Influence of Na2S on the degradation kinetics of CCl4 in the presence of very pure iron

This paper presents the results of kinetic studies to investigate the effect of FeS film formation on the degradation rate of CCl(4) by 99.99% pure metallic iron. The film was formed by submersing metallic iron grains in an oxygen free HCO(3)(-)/CO(3)(2-) electrolyte solution. When the grains had reached a quasi steady-state value of the corrosion potential, Na(2)S((aq)) was injected. Upon injection, a microm thick poorly crystalline FeS film formed immediately on the iron surface. Over time, the iron became strongly corroded and both the FeS film and the metallic iron grains began to crack leading to exposure of bare metallic iron to the solution. The effect of the surface film on the degradation rate of CCl(4) was investigated following four periods of aging, 1, 10, 30, and 60 days. Relative to the controls, the 1-day sulfide-aged iron showed a substantial decrease in rate of degradation of CCl(4.) However, over time, the rate of degradation increased and surpassed the degradation rate obtained in the controls. It has been proposed that CCl(4) is reduced to HCCl(3) by metallic iron by electron transfer. The FeS film is substantially less conducting than the bulk iron metal or non-stoichiometric magnetite and from the results of this study, greatly decreases the rate of CCl(4) degradation relative to iron that has not been exposed to Na(2)S. However, continued aging of the FeS film results in breakdown and stress-induced cracking of the film, followed by dissolution and cracking of the iron itself. The cracking of the bulk iron is believed to be a consequence of hydrogen embrittlement, which is promoted by sulfide. The increase in CCl(4) degradation rate, as the FeS films age, suggests that the process of hydrogen cracking increases the surface area available for charge transfer.     

The effect of nitroaromatics' composition on their toxicity in vivo: novel, efficient non-additive 1D QSAR analysis

Novel 1D QSAR approach that allows analysis of non-additive effects of molecular fragments on toxicity has been proposed. Twenty-eight nitroaromatic compounds including some well-known explosives have been chosen for this study. The 50% lethal dose concentration for rats (LD50) was used as the estimation of toxicity in vivo to develop 1D QSAR models on the framework of Simplex representation of molecular structure. The results of 1D QSAR analysis show that even the information about the composition of molecules provides the main trends of toxicity changes. The necessity of consideration of substituents' mutual impacts for the development of adequate QSAR models of nitroaromatics' toxicity was demonstrated. Statistic characteristics for all the developed partial least squares QSAR models, except the additive ones are quite satisfactory (R2=0.81-0.92; Q2=0.64-0.83; R2 test=0.84-0.87). A successful performance of such models is due to their non-additivity i.e. possibility of taking into account the mutual influence of substituents in benzene ring which plays the governing role for toxicity change and could be mediated through the different C-H fragments of the ring. The correspondence between observed and predicted by these models toxicity values is good. This allowing combine advantages of such approaches and develop adequate consensus model that can be used as a toxicity virtual screening tool.     

The changing sediment load of the Mekong River

The sediment loads of many of the world's major rivers have changed significantly in recent years due to land-use change, reservoir construction, and other human impacts on their drainage basins. For many rivers, the loads have decreased, whereas for others, they have increased. Such changes can have important implications for both the natural functioning of the system as well as for human exploitation of the river system. This paper considers the evidence for recent changes in the sediment load of the Mekong River. The available data have a number of limitations in terms of both sampling frequency and the period of coverage, but they have been processed to provide a basis for considering the changes in the sediment load of the river over the period extending from the early 1960s to 2002. Although there is evidence of increasing loads at some measuring stations, the overall trends show little evidence of major changes, and the system provides evidence of buffering through storage. As of 2002, the construction of major dams on the headwaters in China appears to have had little impact on the sediment load, although as further larger dams are commissioned, the sediment load of the Mekong can be expected to decrease.     

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.     

Influence of tidal regime on the distribution of trace metals in a contaminated tidal freshwater marsh soil colonized with common reed (Phragmites australis)

A historical input of trace metals into tidal marshes fringing the river Scheldt may be a cause for concern. Nevertheless, the specific physicochemical form, rather than the total concentration, determines the ecotoxicological risk of metals in the soil. In this study the effect of tidal regime on the distribution of trace metals in different compartments of the soil was investigated. As, Cd, Cu and Zn concentrations in sediment, pore water and in roots were determined along a depth profile. Total sediment metal concentrations were similar at different sites, reflecting pollution history. Pore water metal concentrations were generally higher under less flooded conditions (mean is (2.32 ± 0.08) × 10⁻³ mg Cd L⁻¹ and (1.53 ± 0.03) × 10⁻³ mg Cd L⁻¹). Metal concentrations associated with roots (mean is 202.47 ± 2.83 mg Cd kg⁻¹ and 69.39 ± 0.99 mg Cd kg⁻¹) were up to 10 times higher than sediment (mean is 20.48 ± 0.19 mg Cd kg⁻¹ and 20.42 ± 0.21 mg Cd kg⁻¹) metal concentrations and higher under dryer conditions. Despite high metal concentrations associated with roots, the major part of the metals in the marsh soil is still associated with the sediment as the overall biomass of roots is small compared to the sediment.     

Mercury concentrations in wild mink (Mustela vison) and river otters (Lontra canadensis) collected from eastern and Atlantic Canada: relationship to age and parasitism

Total mercury (Hg) concentrations were measured in the fur, brain and liver of wild mink (Mustela vison) and river otters (Lontra canadensis) collected from eastern and Atlantic Canada. Total Hg concentrations in fur were strongly correlated with levels in the brain and liver. There was no difference in tissue concentrations between male and female mink; however, female otters had significantly higher fur, brain and liver Hg levels than males. Similarly, there was not a significant relationship between Hg concentration and age of mink, whereas in otters, Hg concentrations in all three tissues decreased significantly with age. In both species, only a very small percentage of the variability in Hg concentration was explained by age. After adjusting the data for site-to-site differences in Hg levels, Hg concentrations in the fur of mink infected by the parasite, Dioctophyma renale, were found to be significantly higher than Hg levels in uninfected mink.     

Degradation and plant uptake of nonylphenol (NP) and nonylphenol-12-ethoxylate (NP12EO) in four contrasting agricultural soils

Nonylphenol polyethoxylates (NPEOs) are surfactants found ubiquitously in the environment due to widespread industrial and domestic use. Biodegradation of NPEOs produces nonylphenol (NP), an endocrine disruptor. Sewage sludge application introduces NPEOs and NP into soils, potentially leading to accumulation in soils and crops. We examined degradation of NP and nonylphenol-12-ethoxylate (NP12EO) in four soils. NP12EO degraded rapidly (initial half time 0.3-5 days). Concentrations became undetectable within 70-90 days, with a small increase in NP concentrations after 30 days. NP initially degraded quickly (mean half time 11.5 days), but in three soils a recalcitrant fraction of 26-35% remained: the non-degrading fraction may consist of branched isomers, resistant to biodegradation. Uptake of NP by bean plants was also examined. Mean bioconcentration factors for shoots and seeds were 0.71 and 0.58, respectively. Removal of NP from the soil by plant uptake was negligible (0.01-0.02% of initial NP). Root concentrations were substantially higher than shoot and seed concentrations.     

锌精炼铅塔燃烧系统烟气温度模糊控制研究

针对锌精馏铅塔动态过程中的非线性、非最小相位特征、不稳定性、时滞和负荷干扰,基于模糊控制策略下给出了锌精馏铅塔燃烧系统新的控制方法.运用模糊控制系统对锌精馏铅塔的烟气温度进行仿真研究和实时控制结果表明,该研究所设计的模糊控制器能够克服许多干扰因素,产生了良好的控制效果.     

Effect of spatial variation on salinity tolerance of macroinvertebrates in Eastern Australia and implications for ecosystem protection trigger values

Salinisation of freshwater has been identified as a serious environmental issue in Australia and around the world. Protective concentrations (trigger values) for salinity can be used to manage salinity impacts, though require locally relevant salinity tolerance information. 72-h acute salinity tolerance values were determined for 102 macroinvertebrates collected from 11 locations in four biologically distinct freshwater bio-regions in Northeast Australia and compared with sensitivities observed in Southeast Australia. The salinity tolerance of individual taxa was consistent across Northeast Australia and between Northeast and Southeast Australia. However, two distinct communities were identified in Northeast Australia using distributions of the acute tolerance values and a calculated index of salinity sensitivity. Salinity trigger values should therefore be representative of local or regionally relevant communities and may be adequately calculated using sensitivity values from throughout Eastern Australia. The results presented provide a basis for assessing salinity risk and determining trigger values for salinity in freshwater ecosystems at local and regional scales in Eastern Australia.