Ozone (O₃) is a harmful pollutant when present in the lowermost layer of the atmosphere. Therefore, the European Commission formulated directives to regulate O₃ concentrations in near-surface air. However, almost 50% of the 5068 air quality stations in Europe do not monitor O₃ concentrations. This study aims to provide a hybrid modeling system that fills these gaps in the hourly surface O₃ observations on a site scale with much higher accuracy than existing O₃ models. This hybrid model was developed using estimations from multiple linear regression-based eXtreme Gradient Boosting Machines (MLR-XGBM) and O₃ reanalysis from European regional air quality models (CAMS-EU). The binary classification of extremely high O₃ events and the 1- and 24-h forecasts of hourly O₃ were investigated as secondary aims. In this study thirteen stations in Northern Bavaria, out of which six do not monitor O₃, were chosen as test sites. Considering the computational complexity of machine learning algorithms (MLAs), we also applied two recent MLA interpretation methods, namely SHapley Additive exPlanations (SHAP) and Local interpretable model-agnostic explanations (LIME).With SHAP, we showed an increasing effect of temperature on O₃ concentrations which intensifies for temperatures exceeding 17 °C. According to LIME, O₃ concentration peaks are mainly governed by meteorological factors under dry and warm conditions on a regional scale, whereas local nitrogen oxide concentrations control base O₃ concentrations during cold and wet periods.While recently developed MLAs for the spatial estimation of hourly O₃ concentrations had a station-based root-mean-square error (RMSE) above 27 μg/m³, our proposed model significantly reduced the estimation errors by about 66% with an RMSE of 9.49 μg/m³. We also found that logistic regression (LR) and MLR-XGBM performed best in the site-scale classification and 24-h forecast of O₃ concentrations (with a station-averaged accuracy and RMSE of 0.95 and 19.34 μg/m³, respectively).

Frequency and intensity of wildfire occurrences are dramatically increasing worldwide due to global climate change, having a devastating effect on the entire ecosystem including plants. Moreover, distribution of fire-smoke can influence the natural environment over very long distances, i.e. hundreds of kilometres. Dry plant matter contains 0.1–0.9% (w/w) sulphur, which is mainly released during combustion into the atmosphere as sulphur dioxide (SO₂) resulting in local concentrations of up to 3000 nL L⁻¹. SO₂ is a highly hazardous gas, which enters plants mostly via the stomata. Toxic sulphite is formed inside the leaves due to conversion of SO₂. Plants as sessile organisms cannot escape from threats, why they evolved an impressive diversity of molecular defence mechanisms. In the present study, two recent wildfires in Germany were evaluated to analyse the effect of SO₂ released into the atmosphere on deciduous trees: the Meppen peat fire in 2018 and the forest fire close to Luebtheen in 2019. Collected leaf material from beech (Fagus sylvatica) and oak (Quercus robur) was examined with respect to detoxification of sulphur surplus due to the exposure to elevated SO₂. An induced stress reaction in both species was indicated by a 1.5-fold increase in oxidized glutathione. In beech leaves, the enzymatic activities of the sulphite detoxification enzymes sulphite oxidase and apoplastic peroxidases were increased 5-fold and a trend of sulphate accumulation was observed. In contrast, oaks did not regulate these enzymes during smoke exposure, however, the constitutive activity is 10-fold and 3-fold higher than in beech. These results show for the first time sulphite detoxification strategies of trees in situ after natural smoke exposure. Beech and oak trees survived short-term SO₂ fumigation due to exclusion of toxic gases and different oxidative detoxification strategies. Beeches use efficient upregulation of oxidative sulphite detoxification enzymes, while oaks hold a constitutively high enzyme-pool available.

Copper-containing antifouling paints (AFP) are widely used for leisure boat maintenance. Cu emitted from AFP into German surface water bodies has been suggested to be a significant source of heavy metal pollution, threatening water quality. We developed two scenarios to model Cu emissions from AFP applied on leisure boats on national scale, which allow identifying regional hotspots. The top-down approach (scenario A) was based on a previous study on national AFP consumption, while in the bottom-up approach (scenario B), median and interquartile range of Cu release rates depending on salinity conditions were considered for emission estimation. Both scenarios clearly highlighted the locally high emission pressure on inland waters in popular watersport regions, identifying these as requiring intense protection. Scenario B generally predicted lower Cu emissions (sea: 11.05–25.53 t a⁻¹, inland: 14.15–34.59 t a⁻¹) than scenario A (sea: 22.53 t a⁻¹, inland: 47.97 t a⁻¹). To evaluate their relevance, scenario results were compared to emissions modelled with MoRE (Modelling of Regionalized Emissions), which is used as reporting tool on substance emissions by Germany. According to scenarios A and B, the emission from AFP accounted for 13 % and 4–9 % of the total Cu emissions into inland waters in 2016, respectively. Scenario results were similar or higher than other emission pathways such as industrial direct dischargers. Thus, we consider Cu emissions from AFP as a significant pathway to be included in the MoRE emission inventory. We recommend scenario B for implementation as it allows a more flexible adaptation for future modelling.

Short- and medium-chain chlorinated paraffins (SCCPs, MCCPs) are high-production volume industrial chemicals that have been previously reported to occur in food, packaging material and the environment. This study presents an assessment of dietary exposure for consumers in Southern Germany based on three different sampling approaches: (i) a classical market basket study (n = 154), (ii) the analysis of ready-made meals from restaurants (n = 10), and (iii) a total diet approach (n = 21). In 35% of the samples, CPs were below the method limit of quantification. Highest amounts of SCCPs and MCCPs were found especially in extra virgin olive oils (EVOOs) and fish. Homologue patterns indicated the partial removal of CPs during the refining of (other) edible oils. Ready-made meals contained only low amounts of CPs equal to estimations based on market basket samples. Total diet samples from the same hospital were generally comparable with each other regardless of diet, although vegetarian meal plans with high amounts of cheese and other dairy products contained up to an order of magnitude more CPs than other diets. Taking all approaches into account, calculated daily exposures for adults ranged 35–420 ng/kg bw/day for ΣSCCPs and 22–840 ng/kg bw/day for ΣMCCPs, which is between one and two orders of magnitude higher than the current dietary intake of polychlorinated biphenyls (indicator PCBs) in Europe.

To date, micropollutants from anthropogenic sources cannot be completely removed from effluents of wastewater treatment plants and therefore enter freshwater systems, where they may impose adverse effects on aquatic organisms, for example, on fish. Advanced treatment such as ozonation aims to reduce micropollutants in wastewater effluents and, thus, to mitigate adverse effects on the environment. To investigate the impact and efficiency of ozonation, four different water types were tested: ozonated wastewater (before and after biological treatment), conventionally-treated wastewater, and water from a river (River Ruhr, Germany) upstream of the wastewater treatment plant effluent. Zebrafish (Danio rerio) embryos were used to study lethal and sublethal effects in a modified fish early life-stage test. Mortality occurred during exposure in the water samples from the wastewater treatment plant and the river in the first 24 h post-fertilization, ranging from 12% (conventional wastewater) to 40% (river water). Regarding sublethal endpoints, effects compared to the negative control resulted in significantly higher heart rates (ozonated wastewater), and significantly reduced swimming activity (highly significant in ozonated wastewater and ozone reactor water, significant in only the last time interval in river water). Moreover, the respiration rates were highly increased in both ozonated wastewater samples in comparison to the negative control. Significant differences between the ozonated wastewater samples occurred in the embryonic behavior and heart rates, emphasizing the importance of subsequent biological treatment of the ozonated wastewater. Only the conventionally-treated wastewater sample did not elicit negative responses in zebrafish, indicating that the discharge of conventional wastewater poses no greater risk to embryonic and larval zebrafish than water from the river Ruhr itself. The sublethal endpoints embryonic- and larval behavior, heart rates, and respiration were found to be the most sensitive endpoints in this fish early life-stage test and can add valuable information on the toxicity of environmental samples.

Microplastic (MP) has been detected ubiquitously in freshwater systems. Until now MP sampling, however, is predominantly based on short-term net or pumping and filtration systems which can only provide snapshots of MP abundance; especially in flowing water bodies. To improve representativeness in the determination of MP occurrences in these aquatic compartments, an integrative approach that covers larger water volumes for a longer period of time is required. In this regard, surface water supplied drinking water treatment plants (DWTPs) represent an opportunity. In DWTPs, suspended solids from thousands of cubic metres of raw water are continuously removed over several hours and enriched in coagulation/flocculation and filtration processes. Our hypothesis was that MP is also removed to a full extent, like suspended solids, and that an integrative approach for identification and quantification in raw water can be derived from the analysis of MP in the treatment sludge. To prove this hypothesis, treatment sludge from a riverside DWTP (Warnow river, North-Eastern Germany) was analysed for MP > 50 μm. A sample purification protocol overcoming potential matrix effects caused by coagulants and flocculants was developed and validated. MP was analysed using micro-Raman spectroscopy. MP occurrence determined for the Warnow river was compared with in situ reference sampling using an established pumping and filtration system at relatively stable flow conditions. As result, the number of MP particles derived from treatment sludge was extrapolated to 196 ± 42 m⁻³ for the Warnow river and is statistically insignificantly different from 233 ± 36 m⁻³ identified by conventional water sampling. In addition, the polymer distribution and particles shape indicated the validity of the integrative concept. Consequently, the determination of MP abundance for freshwater systems based on DWTP treatment sludge represents an adequate method to estimate MP concentrations in flowing waters in an integrative way.

The historical air pollution with halogenated flame retardants (HFRs) in Germany was assessed by investigating tree leaf and shoot samples which have been archived in the German environmental specimen bank. Samples covered the period from 1985 to 2016. 43 HFRs comprising polybrominated diphenyl ethers as well as emerging brominated and chlorinated compounds such as Dechlorane Plus, DBDPE, or DPTE, were analysed in 115 samples from ten sub sites originating from six areas characterised by different land uses, including urban as well as a background site. HFRs were observed in each sample showing the widespread distribution of HFRs in Germany in tree leaves and shoots as bioindicators of past and present atmospheric pollution. Analytes observed at elevated concentrations were BDE 209, DBDPE and DPTE. Observed HFR-levels differed between analytes as well as sampling locations, particularly prior to the year 2000. They were typically highest at conurbation areas. Concentrations at the background site often belonged to the lowest ones observed, however, lowest values were not exclusively found there. The quantification frequencies appeared to decrease from the past to most recent samples. With few exceptions, atmospheric pollution of both, legacy and emerging HFRs, decreased significantly.

Elevated levels of particulate matter (PM) in urban atmospheres are one of the major environmental challenges of the Anthropocene. To effectively lower those levels, identification and quantification of sources of PM is required. Biomonitoring methods are helpful tools to tackle this problem but have not been fully established yet. An example is the sampling and subsequent analysis of spider webs to whose adhesive surface dust particles can attach. For a methodical inspection, webs of orb-weaving spiders were sampled repeatedly from 2016 to 2018 at 22 locations in the city of Jena, Germany. Contents of Ag, Al, As, B, Ba, Ca, Cd, Co, Cr, Cs, Cu, Fe, K, La, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Si, Sn, Sr, Th, Ti, V, Y, Zn and Zr were determined in the samples using inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES) after aqua regia digestion.Multivariate statistical methods were applied for a detailed evaluation. A combination of cluster analysis and principal component analysis allows for the clear identification of three main sources in the study area: brake wear from car traffic, abrasion of tram/train tracks and particles of geogenic origin. Quantitative source contributions reveal that high amounts of most of the metals are derived from a combination of brake wear and geogenic particles, the latter of which are likely resuspended by moving vehicles. This emphasizes the importance of non-exhaust particles connected to road traffic.Once a source identification has been performed for an area of interest, classification models can be applied to assess air quality for further samples from within the whole study area, offering a tool for air quality assessment. The general validity of this approach is demonstrated using samples from other locations.

Non-optimum ambient temperature has been associated with a variety of health outcomes in the elderly population. However, few studies have examined its adverse effects on neurocognitive function. In this study, we explored the temperature-cognition association in elderly women. We investigated 777 elderly women from the German SALIA cohort during the 2007–2010 follow-up. Cognitive function was evaluated using the CERAD-Plus test battery. Modelled data on daily weather conditions were assigned to the residential addresses. The temperature-cognition association over lag 0–10 days was estimated using multivariable regression with distributed lag non-linear model. The daily mean temperature ranged between −6.7 and 26.0 °C during the study period for the 777 participants. We observed an inverse U-shaped association in elderly women, with the optimum temperature (15.3 °C) located at the 68th percentile of the temperature range. The average z-score of global cognitive function declined by −0.31 (95%CI: 0.73, 0.11) for extreme cold (the 2.5th percentile of temperature range) and −0.92 (95%CI: 1.50, −0.33) for extreme heat (the 97.5th percentile of temperature range), in comparison to the optimum temperature. Episodic memory was more sensitive to heat exposure, while semantic memory and executive function were the two cognitive domains sensitive to cold exposure. Individuals living in an urban area and those with a low educational level were particularly sensitive to extreme heat. In summary, non-optimum temperature was inversely associated with cognitive function in elderly women, with the effect size for heat exposure particularly substantial. The strength of association varied by cognitive domains and individual characteristics.

This study reviews existing legal, institutional and policy tools and frameworks, relevant to the introduction and adoption of new marine litter clean-up technologies in two regional European seas, the Mediterranean and the Baltic. A combination of desk studies in six countries bordering the Baltic (Estonia, Germany, Sweden) and the Mediterranean (Greece, Italy, Tunisia), and interviews with experts and stakeholders, is used to identify key drivers and barriers to the adoption and diffusion of marine litter technologies. The main conclusion of the study is that the most influential pieces of legislation relevant to marine litter management are top-down EU policies, often forming the basis of regional and national plans. Moreover, the study finds that several drivers of marine litter technologies may at the same time be critical barriers. These factors include public awareness, consumer behaviour, enforcement of legislation, and the rise of SMEs engaged in recycling and eco-labelling of marine litter.