Tracking complex mixtures of chemicals in our changing environment.

Chemicals have improved our quality of life, but the resulting environmental pollution has the potential to cause detrimental effects on humans and the environment. People and biota are chronically exposed to thousands of chemicals from various environmental sources through multiple pathways. Environmental chemists and toxicologists have moved beyond detecting and quantifying single chemicals to characterizing complex mixtures of chemicals in indoor and outdoor environments and biological matrices.

LC-MS screening of poly- and perfluoroalkyl substances in contaminated soil by Kendrick mass analysis.

The application of contaminated paper sludge on arable land in southwest Germany caused the occurrence of a broad range of poly- and perfluoroalkyl substances (PFASs) on soil. Recently, the dead-end transformation products (TPs) perfluorooctanoic acid and perfluorooctanesulfonic acid were detected in groundwater and drinking water. The precursors and other transformation products mostly remained unknown.

Photochemistry of iron in aquatic environments.

Light energy is a driver for many biogeochemical element cycles in aquatic systems. The sunlight-induced photochemical reduction of ferric iron (Fe(iii) photoreduction) to ferrous iron (Fe(ii)) by either direct ligand-to-metal charge transfer or by photochemically produced radicals can be an important source of dissolved Fe in aqueous and sedimentary environments. Reactive oxygen species (ROS) are formed by a variety of light-dependent reactions.

The method controls the story - Sampling method impacts on the detection of pore-water nitrogen concentrations in streambeds.

Biogeochemical gradients in streambeds are steep and can vary over short distances often making adequate characterisation of sediment biogeochemical processes challenging. This paper provides an overview and comparison of streambed pore-water sampling methods, highlighting their capacity to address gaps in our understanding of streambed biogeochemical processes. This work reviews and critiques available pore-water sampling techniques to characterise streambed biogeochemical conditions, including their characteristic spatial and temporal resolutions, and associated advantages and limitations.

Fe(III) Photoreduction Producing Fe in Oxic Freshwater Sediment.

Iron(III) (Fe(III)) photoreduction plays an important role in Fe cycling and Fe(II) bioavailability in the upper ocean. Although well described for water columns, it is currently unknown to what extent light impacts the production of dissolved Fe(II) (Fe) in aquatic sediments. We performed high-resolution voltammetric microsensor measurements and demonstrated light-induced Fe release in freshwater sediments from Lake Constance.

Deciphering the Variability of Stable Isotope (C, Cl) Fractionation of Tetrachloroethene Biotransformation by strains Carrying Different Reductive Dehalogenases Enzymes.

Kinetic isotope effects have been used successfully to prove and characterize organic contaminant transformation on various scales including field and laboratory studies. For tetrachloroethene (PCE) biotransformation, however, causes for the substantial variability of reported isotope enrichment factors (ε) are still not deciphered (ε = -0.4 to -19.

Experimental Validation of Mass Balance Models for in Vitro Cell-Based Bioassays.

The freely dissolved concentration in the assay medium () and the total cellular concentration () are essential input parameters for quantitative in vitro-to-in vivo extrapolations (QIVIVE), but available prediction tools for and have not been sufficiently validated with experimental data. In this study, medium-water distribution ratios () and cell-water distribution ratios () for four different cells lines were determined experimentally for 12 neutral and five ionizable chemicals. Literature data for seven organic acids were added to the dataset, leading to 24 chemicals in total.

Stable carbon isotope analysis of polyphosphonate complexing agents by anion chromatography coupled to isotope ratio mass spectrometry: method development and application.

Compound-specific carbon isotope analysis (carbon CSIA) by liquid chromatography/isotope ratio mass spectrometry (LC-IRMS) is a novel and promising tool to elucidate the environmental fate of polar organic compounds such as polyphosphonates, strong complexing agents for di- and trivalent cations with growing commercial importance over the last decades. Here, we present a LC-IRMS method for the three widely used polyphosphonates 1-hydroxyethane 1,1-diphosphonate (HEDP), amino tris(methylenephosphonate) (ATMP), and ethylenediamine tetra(methylenephosphonate) (EDTMP). Separation of the analytes, as well as ATMP and its degradation products, was carried out on an anion exchange column under acidic conditions.

Future large hydropower dams impact global freshwater megafauna.

Dam construction comes with severe social, economic and ecological impacts. From an ecological point of view, habitat types are altered and biodiversity is lost. Thus, to identify areas that deserve major attention for conservation, existing and planned locations for (hydropower) dams were overlapped, at global extent, with the contemporary distribution of freshwater megafauna species with consideration of their respective threat status.

Rice production threatened by coupled stresses of climate and soil arsenic.

Projections of global rice yields account for climate change. They do not, however, consider the coupled stresses of impending climate change and arsenic in paddy soils. Here, we show in a greenhouse study that future conditions cause a greater proportion of pore-water arsenite, the more toxic form of arsenic, in the rhizosphere of Californian Oryza sativa L.

Effect-Directed Analysis of Progestogens and Glucocorticoids at Trace Concentrations in River Water.

Effect-based monitoring is increasingly applied to detect and-in conjunction with chemical analysis-to identify endocrine-disrupting compounds (EDCs) in the environment. Although this approach of effect-directed analysis has been successfully demonstrated for estrogenicity and androgenicity, data on progestogens and glucocorticoids driving endocrine disruption are quite limited. We investigated progestogenic and glucocorticoid activities in Danube River water receiving untreated wastewater from Novi Sad, Serbia.

Recommendations for Improving Methods and Models for Aquatic Hazard Assessment of Ionizable Organic Chemicals.

Ionizable organic chemicals (IOCs) such as organic acids and bases are an important substance class requiring aquatic hazard evaluation. Although the aquatic toxicity of IOCs is highly dependent on the water pH, many toxicity studies in the literature cannot be interpreted because pH was not reported or not kept constant during the experiment, calling for an adaptation and improvement of testing guidelines. The modulating influence of pH on toxicity is mainly caused by pH-dependent uptake and bioaccumulation of IOCs, which can be described by ion-trapping and toxicokinetic models.

Designing field-based investigations of organic micropollutant fate in rivers.

Organic micropollutants in rivers are emitted via diffuse and point sources like from agricultural practice or wastewater treatment plants (WWTP). Extensive laboratory and field experiments have been conducted to understand emissions and fate of these pollutants in freshwaters. Nevertheless, data is often difficult to compare since common protocols for appropriate approaches are largely missing.

Author Correction: Mapping the world's free-flowing rivers.

An Amendment to this paper has been published and can be accessed via a link at the top of the paper.

Exposure to disinfection by-products in swimming pools and biomarkers of genotoxicity and respiratory damage - The PISCINA2 Study.

Background: Swimming in pools is a healthy activity that entails exposure to disinfection by-products (DBPs), some of which are irritant and genotoxic.

Objectives: We evaluated exposure to DBPs during swimming in a chlorinated pool and the association with short-term changes in genotoxicity and lung epithelium permeability biomarkers.

Methods: Non-smoker adults (N = 116) swimming 40 min in an indoor pool were included.

Baseline Toxicity and Volatility Cutoff in Reporter Gene Assays Used for High-Throughput Screening.

Most studies using high-throughput cell-based bioassays tested chemicals up to a certain fixed concentration. It would be more appropriate to test up to concentrations predicted to elicit baseline toxicity because this is the minimal toxicity of every chemical. Baseline toxicity is also called narcosis and refers to nonspecific intercalation of chemicals in biological membranes, leading to loss of membrane structure and impaired functioning of membrane-related processes such as mitochondrial respiration.

Air-soil diffusive exchange of PAHs in an urban park of Shanghai based on polyethylene passive sampling: Vertical distribution, vegetation influence and diffusive flux.

Compared with dry and wet deposition rates, air-soil exchange fluxes cannot be directly measured experimentally. Polyethylene passive sampling was applied to assess transport directions and to measure concentration gradients in order to calculate diffusive fluxes of polycyclic aromatic hydrocarbons (PAHs) across the air-soil interface in an urban park of Shanghai, China. Seven campaigns with high spatial resolution sampling at 18 heights between 0 and 200 cm above the ground were conducted in 2017-2018.

Mass Transfer Limitation during Slow Anaerobic Biodegradation of 2-Methylnaphthalene.

While they are theoretically conceptualized to restrict biodegradation of organic contaminants, bioavailability limitations are challenging to observe directly. Here we explore the onset of mass transfer limitations during slow biodegradation of the polycyclic aromatic hydrocarbon 2-methylnaphthalene (2-MN) by the anaerobic, sulfate-reducing strain NaphS2. Carbon and hydrogen compound specific isotope fractionation was pronounced at high aqueous 2-MN concentrations (60 μM) (ε = -2.

Effects of Leachates from UV-Weathered Microplastic in Cell-Based Bioassays.

Standard ecotoxicological testing of microplastic does not provide insight into the influence that environmental weathering by, e.g., UV light has on related effects.

Long-term mass flux assessment of a DNAPL source area treated using bioremediation.

This study assessed the long-term effectiveness of bioremediation as a remedial strategy for a chlorinated, ethene dense, non-aqueous phase liquid (DNAPL) source area, consisting of a higher- and a lower-permeability zone at Alameda Point, California. The evaluation was performed over 3.7 years after cessation of active source area bioremediation using passive flux meters (PFMs), push-pull tracer tests, and soil cores.

Quantification of freely dissolved effect concentrations in in vitro cell-based bioassays.

Improved understanding of chemical exposure in in vitro bioassays is required for quantitative in vitro-in vivo extrapolation (QIVIVE). In this study, we quantified freely dissolved concentrations in medium sampled from in vitro cell-based bioassays (C) for nine chemicals with different hydrophobicity and speciation at the time point of dosing and after an incubation period of 24 h using solid-phase microextraction. The chemicals were tested in two reporter gene assays, the AREc32 assay indicative of the oxidative stress response and the PPARγ-GeneBLAzer assay that responds to chemicals which bind to the peroxisome proliferator-activated receptor gamma.

Combined Ion-Trapping and Mass Balance Models To Describe the pH-Dependent Uptake and Toxicity of Acidic and Basic Pharmaceuticals in Zebrafish Embryos ( Danio rerio).

The aim of the current study was to understand and develop models to predict the pH-dependent toxicity of ionizable pharmaceuticals in embryos of the zebrafish Danio rerio. We found a higher uptake and toxicity with increasing neutral fraction of acids (diclofenac, genistein, naproxen, torasemide, and warfarin) and bases (metoprolol and propranolol). Simple mass balance models accounting for the partitioning to lipids and proteins in the zebrafish embryo were found to be suitable to predict the bioconcentration after 96 h of exposure if pH values did not differ much from the internal pH of 7.

The Multi-Purpose Airborne Sensor Carrier MASC-3 for Wind and Turbulence Measurements in the Atmospheric Boundary Layer.

For atmospheric boundary-layer (ABL) studies, unmanned aircraft systems (UAS) can provide new information in addition to traditional in-situ measurements, or by ground- or satellite-based remote sensing techniques. The ability of fixed-wing UAS to transect the ABL in short time supplement ground-based measurements and the ability to extent the data horizontally and vertically allows manifold investigations. Thus, the measurements can provide many new possibilities for investigating the ABL.

Mapping the world's free-flowing rivers.

Free-flowing rivers (FFRs) support diverse, complex and dynamic ecosystems globally, providing important societal and economic services. Infrastructure development threatens the ecosystem processes, biodiversity and services that these rivers support. Here we assess the connectivity status of 12 million kilometres of rivers globally and identify those that remain free-flowing in their entire length.