Ion Analysis of Hydraulic Fluids in Fracking Process

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1 Ion Analysis of Hydraulic Fluids in Fracking Process Presented by Jay Gandhi *, PhD Metrohm USA NEMC

2 NEMC

3 What we will cover today Background Hydraulic Fracking Ion Analysis Applications Wet Chemistry methods Anions Cations Organic Acids Summary NEMC

4 6000 to 8000 feet Hydraulic Fracking Water Cycle 1 to 2 miles NEMC

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6 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

7 List of Chemicals from various sources NEMC

8 Hydraulic Fracking pre-drilling tests Ion Analysis NEMC

9 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

10 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

11 Ion Analysis Hydraulic Fracking Fluids NEMC

12 Titration TitrIC Ion Chromatography Voltammetry NEMC

13 Wet Chemistry Methods ph Conductivity Alkalinity NEMC

14 TitrIC - the principle One Sample Changer One Datbase for all systems Sample Changer Ion Chromatography Direct Measurements Titration Report Database NEMC

15 TitrIC pro the basic setup IC Tit NEMC

16 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

17 TitrIC pro the basic setup IC Tit NEMC

18 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

19 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

20 TitrIC pro TitrIC pro II Analysis of: conductivity, temperature, ph m p AnCat NEMC

21 TitrIC pro TitrIC pro II Analysis of: conductivity, temperature, ph m p AnCat + MiPT NEMC

22 TitrIC pro TitrIC pro II Analysis of: conductivity, temperature, ph m p AnCat + Dilution NEMC

23 TitrIC pro - Time management Start HW IC liquid handling and chromatography combined report Rinsing Conductivity ph m- & p- values Start det. loop NEMC

24 TitrIC pro - Time management - Dilution Start HW IC liquid handling and chromatography combined report Rinsing Conductivity ph m- & p- values Start det. loop NEMC

25 Ion Chromatography - Anions - Cations - Organic Acids NEMC

26 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

27 Anions Fracking Fluids NEMC

28 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

29 Instrument set-up NEMC

30 Metrohm Inline Dilution with filtration Sample Sample preparation IC-System suppressed cond NEMC

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32 Ion Chromatography (USEPA Region-6) Anions with in-line filtration NEMC

33 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 mM NaHCO 3 + 2% Acetonitrile 100mM Sulfuric Acid + 10% Acetonitrile UHP DI water + 10% Acetonitrile Suppressed Conductivity with Tandem UV NEMC

34 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

35 IC-MS Applications NEMC

36 IC-MS Anions Metrosep A Supp ; 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

37 IC-MS Anions Oxyhalides Metrosep A Supp Chlorite 67 2 Bromate Chlorate 83 5 Bromide 79 6 Nitrate 62 7 Phosphate 79 8 Phosphate 97 9 Sulfate /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

38 IC-MS Anions Halo Acetic Acids: Standard A Supp 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

39 IC-MS Anions Halo Acetic Acids: Standard MS A Supp A Supp 1 1 MCAA 93 2 MBAA DCAA BCAA DBAA TCAA CO m/z 10 ppm Cl -, NO 3-, SO /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

40 Cation Analysis Suppressed or Non-Suppressed? NEMC

41 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 US Also Low Molecular weight Amines NEMC

42 AW IC US 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

43 AW IC US Cations and Amines Fracking Solutions NEMC

44 Low Level Ammonium Ion in presence of High Sodium Ion NEMC

45 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

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47 Calibration from 0.1 ppm to 10.0 ppm NEMC

48 IC-MS Cations Ultra Trace Analysis of Amines Metrosep C Diethylamine 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

49 AW IC US Low Molecular weight Organic Acids Fracking Fluids USEPA RSK based method NEMC

50 AW IC US 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

51 AW IC US 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

52 AW IC US Inline Automatic Dilution, filtration and cation removal setup NEMC

53 AW IC US Organic Acids Fracking Solutions 0.1 ppm Organic Acids in Reagent Water Lactic Formic Acetic Propionic Iso-Butyric Butyric NEMC

54 AW IC US Calibration Curves Calibration Range 0.1ppm to 50ppm NEMC

55 AW IC US ppm OA in 3% NaCl matrix NEMC

56 Summary History of Hydraulic Fracking Ion Analysis (Combined automated systems) for Wet Chemistry Ion Chromatography NEMC

57 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

58 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

59 Thank you for listening The many faces of Metrohm Applications Let us help you become the expert in your lab! NEMC

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