Mutagenic nitrated benzo[a]pyrene derivatives in the reaction product of benzo[a]pyrene in NO2-air in the presence of O3 or under photoirradiation

In order to clarify the contribution of nitrated products to the direct-mutagenic activity of products of the reactions of benzo[a]pyrene in NO2-air under various conditions, heterogeneous reactions of BaP deposited on filter in the air containing 10 ppm of NO2 have been conducted in dark or under photoirradiation. The reaction products have been analyzed by gas chromatography and mutagenicity of the products fractionated by preparative HPLC was assayed for Salmonella typhimurium strains TA98 and YG1024 in the absence of S9 mix. 3,6-dinitrobenzo[a]pyrene and 1,3-dinitrobenzo[a]pyrene, which are strong direct-acting mutagens, largely contributed to the total direct-acting mutagenicity of the dark reaction products in NO2-air. On the other hand, both the dark reaction in the presence of O3 and the photoreaction in NO2-air resulted in the formation of much smaller amounts of nitrobenzo[a]pyrenes than that observed in the dark reaction in the absence of O3. These results show that the contribution of other direct-acting mutagens to the total direct-acting mutagenicity of the products in these reactions should be considered. Benzo[a]pyrene lactones were identified in a highly mutagenic fraction of the products of the dark reaction in the presence of O3 and photoreaction and a nitrobenzo[a]pyrene lactone was also identified in a highly mutagenic fraction of the dark reaction products in the presence of O3. Nitrated oxygenated benzo[a]pyrene derivatives such as nitrobenzo[a]pyrene lactone were considered to largely contribute to direct-acting mutagenicity of the products of the dark reaction in the presence of O3 and photoreaction.     

Vertical distribution of Cd, Pb and Zn in soils near smelters in the North of France

The analysis of the horizons of 12 soil profiles confirm occasionally significant levels of Cd, Pb and Zn contamination in the areas surrounding two lead and zinc smelters in the North of France. A pedological approach enabled the original Cd, Pb and Zn content of the horizons to be estimated, based on physico-chemical characteristics of soil unaffected by contamination. The main contamination was found in the upper 20-30 cm. Traces of Cd and Zn contamination were found at a depth of around 2 m. The mobility of the metals may be classified in the following order: Cd>Pb> or =Zn. The concentration profile of a metal seems insufficient to evaluate its movement as the metal could have been leached beyond the contaminated horizons. The depth reached by the metals increases with their concentration in the surface horizon; a decrease in pH and an increase in sand content seem to facilitate their movement. The depth reached by Zn increases with the organic carbon content in the surface horizon. Earthworm galleries act as paths via which metals migrate downwards     

Acid rain and acidification in China: the importance of base cation deposition

Acid deposition has been recognized as a serious environmental problem in China. Most acid deposition studies have focused on sulfur deposition and the pH of precipitation. However, as high concentration of alkaline dust is an important feature of the atmosphere in large parts of China, base cation deposition must be taken into account when discussing possible effects on soils and vegetation from acid deposition. We estimate the deposition of sulfur as well as calcium, i.e. the dominating anion and cation, on a regional scale in China using data both from measurements and modeling. The ratio of sulfur/calcium in deposition is then used as an indicator for identifying areas where deposition acidity exceeds alkalinity, and where soils may be at risk to acidification. The dynamic soil acidification model MAGIC is applied with data from two sites receiving high deposition loads in southwest China. The model predictions indicate that considerable soil acidification has been going on for the last decades due to acid deposition inputs. Effects on the spatial distribution of acidic deposition in China, using different future deposition scenarios, are illustrated. As the size of the anthropogenic fraction of the base cation deposition is unknown, different possible future trends in calcium deposition were used. Soil response, according to the model, using different combinations of sulfur and calcium deposition scenarios is shown. Applying the most strict measures to reduce sulfur emission will almost eliminate the acid deposition problem; however, such a scenario is not economically feasible in the short term. A strict, but possibly realistic, future scenario for sulfur may be enough to keep the situation at the present level, assuming only moderate reductions in calcium deposition. With large decreases in base cation deposition, increased soil acidification can be expected even with considerable sulfur emission reductions.     

Application of GC-MS/MS for the analysis of PCDD/Fs in sewage effluents

The application of high resolution gas chromatography in combination with tandem mass spectrometry in an ion trap was tested to substitute the expensive high resolution mass spectrometry in analysing polychlorinated dibenzo-p-dioxins and furans in sewage effluents. In tandem mass spectrometry, a set of parameters has to be optimised in order to attain the required sensitivity. To the best of our knowledge, this is the first time a method development for analysing PCDD/Fs with GC-MS/MS in an ion trap is described in this detail. Nine parameters are varied, including isolation window, collision induced dissociation (CID) amplitude, CID time, acquisition mass range, broadband amplitude, CID bandwidth, modulation range, filament current and ion trap temperature. This technique can be adapted to other analytes. By this optimisation, limits of detection of 0.01-0.05 ng/l are obtained. With its selectivity and sensitivity, tandem mass spectrometry is a powerful tool for the determination of PCDD/Fs in water samples. 55 sewage effluent samples from Germany were analysed.     

Profile analysis of organic micropollutants in the environment of a coal burning area, NW Greece

The concentrations and profiles of dibenzo-p-dioxins, dibenzofurans, polychlorinated biphenyls and polynuclear aromatic compounds in various environmental matrices are presented in this study. The examined environmental matrices are total suspended particles, fly ash and soil collected in NW Greece, an area characterized by intensive coal burning for electrical power generation. Moreover, the occurrence of organic micropollutants in soot after an accidental fire was examined and the possible impact on the outdoor environment was evaluated. Results were statistically treated to obtain information on representative PCDD/F profiles in each matrix and to compare these profiles with the compositional patterns of possible sources from literature. Coal combustion, fly ash and vehicle exhausts appeared to be the most possible sources in local atmosphere.     

The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer

Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.     

Source apportionment of indoor, outdoor, and personal PM2.5 in Seattle, Washington, using positive matrix factorization

As part of a large exposure assessment and health-effects panel study, 33 trace elements and light-absorbing carbon were measured on 24-hr fixed-site filter samples for particulate matter with an aerodynamic diameter <2.5 microm (PM2.5) collected between September 26, 2000, and May 25, 2001, at a central outdoor site, immediately outside each subject's residence, inside each residence, and on each subject (personal sample). Both two-way (PMF2) and three-way (PMF3) positive matrix factorization were used to deduce the sources contributing to PM2.5. Five sources contributing to the indoor and outdoor samples were identified: vegetative burning, mobile emissions, secondary sulfate, a source rich in chlorine, and a source of crustal-derived material. Vegetative burning contributed more PM2.5 mass on average than any other source in all microenvironments, with average values estimated by PMF2 and PMF3, respectively, of 7.6 and 8.7 microg/m3 for the outdoor samples, 4 and 5.3 microg/m3 for the indoor samples, and 3.8 and 3.4 microg/m3 for the personal samples. Personal exposure to the combustion-related particles was correlated with outdoor sources, whereas exposure to the crustal and chlorine-rich particles was not. Personal exposures to crustal sources were strongly associated with personal activities, especially time spent at school among the child subjects.     

Seasonal variability of 1-chloropyrene on atmospheric particles and photostability in toluene

The occurrence of a mutagenic compound, 1-chloropyrene (Cl-Py), in extracts of ambient particulate matter at an urban site in Japan has been investigated. Samples were collected with a high-volume air sampler for 24 h periods over the course of 1 week in winter (February), spring (May), summer (August), and autumn (November) 2002. The Cl-Py levels showed seasonal variation, ranging from 2.4 pg/m(3) (summer) to 18.9 pg/m(3) (winter). This variation would indicate that the lower temperatures in winter results in an increased distribution of Cl-Py from vapor phase to the particle phase. In addition, there is also the possibility that ambient Cl-Py is emitted from seasonal sources or is susceptible to photodegradation by sunlight, or both. The photodegradation of Cl-Py in a laboratory experiment was conducted to simulate the compound's fate on airborne particle surfaces. The degradation of Cl-Py proceeded by a first-order reaction with a rate constant of 0.72 h(-1). In the presence of a radical sensitizer, 9,10-anthraquinone (AQ), the photodegradation rate of Cl-Py was elevated in comparison with the rate in the absence of AQ. In addition, the dechlorination of Cl-Py (i.e., the formation of Py) occurred in the presence of AQ.     

Synthesis of effects in four Arctic subregions

An assessment of impacts on Arctic terrestrial ecosystems has emphasized geographical variability in responses of species and ecosystems to environmental change. This variability is usually associated with north-south gradients in climate, biodiversity, vegetation zones, and ecosystem structure and function. It is clear, however, that significant east-west variability in environment, ecosystem structure and function, environmental history, and recent climate variability is also important. Some areas have cooled while others have become warmer. Also, east-west differences between geographical barriers of oceans, archipelagos and mountains have contributed significantly in the past to the ability of species and vegetation zones to relocate in response to climate changes, and they have created the isolation necessary for genetic differentiation of populations and biodiversity hot-spots to occur. These barriers will also affect the ability of species to relocate during projected future warming. To include this east-west variability and also to strike a balance between overgeneralization and overspecialization, the ACIA identified four major sub regions based on large-scale differences in weather and climate-shaping factors. Drawing on information, mostly model output that can be related to the four ACIA subregions, it is evident that geographical barriers to species re-location, particularly the distribution of landmasses and separation by seas, will affect the northwards shift in vegetation zones. The geographical constraints--or facilitation--of northward movement of vegetation zones will affect the future storage and release of carbon, and the exchange of energy and water between biosphere and atmosphere. In addition, differences in the ability of vegetation zones to re-locate will affect the biodiversity associated with each zone while the number of species threatened by climate change varies greatly between subregions with a significant hot-spot in Beringia. Overall, the subregional synthesis demonstrates the difficulty of generalizing projections of responses of ecosystem structure and function, species loss, and biospheric feedbacks to the climate system for the whole Arctic region and implies a need for a far greater understanding of the spatial variability in the responses of terrestrial arctic ecosystems to climate change.     

Detection of lead-induced oxidative stress in the rat epididymis by chemiluminescence

It has been shown that lead (Pb) is able to induce lipid peroxidation, one of the main manifestations of oxidative stress. In this study we examined the relationship between chronic Pb exposure and level of reactive oxygen species (ROS) in reproductive system tissues of sexually mature male Wistar rats. One group of animals (control, K) was allowed to drink distilled water, the second group (Pb) was allowed to drink freely 1% aqueous solution of lead acetate. Another groups had a following supplements: rats were allowed to drink distilled water containing vitamin C (vit C) at concentration of 500 mg/l or Trolox (a vitamin E analog) at concentration of 48 mg/l or vit C (500 mg/l) + Trolox (48 mg/l). The similar groups among Pb-treated animals were examined after treatment with the same vitamins and using the same vitamin doses, dissolved in 1% aqueous solution of lead acetate. In all cases the time of drinking was 6 months. It was found that lead content in samples of tissues from testis, epididymis and in a whole blood in Pb- and Pb with antioxidants treated rats was significantly elevated. Chemiluminescence (CL) emitted by the Pb-treated tissues was significantly higher when compared to the light emission by tissues isolated from the animals of control group. The increase in the CL caused by lead occurs in the following increasing order within the studied tissues: cauda of epididymis < testis < caput of epididymis (19%, 39% and 51%, respectively). Dietary vit C supplementation to the Pb-treated rats for 6 months period decreased the CL from caput of epididymis, cauda of epididymis and testis (by 43%, 24%, 39%, respectively) more effectively in comparison to the control group (35%, 17%, 33%, respectively). Also stronger quenching effect on the light emission from the above mentioned tissues after Trolox supplementation was observed in the Pb-treated group (42%, 21%, 35%, respectively) than in the control group (23%, 13%, 13% respectively). The combination of both antioxidants treatments (vit C and Trolox) did not give a higher significant quenching effect compared to the treatment with the vitamins separately. No ultrastructural changes were found in the seminiferous epithelium of Pb-treated animals. However, we found abnormalities in ultrastructure of epididymal epithelial cells and epididymal spermatozoa in rats of Pb-treated groups. These findings provide ex vivo evidence that Pb causes oxidative cellular damage in reproductive system tissues of adult male rats, which may be closely associated with the ROS production.