River and lake nutrient targets that support ecological status: European scale gap analysis and strategies for the implementation of the Water Framework Directive.

Eutrophication caused by an excessive presence of nutrients is affecting large portions of European waters with more than 60% of the surface water bodies failing to achieve the primary ambition of water management in Europe, that of good ecological status (GES) with diffuse emission from agriculture being the second most important pressure affecting surface waters. We developed EU wide and regional nutrient targets that define the boundary concentrations between good and moderate status for river and lake total P (TP) and total N (TN) and assessed the gap between actual nutrient concentrations and these targets and considered strategies of nutrient reductions necessary to achieve GES and deliver ecosystem services. The nutrient targets established for rivers ranged from 0.5-3.5 mg/L TN and 11-105 µg/L TP and for lakes 0.5-1.8 mg/L TN and 10-60 µg/L TP. Based on the EU wide targets, 59% of the TN and 57% of the TP river monitoring sites and 64% of the TN and 61% of the TP lake monitoring sites exceed these value and are thus at less than GES. The PCA and step-wise regression for EU basins clearly showed that the basin nutrient export is predominantly related to agricultural inputs. In addition, the step-wise regression models for TN and TP provided the ability to extrapolate the results and quantify the input reductions necessary for reaching the nutrient targets at the EU level. The results suggest that a dual water management strategy would be beneficial and should focus a) on those less polluted rivers and lakes that can easily attain the GES goal and b) on the more highly polluted systems that will improve the delivery of ecosystem services.

Estimation of the uncertainty of hydrologic predictions in a karstic Mediterranean watershed.

The Koiliaris River basin is a semi-arid Mediterranean karstic watershed where water needs during the summer are exclusively covered by the karstic springs flow. Uncertainty assessment of the hydrologic projections for karstic watersheds may reveal possible water deficits that cannot otherwise be taken into account. The Soil Water Assessment Tool (SWAT) along with a karstic model (Karst-SWAT) is used to assess the composite spring and surface flow. The parameter uncertainty of both the surface and karstic flow models is estimated by combining the SUFI2 interface and the @RISK by PALISADE software. Eleven combinations of five Regional Climate Models (RCMs) and three Representative Concentration Pathways (RCPs) provide input to the hydrologic models. Representative rainfall time series for certain scenarios are stochastically modeled with the LARS weather generator. Monte Carlo simulations are used to investigate the effect of input internal variability on the flow output. The uncertainty of karstic flow due to the parameter uncertainty of the SWAT and Karst-SWAT models is 10.0% (Coefficient of Variation), which is comparable to the estimated uncertainty due to climate change scenarios (10.1%) until 2059. The combined uncertainty for the total flow at the basin exit due to both models' parameter uncertainty is 6.6%, comparable to the uncertainty due to the internal variability (5.6%). The total uncertainty of karstic flow, combining model parameter uncertainty and the internal variability of the climate scenarios is 11.0%. The total uncertainty estimate is used in conjunction with the lowest karstic flow projection to assess the most adverse scenario for the future mean annual karstic flow. This is the first study which estimates the combined uncertainty of surface and karstic flow prediction due to model parameter uncertainty and internal variability. Our study provides a rigorous methodology for uncertainty estimation and analysis which is transferable to other karstic regions of the world.

Research questions to facilitate the future development of European long-term ecosystem research infrastructures: A horizon scanning exercise.

Distributed environmental research infrastructures are important to support assessments of the effects of global change on landscapes, ecosystems and society. These infrastructures need to provide continuity to address long-term change, yet be flexible enough to respond to rapid societal and technological developments that modify research priorities. We used a horizon scanning exercise to identify and prioritize emerging research questions for the future development of ecosystem and socio-ecological research infrastructures in Europe. Twenty research questions covered topics related to (i) ecosystem structures and processes, (ii) the impacts of anthropogenic drivers on ecosystems, (iii) ecosystem services and socio-ecological systems and (iv), methods and research infrastructures. Several key priorities for the development of research infrastructures emerged. Addressing complex environmental issues requires the adoption of a whole-system approach, achieved through integration of biotic, abiotic and socio-economic measurements. Interoperability among different research infrastructures needs to be improved by developing standard measurements, harmonizing methods, and establishing capacities and tools for data integration, processing, storage and analysis. Future research infrastructures should support a range of methodological approaches including observation, experiments and modelling. They should also have flexibility to respond to new requirements, for example by adjusting the spatio-temporal design of measurements. When new methods are introduced, compatibility with important long-term data series must be ensured. Finally, indicators, tools, and transdisciplinary approaches to identify, quantify and value ecosystem services across spatial scales and domains need to be advanced.

Innovative methodology for the prioritization of the Program of Measures for integrated water resources management of the Region of Crete, Greece.

An innovative multi-criteria methodology was proposed for the prioritization of the Program of Measures (PoM) in the Water Region of Crete, and applied specifically to the basin of Geropotamos river according to the requirements of the Water Framework Directive. This study relied on the four pillars of sustainability and the EU cross-compliance legislative objective for the minimization of the climate change impact. The multi-criteria evaluation methodology was based on the results of four different types of analyses: a DPSIR analysis, a SWOT analysis, a Cost-Benefit Analysis and a climate change impacts analysis. Public participation on the results of the study with local stakeholders was used at every stage of the multi-criteria evaluation process, from the selection and weighing of the criteria to the final ranking and measures' prioritization. The PoM contains two types of measures: basic measures which deal with the implementation of existing legislation and are the same for all regions of Greece and additional measures which are specified for the Region of Crete. The results of the prioritization process in Geropotamos Basin suggests that improving the water quality and ecological status of available water resources do not always require significant financial resources and can have a high impact in terms of achieving "good" quality status.

Identifying the controlling mechanism of geogenic origin chromium release in soils.

A laboratory study was conducted to assess the mobility and mechanisms of chromium release from soils obtained from an area of wide spread geogenic contamination. The agricultural soil sample used in this study was taken from the Schimatari area in Asopos River basin in Greece. In order to refine the isolation of minerals contained in the soil, two types of separation analysis were conducted. First, a size fractionation with hydrocyclone and second, a weight fractionation with heavy liquids. The separated fractions were characterized using chemical, mineralogical and surface analysis. The results provided consistent evidence that the heavy fraction of the soil is related directly to the mobile fraction of chromium. At acidic pHs, the clay-sized fraction also plays an additional important role in the mobility of Cr, due to the fact that this fraction has high surface area and chromium reactivity index. In addition, pH-edge leaching studies showed a high correlation between Cr-Ni, Cr-Mn and Cr-Y released from the soil which also suggests that the mobility of chromium is controlled by chromite weathering which is the case observed in Asopos river basin.

Uncertainty of modelled flow regime for flow-ecological assessment in Southern Europe.

Sustainable water basin management requires characterization of flow regime in river networks impacted by anthropogenic pressures. Flow regime in ungauged catchments under current, future, or natural conditions can be assessed with hydrological models. Developing hydrological models is, however, resource demanding such that decision makers might revert to models that have been developed for other purposes and are made available to them ('off-the-shelf' models). In this study, the impact of epistemic uncertainty of flow regime indicators on flow-ecological assessment was assessed at selected stations with drainage areas ranging from about 400 to almost 90,000km2 in four South European basins (Adige, Ebro, Evrotas and Sava). For each basin, at least two models were employed. Models differed in structure, data input, spatio-temporal resolution, and calibration strategy, reflecting the variety of conditions and purposes for which they were initially developed. The uncertainty of modelled flow regime was assessed by comparing the modelled hydrologic indicators of magnitude, timing, duration, frequency and rate of change to those obtained from observed flow. The results showed that modelled flow magnitude indicators at medium and high flows were generally reliable, whereas indicators for flow timing, duration, and rate of change were affected by large uncertainties, with correlation coefficients mostly below 0.50. These findings mirror uncertainty in flow regime indicators assessed with other methods, including from measured streamflow. The large indicator uncertainty may significantly affect assessment of ecological status in freshwater systems, particularly in ungauged catchments. Finally, flow-ecological assessments proved very sensitive to reference flow regime (i.e., without anthropogenic pressures). Model simulations could not adequately capture flow regime in the reference sites comprised in this study. The lack of reliable reference conditions may seriously hamper flow-ecological assessments. This study shows the pressing need for improving assessment of natural flow regime at pan-European scale.

Identifying efficient agricultural irrigation strategies in Crete.

Water scarcity and droughts are a major concern in most Mediterranean countries. Agriculture is a major user of water in the region and releases significant amounts of surface and ground waters, endangering the sustainable use of the available resources. Best Management Practices (BMPs) can mitigate the agriculture impacts on quantity of surface waters in agricultural catchments. However, identification of efficient BMPs strategies is a complex task, because BMPs costs and effectiveness can vary significantly within a basin. In this study, sustainable agricultural practices were studied based on optimal allocation of irrigation water use for dominant irrigated crops in the island of Crete, Greece. A decision support tool that integrates the Soil and Water Assessment Tool (SWAT) watershed model, an economic model, and multi-objective optimization routines, was used to identify and locate optimal irrigation strategies by considering crop water requirements, impact of irrigation changes on crop productivity, management strategies costs, and crop market prices. Three spatial scales (crop type, fields, and administrative regions) were considered to point out different approaches of efficient management. According to the analysis, depending on the spatial scale and complexity of spatial optimization, water irrigation volumes could be reduced by 32%-70% while preserving current agricultural benefit. Specific management strategies also looked at ways to relocate water between administrative regions (4 prefectures in the case of Crete) to optimize crop benefit while reducing global water use. It was estimated that an optimal reallocation of water could reduce irrigation water volumes by 52% (148 Mm3/y) at the cost of a 7% (48 M€) loss of agricultural income, but maintaining the current agricultural benefit (626.9 M€). The study showed how the identification of optimal, cost-effective irrigation management strategies can potentially address the water scarcity issue that is becoming crucial for the viability of agriculture in the Mediterranean region.

Assessing the impact of geogenic chromium uptake by carrots (Daucus carota) grown in Asopos river basin.

A methodology was developed to assess the impact of geogenic origin hexavalent chromium uptake by carrots, and the risk of human consumption of carrots grown in Asopos River basin in Greece. A field scale experiment was conducted with carrots cultivated in treatment plots, with and without compost amendment, in order to assess the impact of carbon in the mobility and uptake of chromium by plants. The results suggested that there is a trend for chromium mobilization and uptake in the surface and the leaves of the carrots cultivated in the treatment plot with the higher carbon addition, but not in the core of the carrots. Limited mobility of hexavalent chromium in the soil-plant-water system is presented due to the affinity of chromium to be retained in the solid phase and be uptaken by plants. Hexavalent chromium tolerant bacterial strains were isolated from the carrots. These endophytic bacteria, present in all parts of the plant, were able to reduce hexavalent chromium to trivalent form to levels below the detection limit. Finally, a site-specific risk assessment analysis suggested no adverse effects to human health due to the consumption of carrots. These findings are of particular importance since they confirm that carrots grown in soils with geogenic origin chromium does not pose any adverse risk for human consumption, but could also have the beneficial effect of the micronutrient trivalent chromium.

Large scale groundwater flow and hexavalent chromium transport modeling under current and future climatic conditions: the case of Asopos River Basin.

In recent years, high concentrations of hexavalent chromium, Cr(VI), have been observed in the groundwater system of the Asopos River Basin, raising public concern regarding the quality of drinking and irrigation water. The work described herein focuses on the development of a groundwater flow and Cr(VI) transport model using hydrologic, geologic, and water quality data collected from various sources. An important dataset for this goal comprised an extensive time series of Cr(VI) concentrations at various locations that provided an indication of areas of high concentration and also served as model calibration locations. Two main sources of Cr(VI) contamination were considered in the area: anthropogenic contamination originating from Cr-rich industrial wastes buried or injected into the aquifer and geogenic contamination from the leaching process of ophiolitic rocks. The aquifer's response under climatic change scenario A2 was also investigated for the next two decades. Under this scenario, it is expected that rainfall, and thus infiltration, will decrease by 7.7 % during the winter and 15 % during the summer periods. The results for two sub-scenarios (linear and variable precipitation reduction) that were implemented based on A2 show that the impact on the study aquifer is moderate, resulting in a mean level decrease less than 1 m in both cases. The drier climatic conditions resulted in higher Cr(VI) concentrations, especially around the industrial areas.

Environmental drivers of the distribution of nitrogen functional genes at a watershed scale.

To date only few studies have dealt with the biogeography of microbial communities at large spatial scales, despite the importance of such information to understand and simulate ecosystem functioning. Herein, we describe the biogeographic patterns of microorganisms involved in nitrogen (N)-cycling (diazotrophs, ammonia oxidizers, denitrifiers) as well as the environmental factors shaping these patterns across the Koiliaris Critical Zone Observatory, a typical Mediterranean watershed. Our findings revealed that a proportion of variance ranging from 40 to 80% of functional genes abundance could be explained by the environmental variables monitored, with pH, soil texture, total organic carbon and potential nitrification rate being identified as the most important drivers. The spatial autocorrelation of N-functional genes ranged from 0.2 to 6.2 km and prediction maps, generated by cokriging, revealed distinct patterns of functional genes. The inclusion of functional genes in statistical modeling substantially improved the proportion of variance explained by the models, a result possibly due to the strong relationships that were identified among microbial groups. Significant relationships were set between functional groups, which were further mediated by land use (natural versus agricultural lands). These relationships, in combination with the environmental variables, allow us to provide insights regarding the ecological preferences of N-functional groups and among them the recently identified clade II of nitrous oxide reducers.

Characterization and mobility of geogenic chromium in soils and river bed sediments of Asopos basin.

A field and laboratory study was conducted to assess the origin and mobility of CrVI in Asopos basin in Greece. Sampling was designed in such way as to capture the spatial variability of chromium occurring in sediments and soils in different lithological units in the area. Physicochemical and geochemical characterization of surface agricultural soils obtained from river terraces and river bed sediments was conducted in order to determine the natural background of chromium. Lithologies with strong calcareous, siliceous and ultramafic components were identified using principal component analysis. Laboratory mobility studies quantified the rates of chromium sorption and release from soils and their capacity to adsorb chromium. Heavy metal analysis and local geology study support the hypothesis that the main source of chromium is of geogenic origin. Chromium distribution in Asopos river bed was influenced from the eroded products derived from extensive areas with ultramafic rocks the last 5Ma. The mobility studies showed that leaching process was very fast and sorption capacity was significant and capable to retain chromium in case of waste release in the river. Finally the mobility of chromium release is limited due to existing attenuation capacity controlled by ferric oxides coatings on the soil and sediments.

Mitigation measures for chromium-VI contaminated groundwater - The role of endophytic bacteria in rhizofiltration.

A constructed wetland pilot with Juncus acutus L. plants was investigated for its rhizofiltration efficiency in treating Cr(VI)-contaminated groundwater. Measurements of Cr(VI) and total Cr were performed to estimate the rate of removal. In addition, Cr concentration in plant tissues was measured and the role of endophytic bacteria on plant's tolerance to Cr(VI) toxicity was investigated. The results support that J. acutus is able to rhizofiltrate Cr(VI) from contaminated water with up to 140µg/L while Cr content analysis in plant tissues revealed that the majority of Cr was accumulated by the plants. Moreover, two leaf (Acidovorax sp. strain U3 and Ralstonia sp. strain U36) isolated endophytic bacteria were found to tolerated 100mg/L Cr(VI) while nine root isolates showed resistance to 500mg/L Cr(VI). The endophytic bacteria Pseudomonas sp. strain R16 and Ochrobactrum sp. strain R24 were chosen for Cr(VI) reduction assays. All four strains exhibited a strong potential to reduce Cr(VI) to Cr(III) aerobically. Among them Pseudomonas sp. strain R16 was found able to completely reduced 100mg/L Cr(VI) after 150h of incubation. These results suggest that J. acutus is an excellent choice for CWs whose function is the removal of Cr(VI) from contaminated groundwater for subsequent use in crop irrigation.

Environmental drivers of soil microbial community distribution at the Koiliaris Critical Zone Observatory.

Data on soil microbial community distribution at large scales are limited despite the important information that could be drawn with regard to their function and the influence of environmental factors on nutrient cycling and ecosystem services. This study investigates the distribution of Archaea, Bacteria and Fungi as well as the dominant bacterial phyla (Acidobacteria, Actinobacteria, Bacteroidetes, Firmicutes), and classes of Proteobacteria (Alpha- and Betaproteobacteria) across the Koiliaris watershed by qPCR and associate them with environmental variables. Predictive maps of microorganisms distribution at watershed scale were generated by co-kriging, using the most significant predictors. Our findings showed that 31-79% of the spatial variation in microbial taxa abundance could be explained by the parameters measured, with total organic carbon and pH being identified as the most important. Moreover, strong correlations were set between microbial groups and their inclusion on variance explanation improved the prediction power of the models. The spatial autocorrelation of microbial groups ranged from 309 to 2.226 m, and geographic distance, by itself, could explain a high proportion of their variation. Our findings shed light on the factors shaping microbial communities at a high taxonomic level and provide evidence for ecological coherence and syntrophic interactions at the watershed scale.

SoilTrEC: a global initiative on critical zone research and integration.

Soil is a complex natural resource that is considered non-renewable in policy frameworks, and it plays a key role in maintaining a variety of ecosystem services (ES) and life-sustaining material cycles within the Earth's Critical Zone (CZ). However, currently, the ability of soil to deliver these services is being drastically reduced in many locations, and global loss of soil ecosystem services is estimated to increase each year as a result of many different threats, such as erosion and soil carbon loss. The European Union Thematic Strategy for Soil Protection alerts policy makers of the need to protect soil and proposes measures to mitigate soil degradation. In this context, the European Commission-funded research project on Soil Transformations in European Catchments (SoilTrEC) aims to quantify the processes that deliver soil ecosystem services in the Earth's Critical Zone and to quantify the impacts of environmental change on key soil functions. This is achieved by integrating the research results into decision-support tools and applying methods of economic valuation to soil ecosystem services. In this paper, we provide an overview of the SoilTrEC project, its organization, partnerships and implementation.

Nutrient mitigation in a temporary river basin.

We estimate the nutrient budget in a temporary Mediterranean river basin. We use field monitoring and modelling tools to estimate nutrient sources and transfer in both high and low flow conditions. Inverse modelling by the help of PHREEQC model validated the hypothesis of a losing stream during the dry period. Soil and Water Assessment Tool model captured the water quality of the basin. The 'total daily maximum load' approach is used to estimate the nutrient flux status by flow class, indicating that almost 60% of the river network fails to meet nitrogen criteria and 50% phosphate criteria. We recommend that existing well-documented remediation measures such as reforestation of the riparian area or composting of food process biosolids should be implemented to achieve load reduction in close conjunction with social needs.

Effects of olive mill wastewater on soil carbon and nitrogen cycling.

This study investigated the cycling of C and N following application of olive mill wastewater (OMW) at various rates (0, 42, 84, and 168 m(3)/ha). OMW stimulated respiration rate throughout the study period, but an increase in soil organic matter was observed only at the highest rate. Soil phenol content decreased rapidly within 2 weeks following application but neither phenol oxidase and peroxidase activity nor laccase gene copies could explain this response. Soil NH4 (+)-N content increased in response to OMW application rate, while an opposite trend observed for NO3 (-)-N, which attributed to immobilization. This decrease was in accordance with amoA gene copies of archaeal and bacterial ammonia oxidizers in the first days following OMW application. Afterwards, although amoA gene copies and potential nitrification rates recovered to values similar to or higher than those in the non-treated soils, NO3 (-)-N content did not change among the treatments. A corresponding increase in denitrifying gene copies (nirK, nirS, nosZ) during that period indicates that denitrification, stimulated by OMW application rate, was responsible for this effect; a hypothesis consistent with the decrease in total Kjeldahl nitrogen content late in the season. The findings suggest that land application of OMW is a promising practice for OMW management, even at rates approaching the soil water holding capacity.

Natural attenuation of nutrients in a Mediterranean drainage canal.

This research is aimed at elucidating the removal mechanisms of nutrients due to natural attenuation in drainage canals in Evrotas River delta in Greece. We investigated nutrients fluxes in groundwater, sediments, and reeds (Phragmites Australis and Arundo Donax) of the drainage canal. Groundwater fluxes indicated that the rate of mineralization was 37.6 mg N/m(2) day. The accumulation of toxic ammonia was prevented through the nitrification process (26.6 mg N m(-2) day(-1)). The decrease of NO(3)-N flux in groundwater in the riparian zone was calculated to be 56.1 mg N m(-2) day(-1) (20.48 g N m(-2) year(-1)). Phosphate was adsorbed to sediments and its load to the drainage canal was minimized. Harvesting of above ground reed biomass in mid June, when maximum standing stock of nutrients was attained for both plants, would remove 2.73 g P m(-2) and 11.2 g N m(-2). All the phosphorous (1.39 g P/m(2) year(-1)) and 76.5% of the nitrate nitrogen (14.64 g N m(-2) year(-1)) entering the drainage canal was taken up by plants. Drainage canal management is suggested as an efficient low cost-high gain agri-environmental measure, which is easy to be adapted by farmers, to reduce diffuse nutrient pollution.

Simultaneous photocatalytic oxidation of As(III) and humic acid in aqueous TiO2 suspensions.

The simultaneous photocatalytic oxidation of As(III) and humic acid (HA) in aqueous Degussa P25 TiO(2) suspensions was investigated. Preliminary photocatalytic studies of the binary As(III)/TiO(2) and HA/TiO(2) systems showed that As(III) was oxidized more rapidly than HA and the extent of photocatalytic oxidation of each individual component (i.e. As(III) or HA) increased with decreasing its initial concentration and/or increasing catalyst loading. The simultaneous photocatalytic oxidation of As(III) and HA in the ternary As(III)/HA/TiO(2) system showed that both As(III) and HA oxidation was reduced in the ternary system compared to the corresponding binary systems. The effect of operating conditions in the ternary system, such as initial As(III), HA and TiO(2) concentrations (in the range 3-20mg/L, 10-100mg/L and 50-250 mg/L respectively), initial solution pH (3.6-6.7) and reaction time (10-30 min), on photocatalytic As(III) and HA oxidation was assessed implementing a two-level factorial experimental design methodology. Seven and ten factors were found statistically important in the case of photocatalytic As(III) and HA oxidation respectively. Based on these statistically significant factors, a first order polynomial model describing As(III) and HA photocatalytic oxidation was constructed and a very good agreement was obtained between the experimental values and those predicted by the model, while the observed differences may be readily explained as random noise.

Arsenic mobility and stabilization in topsoils.

Agricultural topsoil can be polluted with arsenic due to irrigation with contaminated water from geothermal sources. This work evaluates the mobility of arsenic in topsoils and stabilization of arsenic with zero valent iron (ZVI), in short term experiments. The objective of this study was the development of a simplified empirical model that can predict the concentration of iron released from ZVI and the concentration of arsenic remaining in the solution during short term stabilization experiments. The empirical model correlates the release of arsenic from soil with dissolved iron concentration during stabilization experiments, in different pH and ZVI/solution ratios. Reaction time and the ratio of ZVI/soil affect the efficiency of arsenic stabilization in topsoils with ZVI. In addition, the release/desorption experiments and adsorption experiments, under different conditions, showed that the concentration of arsenate desorbed from soil depends on the temperature. Higher concentrations of arsenate were reported, as the temperature increased.