Innovative analytical methodologies for characterizing chemical exposure with a view to next-generation risk assessment.

The chemical burden on the environment and human population is increasing. Consequently, regulatory risk assessment must keep pace to manage, reduce, and prevent adverse impacts on human and environmental health associated with hazardous chemicals. Surveillance of chemicals of known, emerging, or potential future concern, entering the environment-food-human continuum is needed to document the reality of risks posed by chemicals on ecosystem and human health from a one health perspective, feed into early warning systems and support public policies for exposure mitigation provisions and safe and sustainable by design strategies. The use of less-conventional sampling strategies and integration of full-scan, high-resolution mass spectrometry and effect-directed analysis in environmental and human monitoring programmes have the potential to enhance the screening and identification of a wider range of chemicals of known, emerging or potential future concern. Here, we outline the key needs and recommendations identified within the European Partnership for Assessment of Risks from Chemicals (PARC) project for leveraging these innovative methodologies to support the development of next-generation chemical risk assessment.

Investigation of pH-dependent extraction methods for PFAS in (fluoropolymer-based) consumer products: A comparative study between targeted and sum parameter analysis.

Here, we report a comparative study of different sum parameter analysis methods for the extraction of per- and polyfluoroalkyl substances (PFAS) from manufactured consumer products, which can be measured by combustion ion chromatography (CIC). Therefore, a hydrolysis-based extraction method was further developed, which accounts for the addition of hydrolyzable covalently bound polyfluoroalkylated side-chain polymers (SFPs) to the extractable organic fluorine portion of the mass balance proposed as "hydrolyzable organically bound fluorine" (HOF). To test this hypothesis, the method was applied to 39 different consumer products containing fluoropolymers or monomeric PFAS taken from four different categories: outdoor textiles, paper packaging, carpeting, and permanent baking sheets. We also evaluated the method's efficiency by extracting four synthesized fluorotelomer polyacrylate reference compounds. The total fluorine (TF) and extractable organically bound fluorine (EOF) values were measured through CIC using established protocols. The TF values ranged from sub-ppb to %-levels, depending on the compound class. All samples showed results for hydrolyzed organofluorine (HOF) between 0.03 and 76.3 µg/g, while most EOF values were lower (

Long-term trend data for PFAS in soils from German ecosystems, including TOP assay.

In this study, soil top layers from the German Environmental Specimen Bank (ESB) covering a period from 2002 to 2018 and 11 sampling sites representing four ecosystem types were analysed for 24 PFAS (11 PFCA, 7 PFSA, and 6 precursors), including the total oxidizable precursor (TOP) assay. Median ΣPFAS levels before and after TOP assay ranged from 0.31 to 19.7 µg/kg dry weight (dw) and 0.32 to 20.4 µg/kg dw, respectively. The most frequently measured PFAS above LOQ were PFOS and PFOA, which were present at concentrations above 0.1 µg/kg dw in each sample. Both accounted, on average, for half to two-thirds of the total identified PFAS load at most sites. The investigated samples from the near-natural and forestry ecosystem types each had significantly higher PFAS levels than those from the urban-industrial ecosystem type, while samples from the agricultural ecosystem type did not differ distinctly from the others. Increases of median ΣPFAS levels after TOP assay ranged up to slightly >20 %, indicating that precursor compounds do not play a major role in the substance spectrum of German ESB soil samples from different ecosystem types. Total organic carbon (TOC) content in analysed samples ranged from about 1 % in sandy soil to >40 % in litter layer and showed a strong positive correlation with PFAS concentrations. It is therefore highly recommended that TOC content is reported along with PFAS levels in soils. PFAS trend analysis for nine sampling sites before and after TOP assay showed that concentration levels at most sites have remained more or less stable for the sampled period of almost two decades. The constant PFAS levels in soil samples indicate that PFOS and PFOA regulations have not yet had a positive effect on the exposure situation in this environmental compartment.

Using Environmental Simulations to Test the Release of Hazardous Substances from Polymer-Based Products: Are Realism and Pragmatism Mutually Exclusive Objectives?

The potential release of hazardous substances from polymer-based products is currently in the focus of environmental policy. Environmental simulations are applied to expose such products to selected aging conditions and to investigate release processes. Commonly applied aging exposure types such as solar and UV radiation in combination with water contact, corrosive gases, and soil contact as well as expected general effects on polymers and additional ingredients of polymer-based products are described. The release of substances is based on mass-transfer processes to the material surfaces. Experimental approaches to investigate transport processes that are caused by water contact are presented. For tailoring the tests, relevant aging exposure types and release quantification methods must be combined appropriately. Several studies on the release of hazardous substances such as metals, polyaromatic hydrocarbons, flame retardants, antioxidants, and carbon nanotubes from polymers are summarized exemplarily. Differences between natural and artificial exposure tests are discussed and demonstrated for the release of flame retardants from several polymers and for biocides from paints. Requirements and limitations to apply results from short-term artificial environmental exposure tests to predict long-term environmental behavior of polymers are presented.

Polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) in blood plasma - Results of the German environmental survey for children and adolescents 2014-2017 (GerES V).

The German Environmental Survey for Children and Adolescents 2014-2017 (GerES V) investigated the current internal exposure to polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP). These analyses were carried out for a population-representative sub-sample of 1135 children and adolescents (aged 3-17 years) of all 2394 GerES V participants. Blood plasma samples were analyzed for seven indicator PCB (PCB 28, PCB 52, PCB 101, PCB 118, PCB 138, PCB 153 and PCB 180) and selected OCP (hexachlorobenzene, three hexachlorocyclohexane isomers, 4,4'-DDT, 4,4'-DDD and 4,4'-DDE). Despite risk mitigation measures and bans put into force some decades ago children and adolescents living in Germany are still exposed to PCB and OCP: Highest geometric mean plasma concentrations were measured for 4,4'-DDE (0.158 µg/L), followed by PCB 138 (0.049 µg/L), PCB 153 (0.066 µg/L) and PCB 180 (0.032 µg/L). Different application patterns of compounds between former East and former West Germany are still reflected by differences in plasma concentrations. Significant differences between age groups and by sexes were found. Moreover, the influence of breastfeeding and fish consumption, which was also found in other studies, was confirmed. Comparison with the results of GerES 2003-2006 confirms a decreasing trend in blood samples observed world-wide. Currently, health-based guidance values for PCB are still exceeded, though to a very limited extent. Also, the widespread occurrence of these compounds underlines the need for further monitoring of these compounds in humans although they are no longer marketed.

Assessment of leachates from reactive fire-retardant coatings by chemical analysis and ecotoxicity testing.

The environmental compatibility of reactive fire-retardant coatings (intumescent paints) was investigated by a combination of leaching and ecotoxicological tests. Three representative fire-retardant coating systems were tested using two leaching procedures: "Horizontal Dynamic Surface Leaching Test" (DSLT) and the "Intermittent Immersion Test" (IIT). All eluate fractions (8 for DSLT and 9 for IIT) were analyzed for pH, conductivity, concentration of total organic carbon and selected anions und cations. Additionally, a GC-MS screening of selected fractions was conducted for identification of organic compounds. Eluate fractions 1 + 2 and fraction 7 of the DSLT were analyzed in four ecotoxicological tests (algae, daphnia, fish egg, luminescent bacteria) and in one genotoxicity test (umu). Concentration of most analytes was rather low or below limit of detection for many eluates. Analytes detected in eluates of all three products are Zn, Ba, SO42- and PO43-. Release patterns do not indicate a general trend: some compounds show maximum release in the first fractions while for others the maximum was observed in later test stages. Ecotoxic effects in eluates were found, which were higher in the eluate fraction 7 (maximum lowest ineffective dilution for luminescent bacteria (LIDL) 256) than in the eluate fraction 1 + 2 (maximum LIDL = 24). The sensitivity of the test systems was very different with highest effects for luminescent bacteria, followed by algae and daphnia and without effects in the fish egg test and umu test. A biotest battery for the comprehensive assessment is therefore advisable.

The influence of facial expressions on attack recognition and response behaviour in karate kumite.

Facial expressions play a crucial role in human daily life interactions, so it is possible that they contain relevant anticipatory cues. Therefore, we conducted two studies in karate kumite to analyse the influence of facial expressions on the attack recognition (study A) and on the response behaviour (study B). In study A, 10 karate athletes (age 14-26 years, national and international level) had to recognize temporally occluded karate attacks in 2 conditions (normal and blurred face of the attacker) and identify the upcoming attack (verbal reports). In study B, a natural fight was initiated with 12 karate athletes (age 15-32 years, national and international level) in 3 conditions: an attacker with a normal face, wearing a ski mask, and wearing a ski mask together with sunglasses. The measured parameters response quality and time for response were calculated applying the McNemar test (study A) and Friedman test (study B). Results of study A showed a significant improvement in the attack recognition in the blurred face condition compared to the normal face condition. In study B a significant improvement in time for response was observed in the ski mask and ski mask plus sunglasses conditions (r < 0.1). No significant difference for response quality was found in any of the three conditions. The results of our work indicate that the disguise of the attacker's face leads to a better attack recognition and response behaviour. We conclude that anticipatory cues in karate kumite context mainly lie in the attacker's movements and not in the attacker's face.

Evaluation of the impact of construction products on the environment by leaching of possibly hazardous substances.

Construction products are in contact with water (e.g., rain, seepage water) during their service lifetime and may release potentially harmful compounds by leaching processes. Monitoring studies showed that compounds attributed to construction products are found in storm water and the receiving bodies of water and that the release of biocides in urban areas can be comparable to the input of pesticides from agricultural uses. Therefore, a prospective risk assessment of such products is necessary. Laboratory leaching tests have been developed by the Technical Committee CEN/TC 351 and are ready to use. One major task in the future will be the evaluation of the leaching test results, as concentrations found in laboratory experiments are not directly comparable to the field situations. Another task will be the selection of compounds to be considered for construction products, which are often a complex mixture and contain additives, pigments, stabilization agents, etc. The formulations of the products may serve as a starting point, but total content is a poor predictor for leachability, and analysis of the eluates is necessary. In some cases, non-targeted approaches might be required to identify compounds in the eluates. In the identification process, plausibility checks referring to available information should be included. Ecotoxicological tests are a complementary method to test eluates, and the combined effects of all compounds-including degradation products-are included. A bio test battery has been applied in a round robin test and was published in a guidance document. Published studies on the ecotoxicity of construction products show the tests' suitability to distinguish between products with small and larger effects on the environment.

Recommendation for a test battery for the ecotoxicological evaluation of the environmental safety of construction products.

The European Construction Products Regulation allows Member States to adopt rules for evaluating the environmental impact of their buildings. The aim of the project was to develop recommendations for a test battery for the ecotoxicological assessment of the environmental impact of construction products for outdoor use and contribute to the European harmonization of test methods. From a shortlist of 39 products 20 products were included in the ecotoxicological testing program. Monolithic and plate-like construction products were eluted in the Dynamic Surface Leaching test (DSLT) in accordance with CEN/TS 16637-2, granular products were eluted in a one stage batch test in accordance with DIN EN 12457-1. The eluates were examined in four aquatic toxicity tests (algae, daphnia, luminescent bacteria, fish eggs), a genotoxicity test (umu test) and in the respirometer test (OECD 301 F). Here, low to very high ecotoxicity was observed (up to a dilution factor of 1536). Six out of 8 eluates, whose TOC exceeded 10 mg L-1 showed a good biodegradability above 75%. The intra-laboratory repeatability of the Lowest Ineffective Dilution (LID) usually was within ±1 dilution steps (ecotoxicity tests) and ±2 dilution steps (leaching and ecotoxicity tests). This is acceptable, when considering that the overall variability of sample preparation, leaching test, and bioassays add up. The conclusions lead to practical recommendations for a suitable combination of leaching and ecotoxicity tests.

Analysis of anticipation by 3D motion capturing - a new method presented in karate kumite.

Anticipation is an important performance factor in karate kumite. A new approach analysing anticipation in realistic combat situations by motion capturing with a high temporal resolution is presented. The advantage of this approach is that both karate athletes interacting sports specific can be recorded synchronously; thus, the presented method has the potential to analyse visual information pickup due to coordination pattern of interaction between real athletes. The aim is to demonstrate the usability of the current method for anticipation research and to investigate if the distance between two athletes and their attacking technique play a role in the reaction of the defending athlete. Furthermore, relevant cues lying within each attacking technique and little individual differences are shown. Four male karate athletes took part in this study. Logistic regression indicated that both factors (distance × attacking technique) play a significant role in reaction. However, a correlation between these factors shows that only the attacking technique is a good predictor for reaction. Results show that the attacking technique jabbing punch (jap. Kizami-Zuki) was easier to anticipate than the attacking techniques reverse punch (jap. Gyaku-Zuki) and the round kick (jap. Mawashi-Geri).

Significance of cadmium from artists' paints to agricultural soil and the food chain.

BACKGROUND: An Annex XV restriction dossier for cadmium in artists' paints was submitted by an EU member state to the European Chemicals Agency ECHA. By cleaning, used brushes under the tap cadmium can enter the food chain via waste water treatment and subsequent agricultural application of the sewage sludge. It was estimated that 110 kg Cd per year is spread on agricultural land via this exposure route. Other sources of Cd amount to almost 120 tons per year. RESULTS: The mobility of Cd from pigments was studied in a field-like scenario by leaching experiments using soil samples amended with sewage sludge and spiked with Cd pigments in percolation columns. The redox conditions were confirmed to be the decisive factor for the release of Cd. The release of Cd from artists' paints was in most cases 1 % or lower in the experiments performed. CONCLUSIONS: Application of sewage sludge containing Cd from artist paints does not increase the amount of Cd leached from this soils. Furthermore, the quantity of Cd from artists' paints calculated in the restriction dossier is negligible compared to other sources of Cd to agricultural soil. Therefore, ECHA did not consider the proposed restriction to be the most appropriate EU wide measure to address the negligible level of risk.

Calibration and field application of passive sampling for episodic exposure to polar organic pesticides in streams.

Rainfall-triggered runoff is a major driver of pesticide input in streams. Only few studies have examined the suitability of passive sampling to quantify such episodic exposures. In this study, we used Empore™ styrene-divinylbenzene reverse phase sulfonated disks (SDB disks) and event-driven water samples (EDS) to assess exposure to 15 fungicides and 4 insecticides in 17 streams in a German vineyard area during 4 rainfall events. We also conducted a microcosm experiment to determine the SDB-disk sampling rates and provide a free-software solution to derive sampling rates under time-variable exposure. Sampling rates ranged from 0.26 to 0.77 L d(-1) and time-weighted average (TWA) concentrations from 0.05 to 2.11 µg/L. The 2 sampling systems were in good agreement and EDS exceeded TWA concentrations on average by a factor of 3. Our study demonstrates that passive sampling is suitable to quantify episodic exposures from polar organic pesticides.

Effect propagation in a toxicokinetic/toxicodynamic model explains delayed effects on the growth of unicellular green algae Scenedesmus vacuolatus.

Ecotoxicological standard tests assess toxic effects by exposing an organism to high concentrations over defined periods of time. To evaluate toxicity under field conditions such as fluctuating and pulsed exposures, process-based toxicokinetic/toxicodynamic (TK/TD) models may be used for extrapolation from the existing evidence. A TK/TD model was developed that simulates the effect on growth of the green algae Scenedesmus vacuolatus continuously exposed to the model chemicals norflurazon, triclosan, and N-phenyl-2-naphthylamine. A pharmacological time-response model describing the effects of anticancer treatments on cancer cell growth was adapted and modified to model the affected growth of synchronized algae cells. The TK/TD model simulates the temporal effect course by linking the ambient concentration of a chemical to the observable adverse effect via an internal concentration and a sequence of biological events in the organism. The parameters of the toxicodynamic model are related to the growth characteristics of algae cells, a no effect concentration, the chemical efficacy as well as the ability of recovery and repair, and the delay during damage propagation. The TK/TD model fits well to the observed algae growth. The effect propagation through cumulative cell damage explained the observed delayed responses better than just the toxicokinetics. The TK/TD model could facilitate the link between several effect levels within damage propagation, which prospectively may be helpful to model adverse outcome pathways and time-dependent mixture effects.

Titanium dioxide nanoparticles detoxify pirimicarb under UV irradiation at ambient intensities.

Titanium dioxide nanoparticles (nTiO2) form reactive oxygen species (ROS) under irradiation by ultraviolet light (UV). This known photocatalytic activity may finally affect the presence and toxicity of organic environmental chemicals, which have not yet been studied at ambient UV intensity. The authors used a three-factorial design to evaluate the interaction of the carbamate insecticide pirimicarb (initial nominal concentration, 20 µg/L), ambient UV irradiation (40 W/m² for 15 min), and nTiO2(~100 nm; 2.0 mg/L). Pirimicarb, pirimicarb × UV, and pirimicarb × nTiO2 treatments revealed a median immobilization of Daphnia magna after 72 h ranging between 70 and 80%. This effect seemed to be caused by the initial nominal pirimicarb concentration. However, UV irradiation before an exposure of daphnids in the presence of 2.0 mg nTiO2/L reduced pirimicarb concentrations to values below the limit of quantification, likely because of the formation of ROS. This reduction was associated with an almost complete removal of toxicity for D. magna. Furthermore, during a second experiment, 0.2 mg nTiO2/L in combination with 15 min UV irradiation reduced pirimicarb concentrations by approximately 30%. These results indicate a detoxification and therefore remediation potential of the combined application of nTiO2 and UV irradiation at ambient levels. This potential has not been documented to date in surface waters, where nTiO2 concentrations in the low to medium µg/L range may occur.

Application of nd-SPME to determine freely dissolved concentrations in the presence of green algae and algae-water partition coefficients.

Biological tests are essential for toxicity assessment of chemicals to aquatic organisms. Since awareness is increasing that freely dissolved concentrations in test media may change during exposure and deviate significantly from nominal concentrations there is a need for concentration monitoring in biotests. Biotests are increasingly miniaturized with effect amounts of toxicants that are close to or below quantification limits of conventional analytical methods. Thus, the suitability of pre-equilibrium non-depletive (nd) solid phase microextraction (SPME) as an analytical method for small test volumes in the presence of green algae Scenedesmus vacuolatus was investigated. The method was validated for several compounds with different physical-chemical properties and effect concentrations. Limits of quantification were at least about 10 times smaller than the EC(50) of the compounds determined in earlier studies in a cell multiplication inhibition tests with Scenedesmus vacuolatus. Fouling of the fibres due to attached algae cells could be excluded and the method was found to be well suited to measure free concentrations in the algae test. The nd-SPME-method was applied to determine partitioning coefficients between algae and the surrounding aqueous phase and can be used to determine real exposure concentrations in a cell multiplication inhibition test with green algae.

Effect-directed analysis of contaminated sediments with partition-based dosing using green algae cell multiplication inhibition.

Effect-directed analysis (EDA) has been frequently and successfully used to identify key toxicants in sediment extracts. However, by disregarding bioavailability this approach may lead to a biased prioritisation of fractions and toxicants with respect to hazards and risks. To overcome this problem the present EDA of sediment components from the Bílina river (Most Czech Republic), that inhibit growth of the green algae Scenedesmus vacuolatus, applies a novel partition-based dosing technique to prioritize and identify major toxic fractions and compounds in comparison to conventional solvent dosing. The novel dosing technique is based on partitioning from loaded silicone rods to the aqueous phase similar to partition processes that determine exposure in native sediment-water systems. In the present study the application of partition-based dosing had a big influence suggesting polar compounds such as triclosan as key toxicants while polycyclic aromatic hydrocarbon (PAH) fractions did not exhibit significant effects. In contrast, conventional dosing prioritized mainly PAHs in agreement with previous studies. For both approaches individual toxicants could be confirmed quantitatively based on the index of confirmation quality (ICQ), which compares the effect of fractions and artificial mixtures of identified and quantified toxicants over the full range of effect levels.

Partitioning-based dosing: an approach to include bioavailability in the effect-directed analysis of contaminated sediment samples.

One of the major challenges of effect-directed identification of hazardous chemicals in sediments is the appropriate consideration of bioavailability for a hazard-based prioritization of fractions and toxicants. The equilibrium partitioning approach is frequently used to estimate the bioavailability of sediment contaminants. To simulate partitioning ofthe constituents of complex sediment contaminations in the sediment-water-biota system, a new dosing technique based on silicone elastomer stirrer bars (silicone rods) for use in a growth inhibition test with the green algae Scenedesmus vacuolatus was developed. The dosing technique has a high loading capacity and a fast achievement of equilibrium (5-50 min) for a broad range of model compounds. The subsequent delivery of compounds stored by the silicone during the bioassay compensates possible losses of compounds and keeps the concentrations constant. Furthermore, a dose-dependent response is achieved for single compounds and complex mixtures from sediment extracts. The extracts of three sediment samples from the Elbe River Basin were fractionated using a multistep HPLC method and investigated in the bioassay using conventional DMSO dosing and loaded silicone rods. The results of the toxicity test clearly show that the toxicity patterns are quite different for the two dosing techniques, whereas the differences between the sampling locations are less pronounced. We suggestthat partitioning-based dosing better reflects exposure in sediments and thus provides a more realistic identification of key toxicants.