Priority assessment of toxic substances in life cycle assessment. Part I: calculation of toxicity potentials for 181 substances with the nested multi-media fate, exposure and effects model USES-LCA

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. In most cases, toxicity potentials are calculated with multi-media fate models. Until now, unrealistic system settings were used for these calculations. The present paper outlines an improved model to calculate toxicity potentials: the global nested multi-media fate, exposure and effects model USES-LCA. It is based on the Uniform System for the Evaluation of Substances 2.0 (USES 2.0). USES-LCA was used to calculate for 181 substances toxicity potentials for the six impact categories freshwater aquatic ecotoxicity, marine aquatic ecotoxicity, freshwater sediment ecotoxicity, marine sediment ecotoxicity, terrestrial ecotoxicity and human toxicity, after initial emission to the compartments air, freshwater, seawater, industrial soil and agricultural soil, respectively. Differences of several orders of magnitude were found between the new toxicity potentials and those calculated previously.     

Application of artificial neural networks to modeling and prediction of ambient ozone concentrations

The deterministic modeling of ambient O3 concentrations is difficult because of the complexity of the atmospheric system in terms of the number of chemical species; the availability of accurate, time-resolved emissions data; and the required rate constants. However, other complex systems have been successfully approximated using artificial neural networks (ANNs). In this paper, ANNs are used to model and predict ambient O3 concentrations based on a limited number of measured hydrocarbon species, NOx compounds, temperature, and radiant energy. In order to examine the utility of these approaches, data from the Coastal Oxidant Assessment for Southeast Texas (COAST) program in Houston, TX, have been used. In this study, 53 hydrocarbon compounds, along with O3, nitrogen oxides, and meteorological data were continuously measured during summer 1993. Steady-state ANN models were developed to examine the ability of these models to predict current O3 concentrations from measured VOC and NOx concentrations. To predict the future concentrations of O3, dynamic models were also explored and were used for extraction of chemical information such as reactivity estimations for the VOC species. The steady-state model produced an approximation of O3 data and demonstrated the functional relationship between O3 and VOC-NOx concentrations. The dynamic models were able to the adequately predict the O3 concentration and behavior of VOC-NOx-O3 system a number of hourly intervals into the future. For 3 hr into the future, O3 concentration could be predicted with a root-mean squared error (RMSE) of 8.21 ppb. Extending the models further in time led to an RMSE of 11.46 ppb for 5-hr-ahead values. This prediction capability could be useful in determining when control actions are needed to maintain measured concentrations within acceptable value ranges.     

Screening of bean cultivars for their response to ozone as evaluated by visible symptoms and leaf chlorophyll fluorescence

Fourteen Italian cultivars of Phaseolus vulgaris were exposed to a single pulse of ozone (O(3), 150 nl l(-1)) or to filtered air (<3 nl l(-1)) for 3.5 h. O(3) sensitivity was assessed by recording the extent of visible symptoms, effects on chlorophyll (Chl) content and changes in Chl a fluorescence parameters. This paper reports the results of an initial screening of 14 bean cultivars that was used to select a small number of cultivars for further work. Seven cultivars showed visible symptoms of injury in the range of 2-60 h after the end of the O(3) fumigation. O(3) significantly depressed total Chl content in most cultivars and a significant correlation was found between Chl content and visible symptoms. Most cultivars showed a significant change in the F(v)/F(m) ratio, even when there were no visual symptoms. There was no relationship between the extent of visual symptoms and quenching coefficients, indicating that these parameters were of no use in the determination of sensitivity to O(3) stress.     

Anaerobic incorporation of the radiolabeled explosive TNT and metabolites into the organic soil matrix of contaminated soil after different treatment procedures

Four bioreactor designs were performed to evaluate the level of incorporation of 14C-labeled 2,4,6-trinitrotoluene (TNT) and metabolites into the organic soil matrix of different anaerobically treated contaminated soils. The contaminated soils were amended with molasses slivers (80:20% per weight) as auxiliary substrate to enhance microbial activity. After 5 weeks (bioreactors 1 and 2), 8 weeks (bioreactor 3) and 12 weeks (bioreactor 4) of anaerobic incubation, we determined 41%, 58%, 72%, and 54%, respectively, of the initially applied radioactivity immobilized in various soil fractions. After alkaline hydrolyses of the solvent-extracted soils, low quantities of radiolabel were found in the humic and fulvic acid fractions, whereas the bulk of 14C activity was found to be strongly bound to the humin fraction (solid soil residues). The amounts of solvent extractable radioactivity were 53%, 40%, 16%, and 29% for bioreactors 1, 2, 3, and 4, respectively. The level of TNT transformation at the end of the experiments was within 90-94%. Regarding the results presented in this study, we can assume that there is the possibility of high incorporation levels of TNT metabolites into the soil organic matrix mediated by microbial cometabolism under strictly anoxic conditions.     

Airborne pollutants along a roadside: assessment using snow analyses and moss bags

Vertical snow sampling and moss bag transplants were used to estimate the local inorganic and organic pollutant load deposited from traffic along a major highway in Finland. The pH and concentrations of Cl(-), NO(3)(-), SO(4)(2-), Ca(2+), Na(+) and polyaromatic hydrocarbons (PAHs) were determined from snow samples collected in winter at different sites along the highway. In summer, moss bags containing 20 g of fresh red-stemmed feather moss (Pleurozium schreberi) were transplanted at the same sites. The moss bag transplants remained exposed to roadside traffic for a period of one month following which the samples were collected and the PAH profiles and concentrations were analysed. The deposition of inorganic and organic pollutants from road traffic was observed up to 60 m from the road. The prevailing winds had a significant effect on the dispersion of pollutants. Snow appears to be a good collector of inorganic pollutants from the atmosphere and can be used to monitor local airborne pollution from road traffic. Snow packs can also be used as passive collectors of organic pollutant loads from road traffic on a local scale. To monitor organic PAH deposition from the road traffic, moss bags appeared to be better indicators compared to snow sampling. The efficiency of moss bags in accumulating PAH compounds indicate that vegetation may be an important sink for traffic pollution.     

Genetic damage in urban mice exposed to traffic pollution

Wild rodents (Mus domesticus) were collected in three areas in Rome exposed to different traffic flows to ascertain a possible correlation between genetic damage and heavy metal concentration. The concentration of lead, cadmium and zinc were determined in liver, kidney and bones and two mutagenicity tests (micronucleus test and sperm abnormality assay) were employed. The results obtained showed that the contents of lead and cadmium were higher in animals collected in areas with high traffic flows than in those from control areas. A statistically significant increase of the frequency of micronucleated erythrocytes and of abnormal sperm cells was also obtained in animals collected in sites with high traffic flows. The investigation confirmed the suitability of using wild rodents as bioindicators of environmental pollution and as key-organisms in programs of pollution monitoring and environmental conservation.     

Responses of spring wheat (Triticum aestivum L.) to ozone produced by either electric discharge and dry air or by UV-lamps and ambient air

The aim of the present study was to examine if ozone produced similar effects on spring wheat growth with and without small amounts of nitrogen oxides. Two methods were used to produce ozone: the first method consisted of dry pressurized air fed to an electric discharge generator generating the byproducts, N2O5 and N2O, the second method consisted of ambient air fed to UV-lamps. Two spring wheat cultivars (Triticum aestivum L. cvs Minaret and Eridano) were exposed in small open-top chambers to charcoal-filtered air, non-filtered ambient air, and non-filtered ambient air with the addition of ozone for 8 h (0900 to 1700 h) daily, for five weeks. Plants were harvested every week. The growth of Minaret was shown to be more sensitive to O3 than that of Eridano. Leaf senescence increased with increasing ozone level in both cultivars. The total above-ground biomass dry weight decreased with increasing ozone concentration in Minaret, but not in Eridano. The Minaret plants reacted with more damaged leaf dry weight and inhibition of growth when O3 was produced by UV-lamps than when O3 was produced by air fed to an electric discharge generator. This could be explained by more nitrogen content per plant but not by increased nitrogen concentration in plant tissue in plants exposed to increased O3 and small amounts of incidental nitrogen oxides.     

Nitrous oxide emissions from tundra soil and snowpack in the maritime Antarctic

The nitrous oxide emissions were measured at three tundra sites and one snowpack on the Fildes Peninsula in the maritime Antarctic in the summertime of 2002. The average fluxes at two normal tundra sites were 1.1 ± 2.2 and 0.6 ± 1.7 μg N₂O m⁻² h⁻¹, respectively. The average flux from tundra soil site with penguin dropping addition was 3.7 ± 2.0 μg N₂O m⁻² h⁻¹, 3–6 times those from the normal tundra soils, suggesting that the deposition of fresh droppings enhanced N₂O emissions during penguin breeding period. The summer precipitation had an important effect on N₂O emissions; the flux decreased when heavy precipitation occurred. The diurnal cycle of the N₂O fluxes from Antarctic tundra soils was not obtained due to local fluky weather conditions. The N₂O fluxes through four snowpack sites were obtained by the vertical N₂O concentration gradient and their average fluxes were 0.94, 1.36, 0.81 and 0.85 μg N₂O m⁻² h⁻¹, respectively. The tundra soils under snowpack emitted N₂O in the maritime Antarctic and increased local atmospheric N₂O concentrations; therefore these fluxes could constitute an important part of the annual N₂O budget for Antarctic tundra ecosystem.     

Dynamics of Cd, Cu and Zn accumulation in organs and sub-cellular fractions in field transplanted juvenile yellow perch (Perca flavescens)

Juvenile yellow perch (Perca flavescens) were caught in a reference lake and transplanted to cages held within a lake impacted by mining activities, with elevated levels of aqueous bioavailable copper (Cu(2+)), zinc (Zn(2+)) and cadmium (Cd(2+)). Fish were sampled from the cages over 70 d and changes in metal concentrations were followed over time in the gills, gut, liver and kidney. In addition, the hepatic sub-cellular partitioning of the three metals was determined by differential centrifugation of liver samples, yielding the following fractions: cellular debris; organelles; heat-denaturable proteins (HDP); and heat-stable proteins (HSP) (including metallothionein). In transplanted fish, Cd concentrations increased in all the organs sampled, whereas Cu mainly increased in the gills, gut and liver but not the kidney; some slight accumulation of Zn occurred in the kidneys and gills of the transplanted fish. The sub-cellular partitioning results demonstrated that metal-handling strategies in juvenile yellow perch differed among metals. Cellular sequestration in the HSP fraction was an important strategy used by these fish in response to increased ambient Cd. Accumulation of Zn was not seen in the organs examined, indicating that transplanted perch were able to either reduce influx, or increase efflux rates of this metal. The response of yellow perch to elevated ambient Cu appeared to combine the strategies used for Cd and Zn, as both cellular sequestration and reduced accumulation were observed in transplanted fish.     

Investigation on the influence of methanol on adsorption and leaching of pesticides with soil column liquid chromatography

The effect of methanol of low concentration on adsorption and leaching of atrazine and tebuconazole was studied in this paper. The adsorption coefficients and the retardation factors (R^m) of pesticides on EUROSOIL 3# log-linearly decreased as volumetric fraction of methanol (f^c) was increased in the binary solvent mixtures of methanol and water. These data are consistent with solvophobic theory formerly outlined for describing the adsorption and transport of hydrophobic organic chemicals from mixed solvents. Nevertheless, the adsorption of these pesticides in soil–water system slightly increased when the soil was pre-washed with methanol in comparison with that pre-washed with water (pure water system). Furthermore, their adsorption coefficients were still higher in binary solvent systems with methanol of very low concentrations, i.e. f^c<0.03 for atrazine and f^c<0.01 for tebuconazole, than those in pure water system. The adsorption coefficients (logK^w) of atrazine and tebuconazole predicted by solvophobic theory were 0.5792 and 1.6525, respectively, and their experimental logK^w were 0.3701 and 1.6275 in pure water system. Obviously, the predicted logK^w of the two pesticides was higher than the experimental log K^w in pure water system. The predicted K^w and the retardation factor (R^w) in pure water system by solvophobic theory are thus possibly inaccurate.