壬基酚聚氧乙烯醚(NPEOs)在净水厂中的监测

低浓度内分泌干扰物长期作用会对人体健康产生不可忽视的负面影响.较详细地研究了北方某给水厂现有净水处理工艺对低浓度NPEOs的控制特性,结果表明,该厂常规工艺单元(无预氯化)对NPEOs(聚合度n＝4～15)基本上没有去除作用,后续活性炭单元对NPEOs的去除作用也不是很明显,有待进一步研究.由于氯的强氧化作用的存在,加氯能明显降低水中的NPEOs浓度.     

Behaviour of bisphenol A (BPA), 4-nonylphenol (4-NP) and 4-nonylphenol ethoxylates (4-NP1EO, 4-NP2EO) in oxidative water treatment processes.

Endocrine disrupting chemicals (EDCs) such as natural and synthetic hormones or industrial chemicals can adversely affect the endocrine system at very low concentrations. As such substances can be present in raw water used for drinking-water production, they potentially pose a health risk to humans. In this study laboratory tests were performed to determine removal efficiencies of selected oxidative drinking water treatment processes, namely ozonation (1.4 mg/l O3) and chlorination, using sodium hypochlorite (0.5 mg/l NaClO) and chlorine dioxide (0.4-0.6 mg/l ClO2) under conditions applied in technical plants. 500-300,000 ng/l of bisphenol A (BPA), 4-nonylphenol (4-NP) and 4-nonylphenol-n-ethoxylates (NPnEO) were selected for investigations and measured by HPLC/FLD and HPLC/MS. To investigate possible oxidation by-products, adsorbable organic halogens (AOX) were determined and estrogenic activities were assessed with the help of an estrogen receptor binding assay (YES). Ozonation and chlorination with ClO2 removed both 4-NP and BPA below detection limits, corresponding with AOX and estrogenic activity. Concerning NPnEO ozonation removed NP1EO and NP2EO up to 28% and 30%, respectively, whereas ClO2 showed high removal efficiencies, eliminating >94% and 92%, respectively. NaCIO removed 4-NP and BPA below detection limits, but estrogenic activities increased and AOX could be measured. NP1EO and NP2EO were only marginally reduced corresponding to the slight decrease of estrogenic potential.     

Occurrence of nonylphenol, nonylphenol ethoxylate surfactants and nonylphenol carboxylic acids in wastewater in Japan.

Nonylphenol (NP) is known to be a byproduct of nonylphenol ethoxylates (NPnEO) which are used as detergents in industry. It is important that not only NP but also NPnEO and their related substances are analysed when behaviour of NP in the wastewater treatment process is surveyed. NPnEO are biodegraded to shorter ethoxylate (EO) chain NPnEO or nonylphenol carboxylates (NPnEC) under aerobic conditions, and then biodegraded to NP under anaerobic conditions. NP is one of the suspected endocrine disruptors (ED). Moreover, shorter EO chain NPnEO has greater toxicity than longer EO chain NPnEO. We conducted a field survey of NP and its related substances in 20 wastewater treatment plants (WWTP). The concentrations (median) of NP and its related substances in the WWTPs' influent ranged from 0.1 to 8.3 microg/L, showing NP concentration as the same level as those previously reported. The reduction of the long EO chain NPnEO in the WWTPs was almost complete, while the removal efficiency for the short EO chain NPnEO was less significant than the long EO chain NPnEO, suggesting that the degradation rate of the short EO chain NPnEO was lower than that of the long EO chain NPnEO in the wastewater treatment     

Plasticizers and related toxic degradation products in wastewater sludges.

Plasticizers can persist during the treatment of wastewaters in sewage treatment plants (STPs) and can be discharged in effluents and/or accumulated in sewage sludges. For example, di-2-ethylhexyl phthalate (DEHP) is a common plasticizer that is now considered a priority pollutant and is known to accumulate in sludges. This may add constraints to the exploitation of the beneficial uses of sludges that contain significant quantities of plasticizers. Recently, it was demonstrated in studies with pure cultures that the biodegradation of plasticizers including DEHP and di-ethylhexyl adipate (DEHA) generates toxic metabolites including 2-ethylhexanoic acid, 2-ethylhexanol, and 2-ethylhexanal. However, the environmental impacts and fate of the degradation products arising from plasticizers are unknown. Therefore, this work investigated the concentrations of DEHP and DEHA and their metabolites in the sludges from several STPs in Quebec, Canada. DEHP and DEHA were found in concentrations ranging from 15 to 346 mg kg(-1) and 4 to 743 mg kg(-1), respectively, in primary, secondary, digested, dewatered or dried sludges. Metabolites were detected in almost all sludges, except those that had undergone a drying process at high temperature. It is concluded that sludges can represent significant sources of plasticizers and their toxic metabolites in the environment.     

Occurrence of perfluoroalkyl sulfonates and carboxylates in German drinking water sources compared to other countries.

Different homologues of C4 to C8 perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFASs) were detected in German surface waters, bank filtrates, artificially recharged groundwaters, and drinking waters. If no point sources are located nearby, the typically measured levels are in the low ng/L range. In the presence of point sources, such as a fluorochemical production site, a leaching agricultural fertilizer contaminated with PFCAs and PFASs, or drained PFC containing fire-fighting foams, much higher concentrations in the microg/L range occur. This situation is similar in Germany and other countries.     

Technical development of UV-C- and VUV-photochemically induced oxidative degradation processes.

Technical development work is presented, where the VUV photochemically induced oxidative degradation is used: (i) for analytic purposes, and (ii) for small to medium scale (< 10 m2/d) waste water treatment processes or ultrapure water production. In the first case, small Xe-excimer radiation sources with an integrated reaction space designed for optimal conditions, as far as incident photon flux density, turbulence and concentration of dissolved molecular oxygen are concerned, have been built and tested. Under conditions of exhaustive oxidation and/or mineralization of pollutants in a continuous regime, they may be used for sample pre-treatment modules prior TOC, TOX and electrochemical trace metal analysis. Under conditions of partial oxidation or mineralization, the same lamp/reactor combination may be used for functionalization purposes prior to e.g. GC or HPLC analyses. In the second case, mass transfer limitations between the non-irradiated bulk volume and the irradiated volume are overcome by the electrochemical generation of molecular oxygen within or close to the irradiated volume and by the design of the photochemical part of the reactor.     

Modeling the formation of soluble microbial products （SMP） in drinking water biofiltration

Both a theoretical and an empirical model were developed for predicting the formation of soluble microbial products （SMP） during drinking water biofiltration. Four pilot-scale biofilters with ceramsite as the medium were fed with different acetate loadings for the determination of SMP formation. Using numerically simulated and measured parameters, the theoretical model was developed according to the substrate and biomass balance. The results of this model matched the measured data better for higher SMP formation but did not fit well when SMP formation was lower. In order to better simulate the reality and overcome the difficulties of measuring the kinetic parameters, a simpler empirical model was also developed. In this model, SMP formation was expressed as a function of fed organic loadings and the depth of the medium, and a much better fit was obtained.     

Evaluation of pharmaceuticals and personal care products (PPCPs) in drinking water originating from Lake Erie

This project evaluated pharmaceuticals and personal care products (PPCPs) concentrations in drinking water originating from Lake Erie. Raw and treated water samples were collected from the local water treatment plant in Erie, Pennsylvania over a 10 month period. Along with grab samples, long-term samples were collected using Polar Organic Chemical Integrative Samplers (POCIS). The samples were analyzed for 17 PPCPs (acetaminophen, ampicillin, atrazine, bisphenol-A, caffeine, carbamazepine, cimetidine, ciprofloxacin, digoxin, gemfibrozil, ibuprofen, metformin, naproxen, simazine, sulfamethoxazole, sulfathiazole, trimethoprim) in raw and treated drinking water. For grab samples, six of the 17 PPCPs were found at detectable levels in raw or treated drinking water including atrazine, bisphenol-A, caffeine, ibuprofen, metformin, and simazine. Detectable PPCP levels in treated water samples were usually lower than those in raw water. For long-term samples, an additional four PPCPs (ten total) were found at detectable levels including gemfibrozil, naproxen, sulfamethoxazole, and trimethoprim. Aqueous phase concentrations of PPCPs were estimated using sampling rates, deployment periods, and analytical results of POCIS samplers.     

离子色谱-电感耦合等离子体质谱联用法同时分析水中碘酸根和碘离子

以离子色谱与电感耦合等离子体质谱联用法对水中碘的两种形态:碘酸根和碘离子进行同时检测,对流动相、记忆效应、进样量进行了研究。试验表明,以IonPac AS14分析柱,30mmol/L(NH4)2CO3(氨水调至pH10)为淋洗液,1mL/min流速,1mL的进样量,IO3-和I-的方法检测限(MDL)分别为0.066μg/L和0.045μg/L,回收率分别为95.7%和103.4%,相对标准偏差(n=7)为1.42%和1.86%。     

Analysis of nonylphenol polyethoxylates and their metabolites in water samples by high-performance liquid chromatography with electrospray mass spectrometry detection.

Evidence that some alkylphenol polyethoxylates (APEOs) breakdown products are estrogenic has intensified the interest over their environmental and human health effects. Different quantitative methods but one single preparation and extraction method for the analysis of nonylphenol polyethoxylates (NPEOs) and their metabolites in water samples using solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) with electrospray mass spectrometry detection (ESI-MS), are described. Quantification limits range about the low ng/l for the enrichment of 500 ml water samples and mean recoveries of 70% are achieved. These methods were subsequently applied to water samples coming from Austrian treatment plants.     

Use of iron(VI) and iron(V) in water and wastewater treatment.

Fe(VI) (Fe(VI)O4(2-)) and Fe(V) (Fe(V)O4(3-)) have high oxidizing power, selectivity, and upon decomposition produce a non-toxic by-product, Fe(III), which makes them potential oxidants in water and wastewater treatment. Rates of oxidation increase with a decrease in pH and are related to protonation of Fe(VI)O4(2-) and Fe(V)O4(3-). Oxidation of sulfur- and nitrogen-containing pollutants by Fe(VI) can be accomplished in seconds to minutes with formation of non-hazardous products. Fe(VI) can easily oxidize the amino acid components of microcystins and is a suitable disinfectant for detoxifying toxins in water. The oxidation of pollutants and amino acids with Fe(V) is 3-5 orders of magnitude faster than with Fe(VI). The use of ionizing radiation and photocatalytic techniques in the presence of Fe(VI) results in Fe(V) formation and may have synergistic effects on the oxidation of pollutants and removal of toxins in water and wastewater. This paper summarizes the results of multi-functional properties of Fe(VI) and Fe(V) to treat water and wastewater.     

Distribution of estrogen, nonylphenol and its derivatives in the sediments of a shallow lake.

To determine the distribution of endocrine disruptors (EDs) in lake water and sediments, field investigation was conducted in Lake Teganuma, which is a shallow eutrophic lake, highly affected by human activities. Concentration profiles with sediment depths were obtained for estrogens, nonylphenol (NP), nonylphenol ethoxylates (NPnEO), and nonylphenoxy acetic acids (NPnEC). 17beta-Estradiol (E2) was rarely detected, and 17alpha-ethynylestradiol (EE2) and estriol (E3) were undetected at all depths (0-98 cm) in any of the sediment core samples. The sediment concentrations of estrone (E1) ranging from <0.05 to 3.5 microg/kg-dry wt. and NP from 11.8 microg/kg-dry wt. to 21 mg/kg-dry wt. were obtained. The maximum concentrations of NPnEO and NPnEC in the core sediments were 2.5 mg/kg-dry wt. and 1.4 mg/kg-dry wt., respectively. The EDs concentrations are higher at the inlet than at the outlet (except for NP) in the sediments near the surface. The longitudinal distributions of E1, NPnEO and NPnEC in the benthic sediments show that the concentrations are highest at the inlet, and are fairly constant at lower levels towards the downstream. The obtained results also indicate that NP tends to be adsorbed to the organic particulates produced by algae, followed by sedimentation near the outlet of the lake.     

SPME-GC/MS/MS法测定水中2-甲基异莰醇和土臭素

研究了固相微萃取-气相色谱/二级质谱联用法测定水中2-甲基异坎醇(2-MIB)和土臭素(GSM)的方法.确定了最佳固相微萃取条件,NaCl加入量3 g,萃取温度60 ℃,搅拌时间30 min,搅拌速度800 r/min.在优化的仪器条件对臭味物质的测定结果显示,此方法灵敏度高,具有良好的精密度和准确度.2-MIB和GSM的相关系数均大于0.999;检出限及RSD分别为0.2 ng/L、0.4 ng/L和5.86%、6.50%;加标回收率分别为100.6%和92.3%.该方法操作简单省时,可满足水中痕量异臭物质的测定.     

Workshop 3 (synthesis): climate variability, water systems and management options.

Addressing climate variability now will better prepare us for future impacts of climate change. Sustained, multi-stakeholder dialogue at local through national levels is an approach that will reach the widest audience, helped by tools that illustrate vulnerability such as the Climate Vulnerability Index. Integrated water resources management deals with managing for variability and change and is therefore highly appropriate for dealing with climate impacts.     

Examining the biodegradation of endocrine disrupting bisphenol A and nonylphenol in WWTPs.

The aim of this work was to examine biodegradation of the endocrine disrupting chemicals bisphenol A (BPA) and nonylphenol (NP) in activated sludge. Experiments were performed in a pilot wastewater treatment plant (WWTP) in Copenhagen, Denmark. During standard operation the BPA concentration was halved whereas the NP concentration was unchanged. Step-addition experiments showed that biomass adaptation to increased BPA and NP concentrations took 10 to more than 40 days depending on temperature, hydraulic retention time, and pre-exposure of the biomass. Mass-balance experiments showed that above 99% of the dosed BPA and 90% of the dosed NP is removed by biodegradation at steady-state. Batch experiments showed that BPA biodegradation occur solely under aerobic conditions. The work is believed to add vital knowledge to our understanding of parameters and processes governing biodegradation of EDCs in WWTPs.     

Photocatalytic degradation of di(2-ethylhexyl)phthalate adsorbed by chitin A.

Di(2-ethylhexyl)phthalate (DEHP) is a ubiquitous environmental contaminant due to its extensive use as a plasticiser and its persistence. Currently, there is no cost-effective treatment method for its removal from industrial wastewater. In a previous study, DEHP was effectively adsorbed from aqueous solution by biosorption onto chitinous materials. Biosorption can pre-concentrate DEHP from the aqueous phase for further treatment. As biosorption cannot degrade DEHP, in this study the degradation (and detoxification) of DEHP adsorbed onto chitinous material by photocatalytic oxidation (PCO) is attempted. PCO relies on hydroxyl radical (.OH), which is a strong oxidising agent, for the oxidative degradation of pollutants. It is a non-selective process which can degrade DEHP adsorbed onto chitinous material. The first part of this study is the optimisation of the degradation of adsorbed DEHP by PCO. Adsorption was carried out in the physicochemical conditions optimised in the previous study, with 500 mg/L chitin A and 40 mg/L DEHP at initial pH 2, 22+/-2 degrees C and 150 rpm agitation for 5 min. After optimisation of PCO, a 61% removal efficiency of 10 mg/L of DEHP was achieved within 45 min under 0.65 mW/cm2 of UV-A with 100 mg/L TiO2, and 10 mM of H2O2 at initial pH 12. The optimisation study showed that UV-A and TiO(2) are essential for the degradation of DEHP by PCO. The degradation intermediates/products were identified by GC-MS analysis. GC-MS results showed that the di(2-ethylhexyl) side chain was first degraded, producing phthalates with shorter side chains. Further reaction produced phathalic anhydride and aliphatic compounds such as alkanol and ester. The toxicities of parental and degradation intermediates in the solution phase and on chitinous materials were followed by the Microtox test. Results indicated that toxicity can be removed after 4 h treatment by PCO. Thus the decontamination of DEHP by integrating biosorption and PCO is feasible.     

Disinfection performance of Fe(VI) in water and wastewater: a review.

Ferrate(VI) [FeVIO4(2-), Fe(VI)] has excellent disinfectant properties and can inactivate a wide variety of microorganisms at low Fe(VI) dosages. The final product of Fe(VI) is Fe(III), a non-toxic compound. The treatment by Fe(VI) does not give any chlorination by-products, which makes Fe(VI) an environmentally-friendly ion. The results demonstrate that Fe(VI) can inactivate Escherichia coli (E. coli) at lower dosages or shorter contact time than hypochlorite. Fe(VI) can also kill many chlorine resistant organisms, such as aerobic spore-formers and sulphite-reducing clostridia, and would be highly effective in treating emerging toxins in the aquatic environment. Fe(VI) can thus be used as an effective alternate disinfectant for the treatment of water and wastewater. Moreover, Fe(VI) is now becoming economically available in commercial quantities and can be used as a treatment chemical to meet the water demand of this century. This paper reviews the potential role of Fe(VI) as disinfectant in water and wastewater treatment processes.     

GRACE, GLDAS and measured groundwater data products show water storage loss in Western Jilin, China

Water storage depletion is a worsening hydrological problem that limits agricultural production in especially arid/semi-arid regions across the globe. Quantifying water storage dynamics is critical for developing water resources management strategies that are sustainable and protective of the environment. This study uses GRACE (Gravity Recovery and Climate Experiment), GLDAS (Global Land Data Assimilation System) and measured groundwater data products to quantify water storage in Western Jilin (a proxy for semi-arid wetland ecosystems) for the period from January 2002 to December 2009. Uncertainty/bias analysis shows that the data products have an average error <10% (p < 0.05). Comparisons of the storage variables show favorable agreements at various temporal cycles, with R(2) = 0.92 and RMSE = 7.43 mm at the average seasonal cycle. There is a narrowing soil moisture storage change, a widening groundwater storage loss, and an overall storage depletion of 0.85 mm/month in the region. There is possible soil-pore collapse, and land subsidence due to storage depletion in the study area. Invariably, storage depletion in this semi-arid region could have negative implications for agriculture, valuable/fragile wetland ecosystems and people's livelihoods. For sustainable restoration and preservation of wetland ecosystems in the region, it is critical to develop water resources management strategies that limit groundwater extraction rate to that of recharge rate.     

Characterization and degradation process of sludge profiles inside a facultative pond (Patagonia, Argentina)

To investigate the characteristics and degradation process in sludge profile, three sampling sessions were made in three different places inside the primary facultative pond of Puerto Madryn city, which was located in a region with a temperate climate in coastal Patagonia (Argentina). The sludge showed an extremely negative redox potential (between -441 and -282 mV) and elevated water content and organic matter concentration, ranging from 83.3 to 97.1% for porosity and from 22.5 to 64.4% for organic matter. The surface layer at the Outlet station during the summer showed the greatest concentration of pigments, reaching a maximum value of 10.6 mg/g for chlorophyll-a and 40.9 mg/g for phaeophytin, and a fast diminution with sediment depth. The important concentration of pigment in the surface layer, coincident with phytoplankton bloom in the water column, could support the importance of nitrogen removal via uptake and organic sedimentation in the water column. In warm months the degradation rate was clear, as reflected in a decrease in sediment layer, and even part of the clay bottom was captured inside an 8 cm core sample, registering extremely low concentrations of pigments, carbohydrates, proteins and lipids. The season and the degree of treatment have an influence on sludge characteristics and the organic matter degradation process.