Marion Junghans

How a Complete Pesticide Screening Changes the Assessment of Surface Water Quality

A comprehensive assessment of pesticides in surface waters is challenging due to the large number of potential contaminants. Most scientific studies and routine monitoring programs include only 15-40 pesticides, which leads to error-prone interpretations. In the present study, an extensive analytical screening was carried out using liquid chromatography-high-resolution mass spectrometry, covering 86% of all polar organic pesticides sold in Switzerland and applied to agricultural or urban land (in total 249 compounds), plus 134 transformation products; each of which could be quantified in the low ng/L range. Five medium-sized rivers, containing large areas of diverse crops and urban settlements within the respective catchments, were sampled between March and July 2012. More than 100 parent compounds and 40 transformation products were detected in total, between 30 and 50 parent compounds in each two-week composite sample in concentrations up to 1500 ng/L. The sum of pesticide concentrations was above 1000 ng/L in 78% of samples. The chronic environmental quality standard was exceeded for 19 single substances; using a mixture toxicity approach, exceedances occurred over the whole measurement period in all rivers. With scenario calculations including only 30-40 frequently measured pesticides, the number of detected substances and the mixture toxicity would be underestimated on average by a factor of 2. Thus, selecting a subset of substances to assess the surface water quality may be sufficient, but a comprehensive screening yields substantially more confidence.

S-metolachlor pulse exposure on the alga Scenedesmus vacuolatus: Effects during exposure and the subsequent recovery

In streams and creeks, the aquatic flora is exposed to fluctuating concentrations of herbicides during and following their application. Peak concentrations of herbicides, like the chloroacetanilide S-metolachlor, are usually detected following rain events. In this study, we assessed the effect of S-metolachlor pulse exposure on the algae Scenedesmus vacuolatus. We measured the time-dependency of effects during exposure on algae population and identified the algae development stage most sensitive to S-metolachlor. Furthermore, we assessed the time-to-recovery of the algae following exposure. A 6h pulse exposure at 598microgl(-1) was sufficient to inhibit cell reproduction by 50%. However, the exposure period had to coincide with the cell development stage specifically inhibited by S-metolachlor, which is the end of the cell growth phase. In algae populations composed of cells at all development stages, we initially observed an increase in the size of some algal cells, ultimately leading to an inhibition of the growth rate. In these experimental conditions, effects were observed after 18h of exposure and greatly increased with time. The recovery of algae following exposure to strongly inhibiting S-metolachlor concentrations was delayed and only occurred after 29h. These findings suggest that peak exposure to S-metolachlor may affect the growth of sensitive alga in surface waters, considering that the effects extend beyond the period of exposure.

A decision tree for assessing effects from exposures to multiple substances

BackgroundThe Cefic Mixtures Industry Ad-hoc Team (MIAT) has investigated how risks from combined exposures can be effectively identified and managed using concepts proposed in recent regulatory guidance, new advances in risk assessment, and lessons learned from a Cefic-sponsored case study of mixture exposures.ResultsA series of tools were created that include: a decision tree, a system for grouping exposures, and a graphical tool (the MCR-HI plot). The decision tree allows the division of combined exposures into different groups, exposures where one or more individual components are a concern, exposures that are of low concern, and exposures that are a concern for combined effects but not for the effects of individual chemicals. These tools efficiently use available data, identify critical data gaps for combined assessments, and prioritize which chemicals require detailed toxicity information. The tools can be used to address multiple human health endpoints and ecological effects.ConclusionThe tools provide a useful approach for assessing risks associated with combined exposures to multiple chemicals.

QSAR analysis and specific endpoints for classifying the physiological modes of action of biocides in synchronous green algae.

We propose the use of additional physiological endpoints in the 24h growth inhibition test with synchronous cultures of Scenedesmus vacuolatus for the classification of physiological modes of toxic action of chemicals in green algae. The classification scheme is illustrated on the example of one baseline toxicant (3-nitroaniline) and five biocides (irgarol, diuron, Sea-Nine, tributyltin (TBT) and norflurazon). The well-established endpoint of inhibition of reproduction is used for an analysis of the degree of specificity of toxicity by comparing the experimental data with predictions from a quantitative structure-activity relationship (QSAR) for baseline toxicity (narcosis). For those compounds with a toxic ratio greater than 10, i.e. a 10 times higher effect in reproduction than predicted by baseline toxicity, additionally the physiological endpoints inhibition of photosynthesis, cell division and cell volume growth were experimentally assessed. Depending on the relative sensitivity of the different endpoints the chemicals were classified into five different classes of modes of toxic action using a flow chart that was developed in the present study. The advantage of the novel classification scheme is the simplicity of the experimental approach. For the determination of the inhibition of reproduction, the cell size and numbers are quantified with a particle analyzer. This information can be used to derive also the physiological endpoints of cell volume growth and inhibition of cell division. The only additional measurement is the inhibition of the photosynthesis efficiency, which can be easily performed using the non-invasive saturation pulse method and pulse-modulated chlorophyll fluorometry with the Tox-Y-PAM instrument. This mechanistic approach offers a great future potential in ecotoxicology for the physiological mode of action classification of chemicals in algae, which should be a crucial step considered in the risk assessment of chemicals.

Assessment of micropollutants from municipal wastewater - Combination of exposure and ecotoxicological effect data for Switzerland

Micropollutants (MPs) from municipal wastewater are frequently detected in surface waters and occur in ecotoxicologically relevant concentrations. Therefore a broadly accepted method for the assessment of MPs is needed. Here we propose a procedure for the assessment of MPs from municipal wastewater. The method suggested comprises (1) an approach for the identification of potentially polluted sites, (2) a compilation of a substance list with relevant MPs, (3) (eco)toxicologically based quality criteria, (4) a sampling strategy that considers the input-dynamics of chemicals and (5) a scheme to rate water quality with respect to MP contamination. In the proposed concept the assessment focuses upon those substances found repeatedly in municipal wastewaters (continuous inputs). Additionally, we explain how the Environmental Quality Standard (EQS) proposals were derived in accordance with the Water Framework Directive (WFD), and the currently developed Technical Guidance Document for EQS (TGD for EQS). Based on the proposed EQS, we provide a Swiss-wide risk assessment for 6 selected MPs.

Pesticides drive risk of micropollutants in wastewater-impacted streams during low flow conditions

Micropollutants enter surface waters through various pathways, of which wastewater treatment plants (WWTPs) are a major source. The large diversity of micropollutants and their many modes of toxic action pose a challenge for assessing environmental risks. In this study, we investigated the potential impact of WWTPs on receiving ecosystems by describing concentration patterns of micropollutants, predicting acute risks for aquatic organisms and validating these results with macroinvertebrate biomonitoring data. Grab samples were taken upstream, downstream and at the effluent of 24 Swiss WWTPs during low flow conditions across independent catchments with different land uses. Using liquid chromatography high resolution tandem mass spectrometry, a comprehensive target screening of almost 400 organic substances, focusing mainly on pesticides and pharmaceuticals, was conducted at two time points, and complemented with the analysis of a priority mixture of 57 substances over eight time points. Acute toxic pressure was predicted using the risk assessment approach of the multi-substance potentially affected fraction, first applying concentration addition for substances with the same toxic mode of action and subsequently response addition for the calculation of the risk of the total mixture. This toxic pressure was compared to macroinvertebrate sensitivity to pesticides (SPEAR index) upstream and downstream of the WWTPs. The concentrations were, as expected, especially for pharmaceuticals and other household chemicals higher downstream than upstream, with the detection frequency of plant protection products upstream correlating with the fraction of arable land in the catchments. While the concentration sums downstream were clearly dominated by pharmaceuticals or other household chemicals, the acute toxic pressure was mainly driven by pesticides, often caused by the episodic occurrence of these compounds even during low flow conditions. In general, five single substances explained much of the total risk, with diclofenac, diazinon and clothianidin as the main drivers. Despite the low predicted acute risk of 0%-2.1% for affected species, a significant positive correlation with macroinvertebrate sensitivity to pesticides was observed. However, more effect data for pharmaceuticals and a better quantification of episodic pesticide pollution events are needed for a more comprehensive risk assessment.

Assessing the reliability of ecotoxicological studies: An overview of current needs and approaches

In general, reliable studies are well designed and well performed, and enough details on study design and performance are reported to assess the study. For hazard and risk assessment in various legal frameworks, many different types of ecotoxicity studies need to be evaluated for reliability. These studies vary in study design, methodology, quality, and level of detail reported (e.g., reviews, peer-reviewed research papers, or industry-sponsored studies documented under Good Laboratory Practice [GLP] guidelines). Regulators have the responsibility to make sound and verifiable decisions and should evaluate each study for reliability in accordance with scientific principles regardless of whether they were conducted in accordance with GLP and/or standardized methods. Thus, a systematic and transparent approach is needed to evaluate studies for reliability. In this paper, 8 different methods for reliability assessment were compared using a number of attributes: categorical versus numerical scoring methods, use of exclusion and critical criteria, weighting of criteria, whether methods are tested with case studies, domain of applicability, bias toward GLP studies, incorporation of standard guidelines in the evaluation method, number of criteria used, type of criteria considered, and availability of guidance material. Finally, some considerations are given on how to choose a suitable method for assessing reliability of ecotoxicity studies. Integr Environ Assess Manag 2017;13:640-651.

An application of a decision tree for assessing effects from exposures to multiple substances to the assessment of human and ecological effects from combined exposures to chemicals observed in surface waters and waste water effluents

BackgroundA decision tree has been developed for evaluating risks posed by combined exposures to multiple chemicals. The decision tree divides combined exposures of humans and ecological receptors into groups where one or more components are a concern by themselves, where risks from the combined exposures are of low concern, and where there is a concern for the effects from the combined exposures but not from individual chemicals. This paper applies the decision tree to real-world examples of exposures to multiple chemicals, evaluates the usefulness of the approach, and identifies issues arising from the application.ResultsThe decision tree was used to evaluate human health and ecological effects from the combined exposure to 559 mixtures of substances measured in surface waters and effluents. The samples contained detectable levels of 2 to 49 substances. The key findings were, 1) the need for assessments of the combined exposures varied for ecological and human health effects and with the source of the monitoring data, 2) the majority of the toxicity came from one chemical in 44% of the exposures (human health) and 60% of exposures (ecological effects), 3) most cases, where risk from combined exposures was a concern, would have been identified using chemical-by-chemical assessments. Finally, the tree identified chemicals where data on the mode of action would be most useful in refining an assessment.ConclusionsThe decision tree provided useful information on the need for combined risk assessments and guidance on the questions that should be addressed in future research.

Aquatic exposures of chemical mixtures in urban environments: Approaches to impact assessment

Urban regions of the world are expanding rapidly, placing additional stress on water resources. Urban water bodies serve many purposes, from washing and sources of drinking water to transport and conduits for storm drainage and effluent discharge. These water bodies receive chemical emissions arising from either single or multiple point sources, diffuse sources which can be continuous, intermittent, or seasonal. Thus, aquatic organisms in these water bodies are exposed to temporally and compositionally variable mixtures. We have delineated source-specific signatures of these mixtures for diffuse urban runoff and urban point source exposure scenarios to support risk assessment and management of these mixtures. The first step in a tiered approach to assessing chemical exposure has been developed based on the event mean concentration concept, with chemical concentrations in runoff defined by volumes of water leaving each surface and the chemical exposure mixture profiles for different urban scenarios. Although generalizations can be made about the chemical composition of urban sources and event mean exposure predictions for initial prioritization, such modeling needs to be complemented with biological monitoring data. It is highly unlikely that the current paradigm of routine regulatory chemical monitoring alone will provide a realistic appraisal of urban aquatic chemical mixture exposures. Future consideration is also needed of the role of nonchemical stressors in such highly modified urban water bodies. Environ Toxicol Chem 2018;37:703-714.

Multiple stressor effects in Chlamydomonas reinhardtii – Toward understanding mechanisms of interaction between effects of ultraviolet radiation and chemical pollutants

The effects of chemical pollutants and environmental stressors, such as ultraviolet radiation (UVR), can interact when organisms are simultaneously exposed, resulting in higher (synergistic) or lower (antagonistic) multiple stressor effects than expected based on the effects of single stressors. Current understanding of interactive effects is limited due to a lack of mechanism-based multiple stressor studies. It has been hypothesized that effect interactions may generally occur if chemical and non-chemical stressors cause similar physiological effects in the organism. To test this hypothesis, we exposed the model green alga Chlamydomonas reinhardtii to combinations of UVR and single chemicals displaying modes of action (MOA) similar or dissimilar to the impact of UVR on photosynthesis. Stressor interactions were analyzed based on the independent action model. Effect interactions were found to depend on the MOA of the chemicals, and also on their concentrations, the exposure time and the measured endpoint. Indeed, only chemicals assumed to cause effects on photosynthesis similar to UVR showed interactions with UVR on photosynthetic yield: synergistic in case of Cd(II) and paraquat and antagonistic in case of diuron. No interaction on photosynthesis was observed for S-metolachlor, which acts dissimilarly to UVR. However, combined effects of S-metolachlor and UVR on algal reproduction were synergistic, highlighting the importance of considering additional MOA of UVR. Possible mechanisms of stressor effect interactions are discussed.