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Development and testing of an efficient micropollutant monitoring strategy across a large watershed
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Background
The European Water Framework Directive foresees the establishment of emission inventories for micropollutants (MP) to facilitate an evidence-based development of mitigation measures. Regionalized pathway analysis constitutes a moderately data-intensive approach to quantify the contribution of different pathways to the total pollution of surface waters. So far, only few European member states have created an inventory that includes diffuse pathways. The fundamental basis to enable it is an accessible, well-structured and harmonized database with data on the concentration of MPs in multiple compartments, such as soils, groundwater, atmospheric deposition and urban systems. Combined with the water and suspended substance balance in river basins, such data enables the estimation of emission loads via specific pathways. In the Danube River Basin, but in general in Europe, a public data management platform with such scope and criteria is still lacking.
Results
We collected and harmonized MP measurements across multiple compartments and countries together with key metadata, harmonized and combined them into a new database. The resulting tool, available for download, facilitates the assessment of current data availability, in terms of quantity and quality. For example, while the majority of available data stems from groundwater and surface water, other highly relevant compartments are scarcely represented. By examining differences in MP concentration level across compartments, the database can lead to understand the relevance of specific emission pathways and thus to prioritize data-retrieval and calculation efforts in modelling applications. Selected examples show how to exploit the metadata associated to the measurements to extrapolate the results to regions not covered by specific monitoring programmes. For example, PFAS concentrations in treated wastewater show significant dependence on the design capacity of the treatment plant.
Conclusions
This study showcases how such database can support the setup of emission inventories, guide data providers and national authorities in prioritizing the allocation of resources for new surveys and in optimizing their national data collection and management systems. The process tested showed a great need for enhanced data literacy across countries and institutions to increase data availability and quality to secure the exploitation of the full information potential generated via monitoring programmes.
Zinc (Zn) is essential to sustain crop production and human health, while it can be toxic when present in excess. In this manuscript, we applied a machine learning model on 21,682 soil samples from the Land Use and Coverage Area frame Survey (LUCAS) topsoil database of 2009/2012 to assess the spatial distribution in Europe of topsoil Zn concentrations measured by aqua regia extraction, and to identify the influence of natural drivers and anthropogenic sources on topsoil Zn concentrations. As a result, a map was produced showing topsoil Zn concentrations in Europe at a resolution of 250 m. The mean predicted Zn concentration in Europe was 41 mg kg-1, with a root mean squared error of around 40 mg kg-1 calculated for independent soil samples. We identified clay content as the most important factor explaining the overall distribution of soil Zn in Europe, with lower Zn concentrations in coarser soils. Next to texture, low Zn concentrations were found in soils with low pH (e.g. Podzols), as well as in soils with pH above 8 (i.e., Calcisols). The presence of deposits and mining activities mainly explained the occurrence of relatively high Zn concentrations above 167 mg kg-1 (the one percentile highest concentrations) within 10 km from these sites. In addition, the relatively higher Zn levels found in grasslands in regions with high livestock density may point to manure as a significant source of Zn in these soils. The map developed in this study can be used as a reference to assess the eco-toxicological risks associated with soil Zn concentrations in Europe and areas with Zn deficiency. In addition, it can provide a baseline for future policies in the context of pollution, soil health, human health, and crop nutrition.
An inadvertent consequence of pesticide use is aquatic pesticide pollution, which has prompted the implementation of mitigation measures in many countries. Water quality monitoring programs are an important tool to evaluate the efficacy of these mitigation measures. However, large interannual variability of pesticide losses makes it challenging to detect significant improvements in water quality and to attribute these improvements to the application of specific mitigation measures. Thus, there is a gap in the literature that informs researchers and authorities regarding the number of years of aquatic pesticide monitoring or the effect size (e.g., loss reduction) that is required to detect significant trends in water quality. Our research addresses this issue by combining two exceptional empirical data sets with modelling to explore the relationships between the achieved pesticide reduction levels due to mitigation measures and the length of the observation period for establishing statistically significant trends. Our study includes both a large (Rhine at Basel, ~36,300 km2) and small catchment (Eschibach, 1.2 km2), which represent spatial scales at either end of the spectrum that would be realistic for monitoring programs designed to assess water quality. Our results highlight several requirements in a monitoring program to allow for trend detection. Firstly, sufficient baseline monitoring is required before implementing mitigation measures. Secondly, the availability of pesticide use data helps account for the interannual variability and temporal trends, but such data are usually lacking. Finally, the timing and magnitude of hydrological events relative to pesticide application can obscure the observable effects of mitigation measures (especially in small catchments). Our results indicate that a strong reduction (i.e., 70-90 %) is needed to detect a change within 10 years of monitoring data. The trade-off in applying a more sensitive method for change detection is that it may be more prone to false-positives. Our results suggest that it is important to consider the trade-off between the sensitivity of trend detection and the risk of false positives when selecting an appropriate method and that applying more than one method can provide more confidence in trend detection.
Direct and indirect threats by organic micropollutants can only be reliably assessed and prevented if the exposure to these chemicals is known, which in turn requires a confident estimate of their emitted amounts into the environment. APIs (Active Pharmaceutical Ingredients) enter surface waters mostly through the sewer system and wastewater treatment plants (WWTPs). However, their effluent fluxes are highly variable and influenced by several different factors that challenge robust emission estimates. Here, we defined a dimensionless, theoretically consumption-independent 'escape factor' (kesc) for estimating the amount of APIs (expected to be) present in WWTP effluents. The factor is determined as the proportion of marketed and actually emitted amounts of APIs. A large collection of German and Swiss monitoring datasets were analyzed to calculate stochastic kesc values for 31 APIs, reflecting both the magnitude and uncertainty of consumption-normalised emissions. Escape factors provide an easy-to-use tool for the estimation of average API emissions and expected variability from numerous WWTPs given that consumption data are provided, thereby supporting simulation modeling of the fate of APIs in stream networks or exposure assessments.
The EU Commission published on the 26th of October 2022 its proposal for amending three central water management Directives, the Water Framework Directive, the Groundwater Directive, and the Directive on Environmental Quality Standards. The proposal introduces a series of amendments and changes to remedy shortcomings that were identified in the previous fitness check of the European water legislation and to align the legal framework with the scientific and technical progress of the last decades. This commentary briefly summarizes and evaluates the new elements that are most relevant from a toxicological and ecotoxicological perspective.
The Commission proposal substantially extends the list of WFD priority substances and now includes 68 substances and substance groups. It also identifies five substances and substance groups as a priority for groundwater management. In several instances, generic sum-EQS values are suggested for selected substance groups, an approach that lacks scientific underpinning and might not always be sufficiently protective. EQS values for substances groups are certainly needed, but are better set using relative potency factors or other implementations of the Concentration Addition concept. The Commission proposal employs this approach for setting groupwise EQS values for PFAS chemicals and PAHs and it should be systematically applied also to other groups of priority substances.
Effect-based methods (EBMs) are now included in the legal text of the WFD, which is highly welcome. However, the Commission proposal limits EBMs to explorative studies and does not include the setting of EQS values based on EBM-methods.
Revising the major legislative frameworks offers opportunities to streamline water pollution management in the spirit of the “one substance, one assessment” idea. Further details on how substance evaluations performed in the context of water management can be harmonized with those performed by EFSA, ECHA and EMA during substance registration and authorization would have been welcome.
Identifying a chemical's potential for biotransformation in the aquatic environment is crucial to predict its fate and manage its potential hazards. Due to the complexity of natural water bodies, especially river networks, biotransformation is often studied in laboratory experiments, assuming that study outcomes can be extrapolated to compound behavior in the field. Here, we investigated to what extent outcomes of laboratory simulation studies indeed reflect biotransformation kinetics observed in riverine systems. To determine in-field biotransformation, we measured loads of 27 wastewater treatment plant effluent-borne compounds along the Rhine and its major tributaries during two seasons. Up to 21 compounds were detected at each sampling location. Measured compound loads were used in an inverse model framework of the Rhine river basin to derive k'bio,field values - a compound-specific parameter describing the compounds' average biotransformation potential during the field studies. To support model calibration, we performed phototransformation and sorption experiments with all the study compounds, identifying 5 compounds that are susceptible towards direct phototransformation and determining Koc values covering four orders of magnitude. On the laboratory side, we used a similar inverse model framework to derive k'bio,lab values from water-sediment experiments run according to a modified OECD 308-type protocol. The comparison of k'bio,lab and k'bio,field revealed that their absolute values differed, pointing towards faster transformation in the Rhine river basin. Yet, we could demonstrate that relative rankings of biotransformation potential and groups of compounds with low, moderate and high persistence agree reasonably well between laboratory and field outcomes. Overall, our results provide evidence that laboratory-based biotransformation studies using the modified OECD 308 protocol and k'bio values derived thereof bear considerable potential to reflect biotransformation of micropollutants in one of the largest European river basins.
Aquatic pesticide pollution is an important issue worldwide. Countries rely on monitoring programs to observe water bodies quality and on models to evaluate pesticide risks for entire stream networks. Measurements are typically sparse and discontinuous which lead to issues in quantifying pesticide transport at the catchment scale. Therefore, it is essential to assess the performance of extrapolation approaches and provide guidance on how to extend monitoring programs to improve predictions. Here we present a feasibility study to predict pesticide levels in a spatially explicit manner in the Swiss stream network based on the national monitoring program quantifying organic micropollutants at 33 sites and spatially distributed explanatory variables. Firstly, we focused on a limited set of herbicides used on corn crops. We observed a significant relationship between herbicide concentrations and the areal fraction of hydrologically connected cornfields. Neglecting connectivity revealed no influence of areal corn coverage on the herbicide levels. Considering chemical properties of the compounds slightly improved the correlation. Secondly, we analysed a set of 18 pesticides widely used on different crops and monitored across the country. In this case, the areal fractions of arable or crop lands showed significant correlations with average pesticide concentrations. Similar results were found with average annual discharge or precipitation if two outlier sites were neglected. The correlations found in this paper explained only about 30 % of the observed variance leaving most of the variability unexplained. Accordingly, extrapolating the results from the existing monitoring sites to the Swiss river network comes with substantial uncertainty. Our study highlights possible reasons for weak matches, such as missing pesticide application data, limited set of compounds in the monitoring program, or a limited understanding of factors differentiating the loss rates from different catchments. Improving the data on pesticide applications will be essential to progress in this regard.
Polycyclic aromatic hydrocarbons (PAHs) are contaminants introduced by different pathways in the marine ecosystem, affecting both aquatic and sediment bodies. Identification of their sources is of vital importance for protecting the marine ecosystem. The attribution of the pollution sources is usually made by using diagnostic molecular ratios of PAHs isomers. The reliability of this approach diminishes when PAHs contents are measured far from their original source, for example in water bodies or in bottom sediments. Conventionally the source attribution is based on time consuming univariate methods. In the present work coupling of molecular ratios with advanced supervised statistical techniques was used to increase the accuracy of the PAH source attribution in bottom sediments. Data on PAHs distribution within 5 port areas, with known pattern port activity, were collected. Evaluation of multiple PAHs ratios at once by means of supervised OPLS-DA technique was performed. A robust descriptive and predictive model was set up and successfully validated. The proposed methodology helps identify PAH transport pathways, highlighting interactions between pollution patterns, port activities and coastal land-use supporting decision makers in defining monitoring and mitigation procedures.
The cement industry is the second largest source of anthropogenic mercury (Hg) emissions in Europe, accounting for 11% of global anthropogenic Hg emissions. The main objective of this study was to examine the influence of Hg emissions from the Salonit Anhovo cement plant on Hg levels measured in the ambient air at Vodarna, 1 km downwind from the flue gas chimney. The findings reveal that the plant raw mill operational status plays an important role in Hg concentrations in the flue gas emitted from the plant. Emitted total gaseous mercury was, on average, higher (49.4 μg/m³) when raw mills were in the direct mode (both raw mills-off) and lower (23.4 μg/m³) in the combined mode (both raw mills-on). The average Hg concentrations in Vodarna were 3.14 ng/m³ for gaseous elemental mercury, 53.7 pg/m³ for gaseous oxidised mercury, and 41.9 pg/m³ for particulate bound mercury for the whole measurement period. Atmospheric Hg speciation in Vodarna, coupled with plant emissions and wind data, has revealed that the total gaseous mercury emitted from the cement plant is clearly related to all Hg species measured in Vodarna. Wind blowing from the northeastern quadrant (mostly NE, ENE) is responsible for the elevated Hg levels in Vodarna, where gaseous oxidised mercury levels are highly linked to the cement plant emissions. However, elevated levels of Hg species in the absence of northeastern winds indicate potential inputs from other unknown local sources as well as inputs from regional and global transport mechanisms.
Surface water pollution with poly- and perfluorinated compounds (PFAS) is a well-recognized problem, but knowledge about contribution of different emission pathways, especially diffuse ones, is very limited. This study investigates the potential of the pathway oriented MoRE model in shedding light on the relevance of different emission pathways on regional scale and in predicting concentrations and loads in unmonitored rivers. Modelling was supported with a tailor-made monitoring programme aimed to fill gaps on PFAS concentration in different environmental compartments. The study area covers the whole Austrian territory including some additional transboundary catchments and it focuses on perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). These two PFAS are regulated and therefore their production and use in Europe are currently decreasing. Nevertheless, these compounds are still emitted into the environment via legacy pollution and as transformation products from other PFAS. These two compounds were selected for this study in view of the larger information availability compared to other PFAS. Despite considerable uncertainties in the input data, model validations show that this approach performs significantly better than previous modelling frameworks based on population-specific emission factors, population density and wastewater treatment plant information. The study reveals the predominance of emissions via municipal wastewater treatment plants for PFOS and a relevant role of diffuse emission pathways for PFOA. Results suggest that unpaved areas contribute the biggest share to total diffuse emissions, but the estimation of these pathways is affected by the highest uncertainty in the input data and requires better input data from monitoring. Once the currently growing substance-specific data sets on the concentration of PFAS, others than PFOS and PFOA, in different environmental compartments, will reach an adequate quality, the model presented here will be easily applicable to them.
We submit that the safe operating space of the planetary boundary of novel entities is exceeded since annual production and releases are increasing at a pace that outstrips the global capacity for assessment and monitoring. The novel entities boundary in the planetary boundaries framework refers to entities that are novel in a geological sense and that could have large-scale impacts that threaten the integrity of Earth system processes. We review the scientific literature relevant to quantifying the boundary for novel entities and highlight plastic pollution as a particular aspect of high concern. An impact pathway from production of novel entities to impacts on Earth system processes is presented. We define and apply three criteria for assessment of the suitability of control variables for the boundary: feasibility, relevance, and comprehensiveness. We propose several complementary control variables to capture the complexity of this boundary, while acknowledging major data limitations. We conclude that humanity is currently operating outside the planetary boundary based on the weight-of-evidence for several of these control variables. The increasing rate of production and releases of larger volumes and higher numbers of novel entities with diverse risk potentials exceed societies’ ability to conduct safety related assessments and monitoring. We recommend taking urgent action to reduce the harm associated with exceeding the boundary by reducing the production and releases of novel entities, noting that even so, the persistence of many novel entities and/or their associated effects will continue to pose a threat.
In this review, we examined the European legislative context on water protection concerning pesticide residues monitoring and the relevant National Action Plans and strategies that were undertaken in European countries to better identify and manage the problem in water bodies.
Furthermore, we illustrated the development of analytical methodologies and criticalities connected to determine pesticide residues in water matrices, including sampling, sample preparation approaches, instrumental techniques and specific applications emphasising those works published after 2015.
Details about sampling strategies, analytical feasibility, official methods, degradation products and behaviour in the environment for a subset of 160 pesticides are also provided.
Mapping of surface soil Hg concentrations, a priority pollutant, at continental scale is important in order to identify hotspots of soil Hg distribution (e.g. mining or industrial pollution) and identify factors that influence soil Hg concentrations (e.g. climate, soil properties, vegetation). Here we present soil Hg concentrations from the LUCAS topsoil (0-20 cm) survey including 21591 samples from 26 European Union countries (one sample every ~200 km²). Deep Neural Network (DNN) learning models were used to map the European soil Hg distribution. DNN estimated a median Hg concentration of 38.3 μg kg⁻¹ (2.6 to 84.7 μg kg⁻¹) excluding contaminated sites. At continental scale, we found that soil Hg concentrations increased with latitude from north to south and with altitude. A GLMM revealed a correlation (R² = 0.35) of soil Hg concentrations with vegetation activity, normalized difference vegetation index (NDVI), and soil organic carbon content. This observation corroborates the importance of atmospheric Hg⁰ uptake by plants and the build-up of the soil Hg pool by litterfall over continental scales. The correlation of Hg concentrations with NDVI was amplified by higher soil organic matter content, known to stabilize Hg in soils through thiol bonds. We find a statistically significant relation between soil Hg levels and coal use in large power plants, proving that emissions from power plants are associated with higher mercury deposition in their proximity. In total 209 hotspots were identified, defined as the top percentile in Hg concentration (>422 μg kg⁻¹). 87 sites (42 % of all hotspots) were associated with known mining areas. The sources of the other hotspots could not be identified and may relate to unmined geogenic Hg or industrial pollution. The mapping effort in the framework of LUCAS can serve as a starting point to guide local and regional authorities in identifying Hg contamination hotspots in soils.
Implementation of an extensive urban runoff monitoring program, targeting the quantification of heavy metal and organic micropollutant loads, necessitated the development of an autonomous water sampler. The design requirements for the device were to fulfill flow-proportional continuous composite sampling of urban runoff events in a widely customizable, relatively inexpensive, and simple way. In this paper, we introduce the concept along with the experiences gained from the first several months of field tests at seven pilot areas in Hungary that represent a wide range of urban environments. During the test period, prototype samplers were placed in natural (urban) streams as well as stormwater drainage pipes, resulting in a total of 97 automatic composite runoff samples. At two sites, an additional 28 manual grab samples were collected to represent time series from five distinct runoff events. Sampling efficiency was checked by comparing collected volumes with the theoretical ones (derived from pump mileage data). Ranges and ratios of concentrations measured from composite and grab samples were graphically interpreted in order to evaluate their representativeness. It has been shown that the concept is suitable for conducting cost-effective urban runoff characterization surveys targeting inter-event variability.
Knowledge of exposure to a wide range of chemicals, and the spatio-temporal variability thereof, is urgently needed in the context of protecting and restoring aquatic ecosystems. This paper discusses a computational material flow analysis to predict the occurrence of thousands of man-made organic chemicals on a European scale, based on a novel temporally and spatially resolved modelling framework. The goal was to increase understanding of pressures by emerging chemicals and to complement surface water monitoring data. The ambition was to provide a first step towards a “real-life” mixture exposure situation accounting for as many chemicals as possible. Comparison of simulated concentrations and chemical monitoring data for 226 substance/basin combinations showed that the simulated concentrations were accurate on average. For 65% and 90% of substance/basin combinations the error was within one and two orders of magnitude respectively. An analysis of the relative importance of uncertainties revealed that inaccuracies in use volume or use type information contributed most to the error for individual substances. To resolve this, we suggest better registration of use types of industrial chemicals, investigation of presence/absence of industrial chemicals in wastewater and runoff samples and more scientific information exchange.
The contamination of waters with nutrients, especially nitrogen and phosphorus originating from various diffuse and point sources, has become a worldwide issue in recent decades. Due to the complexity of the processes involved, watershed models are gaining an increasing role in their analysis. The goal set by the EU Water Framework Directive (to reach "good status" of all water bodies) requires spatially detailed information on the fate of contaminants. In this study, the watershed nutrient model MONERIS was applied to the Hungarian part of the Danube River Basin. The spatial resolution was 1078 water bodies (mean area of 86 km 2); two subsequent 4 year periods (2009-2012 and 2013-2016) were modeled. Various elements/parameters of the model were adjusted and tested against surface and subsurface water quality measurements conducted all over the country, namely (i) the water balance equations (surface and subsurface runoff), (ii) the nitrogen retention parameters of the subsurface pathways (excluding tile drainage), (iii) the shallow groundwater phosphorus concentrations, and (iv) the surface water retention parameters. The study revealed that (i) digital-filter-based separation of surface and subsurface runoff yielded different values of these components, but this change did not influence nutrient loads significantly; (ii) shallow groundwater phosphorus concentrations in the sandy soils of Hungary differ from those of the MONERIS default values; (iii) a significant change of the phosphorus in-stream retention parameters was needed to approach measured in-stream phosphorus load values. Local emissions and pathways were analyzed and compared with previous model results.
The European Union Water Framework Directives aims at achieving good ecological status in member states’ water bodies. Insufficient ecological status could be the result of different interacting stressors, among them the presence of many thousands of chemicals. The diagnosis of the likelihood that these chemicals negatively affect the ecological status of surface waters or human health, and the subsequent development of abatement measures usually relies on water quality monitoring. This gives an incomplete picture of chemicals’ contamination, due to the limited number of monitoring stations, samples and substances. Information gaps thus limit the possibilities to protect against and effectively manage chemicals in aquatic ecosystems. The EU FP7 SOLUTIONS project has developed and validated a collection of integrated models (“Model Train”) to increase our understanding of issues related to emerging chemicals in Europe’s river basins and to complement information and knowledge derived from field data. Unlike pre-existing models, the Model Train is suitable to model mixtures of thousands of chemicals, to better approach a “real-life” mixture exposure situation. It can also be used to model new chemicals at a stage where not much is known about them. The application of these models on a European scale provides temporally and spatially variable concentration data to fill gaps in the space, time and substance domains left open by water quality monitoring, and it provides homogeneous data across Europe where water quality data from monitoring are missing. Thus, it helps to avoid overlooking candidate chemicals and possible hot spots for management intervention. The application of the SOLUTIONS Model Train on a European scale presents a relevant line of evidence for water system level prognostic and diagnostic impact assessment related to chemical pollution. The application supports the design of cost-effective programmes of measures by helping to identify the most affected sites and the responsible substances, by evaluating alternative abatement options and by exploring the consequences of future trends.
Occurrence and concentration of a broad spectrum of micropollutants are investigated in Austrian river catchments, namely polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), organotin compounds, perfluoroalkyl acids (PFAAs) and metals. The parallel analysis across multiple environmental and engineered compartments sheds light on the ratio of dissolved and particulate transport and on differences in concentration levels between point and diffuse emission pathways. It is found that some PAHs and organotins are present in rivers, groundwater and bulk deposition at higher concentrations than in municipal wastewater effluents. Among PFAAs and metals, highest concentrations were recorded either in atmospheric deposition or in discharges from wastewater treatment plants. The relevance of the analysis across compartments is best shown by the case of perfluorooctanesulfonic acid (PFOS). Despite municipal wastewater effluents being the emission pathway with highest concentrations, this study reveals that not only rivers, but also atmospheric deposition and groundwater sometimes exceed the environmental quality standard for surface waters. Moreover, this work reveals partially counterintuitive patterns. In rivers with treated wastewater discharges, increasing levels of dissolved compounds were measured at rising flow conditions, whereas the opposite would be expected owing to the dilution effect. This might derive from the mobilisation from soil or suspended particulate matter or rather find its explanation in high concentrations in atmospheric deposition. These hypotheses require however being tested through targeted studies. Additional future research includes the analysis of how regional or catchment specific characteristics might alter the relative importance of different emission pathways, and the modelling of emission and river loads to assess their relative contribution to river pollution.
Impairment of water quality by organic micropollutants such as pesticides, pharmaceuticals or household chemicals is a problem in many catchments worldwide. These chemicals originate from different urban and agricultural usages and are transferred to surface waters from point or diffuse sources by a number of transport pathways. The quantification of this form of pollution in streams is challenging and especially demanding for diffuse pollution due to the high spatio-temporal concentration dynamics, which require large sampling and analytical efforts to obtain representative data on the actual water quality.
Models can also be used to predict to what degree streams are affected by these pollutants. However, spatially distributed modelling of water quality is challenging for a number of reasons. Key issues are the lack of such models that incorporate both urban and agricultural sources of organic micropollutants, the large number of parameters to be estimated for many available water quality models, and the difficulty to transfer parameter estimates from calibration sites to areas where predictions are needed.
To overcome these difficulties, we used the parsimonious iWaQa model that simulates herbicide transport from agricultural fields and diffuse biocide losses from urban areas (mainly façades and roof materials) and tested its predictive capabilities in the Rhine River basin. The model only requires between one and eight global model parameters per compound that need to be calibrated. Most of the data requirements relate to spatially distributed land use and comprehensive time series of precipitation, air temperature and spatial data on discharge. For larger catchments, routing was explicitly considered by coupling the iWaQa to the AQUASIM model.
The model was calibrated with datasets from three different small catchments (0.5–24.6 km2) for three agricultural herbicides (isoproturon, S-metolachlor, terbuthylazine) and two urban biocides (carbendazim, diuron). Subsequently, it was validated for herbicides and biocides in Switzerland for different years on 12 catchments of much larger size (31–35 899 km2) and for herbicides for the entire Rhine basin upstream of the Dutch–German border (160 000 km2) without any modification. For most compound–catchment combinations, the model predictions revealed a satisfactory correlation (median r2: 0.5) with the observations. The peak concentrations were mostly predicted within a factor of 2 to 4 (median: 2.1 fold difference for herbicides and 3.2 for biocides respectively). The seasonality of the peak concentration was also well simulated; the predictions of the actual timing of peak concentrations, however, was generally poor.
Limited spatio-temporal data, first on the use of the selected pesticides and second on their concentrations in the river network, restrict the possibilities to scrutinize model performance. Nevertheless, the results strongly suggest that input data and model structure are major sources of predictive uncertainty. The latter is for example seen in background concentrations that are systematically overestimated in certain regions, which is most probably linked to the modelled coupling of background concentrations to land use intensity.
Despite these limitations the findings indicate that key drivers and processes are reasonably well approximated by the model and that such a simple model that includes land use as a proxy for compound use, weather data for the timing of herbicide applications and discharge or precipitation as drivers for transport is sufficient to predict the timing and level of peak concentrations within a factor of 2 to 3 in a spatially distributed manner at the scale of large river basins.
Copper (Cu) distribution in soil is influenced by climatic, geological and pedological factors. Apart from geological sources and industrial pollution, other anthropogenic sources, related to the agricultural activity, may increase copper levels in soils, especially in permanent crops such as olive groves and vineyards. This study uses 21,682 soil samples from the LUCAS topsoil survey to investigate copper distribution in the soils of 25 European Union (EU) Member States.
Generalized Linear Models (GLM) were used to investigate the factors driving copper distribution in EU soils. Regression analysis shows the importance of topsoil properties, land cover and climate in estimating Cu concentration. Meanwhile, a copper regression model confirms our hypothesis that different agricultural management practices have a relevant influence on Cu concentration. Besides the traditional use of copper as a fungicide for treatments in several permanent crops, the combined effect of soil properties such as high pH, soil organic carbon and clay, with humid and wet climatic conditions favours copper accumulation in soils of vineyards and tree crops. Compared to the overall average Cu concentration of 16.85 mg kg−1, vineyards have the highest mean soil Cu concentration (49.26 mg kg−1) of all land use categories, followed by olive groves and orchards.
Water analysis has been an important area since the beginning of analytical chemistry. The focus though has shifted substantially: from minerals and the main constituents of water in the time of Carl Remigius Fresenius to a multitude of, in particular, organic compounds at concentrations down to the sub-nanogram per liter level nowadays. This was possible only because of numerous innovations in instrumentation in recent decades, drivers of which are briefly discussed. In addition to the high demands on sensitivity, high throughput by automation and short analysis times are major requirements. In this article, some recent developments in the chemical analysis of organic micropollutants (OMPs) are presented. These include the analysis of priority pollutants in whole water samples, extension of the analytical window, in particular to encompass highly polar compounds, the trend toward more than one separation dimension before mass spectrometric detection, and ways of coping with unknown analytes by suspect and nontarget screening approaches involving high-resolution mass spectrometry. Furthermore, beyond gathering reliable concentration data for many OMPs, the question of the relevance of such data for the aquatic system under scrutiny is becoming ever more important. To that end, effect-based analytics can be used and may become part of future routine monitoring, mostly with a focus on adverse effects of OMPs in specific test systems mimicking environmental impacts. Despite advances in the field of water analysis in recent years, there are still many challenges for further analytical research.
Graphical abstractRecent trends in water analysis of organic micropollutants that open new opportunities in future water monitoring. HRMS high-resolution mass spectrometry, PMOC persistent mobile organic compounds
This paper presents the results of a field campaign that was aimed to assess the total amount and the spatial variation in the cross-sectional surface loads of four selected heavy metals (Zn, Cu, Pb and Sb) at three different locations of a downtown street at Budapest, Hungary. The distribution of surface loads were found to be determined by their prevailing emission source: brake wear dominated metals show distinctive cross-sectional gradients (depending on traffic dynamics) and are only above the background values at the curbside, while tire wear dominated ones feature only a weak gradient and are consistently higher than the background values, over the entire road surface. The relative strength of post-precipitation resuspension was further investigated in the case of principally airborne brake-emitted particles by studying the changes in the ratios of selected metals in dry and wet roadside dust samples, in comparison with the typical values for urban road runoff. The results suggest that roughly 70% of brake-emitted metals that are left behind by the curb after a rainfall event will return into the atmosphere by resuspension as the wet dust dries up. The improved insight into this process has important implications on the effectiveness of stormwater treatment technologies.
Agrochemicals have enabled to more than duplicate food production during the last century, and the current need to increase food production to feed a rapid growing human population maintains pressure on the intensive use of pesticides and fertilizers. However, worldwide surveys have documented the contamination and impact of agrochemical residues in soils, and terrestrial and aquatic ecosystems including coastal marine systems, and their toxic effects on humans and nonhuman biota. Although persistent organic chemicals have been phased out and replaced by more biodegradable chemicals, contamination by legacy residues and recent residues still impacts on the quality of human food, water, and environment. Current and future increase in food production must go along with production of food with better quality and with less toxic contaminants. Alternative paths to the intensive use of crop protection chemicals are open, such as genetically engineered organisms, organic farming, change of dietary habits, and development of food technologies. Agro industries need to further develop advanced practices to protect public health, which requires more cautious use of agrochemicals through prior testing, careful risk assessment, and licensing, but also through education of farmers and users in general, measures for better protection of ecosystems, and good practices for sustainable development of agriculture, fisheries, and aquaculture. Enhanced scientific research for new developments in food production and food safety, as well as for environmental protection, is a necessary part of this endeavor. Furthermore, worldwide agreement on good agriculture practices, including development of genetically modified organisms (GMOs) and their release for international agriculture, may be urgent to ensure the success of safe food production. © 2017 John Wiley & Sons Ltd and the Association of Applied Biologists.
An accurate budget of substance emissions is fundamental for protecting freshwater
resources. In this context, the European Union asks all member states to report an emission
inventory of substances for river basins. The river basin management system MoRE (Modeling
of Regionalized Emissions) was developed as a flexible open-source instrument which is able to
model pathway-specific emissions and river loads on a catchment scale. As the reporting tool for
the Federal Republic of Germany, MoRE is used to model annual emissions of nutrients, heavy
metals, micropollutants like polycyclic aromatic hydrocarbons (PAH), Bis(2-ethylhexyl)phthalate
(DEHP), and certain pharmaceuticals. Observed loads at gauging stations are used to validate the
calculated emissions. In addition to its balancing capabilities, MoRE can consider different variants
of input data and quantification approaches, in order to improve the robustness of different modeling
approaches and to evaluate the quality of different input data. No programming skills are required
to set up and run the model. Due to its flexible modeling base, the effect of reduction measures can
be assessed. Within strategic planning processes, this is relevant for the allocation of investments or
the implementation of specific measures to reduce the overall pollutant emissions into surface water
bodies and therefore to meet the requirements of water policy.
Over 2000 surface, ground and raw drinking water samples have been analyzed in the frame of different monitoring projects in Hungary and watercourses in neighboring countries between 1990 and 2015. Effects of pesticide contamination on ecological farming and drinking water supply have been assessed. Main water pollutant ingredients of agricultural origin in Hungary are herbicides related to maize production. After EU pesticide re-registration, diazinon, atrazine, and trifluralin gradually disappeared as contaminants. High levels of water soluble pollutants (e.g., acetochlor) in surface water result in temporarily enhanced levels in raw drinking water as well. Extreme levels observed for herbicide residues were of agrochemical industrial origin.
The need to reduce pollution to levels that minimize adverse effects on human health involve the monitoring of air quality, including dry depositions and their metal content. The analysis of these parameters aims to investigate the air quality in Maramures County (with nonferrous mining activities) and in the Romanian - Ukraine transboundary area. The paper presents the experimental results obtained for dry atmospheric deposition of copper and zinc using flame atomic absorption spectrometry (FAAS). The samples were collected from four location/cities of Maramures County (Baia Mare, Sighetu Marmatiei, Viseu de Sus and Borsa) during May-October 2014. The highest average values of copper concentration in the dry depositions were found in Baia Mare (199.88 μg/g), that is the most important industrial centre in Maramures County, followed by Borsa (111.49 μg/g), that used to be a nonferrous mining centre. In Viseu de Sus and Sighetu Marmatiei the average concentrations of copper in the dry depositions were lower: 75.63 μg/g and 64.26 μg/g, respectively. Zn average concentrations in dry depositions were 6.4-12 times higher than Cu concentrations. In Viseu de Sus and Borsa relative high values of Pearson correlation coefficients between the logarithm of Cu and Zn content in the dry deposition were found (0.702 and 0.737, respectively) estimating that both pollutants in the ambient air have the same sources, probably the re-suspension of the dust from the tailing ponds. This study is implemented within the frame of ENPI Cross-border Cooperation Programme Hungary-Slovakia-Romania-Ukraine 2007-2013, in the project Clean Air Management in the Romania-Ukraine Transboundary Area - (CLAMROUA), financed by the European Union
One and a half year long field sampling was established in order to evaluate the contamination of storm water runoff. The event means (EMC) total petroleum hydrocarbons (TPH) concentration of the runoff was a function of the actual traffic intensity and the rainfall depth. It was concluded that this TPH, of which dominant component is the engine-oil (characteristically C28) does not form an oil-in-water' type emulsion in the condition of normal motorway-operation, but is interlocked to asphalt, rubber and soot particles of maximum some ten microns size. This condition influences the possibility, way and extent of separation alike. The separation equipments and their sizing applied so far are not suitable to achieve efficient surface water protection. Practical prevention method of accidental type environment pollution was also suggested. On the basis of the international literature evaluation, technical solutions capable to decrease the runoff pollution were summarized. Among these, useful calculation method was developed for designers to determine the sufficient storage capacity (water quality volume) of reservoirs applied for water quality protection. Monitoring technique of runoffs, which are characterized time dependent, variable pollutant concentrations by their nature, was proposed. It was stated that the administrative regulation should aim at the EMC instead of current concentration. Beside TPH information was gained on polycyclic aromatic hydrocarbons (PAHs), suspended solids, heavy metals, pH, and nutrient (N, P) pollution of the runoff, which are valuable for the grounding of further research results.
Polycyclic aromatic hydrocarbons (PAHs) were measured in atmospheric deposition in a Nature Park located in the North of Spain over a period of one year (June 2010-May 2011). Total PAH deposition was evaluated monthly by combining samples collected over two-week periods, using 6 throughfall and 2 bulk precipitation collectors distributed over the study area. The latter consisted of glass funnels (with vertical sides) attached to Pyrex glass bottles. PAH determination was performed by liquid-liquid extractions and analysis by high-performance liquid chromatography associated with fluorescence detection. Throughfall deposition revealed a loss under the canopy of 12% of the total atmospheric PAH deposition due to precipitation interception. Spatial variability between the 6 throughfall collectors reached a maximum of 25% during the wet season. Temporal trends showed significant variations of 27 to 54% throughout the year. PAH deposition increased during winter, due to higher emissions from domestic heating, less photoreactivity of the compounds and intense leaching of the atmosphere by wet deposition. Average daily fluxes were estimated for 6 quantified PAHs (PHE, ANT, PYR, B(b)F, B(k)F and B(a)P) at 182 ± 27 ng m-2 d-1, which agreed with studies previously carried out in other local rural areas. The major compounds were phenanthrene and pyrene, both markers of traffic emissions.
Parent and alkyl PAHs (51 compounds and alkyl homologues) have been quantified in suspended particulates and sediments (345 samples) from the Fraser River system, British Columbia, Canada. The best potential to distinguish natural and anthropogenic sources is exhibited by ratios of the principal mass 178, 202, 228 and 276 parent PAHs, 1,7/2,6+1,7-DMP (dimethylphenanthrene), the phenanthrene/anthracene and fluoranthene/pyrene alkyl PAH series and several less commonly applied PAHs (e.g. acephenanthrylene and pentaphene). Using these ratios we infer sources of PAH to the Fraser basin and evaluate the consistency of these source assignments and the suitability of various commonly applied PAH ratios as indicators. PAH ratios and total concentration data reveal a basin lightly impacted by a variety of sources in its remote regions, especially near roads, but heavily impacted in urban areas, particularly near Vancouver. Contamination sources shift from biomass (e.g. wood and grass) burning to vehicle emissions between remote and urban locations. Stormwater and wastewater discharges appear to collect PAH from urban areas and release them as point sources. In contaminated areas ratios are specific for combustion vs. petroleum sources, and some ratios (202 and 276) distinguish biomass or coal from liquid fossil fuel combustion. At lower concentrations multiple sources at times make interpretations based on a single ratio misleading and the higher mass ratios (228 and 276) may be most applicable to urban areas. In all cases the examination of a variety of PAH indicator ratios that encompass a range of masses is necessary for a robust interpretation.
Due to the potential ecological and human health risks, pharmaceuticals and personal care products (PPCPs) are considered as contaminants of emerging concern. PPCPs can be discharged to the aquatic environment from various sources, including municipal wastewater treatment plants (WWTPs), animal feeding operations, hospitals, and pharmaceutical manufacturers. A major challenge to regional characterization of ecological and human health risks is identification of the environmental emissions of PPCPs. This study established a facile approach for calculation of PPCP emission factors from raw wastewater and wastewater effluent. Using reported concentrations from WWTPs, nine PPCPs, namely carbamazepine, ciprofloxacin, erythromycin, ibuprofen, ketoprofen, ofloxacin, sulfadiazine, sulfamethoxazole, and trimethoprim, were identified as priority contaminants based on environmental significance (i.e., high detection frequency and potential ecological risk) and data availability. Emission factors were calculated for the nine PPCPs in raw wastewater, secondary effluent, and tertiary effluent for low, medium and high emission scenarios according to the concentration distributions of these nine PPCPs. The emission factors were used to estimate the mass of the PPCPs discharged from the nine provinces and two municipalities of the Yangtze River valley. The total mass of the nine PPCPs emitted into the watershed was estimated as 3867 kg, 8808 kg and 21,464 kg for low, medium and high emission scenarios respectively in 2018. Although uncertainty is inevitable in the emission factors, the reported approach provides a viable alternative to top-down and multimedia fugacity estimation strategies that require an abundance of sewershed-, WWTP-, and compound-specific information that is difficult to collect in developing countries.
Despite the fact that the occurrence of emerging contaminants in the environment has become frequent in recent decades, the seasonal dynamics of contaminants in different environmental compartments are little studied in protected areas influenced by effluent discharges. In this study, the seasonal and spatial occurrence of 33 pharmaceuticals and personal care products (PPCPs) was investigated in surface waters and sediments from Anil and Bacanga rivers (northeast of Brazil). The studied area is located within a Wetland of International Importance by Ramsar Convention (Amazon Estuary and its Mangroves). Sample preparation was carried out using solid-phase extraction and QuEChERS, for water and sediment samples, respectively and all determinations were performed by liquid chromatography tandem mass spectrometry. Eleven PPCPs were detected in water samples and 14 in sediments. In aqueous samples, caffeine was the most occurring compound reaching 13,798 ng L⁻¹. In addition, high levels of acetaminophen, ibuprofen, sulfamethoxazole, carbamazepine and diclofenac were also observed. In the sediment samples, triclocarban, benzophenone-3, ketoconazole and methylparaben were also detected. The spatial and temporal distribution of the assessed molecules indicates urbanization and anthropic activities as relevant sources of PPCPs in the region. Moreover, the levels of acetaminophen, caffeine, diclofenac, ibuprofen, benzophenone-3, triclosan and triclocarban measured within the Ramsar site pose a high risk to aquatic and terrestrial organisms. These findings indicate potential threats to the allegedly protected biodiversity and, therefore, urgent actions are needed to effectively protect this unique and vulnerable area.
The application of multimedia fugacity models is useful to facilitate understanding of the behaviour of emerging contaminants during wastewater treatment, as well as after their release to the environment. In this paper, twenty-two fugacity modelling applications (reported over 1995-2019) describing the distribution of organic micropollutants in wastewater treatment plants and surface water bodies were analysed in terms of model application and modelling strategy. Disparities and similarities in strategies including selection of micropollutants, data sources for internal and external model inputs, sensitivity and uncertainty analysis, as well as model validation were discussed. This review confirmed that fugacity modelling is very applicable for providing qualitative predictions of the fate and removal of organic micropollutants in the various aqueous systems. However, it was also noted that there are issues related to the uncertainties and sensitivities of fugacity models such as the sources of model inputs and selection of default settings. The issues associated with the uncertainties in the investigated fugacity models are pointed out. Recommendations are given regarding the selection of the sources of model inputs, sensitivity analysis strategies and model validation methods. This review presents the challenges and opportunities for improving multimedia fugacity models, and so paves the way for future research in this field.
Among different stressors like drought, hydro-morphological alterations, and pollution from agricultural activities, nutrients, organic compounds and discharges from wastewater treatment plants (WWTPs), potentially toxic elements (PTE) may also contribute to the overall pollution of the Evrotas River, Greece. Nevertheless, information on pollution of elements in water and sediments in this river is scarcely documented. There is also no information available on the impact of elemental pollution from the aquatic environmental compartments on biota. To fill these gaps, in this study, water, sediment and fish samples were collected from four sampling sites along the Evrotas River under variable flow regimes (July 2015, higher discharge; June 2016, low discharge and September 2016, minimum discharge). Total and dissolved element concentrations in water samples, total and acetic acid extractable contents in sediments, and element concentrations in fish samples were determined by inductively coupled plasma mass spectrometry and significant relationships between samples were established using correlation analysis. The concentrations of PTE (Ni, Cr, Cd, As, Pb, Zn and Cu) in water were generally low, while elevated Ni and Cr contents were found in sediments (up to 150 and 300 mg/kg, respectively), with total Cr concentration in water and sediment being positively correlated. The ecological risk posed by the simultaneous presence of PTE in sediments evaluated by calculating the Probable Effect Concentration Coefficient (PEC-Q), demonstrated that PEC-Qs, which were above the critical value of 0.34, derived mostly from Cr and Ni inputs. Since their mobile sediment fraction was extremely low, Cr and Ni origin is most probably geogenic. The analysis of elements in the target fish species, the Evrotas chub, showed low to moderate PTE concentrations, with Pb being positively correlated with total Pb concentration in water. Moderate Zn concentrations found in fish samples from the Evrotas are possibly derived from pesticides and fertilizers.
Soils deliver crucial ecosystem services, such as climate regulation through carbon (C) storage and food security, both of which are threatened by climate and land use change. While soils are important stores of terrestrial C, anthropogenic impact on the lateral fluxes of C from land to water remains poorly quantified and not well represented in Earth system models. In this study, we tested a novel framework for tracing and quantifying lateral C fluxes from the terrestrial to the aquatic environment at a catchment scale. The combined use of conservative plant-derived geochemical biomarkers n-alkanes and bulk stable δ(13)C and δ(15)N isotopes of soils and sediments allowed us to distinguish between particulate organic C sources from different land uses (i.e. arable and temporary grassland vs. permanent grassland vs. riparian woodland vs. river bed sediments) (p<0.001), showing an enhanced ability to distinguish between land use sources as compared to using just n-alkanes alone. The terrestrial-aquatic proxy (TAR) ratio derived from n-alkane signatures indicated an increased input of terrestrial-derived organic matter (OM) to lake sediments over the past 60years, with an increasing contribution of woody vegetation shown by the C27/C31 ratio. This may be related to agricultural intensification, leading to enhanced soil erosion, but also an increase in riparian woodland that may disconnect OM inputs from arable land uses in the upper parts of the study catchment. Spatial variability of geochemical proxies showed a close coupling between OM provenance and riparian land use, supporting the new conceptualization of river corridors (active river channel and riparian zone) as critical zones linking the terrestrial and aquatic C fluxes. Further testing of this novel tracing technique shows promise in terms of quantification of lateral C fluxes as well as targeting of effective land management measures to reduce soil erosion and promote OM conservation in river catchments.
The contamination of fresh water is a global concern. The huge impact of natural and anthropogenic organic substances that are constantly released into the environment, demands a better knowledge of the chemical status of Earth's surface water. Water quality monitoring studies have been performed targeting different substances and/or classes of substances, in different regions of the world, using different types of sampling strategies and campaigns. This review article aims to gather the available dispersed information regarding the occurrence of priority substances (PSs) and contaminants of emerging concern (CECs) that must be monitored in Europe in surface water, according to the European Union Directive 2013/39/EU and the Watch List of Decision 2015/495/EU, respectively. Other specific organic pollutants not considered in these EU documents as substances of high concern, but with reported elevated frequency of detection at high concentrations, are also discussed. The search comprised worldwide publications from 2012, considering at least one of the following criteria: 4 sampling campaigns per year, wet and dry seasons, temporal and/or spatial monitoring of surface (river, estuarine, lake and/or coastal waters) and ground waters. The highest concentrations were found for: (i) the PSs atrazine, alachlor, trifluralin, heptachlor, hexachlorocyclohexane, polycyclic aromatic hydrocarbons and di(2-ethylhexyl)phthalate; (ii) the CECs azithromycin, clarithromycin, erythromycin, diclofenac, 17α-ethinylestradiol, imidacloprid and 2-ethylhexyl 4-methoxycinnamate; and (iii) other unregulated organic compounds (caffeine, naproxen, metolachlor, estriol, dimethoate, terbuthylazine, acetaminophen, ibuprofen, trimethoprim, ciprofloxacin, ketoprofen, atenolol, Bisphenol A, metoprolol, carbofuran, malathion, sulfamethoxazole, carbamazepine and ofloxacin). Most frequent substances as well as those found at highest concentrations in different seasons and regions, together with available risk assessment data, may be useful to identify possible future PS candidates.
In recent years, many of micropollutants have been widely detected because of continuous input of pharmaceuticals and personal care products (PPCPs) into the environment and newly developed state-of-the-art analytical methods. PPCP residues are frequently detected in drinking water sources, sewage treatment plants (STPs), and water treatment plants (WTPs) due to their universal consumption, low human metabolic capability, and improper disposal. When partially metabolized PPCPs are transferred into STPs, they elicit negative effects on biological treatment processes; therefore, conventional STPs are insufficient when it comes to PPCP removal. Furthermore, the excreted metabolites may become secondary pollutants and can be further modified in receiving water bodies. Several advanced treatment systems, including membrane filtration, granular activated carbon, and advanced oxidation processes, have been used for the effective removal of individual PPCPs. This review covers the occurrence patterns of PPCPs in water environments and the techniques adopted for their treatment in STP/WTP unit processes operating in various countries. The aim of this review is to provide a comprehensive summary of the removal and fate of PPCPs in different treatment facilities as well as the optimum methods for their elimination in STP and WTP systems.
In Central and Eastern Europe huge wastewater treatment (WWT) developments have been carried out in the last 25 years. These include the building and upgrading of wastewater treatment plants (WWTPs), especially extending their lifetimes through nutrient removal and digester gas production. In Hungary, for example, in 1990, 42% of households were connected to a WWT, and this number had increased to 75% by 2015, an increase of 33%. Currently, medium-sized WWTPs with a capacity of up to around 120,000 population equivalent (PE) are facing further development needs, especially in their technical and energy-efficiency aspects. This paper presents the results of a comprehensive investigation program that included 21 WWTPs with capacities ranging from 10,000 to 120,000 PE. The investigations included an evaluation of all important parameters, such as inflowing wastewater (WW) characteristics, mechanical and biological WWT, and effluent wastewater quality and removal efficiency. These were investigated with reference to their electrical energy consumption. The extension of these WWTPs with anaerobic sludge digestion has led to the possibility of producing electricity from digester gas. This prospect is currently of great interest for medium-sized WWTPs and so was also investigated. The results are also compared to international data, standards, and guidelines obtained for this research. As a basis for a development strategy, the main bottleneck areas of design and operation are considered, and further upgrading requirements are explored.
Effective management of water quality in large rivers requires information on the influence of activities within the catchment (urban and rural) throughout the whole river basin. However, traditional water quality monitoring programmes undertaken by individual agencies normally relate to specific objectives, such as meeting quality criteria for wastewater discharges, and fail to provide information on basin-scale impacts, especially in transboundary river basins. Ideally, monitoring in large international river basins should be harmonised to provide a basin-scale assessment of sources and impacts of human activities, and the effectiveness of management actions. This paper examines current water quality issues in the Danube River Basin and evaluates the approach to water quality monitoring in the context of providing information for a basin-wide management plan. Lessons learned from the monitoring programme in the Danube are used to suggest alternative approaches that could result in more efficient generation of water quality data and provide new insights into causes and impacts of variations in water quality in other large international river basins.
Soil contamination is one of the greatest concerns among the threats to soil resources in Europe and globally. Despite of its importance there was only very course scale (1/5000km2) data available on soil heavy metal concentrations prior to the LUCAS topsoil survey, which had a sampling density of 200km2. Based on the results of the LUCAS sampling and auxiliary information detailed and up-to-date maps of heavy metals (As, Cd, Cr, Cu, Hg, Pb, Zn, Sb, Co and Ni) in the topsoil of the European Union were produced. Using the maps of heavy metal concentration in topsoil we made a spatial prediction of areas where local assessment is suggested to monitor and eventually control the potential threat from heavy metals. Most of the examined elements remain under the corresponding threshold values in the majority of the land of the EU. However, one or more of the elements exceed the applied threshold concentration on 1.2Mkm2, which is 28.3% of the total surface area of the EU. While natural backgrounds might be the reason for high concentrations on large proportion of the affected soils, historical and recent industrial and mining areas show elevated concentrations (predominantly of As, Cd, Pb and Hg) too, indicating the magnitude of anthropogenic effect on soil quality in Europe.
This study investigates the variations of polycyclic aromatic hydrocarbon (PAH) levels in surface water, suspended particulate matter (SPM) and sediment upstream and downstream of the discharges of two wastewater treatment plant (WWTP) effluents. Relationships between the levels of PAHs in these different matrices were also investigated. The sum of 16 US EPA PAHs ranged from 73.5 to 728.0 ng L(-1) in surface water and from 85.4 to 313.1 ng L(-1) in effluent. In SPM and sediment, ∑16PAHs ranged from 749.6 to 2,463 μg kg(-1) and from 690.7 μg kg(-1) to 3,625.6 μg kg(-1), respectively. Investigations performed upstream and downstream of both studied WWTPs showed that WWTP discharges may contribute to the overall PAH contaminations in the Loue and the Doubs rivers. Comparison between gammarid populations upstream and downstream of WWTP discharge showed that biota was impacted by the WWTP effluents. When based only on surface water samples, the assessment of freshwater quality did not provide evidence for a marked PAH contamination in either of the rivers studied. However, using SPM and sediment samples, we found PAH contents exceeding sediment quality guidelines. We conclude that sediment and SPM are relevant matrices to assess overall PAH contamination in aquatic ecosystems. Furthermore, we found a positive linear correlation between PAH contents of SPM and sediment, showing that SPM represents an integrating matrix which is able to provide meaningful data about the overall contamination over a given time span.
This article assesses the current challenges to water management in the Tisza River basin. We overview the environmental characteristics of the Tisza river basin and consider the economic setting within which water policy making must be conducted, before characterizing the principal water pollution sources in the region and assessing water quality monitoring data. We then compare the current status of the region's waters to the normative goals for water quality improvement specified in the European Union Water Framework Directive. Lastly, we assess the future outlook for water quality in the Tisza basin, given the current status of water quality in the region and the prospects for successfully implementing water policy objectives.
Praise for the First Edition . . . an excellent addition to an upper-level undergraduate course on environmental statistics, and . . . a 'must-have' desk reference for environmental practitioners dealing with censored datasets. -Vadose Zone Journal. Statistical Methods for Censored Environmental Data Using Minitab® and R, Second Edition introduces and explains methods for analyzing and interpreting censored data in the environmental sciences. Adapting survival analysis techniques from other fields, the book translates well-established methods from other disciplines into new solutions for environmental studies. This new edition applies methods of survival analysis, including methods for interval-censored data to the interpretation of low-level contaminants in environmental sciences and occupational health. Now incorporating the freely available R software as well as Minitab® into the discussed analyses, the book features newly developed and updated material including: A new chapter on multivariate methods for censored data. Use of interval-censored methods for treating true nondetects as lower than and separate from values between the detection and quantitation limits ("remarked data") A section on summing data with nondetects. A newly written introduction that discusses invasive data, showing why substitution methods fail. Expanded coverage of graphical methods for censored data. The author writes in a style that focuses on applications rather than derivations, with chapters organized by key objectives such as computing intervals, comparing groups, and correlation. Examples accompany each procedure, utilizing real-world data that can be analyzed using the Minitab® and R software macros available on the book's related website, and extensive references direct readers to authoritative literature from the environmental sciences. Statistics for Censored Environmental Data Using Minitab® and R, Second Edition is an excellent book for courses on environmental statistics at the upper-undergraduate and graduate levels. The book also serves as a valuable reference for?environmental professionals, biologists, and ecologists who focus on the water sciences, air quality, and soil science.
Groundwater resources in the Pannonian Basin (Hungary, Romania, Croatia and Serbia) are known to contain elevated naturally occurring As. Published estimates suggest nearly 500,000 people are exposed to levels greater than the EU maximum admissible concentration of 10 μg/L in their drinking water, making it the largest area so affected in Europe. In this study, a variety of groundwaters were collected from Romania and Hungary to elucidate the general geochemistry and identify processes controlling As behaviour. Concentrations ranged from <0.5 to 240 μg/L As(tot), with As predominantly in the reduced As(III) form. Using cluster analysis, four main groups of water were identified. Two groups (1 and 2) showed characteristics of water originating from reducing aquifers of the area with both groups having similar ranges of Fe concentrations, indicating that Fe-reduction occurs in both groups. However, As levels and other redox characteristics were very different. Group 1, indicative of waters dominated by methanogenesis contained high As levels (23–208 μg/L, mean 123 μg/L), with group 2 indicative of waters dominated by -reduction containing low As levels (<0.5–58 μg/L, mean 11.5 μg/L). The remaining two groups were influenced either by (i) geothermal and saline or (ii) surface contamination and rain water inputs. Near absence of As in these groups, combined with positive correlations between δ7Li (an indicator of geothermal inputs) and As(tot) in geothermal/saline influenced waters indicate that elevated As is not from an external input, but is released due to an in-aquifer process. Geochemical reasoning, therefore, implies As mobilisation is controlled by redox processes, most likely microbially mediated reductive dissolution of As bearing Fe-oxides, known to occur in sediments from the area. More important is an overlying retention mechanism determined by the presence or absence of . Ongoing -reduction will release S2−, removing As from solution either by the formation of As-sulfides, or from sorption onto Fe-sulfide phases. In methanogenic waters, As released by reductive dissolution is not removed from solution and can rise to the high levels observed. Levels of organic C are thought to be the ultimate control on the redox conditions in these 2 groups. High levels of organic C (as found in group 1) would quickly exhaust any present in the waters, driving the system to methanogenesis and subsequent high levels of As. Group 2 has much lower concentrations of organic C and so is not exhausted. Therefore, As levels in waters of the Pannonian Basin are controlled not by release but by retention mechanisms, ultimately controlled by levels of TOC and in the waters.δD and δ18O analysis showed that groundwaters containing elevated As dated mostly from the last ice-age, and are sourced from Late Pliocene to Quaternary aquifers. The importance of TOC and retention capabilities of -reduction have only previously been suggested for recent (Holocene) sediments and groundwater, most notably those in SE Asia as these are the most likely to contain the right combination of factors to drive the system to a redox situation leading to high aqueous As concentrations. In contrast, it is shown here that a much older system containing As bearing Fe-oxides, also has the potential to produce elevated levels of As if the TOC is suitable for the microbial population to drive the system to the correct redox situation and is either absent or wholly consumed.Graphical abstractElevated As levels in the Pannonian Basin are mainly present in very old (Palaeo) groundwater of methanogenic Pliocene/Quaternary aquifers, which is in contrast to Asian regions where arsenic-enriched groundwater is generally much younger.Research highlights► Arsenic originates from Late Pliocene/Quaternary aquifers and some very old waters. ► Arsenic levels are controlled by both mobilisation and retention mechanisms. ► Mobilisation is caused by biogeochemical reductive dissolution. ► Sufficient sulfate supply triggers arsenic retention in sulfide precipitates. ► Nearly 500,000 people are exposed to elevated arsenic in their drinking water.
In the central part of the Pannonian Basin, factors controlling the distribution of As in sediments and groundwater of the upper 500 m were studied. In core samples, the amounts of As, Fe and Mn extractable with hydroxylamine hydrochloride (NH2OH · HCl) in 25% acetic acid, the proportion of the <0.063 mm size fraction, and the sediment organic C (Corg) contents were measured. In the groundwaters concentrations of As, humic substances, and selected major chemical components were determined. In most core samples extractable Fe, as FeOOH, and Corg are correlated, but some samples have excess Fe, or organic matter. In cases where either excess Fe or excess organic matter is found, the amount of As is also elevated. The spatial distribution of As in the groundwater and the lack of a consistent correlation of As with a single component indicate that there is no single factor controlling the concentration of dissolved As over the entire study area. The only consistent feature is enrichment of As relative to Fe in the groundwater, compared to the sediments. This suggests that the dissolution of Fe minerals, which primarily adsorb As, is not congruent. In reducing conditions Fe(III) oxyhydroxides together with adsorbed As dissolve, and siderite with little or no As precipitates. When sub-regions are separated and studied individually, it can be shown that hydrogeological features of the sediments, the proportions of Fe minerals and sedimentary organic matter, and the concentration of dissolved humic materials, all influence the accumulation and mobilization of As. The significance of the different mobilizing processes, however, and the mean concentration of As, is different in the recharge, through-flow and discharge areas.
In January and March 2000 two tailings dam failures in Maramureş County, northwest Romania, resulted in the release of 200,000 m3 of contaminated water and 40,000 tonnes of tailings into tributaries of the Tisa River, a major tributary of the Danube. The high concentrations of cyanide and contaminant metals released by these dam failures resulted in pollution and fish deaths not only in Romania, but also downstream in the Tisa and Danube rivers within Hungary, Serbia and Bulgaria. Following these accidents, a research programme was initiated in northwest Romania to establish metal levels in rivers affected by the tailings dam failures and to compare these to metal values in river systems contaminated by historic mining and industrial activity. In July 2000, 65 surface water, 65 river sediment and 45 floodplain sediment samples were collected from trunk streams and principal tributaries of the Lapuş/Someş rivers (affected by the January 2000 spill) and the Vişeu/Tisa rivers (affected by the March 2000 Novat spill) down to the Hungarian and Ukrainian borders, respectively. Sample analyses for Pb, Zn Cu and Cd show that metal contamination in surface water and river sediment decreases rapidly downstream away from presently active mines and tailings ponds. Concentrations of heavy metals in water and sediment leaving Romania, and entering Hungary and the Ukraine, generally fall below EC imperative and Dutch intervention values, respectively. However, Zn, Cu and Cd concentrations in river sediments approach or exceed intervention values at the Romanian border. The results of this survey are compared with earlier surveys to ascertain the long-term fate and environmental significance of contaminant metals released by mine tailings dam failures in Maramureş County.