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

Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of American 112 (2015): 13184-13189, doi: 10.1073/pnas.1511474112 .Hundreds of organic chemicals are utilized during natural gas extraction via high volume hydraulic fracturing (HVHF). However, it is unclear if these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and impact local water quality, either from deep underground 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 (GRO; 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 1) inorganic chemical fingerprinting of deep saline groundwater, 2) characteristic noble gas isotopes, and 3) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety (EHS) violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and a 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.The authors thank Duke University’s Pratt School of Engineering and the National Science Foundation’s CBET Grant Number 1336702 and NSF EAGER (EAR-1249255) for financial support.2016-04-1

Long-term attitude change after a single-day manager training addressing mental health at the workplace

Mental health problems have become one of the most common causes of incapacity for work, and engender high costs to society. Especially managerial behavior was found to have a great impact on employees’ well-being. In order to support those in leading positions in dealing with their own, as well as their employees’, psychological stress factors, we conducted a specific manager training. At the same time, we wanted to find out about the training’s short- and long-term e ects. Participants were asked to give information about their knowledge and attitudes concerning mental health (Mental Health Knowledge Schedule, Social Distance Scale), as well as to comment on their own health condition (12-Item Short Form Health Survey, Patient Health Questionnaire) and working situation (E ort–Reward Inventory, Irritation Scale). Data were collected at baseline, as well as 3 and 12 months after the training. Results show long-term improvements in knowledge and attitudes measured by the Mental Health Knowledge Schedule (MAKS: Mt1 = 22.88, Mt2 = 23.79, Mt3 = 23.79, p = 0.005) but not in the Social Distance Scale (SoDi: Mt1 = 0.96, Mt2 = 0.85, Mt3 = 0.84, p = 0.165). Over the period of time observed, no changes were found regarding health- or work-related instruments. Due to the uncontrolled design of the study, further research is needed to determine the exact effectiveness

Long-Term Attitude Change After a Single-Day Manager Training Addressing Mental Health at the Workplace

Mental health problems have become one of the most common causes of incapacity for work, and engender high costs to society. Especially managerial behavior was found to have a great impact on employees’ well-being. In order to support those in leading positions in dealing with their own, as well as their employees’, psychological stress factors, we conducted a specific manager training. At the same time, we wanted to find out about the training’s short- and long-term effects. Participants were asked to give information about their knowledge and attitudes concerning mental health (Mental Health Knowledge Schedule, Social Distance Scale), as well as to comment on their own health condition (12-Item Short Form Health Survey, Patient Health Questionnaire) and working situation (Effort–Reward Inventory, Irritation Scale). Data were collected at baseline, as well as 3 and 12 months after the training. Results show long-term improvements in knowledge and attitudes measured by the Mental Health Knowledge Schedule (MAKS: Mt1 = 22.88, Mt2 = 23.79, Mt3 = 23.79, p = 0.005) but not in the Social Distance Scale (SoDi: Mt1 = 0.96, Mt2 = 0.85, Mt3 = 0.84, p = 0.165). Over the period of time observed, no changes were found regarding health- or work-related instruments. Due to the uncontrolled design of the study, further research is needed to determine the exact effectiveness

Natural Gas Residual Fluids: Sources, Endpoints, and Organic Chemical Composition after Centralized Waste Treatment in Pennsylvania

Volumes of natural gas extraction-derived wastewaters have increased sharply over the past decade, but the ultimate fate of those waste streams is poorly characterized. Here, we sought to (a) quantify natural gas residual fluid sources and endpoints to bound the scope of potential waste stream impacts and (b) describe the organic pollutants discharged to surface waters following treatment, a route of likely ecological exposure. Our findings indicate that centralized waste treatment facilities (CWTF) received 9.5% (8.5 × 10⁸ L) of natural gas residual fluids in 2013, with some facilities discharging all effluent to surface waters. In dry months, discharged water volumes were on the order of the receiving body flows for some plants, indicating that surface waters can become waste-dominated in summer. As disclosed organic compounds used in high volume hydraulic fracturing (HVHF) vary greatly in physicochemical properties, we deployed a suite of analytical techniques to characterize CWTF effluents, covering 90.5% of disclosed compounds. Results revealed that, of nearly 1000 disclosed organic compounds used in HVHF, only petroleum distillates and alcohol polyethoxylates were present. Few analytes targeted by regulatory agencies (e.g., benzene or toluene) were observed, highlighting the need for expanded and improved monitoring efforts at CWTFs

Indications of Transformation Products from Hydraulic Fracturing Additives in Shale-Gas Wastewater

Unconventional natural gas development (UNGD) generates large volumes of wastewater, the detailed composition of which must be known for adequate risk assessment and treatment. In particular, transformation products of geogenic compounds and disclosed additives have not been described. This study investigated six Fayetteville Shale wastewater samples for organic composition using a suite of one- and two-dimensional gas chromatographic techniques to capture a broad distribution of chemical structures. Following the application of strict compound-identification-confidence criteria, we classified compounds according to their putative origin. Samples displayed distinct chemical distributions composed of typical geogenic substances (hydrocarbons and hopane biomarkers), disclosed UNGD additives (e.g., hydrocarbons, phthalates such as diisobutyl phthalate, and radical initiators such as azobis­(isobutyronitrile)), and undisclosed compounds (e.g., halogenated hydrocarbons, such as 2-bromohexane or 4-bromoheptane). Undisclosed chloromethyl alkanoates (chloromethyl propanoate, pentanoate, and octanoate) were identified as potential delayed acids (i.e., those that release acidic moieties only after hydrolytic cleavage, the rate of which could be potentially controlled), suggesting they were deliberately introduced to react in the subsurface. In contrast, the identification of halogenated methanes and acetones suggested that those compounds were formed as unintended byproducts. Our study highlights the possibility that UNGD operations generate transformation products and underscores the value of disclosing additives injected into the subsurface