Titanium dioxide photocatalysis for pharmaceutical wastewater treatment

Heterogeneous photocatalysis using the semiconductor titanium dioxide (TiO₂) has proven to be a promising treatment technology for water purification. The effectiveness of this oxidation technology for the destruction of pharmaceuticals has also been demonstrated in numerous studies. This review highlights recent research on TiO₂ photocatalytic treatment applied to the removal of selected pharmaceuticals. The discussions are tailored based on the therapeutic drug classes as the kinetics and mechanistic aspects are compound dependent. These classes of pharmaceuticals were chosen because of their environmental prevalence and potential adverse effects. Optimal operational conditions and degradation pathways vary with different pharmaceutical compounds. The main conclusion is that the use of TiO₂ photocatalysis can be considered a state-of-the-art pharmaceutical wastewater treatment methodology. Further studies are, however, required to optimize the operating conditions for maximum degradation of multiple pharmaceuticals in wastewater under realistic conditions and on an industrial scale.     

色谱及联用技术在药物污染检测中的应用

医药品是一类新型环境污染物,由于其具有长期输入、环境中降解/去除缓慢、生物效应显著等特性被界定为"准持久性"污染物,受到社会各界的广泛关注.为更好了解该类污染物在环境中的迁移转化规律和生物效应,分析检测是必不可少的环节,本文就近年来我国运用色谱及联用技术检测药物污染的方法进行综述.     

Effect of pH on the sonochemical degradation of organic pollutants

An increasing number of organic compounds are manufactured, consumed, and discarded every year. Incomplete destruction of these compounds in wastewater treatment plants leads to pollution of natural waters, posing great health and ecological concerns. Ultrasound, as an emerging advanced oxidation technology, can quickly and effectively degrade organic pollutants in waters. To improve removal efficiency of organic pollutants in an ultrasonic system, operational parameters, especially pH, have been frequently evaluated and optimized. This review show that pH-induced changes in volatility, hydrophobicity and Coulombic force between the target compound and cavitation bubbles leads to higher degradation at acidic pH for most compounds. In addition, pH also changes free radical formation and reactivity in water during sonication, thereby altering degradation kinetics of target compounds. However, the influence of pH is not always consistent for various organic pollutants covering a broad range of physicochemical properties and reactivities. A systematic investigation on the pH effect is necessary to elucidate how pH alters cavitation bubble dynamics and collapse, radical yield and reactivity, distribution of target compounds in the vicinity of cavitation bubbles, water matrices transformation, and ultimately the degradation kinetics of organic pollutants. This first systematic review provides valuable insight into the pH effects on organic pollutant sonolysis, helps to improve our mechanistic understanding of the sonochemical system, and sheds light on future application of ultrasound in water engineering.     

Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

Occurrence and behavior of pharmaceuticals in sewage treatment plants in eastern China

The occurrence and removal efficiency of seven pharmaceuticals (norfloxacin, trimethoprim, roxithromycin, sulfamethoxazole, ibuprofen, diclofenac and carbamazepine) were determined in three sewage treatment plants (STPs) with anaerobic/anoxic/oxic, anoxic/oxic and oxidation ditches processes in Xuzhou City, Eastern China. The results showed that seven pharmaceuticals were detected in the influent samples with concentrations ranging from 93 to 2540 ng·L⁻¹. The removal of these substances among the three different STPs varied from 36 to 84%, with the highest performance obtained by the wastewater treatment works with tertiary treatment (sand filtration). Most of the compounds were removed effectively during biologic treatment while sand filtration treatment also made a contribution to the total elimination of most pharmaceuticals. The efficiency comparison of the three sewage treatment processes showed that the STP which employed anaerobic/anoxic/oxic was more effective to remove pharmaceuticals than the oxidation ditches and anoxic/oxic.     

Fast and complete removal of the 5-fluorouracil drug from water by electro-Fenton oxidation

Cytostatic drugs are a troublesome class of emerging pollutants in water owing to their potential effects on DNA. Here we studied the removal of 5-fluorouracil from water using the electro-Fenton process. Galvanostatic electrolyses were performed with an undivided laboratory-scale cell equipped with a boron-doped diamond anode and a carbon felt cathode. Results show that the fastest degradation and almost complete mineralization was obtained at a Fe²⁺ catalyst concentration of 0.2 mM. The absolute rate constant for oxidation of 5-fluorouracil by hydroxyl radicals was 1.52 × 10⁹ M^?1 s^?1. Oxalic and acetic acids were initially formed as main short-chain aliphatic by-products, then were completely degraded. After 6 h the final solution mainly contained inorganic ions (NH₄ ⁺, NO₃ ^? and F^?) and less than 10% of residual organic carbon. Hence, electro-Fenton constitutes an interesting alternative to degrade biorefractory drugs.     

Contaminants in water: non-target UHPLC/MS analysis

Contamination of water resources is one of the major problems to be faced for environment preservation and sustainability. The monitoring of target compounds based on mass spectrometry and selected reaction monitoring mode is often insufficient to definitely assess the quality of surface water. Also potentially harmful non-target pollutants simultaneously present must be taken into account. Liquid chromatography coupled with tandem mass spectrometry is suitable to obtain complete information on water composition. Hybrid mass spectrometers such as triple quadrupole/linear ion trap, hybrid quadrupole/time-of-flight and linear ion trap/orbitrap analyzers should be used. Here, we review ultra-high performance liquid chromatography coupled with mass spectrometry methods developed for post-target and non-target screening analysis of water emerging contaminants, such as pesticides and their degradation products, pharmaceuticals and drug side-reaction products, surfactants and illicit drugs. The major points are the following: (1) the possibility of performing retrospective analysis only by high-resolution mass analyzer; (2) the compatibility of mass analyzer with ultra-high performance liquid chromatography; (3) the use of deconvolution software to detect unknowns; and (4) the limited availability of library database.     

Removal of organic pollutants by peroxicoagulation

Peroxicoagulation is an electrochemical advanced oxidation processes in which both ferrous ions and hydrogen peroxide are generated in the cell. Organic pollutants are thus removed by degradation and coagulation. The peroxicoagulation process is a combination of electro-Fenton and electrocoagulation processes. The peroxicoagulation process is very efficient for the removal of aniline and herbicides from water and for the treatment of landfill leachate and textile wastewaters. Under acidic conditions, electro-Fenton is the predominant removal means, whereas electrocoagulation is the main removal means under neutral and alkaline conditions. As a consequence, pH regulation to acidic conditions is essential for the mineralization of organic pollutants.     

Unexpected removal of the most neutral cationic pharmaceutical in river waters

Contamination of surface waters by pharmaceuticals is now widespread. There are few data on their environmental behaviour, particularly for those which are cationic at typical surface water pH. As the external surfaces of bacterio-plankton cells are hydrophilic with a net negative charge, it was anticipated that bacterio-plankton in surface-waters would preferentially remove the most extensively-ionised cation at a given pH. To test this hypothesis, the persistence of four, widely-used, cationic pharmaceuticals, chloroquine, quinine, fluphenazine and levamisole, was assessed in batch microcosms, comprising water and bacterio-plankton, to which pharmaceuticals were added and incubated for 21 days. Results show that levamisole concentrations decreased by 19 % in microcosms containing bacterio-plankton, and by 13 % in a parallel microcosm containing tripeptide as a priming agent. In contrast to levamisole, concentrations of quinine, chloroquine and fluphenazine were unchanged over 21 days in microcosms containing bacterio-plankton. At the river-water pH, levamisole is 28 % cationic, while quinine is 91–98 % cationic, chloroquine 99 % cationic and fluphenazine 72–86 % cationic. Thus, the most neutral compound, levamisole, showed greatest removal, contradicting the expected bacterio-plankton preference for ionised molecules. However, levamisole was the most hydrophilic molecule, based on its octanol–water solubility coefficient (K _ow). Overall, the pattern of pharmaceutical behaviour within the incubations did not reflect the relative hydrophilicity of the pharmaceuticals predicted by the octanol–water distribution coefficient, D _ow, suggesting that improved predictive power, with respect to modelling bioaccumulation, may be needed to develop robust environmental risk assessments for cationic pharmaceuticals.     

Application of permanganate in the oxidation of micropollutants: a mini review

As a green oxidant, permanganate has received considerable attention for the removal of micropollutants in drinking water treatment. To provide a better understanding of the oxidation of organic micropollutants with permanganate, the oxidation kinetics of 32 micropollutants were compiled. The pollutants include algal toxins, endocrine disrupting chemicals (EDCs), and pharmaceuticals. The oxidation kinetics of micropollutants by permanganate were found to be first order with respect to both contaminant and permanganate concentrations from which second-order rate constants (k″) were obtained. Permanganate oxidized the heterocyclic aromatics with vinyl moiety (i.e., microcystins, carbamazepine, and dichlorvos) by the addition of double bonds. For the polycyclic aromatic hydrocarbons (PAHs) with alkyl groups, permanganate attacked the benzylic C-H through abstraction of hydrogen. The mechanism for the oxidation of phenolic EDCs by permanganate was a single electron transfer and aromatic ring cleavage. The presence of background matrices could enhance the oxidation of some phenolic EDCs by permanganate, including phenol, chlorinated phenols, bisphenol A, and trichlosan. The toxicity of dichlorvos solution increased after permanganate oxidation, and the estrogenic activity of bisphnol A/estrone increased significantly at the beginning of permanganate oxidation. Therefore, the toxicity of degradation products or intermediates should be determined in the permanganate oxidation processes to better evaluate the applicability of permanganate. The influence of background ions on the permanganate oxidation process is far from clear and should be elucidated in the future studies to better predict the performance of permanganate oxidation of micropollutants. Moreover, methods should be employed to catalyze the permanganate oxidation process to achieve better removal of micropollutants.     

Developments in forward osmosis and membrane distillation for desalination of waters

Membrane technology has become a common separation technology over the past decennia. Membranes are used more and more for the production of drinkable water from groundwater, surface water and wastewater. Membranes are now competitive versus conventional techniques. Desalination is predominantly used to eradicate the problem of water scarcity. The sustainability of all desalination processes depends mainly on the reduction of energy costs (production cost) and the increase in water recovery. Forward osmosis and membrane distillation are emerging technologies for sustainable desalination. Here we review membrane processes of forward osmosis and membrane distillation and the advancements in membrane material and modules. We also discuss the capability of membrane distillation in treating highly concentrated aqueous solutions derived from other desalination processes. Furthermore, the advancements in fabrication of high-performance membrane is reviewed and the performance of different membranes and optimization of membrane distillation process are summarized.     

Chemistry,abundance, detection and treatment of per- and polyfluoroalkyl substances in water: a review

Per- and polyfluoroalkyl substances (PFAS) encompass a wide range of compounds containing carbon–fluorine bonds. Due the strength of this bond and the high electronegativity of fluorine atoms, PFAS display stability, wettability and other characteristics that are unique for industrial applications and products. However, PFAS induce adverse effects on the environment and human health. Here we review the chemistry, synthesis, properties, analysis, occurrence in water, filtration, removal and oxydation of PFAS.  We highlight emerging hybrid treatments to remove PFAS from water.

     

Occurrence of bisphenol A in surface and drinking waters and its physicochemical removal technologies

Bisphenol A (BPA), an endocrine disrupting compound, has caused wide public concerns due to its wide occurrence in environment and harmful effects. BPA has been detected in many surface waters and drinking water with the maximum concentrations up to tens of μg·L^-1. The physicochemical technology options in eliminating BPA can be divided into four categories: oxidation, advanced oxidation, adsorption and membrane filtration. Each removal option has its own limitation and merits in removing BPA. Oxidation and advanced oxidation generally can remove BPA efficiently while they also have some drawbacks, such as high cost, the generation of a variety of transformation products that are even more toxic than the parent compound and difficult to be mineralized. Only few advanced oxidation methods have been reported to be able to mineralize BPA completely. Therefore, it is important not only to identify the major initial transformation products but also to assess their estrogenic activity relative to the parent compounds when oxidation methods are employed to remove BPA. Without formation of harmful by-products, physical separation methods such as activated carbon adsorption and membrane processes are able to remove BPA in water effluents and thus have potential as BPA removal technologies. However, the necessary regeneration of activated carbon and the low BPA removal efficiency when the membrane became saturated may limit the application of activated carbon adsorption and membrane processes for BPA removal. Hybrid processes, e.g. combining adsorption and biologic process or combining membrane and oxidation process, which can achieve simultaneous physical separation and degradation of BPA, will be highly preferred in future.     

Up to 95 % reduction of chemical oxygen demand of slaughterhouse effluents using Fenton and photo-Fenton oxidation

Meat industries produce effluents containing high concentrations of organic and inorganic compounds, which must be removed before being discharged or reused. Advanced oxidation processes using Fenton reaction coupled with UV, solar radiation, and electrochemical oxidation are promising methods. Here, we treated the effluent from an anaerobic digester using: (a) the photoelectro-Fenton process, using a system with a Ti-RuO₂ anode and a carbon felt cathode, (b) the solar photo-Fenton process, using a batch reactor and a compound parabolic collector, and (c) a combination of Fenton and solar photo-Fenton processes. The effluent had an initial chemical oxygen demand (COD) of 1159 mgL^?1, and we obtained high removal efficiencies of COD, up to 95 %, using the combination of Fenton and solar photo-Fenton processes.     

Construction of MOFs-based nanocomposite membranes for emerging organic contaminants abatement in water

● Application of the MOF-composite membranes in adsorption was discussed. ● Recent application of MOFs-membranes for separation was summarized. ● Separation and degradation for emerging organic contaminants were described. Presence of emerging organic contaminants (EOCs) in water is one of the major threats to water safety. In recent decades, an increasing number of studies have investigated new approaches for their effective removal. Among them, metal-organic frameworks (MOFs) have attracted increasing attention since their first development thanks to their tunable metal nodes and versatile, functional linkers. However, whether or not MOFs have a promising future for practical application in emerging contaminants-containing wastewater is debatable. This review summarizes recent studies about the removal of EOCs using MOFs-related material. The synthesis strategies of both MOF particles and composites, including thin-film nanocomposite and mixed matrix membranes, are critically reviewed, as well as various characterization technologies. The application of the MOF-based composite membranes in adsorption, separation (nanofiltration and ultrafiltration), and catalytic degradation are discussed. Overall, literature survey shows that MOFs-based composite could play a crucial role in eliminating EOCs in the future. In particular, modified membranes that realize separation and degradation might be the most promising materials for such application.     

Surface-enhanced Raman spectroscopy for emerging contaminant analysis in drinking water

● Definition of emerging contaminants in drinking water is introduced. ● SERS and standard methods for emerging contaminant analysis are compared. ● Enhancement factor and accessibility of SERS hot spots are equally important. ● SERS sensors should be tailored according to emerging contaminant properties. ● Challenges to meet drinking water regulatory guidelines are discussed. Emerging contaminants (ECs) in drinking water pose threats to public health due to their environmental prevalence and potential toxicity. The occurrence of ECs in our drinking water supplies depends on their physicochemical properties, discharging rate, and susceptibility to removal by water treatment processes. Uncertain health effects of long-term exposure to ECs justify their regular monitoring in drinking water supplies. In this review article, we will summarize the current status and future opportunities of surface-enhanced Raman spectroscopy (SERS) for EC analysis in drinking water. Working principles of SERS are first introduced and a comparison of SERS and liquid chromatography-tandem mass spectrometry in terms of cost, time, sensitivity, and availability is made. Subsequently, we discuss the strategies for designing effective SERS sensors for EC analysis based on five categories—per- and polyfluoroalkyl substances, novel pesticides, pharmaceuticals, endocrine-disrupting chemicals, and microplastics. In addition to maximizing the intrinsic enhancement factors of SERS substrates, strategies to improve hot spot accessibilities to the targeting ECs are equally important. This is a review article focusing on SERS analysis of ECs in drinking water. The discussions are not only guided by numerous endeavors to advance SERS technology but also by the drinking water regulatory policy.     

Considerations of temperature in the context of the persistence classification in the EU

Simulation degradation studies for industrial chemicals, biocidal products and plant protection products are required in the EU to estimate half-lives in soil, water and sediment for the comparison to persistence criteria for hazard (P/vP) assessment, and for use in exposure assessments. There is a discrepancy between European regulatory approaches regarding the temperature at which degradation half-lives should be (1) measured in simulation degradation testing of environmental compartments, and (2) compared to the P/vP criteria. In this paper, an opinion is provided on the options for the experimental temperature and extrapolation to other conditions. A review of the historical development of persistence criteria did not give conclusive evidence of the temperature at which the half-lives that underpin the P-criteria were measured, but room temperature is likely. Half-lives measured at 20 °C are in line with the intentions of some international agreements, but in the EU there is a continued political debate regarding the relevant temperature for comparison with persistence criteria. Measuring degradation at 20 °C has the advantage that metabolites/transformation products can be identified with greater accuracy, and that kinetic fits to determine half-lives for parent compounds and metabolites carry less uncertainty. Extrapolation of half-lives to lower temperatures is possible for assessing environmental exposure, but the uncertainty of the persistence classification is smaller when measured half-lives are used for direct comparison with P/vP criteria, without extrapolation. Model simulations demonstrate the pattern of concentrations that can be expected for realistic worst case climate scenarios in the EU based on the half-life of 120 days in soil at 20 °C and of 40 days in water at 20 °C, and their temporal and spatial variability.     

新型污染物及其生态和环境健康效应

近年来,随着现代分析手段的改进和发展,各种污染物检测能力的提高,以及新的毒作用模式的发现、新合成化合物的制造和使用等,一些物质成为广受国内外关注的新型污染物.新型污染物已在世界范围内对环境和生态系统造成了污染,对生态系统中包括人类在内的各种生物均构成了潜在的危害.目前,人们关注较多的新型污染物主要有全氟有机化合物、人用与兽用药物、饮用水消毒副产物、遮光剂/滤紫外线剂、人造纳米材料、汽油添加剂、溴化阻燃剂等.论文在总结国内外相关研究基础上,对一些重点新型污染物的生态效应及其潜在健康影响进行了简要综述,为我国开展这方面的研究提供了一定的参考.     

Tetracycline antibiotics in the environment: a review

Tetracycline antibiotics are one of the primarily antibiotics groups used for veterinary purposes, for human therapy and for agricultural purposes. Amongst the different antibiotics used, more attention is paid to tetracycline’s as it exhibits serious environmental problems including ecological risks and human health damages. Due to their extensive usage, most of the actual evidence suggests that tetracycline antibiotics are omnipresent compounds found in different ecological compartments. After medication, more than 70 % of tetracycline antibiotics are excreted and released in active form into the environment via urine and feces from humans and animals. Their highly hydrophilic character and low volatility have resulted in significant persistence in the aquatic environment. Very few studies describe the fate and toxicity of tetracycline antibiotics in the environment. Here, we review several important issues with regard to: (1) the toxicity of these compounds on aquatic and terrestrial organisms; (2) their estrogenic effects; (3) their behavior in different ecological systems and; (4) the by-products generated during water treatment. These antibiotics residues promote the development of antibiotic resistant microorganisms, which can induce adverse effect to human health by increasing the risk of certain infections. Based on recent research results, the occurrence of tetracycline antibiotics in the environment inhibits the growth of some terrestrial and aquatic species. Besides, the residual concentrations of such drugs could affect steroidogenic pathway and consequently may cause endocrine disruption of aquatic species. Most of the wastewater treatment plants are not capable of removing effectively the tetracycline antibiotics. Therefore, there is a need to develop alternative processes to remove them from waters. Advanced oxidation processes have been proposed as alternative methods to ensure higher degradation and mineralization of tetracycline antibiotics are present in waters.     

Waste control by waste: efficient removal of bisphenol A with steel slag,a novel activator of peroxydisulfate

Activated persulfates are efficient reagents for oxidation of organic contaminants and water treatment. Various compounds are currently used to activate persulfates, but there is a need for cheap and efficient activators. Here, we report the first use of steel slag, an industrial solid waste, as a solid activator for peroxydisulfate activation. We tested this system for bisphenol A degradation. Results indicate that about 70% of bisphenol A can be removed within 1 h. Conditions were 50 μg/L of bisphenol A, 2 g/L of peroxydisulfate, 3 g/L of steel slag and temperature of 298 K. The components and surface morphology of unused and recycled steel slag were analyzed by X-ray diffraction and scanning electron microscopy, whereas the main reactive oxygen species were elucidated by using radical scavengers. Findings show that both base oxides and iron oxides are responsible for peroxydisulfate activation. A redox mechanism involving liquid and solid phases is proposed. Overall, this study reveals the successful recycling of steel slag to activate persulfates for water treatment, following the principle of ‘waste control by waste.’