Anions and Metals Analysis for Waters
Impacted by Hydraulic Fracturing
Richard Jack, Ph.D.
Manager, Global Market Developm...
Hydraulic Fracturing (Fracking) Controversy

2
Hundreds of Known Chemicals in Fracking Solutions
• Hundreds of chemicals in fracking solutions
• 50,000 mg/L salt (10–20x...
Pennsylvania Regulations for Wastewater from Fracking
• In lieu of the trace analysis described in Subsection b, the chemi...
Monitoring Environmental Impact
• Public concern poses a challenge to environmental laboratories.
• Some contaminants do n...
Thermo Scientific Dionex Ion Chromatography (IC)
Systems for Anion and Cation Analysis
Reagent-Free™ IC (RFIC™) Systems

D...
Thermo Scientific Dionex IonPac Anion-Exchange
Columns
Column
Dionex IonPac™
AS19

0.4 × 250 mm
2 × 250 mm
4 × 250 mm

Rec...
Comparison of Hydroxide and Carbonate Eluent for
Separation of Common Anions
05
.

A

4

1

8

91
0

Column/Eluent: A) Dio...
AA, ICP and ICP-MS—Speed and Detection Limit
> 1ppb
DL

Higher Cost
< 1ppt DL

ICP-OES

ICP-MS

60s for 10 elements

Speed...
Complete Inorganic Elemental Analysis
He

H
Li

Be

B

C

N

O

F

Ne

Na

Mg

Al

Si

P

S

Cl

Ar

K

Ca

Sc

Ti

V

Rb
...
Anion Analysis of Water Associated with
Unconventional Natural Gas Extraction
John F. Stolz, Ph.D, Duquesne University, Pi...
What is Marcellus Shale?

www.getmoneyenergy.com/wp-content/uploads/2010/01/shale-gas-basins-in-usa.jpg
Horizontal Drilling and Fracking

http://app1.kuhf.org/userfiles/hydraullic_fracturing_natural_gas.gif
Produced Water
High Total Dissolved Solids (60–250,000 mg/L)
Chloride, bromide, strontium, barium

Gaudlip et al., 2008. S...
The System
 Thermo Scientific Dionex ICS-1100 with:


DS6 Heated Conductivity Cell



AS-DV Autosampler

 Thermo Scien...
Running Conditions
Eluent:

4.6 mM sodium carbonate/
1.4 mM sodium bicarbonate

Flow Rate:

0.25 ml/min

Samples:

Filtere...
Standards (Retention Time):


Bromide (6.887 min)



Floride (3.377 min)



Chloride (4.847 min)



Nitrate (7.654 min...
Five-Point Calibration Curves:
a: 0.5, 1, 2.5, 5, 10 ppm
Bromide, Floride, Chloride
b: 2.5, 10, 25, 50, 100 ppm
Nitrate, N...
Table 1: Anion data for impoundment water, coal mine effluent, and freshwater stream water

Unit
Conductivity
pH
Sulfate
N...
Conclusions
 The Dionex ICS-1100, equipped with the DS6 Heated
Conductivity Cell provides a rapid means for separation
an...
Hydraulic Fracturing
Flowback Water Analysis
by ICP-OES and ICP-MS
Joelle Streczywilk
Senior Group Leader
Geochemical Test...
Outline








The importance of trace analysis of flowback water
Sample preparation
Choosing an analysis techniqu...
Importance of Flowback Water
Trace Analysis






Gas exploration and development is growing
quickly and analysis tech...
Sample Preparation







EPA Method 200.2 is adequate for most flowback
samples.
Use 1% nitric and 0.5% hydrochloric...
Sample Preparation






Flowback waters can
be saturated with salts
and precipitation may
occur.
Precipitation will le...
Analysis Techniques




ICP-OES and ICP-MS
Governed by the elements of interest, detection
limits required and the make...
Flowback Water Analysis by ICP-MS




Uranium analysis should be conducted on the
ICP-MS because uranium is a heavy isot...
ICP-MS Spectral Interferences


Isobaric overlaps: some isotopes occur at the
same mass number.
–
–



Choose and monito...
ICP-MS Physical and
Matrix Interference


High TDS (some flowback waters are over 10%
TDS)
–
–
–



Viscosity—consistent...
Flowback Water Analysis
by ICP-OES



Most analytes of interest in flowback water can be
analyzed accurately with ICP-OE...
ICP-OES Line Selection


Line sensitivity
–
–
–
–

Is based on detection limit required.
Avoid lines that require complex...
Flowback
Example
on iCAP 6500
• Diluted prior to
digestion
• ^ and * on Barium and
Strontium: peak
saturation
• ChkFail: c...
Minimizing Physical Interferences






Avoidance: dilute if possible
High solids nebulizer to minimize “salting out”...
Internal Standard Compensation


Plasma loading from flowback waters
–

Readings are generally suppressed
Calibration
Bla...
Flowback Water and Calibration
Blank Comparison

Low axial Sc 227

Low axial Se 196
Managing Spectral Interferences


Background interference
–



Routine and relatively easy to deal with

Direct spectral...
Interfering Element Corrections


IECs may be calculated, but should be checked
after every calibration.
–




Use mult...
Spectral Interferences




Spectral tables can be helpful but not
depended on.
A matrix study is also important for flo...
Low Axial View of a Flowback
Sample with Blank Subtraction
Fullframe of 1000 µg/mL Strontium
Summary







The complex matrices of flowback waters make
accurate trace analysis difficult.
ICP-OES analysis is mo...
Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing
Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing
Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing
Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing
Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing
Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing
Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing
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Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing

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U.S. EPA and many state agencies are investigating fracking in Marcellus Shale’s impact on environmental water quality. Public outcry has led to drafting legislation. Increased levels of bromide in drinking water systems correlate to higher levels of brominated disinfection byproducts. Trace metals (i.e., arsenic, selenium, lead), important constituents of flowback water, must be accurately determined for regulatory compliance, challenging due to high levels of dissolved salts which can cause physical and spectral interferences. Here, experts discuss monitoring and measuring anion concentrations in water from recycling impoundments, the typical constituents reported for Marcellus Shale fracking operations, flowback water preparation, and ICP-OES and ICP-MS metals analysis.

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Chromatography: Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing

  1. 1. Anions and Metals Analysis for Waters Impacted by Hydraulic Fracturing Richard Jack, Ph.D. Manager, Global Market Development The world leader in serving science 1
  2. 2. Hydraulic Fracturing (Fracking) Controversy 2
  3. 3. Hundreds of Known Chemicals in Fracking Solutions • Hundreds of chemicals in fracking solutions • 50,000 mg/L salt (10–20x sea water) • The EPA has narrowed the list of compounds down to less than 20. • The EPA is in the process of developing analytical methods for these target compounds. 3
  4. 4. Pennsylvania Regulations for Wastewater from Fracking • In lieu of the trace analysis described in Subsection b, the chemical analysis of wastewater produced from the drilling, completion and production of a Marcellus Shale or other shale gas well must include the following: Acidity Ethylene Glycol pH Alkalinity (Total as CaCO3) Aluminum Ammonia Nitrogen Arsenic Barium Benzene Beryllium Biochemical Oxygen Boron Bromide Cadmium Calcium Chemical Oxygen Demand Chlorides Chromium Cobalt Copper Gross Alpha Gross Beta Hardness (Total as CaCO3) Iron – Dissolved Iron – Total Lead Lithium Magnesium Manganese MBAS (Surfactants) Mercury Molybdenum Nickel Nitrite-Nitrate Nitrogen Oil & Grease Phenolics (Total) Radium 226 Radium 228 Selenium Silver Sodium Specific Conductance Strontium Sulfates Thorium Toluene Total Dissolved Solids Total Kjeldahl Nitrogen Total Suspended Solids Uranium Zinc • Additional constituents that are expected or known to be present in the wastewater. *Note: All metals reported as total. 4
  5. 5. Monitoring Environmental Impact • Public concern poses a challenge to environmental laboratories. • Some contaminants do not have approved EPA analytical methods. • Matrix issue—hypersaline fracking waters can affect analysis of certain compounds. • Robust analytical methods needed to assess environmental impact from fracking processes. • Following speakers will discuss inorganic analysis methods for anions and metals. 5
  6. 6. Thermo Scientific Dionex Ion Chromatography (IC) Systems for Anion and Cation Analysis Reagent-Free™ IC (RFIC™) Systems Dionex ICS-2100 Dionex ICS-4000 Dionex ICS-5000 Dionex ICS-1600 Dionex ICS-900 Starter Line IC System Compact Design Chem. Suppression DCR Mode 6 Dionex ICS-1100 Basic Integrated RFIC System Compact Design Electr. Suppression Integrated Sample Prep Eluent Regeneration Standard Integrated RFIC System Compact Design Electr. Suppression LCD Front Panel Column Heater Integrated Sample Prep Eluent Regeneration Superior Integrated RFIC System Compact Design Eluent Generation RFIC Gradient Electr. Suppression LCD Front Panel Column Heater Integrated Sample Prep Capillary High-Pressure Integrated RFIC System Capillary HPIC™ Eluent Generation RFIC Gradient Multiple Detectors, Including Electrochemical (ED) and Charge (QD) Premier Modular RFIC System Capillary HPIC Modular Flexible Single or Dual Channel Eluent Generation Proportioned and RFIC Gradients Multiple Detectors Multiple Thermal Zones
  7. 7. Thermo Scientific Dionex IonPac Anion-Exchange Columns Column Dionex IonPac™ AS19 0.4 × 250 mm 2 × 250 mm 4 × 250 mm Recommended hydroxide-selective column for inorganic anions and oxyhalides, e.g., trace bromate in drinking water Dionex IonPac AS18 0.4 × 250 mm 2 × 250 mm 4 × 250 mm High capacity hydroxide-selective column for the analysis of common inorganic anions Dionex IonPac AS18-Fast 0.4 × 150 mm 2 × 150 mm 4 × 150 mm Hydroxide-selective column for fast analysis of common inorganic anions Dionex IonPac AS23 2 × 250 mm 4 × 250 mm Recommended carbonate-based column for inorganic anions and oxyhalides, e.g., trace bromate in drinking water (better solution for Dionex IonPac AS9-HC users) Dionex IonPac AS22 7 Formats Primary Application 2 × 250 mm 4 × 250 mm Recommended carbonate-based column for fast analysis of common inorganic anions (better solution for Dionex IonPac AS14, AS14A and AS4A users)
  8. 8. Comparison of Hydroxide and Carbonate Eluent for Separation of Common Anions 05 . A 4 1 8 91 0 Column/Eluent: A) Dionex IonPac AS19 using hydroxide eluent B) Dionex IonPac AS23 using carb/bicarb eluent 1 1 Detection: 7 µ S A 6 2 3 Peaks 5 02 . 07 . B 4 1 µ S 8 1 1 1 0 8 5 µg/L 11.3 5.1 9.5 • Both eluents show excellent anion separation. 567 –01 . 0 1. Fluoride 2. Chlorite 8.8 3. Bromate 4.7 4. Chloride 5. Nitrite 6. Chlorate 13.5 7. Bromide 8. Nitrate 9. Carbonate 10. Sulfate 11. Phosphate B 9 3 2 Suppressed conductivity 1 0 1 5 Minutes 2 0 2 5 3 0 • Trace anions are well resolved. • Hydroxide does not show the water dip.
  9. 9. AA, ICP and ICP-MS—Speed and Detection Limit > 1ppb DL Higher Cost < 1ppt DL ICP-OES ICP-MS 60s for 10 elements Speed 120s for 10 elements Rugged Multielement Technique Sensitive Multielement Technique Furnace AA 20 mins for 10 element Single Element Technique 9 Flame AA 300s for 10 element Ppm DL Single Element Technique > 100ppt DL Detection Limit
  10. 10. Complete Inorganic Elemental Analysis He H Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Rb Sr Y Zr Nb Mo Tc Cs Ba La Hf Ta W Re Fr Ra Ac Ce Pr Nd Pm Sm Th Pa Cr Mn U Co Ni Cu Zn Ga Ge As Se Br Kr Ru Rh Pd Ag Cd In Sn Sb Te I Xe Os Pt Au Hg Tl Pb Bi Po At Rn Eu Gd Tb Dy Ho Er Tm Yb Lu Pu Am Cm Bk Cf Es Fm Md No Lw Fe Np Ir AA/ICP/ICP-MS ICP/ICP-MS ICP-MS Not measurable Unstable elements IC IC is also used for additional anions, such as oxyhalides, SO4 and NO3. 10
  11. 11. Anion Analysis of Water Associated with Unconventional Natural Gas Extraction John F. Stolz, Ph.D, Duquesne University, Pittsburgh, PA
  12. 12. What is Marcellus Shale? www.getmoneyenergy.com/wp-content/uploads/2010/01/shale-gas-basins-in-usa.jpg
  13. 13. Horizontal Drilling and Fracking http://app1.kuhf.org/userfiles/hydraullic_fracturing_natural_gas.gif
  14. 14. Produced Water High Total Dissolved Solids (60–250,000 mg/L) Chloride, bromide, strontium, barium Gaudlip et al., 2008. SPE 119898
  15. 15. The System  Thermo Scientific Dionex ICS-1100 with:  DS6 Heated Conductivity Cell  AS-DV Autosampler  Thermo Scientific Dionex DAD-3000 UltiMate 3000 Diode Array Detector (UV-vis)  Thermo Scientific Dionex OnGuard II M Cartridge  Thermo Scientific Dionex IonPac AS-22 Anion Exchange Column
  16. 16. Running Conditions Eluent: 4.6 mM sodium carbonate/ 1.4 mM sodium bicarbonate Flow Rate: 0.25 ml/min Samples: Filtered 0.22 um (PES filter0) Run Time: 20 min Conductivity Range: 0–1500 uS/cm UV-vis: 195 nm (ch 1), 200 nm (ch 2), 205 nm (ch 3), 215 (ch 4)
  17. 17. Standards (Retention Time):  Bromide (6.887 min)  Floride (3.377 min)  Chloride (4.847 min)  Nitrate (7.654 min)  Nitrite (6.201 min)  Phosphate (10.534 min)  Sulfate (11.781 min)  Arsenate (19.05 min)  Arsenite (4.357 min)  Monomethylarsonic acid (9.967 min)  Dimethylarsonic acid (2.623 min)
  18. 18. Five-Point Calibration Curves: a: 0.5, 1, 2.5, 5, 10 ppm Bromide, Floride, Chloride b: 2.5, 10, 25, 50, 100 ppm Nitrate, Nitrite, Phosphate, Sulfate c: 10, 50, 100, 250, 500 uM Arsenate, Arsenite, Monomethylarsonic acid, Dimethylarsonic acid
  19. 19. Table 1: Anion data for impoundment water, coal mine effluent, and freshwater stream water Unit Conductivity pH Sulfate Nitrate Bromide Chloride Arsenic uS cm-3 mg/L mg/L mg/L mg/L ug/L Field Sample Impoundment Water Sample #1 Field Sample Impoundment Water Sample #2 Field Sample Coal Mine Effluent Sample #3 Field Sample Freshwater Stream Fonner Run Field Sample Freshwater Stream Bates Run 102,864 5.38 8.64 ND 255 30,683 BDL 61,477 5.67 10.21 ND 226 27,700 BDL 6,400 7.53 3,826 1.81 14.25 1,241 BDL 387 7.91 25.07 0.11 ND 1.29 BDL 476 7.67 24.46 0.58 ND 6.00 BDL ND - not detected J.L. Eastham, 2012 BDL - below detection limit
  20. 20. Conclusions  The Dionex ICS-1100, equipped with the DS6 Heated Conductivity Cell provides a rapid means for separation and detection of anions (e.g., Cl, Br) commonly found in flowback and produced water associated with unconventional shale gas extraction.  Produced water from Marcellus Shale is higher in chloride and bromide but lower in sulfate, and can be distinguished from coal wastewater and natural streams.  The addition of the Dionex DAD-3000 UltiMate™ 3000 Diode Array Detector in tandem with the Conductivity Cell allowed for the detection of additional anions, e.g., As(III), and arsenic speciation.
  21. 21. Hydraulic Fracturing Flowback Water Analysis by ICP-OES and ICP-MS Joelle Streczywilk Senior Group Leader Geochemical Testing
  22. 22. Outline        The importance of trace analysis of flowback water Sample preparation Choosing an analysis technique Analysis using the Thermo Scientific iCAP 6500 Duo View ICP Spectrometer Minimizing physical interferences Managing spectral interferences Summary
  23. 23. Importance of Flowback Water Trace Analysis     Gas exploration and development is growing quickly and analysis techniques should evolve with the Marcellus industry. Flowback water is the main source of wastewater from Marcellus shale gas drilling. Flowback water can be treated and reused or treated and discharged. Metals analysis is essential for many reasons: – – – Ensures that treatment processes are functioning properly. Meets discharge or storage requirements. Assesses the hazards that could be related to a spill or leak.
  24. 24. Sample Preparation      EPA Method 200.2 is adequate for most flowback samples. Use 1% nitric and 0.5% hydrochloric acid digestion (a nitric only digestion may be preferred if analysis will be conducted by ICP-MS). Reduce sample to approximately 20% of original volume at 85 °C. Cover sample with watch glass and reflux for 30 minutes. Fill to original volume with DI water.
  25. 25. Sample Preparation    Flowback waters can be saturated with salts and precipitation may occur. Precipitation will lead to inaccurate results for both major and trace element analysis. Avoid crystallization by diluting the sample prior to digestion.
  26. 26. Analysis Techniques    ICP-OES and ICP-MS Governed by the elements of interest, detection limits required and the makeup of the sample The constituents and permitting needs of flowback water vary greatly so analysis techniques should be sample specific.
  27. 27. Flowback Water Analysis by ICP-MS   Uranium analysis should be conducted on the ICP-MS because uranium is a heavy isotope with a simple spectrum and a slight interference from 206Pb16O (ICP-OES: weak signal and severe 2 interference). Many other analytes of interest may be analyzed on the ICP-MS with caution due to interferences and high total dissolved solids (TDS). The use of reaction or collision cells can minimize or resolve many interference issues.
  28. 28. ICP-MS Spectral Interferences  Isobaric overlaps: some isotopes occur at the same mass number. – –  Choose and monitor alternate isotopes. Correction equation Polyatomic overlaps: dimers, oxides, hydrides, etc. – Dynamic or empirical correction equations (may not be accurate depending on the intensity of the interference)
  29. 29. ICP-MS Physical and Matrix Interference  High TDS (some flowback waters are over 10% TDS) – – –  Viscosity—consistent aerosol formation is desired Plasma loading—reduces ions generated by the plasma Instrument drift—clogs cones Minimized by internal standards, robust plasma conditions, keeping dissolved solids below 0.5% – Dilutions: introduce error, raise practical quantitation limit (PQL), detector life
  30. 30. Flowback Water Analysis by ICP-OES   Most analytes of interest in flowback water can be analyzed accurately with ICP-OES. iCAP™ 6500 Duo View ICP Spectrometer has the advantage of viewing the plasma both axially and radially. – Enables the analysis of trace metals at low and high concentrations simultaneously
  31. 31. ICP-OES Line Selection  Line sensitivity – – – – Is based on detection limit required. Avoid lines that require complex spectral correction algorithms. Select a radial or an axial view of the plasma. Line switching is available for analyte measurements that are found at both high and low concentrations (extends linear range).
  32. 32. Flowback Example on iCAP 6500 • Diluted prior to digestion • ^ and * on Barium and Strontium: peak saturation • ChkFail: check table limit (Ba, Sr, Ca, Li, Mg and Na) • Sodium defaulted to the low line (linearity and interfering element corrections [IECs]) • RSDs less than 3% for all analytes above the MDL
  33. 33. Minimizing Physical Interferences      Avoidance: dilute if possible High solids nebulizer to minimize “salting out” effects (Noordermer v-groove) Humidify argon stream Intelligent rinse Use of internal standard
  34. 34. Internal Standard Compensation  Plasma loading from flowback waters – Readings are generally suppressed Calibration Blank Cts/S Flowback Sample Cts/S Internal Standard Recovery Low axial Sc 4122 3486 85% High radial Sc 19812 17357 88% High axial Sc 405400 313240 77%
  35. 35. Flowback Water and Calibration Blank Comparison Low axial Sc 227 Low axial Se 196
  36. 36. Managing Spectral Interferences  Background interference –  Routine and relatively easy to deal with Direct spectral overlap – Avoidance  – Use different line(s) Complete a full spectral interference study  Trace metals should be studied at a concentration of at least 1000 µg/mL of interferant
  37. 37. Interfering Element Corrections  IECs may be calculated, but should be checked after every calibration. –   Use multiple check solutions. IECs must not be used if the interferer concentration is above the linear range. IECs should be calculated quarterly and with each nebulizer or torch change.
  38. 38. Spectral Interferences    Spectral tables can be helpful but not depended on. A matrix study is also important for flowback water sample analysis. Conduct fullframe analyses of all views in use (high radial, low axial, and high axial).
  39. 39. Low Axial View of a Flowback Sample with Blank Subtraction
  40. 40. Fullframe of 1000 µg/mL Strontium
  41. 41. Summary      The complex matrices of flowback waters make accurate trace analysis difficult. ICP-OES analysis is more conducive to multielement determinations for both high and most low analyte concentrations. ICP-MS is required only for uranium, however it can be used to determine most other elements as well. Avoidance is the key with both techniques. If avoidance is impossible, caution must be used in every determination.
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