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.

Reduction of excess sludge production by membrane bioreactor coupled with anoxic side-stream reactors.

While cleaning wastewater, biological wastewater treatment processes such as membrane bioreactors (MBR) produce a significant amount of sludge that requires costly management. In the oxic-settling-anoxic (OSA) process, sludge is retained for a temporary period in side-stream reactors with low oxygen and substrate, and then it is recirculated to the main reactor. In this way, excess sludge production is reduced. We studied the influence of the rate of sludge exchange between MBR and side-stream anoxic reactors on sludge yield reduction within MBR. Two MBRs, namely, MBROSA and MBRcontrol, each coupled with separate external anoxic side-stream reactors, were run in parallel for 350 days. Unlike MBRcontrol, MBROSA had sludge exchange with the external reactors connected to it. During the investigation over a sludge interchange rate (SIR) range of 0-22%, an SIR of 11% achieved the highest sludge reduction (58%). Greater volatile solids destruction i.e., bacterial cell lysis and extracellular polymeric substance (EPS) destruction occurred at the SIR of 11%, which helped to achieve the highest sludge reduction. The enhanced volatile solids destruction was evident by the release of nutrients in the external anoxic reactors. It was confirmed that the sludge yield reduction was achieved without compromising the wastewater treatment quality, sludge settleability and hydraulic performance of the membrane in MBR.

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.

Impact of wastewater derived dissolved interfering compounds on growth, enzymatic activity and trace organic contaminant removal of white rot fungi - A critical review.

White-rot fungi (WRF) and their ligninolytic enzymes have been investigated for the removal of a broad spectrum of trace organic contaminants (TrOCs) mostly from synthetic wastewater in lab-scale experiments. Only a few studies have reported the efficiency of such systems for the removal of TrOCs from real wastewater. Wastewater derived organic and inorganic compounds can inhibit: (i) WRF growth and their enzyme production capacity; (ii) enzymatic activity of ligninolytic enzymes; and (iii) catalytic efficiency of both WRF and enzymes. It is observed that essential metals such as Cu, Mn and Co at trace concertation (up to 1 mM) can improve the growth of WRF species, whereas non-essential metal such as Pb, Cd and Hg at 1 mM concentration can inhibit WRF growth and their enzyme production. In the case of purified enzymes, most of the tested metals at 1-5 mM concentration do not significantly inhibit the activity of laccases. Organic interfering compounds such as oxalic acid and ethylenediaminetetraacetic acid (EDTA) at 1 mM concentration are potent inhibitors of WRF and their extracellular enzymes. However, inhibitory effects induced by interfering compounds are strongly influenced by the type of WRF species as well as experimental conditions (e.g., incubation time and TrOC type). In this review, mechanisms and factors governing the interactions of interfering compounds with WRF and their ligninolytic enzymes are reviewed and elucidated. In addition, the performance of WRF and their ligninolytic enzymes for the removal of TrOCs from synthetic and real wastewater is critically summarized.

Holistic sludge management through ozonation: A critical review.

This paper critically reviews the multidimensional benefits of ozonation in wastewater treatment plants. These benefits include sludge reduction, removal of emerging trace organic contaminants (TrOC) from wastewater and sludge, and resource recovery from sludge. Literature shows that ozonation leads to sludge solubilisation, reducing overall biomass yield. Sludge solubilisation is primarily influenced by ozone dosage, which, in turn, depends on the fraction of ozonated sludge, ozone concentration, and sludge concentration. Additionally, sludge ozonation facilitates the removal of TrOCs from wastewater. On the other hand, by inducing cell lysis, ozonation increases the chemical oxygen demand (COD) and nutrient concentration of the sludge supernatant, which deteriorates effluent quality. This issue can be resolved by implementing resource recovery. Thus far, successful retrieval of phosphorous from ozonated sludge supernatant has been performed. The recovery of phosphorous and other resources from sludge could help offset the operation cost of ozonation, and give greater incentive for wastewater treatment plants to adapt this approach.

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 Drying-Free, Water-Based Process for Fabricating Mixed-Matrix Membranes with Outstanding Pervaporation Performance.

Despite much progress in the development of mixed matrix membranes (MMMs) for many advanced applications, the synthesis of MMMs without particle agglomeration or phase separation at high nanofiller loadings is still challenging. In this work, we synthesized nanoporous zeolitic imidazole framework (ZIF-8) nanoparticles with a particle size of 60 nm and a pore size of 0.34 nm in water and directly added them into an aqueous solution of the organic polymer poly(vinyl alcohol) (PVA) without an intermediate drying process. This approach led to a high-quality PVA/ZIF-8 MMM with enhanced performance in ethanol dehydration by pervaporation. The permeability of this MMM is three times higher than that of pristine PVA, and the separation factor is nearly nine times larger than that of pristine PVA. The significantly improved separation performance was attributed to the increase in the fractional free volume in the membranes.

Elucidating the performance of UV-based photochemical processes for the removal of trace organic contaminants: Degradation and toxicity evaluation.

In this study, the performance of standalone ultraviolet (UV) photolysis and UV-based advanced oxidation processes (AOPs), namely, UV/hydrogen peroxide, UV/chlorine, UV/persulphate, and UV/permonosulphate, were investigated for the degradation of 31 trace organic contaminants (TrOCs). Under the tested conditions, standalone UV photolysis did not achieve effective removal of TrOCs. To improve the degradation efficiency of UV photolysis, four different oxidants were added individually to the test solution. The effect of these oxidants in the absence of UV irradiation was also explored and only chlorine showed promising degradation of some contaminants. During the chlorination of 31 investigated TrOCs, only six demonstrated greater than 50% degradation. The combined UV-based AOPs demonstrated much improved degradation (ranging from 65 to 100%) depending on TrOC-structure and oxidant concentration. The UV/hydrogen peroxide process showed similar degradation of TrOCs, irrespective of the functional groups (i.e., electron withdrawing groups, EWGs and electron donating groups, EDGs) present in their structures. Conversely, the UV/sulphate and UV/chlorine based processes achieved better degradation of the TrOCs with EDGs in their structures. TrOCs degradation improved up to 40% when oxidants concentrations were increased from 0.1 to 1 mM, and further increasing the concentration to 2 mM did not improve degradation. Toxicity evaluation using bioluminescence test (BLT assay) demonstrated that except for UV/hydrogen peroxide, all UV-based AOPs increased the toxicity of the treated effluent, indicating generation of toxic by-products. This study elucidates the performance of four different UV-based AOPs for the removal of commonly detected diverse TrOCs for the first time.

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.

Coupling granular activated carbon adsorption with membrane bioreactor treatment for trace organic contaminant removal: breakthrough behaviour of persistent and hydrophilic compounds.

This study investigated the removal of trace organic contaminants by a combined membrane bioreactor - granular activated carbon (MBR-GAC) system over a period of 196 days. Of the 22 compounds investigated here, all six hydrophilic compounds with electron-withdrawing functional groups (i.e., metronidazole, carbamazepine, ketoprofen, naproxen, fenoprop and diclofenac) exhibited very low removal efficiency by MBR-only treatment. GAC post-treatment initially complemented MBR treatment very well; however, a compound-specific gradual deterioration of the removal of the above-mentioned problematic compounds was noted. While a 20% breakthrough of all four negatively charged compounds namely ketoprofen, naproxen, fenoprop and diclofenac occurred within 1000-3000 bed volumes (BV), the same level of breakthrough of the two neutral compounds metronidazole and carbamazepine did not occur until 11,000 BV. Single-solute isotherm parameters did not demonstrate any discernible correlation individually with any of the parameters that may govern adsorption onto GAC, such as log D, number of hydrogen-bond donor/acceptor groups, dipole moment or aromaticity ratio of the compounds. The isotherm data, however, could differentiate the breakthrough behaviour between negatively charged and neutral trace organic contaminants.

Removal of trace organic contaminants by nitrifying activated sludge and whole-cell and crude enzyme extract of Trametes versicolor.

The resistance of certain anthropogenic trace organic contaminants (TrOCs) to conventional wastewater treatment and their potential adverse effects on human and ecological health raise significant concerns and have prompted research on their bioremediation by white-rot fungi. This study compared the removal efficiencies of four widespread TrOCs: carbamazepine (CBZ), sulfamethoxazole (SMX), bisphenol A (BPA) and diclofenac (DCF), by nitrifying activated sludge as well as whole-cell and extracellular enzyme (laccase) extract of the white-rot fungus Trametes versicolor. Fungal whole-cell culture removed only BPA and DCF but with high efficiencies (>90%) while the mixed nitrifying culture removed all compounds, although by levels of only 5-40%. Rapid initial sorption on fungal mycelium (44 ± 13% for DCF) was observed; however, biodegradation governed the overall removal. Performance comparison between fungal whole-cell and extracellular extract revealed that, unlike BPA, a catalytic pathway independent of extracellular laccase was responsible for DCF removal. Addition of mediator (1-hydroxybenzotriazole) to extracellular extract improved the removal of SMX which bears an electron donor group, but not that of the resistant compound CBZ.

Impact of molar absorbance on anthocyanin content of the foods.

Anthocyanins are present in bright colored fruit and vegetables with growing evidence for their health benefits. Several methods exist in the literature to measure the total monomeric anthocyanin content in foods. Although the simplest method uses UV-Vis spectrophotometry, it requires the use of anthocyanin molar absorption coefficients (Ɛ). While commonly reported for some compounds, these values vary substantially between studies. This study collated and compared existing Ɛ values for a range of anthocyanin-3-glucosides, measured new Ɛ values for these compounds and underwent an inter-laboratory validation of spectrometry methods. The Ɛ values used for the determination of anthocyanin content in Australian blueberries, were shown to greatly affect the estimated total anthocyanin. Significant differences in the Ɛ values were observed when measured at 520 nm, or their absorbance maximum and substantial difference in the estimated total anthocyanins were observed when expressed as equivalent of cya-3-glu or mal-3-glu.

The chaperone action of bovine milk αS1- and αS2-caseins and their associated form αS-casein.

α(S)-Casein, the major milk protein, comprises α(S1)- and α(S2)-casein and acts as a molecular chaperone, stabilizing an array of stressed target proteins against precipitation. Here, we report that α(S)-casein acts in a similar manner to the unrelated small heat-shock proteins (sHsps) and clusterin in that it does not preserve the activity of stressed target enzymes. However, in contrast to sHsps and clusterin, α-casein does not bind target proteins in a state that facilitates refolding by Hsp70. α(S)-Casein was also separated into α- and α-casein, and the chaperone abilities of each of these proteins were assessed with amorphously aggregating and fibril-forming target proteins. Under reduction stress, all α-casein species exhibited similar chaperone ability, whereas under heat stress, α-casein was a poorer chaperone. Conversely, α(S2)-casein was less effective at preventing fibril formation by modified κ-casein, whereas α- and α(S1)-casein were comparably potent inhibitors. In the presence of added salt and heat stress, α(S1)-, α- and α(S)-casein were all significantly less effective. We conclude that α(S1)- and α-casein stabilise each other to facilitate optimal chaperone activity of α(S)-casein. This work highlights the interdependency of casein proteins for their structural stability.

A critical review on advanced oxidation processes for the removal of trace organic contaminants: A voyage from individual to integrated processes.

Advanced oxidation processes (AOPs), such as photolysis, photocatalysis, ozonation, Fenton process, anodic oxidation, sonolysis, and wet air oxidation, have been investigated extensively for the removal of a wide range of trace organic contaminants (TrOCs). A standalone AOP may not achieve complete removal of a broad group of TrOCs. When combined, AOPs produce more hydroxyl radicals, thus performing better degradation of the TrOCs. A number of studies have reported significant improvement in TrOC degradation efficiency by using a combination of AOPs. This review briefly discusses the individual AOPs and their limitations towards the degradation of TrOCs containing different functional groups. It also classifies integrated AOPs and comprehensively explains their effectiveness for the degradation of a wide range of TrOCs. Integrated AOPs are categorized as UV irradiation based AOPs, ozonation/Fenton process-based AOPs, and electrochemical AOPs. Under appropriate conditions, combined AOPs not only initiate degradation but may also lead to complete mineralization. Various factors can affect the efficiency of integrated processes including water chemistry, the molecular structure of TrCOs, and ions co-occurring in water. For example, the presence of organic ions (e.g., humic acid and fulvic acid) and inorganic ions (e.g., halide, carbonate, and nitrate ions) in water can have a significant impact. In general, these ions either convert to high redox potential radicals upon collision with other reactive species and increase the reaction rates, or may act as radical scavengers and decrease the process efficiency.

Impact of Inorganic Ions and Organic Matter on the Removal of Trace Organic Contaminants by Combined Direct Contact Membrane Distillation-UV Photolysis.

This study investigated the degradation of five trace organic contaminants (TrOCs) by integrated direct contact membrane distillation (DCMD) and UV photolysis. Specifically, the influence of inorganic ions including halide, nitrate, and carbonate on the performance of the DCMD-UV process was evaluated. TrOC degradation improved in the presence of different concentrations (1-100 mM) of fluoride ion and chloride ion (1 mM). With a few exceptions, a major negative impact of iodide ion was observed on the removal of the investigated TrOCs. Of particular interest, nitrate ion significantly improved TrOC degradation, while bicarbonate ion exerted variable influence-from promoting to inhibiting impact-on TrOC degradation. The performance of DCMD-UV photolysis was also studied for TrOC degradation in the presence of natural organic matter, humic acid. Results indicated that at a concentration of 1 mg/L, humic acid improved the degradation of the phenolic contaminants (bisphenol A and oxybenzone) while it inhibited the degradation of the non-phenolic contaminants (sulfamethoxazole, carbamazepine, and diclofenac). Overall, our study reports the varying impact of different inorganic and organic ions present in natural water on the degradation of TrOCs by integrated DCMD-UV photolysis: the nature and extent of the impact of the ions depend on the type of TrOCs and the concentration of the interfering ions.

Validated liquid chromatography separation methods for identification and quantification of anthocyanins in fruit and vegetables: A systematic review.

Food composition data are challenged by data availability and quality. Anthocyanins are the bright colored pigments found in fruits and vegetables with growing evidence for health benefits. For the estimation of anthocyanin content in the foods, it is imperative to find an ideal analytical method. To quantify anthocyanin components, liquid chromatography-based methods are commonly used. This review addresses the variability of liquid chromatography (LC) mass spectrometry (MS) methods for the identification and quantification of anthocyanins. Published studies for all years until February 2020 reporting LC methods for anthocyanins in fruits and vegetables were screened from 7660 studies. Only 29 studies met the eligibility criteria of method type and of these, only 13 studies reported a validated LC method. A wide range of validation parameters were identified including specificity, calibration, stability, and limits of detection. Differences in the sampling amounts for extraction were observed in all of the included studies. The quantification of multiple anthocyanin types without their corresponding analytical standards was observed in eight studies. The included 13 studies used reverse phase liquid chromatography separation with C18 type or similar stationary phases and acidified aqueous or acidified aqueous: organic (usually methanol or acetonitrile) binary gradient mobile phases. Although all of the studies used mass spectrometry for identification, ultraviolet absorbance quantification was often used in conjunction with a photo-diode array (DAD/PDA) detector using reference standards where available. Extraction and preparation of samples remains the key concern for analysis as the oxidative stability of anthocyanins are a major impediment for accurate quantification of the components in foods. This review provides a summary of validated LC methods to assist analysts and nutritionists in the quantification of anthocyanin food components as the nutrient profiles of foods are challenged by the variability of the analytical methods.

Occurrence of phytoestrogens in municipal wastewater and surface waters.

Phytoestrogens (isoflavones, enterolignans and coumestrol) in wastewater samples and surface water samples have been analysed by LC-ESI-MS(n). In wastewater samples, high levels of enterolactone (581-2111 ng/L), daidzein (341-1688 ng/L) and enterodiol (60-834 ng/L) were detected in raw sewage, but the vast majority of the analysed phytoestrogens were removed effectively in the treatment process. The removal rates of the analysed phytoestrogens in the two advanced tertiary treatment plants were >99%; a case study in one of the treatment plants showed that most of the residual phytoestrogens were removed by biological treatment using activated sludge. In surface water samples, daidzein was found at concentrations ranging from 2 ng/L to 33 ng/L in samples from two creeks, and up to 120 ng/L in surface water (pond) on a dairy farm. The analytical results suggest that direct excretions of livestock discharged from farmyards can be another potential source of phytoestrogen contamination in the aquatic environment.

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.