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Analysis of Flowback Water from Marcellus Unconventional Gas Extraction Using IC and ICP-OES

Richard Jack, Tetiana Kondratyuk, and John Stolz

PITTCON™ Conference & Expo

March 3, 2014

OT70968_E 03/14

2

Hydraulic Fracturing

• Method of extracting energy resources from unconventional

reservoirs, such as coalbeds, shales, and tight sands.

• Pressurized injection of a cocktail of water, chemical

additives, and proppants into geological formations, thereby

fracturing the formation and facilitating the recovery of natural

gas.

• After the fracturing event, the pressure is decreased and the

direction of fluid flow is reversed, allowing fracturing fluid and

naturally occurring substances to flow out of the well bore to

the surface. This mixture of fluids is called flowback.

• The hydraulic fracturing process mobilizes salts, metals, and

radioisotopes from the subsurface and returns hypersaline

flowback water to the surface.

3

Granberg, A. Hydraulic Fracturing Natural Gas, KUHF News for Houston [Online]

http://app1.kuhf.org/userfiles/hydraullic_fracturing_natural_gas.gif (accessed Feb 24, 2014).

Horizontal Drilling and Fracking

4

What is Marcellus Shale?

MoneyEnergy, a Canadian Dividend Investment Blog [Online] www.getmoneyenergy.com/wp-content/uploads/2010/01/shale-gas-basins-in-usa.jpg

(accessed Feb 24, 2014).

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Fracking Solutions

6

In the News

7

Well Injection

What are the possible impacts of the injection and fracturing process on drinking water resources?

8

• Hundreds of chemicals are in fracking solutions.

• The EPA has narrowed the list of compounds down to less than 20.

• The EPA is in the process of developing analytical methods for these

target compounds.

• Most compounds are not toxic

• But, industry is constantly changing which

chemicals are used.

Fracking Solutions

9

For What Are the Fracking Chemicals Used?

10

Injection Fluids

Flowback and

Produced Water

Glycols, Ethoxylated Alcohols, Alcohols, Alcohol Amines,

Amides, Aldehydes, Aromatic Hydrocarbons, Inorganic

Elements, Radionuclides, Halogens

Glycols, Ethoxylated Alcohols, Alcohols, Alcohol Amines,

Amides, Aldehydes, Aromatic Hydrocarbons

Water Use in Hydraulic

Fracturing Operations

EPA Overview of Analytical Method Research

11

Chemical Name Base Method Challenge

Glycols & Related Compounds

(glycol ethers)

SW-846 Methods 8000C and

8321B + ASTM D7731-11

No Standard Method Available

to Cover All Compounds—

Detection Limits Too High

Ethoxylated Alcohols ASTM D7485-09 and ASTM

D7742-11

No Standard Method Available to

Cover All Compounds

Alcohols SW-846 Method 5030 and

8260C

Confirmation in Hydraulic

Fracturing Related Matrices

Alcohol Amines

(diethanolamine,

triethanolamine)

No Standard Method No Standard Method Available

Amides (acrylamide) SW-846 Method 8032A Matrix Interferences and Poor

Extractability

Disinfection Byproducts

(bromide, bromate, THM, HAA,

and N-nitrosamines)

SDWA Methods 521, 551,

and 552 Matrix Interferences

Some Fracking Chemicals

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Chemical Name Base Method Concerns

Aldehydes SW-846 Method 8315

Complex Method, Confirmation in

Hydraulic Fracturing Matrices—

Detection Limits Too High

Aromatic Hydrocarbons SW-846 Methods 5030 and

8260C

Confirmation in Hydraulic

Fracturing Related Matrices

Inorganic Elements SW-846 Methods 6010C and

6020A or CWA 200.7 and 200.8 Matrix Interferences

Radionuclides

(gross alpha and beta) SW-846 Method 9310 Matrix Interferences

Halogens SW-846 Method 9056A Matrix Interferences

† Drinking water methods may be found at http://water.epa.gov/scitech/methods/cwa/index.cfm).

Clean Water Act (CWA) methods may be found at http://water.epa.gov/scitech/methods/cwa/index.cfm.

SW-846 Methods may be found at http://www.epa.gov/wastes/hazard/testmethods/sw846/online/index.htm.

ASTM International may be found at http://www.astm.org/

Some Fracking Chemicals

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• Acrylamide used as friction reducer during hydraulic

fracturing

DeArmond, P.D.; DiGoregorio, A.L. Anal. Bioanal. Chem. 2013, 405, 4159–4166.

• Chromatogram of acrylamide extracted from

produced water

• Separation achieved with Dionex IonPac

ICE-AS1 ion-exclusion column

• Isocratic elution with 50/50 H2O/CH3CN

(0.1% FA)

• Flow rate 0.18 mL min-1

RT = 19.1 min

MDL = 3 ng/L

EPA Analytical Method Development: Acrylamide

• Current EPA Methods 8032A (GC-ECD) and 8316 (HPLC-UV)

• Developed solid-phase extraction (SPE, activated carbon) and

LC-MS/MS-based method to overcome challenges of EPA standard methods.

• Demonstrated in flowback and produced water ranging from 20,000–300,000

mg/L total dissolved solids (TDS).

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Inorganic

Organic

Techniques

Metals

Anions

Surfactants

CL-, Br-, SO4-

IC

Ethoxylated Phenols, Acrylamide

LC-MS/MS

Sr, Ba, Ca, Mn, Ar, etc.

IC, ICP-OES, ICP-MS, HR-ICP-MS Cations

Radiation

Water Chemistry

Basic

Sediments

HF Fluid

Composition

Flowback and

Wastewater Produced

Water

Pre- & Postsite

Monitoring

Natural Gas Methane

GC

Gross Alpha, beta, Gamma, Radium 226, 228

NaI

Isotopes Ratios

Organic Acids

IC

Brines

TDS, Alkalinity, pH, Conductivity, DO

Multiple

13C-CH4 , 18O 87Sr/86Sr

stable gas IRMS HR-ICP-MS, TIMS, MC-ICP-MS

Hydraulic Fracturing Workflows A

naly

tes

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Aspects of Hydraulic Fracturing for Water Quality

• Constituents in shale gas extracted wastewater, such as total TDS, have been

found to be present at concentrations ranging from 280 mg/l to 345,000 mg/l.

• Chloride has been reported in concentrations up to 196,000 mg/l.

• TDS is not significantly removed by most conventional publicly owned treatment

works (POTW) sytems; therefore, pretreatment of the wastewater would be

required prior to discharge to the POTW. However, very little comprehensive data

have been collected nationwide on TDS treatment capability at POTWs.

• Common constituents of TDS include calcium and magnesium (also a measure of

hardness), phosphates, nitrates, sodium, potassium, sulfates, chloride, and even

barium, cadmium, and copper.

• Individual constituents of TDS may result in:

• POTW process inhibition in activated sludge

• Nitrification, and anaerobic digestion processes

• POTWs may exhibit these process inhibitions from these individual constituents

at concentrations that are several magnitudes lower than the composite TDS

found in shale gas wastewater.

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What are the possible impacts of inadequate treatment of hydraulic fracturing wastewater on drinking water resources?

Wastewater Treatment and Waste Disposal

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Environmental Impact of Flowback Waters

• Because there is a significant possibility that shale gas wastewater may:

• Pass through the POTW and cause a permit violation

• Cause interference with the POTW’s operation

• Cause contamination of biosolids

• Acceptance of the waste is not advisable unless it’s effects on the

treatment system are well understood.

• Anions

• Bromide present in source water for drinking water utilities can lead to increased

disinfection byproducts

• Sulfate at 400–1000 mg/L, disrupting anaerobic digestion processes

• Chloride at 180 mg/L, disrupting nitrification processes

• High concentrations of chloride can disrupt biological treatment units

• Cations and Metals

• Toxicity

• Metals can precipitate (scaling) during the treatment process

• Contaminate biosolids and affect sludge disposal in landfills and farms.

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Effect of Increased Bromide on Drinking Water

• Bromide in concentration is 1–3 higher

downstream compared to upstream from

Industrial Waste Plant A.

• Bromide present in source waters results in

increased brominated trihalomethanes.

• Brominated trihalomethanes are more toxic.

• Industrial Waste Plant A is know to treat water

from Marcellus Shale operations. Data courtesy of Stanley States, WQTC, 2011.

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Proposed Colorado Regulations for 300 Series

• Requirements for drilling, completion, production and storage (DCPS)

operations at new oil and gas locations in the intermediate buffer zone

• A. pH

• B. Alkalinity

• C. Specific conductance

• D. Major cations/anions (chloride, fluoride, sulfate, sodium)

• E. Total dissolved solids

• F. BTEX/GRO/DRO

• G. TPH

• H. PAH’s (including benzo(a)pyrene)

• I. Metals (arsenic, barium, calcium, chromium, iron, magnesium, selenium).

Current applicable EPA-approved analytical methods for drinking water must be used and analyses must

be performed by laboratories that maintain state or nationally accredited programs.

• Notification of potentially impacted public water systems within fifteen

stream miles downstream of the DCPS operation prior to commencement

of new surface disturbing activities at the site

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Pennsylvania Regulations for Wastewater from Fracking

• In lieu of the trace analysis described in Subsection b, the chemical

analysis of wastewater produced from the drilling, completion, and

production of a Marcellus Shale or other shale gas must include the

following:

• Additional constituents that are expected or known to be present in the

wastewater.

* Note: All metals reported as total.

Acidity

Alkalinity (Total as CaCO3)

Aluminum

Ammonia Nitrogen

Arsenic

Barium

Benzene

Beryllium

Biochemical Oxygen

Boron

Bromide

Cadmium

Calcium

Chemical Oxygen Demand

Chlorides

Chromium

Cobalt

Copper

Ethylene Glycol

Gross Alpha

Gross Beta

Hardness (Total as

CaCO3)

Iron – Dissolved

Iron – Total

Lead

Lithium

Magnesium

Manganese

MBAS (Surfactants)

Mercury

Molybdenum

Nickel

Nitrite-Nitrate Nitrogen

Oil & Grease

pH

Phenolics (Total)

Radium 226

Radium 228

Selenium

Silver

Sodium

Specific Conductance

Strontium

Sulfates

Thorium

Toluene

Total Dissolved Solids

Total Kjeldahl Nitrogen

Total Suspended Solids

Uranium

Zinc

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Bromide Monitoring

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United States Environmental Protection Agency Environmental Monitoring Systems Laboratory Cincinnati, OH 45268 Office of Research and Development: Revised August 1993

Method 300.0

Determination of Inorganic Anions by Ion Chromatography Revision 2.1

John D. Pfaff

U.S. EPA Method 300.0

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Anion Analysis of a Marcellus Shale Flowback Sample

0.0

0.65

µS

Minutes

0 2 4 8

0

2,400

µS

3 Column: Thermo Scientific™ Dionex™ IonPac™

AG18/AS18, 4 × 250 mm

Eluent Source: Thermo Scientific Dionex EGC III KOH cartridge

Eluent: 39 mM KOH

Flow Rate: 1 mL/min

Inj. Volume: 25 µL

Temperature: 30 °C

Detection: Suppressed conductivity, Thermo Scientific™

Dionex™ ASRS™ 300, recycle mode

1 2

3

4

5

6

0 2 4 8 6

5

4

1 2

Sample: 100-fold fracking flowback water, filtered, 0.2 µm

Peaks: 1. Acetate <5 mg/L

2. Formate <5

3. Chloride 94,000

4. Sulfate 12

5. Bromide 890

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Anion Analysis of Marcellus Shale Flowback by Fraction

0

10,000

20,000

30,000

40,000

50,000

60,000

70,000

80,000

90,000

100,000

F1 F2 F3 F4 F5 F6 F7 F8 F9 F10

Co

nc

en

tra

tio

n (

mg

/L)

Fraction

Cl

Br

Sulfate

Acetate

Formate

0

200

400

600

800

1,000

F1 F2 F3 F4 F5 F6 F7 F8 F9 F10

Co

nc

en

tra

tio

n (

mg

/L)

Fraction

Br

Sulfate

Acetate

Formate

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ICP-OES

26

Three Trace Elemental Techniques That Can Be Used

H

Li

Fr Ra

Sc

Ac

Zr

Hf

Nb

Ta

Tc

Re

Ru

Os

Rh

Ir Hg

In

Tl

Ge

Sb

Bi

S

Te

Po

Cl

F

At

He

Ar

Ne

Kr

Xe

Rn

Pa Pu Am Cm Bk Cf Es Fm Md No Lw Np

Not Measurable

ICP-MS

Unstable Elements

AA/ICP/ICP-MS ICP/ICP-MS

IC

Na

K

Rb

Cs

Be

Mg

Ca

Sr

Ba

Y

La

Ti V Cr

Mo

W

Mn Fe Co Ni

Pd

Pt

Cu

Ag

Au

Zn

Cd

Al

Ga

Sn

Pb

B C O N

Br

I

Si P

As Se

Ce Pr

Th

Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

U

Trace Metal Elements

AA = Atomic Absorption, ICP = Inductively Coupled Plasma, MS = Mass Spectrometry

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Recommended Instrument for Fracking Analysis: ICP-OES

• The inductively coupled plasma optical emission

spectrometer (ICP-OES):

• Offers fast multielement analysis (60+ elements, 1–2 minutes per

sample)

• Is rugged and reliable for clean or dirty liquid samples

• Handles up to 30% dissolved solids

• Has detection capability of 1ppb typically

• Meets EPA water analysis requirements

Thermo Scientific™ iCAP™ 7400 ICP-OES Analyzer

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Handling Interferences with ICP-OES

• There are several types of interference in ICP-OES analysis

• Physical Interference

• High concentrations of dissolved solids contained in the sample reduce plasma

processing power for key analytes and cause excessive deposition on sample

introduction components

• Chemical Interference

• High concentrations of easily ionized elements (EIE) cause no linearity

• Spectral Interference

• False backgrounds are created by the sample matrix, i.e., high acid or salts

• Elements in the sample emit optical lines very close to those being measured

• Best Practices to Overcome These Effects

• Carefully pick the emission lines used to avoid many of the interferences

• Reduce the amount of dissolved solids in your sample

• Matrix match your samples, quality controls, and calibration standards, which

compensates for most matrix effects

• Use an internal standard such as Y, Sc, or Ge to compensate for suppression,

any additional matrix effects and drift.

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The iCAP 7000 Series ICP-OES—Core Components

Plasma

Torch &

Duo

Viewing

Clip-In

Sample

Intro

Systems

Drain

Sensor

CID

Detector

Optical

Design

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iCAP 7000 ASX520 Operating Conditions

Plasma Gas Flow 12 L/min

Auxillary Gas Flow 0.5 L/min

Nebulizer Gas Flow 0.65 L/min

RF Power 1350 watts

Plasma View Axial or Radial

Read Delay 60 s

Pump Speed 70 rpm

Flush Pump Speed 100 rpm

Pump Stabilization Time 7 s

Analysis Mode Speed

Sample Tubing Standard PVC Tubing 0.38 mm i.d.

Drain Tubing Standard PVC Tubing 1.52 mm i.d.

Internal Standard Tubing Standard PVC Tubing 0.76 mm i.d.

Replicates 3

Resolution Normal

Total Acquisition Time 3.30 min

Analysis Time 6 min (Sample to Sample)

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Importance of Baseline Monitoring

• How can we distinguish environmental impact from hydraulic fracturing vs ?

Anion Data for Impoundment Water, Coal Mine Effluent,

and Fresh Stream Water Field Samples

Unit Sample 1 Sample 2 Sample 3 Fonner Run Bates Run

Conductivity µS Cm-3 102,864 61,477 6,400 387 476

Ph 5.38 5.67 7.53 7.91 7.67

Sulfate mg/L 8.64 10.21 3,826 25.07 24.46

Nitrate mg/L ND ND 1.81 0.11 0.58

Bromide mg/L 255 226 14.25 ND ND

Chloride mg/L 30,683 27,700 1,241 1.29 6.00

Arsenic µg/L BDL BDL BDL BDL BDL

ND: Not Detected BDL: Below Detection Limit

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Typical Flowback Samples

33

0.0

10000.0

20000.0

30000.0

40000.0

50000.0

60000.0

70000.0

80000.0

90000.0

0 5 10 15 20 25 30

Chloride by Ion Chromatography

ICS Analyses of Flowback/Produced Water Series

Series # Chloride Bromide Sulfate

FB01 87.9 25.2 450.9

FB02 38278.9 192.0 489.2

FB03 49088.4 233.4 575.6

FB04 47285.3 219.7 562.1

FB05 47431.1 244.0 595.5

FB06 46813.3 242.9 602.4

FB07 53580.3 260.2 567.6

FB08 54137.8 251.5 561.7

FB09 54808.0 296.6 588.8

FB10 58589.9 316.6 602.1

FB11 59795.9 308.9 603.3

FB12 60836.7 352.7 660.8

FB13 65843.7 323.3 587.9

FB14 69910.5 339.2 604.8

FB15 73837.9 360.8 624.0

FB16 74116.3 362.1 611.7

FB17 75931.0 373.2 633.7

FB18 75859.3 356.8 622.6

FB19 77605.7 379.9 613.8

FB20 79845.9 383.0 571.6

FB21 81831.6 256.3 383.8

FB22 77635.4 392.4 538.7

FB23 75376.7 420.8 556.9

FB24 78273.8 442.1 581.3

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Wavelengths Monitored and Viewing Modes Used

Element Wavelength View Element Wavelength View

Al 167.079 {502} Axial P 213.618 {458} Axial

As 189.042 {478} Axial Pb 220.353 {453} Axial

B 208.893 {461} Axial S 182.034 {485} Axial

Ba 234.758 {144} Radial Sb 206.833 {463} Axial

Be 313.042 {108} Axial Se 196.090 {472} Axial

Ca 315.887 {107} Radial Si 251.611 {134} Axial

Cd 226.502 {449} Axial Sn 189.989 {477} Axial

Co 230.786 {446} Axial Ti 323.452 {104} Axial

Cr 357.869 { 94} Axial Tl 190.856 {477} Axial

Cu 224.700 {450} Axial V 311.071 {108} Axial

Fe 259.940 {130} Radial Zn 202.548 {466} Axial

K 769.896 { 44} Radial Li 670.784 { 50} Axial

Mg 279.079 {121} Radial Sr 346.446 { 97} Axial

Mn 257.610 {131} Axial Ag 328.068 {103} Axial

Mo 202.030 {467} Axial Y* 377.433 { 89} Axial/Radial

Na 330.237 {102} Radial Y* 224.306 {450} Axial

Ni 231.604 {445} Axial *internal standard

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Minimum Detection Limits

Element Wavelength (nm) MDL in ppb Element Wavelength (nm) MDL in ppb

Al 167.079 1.24 Mo 202.030 0.66

As 189.042 6.56 Na 330.237 ND

Ag 328.068 2.12 Ni 231.604 1.68

B 208.893 8.98 P 213.618 9.52

Ba 234.758 213.56 Pb 220.353 4.34

Be 313.042 0.08 S 182.034 17.76

Ca 315.887 47.96 Sb 206.833 5.68

Cd 226.502 0.54 Se 196.090 12.06

Co 228.616 1.02 Si 251.611 14.58

Cr 357.869 4.70 Sr 346.446 2.72

Fe 261.187 33.78 Sn 189.989 2.28

K 769.896 497.42 Ti 323.452 1.30

Li 460.286 60.66 Tl 190.856 5.24

Mg 279.079 102.14 V 311.071 2.02

Mn 257.610 0.22 Zn 202.548 0.42

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Typical Flowback Samples

37

ICP-OES Analyses of Produced Water Sample

Element

Flowback Water Sample

5 dilution

(ppm)

Element

Flowback Water Sample

5 dilution

(ppm)

Li 10.23 Ni bdl

B 0.0019 Cu 0.132

Be 154.68 Zn 0.299

Na 40080.28 As 0.079

Mg 544.36 Se 0.035

Al 0.004 Sr 369.35

Si 23.66 Mo 0.316

P 0.237 Ag 0.373

K 3440.28 Cd 0.0006

Ca 5262.58 Sn 0.0201

Ti bdl Sb 0.013

V bdl Ba 4.17

Cr 0.035 Tl 0.0304

Mn 1.93 Pb 0.0528

Fe 30.56 S 302.95

Co bdl

38

0

2000

4000

6000

8000

10000

12000

14000

0 5 10 15 20

Ca ICP-OES

0

50

100

150

200

250

300

0 5 10 15 20

Ba ICP-OES

0

5000

10000

15000

20000

25000

30000

35000

0 5 10 15 20

Na ICP-OES

0

200

400

600

800

1000

1200

1400

1600

1800

2000

0 5 10 15 20

Sr ICP-OES

ICP-OES Analyses of Flowback/Produced Water Series

39

0

2

4

6

8

10

12

14

16

0 5 10 15 20

Mn ICP-OES

0

200

400

600

800

1000

1200

1400

0 5 10 15 20

Mg ICP-OES

0

100

200

300

400

500

600

700

0 5 10 15 20

K ICP-OES

ICP-OES Analyses of Flowback/Produced Water Series

40

0

50

100

150

200

250

300

350

400

450

500

0 5 10 15 20

Sr ICP-OES

Sr ICP-MS

0

100

200

300

400

500

600

700

0 5 10 15 20

Mg ICP-OES

Mg ICP-MS

0

0.5

1

1.5

2

2.5

3

0 5 10 15 20

Mn ICP-OES

Mn ICP-MS

0

1000

2000

3000

4000

5000

6000

7000

8000

0 5 10 15 20

Ca ICP-OES

Ca ICP-MS

Comparison of Flowback Water Series Analyzed by

ICP-OES and ICP-MS

41

0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20

Fe ICP-OES

Fe ICP-MS

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0 5 10 15 20

As ICP-OES

As ICP-MS

Comparison of Flowback Water Series Analyzed by

ICP-OES and ICP-MS

Arsenic Determination (ppm)

Sample ICP-OES ICP-MS

Impoundment 1 0.033 0.527

Impoundment 2 0.029 0.800

Mono Lake 18.535 15.867

42

Comparison of Flowback Water and Impoundment

Water Analyzed by ICP-OES

Element

Flowback Sample

5 Dilution

(ppm)

Impoundment

5 Dilution

(ppm)

Element

Flowback Sample

5 Dilution

(ppm)

Impoundment

5 Dilution

(ppm)

Li 10.23 37.52 Ni Bdl bdl

B 0.0019 4.72 Cu 0.132 0.004

Be 154.68 bdl Zn 0.299 0.110

Na 40080.28 15907.95 As 0.079 0.005

Mg 544.36 582.63 Se 0.035 0.032

Al 0.004 0.027 Sr 369.35 804.58

Si 23.66 12.08 Mo 0.316 0.011

P 0.237 0.316 Ag 0.373 bdl

K 3440.28 194.23 Cd 0.0006 bdl

Ca 5262.58 5613.82 Sn 0.0201 na

Ti Bdl 0.167 Sb 0.013 bdl

V Bdl bdl Ba 4.17 103.55

Cr 0.035 bdl Tl 0.0304 bdl

Mn 1.93 3.11 Pb 0.0528 0.017

Fe 30.56 3.80 S 302.95 11.93

Co bdl bdl

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Analysis of Certified Groundwater Reference Material

ERM CA 615 Certified Amount ICP-OES % ICP-MS %

As (ppb) 9.92 9.42 95.0 9.49 95.7

Fe (ppm) 5.107 4.89 95.8 5.107 100

Pb (ppb) 7.11 9.9 139.2 6.92 97.3

Mn (ppb) 107.4 123.6 115.1 101.4 94.4

Ni (ppb) 25.27 27.4 108.4 23.05 91.2

44

Comparison of Flowback Water, Impoundment Water,

and Well Water

Element

Flowback

Sample

5 Dilution

(ppm)

IMP

5 Dilution

(ppm)

Well Water

w/out

Dilution

(ppm)

Element

Flowback

Sample

5 Dilution

(ppm)

IMP

5 Dilution

(ppm)

Well Water

w/out

Dilution

(ppm)

Li 37.52 10.23 0.024 Ni bdl bdl bdl

B 4.72 0.0019 0.00006 Cu 0.004 0.132 0.005

Be bdl 154.68 0.148 Zn 0.110 0.299 0.006

Na 15907.95 40080.28 30.62 As 0.005 0.079 0.003

Mg 582.63 544.36 13.37 Se 0.032 0.035 0.015

Al 0.027 0.004 0.029 Sr 804.58 369.35 0.29

Si 12.08 23.66 8.84 Mo 0.011 0.316 0.0008

P 0.316 0.237 0.023 Ag bdl 0.373 bdl

K 194.23 3440.28 2.13 Cd bdl 0.0006 bdl

Ca 5613.82 5262.58 50.74 Sn na 0.0201 na

Ti 0.167 bdl 0.029 Sb bdl 0.013 0.005

V bdl bdl bdl Ba 103.55 4.17 0.46

Cr bdl 0.035 bdl Tl bdl 0.0304 bdl

Mn 3.11 1.93 0.409 Pb 0.017 0.0528 0.0013

Fe 3.80 30.56 3.30 S 11.93 302.95 9.35

Co bdl bdl bdl

45

Flowback Water Composition

46

Conclusions

• Flowback and Produced water are multi-phased (particulate/aqueous/organic)

fluids that are characteristically high in total dissolved solids (TDS).

• Inductively Coupled Plasma - Optical Emissions Spectroscopy (ICP-OES)

analysis of several flow back/produced water series indicated a significant

difference from the initial flow back (0-5,000 barrels) to subsequent produced

water samples from the same well.

• The major constituents as detected by ICP-OES were barium, boron, calcium,

iron, potassium, lithium, sodium, strontium, magnesium, manganese

• Comparison of ICP-OES to ICP-MS analyses of the same samples revealed

comparable results for most elements tested (e.g., barium, boron, cadmium,

calcium, lead, lithium, magnesium, manganese, potassium, silcon, sodium,

strontium, titanium, zinc).

• ICP-OES required more sample but less dilution (5X vs 200X) than ICP-MS.

• ICP-OES did not appear to be affected by chloride concentration for arsenic

detection and determination.

• Drinking water well samples could be run undiluted.

47