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The world leader in serving science

Richard Jack, PhD

Vertical Marketing DirectorEnvironmental and Industrial

Leong Ying, PhD

RMSI Global Sales Manager

June 12, 2014

New Techniques for Anions, Cations, and Radioisotope Analysis of Marcellus Shale Flowback Waters

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

Hydraulic Fracturing (Fracking)

FlowbackWastewater

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Environmental Impact of Hydraulic Fracturing

• Problem• Impact of hydraulic fracturing on water, soil and air

• Compliance to clean water act and shale gas regulations

• Protection of drinking water sources

• Optimization of fracturing processes

• Solution• Water quality

• Trace elements

• Chemical analysis

• Radiation monitoring

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Hydraulic Fracturing Workflow

Well 1

Desalination

Frack Chemical Pre-Injection Site assessment

Recycle

Flowback / Produced

Brin

es

Waste Disposal

Deep Well Injection

Gas Production

Monitoring Well Monitoring Well

Frack Chemical

Well 2

Water

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Hydraulic Fracturing Workflow Monitoring

Inorganic

Organic

Metals

Anions

Surfactants

Cl-, Br-, SO4-

IC, Discrete Analyzer

Ethoxylated phenols, acrylamideLC-MS/MS, LC-CAD

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

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

Ana

lyte

s

Radiation

Water Chemistry

Sediments HF Water CompositionFrack Design

Flowback and Wastewater

Produced WaterSite Monitoring

Natural Gas Methane, BTEXGC

Gross Alpha, Beta, Gamma, Radium 226, 228

GM, NaI

Isotopes ratios

Organic acidsIC

Brines

TDS, alkalinity, pH, conductivity, DOmultiple

13C-CH4 , 18O 87Sr/86Sr stable gas IRMS HR-ICP-MS, TIMS, MC-ICP-MS

Instrumentation

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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

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Analytes in Flowback Wastewater Measured by IC

• Cations• Potassium, sodium

• Impacts effectiveness of additives (reuse)

• Lithium • Human toxicity

• Ammonium• Corrosive

• Magnesium, calcium, barium• Scale buildup

• Strontium• Radioactive

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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 4 110

12,000

µS

Minutes6 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

Injecting Less Sample• Smaller sample loop• Partial loop• Automated sample dilution

• Lower amount of sample loaded

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Automated Analysis: AutoDilution

Flowback Wastewater

Centrifugation

Filtration

Automated Sample Dilution

Report

Chromatogram

Thermo Scientific Dionex AS-APAutosampler

No

Yes Does peak area or height exceed

cutoff?

AutoDilution

Thermo Scientific™ Dionex™

Chromeleon™ Chromatography Data

System (CDS) Software

IC System

Thermo Scientific™ Dionex™

ICS-2100 Reagent-Free™ Ion

Chromatography (RFIC™) System

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Automated Analysis: In-line Conductivity and Automated Dilution

Flowback Wastewater

Centrifugation

Filtration

Thermo Scientific Dionex Sample Conductivity and pH Accessory

Automated Sample Dilution

Does conductivity exceed cutoff?

Yes

No

Report

Chromatogram

Dionex AS-APAutosampler

Chromeleon CDS Software

IC System

Dionex ICS-2100

RFIC System

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In-line Conductivity and Automated Dilution

• Chromeleon CDS software audit trail:

• Automated dilution• Single vial or vial to vial

• 100-fold: 20 µL sample + 1980 µL water

• Mix by • Carousel shaking

• Draw/dispense

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Autodilution Precision and Accuracy

Conductivity µS/cm

Cl (g/L) Avg. %RSD

2 6545 0.058

0.02 683.1 0.034

Draw/ DispenseSpeed

(μL/sec)Volume (µL) Cl (µg) %RSD %Accuracy

50/25 4950 4926.9 0.0032 99.5

50/25 1980 1968.9 0.0747 99.4

10/5 70 71.2 0.12 99.8

10/5 20 15.3 0.86 98.4

N = 5 injections

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Analysis of Anions in Automatically Diluted Fracking Flowback Wastewater

Peaks: Measured Undiluted

1. Acetate < 0.05 mg/L < 52. Formate < 0.05 < 53. Chloride 940.0 94,000 4. Sulfate 0.12 12 5. Bromide 8.90 890

0.0

0.65

µS

Minutes

0 2 4 8

0

2,400

µS

Minutes

3

1 2

3

4

5

6

0 2 4 86

5

4

1 2

Column: Thermo Scientific™ Dionex™ IonPac™ AG18/AS18 columns, 4 mmEluent Source: Thermo Scientific Dionex

EGC III KOH cartridgeEluent: 39 mM KOHFlow Rate: 1 mL/minInj. Volume: 25 µLCol. Temp.: 30 °CDetection: Suppressed conductivity,

Thermo Scientific™ Dionex™ ASRS™ 300 Anion Self- Regenerating Suppressor, recycle modeSample: 100-fold fracking flowback, filtered, 0.2 µm

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Change in Organic Acid Composition

Peaks: A

1. Fluoride 0.5 mg/L2. Acetate 2.53. Propionate/ -- Formate4. Formate 1.0

4.8

µS

Column: Dionex IonPac AG18/AS18 columns, 4 mm

Eluent: 23 mM KOHFlow Rate: 1 mL/minInj. Volume: 25 µLCol. Temp.: 30 °CDetection: Suppressed conductivity,

Dionex ASRS 300 Suppressor, recycle mode

Sample: A. StandardB–E. 100-fold fracking flowback F1,F2, F5, and F10, filtered, 0.2 µm

2

1

E (F10)

A (Standard)

3

B (F1)

C (F2)

D (F5)

4

0

Minutes2.5 3 3.5 4

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Change in Flowback Water Inorganic Anion and Organic Acid Concentration

F1 F2 F3 F4 F5 F6 F7 F8 F9 F100

100200300400500600700800900

1,000

Bromide

Acetate

Sulfate

Formate

FractionC

on

cen

tra

tion

(m

g/L

)

F1 F2 F3 F4 F5 F6 F7 F8 F9 F100

10,00020,00030,00040,00050,00060,00070,00080,00090,000

100,000

Fraction

Co

nce

ntr

atio

n (

mg

/L)

Chloride

0 gallons 140,000

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Determination of Cations in Fracking Flowback Water

Column: Dionex IonPac CG16/CS16 columns, 5 mm i.d.

Eluent Source: Thermo Scientific Dionex EGC-MSA (capillary) cartridgeGradient: 30–40 mM MSA (0–9 min)

40–55 mM MSA (9–18 min)55 mM MSA (18–35 min)30 mM MSA (35–41 min)

Flow Rate: 1 mL/minInj. Volume: 25 µLCol. Temp.: 40 °CDetection: Suppressed conductivity, Thermo Scientific™ Dionex™ CERS™ 500

Cation Electrolytic Suppressor, recycle modeSample: 100-fold diluted flowback water, filtered, 0.2 µm

0

6

µS

Minutes

0 5 10 25

0

550

µS

Minutes

3

1

2

3

4

5

15

5

4

1

2

6

20

67

8

7 8

35

0 5 10 2515 20 35

30

30

Peaks: Measured Undiluted

1. Lithium 0.34 mg/L 34 mg/L2. Sodium 330.0 33,0003. Ammonium 1.8 180 4. Potassium 5.9 5905. Magnesium 13.0 1,300 6. Calcium 130.0 13,0007. Strontium 14.0 1,4008. Barium 2.2 220

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Change in Cation Concentration of Flowback Water

1 2 3 4 5 6 7 8 9 100

5,000

10,000

15,000

20,000

25,000

30,000

35,000

40,000

45,000

SodiumCalcium

Fraction

Co

nce

ntr

atio

n (

mg

/L)

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Change in Cation Concentration of Flowback Water

1 2 3 4 5 6 7 8 9 100

200400600800

1,0001,2001,4001,6001,8002,000

StrontiumMagnesiumPotassium

Fraction

Co

nce

ntr

atio

n (

mg

/L)

1 2 3 4 5 6 7 8 9 100

50

100

150

200

250

300

350

400

BariumAmmoniumLithium

Fraction

Co

nce

ntr

atio

n (

mg

/L)

Ion composition → wastewater reuse or treatment

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Conclusion

• Wastewater containing high salt can be challenging to analyze

Automated sample pre-screening and dilution

Accurate and consistent determination of anions, cations, and organic acids

Formulate wastewater reuse or treatment strategy

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Technical 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

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 SystemThermo Scientific™ Dionex™ ICS-5000+ HPIC System

HPIC

The Dionex Ion Chromatography Product Line

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Reagents for Environmental Applications

• Certified purity• Rigorous QC

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The world leader in serving science

Leong Ying, PhD

RMSI Global Sales Manager

Shale Hydraulic FracturingRadiological Contaminations

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Radioactive Materials

Classifications Isotopes

Primordial Nuclides< age of Universe

K40, Sm146, Th232, U235, U238, Pu244

Special Nuclear Materials1954 Atomic Energy Act

U235 (enrichment of naturally occurring isotopes)U233, Pu239 (manmade from nuclear reactors)

Industrial C14, Fe55, Cd109, Cs137, Ir192, Cf252 (analysis)H3, S35, Kr85, Pm147, Pu238, Am241 (device)

Medical N13, F18, Ga67, In111, I123, Tl201 (cyclotron)Ga68, Rb82, Sr87, Tc99, In113 (generator)Na24, P32, K42, Cr51, Fe59, Se75, I131 (reactor)

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TENORM

TENORM = Technologically-Enhanced Naturally-Occurring Radioactive Materials

Radioactive Materials

Man-Made TENORMNORM

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Thorium-232 Decay Series

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Uranium-238 Decay Series

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Radium Contaminations

Radium IsotopesRa224, Ra226, Ra228

Radon GasesRn220, Rn222

α

α

α

β β

α

21,000 Annual US DeathsEPA 402-R-03-003

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Industrial NORM

Isotopes CoalIAEA Report 419 (2003)

Oil and GasIAEA Report 34 (2003)

Australia(pCi/g)

USA(pCi/g)

Sludge(pCi/g)

Water(pCi/L)

K40 0.6-3.8

Pb210 0.5-0.9 0.3-2.1 2.7-35,100 1.4-5,130

Po210 0.4-0.8 0.1-1.4 0.1-4,320

Ra224 1.4-1,080

Ra226 0.5-0.6 0.2-1.6 1.4-21,600 0.1-32,400

Ra228 0.3-1.7 13.5-1,350 8-4,860

Th232 0.3-1.9 0.1-0.6 0.1-0.3

U238 0.2-1.3 0.2-2.0 0.1-0.3

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Radiation Detectors

Ionization

• Radiation causes ionization in low pressure inert gas-filled chamber

• Ionizing charges induce electrical pulses in processing circuit

• Radiation counter or for dose rate use energy compensated tube

• Thin window allows for detection of alpha, beta, gamma and x-rays

Scintillation

• Radiation causes photo-luminescence in scintillator material

• Coupled to electronic light sensor to generate electrical pulses

• Signals proportional to energy gives spectroscopic identification

• Thick window restricts detection typically to gamma and neutrons

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Radiological Methods

Radiochemical Spectroscopy

ASTM D2460 and D3454EPA 903.0 and 903.1

ASTM D3649 and D4962

Radium isotopes determined by alpha particle counting through dry chemical precipitation or wet chemical emanation

Radium isotopes determined by direct gamma-ray energy identification or through indirect daughter decay products

<1% Ra226 recovery1 100% Ra226 recovery1

1. Environmental Science and Technology Letter 2014, 204-208 based on measurements conducted on high-salinity flowback wastewaters extracted from Marcellus shale

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Shielded RIIDEye Analyzer

1-min backgroundoutside shield

1-min backgroundinside shield

1-min shale sludge sample

6-min shale sludge sample

NORM

Sample

TENORM = Sample – NORM

Sensitivity <0.5pCi/g (18.5Bq/kg)

1.46MeVK40

Methodology and procedure published in Applied Radiation and Isotopes 80 (2013) 95-98

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Quadratic Conversion Compression

Eu152 over 1,024 Linear Channels

• Scintillation detectors have non- linear energy response

• Linear MCA leads to distorted peaks over full energy range

Eu152 over 512 QCC Channels

• Apply quadratic algorithm to signal processor

• Compressed peaks are faster and more accurate to identify

344keV122keV

41keV X-Rays

841keV 963keV 1315keV

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Comparing NaI to HPGe Gamma Spectroscopy

Day 1

Day 3

75-77keV X-Ray

1461keV K40

Total Dose-Rate ~17uRem/hr

NaI Detector (Shale Testing Solutions) HPGe Detector (Ohio DOH)

Parameters (STS calculations):ε = Calibrated with NIST-traceable radium standard sourcest = 1800sM = 1388gIsotopes Energy(keV) STS(pCi/g) DOH(pCi/g)Ra226 186 27.5 31.5Pb214 (Ra226) 295 15.4 20.2Bi214 (Ra226) 609 18.8 21.6Pb212 (Ra228) 239 4.0 1.4Ac228 (Ra228) 338 22.2 8.2K40 (ε=0.5 un-calibrated) 1461 1.3 5.2

Results are in good agreement with previously published research article by Randy Whicker et al, Mobile Soils Lab, Health Physics Society, Volume 91, S24-S31,August 2006:• NaI detector is effective solution as mobile analyzer for estimating soil radionuclide concentrations.• NaI calibrated against HPGe produced consistent accurate quantifiable values.• Ingrowth of Rn222 progeny over 21 days was approximately 30%.

0

5

10

15

20

25

30

35

40

K40

Pb212

Pb214

Bi214

Ra226 (186keV)

Ra228 (Ac228)

1 3 9 14 17 21Days

Act

ivit

y (p

Ci/

g)

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Comparing NaI to Radiochemical Analysis

Mobile Analyzer for Quantification of Shale Produced TENORM19-22 May 2014, Crowne Plaza Ravinia, Atlanta, Georgia

46th Annual National Conference on Radiation Control

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Shale Fracking Summary

US Industrial Facts:- Third of natural gas supply- 15 shale basins- 600,000 direct jobs- $4/kcu.ft (x2 UK, x4 Japan)

Radiation Contaminations:- Uranium extracted from wells- Main concerns Ra226 and

Ra228

TENORM Analysis Results:- 5pCi/g (185Bq/kg) EPA limit- 0.5pCi/g sensitivity

US Water Treatment Plants:- 22,000 Public works- 1B gallons treated daily

US Landfills:- 2,000 Municipal waste sites- 250M tons annual deposits

RIIDEye:- Qualitative inspectionsShielded RIIDEye:- Quantitative analysis

US Shale Sludge Processors:- 1,000 Private facilities- 1M tons annually processed

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Proposed Test Flowchart

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Proposed Test Procedures

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Conclusions

• Mobile shield Nal detector is an effective instrument for on-site analysis of activity concentration for shale produced radioactive wastes, including TENORM.

• For higher accuracy, the Nal spectrometer can either be directly calibrated with radium standard sources or indirectly with comparative sampling by high-resolution efficiency-calibrated HPGe detector.

• In-growth effects for determining high activity levels of Ra226 can be factored in with 30% coefficient to the zero day measurements. For low level activities <5pCi/g there appeared to be minimal in-growth effects likely due to low radionuclide concentrations and low migration rates of radon gas through viscous sludge composition.1

• Research comparing analytical methods on high-salinity brine indicates poor accuracy <1% for radiochemical due to saturation of precipitation sales and 100% accuracy for gamma spectroscopy.2

1. Dadong Iskandar et al, Determination of Rn-222 diffusion coefficient in Japanese soils, IRPA-10, P-1b-48, 1-6, May 2010 2. Andrew Nelson et al, Matrix Complications in the Determination of Radium Levels in Hydraulic Fracturing Flowback Water from Marcellus

Shale, Environ. Sci. Technol. Lett., Volume 1, 204-208, 2014

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Thank you!

WS71146_E 06/14S