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The world leader in serving science

Carl Fisher

Application Chemist/Marketing Specialist

Ion Chromatography/Sample Preparation

Thermo Fisher Scientific

Sunnyvale, CA

Analysis of Anions and Cations in Produced Water from Hydraulic Fracturing Using Ion Chromatography

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http://stateimpact.npr.org/texas/tag/fracking/

Hydraulic Fracturing (Fracking)

Flowback and

Produced

Water

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Environmental Impact of Hydraulic Fracturing

• Challenges

• Potential for contamination of water, soil, and air

• Compliance to clean water act and shale gas regulations

• Optimization of fracturing processes

• Solution

• Water quality monitoring

• Anion and cations

• Metals

• Organics

• Radiation

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Hydraulic Fracturing Workflow

Well 1

Desalination

Frack Chemicals Pre-Injection Site

assessment

Recycle

Flowback / Produced

Brin

es

Waste

Disposal

Deep Well

Injection

Gas Production

Monitoring Well Monitoring Well

Frack Chemicals

Well 2

Water

Fresh Water

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Hydraulic Fracturing Workflow Monitoring

Inorganic

Organic

Metals

Anions

Surfactants

Cl-, Br-, SO4-

IC, Discrete Analyzer

Ethoxylated phenols, acrylamide

LC-MS/MS, LC-CAD

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

IC, AAS, ICP-OES, ICP-MS, HR-ICP-MSCations

Analy

tes

Radiation

Water Chemistry

Sediments HF Water

Composition

Frack Design

Flowback and

Produced WaterSite Monitoring

Natural Gas Methane, BTEX

GC

Gross Alpha, Beta, Gamma, Radium 226, 228

GM, 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

Instrumentation

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Analytes in Wastewater Measured by IC

• Inorganic anions

• Chloride

• Impacts effectiveness of additives (reuse)

• Disrupts nitrification processes

• Bromide

• Ozonation, chlorination -> disinfection by-products: brominated

trihalomethanes, bromate

Carcinogenic

• Sulfate

• Can disrupt anaerobic digestion processes

• Organic acids

• Formic and acetic acids

• pH balance is important for efficient fracking

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Analytes in Wastewater Measured by IC

• Cations

• Potassium, sodium

• Impacts effectiveness of additives (reuse)

• Lithium

• Human toxicity

• Ammonium

• Corrosive

• Magnesium, calcium, barium, strontium

• Scale buildup

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Challenge of Wastewater Analysis

High concentrations of dissolved salts:

• Exceed column capacity

• Poor chromatography

• Peak suppression

• Inaccurate reporting

• Exceed linear calibration range

• Analyte specific

• Inaccurate results

• Decrease column lifetime

0 2 4 11

0

12,000

µS

Minutes

6 8 10

0

50

µS

0 2 4 116 8 10

Minutes

Undiluted

Diluted

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Obtaining Accurate Data From High Salt Samples

Manual Analysis

• Post-run

• Determine concentration from chromatogram peak area

• Exceed limit → dilute → re-run sample

• Pre-run

• Manual conductivity measurement

• Exceed limit → dilute → run sample

• Tedious

• Dilution prone to errors

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Obtaining Accurate Data From High Salt Samples

Automated Analysis

• “AutoDilution”

• Post-run analysis using ion chromatograph software

• Exceeding peak height or area -> re-run with less sample loaded

• In-line Conductivity

• Conductivity measured prior to loading sample onto column

• Exceeding upper limit -> less sample loaded

Less Sample

• Smaller sample loop

• Partial loop

• Automated sample dilution

• Lower amount of sample loaded

Thermo Scientific™

Dionex™ Chromeleon™

Chromatography Data

System (CDS) Software

Thermo Scientific™

Dionex™

AS-AP Autosampler

+

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Automated Dilution: Precision and Accuracy

Draw/Dispense

Speed

(μL/sec)

Set Volume

(µL)

Liquid

Dispensed

(µg)

%RSD %Accuracy

50/25 4950 4926.9 0.0032 99.5

50/25 1980 1968.9 0.0747 99.4

10/5 50 50.5 0.38 99.0

10/5 20 20.1 0.67 98.4

N = 10 injections

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www.getmoneyenergy.com/wp-content/uploads/2010/01/shale-gas-basins-in-usa.jpg

Wastewater Locations

CA

TX

ND

Produced

Water

(Formation)

Flowback

Water

(Fracking

fluid +

Formation)

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Chloride is the Primary Anion in Produced Water

Column: Thermo Scientific™ Dionex™ IonPac™

AG18/AS18 columns, 2 mm i.d.

Eluent Source: Thermo Scientific Dionex EGC KOH

cartridge

Gradient: 15 mM KOH (0–3 min)

15–29 mM KOH (3–4 min)

29 mM KOH (4–12 min)

15 mM KOH (12–17 min)

Flow Rate: 0.25 mL/min

Inj. Volume: 2.5 µL

Col. Temp.: 30 °C

Detection: Suppressed conductivity

Sample: A: Standard

Produced water, filtered, diluted

B: 50-fold dil. TX

C: 200-fold dil. CA

D: 500-fold dil. ND

0

430

µS

Minutes

5

4

6

7

4 80 6 12

1

23

AB

102

CD

µS µS

1.0

0118.8

Minutes

1.0

0

Minutes

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4.33.2 Peaks:

A B C D

1. Fluoride 0.4 mg/L 0.078 -- --

2. Acetate 0.4 0.88 0.020 0.048

3. Formate 0.4 0.070 0.057 0.058

4. Chloride 16 160 260 380

5. Carbonate -- -- -- --

6. Bromide 0.4 0.66 0.13 1.7

7. Sulfate 0.4 0.39 0.54 0.36

8. Nitrate 0.4 -- -- --

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Total Anion Concentrations in Produced Water

Concentration (mg/L)

Texas California North Dakota

Fluoride 3.9 -- --

Acetate 44 4.0 24

Formate 3.5 11 29

Chloride 8,000 52,000 190,000

Bromide 33 26 850

Sulfate 20 110 180

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Comparison of Anions in Produced and Flowback Water

0

20,000

40,000

60,000

80,000

100,000

120,000

140,000

160,000

180,000

200,000

Con

ce

ntr

atio

n (

mg

/L)

TX

CA

ND

MarcellusFB (F10)

0

100

200

300

400

500

600

700

800

900

Con

ce

ntr

atio

n (

mg

/L)

Ion composition → variability based on geology

Produced

Water

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Sodium is the Primary Cation in Produced Water

Column: Dionex IonPac CG16/CS16

columns, 0.5 mm i.d.

Eluent Source: Thermo Scientific Dionex EGC-MSA

(capillary) cartridge

Gradient: 20–30 mM MSA (0–10 min)

30–55 mM MSA (10–18 min)

55 mM MSA (18–34 min)

20 mM MSA (34–40 min)

Flow Rate: 0.010 mL/min

Inj. Volume: 0.4 µL

Col. Temp.: 40 °C

Detection: Suppressed conductivity

Sample: Produced water, diluted, filtered,

A: 50-fold dil. TX

B: 200-fold dil. CA

C: 1000-fold dil. ND

0

280

µS

Minutes

54

6

7

10 200 15 30

1

2

3

AB

255

C

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Peaks:

A B C

1. Lithium 0.28 mg/L -- 0.049

2. Sodium 86 140 92.0

3. Ammonium 1.0 0.088 3.7

4. Potassium 1.3 0.64 6.2

5. Magnesium 0.48 2.7 1.6

6. Calcium 10.0 11.0 21.0

7. Strontium 0.25 -- 0.53

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Total Cation Concentrations in Produced Water

Concentration (mg/L)

Texas California North Dakota

Lithium 14.0 -- 49

Sodium 4,300 28,000 92,000

Ammonium 50.0 18.0 3,700

Potassium 65.0 130 6,300

Magnesium 24.0 540 1,600

Calcium 500 2,200 21,000

Strontium 13.0 -- 530

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Comparison of Cations in Produced and Flowback Water

0

10,000

20,000

30,000

40,000

50,000

60,000

70,000

80,000

90,000

100,000

Con

ce

ntr

atio

n (

mg

/L)

TX

CA

ND

MarcellusFB (F10)

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000C

on

ce

ntr

atio

n (

mg

/L)

0

50

100

150

200

250

300

350

400

Co

nce

ntr

atio

n (

mg

/L)

Ion composition → high variance → treatment and reuse

PW

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Conclusion

• Produced water can be challenging to analyze

• Geology influences relative ion concentrations

Automated sample pre-screening and dilution

Accurate and consistent determination of anions,

organic acids, and cations

Formulate wastewater treatment and reuse strategy

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Technical and Application Notes

• TN 139: Determination of Anions in Fracking Flowback Water

From the Marcellus Shale Using Automated Dilution and Ion

Chromatography

• AN 1094: Determination of Cations in Hydraulic Fracturing

Flowback Water from the Marcellus Shale

• AN 1105: Determination of Anions and Cations in Produced

Water from Hydraulic Fracturing

www.thermoscientific.com/ic

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RFIC

Thermo

Scientific Dionex

ICS-900 System

Thermo

Scientific Dionex

ICS-1100

System

Thermo Scientific™

Dionex™

ICS-4000 Capillary

HPIC™ System

Dionex

ICS-2100 RFIC

System

Thermo Scientific

Dionex

ICS-1600 System

Thermo Scientific™ Dionex™ ICS-5000+ HPIC™ System

HPIC

The Dionex Ion Chromatography Product Line

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Thank you!

OT71343-EN 1014S.