New Techniques for Anion, Cation, and Radioisotope Analysis of Marcellus Shale Flowback Waters
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Transcript of New Techniques for Anion, Cation, and Radioisotope Analysis of Marcellus Shale Flowback Waters
1
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
39
Proposed Test Flowchart
40
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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