RESUMO
During the 20th century, thousands of tons of munitions containing organoarsenic chemical warfare agents (CWAs) were dumped into oceans, seas and inland waters around the world. As a result, organoarsenic CWAs continue to leak from corroding munitions into sediments and their environmental concentrations are expected to peak over the next few decades. There remains, however, a lack of knowledge about their potential toxicity to aquatic vertebrates, such as fish. The aim of this study was to fill in this gap in research, by investigating the acute toxicity of organoarsenic CWAs on fish embryos, using the model species, Danio rerio. To estimate the acute toxicity thresholds of organoarsenic CWAs (Clark I, Adamsite, PDCA), a CWA-related compound (TPA), as well as four organoarsenic CWA degradation products (Clark I[ox], Adamsite[ox], PDCA[ox], TPA[ox]), standardized tests were performed following the OECD no. 236 Fish Embryo Acute Toxicity Test guidelines. Additionally, the detoxification response in D. rerio embryos was investigated by analysing the mRNA expression of five genes encoding antioxidant enzymes (CAT, SOD, GPx, GR and GST). During the 96 h of exposure, organoarsenic CWAs induced lethal effects in D. rerio embryos at very low concentrations (classified as 1st category pollutants according to GHS categorization), and were therefore deemed to be serious environmental hazards. Although TPA and the four CWA degradation products caused no acute toxicity even at their maximum solubility, the transcription of antioxidant-related genes was altered upon exposure to these compounds, indicating the need for further testing for chronic toxicity. Incorporating the results of this study into ecological risk assessments will provide a more accurate prediction of the environmental hazards posed by CWA-related organoarsenicals.
RESUMO
The Baltic Sea is a severely disturbed marine ecosystem previously used as a dumping ground for chemical warfare agents (CWA), which are now known to enter its food web. We have performed a modelling exercise using a calibrated and validated Central Baltic Ecopath with Ecosim (EwE) model to recreate the potential environmental pathways of the infamous Clark I (diphenylchlorarsine). Observations from modelling timestamps covering recent times correspond with in situ detections in sediments and Atlantic cod (Gadus morhua). Under applied modelling conditions and scenarios, there is an active transfer of Clark I from sediments through the Baltic Sea food-web. According to our results, Clark I bioaccumulates within the Baltic Sea food web exclusively throughout the detritus-based food chain. The EwE model for the Central Baltic Sea also allows the simulation of changes in the food web under multiple anthropogenic stressors and management efforts, including recommendations from the Helsinki Commission Baltic Sea Action Plan (HELCOM BSAP). Among all investigated scentarios and factors, the commercial fishing is the most impactful on Clark I accumulation rate and contamination transfer within the Baltic Sea food web. The study indicates the need to extend the existing monitoring approach by adding additional species representing a broader range of ecological niches and tiers within the food chains. From the environmental perspective, the remediation of Chemical Weapons by removal should be considered as part of the integrated management of the Baltic Sea.