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  • Accurate mass analysis of hydraulic fracturing waters: Identification of polyethylene glycol surfactants by LC/Q-TOF-MS

    Agilent Technologies, Inc.

    June 2015

    May 21, 2015 Confidentiality Label 1

  • W h a t i s H y d r a u l i c F r a c t u r i n g ? W h y i s i t i m p o r t a n t ?

    • Thermogenic Methane

    • Natural Gas & Oil

    • 45,000 Wells in US

    • 7500 Wells in Colorado

    • Natural Gas Prices Down

    • US Energy Reserves UP

    • High Water Use per well

    106 Gallons

    • Greenhouse Gases

    • Groundwater Contam

    • Aesthetics

    • Risks Shallow Aquifers

    • Methane and HC

    • Fracking Fluids

    • Metals

    • Radionuclides

    • Salts

    21 May 2015

    Confidentiality Label

    2

  • S h a l e G a s F i e l d s L o w e r 4 8 S t a t e s

  • Hydraulic Fracturing Production Activity Price per Wellhead

    24 June 2015

    Confidentiality Label

    4

    Vengosh et al. 2014 ES&T

  • Hydraulic Fracturing for Natural Gas Contamination Risks

    24 June 2015

    Confidentiality Label

    5

  • Hydraulic Fracturing for Natural Gas Potential Risks

    24 June 2015

    Confidentiality Label

    6

  • LC/QTOF-MS with High Resolution and Accurate Mass In Search of “Tracers” of “Fracking” Contaminates

    24 June 2015

    Confidentiality Label

    7

    • Six flowback samples from

    Colorado

    • Dilute 1/10, filter through

    PFTE 0.1 micron

    • Use slow gradient with C-8

    column, 3.5 micron, 0.1%

    Formic acid/ACN gradient

    • High Res Q-TOF analysis

    with accurate mass

    – 1290 Agilent UHPLC

    – 6540 Agilent Q/TOF

    – 1 ppm Mass Accuracy

    – 25,000 Resolving Power

    Samples and Prep

    Work performed by Dr. Michael Thurman, University of Colorado, Boulder

  • Total Ion Chromatogram Production flow-back water from Niobrara Formation

    24 June 2015

    Confidentiality Label

    8

    Hydrophilic Series

    Hydrophobic Series

    • Series of Peaks early and late in the chromatogram

    • A Hydrophilic Series and a Hydrophobic series

    • Masses Differ by 44 mass units suggesting CH2-CH2-O structure for both

  • Fracturing Fluid Composition What is injected into the well?

    24 June 2015

    Confidentiality Label

    9

    Proprietary “mixture” containing:

    • Water, sand, surfactants, biocides, solvents, distillates, simple

    alcohols and glycols, recycled water

    Ingredient disclosure required in Colorado

    Glycols -CH2-CH2-O = 44 u

  • Fracturing Fluid Composition Mass Difference among HPI and HPO Series (Ethoxylates?)

    24 June 2015

    Confidentiality Label

    10

  • Calculating Kendrick Mass Scaling Factor for [CH2-CH2-O]

    24 June 2015

    Confidentiality Label

    11

    KM Scaling Factor = Isobaric Mass of CH2-CH2-O /

    Accurate mass of CH2-CH2-O

    KMSF = 44.0000/ 44.0265

    KMSF = 0.999404559

  • Calculating Kendrick Mass Scaling Factor for [CH2-CH2-O]

    24 June 2015

    Confidentiality Label

    12

    KM = Measured Accurate mass x KMSC

    KM Defect = Nominal KM-Exact KM

    Why it works: adding exactly 44.0000 mass units

    to each new polymeric species, i.e. EO-5 to EO-6, etc.;

    therefore, mass defect remains the same. Multiplication of

    0.999404559 makes this correction for all related

    compounds.

  • Applying the Kendrick Mass Defect to Measured Masses in HPI-Series

    24 June 2015

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    13

    Time Measured Mass Kendrick Putative Identification Exact Mass Error

    (Min) (m/z) Mass (m/z) (ppm)

    3.5 173.0784 172.975 PEG-EO3 Na Adduct 173.0784 0.0

    4.2 217.1042 216.975 PEG-EO4 Na Adduct 217.1046 2.0

    5.4 261.1304 260.975 PEG-EO5 Na Adduct 261.1309 2.0

    7.3 305.1569 304.975 PEG-EO6 Na Adduct 305.1571 0.7

    9.5 349.1833 348.975 PEG-EO7 Na Adduct 349.1833 0.0

    10.2 393.2092 392.975 PEG-EO8 Na Adduct 393.2095 0.8

    10.7 432.2802 432.023 PEG-EO9 NH4 Adduct 432.2803 0.2

    11.0 476.3066 476.023 PEG-EO10 NH4 Adduct 476.3065 0.2

    11.3 520.3324 520.023 PEG-EO11 NH4 Adduct 520.3328 0.8

    11.5 564.3585 564.022 PEG-EO12 NH4 Adduct 564.3590 0.9

    11.7 608.3856 608.023 PEG-EO13 NH4 Adduct 608.3852 0.7

    11.9 652.4113 652.023 PEG-EO14 NH4 Adduct 652.4114 0.2

    • Formula Generation from m/z 173.0784

    • C6H14O4-Na+ ------Chem Spider Search

    • Identification of PEGs

    • Next test Model with MS/MS, PEG EO-6 and EO-12

  • MS/MS of m/z 283 (1) and MS/MS of EO-12 at m/z 564 (2) May be the EO-6 H+

    24 June 2015

    Confidentiality Label

    14

    44.01267

    44.01254

    44.01261

    44.01257

    44.01256

    44.01263 44.01255 CH2=CHOH

    18.0110

    MH+

    MNH4+

    MNa+

    1

    2

  • MS/MS of m/z 283 and MS/MS of EO-12 at m/z 564 May be the EO-6 H+

    24 June 2015

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    15

    Two Series of Fragmentations

    • H20 and CH2=CHOH to 3 diagnostic ions

    • CH2=CHOH and H20 to 3 diagnostic ions

    89, 133, 177 (Ferrer et al. 2003)

    O OH

    C4H9O2+

    Exact Mass: 89.0597

    O O

    OH

    C6H13O3+

    Exact Mass: 133.0859

    O O

    O

    OH

    C8H17O4+

    Exact Mass: 177.1121

    O

    HO

    HO

    O O

    O

    OO

    HO

  • Chromatogram of PEG-400 Standard (Mixture)

    24 June 2015

    Confidentiality Label

    16

    EO-6

    EO-6 Na+

    EO-6 H+

    283.1751

    564.3585 EO-12

  • Na+ H+

    NH4+

    PEG-EO7

    PEG-EO8

    PEG-EO9

    NH4+

    NH4+

    H+

    H+

    Na+

    Na+

    OH(CH2CH2O)8H

    H

    C16H35O9+

    Exact Mass: 371.2276

    OH(CH2CH2O)7H

    H

    C14H31O8+

    Exact Mass: 327.2013

    OH(CH2CH2O)9H

    H

    C18H39O10+

    Exact Mass: 415.2538

  • Proposed Crown Ether Structure Ammonium Adduct Formation

    24 June 2015

    Confidentiality Label

    18

    O

    O

    O

    O

    O

    O

    O

    O

    OHN

    H

    H

    HH

    OH

    Ionic Radii

    Na+ =0.102 nm, H3O+ = 0.143 nm

    K + = 0.138, NH4+ = 0.145 nm

    Percent Adduct Type

    EO-8 PEG H+ Na+ NH4+

    % % %

    EO-4 4 96

    EO-5 15 85

    EO-6 33 66

    EO-7 60 40

    EO-8 40 20 40EO-9 20 20 60

    EO-10 15 15 70

    EO-11 6 14 80

    EO-12 5 15 80

    EO-13 6 14 80

    EO-14 6 14 80

    PEG H+ Na+ NH4+% % %

    EO-4 1 99

    EO-5 8 92

    EO-6 20 80

    EO-7 40 60

    EO-8 33 33 33EO-9 20 30 50

    EO-10 10 25 65

    EO-11 5 25 70

    EO-12 5 25 70

    EO-13 5 25 70

    EO-14 5 25 70

    //upload.wikimedia.org/wikipedia/commons/9/9f/Atomic_&_ionic_radii.svg

  • NH4+ Na+

    Density Functional Theory DFT Calculations by Jens Blotvogel, CSU

    Table S3: Total free energies, binding constants, and atomic distances for the PEG-EO9

    ammonium complex as a function of the number of interacting oxygen atoms calculated

    at the IEFPCM/B3LYP/6-311G(d,p) level of theory.

    No. of

    interacting O

    Total Free

    Energy

    (hartree)

    Binding

    Constant

    log K

    Min. H-O

    Distance

    (Å)

    Avg. H-O

    Distance

    (Å)

    Min. N-O

    Distance

    (Å)

    Avg. N-O

    Distance

    (Å)

    6 -1517.854737 4.5 1.86 3.44 2.85 4.18

    7 -1517.856880 5.5 1.86 2.99 2.86 3.64

    8 -1517.861084 7.4 1.90 2.73 2.92 3.48

    9 -1517.862942 8.3 1.84 2.60 2.87 3.31

    10 -1517.866147 9.7 1.84 2.44 2.87 3.14

    Table S4: Total free energies, binding constants, and atomic distances for the PEG-EO9

    sodium complex as a function of the number of interacting oxygen atoms calculated at

    the IEFPCM/B3LYP/6-311G(d,p) level of theory.

    No. of

    interacting O Total Free Energy

    (hartree) Binding

    Constant log K Min. Na-O

    Distance (Å) Avg. Na-O

    Distance (Å)

    6 -1623.106201 2.6 2.44 4.03

    7 -1623.109024 3.9 2.46 3.54

    8 -1623.109559 4.1 2.49 3.22

    9 -1623.111726 5.1 2.49 3.16

    10 -1623.117648 7.9 2.44 3.00

  • Table S5: Total free energies and binding constants for the PEG-cation complexes

    calculated at the IEFPCM/B3LYP/6-311G(d,p) level of theory.

    Na+ NH4

    + Δ log K

    (NH4+ - Na

    +)

    Total Free

    Energy

    (hartree)

    Binding

    Constant log

    K

    Total Free

    Energy

    (hartree)

    Binding

    Constant log K

    PEG EO9 -1623.117648 7.9 -

    1517.866147 9.7 1.8

    PEG EO8 -1469.300690 10.0 -

    1364.047481 11.1 1.1

    PEG EO7 -1315.483483 12.2 -

    1210.227166 11.8 -0.4

    This result explains why we see the PEG prefer NH4+ ion over Na+ at EO-8.

    60X

    NH4

    Free Energy and Binding Constants

  • Changes in Adduct Formation

    EO-20 changes to NH4+ and NH4+

    OO

    O

    OO

    O

    OOO

    HO

    OO

    O

    OO

    O

    OO

    HO

    NH H

    H

    H

    N HH

    H

    H

    H3O+ = 0.143 nm

    H+

  • Hydrophobic Series

    Total Ion Chromatogram - Production Water

    • Late Series of peaks in the chromatogram

    • Masses Differ by 44 mass units suggesting CH2-CH2-O structure

    • Elution reverses, more EOs the shorter the retention time

    26.05 820.5996 820.111 C-12 EO-14 NH4

    26.28 776.5740 776.112 C-12 EO-13 NH4 44.0256

    26.49 732.5475 732.111 C-12 EO-12 NH4 44.0265

    26.71 688.5215 688.112 C-12 EO-11 NH4 44.0260

    26.93 644.4952 644.111 C-12 EO-10 NH4 44.0263

    27.16 600.4686 600.111 C-12 EO-9 NH4 44.0266

    27.40 556.4422 556.111 C-12 EO-8 NH4 44.0264

    27.65 512.4160 512.111 C-12 EO-7 NH4 44.0262

    27.89 468.3898 468.111 C-12 EO-6 NH4 44.0262

    • Kendrick Mass Defect all equal, EO accurate mass

    • Formula for m/z 468.3898 is C24H54NO7 • Chem Spider matches a C-12 ethoxylate

    • MS/MS is next

  • MS/MS of m/z 468.3896 C-12 EO-6 NH4

    468.3896

    -17.0010

    NH3

    -168.1883

    -18.0101

    -44.0262

    Na+ 21.9821

    HO

    (CH 2CH 2O )6H

    N H 3C 24H 54N O 7+

    Exact M ass: 468.3895

    C -12 EO 6

    C12H24Exact Mass: 168.1878

  • H+H+

    H+NH4+

    H+Na+

    Na+Na+

    NH4+NH4

    + NH4

    +Na+

    PEG EO17

    Mass Spectrum for doubly charged PEG EO17 with mixed double adducts of Na+, NH4+,

    and H+ for sample SF-1. The singly charged PEG EO17 also formed at a lesser

    concentration with adducts of H+, Na+, and NH4+ (data not shown). The doubly charged

    species shown here were the major ions found in the mass spectrum.

    Mass Spectrum for doubly charged PEG EO17

  • SF-1

    107

    107

    21 PEGs

    30 PEGs

    20 PEGs

    GF-1

    SF-2 107 EO-9

    EO-9

    EO-9

    EO-21

    Bimodal PEGs

    Figure S3. Frac-t-Gram for PEG surfactants in three flowback samples.

  • Conclusions

    PEG Composition

    1. PEGs (in all 3 flowback samples)

    2. Alkyl-EOs present in (2) flowback samples

    3. Produced Water has PEGs

    Kendrick Mass Defect

    1. KMD works to find related EO’s

    2. KMD finds multiply charged species

    3. KMD finds mixed adducts

  • Acknowledgments

    Tom Evans of Protreat Technologies, Denver, CO, for

    Flowback Samples

    Joe Weitzel and Jerry Zweigenbaum of Agilent

    Technologies, Inc. for LC/QTOF-MS support

  • Acknowledgments

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