Determination of non-extractable residues in soils: Towards a standardised approach.

After exposure of soils to anthropogenic organic chemicals non-extractable residues (NER) can be formed. The quantitative proportion of a compound which remains non-extractable is operationally defined by the extraction procedure employed and can be quantified only when using isotope labelled compounds (e.g. 14C or 13C). In Germany and the EU, there is no standardised procedure, how to determine NER, especially when different legal regulations apply. Consequently, the comparability of NER data is low. Hence, a major task of this study was the development of a general approach for the quantification of non-extractable residues (NER) in soils using radiotracer analysis. For that, extraction efficiencies were determined for 42 non-labelled organic chemicals spiked onto 3 soils applying a number of extraction techniques and conditions, developing an extraction procedure which provides high extraction efficiencies and a low variability for a broad spectrum of analytes. Additionally, NER generated within soil transformation studies according to OECD 307 using 14C-triclosan, 14C-fenoxycarb and 14C-acetaminophen were analysed using sequential batch extraction and pressurised liquid extraction (PLE). Depending on the extraction procedure used, the NER fraction related to 14C-triclosan in a soil varied greatly between 96% and 28%. In this study a widely universal extraction procedure was developed to improve the comparability of the NER data and limit overestimation of NER, which can be of enormous consequence for the assessment of persistence and environmental risk of organic chemicals. Furthermore, silylation, EDTA-extraction and HCl-treatment were compared regarding a further analysis of NER using radiotracer analysis.

Quaternary (triphenyl-) phosphonium compounds: Environmental behavior and toxicity.

An analytical method based on high resolution mass spectrometry coupled with liquid chromatography (LC-HRMS) for 25 quaternary phosphonium compounds (QPCs) and derived phosphine oxides (POs) was developed and validated. To investigate the occurrence and fate of QPCs in the aquatic environment, water, suspended solids and sediments from the rivers Rhine and Elbe (upper and middle Elbe as well as tidal Elbe) were analyzed, as well as samples from tributaries bearing significant loads of QPCs. For the first time, the quaternary phosphonium compound tetrabutylphosphonium (Bu4P+) was detected. In the river Elbe concentrations were determined of up to 4700 ng/L (surface water) and 1000 µg/kg (sediment), respectively. Analysis of a time series of suspended solids (2005-2015) showed that QPCs have been present in the Elbe and Rhine catchment for at least one decade, with partly rising tendency. A degradation experiment with Rhine sediment revealed that triphenylphosphonium compounds (R-Ph3P+) and Bu4P+ are persistent in contact with sediment and suspended solids and tend to sorb onto sediment particles. Toxicological studies (reactive oxygen species (ROS) after substance exposure, Ames test, Micronucleus test, determination of cytotoxicity) with selected QPCs confirmed that all of them exhibit cytotoxicity and some even genotoxic potential at elevated concentrations, which emphasizes the need for an emission regulation of these compounds.