EPA 660/2-74-001
JANUARY 1974
Environmental Protection Technology Series
Multielement Analysis of Environmental
Samples By Spark Source
Mass Spectrornetry
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Corvallis, Oregon 97330
-------
RESEARCH REPORTING SERIES
Research reports of the Oft'ice of Research and
Monitoring, Environmental Protection Avjency, have
been grouped into five series. These five bread
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Eesearch
2. Environmental Protection Technology
3. Ecological Research
U. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
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.
-------
EPA-660/2-74-001
January 1974
MULTIELEMENT ANALYSIS OF ENVIRONMENTAL SAMPLES
BY SPARK SOURCE MASS SPECTROMETRY
by
Charles E. Taylor
William J. Taylor
Southeast Environmental Research Laboratory
College Station Road
Athens, Georgia 30601
Project 16ADN-22
Program Element #1BA027
National Environmental Research Center
Office of Research and Development
U. S. Environmental Protection Agency
Corvallis, Oregon 97330
For sale by the Superintendent ol Documents, U.S. Government Printing Office
Washington, D.C. 20402 - Price 65 cents
-------
ABSTRACT
A spark source mass spectrometer that uses electronic
detection- and a dedicated data analysis system was
applied to a survey type trace analysis for chemical
elements. Errors in the data system software were
identified and corrected. Modifications to the system
permit identification and quantitation of 72 elements
at the part per billion level in water samples.
ii
-------
CONTENTS
Page
Abstract ii
List of Figures
List of Tables
Acknowledgements
Sections
I Conclusions 1
II Recommendations 2
III Introduction 3
IV Experimental 4
V Results and Discussion g
VI References 23
iii
-------
FIGURES
Page
1 Accurate Mass Data 9
2 Original Interpretation of Data 10
3 Modified Interpretation of +1 and +2 12
Ion Data
4 Sample #1 Bar Graph 14
5 Sample #2 Bar Graph 15
-------
TABLES
No.
1 Group I Coefficients of Variation 16
2 Group II Coefficients of Variation 17
3 SS Analysis of Effluent Sample 18
4 Relative Sensitivity Study in Sediment 19
Sample
5 SS Analysis of Reservoir Water 21
-------
ACKNOWLEDGMENTS
The help of W. H. McDaniel, Environmental Protection
Agency, Surveillance and Analysis Division, Chemical
Services Bnfcnch, Region IV, in providing comparison
analyses by atomic absorption is gratefully acknowledged
Vi
-------
SECTION I
CONCLUSIONS
Survey type analysis for trace elements in natural
samples can be accomplished using spark source mass
spectrometry (SSMS). Weight ratios of up to 100:1 in
synthetic samples showed no detrimental effect on spark
source data. Valid results have been obtained for multi-
element analyses of sediments. The concentration of
elements in sediments ranged from the percentage level
to the part per million level. Using the modified
software programs and existing SSMS equipment, 72
naturally occurring elements can be identified and
quantitated at the part per billion (ppb) level in water
samples.
-------
SECTION II
RECOMMENDATION
Spark source mass spectrometry should be used for survey
multielement analyses to clearly and rapidly identify
problem elements in the environment. Because spark source
is not so limited by interference, it should also be
used as a back-up for more limited analytical techniques,
such as atomic absorption and emission spectroscopy.
-------
SECTION III
INTRODUCTION
Any elements or their compounds are pollutants if they
occur at concentrations that adversely affect water
usage. Because these concentrations may be very low, a
method of trace analysis for a broad survey of chemical
elements is essential to pollution monitoring. Emission
and atomic absorption spectroscopy are each,currently
used for such applications. However, using emission
spectroscopy, one can routinely analyze for only 18-20
elements; atomic absorption is even more limited. The
spark source mass spectrometer with its related data
system combines sensitivity and broad range analysis
capability with convenient analysis time. To assess the
applicability of spark source mass spectrometry to the
analysis of water and sediments we conducted this study
evaluating a new computerized electronic detection
system.
-------
SECTION IV
EXPERIMENTAL.
The instrument used was an AEI MS 702 spark source mass
spectrometer equipped with electronic detection. Acces-
sories allow either peak switching or scanning for data
collection.
Peak switching is used when the analyst is interested in
a more precise recording of a few peak intensities than
is provided by a normal scan. It is used when major
interest is in 2 or 3 elements. Switching is also used
when isotopic dilution methods are required for ultimate
accuracy in spark source (SS) analyses. Scanning is a
survey analysis application and can include the total
spectrum to encompass all known isotopes. The less
precise measurements obtained from scanning are accept-
able when the analyst requires a rapid survey, trace
analysis system.
The spark source mass spectrometer is equipped with an
AEI data reduction system; this includes a SS interface,
a Digital Equipment Corporation (DEC) PDP8/e 4K Computer,
a 12-bit A/D Converter, a DF 32 and DS 32 disc memory,
a teletype and high speed reader/punch and vendor-
supplied DS-40 software. All data to be discussed were
taken using the electronic detection and data system.
The data system is functional only when the SS system
operates in the scanning mode. The DS-40 software is
not equipped for photographic plate or peak switching
data.
Calibration standards and other synthetic samples used
to obtain relative sensitivites and to check out the
4
-------
system were made up from commercially available metals,
powders, and solutions. Standard samples were mixed
in solution and dried onto high purity graphite. The
graphite- sample was mixed using a Spex mill and pressed
into electrodes using an AEI die and polyethylene slugs.
Although graphite was a very good matrix for electrode
material, it presented some problems to the original
software. The complex ions, C~, C, , ..., Con (composed
12 13
of both isotopes, C and C) caused false elemental
identification and some erroneous quantitative data.
Changes of analytical and confirmatory mass-to-charge
ratios (m/e's) were required in the software. The
necessary changes were made as single element tapes that
replaced original software data on the disc memory
system.
Relative sensitivities were determined in a series of
samples that contained yttrium and one or more of the
70 elements of interest in equal portions by weight.
Using yttrium as the internal standard, the relative
sensitivity data were combined with the weight conver-
sion factor to yield the parameter K in the concentra-
tion equation (Equation 1) .
Equation 1
Concentration Calculation
= Concentration
where Ael = Area of analytical isotope of element
in question
Astd = Area of analytical isotope of standard
-------
= Abundance factor of element in question
(100/isotopic abundance of analytical
isotope)
Fstd = Abidance factor of standard (100/isotopic
abundance of analytical isotope)
Cgtd = Concentration of standard element. The
units used to express the standard con-
centration value define the units of
"concentration," since the remainder of
the equation is unitless.
K = [weight conversion factor x relative
sensitivity]
Weight conversion factor = a.m.u.
element/a. m.u. standard
Using standards in various mixtures of elements and in
various concentration ranges, we identified two major
problems with the original data system software supplied
by the vendor. Multiply-charged ions are very important
in SS analysis using electronic detection since the low
resolution inherent in this mode of operation does not
allow reliable isotope ratio confirmation. False inter-
pretations in some analyses were made by the data system
when ions of +2 and/or +3 charges (+2 and/or +3 ions)
were used as the analytical m/e or the confirming multiply-
charged ion. This problem occurred at masses of £ 80 amu,
where + 2 and +3 ions may occur.
The original software used a +_ 0.2 amu tolerance to
accept or reject a singal as the analytical or confirming
mass of a given element. For example, for an iron analysis
at 56 amu, the computer-calculated signal had only to fall
between 55.8 amu and 56.2 amu to be accepted at the 56Fe.
The tolerance window of + 0.2 amu was changed to + 0.09
amu, a figure based on tests involving a series of stand-
ards. Samples of elements at a 100:1 weight ratio were
used for this test. The complex spectra in the < 80 mass
-------
range yielded no false analyses using the +0.09 amu
tolerance.
Changing the tolerance window brought to light another,
less obvious, problem. Using the +0.09 tolerance, we
found that isotopic weight values in one subroutine had
been programmed using nominal instead of accurate mass
values, e.g., 89 instead of 88.91 for Y. The programming
was not consistent, since some subroutines of the soft-
ware used accurate mass values. When the +0.09 amu
tolerance was applied, the error had to be corrected.
Further explanation of the interpretation details2'3'4
is in the literature and will not be fully explored here.
Incorporation of all software changes were made, and the
revised program was copied onto punched tape using a
SERL Disc Dump/Restore tape and DEC-08-YXlA-PD-Binary
Punch Teletype tape. The modified program now can be
loaded into the data system in about 10 minutes compared
to 45 minutes for the original software. The present
program does not require manual changes of any values;
the original program required 6 hours of manual entry of
necessary changes.
-------
SECTION V
RESULTS AND DISCUSSION
Equation 1 is used in the software for analytical cal-
culations. The values in the original software were
converted from ppm atomic to a weight basis by making
K a product of the weight conversion factor and the
relative sensitivity of the element in question.
Figure 1 is an accurage mass listing of a complex syn-
thetic sample. Peaks are numbered (Pk.No.) starting
with the highest mass detected, designated "1", down to
the lowest mass, assigned the highest peak number. The
normalized intensity (Norm.Inty.) is the integrated
peak area normalized to the peak with the greatest raw
intensity in the recorded spectrum. The accurate masses
(Ace.Mass.) are calculated for each peak using the
operator-supplied reference peaks, indicated by the
letter (R) to the right of the accurate mass data. This
part of the program was the portion of the original soft-
ware that used accurate masses and was incompatible with
the nominal values in the data interpretation program
discussed earlier.
Figure 2 shows interpreted data as processed by the
original software. The column heading "Mass" denotes
the analytical m/e. "Element" is the corresponding
element. "PPM atomic" is the concentration expressed
"++3"
in ppm on an atomic basis. "+++?» indicates the con-
firmation or non-confirmation of am element determined
by the presence or absence of the multiply-charged ions.
"Confirm isotopes" indicates whether or not a specified
ratio of a given set of isotopes has been found for the
8
-------
PK. NORM. ACC.
HO. IHTT. MASS
1 11 £73.55
e 74 271.18
3 10 £61.22
4 34 260.25
5 43 245.94
6 156 E4U.6B
7 9 232.72
8 13 231.S2
9 225 230.38
10 19 219.14
11 9 217.93
IE 21B lit. 96
13 5 209.40
14 11 288.40
IS 15 £07.34
16 S 206.32
17 *1 2*5.33
IB 13 2B4.41
19 69 284. IS
20 £38 19B.0S
21 3B74 197.82
22 1163 196.09
23 2159 I94.9B
£4 1382 193.99
25 77 192.94
£6 £53 191.97 R
27 12 191.02
£8 4 190.03
£9 9 189.78
30 35 166.92
31 IEB 186.88
32 4 184.78
33 9 163.89
34 81 182.68
35 30 181.89
36 428 180.69
37 531 179.95 R
38 £7 178.85
39 9 I77i86
4* 13 176.85
41 479 175.96
42 21 174.95
43 IB5S 173.92
44 14»3 172.94
45 1339 171.93
46 701 110.93
47 1129 169.94 R
48 4483 168.95
49 £548 167.97
S* ISM 166.95
St £191 165.93
58 482« 164.96
PK. HO EW. ACC.
HO. IMTY. MASS
S3 1985 163.96
54 8864 162.94
SS 94B 1*1.96
56 946 160. 9T
57 1454 159.93
58 4278 IS3.9S
59 MBS 157.93 R
60 737 156.91
61 1964 155.94
68 784 154.94
63 1688 153.91
64 1797 152.95
65 3119 151.93
66 1528 158.94
67 1125 149.98 R
6B 1139 148.94
69 1497 147.93
79 593 146.96
71 1022 145.91
78 7»» 144.9»
73 89* 143.93
74 736 142.9S
7S 8116 141.91
76 1873 148.92
11 7S 139.90
78 5639 138.91 *
79 9 137.91
B0 72 116.88
81 321 138.95
88 674 131.98
S3 46 129.92
84 43 127.9*
85 £0 125.88
86 9 184.84
87 11 123.86
88 84 111.88
89 £45 180.95
99 448 119.91 R
91 181 18.84
Figure 1
Accurate Mti. oat»
PK. NOAH. ACC.
NO. 1NTT. MASS
92 41 117.82
93 33 116.87
94 74 115.82
95 267 114. 87
96 ft 113.se
97 £24 112.36
98 u in. as
99 13 110.36
100 1252 109. aa
101 60 lee. 96
IBS 4227 107.91 R
103 ES99 1SS.9S
104 1957 104.90
105 3286 103.90
106 6B4E IDE. 99
107 E61C lfil.92
10B 179B 1 90.91
109 1182 99.91
110 1474 98.93
III 418 98.58
112 357 97.96
113 1B4 97.51!
114 £56 97.00
US 9»6 95.97
116 19 94.91
117 17 93.94
118 £8 92.94
119 21 91.93
129 6 S9.9S
181 3S12 88.91 R
122 173 >7.99
123 495 86.98
124 256 86.43
125 361 SS.99
126 £14 8S.49
127 79S 84.97
128 28B2 84.48
129 £127 84.00
139 425 83.48
131 884 82. 98
132 £018 82.48
133 $76 81.99
134 see 81.49
131 505 80.99
136 327 80.48
137 SSS 19.97
138 ESBS 79.48
139 490 78.98
14* £81 78.48
141 484 17.98
142 £92 77.48
143 629 76.97
PK. Nu.>i,. ACC.
NO. IHTY. MASS
144 1696 76.48
145 777 75.97
146 1394 75.47
147 371 74.97
148 341 74.46 R
149 S3» 71.9*
158 374 73.47
151 794 72.97
1M> 195 72.45
153 1788 71.97
154 £89 71.45
155 699 70.95
156 8827 79.45
1ST 53 69.94
153 394B 69.4*
159 101 «.93
160 23 66.43
161 19 65.95
162 111 »*»»
163 46 65.29
164 1*S 64.96
165 84 64.62
166 33 63.9 1
167 17 6(.««
168 £9 6I.9£
169 432 68.94 II
17* 3918 59.93
171 12 58.39
17E 36 58.60
173 106 57. 9£
174 43 57.60
175 *1 57.39
176 51 56.92
177 64 56.6*
178 361 56.27
179 866 55.91
180 92 55.61
It | 142 55. £7
1*8 4452 54.87
1*3 181 54.60
PK. NOS.-1. ACC.
NO. INTY. MASS
184 62 54. £8
IBS 640 53.93
186 S3 53.61
187 65 53.28
IBB 1147 52.94
109 B3 52.62
198 JtsS SE.44
19 1 55 S£.£9
192 SSI 51.94
193 46 51.63
194 £978 51.44
195 1162 50. 95 R
196 57 50.63
197 332 S0.«0
198 303 49.96
199 £7 49.63
E00 E24 49.45
£81 61 49.30
202 SV1 48.98
£03 73 48.64
* 204 6 48.48
295 24 48.31
216 48*3 47. «9
£07 30 47.64
E0B 118 47.31
£89 574 46.98
21* 869 46.92
211 76 45.97
£12 6S73 44.97
213 4B3S 4«.47
214 S42 44.811
£15 19 43.46
£16 8 42.98
217 £9 42. CB
2U 16 42.85
219 35 41.99
220 16 41.24
££1 112 48.9«
222 8392 39.97
2£3 19 39.74
£24 1718 38.97 R
2ES 67 36. «
£26 7989 36.99
£27 ££ 16.65
22* 9327 36.01
829 95 35.E9
23* T89B 34.99
231 16 34.75
£3K «£ 34.65
£33 £99 34.32
£14 133 31.99
135 97 33.65
HO'. 1HTTV MASS
236 79 33.33
C37 54 32.99
E3B 246 32***
£39 793 31.0*
£40 4*£ 30.01
«41 l»1£ S9.6T
£42 423 £9.01
243 745E 88.91
f«4 6 C7.49
£45 3845 87.01
£46 C4I 26.02
£47 14 E5.76
148 84 £S.S*
£49 3*9 £ £S.»S
S3* 14 £4.S»
231 3M2 24V84
SS2 23 83- «»
(S3 8685 83.**
SS4 9316 £2.48 R
JSS 44 81.99
SS6 18 M.99
. J5-J 4 £».49
£58 8769 2*.**
259 75 19.5*
86* S 19.11
261 1218 U.'S»
262 517 16.62
263 4578 17.5*
264 £55 17.08
£65 640E 16.81
£66 173 15.49 R
267 BS4 14.99
268 !» 14. Bl
269 ' 8*6 13. 56
£7* 71 11.67
£71 19 11.31
272 >73 11.13
£73 231 l*.*3
S74 46 9.33
(75 4579 9.08 X
INTCRPRIT 7 IT
-------
Figure 2
MASS CLEMENT
197 C-OLD
195 PLATINUM
193 1RID1UM
189 OSHIUtl
182* TUNGSTEN
181 TANTALUM
176 HAFNIl'W
175 LUTECIUM
1(9 THULIUM
166 ERBIUM
165 HOLM KIM
163 DYSPROSIUM
159 TERBIUM
158 GADOLINIUM
S3 EUROPIUM
47 SAHAP11IM
46 NEODTMIUM
41 PRASEODYME
40 CERIUM
139 LANTHANUM
138 BARIUM
133 CESIUM
123 TELLURIUM
121 ANTIMONY
IIS TIM
H5 INDIUM
111 CADMIUM
105 PALLADIUM
183 RHODIUM
let RUTHENIUM
93 NIOBIUM
90 Zl RCON1 UM
89 YTTRIUM
83 STRONTIUM
85 RUBIDIUM
79 BROMINE
SB SELENIUM
75 ARSENIC
72 GERMANIUM
69 GALLIUM
66 ZINC
MASS ELEMENT
63 COPPER
60 NICKEL
59 COBALT
9« I RON
55 MANGANESE
58 CHROMIUM
51 VANADIUM
48 TITANIUM
4S SCAND1IM
40 CALCIUM
3V POTASSIUM
34 SULPHUR
31 PHOSPHORUS
28 SILICON
27 ALIMINIUM
24 MAGNE SI UM
23 SODIUM
10 FLUORINE
16 OXYGEN
14 NITROGEN
1 1 BORON
9 BERYLLIUM
PPM
ATOM1 C
66 73
1 11.58
2. 12
3.81
1.96
7.37
.60
.37
77.CH
1 13.20
69.37
155.98
73.68
97.06
58*62
67.48
102*14
66.71
1.42
97.11
.24
5.54
2*40
7.60
2.99
3.56
1.85
151.71
117.64
182.76
.49
STANDARD
3.58
19.17
16.68
IS. 09
6.43
1 1 3. S6
2.96
1.21
PPM
ATOMIC
.46
.21
3.05
76.60
16.96
2«.0£
us. a*
104.60
41.20
32.40
55.00
13.66
141.18
55.69
67.22
144.56
.09
1 10*27
172.22
SB. IS
78.86
END OF
f*T
***?
2*
NO
NO
NO
NO
NO
NO
2+
2*
2*
2*
2+
2*
2*
2+
2*
2*
NO
8+
NO
2*
NO
NO
NO
2+
2+
2*
2+
2+
a*
NO
2+
NO
NO
NO
2+
2*
2+
**7
*»»7
NO
2*
3*
2*
NO
2*
2+
2*
NO
2*
NO
2*
NO
2*
NO
8*
a*
NO
NO
MO
NO
RIM
CONFIRM
ISOTOPES
YES
NO
NO
NO
-
NO
NO
.
NO
-
YES
-
YES
YES
NO
YES
-
NO
-
NO
-
YES
NO
YES
NO
NO
NO
-
YES
-
NO
NO
YES
NO
.
NO
NO
YES
COMF1 m
ISOTOPES
NO
.
NO
_
NO
-
YES
_
NO
NO
NO
-
NO
.
NO
_
-
-
.
YES
-
CHECK COMPLEX
OVERLAP IONS
176
174
172
170
174
156
162
160
154
156
150
144
146
140
142
132
198
128
192
06 >
87)
86)
95)
87)
79)
81)
80)
77)
78)
75)
72>
73)
74)
71)
66)
661
64)
64)
CHECK COMPLEX
OVERLAP IONS
126<
189<
130(
|95(
!I6<
I74(
1 1*J<
177C
I6«<
I08(
I62C
104(
156(
I0*<
159<
108(
I53<
UK
B6(
82(
108<
66(
99t
»6<
97<
60(
48(
52(
78 (
3tt(
ST<
34 (
SI
20
30
45
e*
30
63)
63>
65)
65)
5(1)
56)
59>
59)
56)
54 >
54)
SC)
52)
53)
53)
51)
51)
4?)
43)
Ml
34)
33)
33)
32)
S9t
30)
24)
26)
26)
19 >
19)
17)
17)
14)
15)
15)
10)
10)
10
-------
element. This column should be of little interest be-
cause of interference from other isotopes and complex
ions. "Check overlap" reminds the operator of possible
multiply-charged ion interferences. "Complex ions" is
a printout of matrix atoms that could possibly interfere
at a given m/e. These ions, in general, in a graphite
matrix-water analysis are constant and this portion of
the analysis is bypassed to save computer time.
The1choice of a reliable analytical mass is exemplified
in Figures 2 and 3. Titanium has isotopes of 46, 47,
48, 49, and 50 amu, all of which are listed in Figure 1.
Since polycarbon ion interference exists at 48 and 49
amu, the choices are reduced to 46, 47, and 50 amu.
Possible interfering isotopes are Ca and V, leaving
47 as a probable analytical mass. Possible interference
exists at mass 47 from a multiply-charged ion of mass
94, which, in this case, is listed as present in Figure
1. These interferences leave only two logical choices
47
for the analytical mass. Since Ti is a more abundant
49
isotope than Ti t the other available odd number mass,
47
the multiply-charged Ti isotope at 23.5 amu is used
for identification and quantitation.
Errors present in the use of multiply-charged ions in
the original program have been corrected. These errors
occurred in analyses that had detectable 4-2 and/or +3
ions occurring within a nominal amu (Figure 1). This
error was possible because of a wide tolerance (0.2 amu)
in the original software.
After the tolerance was changed to £ 0.09 amu, all masses
used in data interpretation had to be changed in the
software, since the original software used nominal masses
for data interpretation. The differences between
11
-------
Figure 3
Modified Interpretation of +1 and +2 Ion Data
JULY
SEVENTEEN
197
195
191
189
182
175
172
85
167
165
163
159
158
153
147
143
141
140
139
138
66
188
118
its
III
IBS
51
50
95
89
43
28
25
24
83
20
20
18
16
14
12
19
16
GOLD
PLATINUM
I RI DI UN
OSMIUM
TUNGSTEN
LUTECIUM
YTTERBIUM
THULIUM
ERBIUM
HOLMIUM
DYSPROSIUM
TERBI UM
GADOLINIUM
EUROPIUM
SAMARIUM
NEODYMIUM
PRASEODYME
CERIUM
LANTHANUM
BARIUM
CESIUM
TELLURI UM
TIN
INDIUM
CADMIUM
PALLADI UM
RHODIUM
RUTHENIUM
MOLYBDENUM
YTTRI UM
RUBI DI UM
MANGANESE
VANADI UM
TITANIUM
SCANDIUM
CALCIUM
POTASSIUM
CHLORINE
PHOSPHORUS
ALUMINIUM
SODIUM
FLUORINE
OXYGEN
CONCEN
TRATIONS
88.75
258.88
2.88
8. IS
7.29
.52
146.22
87.23
136.39
102.67
230.85
126.73
222.27
104.18
116.74
152.42
96.06
8.04
67. "01
.31
.49
2.8 1
1.89
2.32
3.80
101.65
52.31
77.83
1.41
STANDARD
.66
.01
.70
1.47
103.97
3.86
.21
220.39
.41
.58
.63
.03
19.84
++7
+++7
2+
2+
NO
NO
NO
NO
2*
2+
2+
2+
2+
2+
2*
2+
2+
2*
2+
NO
2+
NO
2+
NO
NO
NO
NO
2+
2*
2+
NO
2+
2+
2*
2+
2+
NO
2+
2+
2+
2+
2*
NO
NO
CONFIRM
CHECK COMPLEX
ISOTOPES OVERLAP IONS
YES
NO
NO
NO
NO
YES
YES
~
YES
-
YES
YES
NO
NO
-
NO
NO
-
YES
NO
NO
NO
NO
NO
-
-
-
-
NO
-
NO
YES
-
-
-
-
-
-
I69<
J03C
10IC
190C
85(
I70(
55(
82(
SIC
76<
47<
7 1 {
4SC
40(
60(
39 (
82(
3S(
31(
27(
23(
38C
57C
34 C
5I(
85)
51)
50)
95)
43)
85)
28)
28)
25)
25)
24)
24)
23)
20)
20)
20)
41)
18)
16)
14)
12)
19)
19)
17)
17)
JULY
SEVENTEEN
(4 NITROGEN
11 BORON
9 BERYLLI UM
27.55
++T
NO
1.18 NO
.94 NO
END OF RUN
CONFIRM
ISOTOPES
NO
CHECK
OVERLAP
COMPLEX
IONS
28(
30<
4SC
20(
30<
14)
15)
IS)
10)
10)
12
-------
nominal mass and accurate mass calculated by the computer
were in some cases greater than the new tolerance. In
other cases, they allowed for very little instrumental
and hardware error.
The value of these changes can be seen by comparing the
accurate mass, the original interpretation, and the
modified system (Figures 1, 2, and 3). In the original
interpretation (Figure 2) niobium is incorrectly reported
and confirmed using the +2 ion. Confirmation of +2 for
niobium was supposedly made at 93/2 amu or 46.5 amu. In
checking the accurate mass listing (Figure 1) the only
ion occurring between 46 and 47 amu is 46.32 amu, which
139
is a +3 ion of La. This error is due to the + 0.2
amu as the 46.5 amu confirmation. It can be seen in the
output of the corrected system (Figure 3) that niobium
is neither reported nor confirmed. This error occurred
also for gallium, zinc, cobalt, and iron in the original
data (figure 2).
Using the modified software system, a series of samples
having highly varying concentration ratios and atomic
weight differences has been analyzed. Results are shown
in Figures 4 and 5. Coefficients of variation for each
element are given in Tables 1 and 2. These values are
based on 9 separate runs using a fresh set of electrodes
for each analysis. The statistical data shown agree
with those reported earlier by this laboratory.2
Results of the analyses of natural samples show compar-
able precision to the data shown in Tables 1 and 2.
Tables 3 and 4 represent the analysis of an effluent
sample sent to our laboratory. The sample was prepared
by centrifugation. The liquid was then decanted carefully
to preserve the integrity of the pellet. Two one-
13
-------
FIGURE 4
SAMPLE #1
GROUP I
5.5
5.0
4.5
4.0
^ ^
3.5
3.0
Z.5
2.0
1.5
1.0
0.5
0
-
_
+
_
-
1
! T ..
1
2
>
1
"
1
h
' 1
1
1 '
«J
+
mi
|
2
+ 2
1 l
> 4
(
111]
+ 2
4
2
KEY
I
+ 2
+
i
*2 1
I.
1 1 1
high valuer
Average
:.<>.» Value?
Actuc 1 Co^C ( ppb J
-|-
2
(
1
1 >
..T
' T
-* -*-
1
Ce Cs Te Sn In Rb Se Ge
Ti Co
Al
6 Be
SAMPLE *l
GROUP IE
500
450
400
350
300
250
20O
ISO
100
50
25
-
-
I
-1-;
-
Au f
+
i
t Y
2
i
b 1
.. i
m E
i -J
'r H
II
...
o Dy 1
i
i
~"~
b (
KE
!
i
4 i
1
1 1
id EJ S
Y
1 i
m fi
High Value:-
Average
Low Values
Ac'uo' CoriC- (ppti)
"
+;
1 -I T " T ° '
I 9 JL. T
-"-
, , , i .L 1
Jd Pr La Pd Rh Ru S
14
-------
500
450
40O
350
300
250
200
150
100
50
25
FIGURE 5
SAMPLE *2
GROUP I
4-2
-J+i- r-M~
KEY
-p
^^
High Values
Average
Low Values
Aciuol Cone, (ppb)
Ce Cs Te Sn
In
Mo Rb Se Ge
Ti Co
Al B
SAMPLE *2
GROUP H
4.0
3,5
3.0
2.5
ZO
1.5
1.0
0.5
0
-
KEY
: ]
_
[
High Value*
Average
Low Values
_ Mciua* tone- ippo;
-
- .... -. -*
(
.-.-.
> 4
L -1
.....
' <
- V2 -
Ell
. i
... 4 .
<
»
» * «i
»
^ . » j
i i .j
i
^
h ....
<
i
<
i __
.... .
<
^ _
».-*.
i
«
1 1 1 i I
»
i
. 1 ~T"
[yn
*
I
I
i i I » i i
Au Pt Yb Tm Er Ho Dy Tb Gd Em Sm NO Pr La Pd Rh Ru Sc
15
-------
Table 1. GROUP I COEFFICIENTS OF VARIATION EXPRESSED
IN PERCENT
Element
Ce
Cs
Te
Sn
In
Rb
Se
Ge
V
Ti
Ca
K
P
Al
B
Be
Sample #1.
SxlO1
2X101
2X101
SxlO1
2X101
SxlO1
SxlO1
2X101
SxlO1
2X101
IxlO1
SxlO1
SxlO1
3X101
2X101
2X101
Sample #2
38
53
73
60
70
38
33
16
16
21
19
45
33
31
33
53
16
-------
Table 2. GROUP II COEFFICIENTS OF VARIATION EXPRESSED
IN PERCENT
Element
Au
Pt
Yb
Tm
Er
Ho
Dy
Tb
Gd
Eu
Sm
Nd
Pr
La
Pd
Rh
Ru
Sc
Sample #1
17
27
54
38
59
43
22
45
41
25
31
58
32
16
36
32
50
32
Sample #2
4X101
SxlO1
4X101
2X101
4X101
4X101
1
3X101
SxlO1
SxlO1
T
4X10-1
lOxlO1
3X101
6X101
2X101
4X101
i
10x10
4X101
17
-------
Table 3. ANALYSES OF EFFLUENT SAMPLE
Part I - SS Analysis of Water (Results Expressed in Parts
Per Million by Weight)
Element
Mg
P
Ca
K
Fe
Al
Avg
20
15
10
9
7
7
#1
27
15
12
14
7
11
#2
14
15
8
6
6
5
Element
Pb
Cu
Zn
Mn
Sr
Co
Avg
0.6
0.6
0.5
0.3
0.2
0.1
.#1
0.8
0.5
0.6
0.4
0.2
0.09
#.2
0.4
0.7
0.4
0.2
0.2
0.08
Part II - SS Analysis of Major Concentration Elements
in Sediment Analysis (Results in Weight Percent)
Element
Fe
Mg
Ca
Mn
Avg
10
4
2
0.8
#1
10.1
6
2.9
1.0
#2
9.8
3
1.8
0.6
Element
K
Al
P
Avg
0.3
0.3
0.2
#1
0.22
0.27
0.24
.#2
0.40
0,35
0.12
Part III - SS Analysis for the Lower Concentration
Elements in Sediment (Results Expressed in
Parts Per Million by Weight)
Element
Sr
Ba
Ti
Zn
Zr
Ce
Y
Co
Er
Nd
Avg
45
40
14
11
8
6
5
5
3
3
#1
35
33
18
14
10
8
6
8
3
3
#2
55
47
11
8
6
5
4
3
3
Element
Sc
La
Sm
Cu
V
Pb
Nb
Rb
As
Be
Cs
Avg
3
2
2
2
2
1
1
1
1
1
0.5
#1
3.0
1.6
2.0
3.2
1.4
0.9
1.4
0.96
0.5
0.8
0.5
#2
3.4
3.1
2.7
1.1
2.5
1.4
0.4
0.60
1.5
1.5
0.47
18
-------
Table. 4. RELATIVE SENSITIVITY STUDY IN SEDIMENT USING
INDIUM AND YTTRIUM CROSS CHECK (Established
Relative Sensitivities Have Been Applied to
All Results)
Part I Sediment Plus Standards
Calculated Weight Percent
Major
Element
Fe
Mn
Ca
K
p
Al
Mg
Yttrium
Standard
10
0.8
2.3
0.3
0.2
0.3
4.0
Indium
Standard
9
1.0
2.5
0.2
0.1
0.2
4.4
Part II Dilution of Above Sample with More
Unspiked Sample
Calculated Concentration in ppm by Weight
Minor
Element
Ce
Ti
La
Ba
Nb
Zr
Sr
Yttrium
Standard
6
14
4
40
1
8
45
Indium
Standard
10
11
2
58
1
10
38
Part IIISediment with Added Elements
Weighed amounts of these elements were aflded to the
sediment for analysis using yttrium as the internal
standard and applying relative sensitivities
Weight Percent
Added Found
Ba
Zr
Sr
6.8
4.7
3.8
7.2
4.2
3.4
19
-------
railliliter water samples were spiked with yttrium as the
internal standard. These were dried on graphite and
compacted into electrodes for analysis. The sediment
samples were dried at 110°C for two hours, weighed
and spiked dry Using yttrium and indium as the internal
standards.
The validity of using relative sensitivity coefficients,
which were obtained from very dilute solutions, in
analyzing sediments was tested by two experiments. In
the first of these, the sediment samples mentioned above
were spiked with both yttrium and indium and analyzed
using first yttrium and then indium as the internal
standard. Table 4 (Parts I and II) shows a negligible
difference between the values, establishing the validity
of a single reference standard.
In the second experiment, relatively gross amounts of
barium, strontium, and zirconium salts were added to the
sediment; the sample was analyzed using the dilute-
solution-derived sensitivity coefficients relative to
yttrium. Results (Table 4, Part III) are in excellent
agreement with the known concentrations. The relative
sensitivities calculated from solutions with concentra-
tions at the ppm levels, were therefore suitable for
this analysis with concentrations in the percent range.
Taken together, these two experiments indicate that, for
these elements, there is no significant shift in relative
sensitivity coefficients between very dilute solutions
and complex sediments.
Background data from a reservoir study (Table 5) show
another application of SS analysis of natural samples.
The reservoir has been the site of a number of recurring
fish kills. The SS data will be compared later to data
20
-------
Table 5. SS ANALYSES OF RESERVOIR WATER
Element
Pb
Ba
Ce
Te
Sn
Cu
Ni
Co
Cr
V
Zn
Ti
Fe
Mn
P
Sr
SS
2 ppb
160 ppb
2 ppb
1 ppb
10 ppb
5 ppb
8 ppb
5 ppb
20 ppb
3 ppb
60 ppb
20 ppb
2 ppm
60 ppb
30 ppb
2 ppm
AA
<_ 50 ppb*
12 ppb
<_ 50 ppb*
< 50 ppb*
40 ppb
3.5 ppm
*AA detection limit for method used
21
-------
to be taken at the time of future fish kills. Comparison
results with atomic absorption (AA) were available for
some elements and are noted. Coefficients of variation
for these SS data range from 19 to 50% and average 33%
on the analysis.
22
-------
SECTION VI
REFERENCES
McKee, J. E., and H. W. Wolf, Editors. Potential
Pollutants. In: Water Quality Criteria, Second
Edition. California State Water Resources Control
Board. Pasadena, California. Publication 3-A.
1963. p. 123-299.
Taylor, C. E., J. M. McGuire, and W. H. McDaniel.
Spark Source Mass Spectra for Water Analysis.
U. S. Environmental Protection Agency. (Presented
at the 20th Annual Conference on Mass Spectrometry).
Dallas, Texas. June 4-9, 1972.
Bingham, R.f P. Powers, and W. Wolstenholme. Spark
Source Mass Spectrometry using "Autospark" Sample
Control and On-Line Data Processing. GEC-AEI
(Electronics) Ltd., Scientific Apparatus Division.
Publication T.P. 30.
Brown, R., P. Powers, and W. Wolstenholme.
Computerized Recording and Interpretation of Spark
Source Mass Spectra. Analytical Chemistry. Vol. 43,
£:1079-1085, July 1971.
23
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
1. Rep
Accession Wo.
w
4. Title
MULTIELEMENT ANALYSIS OF ENVIRONMENTAL SAMPLES
BY SPARK SOURCE MASS SPECTROMETRY
Charles E. Taylor and William .J. Taylor
Analytical Chemistry Branch
Southeast Environmental Research Laboratory
5.
8. Pefforrainrr
Report No.
10. Project No.
16ADN-22
11. ComractjGrsntNo.
13. Type (- Repor> und
Period Coveted
12.
Environmental Protection Agency
IS. S
Environmental Protection Agency report number
EPA-660/2-74-001, January 1974
If!. Abstraci
A spark source mass spectrometer that uses electronic detection and
a dedicated data analysis system was applied to a survey type trace
analysis for chemical elements. Errors in the data system software
were identified and corrected. Modifications to the system permit
identification and quantitation of 72 elements at the part per
billion level in water samples.
i7a. Descriptors *MaSS Spectrometry, *Trace Analysis, *Survey Analysis,
*Analytical Techniques, *Water Pollution, *Sediment Analysis
*spark Source Mass Spectrometry, Computerized Data System,
Electrical Detection
COWRR Field & Group Q 5A
IS. Avail AbUity
19. S' "Utity C 'ass.
(Report)
20. Securny Class.
21. i:-.\ of
Pages
22, Price
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON, D. C. 2O24O
f/.-K-fo- Charles E. Taylor [institution Southeast Environmental Res. Lab.
------- |