The use of enzyme-linked immunosorbent assays (ELISA) for the determination of pollutants in environmental and industrial wastes.

Twelve enzyme-linked immunosorbent assays (ELISA), for the determination of surfactants [linear alkylbenzene sulfonates (LAS), alkyl ethoxylates (AE), and alkylphenol ethoxylates (APE)], endocrine disruptors [alkylphenol (AP), AP + APE, and bisphenol A (BPA)], estrogens [17beta-estradiol (E2), estrone (El), estrogen (ES: El + E2 + estriol (E3)), 1 7alfa-ethynylestradiol (EE2)], dioxins and polychlorinated biphenyls (PCBs), were validated on environmental water and industrial wastes. The lowest quantification limits of these ELISAs were 0.05 microg/L (BPA, E2, El, ES and EE2), 2 microg/L (AE), 3 microg/L (dioxins and PCBs), 5 microg/L (AP, AP + APE) and 20 microg/L (LAS and APE). To apply these ELISAs to environmental or industrial waste samples, simple and appropriate pre-treatment methods were also developed for each ELISA. With optimized pre-treatments, the values of ELISAs were well co-related, in all cases, to those of instrumental analytical methods such as liquid chromatography (HPLC), liquid chromatography-tandem mass spectrometry (LC-MS/MS), and high-resolution gas chromatography mass spectrometry (HR-GC-MS), etc.     

Evaluation of MBR effluent characteristics for reuse purposes.

One of the advantages of MBR is its excellent effluent quality, which is suitable for a wide range of reuse purposes. We investigated the characteristics of MBR effluent and evaluated them based on the Japanese guideline for the reuse of treated wastewater. As the result, MBR effluent showed qualitative coaracteristics that satisfy the requirement except chromaticity for recreational purpose. Further treatment, such as by oxone or activated carbon, will be required to remove the remaining color. MBR shows high removal efficiency of bacteria and other hazardous microorganisms such as Cryptosporidium. We investigated the removal efficiency of virus by MBR using coliphage as an alternative index. The results showed that high removal efficiency for coliphage could be obtained by MBR. The removal mechanism appears to be that coliphage are attached to the activated sludge and thus rejected by the membrane together with activated sludge particles. With regard to the endocrine disrupters, no significant differences were observed between MBR and CAS in the removal of main endocrine disrupters.     

Endocrine disrupters in the aquatic environment: the Austrian approach--ARCEM.

A consortium of Austrian scientists (ARCEM) carried out a multidisciplinary environmental study on Austrian surface and ground waters including chemical monitoring, bioindication, risk assessment and risk management for selected endocrine disrupters: 17beta-estradiol, estriol, estrone, 17alpha-ethinylestradiol, 4-nonylphenol, 4-nonylphenol ethoxylates (4-NP1EO, 4-NP2EO) and their degradation products, ocytlphenol, ocytlphenol ethoxylates (OP1EO, OP2EO) as well as bisphenol A. To obtain data representative for Austria, a material flow analysis served to select relevant compounds and water samples were collected monthly over one year at those sites routinely used in Austrian water quality control. The following results were obtained and conclusions drawn: 1. Chemical monitoring: As compared to other countries, relatively low levels of pollution with endocrine disrupters were detected. 2. Bioindication: In the surface waters under study, male fish showed significant signs of feminization and demasculinization (increased production of the egg-yolk protein and histological changes of the gonads. 3. Risk assessment: For humans, exposure via either drinking water abstraction (ground water) or fish consumption was considered. The exposure levels of the compounds under study were below those considered to result in human health risks. Likewise, for bisphenol A and octylphenols, there was no indication for risk posed upon the aquatic environment (fish). However, nonylphenol or 17alpha-ethinylestradiol exposure along with results of bioindication (2) suggest a borderline estrogenic activity in a considerable number of surface waters. Consequently the emissions of these substances into the surface waters affected have to be reduced. 4. Risk management: Waste water treatment experiments revealed a positive correlation between the removal rate of endocrine disrupters from the waste water and the sludge retention time in the treatment plants. These substances are removed to a higher extend at low loaded plants designed for nutrient removal than at plants that remove carbon and/or employ nitrification only. As to drinking water treatment, chlorine dioxide and ozone were found to eliminate all investigated substances, except nonylphenol ethoxylates. (For the complete study see: www.arcem.at)     

地表水体中重金属类内分泌干扰物的环境行为

重金属中的Hg、Cd、Pb是环境内分泌干扰物的重要组成部分。我国各水系中普遍存在着重金属类内分泌干扰物的污染现象,更值得注意的是饮用水源地污染也较为常见。简要阐述我国地表水体中重金属类内分泌干扰物的污染现状,介绍了重金属类内分泌干扰物在悬浮颗粒物/水界面和沉积物/水界面之间的迁移转化行为及其影响因素,概述它们在水生生物食物链中的转化过程。     

Removal of endocrine disrupting chemicals in a large scale membrane bioreactor plant combined with anaerobic-anoxic-oxic process for municipal wastewater reclamation

The removal of eight typical endocrine disrupting compounds (EDCs) in a full scale membrane bioreactor combined with anaerobic-anoxic-oxic process (A(2)/O-MBR) for municipal wastewater reclamation located in Beijing was investigated. These EDCs, including 4-octylphenol (4-OP), 4-n-nonylphenol (4-n-NP), bisphenol A (BPA), estrone (E1), 17α-estradiol (17α-E2), 17β-estradiol (17β-E2), estriol (E3) and 17α-ethinylestradiol (EE2), were simultaneously analyzed by gas chromatography/mass spectrometry after derivatization. The concentrations of eight EDCs were also measured in sludge of anaerobic, anoxic, oxic and membrane tanks to measure sludge-water distribution coefficients (K(d) values) as the indicator of adsorption propensity of target compound to sludge. The removal efficiencies of EDCs reached above 97%, except for 4-n-NP removal efficiency of 72%, 4-OP removal efficiency of 75% and EE2 removal efficiency of 87% in the A(2)/O-MBR process. The high K(d) values indicated that the sludge had a large adsorption capacity for these EDCs, and significantly contributed to removal of EDCs. Yeast estrogen screen assay was performed on samples to assess the total estrogenic activity by measuring the 17β-E2 equivalent quantity (EEQ), expressed in ng-EEQ/L. The measured EEQ value was markedly reduced from 72.1 ng-EEQ/L in the influent to 4.9 ng-EEQ/L in the effluent. Anoxic tank and anaerobic tank contributed to 80% and 37% in total EEQ removal, respectively.     

Emerging contaminants and treatment options in water recycling for indirect potable use.

Solutions to global water stress problems are urgently needed yet must be sustainable, economical and safe. The utilisation of alternative water sources like reclaimed municipal wastewater is one of the most obvious and promising options in integrated water resources management. Among the various beneficial uses of reclaimed wastewater Aquifer Recharge (AR) receives growing attention because it features advantages such as additional natural treatment, storage capacity to buffer seasonal variations of supply and demand as well as mixing with natural water bodies which promotes the acceptance of further uses, particularly indirect potable use. Major concerns about the safety of this exploitation route of an alternative water source are connected to microbial and chemical contaminants occurring in wastewater, among which are emerging trace organics like endocrine disrupters and pharmaceuticals. This paper reviews the current international debate about the relevance of emerging contaminants and technical mitigation options in water recycling for indirect potable use.     

The Niagara River mussel biomonitoring program (Elliptio complanata): 1983-2009

The Ontario Ministry of the Environment has monitored the concentrations of contaminants in mussel (Elliptio complanata) tissue and bottom sediments at sites in the Niagara River since 1983 to describe the general contamination of the river and identify contaminant sources. More recently, the data have been used to document the effectiveness of remedial actions implemented at identified sources along the river. Results from Canadian sites and five U.S. sites at which remedial actions have been implemented [Bloody Run Creek (Hyde Park Hazardous Waste Site); Gill Creek; Occidental Chemical Company (Buffalo Avenue Plant); 102nd Street Hazardous Waste Site; and Pettit Flume Cove] are discussed. p,p′-DDE, PCBs and dioxins were the only contaminants detected at Canadian sites at concentrations probably representative of background. Results from the five sites showed the effectiveness of implemented remedial actions in reducing the flow of contaminants to the river ranged between very effective (Gill Creek: PCBs; and 102nd Street, CBs) to no effect (Bloody Run Creek: PCBs, CBs, and dioxins). Remedial actions at the Pettit Flume Cove (for dioxins/furans) initially appeared to be effective, but were subsequently shown to have missed a source to the cove. The effectiveness of the actions taken at these sites in improving contaminant conditions in the Niagara River since the 1980s as demonstrated by our mussel and sediment results is corroborated by the data from other fish and water quality monitoring programs. Additional remedial efforts are still required at these sites and other known sources of contaminants to the river.     

Use of comprehensive two-dimensional gas chromatography for the broad screening of hazardous contaminants in urban wastewaters.

The list of priority chemicals included in various regulations such as the European Water Framework Directive, as well as the list of hazardous contaminants identified in the aquatic environment, are increasing at an accelerated pace. Therefore, there is a need for broad spectrum methods capable of simultaneously determining hundreds, if not thousands, of contaminants. For the analysis of non-polar or semi-polar contaminants, comprehensive two-dimensional gas chromatography (GC x GC) is more powerful than conventional gas chromatography thanks to a separation on two different stationary phases. This paper reports the use of GC x GC for a broad screening of hazardous contaminants in an urban wastewater plant. Comparison between the raw and treated wastewater has been carried out using a semi-quantitative approach. A variety of drugs, personal care products, pesticides, carcinogens and compounds toxic for reproduction, were identified. Most of these compounds were removed or decreased by this wastewater treatment plant. Preliminary results from this single plant will need to be confirmed by a more extensive study before drawing conclusions on the removal efficiency of 2D-GC amenable compounds.     

Methods for monitoring of pesticide residues in water: current status and recent trends

An overview of analytical methods currently used for the determination of pesticide residues in water samples is presented. As liquid chromatography and gas chromatography, coupled to mass spectrometry, are considered to be the most appropriate techniques for determination of pesticides in environmental waters, the most recent developments and applications in this field are discussed, as well as the extraction procedures employed for analyte isolation and preconcentration.     

Distribution of dioxins in surface soils and river-mouth sediments and their relevance to watershed properties.

The dioxins toxic equivalent (TEQ) concentration in surface soils, river sediments and river-mouth sediments was measured by the CALUX assay in the Yasu and Ado River basins around Lake Biwa, Japan. In order to examine the distribution of dioxins in each watershed, we evaluated and compared the correlation between the dioxins TEQ concentration and the solid characteristics (i.e. organic carbon content and particle size distribution) of all samples. In both basins, the dioxins TEQ concentration in forest soil correspondingly showed a very good linear relationship to organic carbon content. On the other hand, the dioxins TEQ concentration in paddy field was significantly high, although organic carbon content was relatively low. Generally, the smaller particles have the higher dioxins TEQ concentrations in surface soils, and river sediments were composed of very coarse particles and had relatively low dioxins TEQ concentration. Therefore, we expected high dioxins TEQ concentration in river-mouth sediment, which was, however, not the case. Although the dioxins TEQ concentration in river-mouth sediments is low, the degree of dioxins pollution was different in each basin. The difference was considered to come from the difference of watershed properties including land use, river-slope, dam construction as well as the surface soil pollution.     

Evaluation of a MF membrane system composed of pre coagulation-sedimentation and chlorination for water reuse.

In this research, we investigated the variation of transmembrane pressure and permeate water quality in pre-coagulation and sedimentation with iron based coagulant, and chlorination of feed water for PVDF (Polyvinylidene fluoride) based MF membrane filtration. NaCIO was fed to the membrane module at a dosage of 0.5 mg/L and maintained during filtration. To observe the effect of raw water, three types of raw and processed waters, including river surface water, coagulated water and coagulated-settled water, were employed. In the case of river surface water, the transmembrane pressure increased abruptly in 500 hours operation. On the contrary, no significant increase in transmembrane pressure was observed for coagulated water and coagulated-settled water for 1200 hours operation. The turbidity of permeate was lower than the detection limit for all applied waters. The removal efficiency for humic substances in coagulated water and coagulated-settled water was approximately ten times higher than that in surface river water. And, the removal efficiency for TOC and DOC was approximately two times higher than that in surface river water. From the results of the operation, it can be observed that it is possible to maintain stable operation at 0.9 m(3)/m(2)-day filtration flux through a combination of pre-coagulation and pre-chlorination. However, the water quality of permeate was the best when the pre-coagulation-sedimentation process was combined with pre-chlorination. With respect to fouling reduction and operation efficiency increase in membrane filtration, the pre-coagulation/sedimentation process is a promising alternative.     

Removal of trace organic chemical contaminants by a membrane bioreactor

Emerging wastewater treatment processes such as membrane bioreactors (MBRs) have attracted a significant amount of interest internationally due to their ability to produce high quality effluent suitable for water recycling. It is therefore important that their efficiency in removing hazardous trace organic contaminants be assessed. Accordingly, this study investigated the removal of trace organic chemical contaminants through a full-scale, package MBR in New South Wales, Australia. This study was unique in the context of MBR research because it characterised the removal of 48 trace organic chemical contaminants, which included steroidal hormones, xenoestrogens, pesticides, caffeine, pharmaceuticals and personal care products (PPCPs). Results showed that the removal of most trace organic chemical contaminants through the MBR was high (above 90%). However, amitriptyline, carbamazepine, diazepam, diclofenac, fluoxetine, gemfibrozil, omeprazole, sulphamethoxazole and trimethoprim were only partially removed through the MBR with the removal efficiencies of 24-68%. These are potential indicators for assessing MBR performance as these chemicals are usually sensitive to changes in the treatment systems. The trace organic chemical contaminants detected in the MBR permeate were 1 to 6 orders of magnitude lower than guideline values reported in the Australian Guidelines for Water Recycling. The outcomes of this study enhanced our understanding of the levels and removal of trace organic contaminants by MBRs.     

Relevance of the sludge retention time (SRT) as design criteria for wastewater treatment plants for the removal of endocrine disruptors and pharmaceuticals from wastewater.

Wastewater treatment plants (WWTPs) represent a significant source for the input of micro pollutants as endocrine disruptors (EDs) or pharmaceutically active compounds (PhACs) into the aquatic environment. Treatment efficiency of WWTPs often is reported, taking into account only inflow and effluent concentrations without further specification of the WWTP investigated. In order to allow comparison and evaluation of the removal efficiency of different layouts and concepts in wastewater treatment, additional information like the sludge retention time (SRT) and sludge load (F/M ratio) are necessary. Presented results from different WWTPs show correlation of removal of EDs and PhACs to the SRT. Compared to WWTPs with high F/M ratio implementation of the nitrification process on WWTPs results in a significant increase of the removal efficiency for EDs and PhACs. This paper describes an approach to determine comparable removal rates for different activated sludge systems based on mass balance and SRT.     

Seasonal changes predominant over manure application in driving dissolved organic matter shifts in agricultural runoff

Non-point source nutrient pollution can cause eutrophication, hypoxic events, and harmful algal blooms in surface waters. Surface water eutrophication is frequently attributed to agricultural runoff, a known source of inorganic and organic nutrients to surface and subsurface waters. Analysis of dissolved organic matter (DOM) using ultrahigh resolution mass spectrometry is an effective tool for characterizing diverse organic nitrogen and phosphorus components of DOM that may be mineralized and/or assimilated and ultimately contribute to eutrophication. An anion exchange resin was applied to extract DOM from surface and subsurface tile runoff from agricultural plots located within the Maumee River watershed (Ohio, USA) that received raw liquid manure, polymer-treated dewatered manure, or no manure (control). DOM extracts were analyzed using Fourier transform ion cyclotron resonance mass spectrometry prior to manure application and during three runoff events after manure application. Organic nitrogen compounds were predominant, making up 38–48% of the total assigned formulas. Principle coordinates analysis indicated clustering predominately by sample month and secondarily by treatment. These findings show that a large amount of variability in DOM in runoff was observed regardless of manure application, indicating the important role played by natural processes in driving transformation of the DOM pool during the growing season. Molecular ions unique to runoff from manure-applied plots were also identified that may be useful in source-tracking of non-point source nutrient pollution in waters draining to Lake Erie.     

Comprehensive management of chemical substances in a water environment using PRTR data.

The annual quantity of discharge of 354 chemical substances from each business has been released based on PRTR law in Japan since 2003. MLIT and municipalities should be responsible for managing chemical risk in public water bodies through communication with stakeholders, such as the public and businesses. However, it is economically difficult to measure the discharge loads and behaviour of all chemical substances and reveal which substances should be particularly managed in each basin. NILIM has begun studies on survey methods to understand the discharge and behaviour of chemical substances in each basin based on PRTR information, and to conduct risk management of chemical substances in cooperation with stakeholders such as the public and businesses. We selected 30 chemical substances, such as those listed or nominated in environmental criteria and endocrine disrupters, collected the volume of discharge of chemical substances from public and industrial wastewater treatment plants using PRTR information, and surveyed their behaviour in the river in the model area. As a result, the discharge of 12 chemical substances were reported in PRTR, and 17 substances were detected in the river. Some inorganic compounds were detected intensively near discharge sites reported in the PRTR. But some organic compounds and endocrine disrupters, such as oestrone, were detected although their discharge was not reported in the model area in the PRTR. It suggested that PRTR information is useful to identify hot spots, but further study is needed to understand the discharge of chemical substances from small businesses, farmland and houses.     

Removal of 17beta-estradiol (E2) and its chlorination by-products from water and wastewater using non-imprinted polymer (NIP) particles

Endocrine disrupting compounds and their chlorination by-products are two classes of emerging contaminants. Surface water and wastewater treatment technologies have limitations in removing these contaminants. This study evaluated the ability of non-imprinted polymer particles (NIP) to remove the endocrine disruptor 17beta-estradiol (E2) and its chlorination by-products from water and wastewater. NIP effectively removed 98% of 10 mg/L E2 from wastewater. NIP were also effective in removing chlorination by-products of E2 by 84.9% after 10 mg/L E2 in water was chlorinated at 5 mg/L. In the presence of 5 mg/L humic acid, NIP were able to achieve removal of 10 mg/L E2 by greater than 99.9%. Furthermore, after chlorination of 10 mg/L E2 and 5 mg/L humic acid at 10 mg/L chlorine, NIP were also able to remove the chlorination by-products formed as well as the remaining E2 by greater than 99.9%. The presence of 5 mg/L humic acid did not adversely affect the adsorption efficiency. The results of this research indicate that NIPs have good potential as a final treatment step for surface water and wastewater treatment.     

Fate of nonylphenol and 17beta-estradiol contained in composted sewage sludge after land application.

Many environmental problems caused by endocrine disrupters (EDs) have been reported. Because little is known about the fate of EDs accumulated in sewage sludge, we carried out a study to clarify the fate of EDs in composted sludge after its application to soil. Nonylphenol (NP) and 17beta-estradiol (E2) were measured for leachate and soil. High concentrations of NP and E2 were detected in the leachate at the early stage, but they decreased rapidly. Also, the high contents of NP and E2 in soil decreased significantly within 300 days. Because the decrease of NP and E2 in the soil was much larger than that of NP and E2 in the leachate, there must have been a physicochemical or biological decomposition mechanism in the soil layer. We also tried to clarify the transfer of NPs to plants from compost. In the experimental conditions of this study, the transfer of NPs to plants from compost was not observed.     

多种修复技术对城市内河水质及微生物群落的影响

采集城市内河水样,分别采用曝气增氧、碳源添加、生物投菌和综合修复等技术,在实验室进行水质修复模拟实验,并以水质参数、微生物多样性及丰度为鉴定指标,分析不同修复技术对城市河流水质的修复效果及其对河流微生物群落结构的影响。结果表明,曝气、生物投菌和综合修复技术可以提高河流微生物群落结构多样性,水体微生物群落以变形菌门(Proteobacteria)、拟杆菌门(Bacteroidetes)、放线菌门(Actinobacteria)和疣微菌门(Verrucomicrobia)为主;而使用碳源添加技术的水样,河流微生物的多样性下降明显,变形菌门(Proteobacteria)的相对丰度达到了93%;水质修复方面,曝气增氧技术和生物投菌技术都仅能降低水体COD质量浓度,无法降低水体TN及NH+4-N质量浓度;碳源添加和综合修复技术,对水体TN和NH+4-N的去除效果明显,但投加碳源的河流水体中的COD质量浓度显著上升;相关性分析结果表明,影响水体微生物群落结构的主要环境因子为COD和DO。     

Drainage basin security of hazardous chemical fluxe in the Yodo River basin.

The Yodo River basin consists of three major tributary basins (and other small river basins) namely Uji, Katsura and Kizu, which overlap respectively Shiga, Kvoto and Nara prefectures' administrative areas. Lake Biwa, the largest lake in Japan, drains water through the Uji river. The water quality of the lake, in terms of BOD, continuously improved over the last decade. However, the quality in terms of COD did not show any improvement in spite of a large amount of infrastructure finance being introduced. Eutrophication of the lake still continues, showing no improvement in the nitrogen concentration level. Non-point as well as point source control is not strong enough. There is a gap between BOD and COD evaluations of the lake water quality. Hazardous chemical fluxes are estimated based upon PRTR reports of Japan (2001). PCBs are still discharged into the lake, although the report of Shiga Prefecture showed zero discharge. Dace fish monitoring clearly showed that PCB contamination of the fish had not changed since the 1980s in spite of a ban on use and production of PCBs in the 1970s. There is still leakage of PCBs into the lake. The major exposure of dioxins to Japanese is fish rather than meat and eggs. The risk of water contamination must take into consideration not only drinking water safety but also ecological magnification of food chains in water. The ecological health aspect of hazardous chemicals is also important, such as organotins with imposex of sea snails. Finally, public participation in hazardous chemical management is very important using the method of risk communication based upon the annual report of PRTR in Japan.     

Studies of Trace Contaminants,Nutrients, and Bacteria Levels in the Niagara River

Sediment and water quality of the Niagara River were investigated during 1979 and 1980 to determine spatial and temporal differences in the levels of trace contaminants (heavy metals, phenolics, PCBs, and organochlorine pesticides) as well as nutrients and bacteria. Data from these studies as well as recent biomonitoring studies indicate that the Niagara River continues to be a source of such contaminants as PCBs, BHCs, mirex, and heavy metals to Lake Ontario. The major source of the contaminants is the highly industrialized and urbanized Tonawanda Channel area in the upper section of the river. Although a substantial improvement in phenolics levels was noted in the river since earlier surveys in 1971, bacterial and phosphorus levels show no significant changes, particularly near the U.S. mainland shore of the Tonawanda Channel and near the Buffalo River mouth.