Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT)

Munitions wastes such as TNT are widespread contaminants in soils and ground waters. We investigated a coupled abiotic-biotic treatment scheme for remediation of aqueous solutions of TNT. Mineralization of aqueous TNT (0.22 mM) was initially optimized with minimum reactant use (Fe3+ and H2O2) in light-assisted and dark, modified Fenton reactions at acidic and neutral pH. Complete TNT degradation occurred under all reaction conditions within 24 h. Using the optimum reactant concentrations, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 47 to 80%, after biomass addition to the acidic, dark Fenton-like reaction. Comparable increases of TNT mineralization were observed under neutral pH with similar reaction conditions. In light-assisted Fenton-like reactions at neutral pH, no increase in cumulative TNT mineralization (66%) was seen in coupled abiotic-biotic reactions. Abiotic photo-Fenton-like reactions alone, at acidic pH, produced complete TNT mineralization and required no biotic assistance. While light-enhanced Fenton reactions alone can provide high levels of TNT mineralization, the dark abiotic-biotic reaction scheme has perhaps a wider use due to a similar extent of TNT mineralization in the absence of light, leading to possible applications in soil slurry and in situ processes in the subsurface.     

Use of pyrolysis molecular beam mass spectrometry (py-MBMS) to characterize forest soil carbon: method and preliminary results

The components of soil organic matter (SOM) and their degradation dynamics in forest soils are difficult to study and thus poorly understood, due to time-consuming sample collection, preparation, and difficulty of analyzing and identifying major components. As a result, changes in soil organic matter chemical composition as a function of age, forest type, or disturbance have not been examined. We applied pyrolysis molecular beam mass spectrometry (py-MBMS), which provides rapid characterization of SOM of whole soil samples. to the Tionesta soil samples described by Hoover, C.M., Magrini, K.A., Evans, R.J., 2002. Soil carbon content and character in an old growth forest in northwestern Pennsylvania: a case study introducing molecular beam mass spectrometry (PY-MBMS). Environmental Pollution 116 (Supp. 1), S269-S278. Our goals in this work were to: (1) develop and demonstrate an advanced, rapid analytical method for characterizing SOM components in whole soils, and (2) provide data-based models to predict soil carbon content and residence time from py-MBMS analysis. Using py-MBMS and pattern recognition techniques we were able to statistically distinguish among four Tionesta sites and show an increase in pyrolysis products of more highly decomposed plant materials at increasing sample depth. For example, all four sites showed increasing amounts of older carbon (phenolic and aromatic species) at deeper depths and higher amounts of more recent carbon (carbohydrates and lignin products) at shallower depths. These results indicate that this type of analysis could be used to rapidly characterize SOM for the purpose of developing a model, which could be used in monitoring the effect of forest management practices on carbon uptake and storage.     

Bioavailability of calcium from sweetpotato and soy flour supplemented diets in hamsters

The bioavailability of calcium from two varieties of sweetpotatoes and supplementation of sweetpotatoes with soy flour was investigated in hamsters using plasma calcium concentration and femur calcium content as indicators. Five different diets were fed to five groups of animals for 28 days. There was no significant difference in plasma calcium concentrations of hamsters in all the diet groups. However, the femur calcium content of hamsters with transgenic sweetpotato flour (TSPF) and parent nontransgenic (from which transgenic was produced) sweetpotato flour (NTSPF) diets was significantly higher than that of the transgenic sweetotato flour supplemented with soy flour (TSPF + SF) and parent nontransgenic sweetpotato flour supplemented with soy flour (NTSPF + SF) diets. The relative bioavailability of calcium from the control (100%), TSPF+SF (30%), NTSPF+SF (23%), TSPF (57%) and NTSPF (46%) indicated that sweetpotatoes could be the better source of calcium, however, supplementation with soy flour might reduce the bioavailability of calcium.     

Comparative studies of health hazard from radon (Rn-222) in two selected lithologic formations in the Suwałki region (in Poland)

The aim of this work was to make a comparison of indoor radon concentrations in dwellings and in soil air in the area of two geological formations in the Suwa?ki region (Poland). The mean arithmetic airborne concentration was found to be the highest (301 Bq m (-3)) in the basements of buildings in the gravel and sand areas, whereas in the boulder clay areas it reached 587 Bq m (-3). Out of 54 measurements of radon concentrations performed at the ground floor, in eight cases concentrations were found to exceed 200 Bq m (-3) - permissible radon level in new-built houses in Poland and in three cases these values were even higher than 400 Bq m (-3). The highest radon levels were noted in houses with earthen basement floors and with direct entrance from the basement to rooms or kitchens. The mean arithmetic radon concentration in the soil air in the sandy and gravel formations was 39.7 kBq m (-3) and in clay formation it was 26.5 kBq m (-3). Higher radon levels were also found in the water obtained from household wells reaching 8367 Bq m (-3) as compared with tap water (2690 Bqm (-3)). The mean indoor concentration for the whole area under study was found to be 169.4 Bq m (-3), which is higher than the mean value for Poland (49.1 Bq m (-3)) by a factor of 3.5.     

Modelling the long-term dynamics of radiocaesium in closed lakes

During the years after the Chernobyl accident the radioceasium activity concentration in most contaminated aquatic ecosystems decreased markedly. Lakes with no permanent inflows and outflows (closed lakes), however, still present a radioecological problem which is expected to continue for some time. In this paper, a mechanistic model for the long-term prediction of radiocaesium behaviour in closed lakes is developed. The model of Prokhorov (Radiokhimiya (Radiochemistry) 11 (1969) 317) was modified to describe the effects of bottom sediment bioturbation, surface runoff from the catchment and suspended solids formation and sedimentation. The model input parameters are the effective diffusion coefficient in bottom sediments, depth of the completely mixed layer, the distribution coefficient in the sediment-water system, the runoff coefficient, sedimentation rate, and deposition density. Values of all these parameters can be independently estimated or measured in a short-term experiment. Given negligible runoff and sedimentation, the dynamics of radiocaesium in lake water is described by a simple equation with only one unknown parameter. This allows us to make long-term predictions on the basis of a series of measurements carried out during the relatively short period. The model was tested against 137Cs activity concentrations measured between 1993 and 1999 in Svyatoe lake in the Bryansk region of Russia. Calculated and measured activity concentrations are in good agreement.     

Use of 129I and 137Cs in soils for the estimation of 131I deposition in Belarus as a result of the Chernobyl accident

Using radioactivity measurements for 131I and 137Cs and nuclear activation analysis (NAA) or accelerator mass spectrometry (AMS) for 129I, ratios of 131I/137Cs and 129I/137Cs have been determined in soils from Belarus. We find that the pre-Chernobyl ratio of 129I/137Cs in Belarus is significantly larger than expected from nuclear weapons fallout. For the Chernobyl accident, our results support the hypothesis that there was relatively little fractionation of iodine and caesium during migration and deposition of the radioactive cloud. For sites having 137Cs > 300 Bq/kg, 129I can potentially give more reliable retroactive estimates of Chernobyl 131I deposition. However, our results suggest that 137Cs can also give reasonably good (+/-50%) estimates for 131I in Belarus.     

Distribution of long-lived radionuclides of the 238U series in the sediments of a small river in a uranium mineralized region of Spain

A study is presented on the distribution and mobilization of the natural U isotopes (238U and 234U), 230Th, and 226Ra in the sediments of a small river crossing an uranium mineralized zone where a disused uranium mine is located. Due to the preferential directions for surface run-off waters and to the mine's situation, one sampling point along the river bed was identified as a point of accumulation of radionuclides. The average values of the activity concentrations (Bq/kg) in this sediment sample were 5,025, 5,055, 5,915 and 1,694 for 238U, 234U, 230Th and 226Ra, respectively, while the respective average values of the activity concentrations (Bq/kg) for the sediment sample considered to give the background level were 125, 124, 131 and 370. Isotopic ratios between the descendants of 238U served to clarify some paths of distribution, involving the soils nearest to the sampling points and the location of these points with respect to the disused mine. The differences in behaviour found between the uranium, thorium and radium isotopes were associated to the mobility of these radionuclides in the fluvial system studied. Correlations between the radionuclide activity concentration ratios and stable element concentrations in the sediment samples were also investigated.     

Enhanced transport of pesticides in a field trial with treated sewage sludge

This study was designed to provide high-density data on spatial distribution of three herbicides with different physiochemical characteristics in a sludge-amended and non-amended control field over the course of an irrigation season. The field experiment was carried out on a sandy loam Hamra Red Mediterranean soil (Rhodoxeralf) at Bet Dagan, Israel. After a single 50 mm irrigation event, the mean centers of mass (COM) in the control field were at 15.6, 14.9, and 17 cm for bromacil, atrazine and terbuthylazine, respectively; in the sludge-amended field, mean COMs were at 28.8, 31.2, and 34.1 cm, respectively. After 500 mm of irrigation in the control field, the COM depth distribution of the three pesticides was inversely correlated with octanol-water (Kow) distribution coefficients and soil sorption coefficients (Koc), and positively correlated with aqueous solubilities. After 500 mm irrigation in the sludge-amended field, the mean terbuthylazine COM was at 19.8 cm versus 13.8 cm for the control field, demonstrating a sustained enhanced effect on terbuthylazine transport. Downward transport of atrazine was also enhanced by sludge amendment, albeit less than terbuthylazine. Bromacil was preferentially accumulated in the upper soil layers of the sludge-amended field as compared with the control field after 500 mm irrigation. The enhanced transport of all three pesticides in the sludge-amended field after a single irrigation event is attributed to development of preferential flow pathways around hydrophobic clods of sludge. Enhanced transport of terbuthylazine, and to a lesser extent, atrazine, throughout the irrigation season, is attributed to their transport as complexes with dissolved, colloidal and suspended organic matter derived from sludge degradation.     

Seasonal aerosol sulfate trends for selected regions of the United States

Site and regional trends in seasonally averaged particle SO4(2-) concentrations were examined for a large portion of the United States using data collected by the CASTNet air monitoring network. Trends were analyzed for overlapping periods of 1988-1999 and 1992-1999. The largest absolute SO4(2-) decreases--approximately -0.4 microg/m3/yr--between 1988 and 1999 occurred in summer for sites in the Ohio River Valley and areas to the east. Generally, the largest SO4(2-) reductions were found for summer, but larger relative reductions often occurred for spring and autumn. Sulfate changes during 1992-1999 were quite different from those found for 1988-1999 and were not entirely consistent with changes in SO2 emissions. In some locations, the 1992-1999 period saw smaller declines in SO4(2-), while in other places seasonal SO4(2-) actually increased. Increases were mostly confined to summer and autumn across the southern and southwestern states. Multivariate analysis of ambient sulfur levels, by region, versus SO2 emissions reveals that annual emissions are associated with more than 80% of the variance in seasonal sulfur (SO2 and SO4(2-)) in more than three-quarters of the cases examined. The weakest associations were found for the southeastern United States.     

Activity of glutathione S-transferase in Spodoptera exigua larvae exposed to cadmium and zinc in two subsequent generations

The aim of our study was to establish changes in activity of important in detoxification enzyme-glutathione S-transferase (GST): in alimentary tract, fat body and Malpighian tubules of Spodoptera exigua larvae being under cadmium and zinc exposure through the first as well as the second generation. There was registered enhancement of the enzyme activity in the fat body and the Malpighian tubules caused by zinc as well as its decrease in the Malpighian tubules under cadmium action. Amounts of metals in the alimentary tract were either several times higher than in the diet ingested by larvae or than in the fat body. Metal concentration in the fat body correlated with the level of the enzyme activity (positive correlation for zinc and negative for cadmium). The effect of metal action differentiated dependently on time exposition.