Acid mine drainage and sewage impacted groundwater treatment by membrane distillation: Organic micropollutant and metal removal and membrane fouling.

Groundwater is the dominant source of freshwater in many countries around the globe, and the deterioration in its quality by contaminants originating from anthropogenic sources raises serious concern. In this study, a scenario where groundwater is contaminated by acid mine drainage (AMD) from mining activities and/or sewage was envisaged, and the performance of a direct contact membrane distillation (DCMD) system was investigated comprehensively for different compositions of the AMD- and sewage-impacted groundwater. Regardless of the composition, MD membrane achieved 98-100% removal of metals and bulk organics, while the removal of the selected micropollutants ranged between 80 and 100%. Effective retention of contaminants by the MD led to their accumulation over time, which affected the hydraulic performance of the MD membrane by reducing the permeate flux by 29-76%. When persulfate (PS)-mediated oxidation process was integrated with the DCMD, degradation of bulk organics (50-71%) and micropollutants (50-100%) by PS reduced their accumulation. Characterisation of the fouling layer revealed the occurrence of membrane scaling that was mainly due to the deposition of iron oxide or oxyhydroxide precipitates. For an identical composition of the AMD- and sewage-impacted groundwater, flux decline was 10% less in PS-assisted DCMD as compared to that in the standalone DCMD. However, this did not prevent the formation of iron oxide scales on MD membrane during the operation of PS-assisted DCMD. This study demonstrates the long-term performance of a standalone and PS-assisted DCMD operated in continuous-flow mode to treat AMD- and sewage-impacted groundwater for the first time.

Seawater-driven forward osmosis for pre-concentrating nutrients in digested sludge centrate.

Seawater-driven forward osmosis to enrich nutrients from sludge centrate and reduce membrane fouling is demonstrated. Due to enrichment and pH increase in the feed solution, without appropriate control measure, nutrient precipitation can occur directly on the membrane surface causing severe membrane fouling and reducing nutrient enrichment efficiency. Indeed without agitating the feed, there was less precipitation on the membrane surface, compared to with agitation. In addition, increase in the membrane area over permeate volume ratio significantly reduced the filtration time and nutrient precipitation. A novel technique to maintain the draw solution (DS) at an acidic condition was developed to improve nutrient enrichment and reduce membrane fouling. By using this technique and a high membrane surface to permeate volume ratio, nutrient enrichment similar to the theoretical efficiency was successfully demonstrated. Our technique reduced the filtration time to achieve 70% water recovery by over 90% (compared to unbuffered seawater as the DS, small membrane area, and feed agitation), as a result of significantly less membrane fouling. The amount of phosphorus precipitate on the membrane surface decreased by more than 10 times. The enrichment of ammonia and phosphorus as a function of water recovery was similar to the theoretical calculation, indicating negligible nutrient loss due to precipitation.

An Osmotic Membrane Bioreactor-Membrane Distillation System for Simultaneous Wastewater Reuse and Seawater Desalination: Performance and Implications.

In this study, we demonstrate the potential of an osmotic membrane bioreactor (OMBR)-membrane distillation (MD) hybrid system for simultaneous wastewater reuse and seawater desalination. A stable OMBR water flux of approximately 6 L m-2 h-1 was achieved when using MD to regenerate the seawater draw solution. Water production by the MD process was higher than that from OMBR to desalinate additional seawater and thus account for draw solute loss due to the reverse salt flux. Amplicon sequencing on the Miseq Illumina platform evidenced bacterial acclimatization to salinity build-up in the bioreactor, though there was a reduction in the bacterial community diversity. In particular, 18 halophilic and halotolerant bacterial genera were identified with notable abundance in the bioreactor. Thus, the effective biological treatment was maintained during OMBR-MD operation. By coupling biological treatment and two high rejection membrane processes, the OMBR-MD hybrid system could effectively remove (>90%) all 30 trace organic contaminants of significant concern investigated here and produce high quality water. Nevertheless, further study is necessary to address MD membrane fouling due to the accumulation of organic matter, particularly protein- and humic-like substances, in seawater draw solution.

Continuous transformation of chiral pharmaceuticals in enzymatic membrane bioreactors for advanced wastewater treatment.

This study demonstrates continuous enantiomeric inversion and further biotransformation of chiral profens including ibuprofen, naproxen and ketoprofen by an enzymatic membrane bioreactor (EMBR) dosed with laccase. The EMBR showed non-enantioselective transformations, with high and consistent transformation of both (R)- and (S)-ibuprofen (93 ± 6%, n = 10), but lower removals of both enantiomers of naproxen (46 ± 16%, n = 10) and ketoprofen (48 ± 17%, n = 10). Enantiomeric analysis revealed a bidirectional but uneven inversion of the profens, for example 14% inversion of (R)- to (S)- compared to 4% from (S)- to (R)-naproxen. With redox-mediator addition, the enzymatic chiral inversion of both (R)- and (S)-profens remained unchanged, although the overall conversion became enantioselective; except for (S)-naproxen, the addition of redox mediator promoted the degradation of (R)-profens only.

A forward osmosis-membrane distillation hybrid process for direct sewer mining: system performance and limitations.

This study demonstrates the robustness and treatment capacity of a forward osmosis (FO)-membrane distillation (MD) hybrid system for small-scale decentralized sewer mining. A stable water flux was realized using a laboratory-scale FO-MD hybrid system operating continuously with raw sewage as the feed at water recovery up to 80%. The hybrid system also showed an excellent capacity for the removal of trace organic contaminants (TrOCs), with removal rates ranging from 91 to 98%. The results suggest that TrOC transport through the FO membrane is governed by "solute-membrane" interaction, whereas that through the MD membrane is strongly correlated to TrOC volatility. Concentrations of organic matter and TrOCs in the draw solution increased substantially as the water recovery increased. This accumulation of some contaminants in the draw solution is attributed to the difference in their rejection by the FO and MD systems. We demonstrate that granular activated carbon adsorption or ultraviolet oxidation could be used to prevent contaminant accumulation in the draw solution, resulting in near complete rejection (>99.5%) of TrOCs.

Effects of fouling on separation performance by forward osmosis: the role of specific organic foulants.

In this study, forward osmosis (FO) membranes and fouling solutions were systematically characterized to elucidate the effects of organic fouling on the rejection of two pharmaceutically active compounds, namely, sulfamethoxazole and carbamazepine. Municipal wastewater resulted in a more severe flux decline compared to humic acid and sodium alginate fouling solutions. This result is consistent with the molecular weight distribution of these foulant solutions. Liquid chromatography with organic carbon detection analysis shows that municipal wastewater consists of mostly low molecular weight acids and neutrals, which produce a more compact cake layer on the membrane surface. By contrast, humic acid and sodium alginate consist of large molecular weight humic substances and biopolymers, respectively. The results also show that membrane fouling can significantly alter the membrane surface charge and hydrophobicity as well as the reverse salt flux. In particular, the reverse salt flux of a fouled membrane was significantly higher than that under clean conditions. Although the rejection of sulfamethoxazole and carbamazepine by FO membrane was high, a discernible impact of fouling on their rejection could still be observed. The results show that size exclusion is a major rejection mechanism of both sulfamethoxazole and carbamazepine. However, they respond to membrane fouling differently. Membrane fouling results in an increase in sulfamethoxazole rejection while carbamazepine rejection decreases due to membrane fouling.

Understanding the mechanisms of trace organic contaminant removal by high retention membrane bioreactors: a critical review.

High retention membrane bioreactors (HR-MBR) combine a high retention membrane separation process such as membrane distillation, forward osmosis, or nanofiltration with a conventional activated sludge (CAS) process. Depending on the physicochemical properties of the trace organic contaminants (TrOCs) as well as the selected high retention membrane process, HR-MBR can achieve effective removal (80-99%) of a broad spectrum of TrOCs. An in-depth assessment of the available literature on HR-MBR performance suggests that compared to CAS and conventional MBRs (using micro- or ultra-filtration membrane), aqueous phase removal of TrOCs in HR-MBR is significantly better. Conceptually, longer retention time may significantly improve TrOC biodegradation, but there are insufficient data in the literature to evaluate the extent of TrOC biodegradation improvement by HR-MBR. The accumulation of hardly biodegradable TrOCs within the bioreactor of an HR-MBR system may complicate further treatment and beneficial reuse of sludge. In addition to TrOCs, accumulation of salts gradually increases the salinity in bioreactor and can adversely affect microbial activities. Strategies to mitigate these limitations are discussed. A qualitative framework is proposed to predict the contribution of the different key mechanisms of TrOC removal (i.e., membrane retention, biodegradation, and sorption) in HR-MBR.

An anaerobic membrane bioreactor - membrane distillation hybrid system for energy recovery and water reuse: Removal performance of organic carbon, nutrients, and trace organic contaminants.

In this study, a direct contact membrane distillation (MD) unit was integrated with an anaerobic membrane bioreactor (AnMBR) to simultaneously recover energy and produce high quality water for reuse from wastewater. Results show that AnMBR could produce 0.3-0.5L/g CODadded biogas with a stable methane content of approximately 65%. By integrating MD with AnMBR, bulk organic matter and phosphate were almost completely removed. The removal of the 26 selected trace organic contaminants by AnMBR was compound specific, but the MD process could complement AnMBR removal, leading to an overall efficiency from 76% to complete removal by the integrated system. The results also show that, due to complete retention, organic matter (such as humic-like and protein-like substances) and inorganic salts accumulated in the MD feed solution and therefore resulted in significant fouling of the MD unit. As a result, the water flux of the MD process decreased continuously. Nevertheless, membrane pore wetting was not observed throughout the operation.

Assessing the integration of forward osmosis and anaerobic digestion for simultaneous wastewater treatment and resource recovery.

This study assessed the performance and key challenges associated with the integration of forward osmosis (FO) and anaerobic digestion for wastewater treatment and resource recovery. Using a thin film composite polyamide FO membrane, maximising the pre-concentration factor (i.e. system water recovery) resulted in the enrichment of organics and salinity in wastewater. Biomethane potential evaluation indicated that methane production increased correspondingly with the FO pre-concentration factor due to the organic retention in the feed solution. At 90% water recovery, about 10% more methane was produced when using NaOAc compared with NaCl because of the contribution of biodegradable reverse NaOAc flux. No negative impact on anaerobic digestion was observed when wastewater was pre-concentrated ten-fold (90% water recovery) for both draw solutes. Interestingly, the unit cost of methane production using NaOAc was slightly lower than NaCl due to the lower reverse solute flux of NaOAc, although NaCl is a much cheaper chemical.

Effect of hydraulic retention time on the performance of a hybrid moving bed biofilm reactor-membrane bioreactor system for micropollutants removal from municipal wastewater.

This study evaluated micropollutants removal and membrane fouling behaviour of a hybrid moving bed biofilm reactor-membrane bioreactor (MBBR-MBR) system at four different hydraulic retention times (HRTs) (24, 18, 12 and 6h). The results revealed that HRT of 18h was the optimal condition regarding the removal of most selected micropollutants. As the primary removal mechanism in the hybrid system was biodegradation, the attached growth pattern was desirable for enriching slow growing bacteria and developing a diversity of biocoenosis. Thus, the efficient removal of micropollutants was obtained. In terms of membrane fouling propensity analysis, a longer HRT (e.g. HRTs of 24 and 18h) could significantly mitigate membrane fouling when compared with the shortest HRT of 6h. Hence, enhanced system performance could be achieved when the MBBR-MBR system was operated at HRT of 18h.

Impact of simultaneous retention of micropollutants and laccase on micropollutant degradation in enzymatic membrane bioreactor.

This study systematically compares the performance of ultrafiltration (UF) and nanofiltration (NF) based enzymatic membrane bioreactors (EMBRs) for the degradation of five micropollutants, namely atrazine, carbamazepine, sulfamethoxazole, diclofenac and oxybenzone to elucidate the impact of effective membrane retention of micropollutants on their degradation. Based on the permeate quality, NF-EMBR achieved 92-99.9% micropollutant removal (i.e., biodegradation + membrane retention), while the removal of these micropollutants by UF-EMBR varied from 20 to 85%. Mass balance analysis revealed that micropollutant degradation was improved by 15-30% in NF-EMBR as compared to UF-EMBR, which could be attributed to the prolonged contact time between laccase and micropollutants following their effective retention by the NF membrane. A small decline in permeate flux was observed during EMBR operation. However, the flux could be recovered by flushing the membrane with permeate.

Biocatalytic degradation of pharmaceuticals, personal care products, industrial chemicals, steroid hormones and pesticides in a membrane distillation-enzymatic bioreactor.

Laccase-catalyzed degradation of a broad spectrum of trace organic contaminants (TrOCs) by a membrane distillation (MD)-enzymatic membrane bioreactor (EMBR) was investigated. The MD component effectively retained TrOCs (94-99%) in the EMBR, facilitating their continuous biocatalytic degradation. Notably, the extent of TrOC degradation was strongly influenced by their molecular properties. A significant degradation (above 90%) of TrOCs containing strong electron donating functional groups (e.g., hydroxyl and amine groups) was achieved, while a moderate removal was observed for TrOCs containing electron withdrawing functional groups (e.g., amide and halogen groups). Separate addition of two redox-mediators, namely syringaldehyde and violuric acid, further improved TrOC degradation by laccase. However, a mixture of both showed a reduced performance for a few pharmaceuticals such as primidone, carbamazepine and ibuprofen. Mediator addition increased the toxicity of the media in the enzymatic bioreactor, but the membrane permeate (i.e., final effluent) was non-toxic, suggesting an added advantage of coupling MD with EMBR.

Osmotic versus conventional membrane bioreactors integrated with reverse osmosis for water reuse: Biological stability, membrane fouling, and contaminant removal.

This study systematically compares the performance of osmotic membrane bioreactor - reverse osmosis (OMBR-RO) and conventional membrane bioreactor - reverse osmosis (MBR-RO) for advanced wastewater treatment and water reuse. Both systems achieved effective removal of bulk organic matter and nutrients, and almost complete removal of all 31 trace organic contaminants investigated. They both could produce high quality water suitable for recycling applications. During OMBR-RO operation, salinity build-up in the bioreactor reduced the water flux and negatively impacted the system biological treatment by altering biomass characteristics and microbial community structure. In addition, the elevated salinity also increased soluble microbial products and extracellular polymeric substances in the mixed liquor, which induced fouling of the forward osmosis (FO) membrane. Nevertheless, microbial analysis indicated that salinity stress resulted in the development of halotolerant bacteria, consequently sustaining biodegradation in the OMBR system. By contrast, biological performance was relatively stable throughout conventional MBR-RO operation. Compared to conventional MBR-RO, the FO process effectively prevented foulants from permeating into the draw solution, thereby significantly reducing fouling of the downstream RO membrane in OMBR-RO operation. Accumulation of organic matter, including humic- and protein-like substances, as well as inorganic salts in the MBR effluent resulted in severe RO membrane fouling in conventional MBR-RO operation.

Factors governing the pre-concentration of wastewater using forward osmosis for subsequent resource recovery.

This study demonstrated a technique using forward osmosis (FO) to pre-concentrate the organic matter in raw wastewater, thereby transforming low strength wastewater into an anaerobically digestible solution. The chemical oxygen demand (COD) of raw wastewater was concentrated up to approximately eightfold at a water recovery of 90%. Thus, even low strength wastewater could be pre-concentrated by FO to the range suitable for biogas production via anaerobic treatment. Excessive salinity accumulation in pre-concentrated wastewater was successfully mitigated by adopting ionic organic draw solutes, namely, sodium acetate, and EDTA-2Na. These two draw solutes are also expected to benefit the digestibility of the pre-concentrated wastewater compared to the commonly used draw solute sodium chloride. Significant membrane fouling was observed when operating at 90% water recovery using raw wastewater. Nevertheless, membrane fouling was reversible and was effectively controlled by optimising the hydrodynamic conditions of the cross-flow FO system.

Effects of salinity build-up on the performance of an anaerobic membrane bioreactor regarding basic water quality parameters and removal of trace organic contaminants.

The effects of elevated inorganic salt concentration on anaerobic membrane bioreactor (AnMBR) treatment regarding basic biological performance and trace organic contaminant (TrOC) removal were investigated. A set of 33 TrOCs were selected to represent pharmaceuticals, steroids, and pesticides in municipal wastewater. Results show potential adverse effects of increase in the bioreactor salinity to 15g/L (as NaCl) on the performance of AnMBR with respect to chemical oxygen demand removal, biogas production, and the removal of most hydrophilic TrOCs. Furthermore, a decrease in biomass production was observed as salinity in the bioreactor increased. The removal of most hydrophobic TrOCs was high and was not significantly affected by salinity build-up in the bioreactor. The accumulation of a few persistent TrOCs in the sludge phase was observed, but such accumulation did not vary significantly as salinity in the bioreactor increased.

Effects of salinity build-up on the performance and bacterial community structure of a membrane bioreactor.

This study investigated the effects of salinity increase on bacterial community structure in a membrane bioreactor (MBR) for wastewater treatment. The influent salt loading was increased gradually to simulate salinity build-up in the bioreactor during the operation of a high retention-membrane bioreactor (HR-MBR). Bacterial community diversity and structure were analyzed using 454 pyrosequencing of 16S rRNA genes of MBR mixed liquor samples. Results show that salinity increase reduced biological performance but did not affect microbial diversity in the bioreactor. Unweighted UniFrac and taxonomic analyses were conducted to relate the reduced biological performance to the change of bacterial community structure. In response to the elevated salinity condition, the succession of halophobic bacteria by halotolerant/halophilic microbes occurred and thereby the biological performance of MBR was recovered. These results suggest that salinity build-up during HR-MBR operation could be managed by allowing for the proliferation of halotolerant/halophilic bacteria.

Laccase-syringaldehyde-mediated degradation of trace organic contaminants in an enzymatic membrane reactor: Removal efficiency and effluent toxicity.

Redox-mediators such as syringaldehyde (SA) can improve laccase-catalyzed degradation of trace organic contaminants (TrOCs) but may increase effluent toxicity. The degradation performance of 14 phenolic and 17 non-phenolic TrOCs by a continuous flow enzymatic membrane reactor (EMR) at different TrOC and SA loadings was assessed. A specific emphasis was placed on the investigation of the toxicity of the enzyme (laccase), SA, TrOCs and the treated effluent. Batch tests demonstrated significant individual and interactive toxicity of the laccase and SA preparations. Reduced removal of resistant TrOCs by the EMR was observed for dosages over 50µg/L. SA addition at a concentration of 10µM significantly improved TrOC removal, but no removal improvement was observed at the elevated SA concentrations of 50 and 100µM. The treated effluent showed significant toxicity at SA concentrations beyond 10µM, providing further evidence that higher dosage of SA must be avoided.

The role of forward osmosis and microfiltration in an integrated osmotic-microfiltration membrane bioreactor system.

This study investigates the performance of an integrated osmotic and microfiltration membrane bioreactor (O/MF-MBR) system for wastewater treatment and reclamation. The O/MF-MBR system simultaneously used microfiltration (MF) and forward osmosis (FO) membranes to extract water from the mixed liquor of an aerobic bioreactor. The MF membrane facilitated the bleeding of dissolved inorganic salts and thus prevented the build-up of salinity in the bioreactor. As a result, sludge production and microbial activity were relatively stable over 60 days of operation. Compared to MF, the FO process produced a better permeate quality in terms of nutrients, total organic carbon, as well as hydrophilic and biologically persistent trace organic chemicals (TrOCs). The high rejection by the FO membrane also led to accumulation of hydrophilic and biologically persistent TrOCs in the bioreactor, consequently increasing their concentration in the MF permeate. On the other hand, hydrophobic and readily biodegradable TrOCs were minimally detected in both MF and FO permeates, with no clear difference in the removal efficiencies between two processes.

Effects of salinity build-up on biomass characteristics and trace organic chemical removal: implications on the development of high retention membrane bioreactors.

This study investigated the impact of salinity build-up on the performance of membrane bioreactor (MBR), specifically in terms of the removal and fate of trace organic chemicals (TrOCs), nutrient removal, and biomass characteristics. Stepwise increase of the influent salinity, simulating salinity build-up in high retention MBRs, adversely affected the metabolic activity in the bioreactor, thereby reducing organic and nutrient removal. The removal of hydrophilic TrOCs by MBR decreased due to salinity build-up. By contrast, with the exception of 17α-ethynylestradiol, the removal of all hydrophobic TrOCs was not affected at high salinity. Moreover, salinity build-up had negligible impact on the residual accumulation of TrOCs in the sludge phase except for a few hydrophilic compounds. Additionally, the response of the biomass to salinity stress also dramatically enhanced the release of both soluble microbial products (SMP) and extracellular polymeric substances (EPS), leading to severe membrane fouling.

Evaluation of micropollutant removal and fouling reduction in a hybrid moving bed biofilm reactor-membrane bioreactor system.

A hybrid moving bed biofilm reactor-membrane bioreactor (MBBR-MBR) system and a conventional membrane bioreactor (CMBR) were compared in terms of micropollutant removal efficiency and membrane fouling propensity. The results show that the hybrid MBBR-MBR system could effectively remove most of the selected micropollutants. By contrast, the CMBR system showed lower removals of ketoprofen, carbamazepine, primidone, bisphenol A and estriol by 16.2%, 30.1%, 31.9%, 34.5%, and 39.9%, respectively. Mass balance calculations suggest that biological degradation was the primary removal mechanism in the MBBR-MBR system. During operation, the MBBR-MBR system exhibited significantly slower fouling development as compared to the CMBR system, which could be ascribed to the wide disparity in the soluble microbial products (SMP) levels between MBBR-MBR (4.02-6.32 mg/L) and CMBR (21.78 and 33.04 mg/L). It is evident that adding an MBBR process prior to MBR treatment can not only enhance micropollutant elimination but also mitigate membrane fouling.