Geochemical fingerprinting and statistical variation of 35 elements in produced water and rock material from offshore chalk reservoirs.

Trace metals and metalloids occur in small quantities in the subsurface water generated from oil wells, called produced water (PW). While these substances are present in low concentrations, PW volumes are sufficiently large that they are still a potential environmental concern. This study has focused on quantifying 71 trace metals and metalloids present in PW from Danish offshore oil production sites. These metals are often a challenge to measure and are globally underreported. By employing optimized sample treatment and ICP-OES and ICP-SFMS methods, the full elemental screening of PW samples collected from various offshore platforms has been carried out with high accuracy. Distinct geochemical signatures involving 35 elements have been discovered and they are associated with significant site-specific variations in the concentrations of key trace metals, including W, Ba, Mo, Cu, and Tl. Utilizing Principal Component Analysis (PCA), the study has effectively distinguished between PW samples from different fields, highlighting the relevance of certain trace metals and elemental ratios as potential geochemical markers. Geochemical analysis of the chalk rock material from the same production wells as the fluid samples has shown a correlation of key elements Tl, W, Cu, Mo, Ba, and As in the chalk with the produced water, indicating the origin of the metals. The study has revealed a high compositional variability of PW and found that elements including Zn, Co, Hg, and Cs occur in concentrations of magnitude higher than previous estimates. In addition, there is high variability in concentrations at different sampling times, underlining the need for environmental monitoring and developing more informed management strategies for the main offshore PW stream. The variability in concentrations in space and time leads to large uncertainties in environmental reporting based on a few samples. The detailed sampling campaign reported here for the first time highlights need for much more frequent sampling, ideally continuous monitoring. The safety of produced water discharge to sea can be significantly underestimated by limited sampling. This paper provides the first field-specific and time varied screening of heavy metals in real produced water and shows the discrepancy in our understanding of the environmental impact of PW.

Recovery of Petroleum Brine-Contaminated Soil by Eleocharis sp. in a Tropical Marshland.

Almost all research on natural attenuation and phytoremediation of sites contaminated with briny produced water has been conducted in temperate climates, however, there is a dearth of information on the use of tropical species for this purpose. It is within this context, that we investigated a spontaneously growing hypersaline spikerush from a contaminated site in southeast Mexico, to determine its soil salinity limits, the relationship between soil organic matter and salinity, and for preliminary documentation of floristic succession with Typha sp. for phytoremediation o f brine s pills. Soil was sampled (0 cm-20 cm) three times between 2018-2021, focusing on the end of the dry season (most critical period). The species tentatively identified as Eleocharis mutata was tolerant to soil hypersalinity (Electrical Conductivity: 125 dS/m) and appeared to generate a cyclic process of succession to recover areas with soil salinity levels higher than it could otherwise tolerate. A salinity gradient was found between the most heavily contaminated part of the site ("kill zone", > 212 dS/m), the first Eleocharis sp. individuals (125 dS/m), slowly advancing through the main spikerush stand, and finally into a cattail stand (< 8.02 dS/m). Similarly, an inverse relationship between Soil Organic Matter content and soil salinity was observed. This is the first time this species has been identified with a brine spill, its salinity limits determined, and investigated for use in phytoremediation of this kind.

Application of green solvents for arsenic removal from petroleum produced water: Statistical, DFT and McCabe-Thiele determination.

This work presents the novel application of green oils to extract arsenic ions from petroleum produced water via liquid-liquid extraction (LLE). In the experiment, the removal of arsenic ions from synthetic petroleum produced water is investigated, using five green oils: canola oil, corn oil, linseed oil, rice bran oil, and sunflower oil, in place of petroleum-based solvents: toluene and kerosene. Both extraction and stripping optimizations are examined. For extractants, Aliquat 336 and Cyanex 921 are implemented. The initial arsenic concentration (3.984 mg L-1) of petroleum produced water is examined. Results demonstrate that Aliquat 336 in corn oil proved to be most effective for arsenic removal. At optimal conditions via response surface methodology (RSM), the highest extraction and stripping percentages reached 99.95 % and 100.00 %, respectively. In accordance with the World Health Organization (WHO) levels of ≤0.01 mg L-1, arsenic concentration remaining in the extracted water (0.002 mg L-1), is seen to fulfill the requirement needed. The extraction and stripping kinetics are of first and second-order. Mechanisms of arsenic removal are evaluated via density functional theory (DFT). Further, selectivity, recycling of the organic phase, and the number of stages via McCabe-Thiele theory are determined under optimal conditions.

Fertilizer-driven FO and MD integrated process for shale gas produced water treatment: Draw solution evaluation and PAC enhancement.

It is a great challenge for effective treatment of shale gas produced water (SGPW), a typical industrial wastewater with complex composition. Single forward osmosis (FO) or membrane distillation (MD) process has been widely used for desalination of SGPW, with membrane fouling not well addressed. Fertilizer draw solution (DS) with high osmotic pressure is less likely to cause FO fouling and can be used for irrigation. An integrated process using fertilizer-driven FO (FDFO) and MD process was proposed for the first time for SGPW treatment, and characteristics of fertilizer DS and powdered activated carbon (PAC) enhancement were assessed. The DS using KCl and (NH4)2SO4 had high MD fluxes (36.8-38.8 L/(m2·h)) and low permeate conductivity (below 50 µS/cm), increasing the contact angle of the MD membrane by 113 % than that without FO, while the DS using MgCl2 and NH4H2PO4 produced a lower reverse salt flux (0.9-3.2 g/(m2·h)). When diluted DS was treated using PAC, the MD permeate conductivity was further reduced to 35 µS/cm without ammonia, and the membrane hydrophobicity was maintained to 71-83 % of the original. The mechanism of the FDFO-MD integrated process for mitigating MD fouling and improving permeate quality was analyzed, providing guidance for efficient SGPW treatment.

Principles, challenges and prospects for electro-oxidation treatment of oilfield produced water.

The oil industry is facing substantial environmental challenges, especially in managing waste streams such as Oilfield Produced Water (OPW), which represents a significant component of the industrial ecological footprint. Conventional treatment methods often fail to effectively remove dissolved oils and grease compounds, leading to operational difficulties and incomplete remediation. Electrochemical oxidation (EO) has emerged as a promising alternative due to its operational simplicity and ability to degrade pollutants directly and indirectly, which has already been applied in treating several effluents containing organic compounds. The application of EO treatment for OPW is still in an initial stage, due to the intricate nature of this matrix and scattered information about it. This study provides a technological overview of EO technology for OPW treatment, from laboratory scale to the development of large-scale prototypes, identifying design and process parameters that can potentially permit high efficiency, applicability, and commercial deployment. Research in this domain has demonstrated notable rates of removal of recalcitrant pollutants (>90%), utilizing active and non-active electrodes. Electro-generated active species, primarily from chloride, play a pivotal role in the oxidation of organic compounds. However, the highly saline conditions in OPW hinder the complete mineralization of these organics, which can be improved by using non-active anodes and lower salinity levels. The performance of electrodes greatly influences the efficiency and effectiveness of OPW treatment. Various factors must be considered when selecting the electrode material, such as its conductivity, stability, surface area, corrosion resistance, and cost. Additionally, the specific contaminants present in the OPW, and their electrochemical reactivity must be considered to ensure optimal treatment outcomes. Balancing these considerations can be challenging, but it is crucial for achieving successful OPW treatment. Active electrode materials exhibit a high affinity for chloride molecules, generating more active species than non-active materials, which exhibit more significant degradation potential due to the production of hydroxyl radicals. Regarding scale-up, key challenges include low current efficiency, the formation of by-products, electrode deactivation, and limitations in mass transfer. To address these issues, enhanced mass transfer rates and appropriate residence times can be achieved using flow-through mesh anodes and moderate current densities, which have proven to be the optimal configuration for this process.

Determining Marine Biodegradation Kinetics of Chemicals Discharged from Offshore Oil Platforms─Whole Mixture Testing at High Dilutions Increases Environmental Relevance.

Offshore oil platforms discharge enormous volumes of produced water that contain mixtures of petrochemicals and production chemicals. It is crucial to avoid the discharge of particularly those chemicals that are persistent in the marine environment. This study aims to (1) develop a biodegradation testing approach for discharged chemicals by native marine microorganism, (2) determine how dilution affects biodegradation, and (3) determine biodegradation kinetics for many discharged chemicals at low and noninhibitory concentrations. Produced water from an offshore oil platform was diluted in the ratio of 1:20, 1:60, and 1:200 in seawater from the same location and incubated for 60 days at 10 °C. Automated solid-phase microextraction GC-MS was used as a sensitive analytical technique, and chemical-specific primary degradation was determined based on peak area ratios between biotic test systems and abiotic controls. Biodegradation was inhibited at lower dilutions, consistent with ecotoxicity tests. Biodegradation kinetics were determined at the highest dilution for 139 chemicals (43 tentatively identified), and 6 chemicals were found persistent (half-life >60 days). Nontargeted analysis by liquid chromatography-high-resolution MS was demonstrated as a proof-of-principle for a comprehensive assessment. Biodegradation testing of chemicals in discharges provides the possibility to assess hundreds of chemicals at once and find the persistent ones.

Dual COF functionalized magnetic MXene composite for enhancing magnetic solid phase extraction of thiophene compounds from oilfield produced waters prior to GC-MS/MS analysis.

In this study, a novel COFTABT@COFTATp modified magnetic MXene composite (CoFe2O4 @Ti3C2 @COFTABT@COFTATp) was synthesized by Schiff base reaction and irre-versible enol-keto tautomerization, and employed to establish a sensitive monitoring method for six thiophene compounds in oilfield produced water samples based on magnetic solid-phase extraction (MSPE) prior to gas chromatography coupled with a triple quadruple mass spectrometer (GC-MS/MS). The designed magnetic materials exhibited unexpected enrichment ability to target thiophene compounds and achieved good extraction efficiencies ranging from 83 % to 98 %. The developed MSPE/GC-MS/MS method exhibited good linearity in the range of 0.001-100 µg L-1, and obtained lower limits of detection ranging from 0.39 to 1.9 ng L-1. The spiked recoveries of thiophene compounds obtained in three oilfield produced water samples were over the range of 96.26 %-99.54 % with relative standard deviations (RSDs) less than 3.7 %. Notably, benzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene were detected in three oilfield-produced water samples. Furthermore, the material still kept favorable stability after six recycling experiments. The adsorption kinetics, adsorption isotherms as well as adsorption thermodynamics of thiophene compounds were investigated in detail to provide insight into the mechanisms. Overall, the present work contributed a promising strategy for designing and synthesizing new functionalized materials for the enrichment and detection of typical pollutants in the environment.

Wastewaters Coproduced with Shale Gas Drive Slight Regional Salinization of Groundwater.

While unconventional oil and gas (UOG) development is changing the world economy, processes that are used during UOG development such as high-volume hydraulic fracturing ("fracking") have been linked with water contamination. Water quality risks include leaks of gas and salty fluids (brines) that are coproduced at wellpads. Identifying the cause of contamination is difficult, however, because UOG wells are often colocated with other contaminant sources. We investigated the world's largest shale gas play with publicly accessible groundwater data (Marcellus Shale in Pennsylvania, U.S.A. with ∼29,000 analyses) and discovered that concentrations of brine-associated barium ([Ba]) and strontium ([Sr]) show small regional increases within 1 km of UOG development. Higher concentrations in groundwaters are associated with greater proximity to and density of UOG wells. Concentration increases are even larger when considering associations with the locations of (i) spill-related violations and (ii) some wastewater impoundments. These statistically significant relationships persist even after correcting for other natural and anthropogenic sources of salts. The most likely explanation is that UOG development slightly increases salt concentrations in regional groundwaters not because of fracking but because of the ubiquity of wastewater management issues. These results emphasize the need for stringent wastewater management practices across oil and gas operations.

Gravity-driven membrane integrated with membrane distillation for efficient shale gas produced water treatment.

Substantial volumes of hazardous shale gas produced water (SGPW) generated in unconventional natural gas exploration. Membrane distillation (MD) is a promising approach for SGPW desalination, while membrane fouling, wetting, and permeate deterioration restrict MD application. The integration of gravity-driven membrane (GDM) with MD process was proposed to improve MD performance, and different pretreatment methods (i.e., oxidation, coagulation, and granular filtration) were systematically investigated. Results showed that pretreatment released GDM fouling and improved permeate quality by enrich certain microbes' community (e.g., Proteobacteria and Nitrosomonadaceae), greatly ensured the efficient desalination of MD. Pretreatment greatly influences GDM fouling layer morphology, leading to different flux performance. Thick/rough/hydrophilic fouling layer formed after coagulation, and thin/loose fouling layer formed after silica sand filtration improved GDM flux by 2.92 and 1.9 times, respectively. Moreover, the beneficial utilization of adsorption-biodegradation effects significantly enhanced GDM permeate quality. 100 % of ammonia and 53.99 % of UV254 were efficiently removed after zeolite filtration-GDM and granular activated carbon filtration-GDM, respectively. Compared to the surged conductivity (41.29 µS/cm) and severe flux decline (>82 %) under water recovery rate of 75 % observed in single MD for SGPW treatment, GDM economically controlled permeate conductivity (1.39-19.9 µS/cm) and MD fouling (flux decline=8.3 %-27.5 %). Exploring the mechanisms, the GDM-MD process has similarity with Janus MD membrane in SGPW treatment, significantly reduced MD fouling and wetting.

Distribution and Characterization of Quaternary Ammonium Biocides Resistant Bacteria in Different Soils, in South-Western China.

Quaternary ammonium compounds (QACs) are active ingredients in hundreds of disinfectants for controlling the epidemic of infectious diseases like SARS-CoV-2 (COVID-19), and are also widely used in shale gas exploitation. The occurrence of QAC-resistant bacteria in the environment could enlarge the risk of sterilization failure, which is not fully understood. In this study, QAC-resistant bacteria were enumerated and characterized in 25 soils collected from shale gas exploitation areas. Total counts of QAC-resistant bacteria ranged from 6.81 × 103 to 4.48 × 105 cfu/g, accounting for 1.59% to 29.13% of the total bacteria. In total, 29 strains were further purified and identified as Lysinibacillus, Bacillus, and Klebsiella genus. There, bacteria covering many pathogenic bacteria showed different QACs tolerance with MIC (minimum inhibition concentration) varying from 4 mg/L to 64 mg/L and almost 58.6% of isolates have not previously been found to tolerate QACs. Meanwhile, the QAC-resistant strains in the produced water of shale gas were also identified. Phylogenetic trees showed that the resistant species in soil and produced water are distinctly different. That is the first time the distribution and characterization of QAC-resistant bacteria in the soil environment has been analyzed.

Benchmarking produced water treatment strategies for non-toxic effluents: Integrating thermal distillation with granular activated carbon and zeolite post-treatment.

The management of produced water (PW) generated during oil and gas operations requires effective treatment and comprehensive chemical and toxicological assessment to reduce the environmental risks associated with reuse or discharge. This study evaluated a treatment train that included a low-temperature thermal distillation pilot system followed by granular activated carbon (GAC) and zeolite post-treatment for processing hypersaline Permian Basin PW. Our study provides a unique and comprehensive assessment of the treatment efficiency considering a targeted chemical scheme together with whole effluent toxicity (WET) tests across four trophic levels regarding aquatic critical receptors of concern (ROC): Raphidocelis subcapitata, Vibrio fischeri, Ceriodaphnia dubia, and Danio rerio. The distillate from the thermal distillation process met various numeric discharge standards for salinity and major ions. However, it did not meet toxicity requirements established by the United States National Pollutant Discharge Elimination System program. Subsequent post-treatment using GAC and zeolite reduced the concentration of potential stressors, including volatile organics, NH3, Cd, Cr, Zn, and Mn in the final effluent to below detection limits. This resulted in a consistent toxicity reduction across all WET tests, with no observable adverse effects for R. subcapitata, C. dubia, and D. rerio (no observed effect concentration >100%), and V. fischeri effects reduced to 19%. This study realizes the feasibility of treating PW to non-toxic levels and meeting reuse and discharge requirements. It underscores the importance of implementing integrated treatment trains to remove the contaminants of concern and provides a systematic decision framework to predict and monitor environmental risks associated with PW reuse.

Utica/Point Pleasant brine isotopic compositions (δ7Li, δ11B, δ138Ba) elucidate mechanisms of lithium enrichment in the Appalachian Basin.

Global Li production will require a ∼500 % increase to meet 2050 projected energy storage demands. One potential source is oil and gas wastewater (i.e., produced water or brine), which naturally has high total dissolved solids (TDS) concentrations, that can also be enriched in Li (>100 mg/L). Understanding the sources and mechanisms responsible for high naturally-occurring Li concentrations can aid in efficient targeting of these brines. The isotopic composition (δ7Li, δ11B, δ138Ba) of produced water and core samples from the Utica Shale and Point Pleasant Formation (UPP) in the Appalachian Basin, USA indicates that depth-dependent thermal maturity and water-rock interaction, including diagenetic clay mineral transformations, likely control Li concentrations. A survey of Li content in produced waters throughout the USA indicates that Appalachian Basin brines from the Marcellus Shale to the UPP have the potential for economic resource recovery.

Ferrate(VI)-based oxidation for ultrafiltration membrane fouling mitigation in shale gas produced water pretreatment: Role of high-valent iron intermediates and hydroxyl radicals.

Ultrafiltration (UF) is increasingly used in the pretreatment of shale gas produced water (SGPW), whereas severe membrane fouling hampers its actual operation. In this work, ferrate(VI)-based oxidation was proposed for membrane fouling alleviation in SGPW pretreatment, and the activation strategies of calcium peroxide (CaO2) and ultraviolet (UV) were selected for comparison. The findings indicated that UV/Fe(VI) was more effective in removing fluorescent components, and the concentration of dissolved organic carbon was reduced by 24.1 %. With pretreatments of CaO2/Fe(VI) and UV/Fe(VI), the terminal specific membrane flux was elevated from 0.196 to 0.385 and 0.512, and the total fouling resistance diminished by 52.7 % and 76.2 %, respectively. Interfacial free energy analysis indicated that the repulsive interactions between pollutants and membrane were notably enhanced by Fe(VI)-based oxidation, thereby delaying the deposition of cake layers on the membrane surface. Quenching and probe experiments revealed that high-valent iron intermediates (Fe(IV)/Fe(V)) played significant roles in both CaO2/Fe(VI) and UV/Fe(VI) processes. Besides, hydroxyl radicals (•OH) were also important reactive species in the UV/Fe(VI) treatment, and the synergistic effect of Fe(IV)/Fe(V) and •OH showed a positive influence on SGPW fouling mitigation. In general, these findings establish a theoretical underpinning for the application of Fe(VI)-based oxidation for UF membrane fouling mitigation in SGPW pretreatment.

Distribution characteristics and ecological risk analysis of microplastics in sediments and effluents related to offshore oil and gas activities in the Bohai Sea, China.

Oil and gas activities are sources of marine microplastics (MPs) but have received less attention globally. This study assessed the distribution characteristics and ecological risks of MPs in 31 sediment samples and effluent samples of 5 oil and gas platforms related to offshore oil and gas activities in the Bohai Sea. The results showed that the mean abundance of MPs in sediment, produced water, and domestic sewage was 205.7 ± 151.5 items/kg d.w., 18 ± 11 items/L, and 26 ± 39 items/L, respectively. The MPs in sediments and effluents were dominated by transparent, rayon, and fibers <1 mm. Oil and gas activities may influence the abundance of MPs in the sediments. The sediments in the area were at a low level of risk, but some samples exhibited indexes beyond low levels. The mass of MPs carried by the effluents from oil and gas platforms in the Bohai Sea was less than that of other sources.

Improving membrane distillation performance by Fe(II) activated sodium percarbonate oxidation during the treatment of shale gas produced water.

Membrane distillation (MD) offers promise for recycling shale gas produced water (SGPW), while membrane fouling is still a major obstacle in standalone MD. Herein, sodium percarbonate (SPC) oxidation was proposed as MD pretreatment, and the performance of the single MD, SPC-MD hybrid process and Fe(II)/SPC-MD hybrid process for SGPW treatment were systematically evaluated. Results showed that compared to raw SGPW, the application of SPC and Fe(II)/SPC led to the decrease of the fluorescent organics by 28.54 % and 54.52 %, respectively. The hydrophobic fraction decreased from 52.75 % in raw SGPW to 37.70 % and 27.20 % for SPC and Fe(II)/SPC, respectively, and the MD normalized flux increased from 0.19 in treating raw SGPW to 0.65 and 0.81, respectively. The superiority of SPC oxidation in reducing the deposited membrane foulants and restoring membrane properties was further confirmed through scanning electron microscopy observation, attenuated total reflection fourier transform infrared, water contact angle and surface tension analyses of fouled membranes. Correlation analysis revealed that hydrophobic/hydrophilic matters and fluorescent organics in SGPW took a crucial role in MD fouling. The mechanism of MD fouling mitigation by Fe(II)/SPC oxidation was attributed to the decrease in concentrations and hydrophobicity of organic by synergistic oxidation, coagulation and adsorption.

Produced water treatment by semi-continuous sequential bioreactor and microalgae photobioreactor.

Produced water (PW) from oil and gas exploration adversely affects aquatic life and living organisms, necessitating treatment before discharge to meet effluent permissible limits. This study first used activated sludge to pretreat PW in a sequential batch reactor (SBR). The pretreated PW then entered a 13 L photobioreactor (PBR) containing Scenedesmus obliquus microalgae culture. Initially, 10% of the PW mixed with 90% microalgae culture in the PBR. After the exponential growth of the microalgae, an additional 25% of PW was added to the PBR without extra nutrients. This study reported the growth performance of microalgae in the PBR as well as the reduction in effluent's total organic carbon (TOC), total dissolved solids (TDS), electrical conductivity (EC), and heavy metals content. The results demonstrated removal efficiencies of 64% for TOC, 49.8% for TDS, and 49.1% for EC. The results also showed reductions in barium, iron, and manganese in the effluent by 95, 76, and 52%, respectively.

Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds.

Naphthenic acids (NA) are organic compounds commonly found in crude oil and produced water, known for their recalcitrance and toxicity. This study introduces a new adsorbent, a polymer derived from spent coffee grounds (SCGs), through a straightforward cross-linking method for removing cyclohexane carboxylic acid as representative NA. The adsorption kinetics followed a pseudo-second-order model for the data (0.007 g min-1 mg-1), while the equilibrium data fitted the Sips model ( q m = 140.55 mg g-1). The process's thermodynamics indicated that the target NA's adsorption was spontaneous and exothermic. The localized sterical and energetic aspects were investigated through statistical physical modeling, which corroborated that the adsorption occurred indeed in monolayer, as suggested by the Sips model, but revealed the contribution of two energies per site ( n 1 ; n 2 ). The number of molecules adsorbed per site ( n ) was highly influenced by the temperature as n 1 decreased with increasing temperature and n 2 increased. These results were experimentally demonstrated within the pH range between 4 and 6, where both C6H11COO-(aq.) and C6H11COOH(aq.) species coexisted and were adsorbed by different energy sites. The polymer produced was naturally porous and amorphous, with a low surface area of 20 to 30 m2 g-1 that presented more energetically accessible sites than other adsorbents with much higher surface areas. Thus, this study shows that the relation between surface area and high adsorption efficiency depends on the compatibility between the energetic states of the receptor sites, the speciation of the adsorbate molecules, and the temperature range studied.

Nickel augmented biochar for sustaining produced water treatment to decarbonize oil and gas industrial waste using anaerobic-aerobic granular cylindrical periodic discontinuous batch reactors.

This study assessed the efficacy of granular cylindrical periodic discontinuous batch reactors (GC-PDBRs) for produced water (PW) treatment by employing eggshell and waste activated sludge (WAS) derived Nickel (Ni) augmented biochar. The synthesized biochar was magnetized to further enhance its contribution towards achieving carbon neutrality due to carbon negative nature, Carbon dioxide (CO2) sorption, and negative priming effects. The GC-PDBR1 and GC-PDBR2 process variables were optimized by the application of central composite design (CCD). This is to maximize the decarbonization rate. Results showed that the systems could reduce total phosphorus (TP) and chemical oxygen demand (COD) by 76-80% and 92-99%, respectively. Optimal organic matter and nutrient removals were achieved at 80% volumetric exchange ratio (VER), 5 min settling time and 3000 mg/L mixed liquor suspended solids (MLSS) concentration with desirability values of 0.811 and 0.954 for GC-PDBR1 and GC-PDBR2, respectively. Employing four distinct models, the biokinetic coefficients of the GC-PDBRs treating PW were calculated. The findings indicated that First order (0.0758-0.5365) and Monod models (0.8652-0.9925) have relatively low R2 values. However, the Grau Second-order model and Modified Stover-Kincannon model have high R2 values. This shows that, the Grau Second Order and Modified Stover-Kincannon models under various VER, settling time, and MLSS circumstances, are more suited to explain the removal of pollutants in the GC-PDBRs. Microbiological evaluation demonstrated that a high VER caused notable rises in the quantity of several microorganisms. Under high biological selective pressure, GC-PDBR2 demonstrated a greater percentage of nitrogen removal via autotrophic denitrification and a greater number of nitrifying bacteria. The overgrowth of bacteria such as Actinobacteriota spp. Bacteroidota spp, Gammaproteobacteria, Desulfuromonas Mesotoga in the phylum, class, and genus, has positively impacted on granule formation and stability. Taken together, our study through the introduction of intermittent aeration GC-PDBR systems with added magnetized waste derived biochar, is an innovative approach for simultaneous aerobic sludge granulation and PW treatment, thereby providing valuable contributions in the journey toward achieving decarbonization, carbon neutrality and sustainable development goals (SDGs).

Metagenome-assembled genomes provide insight into the metabolic potential during early production of Hydraulic Fracturing Test Site 2 in the Delaware Basin.

Demand for natural gas continues to climb in the United States, having reached a record monthly high of 104.9 billion cubic feet per day (Bcf/d) in November 2023. Hydraulic fracturing, a technique used to extract natural gas and oil from deep underground reservoirs, involves injecting large volumes of fluid, proppant, and chemical additives into shale units. This is followed by a "shut-in" period, during which the fracture fluid remains pressurized in the well for several weeks. The microbial processes that occur within the reservoir during this shut-in period are not well understood; yet, these reactions may significantly impact the structural integrity and overall recovery of oil and gas from the well. To shed light on this critical phase, we conducted an analysis of both pre-shut-in material alongside production fluid collected throughout the initial production phase at the Hydraulic Fracturing Test Site 2 (HFTS 2) located in the prolific Wolfcamp formation within the Permian Delaware Basin of west Texas, USA. Specifically, we aimed to assess the microbial ecology and functional potential of the microbial community during this crucial time frame. Prior analysis of 16S rRNA sequencing data through the first 35 days of production revealed a strong selection for a Clostridia species corresponding to a significant decrease in microbial diversity. Here, we performed a metagenomic analysis of produced water sampled on Day 33 of production. This analysis yielded three high-quality metagenome-assembled genomes (MAGs), one of which was a Clostridia draft genome closely related to the recently classified Petromonas tenebris. This draft genome likely represents the dominant Clostridia species observed in our 16S rRNA profile. Annotation of the MAGs revealed the presence of genes involved in critical metabolic processes, including thiosulfate reduction, mixed acid fermentation, and biofilm formation. These findings suggest that this microbial community has the potential to contribute to well souring, biocorrosion, and biofouling within the reservoir. Our research provides unique insights into the early stages of production in one of the most prolific unconventional plays in the United States, with important implications for well management and energy recovery.

Technical Feasibility of Extraction of Freshwater from Produced Water with Combined Forward Osmosis and Nanofiltration.

This study assesses the technical feasibility of a forward-osmosis-based system for concentrating produced water and extracting freshwater. Forward osmosis was combined with nanofiltration, the latter system used to restore the initial osmotic pressure of the diluted draw solutions while concurrently obtaining the final freshwater product. Three draw solutions, namely, MgCl2, NaCl, and C3H5NaO2, were initially tested against a synthetic water mimicking a pretreated produced water effluent having an osmotic pressure equal to 16.3 bar. MgCl2 was thus selected for high-recovery experiments. Different combinations of draw solution osmotic pressure (30, 40, 60, 80, and 120) and draw-to-feed initial volume ratios (1, 1.6, and 2.2) were tested at the laboratory scale, achieving recovery rates between roughly 35% and 70% and water fluxes between 4 and 8 L m-2h-1. One-dimensional, system-wide simulations deploying the analytical FO water flux equation were utilized to validate the experiments, investigate co-current and counter-current configurations, and understand the system potential. The diluted draw solutions were then transferred to nanofiltration to regenerate their original osmotic pressure. There, the highest observed rejection was 96.6% with an average flux of 21 L m-2h-1, when running the system to achieve 100% relative recovery.