Contaminant Characteriz

Effluent from Pennsylvan

Pennsylvan

Treatment Inc., Josephine 

Implications for Disposal of O

Fl bk ow ac Fl id u s from Brine Trea

EPA Hydraulic Fracturing Study Technic

Fate and Transport

March 28‐29, 2011, EPA Potomac Yard

Facility

Conrad D. Volz, DrPH, MPH, Kyle Ferrar, MPH, 

MPH, CPH, Charles Christen, DrPH, MEd, Shan

CPH, Matt Kelso, BS and Samantha Malo

Department of Environmental and Occup

Center for Healthy Environments and C

http://www.chec.pitt.edu http://www.cdv5@pitt.edu
Volz, C.D. et al., 2011 http://www.fractracker.org
Pennsylvania Brine Treatment, Josephine Facility Off

[Picture [Picture taken by Kyle Ferrar, December December 1, 2010, at location location (40 826 . °N, 79 172 . °

Volz, C.D. et al., 2011
Concentrations of Selected Impo

Contaminants from Marcellus S

Flowback Water

Total Dissolved Solids (TDS): 161,636 mg/L*B i 2 950 /L*

Flowback Water

Barium: 2,950 mg/L*Strontium: 3,280 mg/L*Chloride: 95 400 , mg/L** From Blauch, MF et al, 2009, Marcellus Shale Po

Fl bk ow ac Water‐Where is all the Salt Coming FSPE 125740.

Volz, C.D. et al., 2011 http://www.fractracker.org
Volz, et al., 2011 http://www.fractracker.org
PBT‐Josephine Facility Outfall on Blacklick Cree

Interpolation of Instream TDS and Sali
Contaminants of environmental public h

importance importance that were detected detected in all sa

sa

taken over the 24 hour period

Contaminants over MCL’s, MRL’s, consumption of fish c

and/or aquatic CMC CCC concentrations;

• barium (Ba) [mean, 27.3 ppm; maximum, 37.0 ppm]• bromides (Br) [mean, 1068.8 ppm; maximum, 1100.0 • strontium (Sr) [mean, 2983.1 ppm, maximum 3120.0 • benzene [mean 0 012 . ppm; maximum 0 013 . ppm]• 2 butoxyethanol (2‐BE) [mean 59ppm; maximum 66 Detected Contaminants• ethylbenzene (mean, 0.002 ppm)• toluene ( , mean 0.025 pp ) m• xylenes (mean, 0.028 ppm)
Contaminant concentrations of ecologic

secondary drinking water importance in

• chlorides chlorides (Cl) [mean 117 625 , ppm, maximum maximum 125 000 125,000 p• magnesium (Mg) [mean 1247.5 ppm; maximum 1300.0 

• manganese (Mn) [ mean 0.08 mg/L; maximum 0.15]

• total dissolved solids (TDS) [mean 186,625 ppm; maxim

190,000 ppm]

• sulfate (SO4) [mean 560 ppm; maximum 585 ppm], an

9.58 units; maximum 10 units].
Barium in PBT‐Josephine Facility Eff

[Ba Mean] = 27.30 mg/L; σ = 6.96 [Min.] = 20

mg/L; [Max.] = 37 mg/L; MDL; 0.002 mg/L

• [Mean Ba] ≈14 x (MCL) of Ba in drinking

water of 2 ppm

40

PA Brine Treatment Jose

12/10/2010

water of 2 ppm.

• The Ba ATSDR MRL’s oralintermediate/chronic exposure are .2

mg/kg/day. Derived MRLs for barium in

d i ki 6 89 5 77 d 3 04 ( /L/d )

3035

drinking are 6.89, 5.77, and 3.04 (mg/L/day)

for adult men, adult women, and children,respectively (renal). [Mean Ba] is 3.96, 4.73,

and 8.98 X the derived drinking water MRL’s 15

2025

mg/L

for intermediate and chronic exposures for

adult men, women, and children, respectively.

•The Ba consumption concentration of “water

and organism” and “organism alone” is 1 5

10

15

g g

ppm. The [Ba Mean] is over 27 times these

criteria.•EPA Ba CMC of 21 ppm exceeded; EPA CCC Ba

is 4 1 ppm 6 66X [Mean Ba]

0

12345

3 Hour Intervals

is 4.1 ppm, 6.66X [Mean Ba].

Volz, C.D. et al., 2011 http://www.fractracker.org
Strontium in PBT‐Josephine Facility E

[Mean Sr]= 2981 mg/ ; L  σ = 82.71[Min.] = 2,880 mg/L; [Max.] = 3,120

mg/L; MDL; 0.03 mg/L•Sr ATSDR MRL for oral route,

3,150

PA Brine Treatment Josep

12/10/2010

,

intermediate exposure is 2 mg/kg of

body mass/day (musculoskeletal

endpoints). The derived Sr MRL’s adult 3 000

3,0503,100

men, and women, and children are

68.87 mg/L/day, 57.67 mg/L/day, and

30.45 mg/L/day, respectively. 2,900

2,9503,000

mg/L

•[Mean Sr] is 43.29, 51.68 and 97.90 X

the derived drinking water MRL’s for

intermediate exposures for adult men,

d hild i l

2,8002,850

women, and children, respectively.

• The [Mean Sr] is 29,811 and 5,962

times the 100 ppb and 500 ppb

ifi i l l i d b i PA

2,750

12345

3 Hour Intervals

notification levels required by its PA

DEP NPDES permit.

Volz, C.D. et al., 2011 http://www.fractracker.org
Bromide in PBT‐Josephine Facility Ef

[ ] Mean = 1068.75 mg/ ; L  σ = 26.96 [ ] Min. = PA Brine Treatment Jo1020 mg/L; [Max.] = 1100 mg/L; MDL;

0.016 mg/L

•Bromide can be involved in reactions

1 1001,120

PA Brine Treatment Jo

12/10/2010

between chlorine and naturally occurring

organic matter in drinking‐water, forming

brominated and mixed chloro‐bromo

b d h hl h

1,0801,100

byproducts, such as trihalomethanes or

halogenated acetic acids.• There is general agreement that

background bromide levels in fresh water

1,0401,060

mg/L

background bromide levels in fresh‐water

sources be kept at about 0.1 ppm

(Bonacquisti, 2006).

•[Mean Br] which is 1 068 800 ppb; is 1,000

1,020

mg/L

[Mean Br], which is 1,068,800 ppb; is

10,688X the 100 ppb level at which

authorities become concerned.

•Reports from PSWA and other SW PA

980

12345

p 3 Hour Interv

authorities indicate upward trends of

THM’s.Volz, C.D. et al., 2011 http://www.fractracker.org
2‐butoxyethanol in PBT‐Josephine Ef

[Mean 2‐BE] = 59 0 mg/L; σ = 4 9; [Min ] = 49 PA B i Tt [Mean 2‐BE] = 59.0 mg/L; σ = 4.9; [Min.] = 49

mg/L; [Max.] = 66 mg/L; MDL; 0.63 mg/L

• 2‐BE, glycol either, anti‐foaming and anti‐

70

PA Brine Treatmen

12/10/20

2 BE, glycol either, anti foaming and anti

corrosion agent in slickwater formulations.

• ATSDR MRL for oral route, acute exposures is

0.4 mg/kg/day (hematological effects), [UF= 60

65

90]; MRL for oral route, intermediate exposure

is 0.07 mg/kg/day (hepatic) [UF= 1000].

•The derived water MRL’s acute exposure for

55

mg/L 

adult men, adult women, and children are

13.77, 11.53, and 6.09 (mg/L/day), respectively.

•The derived MRL’s for 2‐BE in drinking water for

intermediate exposure for adult men adult

4550

intermediate exposure for adult men, adult

women, and children are 2.41, 2.02 , and 1.07

(mg/L/day), respectively.•[Mean 2‐BE] is 4 28 5 12 and 9 69 X and

40

12345

3 Hour Interva

[Mean 2 BE] is 4.28, 5.12, and 9.69 X and

24.48, 29.21, and 55.14 X the derived acute and

intermediate MRL’s, respectively, for adult

males and females, and children, respectively. Volz, C.D. et al., 20
Chloride in PBT‐Josephine Fa

Effluent

[Mean Cl] = 117,625 mg/L; σ = 3,815; 130,000

PA Brine Treatment Jo

12/10/2010

[Min.] = 111,000 mg/L; [Max.] =

125,000 mg/L; MDL; 1.5 mg/L•[Mean Cl] is 470.5 times the SMCL

f hl d d k f

125,000

or chlorides in drinking water of 250

mg/L.•To protect aquatic communities, the

EPA CMC for chlorides in surface

115,000120,000

mg/L 

EPA CMC for chlorides in surface

water is 860 mg/L, and the EPA CCC

for chlorides in surface water is 230

mg/L 105,000

110,000

mg/L

.

•The [Mean Cl] was 138 times the

CMC and 511 times the CCC. 100,000

105,000

12345

3 Hour Interva

Volz, C.D. et al., 2011 http://www.fractracker.org
Total Dissolved Solids (TDS) in 

Josephine Facility Effluen

• EPA SMCL for TDS in drinking

PA Brine Treatment Jos

12/10/2010

water is 500 mg/L; the mean

concentration of TDS in effluentwater is 373 times the SMCL.

187,000.00189,000.00191,000.00 12/10/2010

• It should be noted that new or

expanded discharges of TDS in

Pennsylvania are limited to

di h i l 00 / f S

183,000.00185,000.00

mg/L

discharging only 500 mg/L of TDS

as a monthly average.

• The DEP permit allows the PBT‐

J hi l di h

179,000.00181,000.00

mg/L 

Josephine plant to discharge

unlimited levels of chloride and

TDS into Blacklick Creek, and only

requires monitoring and

175,000.00177,000.00

123456

requires monitoring and 3 Hour Intervals

reporting of these discharges.

3 Hour Intervals

http://www.fractracker.org
•TDS and Cl levels from Kriged Interpolation indicate potential for Go

bloom in Blacklick Creek

St fl d i S t b 2010 h d l f 25 f

Volz, C.D. et al., 2011 http://www.fractracker.org

•Stream flow 

during 

Septem

ber 2010 reac

h

e

d a low of 25 cfs.
Volz, C.D. et al., 2011
Volz, C.D. et al., 2011
Volz, C.D. et al., 2011
Volz, C.D. et al., 2011
Volz, C.D. et al., 2011
Environmental Public Health

Recommend i at ons

• Operations at this plant should be halted until all contaminants 

and aquatic health concern in accepted oil and gas fluids are kn

can be determined that the treatment processes used at the p

effectively remove these contaminants from the fluids being tr

• The PA DEP should reevaluate the permit given to this operato

clearly allows for chlorides and total dissolved solids to be disc

levels exceeding aquatic health criteria.

• All approaches to the effluent discharge area and a reasonable 

downstream (at least 100 meters) from streamside and landsid

posted with warning signs. These signs should discourage any u

and/or contact wi ht stream water.

• An advisory to all anglers should be issued stating that fish take

stream, both up and down stream may be contaminated in ord

discourage fi hs take and consumption.
Environmental Public Health

Recommend i at ons

• Studies to determine the levels of all potential Marcellus Shale 

fluid contaminants in downstream water, sediments and pore w

should be undertaken immediately.

• Residential and other private well water users downstream of t

outfall of the PBT‐Josephine Facility should be advised that the

contaminants in their well water and discouraged from using it 

drinking, cooking or bathing until such water is tested for conti

use.

• Municipal water authorities downstream of this outfall should 

of the contaminants found in effluent from the PBT‐ Josephine 

other possible contaminants in M ll arce us Sh l a e fl b k ow ac fl id u s 

gas wastewater, and that there are other treatment facilities an

in the Blacklick, Conemaugh, and Kiskikiminetas drainages that 

discharge discharge oil and gas waste fluids into surface surface water.
Environmental Public Health

Recommend i at ons

• All municipal water authorities at reasonable distances downst

“brine treatment” and POTW’s accepting Marcellus Shale flow

and other oil and gas wastewater in the region extending eastw

Ohio, Pennsylvania and West Virginia and New York should be 

these results.

• The PA DEP and other state and federal regulatory authorities s

immediately review all surface water discharge permits grante

treatment f ili i facilities and PO ’ TW s that accept Marcellus Sh l a e fl 

o

fluids and oil and gas wastewater, to ensure that 2‐BE concentr

being discharged are below all applicable standards, guidelines 

criteria criteria. This review should be informed informed by results results of this repor

should be extended to all known contaminants in flowback and 

and gas wastewater.