Inorganic Geochemistry of Pennsylvania

Marcellus Flowback Waters

Carl S. Kirby

Department of Geology

Di t rec or, BU M ll arce us Sh l a e I iti ti Initiative

http://www geosc http://www.geosc.marcellus.html

Acknowledgments:

Molly Pritz ’10 for chemistry data

Luke Swenson ‘11 for Conductivity research

Scott Lunde ’12 and Garyn Tate ‘12 for data mining

BU Ei l C (L F di ) &

Photos from N

BU Environmental Center (Luce Foundation) &Katherine Mabis McKenna Foundation

Degenstein FoundationForum for Pennsylvania Heartland

US EPA Hydraulic F
Bucknell MSI Database

http://www.bucknell.edu/script/environmentalcenter/marcellus/defa
Slickwater Slickwater + Oil Field Brine (+/dissolut

(+/dissolut

flowback water

slickw

Flowb

ater

ack water

Oil fieldbrine
Flowback water must be stored

t td ranported, and then t td rea e or reij 

n 

Photos from Molly Pritz ’10
Marcellus core section with

salt blebs along bedding bedding

From Blauch et al., 2009
Marcellus Flowback Water Geoch

D t S

• 5 Bradford County, PA, wells

Data Sources:

y, ,

• Data from energy companies provided to a private

wastewater treatment facility

• Data from energy companies provided to a private wawater hauler• Data provid de by energy companies to the PA Dept of

Env Protection as required yearly by Form 26R (PA DEP,2010)

• Data from a report prepared for the Marcellus Shale

Coalition (Hayes, 2009)

• Data from Blauch et al., (2009).
Marcellus Flowback Water Geoch

•Na/Ca/Cl dominated• High TDS, Specific Conductance• Often have very hi hg Ba, Sr

• Most are radioactive

• Low Mg, SO4• Near‐neutral pH• Endocrine disruptors?? Other

organics
Marcellus fracwater has

distinctive Na/ / Ca Cl signature

Some of the fracwaters

are 1/3 solids!
Marcellus Flowback Water Geoch
Volume of flowback water versus time of flowback from Marc

1000000 88%

800000

ons

48%

600000

flowback, gallo

15%

19%

22%

200000400000

Volume off

53%

65%

0

200000

0 20 40 60 80

31%

0 20 40 60 80

Time of flowback, days

Data are from four horizontal and four vertical wells in Hayes (2009)

that had data for 0 (injected water), 1, 5, 14, and 90‐day flowback.
70000 2000

Salinity increases with flowback tim

10001200140016001800

30000400005000060000

tion SO4, mg/L ration, mg/L

Na CaCl SO4

0

200400600800

0

1000020000

30000

Concentrat

Concentr

0 5000 10000 15000

Flowback, barrels

100015002000

mg/L

ba SrMg K

0

500

1000

Concentration,

‐500

0

0 5000 10000 15000

Flowback, barrels

Da

Bla

Some clear correlations with TDS

y = 0.0253x + 102.77

R2 = 0.8177 8000

Some lack enough data 

y = 0.5883x + 3967.5

R2 = 0.9013

6000080000

100000120000140000160000180000

oncentration, mg/L Cl 2000 3000 4000 5000 6000 7000

8000

oCuires/L

Gross Beta

0

2000040000

60000

0 50000 100000 150000 200000 250000 300000

Co

TDS, mg/L

-1000

0

1000

0 50000 100000 150000 

,pico

TDS, mg/L

Some mixed correlations with TDS

y = 0.0159x + 18.274

R2 = 0.587

400050006000

tration, mg/L Sr 20000 25000

30000

tration, mg/L Ba

0

100020003000

0 50000 100000 150000 200000 250000 300000

Concent

y = 0.036x + 361

R2 = 0.2814

0

5000

1000015000

0 50000 100000 150000 

Concent

TDS, mg/L TDS, mg/L

Volatile Dissolved Solids may suggest organic com

that can complex metals such as Ba

250000

/L

Dissolved Solids

150000200000

tration, mg/

Volatile Dissolved Solids Fixed Dissolved Solids

50000

100000

olids concent

0

12345

So

f

Well, 

Bradford County 

Western PA Acid Mine Drainage

n

Western/Central PA Produced Waters

MarcellusFlowback

Venango Brine

n

+10 20 30 40 50 60 70 80 90 100 110 120 1

εSW

g

Sr

Chapman, Capo, Stewart
Alkalinity
Geochemical modeling (PHREEQCI)
SI Barite Conc Of SO 2‐ vs Temperat

Geochemical modeling (PHREEQCI)

SI Barite, Conc. Of SO4 vs. Temperat
pH SI Gases vs T

Geochemical modeling (PHREEQCI)

pH, SI Gases vs. T
Radiation in flowback waters

2000025000

, pCi/L North Central PA, known location, n=8 private waste water hauler, n=3

15000

adiation, private treatment facility, n=7

5000

10000

Alpha Ra

0

5000

0 100000 200000 300000 

Gross A

0 100000 200000 300000 

Total Dissolved Solids, mg/L
14000

Radiation in flowback waters

1200014000

/L

North Central PA, known Location, n=8private waste water hauler, n=3

8000

10000

ion, pCi/private treatment, n=7

40006000

a Radiati

0

2000

0 100000 200000 300000 

oss Beta

0 100000 200000 300000 

Gr

Total Dissolved Solids, mg/L
4500

35004000 226Ra

228Ra

250030003500

Ra, pCi/L228Ra

15002000

6Ra/228

R

500

1000

226

0

0 100000 200000 300000 

Total Dissolved Solids, mg/L
Will increases in stream

conductivity tell us we hav

M ll arce us “l k ea ”?

Not consistently.


AMD and road salt can cause high conductivity. Can we 

Marcellus “leaks” from them with conductivity?

Cl ‐ Marcellus & road salt?

Br – Marcellus?

SO4 – Mine Drainage?
Potential Lack‐of‐Mixing Problems:

Placement of conductivity meters

Susque
Q ti ? uestions

?

Actual and

Potential Impacts
Bucknell University Marcellus Shale Initiative Go

• Fund research in physical & social sciences, engineering, and humawill benefit all stakeholders.• Comprehensive, objective web-based clearinghouse for:

• accurate and verifiable (i.e., peer-reviewed) scientific informatio• annotated non-scientific information from industry, regulatory agand web media, environmental groups, citizens’ groups

• hyperlinked• organized• searchable• critically evaluated

• Facilitate teaching and additional outreach efforts
Marcellus Shale in Outcrop

http://www.geosc.psu.edu/~engelder/marcellus/marcellus.html
Outline

• What & Where is the Marcellus Formation?• Formation of the Marcellus & Natural Gas

• Horizontal Natural Gas Drilling

• Location of Drilling Activity in PA

Characterization of waters Chemical signature signature of fracwater fracwaterMonitoring? Discharge and conductivity with time

 Discharge vs. conductivity curves – hysteresis

 Mass balance modeling

 Problems associated with poor mixing

Actual and Potential Environmental Impacts

Perspective
Could be Marcellus‐influenced
• Inadequate coverage:

8 of 99 USGS gaging stations in PA measureSC. These are on larger streams.

• Data Gaps:

Two years of hydrographs from 9 (7 in the

Marcellus region) gaging stations that collect

SC data showed gaps in SC data between between 4

and 71% of the time for individual stations.

• Hysteresis:

Plots of SC vs. Q for several time periods

show considerable & variable hysteresis

effects dependent upon the stream chosen

and antecedent hydrologic conditions.
6.1 Water Resources

•6.1.1 Water Withdrawals

•6.1.1.1 Reduced Stream Flow

•6112 Degradation of a Stream’s Best Use

New York State SGEIS considers

the following potential environme

•6.1.1.2 Degradation of a Stream s Best Use•6.1.1.3 Impacts to Aquatic Habitat•6.1.1.4 Impacts to Aquatic Ecosystems•6.1.1.5 Impacts to Downstream Wetlands•6.1.1.6 Aquifer Depletion

•6.1.1.7 Cumulative Water Withdrawal Impacts

•6.1.2 Stormwater Runoff•6.1.3 Surface Spills and Releases at the Well Pad

•6.1.3.1 Drilling•6.1.3.2 Hydraulic Fracturing Additives•6.1.3.3 Flowback Water

•6.1.4 Groundwater Impacts Associated With Well Drilling and Construction

•6.1.4.1 Turbidity•6.1.4.2 Fluids Pumped Into the Well

•6.1.4.3 Natural Gas Migration

•6.1.5 Hydraulic Fracturing Procedure

•6151 . . . Wellbore Wellbore Failure Failure•6.1.5.2 Subsurface Pathways

•6.1.6 Waste Transport

•6.1.7 Centralized Flowback Water Surface Impoundments

•6.1.8 Fluid Discharges

•6.1.8.1 Treatment Facilities

•6.1.8.1 Disposal Wells

•6.1.9 Solids Disposal

•6.1.9.1 Naturally Occurring Radioactive Material (NORM) Considerations ‐ Cuttings

•6.1.9.2 Cuttings Volume•6.1.9.3 Cuttings and Liner Associated With Mud‐Drilling

•6.1.10 Potential Impacts to Subsurface NYC Water Supply Infrastructure

•6.1.11 Degradation of New York City’s Drinking Water Supply
New York State SGEIS considers

the following potential environment

6.2 Floodplains6.X Primary and Principal Aquifers6.3 Freshwater Wetlands

6.4 Ecosystems and Wildlife

•6.4.1 Invasive Species

•6.4.1.1 Terrestrial

•6.4.1.2 Aquatic

•6.4.2 Centralized Flowback Water Surface Impoundments
New York State SGEIS considers

The following potential environme

6.5 Air Quality •6.5.1 Regulatory Analysis

•6.5.1.1 NOx ‐ Internal Combustion Engine Emissions

•6512 . . . Natural Natural Gas Production Production Facilities Facilities NESHAP 40 CFR Part 63, Subpart Subpart HH (Glycol (Glycol•Dehydrators)•6.5.1.3 Flaring Versus Venting of Wellsite Air Emissions

•6.5.1.4 Number of Wells Per Pad Site

•6.5.1.5 Emissions Tables

•6.5.1.6 Offsite Gas Gathering Station Engine

•6.5.1.7 Natural Gas Condensate Tanks

•6.5.1.8 Potential Emission of Fracturing Water Additives from Surface Impoundments

•6.5.2 Air Quality Impact Assessment

•6.6.1 Greenhouse Gases

•6.6.2 Emissions from Oil and Gas Operations

•6.6.2.1 Vented Emissions

•6.6.2.2 Combustion Emissions

•6.6.2.3 Fugitive Emissions

•663 . . Eii m ss ons Source Ch t i ti Characterization

•6.6.4 Emission Rates

•6.6.5 Drilling Rig Mobilization, Site Preparation and Demobilization

•6.6.6 Completion Rig Mobilization and Demobilization

•6.6.7 Well Drilling

•6.6.8 Well Completion

•6.6.9 Well Production

6.7 Centralized Flowback Water Surface Impoundments

6.8 Naturally Occurring Radioactive Materials in the Marcellus Sh l a e

6.9 Visual Impacts

6.10 Noise6.11 Road Use
2nd Law of Thermodynamics

“Useful energy is lost in any physical or chemi

transformation”

It takes (fossil fuel) energy to produce energyeach added step makes a fuel less efficient tis used more directly.Greenhouse gasses – how many ft3 of nagas i l ( il l) d i 

equivalent (oil, gas, coal) does it ta

produce 1 ft3 of natural gas?
Slickwater additives

http://www.dec.ny.gov/
Horizontal Drill Rig

Frac jobs take 1‐8 million million gallons gallons of water fro

streams, reservoirs, GW, or reused water

Photos fro
Drilling Activity in Pennsylvania

Map by Carl Kirby from Pennsylvania Spa
How can “leaks” occur?

Hydraulic fracturing operation, h

www.donnan.com well, Bradford County, PA

tiogagaswatch.blo

Transport trucks for water (above) and hydraulic fracturing acid (HCl) (below)
Brine Pit

Courtesy of J. Henry Fair through 
Susquehanna River Basin Commission

Remote Water Quality Monitoring Network

• Plan 30 monitoring stations in PA & NY

• T, pH, conductance, DO, turbidity, stage

R l ea ‐time data on web
Juniata River, 6‐day period

Not in Marcellus region