Ines Zucker

Treating wastewater from a pharmaceutical formulation facility by biological process and ozone

Wastewater from a pharmaceutical formulation facility (TevaKS, Israel) was treated with a biological activated-sludge system followed by ozonation. The goal was to reduce the concentrations of the drugs carbamazepine (CBZ) and venlafaxine (VLX) before discharging the wastewater to the municipal wastewater treatment plant (WWTP). Both drugs were detected at extremely high concentrations in TevaKS raw wastewater ([VLX]=11.72 ± 2.2mg/L, [CBZ]=0.84 ± 0.19 mg/L), and resisted the biological treatment. Ozone efficiently degraded CBZ: at an O3 dose-to-dissolved organic carbon ratio of 0.55 (O3/DOC), the concentration of CBZ was reduced by >99%. A lower removal rate was observed for VLX, which was decreased by ≈ 98% at the higher O3/DOC ratio of 0.87. Decreasing the pH of the biologically treated effluent from 7 to 5 significantly increased the ozone degradation rate of CBZ, while decreasing the degradation rate of VLX. Ozone treatment did not alter the concentration of the effluents DOC and filtered chemical oxygen demand (CODf). However, a significant increase was recorded (following ozonation) in the effluents biological oxygen demand (BOD5) and the BOD5/CODf ratio. This implies an increase in the effluents biodegradability, which is highly desirable if ozonation is followed by a domestic biological treatment. Different organic byproducts were formed following ozone reaction with the target pharmaceuticals and with the effluent organic matter; however, these byproducts are expected to be removed during biological treatment in the municipal WWTP.

Influence of wastewater particles on ozone degradation of trace organic contaminants.

In this Article, we demonstrate the influence of effluent particles (in the range of <50 μm) on ozone degradation of trace organic contaminants (TrOCs) and effluent-quality parameters. Secondary effluent was filtered through different pore-size filters and ozonated at various ozone doses. Degradation of both ozone-reactive and ozone-refractory contaminants improved following ozonation of effluent filtered with smaller pore size filters, indicating that particles in this range may adversely affect ozonation. The inhibitory effect of particles was attributed to their reaction with ozone, reducing available ozone and HO(•) radicals. In addition, increasing filtration level decreased the effluents (instantaneous) ozone demand and increased removal of effluent UV absorbance (UVA254), further establishing that ozone reacts with effluent particles, in competition with dissolved matter. Moreover, ozone was shown to react with particles even during the first seconds of the process, suggesting a high rate of some ozone-particle reactions, comparable to ozone reaction with highly reactive dissolved organic matter moieties. Particle image analysis revealed that particle formation/aggregation and particle disintegration occurs simultaneously during wastewater (WW) ozonation. Our study implies that particles could affect the efficiency of WW ozonation, by increasing the effluents ozone demand and decreasing contaminant degradation.

Enhanced antibacterial activity through the controlled alignment of graphene oxide nanosheets

Significance In biomedical and environmental applications, as well as manufacture and disposal, the interaction of graphene-based nanomaterials (GBNs) with living cells is inevitable and sometimes crucial. While the cytotoxic properties of GBNs are well established, the mechanisms behind the cytotoxicity remain controversial. In this study, we first utilize a magnetic field to form films with aligned graphene oxide (GO), showing that the alignment of sharp GO edges plays a crucial role in the antibacterial activity. We then demonstrate using model systems that GO unequivocally induces physical disruption of lipid bilayers and that oxidation stems from a direct electron transfer mechanism. Altogether, our results elucidate the physicochemical, edge-based cytotoxicity of GBNs, while providing guidance for the design of engineered surfaces using GBNs. The cytotoxicity of 2D graphene-based nanomaterials (GBNs) is highly important for engineered applications and environmental health. However, the isotropic orientation of GBNs, most notably graphene oxide (GO), in previous experimental studies obscured the interpretation of cytotoxic contributions of nanosheet edges. Here, we investigate the orientation-dependent interaction of GBNs with bacteria using GO composite films. To produce the films, GO nanosheets are aligned in a magnetic field, immobilized by cross-linking of the surrounding matrix, and exposed on the surface through oxidative etching. Characterization by small-angle X-ray scattering and atomic force microscopy confirms that GO nanosheets align progressively well with increasing magnetic field strength and that the alignment is effectively preserved by cross-linking. When contacted with the model bacterium Escherichia coli, GO nanosheets with vertical orientation exhibit enhanced antibacterial activity compared with random and horizontal orientations. Further characterization is performed to explain the enhanced antibacterial activity of the film with vertically aligned GO. Using phospholipid vesicles as a model system, we observe that GO nanosheets induce physical disruption of the lipid bilayer. Additionally, we find substantial GO-induced oxidation of glutathione, a model intracellular antioxidant, paired with limited generation of reactive oxygen species, suggesting that oxidation occurs through a direct electron-transfer mechanism. These physical and chemical mechanisms both require nanosheet penetration of the cell membrane, suggesting that the enhanced antibacterial activity of the film with vertically aligned GO stems from an increased density of edges with a preferential orientation for membrane disruption. The importance of nanosheet penetration for cytotoxicity has direct implications for the design of engineering surfaces using GBNs.

A hybrid process of biofiltration of secondary effluent followed by ozonation and short soil aquifer treatment for water reuse

The Shafdan reclamation project facility (Tel Aviv, Israel) practices soil aquifer treatment (SAT) of secondary effluent with hydraulic retention times (HRTs) of a few months to a year for unrestricted agricultural irrigation. During the SAT, the high oxygen demand (>40xa0mgxa0L(-1)) of the infiltrated effluent causes anoxic conditions and mobilization of dissolved manganese from the soil. An additional emerging problem is the occurrence of persistent trace organic compounds (TrOCs) in reclaimed water that should be removed prior to reuse. An innovative hybrid process based on biofiltration, ozonation and short SAT with ∼22xa0d HRT is proposed for treatment of the Shafdan secondary effluent to overcome limitations of the existing system and to reduce the SATs physical footprint. Besides efficient removal of particulate matter to minimize clogging, coagulation/flocculation and filtration (5-6xa0mxa0h(-1)) operated with the addition of hydrogen peroxide as an oxygen source efficiently removed dissolved organic carbon (DOC, to 17-22%), ammonium and nitrite. This resulted in reduced effluent oxygen demand during infiltration and oxidant (ozone) demand during ozonation by 23xa0mgxa0L(-1) and 1.5xa0mgxa0L(-1), respectively. Ozonation (1.0-1.2xa0mg O3 mg DOC(-1)) efficiently reduced concentrations of persistent TrOCs and supplied sufficient dissolved oxygen (>30xa0mgxa0L(-1)) for fully oxic operation of the short SAT with negligible Mn(2+) mobilization (<50xa0μgxa0L(-1)). Overall, the examined hybrid process provided DOC reduction of 88% to a value of 1.2xa0mgxa0L(-1), similar to conventional SAT, while improving the removal of TrOCs and efficiently preventing manganese dissolution.

Determination of oxidant exposure during ozonation of secondary effluent to predict contaminant removal.

The use of kinetic models to predict oxidation performance in wastewater is limited due to fast ozone depletion during the first milliseconds of the reaction. This paper introduces the Quench Flow Module (QFM), a bench-scale experimental technique developed to measure the first 5-500 milliseconds of ozone depletion for accurate determination of ozone exposure in wastewater-ozonation processes. Calculated ozone exposure in QFM experiments was up to 24% lower than in standard batch experiments, strongly depending on the initial sampling point for measurement in batch experiments. However, oxidation rates of slowly- and moderately-reacting trace organic compounds (TrOCs) were accurately predicted from batch experiments based on integration of ozone depletion and removal of an ozone-resistant probe compound to calculate oxidant exposures. An alternative concept, where ozone and hydroxyl radical exposures are back-calculated from the removal of two probe compounds, was tested as well. Although the QFM was suggested to be an efficient mixing reactor, ozone exposure ranged over three orders of magnitude when different probe compounds reacting moderately with ozone were used for the calculation. These effects were beyond uncertainty ranges for apparent second order rate constants and consistently observed with different ozone-injection techniques, i.e. QFM, batch experiments, bubble columns and venturi injection. This indicates that previously suggested mixing effects are not responsible for the difference and other still unknown factors might be relevant. Results furthermore suggest that ozone exposure calculations from the relative residual concentration of a probe compound are not a promising option for evaluation of ozonation of secondary effluents.

The Role of Soil Aquifer Treatment (SAT) for Effective Removal of Organic Matter, Trace Organic Compounds and Microorganisms from Secondary Effluents Pre-Treated by Ozone

ABSTRACT Soil aquifer treatment (SAT) is an effective natural and economically feasible tertiary treatment for wastewater reuse. An innovative hybrid process based on biofiltration, ozonation and short SAT (sSAT, with ~22 days retention time) was demonstrated in a 6 m3/hr pilot system to remove emerging trace organic compounds (TrOCs), organic matter and control Mn2+ dissolution in reclaimed water. The biofiltration stage was proposed for nitrification of ammonia as well as removal of dissolved and particulate organic matter (DOM and POM), to enable efficient ozonation of secondary effluents. The pilot system was operated in two modes, where samples were periodically taken from all pilot stages to observe changes in product water quality. At first (Mode 1), biofiltered effluents were infiltrated through sSAT (i.e., no ozonation prior infiltration). During this operation, ammonia, nitrite and phosphate were completely removed, and pathogens were highly reduced. In addition, all measured TrOCs were effectively removed after sSAT, besides the persistent TrOCs Carbamazepine (CBZ) and Iodine-organic contrast media Iopamidol (IPDL). In Mode 2, biofiltered and ozonated (1.0–1.2 mg ozone/mg DOC) effluents were infiltrated through sSAT. In the final reclaimed product, values of DOC, UVA and Mn2+ were reduced to 0.8 mg/L, 2.2 L/m, and 29–35 µg/L, respectively. Furthermore, ammonia and nitrite were not detected in the product, and good bacterial quality was obtained. Following 56–75 days of operation at Mode 2, all TrOCs were reduced down to <100 ng/L. The delay in the effect of the pretreatment stages on TrOCs removal by sSAT (>56 days instead of ~22 days) could be explained by their displacement retardation in the upper soil layers of the pilot SAT (0–25 cm). In-depth sampling in the observation well after 111 days at Mode 2 showed homogeneity along the overall perforated section of the well (from −14 to −26 m) with 0.7–0.9 mg/L DOC, 2.1–2.2 1/m UVA and <10 ng/L CBZ. This result proved that the ozonated water completely covered the area around the observation well and positively affected the quality of the reclaimed water.

The role of nanotechnology in tackling global water challenges

Sustainable provision of safe, clean and adequate water supply is a global challenge. Water treatment and desalination technologies remain chemically and energy intensive, ineffective in removing key trace contaminants, and poorly suited to deployment in decentralized (distributed) water treatment systems globally. Several recent efforts have sought to leverage the reactive and tunable properties of nanomaterials to address these technological shortcomings. This Review assesses the potential applications of nanomaterials in advancing sustainable water treatment systems and proposes ways to evaluate the environmental risks and social acceptance of nanotechnology-enabled water treatment processes. Future areas of research necessary to realize safe deployment of promising nanomaterial applications are also identified.Despite recent technological progress, providing safe, clean and sufficient water sustainably for all remains challenging. This Review assesses the potential applications of nanomaterials in advancing the sustainability of water treatment systems, and their associated barriers.

Formation and degradation of N-oxide venlafaxine during ozonation and biological post-treatment

While ozonation is considered an efficient treatment to eliminate trace organic compounds (TrOCs) from secondary wastewater effluents, the presence and persistence of transformation products (TPs) resulting from ozonation of TrOCs is a major concern that should be assessed prior to effluent discharge to the environment. Venlafaxine (VLX), an environmentally relevant tertiary amine-containing TrOC, was chosen as the model for this study. TP analysis confirmed that the lone electron pair of the non-protonated amine are the predominant site of oxidant attack, and therefore strongly affected by pH value and VLX speciation. N-oxide VLX (NOV), the primary ozone-induced TP, was formed and degraded simultaneously during ozonation of VLX-containing secondary effluent and reached a maximum yield of 0.44 to 0.85 (NOV-to-VLX0 ratio), depending on pH and hydroxyl (OH) radical presence. Rate constants for the reaction of NOV with ozone (3.1×102M-1s-1) and OH radicals (5.3×109M-1s-1) were determined. A simple kinetic model was developed to fit the kinetics of formation and degradation of NOV during ozonation in secondary effluents, based on a known ozone-reaction kinetic equation. The biodegradability of NOV (degradation rate of 39%) was significantly lower than that of the parent compound (VLX, 92%) after 71days, as evaluated by modified Zahn-Wellens tests, suggesting that N-oxide products are not better removed than the parent compound in a simulated biological post-treatment, which may even result in partial reformation of the parent compound. Lessons learned from this study were supported by a pilot-scale demonstration at the Shafdan wastewater-treatment plant, confirming the presence of NOV after ozonation and its persistence in biological post-treatment. Removal of such persistent TP will require higher dosages or promotion of OH-radicals during ozonation. Nevertheless, further assessment of the toxicity of persistent TPs relative to the parent compound is needed for complete evaluation of concerned TPs.

Reactive, Self-Cleaning Ultrafiltration Membrane Functionalized with Iron Oxychloride Nanocatalysts

Self-cleaning, antifouling ultrafiltration membranes are critically needed to mitigate organic fouling in water and wastewater treatment. In this study, we fabricated a novel polyvinylidene fluoride (PVDF) composite ultrafiltration membrane coated with FeOCl nanocatalysts (FeOCl/PVDF) via a facile, scalable thermal-treatment method, for the synergetic separation and degradation of organic pollutants. The structure, composition, and morphology of the FeOCl/PVDF membrane were extensively characterized. Results showed that the as-prepared FeOCl/PVDF membrane was uniformly covered with FeOCl nanoparticles with an average diameter of 1-5 nm, which greatly enhanced membrane hydrophilicity. The catalytic self-cleaning and antifouling properties of the FeOCl/PVDF membrane were evaluated in the presence of H2O2 at neutral pH. Using a facile H2O2 cleaning process, we showed that the FeOCl/PVDF membrane can achieve an excellent water flux recovery rate of ∼100%, following organic fouling with a model organic foulant (bovine serum albumin). Moreover, the in situ catalytic production of active hydroxyl radicals by the FeOCl/PVDF membrane was elucidated by electron spin resonance (ESR) and UV analysis. The catalytic performance of the FeOCl/PVDF membrane was further demonstrated by the complete degradation of bisphenol A when H2O2 was dosed in the feed solution at neutral pH. Our results demonstrate the promise of utilizing this novel membrane for the treatment of waters with complex organic pollutants.

High Performance Nanofiltration Membrane for Effective Removal of Perfluoroalkyl Substances at High Water Recovery

We demonstrate the fabrication of a loose, negatively charged nanofiltration (NF) membrane with tailored selectivity for the removal of perfluoroalkyl substances with reduced scaling potential. A selective polyamide layer was fabricated on top of a poly(ether sulfone) support via interfacial polymerization of trimesoyl chloride and a mixture of piperazine and bipiperidine. Incorporating high molecular weight bipiperidine during the interfacial polymerization enables the formation of a loose, nanoporous selective layer structure. The fabricated NF membrane possessed a negative surface charge and had a pore diameter of ∼1.2 nm, much larger than a widely used commercial NF membrane (i.e., NF270 with pore diameter of ∼0.8 nm). We evaluated the performance of the fabricated NF membrane for the rejection of different salts (i.e., NaCl, CaCl2, and Na2SO4) and perfluorooctanoic acid (PFOA). The fabricated NF membrane exhibited a high retention of PFOA (∼90%) while allowing high passage of scale-forming cations (i.e., calcium). We further performed gypsum scaling experiments to demonstrate lower scaling potential of the fabricated loose porous NF membrane compared to NF membranes having a dense selective layer under solution conditions simulating high water recovery. Our results demonstrate that properly designed NF membranes are a critical component of a high recovery NF system, which provide an efficient and sustainable solution for remediation of groundwater contaminated with perfluoroalkyl substances.