Appendix A. Supplementary data Application of ICP-OES for Evaluating Energy Extraction and Production Wastewater Discharge Impacts on Surface Waters in Western Pennsylvania Joseph Patrick Pancrasa, Gary A. Norrisb*, Matthew S. Landisb, Kasey D. Kovalcikb, John K. McGeeb, Ali Kamalb a Alion Science and Technology, P.O. Box 12313, Research Triangle Park, North Carolina 27709 b U.S. Environmental Protection Agency, Office of Research and Development, Research Triangle Park, North Carolina 27711 *Corresponding author phone: 919-541-1519 e-mail:
[email protected]
SI Table S1. Routine quality control checks for the ICP-OES analysis. No.
Check name
Purpose
Frequency
EPA HF QAPP limits
Method 200.7 limits
1
Calibration
Establish linear range
At beginning of each analytical sequence
r2 > 0.99
2
Internal standard (IS) recovery
Check for any sample transport issues
100% of samples
80–120%
80–120%
3
Quality control standard (QCS)
Checks accuracy of calibration with a second source standard
Post-calibration
85–115%
95–105%
4
Standard/certified reference material (SRM/CRM)
Checks accuracy of calibration with a certified reference sample
At start and end of an analytical sequence
85–115%
85–115%
5
Spectral interference check sample (SIC)
Commercially available certified samples for ICP to verify absence of interferences
No QAPP-specified criteria
20% userdefined criteria
Not specified
6
Continuing calibration blank verification (CCB)
Continuing check of the blank level by remeasuring the CCB
Every 10 samples analyzed
≤ MDL
≤ IDL
7
Continuing calibration verification (CCV)
Instrument performance check at beginning; then continuing check of instrument accuracy by remeasuring a CCV
At start, then every 10 samples analyzed, and at end
85–115%
90–110%
8
Laboratory Control Sample (LCS)
Continuously track recoveries of elements of interest using certified waters as samples
One per analytical batch
85–115%
9
Duplicate analysis (Dp)
Continuing precision check by reanalyzing a sample
One reanalysis for 10 samples analyzed
80–120%
80–120%
10
Laboratory reagent blank (LRB)
Checks laboratory reagents and sample preparation process for contamination
One per analytical batch
< MDL
< 2.2 x MDL
11
Laboratoryfortified blank (LFB)
Matrix-matched sample with known concentration to verify accuracy of method
One per analytical batch
Not specified
85–115 %
12
Laboratoryfortified matrix (LFM)
Checks recovery of analyte in a matrix by spiking a known quantity into a sample
One per analytical batch
Not specified
85–115 %
SI Table S2. Rare-earth elemental concentrations in µg/L in CUOG wastewaters as compared to PDWS waters, determined by HR-ICPMS. Refer to U.S. EPA, 2015 for method information. Sample type Effluent waters PDWS waters
Metrics MDL (µg/L) % over MDL median range % over MDL median (µg/L) range
La 0.029 100 68.5 32.1 – 108 70 0.246 0.020 – 1.150
*Species not detected at 100 times dilution
Nd 0.029 100 30.6 14.9 – 41.6 87 0.287 0.020 – 1.531
Sm 0.011 100 31.9 7.38 - 262 65 0.112 0.011 – 0.467
Tb 0.015 * * * 26 0.040 0.020 – 0.079
SI Table S3. Percent recoveries of certified reference materials analyzed.
Element Al As B Ba Ca Cd Ce Co Cr Cu Fe K Li Mg Mn Mo Na Ni P Pb S Sb Se Si Sn Sr Ti Tl V Zn
Recovery %, mean 96 92 106 101 100 100
± ± ± ± ± ± ±
SD, % 16 24 4 4 4 15
19.6 39.7 83.7 36.4 562.8
98 99 98 100 98
± ± ± ± ±
3 2 4 8 4
1031.5 39.4 42.6 3075.7 22.2
98 98 94 99 89
± ± ± ± ±
4 3 7 4 5
Certified, µg/L 138.8 59.0 154.0 531.0 31500.0 6.4
Recovery %, mean 99 95.5 104.7 99.8 96.5 103.8
± ± ± ± ± ± ±
SD, % 6 4.4 5.7 3.4 3.1 12.6
26.4 19.9 22.2 95.7 1984.0 17.0 7841.0 38.0 118.5 20230.0 1984.0
95.1 101.0 115.9 101.4 96.8 105.8 97.1 99.8 100.9 98.0 94.0
± ± ± ± ± ± ± ± ± ± ±
3.1 4.0 17.4 8.9 3.2 12.0 2.9 3.2 3.0 3.0 0.1
Certified, µg/L 120.0 80.0
Recovery %, mean 96 99
± ± ±
SD, % 5 3
50.0 35000.0 10.0
100 100 98
± ± ±
2 3 8
25.0 20.0
97 100
± ±
2 3
100.0 2500.0 20.0 9000.0 40.0 100.0 6000.0 60.0
100 99 98 99 101 99 100 92
± ± ± ± ± ± ± ±
3 2 7 3 2 2 2 1
11.7 (a)
97
±
20
19.2
94.7
±
12.3
40.0
97
±
3
4.1 (a) 18.9 (a) 5231.1
82 95 101
± ± ±
33 17 3
56.9 11.7 (a)
94.9 125.9
± ±
4.0 27.0
10 (a) 10.0 (a)
84 108
± ±
18 20
124.5
100
±
4
315.2
14.7 55.8
99 101
± ±
6 5
36.9 76.5
97.8
99.4 101.7
±
± ±
4.6
250.0
100
±
2
2.2 5.5
10.0 (a) 30.0 70.0
135 99 101
± ± ±
37 3 2
Certified, µg/L
Recovery %, mean
97.1
123
8360.0
106
ERA custom mix (n = 3)
ERA-500 (n = 3)
M-172 (n = 31)
HP-T MDW (n = 14)
SRM1643e (n = 31)
SRM 1640a (n = 31) Certified, µg /L 50.7 4.4 (a) 318.1 151.4 5542.7 3.9
Certified, Recovery %, mean µg/L ± SD, % 102 530.0 101 753.0 99 859.0 15 ± 101 827.0 5 ± 91 689.0
3800.0
105
±
4
4730.0
104
±
5
± ± ± ± ± ±
1
215.0 214.0 842.0 795.0
104 100 92 102
± ± ± ±
2 1 1 2
1850.0 575.0
101 102
± ±
2 1
1720.0
97
±
2
460.0 632.0 291.0
98 100 101
± ± ±
1 1 2
12500.0
104
±
5
1350.0
102
±
3
4105.7
109
±
3
5697.4
104
±
2
54.0
105
±
5
65.1
99
±
3
9
744.0 931.0 1330.0
101 100 96
± ± ±
2 1 2
10.3
Empty cells denote certified/reference concentrations for that particular element does not exist. (a) - Certified concentration is below ML but above MDL.
100
±
Recovery %, mean
±
SD, %
45.4
101.5
±
1.8
56.8
102.0
±
0.6
Certified, mg/L SD, % 3 2 1 2
SI Table S4. Analytical and sampling precision of river water analysis. Element Ba K Sr Mg Cu Ca S Na Al Fe Mn Si
ICP-OES Analysis Precisiona, % difference 3.0 4.6 3.2 3.6 8.0 3.4 2.8 3.4 7.3 3.3 3.1 3.2
Overall Sampling Precisionb, % difference 4.2 6.7 4.9 5.7 14.1 6.0 5.4 7.0 20.1 9.5 8.8 10.5
Data from 87 duplicate ICP-OES analysis of river samples were used. Data from 78 concurrently collected sample pairs from one of the PDWS sampling sites were used. a
b
Method: A total of 78 concurrently collected PDWS sample pairs with concentration data within the reporting range (ML – LDR) was used to estimate overall uncertainty. Also, species with low % detectabilities (B, Co, Li, Ni, Pb, Zn) were excluded from this precision analysis. Relative percent difference (RPD) in the concentration pairs, a measure of precision, was calculated as the percent of absolute concentration difference divided by the mean concentration. For instrumental analysis uncertainty, a total 87 duplicate sample analyses, available from all of the PDWS analyses were used. Table S4 presents the results of this uncertainty study. It was found that ‘sampling’ was a major contributor to the overall uncertainties of Al, Fe, Mn, and Si. Analysis precision is approximately half of overall precision for Sr, Mg, Cu, Ca, S, and Na measurements. Measurement uncertainties of Ba, K, and Sr appear predominantly controlled by the analysis method.
SI Table S5. Regression analysis of elements measured at two different emission wavelengths.
396.153 nm radial
r2 1.00
Slope 1.00
Intercept -0.01
249.677 nm axial
249.772 nm radial
0.99
0.91
0.07
233.527 nm radial
493.408 nm radial
1.00
1.02
0.00
0.98
1.14
Element
x variable
y variable
Al
308.215 nm radial
B Ba Ca
396.847 nm radial
315.887 nm radial
1.00
Fe
238.204 nm radial
259.939 nm radial
1.00
1.00
0.00
Mg
279.077 nm radial
285.213 nm radial
1.00
1.01
0.16
Na
588.995 nm radial
589.592 nm radial
1.00
1.03
0.24
1.00
-0.20
1.00
0.01
Mn
257.610 nm axial
257.610 nm radial
1.00
Zn
213.857 nm axial
206.200 nm axial
1.00
SI Table S6. Electro-neutrality in the high-saline produced water samples analysis. Species
Conductivity ClNO3BrFSO4B Ba Ca Fe K Li Mg Mn Na Si Sr ∑anion ∑cation diff,%
Unit
mS.cm-1 meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L meq/L
Produced Water from Conventional Wells 203 205 3257.5 3008.5 0.4 0.3 8.2 10.7 0.0 0.0 0.8 0.3 13.6 14.1 24.4 24.8 847.4 855.5 5.8 5.8 20.2 20.0 24.3 23.6 137.7 136.0 0.6 0.6 1930.2 1925.2 4.9 4.9 86.8 87.9 3266.9 3082.2 2.9
3019.9 3084.3 -1.1
Produced Water from Unconventional Wells 82.8 179 932.7 2528.7 5.9 8.4 1.5 6.8 0.0 0.0 0.1 0.0 7.3 18.5 10.5 68.6 257.9 672.3 3.6 7.0 8.7 11.0 5.4 13.1 34.6 98.9 0.1 0.8 614.3 1432.3 0.7 21.4 21.5 138.2 940.2 957.4 -0.9
2543.9 2463.5 1.6
CUOG Wastewater before CWTF 228 4228.2 0.0 23.9 0.6 2.0 9.0 0.0 1419.6 14.4 33.1 6.9 223.2 3.4 2285.9 0.0 22.9
228 4225.4 0.0 23.7 0.6 2.1 9.1 0.0 1419.2 14.5 33.5 6.9 225.8 3.4 2296.4 0.0 21.8
4254.6 4009.4 3.0
4251.6 4021.5 2.8
SI Figure 1. Effect of sulfur concentrations on barium measurement.
