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PER: and polyfluoroalkyl substances have gained increased attention due to their persistence, ubiquitous presence in the environment, and toxicity. We hypothesised that the formation of non-extractable residues [NER] occurs in soils and contributes to the overall persistence of these priority pollutants, and that NER formation is controlled by temperature. To test these hypotheses, we used 14 C-labelled perfluorooctanoic acid [PFOA] as target compound, added it to two arable soils (Cambisol, Luvisol), and incubated them at 10 °C and 20 °C in the dark. To support potential co-metabolic decomposition, some samples were additionally fed with glucose to enhance microbial activity. The PFOA residues were then sequentially extracted using 0.01 M CaCl 2 , followed by accelerated solvent extraction (ASE) with methanol or methanol/acetic acid after 0, 1, 3, 9, 30, 62, and 90 days of incubation. In addition, we monitored the release of 14 C into the gas phase as well as [ 14 C]-PFOA-NER after dry combustion and liquid scintillation counting. After 90 days, we found that the [ 14 C]-PFOA content declined in the extraction order of CaCl 2 ((bio)available fraction) > ASE (residual fraction) > NER > gas fraction), with most rapid changes occurring in the first 9 days of incubation. NER formation was different in the two soils and reached 5-9% of the applied amount in the Cambisol and Luvisol, respectively. Noteworthy the proportion of 14 C-PFOA in the (bio)available fraction remained relatively stable over time at 56-62% of the applied amount, indicating the reversible transfer into this fraction from a bi-exponentially declining residual (ASE) pool. These dissipation patterns were neither influenced by temperature nor by the addition of glucose. We conclude that NER exist for PFOA, but that the majority of PFOA remains in (bio)available form, thus maintaining toxicity and mobility in soil for prolonged periods of time., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Recent studies revealed that freshwaters are not only polluted by chemicals, but also by persistent synthetic material like microplastics (plastic particles <1 mm). Microplastics include a diverse range of characteristics, e.g. polymer type, size or shape, but also their tendency to sorb pollutants or release additives. Although there is rising concern about the pollution of freshwaters by microplastics, knowledge about their potential effects on organisms is limited. For a better understanding of their risks, it is crucial to unravel which characteristics influence their effects on organisms. Analysing effects by the mere particles is the first step before including more complex interactions e.g. with associated chemicals. The aim of this study was to analyse potential physical effects of microplastics on one representative organism for limnic zooplankton (Daphnia magna). We investigated whether microplastics can be ingested and whether their presence causes adverse effects after short-term exposure. Daphnids were exposed for up to 96 h to 1-μm and 100-μm polyethylene particles at concentrations between 12.5 and 400 mg L(-1). Ingestion of 1-μm particles led to immobilisation increasing with dose and time with an EC50 of 57.43 mg L(-1) after 96 h. 100-μm particles that could not be ingested by the daphnids had no observable effects. These results underline that, considering high concentrations, microplastic particles can already induce adverse effects in limnic zooplankton. Although it needs to be clarified if these concentrations can be found in the environment these results are a basis for future impact analysis, especially in combination with associated chemicals., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Sulfadiazine (SDZ) belongs to the chemical class of sulfonamides, one of the most important groups of antibiotics applied in animal husbandry in Europe. These antibiotics end up in the soil after manure from treated animals is applied as fertilizer. They can inhibit soil microbial functions and enhance the spread of resistance genes among soil microorganisms. In order to assess the exposure of soil microorganisms to SDZ, a conceptual kinetic model for the prediction of temporally resolved antibiotic concentrations in soil was developed. The model includes transformation reactions, reversible sequestration and the formation of non-extractable residues (NER) from SDZ and its main metabolites N(4)-acetyl-sulfadiazine (N-ac-SDZ) and 4-hydroxy-sulfadiazine (OH-SDZ). The optimum model structure and rate constants of SDZ kinetics and its metabolites were determined by fitting different model alternatives to sequential extraction data of a manure-amended Cambisol soil. N-ac-SDZ is degraded to SDZ with a half-life of 4d, whereas OH-SDZ is not. Though, based on the available data, the hydroxylation of SDZ seems to be negligible, it is still included in the model structure since this process has been observed in recent studies. Sequestration into a residual fraction has similar kinetics for SDZ, N-ac-SDZ and OH-SDZ and is one order of magnitude faster than the reverse translocation. The irreversible formation of NER is restricted to SDZ and OH-SDZ. The model shows good agreement when applied to extraction data measured independently for a Luvisol soil. The combination of sequential extraction data and the conceptual kinetic model enables us to gain further insight into the long-term fate and exposure of sulfonamides in soil.

The ionic speciation of sulfonamides is pH-driven and this may be crucial for their bioavailability and sorption to soil constituents, as well as for their uptake into bacterial cells. The inhibition behaviour of a bacterial test strain (Pseudomonas aeruginosa; DSM 1117), which was grown in the presence of different concentrations of 8 sulfonamides at pH values from 5 to 8, could be predicted by models that take the speciation of sulfonamides in- and outside of bacterial cells into account. Assuming a pH of 7.5 inside the cells (pH homeostasis), the strongest inhibition was predicted for the lowest external pH and for sulfonamides with the lowest pK(a) values. Growth experiments with Ps. aeruginosa basically reflected this predicted behaviour. However, Pantoea agglomerans -- a bacterial strain isolated from arable soil -- behaved surprisingly different regarding its pH dependency: all sulfonamides showed the strongest effects at pH 7 to 8 instead of being most effective at lowest pH, although the pK(a) dependencies followed the same pattern. Experimental and modeling results could be brought into good agreement for P. agglomerans if the cell-internal pH was admitted to approximate the external pH instead of implying pH homeostasis for modeling calculations. Thus, besides the actual concentration of sulfonamides, the pH dependent mode of reaction of different bacteria to sulfonamides may additionally govern the population dynamics in soils.

The uptake of sulfonamides into bacterial cells was simulated by a dynamic model to estimate bioavailability and steady-state accumulation of sulfonamides in the cells. Uptake of sulfonamides is modeled as diffusion-like transport of the neutral molecule and the ionic species. Speciation outside and inside the cell depends on the extra- and intracellular pH and the pK(a)-value of the antibiotic active SO(2)NH moiety. The ratio between intra- and extracellular sulfonamide concentration is used as a measure for potential sulfonamide accumulation in bacterial cells. Simulated ratios are in good agreement with experimental data for various sulfonamides with pK(a2) values ranging from 5.0 up to 11.8. Sensitivity analyses indicate that intracellular sulfonamide concentration depend significantly on the degree of ionization in the cytoplasm and the surrounding medium. No accumulation in the cell occurs, if the external pH exceeds the intracellular pH. For sulfonamides with large pK(a)-values the internal activity equals the activity in the extracellular solution. Highest accumulation is reached if the pH gradient from inside to outside the cell is large, which depends on the bacterial pH-regulation mechanisms. The pH-dependent intracellular accumulation of various sulfonamides correlates well with their observed antibiotic effect on selected bacteria.