The adsorption and photodegradation of oxalic acid at the TiO2 surface.

ATR-FTIR measurements in combination with quantum chemical calculations were performed to study chemical reactions taking place at the surface of a thin TiO2 layer immersed in an aqueous oxalic acid solution under UV(A) illumination. It was found that the adsorption of oxalic acid on TiO2 in the dark can be explained in terms of two surface complexes for the anatase phase. Under UV(A) illumination, one of the adsorbed species on the anatase phase preferably undergoes photo-degradation and at the same time more molecules of oxalic acid are adsorbed at the TiO2 surface which is thus enriched in the second complexation mode. The spectral changes observed under UV(A) illumination are explained in the light of different theories: photo-desorption of water molecules as a thermal mechanism induced by the absorption of photons, surface reconstruction, and newly exposed surface area provided by the de-aggregation of the TiO2 particles.     

波、流共存时的床面剪切力和泥沙运动

利用边界层理论,导出了床面剪切力,综合摩阻系数,综合速度和综合摩阻速度,建立了波浪,水流共同作用下的泥沙起动和水体挟沙力公式。     

Water matrix effect on UV photodegradation of perfluorooctanoic acid

The widespread detection of perfluorinated compounds (PFCs) in the water environment has been a concern for the last several years, while effluents from wastewater treatment facilities are the major sources of these compounds. Even advanced oxidation technologies (AOTs) are not useful for mineralization of the compounds due to their very high stability. Photochemical techniques using particularly vacuum UV (VUV) have been found to be very promising in this regard. But the use of VUV in UV-based AOTs has still not progressed much. Moreover, the impact of water quality on PFCs photomineralization is unknown. This investigation aimed to assess photomineralization potentials of perfluorooctanoic acid (PFOA) in ultrapure water (UPW), tap water (TW), surface water and treated wastewater effluent using a reactor setup enabling maximum utilization of VUV emission of low pressure lamp in laboratory batch experiments. Neya River water (NRW) and the Nakahama Wastewater Treatment Plant Effluent (NWWTPE) represented surface water and treated wastewater effluent respectively. Also, tests were carried out in 50% diluted NRW and NWWTPE. PFOA photomineralization in terms of PFOA removal, defluorination and total organic carbon (TOC) removal are discussed. The usefulness of the method for PFOA mineralization in organic-rich wastewaters, and further research needs are also highlighted.     

On the effect of pharmaceuticals on bacterial nitrite oxidation.

Pharmaceuticals or their metabolites are partially excreted with urine or faeces ending up in raw sewage. Many of these substances are not biodegradable and their presence in influents of municipal wastewater treatment plants may cause adverse effects to sensitive biological processes such as nitrification, while on the other hand, they may go through the activated sludge process unreacted. The second step of nitrification, i.e. oxidation of nitrite to nitrate is particularly sensitive. Inhibition of this step under uncontrolled conditions may lead to accumulation of nitrite nitrogen in the plant effluent, a form of nitrogen which is particularly toxic. The effects caused by the presence of seven different pharmaceuticals to a culture of nitrite-oxidizing bacteria isolated from activated sludge are presented. These pharmaceuticals were ofloxacin, propranolol, clofibrate, triclosan, carbamazepine, diclofenac and sulfamethoxazole. Different effects were observed for each of the pharmaceuticals tested in this study. In the cases of ofloxacin and sulfamethoxazole significant inhibition was observed. Triclosan presented a substantial inhibitory effect on the substrate (nitrite) reduction rate. The long-term effect of triclosan on nitrite oxidizers was also examined in a CSTR reactor and conclusions were drawn regarding the reversibility of the inhibition caused by this compound.     

Toxic effect of pharmaceuticals on methanogenesis.

Pharmaceuticals present in sewage may inhibit the biological processes in a sewage treatment plant. In this work, the toxic-effect of six pharmaceuticals (carbamazepine, sulfamethoxazole, propranolol hydrochloride, diclofenac sodium, ofloxacin and clofibric acid) on the anaerobic digestion process is assessed. Acetoclastic methanogenes are the most sensitive group of microorganisms participating in the anaerobic digestion process. Appropriate toxicity tests for these microorganisms were then based on assessing the impact of pharmaceuticals on the specific methanogenic activity (SMA) of the anaerobic biomass. The toxicity was expressed by the IC80 and IC50 values, i.e. the concentration at which bioactivity was 80% and 50% of the control, respectively. Results showed that the pharmaceuticals tested caused a mild inhibition to the methanogenes in most cases, related directly to the tendency of the compounds to adsorb on the anaerobic biomass.     

Occurrence and reduction of pharmaceuticals in the water phase at Swedish wastewater treatment plants

During the last decade, several screening programs for pharmaceuticals at Swedish wastewater treatment plants (WWTPs) have been conducted by research institutes, county councils, and wastewater treatment companies. In this study, influent and effluent concentrations compiled from these screening programs were used to assess the occurrence and reduction of non-antibiotic pharmaceuticals for human usage. The study is limited to full-scale WWTPs with biological treatment. Based on the data compiled, a total of 70 non-antibiotic pharmaceuticals have been detected, at concentrations ranging from a few ng/L to several μg/L, in the influent water. The influent concentrations were compared with the sale volumes and for many pharmaceuticals it was shown that only a small fraction of the amount sold reaches WWTPs as dissolved parent compounds. Pharmaceuticals with low reduction degrees at traditional WWTPs were identified. Further comparison based on the biological treatment showed lower reduction degrees for several pharmaceuticals in trickling filter plants compared with activated sludge plants with nitrogen removal.     

Investigation on the behaviour of selected pharmaceuticals in the groundwater after infiltration of treated wastewater.

In a rural arid area without suitable receiving water the treated wastewater of a low loaded municipal wastewater treatment plant with full nutrient removal and additional post treatment steps is infiltrated into the unsaturated soil for groundwater recharge. Groundwater probes at increasing distances from the infiltration point have been sampled every two months over a period of 14 months. Beside conventional parameters (nutrients, carbon, and bacterial counts) samples were analysed for pharmaceutically active substances. Depending on and corresponding to their chemical structure and their fate during wastewater treatment, the selected substances showed different behaviour in the saturated zone of the groundwater. The antiepileptic Carbamazepine behaves very conservative and only is removed negligible even after long flow times within the subsurface zone. For other substances like the tranquilizer Diazepam or the analgesics Diclofenac a partial elimination during the different steps of wastewater treatment can be observed. Further degradation could be observed during the subsequent subsurface passage. In correlation with flow time additional removal of these substances from the aqueous phase can be observed. The musk substances Galaxolide and Tonalide were removed to some extend but not as good as the previous mentioned compounds.     

Presence and risk assessment of pharmaceuticals in surface water and drinking water

Trace amounts of pharmaceuticals have been detected in surface waters in the nano- to microgram per liter range, and in drinking water in the nanogram/L range. The environmental risks of pharmaceuticals in surface waters have been evaluated and generally found to be low if the wastewater is treated before release to the environment. The human health risks of trace amounts of pharmaceuticals in drinking water have however not been evaluated in any great depth. Preliminary screening level assessments suggest risk to be low--but the public and decision-makers are concerned and would like the matter investigated more thoroughly, especially with regards to mixture effects, chronic long-term effects and sensitive sub-populations. The World Health Organization is currently evaluating the need for credible health based guidance associated with low concentrations of pharmaceuticals in drinking water. The aim of this paper is to summarize the state-of-the-science and the ongoing international debate on the topic.     

Removal efficiency of 66 pharmaceuticals during wastewater treatment process in Japan.

Both biological treatment processes including conventional activated sludge (CAS) and biological nutrient removal (BNR) processes, and physico-chemical treatment processes including ozonation process and Title 22 process consisting of coagulation, sedimentation and filtration followed by UV or chlorination disinfection after the above biological processes, were compared from the viewpoint of removal efficiency. 66 pharmaceuticals including antibiotics, analgesics, psychoneurotic agents were measured with SPE-LC/MS/MS. 26 compounds out of 66 were detected in the influent ranging ng/L to microg/L order. Particularly, disopyramide, sulpiride, and dipyridamole that have been rarely detected before in the WWTP, occurred at concentration levels of more than 100 ng/L. The total concentration of the individual pharmaceuticals in the influent was efficiently removed by 80% during the biological treatment. But removal efficiencies of carbamazepine and crotamiton were less than 30%. The total concentration of the individual pharmaceuticals in the effluent from CAS process was 1.5 times higher than that from BNR process. Further, the total concentration of the individual pharmaceuticals in the discharge from WWTPs applying ozonation following activated sludge process was reduced to less than 20%. Physico-chemical treatment train called Title 22 treatment after CAS could not efficiently remove the pharmaceuticals. However, ozonation process followed by biological activated carbon process could efficiently reduce all the residual pharmaceuticals below their quantification limits.     

Removal of hormones and pharmaceuticals in the Advanced Water Recycling Demonstration Plant in Queensland, Australia.

An advanced water recycling demonstration plant was employed to investigate the effectiveness of a number of treatment technologies in the removal of some residuals of commonly prescribed pharmaceuticals as well as natural and synthetic hormones found in sewage. Analysis of targeted compounds was carried out by solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS). Initial tests were undertaken to determine the background concentrations of the analytes during various stages of treatment. Subsequent tests, undertaken by spiking with standard solutions of the target compounds provided further information on the removal efficiencies of some selected treatment modules. The results of the study indicate that while ozonation, microfiltration and nanofiltration were partially effective, treatment by reverse osmosis was the most universally successful in the removal of the target residuals. While significantly more data is required for a full evaluation, this initial investigation suggests that reverse osmosis may be an effective means of removing a wider range of pharmaceutically active residuals and hormones from treated sewage.     

波、流共同作用下的近底泥沙输移及航道骤淤预报

波、流(包括潮流和风吹流)共同作用下的输沙机理是波浪轨道速度掀沙与挟沙,波浪传质速度、潮流速度和风吹流的合成速度输沙。根据波动水流能量及泥沙运动原理,参考窦国仁推导底沙输沙率的方法,推导出波浪、潮流和风吹流共同作用下的底沙输沙率公式。对于细颗粒泥沙,底沙输沙实质上是近底泥沙(包括浮泥)的输移;应用本文公式对大风期黄骅港外航道的骤淤进行验证计算,得到与天然较符合的结果。另外,根据近年的实践,改进以前的浮泥输沙公式,给出二种输沙的计算模式。本文是作者1987年以来研究此问题的总结。     

Environmental impact assessment and control of pharmaceuticals: the role of environmental agencies.

In 2005, the new legislation for pharmaceuticals came into effect. Since then environmental risk assessments are required for all new marketing authorisation applications. The German Federal Environment Agency has been assessing the environmental impact of 136 veterinary and 134 human pharmaceuticals. The authorisation of pharmaceuticals has shown that the authorisation of some groups of substances have to be combined with risk mitigation measures. Environmental risks may also arise from those pharmaceuticals which were authorised before the environmental risk assessment was added to the requirements of authorisation. Four examples of "existing" pharmaceuticals, i.e. diclofenac, ethinyl estradiol, ivermectin, and florfenicol are highlighted in this article. Risk management options for veterinary and human pharmaceuticals are discussed.     

药品和个人护理用品在水环境中污染状况的研究与展望

系统地综述了药品和个人护理用品(PPCPs)对世界上不同国家和地区的水环境所造成的污染.结果表明,世界各地水环境都检出了PPCPs污染物,其浓度一般达到ng/L～μg/L水平,而且随着季节变化显著波动.水环境中PPCPs主要来源于市政污水、垃圾填埋场渗漏和农业径流等,在水环境中会发生进一步转化.目前急需建立针对性的生态安全评价方法,进行微观和宏观以及短期和长期相结合的调查研究,为确保水环境生态安全提供科学依据,为控制PPCPs污染提供技术指导.     

Fate of pharmaceuticals and bacteria in stored urine during precipitation and drying of struvite

Experiments were conducted to measure the behaviour of eight pharmaceuticals during urine treatment as part of the project 'SANIRESCH - Sustainable sanitary recycling Eschborn'. Urine was collected from 200 people in a public building via waterless urinals and NoMix toilets. It was then stored at room temperature at different pH values to analyse the extent to which bacteria and pharmaceuticals are eliminated over time. Although a partial elimination of pharmaceuticals could be detected, the storage at defined pH values cannot be advised. As the persons tested used pharmaceuticals with different structures, in different amounts and at varying intervals, this method of treatment is insufficient for removing them from urine. Precipitating the urine with MgO, washing it with saturated struvite solution and drying it at 30 °C will result in a free-flowing granular powder of struvite (NH(4)MgPO(4)·6H(2)O) that is free of pharmaceuticals and pathogens and can be used as fertiliser and a source of nitrogen, magnesium and phosphorus.     

在井流影响下的对流－弥散问题研究

本文针对在对流一弥散问题的数值计算中，井点附近容易出现不合理的现象，从理论上推导出井流项（源汇项）在对流一弥散方程中的具体表达式，探讨了问题出现的原因，并提出了求解对流一弥散问题的４种计算方案．最后通过一个算例，验证了本文处理源汇项的可行性，并对４个计算方案进行了比较．计算结果表明，在实际应用中，可以忽略弹性储（释）水对溶质运移的影响，也可把注水井作为浓度第一类边界处理，经这样处理后所引入的误差不超过０．５％．     

The effect of oxidants on 2-MIB concentration with the presence of cyanobacteria.

In this study, the effect of three oxidants, sodium hypochlorite, potassium permanganate, and ozone, were tested for the removal of 2-MIB with presence of cyanobacteria. Algae in water samples from the source water of Feng-Shen waterworks (FSW), Taiwan were cultivated at 30 degrees C with continuous light at an intensity between 2,500 and 3,400 lux. During the cultivating process, water samples were analyzed for nutrients, light absorbance at 665 nm (A665), and 2-MIB concentration. The 2-MIB concentrations within the incubated samples increased to as high as 1,000 ng/L to 2,000 ng/L, although no extra nutrients were added to the raw water. After 2 to 3 days incubation, the intracellular 2-MIB concentration was as high as 70% of the total 2-MIB in the samples. The algae that developed were mainly cyanobateria, and more than 90% belonged to the Genus Oscillatorias. An almost 100% removal of both 2-MIB and geosmin in the raw water was observed after ozonation for 10 minutes at a dosing rate of 0.91 mg/l-min. Chlorine and permanganate were much less effective, both removing only about 11% of the 2-MIB within 60 minutes at oxidant concentration of 10 mg/l. Oxidation of the cultivated samples showed that chlorine and permanganate may damage algae cells causing them to release intracellular 2-MIB. During the 60 minutes of reaction time, the total 2-MIB concentrations (intracellular plus dissolved) varied by no more than 10%, however, the ratios between dissolved and total 2-MIB concentrations increased. Two effects of ozonation on the 2-MIB concentration in the cultivated samples were observed when the algae were young, namely 2-MIB release from damaged cells and 2-MIB oxidization. The rates of 2-MIB release and 2-MIB destruction were similar. However, old algae cells were more easily damaged. As a result, intracellular 2-MIB was released faster, and the soluble 2-MIB was destroyed more quickly by ozonation.     

药物和个人护理用品在水环境中的现状与去除研究

未经处理或在城市污水处理工艺中未被去除的药品及个人护理用品(PPCPs)会进入水环境污染地表水和地下水。通过对现有研究结果分析,归纳了当前国内外水环境中PPCPs的污染现状、预测和检测方法。结合城市给水厂常规工艺和深度处理技术对PPCPs的去除情况分析,指出我国开展相关研究的必要性及方向。     

某市饮用水系统中药品和个人护理用品的调查研究

采用固相萃取和液相色谱双质谱联用技术,调查研究了某市水源水、净水厂和小区管网(龙头)等水样中的65种药品和个人护理用品(PPCPs)分布和浓度情况。结果表明,在水源水、净水厂原水和小区管网(龙头)水中分别检出11、12和5种PPCPs,其平均浓度分别在0～11.20ng/L、0～12.35ng/L、0～1.31ng/L范围内;检出频率较高的污染物主要有4种抗生素类药(磺胺甲恶唑、氧苄氨嘧啶、泰妙菌素、林肯霉素)、2种消炎解热镇痛药(氨糖美辛、安替比林)、1种抗精神病药(舒必利)、1种血液循环系统药物(卡巴克络)、1种抗心律失常药(达舒平)、1种β阻滞剂(阿替洛尔);常规处理工艺并不能对所有目标物质有很好的去除效果,卡巴克络、磺胺甲恶唑等物质仍能在常规工艺出水中检出,而深度处理工艺的臭氧单元能对所检测的物质起到很好的去除作用,在深度处理工艺出水中检测不到任何目标污染物。     

NF/RO膜去除饮用水中药品的影响因素研究进展

药品是近几年在水体中普遍发现的痕量有机污染物,它对环境和人体健康带来的威胁受到了人们极大的关注.高压膜技术如纳滤和反渗透被认为是理想的药品去除方法.结合国内外的研究进展,重点阐述了纳滤和反渗透膜对药品去除效果的各种影响因素.     

Classification of the degradability of 30 pharmaceuticals in water with ozone, UV and H2O2.

Experiments were conducted to assess the degradability of 30 PPCPs, selected on the basis of consumption and environmental relevance, by O3 process, UV process and AOPs consisting of UV/ H2O2, O3/UV and O3/H2O2. A batch reactor with volume of 22L of water including the PPCPs was used. For UV process, combination of UV and H2O2 or O3 that can generate OH radicals was capable of degrading the PPCPs faster than UV radiation alone. On the other hand, O3 process and O3-based/UV-based AOPs could remove a variety of the PPCPs effectively, while some PPCPs such as 2-QCA, DEET and cyclophosphamide showed a relatively low degradability compared with the other PPCPs. However, further evaluation on formation of intermediate products resulting from the degradation of the parent PPCPs will be needed because DOC concentration was not decreased with lowered concentrations of the PPCPs.