Historic and Contemporary Surface Disposal of Produced Water Likely Inputs Arsenic and Selenium to Surficial Aquifers.

Oil and gas development generates large amounts of wastewater (i.e., produced water), which in California has been partially disposed of in unlined percolation/evaporation ponds since the mid-20th century. Although produced water is known to contain multiple environmental contaminants (e.g., radium and trace metals), prior to 2015, detailed chemical characterizations of pondwaters were the exception rather than the norm. Using a state-run database, we synthesized samples (n = 1688) collected from produced water ponds within the southern San Joaquin Valley of California, one of the most productive agricultural regions in the world, to examine regional trends in pondwater arsenic and selenium concentrations. We filled crucial knowledge gaps resulting from historical pondwater monitoring by constructing random forest regression models using commonly measured analytes (boron, chloride, and total dissolved solids) and geospatial data (e.g., soil physiochemical data) to predict arsenic and selenium concentrations in historical samples. Our analysis suggests that both arsenic and selenium levels are elevated in pondwaters and thus this disposal practice may have contributed substantial amounts of arsenic and selenium to aquifers having beneficial uses. We further use our models to identify areas where additional monitoring infrastructure would better constrain the extent of legacy contamination and potential threats to groundwater quality.

Composition, Emissions, and Air Quality Impacts of Hazardous Air Pollutants in Unburned Natural Gas from Residential Stoves in California.

The presence of hazardous air pollutants (HAPs) entrained in end-use natural gas (NG) is an understudied source of human health risks. We performed trace gas analyses on 185 unburned NG samples collected from 159 unique residential NG stoves across seven geographic regions in California. Our analyses commonly detected 12 HAPs with significant variability across region and gas utility. Mean regional benzene, toluene, ethylbenzene, and total xylenes (BTEX) concentrations in end-use NG ranged from 1.6-25 ppmv─benzene alone was detected in 99% of samples, and mean concentrations ranged from 0.7-12 ppmv (max: 66 ppmv). By applying previously reported NG and methane emission rates throughout California's transmission, storage, and distribution systems, we estimated statewide benzene emissions of 4,200 (95% CI: 1,800-9,700) kg yr-1 that are currently not included in any statewide inventories─equal to the annual benzene emissions from nearly 60,000 light-duty gasoline vehicles. Additionally, we found that NG leakage from stoves and ovens while not in use can result in indoor benzene concentrations that can exceed the California Office of Environmental Health Hazard Assessment 8-h Reference Exposure Level of 0.94 ppbv─benzene concentrations comparable to environmental tobacco smoke. This study supports the need to further improve our understanding of leaked downstream NG as a source of health risk.

Physical-chemical evaluation of hydraulic fracturing chemicals in the context of produced water treatment.

Produced water is a significant waste stream that can be treated and reused; however, the removal of production chemicals-such as those added in hydraulic fracturing-must be addressed. One motivation for treating and reusing produced water is that current disposal methods-typically consisting of deep well injection and percolation in infiltration pits-are being limited. Furthermore, oil and gas production often occurs in arid regions where there is demand for new water sources. In this paper, hydraulic fracturing chemical additive data from California are used as a case study where physical-chemical and biodegradation data are summarized and used to screen for appropriate produced water treatment technologies. The data indicate that hydraulic fracturing chemicals are largely treatable; however, data are missing for 24 of the 193 chemical additives identified. More than one-third of organic chemicals have data indicating biodegradability, suggesting biological treatment would be effective. Adsorption-based methods and partitioning of chemicals into oil for subsequent separation is expected to be effective for approximately one-third of chemicals. Volatilization-based treatment methods (e.g. air stripping) will only be effective for approximately 10% of chemicals. Reverse osmosis is a good catch-all with over 70% of organic chemicals expected to be removed efficiently. Other technologies such as electrocoagulation and advanced oxidation are promising but lack demonstration. Chemicals of most concern due to prevalence, toxicity, and lack of data include propargyl alcohol, 2-mercaptoethyl alcohol, tetrakis hydroxymethyl-phosphonium sulfate, thioglycolic acid, 2-bromo-3-nitrilopropionamide, formaldehyde polymers, polymers of acrylic acid, quaternary ammonium compounds, and surfactants (e.g. ethoxylated alcohols). Future studies should examine the fate of hydraulic fracturing chemicals in produced water treatment trains to demonstrate removal and clarify interactions between upstream and downstream processes.

Impact of co-digestion on existing salt and nutrient mass balances for a full-scale dairy energy project.

Anaerobic digestion of manure and other agricultural waste streams with subsequent energy production can result in more sustainable dairy operations; however, importation of digester feedstocks onto dairy farms alters previously established carbon, nutrient, and salinity mass balances. Salt and nutrient mass balance must be maintained to avoid groundwater contamination and salination. To better understand salt and nutrient contributions of imported methane-producing substrates, a mass balance for a full-scale dairy biomass energy project was developed for solids, carbon, nitrogen, sulfur, phosphorus, chloride, and potassium. Digester feedstocks, consisting of thickened manure flush-water slurry, screened manure solids, sudan grass silage, and feed-waste, were tracked separately in the mass balance. The error in mass balance closure for most elements was less than 5%. Manure contributed 69.2% of influent dry matter while contributing 77.7% of nitrogen, 90.9% of sulfur, and 73.4% of phosphorus. Sudan grass silage contributed high quantities of chloride and potassium, 33.3% and 43.4%, respectively, relative to the dry matter contribution of 22.3%. Five potential off-site co-digestates (egg waste, grape pomace, milk waste, pasta waste, whey wastewater) were evaluated for anaerobic digestion based on salt and nutrient content in addition to bio-methane potential. Egg waste and wine grape pomace appeared the most promising co-digestates due to their high methane potentials relative to bulk volume. Increasing power production from the current rate of 369 kW to the design value of 710 kW would require co-digestion with either 26800 L d(-1) egg waste or 60900 kg d(-1) grape pomace. However, importation of egg waste would more than double nitrogen loading, resulting in an increase of 172% above the baseline while co-digestion with grape pomace would increase potassium by 279%. Careful selection of imported co-digestates and management of digester effluent is required to manage salt and nutrient mass loadings and reduce groundwater impacts.

Natural gas odorants: A scoping review of health effects.

PURPOSE OF REVIEW: Organosulfur compounds are intentionally added to natural gas as malodorants with the intent of short-term nasal inhalation to aid in leak detection. Regulatory exposure limits have not been established for all commonly used natural gas odorants, and recent community-level exposure events and growing evidence of indoor natural gas leakage have raised concerns associated with natural gas odorant exposures. We conducted a scoping review of peer-reviewed scientific publications on human exposures and animal toxicological studies of natural gas odorants to assess toxicological profiles, exposure potential, health effects and regulatory guidelines associated with commonly used natural gas odorants. RECENT FINDINGS: We identified only 22 studies which met inclusion criteria for full review. Overall, there is limited evidence of both transient nonspecific health symptoms and clinically diagnosed causative neurotoxic effects associated with prolonged odorant exposures. Across seven community-level exposure events and two occupational case reports, consistent symptom patterns included: headache, ocular irritation, nose and throat irritation, respiratory complaints such as shortness of breath and asthma attacks, and skin irritation and rash. Of these, respiratory inflammation and asthma exacerbations are the most debilitating, whereas the high prevalence of ocular and dermatologic symptoms suggest a non-inhalation route of exposure. The limited evidence available raises the possibility that organosulfur odorants may pose health risks at exposures much lower than presently understood, though additional dose-response studies are needed to disentangle specific toxicologic effects from nonspecific responses to noxious organosulfur odors. Numerous recommendations are provided including more transparent and prescriptive natural gas odorant use practices.

Comparison of chemical-use between hydraulic fracturing, acidizing, and routine oil and gas development.

The potential hazards and risks associated with well-stimulation in unconventional oil and gas development (hydraulic fracturing, acid fracturing, and matrix acidizing) have been investigated and evaluated and federal and state regulations requiring chemical disclosure for well-stimulation have been implemented as part of an overall risk management strategy for unconventional oil and gas development. Similar evaluations for chemicals used in other routine oil and gas development activities, such as maintenance acidizing, gravel packing, and well drilling, have not been previously conducted, in part due to a lack of reliable information concerning on-field chemical-use. In this study, we compare chemical-use between routine activities and the more closely regulated well-stimulation activities using data collected by the South Coast Air Quality Monitoring District (SCAQMD), which mandates the reporting of both unconventional and routine on-field chemical-use for parts of Southern California. Analysis of this data shows that there is significant overlap in chemical-use between so-called unconventional activities and routine activities conducted for well maintenance, well-completion, or rework. A comparison within the SCAQMD shows a significant overlap between both types and amounts of chemicals used for well-stimulation treatments included under State mandatory-disclosure regulations and routine treatments that are not included under State regulations. A comparison between SCAQMD chemical-use for routine treatments and state-wide chemical-use for hydraulic fracturing also showed close similarity in chemical-use between activities covered under chemical disclosure requirements (e.g. hydraulic fracturing) and many other oil and gas field activities. The results of this study indicate regulations and risk assessments focused exclusively on chemicals used in well-stimulation activities may underestimate potential hazard or risk from overall oil field chemical-use.

Identifying chemicals of concern in hydraulic fracturing fluids used for oil production.

Chemical additives used for hydraulic fracturing and matrix acidizing of oil reservoirs were reviewed and priority chemicals of concern needing further environmental risk assessment, treatment demonstration, or evaluation of occupational hazards were identified. We evaluated chemical additives used for well stimulation in California, the third largest oil producing state in the USA, by the mass and frequency of use, as well as toxicity. The most frequently used chemical additives in oil development were gelling agents, cross-linkers, breakers, clay control agents, iron and scale control agents, corrosion inhibitors, biocides, and various impurities and product stabilizers used as part of commercial mixtures. Hydrochloric and hydrofluoric acids, used for matrix acidizing and other purposes, were reported infrequently. A large number and mass of solvents and surface active agents were used, including quaternary ammonia compounds (QACs) and nonionic surfactants. Acute toxicity was evaluated and many chemicals with low hazard to mammals were identified as potentially hazardous to aquatic environments. Based on an analysis of quantities used, toxicity, and lack of adequate hazard evaluation, QACs, biocides, and corrosion inhibitors were identified as priority chemicals of concern that deserve further investigation.

Physical, chemical, and biological characteristics of compounds used in hydraulic fracturing.

Hydraulic fracturing (HF), a method to enhance oil and gas production, has become increasingly common throughout the U.S. As such, it is important to characterize the chemicals found in HF fluids to evaluate potential environmental fate, including fate in treatment systems, and human health impacts. Eighty-one common HF chemical additives were identified and categorized according to their functions. Physical and chemical characteristics of these additives were determined using publicly available chemical information databases. Fifty-five of the compounds are organic and twenty-seven of these are considered readily or inherently biodegradable. Seventeen chemicals have high theoretical chemical oxygen demand and are used in concentrations that present potential treatment challenges. Most of the HF chemicals evaluated are non-toxic or of low toxicity and only three are classified as Category 2 oral toxins according to standards in the Globally Harmonized System of Classification and Labeling of Chemicals; however, toxicity information was not located for thirty of the HF chemicals evaluated. Volatilization is not expected to be a significant exposure pathway for most HF chemicals. Gaps in toxicity and other chemical properties suggest deficiencies in the current state of knowledge, highlighting the need for further assessment to understand potential issues associated with HF chemicals in the environment.