP
±a,ng/l
2
0.04
O.Q
0.3
0.2
n.4
0.4
0.6
0.02
\
AAS
±omg/l
n.A
n.nd
d
0.08
0.9
1
0.6
0.8
0.04
' 1 '
(over 6 weei
* Curcumin Method
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
I CAP
%
104
83
ion
88
94
92
97
91
130
MS
%
102
72
104*
90
100
100
100
97
137
Mg
Hn
Mo
Ni
Pb
Sn
Ti
V
Zn
I CAP
%
95
95
99
91
90
90
94
96
AAS
of
a
Q5
102
°3
91
iru
85
n?.
100
* Curcumin Method
RELATIVE RECOVERY IN A
STP ( INDUSTRIAL & RESIDENTIAL WASTES)
TABLE 27
Relative Recovery = Hjgh Cone. - Low Cone. 10
J Spike Cone, * IL
-------
Ag
*y
AT
B
Ba
Ca
Cd
Co
Cr
Cu
Vs U
Fe
I CAP
mg/1
0.257
11.0
0.56
9.2
122
0.258
1.90
1.03
1.02
2.59
AAS
mg/1
0.259
9.9
0.55*
9.0
125
0.2^.9
2.02
0.99
1.04
2.37
Hg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
I CAP
nig /I
23.7
1.15
25.7
5.24
5.37
10.1
9.7
9.9
0.600
AAS
mg/1
24.0
1.14
2P
5.04
5.1
10. ?
10.6
9.5
0.55
LOW CONCENTRATION IN THE CALUMET RIVER
TABLE 28
(The Calumet River is very polluted, its waters resemble discharges from
industrial steel mill plants.)
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
n
I CAP
±cir.g/l
0.009
0.2
0.03
0.2
0.9
0.005
0.04
0.03
0.02
0.04
6
AAS
±amg/l
0.008
0.06
0.04*
0.3
1
0.004
0.02
0.01
0.08
0.03
3
Mg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
n
I CAP
iJmg/1
0.8
n.02
0.7
0.09
0.08
0.2
0.3
0.3
0.009
AAS
±amg/l
1
0.7
0.02
2
0.08
0.3
0.4
0.8
n.3
0.03
6 | 3
PRECISION STUDY - LOW CONCENTRATION - CALUMET RIYER
'over 6 week
TABLE 29
* Curcumin Met
-------
1
Ag
Al
B
u
Ba
Ca
Cd
Co
Cr
Cu
Fe
!
I CAP
mg/1
0.49
15.2
AAS
mg/1
-4
0.50
13.9
1.02 ' l.K-H
13.8
119.1
0.49
2.8
1.96
1.90
3.5
14.0
119.6
1 0.50
3.0
1.98
2.01
3.24
I CAP
mg/1
AAS
nig/I
Mg
Mn
Mo
N1
Pb
Sn
Ti
V
Zn
37
2.06
5n
9.7
°.7
18.7
18.4
18.6
1.02
37.9
2.02
51
9. A3
9.5
21.4
19.3
18.3
0.37
HIGH CONCENTRATION IN THE CALUMET RIVER
TABLE 30
0.01
0.2
0.09
0.09
0.08
0.02
0.1
0.06
0.08
0.1
PRECISION
, STUDY - HIGH CONCENTRATION - CALUMET RIVER
Cover 5 weet
TABLE 31
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
I CAP
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
Slope
1.02
0.87
1.07
1.03
1.00
1.03
1.08
1.02
1.07
0.97
INTCP
yg/1
+O.OC3
+0.800
-0.035
-0.458
1.36
-0.014
-0.019
-0.048
-0.039
-0.126
k
Hg
Mn
Mo
Ni
Pb
Sn
Ti
V
Zn
Slope
1.05
O.Q7
1.02
0.96
O.Q8
1J1
O.Q8
0.99
1.01
INTCP
yg/1
-D.Q25
+0.0^3
-0.479
+0.003
+0.15Q
-0.905
+O.Q58
+0.3Q8
-0.067
* Curcumin Method
Slope = *£
AICAP
TOTAL STUDY I COMPARISON
LINEAR CORRELATION
TABLE 33
This data is the least squares slope and intercept of all data collected
in Study I. The AAS Values are plotted on the y axis v.s. the ICAP values
on the x axis.
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
I CAP
-------
STUDY II
COMPARISON OF ICAP AND AAS
FOR
SAMPLE AND SPIKED SAMPLE PAIRS
FROM
NORMAL LABORATORY AQC PROGRAM
WITH
ALL SAMPLES CHOSEN AT RANDOM
-------
Element
AT
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
I CAP
ug/1
<14
< 4
41
23
609
62
*30
ty
203
AAS
ug/1
132
15
40
32
579
65
16
22
219
Spiked Sample
I CAP
yg/l
672
208
244
211
1715
271
181
218
404
AAS
yg/l
940
2f)h
239
232
1586
267
256
231
422
Recovery
ICAP
%
84
102
101
94
no
104
91
99
100
AAS
o/
t'O
ini
95
Q0. 5
mo
mi
mi
120
lOd
102
TABLE 35
lr
Element
Al
Ba
Sample
ICAP
<-g/i
96
119
AAS
ug/1
328
104
Cd <4 j 10
Cr I 11 ! 4
Cu
Fe
Mn
Ni
1 Pb
I Zn
oO j 49
1 290 \ } 1 28
52
<30
26
113
48
22
37
109
Spiked Sample
ICAP
yg/l
986
1 004
228
230
250
2550
282
203
250
332
MS
yg/l
11 An
932
203
177
237
22^3
250
236
24 1
2°5
Recovery
ICAP
a/
iC
111
111
112
109
100
12P
115
107
11?
10°
AAS
a/
&
in2
10d
Q7
8£
a A
111
ini
in7
in?
°3
SIP rr8392
TABLE 36
-------
Element
AT
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
ICAP
yg/1
730
K 4
9
10
156
54
<30
15
36
AAS
ug/1
1020
/
10
12
HI
54
22
26
40
Spiked Sample
ICAP
vg/i
1549
19?
201
189
1240
259
173
209
225
AAS
vg/l
1828
213
204
206
11M
261
232
228
232
Recovery
ICAP
n
,x>
102
mo
96
90
108
103
87
97
95
AAS
o/
n
101
1^3
inn
QP
100
103
105
101
Of
STP 3 01142
TABLE 37
Element
Al
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
ICAP
ug/1
K4
K
n
y
565
61
<30
25
50
AAS
ug/l
0
10
iU
496
55
30
26
*6
Spiked Sample
ICAP
M9/1
211
215
199
1774
276
18n
238
270
AAS
ug/l
IQQ
185
210
1515
25Q
233
220
2/15
Recovery
ICAP , AAS
O/ ! C/
,0 | /O
1
w&
in?
95
121
107
°0
106
105
Q7
^7
inn
in2
10?
in?
0£
inn
STP =01170
TABLE 38
-------
Element
Al
Ba
Cd
Cr
Cu
Fe
Hn
Ni
Pb
Zn
Sample
I CAP
pg/i
706
< 4
40
19
1650
162
<30
46
193
1
AAS
ug/1
804
y
35
26
1744
179
26
67
213
Spiked Sample
I CAP
yg/1
1425
IHZ
231
204
2744
367
181
248
393
AAS
ug/1
1528
21 a
222
223
2768
38K
222
264
*15
Recovery
I CAP
»/
K3
90
yb
%
93
109
103
01
97
100
AAS
of
a
Ql
103
Qd
99
102
104
°8
QO
101
STP ^1298
TABLE 39
Element
Al
Ba
Cd
Cr
Cu
Fe
Hn
Ni
Pb
Zn
i
Sample
ICAP
ug/1
<4
8
/b
611
1 DO
<30
31
93
AAS
yg/l
7
5
28
506
, 42
20
50
103
Spiked Sample
ICAP
yg/i
212
213
228
1734
372
IOQ
253
287
AAS
yg/1
196
180
232
1*74
342
216
264
307
Recovery
ICAP
-------
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
I CAP
ug/l
830
117
275
164
7132
241
228
1 55
557
AAS
vg/l
800
120
20
261
216
7100
255
2*8
150
7OS
Spiked Sample
ICAP
yg/1
1552
852
209
468
339
8516
ddd
*15
331
396
AAS
ug/l
1634
872
203
ddQ
3*6
8400
458
438
3^6
880
Recovery
ICAP
96
02
Q3
87
88
102
94
88
... 1U
AAS
ol
,rj
103
aq
Ofi
Od
Q?.
in?
as
as
an
STP 321361
TABLE 41
,
.Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
ICA?
ug/l
1074
112
c. ^
158
195
7488
203
248
162
822
AAS
ug/l
1152
<100
34
K2
216
7700
212
282
172
8^4
Spiked Sample '
ICAP
yg/1
1397
352
219
3^7
371
8824
404
447
362
1027
MS
ug/l
I960
848
219
32°
3Q8
S^nn
408
480
376
11HQ
Recovery
ICA?
o/
,0
103
93
05
Od
88
inn
ion
100
1H2
AAS
^
,0
1P1
n/i
03
Qd
Ql
98
no
102
8R
STP =?21324
TABLE 42
-------
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
I CAP
yg/1
153
i
AAS
yg/1
173
Spiked Sample
I CAP
yg/i
1079
AAS
yg/i
1142
i i i
Recovery
I CAP
of
&
93
AAS
o/
1(3
Q7
I
ST? £8443
TABLE 43
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
I CAP
yg/1
238
AAS
yg/1
444
< 4 :< 0
10 I 10
10
33°
24
<30
<24
17
8
338
27
21
22
10
Spiked Sample
ICAP
yg/i
969
198
202
179
1397
226
186
216
208
AAS
yg/l
1268
203
191
204
1304
234
210
227
198
- i
Recovery
ICAP
o/
f3
92
QQ
%
87
106
101
93
l no
96
AAS
V
3
103
I n? -i
Ql
"8
07
104.
00
103
on
ELECTRIC POWER GENERATING PLANT =1227
TABLE 44
-------
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
I CAP
yg/1
549
98
< 4
- 16
11
224
15
<30
J4
19
v 158
AAS
yg/1
516
80
11
14
19
240
16
35
34
20
K100
Spiked Sample
I CAP
yg/T
1476
551
216
?25
2Q6
1416
237
208
239
232
2195
AAS
yg/1
1300
516
91 a.
?lo
222
1254
228
237
237
22^
2272
Recovery
I CAP
o/
,o
llfi
107
ina
98
120
111
10*"
102
infi
102
AAS
«/
tj
98
102
°8_
102
101
107
_._.1Q1
102
103
112
ELECTRIC POWER GENERATING PLANT =1248
TABLE 45
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
ICAP
ug/1
*C
13
K
1877
<30
3y
29
AAS
yg/1
-------
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
ICAP
ug/1
3
908
7
22
i
AAS
yg/1
<20
862
,10
55
Spiked Sample
ICAP
yg/l
179
160
1668
183
172
230
1
AAS
yg/l
198
204
1850
212
230
263
Recovery
ICAP
e/
r'O
88
80
7*
88
36
irvt
1
AAS
°6
98
00
10?
101
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sa
ICAP
ug/l
<20
4
mple
AAS
ug/l
20
4
MILITARY ARS
TABLE
Spi keti
ICAP
yg/i
622
208
ENAL ^1346
47
Sample |
AAS
ug/l
763
183
Recovery
ICAP AAS
01 1'
,0 ,3
1
78 94
102 °0
J
DRINKING WATER =1130
TABLE 48
-------
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
ICAP
yg/i
<14
< 4
9
H
186
91
<£0
19
?4
AAS
ug/1
136
<10
<20
16
184
9Z
<30
<40
25
Spiked Sample
ICAP
yg/1
672
201
204
193
1272
297
168
2U
2^4
AAS
yg/1
940
210
189
218
1200
300
219
238
227
Recovery
ICAP
ol
10
84
101
Q5
88
To3
8A
98
qq
AAS
o/
,fj
102
"38
Q4
Q]
Tins
102
98
inn
I !
GENERAL INDUSTRIAL ?129Q
TABLE 49
Samole
Spiked Sample
Recovery
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
ICAP
ug/1
-------
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
I CAP
yg/1
132
10
AAS
ug/l
132
<20
Spiked Sample
I CAP
yg/1
792
224
1
AAS
yg/1
924
173
Recovery
I CAP
%
83
107
i
AAS
o/
iO
99
PF
AUTOMOTIVE INDUSTRIAL =7434
TABLE 51
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
1 Zn
Sample
ICAP
ug/l
< 4
25
17
1613
<30
AAS
yg/l
9
16
24
lP6n
77
Spiked Sample
ICAP
yg/1
192
212
198
?££U
196
AAS
yg/1
198
206
222
31Sd
283
Recovery
ICAP
;/
,0
95
Oil
QO
107
98
AAS
»/
IS
95 ~1
95
no
123
103
GENERAL INDUSTRIAL #1249
TABLE 52
-------
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
I CAP
yg/i
<14
35
<24
i
AAS
vg/1
36
35
30
Spiked Sample
I CAP
ug/1
539
206
220
AAS
yg/i
840
224
205
Recovery
I CAP
%
86
no
AAS
of
(V
mi
05
104
TIRE COMPANY ?3445
TABLE 53
1
Element
Al
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sa
ICA?
ug/1
<4
20
166
12?6
59
55
208
iiple
AAS
ug/1
< 10
< 20
200
1380
75
40
229
Spikec
ICAP
yg/i
184
200
3^1
2287
236
237
394
! Sample
AAS
ug/l
201
?/;1-
403
2^30
277
232
418
Recov
ICAP
=/
/o
9?
°0
38
QQ
P,Q
Ql
93
cry
AAS
c/
<'3
op i
in^
10]
ins
in,
102
°5
PAPER INDUSTRY =7007
TABLE 54
-------
Element
A1
Ba
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Zn
Sample
I CAP
pg/i
4
178
61
13
:<24
39
AAS
ug/l
iclO
162
58
<30
<£0
12
i
Spiked Sample
ICAP
ug/1
204
1286
277
210
194
238
MS
ug/1
204
TIPO
262
224
216
?09
Recovery
ICAP
o/
&
100
in
108
QO
97
inn
t
AAS
%
102
inr
102
in?
inn
00
COMMUNICATIONS INDUSTRY =0018
TABLE 55
Element
Al
Ba
! Cd
Cr
Cu
t Fe
Mn
Ni
Pb
Zn
bample
ICAP
AAS
ug/1 1 ug/1
0
5.6
5
5.6
bpiiced bample
ICAP
yg/i
103
6.2
P\ecovery
MS i ICAP AAS
yg/i
1 07
-.1
'' \ a/
\
0,1 mi
COMMUNICATIONS INDUSTRY ?8494
TABLE 56
-------
Ag
Al
B
Ba
Ca
Cd
Co
Cr
Cu
Fe
ICAP MS
% ± a % ± a
106 ±12 100 ± 4
98 ±11 98 ± 6
99 ± 6 98 ± 4
98 ±6 93 ± 6
91 ± 6 97 ± 3
105±13 101 ± 9
#
Sample
14
3
16
18
18
16
>
Mg
Mn
Mo
Mi
Pb
Sn
Ti
V
Zn
ICAP AAS
%± a « ± o
103 ±7 103 + 2
94 ±6 103 ± 6
99 ±8 101 ± 3
102 112
100 ±7 98 ± 5
n
,!
Samples
14
16
17
1
15
SUMMARY OF % RECOVERY
IN
STUDY II
TABLE 57
------- |