Formation pathways of brominated products from benzophenone-4 chlorination in the presence of bromide ions

The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were p H-dependent,while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.     

Challenges in assessing the toxic effects of polycyclic aromatic hydrocarbons to marine organisms: a case study on the acute toxicity of pyrene to the European seabass (Dicentrarchus labrax L.)

The acute toxicity (96 h) of pyrene (PY) to European seabass (Dicentrachus labrax) juveniles assessed in a semi-static bioassay (SSB) with medium renewal at each 12 h, and in a static bioassay (SB) without medium renewal was compared in laboratorial conditions (water PY concentrations: 0.07-10 mg L⁻¹). Main findings in the SSB that assessed mainly the toxicity of PY and its metabolites were: increased levels of bile PY metabolites in good agreement with the profile of lipid peroxidation levels (LPO) in exposed fish relating PY exposure and oxidative damage; increased levels of PY-type compounds in the brain indicating their ability to cross the blood-brain barrier; increased levels of these substances in liver and muscle which are edible tissues for humans thus raising concern on potential adverse effects on consumers of fish from PY contaminated areas; a significant inhibition of glutathione S-transferase activity suggesting its involvement in PY detoxication as toxicant scavenger; finally, an almost complete impairment of the swimming velocity at all the PY concentrations linking sub-individual to higher population level effects. In the SB, where the overall toxicity of PY, its metabolites and environmental degradation products was evaluated, 19% and 79% of PY decay in test media was found at 12 and 96 h, respectively. In general, the effects were similar to those of SSB but with significant effects being induced at higher PY concentrations indicating that the parental compound is more toxic than its environmental degradation products. The other main differences relatively to the SSB were: increased levels of PY-type substances in the liver suggesting more accumulation in this organ. Therefore, these findings highlight the need of carefully considering experimental design options when assessing the toxicity of readily degradable substances to marine fish, and stress the importance of taking into consideration the toxicity of environmental degradation products in addition to toxic effects of the parental substance and its metabolites for marine ecological risk assessment.     

Simulation of a Hazardous and Noxious Substances (HNS) spill in the marine environment: Lethal and sublethal effects of acrylonitrile to the European seabass

Despite the extensive maritime transportation of Hazardous and Noxious Substances (HNS), there is a current lack of knowledge on the effects posed by HNS spills on the marine biota. Among the HNS identified as priority, acrylonitrile was selected to conduct ecotoxicological assays. We assessed the acute and subletal effects of acrylonitrile in seabass, followed by a recovery phase to simulate the conditions of a spill incident. The work aimed at testing a broad range of biological responses induced by acrylonitrile. Sublethal exposure to the highest two doses increased the fish mortality rate (8.3% and 25% mortality in 0.75 and 2 mg L⁻¹ acrylonitrile concentrations), whereas no mortality were observed in control and 0.15 mg L⁻¹ treatments. Additionally, important alterations at sub-individual level were observed. Acrylonitrile significantly induced the activities of Catalase– CAT and Glutathione S-Transferase – GST; and the levels of DNA damage were significantly increased. Conversely, Superoxide Dismutase– SOD – activity was found to be significantly inhibited and no effects were found on Lipid Peroxidation– LPO and ethoxyresorufin O-deethylase – EROD – activity. Following a 7 d recovery period, the levels of CAT, GST and EROD fell to levels at or below those in the control. In the 2 mg L⁻¹ group, SOD remained at the levels found during exposure phase. This study has gathered essential information on the acute and subletal toxicity of acrylonitrile to seabass. It also demonstrated that 7 d recovery allowed a return of most endpoints to background levels. These data will be useful to assist relevant bodies in preparedness and response to HNS spills.     

A biology-based dynamic approach for the reconciliation of acute and chronic toxicity tests: application to Daphnia magna

There is the need to integrate existing toxicity data in a coherent framework for extending their domain of applicability as well as their extrapolation potential. This integration would also reduce time and cost-consuming aspects of these tests and reduce animal usage. In this work, based on data extracted from literature, we have assessed the advantages that a dynamic biology-toxicant fate coupled model for Daphnia magna could provide when assessing toxicity data, in particular, the possibility to obtain from short-term (acute) toxicity test long-term (chronic) toxicity values taking into account the inherent variability of D. magna populations and the multiple sources of data. The results show that this approach overcomes some of the limitations of existing toxicity tests and that the prediction errors are considerably reduced when compared with the factor from 2 to 5 obtained using acute-to-chronic ratios.     

Polybrominated diphenyl ethers and organochlorine compound levels in brown trout (Salmo trutta) from Andean Patagonia, Argentina

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), DDTs and endosulfan residues were analyzed in muscle, liver, gonads, gills and stomach content of brown trout (Salmo trutta) from the Andean Patagonia. PBDEs, PCBs and DDTs levels were positively correlated with lipid content, while less hydrophobic endosulfans showed a poor correlation. Endosulfan levels were about 99.9% of total contaminant (highest levels in liver 500 × 10³ ng g⁻¹ lipid weight), with α-/β-isomers ratio >1 in all organs. These results are in agreement to the current-use of the technical endosulfan and also suggest acute exposure to this insecticide. Conversely, DDT/DDE ratio reflects fish exposure to old DDT sources, showing a DDE predominance. Gills had the highest levels of DDTs, PCBs and PBDEs, indicating they represent the main uptake pathway for such hydrophobic compounds from water column. PCBs showed the lowest levels in all organs and the PBDEs/PCBs ratios >1 agree with worldwide trends. PBDEs levels in gonads, gills, liver and muscle exceeded 80 ng g⁻¹ (lipid weight) and were higher than other values reported in the Southern Hemisphere. BDE-47 was the predominant congener, suggesting higher bioaccumulation potential and possible brown trout metabolism of higher congeners. Since there is no point source of PBDEs in the region and residues were dominated by lower brominated congeners, atmospheric transport could be the main source of these compounds. This first report of PBDEs levels in fish from Argentina contributes to the knowledge about environmental trends of these persistent organic pollutants (POPs) in remote areas such as the Andean Patagonia.     

Safety testing of pesticides and methods of evaluating human exposure in the field

Abstract

The importance of field surveys to provide data on acute pesticide hazards is discussed. The types of questions which small field surveys of pesticide exposure should answer are presented. In addition to protective clothing, the value of distance, time, and personal hygiene in reducing exposure are considered. Finally, the importance of an adequate data base for the development of protocols and guidelines for public protection is discussed.     

化学工业固体废物毒性鉴别分析

该文介绍了对硫酸烧渣和磷石膏两种固体废物进行急性毒性和浸出毒性鉴别试验的过程与结果 ,并对磷石膏由危险废物转变为非危险废物的原因进行了探讨 ,为硫酸烧渣和磷石膏的处置和利用提供了依据     

Acute exposure to chemicals during ‘do-it-yourself’ activities: survey of enquiries to the Swedish Poisons Information Centre in 1996

In 1996 the Swedish Poisons Information Centre performed a follow-up study concerning poisonings related to ‘do-it-yourself’ activities. The study was supported by the National Institute of Public Health in Sweden. The objectives were to investigate and define monthly variations, route of exposure, type of products and, in particular, exposures to corrosives, age and sex groups, place of treatment, severity of symptoms, place of the accident, special risk products and risk situations. The Poisons Information Centre was contacted concerning 1609 cases, with a peak during the summer months. There was no or uncertain connection between exposure and symptoms in 117 cases. This means that 1492 cases were left to study. Inhalation and eye exposure were the predominant routes, followed by skin exposure and ingestion. Cleaning agents were the most common type of products involved. Of the 1492 cases included in the study 1033 were possible to follow up. Among these, 20–29 year olds and 30–39 year olds predominated, and there was a dominance for men. In total, 28% of those exposed were subject to medical attention, either in hospital or in outpatient clinics. According to the Poisoning Severity Score 78% had mild (grade 1) and 7% moderate (grade 2) symptoms. There were no severe intoxications and no deaths. Severity grade 2 occurred 3.6 times more often among those with exposures involving risk of corrosive damage than among others in the study population. Most accidents occurred in the home. Special risk products and risk situations were exposure to corrosive products, release of chlorine when mixing hypochlorite and acid, ‘fire-eating’, siphoning gasoline and diesel fuel, welding, and inhalation of carbon monoxide from exhaust gases. The Swedish Poisons Information Centre registered 1609 cases of poisoning accidents during ‘do-it-yourself’ activities, which means an average of four to five cases per day. Although this type of accidents is not uncommon, significant poisoning seems to be rare. Some special risk situations were identified.