Environmental Risks of Medium-Chain Chlorinated Paraffins (MCCPs): A Review

Chlorinated paraffins are industrial chemicals that can be subdivided into short-chain (SCCP), medium-chain (MCCP), and long-chain (LCCP) chlorinated paraffins. The global production volumes of MCCPs are nowadays suspected to be much higher than those of S- and LCCPs, and the few available studies on the environmental occurrence of chlorinated paraffins report often higher MCCP concentrations than S- or LCCP concentrations in the environment. The present review focuses, therefore, on MCCPs specifically and provides a literature overview and a data analysis of the production volumes, PBT properties (persistence, bioaccumulation potential, and toxicity), and the worldwide measured concentrations of MCCP in environmental samples, biota, and humans. Furthermore, we include our own measurements of technical CP formulations from China, the major global producing country, to estimate the global production amounts of MCCPs. The key findings from this review are that (1) MCCPs are toxic to the aquatic environment, and the available data suggest that they are also persistent; (2) available time trends for MCCPs in soil, biota, and most of the sediment cores show increasing time trends over the last years to decades; and (3) MCCP concentrations in sediment close to local sources exceed toxicity thresholds (i.e., the PNEC). Our study shows that overall, MCCPs are of growing concern, and regulatory actions should be considered seriously

Deconvolution of Mass Spectral Interferences of Chlorinated Alkanes and Their Thermal Degradation Products: Chlorinated Alkenes

Chlorinated paraffins (CPs) are high production volume chemicals and ubiquitous environmental contaminants. CPs are produced and used as complex mixtures of polychlorinated <i>n</i>-alkanes containing thousands of isomers, leading to demanding analytical challenges. Due to their high degree of chlorination, CPs have highly complex isotopic mass patterns that often overlap, even when applying high resolution mass spectrometry. This is further complicated in the presence of degradation products such as chlorinated alkenes (CP-enes). CP-enes are formed by dehydrochlorination of CPs and are expected thermal degradation products in some applications of CPs, for example, as metal working fluids. A mathematical method is presented that allows deconvolution of the strongly interfered measured isotope clusters into linear combinations of isotope clusters of CPs and CP-enes. The analytical method applied was direct liquid injection into an atmospheric pressure chemical ionization source, followed by quadrupole time-of-flight mass spectrometry (APCI-qTOF-MS), operated in full scan negative ion mode. The mathematical deconvolution method was successfully applied to a thermally aged polychlorinated tridecane formulation (Cl₅–Cl₉). Deconvolution of mass patterns allowed quantifying fractions of interfering CPs and CP-enes. After exposure to 220 °C for 2, 4, 8, and 24 h, fractions of CP-enes within the respective interfering clusters increased from 0–3% at 0 h up to 37–44% after 24 h. It was shown that thermolysis of CPs follows first-order kinetics. The presented deconvolution method allows CP degradation studies with mass resolution lower than 20000 and is therefore a good alternative when higher resolution is not available

Screening of Pesticide and Biocide Patterns As Risk Drivers in Sediments of Major European River Mouths: Ubiquitous or River Basin-Specific Contamination?

Pesticides and biocides (PaB) are ubiquitously present in aquatic ecosystems due to their widespread application and have been detected in rivers at concentrations that may cause distress to aquatic life. Many of these compounds accumulate in sediments acting as long-term source for aquatic ecosystems. However, data on sediment contamination with current-use PaB in Europe are scarce. Thus, in this study, we elucidated PaB patterns and associated risks in sediments of seven major European rivers focusing on their last stretch as an integrative sink of particles transported by these rivers. Sediments were extracted with pressurized liquid extraction (PLE) using a broad-spectrum method recovering many compound classes with a wide range of physicochemical properties. Altogether 126 compounds were analyzed and 81 of them were detected with LC-HRMS and GC-NCI-MS/MS at least in one of the sediments. The highest number of compounds was detected (59) in River Elbe sediments close to Cuxhaven with outstanding concentrations ranging from 0.8 to 1691 mg/g organic carbon. Multivariate analysis identified a cluster with 3 ubiquitous compounds (cyhalothrin, carbendazim, fenpropimorph) and three clusters of chemicals with higher variability within and between rivers. Risk assessment indicates an acute toxic risk to benthic crustaceans at all investigated sites with the pyrethroids tefluthrin and cyfluthrin together with the fungicide carbendazim as the main drivers. Risks to algae were driven at most sites almost exclusively by photosynthesis inhibitors with estuary-specific herbicide mixtures, while in the rivers Po and Gironde cell division inhibitors played an important role at some sites. Mixtures of specific concern have been defined and suggested for integration in future monitoring programs