Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities

Brian D. Drollette, Kathrin Hoelzer, Nathaniel Richard Warner, Thomas H. Darrah, Osman Karatum, Megan P. O'Connor, Robert K. Nelson, Loretta A. Fernandez, Christopher M. Reddy, Avner Vengosh, Robert B. Jackson, Martin Elsner, Desiree L. Plata

Research output: Contribution to journalArticle

71 Citations (Scopus)

Abstract

Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency's maximum contaminant levels, and low levels of both gasoline range (0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.

Original languageEnglish (US)
Pages (from-to)13184-13189
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume112
Issue number43
DOIs
StatePublished - Oct 27 2015

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Groundwater
Gases
Natural Gas
Inorganic Chemicals
Diethylhexyl Phthalate
Organic Chemicals
Oil and Gas Fields
Noble Gases
Volatile Organic Compounds
United States Environmental Protection Agency
Gasoline
Environmental Health
Water Quality
Isotopes
Safety
Injections
Water
Hydraulic Fracking

All Science Journal Classification (ASJC) codes

  • General

Cite this

Drollette, Brian D. ; Hoelzer, Kathrin ; Warner, Nathaniel Richard ; Darrah, Thomas H. ; Karatum, Osman ; O'Connor, Megan P. ; Nelson, Robert K. ; Fernandez, Loretta A. ; Reddy, Christopher M. ; Vengosh, Avner ; Jackson, Robert B. ; Elsner, Martin ; Plata, Desiree L. / Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities. In: Proceedings of the National Academy of Sciences of the United States of America. 2015 ; Vol. 112, No. 43. pp. 13184-13189.
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abstract = "Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency's maximum contaminant levels, and low levels of both gasoline range (0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.",
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Drollette, BD, Hoelzer, K, Warner, NR, Darrah, TH, Karatum, O, O'Connor, MP, Nelson, RK, Fernandez, LA, Reddy, CM, Vengosh, A, Jackson, RB, Elsner, M & Plata, DL 2015, 'Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities', Proceedings of the National Academy of Sciences of the United States of America, vol. 112, no. 43, pp. 13184-13189. https://doi.org/10.1073/pnas.1511474112

Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities. / Drollette, Brian D.; Hoelzer, Kathrin; Warner, Nathaniel Richard; Darrah, Thomas H.; Karatum, Osman; O'Connor, Megan P.; Nelson, Robert K.; Fernandez, Loretta A.; Reddy, Christopher M.; Vengosh, Avner; Jackson, Robert B.; Elsner, Martin; Plata, Desiree L.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 112, No. 43, 27.10.2015, p. 13184-13189.

Research output: Contribution to journalArticle

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T1 - Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities

AU - Drollette, Brian D.

AU - Hoelzer, Kathrin

AU - Warner, Nathaniel Richard

AU - Darrah, Thomas H.

AU - Karatum, Osman

AU - O'Connor, Megan P.

AU - Nelson, Robert K.

AU - Fernandez, Loretta A.

AU - Reddy, Christopher M.

AU - Vengosh, Avner

AU - Jackson, Robert B.

AU - Elsner, Martin

AU - Plata, Desiree L.

PY - 2015/10/27

Y1 - 2015/10/27

N2 - Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency's maximum contaminant levels, and low levels of both gasoline range (0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.

AB - Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency's maximum contaminant levels, and low levels of both gasoline range (0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.

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