Facilely tuning the intrinsic catalytic sites of the spinel oxide for peroxymonosulfate activation: From fundamental investigation to pilot-scale demonstration.

Heterogeneous peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) have shown a great potential for pollutant degradation, but their feasibility for large-scale water treatment application has not been demonstrated. Herein, we develop a facile coprecipitation method for the scalable production (∼10 kg) of the Cu-Fe-Mn spinel oxide (CuFeMnO). Such a catalyst has rich oxygen vacancies and symmetry-breaking sites, which endorse it with a superior PMS-catalytic capacity. We find that the working reactive species and their contributions are highly dependent on the properties of target organic pollutants. For the organics with electron-donating group (e.g., -OH), high-valent metal species are mainly responsible for the pollutant degradation, whereas for the organics with electron-withdrawing group (e.g., -COOH and -NO2), hydroxyl radical (•OH) as the secondary oxidant also plays an important role. We demonstrate that the CuFeMnO-PMS system is able to achieve efficient and stable removal of the pollutants in the secondary effluent from a municipal wastewater plant at both bench and pilot scales. Moreover, we explore the application prospect of this PMS-based AOP process for large-scale wastewater treatment. This work describes an opportunity to scalably prepare robust spinel oxide catalysts for water purification and is beneficial to the practical applications of the heterogeneous PMS-AOPs.

Hydrogel-based biocontainment of bacteria for continuous sensing and computation.

Genetically modified microorganisms (GMMs) can enable a wide range of important applications including environmental sensing and responsive engineered living materials. However, containment of GMMs to prevent environmental escape and satisfy regulatory requirements is a bottleneck for real-world use. While current biochemical strategies restrict unwanted growth of GMMs in the environment, there is a need for deployable physical containment technologies to achieve redundant, multi-layered and robust containment. We developed a hydrogel-based encapsulation system that incorporates a biocompatible multilayer tough shell and an alginate-based core. This deployable physical containment strategy (DEPCOS) allows no detectable GMM escape, bacteria to be protected against environmental insults including antibiotics and low pH, controllable lifespan and easy retrieval of genomically recoded bacteria. To highlight the versatility of DEPCOS, we demonstrated that robustly encapsulated cells can execute useful functions, including performing cell-cell communication with other encapsulated bacteria and sensing heavy metals in water samples from the Charles River.

Removal of Cr(VI) from Aqueous Solutions Using Biowastes: Tella Residue and Pea (Pisum sativum) Seed Shell.

The wide use of chromium (Cr) in different industries led to the release of a considerable amount of Cr(VI) into water bodies. Exposure to Cr(VI) can cause diseases in humans and animals. Therefore, low-cost technology for Cr(VI) removal is required. In this study, the biowastes, "Tella" residue (TR) and Pea (Pisum sativum) seed shell (PSS), were evaluated for their Cr(VI) removal efficiency from aqueous solutions. The physicochemical properties of adsorbents were studied, and the adsorbents were further characterized using FTIR and XRD. Batch adsorption experiments have shown that the Cr(VI) uptake was pH-dependent and found to be effective in a wide range of pH values (pH 1 to 10) for PSS. The kinetics of Cr(VI) removal by the adsorbents was well expressed by the pseudo-second-order model. The experimental equilibrium adsorption data fitted well with Freundlich isotherm indicating multilayers adsorption. The estimated Cr(VI) adsorption capacities of TR and PSS were 15.6 mg/g and 8.5 mg/g, respectively. On top of this, the possibility of reusing adsorbents indicates the potential applicability of TR and PSS for the treatment of Cr(VI) contaminated water. Further study on the evaluation of the efficiency of the adsorbents using real chromium-contaminated wastewater is recommended.

P=O Functionalized Black Phosphorus/1T-WS2 Nanocomposite High Efficiency Hybrid Photocatalyst for Air/Water Pollutant Degradation.

Research on layered two-dimensional (2D) materials is at the forefront of material science. Because 2D materialshave variousplate shapes, there is a great deal of research on the layer-by-layer-type junction structure. In this study, we designed a composite catalyst with a dimension lower than two dimensions and with catalysts that canbe combined so that the band structures can be designed to suit various applications and cover for each other's disadvantages. Among transition metal dichalcogenides, 1T-WS2 can be a promising catalytic material because of its unique electrical properties. Black phosphorus with properly controlled surface oxidation can act as a redox functional group. We synthesized black phosphorus that was properly surface oxidized by oxygen plasma treatment and made a catalyst for water quality improvement through composite with 1T-WS2. This photocatalytic activity was highly efficient such that the reaction rate constant k was 10.31 × 10-2 min-1. In addition, a high-concentration methylene blue solution (20 ppm) was rapidly decomposed after more than 10 cycles and showed photo stability. Designing and fabricating bandgap energy-matching nanocomposite photocatalysts could provide a fundamental direction in solving the future's clean energy problem.

Impact of sublethal phenol in freshwater fish Labeo rohita on biochemical and haematological parameters.

Phenol, an aromatic chemical commonly found in domestic and industrial effluents, upon its introduction into aquatic ecosystems adversely affects the indigenous biota, the invertebrates and the vertebrates. With the increased demand for agrochemicals, a large amount of phenol is released directly into the environment as a byproduct. Phenol and its derivatives tend to persist in the environment for longer periods which in turn poses a threat to both humans and the aquatic ecosystem. In our current study, the response of Labeo rohita to sublethal concentrations of phenol was observed and the results did show a regular decrease in biochemical constituents of the targeted organs. Exposure of Labeo rohita to sublethal concentration of phenol (22.32 mg/L) for an epoch of 7, 21 and 28 days shows a decline in lipid, protein, carbohydrate content and phosphatase activity in target organs such as the gills, muscle, intestine, liver and kidney of the fish. The present study also aims to investigate the toxic effects of phenol with special reference to the haematological parameters of Labeo rohita. At the end of the exposure period, the blood of the fish was collected by cutting the caudal peduncle with a surgical scalpel. And it was observed that the red blood corpuscle count (RBC), white blood corpuscle (WBC), haemoglobin count (Hb), packed cell volume (PCV), mean corpuscular volume (MCV), mean corpuscular haemoglobin (MCH) and mean corpuscular haemoglobin concentration (MCHC) values showed a decline after exposure to phenol for 7 days, while white blood corpuscle (WBC) shows an increased count. At 21 days and 28 days, all the haematological parameters showed a significant decrease.

Comprehensive evaluation of manganese oxides and iron oxides as metal substrate materials for constructed wetlands from the perspective of water quality and greenhouse effect.

Manganese oxides and iron oxides have been widely introduced in constructed wetlands (CWs) for sewage treatment due to their extensiveness in nature and their ability to participate in various reactions, but their effects on greenhouse gas (GHG) emissions remain unclear. Here, a set of vertical subsurface-flow CWs (Control, Fe-VSSCWs, and Mn-VSSCWs) was established to comprehensively evaluate which are the better metal substrate materials for CWs, iron oxides or manganese oxides, through water quality and the global warming potential (GWP) of nitrous oxide (N2O), methane (CH4), and carbon dioxide (CO2). The results revealed that the removal efficiencies of chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) in Mn-VSSCWs were all higher than that in Fe-VSSCWs, and manganese oxides could almost completely suppress the CH4 production and reduce GWP (from 8.15 CO2-eq/m2/h to 7.17 mg CO2-eq/m2/h), however, iron oxides promoted GWP (from 8.15 CO2-eq/m2/h to 10.84 mg CO2-eq/m2/h), so manganese oxides are the better CW substrate materials to achieve effective sewage treatment while reducing the greenhouse gas effect.

Salt-template preparation of Mo5N6 nanosheets with peroxidase- and catalase-like activities and application for colorimetric determination of 4-aminophenol.

Mo5N6 nanosheets were synthesized by a nickel-induced growth method and were found to possess peroxidase-like activity in acidic condition and catalase-like activity in weak basic condition. In acidic condition, Mo5N6 nanosheets can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to form a blue color product (TMBOX). At the co-existence of 4-aminophenol (4-AP), 4-AP can react with H2O2 and TMBOX, resulting in the decrease of TMBOX and the fading of blue color. Therefore, a facile, sensitive colorimetric method for the quantitative detection of 4-AP was developed. The linear range for 4-AP was 1.0 to 80.0 µmol⋅L‒1 (R2 = 0.999), and the detection limit was 0.56 µmol⋅L‒1 based on 3σ/k. Resorcinol, aniline, humic acid, and common ions and anions in surface water did not interfere the determination of 4-AP. This colorimetric method was applied to measure the 4-AP in real water sample from Wulong River in Fujian Province of China. The relative standard deviation for the determination of 4-AP was ranged from 0.03 to 1.88%, and the recoveries from spiked samples were ranged between 99.2 and 107.6%. The determination results were consistent with those obtained by HPLC.

Salting our freshwater lakes.

The highest densities of lakes on Earth are in north temperate ecosystems, where increasing urbanization and associated chloride runoff can salinize freshwaters and threaten lake water quality and the many ecosystem services lakes provide. However, the extent to which lake salinity may be changing at broad spatial scales remains unknown, leading us to first identify spatial patterns and then investigate the drivers of these patterns. Significant decadal trends in lake salinization were identified using a dataset of long-term chloride concentrations from 371 North American lakes. Landscape and climate metrics calculated for each site demonstrated that impervious land cover was a strong predictor of chloride trends in Northeast and Midwest North American lakes. As little as 1% impervious land cover surrounding a lake increased the likelihood of long-term salinization. Considering that 27% of large lakes in the United States have >1% impervious land cover around their perimeters, the potential for steady and long-term salinization of these aquatic systems is high. This study predicts that many lakes will exceed the aquatic life threshold criterion for chronic chloride exposure (230 mg L-1), stipulated by the US Environmental Protection Agency (EPA), in the next 50 y if current trends continue.

Double surfactants-assisted electromembrane extraction of cyromazine and melamine in surface water, soil and cucumber samples followed by capillary electrophoresis with contactless conductivity detection.

BACKGROUND: Cyromazine (CYR) and its main degradation product melamine (MEL) are attracting wide attention due to their potential hazards to the environment and humans. In this work, double surfactants-assisted electromembrane extraction (DS-EME) by Tween 20 and alkylated phosphate was firstly used for purification and extraction of CYR and MEL, and the extract was directly analyzed by capillary electrophoresis with capacitively coupled contactless conductivity detection. RESULTS: Under the optimum conditions, two targets could be well separated from the main interferences, including common biogenic amines and inorganic cations within 14 min. This developed method was successfully applied to the analyses of surface water, soil and cucumber samples, and the average recoveries were in the range 93.3-112%. DS-EME provided a synergistic purification and enrichment effect for CYR and MEL by adding Tween 20 and alkylated phosphate into donor phase and supporting liquid membrane, respectively. Satisfactory limits of detection [0.2-1.5 ng mL-1 , signal-to-noise ratio (S/N) = 3] could be obtained in the tested sample matrices, and the corresponding enrichment factors were up to 115∼123 times. CONCLUSION: This developed method provides an alternative for the simultaneous analysis of CYR and MEL in complex real-world samples. © 2019 Society of Chemical Industry.

Water reuse: An alternative to minimize the environmental impact on the leather industry.

Tanneries are industries that may cause high environmental impact. Consequently, they are responsible for generating a large amount of wastewater with high concentrations of contaminants that require significant investment and operating costs in their treatment in order to accomplish the emission standards required by environmental legislation. This work has as main objective to minimize the environmental impact of the water used by tanneries through the study of reuse possibilities of wastewater tanning floats. The major concern is related to the pollutant chromium in the environment, since it is the tanning product that gives the best characteristics to leather and consequently the most used product. The reuse tests were performed on pilot and industrial scales. During the experiments, the following process control parameters were evaluated: pH, density, acid-base indicators for hide and shrinkage temperature. To validate the water reuse in tanneries, samples of wet-blue leather and residual floats were collected from pilot and industrial processes to perform chemical analyses to prove the validity of the process with reuse. Research has shown that reuse techniques, when properly evaluated, can be used in industries. In addition to reducing water demand, the reuse of wastewater in tanning processes minimizes the disposal of the wastewater with chromium and uses the residual chromium float.

Graphene-Based Catalysts for Ozone Processes to Decontaminate Water.

The use of graphene-based materials as catalysts in both ozone and ozone/radiation processes is creating interest among researchers devoted to the study of advanced oxidation processes (AOPs) for the degradation of organic pollutants in water. In this review, detailed explanations of catalytic and photocatalytic ozonation processes mediated by graphene-based materials are presented, focusing on aspects related to the preparation and characterization of catalysts, the nature of the water pollutants treated, the type of reactors and radiation sources applied, the influence of the main operating variables, catalyst activity and stability, and kinetics and mechanisms.

FeNiCeOx ternary catalyst prepared by ultrasonic impregnation method for diclofenac removal in Fenton-like system.

FeNiCeOx was firstly prepared by ultrasonic impregnation method and used to remove diclofenac in a Fenton-like system. The catalytic activity was improved successfully by doping Ni into FeCeOx. The diclofenac removal efficiency reached 97.9% after 30 min reaction. The surface morphology and properties of FeNiCeOx were characterized by Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Raman and X-ray photoelectron spectroscopy (XPS) analyses. FeNiCeOx in this paper had larger specific surface area than those prepared by other methods, which was attributed to the cavitation effect and hot-spot effect during the ultrasonic synthesis process. Low crystallinity of Fe2O3 and NiO showed by characterization could lead to high interaction of Fe and Ni ions with support of CeO2. They substituted Ce in CeO2, caused lattice contraction and formed more oxygen vacancies, which favoured the catalytic reaction. Meanwhile, Fe and Ce ions both had redox cycles of Fe3+/Fe2+ and Ce4+/Ce3+, which facilitated the electron transfer in the reaction. The synergistic effect among Fe, Ni and Ce might lead to better catalytic performance of FeNiCeOx than any binary metal oxides constituted from the above three elements. Finally, the potential mechanism of diclofenac removal in FeNiCeOx-H2O2 system is proposed.

Particular internal recirculation frequency scope for enhancing denitrifying phosphorus removal in an oxidation ditch.

This study investigated the influence of the unique internal recirculation characteristics of an oxidation ditch (OD) system, namely, the internal recirculation frequency (IRF) on denitrifying phosphorus removal (DNPR). The ratios of denitrifying polyphosphate-accumulating organisms (DPAOs) to polyphosphate-accumulating organisms (PAOs) under different IRF conditions were measured using a batch experiment. On this basis, the variation of nutrient transformations was studied using the IRF changes by the mass balance method. The results showed that, for the OD system that had an anaerobic zone upstream from the circular corridor and set anoxic and aerobic zones along the circular corridor, when the IRF was between 3.4 h-1 and 7.5 h-1, the DPAOs/PAOs ratio reached about 50%. Approximately 20% of the total phosphorus (TP) was removed and over 11% of the total nitrogen (TN) was transformed into nitrogen gas by the DNPR process, and meanwhile the total removal efficiencies of the TP and TN were over 93% and 80%. When the IRF was greater than 11.5 h-1, the TN removal efficiency decreased significantly, and this was not conducive to simultaneous nitrogen and phosphorus removal. The results indicated that the OD process would possess a better DNPR potential if the IRF were controlled within the proper scope.

Current status of applying microwave-associated catalysis for the degradation of organics in aqueous phase - A review.

Interactions between microwaves and certain catalysts can lead to efficient, energy-directed convergence of a relatively dispersed microwave field onto the reactive sites of the catalyst, which produces thermal or discharge effects around the catalyst. These interactions form "high-energy sites" (HeS) that promote energy efficient utilization and enhanced in situ degradation of organic pollutants. This article focuses on the processes occurring between microwaves and absorbing catalysts, and presents a critical review of microwave-absorbing mechanisms. This article also discusses aqueous phase applications of relevant catalysts (iron-based, carbon-based, soft magnetic, rare earth, and other types) and microwaves, special effects caused by the dimensions and structures of catalytic materials, and the optimization and design of relevant reactors for microwave-assisted catalysis of wastewater. The results of this study demonstrate that microwave-assisted catalysis can effectively enhance the degradation rate of organic compounds in an aqueous phase and has potential applications to a variety of engineering fields such as microwave-assisted pyrolysis, pollutant removal, material synthesis, and water treatment.

Using fluorescence surrogates to track algogenic dissolved organic matter (AOM) during growth and coagulation/flocculation processes of green algae.

Tracking the variation of the algogenic organic matter (AOM) released during the proliferation of green algae and subsequent treatment processes is crucial for constructing and optimizing control strategies. In this study, the potential of the spectroscopic tool was fully explored as a surrogate of AOM upon the cultivation of green algae and subsequent coagulation/flocculation (C/F) treatment processes using ZrCl4 and Al2(SO4)3. Fluorescence excitation emission matrix coupled with parallel factor analysis (EEM-PARAFAC) identified the presence of three independent fluorescent components in AOM, including protein-like (C1), fulvic-like (C2) and humic-like components (C3). Size exclusion chromatography (SEC) revealed that C1 in AOM was composed of large-sized proteins and aromatic amino acids. The individual components exhibited their unique characteristics with respect to the dynamic changes. C1 showed the highest correlation with AOM concentrations (R2 = 0.843) upon the C/F processes. C1 could also be suggested as an optical predictor for the formation of trihalomethanes upon the C/F processes. This study sheds a light for the potential application of the protein-like component (C1) as a practical surrogate to track the evolution of AOM in water treatment or wastewater reclamation systems involving Chlorella vulgaris green algae.

Etiology of Balkan Endemic Nephropathy: An Update on Aristolochic Acids Exposure Mechanisms.

Aristolochic acid released from decaying Aristolochia clematitis weed is contaminating soil and food crops in Eastern Europe and is one of the major causes to Balkan endemic nephropathy. Measures should be taken to prevent people from being exposed to these highly potent phytotoxins. Research needs to develop remediation methods.

Evaluation of Moringa oleifera seed extract by extraction time: effect on coagulation efficiency and extract characteristic.

The seed of Moringa oleifera (MO) is a well-known coagulant used in water and wastewater treatment, especially in developing countries. The main mechanism of MO seed extract in coagulation is the positive protein component for charge neutralization. The method for efficient extraction of MO seed is very important for high coagulation activity. In this study, the effects of extraction mixing speed and extraction time of MO on coagulation activity were evaluated using a distilled water extraction method. Although the rotation per minute for extraction did not affect the coagulation efficiency, the extraction time strongly affected the coagulation efficiency of the extract. To evaluate the characteristic change of MO extract by extraction time, the charge of MO extract and protein characteristic in MO extract were analysed. As the extraction time was short, more positive charge and higher protein content were observed. For detailed protein analysis, the fluorescence spectroscopic study (EEM analysis) was performed. The tryptophan-like peak increased at longer extraction times. For efficient extraction of MO seed, a short extraction time is strongly recommended.

Optimization of HNO3 leaching of copper from old AMD Athlon processors using response surface methodology.

The present study investigates the optimization of HNO3 leaching of Cu from old AMD Athlon processors under the effect of nitric acid concentration (%), temperature (°C) and ultrasonic power (W). The optimization study is carried out using response surface methodology with central composite rotatable design (CCRD). The ANOVA study concludes that the second degree polynomial model is fitted well to the fifteen experimental runs based on p-value (0.003), R2 (0.97) and Adj-R2 (0.914). The study shows that the temperature is the most significant process variable to the leaching concentration of Cu followed by nitric acid concentration. However, ultrasound power shows no significant impact on the leaching concentration. The optimum conditions were found to be 20% nitric acid concentration, 48.89 °C temperature and 5.52 W ultrasound power for attaining maximum concentration of 97.916 mg/l for Cu leaching in solution.

Practical Application of Aptamer-Based Biosensors in Detection of Low Molecular Weight Pollutants in Water Sources.

Water pollution has become one of the leading causes of human health problems. Low molecular weight pollutants, even at trace concentrations in water sources, have aroused global attention due to their toxicity after long-time exposure. There is an increased demand for appropriate methods to detect these pollutants in aquatic systems. Aptamers, single-stranded DNA or RNA, have high affinity and specificity to each of their target molecule, similar to antigen-antibody interaction. Aptamers can be selected using a method called Systematic Evolution of Ligands by EXponential enrichment (SELEX). Recent years we have witnessed great progress in developing aptamer selection and aptamer-based sensors for low molecular weight pollutants in water sources, such as tap water, seawater, lake water, river water, as well as wastewater and its effluents. This review provides an overview of aptamer-based methods as a novel approach for detecting low molecular weight pollutants in water sources.

Enhanced removal of selenate from mining effluent by H2O2/HCl-pretreated zero-valent iron.

Direct use of zero-valent iron (ZVI) in reductive removal of selenate (Se(VI)) is inefficient due to the intrinsic passive layer of ZVI. Here we observed that ZVI pretreated with H2O2 (P-ZVI-O) performs much better in Se(VI) removal from a mining effluent than other three modes of ZVI alone, acid washing ZVI (P-ZVI-A), and simultaneous addition of H2O2 and ZVI (ZVI-O) as well. The P-ZVI-O exhibits exceptionally high Se(VI) removal at a low dosage, wide pH range, with Se dropping down from 93.5 mg/L to <0.4 µg/L after 7-h reaction. Interestingly, the initial pH (2-6) of the mining effluent exerted little influence on the final Se(VI) removal. H2O2/HCl pretreatment results in the formation of various reducing corrosion products (e.g. Fe3O4, FeO and Fe2+), which greatly favors the efficient Se(VI) removal. In addition, surface-bound Fe2+ ions participated in the reduction of Se(VI). Combined with the influence of Se valence as well as pH and Fe2+ (whether dissolved or surface bound), it is deduced that the P-ZVI-O mode induced efficient Se(VI) removal via the adsorption-reduction and/or co-precipitation. This study demonstrates that H2O2/HCl pretreatment of ZVI is a very promising option to enhance the efficiency of reductive removal of Se(VI) from real effluents.