Appendices for:

The Impact of Commercially Treated Oil and Gas Produced Water Discharges on Bromide 

Concentrations and Modeled Brominated Trihalomethane Disinfection Byproducts at two 

Downstream Municipal Drinking Water Plants in the Upper Allegheny River, Pennsylvania, USA

Matthew S. Landis,* Ali S. Kamal, Kasey D. Kovalcik, Carry Croghan, Gary A. Norris

US EPA, Office of Research and Development, Research Triangle Park, NC 27709

Amy Bergdale

US EPA Region 3, Office of Monitoring and Assessment, Wheeling, WV 26003

*Corresponding author phone: (919) 541-4841; landis.matthew@epa.gov

Appendix A: Tables

Table A.1: Distances of Allegheny River sampling sites and USGS gage stations from the CWTF discharge.

Table A.2: YSI multi-parameter instrument summary statistics for Allegheny River sites.

Table A.3: Dionex model ICS-2000 ion chromatography method performance characteristics.

Table A.4: Disinfection byproduct empirical raw water model input parameters.

Appendix B: Figures

Figure B.1: Relationship between Onset in-river sonde and Isco sample bottle specific conductivity.

Figure B.2: Allegheny River and tributary flow (m3 min-1) line diagram for study domain during high and 

low discharge sampling campaigns.

Figure B.3: Historical USGS Allegheny River Franklin, PA gage (#03025500) water volumes during (a) high 

discharge (b) low discharge.

Figure B.4: Comparison of Allegheny River high and low river discharge regimes (a) specific conductivity, 

(b) chloride, (c) bromide, (d) chloride/bromide ratio, and (e) sulfate by site location. Dashed 

lines indicates median “baseline” values at S01-upstream1 site during each flow regime.

Figure B.5: Plot depicting example in-river sonde specific conductivity observations at S03-Downstream1 

during high discharge sampling campaign demonstrating how the collocated Isco sampling times 

were offset from periods of maximum CWTF discharge impact. Drop down lines represent Isco 

sampling times (09:00 & 12:00 EST) and the grey boxes represent the plume transport time 

corrected CWTF discharge impact periods.

Figure B.6: Time series plot of S06-PDW2 quarterly THM prior to installation of new microfiltration plant 

in 2013-Q3.

Figure B.7: Time series plot of S06-PDW2 quarterly mean Br- and TOC.
Table Appendix A.1. Distances of Allegheny River sampling sites and USGS gage stations from the 

CWTF discharge.

Site CWTF Discharge Distance 

(km)

Allegheny River km

River Gage #03025500 -3.1 200.2

S01 - Upstream -1.6 198.7

S02 - CWTF 0 197.1

S03 - Downstream1 12.3 184.8

S04 - Downstream2 43.5 153.6

S05 - PDW1 51.8 145.3

River Gage #03031500 62.9 134.2

S06 - PDW2 149.6 47.5

Table Appendix A.2. YSI multi-parameter instrument summary statistics for Allegheny River sites.

Site Season n pH Specific Conductivity (s cm-1

) Total Dissolved Solids (g l-1

) Temperature (oC)

S01

Upstream

Spring 8 7.8 ± 0.3 130 ± 11 0.075 ± 0.031 13.2 ± 2.9

Summer 8 8.9 ± 0.3 170 ± 10 0.110 ± 0.007 28.5 ± 1.1

Fall 3 8.9 ± 0.2 179 ± 23 0.117 ± 0.015 18.7 ± 1.4

S02

CWTF

Spring 6 8.7 ± 0.3 109548 ± 6193 71.178 ± 4.024 15.6 ± 3.5

Summer 5 8.6 ± 0.1 136256 ± 9945 88.530 ± 6.461 26.9 ± 0.7

Fall 3 8.4 ± 0.6 130854 ± 5306 85.021 ± 3.447 17.6 ± 2.0

S03

Downstream 1

Spring 7 7.8 ± 0.3 140 ± 16 0.091 ± 0.011 13.1 ± 2.7

Summer 9 8.3 ± 0.4 173 ± 10 0.112 ± 0.007 26.8 ± 1.1

Fall 4 8.2 ± 0.3 219 ± 49 0.142 ± 0.032 18.1 ± 2.5

S04

Downstream 2

Spring 7 7.8 ± 0.2 139 ± 12 0.090 ± 0.008 14.9 ± 2.6

Summer 8 8.7 ± 0.3 191 ± 9 0.124 ± 0.006 27.3 ± 0.7

Fall 4 8.4 ± 0.3 203 ± 20 0.132 ± 0.013 18.1 ± 2.6

S05

PDW 1

Spring 6 7.5 ± 0.1 159 ± 13 0.103 ± 0.008 13.8 ± 2.3

Summer 7 7.8 ± 0.3 215 ± 32 0.140 ± 0.020 26.4 ± 1.4

Fall 4 8.2 ± 0.3 209 ± 22 0.136 ± 0.014 18.4 ± 2.1

S06

PDW 2

Spring 5 7.5 ± 0.2 184 ± 26 0.120 ± 0.017 14.8 ± 2.5

Summer 6 7.3 ± 0.1 344 ± 65 0.223 ± 0.042 27.8 ± 0.9

Fall 5 7.4 ± 0.1 303 ± 24 0.197 ± 0.015 18.9 ± 1.8
Table Appendix A.3. Dionex Model ICS-2000 ion chromatography method performance characteristics.

Species IDL 

(ppb)

MDL 

(ppb)*

n Analytical Precision 

(%)

n Collocated Precision

(%)

Chloride 2.2 25.8 130 100 ± 1 122 99 ± 2

Bromide 1.5 6.3 58 99 ± 2 117 98 ± 6

Sulfate 0.7 12.9 120 100 ± 1 117 96 ± 10

*CWTF samples were diluted 1000x, therefore the raw sample MDLs are ppm

Table Appendix A.4. Disinfection byproduct empirical raw water model input parameters.

Site Condition Bromide

(ppb) pH Temp(°C)

DOC

(mg liter-1)

Chlorine

(mg liter-1)

Contact Time

(hours)

S05-PDW1 Baseline 70 8.0 26.4 3.00 3.5 24

CWTF Impacted 93 8.0 26.4 3.00 3.5 24

S06-PDW2 Baseline 83 7.5 27.8 2.98 8.0 16

CWTF Impacted 132 7.3 27.8 2.98 8.0 16
Figure Appendix B.1. Relationship between Onset in-river sonde and Isco sample bottle conductivity. 

1:1 line is plotted.
Figure Appendix B.2. Allegheny River and tributary mean water discharge (m3 min-1

) line diagram for 

study domain during high and low (in parenthesis) discharge sampling campaigns.

Tributary Name USGS Gage Station

Allegheny River (Franklin, PA) 03025500

Clarion River (Piney, PA) 03030500

Allegheny River (Parker, PA) 03031500

Redbank Creek (St. Charles, PA) 03032500

Mahoning Creek (Mahoning Dam, PA) 03036000

Crooked Creek (Crooked Creek Dam, PA) 03039000

Kiskiminetas River (Vandergrift, PA) 03048500

Blacklick Creek (Josephine, PA) 03042000

Buffalo Creek (Freeport, PA) 03049000

Allegheny River (Natrona, PA) 03049500
Figure Appendix B.3a. Historical USGS Allegheny River Franklin, PA gage (#03025500) water volume

means during the high river discharge (>8500 m-3 min-1) regime. 2007 2008 2009 2010 2011 2012 Campaign 2013* 2014* Allegheny River Discharge (m

3 min-1

)

0

20000

40000

60000

80000

100000

(a)

*USGS Provisional Data
Figure Appendix B.3b. Historical USGS Allegheny River River Franklin, PA gage (#03025500) water 

volume means during the low river discharge (<8500 m-3 min-1) regime. 2008 2009 2010 2011 2012 Campaign 2013* 2014* Allegheny River Discharge (m

3 min- 1

)

0

2000

4000

6000

8000

10000

(b)

*USGS Provisional Data
Figure Appendix B.4a. Comparison of Allegheny River high and low river discharge regimes specific 

conductivity by site location. Dashed lines indicates median “baseline” values at 

S01-upstream1 site during each flow regime.

(a)

Specific Conductivity ( S cm-1

)

0.0

100.0

200.0

300.0

400.0

500.0

600.0

S01 - Upstream S03 - Downstream 1

~12 km

S04 - Downstream 2

~ 43 km

S05 - PDW 1

~ 52 km

S06 - PDW 2

~ 150 km

High Low High Low High Low High Low High Low
Figure Appendix B.4b. Comparison of Allegheny River high and low river discharge regimes chloride by 

site location. Dashed lines indicates median “baseline” values at S01-upstream1 

site during each flow regime.

(c)

Chloride (ppm)

10.0

15.0

20.0

25.0

30.0

35.0

40.0

45.0

S01 - Upstream S03 - Downstream 1

~12 km

S04 - Downstream 2

~ 43 km

S05 - PDW 1

~ 52 km

S06 - PDW 2

~ 150 km

High Low High Low High Low High Low High Low
Figure Appendix B.4c. Comparison of Allegheny River high and low river discharge regimes bromide by 

site location. Dashed lines indicates median “baseline” values at S01-upstream1 

site during each flow regime.

(b)

Bromide (ppm)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

S01 - Upstream S03 - Downstream 1

~12 km

S04 - Downstream 2

~ 43 km

S05 - PDW 1

~ 52 km

S06 - PDW 2

~ 150 km

High Low High Low High Low High Low High Low
Figure Appendix B.4d. Comparison of Allegheny River high and low river discharge regimes Cl-

/Brratio

by site location. Dashed lines indicates median “baseline” values at S01-

upstream1 site during each flow regime. The S02-CWTF discharge Cl-/Br- ratio 

was 110.6 ± 6.2 and 90.4 ± 2.4 for the high and low river discharge regimes, 

respectively.

(d) Chloride/Bromide Ratio

100

200

300

400

500

600

700

800

S01 - Upstream S03 - Downstream 1

~12 km

S04 - Downstream 2

~ 43 km

S05 - PDW 1

~ 52 km

S06 - PDW 2

~ 150 km

High Low High Low High Low High Low High Low
Figure Appendix B.4e. Comparison of Allegheny River high and low river discharge regimes sulfate by 

site location. Dashed lines indicates median “baseline” values at S01-upstream1 

site during each flow regime.
Figure Appendix B.5. Plot depicting example in-river sonde specific conductivity observations at S03-Downstream1 during high

discharge sampling campaign demonstrating how the collocated Isco sampling times were offset from periods 

of maximum CWTF discharge impact. Drop down lines represent Isco sampling times (09:00 & 12:00 EST) 

and the grey boxes represent the plume transport time corrected CWTF discharge impact periods.
Figure Appendix B.6. Time series plot of PDW2 quarterly THM prior to installation of new 

microfiltration treatment plant in 2013-Q3. The box delineates the two 

quarters during the 2012 EPA field sampling campaigns.
Figure Appendix B.7. Time series plot of S06-PDW2 quarterly mean bromide and total organic 

carbon (trend is not significant at α = 0.05). The box delineates the two 

quarters during the 2012 EPA field sampling campaigns.