Application of preparative capillary gas chromatography (pcGC), automated structure generation and mutagenicity prediction to improve effect-directed analysis of genotoxicants in a contaminated groundwater

Background, aim and scope  

The importance of groundwater for human life cannot be overemphasised. Besides fulfilling essential ecological functions, it is a major source of drinking water. However, in the industrial area of Bitterfeld, it is contaminated with a multitude of harmful chemicals, including genotoxicants. Therefore, recently developed methodologies including preparative capillary gas chromatography (pcGC), MOLGEN-MS structure generation and mutagenicity prediction were applied within effect-directed analysis (EDA) to reduce sample complexity and to identify candidate mutagens in the samples. A major focus was put on the added value of these tools compared to conventional EDA combining reversed-phase liquid chromatography (RP-LC) followed by GC/MS analysis and MS library search.     

REAL-TIME SNOW SIMULATION MODEL FOR THE MONONGAHELA RIVER BASIN1

ABSTRACT: The Pittsburgh District, U.S. Army Corps of Engineers, is responsible for operating two multipurpose reservoirs in the 7384 square mile (19198 square kilometer) Monongahela Basin. A third reservoir, presently under construction, will soon be operating. The real-time forecasting of runoff for operational purposes requires simulation of snow accumulation and snowmelt throughout the Basin during the winter season. This article describes capabilities of SNOSIM, a model being developed for performing such simulation. The application of this model as part of a comprehensive system of water control software, and some initial simulation results are presented.     

Photochemistry and photoinduced toxicity of acifluorfen, a diphenyl-ether herbicide

Photochemistry studies can be helpful in assessing the environmental fate of chemicals. Photochemical reactions lead to the formation of by-products that can exhibit different toxicological properties from the original compound. For this reason the photochemical behavior of the herbicide acifluorfen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in the presence of different solvents was studied. Photochemical reactions were carried out using a high-pressure mercury arc and a solar simulator. Kinetic parameters and quantum yields were determined. The identification of photoproducts was performed by mass spectrometry and [1H] nuclear magnetic resonance (NMR). Nitrofluorfen, hydroxy-nitrofluorfen, 2-chloro-4-(trifluoromethyl)phenol, 5-trifluoromethyl-5'-nitrodibenzofuran, and other derivatives were identified. The photochemical reactions were also carried out in the presence of either a singlet or a triplet quencher, and in the presence of either a radical initiator or a radical inhibitor. Substances used as inhibitors of the excited levels T1 and S1 showed that photodegradation of acifluorfen begins from a singlet state S1 through a pi,pi* transition. The role of free radicals in the photodegradation of acifluorfen was determined and a radical mechanism was proposed. Toxicity tests against Daphnia magna Strauss showed that acifluorfen was not toxic at a concentration of 0.1 mM; however, photoproducts formed after 36 h of UV exposure of the herbicide induced a remarkable toxicity to the test organism.     

Effects of 17alpha-ethinylestradiol on the reproduction of the cladoceran species Ceriodaphnia reticulata and Sida crystallina

Single-species tests allow the assessment of chronical effects of endocrine disruptors on organisms under laboratory conditions. In the current study, three-generation tests with Ceriodaphnia reticulata and Sida crystallina were carried out to examine the influence of the synthetic hormone 17alpha-ethinylestradiol (EE) on the reproduction of these cladoceran species. For each species, six different concentrations (10-500 microg/l EE) and two controls were tested with eight replicates for a duration of 4 weeks. The test was initiated by transferring one neonate individual into a test vessel which was incubated under standardized conditions. Every 2 days, the medium was renewed and life history parameters such as survivorship of the adults and juveniles, clutch size, first appearance and number of produced offspring were investigated. Acute toxicity tests showed that C. reticulata (EC50 (24 h) 1814 microg/l) was more sensitive towards the substance compared to S. crystallina (EC50 (24 h) >4100 microg/l). The juvenile phase of S. crystallina was significantly shorter at concentrations above 100 microg/l EE. For C. reticulata, 17alpha-ethinylestradiol caused a higher mortality of the newly hatched juveniles at EE concentrations above 200 microg/l. No effects were found for mortality of adult animals, birth rate, number of juveniles per female and net reproduction rate of S. crystallina and C. reticulata. Thus, sublethal effects on parental generation exposed to EE lead to disturbances in reproduction and to affection of their offspring. Negative consequences for the population dynamic cannot be excluded, e.g. the decrease of a population.     

Methane and nitrous oxide emissions from a subtropical coastal embayment (Moreton Bay, Australia)

Surface water methane (CH₄) and nitrous oxide (N₂O) concentrations and fluxes were investigated in two subtropical coastal embayments (Bramble Bay and Deception Bay, which are part of the greater Moreton Bay, Australia). Measurements were done at 23 stations in seven campaigns covering different seasons during 2010-2012. Water-air fluxes were estimated using the Thin Boundary Layer approach with a combination of wind and currents-based models for the estimation of the gas transfer velocities. The two bays were strong sources of both CH₄ and N₂O with no significant differences in the degree of saturation of both gases between them during all measurement campaigns. Both CH₄ and N₂O concentrations had strong temporal but minimal spatial variability in both bays. During the seven seasons, CH₄ varied between 500% and 4000% saturation while N₂O varied between 128 and 255% in the two bays. Average seasonal CH₄ fluxes for the two bays varied between 0.5 ± 0.2 and 6.0 ± 1.5 mg CH₄/(m²·day) while N₂O varied between 0.4 ± 0.1 and 1.6 ± 0.6 mg N₂O/(m²·day). Weighted emissions (t CO₂-e) were 63%-90% N₂O dominated implying that a reduction in N₂O inputs and/or nitrogen availability in the bays may significantly reduce the bays' greenhouse gas (GHG) budget. Emissions data for tropical and subtropical systems is still scarce. This work found subtropical bays to be significant aquatic sources of both CH₄ and N₂O and puts the estimated fluxes into the global context with measurements done from other climatic regions.     

Signs that encourage internalized recycling: Clinical validation, weak messages and “creative elaboration”

Two experiments examined clinical validation's ability to increase examination of a persuasive message and increase long-term recycling. In Experiment 1, validating (acknowledging) recycling's inconvenience decreased criticism of the persuasive message, supporting validation's ability to reduce reactance and open the reader to new ideas. Validation did not improve attitudes towards the sign's author, removing liking for the communicator as an alternate explanation for attitude change. In Experiment 2, different recycling signs were created from a 2(no validation/validation) by 2(weak/strong arguments) factorial design, and placed in university buildings. The validation weak sign increased recycling more than the validation strong sign, especially after the signs were removed. We suggest that validation induced people to scrutinize the weak message and use their existing pro-recycling attitudes to “creatively elaborate” it. Discussion emphasizes clinical validation and the Elaboration Likelihood Model as theoretical tools, as well as the potential for thought provoking signs to have long-term effects.