Improved overall water splitting for hydrogen production on aluminium-doped SrTiO3 photocatalyst via tuned surface band bending

Environmental Chemistry Letters - Future carbon neutrality and the energy crisis are calling for advanced methods to produce sustainable fuels such as hydrogen production by photocatalytic water...     

Visible-light-driven heterostructured g-C3N4/Bi-TiO2 floating photocatalyst with enhanced charge carrier separation for photocatalytic inactivation of Microcystis aeruginosa

• Bi doping in TiO₂ enhanced the separation of photo-generated electron-hole. • The performance of photocatalytic degradation of MC-LR was improved. • Coexisting substances have no influence on algal removal performance. • The key reactive oxygen species were h⁺ and ^•OH in the photocatalytic process. The increase in occurrence and severity of cyanobacteria blooms is causing increasing concern; moreover, human and animal health is affected by the toxic effects of Microcystin-LR released into the water. In this paper, a floating photocatalyst for the photocatalytic inactivation of the harmful algae Microcystis aeruginosa (M. aeruginosa) was prepared using a simple sol-gel method, i.e., coating g-C₃N₄ coupled with Bi-doped TiO₂ on Al₂O₃-modified expanded perlite (CBTA for short). The impact of different molar ratios of Bi/Ti on CBTA was considered. The results indicated that Bi doping in TiO₂ inhibited photogenerated electron-hole pair recombination. With 6 h of visible light illumination, 75.9% of M. aeruginosa (initial concentration= 2.7 × 10⁶ cells/L) and 83.7% of Microcystin-LR (initial concentration= 100 μg/L) could be removed with the addition of 2 g/L CBTA-1% (i.e., Bi/Ti molar ratio= 1%). The key reactive oxygen species (ROSs) in the photocatalytic inactivation process are h⁺ and ^•OH. The induction of the Bi⁴⁺/Bi³⁺ species by the incorporation of Bi could narrow the bandgap of TiO₂, trap electrons, and enhance the stability of CBTA-1% in the solutions with coexisting environmental substances.     

Optimization and modeling of coagulation-flocculation to remove algae and organic matter from surface water by response surface methodology

Charge neutralization and sweep flocculation were the major mechanisms. Effect of process parameters was investigated. Optimal coagulation conditions were studied by response surface methodology. ANN models presented more robust and accurate prediction than RSM. Seasonal algal blooms of Lake Yangcheng highlight the necessity to develop an effective and optimal water treatment process to enhance the removal of algae and dissolved organic matter (DOM). In the present study, the coagulation performance for the removal of algae, turbidity, dissolved organic carbon (DOC) and ultraviolet absorbance at 254 nm (UV₂₅₄) was investigated systematically by central composite design (CCD) using response surface methodology (RSM). The regression models were developed to illustrate the relationships between coagulation performance and experimental variables. Analysis of variance (ANOVA) was performed to test the significance of the response surface models. It can be concluded that the major mechanisms of coagulation to remove algae and DOM were charge neutralization and sweep flocculation at a pH range of 4.66–6.34. The optimal coagulation conditions with coagulant dosage of 7.57 mg Al/L, pH of 5.42 and initial algal cell density of 3.83 × 10⁶ cell/mL led to removal of 96.76%, 97.64%, 40.23% and 30.12% in term of cell density, turbidity, DOC and UV₂₅₄ absorbance, respectively, which were in good agreement with the validation experimental results. A comparison between the modeling results derived through both ANOVA and artificial neural networks (ANN) based on experimental data showed a high correlation coefficient, which indicated that the models were significant and fitted well with experimental results. The results proposed a valuable reference for the treatment of algae-laden surface water in practical application by the optimal coagulation-flocculation process.     

Fluoride removal from secondary effluent of the graphite industry using electrodialysis: Optimization with response surface methodology

RSM was utilized to optimize and model influential parameters on fluoride removal. Regression models involving independent variables and main response were developed. Interactive effects and optimum of process factors were illuminated and determined. Fluoride removal efficiency of 99.69% was observed in optimal process conditions. Response surface methodology was utilized to model and optimize the operational variables for defluoridation using an electrodialysis process as the treatment of secondary effluent of the graphite industry. Experiments were conducted using a Box-Behnken surface statistical design in order to evaluate the effects and the interaction of the influential variables including the operational voltage, initial fluoride concentration and flow rate. The regression models for defluoridation and energy consumption responses were statistically validated using analysis of variance (ANOVA); high coefficient of determination values (R² = 0.9772 and R² = 0.9814; respectively) were obtained. The quadratic model exhibited high reproducibility and a good fit of the experimental data. The optimum values of the initial fluoride concentration, voltage and flow rate were found to be 13.9 mg/L, 13.4 V, 102.5 L/h, respectively. A fluoride removal efficiency of 99.69% was observed under optimum conditions for the treatment of the secondary effluent of the graphite industry.     

Evaluation of the technoeconomic feasibility of electrochemical hydrogen peroxide production for decentralized water treatment

• Gas diffusion electrode (GDE) is a suitable setup for practical water treatment. • Electrochemical H₂O₂ production is an economically competitive technology. • High current efficiency of H₂O₂ production was obtained with GDE at 5–400 mA/cm². • GDE maintained high stability for H₂O₂ production for ~1000 h. • Electro-generation of H₂O₂ enhances ibuprofen removal in an E-peroxone process. This study evaluated the feasibility of electrochemical hydrogen peroxide (H₂O₂) production with gas diffusion electrode (GDE) for decentralized water treatment. Carbon black-polytetrafluoroethylene GDEs were prepared and tested in a continuous flow electrochemical cell for H₂O₂ production from oxygen reduction. Results showed that because of the effective oxygen transfer in GDEs, the electrode maintained high apparent current efficiencies (ACEs,>80%) for H₂O₂ production over a wide current density range of 5–400 mA/cm², and H₂O₂ production rates as high as ~202 mg/h/cm² could be obtained. Long-term stability test showed that the GDE maintained high ACEs (>85%) and low energy consumption (<10 kWh/kg H₂O₂) for H₂O₂ production for 42 d (~1000 h). However, the ACEs then decreased to ~70% in the following 4 days because water flooding of GDE pores considerably impeded oxygen transport at the late stage of the trial. Based on an electrode lifetime of 46 days, the overall cost for H₂O₂ production was estimated to be ~0.88 $/kg H₂O₂, including an electricity cost of 0.61 $/kg and an electrode capital cost of 0.27 $/kg. With a 9 cm² GDE and 40 mA/cm² current density, ~2–4 mg/L of H₂O₂ could be produced on site for the electro-peroxone treatment of a 1.2 m³/d groundwater flow, which considerably enhanced ibuprofen abatement compared with ozonation alone (~43%–59% vs. 7%). These findings suggest that electrochemical H₂O₂ production with GDEs holds great promise for the development of compact treatment technologies for decentralized water treatment at a household and community level.     

Photobiological production of hydrogen by the waste water treatment with anaerobic photosynthetic Purple bacteria

In this paper selected references about experience gained with photosynthetic bacteria in anaerobic process for either water treatment or hydrogen production are given. In particular experimental data about the hydrogen evolution rate, hydrogen yield and substrate efficiency in relationship to the nutrient conditions as well as about the behavior of some different species are presented. The limiting role of the nitrogen source is being discussed.     

Optimization of the O3/H2O2 process with response surface methodology for pretreatment of mother liquor of gas field wastewater

• Real ML-GFW with high salinity and high organics was degraded by O₃/H₂O₂ process. • Successful optimization of operation conditions was attained using RSM based on CCD. • Single-factor experiments in advance ensured optimal experimental conditions. • The satisfactory removal efficiency of TOC was achieved in spite of high salinity. • The initial pH plays the most significant role in the degradation of ML-GFW. The present study reports the use of the O₃/H₂O₂ process in the pretreatment of the mother liquor of gas field wastewater (ML-GFW), obtained from the multi-effect distillation treatment of the gas field wastewater. The range of optimal operation conditions was obtained by single-factor experiments. Response surface methodology (RSM) based on the central composite design (CCD) was used for the optimization procedure. A regression model with Total organic carbon (TOC) removal efficiency as the response value was established (R² = 0.9865). The three key factors were arranged according to their significance as: pH>H₂O₂ dosage>ozone flow rate. The model predicted that the best operation conditions could be obtained at a pH of 10.9, an ozone flow rate of 0.8 L/min, and H₂O₂ dosage of 6.2 mL. The dosing ratio of ozone was calculated to be 9.84 mg O₃/mg TOC. The maximum removal efficiency predicted was 75.9%, while the measured value was 72.3%. The relative deviation was found to be in an acceptable range. The ozone utilization and free radical quenching experiments showed that the addition of H₂O₂ promoted the decomposition of ozone to produce hydroxyl radicals (·OH). This also improved the ozone utilization efficiency. Gas chromatography-mass spectrometry (GC-MS) analysis showed that most of the organic matters in ML-GFW were degraded, while some residuals needed further treatment. This study provided the data and the necessary technical supports for further research on the treatment of ML-GFW.     

One-pot hydrothermal fabrication of BiVO4/Fe3O4/rGO composite photocatalyst for the simulated solar light-driven degradation of Rhodamine B

• BiVO₄/Fe₃O₄/rGO has excellent photocatalytic activity under solar light radiation. • It can be easily separated and collected from water in an external magnetic field. • BiVO₄/Fe₃O₄/0.5% rGO exhibited the highest RhB removal efficiency of over 99%. • Hole (h⁺) and superoxide radical (O₂^•−) dominate RhB photo-decomposition process. • The reusability of this composite was confirmed by five successive recycling runs. Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application. In this study, a novel ternary magnetic photocatalyst BiVO₄/Fe₃O₄/reduced graphene oxide (BiVO₄/Fe₃O₄/rGO) was synthesized via a facile hydrothermal strategy. The BiVO₄/Fe₃O₄ with 0.5 wt% of rGO (BiVO₄/Fe₃O₄/0.5% rGO) exhibited superior activity, degrading greater than 99% Rhodamine B (RhB) after 120 min solar light radiation. The surface morphology and chemical composition of BiVO₄/Fe₃O₄/rGO were studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The free radicals scavenging experiments demonstrated that hole (h⁺) and superoxide radical (O₂^•−) were the dominant species for RhB degradation over BiVO₄/Fe₃O₄/rGO under solar light. The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field. The BiVO₄/Fe₃O₄/rGO composite was easily separated, and the recycled catalyst retained high photocatalytic activity. This study demonstrates that catalyst BiVO₄/Fe₃O₄/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use. The current study provides a possibility for more practical and sustainable photocatalytic process.     

Emergy analysis applied to the estimation of the recovery of costs for water services under the European Water Framework Directive

In this paper, the European Union's Water Framework Directive 2000/60/EC (WFD) that is intended to foster protection of water resources is examined, focusing on the improvement of ecological and chemical quality of surface and groundwater. The WFD includes the concept of full cost recovery (FCR) in accordance with the Polluter-Pays Principle, as one of the tools of an adequate and sustainable water resource management system. The WFD defines three different costs associated with water: resource costs (RC), financial costs (FC), and environmental costs (ECs).The FCR of water is examined from a biophysical perspective using emergy evaluation to: (1) establish resource values of water from different sources, (2) establish the full economic costs associated with supplying water, and (3) the societal costs of water that is used incorrectly; from which the resource costs, financial costs, and environmental costs, respectively, can be computed. Financial costs are the costs associated with providing water including energy, materials, labor and infrastructure. The emergy based monetary values vary between 0.15 and 1.73 €/m³ depending on technology. The emergy based, global average resource value (from which resource costs can be computed) is derived from two aspects of water: its chemical potential and its geopotential. The chemical potential monetary value of different sources such as rain, groundwater, and surface water derived from global averages of emergy inputs varies from 0.03 to 0.18 €/m³, depending on source, and the geopotential values vary from 0.03 to 2.40 €/m³, depending on location in the watershed. The environmental costs of water were averaged for the county of Spain and were 1.42 €/m³.Time of year and spatial location within the watershed ultimately influence the resource costs (computed from emergy value of chemical potential and geopotential energy) of water. To demonstrate this spatial and temporal variability, a case study is presented using the Foix watershed in northeastern Spain. Throughout the year, the resource value of water varies from 0.21 to 3.17 €/m³, depending on location within the watershed. It is concluded that FCR would benefit from the evaluation of resource costs using spatially and temporally explicit emergy accounting.     

Monofunctionalized cyclodextrin polymers for the removal of organic pollutants from water

Water is an important resource for domestic, industrial, agricultural and recreational purposes. The quality of water is however significantly deteriorating due to the accumulation of organic pollutants in aqueous systems. Conventional water treatment technologies fail to remove these contaminants to desirable levels. Recent studies have revealed that cyclodextrin nanoporous polymers are capable of absorbing pollutants from water to parts per billion levels. We have demonstrated that functionalised cyclodextrin polymers have enhanced absorption capacities for some organic pollutants. Here we report the synthesis of several insoluble monosubstituted cyclodextrin polymers or “nanosponges”. We show that these polymers have improved abilities in the absorption of p-nitrophenol and pentachlorophenol from aqueous solutions.     

Enhancement of the polynomial functions response surface model for real-time analyzing ozone sensitivity

• The calculation process and algorithm of response surface model (RSM) were enhanced. • The prediction errors of RSM in the margin and transition areas were greatly reduced. • The enhanced RSM was able to analyze O₃-NO_x-VOC sensitivity in real-time. • The O₃ formations were mainly sensitive to VOC, for the two case study regions. Quantification of the nonlinearities between ambient ozone (O₃) and the emissions of nitrogen oxides (NO_x) and volatile organic compound (VOC) is a prerequisite for an effective O₃ control strategy. An Enhanced polynomial functions Response Surface Model (Epf-RSM) with the capability to analyze O₃-NO_x-VOC sensitivities in real time was developed by integrating the hill-climbing adaptive method into the optimized Extended Response Surface Model (ERSM) system. The Epf-RSM could single out the best suited polynomial function for each grid cell to quantify the responses of O₃ concentrations to precursor emission changes. Several comparisons between Epf-RSM and pf-ERSM (polynomial functions based ERSM) were performed using out-of-sample validation, together with comparisons of the spatial distribution and the Empirical Kinetic Modeling Approach diagrams. The comparison results showed that Epf-RSM effectively addressed the drawbacks of pf-ERSM with respect to over-fitting in the margin areas and high biases in the transition areas. The O₃ concentrations predicted by Epf-RSM agreed well with Community Multi-scale Air Quality simulation results. The case study results in the Pearl River Delta and the north-western area of the Shandong province indicated that the O₃ formations in the central areas of both the regions were more sensitive to anthropogenic VOC in January, April, and October, while more NO_x-sensitive in July.     

An Integrated Monte Carlo Methodology for the calibration of water quality models

This paper proposes an Integrated Monte Carlo Methodology (IMCM) to solve the parameter estimation problem in water quality models. The methodology is based on Bayesian approach and Markov Chain Monte Carlo techniques and it operates by means of four modules: Markov Chain Monte Carlo (MCMC), Moving Feasible Ranges (MFR), Statistical Analysis of the Joint Posterior Distribution (SAD) and Uncertainty Propagation Analysis (UPA). The main innovation of the new proposal lies in the combination of MCMC and MFR modules which provides the joint posterior distribution of the calibrated parameters following the classical Bayesian approach. While MCMC module, based on Shuffled Complex Evolution Metropolis (SCEM-UA) algorithm, is specially designed to sample complex joint posterior shapes within certain parameter ranges, the MFR readjusts these ranges until the coverage of the feasible parameter space is guaranteed. Once the joint posterior distribution is properly defined, the SAD provides the parameter statistics and the UPA performs an analysis of the uncertainty propagation through the model. The possibilities of the new proposal have been tested on the basis of a simple model featuring different activated sludge batch experiments. IMCM has been implemented in Matlab and it is prepared to be easily connected to any software package.     

绿色食品产地灌溉水中多环芳烃测定方法的研究

对绿色食品产地的灌溉水中6种多环芳烃的高效液相色谱分析法进行了研究。对前处理使用的萃取溶剂做了对比,从加标回收率方面,得出了环己烷最好;其次是正己烷;再其次是二氯甲烷。检测采用甲醇和水(V∶V=90∶10)做流动相,恒度洗脱,只设置两段程序波长即可得到很好响应值。6种PAHs的浓度与其色谱峰面积的线性良好(r在0.9976～0.9999之间),方法精密度RSD的平均值为1.33%(n=5)。本方法参考国标、国际标准对流动相的组成、洗脱条件及荧光波长的设置都做了相应的改进,使得6种PAHs的分离比国标好,基线更平稳,方法更简便,操作也更容易,是测定绿色食品产地灌溉水中PAHs的较好方法。     

上海市松江镇饮用水水源区的保护与环境管理方案

保护集镇饮用水河流是当前水污染防治工作的重点。本文通过现状分析，针对城乡结合部河流以面源为主的特点，找出影响饮用水河流水质的主要污染源及污水排放特征．用系统分析方法，将集镇的经济、人口、环境统计资料作为环境管理模型的主要输入信息，经计算机仿真，得出保护水源水质应采取的对策与治理方案。     

Ecological network analysis for water use systems—A case study of the Yellow River Basin

Ecological network analysis (ENA) is introduced in this paper as a promising approach to study water use systems. Information indices from ENA involving total system throughput (TST), ascendency and overhead are calculated here. Two related aspects including organization inherent in system structures and synthesized water use intensity related with sustainable development of water use systems are analyzed. The indices of ascendency and overhead are applied for analyzing and characterizing water use network organization. For comparison of sustainability of water use systems from integrated aspects of environment, society and economy and based on TST, a new indicator termed as total system throughput intensity (TSTI) is constructed incorporating parameters of land, precipitation, population, GDP and environmental flow, which can be used as a measure of sustainability in terms of synthesized water use intensity. The Yellow River Basin in China during 1998–2006 is chosen as the case study and divided into subsystems according to the six river sections as from source to Lanzhou (S1-L1), Lanzhou to Toudaoguai (L1-T), Toudaoguai to Longmen (T-L2), Longmen to Sanmenxia (L2-S2), Sanmenxia to Huayuankou (S2-H) and Huayuankou to the mouth of Bo Sea (H-B). The results show that (i) the organization levels of L1-T and H-B are better than those of S1-L1 and T-L2, with those of L2-S2 and S2-H the worst; (ii) the synthesized water use intensity has been improving, of which T-L2, L2-S2 and S2-H are at the highest levels while H-B the lowest. In addition, the comparison between TSTI and other metrics and the relationship between ascendency and TSTI are discussed, from which the importance of TSTI is reflected and the optimization criterions for sustainable development of six subsystems are derived. It can be concluded that the application of ENA in water use systems can provide new angles for water resource management to address the challenges of assessing and optimizing options to obtain more sustainable water use.     

The Extended Kalman Filter (EKF) as a tool for the assimilation of high frequency water quality data

The Extended Kalman Filter (EKF) was applied to the analysis of high frequency field measurements of dissolved oxygen (DO), water temperature, salinity, collected by multiparametric sensors in the lagoon of Venice. This paper focuses on the practical aspects of the implementation of the EKF as a data assimilation technique and does not deal with the problems associated with the identification of the model. In this regard, the EKF has proved to be a useful tool for the updating of the estimates of the parameters of a simple DO-chlorophyll model, which can be used for linking the high frequency data to meteorological forcings, such as solar radiation and wind, and to other low frequency measurements of water quality parameters, such as the concentrations of Chlorophyll a and nutrients. The model can subsequently be used as a tool for checking the consistency of all this data, and may also be employed for controlling the quality of the data collected by the multiparametric sensors.     

From meso- to macro-scale dynamic water quality modelling for the assessment of land use change scenarios

The implementation of the European Water Framework Directive requires reliable tools to predict the water quality situations in streams caused by planned land use changes at the scale of large regional river basins. This paper presents the results of modelling the in-stream nitrogen load and concentration within the macro-scale basin of the Saale river (24,167 km²) using a semi-distributed process-based ecohydrological dynamic model SWIM (Soil and Water Integrated Model). The simulated load and concentration at the last gauge of the basin show that SWIM is capable to provide a satisfactory result for a large basin. The uncertainty analysis indicates the importance of realistic input data for agricultural management, and that the calibration of parameters can compensate the uncertainty in the input data to a certain extent. A hypothesis about the distributed nutrient retention parameters for macro-scale basins was tested aimed in improvement of the simulation results at the intermediate gauges and the outlet. To verify the hypothesis, the retention parameters were firstly proved to have a reasonable representation of the denitrification conditions in six meso-scale catchments. The area of the Saale region was classified depending on denitrification conditions in soil and groundwater into three classes (poor, neutral and good), and the distributed parameters were applied. However, the hypothesis about the usefulness of distributed retention parameters for macro-scale basins was not confirmed. Since the agricultural management is different in the sub-regions of the Saale basin, land use change scenarios were evaluated for two meso-scale subbasins of the Saale. The scenario results show that the optimal agricultural land use and management are essential for the reduction in nutrient load and improvement of water quality to meet the objectives of the European Water Framework Directive and in view of the regional development plans for future.     

选择性催化还原(SCR)脱硝催化剂钛钨粉原始粉体的对比

采用XRF、XRD、低温N2吸附曲线、SEM和FT-IR考察了国产和进口钛钨(WO3/TiO2)粉的组成及其微观结构.结果表明,国产和进口钛钨粉中Ti和W的含量相差不大,但是国产钛钨粉都含有少量P,而国外钛钨粉O和S含量较大.国产和进口钛钨粉中TiO2都为锐钛矿型晶型;其表面官能团基本相同;钛钨粉颗粒形貌类似,都为多孔物质,其比表面积相差不大,但是进口样品的孔容高于国产样品.