The slickwater stimulation of unconventional gas and oil shale plays creates flowback water with a composition that is unique to particular shale formations. Characteristically, these fluids contain high concentrations of salts (e.g., chloride, bromide) which are routinely determined using ion chromatography. This analysis typically requires sample preparation, including manual dilution, which can significantly increase the cost of analysis. Results presented will show highly reproducible determination of anions and cations from Marcellus Shale flowback water using inline conductivity to identify high salt samples and then automatically diluting them prior to injection, saving time and column life.
Artificial Intelligence In Microbiology by Dr. Prince C P
Title Environmental Impact of Hydraulic Fracturing
1. 1
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Richard Jack, PhD
Vertical Marketing Director
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Leong Ying, PhD
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June 12, 2014
New Techniques for Anions, Cations,
and Radioisotope Analysis of Marcellus
Shale Flowback Waters
3. 3
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
4. 4
Hydraulic Fracturing Workflow
Well 1
Desalination
Frack Chemical Pre-Injection Site
assessment
Recycle
Flowback / Produced
Brines
Waste
Disposal
Deep Well
Injection
Gas Production
Monitoring Well Monitoring Well
Frack Chemical
Well 2
Water
5. 5
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
Analytes
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
6. 6
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
7. 7
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
9. 9
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
10. 10
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
11. 11
Automated Analysis: AutoDilution
Flowback Wastewater
Centrifugation
Filtration
Automated
Sample Dilution
Report
Chromatogram
Thermo Scientific
Dionex AS-AP
Autosampler
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
12. 12
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-AP
Autosampler
Chromeleon CDS
Software
IC System
Dionex
ICS-2100
RFIC System
13. 13
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
21. 21
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
22. 22
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
23. 23
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
32. 32
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
33. 33
Radiological Methods
Radiochemical Spectroscopy
ASTM D2460 and D3454
EPA 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
35. 35
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
36. 36
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 sources
t = 1800s
M = 1388g
Isotopes Energy(keV) STS(pCi/g) DOH(pCi/g)
Ra226 186 27.5 31.5
Pb214 (Ra226) 295 15.4 20.2
Bi214 (Ra226) 609 18.8 21.6
Pb212 (Ra228) 239 4.0 1.4
Ac228 (Ra228) 338 22.2 8.2
K40 (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
Activity(pCi/g)
1 3 9 14 17 21
Days
K40
Pb212
Pb214
Bi214
Ra226 (186keV)
Ra228 (Ac228)
37. 37
Comparing NaI to Radiochemical Analysis
Mobile Analyzer for Quantification of Shale Produced TENORM
19-22 May 2014, Crowne Plaza Ravinia, Atlanta, Georgia
46th Annual National Conference on Radiation Control
38. 38
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 inspections
Shielded RIIDEye:
- Quantitative analysis
US Shale Sludge Processors:
- 1,000 Private facilities
- 1M tons annually processed
41. 41
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