Screening organic micropollutants in surface waters by SPE extraction and ecotoxicological testing

Complex mixtures of toxic substances occurring in surface waters are difficult to characterise by chemical analyses because each compound occurs at a very low concentration and requires a specific analytical method to be identified. Ecotoxicological tests on water extracts can be used as a screening tool to evaluate quickly and simply the overall quality of a water body with regard to micropollutant contamination. In this work, a pre-concentration procedure based on solid-phase extraction (SPE), suitable for both biological testing and analytical determination, is proposed. The extraction procedure is an improved version of a methodology used to evaluate the toxicity of organic micropollutants occurring in surface waters. It offers the advantage of using disposable commercial cartridges, which are easier to manage than the columns prepared with macromolecular resins. Water extracts from two representative Italian rivers, characterised by a different gradient of potential contamination and prepared according to the new concentration techniques, are used. The acute toxicity of the water extracts is tested on Daphnia magna and the bioluminescence inhibition in Vibrio fischeri. Criteria based on the concentration factor (CF) are proposed for assessing the hazard to aquatic life due to the exposure to toxic substances in surface waters. The aim of hazard ranking is to focus analytical efforts towards those samples that show the highest toxic potential.     

Is the evaluation of “traditional” physicochemical parameters sufficient to explain the potential toxicity of the treated wastewater at sewage treatment plants?

Water scarcity is one of the most important environmental and public health problems of our century. Treated wastewater reuse seems to be the most attractive option for the enhancement of water resources. However, the lack of uniform guidelines at European and/or Mediterranean level leaves room for application of varying guidelines and regulations, usually not based on risk assessment towards humans and the environment. The benefits of complementing the physicochemical evaluation of wastewater with a biological one are demonstrated in the present study using Cyprus, a country with extended water reuse applications, as an example. Four organisms from different trophic levels were used for the biological assessment of the wastewater, namely, Pseudokirchneriella subcapitata, Daphnia magna, Artemia salina and Vibrio fischeri. The physicochemical assessment of wastewater based on “traditional” chemical parameters indicated that the quality of the wastewater complies with the limits set by the relevant national guidelines for disposal. The ecotoxicological assessment, however, indicated the presence of toxicity throughout the sampling periods and most importantly an increase of the toxicity of the treated wastewater during summer compared to winter. The resulting poor correlation between the physicochemical and biological assessments demonstrates that the two assessments are necessary and should be performed in parallel in order to be able to obtain concrete results on the overall quality of the treated effluent. Moreover, a hazard classification scheme for wastewater is proposed, which can enable the comparison of the data sets of the various parameters deriving from the biological assessment in a comprehensive way.     

An Evaluation of Techniques for the Determination of the Photochemical Reactivity of Organic Emissions

The concept that control of organic substances in emissions should be based on the relative ability to cause the effects associated with photochemical air pollution (reactivity) rather than on gross emission levels has gained wide acceptance. Two general types of reactivity response scales have been proposed. One of these is based on rates of hydrocarbon reaction or nitrogen dioxide formation. This scale covers a wide range because of the very high rates associated with olefins having internal double-bonds. The other scale is based on product yields combined with biological effect measurements. This type of scale is considered superior to one based on rates. This latter scale covers a narrow response range because olefins with internal double bonds have only slightly higher product yields and biological effects than do other reactive olefins and alkylbenzenes. Use of a response scale based on product yields and biological effects also permits use of less detailed instrumental procedures. A simple subtractive column technique combined with a flame ionization analyzer should be sufficient to estimate hydrocarbon emissions. Gas chromatographic analyses of hydrocarbon emissions are of value when used with either type of reactivity response scale. However, detailed gas chromatographic analyses are essential for a response scale based on rates. The response scale based on product yields and biological effects indicates much less improvement in reactivity from fuel composition changes than would be predicted from a response scale based on rates. The most desirable approach is to use a variety of control and engine modification techniques to reduce all reactive organics to the lowest level possible.     

Physicochemical and biological quality of soil in hexavalent chromium-contaminated soils as affected by chemical and microbial remediation

Chemical and microbial methods are the main remediation technologies for chromium-contaminated soil. These technologies have progressed rapidly in recent years; however, there is still a lack of methods for evaluating the chemical and biological quality of soil after different remediation technologies have been applied. In this paper, microbial remediation with indigenous bacteria and chemical remediation with ferrous sulphate were used for the remediation of soils contaminated with Cr(VI) at two levels (80 and 1,276 mg kg^?1) through a column leaching experiment. After microbial remediation with indigenous bacteria, the average concentration of water-soluble Cr(VI) in the soils was reduced to less than 5.0 mg kg^?1. Soil quality was evaluated based on 11 soil properties and the fuzzy comprehensive assessment method, including fuzzy mathematics and correlative analysis. The chemical fertility quality index was improved by one grade using microbial remediation with indigenous bacteria, and the biological fertility quality index increased by at least a factor of 6. Chemical remediation with ferrous sulphate, however, resulted in lower levels of available phosphorus, dehydrogenase, catalase and polyphenol oxidase. The result showed that microbial remediation with indigenous bacteria was more effective for remedying Cr(VI)-contaminated soils with high pH value than chemical remediation with ferrous sulphate. In addition, the fuzzy comprehensive evaluation method was proven to be a useful tool for monitoring the quality change in chromium-contaminated soils.     

Evaluation of Absorption Sampling Devices

The information presented in this paper is directed to those with the responsibility of designing and operating air quality monitoring networks. An analytical model for location of monitor sites based upon maximizing a sum of coverage factors for each source is developed. An heuristic solution method from the facilities location analysis literature is used for solution of the model. Results of an example problem are presented and compared with the monitoring network currently In place. The model is shown to be a valuable addition to the methods available to the air quality monitor network designer. Needs for further research are pointed out.     

Evaluation of environmental monitoring strategies

In environmental monitoring, it is important that the monitoring system should emit early warnings when undesired events occur. These events may be sudden or of a more subtle nature. In the design of such monitoring systems, a proper balance between cost and risk must be achieved. There are 2 classic types of risk connected with early warning systems, namely the risk of not detecting significant changes and the risk of false alarms. The purpose of this paper is to describe a method for comparing the performance of different monitoring systems, considering the classic types of risk and cost. The method is applied to the monitoring of the lichen cover as a test case. The expected utility has been used as a measure of performance. When estimating the probabilities of the events, spatial microsimulation and Monte-Carlo simulation techniques have been used. The monitoring programs studied are based on satellite images, aerial photos, field samples, and land-cover maps. The major conclusions of this study are that standardized quality measures are extremely useful for evaluating the usability of environmental monitoring methods. In addition, when estimating gains and costs, spatial microsimulation techniques are useful. To improve the method, however, macroconstraints should also be used for aligning the simulation model.     

Revisions to the derivation of the Australian and New Zealand guidelines for toxicants in fresh and marine waters

The Australian and New Zealand Guidelines for Fresh and Marine Water Quality are a key document in the Australian National Water Quality Management Strategy. These guidelines released in 2000 are currently being reviewed and updated. The revision is being co-ordinated by the Australian Department of Sustainability, Environment, Water, Population and Communities, while technical matters are dealt with by a series of Working Groups. The revision will be evolutionary in nature reflecting the latest scientific developments and a range of stakeholder desires. Key changes will be: increasing the types and sources of data that can be used; working collaboratively with industry to permit the use of commercial-in-confidence data; increasing the minimum data requirements; including a measure of the uncertainty of the trigger value; improving the software used to calculate trigger values; increasing the rigour of site-specific trigger values; improving the method for assessing the reliability of the trigger values; and providing guidance of measures of toxicity and toxicological endpoints that may, in the near future, be appropriate for trigger value derivation. These changes will markedly improve the number and quality of the trigger values that can be derived and will increase end-users’ ability to understand and implement the guidelines in a scientifically rigorous manner.     

Detecting and Tracking Changes in Ozone Air Quality

This paper presents a statistical method for filtering out or moderating the influence of meteorological fluctuations on ozone concentrations. Use of this technique in examining trends in ambient ozone air quality is demonstrated with ozone data from a monitoring location in New Jersey. The results indicate that this method can detect changes in ozone air quality due to changes in emissions in the presence of meteorological fluctuations. This method can be useful in examining the effectiveness of regulatory initiatives in improving ozone air quality.     

Substance-related environmental monitoring

Background  Due to the requirements of the EU Water Framework Directive and other legal regulations (e.g., national laws like the German Federal Soil Protection Act), but also due to the implementation of the new EU chemicals management system REACH, environmental monitoring will gain increasing importance for the surveillance of environmental quality as well as for the assessment of chemicals. Against this background, the Work Group on ‘Environmental Monitoring’ of the Division of ‘Environmental Chemistry and Ecotoxicology’ within the German Chemical Society has compiled a position paper on substance-related environmental monitoring. Scope  Core elements of this position paper are the definitions of important terms like monitoring, exposure monitoring, effect monitoring, and integrated monitoring. Moreover, temporal and spatial aspects (monitoring of spatial distributions, trend monitoring, and retrospective monitoring) and their applications are discussed. The main focus of this position paper is the coverage of aspects which have to be observed for the preparation and implementation of a monitoring program. Essential is the clear specification of the targets of the monitoring which determine the development of the monitoring concept and its realization, e.g., if environmental media (compartments) or organisms are most appropriate as samples for the aim of the study. Of course, also the properties of the target substances are important (e.g., lipophilicity/bioaccumulation as pre-requisite for an exposure monitoring with organisms). Finally, the monitoring phases of sample planning, sampling, storage and transport of samples, selection of analytical methods, quality assurance measures as well as reporting are discussed. Perspectives  An important issue for the future is to link the quantification of chemicals in environmental compartments (exposure and pollution monitoring) more closely to the study of biological effects (effect monitoring) than has been the case up to now. Furthermore, by inclusion of a spatial differentiation, a comprehensive evaluation of the state of an ecosystem can be obtained and the relevance of the results improved. Practical examples of monitoring studies which illustrate various aspects covered in this position paper will be presented in a series of publications by members of the Work Group in the following issues of this journal.

Assessment of hydrochemical trends in the highly anthropised Guadalhorce River basin (southern Spain) in terms of compliance with the European groundwater directive for 2015

One of the key aspects introduced by the European Water Framework Directive 2000/60/EC (WFD) and developed by Groundwater Directive 2006/118/EC was the need to analyse pollution trends in groundwater bodies in order to meet the environmental objectives set in Article 4 WFD. According to this Directive, the main goal of “good status” should be achieved by the year 2015, and having reached this horizon, now is a suitable time to assess the changes that have taken place with the progressive implementation of the WFD. An extensive database is available for the Guadalhorce River basin, and this was used not only to identify in groundwater but also to draw real conclusions with respect to the degree of success in meeting the targets established for this main deadline (2015) The geographic and climate context of the Guadalhorce basin has facilitated the development of a variety of economic activities, but the one affecting the largest surface area is agriculture (which is practised on over 50 % of the river basin). The main environmental impacts identified in the basin aquifers arise from the widespread use of fertilisers and manures, together with the input of sewage from population centres. In consequence, some of the groundwater bodies located in the basin have historically had very high nitrate concentrations, often exceeding 200 mg/L. In addition, return flows, the use of fertilisers and other pressures promote the entry of other pollutants into the groundwater, as well as the salinisation of the main aquifers in the basin. In order to assess the hydrochemical changes that have taken place since the entry into force of the WFD, we performed a detailed trends analysis, based on data from the official sampling networks. In some cases, over 35 years of water quality data are available, but these statistics also present significant limitations, due to some deficiencies in the design or management; thus, data are missing for many years, the results are subject to seasonality effects, there are gaps in the historical records obtained by the monitoring networks and other shortcomings. The results obtained were analysed with the non-parametric Mann-Kendall test and revealed a general upward trend of pollutants in the areas affected by major pressures. In this analysis, we evaluated not only the increase or decrease in pollutants but also the different processes detected and the sources of pollution within the basin area. Our evaluation shows that robust measures should be taken in order to prevent further major degradation of groundwater quality and to enable “good quality” status to be achieved in future extensions of the WFD.     

Overview of passive Chemcatcher sampling with SPE pretreatment suitable for the analysis of NPEOs and NPs

The European Union Water Framework Directive (WFD; 2000/60/EC) is an important piece of environmental legislation that protects rivers, lakes, coastal waters and groundwaters (EC 2000). The implementation of the WFD requires the establishment and use of novel and low-cost monitoring programmes, and several methods, e.g. passive sampling, have been developed to make the sampling process more representative compared to spot sampling. This review considers passive sampling methods focusing mainly on a passive sampler named Chemcatcher®, which has been used for monitoring several harmful compounds in aquatic environments. Also, the sample treatment and analysis of nonylphenol ethoxylates (NPEOs) and nonylphenol (NPs) from water using solid phase extraction (SPE) is briefly summarized. The procedure of Chemcatcher passive sampling is quite similar to that of the SPE extraction since it concentrates the studied compounds from water as well. After sampling, the accumulated substances are extracted from the receiving phase of the sampler. The concentrations of NPEOs and NPs are currently monitored by taking conventional spot samples; SPE can be successfully used as a pretreatment procedure. Chemcatcher® passive sampling technique is a simple and useful monitoring tool and can be applied to new chemicals, such as NPEOs and NPs in aquatic environments.     

Adaptive coastal planning and the European Union's water framework directive: a Swedish perspective

The implementation of the EU Water Framework Directive and the achievement of its water quality objectives will to a large degree depend on scientific knowledge about the sources and status of water resources and the effects of mitigative measures. Coastal waters will be of central interest, since the management of whole river basins may be affected if coastal water status is not satisfactory. The Water Directive's general directions on what information the water authorities need and on suitable methods for obtaining such information leave it to the Member states to decide on more precise instructions. Improved legal mechanisms are needed to assist and guide the managers and scientists charged with implementing the directive and achieving its water quality objectives, particularly when faced with insufficient information, flawed knowledge, or changed circumstances. We assess progress in the current process of implementing the Water Directive in Sweden, focussing on coastal waters, and on general problems arising using this type of legal technique.     

基于聚类分析和水质标识指数的水质评价方法

为探讨一种适用于大尺度、多断面和长时间的水质评价方法,用层次聚类分析将2006~2008年海河5个监测断面的165个水质样本分为20组,并用方差分析验证了结果的可靠性。用综合水质标识指数表示水质样本的综合特征,与单因子评价法相比,该方法充分考虑了最差水质因子的影响,避免了单因子评价法以偏概全的缺陷,且分辨率高。将评价结果分解到各断面,结果表明:密云水库、官厅水库和于桥水库的水质处于II~III类水之间,可满足作为饮用水水源水的要求,三岔口断面大部分时间为IV~V类水,张家口八号桥断面全年有6个月以上水质属于劣V类。     

The groundwater contribution to surface water contamination in a region with intensive agricultural land use (Noord-Brabant, The Netherlands)

Traditionally, monitoring of soil, groundwater and surface water quality is coordinated by different authorities in the Netherlands. Nowadays, the European Water Framework Directive (EU, 2,000) stimulates an integrated approach of the complete soil-groundwater-surface water system. Based on water quality data from several test catchments, we propose a conceptual model stating that stream water quality at different discharges is the result of different mixing ratios of groundwater from different depths. This concept is used for a regional study of the groundwater contribution to surface water contamination in the Dutch province of Noord-Brabant, using the large amount of available data from the regional monitoring networks. The results show that groundwater is a dominant source of surface water contamination. The poor chemical condition of upper and shallow groundwater leads to exceedance of the quality standards in receiving surface waters, especially during quick flow periods.     

A holistic approach for optimal design of air quality monitoring network expansion in an urban area

This paper presents an objective methodology for determining the optimum number of ambient air quality stations in a monitoring network. The methodology integrates the multiple-criteria method with the spatial correlation technique. The pollutant concentration and population exposure data are used in this methodology in different ways. In the first stage, the Fuzzy Analytic Hierarchy Process (FAHP) with triangular fuzzy numbers (TFNs) is used to identify the most desirable monitoring locations. The network configuration is then determined on the basis of the concept of sphere of influences (SOIs). The SOIs are dictated by a predetermined cutoff value (r_c) in the spatial correlation coefficients (r) between the pollutant concentrations at the monitoring stations identified from first step and the corresponding concentrations at neighboring locations in the region. Finally, the optimal station locations are ranked by using combined utility scores gained from the first and second steps. The expansion of air quality monitoring network of Riyadh city in Saudi Arabia is used as a case study to demonstrate the proposed methodology.     

Objective classification of ecological status in marine water bodies using ecotoxicological information and multivariate analysis

Some relevant shortcomings have been identified in the current approach for the classification of ecological status in marine water bodies, leading to delays in the fulfillment of the Water Framework Directive objectives. Natural variability makes difficult to settle fixed reference values and boundary values for the Ecological Quality Ratios (EQR) for the biological quality elements. Biological responses to environmental degradation are frequently of nonmonotonic nature, hampering the EQR approach. Community structure traits respond only once ecological damage has already been done and do not provide early warning signals. An alternative methodology for the classification of ecological status integrating chemical measurements, ecotoxicological bioassays and community structure traits (species richness and diversity), and using multivariate analyses (multidimensional scaling and cluster analysis), is proposed. This approach does not depend on the arbitrary definition of fixed reference values and EQR boundary values, and it is suitable to integrate nonlinear, sensitive signals of ecological degradation. As a disadvantage, this approach demands the inclusion of sampling sites representing the full range of ecological status in each monitoring campaign. National or international agencies in charge of coastal pollution monitoring have comprehensive data sets available to overcome this limitation.     

Application of biological safety index in two Japanese watersheds using a bioassay battery

In order to integratedly evaluate the biological safety as a water quality index, an assessment method based on three toxicity tests (algae growth inhibition, daphnia immobilization and larval fish toxicity) was developed. In this study, the developed method was used to screen, evaluate and rank the biological safety of small rivers near agricultural, industrial and residential areas. Twenty-seven representative water samples were collected from the Kaname River watershed and the Hinata River watershed in Kanagawa Prefecture, Japan. The results indicated that (1) the biological safety of water from the Hinata River ranked much higher than those from the Suzu River and the Shibuta River due to less human activities, (2) the biological safety from outlets of paddy fields ranked much worse than those from point source discharges of toxic pollutants, (3) the use of pesticides significantly affected the water quality of nearby small rivers and ditches during the pesticide application season, (4) the effects of different kinds of pesticides could successfully be classified using one toxicity test component of the bioassay battery, and (5) there was no significant quantitative relationship between the toxicity and dissolved organic carbon (DOC) for the studied water samples. The toxicities of water samples in this study were in agreement with the concentrations of pesticides determined with chemical methods by other researchers, which demonstrated that the developed assessment method was reliable to screen site contaminated with organic chemicals for priority management.     

Water quality index evaluation for major rivers in Gujarat

Environmental Science and Pollution Research - Water quality index (WQI) is used for representing the overall water quality in the form of a number to qualify its use for domestic, irrigation,...     

A comparison of statistical methods for deriving freshwater quality criteria for the protection of aquatic organisms

Species sensitivity distributions (SSDs) are increasingly used in both ecological risk assessment and derivation of water quality criteria. However, there has been debate about the choice of an appropriate approach for derivation of water quality criteria based on SSDs because the various methods can generate different values. The objective of this study was to compare the differences among various methods. Data sets of acute toxicities of 12 substances to aquatic organisms, representing a range of classes with different modes of action, were studied. Nine typical statistical approaches, including parametric and nonparametric methods, were used to construct SSDs for 12 chemicals. Water quality criteria, expressed as hazardous concentration for 5 % of species (HC₅), were derived by use of several approaches. All approaches produced comparable results, and the data generated by the different approaches were significantly correlated. Variability among estimates of HC₅ of all inclusive species decreased with increasing sample size, and variability was similar among the statistical methods applied. Of the statistical methods selected, the bootstrap method represented the best-fitting model for all chemicals, while log-triangle and Weibull were the best models among the parametric methods evaluated. The bootstrap method was the primary choice to derive water quality criteria when data points are sufficient (more than 20). If the available data are few, all other methods should be constructed, and that which best describes the distribution of the data was selected.     

Evaluation of air quality zone classification methods based on ambient air concentration exposure

Air quality zones are used by regulatory authorities to implement ambient air standards in order to protect human health. Air quality measurements at discrete air monitoring stations are critical tools to determine whether an air quality zone complies with local air quality standards or is noncompliant. This study presents a novel approach for evaluation of air quality zone classification methods by breaking the concentration distribution of a pollutant measured at an air monitoring station into compliance and exceedance probability density functions (PDFs) and then using Monte Carlo analysis with the Central Limit Theorem to estimate long-term exposure. The purpose of this paper is to compare the risk associated with selecting one ambient air classification approach over another by testing the possible exposure an individual living within a zone may face. The chronic daily intake (CDI) is utilized to compare different pollutant exposures over the classification duration of 3 years between two classification methods. Historical data collected from air monitoring stations in Kuwait are used to build representative models of 1-hr NO₂ and 8-hr O₃ within a zone that meets the compliance requirements of each method. The first method, the “3 Strike” method, is a conservative approach based on a winner-take-all approach common with most compliance classification methods, while the second, the 99% Rule method, allows for more robust analyses and incorporates long-term trends. A Monte Carlo analysis is used to model the CDI for each pollutant and each method with the zone at a single station and with multiple stations. The model assumes that the zone is already in compliance with air quality standards over the 3 years under the different classification methodologies. The model shows that while the CDI of the two methods differs by 2.7% over the exposure period for the single station case, the large number of samples taken over the duration period impacts the sensitivity of the statistical tests, causing the null hypothesis to fail. Local air quality managers can use either methodology to classify the compliance of an air zone, but must accept that the 99% Rule method may cause exposures that are statistically more significant than the 3 Strike method.

Implications: A novel method using the Central Limit Theorem and Monte Carlo analysis is used to directly compare different air standard compliance classification methods by estimating the chronic daily intake of pollutants. This method allows air quality managers to rapidly see how individual classification methods may impact individual population groups, as well as to evaluate different pollutants based on dosage and exposure when complete health impacts are not known.