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Sind Stoffe persistenter als die Testsysteme glauben lassen?

Hydrolysis is an abiotic degradation process that influences the fate of many water-soluble substances in the environment. The ability of chemicals to undergo hydrolysis is currently tested in purified lab water in accordance with ⁠ OECD ⁠ guideline 111. It has been suggested that the addition of particles such as sediment or microplastic fibers i.e. may result in a change in the rate of hydrolysis. The project showed that adding commonly occurring particles in aquatic environments can lead to a reduced hydrolysis rate of organic substances, probably especially for sorbing cationic compounds. However, this effect is small compared to the influences known to occur for changes of pH or temperature. Veröffentlicht in Texte | 28/2022.

In-situ Raman spectra from Na2ATP solutions with starting pH 3 and 7 at 80,100 and 120 °C for determination of the hydrolysis rate constant of ATP

Abstract

Database of in-situ Raman spectra from N2H2ATP solutions at 80,100 and 120 °C and up to 1666 MPa for determination of the rate constant of the ATP hydrolysis

Abstract

Sind Stoffe persistenter als die Testsysteme glauben lassen? - Überprüfung der Testsysteme zur Persistenzbewertung am Beispiel der Hydrolyse

Die Hydrolyse ist ein entscheidender Prozess für den Abbau vieler wasserlöslicher Substanzen in der Umwelt. Hydrolysestudien mit neuen Substanzen werden derzeit in Reinstwasser durchgeführt. Es besteht die Möglichkeit, dass in natürlichen Gewässern vorkommende (natürliche oder künstliche) Partikel einen Einfluss auf die Hydrolyse von Spurenstoffen haben. Um dies zu testen, wurde in dieser Studie der hydrolytische Abbau von drei Substanzen in reinem Wasser sowie in Anwesenheit von Mikroplastikfasern, Sediment und Huminsäuren untersucht. Bei den ausgewählten Substanzen handelte es sich um das Fungizid Trifloxystrobin (TFX), das Benzodiazepin Oxazepam sowie um (Methoxycarbonylmethyl)triphenylphosphonium-(MCM-TPP-)bromid, ein Zwischenprodukt bei der Synthese von Alkenen. Im Fall von TFX konnte kein Einfluss der Störstoffe auf die Hydrolyse nachgewiesen werden. Auch mit Oxazepam wurde kein signifikanter Einfluss beobachtet, obwohl die Anwesenheit von Sediment und Huminsäuren zu einem leichten, aber nicht signifikanten, Anstieg der Halbwertszeit führte. Im Fall von MCM-TPP führte die Zugabe von Sediment als auch von Huminsäuren zu einer geringen, aber signifikanten Verlangsamung des Abbaus, während Mikroplastikfasern keinen Einfluss auf die Hydrolysegeschwindigkeit hatten. Die in natürlichen Gewässern vorkommende Sediment-Partikel und Huminstoffe können zu einer reduzierten Hydrolyserate bestimmter Spurenstoffe führen. Dies ist vermutlich für sorbierende kationische Verbindungen besonders wahrscheinlich. Dieser Effekt ist allerdings relativ klein im Vergleich zum Einfluss anderer Parameter wie der Änderung von pH-Wert und Temperatur. Auf Grundlage dieser Ergebnisse ergibt sich nicht die Notwendigkeit, die Berücksichtigung verschiedener Störstoffe bei der Bewertung von Chemikalien zu fordern. Allerdings wäre es sinnvoll, zusätzlich zur Konzentration der Ausgangsverbindung auch immer die Konzentration der wichtigsten Hydroly-seprodukte zu bestimmen, um geschlossene Massenbilanzen zu erhalten. Quelle: Forschungsbericht

Sediment contamination of an urban canal - a case study approach for an integrated assessment of organic sediment contamination

Purpose The pesticide DDT and its metabolites represent a contamination risk for the aquatic environment, especially the polar metabolite DDA. The study provides a quantitative assessment of long-term pollution risks from sedimentary DDT residues with a special focus on DDA. It presents an overview of the contamination range of different DDX compounds in the sediments of a canal in Berlin (Germany), resulting from a former industrial point source that has implications for drinking water resources in the nearby area. The comprehensive analysis scheme provides information on free accessible and potentially metabolized precursors also in the non-extractable residues. This allows a quantitative assessment of the DDA pollution potential derived from the sedimentary DDT residues. Materials and methods The area was investigated for fine-grained sediment by means of a geo-electric mapping. Twelve sediment cores were taken in four areas (three in each section). A wider range of precursor metabolites has been included due to their transformation potential to the polar metabolite DDA. The sediments were analysed quantitatively for extractable and easily releasable fractions by application of a variety of degradation techniques as well as a dispersion extraction procedure on the sediment samples. These extracts were fractionated and subsequently analysed by GC-MS. Results and discussion Concentrations were obtained for extractable and bound metabolites. Different scenarios for the calculation of the amount of contaminated sediment are displayed as a tool for contamination assessment. The formation potential of DDA as the water-soluble metabolite is presented. Several precursor metabolites, e.g. DDD and DDMS, extractable from the sediment organic matter, revealed a high potential for a long-term formation of DDA, especially in the easily releasable fraction (via hydrolysis) with a mean concentration of up to 11,000 (micro)g g-1 dry sediment. The resulting DDA contamination potential represents a significant pollution risk for the groundwater from a downstream waterworks area and by remobilisation into the whole ecosystem and adjacent rivers. Conclusions The application of the presented methods provides a tool for a quantitative assessment of the long-term release potential of DDA under different scenarios by a comprehensive analysis of contaminated sediments (and soils). This approach can be transferred to pollutants that are also characterized by a complex metabolism accompanied by bound residue formation. © The Author(s) 2020

The impact of water released from boehmite nanoparticles during curing in epoxy-based nanocomposites

The enhancing effect on mechanical properties of boehmite (y-AlOOH)nanoparticles (BNP) in epoxy-based nanocomposites on the macroscopic scaleencouraged recent research to investigate the micro- and nanoscopic proper-ties. Several studies presented different aspects relatable to an alteration of theepoxy polymer network formation by the BNP with need for further experi-ments to identify the mode of action. With FTIR-spectroscopic methods thisstudy identifies interactions of the BNP with the epoxy polymer matrix duringthe curing process as well as in the cured nanocomposite. The data reveals thatnot the BNP themselves, but the water released from them strongly influencesthe curing process by hydrolysis of the anhydride hardener or protonation ofthe amine accelerator. The changes of the curing processes are discussed indetail. The changes of the curing processes enable new explanation for thechanged material properties by BNP discussed in recent research like alowered glass transition temperature region (Tg) and an interphase formation. © Authors

A parameterization of the heterogeneous hydrolysis of N2O5 for mass-based aerosol models

The heterogeneous hydrolysis of N2O5 on the surface of deliquescent aerosol leads to HNO3 formation and acts as a major sink of NOx in the atmosphere during night-time. The reaction constant of this heterogeneous hydrolysis is determined by temperature (T), relative humidity (RH), aerosol particle composition, and the surface area concentration (S). However, these parameters were not comprehensively considered in the parameterization of the heterogeneous hydrolysis of N2O5 in previous mass-based 3-D aerosol modelling studies. In this investigation, we propose a sophisticated parameterization (NewN2O5) of N2O5 heterogeneous hydrolysis with respect to T, RH, aerosol particle compositions, and S based on laboratory experiments. We evaluated closure between NewN2O5 and a state-of-the-art parameterization based on a sectional aerosol treatment. The comparison showed a good linear relationship (R?=??0.91) between these two parameterizations. NewN2O5 was incorporated into a 3-D fully online coupled model, COSMOŃMUSCAT, with the mass-based aerosol treatment. As a case study, we used the data from the HOPE Melpitz campaign (10Ń25 September 2013) to validate model performance. Here, we investigated the improvement of nitrate prediction over western and central Europe. The modelled particulate nitrate mass concentrations ([NO3-]) were validated by filter measurements over Germany (Neuglobsow, Schmücke, Zingst, and Melpitz). The modelled [NO3-] was significantly overestimated for this period by a factor of 5Ń19, with the corrected NH3 emissions (reduced by 50?%) and the original parameterization of N2O5 heterogeneous hydrolysis. The NewN2O5 significantly reduces the overestimation of [NO3-] by ?~??35?%. Particularly, the overestimation factor was reduced to approximately 1.4 in our case study (12, 17Ń18 and 25 September 2013) when [NO3-] was dominated by local chemical formations. In our case, the suppression of organic coating was negligible over western and central Europe, with an influence on [NO3-] of less than 2?% on average and 20?% at the most significant moment. To obtain a significant impact of the organic coating effect, N2O5, SOA, and NH3 need to be present when RH is high and T is low. However, those conditions were rarely fulfilled simultaneously over western and central Europe. Hence, the organic coating effect on the reaction probability of N2O5 may not be as significant as expected over western and central Europe. Quelle: https://www.atmos-chem-phys.net/

A new concept for the ecotoxicological assessment of plastics under consideration of aging processes

Microplastics are widely distributed in aquatic and terrestrial environments, but up tonow less is known about (eco)toxicological impacts under realistic conditions. Researchso far has focused mainly on impacts on organisms by fresh, single-origin plasticfragments or beads. However, plastics found in the environment are complex incomposition, this means different polymer types and sources, with and withoutadditives and in all stages of age, and therefore, in a more or less advanced stage ofdegradation. For oxidized degradation products that might be released from plasticmaterials during aging, there is a lack of information on potentially adverse effects onaquatic biota. The latter is of particular interest as oxidized degradation products mightbecome more water soluble due to higher polarity and are more bioavailable, therefore.The present study focused on plastic leachates of polystyrene (PS) and polylactic acid(PLA), which were derived from alternating stress by hydrolysis and ultraviolet (UV)radiation-representing a realistic scenario in the environment. Test specimens of PS,PLA, or a PLA/PS layer (each 50%) were alternately exposed to UV radiation for 5 daysfollowed by hydrolysis for 2 days, for several weeks alternating. Ecotoxicological effectsof the storage water (artificial freshwater) of the test specimens and additionally, in asecond experimental setup, the effects of five potential polymer degradation productswere detected by 72 h algae growth inhibition tests withDesmodesmus subspicatus.Results clearly indicate inhibitory effects on algae growth by contaminants in thestorage water of stressed plastics with increasing growth inhibition of proceedinghydrolysis and UV stress times. Different polymers caused variable inhibitions of algaegrowth with stronger inhibitions by PS and less effects by PLA and the mixed layer ofboth. Moreover, not microplastic particles but the resulting dissolved degradationproducts after aging caused theecotoxicological effectsââą Ìwith strong effects by theoxidized degradation products. The existing data highlight the relevance of plastic agingas a framework for microplastic ecotoxicity evaluation and allow a proof of concept. © 2023 The Authors.

Busse Biogas GbR

Die Biogasanlage Busse Biogas GbR plant die Erweiterung der Anlage um eine semiaerobe Hydrolyse mit dem Ziel der schnelleren Abbaubarkeit der Inputstoffe und einer verbesserten Ausbeute hinsichtlich der Gaserzeugung. Die Vorbehandlung schwer abbaubarer Stoffe erfolgt durch Bakterien in einer Anmaische und anschließend in der bestehenden Biogasanlage.

Formation, classification and identification of non-extractable residues of 14C-labelled ionic compounds in soil

The influence of an ionic functional group on the fate of chemicals in the environment, especially the formation of non-extractable residues (NER), has not been systematically investigated. Using 4-n-dodecylphenol[phenylring-14C(U)], 4-n-dodecylbenzenesulfonicacid[phenylring-14C(U)] sodiumsalt (14C-DS-) and 4-n-dodecylbenzyltrimethylammoniumchloride[phenylring-14C(U)] (14C-DA+) all with a high structural similarity, the formation, classification and identification of NER of negatively (14C-DS-), positively (14C-DA+) and uncharged (14C-DP) chemicals were investigated in a sterilized and non-sterilized soil. After 84 days of incubation in non-sterile soil, 40.6%, 21.7% and 33.5% of the applied radioactivity (AR) of 14C-DP, 14C-DS- and 14C-DA+, respectively, were converted to NER. In contrast, in sterile soil NER formation was markedly lower. The NER were further investigated with respect to sequestered, covalently bound and biogenic residues (i.e. NER types I, II, and III). Silylation of 14C-DP, 14C-DS- and 14C-DA+ derived NER released 3.0-23.2% AR, indicating that these were sequestered, whereas the residual NER (12.9-33.1% AR) was covalently bound to the soil. Analysis of extracts derived by silylation showed that 14C-DP, but neither 14C-DS- nor 14C-DA+, were released by silylation, suggesting that DP might be part of the sequestered NER. Acid hydrolysis of the NER containing soil and subsequent analysis of soil extracts for 14C-aminoacids indicated that 2.5-23.8% AR were biogenic residues. Most DP and DS- derived NER were biogenically or covalently bound, whereas DA+ predominantly forms sequestered NER in soil. From these results we propose that chemicals forming high amounts of NER should be investigated regarding types I-III NER because sequestered parent compounds should be considered in persistence assessments. © 2019 The Authors. Published by Elsevier Ltd.

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