How to Adapt Chemical Risk Assessment for Unconventional Hydrocarbon Extraction Related to the Water System.

We identify uncertainties and knowledge gaps of chemical risk assessment related to unconventional drillings and propose adaptations. We discuss how chemical risk assessment in the context of unconventional oil and gas (UO&G) activities differs from conventional chemical risk assessment and the implications for existing legislation. A UO&G suspect list of 1,386 chemicals that might be expected in the UO&G water samples was prepared which can be used for LC-HRMS suspect screening. We actualize information on reported concentrations in UO&G-related water. Most information relates to shale gas operations, followed by coal-bed methane, while only little is available for tight gas and conventional gas. The limited research on conventional oil and gas recovery hampers comparison whether risks related to unconventional activities are in fact higher than those related to conventional activities. No study analyzed the whole cycle from fracturing fluid, flowback and produced water, and surface water and groundwater. Generally target screening has been used, probably missing contaminants of concern. Almost half of the organic compounds analyzed in surface water and groundwater exceed TTC values, so further risk assessment is needed, and risks cannot be waived. No specific exposure scenarios toward groundwater aquifers exist for UO&G-related activities. Human errors in various stages of the life cycle of UO&G production play an important role in the exposure. Neither at the international level nor at the US federal and the EU levels, specific regulations for UO&G-related activities are in place to protect environmental and human health. UO&G activities are mostly regulated through general environmental, spatial planning, and mining legislation.

Effects of high pressure and temperature conditions on the chemical fate of flowback water related chemicals.

Environmental risk assessment is generally based on atmospheric conditions for the modelling of chemical fate after entering the environment. However, during hydraulic fracturing, chemicals may be released deep underground. This study therefore focuses on the effects of high pressure and high temperature conditions on chemicals in flowback water to determine whether current environmental fate models need to be adapted in the context of downhole activities. Crushed shale and flowback water were mixed and exposed to different temperature (25-100 °C) and pressure (1-450 bar) conditions to investigate the effects they have on chemical fate. Samples were analysed using LC-HRMS based non-target screening. The results show that both high temperature and pressure conditions can impact the chemical fate of hydraulic fracturing related chemicals by increasing or decreasing concentrations via processes of transformation, sorption, degradation and/or dissolution. Furthermore, the degree and direction of change is chemical specific. The change is lower or equal to a factor of five, but for a few individual compounds the degree of change can exceed this factor of five. This suggests that environmental fate models based on surface conditions may be used for an approximation of chemical fate under downhole conditions by applying an additional factor of five to account for these uncertainties. More accurate insight into chemical fate under downhole conditions may be gained by studying a fluid of known chemical composition and an increased variability in temperature and pressure conditions including concentration, salinity and pH as variables.

Comparing conventional and green fracturing fluids by chemical characterisation and effect-based screening.

There is public and scientific concern about air, soil and water contamination and possible adverse environmental and human health effects as a result of hydraulic fracturing activities. The use of greener chemicals in fracturing fluid aims to mitigate these effects. This study compares fracturing fluids marketed as either 'conventional' or 'green', as assessed by their chemical composition and their toxicity in bioassays. Chemical composition was analysed via non-target screening using liquid chromatography - high resolution mass spectrometry, while toxicity was evaluated by the Ames fluctuation test to assess mutagenicity and CALUX reporter gene assays to determine specific toxicity. Overall, the results do not indicate that the 'green' fluids are less harmful than the 'conventional' ones. First, there is no clear indication that the selected green fluids contain chemicals present at lower concentrations than the selected conventional fluids. Second, the predicted environmental fate of the identified compounds does not seem to be clearly distinct between the 'green' and 'conventional' fluids, based on the available data for the top five chemicals based on signal intensity that were tentatively identified. Furthermore, Ames fluctuation test results indicate that the green fluids have a similar genotoxic potential than the conventional fluids. Results of the CALUX reporter gene assays add to the evidence that there is no clear difference between the green and conventional fluids. These results do not support the claim that currently available and tested green-labeled fracturing fluids are environmentally more friendly alternatives to conventional fracturing fluids.

Chemical and bioassay assessment of waters related to hydraulic fracturing at a tight gas production site.

Publicly available chemical assessments of hydraulic fracturing related waters are generally based on shale gas practices in the U.S. There is a lack of information on hydraulic fracturing related gas development from EU countries and more generally on other types of extractions. This research fills this knowledge gap by presenting chemical and bioassay assessments of hydraulic fracturing related waters from a tight gas development in the Netherlands. Fracturing fluid, flowback water and groundwater from surrounding aquifers before and after the actual fracturing were analysed by means of high resolution liquid chromatography tandem mass spectrometry, the Ames test and three chemical activated luciferase gene expression bioassays aimed at determining genotoxicity, oxidative stress response and polyaromatic hydrocarbon contamination. After sample enrichment a higher number of peaks can be found in both fracturing fluid and flowback samples. No clear differences in chemical composition were shown in the groundwater samples before and after hydraulic fracturing. Preliminary environmental fate data of the tentatively identified chemicals points towards persistence in water. Clear genotoxic and oxidative stress responses were found in the fracturing fluid and flowback samples. A preliminary suspect screening resulted in 25 and 36 matches in positive and negative ionisation respectively with the 338 possible suspect candidates on the list. Extensive measures relating to the handling, transport and treatment of hydraulic fracturing related waters are currently in place within the Dutch context. The results of the present study provide a scientific justification for such measures taken to avoid adverse environmental and human health impacts.

Forms of phosphorus in suspended particulate matter in agriculture-dominated lowland catchments: Iron as phosphorus carrier.

The fate and environmental effects of phosphorus (P) in natural waters depend on its chemical forms. The particulate P (PP) concentration is dominant over the dissolved P concentration in agriculture-dominated headwaters in the Netherlands. Routine water quality monitoring programmes do not include the chemical fractionation of PP. To quantify the chemical forms of PP under various conditions in six agriculture-dominated lowland catchments in the Netherlands, a sequential chemical extraction method was applied to suspended particulate matter (SPM) samples collected by centrifugation or filtration. Centrifuge samples had lower values for the sum of the PP fractions compared with the filtration samples due to lower contents from PP fractions other than the Fe-P pool. With an average value of 8.8mgg-1, internationally high P contents of the SPM were found. Ferric iron-bound P was the most important PP fraction in SPM samples (38-95%; median 74%), followed by organic P (2-38%; median 15%). Exchangeable P ranged from 0.2 to 27%, with a median of 4.4%, Ca-P ranged from 0.1 to 11% with a median of 3.9% and detrital P was present in only a small fraction (0-6%; median 1.1%). Ferric iron-bound P was the dominant PP pool throughout the entire range of watercourses (from headwater ditches to catchment outlets) and in samples taken during winter months as well as those taken during summer months. Furthermore, the PP fraction distribution did not change markedly when flow conditions were altered from low to high discharge. The dominance of the Fe-P pool denotes the presence of Fe(III) precipitates in SPM that originate from exfiltration of anoxic Fe-bearing groundwater. These Fe(III) precipitates are a major fraction of the total SPM concentration (4 to 67% as Fe(OH)3; median 18%). Although not measured directly, our results suggest that formation of authigenic Fe(III) precipitates causes a rapid transformation of dissolved P in groundwater to PP in surface water. We advise including sequential chemical extraction of SPM monitoring programmes because the composition of particles is critical for P bioavailability, which is a key driving factor for eutrophication.