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Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities
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 injectio...
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Published in: | Proceedings of the National Academy of Sciences - PNAS 2015-10, Vol.112 (43), p.13184-13189 |
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creator | Drollette, Brian D. Hoelzer, Kathrin Warner, Nathaniel R. 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. |
description | 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. |
doi_str_mv | 10.1073/pnas.1511474112 |
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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.</description><identifier>ISSN: 0027-8424</identifier><identifier>EISSN: 1091-6490</identifier><identifier>DOI: 10.1073/pnas.1511474112</identifier><identifier>PMID: 26460018</identifier><language>eng</language><publisher>United States: National Academy of Sciences</publisher><subject>Gas Chromatography-Mass Spectrometry ; Gasoline - analysis ; Groundwater ; Groundwater - chemistry ; Hydraulic fracturing ; Oil and Gas Industry ; Organic chemicals ; Organic Chemicals - analysis ; Physical Sciences ; Trace elements ; Water Pollutants, Chemical - analysis ; Water quality</subject><ispartof>Proceedings of the National Academy of Sciences - PNAS, 2015-10, Vol.112 (43), p.13184-13189</ispartof><rights>Volumes 1–89 and 106–112, copyright as a collective work only; author(s) retains copyright to individual articles</rights><rights>Copyright National Academy of Sciences Oct 27, 2015</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a524t-d92991b9d4ec8f90c97af67e4d567d075c72292bfedf28adf1d57010a0fa8ab33</citedby><cites>FETCH-LOGICAL-a524t-d92991b9d4ec8f90c97af67e4d567d075c72292bfedf28adf1d57010a0fa8ab33</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Uhttp://www.pnas.org/content/112/43.cover.gif</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/26465750$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/26465750$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>230,314,727,780,784,885,27924,27925,53791,53793,58238,58471</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26460018$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Drollette, Brian D.</creatorcontrib><creatorcontrib>Hoelzer, Kathrin</creatorcontrib><creatorcontrib>Warner, Nathaniel R.</creatorcontrib><creatorcontrib>Darrah, Thomas H.</creatorcontrib><creatorcontrib>Karatum, Osman</creatorcontrib><creatorcontrib>O’Connor, Megan P.</creatorcontrib><creatorcontrib>Nelson, Robert K.</creatorcontrib><creatorcontrib>Fernandez, Loretta A.</creatorcontrib><creatorcontrib>Reddy, Christopher M.</creatorcontrib><creatorcontrib>Vengosh, Avner</creatorcontrib><creatorcontrib>Jackson, Robert B.</creatorcontrib><creatorcontrib>Elsner, Martin</creatorcontrib><creatorcontrib>Plata, Desiree L.</creatorcontrib><title>Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities</title><title>Proceedings of the National Academy of Sciences - PNAS</title><addtitle>Proc Natl Acad Sci U S A</addtitle><description>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). 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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.</abstract><cop>United States</cop><pub>National Academy of Sciences</pub><pmid>26460018</pmid><doi>10.1073/pnas.1511474112</doi><tpages>6</tpages><oa>free_for_read</oa></addata></record> |
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subjects | Gas Chromatography-Mass Spectrometry Gasoline - analysis Groundwater Groundwater - chemistry Hydraulic fracturing Oil and Gas Industry Organic chemicals Organic Chemicals - analysis Physical Sciences Trace elements Water Pollutants, Chemical - analysis Water quality |
title | Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities |
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