Summary recommendations on "Analytical methods for substances in the Watch List under the Water Framework Directive".

The Watch List (WL) is a monitoring program under the European Water Framework Directive (WFD) to obtain high-quality Union-wide monitoring data on potential water pollutants for which scarce monitoring data or data of insufficient quality are available. The main purpose of the WL data collection is to determine if the substances pose a risk to the aquatic environment at EU level and subsequently to decide whether a threshold, the Environmental Quality Standards (EQS) should be set for them and, potentially to be listed as priority substance in the WFD. The first WL was established in 2015 and contained 10 individual or groups of substances while the 4th WL was launched in 2022. The results of monitoring the substances of the first WL showed that some countries had difficulties to reach an analytical Limit of Quantification (LOQ) below or equal to the Predicted No-Effect Concentrations (PNEC) or EQS. The Joint Research Centre (JRC) of the European Commission (EC) organised a series of workshops to support the EU Member States (MS) and their activities under the WFD. Sharing the knowledge among the Member States on the analytical methods is important to deliver good data quality. The outcome and the discussion engaged with the experts are described in this paper, and in addition a literature review of the most important publications on the analysis of 17-alpha-ethinylestradiol (EE2), amoxicillin, ciprofloxacin, metaflumizone, fipronil, metformin, and guanylurea from the last years is presented.

A comprehensive health effects assessment of the use of sanitizers and disinfectants during COVID-19 pandemic: a global survey.

COVID-19 has affected all aspects of human life so far. From the outset of the pandemic, preventing the spread of COVID-19 through the observance of health protocols, especially the use of sanitizers and disinfectants was given more attention. Despite the effectiveness of disinfection chemicals in controlling and preventing COVID-19, there are critical concerns about their adverse effects on human health. This study aims to assess the health effects of sanitizers and disinfectants on a global scale. A total of 91,056 participants from 154 countries participated in this cross-sectional study. Information on the use of sanitizers and disinfectants and health was collected using an electronic questionnaire, which was translated into 26 languages via web-based platforms. The findings of this study suggest that detergents, alcohol-based substances, and chlorinated compounds emerged as the most prevalent chemical agents compared to other sanitizers and disinfectants examined. Most frequently reported health issues include skin effects and respiratory effects. The Chi-square test showed a significant association between chlorinated compounds (sodium hypochlorite and per-chlorine) with all possible health effects under investigation (p-value <0.001). Examination of risk factors based on multivariate logistic regression analysis showed that alcohols and alcohols-based materials were associated with skin effects (OR, 1.98; 95%CI, 1.87-2.09), per-chlorine was associated with eye effects (OR, 1.83; 95%CI, 1.74-1.93), and highly likely with itching and throat irritation (OR, 2.00; 95%CI, 1.90-2.11). Furthermore, formaldehyde was associated with a higher prevalence of neurological effects (OR, 2.17; 95%CI, 1.92-2.44). Furthermore, formaldehyde was associated with a higher prevalence of neurological effects (OR, 2.17; 95%CI, 1.92-2.44). The use of sodium hypochlorite and per-chlorine also had a high chance of having respiratory effects. The findings of the current study suggest that health authorities need to implement more awareness programs about the side effects of using sanitizers and disinfectants during viral epidemics especially when they are used or overused.

An indicator to map diffuse chemical river pollution considering buffer capacity of riparian vegetation--a pan-European case study on pesticides.

Vegetated riparian areas alongside streams are thought to be effective at intercepting and controlling chemical loads from diffuse agricultural sources entering water bodies. Based on a recently compiled European map of riparian zones and a simplified soil chemical balance model, we propose a new indicator at a continental scale. QuBES (Qualitative indicator of Buffered Emissions to Streams) allows a qualitative assessment of European rivers exposed to pesticide input. The indicator consists of normalised pesticide loads to streams computed through a simplified steady-state fate model that distinguishes various chemical groups according to physico-chemical behaviour (solubility and persistence). The retention of pollutants in the buffer zone is modelled according to buffer width and sorption properties. While the indicator may be applied for the study of a generic emission pattern and for a chemical of generic properties, we demonstrate it to the case of agricultural emissions of pesticides. Due to missing geo-spatial data of pesticide emissions, a total pesticide emission scenario is assumed. The QuBES indicator is easy to calculate and requires far less input data and parameterisation than typical chemical-specific models. At the same time, it allows mapping of (i) riparian buffer permeability, (ii) chemical runoff from soils, and (iii) the buffered load of chemicals to the stream network. When the purpose of modelling is limited to identifying chemical pollution patterns and understanding the relative importance of emissions and natural attenuation in soils and stream buffer strips, the indicator may be suggested as a screening level, cost-effective alternative to spatially distributed models of higher complexity.

Assessment of riverine load of contaminants to European seas under policy implementation scenarios: an example with 3 pilot substances.

An evaluation of conventional emission scenarios is carried out targeting a possible impact of European Union (EU) policies on riverine loads to the European seas for 3 pilot pollutants: lindane, trifluralin, and perfluorooctane sulfonate (PFOS). The policy scenarios are investigated to the time horizon of year 2020 starting from chemical-specific reference conditions and considering different types of regulatory measures including business as usual (BAU), current trend (CT), partial implementation (PI), or complete ban (PI ban) of emissions. The scenario analyses show that the model-estimated lindane load of 745 t to European seas in 1995, based on the official emission data, would be reduced by 98.3% to approximately 12.5 t in 2005 (BAU scenario), 10 years after the start of the EU regulation of this chemical. The CT and PI ban scenarios indicate a reduction of sea loads of lindane in 2020 by 74% and 95%, respectively, when compared to the BAU estimate. For trifluralin, an annual load of approximately 61.7 t is estimated for the baseline year 2003 (BAU scenario), although the applied conservative assumptions related to pesticide use data availability in Europe. Under the PI (ban) scenario, assuming only small residual emissions of trifluralin, we estimate a sea loading of approximately 0.07 t/y. For PFOS, the total sea load from all European countries is estimated at approximately 5.8 t/y referred to 2007 (BAU scenario). Reducing the total load of PFOS below 1 t/y requires emissions to be reduced by 84%. The analysis of conventional scenarios or scenario typologies for emissions of contaminants using simple spatially explicit GIS-based models is suggested as a viable, affordable exercise that may support the assessment of implementation of policies and the identification or negotiation of emission reduction targets.

Continental scale inverse modeling of common organic water contaminants in European rivers.

The paper presents an analysis of measured riverine concentrations of 16 common organic water contaminants. From observed concentrations we back-calculate emissions and chemical half lives through a simple inverse model. The analysis does not allow identifying a single half life/emission factor combination, but a set of combinations which are Pareto-optimal (or "non-dominated"). The approach is shown to provide a rational basis for the screening of chemicals in rivers: with reference to the 16 chemicals considered here, estimated emission factors and half lives are consistent with the ones reported in other studies. For more precise estimates, prior knowledge about either emission factors or half lives is necessary. For the considered chemicals, loads to European seas can be subsequently estimated with an uncertainty usually within a factor of 2. The approach can be proposed for the inventorying of catchment-specific chemical pollutant emissions required for European environmental policies.

Implementation of a 3D coupled hydrodynamic and contaminant fate model for PCDD/Fs in Thau Lagoon (France): the importance of atmospheric sources of contamination.

A 3D hydrodynamic and contaminant fate model was implemented for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Thau lagoon. The hydrodynamic model was tested against temperature and salinity measurements, while the contaminant fate model was assessed against available data collected at different stations inside the lagoon. The model results allow an assessment of the spatial and temporal variability of the distribution of contaminants in the lagoon, the seasonality of loads and the role of atmospheric deposition for the input of PCDD/Fs. The outcome suggests that air is an important source of PCDD/Fs for this ecosystem, therefore the monitoring of air pollution is very appropriate for assessing the inputs of these contaminants. These results call for the development of integrated environmental protection policies.

Integrated modelling of Polycyclic Aromatic Hydrocarbons in the marine environment: coupling of hydrodynamic, fate and transport, bioaccumulation and planktonic food-web models.

Spatio-temporal variability of pollutants in the environment is a complex phenomenon that requires a combined approach for its analysis. Whereas data on measured levels of contaminants in various environmental compartments is essential, it is not always possible to monitor at the necessary frequency and with the adequate spatial sampling distribution to capture this variability. Therefore a modelling approach able to complement experimental data and close the gaps in the monitoring programs is useful for assessing the contaminant dynamics occurring at different time scales. In this work a 1D water column fate model has been developed and tested for Polycyclic Aromatic Hydrocarbons (PAHs). The model has been coupled with a simple ecological model that includes a bioaccumulation module. Afterwards, the model has been used to study the temporal variability of contaminant concentrations as well as the fluxes between compartments. The results evidence the complex coupling between spatio-temporal scales and its influence on environmental concentration levels.

A bioaccumulation model for herbicides in Ulva rigida and Tapes philippinarum in Sacca di Goro lagoon (Northern Adriatic).

A bioaccumulation model to predict concentrations of s-triazine herbicides in the macroalgae Ulva rigida and in clams Tapes philippinarum has been implemented, calibrated and validated. The model uses input data from a 3D biogeochemical model that provides biomasses in the different compartments, i.e. phytoplankton, zooplankton and bacteria; and from a 3D fate model that provides the herbicides concentrations in the water column as well as in the sediments. Simulated data were compared with experimental data collected during a set of sampling campaigns carried out in 2004 and 2005 in the Sacca di Goro lagoon (Northern Adriatic). The model predicts correctly the concentrations of herbicides measured in Ulva rigida and reproduces with good agreement the values of concentration of herbicides found in clams. Furthermore, the simulated spatial and temporal dynamics in the biota compartment, following those of the water and sediments, are also in agreement with the experimental data. This integrated approach combining biogeochemical, fate and bioaccumulation models provide an overall assessment of the importance of the different environmental compartments and it can also support the testing of different management strategies to improve ecosystem state and functioning. Further research is necessary to elucidate the role and importance of the metabolism of these compounds by clams.

Fate of persistent organic pollutants in the water column: does turbulent mixing matter?

The effect of vertical turbulent mixing on the dynamics of persistent organic pollutants has long been overlooked and its role is still hardly understood. Here we present the first comprehensive analysis of the role of turbulent diffusion on the distribution of those contaminants and its interplay with sinking fluxes. To this end, a 1D dynamic coupled hydrodynamic-contaminant model has been developed and applied to a Mediterranean continental shelf environment. The hydrodynamic sub-model is adapted from COHERENS, the contaminant sub-model is an improvement from the BIODEP model and considers the contaminant in 3 phases: dissolved-colloidal-particulate. The simulation highlights the role of turbulence in determining the POP distribution and variability in the water column. In short, turbulent flux of contaminants strengthens the upward diffusion of sediment entrained contaminants and determines the extent to which inputs from the atmosphere mix into the water column. It acts in parallel with degradation and sinking fluxes, the combined effect yielding a surface enriched - depth depleted - benthic layer enriched region distribution, which presents similarities to reported experimental measures.

Simulation of water flow and nitrogen transport for a Bulgarian experimental plot using SWAP and ANIMO models.

Unsaturated zone models are useful tools in predicting effects of measures and can be used to optimise agricultural practice aiming to minimise the impact on the environment. However, current soil models have a varying degree of abstraction level referring to simulated processes in time and space. In the framework of an EU funded project the SWAP (Soil-Water-Atmosphere-Plant) and ANIMO (Agricultural-Nutrient-Model) models were tested for an experimental arable plot in Bulgaria. SWAP was used to simulate water flow in the soil while ANIMO describes nitrogen movement and transformations. The objectives of this study are: (i) to show results of the combined application of water and nitrogen dynamics of originally Dutch models SWAP and ANIMO for specific Bulgarian soil and hydrological conditions; (ii) to calibrate and evaluate SWAP and ANIMO models by comparing numerical results with field measurements collected for an arable field in western Bulgaria and (iii) to analyse possible contamination of groundwater due to agricultural practice in the considered region. Further a short description of the experimental plot, as well as information about parameters of the investigated soil profiles, is provided. The obtained SWAP results evidenced that the model gives sufficient adaptation for soil water dynamics. The simulations of ANIMO for nitrogen cycle show greater divergence with observations but are satisfactory precise for the purposes of assessing land use impact on groundwater quality. In general, differences between model results and field measurements do not exceed 10-15%. For the experimental plot predictions indicate nitrate-N concentrations less then 5 mg/l in deeper soil compartments and low downward annual flux containing 0.133 kg N/ha. These results indicate that there is no serious pollution of the shallow groundwater table by nitrogen resulting from land use and agricultural activities.