Sediment quality assessment framework for per- and polyfluoroalkyl substances: Results from a preparatory study and regulatory implications.

A preparatory study was performed to develop a sediment quality and risk assessment strategy for Switzerland, addressing the following questions: the sediment fraction to be analyzed chemically (< 63 µm, or alternatively < 2 mm); the suitability of using perfluorooctanesulfonic acid (PFOS) as an indicator of per- and polyfluoroalkyl substances (PFAS) contamination in sediments; the availability of data for the derivation of sediment quality guidelines; and the suitability of normalization to total organic carbon (TOC). The results confirmed PFOS as a suitable indicator of PFAS contamination in sediments from small streams, being the most detected and on average with the highest concentrations among the analyzed PFAS. The fine fraction (< 63 µm) was more appropriate to screening for possible sources and studying the compound profiles at the study sites, but the analysis of the < 2 mm fraction and the normalization to a sample consisting of 100% of the < 63 µm fraction was, in principle, feasible for PFOS. Sediment quality guidelines for PFOS aiming to protect benthic invertebrates from generic adverse effects could be derived, but the available toxicity database is still too sparse. It was only possible to derive preliminary values. Sediment quality guidelines to protect wildlife and human health from secondary poisoning, using the equilibrium partitioning approach and simple trophic web models, were also derived. The use of food web models to derive sediment quality guidelines has not been validated, and the available database of Biota-Sediment Accumulation Factors and Trophic Magnification Factors for PFOS remains limited. However, it is still larger than the effect concentrations database based on sediment studies using benthic invertebrates. Normalization to TOC content in the field (0.2%-12.9%) was decisive in the quality assessment outcome. This is a widely accepted practice for hydrophobic organic contaminants, but its endorsement for PFOS would also benefit from validation. Integr Environ Assess Manag 2021;17:716-725. © 2021 SETAC.

Retrospective screening of high-resolution mass spectrometry archived digital samples can improve environmental risk assessment of emerging contaminants: A case study on antifungal azoles.

Environmental risk assessment associated with aquatic and terrestrial contamination is mostly based on predicted or measured environmental concentrations of a limited list of chemicals in a restricted number of environmental compartments. High resolution mass spectrometry (HRMS) can provide a more comprehensive picture of exposure to harmful chemicals, particularly through the retrospective analysis of digitally stored HRMS data. Using this methodology, our study characterized the contamination of various environmental compartments including 154 surface water, 46 urban effluent, 67 sediment, 15 soil, 34 groundwater, 24 biofilm, 41 gammarid and 49 fish samples at 95 sites widely distributed over the Swiss Plateau. As a proof-of-concept, we focused our investigation on antifungal azoles, a class of chemicals of emerging concern due to their endocrine disrupting effects on aquatic organisms and humans. Our results demonstrated the occurrence of antifungal azoles and some of their (bio)transformation products in all the analyzed compartments (0.1-100 ng/L or ng/g d.w.). Comparison of actual and predicted concentrations showed the partial suitability of level 1 fugacity modelling in predicting the exposure to azoles. Risk quotient calculations additionally revealed risk of exposure especially if some of the investigated rivers and streams are used for drinking water production. The case study clearly shows that the retrospective analysis of HRMS/MS data can improve the current knowledge on exposure and the related risks to chemicals of emerging concern and can be effectively employed in the future for such purposes.

Towards simple tools to assess functional effects of contaminants on natural microbial and invertebrate sediment communities.

Surface sediments can accumulate contaminants that affect microorganisms and invertebrates and disturb benthic ecological functions. However, effects of contaminants on ecological functions supported by sediment communities are understudied. Here, we tested the relevance of two simple tools to assess the ecotoxicological effects of metal contamination on natural sediment communities using particulate organic matter breakdown and decomposition as a functional descriptor. To this aim, we performed a 21-day laboratory microcosm experiment to assess the individual and combined effects of Cu and As (nominal concentration of 40 mg kg-1 dw each) using the bait-lamina method (cellulose, bran flakes, and active coal in PVC strips) as well as artificial tablets (cellulose, bran flakes and active coal embedded in an agar matrix). Sediment toxicity was also evaluated using the standardized ostracod toxicity test. Both the bait-lamina and artificial tablet methods showed low effects of As on organic matter breakdown and decomposition but strong effects of Cu on this important ecological function. Both also showed that the presence of Cu and As in mixture in the sediment induced total inhibition of organic matter breakdown and decomposition. The ostracod toxicity test also showed high toxicity of Cu-spiked and Cu-plus-As-spiked sediments and low toxicity of As-spiked sediments. Besides confirming that artificial organic matter substrates are relevant and useful for assessing the functional effects of contaminants on sediment micro- and macro-organism communities, these results suggest that the proposed methods offer promising perspectives for developing tools for use in assessing functional ecotoxicology in the sediment compartment.

Derivation of sediment Hg quality standards based on ecological assessment in river basins.

The Environmental Quality Standards (EQS) directive was an important improvement of long-term water quality monitoring at the European level, leading to the use of sediments and biota as relevant matrices for assessing priority substances under the European Water Framework directive. Currently, commonly accepted sediment EQS for Hg are missing in Europe. In this study we present a new, tiered approach to deriving sediment quality standards for Hg: the derivation of Predicted No-Effect Concentration (PNEC) from data in the literature, followed by adjusting values at regional scale, using ecological field data (macroinvertebrate community assessment) and field sediment ecotoxicity bioassays. The limited set of effect data available for Hg spiked-sediment ecotoxicity tests has resulted in unreliable PNEC values for sediment quality assessment. Field reference sites (n = 40) where the macroinvertebrate community status was assessed as High or Good were used to define the ecological background and threshold levels in sediments in northern Spain. Sediment QS developed in other areas were not suitable for specific basins in our study area, since they were within the range of our Hg background levels. Temporary sediment Quality Standards (QS) for Hg were developed for the Nalón River basin (where several mining districts occur), using field effect-based approaches such as sediment ecotoxicity data from Tubifex tubifex chronic bioassays and ecological assessment of macroinvertebrate communities. A proposal for Hg quality assessment in freshwater sediments of northern Spain is made based on ecologically relevant QS values, providing benchmark values for No-Effect and Effect Hg sediment concentrations.

Looking at biological community level to improve ecotoxicological assessment of freshwater sediments: report on a first French-Swiss workshop.

The first French-Swiss workshop on ecotoxicology of freshwater sediment communities was co-organized by the French Research Institute of Science and Technology for Environment and Agriculture (Irstea) and the Swiss Centre for Applied Ecotoxicology (Ecotox Centre EAWAG-EPFL) in Villié-Morgon (Beaujolais Region, France) on April 27-28, 2017. The workshop brought together scientists working in different fields of expertise (ecotoxicologists, ecologists, environmental chemists…), environmental stakeholder groups and managers, as well as economic players (start-ups and consultancies) to better connect research needs of potential end-users with research outputs. The objectives of this workshop were (i) to establish the state of the art of research in the characterization of sediment contamination and in the evaluation of the effects on sediment-associated biological communities and ecosystem functioning and (ii) to give an overview of the French and Swiss regulations dealing with the assessment of contaminated sediments in freshwater ecosystems. The ultimate goal was to collectively identify research needs and knowledge gaps, as well as to highlight ways to improve the ecotoxicological assessment of sediments in freshwater environments by further considering the structure and functions of associated microbial and invertebrate communities.

Sediment quality in the Atlantic coast of Spain.

Sediments from the Atlantic coast of Spain have been studied to evaluate environmental quality by using an integrated approach including chemical and toxicological data. Sediment samples were collected in four littoral ecosystems located in Spain, Bay of Cádiz, Guadalquivir River estuary, Ría of Huelva, and Ría of Coruña. To characterize the sediments, organic carbon, granulometric content, total sulfide, eight trace metals (Hg, Cd, Pb, Cu, Zn, As, Ni, and Cr), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) were measured. The toxicity of sediments was assessed with the amphipod Ampelisca brevicornis, the clam Ruditapes philippinarum, juveniles of the fish Solea senegalensis, populations of the estuarine rotifer Brachionus plicatilis, and populations of the bacterium Vibrio fischeri (Microtox). The results obtained show that in general, stations located in the Ría of Huelva were associated with heavy metal contamination and with the highest toxicity. Only chronic toxicity tests were capable of identifying the effects associated with PCB concentrations. The sediment quality guidelines calculated by means of a multivariate analysis approach for contaminants not associated with biological effects (mg/kg) are Hg, 0.54; Cd, 0.51; Pb, 260; Cu, 209; Zn, 513; As, 27.4; and total PCBs, 0.05.