### 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, Wh eeling, 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 m ult i

- parameter instrument summary s tatistics for Allegheny River s ites.

Table A.3 : Dionex model ICS

- 2000 i on c hromatography method performance c haracteristics.

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



### Appendix B: Figures

Figure B. 1: Relationship between Onset in

- river s onde and Isco sample bottle specific c onductivity.

Figure B. 2: Allegheny River and tributary flow (m 3 min

- 1 ) line diagram for study domain during high and

low d ischarge sampling campaigns

. Figure B.3 : Historical USGS Alleghe ny River Franklin, PA g age (#03025500) w ater v olumes d uring (a) h igh

d ischarge (b) l ow d ischarge

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

(b) chloride, (c) bromid e, (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 d epicting example i n

- r iver sonde specific conductivity observations at S03

- Downstream1

during h igh discharge sampling campaign demonstrating how the collocated Isco sampling t imes

were o ffset from p eriods of maximum CWTF d ischarge i mpact

. Drop down lines represent Isco

sam pling 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 Dischar ge Distance

(km) Allegheny River km

River Gage #03025500

- 3.1 200.2

S01

- Upstream

- 1.6 198.7

S02

- CWTF 0 197.1

S03

- Downstream 1 12.3 184.8

S04

- Downstream 2 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 m ulti

- parameter instrument summary statistics for Allegheny River s ites.

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 i on c hromatography m ethod p erformance c haracteristics.

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

. D isinfection 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 c onductivity.

1:1 line is plotted.

### Figure Appendix B. 2

. Allegheny River and t ributary mean water discharge (m 3 

### min

- 1 

### ) line diagram for

study domain during high and l ow (in parenthesis) discharge s ampling c ampaigns

.

Tributary Name USGS Gage Station

Allegheny River (Franklin, PA) 03025500

Clarion River (Piney, PA) 03030 500

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) 0304900 0

Allegheny River (Natrona, PA) 03049500

### Figure App endix B. 3 a

. Historical USGS Allegheny River Franklin, PA g age (#03025500) w ater v olume

mean s d uring the h igh river d ischarge (>8500 m

- 3 

### min

- 1 

### ) regime

.

* 

### USGS Provisional Data

### Figure Appendix B.3 b

. Historical USGS Allegheny River River Franklin, PA g age (#03025500) w ater

v olume mean s d uring the l ow river d ischarge (<8500 m

- 3 

### min

- 1 

### ) regime

.

* 

### USGS Provisional Data

### Figure Appendix B. 4 a. Comparison of Allegheny River high and low river discharge regime s specific

conductivity by site location

. Dashed line s indicates median “baseline” value s at

S01

- upstream1 site during each flow regime

.

### Figure Appendix B. 4 b

. Comparison of Allegheny River high and low river discharge regime s chloride by

site location

. Dashed line s indicates median “baseline” value s at S01

- upstream1

site during each flow regime

.

### Figure Appendix B.4 c

. Comparison of Allegheny River high and low river discharge regime s bromide by

site location

. Dashed line s indicates median “baseline” value s at S01

- upstream1

site during each flow regime

.

### Figure Appendix B. 4 d

. Comparison of Allegheny River high and low river discharge regime s Cl

- 

### / Br



### ratio

by site location

. Dashed line s indicates median “baseline” value s 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.

### Figure Appendix B.4e

. Comparison of Allegheny River high and low river discharge regime s sulfate by

site location

. Dashed line s indicates median “baseline” value s at S01

- upstream1

site during each flow regime

.

### Figure Appendix B. 5

. Plot d epicting example i n

- r iver sonde specific conductivity observations at S03

- Downstream1 during h igh

discharge sampling campaign demonstrating how the collocated Isco sampling t imes were o ffset from p eriods

of maximum CWTF d ischarge i mpact

. Drop down lines represent Isco sam pling 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 T HM 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.