Polychlorodibenzo-p-dioxins and dibenzofurans in technical pentachlorophenol - results of a collaborative analytical exercise

Results of analyses of eight samples of technical pentachlorophenol conducted by three different analytical methods are presented and discussed.     

Phototransformation of fibrate drugs in aqueous media

The photochemical conversion of bezafibrate, gemfibrozil, fenofibrate and fenofibric acid has been examined in aqueous media. Irradiation with a solar simulator in distilled water caused about 10% degradation for the first three drugs after 200 hr, while fenofibric acid was completely degraded after 100 hr. Experiments have also been performed in the presence of nitrates or humic acids, considered as environmental photosensitizers, and only for gemfibrozil a reduction of degradation has been observed. Photoproducts have been characterized and the mechanistic pathways discussed on the basis of experimental and literature data.     

Long term changes in polychlorodibenzo-p-dioxin concentrations in wood treated with technical pentachlorophenol

Wood samples treated with technical pentachlorophenol (PCP), technical sodium pentachlorophenoxide (NaPCP) and octachlorodibenzo-p-dioxin have been exposed outdoors for periods up to $\text{2}\text{1}\text{2}$ years. Analysis of extracts from the samples show that photolytic reductive dechlorination of highly chlorinated dibenzo-p-dioxins to less chlorinated isomers occurs. However there is no discernible increase in polychlorodibenzo-p-dioxin concentrations in the technical PCP treated wood presumably because further photolytic reactions and volatilisation compete effectively with the photolytic formation. There is no evidence for formation of octachlorodibenzo-p-dioxin (OCDD) in technical PCP treated wood in this study, probably because photolytic destruction and volatilisation compete effectively with formation reactions when the initial OCDD concentration is relatively high.     

Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).     

Unusual products of the aqueous chlorination of atenolol

The reaction of the drug atenolol with hypochlorite under conditions that simulate wastewater disinfection was investigated. The pharmaceutical reacted in 1h yielding three products that were separated by chromatographic techniques and characterized by spectroscopic features. Two unusual products 2-(4-(3-(chloro(2-chloropropan-2-yl)amino)-2-hydroxypropoxy)phenyl) acetamide and 2-(4-(3-formamido-2-hydroxypropoxy)phenyl) acetamide were obtained along with 2-(4-hydroxyphenyl) acetamide. When the reaction was stopped at shorter times only 2-(4-(3-amino-2-hydroxypropoxy)phenyl) acetamide and the dichlorinated product were detected. Tests performed on the seeds of Lactuca sativa show that chlorinated products have phytotoxic activity.