Ion Analysis of Hydraulic Fluids in Fracking Process Presented by Jay Gandhi *, PhD Metrohm USA Johnson Mathew USEPA R-6 Lab Houston TX 48th WCTOW - Vancouver Canada 1
Disclaimer working with USEPA *Reference herein to any specific commercial products or nonprofit organization, process, or service by trade name, trademark, manufacturer, or other-wise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government and shall not be used for advertising or product endorsement purposes. 48th WCTOW - Vancouver Canada 2
What we will cover today Background Hydraulic Fracking Ion Analysis Applications Wet Chemistry methods Anions Cations Organic Acids Summary 48th WCTOW - Vancouver Canada 3
Hydraulic Fracking Water Cycle
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Types of Water Matrices Fresh Feed water Flowback water (Produced Water) High Ionic Water (up to 30% Salt Concentration) Recycling water Discharge water (for WTP) 48th WCTOW - Vancouver Canada 6
List of Chemicals from various sources 48th WCTOW - Vancouver Canada 7
Hydraulic Fracking pre-drilling tests Ion Analysis 48th WCTOW - Vancouver Canada 8
Ion Analysis Hydraulic Fracking Fluids 48th WCTOW - Vancouver Canada 9
Wet Chemistry Methods ph Conductivity Alkalinity 48th WCTOW - Vancouver Canada 10
Ion Chromatography -Anions - Cations - Organic Acids 48th WCTOW - Vancouver Canada 11
Anions Fracking Fluids 48th WCTOW - Vancouver Canada 12
Anions of Interest Matrix ranging from 1% Salt up to 30% Salt Analytes of interest and ranges Nitrite-N 0 to 1ppm Bromide 0 to 1ppm Nitrate-N 0 to 1ppm Sulfate 0 to 1ppm 48th WCTOW - Vancouver Canada 13
Instrument set-up 48th WCTOW - Vancouver Canada 14
Metrohm Inline Dilution with filtration Sample Sample preparation IC-System suppressed cond 48th WCTOW - Vancouver Canada 15
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Anions IC Conditions Column: Metrosep ASUPP7-250 (4mm x 250mm) Sample Loop: 10uL Eluent: Eluent Flow: 3.2mM Na 2 CO 3 + 1.0mM NaHCO 3 + 2% Acetonitrile 0.7mls per minute Suppressor Solutions Regen: Rinse: Detection: 100mM Sulfuric Acid + 10% Acetonitrile UHP DI water + 10% Acetonitrile Suppressed Conductivity with Tandem UV 48th WCTOW - Vancouver Canada 17
Anions Fracking Solutions S/cm 8.0 7.0 Chloride Suppressed Conductivity Up to 3% Brine Solution direct inject NO DILUTION!!!!! 6.0 5.0 4.0 3.0 2.0 Bromide mau Nitrate-N 10.0 Sulfate Tandem UV 1.0 8.0 0.0-1.0 6.0 0.0 8.0 16.0 24.0 32.0 min 4.0 0.1ppm Analytes 2.0 Nitrite-N Bromide Nitrate-N Chloride to Analyte Ratio = 30000:0.1 0.0 0.0 8.0 16.0 24.0 32.0 min 48th WCTOW - Vancouver Canada 18
Cation Analysis - Fracking Fluids 48th WCTOW - Vancouver Canada 19
List of target Cations by Ion Chromatography (ASTM D6919) Modification to this ASTM method is required Matrix 30% NaCl solution Flow Back Water Target analytes at 1ppm Detection level Potassium Calcium Manganese Copper Magnesium Nickel Strontium Zinc Barium Cobalt 48th WCTOW - Vancouver Canada 20
AW IC US6-0177-2013 Cation IC Conditions Column: Sample Loop: Eluent: Metrosep C6 (4mm x 100mm) 15uL 2mM Oxalic Acid + 2mM PDCA + 2% Acetonitrile Eluent Flow: 0.9mls per minute Detection: Non Suppressed Conductivity
AW IC US6-0177-2013 Cations and Amines Fracking Solutions 22
Low Molecular weight Organic Acids Fracking Fluids USEPA RSK based method 48th WCTOW - Vancouver Canada 23
List of target Organic Acids Matrix up to 30% NaCl solution Target analytes at 5ppm Detection level Lactic Acid Acetic Acid Formic Acid Propionic Acid Iso-Butyric Acid Butyric Acid This is equivalent of 0.5ppm detection level in 3% NaCl solution 1:10 dilution of 30% NaCl solution 48th WCTOW - Vancouver Canada 24
Organic Acid IC Conditions Column: Metrosep OA-250 (4mm x 250mm) (Ion Exclusion Column) Sample Loop: 50uL (In-line Cation removal MISP) Eluent: 0.5mM H 2 SO 4 Eluent Flow: 0.5mls per minute Metrohm Suppressor Solutions Regenerant: Rinse: Detection: 50mM LiCl UHP DI water Inversed Suppressed Conductivity 48th WCTOW - Vancouver Canada 25
Organic Acids Fracking Solutions S/cm 83.10 83.00 82.90 82.80 82.70 82.60 82.50 0.1 ppm Organic Acids in Reagent Water Lactic Formic Acetic Propionic Iso-Butyric Butryic Lactic Formic Acetic Propionic Iso-Butyric Butyric 82.40 82.30 0.0 4.0 8.0 12.0 16.0 20.0 min 48th WCTOW - Vancouver Canada 26
Calibration Curves S/cm 108.0 Calibration Range 0.1ppm to 50ppm 104.0 100.0 96.0 92.0 88.0 84.0 0.0 4.0 8.0 12.0 16.0 20.0 min 48th WCTOW - Vancouver Canada 27
0.5 ppm OA in 3% NaCl matrix S/cm 86.0 85.5 85.0 84.5 84.0 83.5 83.0 82.5 82.0 81.5 81.0 80.5 0.0 4.0 8.0 12.0 16.0 20.0 min 48th WCTOW - Vancouver Canada 28
Tomorrow's Presentation Detailed Topics covered Current USEPA methods and applicability Anions and Cations Analysis Low Molecular Organic Acid Analysis Challenges and Resolution Selective Ion Determination with specific detectors Total Ion Analysis with automation Using advanced liquid handling 48th WCTOW - Vancouver Canada 29
Summary History of Hydraulic Fracking Ion Analysis (Combined automated systems) for Wet Chemistry Ion Chromatography Questions?? 48th WCTOW - Vancouver Canada 30
Acknowledgements Mr. David Neliegh USEPA Region 6 Dr. Melvin Ritter USEPA Region 6 Mr. William Telliard Retired USEPA - DC Ms. Marvyln Humphrey USEPA Region 6 Metrohm AG applications team especially, Dr. Katinka Ruth and Dr. Andrea Willie Dr. Hari Narayanan Metrohm USA Applications Lab Dr. Chunlong Zhang University of Houston Clearlake Mr. Brian Wilson and Ms. Jahnavi Graduate students 48th WCTOW - Vancouver Canada 31
Thank you for listening The many faces of Metrohm Applications Let us help you become the expert in your lab! 48th WCTOW - Vancouver Canada 32