1

The world leader in serving science

Art Fitchett

Director of NASS Operations and Compliance

Chromatography and Mass Spectrometry

Thermo Fisher Scientific

Bannockburn, IL

Analysis of Cations in Hydraulic Fracturing Flowback Water from the Marcellus Shale Using Ion Chromatography

2

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

3

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

4

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

Wastewater

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

5

Analytes in Flowback 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

6

Superior Resolution Using 4 µm Particle Size Capillary Columns

Dionex IonPac AS11-HC-4µm (0.4 × 250 mm Column)

Column: Thermo Scientific™ Dionex™

IonPac™ AG11-HC-4µm/

AS11-HC-4µm (0.4 × 250 mm)

Eluent Source: Thermo Scientific Dionex

EGC-KOH Cartridge (Capillary)

Eluent: 1 mM KOH for 0.01 min,

1–5 mM KOH in 15 min;

5–55 mM KOH in 25 min

Flow Rate: 15 µL/min

Inj. Volume: 0.4 µL

Temperature: 30 °C

Detection: Suppressed Conductivity,

Thermo Scientific™ Dionex™

ACES™ 300 Anion Capillary

Electrolytic Suppressor, recycle

mode

400 10 20 30-2

20

µS

Minutes

1

2

34

56

7

8

9

10

11 12

1314

15

1617

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

3637

38

39

40

1. Quinate

2. Fluoride

3. Lactate

4. Acetate

5. 2-Hydroxybutyrate

6. Propionate

7. Formate

8. Butyrate

9. Methylsulfonate

10. Pyruvate

11. Isovalerate

12. Valerate

13. Monochloroacetate

14. Bromate

15. Chloride

16. 2-Oxovalerate

17. Nitrite

18. Ethylphosphate

19. Trifluoroacetate

20. Bromide

21. Nitrate

22. Citramalate

23. Malate

24. Carbonate

25. Malonate

26. Citraconitate

27. Maleate

28. Sulfate

29. ɑ-Ketoglutarate

30. Oxalate

31. Fumarate

32. Tungstate

33. Phosphate

34. Phthalate

35. Arsenate

36. Citrate

37. Chromate

38. Isocitrate

39. cis-Aconitate

40. trans-Aconitate

7

Fast Run on the Dionex IonPac AS18-4µm Column

0 1 2 3 4 5

-0.5

5.5

µS

Minutes

1

2

3

4

5 67

Column: Dionex IonPac AS18-4µm, 0.4 × 250 mm

Eluent Source: Dionex EGC-KOH Cartridge (Capillary)

Eluent: 35 mM KOH

Flow Rate: 30 µL/min

Inj. Volume: 0.4 µL

Col. Temp.: 30 °C

IC Cube Temp.: 15 C

Detection: Suppressed conductivity,

Dionex ACES 300 Suppressor, recycle

mode

Peaks: 1. Fluoride 0.2 mg/L (ppm)

2. Chloride 0.5

3. Nitrite 1.0

4. Sulfate 1.0

5. Bromide 1.0

6. Nitrate 1.0

7. Phosphate 2.0

8

Analytes in Flowback Wastewater Measured by IC

• Cations

• Potassium, sodium

• Impacts effectiveness of additives (reuse)

• Lithium

• Human toxicity

• Ammonium

• Corrosive

• Magnesium, calcium, barium, strontium

• Scale buildup

9

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

10

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

11

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

Injecting Less Sample

• Smaller sample loop

• Partial loop

• Automated sample dilution

• Lower amount of sample loaded

Thermo Scientific™

Dionex™

Chromeleon™

Chromatography Data

System (CDS) Software

12

Automated Dilution: Precision and Accuracy

Cl (g/L) Avg. %RSD

2 6545 0.058

0.02 683.1 0.034

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 = 5 injections

N = 10 injections

13

Using a Gradient for Faster Cation Separation

Column: Dionex IonPac CG16/CS16

columns, 5 mm i.d.

Eluent Source: Dionex EGC III MSA

cartridge

Eluent (A): 30 mM MSA

Gradient (B): 20–30 mM MSA (0–10 min)

30–55 mM MSA (10–18 min)

55 mM MSA (18–32 min)

20 mM MSA (32–38 min)

Flow Rate: 1 mL/min

Inj. Volume: 25 µL

Col. Temp.: 40 °C

Detection: Suppressed conductivity,

Thermo Scientific™ Dionex™

CERS™ 500 Cation Eletrolytically

Regenerated Suppressor,

recycle mode

Sample: Mix of standards

0

2.9

µS

Minutes

1 2

35

46

7

8

0 30 6010 40 50

1 2

3

54

6

7

8

A

B

20

Peaks:

1. Lithium 0.1 mg/L 5. Magnesium 0.5

2. Sodium 0.4 6. Calcium 1.0

3. Ammonium 0.5 7. Strontium 5.0

4. Potassium 1.0 8. Barium 5.0

14

High Resolution Cation Analysis Using a DionexIonPac CS16 Column at Different Flow Rates

Minutes

µS

A

B

0 40-1

7

1 2 3

4

5

20

6 C

10 µL/min 1200 psi

20 µL/min 2400 psi

30 µL/min 3600 psi

Column: Dionex IonPac CS16,

2 x 250 mm x 0.5 mm ID

Eluant: 30 mmol/L MSA (EG)

Flow rate: A: 10 µL/min

B: 20 µL/min

C: 30 µL/min

Inj. volume: 0.4 µL

Temperature: 40 °C

Detection: Suppressed conductivity

Thermo Scientific™ Dionex™

CCES™ 300 Cation Capillary

Electrolytic Suppressor,

AutoSuppression, recycle

mode

Peaks: 1. Lithium 0.5 mg/L

2. Sodium 2.0

3. Ammonium 2.5

4. Potassium 5.0

5. Magnesium 2.5

6. Calcium 5.0

15

Determination of Cations in Flowback Wastewater

Column: Dionex IonPac CG16/CS16 columns,

5 mm i.d.

Eluent Source: Dionex EGCIII MSA cartridge

Gradient: 20–30 mM MSA (0–10 min)

30–55 mM MSA (10–18 min)

55 mM MSA (18–32 min)

20 mM MSA (32–38 min)

Flow Rate: 1 mL/min

Inj. Volume: 25 µL

Col. Temp.: 40 °C

Detection: Suppressed conductivity,

Thermo Scientific™ Dionex™ CERS™

500 Cation Electrolytically

Regenerated Suppressor, recycle

mode

Sample: 100-fold diluted flowback water, filtered,

0.2 µm

0

6.8

µS

Minutes

0 5 10 25

0

475

µS

Minutes

3

1

2

3

4

5

15

5

4

1

2

6

20

67

8

7 8

32

0 5 10 2515 20 32

30

30

Peaks:

Measured Undiluted

1. Lithium 0.33 mg/L 33 mg/L

2. Sodium 330.0 33,000

3. Ammonium 1.8 180

4. Potassium 5.9 590

5. Magnesium 13.0 1,300

6. Calcium 130.0 13,000

7. Strontium 14.0 1,400

8. Barium 2.1 210

16

Change in Cation Concentration of Flowback Water

0

5,000

10,000

15,000

20,000

25,000

30,000

35,000

40,000

45,000

1 2 3 4 5 6 7 8 9 10

Co

nce

ntr

atio

n (

mg

/L)

Fraction

Sodium

Calcium

0 gallons 140,000

17

Change in Cation Concentration of Flowback Water

0

200

400

600

800

1,000

1,200

1,400

1,600

1,800

2,000

1 2 3 4 5 6 7 8 9 10

Con

ce

ntr

atio

n (

mg

/L)

Fraction

Strontium

Magnesium

Potassium

0

50

100

150

200

250

300

350

400

1 2 3 4 5 6 7 8 9 10

Con

ce

ntr

atio

n (

mg

/L)

Fraction

Barium

Ammonium

Lithium

Ion composition → wastewater reuse or treatment

18

Conclusion

• Wastewater containing high salt can be challenging to

analyze

Automated sample pre-screening and dilution

Accurate and consistent determination of anions,

organic acids, and cations

Formulate wastewater reuse or treatment strategy

19

Technical and Application Notes

• TN 138: Accurate and Precise Automated Dilution and In-line

Conductivity Measurement Using the AS-AP Autosampler

Prior to Analysis by Ion Chromatography

• 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

www.thermoscientific.com/ic

20

Thank you!

OT71277-EN-0814S.