Nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution

This paper studies the nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution, both in the dark upon addition of hydrogen peroxide and under 360 nm irradiation. In both cases the detected transformation intermediates were phenol (P), nitrobenzene (NB), 2-nitrophenol (2NP) and 4-nitrophenol (4NP). P and NB directly form from benzene, and the initial formation rate of P is at least an order of magnitude higher than that of NB. In our experiments nitrophenols arise from P nitration, as can be inferred by their time evolution and isomer ratio (2NP:4NP=60:40, 3NP below detection limit). Nitrophenols may also form upon hydroxylation of NB, but in a different ratio (2NP:3NP:4NP=45:30:25). The detection of 3NP is thus a marker for the hydroxylation of NB, since this isomer is not formed in P nitration processes. The formation rates of P and NB increase with decreasing pH, both in the presence of HNO₂ + H₂O₂ in the dark (which produce HOONO) and in the presence of NO₂⁻/HNO₂ under irradiation. In the former case the pH dependence reflects the formation rate of HOONO. In the case of the irradiation experiments the pH effect can be accounted for by the higher molar absorbivity and photolysis quantum yield of nitrous acid when compared with nitrite. Interestingly, benzene does not react with HNO₂ alone in the dark. An important feature of benzene nitration in the presence of NO₂⁻/HNO₂ under irradiation is that the process is not inhibited by the addition of hydroxyl scavengers, differently from the case of phenol nitration. This finding indicates that nitrite irradiation might lead to the nitration of certain aromatic compounds in natural waters even in the presence of natural hydroxyl scavenging agents, which are usually thought to limit the environmental role of many photochemical processes.     

纳米二氧化钛在老化环境条件下对铜诱导毒性的影响

纳米二氧化钛颗粒(nTiO₂)可以通过吸附表层水中共生重金属来改变它们对淡水无脊椎动物的毒性。然而,影响这种交互过程的几种环境因子的相对重要性仍不清楚。因此,本研究通过连续72 h的培养试验,评估了老化对Cu与nTiO₂对大型蚤Daphnia magna联合急性毒性的影响。在老化过程中,对老化时间以及离子强度、pH值和不同质量有机物质等因子都进行了考察。研究结果表明,尽管影响效应的大小不同,nTiO₂的存在往往减少了老化后Cu对大型蚤的诱发毒性,在没有nTiO₂的情况下,Cu对大型蚤急性毒性的EC₅₀值提高了3倍之多。此外,各种形态Cu的形成受到介质中的离子组成、pH值以及有机添加剂存在的影响,这一过程受到极大的调控,并随着老化时间对大型蚤生态毒性的响应有一定影响。尽管如此,该研究的结论对nTiO₂在淡水生态系统中不同环境条件下,改变重金属诱发毒性的潜在作用提供了有力的支持。然而,这种模式需要进一步验证,比如结合不同性质的重金属离子与不同的环境因素,如紫外线照射。
精选自Ricki R. Rosenfeldt, Frank Seitz, Ann-Cathrin Haigis, Johanna H?ger, Jochen P. Zubrod, Ralf Schulz, Mirco Bundschuh. Nanosized titanium dioxide influences copper induced toxicity during aging as a function of environmental conditions. Environmental Toxicology and Chemistry: Volume 35, Issue 7, pages 1766–1774, July 2016. DOI: 10.1002/etc.3325
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3325/full
     

Beach macro-litter monitoring on southern Baltic beaches: results,experiences and recommendations

Major objectives were to provide a comprehensive dataset on beach macro-litter for parts of the southern Baltic Sea and to analyse if the methodology is fully applicable and a suitable monitoring method in the Baltic. We carried out a regular macro litter beach monitoring (OSPAR methodology, 4 time a year) on 35 beaches along the German and Lithuanian Baltic coast over 2–5 years. Additional experiments addressed the subjectivity of the field surveys and spatio-temporal variability on different scales. We observed no seasonality of the data and a monthly compared to a 3-monthly sampling resulted in 3 times higher annual item numbers. Along the Lithuanian coast, the average number of items per survey varied between 138 and 340 and along the German Baltic coast between 7 and 404, with a median value of 47. All data showed a very high spatio-temporal variability. Using the Matrix Scoring Technique we assessed beach litter sources. With 50% tourism and recreation was the most important source. 3D–transport simulations helped to explain the minor role of shipping as a source and, compared to the North Sea, the low numbers of items on German Baltic beaches. Floating litter had a short duration time in the western Baltic Sea and offshore drift dominated. Further, the common regular beach cleanings reduced the potential for local litter accumulation and translocation. We suggest a monitoring system on 14 Baltic beaches in Germany and 2 in Lithuania and provide cost calculations. The analysis of macro-litter in cormorant nesting material and the search for beached dead animals did not show any result. We can conclude that the macro-litter beach monitoring method is less suitable for Baltic beaches and should only serve as a complementary method in combination with others.