Elucidating biofouling over thermal and spatial gradients in seawater membrane distillation in hot climatic conditions.

Biofouling is a hurdle of seawater desalination that increases water costs and energy consumption. In membrane distillation (MD), biofouling development is complicated due to the temperature effect that adversely affects microbial growth. Given the high relevance of MD to regions with abundant warm seawater, it is essential to explore the biofouling propensity of microbial communities with higher tolerance to elevated temperature conditions. This study presents a comprehensive analysis of the spatial and temporal biofilm distribution and associated membrane fouling during direct contact MD (DCMD) of the Red Sea water. We found that structure and composition of the biofilm layer played a significant role in the extent of permeate flux decline, and biofilms that built up at 45°C had lower bacterial concentration but higher extracellular polymeric substances (EPS) content as compared to biofilms that formed at 55 °C and 65°C. Pore wetting and bacterial passage to the permeate side were initially observed but slowed down as operating time increased. Intact cells in biofilms dominated over the damaged cells at any tested condition emphasizing the high adaptivity of the Red Sea microbial communities to elevated feed temperatures. A comparison of microbial abundance revealed a difference in bacterial distribution between the feed and biofilm samples. A shift in the biofilm microbial community and colonization of the membrane surface with thermophilic bacteria with the feed temperature increase was observed. The results of this study improve our understanding of biofouling propensity in MD that utilizes temperature-resilient feed waters.

Dead-end membrane distillation with localized interfacial heating for sustainable and energy-efficient desalination.

Membrane distillation (MD) has the high potential to circumvent conventional desalination limitations in treating highly saline brines. However, the performance of MD is limited by its low thermal efficiencyand temperature polarization (TP) effect. Consequently, the driving force decreases when heat loss increases.In this study, we propose to minimize TP through localized heating where the thin feed channel was heated uniformly at the membrane-liquid interface without changing the properties of the membrane.This concept was further improved by implementing a new dead-end MD configuration. Investigated for the first time,this configuration eliminated circulation heat losses, which cannot be realized in conventional MD due to a rapid temperature stratification. In addition, the accumulation of foulants on the membrane surface was successfully controlled by intermittent flushing. 3-Dimensional conjugate heat transfer modeling revealedmore uniform heat transfer and temperature gradient across the membrane due to the increased feed water temperature over a larger membrane area. The increase of water vapor flux (45%) and the reduction of heat lossobserved in the new dead-end concept led to a decrease of the specific energy consumption by 57%, corresponding to a gain output ratio increase of about 132 %, compared to a conventional bulk heating, while preserving membrane integrity. A conjugate heat transfer model was deployed in ANSYS-Fluent framework to elucidate on the mechanism of flux enhancement associated with the proposed technique. This study provides a framework for future sustainable MD developmentby maintaining a stable vapor flux while minimizing energy consumption.

Direct contact ultrasound for fouling control and flux enhancement in air-gap membrane distillation.

Air Gap Membrane distillation (AGMD) is a thermally driven separation process capable of treating challenging water types, but its low productivity is a major drawback. Membrane fouling is a common problem in many membrane treatment systems, which exacerbates AGMD's low overall productivity. In this study, we investigated the direct application of low-power ultrasound (8-23 W), as an in-line cleaning and performance boosting technique for AGMD. Two different highly saline feedwaters, namely natural groundwater (3970 µS/cm) and RO reject stream water (12760 µS/cm) were treated using Polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) membranes. Theoretical calculations and experimental investigations are presented, showing that the applied ultrasonic power range only produced acoustic streaming effects that enhanced cleaning and mass transfer. Attenuated Total Reflection Fourier-Transform Infrared Spectroscopy (ATR FT-IR) analysis showed that ultrasound was capable of effectively removing silica and calcium scaling. Ultrasound application on a fouled membrane resulted in a 100% increase in the permeate flux. Cleaning effects accounted for around 30-50% of this increase and the remainder was attributed to mass transfer improvements. Contaminant rejection percentages were consistently high for all treatments (>99%), indicating that ultrasound did not deteriorate the membrane structure. Scanning Electron Microscopy (SEM) analysis of the membrane surface was used to confirm this observation. The images of the membrane surface demonstrated that ultrasound successfully cleaned the previously fouled membrane, with no signs of structural damage. The results of this study highlight the efficient and effective application of direct low power ultrasound for improving AGMD performance.

Coagulation/flocculation process with polyaluminum chloride for the remediation of oil sands process-affected water: Performance and mechanism study.

This study investigated the application of polyaluminum chloride (PACl) for the treatment of the oil sands process-affected water (OSPW). These coagulants are commonly used in water treatment with the most effective species reported to be Al13. PACl with 83.6% Al13 was synthesized using the slow base titration method and compared with a commercially available PACl in terms of aluminum species distribution, coagulation/flocculation (CF) performance, floc morphology, and contaminant removal. Both coagulants were effective in removing suspended solids, achieving over 96% turbidity removal at all applied coagulant doses (0.5-3.0 mM Al). The removal efficiencies of metals varied among different metals depending on their pKa values with metal cations having pKa values (Fe, Al, Ga, and Ti) below OSPW pH of 6.9-8.1 (dose dependent) being removed by more than 90%, while cations with higher pKa values (K, Na, Ca, Mg and Ni) had removals of less than 40%. Naphthenic acids were not removed due to their low molecular weights, negative charges, and hydrophilic characteristics at the OSPW pH. At the highest applied coagulant dose of 3.0 mM Al, the synthetic PACl reduced Vibrio fischeri inhibition effect to 43.3 ± 3.0% from 49.5 ± 0.4% in raw OSPW. In contrast, no reduction of toxicity was found for OSPW treated with the commercial PACl. Based on water quality and floc analyses, the dominant CF mechanism for particle removal during OSPW treatment was considered to be enmeshment in the precipitates (i.e., sweep flocculation). Overall, the CF using synthesized PACl can be a valuable pretreatment process for OSPW to create wastewater that is more easily treated by downstream processes.

Impact of polymeric membrane filtration of oil sands process water on organic compounds quantification.

The interaction between organic fractions in oil sands process-affected water (OSPW) and three polymeric membranes with varying hydrophilicity (nylon, polyvinylidene fluoride and polytetrafluoroethylene) at different pHs was studied to evaluate the impact of filtration on the quantification of acid-extractable fraction (AEF) and naphthenic acids (NAs). Four functional groups predominated in OSPW (amine, phosphoryl, carboxyl and hydroxyl) as indicated by the linear programming method. The nylon membranes were the most hydrophilic and exhibited the lowest AEF removal at pH of 8.7. However, the adsorption of AEF on the membranes increased as the pH of OSPW decreased due to hydrophobic interactions between the membrane surfaces and the protonated molecules. The use of ultra pressure liquid chromatography-high resolution mass spectrometry (UPLC/HRMS) showed insignificant adsorption of NAs on the tested membranes at pH 8.7. However, 26±2.4% adsorption of NAs was observed at pH 5.3 following the protonation of NAs species. For the nylon membrane, excessive carboxylic acids in the commercial NAs caused the formation of negatively charged assisted hydrogen bonds, resulting in increased adsorption at pH 8.2 (25%) as compared to OSPW (0%). The use of membranes for filtration of soluble compounds from complex oily wastewaters before quantification analysis of AEF and NAs should be examined prior to application.

Removal of organic compounds and trace metals from oil sands process-affected water using zero valent iron enhanced by petroleum coke.

The oil production generates large volumes of oil sands process-affected water (OSPW), referring to the water that has been in contact with oil sands or released from tailings deposits. There are concerns about the environmental impacts of the release of OSPW because of its toxicity. Zero valent iron alone (ZVI) and in combination with petroleum coke (CZVI) were investigated as environmentally friendly treatment processes for the removal of naphthenic acids (NAs), acid-extractable fraction (AEF), fluorophore organic compounds, and trace metals from OSPW. While the application of 25 g/L ZVI to OSPW resulted in 58.4% removal of NAs in the presence of oxygen, the addition of 25 g petroleum coke (PC) as an electron conductor enhanced the NAs removal up to 90.9%. The increase in ZVI concentration enhanced the removals of NAs, AEF, and fluorophore compounds from OSPW. It was suggested that the electrons generated from the oxidation of ZVI were transferred to oxygen, resulting in the production of hydroxyl radicals and oxidation of NAs. When OSPW was de-oxygenated, the NAs removal decreased to 17.5% and 65.4% during treatment with ZVI and CZVI, respectively. The removal of metals in ZVI samples was similar to that obtained during CZVI treatment. Although an increase in ZVI concentration did not enhance the removal of metals, their concentrations effectively decreased at all ZVI loadings. The Microtox(®) bioassay with Vibrio fischeri showed a decrease in the toxicity of ZVI- and CZVI-treated OSPW. The results obtained in this study showed that the application of ZVI in combination with PC is a promising technology for OSPW treatment.

Impact of peroxydisulfate in the presence of zero valent iron on the oxidation of cyclohexanoic acid and naphthenic acids from oil sands process-affected water.

Large volumes of oil sands process-affected water (OSPW) are produced during the extraction of bitumen from oil sands in Alberta, Canada. The degradation of a model naphthenic acid, cyclohexanoic acid (CHA), and real naphthenic acids (NAs) from OSPW were investigated in the presence of peroxydisulfate (S(2)O(8)(2-)) and zerovalent iron (ZVI). For the model compound CHA (50 mg/L), in the presence of ZVI and 500 mg/L S(2)O(8)(2-), the concentration decreased by 45% after 6 days of treatment at 20 °C, whereas at 40, 60, and 80 °C the concentration decreased by 20, 45 and 90%, respectively, after 2 h of treatment. The formation of chloro-CHA was observed during ZVI/S(2)O(8)(2-) treatment of CHA in the presence of chloride. For OSPW NAs, in the presence of ZVI alone, a 50% removal of NAs was observed after 6 days of exposure at 20 °C. The addition of 100 mg/L S(2)O(8)(2-) to the solution increased the removal of OSPW NAs from 50 to 90%. In absence of ZVI, a complete NAs removal from OSPW was observed in presence of 2000 mg/L S(2)O(8)(2-) at 80 °C. The addition of ZVI increased the efficiency of NAs oxidation by S(2)O(8)(2-) near room temperature. Thus, ZVI/S(2)O(8)(2-) process was found to be a viable option for accelerating the degradation of NAs present in OSPW.

Single-walled carbon nanotubes dispersed in aqueous media via non-covalent functionalization: effect of dispersant on the stability, cytotoxicity, and epigenetic toxicity of nanotube suspensions.

As the range of applications for carbon nanotubes (CNTs) rapidly expands, understanding the effect of CNTs on prokaryotic and eukaryotic cell systems has become an important research priority, especially in light of recent reports of the facile dispersion of CNTs in a variety of aqueous systems including natural water. In this study, single-walled carbon nanotubes (SWCNTs) were dispersed in water using a range of natural (gum arabic, amylose, Suwannee River natural organic matter) and synthetic (polyvinyl pyrrolidone, Triton X-100) dispersing agents (dispersants) that attach to the CNT surface non-covalently via different physiosorption mechanisms. The charge and the average effective hydrodynamic diameter of suspended SWCNTs as well as the concentration of exfoliated SWCNTs in the dispersion were found to remain relatively stable over a period of 4 weeks. The cytotoxicity of suspended SWCNTs was assessed as a function of dispersant type and exposure time (up to 48 h) using general viability bioassay with Escherichia coli and using neutral red dye uptake (NDU) bioassay with WB-F344 rat liver epithelia cells. In the E. coli viability bioassays, three types of growth media with different organic loadings and salt contents were evaluated. When the dispersant itself was non-toxic, no losses of E. coli and WB-F344 viability were observed. The cell viability was affected only by SWCNTs dispersed using Triton X-100, which was cytotoxic in SWCNT-free (control) solution. The epigenetic toxicity of dispersed CNTs was evaluated using gap junction intercellular communication (GJIC) bioassay applied to WB-F344 rat liver epithelial cells. With all SWCNT suspensions except those where SWCNTs were dispersed using Triton X-100 (wherein GJIC could not be measured because the sample was cytotoxic), no inhibition of GJIC in the presence of SWCNTs was observed. These results suggest a strong dependence of the toxicity of SWCNT suspensions on the toxicity of the dispersant and point to the potential of non-covalent functionalization with non-toxic dispersants as a method for the preparation of stable aqueous suspensions of biocompatible CNTs.