Ion Analysis of Hydraulic Fluids in Fracking Process Presented by Jay Gandhi *, PhD Metrohm USA NEMC-2013 1
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What we will cover today Background Hydraulic Fracking Ion Analysis Applications Wet Chemistry methods Anions Cations Organic Acids Summary NEMC-2013 3
6000 to 8000 feet Hydraulic Fracking Water Cycle 1 to 2 miles NEMC-2013 4
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Types of Water Matrices Fresh Feed water Flowback water (Produced Water) High Ionic Water (up to 30% Salt Concentration) Characterization of Retention Pond Recycling water Discharge water (for WTP) NEMC-2013 6
List of Chemicals from various sources NEMC-2013 7
Hydraulic Fracking pre-drilling tests Ion Analysis NEMC-2013 8
Water Matrix needs to be considered In any industry, there is no such thing as accident or incident free!!!! Hence in an accident of well casing break, damage or leak there will be a possibility of contaminating Source of Ground water Ground water tables depending of chemical mobility Surface water (rivers and lakes) So for next 1.5 years USEPA is very active to establish baseline of water sources in every state where fracking is involved or potential of fracking is possible NEMC-2013 9
So at every Fracking sites there will be following regulatory methods apply Under safe Drinking Water Act USEPA method 300 USEPA method 552 USEPA method 557 ASTM method 6919 (MUR) All applicable methods for organics and wet chemistry Under OSW Modified USEPA method 300 Modified ASTM method 6919 Method for Low molecular OA Method for Glycols Methods for gas detection Other Methods under development NEMC-2013 10
Ion Analysis Hydraulic Fracking Fluids NEMC-2013 11
Titration TitrIC Ion Chromatography Voltammetry NEMC-2013 12
Wet Chemistry Methods ph Conductivity Alkalinity NEMC-2013 13
TitrIC - the principle One Sample Changer One Datbase for all systems Sample Changer Ion Chromatography Direct Measurements Titration Report Database NEMC-2013 14
TitrIC pro the basic setup IC Tit NEMC-2013 1 15
TitrIC pro a step forward tiamo TM & MagIC Net MagIC Net is the Master tiamo TM is Slave tiamo TM does conductivity, ph, m, p, Ca, Mg upon request Titration data is transfered to MagIC Net database NEMC-2013 16
TitrIC pro the basic setup IC Tit NEMC-2013 1 17
TitrIC pro - titration equipment 905 Titrando iaquatrode plus 856 Conductivity module Conductivity flow trough cell External vessel Additionally for TitrIC pro I: Combined polymembrane electrode Ca NEMC-2013 18
TitrIC pro How are Combo Kits added? All TitrIC pro systems come with a T connector Separate liquid handling for Titration and Ion Chromatography (except for the needle part) NEMC-2013 19
TitrIC pro TitrIC pro II Analysis of: conductivity, temperature, ph m p AnCat NEMC-2013 20
TitrIC pro TitrIC pro II Analysis of: conductivity, temperature, ph m p AnCat + MiPT NEMC-2013 21
TitrIC pro TitrIC pro II Analysis of: conductivity, temperature, ph m p AnCat + Dilution NEMC-2013 22
TitrIC pro - Time management Start HW IC liquid handling and chromatography combined report Rinsing Conductivity ph m- & p- values Start det. loop NEMC-2013 23
TitrIC pro - Time management - Dilution Start HW IC liquid handling and chromatography combined report Rinsing Conductivity ph m- & p- values Start det. loop NEMC-2013 24
Ion Chromatography - Anions - Cations - Organic Acids NEMC-2013 25
Suppression Reduction of the background conductivity and increase of analyte conductivity. MSM CO 2 Suppressor Eluent: Sample: + H + Na + - + HCO 3 H - Na + 2 CO 3 H 2 O + CO 2 high conductivity low conductivity + H Na + + Cl - + H + + Cl - - Na + low high conductivity conductivity all cations are replaced by H + lowest conductivity CO 2 is removed NEMC-2013 26
Anions Fracking Fluids NEMC-2013 27
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 NEMC-2013 28
Instrument set-up NEMC-2013 29
Metrohm Inline Dilution with filtration Sample Sample preparation IC-System suppressed cond NEMC-2013 30
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Ion Chromatography (USEPA Region-6) Anions with in-line filtration NEMC-2013 32
Anions IC Conditions Column: Metrosep ASUPP7-250 (4mm x 250mm) Sample Loop: 10uL Eluent: Eluent Flow: 0.7mls per minute Suppressor Solutions Regen: Rinse: Detection: 3.2mM Na 2 CO 3 + 1.0mM NaHCO 3 + 2% Acetonitrile 100mM Sulfuric Acid + 10% Acetonitrile UHP DI water + 10% Acetonitrile Suppressed Conductivity with Tandem UV NEMC-2013 33
Anions Fracking Solutions Suppressed Conductivity Up to 3% Brine Solution direct inject NO DILUTION!!!!! Tandem UV 0.1ppm Analytes Chloride to Analyte Ratio = 30000:0.1 NEMC-2013 34
IC-MS Applications NEMC-2013 35
IC-MS Anions Metrosep A Supp 5 150 1; 2 Bromide 79; 81 3 Nitrate 62 4; 5 Phosphate 79; 97 6; 7 Sulfate 97;99 8 Oxalate 89 9 Thiosulfate 113 m/z 3.2/1.0 mmol/l Na 2 CO 3 / NaHCO 3 ; 0.7 ml/min; 10 ppm Standard ESI: 13 L/min; 60 psig; 350 C; 3 kv MS: SIM neg.; Frag. 70V NEMC-2013 36
IC-MS Anions Oxyhalides Metrosep A Supp 5 250 1 Chlorite 67 2 Bromate 127 4 Chlorate 83 5 Bromide 79 6 Nitrate 62 7 Phosphate 79 8 Phosphate 97 9 Sulfate 97 3.2/1.0 mmol/l Na 2 CO 3 / NaHCO 3 ; 0.7 ml/min; 10 ppm Standard NEMC-2013 m/z ESI: 13 L/min; 60 psig; 350 C; 3 kv MS: SIM neg.; Frag. 70V 37
IC-MS Anions Halo Acetic Acids: Standard A Supp 5 100 + A Supp 1 Conductivity 1 Fluoride 7 DBAA 2 MCAA 8 Nitrate 3 MBAA 9 Bromide 4 Chloride 10 Phosphat e 5 DCAA 11 TCAA 6 Nitrite + BCAA 12 Sulfate 1 3.2/1.0 mmol/l Na 2 CO 3 / NaHCO 3 ; 0.7 ml/min; 10 ppm Standard NEMC-2013 38
IC-MS Anions Halo Acetic Acids: Standard MS A Supp 5 100 + A Supp 1 1 MCAA 93 2 MBAA 137 3 DCAA 127 4 BCAA 171 5 DBAA 217 6 TCAA CO 2 117 m/z 10 ppm Cl -, NO 3-, SO 4 2-3.2/1.0 mmol/l Na 2 CO 3 / NaHCO 3 ; 0.7 ml/min; Standard 10 ppb HAAs ESI: 13 L/min; 60 psig; 350 C; 5 kv MS: SIM neg.; Frag. 70 V NEMC-2013 39
Cation Analysis Suppressed or Non-Suppressed? NEMC-2013 40
List of target Cations by Ion Chromatography (ASTM D6919) Modification to this ASTM method is required Matrix 30% NaCl solution Flowback Water Target analytes at 1ppm Detection level Potassium Calcium Magnesium Strontium Barium Manganese Copper Nickel Zinc Cobalt AW IC US6-0177-052013 Also Low Molecular weight Amines NEMC-2013 41
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 NEMC-2013 42
AW IC US6-0177-2013 Cations and Amines Fracking Solutions NEMC-2013 43
Low Level Ammonium Ion in presence of High Sodium Ion NEMC-2013 44
Cation IC Conditions Column: Sample Loop: Eluent: Eluent Flow: Metrosep C6 (4mm x 150mm) 10uL 1.75mM Oxalic Acid 0.9mls per minute Detection: Non Suppressed Conductivity NEMC-2013 45
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Calibration from 0.1 ppm to 10.0 ppm NEMC-2013 47
IC-MS Cations Ultra Trace Analysis of Amines Metrosep C 4-100 1 Diethylamine 0.2 2 Triethylamine 0.2 ppb 4.0 mmol/l tartaric acid/ 10 % ACN; 0.5 ml/min; 350 µl; m/z 74 & 102 NEMC-2013 ESI: 13 L/min; 60 psig; 350 C; 3.0 kv MS: SIM pos.; Frag. 70 V 48
AW IC US6 0176-042013 Low Molecular weight Organic Acids Fracking Fluids USEPA RSK based method NEMC-2013 49
AW IC US6 0176-042013 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 NEMC-2013 50
AW IC US6 0176-042013 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: 50mM LiCl Rinse: Detection: UHP DI water Inversed Suppressed Conductivity NEMC-2013 51
AW IC US6 0176-042013 Inline Automatic Dilution, filtration and cation removal setup NEMC-2013 52
AW IC US6 0176-042013 Organic Acids Fracking Solutions 0.1 ppm Organic Acids in Reagent Water Lactic Formic Acetic Propionic Iso-Butyric Butyric NEMC-2013 53
AW IC US6 0176-042013 Calibration Curves Calibration Range 0.1ppm to 50ppm NEMC-2013 54
AW IC US6 0176-042013 0.5 ppm OA in 3% NaCl matrix NEMC-2013 55
Summary History of Hydraulic Fracking Ion Analysis (Combined automated systems) for Wet Chemistry Ion Chromatography NEMC-2013 56
What has not been presented yet Electrochemistry measurement (VA) hyphenated with Ion Chromatography for Metals analysis and Ion Chromatography for Total Ion Balance Ethylene and Propylene glycol analysis at single digit ppb level detection using ONLY Ion Chromatography. NEMC-2013 57
Acknowledgements Mr. David Neliegh USEPA Region 6 Dr. Melvin Ritter USEPA Region 6 Mr. Johnson Mathew 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. Chunlong Zhang University of Houston Clearlake Mr. Brian Wilson and Ms. Jahnavi Graduate students NEMC-2013 58
Thank you for listening The many faces of Metrohm Applications Let us help you become the expert in your lab! NEMC-2013 59
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