The Analysis of Water and Wastes by U.S. EPA Method 200.7 Using the Optima 8300 ICP-OES and prepFAST Auto-Dilution/Calibration System

APPLICATION NOTE
ICP-Optical Emission Spectroscopy
Authors:
Deborah K Bradshaw
Atomic Spectroscopy
Training and Consulting
Laura Thompson
PerkinElmer, Inc.
Shelton, CT
The Analysis of Water
and Wastes by U.S. EPA
Method 200.7 Using the
Optima 8300 ICP-OES and
prepFAST Auto-Dilution/
Calibration System
Introduction
The prevention and control of
water pollution is of critical
importance to protecting human
and environmental health.
Monitoring of water and wastes
is an efficacious way to prevent
the introduction of pollutants
and costly remediation of
drinking and environmentally
important waters. The United States Environmental Protection Agency (U.S.
EPA), along with local regulatory bodies, is responsible for regulating water
and wastes under the Clean Water Act and the Safe Drinking Water Act.
Depending on the number and type of analytes, the number of samples and
the productivity requirements, several different analytical techniques can be
applied to measure trace elements in water and wastes.
U.S. EPA Method 200.7 Version 4.4 covers the use of inductively coupled
plasma optical emission spectroscopy (ICP-OES) in radial and/or axial viewing
for the determination of metals and some non-metals in water and wastes
for regulatory compliance.1 Method 200.7 contains a lengthy description of
procedures for the collection, preservation and preparation of samples for
analysis. The objective of this work was to complete the method using the
PerkinElmer® Optima® 8300 ICP-OES coupled with the prepFAST™ Automated
In-Line Auto-Dilution/Calibration System (Elemental Scientific Inc., Omaha, NE).
The prepFAST™ system provides a number of advantages
over conventional ICP-OES introduction systems, the most
significant of which is higher sample throughput and reduced
memory effects. The prepFAST™ system allows accurate,
syringe-driven auto dilution of samples and standards,
eliminating manual dilution errors and increasing
calibration range. Reducing costly high-purity reagent
and sample consumption, the prepFAST™ Auto-Dilution/
Calibration System is one of the best ways to improve
laboratory productivity.
7)Laboratory reagent blank (LRB) – Analyze one every 20
samples. Should be below MDL.
Summary of Method 200.7
Experimental Conditions
The direct analysis of samples was performed according to
Method 200.7. For samples that require total recoverable
analysis, refer to section 11.2 of EPA Method 200.7 rev 4.4.
Below is a summary of the steps required for compliance
with EPA 200.7 revision 4.4.
Instrumentation
1)For direct analysis (samples with < 1 NTU), dilute, if
necessary, to an appropriate volume and preserve
samples to a pH < 2 with ultrapure HNO3.
2)Optimize the instrument using the plasma solution
(section 10.2.3) after allowing 15-30 minutes for the
plasma to stabilize to the environment.
3)Calibrate the instrument using at least one blank and
one calibration standard.
4)Run the instrument performance check (IPC sample)
immediately following daily calibration and verify its
recovery within 5%. The IPC should also be run after
every 10th sample and at the end of a sample run and
recovered within 10%.
5)Prepare an inter-element correction (IEC) table, if
necessary, and analyze the spectral interference check
(SIC) solution to verify lack of spectral interferents in
the method. This should be repeated on a periodic basis.
2
6)
Perform the initial demonstration of performance (IDP)
a.Instrument detection limit (IDL) – Calculated as 3x
the standard deviation of 10 replicate measurements
of the calibration blank.
b.Method detection limit (MDL) – Calculated as 3.14x
the standard deviation of seven replicate aliquots of
fortified (2-3x estimated IDL) reagent water.
c.Quality control sample (QCS) – Prepared from a
second source. Verify that the mean concentration
of three analyses is recovered within 5%. Also run
QCS quarterly or after new calibration standards
are made.
d.Linear dynamic range (LDR) – Analyze successively
higher standard concentrations until they return
90% of the stated concentration based on a typical
standard curve. Verify annually.
8)Laboratory fortified blank (LFB) – Analyze one with
each batch of samples. Verify within 85-115% recovery.
9)Laboratory fortified matrix (LFM) – Spike 10% of the
samples prior to sample prep. Verify within 70-130%
recovery. Concentration should be ≥ 30% of
background concentration.
10) Reference materials – Should be run when available.
All samples were analyzed with a PerkinElmer Optima 8300®
ICP-OES (Figure 1) equipped with an ESI prepFAST™
Auto-Dilution System with an ESI SC-2 DX Autosampler
(Figure 2). Instrumental parameters are listed in Table 1.
Elements determined and wavelengths used in this study,
the peak area, points per peak, and number of background
points used for each wavelength are listed in Table 2. All
elements were viewed axially. For some elements, alternate
wavelengths were investigated in this study. The use of an
alternate wavelength may be desirable for a variety of
reasons – better sensitivity and greater freedom from
spectral interferences are the two primary reasons. The
wavelengths cited in Method 200.7 are ‘recommended’
with the following footnote: “The wavelengths listed are
recommended because of their sensitivity and overall
acceptability. Other wavelengths may be substituted if they
can provide the needed sensitivity and are treated with the
same corrective techniques for spectral interference
(see Section 4.1).” It is worth investigating these alternate
wavelengths for their applicability to the method. The
wavelengths recommended by Method 200.7 are denoted
in the table, as well as the reason for choosing an alternate
wavelength in this study.
Figure 1. The PerkinElmer Optima 8300 ICP-OES with Flat Plate™ plasma technology.
Table 2. Analytical parameters used for EPA Method 200.7 with the
Optima 8300 ICP-OES
Background Wavelength Points/ Correction
Analyte (nm) Peak
Points
Comments
Al
396.153*
1
1
Al
308.215 3
2
Sb
206.836 1
2
As
188.979*
1
1
Figure 2. The prepFAST™ Auto-Dilution System with an ESI SC-2 DX Autosampler
illustrating a two-step process of loading the sample into a loop and in-line dilution.
Sample and Standard Preparation
As
193.696 1
2
Ba
493.408 1
2
Be
313.042 1
1
B
249.677 1
2
Cd
226.502 1
2
Ca
315.887 1
1
Ce
413.764 1
1
Cr
267.716*
1
2
Greater intensity
Greater freedom from spectral interferences
Greater intensity and greater freedom from spectral interferences
The solutions that were prepared and used for this study are
listed in Table 3. All solutions were diluted in 2% HNO3. For
Sn analysis, solutions were acidified to 1%HCl/2%HNO3. For
calibration, a 1 mg/L (standard 5) and a 5 mg/L (standard
10) standard, depending on the element, were prepared
and the prepFAST™ system was used to automatically dilute
these solutions to prepare standards 1-4 (from standard 5)
and standards 6-9 (from standard 10). The concentration
of each calibration standard, the prepFAST™ dilution
factor, and the elements applied to each standard are
shown in Table 4. The prepFAST™ system was also set up
to automatically dilute samples which were over the range
of the calibration curve. For this reason, several standard
solutions, analyzed as samples, were deliberately prepared
so that the results would be high and the prepFAST™
system would perform a dilution. Yttrium was used as the
internal standard during sample analysis.
Cr
205.560 1
1
Co
228.616 1
2
Cu
324.755 3
2
Fe
259.939 1
2
Pb
220.353 1
2
Li
670.794 1
2
Mg
285.213*
1
2
Mg
279.077 1
2
Mn
257.610 1
1
Mo
203.845 1
2
Ni
231.604 1
2
P
178.223*
1
2
Greater freedom from
spectral interferences
Table 1. Instrumental Parameters
P
177.435*
1
2
Greater freedom from spectral interferences
ParameterValue
Nebulizer Type
ESI PFA
Spray Chamber
Non-baffled cyclonic
InjectorSapphire
P
213.617*
1
2
P
214.914 1
766.490 3
2
Se
196.026 1
1
Si
251.611 1
2
Ag
328.068 1
1
Plasma Gas Flow (L/min)
8
Aux Gas Flow (L/min)
0.2
Na
589.592*
1
2
Neb Gas Flow (L/min)
0.55
Na
588.995 1
1
RF Power (watts)
1500
Sr
421.552 1
2
ResolutionNormal
Tl
190.805 5
2
Read Delay (sec)
50
Sn
189.927 1
2
Peak Processing
Peak area
Ti
334.942 1
1
Calibration Type
Linear, calculated intercept
V
292.402 1
2
Torch Cassette Position
-3
ESI Flow Rate (μL/min)
500
Zn
206.200*
1
2
ESI Loop Size (μL)
3000
Zn
* Alternate wavelengths
1
Software-suggested
wavelength
1
K
213.857 Greater intensity
Argon interference
(shoulder)
Greater freedom from spectral interferences
2
3
Table 3. Solutions used for the calibration and QC procedures in the analysis of water by EPA Method 200.7
Designation
Analytes
Part Number
Preparation
Cal Standard 1-5, IPC Solution
LFM
100 mg/L: Al, Sb, Ba, Be, Cd, Ca, Cr, Co, Cu, Fe,
Pb, Mg, Mn, Mo, Ni, K, Se, Ag, Na, Sr, Tl, Sn, Ti, V, Zn 1000 mg/L: Ce
1000 mg/L: Li
Instrument Cal. Std. 2:
N9301721
N9300110
N9300129
Diluted to 1 mg/L for S5
Cal Standard 6-10
IPC Solution
LFM
1000 mg/L: B
1000 mg/L: P
1000 mg/L: Si
N9303760
N9300139
N9300150
Diluted to 5 mg/L for S10
QCS 1
100 mg/L: As, Be, Ca, Cd, Co, Cr, Cu, Fe, Li, Mg, Mn, Mo, Ni, Pb, Sb, Se, Sr, Ti, Tl, V, Zn
QC Standard 21: N9300281
Diluted to 0.4 mg/L
QCS 2
1000 mg/L: K
QC Standard 7A: 500 mg/L: Si
N9300280
100 mg/L: Al, B, Ba, Na
50 mg/L: Ag
Diluted 1000x
QCS 3
1000 mg/L P
N9303788
Diluted to 0.4 mg/L
QCS 4
1000 mg/L Sn
N9303801
Diluted to 0.4 mg/L
SIC A & SIC B
5000 mg/L: Al, Ca, Mg
Interferents A
2000 mg/L: Fe
N9300226
1000 mg/L: Fe Stock
N9300126
Prepared to 200 mg/L: Al, Ca, Mg;
300 mg/L: Fe
The SIC B was spiked with the solutions
used to prepare the calibration standards
Sample Analytes B Solution:
N9300227
Diluted 10x
Sample
See Tables for Elements and Concentrations
Initial Calibration Verification (ICV):
N9300224
Diluted 10x
Sample
See Tables for Elements and Concentrations
HPS DWSS Secondary Drinking Water Standard
Diluted 10x
Sample
See Tables for Elements and Concentrations
HPS DWPS Primary Drinking Water Sol. A
Diluted 100x
Sample
See Tables for Elements and Concentrations
HPS CRM TMDW Trace Metals in
Drinking Water
No dilution
100 mg/L: Cd, Ni, Zn
60 mg/L: Sb
5 mg/L: Pb
50 mg/L: Ba, Be, Co, Cr, Cu, Mn, V
20 mg/L: Ag
10 mg/L: As
Lab Sample: Sample (LM), First Morning Tap Water
Sample Duplicate (LMdup),
Sample Spike (LFM)
Results
As an initial qualification of the system, the IDLs and MDLs
were determined for each of the wavelengths. The IDLs were
determined over two separate days. All results are shown in
Table 5. Concentrations of the analytes in the fortified
solution used for the MDLs are also listed in Table 5.
To validate the calibration curve, the QCS solution was
analyzed after calibration was complete. The QCS solution
was prepared from an alternate stock source, as is required
by U.S. EPA Method 200.7. Results are shown in Table 6.
The solution used for the alternate source QCS did not
contain Ce. Rather than risk having contamination occur by
spiking in stock, it was decided to leave the solution without
this element.
The QCS should be within 5% of the known value. All of
the values were within this variance except for Na and K.
When calibration was carried to 0.5 mg/L (rather than
1 mg/L), both of these elements were also within 5%.
4
No dilution, acidification to 2% with HNO3
The ruggedness of the prepFAST™ system to dilute solutions
was tested in two different ways. First, standard calibration
curves created by using the prepFAST™ system were run
over several days. In all cases, for all the wavelengths used,
the correlation coefficient was > 0.999, and in most cases >
0.9999. Next, an instrument performance check (IPC) was
Table 4. Standards and dilutions
Analyte
Standard
Std. Number
prepFAST™
Conc. (μg/L) Dilution Factor
Al, Sb, As, Ba, Be, 1
20
Cd, Ce, Ca, Cr, Co, 2
50
Cu, Fe, Pb, Li, Mg, 3
100
Mn, Mo, Ni, K, Se, 4
500
Ag, Na, Sr, Tl, Sn, 5
1000
Ti, V, Zn
B, P, Si
6
7
8
9
10
50x
20x
10x
2x
1x
50
100x
10050x
50010x
10005x
500001x
Table 5. Detection limits using the Optima 8300 ICP-OES with the prepFAST™
Auto-Dilution/Calibration System and EPA Method 200.7 parameters
Wavelength IDL
MDL
Analyte
(nm)
(μg/L) (μg/L)
Spike Concentration
for MDL Solution
(μg/L)
0.280.70 0.4
Table 6. Quality Control Sample (QCS)
Alternate Source
Wavelength QCS
DeterminedRecovery
Analyte(nm)
(μg/L)
(μg/L)
(%)
Al
396.153
Al396.153 100 97.9
97.9
Sb
206.836 1.21.3 3
Sb206.836 400 408
102
As
188.979
0.961.8
As188.979 400 401
101
Ba
493.408
0.010.018 0.05
Ba493.408 100 101
101
Be
313.042
0.060.083 0.4
Be313.042 400 407
102
B
249.677
0.66
B249.677 100 98.6 98.6
Cd
226.502
0.050.050 0.4
Cd226.502 400 415
104
Ca
315.887
0.39
0.58
1
Ca315.887 400 413
103
Ce
413.764
0.49
0.49
1
Ce413.764 ---
---
Cr
267.716
0.12
0.15
0.4
Cr267.716 400 417
104
Co
228.616
0.21
0.22
0.4
Co228.616 400 408
102
Cu
324.755
0.48
0.69
1
Cu324.752 400 416
104
Fe
259.939
0.16
0.12
0.4
Fe259.939 400 415
104
Pb
220.353
1.2
1.1
3
Pb220.353 400 414
104
Li
670.794
0.020.023 0.05
Li670.784 400 396
99.1
Mg
285.213
0.11
Mg285.213
400 419
105
Mn
257.610
0.020.027 0.05
Mn257.610
400 416
104
Mo
203.845
0.37
0.78
1
Mo203.845
400 401
100
Ni
231.604
0.21
0.35
1
Ni231.604 400 409
102
P
178.223
2.5
3.8
5
P178.221 400 400
100
K
766.490
0.37
2.4
1
K766.490 10001045 105
Se
196.026
1.5
1.9
3
Se196.026 400 406
102
Si
251.611
1.7
3.8
5
Si251.611 500 526
105
Ag
328.068
0.170.27 0.4
Ag328.068 50.0 52.1
104
Na
589.592
0.36
Na589.592 100 102
102
Sr
421.552
0.0040.011 0.05
Sr421.552 400 419
105
Tl
190.805
0.04
0.91
1
Tl190.801 400 405
101
Sn
189.927
0.44
0.48
1
Sn189.927 1000 973
97.3
Ti
334.942
0.05
0.07
0.4
Ti334.940 400 410
103
V
292.402
0.15
0.26
0.4
V292.402 400 419
105
Zn
206.200
0.100.88 0.4
Zn206.200 400 409
102
0.55
0.30
1.7
3
3
0.4
1
analyzed after calibration, throughout the analysis, and at
the end of the run. These solutions were prepared from
standards 5 and 10 (depending on the analyte), using the
prepFAST™ system. The results for each wavelength are
shown in Table 7. For all analytes except B, P, and Si, the
dilution factor was 4x. For B, P, and Si, the dilution factor
was 5x. The IPC solution should not vary more than 10%
during an analysis. All readings fell into this range with the
average recovery reported below. WinLab™ for ICP software
can automatically re-analyze any quality control sample that
falls out of range, if necessary.
The effect of potential interferences was investigated. An
interferent solution (SIC A) was prepared from a commercial
solution, and fortified to an Fe concentration of 300 mg/L,
as recommended in the Method (see Table 3). A portion of
this solution was also spiked with a known concentration of
---
most of the analytes and used as SIC B. Only a few of the
wavelengths showed visible spectral peak interference: As,
Cd and V. Several of the other wavelengths suffered from an
effect that produced slight baseline effects. When the
analysis of the SIC A solution produced results of more than
±5.5 µg/L, a baseline effect was decided to have occurred.
At that time, an IEC factor was applied to the data. All
results are shown in Table 8. In all cases, except for Li, the
determined value for the spiked solution, SIC B, was within
10% of the expected value. Contamination occurred during
the SIC B solution preparation; therefore, the Li results are
not reported.
Several solutions of known concentration were analyzed as
samples to determine system reliability. Results are shown in
Tables 9-13. The Analytes B solution (Table 9) showed all but
one diluted result for Sb within 10% of the expected value.
5
Table 7. Initial performance check (IPC) run periodically and at end of run; prepared from calibration standards 5 and 10 by the prepFAST™ system
Wavelength
Analyte
(nm) Check
Concentration
(μg/L) After
Calibration Check #1
Check #2
(μg/L) (μg/L)
(μg/L)
End of Run
Recovery
(μg/L)
Average
(%)
Al
396.153
250 245
243
244
235
96.7
Sb
206.836250
255
253
258
247
101
As
188.979250
253
252
255
249
101
Ba
493.408250
252
250
249
242
99.3
Be
313.042250
245
244
244
247
98.0
B
249.677
1010
1040
1050
1050
104
Cd
226.502250
248
246
247
246
98.7
Ca
315.887250
251
251
251
249
100
Ce
413.764250
252
250
248
240
99.0
Cr
267.716250
249
249
249
240
98.7
Co
228.616250
261
259
262
255
104
Cu
324.752250
251
250
252
239
99.2
Fe
259.939250
249
251
249
245
99.4
Pb
220.353250
257
257
260
242
102
Li
670.784250
239
235
237
234
94.6
Mg
285.213250
248
255
251
237
99.1
Mn
257.610250
248
246
246
237
97.7
Mo
203.845250
254
254
256
237
100
Ni
231.604250
243
243
244
251
98.1
P
178.2211000
1047
1058
1074
1094
107
K
766.490250
239
238
239
229
94.4
Se
196.026250
253
251
255
247
101
Si
251.6111000
1050
1040
1050
1070
105
Ag
328.068250
253
253
255
239
100
Na
589.592250
244
240
244
240
96.8
Sr
421.552250
257
248
254
243
100
Tl
190.801250
253
252
256
249
101
Sn
189.927250
254
252
255
246
101
Ti
334.940250
257
256
256
243
101
V
292.402250
249
249
250
239
98.7
1000 Zn206.200
250 247246 246 264 100
The same is true for the IPC solution (Table 10) – this
solution was diluted 10x by the user and then run using the
prepFAST™ system either directly and/or with a 10x or 100x
dilution. All recoveries for a drinking water secondary
standard (HPS DWSS) were well within acceptable ranges
compared to the known values (Table 11). A trace metals
drinking water (HPS TMDW) standard was analyzed without
dilution of any kind (Table 12). Determined results are within
15% of the certified values, except for Cu and Ag, where
contamination was suspected. A drinking water primary
standard (HPS DWPS) was also run (Table 13).
6
A first-morning tap water was collected to use as a sample
(laboratory matrix, LM). This solution was run in duplicate
and a portion was fortified with the analytes of interest as a
laboratory fortified matrix (LFM). Results are shown in Table 14.
Duplicates were all within acceptable limits and, with the
exception of Ag, all spike results were within 15%. Based on
the determined Zn and Cu concentrations in the sample, the
spiked concentration should have been higher. The low Ag
recovery was caused by a potential precipitation due to a
significant chloride concentration in the sample.
Table 8. Recovery of the SIC solution with and without the use of inter-element correction (IEC) factors
Wavelength
SIC A Analyte
(nm) (μg/L)
Comment SIC B Added
(μg/L)
Sb
Found
(μg/L))
SIC B No IEC
SIC B with IEC
Recovery Found
Recovery
(%)(μg/L) (%)
206.836
6.4
200 203
102
As 188.979
*
200202
101 N/A
NA
Ba 493.408
*
200201
101 N/A
N/A
Be 313.042
*
200194
97.0 N/A
N/A
B
249.677
-12
20002111
106
2122
106
Cd
226.502
39
200
111
184
92.0
Ce
413.764
-7.3
200 186
93.0
193
96.5
Cr
267.716
*
200189
94.5 N/A
N/A
Co 228.616
*
200187
93.5 N/A
N/A
Cu 324.752
10
200214
107 204
102
Pb 220.353
*
200186
93.0 N/A
N/A
Mn 257.610
*
200186
93.0 N/A
N/A
Mo 203.845
*
200191
95.5 N/A
N/A
Ni
231.604
-9.3
200 183
91.5
191
95.5
P
178.221
32
20002098
105
2067
103
Se
196.026
-82.87
200
60.1
198
99.2
Si
251.611
Fe interference
Fe interference
221
120.2
197
98.5
16
20002128
106
2122
106
Ag 328.068
*
200209
104 N/A
N/A
Sr
421.552
*
200200
100 N/A
N/A
Tl
190.801
8.7
200 188
94.0 180
90.0
Sn 189.927
*
200182
91.0 N/A
N/A
Ti
334.940
*
200197
98.5 N/A
N/A
V
292.402
15
200
104
97.0
Zn 206.200
Fe interference
*
208
200197
194
98.5 N/A
N/A
* No baseline effect
Table 9. Sample analysis: recovery of the Analytes B solution+ (referenced to a 10x user prepared dilution) run in duplicate, for most elements, with a further 10x
prepFAST™ dilution
Known
Wavelength
Value
Determined Recovery
Analyte
(nm) (μg/L)
(μg/L) (%) Replicate 1
prepFAST™ Diluted 10x
Recovery (μg/L)
(%)
Replicate 2
prepFAST™
Diluted 10x
Recovery
(μg/L)
(%)
Sb 206.836 6000 5088*84.5 5296
88
---
---
As 188.979 1000 905.390.5903.9
90.4 ---
---
Ba 493.408 5000 4947*98.9 5064
101 4894
97.9
Be 313.042 5000 4855*97.1 4965
99.3 4830
96.6
Cd 226.502 100009830*98.3 10320
103 10130
101
Cr 267.716 5000 4880*97.6 5099
102 4990
99.8
Co 228.616 5000 4941*98.8 4931
98.6 4854
97.1
Cu 324.752 5000 4788*95.8 4860
97.2 ---
---
106
105
Pb
220.353
500
499.7
100
530.5 525.2
Mn 257.610 5000 4834*96.7 4743
94.8 4630
92.6
Ni 231.604 100009695*96.9 10090
101 9876
98.8
Ag 328.068 2000 1952*97.6 2042
102 1999
99.9
V
103 5019
100
102 10000
100
292.402 5000 4922*98.4 5128
Zn 206.200 100009763*97.6 10160
+ Solution was run as a sample, not for any method requirement purposes.
* Indicates over calibration range for sample run directly.
7
Table 10. Sample analysis: recovery of the ICV initial calibration verification solution+ (referenced to 10x user-prepared dilution) with further prepFAST™ dilutions
at 10x or 100x, when necessary
Replicate 1
Replicate 2
Known
prepFAST™ prepFAST™
Wavelength
Value
Determined
Recovery
Dilution
Determined Recovery
Dilution
Analyte
(nm)
(μg/L)
(μg/L) (%) Factor
(μg/L)
(%)
Factor
Al 396.153 2000019900 99.7 100x ---
---
Sb 206.83660006260 10410x ---
--- ---
As 188.97910001010 1010x
---
999 99.9 10x
Ba 493.408 2000020200 101 100x ---
---
---
Be313.042500494 98.6
0x 517 10310x
Cd 226.502 500 480
96.00x
491
98.1 10x
Ca 315.887 5000053000 106 100x ---
---
Cr 267.716 1000 982
98.20x
994
99.4 10x
Co 228.616 5000 4800
98.810x
---
---
Cu 324.75225002750 11110x ---
-----
--- ---
Fe 259.939 100009660
96.6 10x
10400 104 100x
Pb 220.353 300 291
97.00x
---
---
---
Mg 285.213 5000049300 98.6 100x ---
---
---
Mn 257.610 1500 1500
99.810x
---
---
---
Ni 231.604 4000 3880
97.010x
---
---
---
766.490 5000049200 98.5 100x ---
---
---
K
Se 196.026 500 491
98.10x
Ag 328.06810001018 1020x
495
99.0 10x
995 99.5 10x
Na 589.592 5000047400 94.5 100x ---
---
Tl 190.801 1000 952
99.2 10x
95.20x
992
---
V 292.40250005200 10410x ---
--- ---
Zn 206.200 2000 1960
---
97.910x
---
---
+ Solution was run as a sample, not for any method requirement purposes.
Table 11. Recovery of a drinking water secondary standard HPS DWSS (referenced to analyst prepared 10x)
Known
Wavelength
Diluted Value Determined Recovery
Analyte
(nm) (μg/L)
(μg/L) (%) 8
Replicate 1
prepFAST™ Diluted 10x
Recovery (μg/L)
(%)
Replicate 2
prepFAST™
Diluted 10x
Recovery
(μg/L)
(%)
Cu 324.752 5,0004815 96.35040
101 ---
---
Fe
103 9910
99.1
Mn 257.610 5,0004902 98.04850
259.939 10,00010070 101 10000
97.0 4790
95.8
Zn 206.200 5,0005073 101 5170
103 5190
104
Table 12. Recovery of a trace metals drinking water standard HPS TMDW
(no dilutions were made)
Table 13. Recovery of a drinking water primary standard HPS DWPS (referenced
to analyst prepared 100x)
Known
WavelengthValue
Determined Recovery
Analyte(nm)
(μg/L)
(μg/L)
(%)
Known
WavelengthValue
Determined Recovery
Analyte(nm)
(μg/L)
(μg/L)
(%)
Al396.153120
130
110
As188.979 1000
1018
102
Sb206.836 10
11
110
Ba493.408 500
483
96.6
As188.979 80
79
98.4
Cd226.502 500
508
101
Ba493.408 50
48
96.0
Cr205.5601000
907
90.7
Be313.042 20
23
115
Se196.026 500
496
99.4
Cd226.502 10
11
110
Ag328.068 100
1011
101
Ca315.887 35000
36000 102
Cr267.71620
20
100
Co228.616 25
23
92.0
Cu324.752 20
25
125
Fe259.939100
98
98.0
Pb220.353 40
41
102
Mg285.213 9000
9000
99.9
Mn257.610 40
41
102
Mo203.845 100
99
99.0
Ni231.60460
57
95.0
K 766.4902500
2658
94.1
Se196.026 10
10.06
100.1
Ag328.068 2
1.5
76.9
Na589.592 6000
6800
113
Sr421.552250
250
99.6
Tl190.80110
9.2
92.0
V 292.40230
30
100
Zn206.200 70
74
106
9
Table 14. Lab sample analysis with sample duplicate and spike
Analyte
Wavelength
(nm)
LM
LM Duplicate
Fortification
LFM Found
Recovery
(μg/L)(μg/L)(μg/L)(μg/L)(%)
Al
396.153
11.811.8200 216 102
Sb
206.836
13.814.4200 184 85.7
As
188.979
5.6 5.3 20018087.9
Ba
493.408
9.529.70200 210 100
Be
313.042
3.443.48200 201 99.0
B
249.677
17.918.3500 539 104
Cd
226.502
1.181.16200 195 97.0
Ce
413.764
0.7900.904200 191 95.0
Cr
267.716
1.571.56200 194 96.0
Co
228.616
< MDL
Cu
324.752
14631466200 1654101
Fe
259.939
10.810.9200 202 95.5
Pb
220.353
4.1 3.6 20019193.8
Mn
257.610
5.965.99200 189 91.5
Mo
203.845
2.192.22200 195 96.5
Na
589.592
1898118790200 *
Ni
231.604
9.159.43200 213 102
P
178.221
73.3 72.7 10001152107
K
766.490
21592134200 239095.2
Se
196.026
7.097.79200 192 92.6
Si
251.611
17901820500 226094.0
Ag
328.068
0.1120.018200 133.565.5**
Sr
421.552
56.857.4200 252 97.5
Tl
190.801
8.307.63200 188 90.4
Sn
189.927
1.171.12200 193 96.0
Ti
334.940
< MDL V
292.402
2.122.14200 197 97.5
Zn
206.200
41341820060598.4
< MDL
< MDL
200
200
195
195
97.5
*
97.5
* Spike to sample ratio was < 1
** See note in text
Conclusions
This study has demonstrated the capabilities of the PerkinElmer
Optima 8300 ICP-OES to produce results that meet the rigorous
requirements outlined in U.S. EPA Method 200.7. The accuracy
and precision of the instrument allows less time to be spent on
meeting the performance requirements. The ESI prepFAST™
system simplifies sample preparation, allowing higher sample
throughput, while reducing memory effects and minimizing
errors and contamination. The evaluation has clearly
demonstrated that the Optima 8300 ICP-OES coupled with the
prepFAST™ system is well-equipped to handle the real-world
demands of U.S. EPA Method 200.7 for the analysis of water
samples. It has also shown that the analytical accuracy of
reference materials is excellent, together with the spike
recoveries in real-world drinking water samples.
References
1.EPA Method 200.7 Revision 4.4, “Determination of Metals
and Trace Elements in Water and Wastes by Inductively
Coupled Plasma-Atomic Emission Spectrometry.” http://
water.epa.gov/scitech/methods/cwa/bioindicators/
upload/2007_07_10_methods_method_200_7.pdf
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