Recovery of Critical Metals from Aqueous Sources.

Critical metals, identified from supply, demand, imports, and market factors, include rare earth elements (REE), platinum group metals, precious metals, and other valuable metals such as lithium, cobalt, nickel, and uranium. Extraction of metals from U.S. saline aqueous, emphasizing saline, sources is explored as an alternative to hardrock ore mining. Potential aqueous sources include seawater, desalination brines, oil-and-gas produced waters, geothermal aquifers, and acid mine drainage, among others. A feasibility assessment reveals opportunities for recovery of lithium, strontium, magnesium, and several REE from select sources, in quantities significant for U.S. manufacturing and for reduction of U.S. reliance on international supply chains. This is a conservative assessment given that water quality data are lacking for a significant number of critical metals in certain sources. The technology landscape for extraction and recovery of critical metals from aqueous sources is explored, identifying relevant processes along with knowledge gaps. Our analysis indicates that aqueous mining would result in much lower environmental impacts on water, air, and land than ore mining. Preliminary assessments of the economics and energy consumption of recovery show potential for recovery of critical metals.

Transparent exopolymer particles (TEP) removal efficiency by a combination of coagulation and ultrafiltration to minimize SWRO membrane fouling.

This study investigated the impact of coagulation on the transformation between colloidal and particulate transparent exopolymer particles (TEP) in seawater; and the effectiveness of a combined pretreatment consisting of coagulation and UF on minimizing TEP fouling of seawater reverse osmosis (SWRO) membranes. Coagulation with ferric chloride at pH 5 substantially transformed colloidal TEP (0.1-0.4) into particulate TEP (>0.4) leading to a better membrane fouling control. Both 50 and 100 kDa molecular weight cut-off (MWCO) UF membranes removed most of particulate and colloidal TEP without the assistance of coagulation, but coagulation is still necessary for better UF fouling control. The improvement of combined SWRO pretreatment with coagulation and 50 kDa UF membranes was not that much significant compared to UF pretreatment with 50 KDa alone. Therefore, the minimal coagulant dosage for seawater containing TEP should be based on the UF fouling control requirements rather than removal efficiency.

Defluoridation of groundwater using aluminum-coated bauxite: Optimization of synthesis process conditions and equilibrium study.

There is no known effective treatment for fluoride-related health disorders, hence prevention through water defluoridation is necessary. This study explored the possibility of modifying the physico-chemical properties of bauxite, a locally available material in many countries including Ghana, by thermal treatment and an aluminum coating, for water defluoridation. The study mainly focused on investigating the effects of varying synthesis process conditions on the defluoridation efficiency of Granular Aluminum Coated Bauxite (GACB). GACB performed better than raw bauxite (RB) and was able to reduce fluoride concentration in groundwater from 5 ± 0.2 mg/L to ≤ 1.5 mg/L, World Health Organization (WHO) guideline. Based on nonlinear Chi-square (χ(2)) analysis, the best-fitting isotherm model for the fluoride-GACB system was in the order: Freundlich > Redlich-Perterson ≈ Langmuir > Temkin. The fluoride adsorption capacity of GACB (qmax = 12.29 mg/g) based on the Langmuir model was found to be either comparable or higher than the capacities of some reported fluoride adsorbents. Aluminum (Al) coating procedures optimized in this study could therefore be a useful approach for synthesizing an effective fluoride adsorbent using bauxite, a locally available material. Kinetic and isotherm analysis, thermodynamic calculations, as well as FTIR and Raman analysis suggested the mechanism of fluoride adsorption onto GACB was complex and involved both physical adsorption and chemisorption processes.

A novel integrated thermal-/membrane-based solar energy-driven hybrid desalination system: Concept description and simulation results.

In this paper, a hybrid desalination system consisting of vacuum membrane distillation (VMD) and adsorption desalination (AD) units, designated as VMD-AD cycle, is proposed. The synergetic integration of the VMD and AD is demonstrated where a useful effect of the AD cycle is channelled to boost the operation of the VMD process, namely the low vacuum environment to maintain the high pressure gradient across the microporous hydrophobic membrane. A solar-assisted multi-stage VMD-AD hybrid desalination system with temperature modulating unit is first designed, and its performance is then examined with a mathematical model of each component in the system and compared with the VMD-only system with temperature modulating and heat recovery units. The total water production and water recovery ratio of a solar-assisted 24-stage VMD-AD hybrid system are found to be about 21% and 23% higher, respectively, as compared to the VMD-only system. For the solar-assisted 24-stage VMD-AD desalination system having 150 m(2) of evacuated-tube collectors and 10 m(3) seawater storage tanks, both annual collector efficiency and solar fraction are close to 60%.

Membrane fouling and anti-fouling strategies using RO retentate from a municipal water recycling plant as the feed for osmotic power generation.

RO retentate from a municipal water recycling plant is considered as a potential feed stream for osmotic power generation in this paper. The feasibility of using RO retentate from a municipal water recycling plant was examined from two aspects: (a) the membrane fouling propensity of RO retentate, and (b) the efficacy of anti-fouling strategies. The membranes used in this study were the inner selective thin film composite polyethersulfone (TFC/PES) hollow fiber membranes, which possessed a high water permeability and good mechanical strength. Scaling by phosphate salts was found to be one possible inorganic fouling on the innermost layer of the PES membrane, whereas silica fouling was observed to be the governing fouling on the outmost surface of the PES membrane. Two anti-fouling pretreatments, i.e., pH adjustment and anti-scalant pre-treatment for the feed stream, were studied and found to be straightforward and effective. Using RO retentate at pH 7.2 as the feed and 1 M NaCl as the draw solution, the average power density was 7.3 W/m(2) at 20 bar. The average power density increased to 12.6 W/m(2) by modifying RO retentate with an initial pH value of 5.5 using HCl and to 13.4 W/m(2) by adding 1.1 mM ethylenediaminetetraacetic acid (EDTA). Moreover, the flux recovery of the fouled membranes, without the indicated pretreatments, reached 84.9% using deionized (DI) water flushing and 95.0% using air bubbling under a high crossflow velocity of 23.3 cm/s (Re = 2497) for 30 min. After pretreatment by pH adjustment, the flux recovery increased to 94.6% by DI water flushing and 100.0% by air bubbling. After pretreatment by adding 1.1 mM EDTA into RO retentate, flux was almost fully restored by physical cleaning by DI water flushing and air bubbling. These results provide insight into developing an effective pretreatment by either pH adjustment or EDTA addition before PRO and physical cleaning methods by DI water flushing and air bubbling for membrane used in osmotic power generation.

Graphene-Coated Hollow Fiber Membrane as the Cathode in Anaerobic Electrochemical Membrane Bioreactors--Effect of Configuration and Applied Voltage on Performance and Membrane Fouling.

Electrically conductive, graphene-coated, hollow-fiber porous membranes were used as cathodes in anaerobic electrochemical membrane bioreactors (AnEMBRs) operated at different applied voltages (0.7 and 0.9 V) using a new rectangular reactor configuration compared to a previous tubular design (0.7 V). The onset of biofouling was delayed and minimized in rectangular reactors operated at 0.9 V compared to those at 0.7 V due to higher rates of hydrogen production. Maximum transmembrane pressures for the rectangular reactor were only 0.10 bar (0.7 V) or 0.05 bar (0.9 V) after 56 days of operation compared to 0.46 bar (0.7 V) for the tubular reactor after 52 days. The thickness of the membrane biofouling layer was approximately 0.4 µm for rectangular reactors and 4 µm for the tubular reactor. Higher permeate quality (TSS = 0.05 mg/L) was achieved in the rectangular AnEMBR than that in the tubular AnEMBR (TSS = 17 mg/L), likely due to higher current densities that minimized the accumulation of cells in suspension. These results show that the new rectangular reactor design, which had increased rates of hydrogen production, successfully delayed the onset of cathode biofouling and improved reactor performance.

Disinfection by-product formation during seawater desalination: A review.

Due to increased freshwater demand across the globe, seawater desalination has become the technology of choice in augmenting water supplies in many parts of the world. The use of chemical disinfection is necessary in desalination plants for pre-treatment to control both biofouling as well as the post-disinfection of desalinated water. Although chlorine is the most commonly used disinfectant in desalination plants, its reaction with organic matter produces various disinfection by-products (DBPs) (e.g., trihalomethanes [THMs], haloacetic acids [HAAs], and haloacetonitriles [HANs]), and some DBPs are regulated in many countries due to their potential risks to public health. To reduce the formation of chlorinated DBPs, alternative oxidants (disinfectants) such as chloramines, chlorine dioxide, and ozone can be considered, but they also produce other types of DBPs. In addition, due to high levels of bromide and iodide concentrations in seawater, highly cytotoxic and genotoxic DBP species (i.e., brominated and iodinated DBPs) may form in distribution systems, especially when desalinated water is blended with other source waters having higher levels of organic matter. This article reviews the knowledge accumulated in the last few decades on DBP formation during seawater desalination, and summarizes in detail, the occurrence of DBPs in various thermal and membrane plants involving different desalination processes. The review also identifies the current challenges and future research needs for controlling DBP formation in seawater desalination plants and to reduce the potential toxicity of desalinated water.

Attenuation of trace organic compounds (TOrCs) in bioelectrochemical systems.

Microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) are two types of microbial bioelectrochemical systems (BESs) that use microorganisms to convert chemical energy in wastewaters into useful energy products such as (bio)electricity (MFC) or hydrogen gas (MEC). These two systems were evaluated for their capacity to attenuate trace organic compounds (TOrCs), commonly found in municipal wastewater, under closed circuit (current generation) and open circuit (no current generation) conditions, using acetate as the carbon source. A biocide was used to evaluate attenuation in terms of biotransformation versus sorption. The difference in attenuation observed before and after addition of the biocide represented biotransformation, while attenuation after addition of a biocide primarily indicated sorption. Attenuation of TOrCs was similar in MFCs and MECs for eight different TOrCs, except for caffeine and trimethoprim where slightly higher attenuation was observed in MECs. Electric current generation did not enhance attenuation of the TOrCs except for caffeine, which showed slightly higher attenuation under closed circuit conditions in both MFCs and MECs. Substantial sorption of the TOrCs occurred to the biofilm-covered electrodes, but no consistent trend could be identified regarding the physico-chemical properties of the TOrCs tested and the extent of sorption. The octanol-water distribution coefficient at pH 7.4 (log DpH 7.4) appeared to be a reasonable predictor for sorption of some of the compounds (carbamazepine, atrazine, tris(2-chloroethyl) phosphate and diphenhydramine) but not for others (N,N-Diethyl-meta-toluamide). Atenolol also showed high levels of sorption despite being the most hydrophilic in the suite of compounds studied (log DpH 7.4 = -1.99). Though BESs do not show any inherent advantages over conventional wastewater treatment, with respect to TOrC removal, overall removals in BESs are similar to that reported for conventional wastewater systems, implying the possibility of using BESs for energy production in wastewater treatment without adversely impacting TOrC attenuations.

Improved method for measuring transparent exopolymer particles (TEP) and their precursors in fresh and saline water.

Transparent exopolymer particles (TEP) and their precursors produced by phyto-/bacterio-planktons in fresh and marine aquatic environments are increasingly considered as a major contributor to organic/particulate and biological fouling in micro-/ultra-filtration and reverse osmosis membrane (RO) systems. However, currently established methods which are based on Alcian blue (AB) staining and spectrophotometric techniques do not measure TEP-precursors and have the tendency to overestimate concentration in brackish/saline water samples due to interference of salinity on AB staining. Here we propose a new semi-quantitative method which allows measurement of both TEP and their colloidal precursors without the interference of salinity. TEP and their precursors are first retained on 10 kDa membrane, rinsed with ultra-pure water, and re-suspended in ultra-pure water by sonication and stained with AB, followed by exclusion of TEP-AB precipitates by filtration and absorbance measurement of residual AB. The concentration is then determined based on the reduction of AB absorbance due to reaction with acidic polysaccharides, blank correction and calibration with Xanthan gum standard. The extraction procedure allows concentration of TEP and their pre-cursors which makes it possible to analyse samples with a wide range of concentrations (down to <0.1 mg Xeq/L). This was demonstrated through application of the method for monitoring these compounds in algal cultures and a full-scale RO plant. The monitoring also revealed that concentrations of the colloidal precursors were substantially higher than the concentration of TEP themselves. In the RO plant, complete TEP removal was observed over the pre-treatment processes (coagulation-sedimentation-filtration and ultrafiltration) but the TEP precursors were not completely removed, emphasising the importance of measuring this colloidal component to better understand the role of TEP and acidic polysaccharides in RO membrane fouling.

A novel anaerobic electrochemical membrane bioreactor (AnEMBR) with conductive hollow-fiber membrane for treatment of low-organic strength solutions.

A new anaerobic treatment system that combined a microbial electrolysis cell (MEC) with membrane filtration using electrically conductive, porous, nickel-based hollow-fiber membranes (Ni-HFMs) was developed to treat low organic strength solution and recover energy in the form of biogas. This new system is called an anaerobic electrochemical membrane bioreactor (AnEMBR). The Ni-HFM served the dual function as the cathode for hydrogen evolution reaction (HER) and the membrane for filtration of the effluent. The AnEMBR system was operated for 70 days with synthetic acetate solution having a chemical oxygen demand (COD) of 320 mg/L. Removal of COD was >95% at all applied voltages tested. Up to 71% of the substrate energy was recovered at an applied voltage of 0.7 V as methane rich biogas (83% CH4; <1% H2) due to biological conversion of the hydrogen evolved at the cathode to methane. A combination of factors (hydrogen bubble formation, low cathode potential and localized high pH at the cathode surface) contributed to reduced membrane fouling in the AnEMBR compared to the control reactor (open circuit voltage). The net energy required to operate the AnEMBR system at an applied voltage of 0.7 V was significantly less (0.27 kWh/m3) than that typically needed for wastewater treatment using aerobic membrane bioreactors (1-2 kWh/m3).

Irreversible membrane fouling abatement through pre-deposited layer of hierarchical porous carbons.

In this work, dual-templated hierarchical porous carbons (HPCs), produced from a coupled ice-hard templating approach, are shown to be a highly effective solution to the commonly occurring problem of irreversible fouling of low-pressure membranes used for pre-treatment in wastewater reuse. For the first time, dual-templated HPCs, along with their respective counterparts - single-templated meso-porous carbon (MPCs) (without macropores) - are tested in terms of their fouling reduction capacity and ability to remove different effluent organic matter fractions present in wastewater and compared with a commercially available powdered activated carbon (PAC). The synthesized HPCs provided exceptional fouling abatement, a 4-fold higher fouling reduction as compared to the previously reported best performing commercial PAC and ∼2.5-fold better fouling reduction than their respective mesoporous counterpart. Thus, it is shown that not only mesoporosity, but macroporosity is also necessary to achieve high fouling reduction, thus emphasizing the need for dual templating. In the case of HPCs, the pre-deposition technique is also found to outperform the traditional sorbent-feed mixing approach, mainly in terms of removal of fouling components. Based on their superior performance, a high permeability (ultra-low-pressure) membrane consisting of the synthesized HPC pre-deposited on a large pore size membrane support (0.45 µm membrane), is shown to give excellent pre-treatment performance for wastewater reuse application.

Fate of bulk and trace organics during a simulated aquifer recharge and recovery (ARR)-ozone hybrid process.

The attenuation of bulk organic matter and trace organic contaminants (TOrCs) was evaluated for various aquifer recharge and recovery (ARR)-ozone (O3) hybrid treatment process combinations using soil-batch reactor and bench-scale ozonation experiments as a proof of concept prior to pilot and/or field studies. In water reclamation and especially potable reuse, refractory bulk organic matter and TOrCs are of potential health concern in recycled waters. In this study, the role of biotransformation of bulk organic matter and TOrCs was investigated considering different simulated treatment combinations, including soil passage (ARR) alone, ARR after ozonation (O3-ARR), and ARR prior to ozonation (ARR-O3). During oxic (aerobic) ARR simulations, soluble microbial-like substances (e.g., higher molecular weight polysaccharides and proteins) were easily removed while (lower molecular weight) humic substances and aromatic organic matter were not efficiently removed. During ARR-ozone treatment simulations, removals of bulk organic matter and TOrCs were rapid and effective compared to ARR alone. A higher reduction of effluent-derived organic matter, including aromatic organic matter and humic substances, was observed in the ARR-O3 hybrid followed by the O3-ARR hybrid. An enhanced attenuation of recalcitrant TOrCs was observed while increasing the ozone dose slightly (O3: DOC=1). TOrC removal efficiency also increased during the post-ozone treatment combination (i.e., ARR-O3). In addition, the carcinogenic wastewater disinfection byproduct N-nitrosodimethylamine (NDMA) was eliminated below the method reporting limit (<5 ng L(-1)) both during ARR treatment alone and the ARR-ozone hybrid.

Characterization of bacterial and archaeal communities in air-cathode microbial fuel cells, open circuit and sealed-off reactors.

A large percentage of organic fuel consumed in a microbial fuel cell (MFC) is lost as a result of oxygen transfer through the cathode. In order to understand how this oxygen transfer affects the microbial community structure, reactors were operated in duplicate using three configurations: closed circuit (CC; with current generation), open circuit (OC; no current generation), and sealed off cathodes (SO; no current, with a solid plate placed across the cathode). Most (98 %) of the chemical oxygen demand (COD) was removed during power production in the CC reactor (maximum of 640 ± 10 mW/m(2)), with a low percent of substrate converted to current (coulombic efficiency of 26.5 ± 2.1 %). Sealing the cathode reduced COD removal to 7 %, but with an open cathode, there was nearly as much COD removal by the OC reactor (94.5 %) as the CC reactor. Oxygen transfer into the reactor substantially affected the composition of the microbial communities. Based on analysis of the biofilms using 16S rRNA gene pyrosequencing, microbes most similar to Geobacter were predominant on the anodes in the CC MFC (72 % of sequences), but the most abundant bacteria were Azoarcus (42 to 47 %) in the OC reactor, and Dechloromonas (17 %) in the SO reactor. Hydrogenotrophic methanogens were most predominant, with sequences most similar to Methanobacterium in the CC and SO reactor, and Methanocorpusculum in the OC reactors. These results show that oxygen leakage through the cathode substantially alters the bacterial anode communities, and that hydrogenotrophic methanogens predominate despite high concentrations of acetate. The predominant methanogens in the CC reactor most closely resembled those in the SO reactor, demonstrating that oxygen leakage alters methanogenic as well as general bacterial communities.

Appropriate drinking water treatment processes for organic micropollutants removal based on experimental and model studies - a multi-criteria analysis study.

The presence of organic micropollutants (OMPs), pharmaceuticals and personal care products (PPCPs) in potable water is of great environmental and public health concern. OMPs are included in the priority list of contaminants in United States EPA and European framework directives. Advanced treatment processes such as reverse osmosis, nanofiltration, ozonation and adsorption are the usual industry-recommended processes for OMPs removal, however, natural systems, e.g., riverbank filtration and constructed wetlands, are also potentially efficient options for OMPs removal. In this study, a decision support system (DSS) based on multi-criteria analysis (MCA) was created to compare processes for OMPs removal under various criteria. Multi-criteria analysis (MCA), a transparent and reliable procedure, was adopted. Models were built for both experimental and predicted percent-removals for a range of OMPs reflecting different physicochemical properties. The experimental percent-removals for several processes (riverbank filtration (RBF), ozonation, advanced oxidation, adsorption, reverse osmosis, and nanofiltration) were considered. The predicted percent-removals were taken from validated quantitative structure activity relationship (QSAR) models. Analytical methods to detect OMPs in water are very laborious, thus a modeling approach such as QSAR is an attractive option. A survey among two groups of participants including academics (PhD students and post-doctoral research associates) and industry (managers and operators) representatives was conducted to assign weights for the following criteria: treatability, costs, technical considerations, sustainability and time. The process rankings varied depending on the contaminant species and personal preferences (weights). The results indicated that RBF and oxidation were preferable over adsorption and membranes processes. The results also suggest that the use of a hybrid treatment process, e.g., combining a natural system with an advanced treatment (oxidation) process, may provide benefits for OMPs removal. The proposed DSS can be used as a screening tool for experimental planning or a feasibility study preceding the main treatment system selection and design. It can also be considered as an aid in assessing a multi-barrier approach to remove OMPs.

QSAR models for oxidation of organic micropollutants in water based on ozone and hydroxyl radical rate constants and their chemical classification.

Ozonation is an oxidation process for the removal of organic micropollutants (OMPs) from water and the chemical reaction is governed by second-order kinetics. An advanced oxidation process (AOP), wherein the hydroxyl radicals (OH radicals) are generated, is more effective in removing a wider range of OMPs from water than direct ozonation. Second-order rate constants (k(OH) and k(O3) are good indices to estimate the oxidation efficiency, where higher rate constants indicate more rapid oxidation. In this study, quantitative structure activity relationships (QSAR) models for O(3) and AOP processes were developed, and rate constants, k(OH) and [Formula: see text] , were predicted based on target compound properties. The k(O3) and k(OH) values ranged from 5 * 10(-4) to 10(5) M(-1)s(-1) and 0.04 to 18 * (10(9)) M(-1) s(-1), respectively. Several molecular descriptors which potentially influence O(3) and OH radical oxidation were identified and studied. The QSAR-defining descriptors were double bond equivalence (DBE), ionisation potential (IP), electron-affinity (EA) and weakly-polar component of solvent accessible surface area (WPSA), and the chemical and statistical significance of these descriptors was discussed. Multiple linear regression was used to build the QSAR models, resulting in high goodness-of-fit, r(2) (>0.75). The models were validated by internal and external validation along with residual plots.

Effects of effluent organic matter characteristics on the removal of bulk organic matter and selected pharmaceutically active compounds during managed aquifer recharge: Column study.

Soil column experiments were conducted to investigate the effects of effluent organic matter (EfOM) characteristics on the removal of bulk organic matter (OM) and pharmaceutically active compounds (PhACs) during managed aquifer recharge (MAR) treatment processes. The fate of bulk OM and PhACs during an MAR is important to assess post-treatment requirements. Biodegradable OM from EfOM, originating from biological wastewater treatment, was effectively removed during soil passage. Based on a fluorescence excitation-emission matrix (F-EEM) analysis of wastewater effluent-dominated (WWE-dom) surface water (SW), protein-like substances, i.e., biopolymers, were removed more favorably than fluorescent humic-like substances under oxic compared to anoxic conditions. However, there was no preferential removal of biopolymers or humic substances, determined as dissolved organic carbon (DOC) observed via liquid chromatography with online organic carbon detection (LC-OCD) analysis. Most of the selected PhACs exhibited removal efficiencies of greater than 90% in both SW and WWE-dom SW. However, the removal efficiencies of bezafibrate, diclofenac and gemfibrozil were relatively low in WWE-dom SW, which contained more biodegradable OM than did SW (copiotrophic metabolism). Based on this study, low biodegradable fractions such as humic substances in MR may have enhanced the degradation of diclofenac, gemfibrozil and bezafibrate by inducing an oligotrophic microbial community via long term starvation. Both carbamazepine and clofibric acid showed persistent behaviors and were not influenced by EfOM.

Exploration of polyelectrolytes as draw solutes in forward osmosis processes.

The development of the forward osmosis (FO) process has been constrained by the slow development of appropriate draw solutions. Two significant concerns related to draw solutions are the draw solute leakage and intensive energy requirement in recycling draw solutes after the FO process. FO would be much attractive if there is no draw solute leakage and the recycle of draw solutes is easy and economic. In this study, polyelectrolytes of a series of polyacrylic acid sodium salts (PAA-Na), were explored as draw solutes in the FO process. The characteristics of high solubility in water and flexibility in structural configuration ensure the suitability of PAA-Na as draw solutes and their relative ease in recycle through pressure-driven membrane processes. The high water flux with insignificant salt leakage in the FO process and the high salt rejection in recycle processes reveal the superiority of PAA-Na to conventional ionic salts, such as NaCl, when comparing their FO performance via the same membranes. The repeatable performance of PAA-Na after recycle indicates the absence of any aggregation problems. The overall performance demonstrates that polyelectrolytes of PAA-Na series are promising as draw solutes, and the new concept of using polyelectrolytes as draw solutes in FO processes is applicable.

QSAR models for the removal of organic micropollutants in four different river water matrices.

Ozonation is an advanced water treatment process used to remove organic micropollutants (OMPs) such as pharmaceuticals and personal care products (PPCPs). In this study, Quantitative Structure Activity Relationship (QSAR) models, for ozonation and advanced oxidation process (AOP), were developed with percent-removal of OMPs by ozonation as the criterion variable. The models focused on PPCPs and pesticides elimination in bench-scale studies done within natural water matrices: Colorado River, Passaic River, Ohio River and Suwannee synthetic water. The OMPs removal for the different water matrices varied depending on the water quality conditions such as pH, DOC, alkalinity. The molecular descriptors used to define the OMPs physico-chemical properties range from one-dimensional (atom counts) to three-dimensional (quantum-chemical). Based on a statistical modeling approach using more than 40 molecular descriptors as predictors, descriptors influencing ozonation/AOP were chosen for inclusion in the QSAR models. The modeling approach was based on multiple linear regression (MLR). Also, a global model based on neural networks was created, compiling OMPs from all the four river water matrices. The chemically relevant molecular descriptors involved in the QSAR models were: energy difference between lowest unoccupied and highest occupied molecular orbital (E(LUMO)-E(HOMO)), electron-affinity (EA), number of halogen atoms (#X), number of ring atoms (#ring atoms), weakly polar component of the solvent accessible surface area (WPSA) and oxygen to carbon ratio (O/C). All the QSAR models resulted in a goodness-of-fit, R(2), greater than 0.8. Internal and external validations were performed on the models.

Role of biodegradation in the removal of pharmaceutically active compounds with different bulk organic matter characteristics through managed aquifer recharge: batch and column studies.

Natural water treatment systems such as bank filtration have been recognized as providing effective barriers in the multi-barrier approach for attenuation of organic micropollutants for safe drinking water supply. In this study, the role of biodegradation in the removal of selected pharmaceutically active compounds (PhACs) during soil passage was investigated. Batch studies were conducted to investigate the removal of 13 selected PhACs from different water sources with respect to different sources of biodegradable organic matter. Neutral PhACs (phenacetine, paracetamol, and caffeine) and acidic PhACs (ibuprofen, fenoprofen, bezafibrate, and naproxen) were removed with efficiencies greater than 88% from different organic matter water matrices during batch studies (hydraulic retention time (HRT): 60 days). Column experiments were then performed to differentiate between biodegradation and sorption with regard to the removal of selected PhACs. In column studies, removal efficiencies of acidic PhACs (e.g., analgesics) decreased under conditions of limited biodegradable carbon. The removal efficiencies of acidic PhACs were found to be less than 21% under abiotic conditions. These observations were attributed to sorption under abiotic conditions established by a biocide (20 mM sodium azide), which suppresses microbial activity/biodegradation. However, under biotic conditions, the removal efficiencies of these acidic PhACs were found to be greater than 59%. This is mainly attributed to biodegradation. Moreover, the average removal efficiencies of hydrophilic (polar) neutral PhACs (paracetamol, pentoxifylline, and caffeine) with low octanol/water partition coefficients (log Kow less than 1) were low (11%) under abiotic conditions. However, under biotic conditions, removal efficiencies of the neutral PhACs were greater than 98%. In contrast, carbamazepine persisted and was not easily removed under either biotic or abiotic conditions. This study indicates that biodegradation represents an important mechanism for the removal of PhACs during soil passage.