Identification of impurities of phosphate and brominated flame retardants

In the last years, new flame retardants (FRs) have been identified for the first time in products and in environmental samples by using mainly liquid chromatography coupled to high resolution mass spectrometry. For example, 2,2-bis(chloromethyl)propane-1,3-diyl-tetrakis(2-chloroethyl)bis(phosphate), known commercially as “V6”,1 or a triazine-based flame retardant [2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, TTBP-TAZ]2 were recently reported. Not only FRs, but also their byproducts, impurities or degradation products have been very recently identified, such as those derived from tetrabromobisphenol-A (TBBP-A) or tetrabromobisphenol-S.3,4 The persistency and toxicity of these impurities or related compounds, as well as their presence in the environment is still largely unknown. We present and discuss here an overview of our results on the investigations of impurities and degradation products of FRs, namely from TTBP-TAZ2, RDP5, TBBPA and TBBPA-based products6 and the impurity diphenyl phosphate (DPHP) that derives from a variety of phosphorus flame retardants (PFRs

Identification of impurities of phosphate and brominated flame retardants

In the last years, new flame retardants (FRs) have been identified for the first time in products and in environmental samples by using mainly liquid chromatography coupled to high resolution mass spectrometry. For example, 2,2-bis(chloromethyl)propane-1,3-diyl-tetrakis(2-chloroethyl)bis(phosphate), known commercially as “V6”,1 or a triazine-based flame retardant [2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, TTBP-TAZ]2 were recently reported. Not only FRs, but also their byproducts, impurities or degradation products have been very recently identified, such as those derived from tetrabromobisphenol-A (TBBP-A) or tetrabromobisphenol-S.3,4 The persistency and toxicity of these impurities or related compounds, as well as their presence in the environment is still largely unknown. We present and discuss here an overview of our results on the investigations of impurities and degradation products of FRs, namely from TTBP-TAZ2, RDP5, TBBPA and TBBPA-based products6 and the impurity diphenyl phosphate (DPHP) that derives from a variety of phosphorus flame retardants (PFRs

A deep dive into fat: Investigating blubber lipidomic fingerprint of killer whales and humpback whales in northern Norway

In cetaceans, blubber is the primary and largest lipid body reservoir. Our current understanding about lipid stores and uses in cetaceans is still limited, and most studies only focused on a single narrow snapshot of the lipidome. We documented an extended lipidomic fingerprint in two cetacean species present in northern Norway during wintertime. We were able to detect 817 molecular lipid species in blubber of killer whales (Orcinus orca) and humpback whales (Megaptera novaeangliae). The profiles were largely dominated by triradylglycerols in both species and, to a lesser extent, by other constituents including glycerophosphocholines, phosphosphingolipids, glycerophosphoethanolamines, and diradylglycerols. Through a unique combination of traditional statistical approaches, together with a novel bioinformatic tool (LION/web), we showed contrasting fingerprint composition between species. The higher content of triradylglycerols in humpback whales is necessary to fuel their upcoming half a year fasting and energy-demanding migration between feeding and breeding grounds. In adipocytes, we assume that the intense feeding rate of humpback whales prior to migration translates into an important accumulation of triacylglycerol content in lipid droplets. Upstream, the endoplasmic reticulum is operating at full capacity to supply acute lipid storage, consistent with the reported enrichment of glycerophosphocholines in humpback whales, major components of the endoplasmic reticulum. There was also an enrichment of membrane components, which translates into higher sphingolipid content in the lipidome of killer whales, potentially as a structural adaptation for their higher hydrodynamic performance. Finally, the presence of both lipid-enriched and lipid-depleted individuals within the killer whale population in Norway suggests dietary specialization, consistent with significant differences in δ15N and δ13C isotopic ratios in skin between the two groups, with higher values and a wider niche for the lipid-enriched individuals. Results suggest the lipid-depleted killer whales were herring specialists, while the lipid-enriched individuals might feed on both herrings and seals

Search for the evidence of endocrine disruption in the aquatic environment; Lessons to be learned from joint biological and chemical monitoring in the European project COMPREHEND

Between January 1999 and December 2001, the European Community project COMPREHEND was performed. The overall aim of COMPREHEND was to assess endocrine disruption in the aquatic environment in Europe, consequent to effluent discharge, with emphasis on estrogenic activity. COMPREHEND demonstrated the widespread occurrence of estrogenic effluents across Europe and presented evidence of impacts on a range of wild fish species. Using a variety of bioassays in combination with chemical analytical methods, estrogenic steroids of human origin from domestic wastewater effluents were identified as the most pervasive problem, although alkylphenols may be important estrogenic components of some industrial effluents. New tools have been developed for the identification of estrogenic effluents, and recommendations are made for the improvement of existing techniques. We have shown that individual fish within natural populations may be feminized to varying degrees, but it has not been possible to show, using traditional fish population parameters, that the survival of fish populations is threatened. However, laboratory-based fish life-cycle studies demonstrate the sensitivity of fish to estrogen (and androgen) exposure and how this might lead to complex (and potentially damaging) genetic changes at the population level. New approaches to this problem, utilizing recent advances made in the field of molecular and population genetics, are recommended. Finally, a study of estrogenic and androgenic activity of waste waters during the treatment process has shown that some of the existing wastewater treatment technologies have the potential to eliminate or minimize the hormonal activity of the final effluen

Risk assessment of chlorinated paraffins in feed and food

The Panel wishes to thank the hearing expert: Kerstin Krätschmer and EFSA staff member: Kelly Niermans for the support provided to this scientific output. The CONTAM Panel acknowledges all European competent institutions and other stakeholders that provided occurrence data in food and human milk and data on the toxicity of CPs, and supported the data collection for the Comprehensive European Food Consumption Database.Peer reviewedPublisher PD

EDA-EMERGE: an FP7 initial training network to equip the next generation of young scientists with the skills to address the complexity of environmental contamination with emerging pollutants

The initial training network consortium novel tools in effect-directed analysis to support the identification and monitoring of emerging toxicants on a European scale (EDA-EMERGE) was formed in response to the seventh EU framework program call to train a new generation of young scientists (13 PhD fellows and 1 postdoctoral fellow) in the interdisciplinary techniques required to meet the major challenges in the monitoring, assessment, and management of toxic pollution in European river basins. This 4-year project is of particular relevance considering the multidisciplinary analytical chemistry and biology skills required to investigate the enormous complexity of contamination, effects, and cause-effect relationships. By integrating innovative mode-of-action-based biodiagnostic tools including in vitro and in vivo tests, transgenic organisms, and ‘omics’ techniques with powerful fractionation and cutting edge, analytical, and computational structure elucidation tools, powerful new EDA approaches are being developed for the identification of toxicants in European surface and drinking waters. Innovative method development by young researchers at major European universities, research centers, and private companies has been closely interlinked with a joint European demonstration program, higher-tier EDA, and specialized training courses and secondments. Using a simplified protocol based on existing EDA tools, EDA-EMERGE fellows are also being trained to organize and run international and interdisciplinary sampling and monitoring campaigns within selected European river basin sites. Strong networking between academia, the private sector, and leading regulators in the field of river basin management and pollution management ensures the relevance of the research for practice and excellent employment opportunities for the fellows. Additionally, an internationally composed advisory board has been tasked to introduce new perspectives on monitoring, assessment, and management of emerging pollutants within and outside of Europe. The combination of cutting edge science with specialized training in complimentary soft skills is being offered with a strong emphasis on commercial exploitation and media competence which further enhances the employability of the fellows in research, academia, and beyond.publishedVersio

Identification strategy for unknown pollutants using high-resolution mass spectrometry: Androgen-disrupting compounds identified through effect-directed analysis

Effect-directed analysis has been applied to a river sediment sample of concern to identify the compounds responsible for the observed effects in an in vitro (anti-)androgenicity assay. For identification after non-target analysis performed on a high-resolution LTQ-Orbitrap, we developed a de novo identification strategy including physico-chemical parameters derived from the effect-directed analysis approach. With this identification strategy, we were able to handle the immense amount of data produced by non-target accurate mass analysis. The effect-directed analysis approach, together with the identification strategy, led to the successful identification of eight androgen-disrupting compounds belonging to very diverse compound classes: an oxygenated polyaromatic hydrocarbon, organophosphates, musks, and steroids. This is one of the first studies in the field of environmental analysis dealing with the difficult task of handling the large amount of data produced from non-target analysis. The combination of bioassay activity assessment, accurate mass measurement, and the identification and confirmation strategy is a promising approach for future identification of environmental key toxicants that are not included as priority pollutants in monitoring programs

Masking effect of anti-androgens on androgenic activity in European river sediment unveiled by effect-directed analysis

This study shows that the androgen receptor agonistic potency is clearly concealed by the effects of androgen receptor antagonists in a total sediment extract, demonstrating that toxicity screening of total extracts is not enough to evaluate the full in vitro endocrine disrupting potential of a complex chemical mixture, as encountered in the environment. The anti-androgenic compounds were masking the activity of androgenic compounds in the extract with relatively high anti-androgenic potency, equivalent to 200 nmol flutamide equivalents/g dry weight. A two-step serial liquid chromatography fractionation of the extract successfully separated anti-androgenic compounds from androgenic compounds, resulting in a total androgenic potency of 3,820 pmol dihydrotestosterone equivalents/g dry weight. The fractionation simplified the chemical identification analysis of the original complex sample matrix. Seventeen chemical structures were tentatively identified. Polyaromatic hydrocarbons, a technical mixture of nonylphenol and dibutyl phthalate were identified to contribute to the anti-androgenic potency observed in the river sediment sample. With the GC/MS screening method applied here, no compounds with AR agonistic disrupting potencies could be identified. Seventy-one unidentified peaks, which represent potentially new endocrine disrupters, have been added to a database for future investigation

The NORMAN Association and the European Partnership for Chemicals Risk Assessment (PARC): let’s cooperate! [Commentary]

The Partnership for Chemicals Risk Assessment (PARC) is currently under development as a joint research and innovation programme to strengthen the scientific basis for chemical risk assessment in the EU. The plan is to bring chemical risk assessors and managers together with scientists to accelerate method development and the production of necessary data and knowledge, and to facilitate the transition to next-generation evidence-based risk assessment, a non-toxic environment and the European Green Deal. The NORMAN Network is an independent, well-established and competent network of more than 80 organisations in the field of emerging substances and has enormous potential to contribute to the implementation of the PARC partnership. NORMAN stands ready to provide expert advice to PARC, drawing on its long experience in the development, harmonisation and testing of advanced tools in relation to chemicals of emerging concern and in support of a European Early Warning System to unravel the risks of contaminants of emerging concern (CECs) and close the gap between research and innovation and regulatory processes. In this commentary we highlight the tools developed by NORMAN that we consider most relevant to supporting the PARC initiative: (i) joint data space and cutting-edge research tools for risk assessment of contaminants of emerging concern; (ii) collaborative European framework to improve data quality and comparability; (iii) advanced data analysis tools for a European early warning system and (iv) support to national and European chemical risk assessment thanks to harnessing, combining and sharing evidence and expertise on CECs. By combining the extensive knowledge and experience of the NORMAN network with the financial and policy-related strengths of the PARC initiative, a large step towards the goal of a non-toxic environment can be taken