EPA-600/2-77-113
June 1977
Environmental Protection Technology Series
RELIABLE ANALYSES OF WATER
BY INDUCTIVELY COUPLED
PLASMA EMISSION SPECTROSCOPY
J
Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Athens, Georgia 30601
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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 ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution, This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-77-113
June 1977
RELIABLE ANALYSES OP WATER BY INDUCTIVELY COUPLED
PLASMA EMISSION SPECTROSCOPY
by
Charles E. Taylor
Analytical Chemistry Branch
Environmental Research Laboratory
Athens, Georgia 30605
ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
ATHENS, GEORGIA 30605
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DISCLAIMER
This report has been reviewed by the Athens Environmental
Research Laboratory, U.S. Environmental Protection Agency, and
approved for publication. Mention of trade names or commercial
products does not constitute endorsement or recommendation for
use.
11
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FOREWORD
Nearly every phase of environmental protection depends on a
capability to identify and measure specific pollutants in the
environment. As part of this Laboratory^ research on the
occurrence, movement, transformation, impact and control of
environmental contaminants, the Analytical Chemistry Branch
develops and assesses new techniques for identifying and
measuring chemical constituents of water and soil.
Inductively coupled plasma emission spectrometry is a
relatively new instrumental technique for the rapid,
quantitative analysis of water for approximately two dozen trace
elements. This report presents an initial evaluation of one
commercial instrument that embodies the technique.
David W. Duttweiler
Director
Environmental Research Laboratory
Athens, Georgia
111
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ABSTRACT
Reduction of stray light in the inductively coupled plasma
emission spectrometer (ICPES) has greatly increased its
reliability as a technique for the multielemental analysis of
water. Because of interferences introduced by matrix elements,
reliable analysis of some less-sensitive elements has been
impractical at concentrations of < 200 ppb. After surfaces in
the secondary optical system were painted to prevent light
scatter and the aperture at the primary lens was reduced in the
ICPES, some interference corrections were reduced by more than
one order of magnitude. Reduced interferences in the ICPES
along with improved corrections by adding exact concentrations
of calcium and magnesium to reagent blanks run during sample
analyses have definitely improved the accuracy of this
multielement analysis system. Observed background changes
caused by the presence of magnesium were compensated for by
adding matrix elements to calibration standards. Alcohol was
added to standards, reagent blanks, and samples to overcome
problems of background change during analysis of samples of
unknown organic content such as municipal sewage.
iv
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CONTENTS
Foreword .......................
Abstract ....................... iv
Tables ....................... yd.
Abbreviations and Symbols .............. vii
Acknowledgment .................... viii
1. Introduction ............... 1
2. Conclusions and Recommendations ...... 2
3. Equipment ................ 3
4. Experimental Procedures .......... 4
5. Results and Discussions .......... 6
Bibliography .................... 31
v
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TABLES
Number
1 Spectrometer Line Array 10
2 Comparison of Correction Factors 11
3 Correction Factors Presently Required on ARL
QA-137 12
4 Nonlinearity of Ca and Mg Corrections 13
5 Interference of Ca and Mg Mixtures 14
6 Ca-Mg Corrections Versus Ca-Mg Mixture 15
7 Interference of Matrix Elements and Mixtures . . 16
8 Original Attempts to Correct for Ca and Mg
Interference 17
9 Matrix 20 *\» 1 Ratio 18
10 Matrix 100 * 1 Ratio 19
11 Matrix 200 ^ 1 Ratio 20
12 Matrix 1000 * 1 Ratio 21
13 Matrix 2500 * 1 Ratio 22
14 Detection Limits for QA-137 System 23
15 Sewage Effluent V-ll 24
16 Sewage Effluent V-12 25
17 Sewage Influent V-13 26
18 Sewage Influent V-14 27
19 Standard V-15 28
20 ICP Reference Sample 29
21 124 Drinking Water 30
VI
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LIST OF ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
AA
AERL
ARL
CF —
DEC
E+xx
EPA
ERDA
IAG
ICPES
INAA
kW
1/min
LQD
MHz
Vim
ml —
nm
ppb
ppm
RF
SYMBOLS
Ag
Al
As
B
Ba
Be
C
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
atomic absorption
Athens Environmental Research Laboratory
Applied Research Laboratory
correction factor
Digital Equipment Corporation
10XX
Environmental Protection Agency
Energy Research and Development Administration
interagency agreement
inductively coupled plasma emission spectrometer
instrumental neutron activation analysis
kilowatt
liters per minute
lowest qualitative determinable
megahertz
micrometer
milliliter
nanometer
parts per billion
parts per million
radio frequency
silver
aluminum
arsenic
boron
barium
berylium
carbon
calcium
cadmium
cobolt
chromium
copper
iron
mercury
magnesium
manganese
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
— molybdenum
— nickel
~ lead
— antimony
— selenium
— tin
— strontium
— titanium
— vanadium
— yttrium
— zinc
— equal to or less
than
— equal to or
greater than
vii
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ACKNOWLEDGMENTS
The cooperation of Drs. V. A. Fassel, R. K. Winge, and J.
M. Katzenberger of the Ames Laboratory-ERDA and the Department
of Chemistry of Iowa State University in helping to set up and
operate the spectrometer is gratefully acknowledged. We are
particularly indebted to Dr. Katzenberger for his modifications
to the computer software used in this system. The work at the
Ames Laboratory was performed under an interagency agreement
(IAG-04-Ol»17) with EPA.
Appreciation is also expressed to the Central Regional
Laboratory of EPA Region V for its cooperation in supplying
sewage samples and standards to permit comparison of data with
other techniques and laboratories. The work of Ms. T. I. Button
of the Athens ERL on this project is sincerely appreciated.
Vlll
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SECTION 1
INTRODUCTION
The Environmental Protection Agency's responsibilities in
pollutant monitoring, enforcement proceedings, and surveys of
the occurrence of trace elements require analytical capabilities
at state-of-the-art levels. Evaluation of one presently
available instrument for the rapid multielement analysis of
water samples, the inductively coupled plasma emission
spectrometer (ICPES), was conducted at the Athens Environmental
Research Laboratory. Selected for the study was Applied
Research Laboratory's model QA-137, which was considered to be
the best commercially available ICPES based on the evaluation of
such instruments by the Energy Research and Development
Administration's Ames Laboratory under an interagency agreement
with EPA (IAG-D6-0417) .*
During initial evaluation of the instrument at Athens ERL,
spark source mass spectrometer data were compared with IPES data
following analysis of cross-check solutions from plating plants.
Major differences were detected. Further evaluation attributed
these differences to stray light from calcium and magnesium
lines in the ICPES, and work was immediately begun to resolve
the problem. This report describes the steps that were taken to
improve the instrument's performance, describes the Ca and Mg
correction procedures, and compares the improved ICPES with
other analytical instruments in characterizing the same water
samples.
*Winge, R. K., J. M. Katzenberger, and V. A. Fassel. Development
and Application of an Inductively Coupled Plasma Analytical
System for the Simultaneous Multielement Determination of Trace
Elemental Pollutants in Water. Annual progress reports for 1974-
1976 to EPA under Interagency Agreement EPA-IAG-D6-0417. Energy
Research and Development Administration, Ames, IA.
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SECTION 2
CONCLUSIONS AND RECOMMENDATIONS
Changes initiated by the Athens ERL in the inductively
coupled plasma emission spectrometer have resulted in more
reliable analytical results for multielement analyses of water.
Detection limits, in fact, have been improved for 15 of 23
elements routinely determined, including a 10-fold increase in
sensitivity for titanium, vanadium, and yttrium. Because major
matrix elements affect background signals at certain
wavelengths, they must be included in all calibration standards
for analyses that approach the lowest quantitatively
determinable concentrations for trace impurities in water.
Adding exact concentrations of matrix elements to the reagent
blanks is the most precise and reliable technique available to
correct interference and/or background shift. Addition of
alcohol to waters of unknown organic content is an effective
technique to compensate for background differences between
calibration standards and real samples.
Because it is a precise, accurate, and rapid technique,
IPES should be considered for routine multielement
determinations in water. No rigorous preparations or
preconcentrations of fresh waters are required to meet or
surpass most EPA criteria limits for analysis of metals in
water. If early model instruments are used, they should be
updated by installing filters at lower wavelengths and/or
holographic gratings to minimize required corrections caused by
matrix element interference.
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SECTION 3
EQUIPMENT
Excitation source for the QA-137 optical emission
spectrometer evaluated in this study was an inductively coupled
argon plasma device manufactured by the Applied Research
Laboratory (ARL). Data readout and computation was performed by
standard ARL equipment interfaced to a DEC PDF 11/05
minicomputer having an 8K core memory. The inductively coupled
plasma source was powered by a radio frequency (RF) power
supply, operating at 27 MHz with 3 kW rating. Initial
ionization of the argon was started by a Tesla coil; continuous
or sustained operation was maintained by induced heat from a
two-turn induction coil that encircle the torch assembly. The
QA-137 spectrometer was equipped with 31 exit slits (elements
and wavelengths in Table 1); the grating was blazed for * 300
ran. Wavelengths covered by this array ranged from 189.5 to
461.5 nm. Entrance and exit slitwidths were 12 ym and 50 vim,
respectively. The electrical signal from each of the 31
photomultipliers was taken by the readout system and integrated
on a capacitor for a given time. The charge on each capacitor
was then converted to a concentration value from the calibration
curves and stored in the PDP11/05 minicomputer. Concentration
data were printed out using an ASR 33 teletype.
With the computer program used in this study, standard
errors of concentration and intensity from calibration data can
be printed out along with curve coefficients for curves, slopes,
and intercepts. In addition, an error table can print out each
element calibrated and each standard used, including
concentration and intensity residuals. Linearity values for
each standard are also printed in the error tables. The
standard error tables and error tables for calibrations can be
used by the operator as a control on reliability of analytical
data.
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SECTION U
EXPERIMENTAL PROCEDURES
Operating conditions for the inductively coupled plasma
source were those recommended by the vendor:
1. RF power (forward), 1100 W and 1600 W
2. Reflected power, < 2 W
3. Plasma argon flowrate, 16 1/min
4. Auxiliary plasma argon flowrate, 1.U 1/min
5. Aerosol argon flowrate, 1 1/min
6. Integration time, 10 sec
7. Calibration, 7 concentrations for all elements except
Ca and Mg, 3 concentrations for Ca and Mg
8. Warm up time, 1 hour
9. Adjustment of entrance slit placement to optimum each
day
The addition of a microscope slide cover at the magnesium
II, 279.55-nm exit slit reduced the interference of magnesium in
the secondary optics. By decreasing the aperture at the primary
lens to a 5-mm opening, the light allowed into the spectrometer
from the torch was reduced.
Reduction of stray light caused by magnesium in the
secondary optics was accomplished by covering bright surfaces
with black paint. Baffles of black paper were also placed in
the system to prevent reflections from reaching various
detectors.
Correction factors (CF) for calcium and magnesium were
determined and applied using either blank corrected intensity
ratios or concentrations provided in the modified software.
Originally, 12 CF's could be handled by the software, but the
Ames Laboratory expanded this capability to 14.
Mixtures of acid, methyl alcohol, and ethyl alcohol were
checked for the most favorable background levels for most
elements.
No loss of operation time because of instrument down time
occurred during the 6-month period of operation. Instrument
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stability for day-to-day operations was remarkably good;
calibration curves did not change more than 10% between
successive days.
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SECTION 5
RESULTS AND DISCUSSION
Results before and after modifications to the ICPES and
changes in operating procedures are discussed in this section.
Data listed in Table 2 are correction factors for interferences
by calcium (column 1 and 2) and magnesium (column 3 and U) .
Correction factors were calculated using data from 50-ppm
calcium in one solution and 50-ppm magnesium in another; no
other elements were added.
Ratios for the correction factors were calculated using the
blank corrected intensity of the channel to be corrected in the
numerator and the blank corrected intensity of the interfering
element in the denominator as follows:
CF ratio = £J /Ica (1)
_Ca
where 3T.. is the intensity recorded for the aluminium
channel, and
ICa is the intensity for calcium when aspirating
the 50-ppm calcium solution.
These ratios were stored in the computer, and the corrections
applied to the analyses are the product of equation 2.
CF applied = ( /3) (2)
where r; is the blank corrected intensity of calcium
found in the sample of question.
The modified software package supplied by Ames Laboratory
allowed the correction to be applied to the analytical
concentration data or the intensity correction as shown above.
Correction data in the first two columns of Table 2 show
little or no change in calcium interference levels after
painting the bright surfaces and adding the baffles. Data in
columns 3 and 4 show some changes in magnesium interference
correction data after painting and adding of some baffles in the
secondary optics. The significant changes occurring with
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magnesium corrections are at Cd, Cu, Sb, and V wavelengths. The
changes, addition of the microscope slide and reduction of light
at the primary lens, were made after the data in Table 2 were
gathered. Correction factors calculated after the changes of
the microscope slide and reduction of light at the primary lens
are listed in Table 3. comparison of the data in Table 3 with
those of columns 1 and 3 in Table 2, reveals that significant
reductions have been made in corrections to account for
interferences caused by calcium. The data in Tables 2 and 3
show that the most advantageous changes in calcium corrections
resulted from changes in the primary optics, whereas the best
changes for magnesium corrections occurred in the secondary
system.
When interference corrections of the magnitude listed in
columns 1 and 3 of Table 2 were applied to data from analyses
with concentrations of < 0.05 ppm, results in many cases were
unacceptable. Contributions from calcium and magnesium to
analyses of other elements are shown in Table 4. Inspection of
these interferences (Table 4) reveals the nonlinearity of
interference of both calcium and magnesium. Using data from
Table 4, the magnesium correction factor for arsenic is made
using equation 1.
IAs/IMg = O-TOI/SO.O = 2.08E-3
Then using equation 2 to correct an analysis containing 100 ppm
Mg, we find this product.
{IAs/IMg)IMg = 2-08E~3 x 10° = 0.208E+0
Comparing this value (0.208E+0) to the observed value for the
interference caused by 100 ppm magnesium at the arsenic
wavelength (0.333E+0) reveals a difference of 0. 125E+0 ppm that
would be identified as arsenic. Now, to attempt a full
correction for calcium and magnesium interference in arsenic
analysis, magnesium correction (0.208E+0 ppm) and calcium
correction (1.400 ppm = 1.608E+0 ppm) are calculated. Referring
to Table 5 where 100 ppm each of calcium and magnesium was
observed, the correction in fact should be 0.719E+0 ppm, showing
an over correction of 0.889 ppm applied to the arsenic analysis.
Calculated corrections for calcium and magnesium, as with those
discussed for arsenic, are confounded even more as can be seen
in Table 6. The corrections applied to the analyses by the
software are algebraically added to either the intensity or the
concentration data. Taking the values from calcium 50 ppm and
magnesium 50 ppm columns in Table 6, the total for arsenic
should be equal to the third column where 50 ppm each of calcium
and magnesium were observed in the same solution. The total of
the calcium and magnesium columns from Table 6 is 0.624E+0
-------
compared with O.U61E+0 contribution with the two elements mixed,
however, leaving an over correction of 0.163E+0 ppm.
Several elements such as Al-,, B, Cd, Co, Cr, Cu, Fe, Hg,
Mo, Ni, Pt>2» s^r Se> Sn» Ti» v' an<^ Zn snow that calculations
for corrections from pure solutions of calcium and magnesium are
not applicable to multielement analysis. When the ratio of the
Ca and/or Mg concentration to the analyte concentration reaches
1000, significant errors caused by interferences can be
introduced at the analytical wavelengths for Al, As, Hg, Pb, Sb,
Se, and Sn; errors for other elements become significant when
this ratio reaches = 10,000. Data listed in Table 7 show sodium
and potassium to be only minor problems when compared to calcium
and magnesium interferences.
Using ICPES, data from 10 runs of laboratory standard
material were collected in the "as received" state (Table 8).
Calibration of the ICPES was accomplished using no matrix
elements (Ca and Mg) in the solutions containing the remainder
of the elements. Calculated corrections were applied to correct
data for the Ca and Mg in the analyses of the 10 determinations
represented in Table 8. The ratio of Ca or Mg to the remaining
elements is about 2000:1, 100 ppm each of Ca and Mg and 0.05 ppm
for all other elements. After the modifications listed at the
beginning of this section were made, the data listed in Tables 9
through 13 were collected. Calibration of the ICPES was done
using standards containing the matrix elements of Ca and Mg; the
corrections for Ca and Mg were done by using "blank" solutions
containing equal concentrations of the Ca and Mg contained in
the samples.
Examination of these data shows that the latter of the two
techniques yields data that are more reliable when the ratio of
Ca and Mg concentration to other elements approaches 1000.
Detection limits calculated in our laboratory for the ICPES are
listed in Table 1U. Column 1 shows detection limits from data
of the "as received" instrument; column 2 shows results after
the modifications listed at the first of this section. In
column 3, the detection limits are calculated from data while
aspirating 100 ppm Ca and Mg. column 4 is the lowest
quantitatively determinable concentration, which is five times
the detection limit. Comparing data in column H of Table 1U
with those in Tables 9 through 13, one can see that the LQD
concentration is a very conservative estimate for solutions
containing up to 100 ppm each of Ca and Mg. Precision and
accuracy data in Tables 12 and 13 show that As, Hg, Pb, Sb, Se,
and Sn can be determined in those solutions at a concentration
below the calculated LQD concentration. The precision of the
analyses for the afore-mentioned elements is at least a factor
of 10 greater than the remaining list of analytes.
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To demonstrate the applicability of techniques discussed
above, sewage influent and effluent samples were analyzed by
ICPES, INAA, and AA with resultant data presented in Tables 15
through 21. Data listed under the heading ICP-A were determined
at the Athens Environmental Research Laboratory; INAA results
are from the same laboratory at its Neutron Activation Facility.
AA results are averages from 10 different state and Federal
laboratories, and ICP-V results are from another EPA laboratory.
Data in Tables 19 through 21 provide comparisons of standard
samples and a spiked drinking water sample. In most cases,
ICPES data and AA results are in excellent agreement, and each
are in fair agreement with INAA results, both on real samples
(sewage) and standard materials.
The ICP-A instrument was calibrated using standards
containing matrix elements Ca and Mg. Corrections for Ca and Mg
interferences during analyses were done by adding exact amounts
of Ca and Mg to the blank solution, so the corrections are
treated as a blank subtraction from sample data. When running
samples that may have contained waste organics, 1 ml each of
methyl alcohol and ethyl alcohol was added to all calibration
standards and samples to compensate for changes in background
levels caused by organic compounds. Background changes caused
by organics can be significant in analyses that approach LQD
concentrations. Two percent alcohol was added to assure that
the overriding background changes resulting from possible
organic contamination of samples was constant and therefore more
correctly compensated for. When the 2% alcohol solution was
added to water, there was a change in most background signals
toward a smaller value.
The major findings of this evaluation report can be
summarized as follows:
• Corrections for stray light are significant when the
ratio of Ca or Mg to most analytes reaches 1000.
• Calibration standards should contain major impurity
elements that occur in the real samples.
• Compensation for unknown organic impurities can be
made by adding alcohol to the standards and blanks.
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TABLE 1. SPECTROMETER LINE ARRAY
Element* Wavelength, nm
Ag I
Al I
Al I
AS I
B I
Ba II
Be II
C I
Ca II
Cd II
Co II
Cr II
Cu I
Fe II
Hg I
Mg II
Mn II
Mn I
Mo II
Ni II
Pb II
Pb I
Sb I
Se I
Sn I
Sr II
Ti II
V II
Y II
Y II
Zn I
328.07
308.22
396.15
193.76
249.68
455.40
313.04
247.86
315.89
226.50
238.89
267.72
324.75
259.94
253.65
279.55
257.61
403.08
287.15
231.60
220.35
405.78
206.84
196.09
303.41
407.77
334.90
292.40
242.22
371.03
213.86
* I denotes radiation originating from neutral atom.
II denotes radiation originating from singly ionized atoms,
10
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TABLE 2. COMPARISON OF CORRECTION FACTORS
I II III IV
Ca Correction Mg Correction
Unpainted Painted Unpainted Painted
Al
As
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
-3.62E-2
-6.15E-3
-1.08E-3
-1.48E-2
NC
-3.57E-3
-4.08E-3
-5.29E-3
-7.02E-3
-1.93E-3
-2.03E-3
-2.68E-4
-3.30E-3
-4.29E-3
-3.76E-3
-1.49E-3
-8.36E-3
-1.86E-3
NC
NC
-8.94E-3
NC
-1.91E-3
-4.14E-2
-4.50E-3
-1.03E-3
-1.08E-2
NC
-2.61E-3
-3.77E-3
-3.91E-3
-1.56E-3
-2.04E-3
-1.88E-3
-4.01E-4
-2.30E-3
-4.77E-3
-4.22E-3
-1.71E-3
-6.57E-3
-1.90E-3
NC
NC
-7.10E-3
NC
-1.61E-3
-1.68E-4
-8.55E-4
-1.01E-3
-2.68E-4
-2.88E-4
-1.20E-5
-1.59E-4
-1.58E-3
-1.01E-4
-1.51E-5
-6.83E-4
-7.09E-4
-5.02E-4
-1.70E-4
-3.14E-4
-1.75E-5
-1.70E-4
-6.96E-5
-2.52E-4
. -2.86E-4
-3.07E-2
-2.85E-4
-1.73E-4
NC
-1.50E-4
-9.31E-4
NC
NC
-1.55E-6
-1.50E-4
-1.16E-3
NC
NC
-5.63E-4
NC
-2.50E-4
-1.87E-4
-3.90E-4
-3.55E-6
-2.84E-4
-3.20E-5
NC
NC
-2.23E-3
NC
-1.56E-4
NC - No correction required.
11
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TABLE 3. CORRECTION FACTORS PRESENTLY REQUIRED ON ARL QA-137
Al
As
B
Ba
Be
Cd
CO
Cr
Cu
Fe
Hg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
Calcium*
-1.61E-4
-1.96E-3
-7.17E-5
-9.87E-4
NC
-2.15E-4
-1.21E-4
-1.15E-5
NC
-1.12E-4
-l.OOE-4
-6.69E-4
-3.73E-5
-2.46E-4
-4.39E-4
-5.51E-4
-1.12E-3
-9.75E-5
NC
NC
-3.44E-5
-8.90E-5
-4.05E-4
Magnesium*
-2.38E-4
-1.01E-4
-1.10E-3
NC
NC
NC
-1.13E-4
-1.54E-3
NC
NC
-2.58E-4
NC
-2.10E-4
-2.00E-4
-2.26E-4
-3.00E-6
-2.50E-4
NC
NC
NC
NC
NC
-1.70E-4
* Calculated from 1000 yg/ml.
NC - No correction required.
12
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TABLE 4. NONLINEARITY OF Ca AND Mg INTERFERENCE
Al
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mn
Mo
Ni
Pb
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Mg
*50 ppm
0.245E-1
0.843E-2
0.104E+0
0.469E-1
0.316E-2
0.900E-4
0.355E-2
0.404E-2
0.488E-2
-0.138E-2
0.425E-2
0.187E-1
0.109E-2
0.571E-2
0.271E-1
0.951E-2
0.566E-1
0.279E+0
0.546E-1
0.113E+0
0.781E-1
0.800E-4
0.160E-3
0.760E-3
0.229E-2
Mg
*100 ppm
0.208E-1
0.781E-2
0.333E+0
0.210E-1
0.705E-2
0.120E-3
0.157E+0
0.397E-2
0.706E-2
0.718E-2
-0.322E-2
0.839E-2
0.514E-1
0.222E-2
0.479E-2
0.388E-1
0.206E-1
0.104E+0
0.409E+0
0.175E+0
0.288E+0
0.583E-1
0.570E-3
0.200E-3
0.172E-1
0.888E-2
Ca
*50 ppm
0.367E-1
0.186E+0
0.520E+0
-0.306E-2
0.374E-2
0.200E-3
0.508E-2
0.439E-2
-0.320E-2
0.512E-2
0.288E-2
0.308E-1
0.310E-3
-0.178E-1
-0.257E-1
0.399E-2
0.836E-1
-0.477E-1
0.192E+0
0.328E+0
0.201E+0
0.334E-1
-0.145E-2
-0.369E-2
0.218E-2
Ca
*100 ppm
-0.205E-1
0.385E+0
0.752E+0
0.984E-2
0.744E-2
0.900E-4
0.780E-2
0.685E-2
-0.990E-3
-0.512E-2
0.423E-2
0.492E-1
0.134E-2
0.175E-1
-0.927E-2
0.254E-1
0.188E+0
0.625E-1
0.286E+0
0.451E+0
-0.110E+0
0.672E-1
-0.640E-3
-0.307E-2
0.679E-2
Mean of 10 determinations for each element.
Units are equivalents in ppm.
ICP calibrated from ^0.005 to ^5 ppm for all elements except
Ca and Mg.
* Concentrations of Mg or Ca in solution aspirated.
13
-------
TABLE 5. INTERFERENCE OF Ca AND Mg MIXTURES
5 ppm Ca 50 ppm Ca 100 ppm Ca
5 ppm Mg* 50 ppm Mg* 100 ppm Mg*
Al
Al
As
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mn
Mo
Ni
Pb
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
-0.209E-1
0.440E-1
-0.422E-1
0.981E-2
0.670E-3
0.220E-3
0.131E-2
0.663E-2
0.408E-2
0.202E-2
0.221E-2
0.101E-1
0.590E-3
0.413E-1
0.275E-1
0.767E-2
0.242E-1
0.169E+0
-0.149E-1
-0.203E-1
0.195E+0
0.330E-2
0.185E-2
0.120E-2
0.280E-2
-0.288E-1
0.196E+0
0.461E+0
-0.461E-2
0.593E-2
0.120E-3
0.657E-2
0.741E-2
0.398E-2
0.355E-2
0.403E-2
0.384E-1
0.186E-2
0.118E-1
0.215E-1
0.226E-1
0.133E+0
0.213E+0
0.173E+0
0.342E+0
0.545E-1
0.335E-1
-0.400E-3
-0.400E-3
0.910E-2
0.421E-1
0.392E+0
0.719E+0
0.219E-1
0.799E-2
0.210E-3
0.151E-1
0.164E-1
0.104E-1
0.102E-2
0.159E-1
0.810E-1
0.438E-2
0.501E-2
0.839E-1
0.345E-1
0.249E+0
0.594E+0
0.305E+0
0.507E+0
0.246E+0
0.649E-1
0.271E-2
0.152E-2
0.209E-1
Mean of 10 determinations for each element.
Units are equivalents in ppm.
ICP calibrated from ^0.005 to ^5 ppm for all elements except
Ca and Mg.
* Concentrations of Mg and Ca in solution aspirated.
14
-------
All
Al
AS
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mn
Mo
Ni
Pb
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
50 ppm
Ca*
0.367E-1
0.186E+0
0.520E+0
-0.306E-2
0.374E-2
0.200E-3
0.508E-2
0.439E-2
-0.320E-2
0.512E-2
0.288E-2
0.308E-1
0.310E-3
-0.178E-1
-0.257E-1
0.399E-2
0.836E-1
-0.477E-1
0.192E+0
0.328E+0
0.201E+0
0.334E-1
-0.145E-2
-0.369E-2
0.218E-2
50 ppm
Mg*
0.245E-1
0.843E-2
0.104E+0
0.469E-1
0.316E-2
0.900E-4
0.355E-2
0.404E-2
0.488E-2
-0.138E-2
0.425E-2
0.187E-1
0.109E-2
0.571E-2
0.271E-1
0.951E-2
0.566E-1
0.279E+0
0.546E-1
0.113E+0
0.781E-1
0.800E-4
0.160E-3
0.760E-3
0.229E-2
50 ppm Ca
50 ppm Mg*
-0.288E-1
0.196E+0
0.461E+0
-0.461E-2
0.593E-2
0.120E-3
0.657E-2
0.741E-2
0.398E-2
-0.355E-2
0.403E-2
0.384E-1
0.186E-2
0.118E-1
0.215E-1
0.226E-1
0.133E+0
0.212E+0
0.173E+0
0.342E+0
0.545E-1
0.335E-1
-0.400E-3
-0.400E-3
0.910E-2
Mean of 10 determinations for each element.
Units are equivalents in ppm.
ICP calibrated from 'vO.OOS to ^5 ppm for all elements except
Ca and Mg.
* Concentrations of Mg and/or Ca in solution aspirated.
15
-------
TABLE 7. INTERFERENCE OF MATRIX ELEMENTS AND MIXTURES
Al
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mn
Mo
Ni
Pb
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
50 ppro Na
50 ppm K*
-0.111E-1
-0.660E-2
+0.199E-1
-0.127E-1
+0.360E-3
-0.900E-4
-0.330E-3
-0.930E-3
-0.109E-2
-0.560E-3
-0.109E-2
-0.555E-2
-0.130E-3
-0.881E-2
-0.859E-2
-0.481E-2
-0.196E-1
-0.718E-1
-0.116E-1
-0.209E-1
-0.845E-1
+0.170E-3
-0.450E-3
-0.251E-2
-0.338E-2
100 ppm Na
100 ppm K*
-0.251E-1
-0.308E-1
+0.105E-1
-0.508E-1
+0.480E-3
-0.900E-4
-0.259E-2
-0.603E-2
-0.726E-2
-0.380E-3
-0.539E-2
-0.341E-1
-0.580E-3
-0.593E-1
-0.352E-1
-0.141E-1
-0.380E-1
-0.241E+0
-0.150E-1
+0.140E-1
-0.244E+0
+0.430E-3
-0.184E-2
-0.464E-2
-t-0.680E-2
50 Mg
20 K
100 ppm Na
100 ppm Ca*
0.184E-1
0.344E+0
0.585E-I-0
0.642E-2
0.617E-2
0.220E-3
0.909E-2
0.988E-2
0.326E-2
-0.660E-3
0.653E-2
0.502E-1
0.262E-2
0.328E-1
0.196E-1
0.287E-1
0.179E+0
0.216E+0
0.209E+0
0.391E+0
0.553E-1
0.598E-1
-0.310E-3
-0.154E-2
0.159E-1
100 ppm Na*
-0.122E-1
-0.309E-2
+0.210E-1
-0.219E-2
+0.119E-2
-0.800E-4
-0.172E-2
-0.113E-2
-0.165E-2
-0.298E-2
-0.520E-3
+0.130E-1
-0.600E-4
-0.930E-2
+0.419E-2
-0.292E-2
-0.122E-1
-0.457E-1
-0.276E-1
-0.139E-1
-0.302E-1
+0.540E-3
-0.160E-3
-0.232E-2
-0.408E-2
100 ppm Ca*
-0.205E-1
0.385E+0
0.752E+0
0.984E-2
0.744E-2
0.900E-4
0.780E-2
0.685E-2
-0.990E-3
-0.512E-2
0.423E-2
0.492E-1
0.134E-2
0.175E-1
-0.927E-2
0.254E-1
0.188E-1-0
0.625E-1
0.286E+0
0.451E+0
-0.110E+0
0.672E-1
-0.640E-3
-0.307E-2
0.679E-2
50 ppm Na*
-0.119E-1
-0.507E-2
+0.232E-1
+0.720E-2
+0.370E-3
-0.600E-4
+0.572E-1
-0.121E-2
-0.117E-2
-0.131E-2
-0.258E-2
-0.133E-2
-0.865E-2
-0.540E-3
-0.220E-3
-0.130E-1
-0.812E-2
-0.390E-2
-0.803E-2
-0.425E-1
+0.271E-1
+0.173E-1
-0.662E-1
+0.210E-3
-0.290E-3
-0.740E-3
-0.246E-2
50 ppm K*
+0.274E-1
-0.586E-2
-0.235E-1
-0.989E-2
-0.900E-4
+0.130E-3
+0.130E-3
+0.259E-2
-0.840E-3
-0.970E-3
-0.128E-2
-0.380E-3
-0.807E-2
-0.148E-2
-0.110E-3
-0.809E-2
-0.983E-2
-0.398E-2
-0.212E-1
-0.239E-1
-0.125E-1
-0.298E-1
-0.275E-1
-0.200E-4
-0.380E-3
-0.215E-2
-0.549E-2
Mean of 10 determinations for each element. ICP calibrated -\-0.005 to ^5 ppm for each element except
Ca and Mg. * Concentrations of Ca, Mg, Na, and K in solution aspirated.
-------
TABLE 8. ORIGINAL ATTEMPTS TO CORRECT FOR Ca AND Ma INTERFERENCE
Element
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
X 10
Runs
0.0472
0.0804
0.0771
0.0482
0.0504
98.90
0.0565
0.0542
0.0512
0.0471
0.0531
0.0816
98.77
0.0502
0.0524
0.0648
Variance
0.000025
0.0082
0.0035
0.0000015
0.0000072
0.281
0.000011
0.000011
0.0000097
0.000035
0.000011
0.00099
0.0415
0.0000005
0.000096
0.00014
Standard
Deviation
0.0050
0.029
0.0188
0.0012
0.0027
0.53
0.0033
0.0034
0.0031
0.0059
0.0033
0.031
0.20
0.0007
0.0098
0.0118
Overcorrected
0.0909
0.1030
0.0768
0.0514
0.0373
0.0499
0.0500
0.0312
0.0129
0.0021
0.0015
0.0000035
o.oooa2i
0.0000020
0.0000005
0.0000007
0.114
0.0464
0.0384
0.0019
0.0046
0.0014
0.0007
0.0008
Ca and Mg concentration is 100 ppm each, other elements 0.050 ppm.
17
-------
TABLE 9. MATRIX 20
RATIO*
oo
Al
Al
AS
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mn
Mo
Ni
Pb
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Mean
0.468E+1
0.488E+1
0.101E+2
0.516E+1
0.492E+1
0.504E+1
0.505E+1
0.509E+1
0.512E+1
0.501E+1
0.524E+1
0.494E+1
0.504E+1
0.503E+1
0.511E+1
0.501E+1
0.102E+2
0.103E+2
0.523E+1
0.243E+2
0.103E+2
0.506E+1
0.487E+1
0.382E+1
0.515E+1
Variance
0.982E-3
0.266E-3
0.256E-2
0.137E-2
0.119E-2
0.137E-2
0.101E-2
0.461E-3
0.228E-3
0.407E-3
0.244E-3
0.257E-2
0.163E-3
0.222E-3
0.418E-3
0.118E-2
0.367E-2
0.579E-2
0.722E-3
0.201E-1
0.154E-2
0.190E-3
0.391E-3
0.521E-3
0.472E-3
Standard
Deviation
0.313E-1
0.163E-1
0.506E-1
0.370E-1
0.345E-1
0.370E-1
0.319E-1
0.215E-1
0.151E-1
0.202E-1
0.156E-1
0.507E-1
0.128E-1
0.149E-1
0.204E-1
0.344E-1
0.606E-1
0.761E-1
0.269E-1
0.142E+0
0.393E-1
0.138E-1
0.198E-1
0.228E-1
0.217E-1
Added
0.486E+1
0.486E+1
0.996E+1
0.515E+1
0.498E+1
0.514E+1
0.499E+1
0.499E+1
0.508E+1
0.503E+1
0.515E+1
0.500E+1
0.503E+1
0.503E+1
0.500E+1
0.499E+1
0.996E+1
0.996E+1
0.511E+1
0.2423E+2
0.996E+1
0.522E+1
0.495E+1
0.398E+1
0.510E+1
Difference
-0.18E+0
+0.20E-1
+0.14E+0
+0.10E-1
-0.60E-1
-0.10E+0
+0.60E-1
+0.10E+0
+0.40E-1
-0.20E-1
+0.21E+0
-0.60E-1
+0.10E-1
•fO.OOE+0
+0.11E+0
+0.20E-1
+0.20E+0
+0.34E+0
+0.12E+0
+0.10E+0
+0.34E+0
-0.16E+0
-0.80E-1
-0.16E+0
+0.50E-1
%
Error
-4
+0.4
+1.0
+0.2
-1
-2
+1
+2.0
+0.8
- .4
+4.0
-1
+2
0
+2
+0.40
+2.0
+3
+2
+ .41
+3
-3.0
-2
-4.0
+1
Data from 10 determinations. * Ca and Mg concentrations 100 ppm each.
-------
TABLE 10. MATRIX 100
RATIO*
vo
Al
Al
AS
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mn
Mo
Ni
Pb
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Mean
0.101E+1
0.954E+0
0.197E+1
0.106E+1
0.990E+0
0.102E+1
0.988E+0
0.981E+0
0.103E+1
0.997E+0
0.101E+1
0.971E+0
0.101E-KL
0.987E+0
0.102E+1
0.101E+1
0.200E+1
0.197E+1
0.101E+1
0.491E+1
0.209E+1
0.117E+1
0.994E+0
0.988E+0
0.102E+1
Variance
0.443E-3
0.231E-4
0.848E-3
0.268E-4
0.932E-5
0.185E-4
0.134E-4
0.168E-4
0.175E-4
0.610E-5
0.142E-4
0.531E-4
0.124E-4
0.607E-4
0.575E-4
0.443E-4
0.593E-3
0.240E-2
0.451E-3
0.127E-2
0.190E-2
0.292E-4
0.441E-5
0.848E-5
0.326E-4
Standard
Deviation
0.211E-1
0.480E-2
0.291E-1
0.518E-2
0.305E-2
0.430E-2
0.366E-2
0.410E-2
0.418E-2
0.247E-2
0.377E-2
0.728E-2
0.352E-2
0.779E-2
0.758E-2
0.665E-2
0.243E-1
0.490E-1
0.212E-1
0.356E-1
0.436E-1
0.540E-2
0.210E-2
0.291E-2
0.571E-2
Added
0.973E+0
0.973E-I-0
0.1992E+1
0.1029E+1
0.996E+0
0.1027E+1
0.998E+0
0.998E+0
0.1015E+1
0.1006E+1
0.1030E+1
0.1001E+1
0.1006E+1
0.1006E+1
0.1000E+1
0.997E+0
0.1992E+1
0.1992E-KL
0.1022E4-1
0.4845E+1
0.1992E+1
0.1043E+1
0.989E+0
0.978E+0
0.1019E+1
Difference
+ .370E-1
-0.190E-1
- .220E-1
+0.310E-1
-0.600E-2
-0.700E-2
-0.100E-1
-0.170E-1
+0.150E-1
-0.900E-2
-0.200E-1
-0.300E-1
+0.400E-2
-0.190E-1
+0.200E-1
+0.130E-1
+0.800E-2
-0.220E-1
-0.120E-1
+0.650E-1
+0.980E-1
+ .127E+0
-0.500E-2
+0.100E-1
+0.1E-2
%
Error
+3.8
-2
-1.1
+3.0
-0.6
-0.7
-1.0
-1.7
+1.5
-0.9
-2
-3
+0.4
-2
+2
+1,3
+0.4
-1.1
-1.2
+1.3
+5
+12.2
- .5
+1.0
+1
Data from 10 determinations. *Ca and Mg concentrations 100 ppm each.
-------
TABLE 11. MATRIX 200 M. RATIO*
to
o
Al
Al
AS
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mn
Mo
Ni
Pb
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Mean
0.546E+0
0.517E+0
0.915E+0
0.520E+0
0.498E+0
0.517E+0
0.514E+0
0.512E+0
0.512E+0
0.498E+0
0.528E+0
0.520E+0
0.505E+0
0.468E+0
0.500E+0
0.501E+0
0.101E+1
0.104E+1
0.495E+0
0.241E+1
0.106E+1
0.592E+0
0.501E+0
0.495E+0
0.540E+0
Variance
0.312E-3
0.262E-4
0.416E-3
0.134E-4
0.526E-5
0.517E-5
0.665E-5
0.543E-5
0.487E-5
0.352E-5
0.394E-5
0.182E-3
0.267E-5
0.691E-4
0.270E-4
0.117E-4
0.102E-2
0.154E-2
0.145E-3
0.991E-3
0.156E-2
0.721E-5
0.144E-5
0.216E-5
0.323E-4
Standard
Deviation
0.177E-1
0.511E-2
0.204E-1
0.367E-2
0.229E-2
0.227E-2
0.258E-2
0.233E-2
0.221E-2
0.188E-2
0.199E-2
0.135E-1
0.163E-2
0.831E-2
0.520E-2
0.341E-2
0.319E-1
0.393E-1
0.120E-1
0.315E-1
0.395E-1
0.268E-2
0.120E-2
0.147E-2
0.568E-2
Added
0.486E+0
0.486E+0
0.996E+0
0.515E+0
0.498E+0
0.514E+0
0.499E+0
0.499E+0
0.508E+0
0.503E+0
0.515E+0
0.500E+0
0.503E+0
0.503E+0
0.500E+0
0.499E+0
0.996E+0
0.996E+0
0.511E+0
0.2423E+1
0.966E+0
0.522E+0
0.495E+0
0.498E+0
0.510E+0
Difference
+0.6E-1
+0.31E-1
-0.81E-1
-0.5E-2
0
+0.3E-2
+0.15E-1
+0.13E-1
+0.4E-2
-0.5E-2
+0.5E-2
+0.2E-1
+0.2E-2
-0.35E-1
0
+0.2E-2
+0.14E-1
+0.44E-1
-0.16E-1
-0.13E-1
+0.64E-1
+0.7E-1
+0.6E-2
-0.3E-2
+0.3E-1
%
Error
+12
+6.4
-8.1
+1
0
+0.6
+0.6
+2.6
+0.8
-1
+1
+4.0
+0.4
-7
0
+0.4
+1.4
+4.4
-3.1
-0.5
+6.4
+13.4
+1.2
-0.6
+5.9
Data from 10 determinations. *Ca and Mg concentrations 100 ppm each,
-------
TABLE 12,
MATRIX 1000
RATIO*
Al
Al
As
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mn
Mo
Ni
Pb
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Mean
0.113E+0
0.109E+0
0.125E+0
0.113E+0
0.102E+0
0.104E+0
0.106E+0
0.108E+0
0.115E+0
0.113E+0
0.109E+0
0.113E+0
0.103E+0
0.143E+0
0.122E+0
0.104E+0
0.200E+0
0.277E+0
0.712E-1
0.428E+0
0.345E+0
0.131E+0
0.107E+0
0.280E-1
0.106E+0
Variance
0.449E-3
0.166E-4
0.584E-3
0.784E-5
0.615E-6
0.230E-6
0.137E-5
0.113E-5
0.183E-5
0.599E-6
0.132E-5
0.131E-3
0.313E-6
0.724E-4
0.250E-4
0.502E-5
0.169E-3
0.809E-3
0.424E-3
0.231E-3
0.899E-3
0.424E-5
0.281E-6
0.719E-7
0.734E-6
Standard
Deviation
0.212E-1
0.407E-2
0.242E-1
0.280E-2
0.784E-3
0.480E-3
0.117E-2
0.106E-2
0.135E-2
0.774E-3
0.115E-2
0.114E-1
0.559E-3
0.851E-2
0.500E-2
0.224E-2
0.130E-1
0.284E-1
0.206E-1
0.152E-1
0.300E-1
0.651E-3
0.449E-3
0.268E-3
0.857E-3
Added
0.97E-1
0.97E-1
0.199E+0
0.103E+0
0.100E+0
0.103E+0
0.100E+0
0.100E+0
0.102E+0
0.101E+0
0.103E+0
0.100E+0
0.101E+0
0.101E+0
0.100E+0
0.100E+0
0.99E+0
0.199E+0
0.102E+0
0.485E+0
0.398E+0
0.120E+0
0.990E-1
0.350E-1
0.102E+0
Difference
+0.16E-1
+0.12E-1
-0.74E-1
+0.10E-1
+0.20E-2
+0.10E-2
+0.60E-2
+0.80E-2
+0.13E-1
+0.12E-1
+0.60E-2
-0.13E-1
+0.20E-2
+0.42E-1
+0.22E-1
+0.40E-2
+0.10E-2
+0.78E-1
-0.31E-1
-0.57E-1
-0.53E-1
+0.11E-1
+0.80E-2
-0.70E-2
+0.40E-2
%
Error
+16
+12
-37
+10
+20
+10
+6
+8
+13
+12
+6
-13
+2
+42
+27
+4
+5
+39
+30
-12
-13
+9
+8
-20
+4
Data from 10 determinations. *Ca and Mg concentrations 100 ppm each,
-------
TABLE 13,
MATRIX 2500
RATIO *
NJ
NJ
Al
AS
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Zn
Mean
0.246E-1
0.275E-1
0.374E-1
0.217E-1
0.227E-1
0.233E-1
0.234E-1
0.254E-1
0.208E-1
0.227E-1
0.438E-1
0.222E-1
0.324E-1
0.237E-1
0.569E-1
0.447E-1
0.126E+0
0.105E+0
0.267E-1
0.220E-1
0.621E-2
0.147E-1
Variance
0.152E-4
0.432E-3
0.244E-5
0.429E-7
0.224E-7
0.131E-5
0.142E-5
0.134E-5
0.424E-6
0.512E-6
0.736E-4
0.405E-7
0.166E-4
0.666E-5
0.257E-3
0.262E-3
0.967E-4
0.128E-2
0.204E-7
0.153E-6
0.566E-7
0.205E-5
Standard
Deviation
0.390E-2
0.208E-1
0.156E-2
0.207E-3
0.150E-3
0.115E-2
0.119E-2
0.116E-2
0.651E-3
0.716E-3
0.858E-2
0.201E-3
0.407E-2
0.258E-2
0.160E-1
0.162E-1
0.984E-2
0.358E-1
0.143E-3
0.391E-3
0.238E-3
0.143E-2
Added
0.200E-1
0.400E-1
0.400E-1
0.200E-1
0.210E-1
0.200E-1
0.200E-1
0.200E-1
0.200E-1
0.200E-1
0.400E-1
0.200E-1
0.400E-1
0.200E-1
0.400E-1
0.400E-1
0.100E+0
0.104E+0
0.210E-1
0.200E-1
0.500E-2
0.100E-1
Difference
+0.46E-2
-0.125E-1
-0.26E-2
+0.17E-2
+0.17E-2
+0.33E-2
+0.34E-2
+0.54E-2
+0.8E-3
+0.27E-2
+0.38E-2
+0.22E-2
-0.76E-2
+0.37E-2
+0.169E-1
+0.47E-2
+0.26E-1
+0.1E-2
+0.57E-2
+0.20E-2
+0.121E-2
+0.47E-2
%
Error
+23
-31
-6
+8
+8
+16
+17
+27
+4
+14
+19
+11
-12
+18
+42
+12
+26
+1
+27
+10
+24
+47
Data from 10 determinations. *Ca and Mg concentrations 100 ppm each,
-------
TABLE 14. DETECTION LIMITS (pg/1) QA-137 SYSTEM*
*
Al
As
B
Ba
Be
Cd
Co
Cr
Cu
Fe
Hg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
396.15
193.76
249.68
455.40
313.04
226.50
238.89
267.72
324.75
259.94
253.65
257.61
287.15
231.60
220.35
206.84
196.09
303.41
407.77
334.90
292.40
371.03
213.86
Detection limit
produce
a signal
1*
7
50
4
0.2
0.06
1
2
2
2
1
20
0.3
7
4
20
20
20
80
0.1
6
5
5
3
2*
4
50
3
0
0
1
1
1
0
0
15
0
6
4
20
20
20
50
0
0
0
0
3
is the analyte
two times the
.1
.1
.6
.8
.2
.05
.5
.3
.5
3
4
50
3
0
0
2
1
1
1
0
15
0
6
4
20
20
20
50
0
0
0
0
3
*
.1
.1
.6
.1
.01
.4
.2
.5
concentration
standard
4*
20
250
15
0.
0.
10
5
5
5
3
45
0.
30
20
100
100
100
250
0.
2
1
2
6
required
deviation at
5
5
5
05
to
the
analytical line.
1.
2.
3.
4.
Values
Values
Values
LQD is
or five
before modifications.
after modifications.
with 100
yg/ml Ca and
Mg matrix.
the lowest quantitatively determinable concentration
times the detection
limit.
23
-------
TABLE 15. SEWAGE EFFLUENT V-ll
ICP-A INAA AA ICP-V
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
y
Zn
<5E-9
1.51E-6
<5E-8
2.30E-7
1.3E-8
<5E-9
4.29E-5
4.7E-8
3E-9
1.09E-7
7.0E-8
6.08E-7
1.1E-8
1.42E-5
1.38E-7
<5E-9
3.17E-7
2.20E-7
2.2E-8
<5E-8
<5E-8
1.97E-7
<5E-9
<5E-9
<5E-9
2.19E-7
*NR
1.6E-6
6.0E-9
NR
NR
NR
3.2E-5
4.8E-8
1.2E-9
6.2E-8
NR
6.3E-7
1.6E-8
1.3E-5
1.4E-7
2.6E-9
NR
NR
2.6E-7
NR
NR
2.5E-7
NR
NR
NR
2.0E-7
NR
1.53E-6
NR
NR
NR
NR
NR
4.8E-8
NR
1.18E-7
1.09E-7
6.05E-7
NR
NR
1.38E-7
NR
3.06E-7
2.50E-7
NR
NR
NR
NR
NR
NR
NR
2.16E-7
NR
9.20E-7
NR
NR
NR
NR
NR
4.3E-8
NR
1.27E-7
1.05E-7
6.24E-7
NR
NR
1.28E-7
NR
2.68E-7
1.93E-7
NR
NR
NR
NR
NR
NR
NR
2.27E-7
*NR - Not reported.
24
-------
TABLE 16. SEWAGE EFFLUENT V-12
ICP-A INAA AA ICP-V
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
<5E-9
1.72E-6
<5E-8
2.71E-7
1.6E-8
<5E-9
51.6E-5
5.9E-8
1.1E-8
1.29E-7
9.0E-8
6.59E-7
2.0E-8
1.60E-5
1.58E-7
l.OE-8
3.71E-7
2.91E-7
1.8E-8
<5E-8
<5E-8
2.25E-7
5E-9
<5E-9
<5E-9
2.71E-7
NR
1.8E-6
7.8E-9
NR
2.8E-8
NR
4.0E-5
5.1E-8
1.4E-9
8.2E-8
NR
5.8E-7
1.6E-8
1.4E-5
1.7E-7
2.7E-9
NR
NR
3.4E-9
NR
NR
2.5E-7
NR
NR
NR
2.2E-7
NR
1.74E-6
NR
NR
NR
NR
NR
5.8E-8
NR
1.39E-7
1.17E-7
7.23E-7
NR
NR
1.55E-7
NR
3.43E-7
3.00E-7
NR
NR
NR
NR
' NR
NR
NR
2.51E-7
NR
1.07E-6
NR
NR
NR
NR
NR
5.0E-8
NR
1.44E-7
1.20E-7
7.32E-7
NR
NR
1.50E-7
NR
3.17E-7
2.26E-7
NR
NR
NR
NR
NR
NR
NR
2.62E-7
NR - Not reported.
25
-------
TABLE 17. SEWAGE INFLUENT V-13
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
y
Zn
ICP-A
1.1E-8
3.54E-6
9.1E-8
2.21E-7
1.60E-7
<5E-9
5.72E-5
1.37E-7
5.0E-8
4.67E-7
4.58E-7
6.30E-6
1.40E-7
1.87E-5
2.85E-7
<5E-8
1.052E-6
7.85E-7
4.2E-8
<5E-8
<5E-8
2.62E-7
5.7E-8
<5E-8
<5E-8
1.309E-6
INAA
1.8E-8
6.6E-6
6.6E-9
NR
1.4E-7
NR
4.4E-5
1.4E-7
4.7E-9
3.2E-7
NR
6.0E-6
4.7E-8
1.8E-5
3.0E-7
1.5E-8
NR
NR
1.2E-8
1.1E-9
NR
3.6E-7
NR
8.0E-9
NR
l.OE-6
AA
NR
3.094E-6
NR
NR
NR
NR
NR
1.39E-7
NR
4.55E-7
4.72E-7
6.230E-6
NR
NR
2.94E-7
NR
1.075E-6
8.09E-7
NR
NR
NR
NR
NR
NR
NR
1.211E-6
ICP-V
NR
3.133E-6
NR
NR
NR
NR
NR
1.30E-7
NR
4.33E-7
4.62E-7
6.539E-6
NR
NR
2.70E-7
NR
1.037E-6
6.91E-7
NR
NR
NR
NR
NR
NR
NR
1.170E-7
NR - Not reported.
26
-------
TABLE 18. SEWAGE INFLUENT V-14
ICP-A
INAA
AA
ICP-V
Ag
Al
AS
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
1.3E-8
4.273E-6
1.15E-7
2.55E-7
1.86E-7
<5E-9
6.62E-5
1.59E-7
5.5E-8
5.42E-7
5.43E-7
7.482E-6
1.43E-7
2.17E-5
3.31E-7
<5E-8
1.282E-6
8.95E-7
1.4E-8
<5E-8
<5E-8
3.04E-7
6.5E-7
<5E-9
<5E-9
1.518E-6
1.9E-8
8.1E-6
4.4E-9
NR
1.6E-7
NR
4.6E-5
1.6E-7
5.8E-9
3.9E-7
NR
6.7E-6
8.8E-9
2.2E-5
3.6E-7
8.8E-9
NR
NR
1.4E-8
1.4E-9
NR
4.4E-7
7.7E-7
1.2E-8
NR
1.3E-6
NR
4.515E-6
NR
NR
NR
NR
NR
1.61E-7
NR
5.26E-7
5.74E-7
7.090E-6
NR
NR
3.32E-7
NR
1.250E-6
9.57E-7
NR
NR
NR
NR
NR
NR
NR
1.404E-6
NR
3.735E-6
NR
NR
NR
NR
NR
1.52E-7
NR
5.59E-7
5.40E-7
7.617E-6
NR
NR
3.15E-7
NR
1.220E-6
8.04E-7
NR
NR
NR
NR
NR
NR
NR
1.339E-6
jitj.
NR - Not reported.
27
-------
TABLE 19. STANDARD V-15
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
ICP-A
<5E-9
7.83E-7
1.14E-7
1.4E-8
8E-9
<5E-9
NR
2.0E-8
4E-9
9.7E-8
9.4E-8
6.21E-7
1.5E-8
NR
1.23E-7
<5E-9
9E-9
1.36E-7
2 . OE-8
<5E-8
<5E-8
<5E-9
<5E-9
<5E-9
<5E-9
1.13E-7
INAA
NR
8.1E-7
7.8E-8
NR
NR
NR
2.9E-5
2.2E-8
4.4E-10
7.5E-8
NR
6.2E-7
1.2E-8
NR
1.3E-7
NR
NR
NR
6.8E-10
1.7E-8
NR
NR
NR
NR
NR
1.2E-7
AA
NR
7.00E-7
8.8E-8
NR
NR
NR
NR
2. OE-8
NR
9.7E-8
7.8E-8
6.27E-7
NR
NR
1.15E-7
NR
NR
1.12E-7
NR
1.9E-8
NR
NR
NR
NR
NR
1.01E-7
ICP-V
NR
7.00E-7
NR
NR
NR
NR
NR
1.8E-8
NR
l.OOE-7
8. OE-8
5.90E-7
NR
NR
1.20E-7
NR
<2.0E-8
9.5E-8
NR
NR
NR
NR
NR
NR
NR
1.02E-7
NR - Not reported.
28
-------
TABLE 20. ICP REFERENCE SAMPLE
ICP
INAA
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
Y
Zn
1.51E-7
9.83E-7
7.5E-8
4.91E-7
9.77E-7
8.8E-8
2.08E-5
4.23E-7
4.58E-7
3.06E-7
5.04E-7
2.430E-6
7.6E-8
4.73E-6
4.30E-7
1.074E-6
5.48E-7
5.409E-6
<5E-9
5.8E-8
3.70E-7
2.9E-8
6.02E-7
5.33E-7
2.27E-5
3.08E-6
1.4E-7
NR
6.8E-10
NR
7.8E-7
NR
2.7E-5
3.8E-7
3.3E-7
1.8E-7
NR
2.4E-6
2.9E-8
NR
4.6E-7
7.2E-7
NR
NR
1.2E-9
NR
3.2E-7
NR
NR
4.1E-7
NR
2.1E-6
NR - Not reported.
29
-------
TABLE 21. 124 DRINKING WATER
Ag
Al
As
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Hg
Mg
Mn
Mo
Ni
Pb
Sb
Se
Sn
Sr
Ti
V
y
Zn
ICP
<5E-9
2.4E-8
<5E-8
1.50E-7
8.31E-6
<5E-9
5.46E-5
<5E-9
<5E-9
<5E-9
3.6E-8
5.9E-8
<5E-9
2.20E-5
<5E-9
<5E-9
<5E-9
<5E-8
<5E-9
<5E-8
<5E-8
3.24E-6
<5E-9
<5E-9
<5E-9
9.5E-8
INAA
NR
4.5E-8
NR
NR
7.4E-6
NR
3.8E-5
NR
2.6E-9
1.3E-9
NR
3.2E-7
3.0E-8
2.1E-5
1.8E-9
NR
NR
NR
3.5E-10
NR
NR
3.2E-6
NR
NR
NR
9.0E-8
NR - Not reported.
30
-------
BIBLIOGRAPHY
Dickinson, G. W. , and V. A. Fassel. 1969. Emission Spectro-
metric Detection of the Elements at the Nanogram per
Milliliter Level Using Induction Coupled Plasma
Excitation. Analytical Chemistry. 41; 1021.
Padobnik, B., et al. 1965. The Flame Photometric Determination
of Li, Na, K, Ca, Mg, and Sr in Natural and Mineral Waters.
Mikrochim Acta. 1074.
Steiner, R. L. 1969. Rapid Direct Reading Determination of
Elements in Industrial Waste Water. Environmental Science
Technology. 3^: 1192.
Wendet, R. H., and V. A. Fassel. 1965. Induction Coupled
Plasma Spectrometric Excitation Source. Analytical
Chemistry. 37: 920.
31
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-77-113
3. RECIPIENT'S ACCESSIOI»NO.
4. TITLE AND SUBTITLE
RELIABLE ANALYSES OF WATER BY INDUCTIVELY
COUPLED PLASMA EMISSION SPECTROSCOPY
5. REPORT DATE
June 1977 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Charles E. Taylor
9. PERFORMING ORG MMIZATION NAME AND ADDRESS
Environmental Research Laboratory-Athens, GA
Office of Research and Development
U.S. Environmental Protection Agency
Athens, Georgia 30605
10. PROGRAM ELEMENT NO.
1BD713
11. CONTRACT/GRANT NO.
In-house
12. SPONSORING AGENCY NAME AND ADDRESS
"Same as above.
13. TYPE OF REPORT AND PERIOD COVERED
Interim
14. SPONSORING AGENCY CODE
EPA/600/01
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Reduction of stray light in the inductively coupled plasma emission
spectrometer (ICPES) has greatly increased its reliability as a
technique for the multielemental analysis of water. Because of
interferences introduced by matrix elements, reliable analysis of some
less-sensitive elements has been impractical at concentrations of < 200
ppb. After surfaces in the secondary optical system were painted to
prevent light scatter and the aperture at the primary lens was reduced
in the ICPES, some interference corrections were reduced by more than
one order of magnitude. Reduced interferences in the ICPES along with
improved corrections by adding exact concentrations of calcium and
magnesium to reagent blanks run during sample analyses have definitely
improved the accuracy of this multielement analysis system. Observed
background changes caused by the presence of magnesium were compensated
for by adding matrix elements to calibration standards. Alcohol was
added to standards, reagent blanks, and samples to overcome problems
of background change during analysis of samples of unknown organic
content such as municipal sewage.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Emission spectroscopy
Atomic spectroscopy
Chemical analysis
Inductively coupled
plasma emission
spectroscopy
Multielement
analysis of water
Trace analysis of
pollutants in water
07B
21. NO. OF PAGES
40
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
32
I). S. GOVERNMENT PRINTING OFFICE- i $77-757-056/61*52 Reg Ion No. 5-11
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