BackgroundAlthough the crucial importance of sediments in aquatic systems is well-known, sediments are often neglected as a factor in the evaluation of water quality assessment. To support and extend previous work in that field, this study was conducted to assess the impact of surface water and sediment on fish embryos in the case of a highly anthropogenically influenced river catchment in Central Hesse, Germany.ResultsThe results of 96 h post fertilisation fish embryo toxicity test with Danio rerio (according to OECD Guideline 236) revealed that river samples comprising both water and sediment exert pivotal effects in embryos, whereas surface water alone did not. The most prominent reactions were developmental delays and, to some extent, malformations of embryos. Developmental delays occurred at rates up to 100% in single runs. Malformation rates ranged mainly below 10% and never exceeded 25%.ConclusionA clear relationship between anthropogenic point sources and detected effects could not be established. However, the study illustrates the critical condition of the entire river system with respect to embryotoxic potentials present even at the most upstream test sites. In addition, the study stresses the necessity to take into account sediments for the evaluation of ecosystem health in industrialised areas.

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Bio-based polymers have been suggested as one possible opportunity to counteract the progressive accumulation of microplastics in the environments. The gradual substitution of conventional plastics by bio-based polymers bears a variety of novel materials. The application of bioplastics is determined by their stability and bio-degradability, respectively. With the increasing implementation of bio-based plastics, there is also a demand for rapid and non-elaborate methods to determine their bio-degradability. Here, we propose an improved pH Stat titration assay optimized for bio-based polymers under environmental conditions and controlled temperature. Exemplarily, suspensions of poly(lactic acid) (PLA) and poly(butylene succinate) (PBS) microparticles were incubated with proteolytic and lipolytic enzymes. The rate of hydrolysis, as determined by counter-titration with a diluted base (NaOH), was recorded for two hours. PLA was hydrolyzed by proteolytic enzymes but not by lipase. PBS, in contrast, showed higher hydrolysis rates with lipase than with proteases. The thermal profile of PLA hydrolysis by protease showed an exponential increase from 4 to 30 °C with a temperature quotient Q10 of 5.6. The activation energy was 110 kJ·mol−1. pH-Stat titration proved to be a rapid, sensitive, and reliable procedure supplementing established methods of determining the bio-degradability of polymers under environmental conditions.

The progressive substitution of petroleum-based polymers, such as polyethylene, polyvinylchloride, or polyethylene terephtalate, by so-called bioplastics facilitated the development and production of many new materials. The continuously refined properties of bioplastic compounds and their blends enable various applications. With growing production and utilization of bioplastic products, these materials are increasingly discarded into the environment. Although many of these materials are labeled biodegradable, there is limited information about their degradability under environmental conditions. We tested the enzymatic degradability of five bioplastic compounds with the rapid pH-Stat titration assay at environmentally relevant seawater temperatures between 5 and 30°C and pH 8.2. These plastics, issued from the European Horizon 2020 Project ´Bioplastics Europe´, are based on polylactic acid (PLA), polybutylene succinate (PBS), and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV). Suspensions of microparticles (< 200 µm) were incubated with each of the three hydrolytic enzymes, protease, lipase, and esterase. A PLA-based compound blended with polybutylene adipate terephthalate (PBAT) showed the highest hydrolysis rate of 30 nmol·min-1 when incubated with lipase at 30°C. All other materials showed low hydrolysis rates of less than 10 nmol·min-1. Below 20°C, hydrolysis almost ceased. Plate clearing assays with the same enzymes at 37°C and pH 5 and pH 8, respectively, largely confirmed the results of the pH-Stat titration assays. Our findings indicate that there is a potential degradation of most of the materials with at least one of these hydrolytic enzymes. Nonetheless, the rate of enzymatic degradation under environmentally relevant conditions is low, which indicates only a marginal degradability of bioplastics in the marine environment.

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