Removal of 6-methylquinoline from shale gas wastewater using electrochemical carbon nanotubes filter.

6-Methylquinoline (6-MQ) is identified as a high-concentration organic compound pervasive in shale gas wastewater (SGW) and poses a significant risk of environmental pollution. In response, this study aimed to address these challenges by introducing an innovative electrochemical membrane constructed with multi-walled carbon nanotubes (CNTs) for the removal of 6-MQ. The investigation systematically explored the impact of voltage, initial pollutant concentration, and salinity on the performance of the electrochemical CNTs filter. It was found a positive correlation between removal efficiency and increasing voltage and salinity levels. Conversely, as the initial concentration of pollutants increased, the efficiency showed a diminishing trend. The electrochemical CNTs filter exhibited remarkable efficacy in both adsorption removal and electrochemical oxidation of 6-MQ. Notably, the CNTs membrane exhibited robust adsorption capabilities, evidenced by the sustained adsorption of 6-MQ for over 33 hours. Furthermore, applying an electrochemical oxidation voltage of 3 V consistently maintained a removal rate exceeding 34.0% due to both direct and indirect oxidation, underscoring the sustained efficacy of the electrochemical membranes. Besides, real wastewater experiments, while displaying a reduction in removal efficiency compared to synthetic wastewater experiments, emphasized the substantial potential of the electrochemical CNTs filter for practical applications. This study underscores the significant promise of electrochemical membranes in addressing low molecular weight contaminants in SGW, contributing valuable insights for advancing SGW treatment strategies.

Characterizing hazardous substances of shale gas wastewater from the upper Yangtze River: A focus on heavy metals and organic compounds.

In the last decade, rapid shale gas exploration in upper Yangtze River ecological zone in China has led to increasing concerns about the environmental impact of shale gas wastewater (SGW). However, our understanding of the types of potential hazardous substances of SGW remains limited. In this study, eight SGW samples from three shale gas regions in upper Yangtze River: the Sichuan Basin, the Guizhou Plateau, and the Three Gorges Area were collected, and their general water quality, trace metals, and organic compounds were comprehensively analyzed. Our in-depth analysis detected 55 kinds of trace heavy metals, with 24 exceeding detection limits. Most of them were of the concentration below 100 µg/L. Concentrations of primary pollutants, including Cd, Cr, As, Pb, and Ni, remained below Integrated Wastewater Discharge Standard (GB 8978-1996), indicating minimal environmental risk. The organic analysis identified 45 to 104 kinds of volatile and semi-volatile organic compounds in SGW samples from different regions. SGW samples from the Sichuan Basin exhibited a balanced proportion of aliphatic and aromatic compounds, with oxygen and nitrogen-substituted heteroatomic compounds prevailing, while SGW samples from the Guizhou Plateau and the Three Gorges Area were dominated by aromatic compounds, particularly hydrocarbons. Several organic substances exhibited high response strengths across multiple SGW samples, including isoquinoline, dibenzylamine, 2,4-di-tert-butylphenol, 1,2,3,4-tetrahydro-naphthalene, and 1,2,3,4-tetrahydro-6-methyl-naphthalene. The Globally Harmonized System (GHS) of Classification and Labelling of Chemicals classified most high-response organics as high acute and chronic aquatic hazards. Our findings indicate that high salinity and a variety of high-risk organic pollutants, rather than heavy metals, are the primary pollutants in SGW, underscoring the urgency of safety management of SGW.

Shale gas wastewater characterization: Comprehensive detection, evaluation of valuable metals, and environmental risks of heavy metals and radionuclides.

Shale gas wastewater (SGW) has great potential for the recovery of valuable elements, but it also poses risks in terms of environmental pollution, with heavy metals and naturally occurring radioactive materials (NORM) being of major concerns. However, many of these species have not been fully determined. For the first time, we identify the elements present in SGW from the Sichuan Basin and consequently draw a comprehensive periodic table, including 71 elements in 15 IUPAC groups. Based on it, we analyze the elements possessing recycling opportunities or with risk potentials. Most of the metal elements in SGW exist at very low concentrations (< 0.2 mg/L), including rare earth elements, revealing poor economic feasibility for recovery. However, salts, strontium (Sr), lithium (Li), and gallium (Ga) are in higher concentrations and have impressive market demands, hence great potential to be recovered. As for environmental burdens related to raw SGW management, salinity, F, Cl, Br, NO3-, Ba, B, and Fe, Cu, As, Mn, V, and Mo pose relatively higher threats in view of the concentrations and toxicity. The radioactivity is also much higher than the safety range, with the gross α activity and gross ß activity in SGW ranging from 3.71-83.4 Bq/L, and 1.62-18.7 Bq/L, respectively and radium-226 as the main component. The advanced combined process "pretreatment-disk tube reverse osmosis (DTRO)" with pilot-scale is evaluated for the safe reuse of SGW. This process has high efficiency in the removal of metals and total radioactivity. However, the gross α activity of the effluent (1.3 Bq/L) is slightly higher than the standard for discharge (1 Bq/L), which is thus associated with potential long-term environmental hazards.

Efficient removal of organic compounds from shale gas wastewater by coupled ozonation and moving-bed-biofilm submerged membrane bioreactor.

Shale gas wastewater (SGW) with complex composition and high salinity needs an economical and efficient method of treatment with the main goal to remove organics. In this study, a coupled system consisting of ozonation and moving-bed-biofilm submerged membrane bioreactor (MBBF-SMBR) was comprehensively evaluated for SGW treatment and compared with a similar train comprising ozonation and submerged membrane bioreactor (SMBR) without addition of carriers attaching biofilm. The average removal rates of MBBF-SMBR were 77.8% for dissolved organic carbon (DOC) and 37.0% for total nitrogen (TN), higher than those observed in SMBR, namely, 73.9% for DOC and 18.6% for TN. The final total membrane resistance in SMBR was 40.1% higher than that in MBBF-SMBR. Some genera that specifically contribute to organic removal were identified. Enhanced gene allocation for membrane transport and nitrogen metabolism was found in MBBF-SMBR biofilm, implying that this system has significant industrial application potential for organics removal from SGW.

Organics removal from shale gas wastewater by pre-oxidation combined with biologically active filtration.

Biological treatment technology is increasingly explored in shale gas wastewater (SGW) treatment owing to its cost effectiveness and requires efforts to improve its efficacy. In this work, ozone and ferrate(VI) oxidation pre-treatment were evaluated to enhance the performance of the subsequent biologically active filtration (BAF) in the removal of organic contaminants. The oxidation improved the SGW biodegradability and organic composition under relative high salinity (~20 g/L). Due to the degradation activity of microorganisms, the organics removal efficiency in the BAF system was observed to gradually improve and then reaching stability in long-term continuous-mode operation. The removal rate of dissolved organic carbon (DOC) of the ozone-BAF (O3-BAF) and the ferrate(VI)-BAF (Fe(VI)-BAF) systems was 83.2% and 82.8% , respectively, higher than that of BAF alone (80.9%). This increase was attributed to higher activity and content of microorganisms in O3-BAF and Fe(VI)-BAF systems. Two uncultured bacterial species with high abundance of 7.2-21.0% and 2.24-22.31% in genus Rehaibacterium and genus Methyloversatilis were significantly correlated with DOC removal and fluorescent organics removal, respectively. More research is needed to understand whether the species were new and their specific function. This study provides valuable suggestions for extracting safe water from SGW with an efficient treatment train.

Green and sustainable method of manufacturing anti-fouling zwitterionic polymers-modified poly(vinyl chloride) ultrafiltration membranes.

The nonsolvent induced phase separation (NIPS) method for ultrafiltration (UF) membrane fabrication relies on the extensive use of traditional solvents, thus ranking first in terms of ecological impacts among all the membrane fabrication steps. Methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate (PolarClean), as a green solvent, was utilized in this study to fabricate poly(vinyl chloride) (PVC) UF membranes. Subsequently, in post-treatment process, zwitterionic polymer, [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (DMAPS), was grafted onto the membrane surface to enhance its anti-fouling properties using a greener surface-initiated activator regenerated by electron transfer-atom transfer radical polymerization (ARGET-ATRP) reaction. This novel method used low toxicity chemicals, avoiding the environmental hazards of traditional ATRP, and greatly improving the reaction efficiency. We systematically studied the grafting time effect on the resulted membranes using sodium alginate as the foulant, and found that short grafting time (30 min) achieved excellent membrane performance: pure water permeability of 2872 L m-2 h-1 bar-1, flux recovery ratio of 86.4% after 7-hour fouling test, and foulant rejection of 96.0%. This work discusses for the first time the greener procedures with lower environmental impacts in both fabrication and modification processes of PVC UF membranes.

Efficient integrated module of gravity driven membrane filtration, solar aeration and GAC adsorption for pretreatment of shale gas wastewater.

Low-cost and efficient treatment processes are urgently needed to manage highly decentralized shale gas wastewater, which seriously threatens the environment if not properly treated. We propose a simple integrated pretreatment process for on-site treatment, whereby gravity driven membrane filtration is combined with granular activated carbon (GAC) adsorption and solar aeration. The rationale of exploitment of sustainable solar energy is that most shale gas production areas are decentralized and located in desert/rural areas characterized by relatively scarce transportation and power facilities but also by abundant sunshine. In this study, GAC and aeration significantly increased the stable flux (170%) and improved effluent quality. Specifically, the dissolved organic carbon removal rate of the integrated system was 44.9%. The high stable flux was attributed to a reduction of extracellular polymeric substances accumulated on the membrane, as well as to the more porous and heterogeneous biofilm formed by eukaryotes with stronger active predation behavior. The prevailing strains, Gammaproteobacteria (35.5%) and Alphaproteobacteria (56.5%), played an important active role in organic carbon removal. The integrated system has great potential as pretreatment for shale gas wastewater due to its low energy consumption, low operational costs, high productivity, and effluent quality.

Superwettable PVDF/PVDF-g-PEGMA Ultrafiltration Membranes.

Poly(vinylidene fluoride) (PVDF) is a common and inexpensive polymeric material used for membrane fabrication, but the inherent hydrophobicity of this polymer induces severe membranes fouling, which limits its applications and further developments. Herein, we prepared superwettable PVDF membranes by selecting suitable polymer concentration and blending with PVDF-graft-poly(ethylene glycol) methyl ether methacrylate (PVDF-g-PEGMA). This fascinating interfacial phenomenon causes the contact angle of water droplets to drop from the initial value of over 70° to virtually 0° in 0.5 s for the best fabricated membrane. The wetting properties of the membranes were studied by calculating the surface free energy by surface thermodynamic analysis, by evaluating the peak height ratio from Raman spectra, and other surface characterization methods. The superwettability phenomenon is the result of the synergetic effects of high surface free energy, the Wenzel model of wetting, and the crystalline phase of PVDF. Besides superwettability, the PVDF/PVDF-g-PEGMA membranes show great improvements in flux performance, sodium alginate (SA) rejection, and flux recovery upon fouling.

Improving the Performance of PVDF/PVDF-g-PEGMA Ultrafiltration Membranes by Partial Solvent Substitution with Green Solvent Dimethyl Sulfoxide during Fabrication.

Traditional organic solvents used in membrane manufacturing, such as dimethylformamide and tetrahydrofuran, are generally very hazardous and harmful to the environment and human health. Their total or partial substitution with green solvent dimethyl sulfoxide (DMSO) is proposed to fabricate membranes composed of poly(vinylidene fluoride) (PVDF) blended with PVDF-graft-poly(ethylene glycol) methyl ether methacrylate (PEGMA), with the purpose to accomplish a greener chemical process and enhance the membrane performance. Various organic solvent compositions were first investigated using the Hansen solubility theory, and the best mixture was thus applied experimentally. The membrane prepared by a ratio of N,N-dimethylacetamide/DMSO = 7:3 outperformed the membranes prepared by other solvent mixtures. This membrane showed high wetting behavior with the water contact angle declining from 71 to 7° in 18 s and a pure water flux reaching values larger than 700 L m-2 h-1 under 0.07 MPa applied hydraulic pressure. The membrane rejected sodium alginate at a rate of 87%, and nearly complete flux recovery was achieved following fouling and physical cleaning. The introduction of green chemistry concepts to PVDF/PVDF-g-PEGMA blended membranes is a step forward in the goal to increase the sustainability of membrane production.

Effect of volatile solvent and evaporation time on formation and performance of PVC/PVC-g-PEGMA blended membranes.

In order to further improve the performances of fabricated PVC/PVC-graft-poly(ethylene glycol) methyl ether methacrylate (PVC/PVC-g-PEGMA) blended membranes, we investigated the inner connections between affecting parameters during preparation and membrane performances. Two parameters including the composition of casting solutions and the solvent evaporation time were selected. In this study, PVC/PVC-g-PEGMA blended membranes were prepared by non-solvent induced phase separation (NIPS) using 1-methyl-2-pyrrolidinone (NMP) and tetrahydrofuran (THF) as mixing solvents. We found that (1) the membrane morphologies like surface pore size and porosity decreased as the ratio of THF to NMP increased, which resulted in the decrease in pure water flux and the increase of sodium alginate (SA) rejection ratio; (2) the presence of THF in the casting solution could significantly lower the membrane surface roughness compared to only using NMP as a solvent; (3) solvent evaporation for an appropriate time increased the hydrophilicity of the membrane. Among these findings, we achieved a membrane exhibiting the highest flux recovery ratio of 98.65 ± 0.85% with a mixing ratio of 1 : 9 (THF : NMP) at 60 s of evaporation time. High pollutant rejection and high flux recovery ratio were achieved. This study provides more insight into the PVC/PVC-g-PEGMA membrane and a more flexible approach to the application of PVC membranes.