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“Fracking Up” Drinking Water?



    Court D. Sandau, PhD, PChem
     Watertech 2012 – Banff, AB
            April 11, 2012
Recent Headlines

                         December 8, 2011
EPA says fracking likely polluted Wyoming
aquifer
Recent Headlines


                          December 15, 2011
Marcellus firm pays $93K for fouling
Clearfiled County Stream



                          January 17, 2012

Regulators say hydraulic fracturing may have
caused oil spill on farm near Innisfail
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                                   Tighter shale-gas exploration rules recommended                              http://www.calgaryherald.com/technology/Tighter+shale+explor...




                                                                                                                                                               April 3, 2012
Tighter shale-gas exploration rules recommended
                                             “Fracking,” a technique in which water, sand and
                                             chemicals are pumped underground to break apart
                                             natural gas-rich shale, has drawn criticism in the U.S. and
                                             Quebec.
                                             Photograph by: Julia Schmalz , Bloomberg News file photo
                                             QUEBEC — A committee named by Quebec Environment Minister Pierre Arcand to determine whether shale gas can be
                                             extracted while respecting the environment released plans Tuesday for further study and recommended the minister not
                                             authorize hydraulic fracturing, or fracking, even for research purposes.

                                             Arcand, in announcing the strategic environmental assessment last May, had said fracking would be allowed for research
                                             purposes.

                                             Committee chair Robert Joly said in his report that Quebec could rely on laboratory experiments on fracking.

                                             He announced the committee would order several more studies with a deadline of next spring.

                                             He said the final report would be completed sometime in 2013.

                                             Joly reported that the committee learned a lot from public hearings held from November 2011 to January 2012 and said
                                             there would be further hearings, targeted at specific sectors including agriculture.



Postmedia News April 3, 2012
                                             Committee members would also travel to Alberta and British Columbia, and to -Ohio, Pennsylvania and New York where
                                             there are also shale-gas deposits.

                                             © Copyright (c) The Montreal Gazette




                                   7 of 18                                                                                                                    12-04-07 8:42 AM

    Re co m m e n d

    Tweet     3



                                                                                                                                                                                  April 5, 2012
         0



        Story
        Photos ( 1 )


Quebec bans any fracking pending studies
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                      Recent Headlines
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                                                                February 6, 2012
Most Canadians oppose natural-gas 'fracking'

In B.C., 67 per cent support moratorium on controversial extraction method
in shale deposits

By Natalie Stechyson, Postmedia News February 6, 2012

    Re co m m e n d
    Tweet     24


Comment
         2
                                                                  December 12, 2011
1


The majority of Canadians and a strong majority of British Columbians oppose hydraulic fracturing - better known as
"fracking" - and would sup-port a moratorium on the natural gas extraction method, a poll reveals.
    Encana slams EPA’s Wyoming fracking finding
The Environics Research poll, commissioned by the Council of Canadians, found that 62 per cent of the Canadians polled
supported a moratorium on all fracking for natural gas until all environmental reviews are complete.

B.C. residents, at 67 per cent, were most likely to support a moratorium on fracking. B.C. was followed by Atlantic Canada,
where 66 per of those polled supported a moratorium, then Ontario (65 per cent), Manitoba/Saskatchewan (64 per cent),
Alberta (57 per cent) and Quebec (55 per cent).
Dealing with Landowner Claims

  • Landowners with
    O&G knowledge
    can take advantage
  • Guilty until proven
    innocent
  • Insufficient data
    and lack of
    information on
    fluids is problematic
Methods for Identifying Fluids
                 • Frack fluids are complex!
                 • Over 1000 compounds identified in fluid
                   below
                 • Analyzed by GC-TOF-MS
                                                                              QuEChERS Extract
                                Few OH’s



                                            Sulfur’s


Courtesy of Frank Dorman PhD,
Penn State University
                                 Aliphatics, OH’s, esters, COOH’s, etc…     Liquid/Liquid Extract
                                                                          Heavier OH’s

                                                            Mid OH’s
                                                            Sulfur
Case Study

• November – baseline water well sampling
• January – CBM well drilling completed
• February – fracking begins (1.4 km away from
  landowner’s home)
• Early March – fracking complete
• End of March – residential water complaint
Case Study
• June to July – client hired consultant to
  collect water samples for analysis
   – Eight ‘untargeted’ sampling events
   – Routine analysis – CBM package
   – Some samples sent to Health Unit for
     analysis
   – July – fibrous (non-soluble) material
     reported in water – sent to a petrology
     lab
Results from Preliminary Work

          • Toluene found in water well
          • Several exceedances of
            ‘natural’ components
               – Turbidity, TDS, Total Fe,
                 Total Mn, Na
          • White fibrous material
            identified as:
                   “TRIOXANE!”
Symptoms: (includes breakdown into formaldehyde)
 Nausea Vomiting Headaches Dizziness Pain in mouth Difficulty Urinating
   Convulsions Coma    Genotoxic    Fetotoxic Death
Case Study

• July – preliminary results
  reported to landowner and
  regulators
• August – brought onto case,
  might go legal
• August – regulator involvement
  begins

                        Let’s Review
Next Thought?
Data Review


• Fibrous material
                                  Trioxane
  cannot be Trioxane         MW: 90.08 g/mol
                         Solubility: 17.2 g/100 mL
• Solubility too high     White crystalline solid
                             Inherent toxicity
Data Review
• Petrology lab should not be
  determining source
   – XRD/XES not specific enough
   – Used elemental identification
• Trioxane dissolves in acid and base,
  this material did not

      16 % Quartz
      84 % Trioxane


                         =         (     )n
                         Polyacetal by FTIR
Developed a More Formalized
         Approach
• Routine analysis does not help for
  frack fluids
• What should be looked for?
  – Look at MSDS and find target
    compounds
• Determined an approach
  – Legal sample water wells and surface
    water
  – Camera for well integrity & well cleaning
  – Legal sampling water wells and surface
    water
Useless MSDS Information
     Use
 Frack Fluid 1


 Frack Fluid 2




• Frack company not very forth coming
• Assured us that they do not use
  Trioxane
• Relunctantly supplied samples
Determining Analytical Program
                     and Results of Investigation
  Product Name                   Ingredients                      %                 Related Analysis                 Water Sample Results

    Product 1                     Proprietary                 Unknown                Alkanolamine                         Not Detected
                                                                Trade
                            Potassium Metaborate                    Secr        Routine water chemistry              No Indication of Impact
                                                                     et
    Product 2
                             Potassium Hydroxide               0.1 to 25        Routine water chemistry              No Indication of Impact

                               Ethylene Glycol                 0.1 to 25             Glycol screen                        Not Detected

                    No hazardous materials are contained in
    Product 3                                                 Unknown                     N/A                                 N/A
                                this product

                              Secondary Alcohol               Proprietary            Alcohol screen                       Not Detected

                                                                             VOCs / TEHs/ Mineral Oil and
                                Essential Oils                Proprietary                                                 Not Detected
                                                                                       Grease

                                   Alcohols                   Proprietary            Alcohol screen                       Not Detected
    Product 4
                                                                                                                Low levels of toluene detected in
                               Alkyl Alkoxylate               Proprietary            VOCs / TEHs                main well, source identified (next
                                                                                                                              slide)

                                Organic Polyol                Proprietary        Glycol / Alcohol screen                  Not Detected



Routine       CBM
                                                                            Routine Water Chemistry, BTEX,       No Concern, stable pre and post
      Testing
                                     N/A                         N/A        F1-F2, Coliforms, Metals, PAH’s               conditions
      /Additional
                                                                            Dissolved Polyacetal and Trioxane        Trioxane not detected
      Parameters
Legal Sampling

• Legal sampling important
• Data can stand scrutiny
  of litigation proceedings
  (if necessary)
• Process documents
  integrity of sampling
  procedures as well as of
  the samples
Sampling Events
• Regulators wanted to take
  independent samples to analyze
  themselves
• Sampling over long weekend,
  regulator left landowner with sample
  bottles!!
• Legally defensible?
Field Notes & Documentation




Experimental Procedure
• 200mL of HPLC water and ~2.0g of tape, were
                                                    • Field notes
sonicated together for 1 hour                       • Observations from
• 5mL of the tape extracts was analyzed for BTEX    experiment
• Using the exact tape mass, the concentration of
toluene was calculated to be 290 mg/kg
Conclusions
• Investigations can go sideways
  quickly – hire the right consultant to
  take to completion
• Frack fluid composition needs to be
  available to client
• Analyze for appropriate, targeted
  analytes
   – Routine parameters not sufficient
   – Target most soluble, most mobile, and
     highest concentration components
Conclusions

• Trioxane was a polymer, likely the
  pump breaking down
• Toluene from electrical tape on pump
• No constituents from frack fluids
  detected in water samples
• Remaining analytes within normal
  limits
  – Better characterization of well water
    would have helped
Results

• Too much ‘bad’ data
• Timing of poor water quality still
  coincidence to fracking?
• Settled with landowners
Questions?



Contact Info:
Chemistry Matters
Court Sandau
csandau@chemistry-matters.com
www.chemistry-matters.com
Twitter – EnviroCertainty

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Fracking up Drinking Water presented at Watertech 2012

  • 1. “Fracking Up” Drinking Water? Court D. Sandau, PhD, PChem Watertech 2012 – Banff, AB April 11, 2012
  • 2. Recent Headlines December 8, 2011 EPA says fracking likely polluted Wyoming aquifer
  • 3. Recent Headlines December 15, 2011 Marcellus firm pays $93K for fouling Clearfiled County Stream January 17, 2012 Regulators say hydraulic fracturing may have caused oil spill on farm near Innisfail
  • 4. Don't miss: Live chat @ 2 p.m.: Flames vs. Mighty Ducks Recent Headlines Easter week around the world Calgary Stampede 2012 Alberta Election 2012 Cultural Calgary 2012 » Tighter shale-gas exploration rules recommended http://www.calgaryherald.com/technology/Tighter+shale+explor... April 3, 2012 Tighter shale-gas exploration rules recommended “Fracking,” a technique in which water, sand and chemicals are pumped underground to break apart natural gas-rich shale, has drawn criticism in the U.S. and Quebec. Photograph by: Julia Schmalz , Bloomberg News file photo QUEBEC — A committee named by Quebec Environment Minister Pierre Arcand to determine whether shale gas can be extracted while respecting the environment released plans Tuesday for further study and recommended the minister not authorize hydraulic fracturing, or fracking, even for research purposes. Arcand, in announcing the strategic environmental assessment last May, had said fracking would be allowed for research purposes. Committee chair Robert Joly said in his report that Quebec could rely on laboratory experiments on fracking. He announced the committee would order several more studies with a deadline of next spring. He said the final report would be completed sometime in 2013. Joly reported that the committee learned a lot from public hearings held from November 2011 to January 2012 and said there would be further hearings, targeted at specific sectors including agriculture. Postmedia News April 3, 2012 Committee members would also travel to Alberta and British Columbia, and to -Ohio, Pennsylvania and New York where there are also shale-gas deposits. © Copyright (c) The Montreal Gazette 7 of 18 12-04-07 8:42 AM Re co m m e n d Tweet 3 April 5, 2012 0 Story Photos ( 1 ) Quebec bans any fracking pending studies
  • 5. Sun Run Student videos Ski Guide Today's Paper Video Recent Headlines » February 6, 2012 Most Canadians oppose natural-gas 'fracking' In B.C., 67 per cent support moratorium on controversial extraction method in shale deposits By Natalie Stechyson, Postmedia News February 6, 2012 Re co m m e n d Tweet 24 Comment 2 December 12, 2011 1 The majority of Canadians and a strong majority of British Columbians oppose hydraulic fracturing - better known as "fracking" - and would sup-port a moratorium on the natural gas extraction method, a poll reveals. Encana slams EPA’s Wyoming fracking finding The Environics Research poll, commissioned by the Council of Canadians, found that 62 per cent of the Canadians polled supported a moratorium on all fracking for natural gas until all environmental reviews are complete. B.C. residents, at 67 per cent, were most likely to support a moratorium on fracking. B.C. was followed by Atlantic Canada, where 66 per of those polled supported a moratorium, then Ontario (65 per cent), Manitoba/Saskatchewan (64 per cent), Alberta (57 per cent) and Quebec (55 per cent).
  • 6. Dealing with Landowner Claims • Landowners with O&G knowledge can take advantage • Guilty until proven innocent • Insufficient data and lack of information on fluids is problematic
  • 7. Methods for Identifying Fluids • Frack fluids are complex! • Over 1000 compounds identified in fluid below • Analyzed by GC-TOF-MS QuEChERS Extract Few OH’s Sulfur’s Courtesy of Frank Dorman PhD, Penn State University Aliphatics, OH’s, esters, COOH’s, etc… Liquid/Liquid Extract Heavier OH’s Mid OH’s Sulfur
  • 8. Case Study • November – baseline water well sampling • January – CBM well drilling completed • February – fracking begins (1.4 km away from landowner’s home) • Early March – fracking complete • End of March – residential water complaint
  • 9. Case Study • June to July – client hired consultant to collect water samples for analysis – Eight ‘untargeted’ sampling events – Routine analysis – CBM package – Some samples sent to Health Unit for analysis – July – fibrous (non-soluble) material reported in water – sent to a petrology lab
  • 10. Results from Preliminary Work • Toluene found in water well • Several exceedances of ‘natural’ components – Turbidity, TDS, Total Fe, Total Mn, Na • White fibrous material identified as: “TRIOXANE!” Symptoms: (includes breakdown into formaldehyde) Nausea Vomiting Headaches Dizziness Pain in mouth Difficulty Urinating Convulsions Coma Genotoxic Fetotoxic Death
  • 11. Case Study • July – preliminary results reported to landowner and regulators • August – brought onto case, might go legal • August – regulator involvement begins Let’s Review
  • 13. Data Review • Fibrous material Trioxane cannot be Trioxane MW: 90.08 g/mol Solubility: 17.2 g/100 mL • Solubility too high White crystalline solid Inherent toxicity
  • 14. Data Review • Petrology lab should not be determining source – XRD/XES not specific enough – Used elemental identification • Trioxane dissolves in acid and base, this material did not 16 % Quartz 84 % Trioxane = ( )n Polyacetal by FTIR
  • 15. Developed a More Formalized Approach • Routine analysis does not help for frack fluids • What should be looked for? – Look at MSDS and find target compounds • Determined an approach – Legal sample water wells and surface water – Camera for well integrity & well cleaning – Legal sampling water wells and surface water
  • 16. Useless MSDS Information Use Frack Fluid 1 Frack Fluid 2 • Frack company not very forth coming • Assured us that they do not use Trioxane • Relunctantly supplied samples
  • 17. Determining Analytical Program and Results of Investigation Product Name Ingredients % Related Analysis Water Sample Results Product 1 Proprietary Unknown Alkanolamine Not Detected Trade Potassium Metaborate Secr Routine water chemistry No Indication of Impact et Product 2 Potassium Hydroxide 0.1 to 25 Routine water chemistry No Indication of Impact Ethylene Glycol 0.1 to 25 Glycol screen Not Detected No hazardous materials are contained in Product 3 Unknown N/A N/A this product Secondary Alcohol Proprietary Alcohol screen Not Detected VOCs / TEHs/ Mineral Oil and Essential Oils Proprietary Not Detected Grease Alcohols Proprietary Alcohol screen Not Detected Product 4 Low levels of toluene detected in Alkyl Alkoxylate Proprietary VOCs / TEHs main well, source identified (next slide) Organic Polyol Proprietary Glycol / Alcohol screen Not Detected Routine CBM Routine Water Chemistry, BTEX, No Concern, stable pre and post Testing N/A N/A F1-F2, Coliforms, Metals, PAH’s conditions /Additional Dissolved Polyacetal and Trioxane Trioxane not detected Parameters
  • 18. Legal Sampling • Legal sampling important • Data can stand scrutiny of litigation proceedings (if necessary) • Process documents integrity of sampling procedures as well as of the samples
  • 19. Sampling Events • Regulators wanted to take independent samples to analyze themselves • Sampling over long weekend, regulator left landowner with sample bottles!! • Legally defensible?
  • 20. Field Notes & Documentation Experimental Procedure • 200mL of HPLC water and ~2.0g of tape, were • Field notes sonicated together for 1 hour • Observations from • 5mL of the tape extracts was analyzed for BTEX experiment • Using the exact tape mass, the concentration of toluene was calculated to be 290 mg/kg
  • 21. Conclusions • Investigations can go sideways quickly – hire the right consultant to take to completion • Frack fluid composition needs to be available to client • Analyze for appropriate, targeted analytes – Routine parameters not sufficient – Target most soluble, most mobile, and highest concentration components
  • 22. Conclusions • Trioxane was a polymer, likely the pump breaking down • Toluene from electrical tape on pump • No constituents from frack fluids detected in water samples • Remaining analytes within normal limits – Better characterization of well water would have helped
  • 23. Results • Too much ‘bad’ data • Timing of poor water quality still coincidence to fracking? • Settled with landowners
  • 24. Questions? Contact Info: Chemistry Matters Court Sandau csandau@chemistry-matters.com www.chemistry-matters.com Twitter – EnviroCertainty

Editor's Notes

  • #10: Untargeted routine analyses is NOT the answer Don’t collect data to collect data
  • #13: Lots of meaningless data to be explained
  • #14: The toxic thing identified not even correct!