Flowback verses first-flush: new information on the geochemistry of produced water from mandatory reporting.

Unconventional oil and gas development uses the subsurface injection of large amounts of a variety of industrial chemicals, and there are concerns about the return of these chemical to the surface with water produced with oil and gas from stimulated wells. Produced water, including any flowback of injected fluids, must be managed so as to protect human health and the environment, and understanding the chemistry of produced water from stimulated wells is necessary to ensure the safe management of produced water. In 2014, California instituted mandatory reporting for all well stimulations, including sampling produced water two times and comprehensive chemical characterization of fluids injected and fluids recovered from stimulated wells. In this study, we analyzed data from mandatory reporting with the objective of closing previously identified data gaps concerning oil-field chemical practices and the nature of flowback and produced water from stimulated wells. It was found that the plug-flow conceptual model of flowback developed in shale formations, where salinity increases over time as produced water is extracted, was not appropriate for characterizing produced water from unconventional wells in these oil reservoirs, which are predominately diatomite and sandstones. In these formations stimulation caused a "first-flush" phenomena, where salts and metals were initially high and then decreased in concentration over time, as more produced water was extracted. Although widely applied to meet regulatory requirements, total carbohydrate measurement was not found to be a good chemical indicator of hydraulic fracturing flowback. Mandatory reporting closed data-gaps concerning chemical use, provided new information on acid treatments, and allowed more detailed analysis of hydraulic fracturing practices, including comparison of water use by geological formation.

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 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.

Pairing high-frequency data with a link-node model to manage dissolved oxygen impairment in a dredged estuary.

High-frequency data and a link-node model were used to investigate the relative importance of mass loads of oxygen-demanding substances and channel geometry on recurrent low dissolved oxygen (DO) in the San Joaquin River Estuary in California. The model was calibrated using 6 years of data. The calibrated model was then used to determine the significance of the following factors on low DO: excavation of the river to allow navigation of large vessels, non-point source pollution from the agricultural watershed, effluent from a wastewater treatment plant, and non-point source pollution from an urban area. An alternative metric for low DO, excess net oxygen demand (ENOD), was applied to better characterize DO impairment. Model results indicate that the dredged ship channel had the most significant effect on DO (62 % fewer predicted hourly DO violations), followed by mass load inputs from the watershed (52 % fewer predicted hourly DO violations). Model results suggest that elimination of any one factor will not completely resolve DO impairment and that continued use of supplemental aeration is warranted. Calculation of ENOD proved more informative than the sole use of DO. Application of the simple model allowed for interpretation of the extensive data collected. The current monitoring program could be enhanced by additional monitoring stations that would provide better volumetric estimates of low DO.

Treatment of oil-water emulsion from the machinery industry by Fenton's reagent.

An oil-water emulsion from the machinery industry was treated using Fenton's reagent. The objective was to reduce the high chemical oxygen demand (COD) of this waste stream so that it would meet the COD effluent limit of Chinese Standard JS-7740-95. The optimal [H2O2]/[Fe2+] ratio for COD removal was 3. An orthogonal experimental design was developed based on the optimal [H2O2]/[Fe2+] ratio to evaluate the significance of four parameters relevant to the treatment process, namely, H2O2 dosage, initial pH, oxidation time and coagulation pH. The influence of the four parameters on COD removal efficiency decreased as follows: H2O2 dosage>oxidation time>coagulation pH>initial pH. The COD removal efficiency was further investigated based on the most important single-factor parameter, which was H2O2 dosage, as discovered in the orthogonal test. A well-fitted empirical correlation was obtained from the single-factor analysis and up to 98% COD removal was attained using 50 mM H2O2. Using the doses and conditions identified in this study, the treated oil-water emulsion can be discharged according to Chinese Standard JS-7740-95.

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.

Performance of sanitary sewer collection system odour control devices operating in diverse conditions.

Controlling odours from sanitary sewer systems is challenging as a result of the expansive nature of these systems. Addition of oxidizing chemicals is often practiced as a mitigation strategy. One alternative is to remove odorous compounds in the gases vented from manholes using adsorptive media. In this study, odour control devices located at manholes were observed to determine the ability of these systems to reduce hydrogen sulphide from vented gases. The odour control devices incorporated pressure regulation to control gas flow out of manhole covers and adsorptive media to remove hydrogen sulphide in the vented gases prior to release. Pressure regulation was accomplished using a variable volume bladder and two pressure relief valves that permitted gas flow when pressures exceeded 1.3 to 2.5 cm water column. The reduction in gas flow vented from manholes was intended to extend the service life of the adsorptive media, as compared with odour control devices that do not incorporate pressure modulation. Devices were deployed at four locations and three adsorptive media were tested. Although measured collection system hydrogen sulphide concentrations varied from zero to over 1,000 ppm, the removal rates observed using odour control devices were typically above 90%. The lower removal rates observed at one of the sites (50.5 ± 36.1%) appeared related to high gas flow rates being emitted at this location. Activated carbon was used in most of the tests, although use of iron media resulted in the highest removal observed: 97.8 ± 3.6%. The expected service life of the adsorptive media contained within the odour control devices is a function of site-specific hydrogen sulphide concentrations and gas flow rates. The units used in this study were in service for more than 8 to 12 months prior to requiring media replacement.

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.

Modeling the inactivation of microorganisms occluded in effluent wastewater particles to enhance operation of filtration and disinfection systems.

In disinfection systems, incomplete penetration of chlorine into effluent wastewater particles can result in a residual population of viable microorganisms. In this work, a combined experimental and numerical approach was used to quantify inactivation of microorganisms in effluent particles and identify combinations of particle removal and chlorine dose that would result in a reduction of occluded microorganisms for six full-scale facilities in the United States with different nitrification levels. The results reveal that combined chlorine is more effective for inactivating occluded microorganisms than free chlorine; model calibration results suggest that free chlorine is less effective because it is more reactive. However, nitrified effluents appear to have lower effluent particle concentrations, and decreases in particle concentrations significantly reduce the chlorine required. Additionally, in disinfection systems that are designed and operated based on inactivation of indicator organisms, the chlorine dose may be insufficient to inactivate occluded pathogens to levels consistent with current regulations.