Ion Analysis of Hydraulic Fluids in Fracking Process

Presented by

Jay Gandhi*, PhD

Metrohm USA

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What we will cover today

• Background – Hydraulic Fracking

• Ion Analysis Applications • Wet Chemistry methods

• Anions

• Cations

• Organic Acids

• Summary

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Hydraulic Fracking Water Cycle

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60

00

to

80

00

fe

et

1 to 2 miles

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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)

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List of Chemicals from various sources

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Hydraulic Fracking – pre-drilling tests

Ion Analysis

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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

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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

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Ion Analysis

Hydraulic Fracking

Fluids

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Titration

Ion Chromatography

Voltammetry

TitrIC

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Wet Chemistry Methods

• pH

• Conductivity

• Alkalinity

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TitrIC - the principle One Sample Changer – One Datbase for all systems

Ion Chromatography

Titration

Sample Changer

Report – Database

Direct Measurements

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TitrIC pro – the basic setup

IC

Tit

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15

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tiamoTM & MagIC Net

MagIC Net is the Master – tiamoTM is Slave tiamoTM does conductivity, pH, m, p, Ca, Mg upon

request

Titration data is transfered to MagIC Net database

TitrIC pro – a step forward

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TitrIC pro – the basic setup

IC

Tit

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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

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All TitrIC pro systems come with a T connector

Separate liquid handling

for Titration and Ion Chromatography (except for the needle part)

TitrIC pro How are Combo Kits added?

TitrIC pro II

Analysis of: conductivity, temperature, pH m p AnCat

TitrIC pro

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Analysis of: conductivity, temperature, pH m p AnCat + MiPT

TitrIC pro TitrIC pro II

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Analysis of: conductivity, temperature, pH m p AnCat +

Dilution

TitrIC pro TitrIC pro II

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TitrIC pro - Time management

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Start det.

loop

Start

HW

Rinsing

IC liquid handling and chromatography

Conductivity

pH m- & p- values

combined

report

TitrIC pro - Time management - Dilution

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Start det.

loop

Start

HW

Rinsing

IC liquid handling and chromatography

Conductivity

pH m- & p- values

combined

report

Ion Chromatography - Anions - Cations - Organic Acids

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Suppression

Eluent:

- Na+

+ H+

Sample:

all cations are replaced by H+

MSM CO2

Suppressor

CO2 is removed

Reduction of the background conductivity and

increase of analyte conductivity.

high

conductivity

- Na+

+ H+

low

conductivity

high

conductivity

low

conductivity

Na+ + Cl- H+ + Cl-

lowest

conductivity

Na+ + HCO3- H2CO3 H2O + CO2

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Anions

– Fracking Fluids

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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

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Instrument set-up

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Metrohm Inline Dilution with filtration

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Sample Sample preparation IC-System – suppressed cond

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Ion Chromatography (USEPA Region-6)

• Anions with in-line filtration

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Anions IC Conditions

• Column: Metrosep ASUPP7-250 (4mm x 250mm)

• Sample Loop: 10uL

• Eluent: 3.2mM Na2CO3 + 1.0mM NaHCO3 + 2% Acetonitrile

• Eluent Flow: 0.7mls per minute

• Suppressor Solutions

• Regen: 100mM Sulfuric Acid + 10% Acetonitrile

• Rinse: UHP DI water + 10% Acetonitrile

• Detection: Suppressed Conductivity with

Tandem UV

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Anions – Fracking Solutions

Up to 3% Brine Solution

– direct inject NO DILUTION!!!!!

0.1ppm Analytes

Chloride to Analyte

Ratio = 30000:0.1

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Suppressed

Conductivity

Tandem UV

Applications

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IC-MS

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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 Na2CO3/ NaHCO3; 0.7 mL/min; 10 ppm Standard

ESI: 13 L/min; 60 psig; 350°C; 3 kV MS: SIM neg.; Frag. 70V

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IC-MS

Anions – Oxyhalides

ESI: 13 L/min; 60 psig; 350°C; 3 kV MS: SIM neg.; Frag. 70V

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

m/z

3.2/1.0 mmol/L Na2CO3/ NaHCO3; 0.7 mL/min; 10 ppm Standard

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IC-MS

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Anions – Halo Acetic Acids: Standard

A Supp 5 – 100 + A Supp 1

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

3.2/1.0 mmol/L Na2CO3/ NaHCO3; 0.7 mL/min; 10 ppm Standard

1

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IC-MS

Conductivity

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Anions – Halo Acetic Acids: Standard

A Supp 5 – 100 + A Supp 1

1 MCAA 93

2 MBAA 137

3 DCAA 127

4 BCAA 171

5 DBAA 217

6 TCAA – CO2 117

m/z

10 ppm Cl-, NO3-, SO4

2-

3.2/1.0 mmol/L Na2CO3/ NaHCO3; 0.7 mL/min; Standard 10 ppb HAAs

MS

ESI: 13 L/min; 60 psig; 350°C; 5 kV MS: SIM neg.; Frag. 70 V

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IC-MS

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Cation Analysis Suppressed or Non-Suppressed?

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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

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Manganese

Copper

Nickel

Zinc

Cobalt

Also Low Molecular weight Amines

AW IC US6-0177-052013

Cation IC Conditions

• Column: Metrosep C6 (4mm x 100mm)

• Sample Loop: 15uL

• Eluent: 2mM Oxalic Acid + 2mM PDCA + 2% Acetonitrile

• Eluent Flow: 0.9mls per minute

• Detection: Non Suppressed Conductivity

AW IC US6-0177-2013

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Cations and Amines – Fracking Solutions

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AW IC US6-0177-2013

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Low Level Ammonium Ion in presence of High Sodium Ion

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Cation IC Conditions

• Column: Metrosep C6 (4mm x 150mm)

• Sample Loop: 10uL

• Eluent: 1.75mM Oxalic Acid

• Eluent Flow: 0.9mls per minute

• Detection: Non Suppressed Conductivity

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Calibration from 0.1 ppm to 10.0 ppm

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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

ESI: 13 L/min; 60 psig; 350°C; 3.0 kV MS: SIM pos.; Frag. 70 V

IC-MS

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Low Molecular weight

Organic Acids

– Fracking Fluids USEPA “RSK” based method

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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

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This is equivalent of 0.5ppm detection level in 3% NaCl solution

1:10 dilution of 30% NaCl solution

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 H2SO4

• Eluent Flow: 0.5mls per minute

• Metrohm Suppressor Solutions

• Regenerant: 50mM LiCl

• Rinse: UHP DI water

• Detection: Inversed Suppressed Conductivity

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AW IC US6 0176- 042013

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Inline Automatic Dilution, filtration and cation removal setup

AW IC US6 0176- 042013

Organic Acids – Fracking Solutions

• Lactic

• Formic

• Acetic

• Propionic

• Iso-Butyric

• Butyric

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0.1 ppm Organic Acids in Reagent Water

AW IC US6 0176- 042013

Calibration Curves

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Calibration Range

0.1ppm to 50ppm

AW IC US6 0176- 042013

0.5 ppm OA in 3% NaCl matrix

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AW IC US6 0176- 042013

Summary

History of Hydraulic Fracking

Ion Analysis (Combined automated systems) for

Wet Chemistry

Ion Chromatography

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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…….

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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

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The many faces of Metrohm Applications

Let us help you become the expert in your lab!

Thank you for listening

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