This presentation discusses hydraulic fracturing and potential environmental contamination issues. Possible solutions are presented, as well as problems associated with analysis of fracking solutions and production water. For more information, go to ssi.shimadzu.com.

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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?

8. 8 / 98 / 28
Alkalinity
EPAApproved 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
EPAApproved 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)
EPAApproved 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)
EPAApproved 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
EPAApproved 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 101
Pb 0.012 0.013 107 0.012 99 0.013 102
Pd 0.025 0.026 105 0.026 106 0.026 106
Pt 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
EPAApproved 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
EPAApproved 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
16265
279117
25117359 135 203
259 341
397
365305
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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