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Hydraulic Fracturing of Unconventional Shale Gas Wells and Environmental Testing of Water William Lipps Analytical & Measuring Instrument Division Shimadzu Scientific Instruments, Columbia, Md., USA �

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Five Stages of Fracking and Potential Sources of Contamination

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Compound   Percent (%) by Volume  Water and sand   99.51  

Surfactant   0.085  

KCL   0.06  

Gelling Agent   0.056  

Scale inhibitor   0.043  

pH adjustment   0.011  

Breaker   0.01  

Cross linker   0.007  

Iron Control   0.004  

Corrosion Inhibitor   0.002  

Biocide   0.001  

Acid   0.123  

Friction Reducer   0.088  

Example Composition

Example composition of a fracking solution water listing constituents that could be detected in a water sample:

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Component   Concentration (mg/L)  

pH   6.6 (S.U)  

Alkalinity as CaCO3   140  

Total Dissolved Solids (TDS)   67,300  

Total Suspended Solids (TSS)   100  

Total Organic Carbon (TOC)   63  

Biochemical Oxygen Demand (BOD)   3  

Oil & Grease   < 5  

Sodium as Na   18,000  

Calcium as Ca   4,950  

Magnesium as Mg   560  

Barium as Ba   690  

Iron as Fe   40  

Chloride as Cl-   41,850  

Bicarbonate as HCO3-   74  

Ammonium as NH4+   82  

Volatiles   ND – 1 (BTEX and acetone)  

Semi-volatile   ND – 1 ppm (PAH)  

Example Analysis of Flow Back Water

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Component   Concentration (mg/L)  

pH   6.5 – 8.5 (S.U)  

Total Dissolved Solids (TDS)   500  

Foaming Agents (MBAS)   0.5  

Chloride as Cl-  250  

Color   15 (CU)  

Sulfate as SO4 -2  

250  

Manganese as Mn   0.05  

Iron as Fe   0.3  

Barium as Ba   2  

Arsenic as As   0.01  

Selected USEPA Drinking Water Maximum Contaminant Levels (MCL)…

…of contaminants that have been detected in flow-back water.

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However,

•  Methane?

•  Alcohols?

•  Glycols?

Drinking water and source water contamination is easy to detect because of chloride.

Water Contamination

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Wastewater “Pre-Treatment” Requires Analysis by Part 136 Approved Methods

Have these methods been validated in the produced water matrices?

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Alkalinity

EPA Approved Method Interferences

SM 2540C

•  Highly mineralized water may be hygroscopic à prolonged drying, rapid weighing (constant weight?)

•  200 mg residue limit (1 milliliter samples?)

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Ammonia

EPA Approved Method Interferences

EPA 350.1 or SM 4500 NH3

•  Co-distillation of surfactants, fatty acids, amines, ketones, alcohols and aldehydes

•  Surfactants and fatty acids interfere with electrode

•  Amines are detected by electrode •  Amines interfere with Berthelot

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A Possible Solution is to Replace Distillation With Gas Diffusion

EPA ASTM WK42422

Distillation Automated Diffusion

Phenolate Salicylate

EDTA Citrate

0.02 – 2.0 ppm Estimated 0.01 – 10 ppm

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Total Kjeldahl Nitrogen (TKN)

EPA Approved Method Interferences

EPA 351.2 or SM 4500 org

•  High salts raise boiling point à low recovery •  Multiple step procedure •  Incomplete recovery on refractory organics

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A Possible Solution is to Replace TKN With HTCO TN

EPA ASTM WK46665

TKN digestion / distillation 720ºC catalytic oxidation

Titration or Colorimetric Chemiluminescence

Time consuming (hours) < 5 minutes per sample

Boiling sulfuric acid Compressed air, dilute acid

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Oil and Grease (O&G)

EPA Approved Method Interferences

1664

•  Elemental sulfur, surfactants, organic dyes are detected

•  Heavier petroleum and light polar are not detected

•  High salts allows co-extraction of non Oil and Grease

•  Emulsions or samples that don’t filter

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A Possible Solution is to Replace 1664 With ASTM D7575

EPA ASTM D7575

LL or SPE extraction

Selective SPE Extraction

Gravimetric Detection IR Detection

Time consuming (hours)

< 15 minutes per sample

Large volumes (100 – 1000 ml) 10 milliliter sample

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Metals by ICP-AES

EPA Approved Method Interferences

200.7

•  Spectral interferences •  Transport and ionization efficiency

differences •  Clogging of nebulizer

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Possible Solutions for EPA 200.7

•  High salt nebulizer

•  High resolution spectrometer

•  Internal standard and total element correction

STD1 STD2 STD3 STD4 As, Cr, Mn, Pb, Pd, Pt 0 1 5 -

Mg 0 1 5 10 Y 10 10 10 10

Na 5000 5000 5000 5000 HCI (mol/L) 0.36 0.36 0.36 0.36

HNO3 (mol/L) 0.42 0.42 0.42 0.42

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EPA 200.7 Modified to Correct for High Salt Content

In solid (wt%)

Validation Test Value

(%)

In solid (wt%)

Validation Test Value

(%)

In solid (wt%)

Validation Test Value

(%)

As 0.016 0.016 100 0.015 94 0.015 96 Cr 0.017 0.016 95 0.016 95 0.017 98 Mg 0.033 0.032 95 0.033 99 0.033 99 Mn 0.0020 0.0021 105 0.002 101 0.0020 101Pb 0.012 0.013 107 0.012 99 0.013 102Pd 0.025 0.026 105 0.026 106 0.026 106Pt 0.039 0.039 99 0.038 98 0.040 102

Sample 1

Sample Elem-ent

Analysis Result by Validation

Test (wt%)

Analysis Result by Direct Analysis

Internal Standard Method

Total Correction Method

Internal Standard Method and Total

Correction Method

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Volatiles by Purge and Trap GCMS

EPA Approved Method Interferences

624

•  Surfactants may cause excessive foaming •  Variable purge efficiency •  Contamination of purge vessel

•  Target analytes are mostly chlorinated solvents

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Possible Solutions for EPA 624

Replace purge and trap with headspace trap GCMS

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5(x10,000)

VOCs in drinking water at 0.1 ppb RSD < 3%

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Possible Solutions for EPA 624

Highly reproducible and can measure alcohols

Methanol 5000ppm CV%=0.47

0.0 0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

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Headspace Trap is a Very Minimal Modification to 624

Headspace Trap

Equilibrate vial

Pressurize vial

Load trap (pressure and

time) Dry purge

trap Desorb to GC

Purge and Trap

Transfer sample to

sparge Purge sparge

tube Load trap

(Time) Dry purge

trap Desorb to GC

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Replacing Purge with Headspace for EPA 624

•  Maintains BFB tuning criteria

•  Low MDL - <0.1 ppb for most

•  See Shimadzu app note No. AD-0073

•  P&T was developed because in 1970’s GC instruments were not sensitive.

•  TA Bellar and JJ Lichtenberg, Determination of Volatile Organics at Microgram per Litre Levels

by Gas Chromatography, JAWWA, 739-744, December 1974

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Semi-Volatiles by Liquid-Liquid Extraction GCMS

EPA Approved Method Interferences

625

•  Surfactants and other constituents may cause emulsions

•  High organics may require surrogates be “diluted out”

•  Contamination of injection port

•  Target analytes are mostly chlorinated and industrial solvents

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Problems with EPA 625 and Fracking Solutions and Possible Solutions

•  Complex matrices

•  Samples need “cleanup”

•  Use GPC, or

•  Use GCMSMS

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Modify Method 625 to Allow Triple Quadrupole GCMS

7.5   10.0   12.5   15.0   17.5   20.0   22.5   25.0   27.5   30.0   32.5   35.0   37.5   40.0  

0.25  

0.50  

0.75  

1.00  

1.25  (x100,000,000)  

21.25   21.50   21.75   22.00  

1.0  

2.0  

3.0  

4.0  

5.0  

6.0  

(x1,000,000)  

135.00  

28.50   28.75   29.00   29.25  0.25  

0.50  

0.75  

1.00  

1.25  

1.50  (x100)  

357.90>287.90  359.90>289.90  

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Retain Full-Scan Capability (like 625), Only Add MRM for Greater Selectivity and Sensitivity

11.0� 11.5 � 12.0 � 12.5 � 13.0� 13.5� 14.0� 14.5� 15.0� 15.5� 16.0� 16.5� 17.0� 17.5�

1.0�2.0�3.0�4.0�

(x1,000,000)�

0� 50� 100� 150� 200� 250� 300� 350� 400�0�25�50�75�100� %� 97�

223�162�65�

279�117�251�173�59� 135� 203�259� 341� 397�

365�305�13.50� 13.75� 14.00� 14.25�

0.25�0.50�0.75�1.00�(x10,000)�279.00>204.90�279.00>222.90�

Qualification Quantification

Scan Chromatogram

MRM Chromatogram

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Triple Quadrupole is a Very Minimal Modification to 625

625 Extract 1000 ml Sample

Add Internal Standards Inject Full Scan (SQ)

625 modified

Extract 100 ml Sample

Add Internal Standards Inject Full Scan

(SQ) MRM (TQ)

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Summary of Problems Associated with Analysis of Fracking Solutions and Production Water

•  Matrix can be very complex

•  TDS and chloride can be very high

•  Part 136 methods may not be validated

•  May need to add new target analytes

•  Simple modifications can be made

•  Methods need validation

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