Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing phyllosilicates

Abiotic reductive dechlorination of chlorinated ethylenes (tetrachloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (c-DCE), and vinylchloride (VC)) by iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite) was characterized to obtain better understanding of the behavior of these contaminants in systems undergoing remediation by natural attenuation and redox manipulation. Batch experiments were conducted to evaluate dechlorination kinetics and some experiments were conducted with addition of Fe(II) to simulate impact of microbial iron reduction. A modified Langmuir-Hinshelwood kinetic model adequately described reductive dechlorination kinetics of target organics by the iron-bearing phyllosilicates. The rate constants stayed between 0.08 (+/-10.4%) and 0.401 (+/-8.1%) day(-1) and the specific initial reductive capacity of iron-bearing phyllosilicates for chlorinated ethylenes stayed between 0.177 (+/-6.1%) and 1.06 (+/-7.1%) microM g(-1). The rate constants for the reductive dechlorination of TCE at reactive biotite surface increased as pH (5.5-8.5) and concentration of sorbed Fe(II) (0-0.15 mM g(-1)) increased. The appropriateness of the model is supported by the fact that the rate constants were independent of solid concentration (0.0085-0.17 g g(-1)) and initial TCE concentration (0.15-0.60 mM). Biotite had the greatest rate constant among the phyllosilicates both with and without Fe(II) addition. The rate constants were increased by a factor of 1.4-2.5 by Fe(II) addition. Between 1.8% and 36% of chlorinated ethylenes removed were partitioned to the phyllosilicates. Chloride was produced as a product of degradation and no chlorinated intermediates were observed throughout the experiment.     

Determination of herbicides in stemflow and throughfall of beeches (Fagus sylvatica L.) and in rainfall

The pesticide contamination of water samples collected in and nearby a beech forest in northern Germany was evaluated. For this purpose, a method for the collection of water samples from stemflow and throughfall of beeches (Fagus sylvatica L.) and rainfall was developed in response to the demands for the analysis of organic contaminants in water samples. Furthermore a sensitive and selective multiresidue method was developed to determine 18 pesticides, frequently used in Germany, in aqueous samples. The samples collected were taken from the stemflow, the crown throughfall and the rainfall between May and November 2001. Analysis based on reversed-phase liquid chromatography with a pneumatically assisted electrospray mass spectrometer followed a solid phase extraction using C-18 extraction cartridges. Isoproturon, metolachlor, prosulfocarb and terbuthylazine were found during and shortly after their application period. In rainfall metolachlor, terbuthylazine and prosulfocarb were detectable in concentrations between 5 and 65 ng l(-1) and isoproturon in concentrations between 20 and 360 ng l(-1) respectively. In most of the samples, concentrations of those four pesticides were higher and detectable for a longer time in stemflow than in rainfall. Crown throughfall samples were collected from the end of August to November. Absolute deposition of isoproturon to forest soil were up to 70 times higher in comparison to rainwater samples.     

Effects of soil amendments at a heavy loading rate associated with cover crops as green manures on the leaching of nutrients and heavy metals from a calcareous soil

The potential risk of groundwater contamination by the excessive leaching of N, P and heavy metals from soils amended at heavy loading rates of biosolids, coal ash, N-viro soil (1:1 mixture of coal ash and biosolids), yard waste compost and co-compost (3:7 mixture of biosolids to yard wastes), and by soil incorporation of green manures of sunn hemp (Crotalaria juncea) and sorghum sudangrass (Sorghum bicolor x S. bicolor var. sudanense) was studied by collecting and analyzing leachates from pots of Krome very gravelly loam soil subjected to these treatments. The control consisted of Krome soil without any amendment. The loading rate was 205 g pot(-1) for each amendment (equivalent to 50 t ha(-1) of the dry weight), and the amounts of the cover crops incorporated into the soil in the pot were those that had been grown in it. A subtropical vegetable crop, okra (Abelmoschus esculentus L.), was grown after the soil amendments or cover crops had been incorporated into the soil. The results showed that the concentration of NO3-N in leachate from biosolids was significantly higher than in leachate from other treatments. The levels of heavy metals found in the leachates from all amended soils were so low, as to suggest these amendments may be used without risk of leaching dangerous amounts of these toxic elements. Nevertheless the level of heavy metals in leachate from coal ash amended soil was substantially greater than in leachates from the other treatments. The leguminous cover crop, sunn hemp, returned into the soil, increased the leachate NO3-N and inorganic P concentration significantly compared with the non-legume, sorghum sudangrass. The results suggest that at heavy loading rates of soil amendments, leaching of NO3- could be a significant concern by application of biosolids. Leaching of inorganic P can be increased significantly by both co-compost and biosolids, but decreased by coal ash and N-viro soil by virtue of improved adsorption. The leguminous cover crop, sunn hemp, when incorporated into the soil, can cause the concentration of NO3-N to increase by about 7 fold, and that of inorganic P by about 23% over the non-legume. Regarding the metals, biosolids, N-viro soil and coal ash significantly increased Ca and Mg concentrations in leachates. Copper concentration in leachate was increased by application of biosolids, while Fe concentration in leachates was increased by biosolids, coal ash and co-compost. The concentrations of Zn, Mo and Co in leachate were increased by application of coal ash. The concentrations of heavy metals in leachates were very low and unlikely to be harmful, although they were increased significantly by coal ash application.     

Biosorption of cadmium and copper contaminated water by Scenedesmus abundans

Experiments were conducted comparing the individual removals of cadmium and copper from water via biosorption using Scenedesmus abundans, a common green algae, to removal in a multi-component system to determine competitive effects, if any, between the metals. The goal was to characterize the biological treatment of water contaminated with heavy metals using live aquatic species. In addition, experiments were performed to measure cell viability as a function of metal concentration and also to compare metal removal using living species to that using nonliving ones. It was shown that, while both living and nonliving S. abundans removed cadmium and copper from water, living algae significantly outperformed nonliving algae. Further, in characterizing biosorption by three concentrations of live S. abundans, capacity curves were created comparing the metal biosorbed per mass algae to the initial metal concentration in solution. The algae concentration was not a factor in the biosorption of either metal individually, such that the capacity of the algae for the metal increased with decreasing algae concentration. At the lowest algae concentration considered, competitive effects were observed at copper and cadmium concentrations above 4 mg/l each. At the highest algae concentration considered, no competitive effects were observed in the range of cadmium and copper concentrations studied (1-7 mg/l). It was concluded that biological treatment of heavy metal contaminated water is possible and that at adequately high algae concentrations, multi-component metal systems can be remediated to the same level as individual metals.     

Seveso Women's Health Study: does zone of residence predict individual TCDD exposure?

The compound, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), is produced as an unwanted by-product of various chemical reactions and combustion processes, including the manufacture of chlorinated phenols and derivatives. In animals, TCDD exposure is associated with toxic, carcinogenic, developmental, and reproductive effects. In 1976, a chemical plant explosion in Seveso, Italy, exposed the residents in the surrounding community to the highest exposure to TCDD known in humans. Materials from an aerosol cloud of sodium hydroxide, sodium trichlorophenate and TCDD were deposited over an 18.1 km2 area. As evidence of the significant level of TCDD exposure, numerous animals died and 193 cases of chloracne were reported among residents of the area. Initially, the contaminated area was divided into three major exposure Zones (A, B, R) based on the concentration of TCDD in surface soils. To date, the majority of epidemiologic studies conducted in Seveso have used Zone of residence as a proxy measure of exposure. The purpose of the present study is to validate the use of Zone of residence in Seveso as a proxy measure of exposure against individual serum TCDD measurement, and to determine whether questionnaire information can improve the accuracy of the exposure classification. Using data collected from the Seveso Women's Health Study (SWHS), the first comprehensive epidemiologic study of the reproductive health of women in Seveso, we determined that Zone of residence is a good predictor of individual serum TCDD level, explaining 24% of the variance. Using questionnaire information could have improved prediction of individual exposure levels in Seveso, increasing the percent of the variation in serum TCDD levels explained to 42%.     

Modeling the quantum yields of herbicide 2,4-D decay in UV/H2O2 process

The photodecay of herbicide 2,4-D in a hydrogen peroxide-aided photolysis process was studied and modeled. The decay rate of 2,4-D was known to be low in the natural environment, but rate improvement was achieved in an H2O2/UV system. The 2,4-D decay quantum yields under ultraviolet (UV) light at 253.7 nm increased from 4.86 x 10(-6) to 1.30 x 10(-4) as the ratio of [H2O2]/[2,4-D] increased from 0.05 to 12.5. Apparently, in the presence of UV light, the decay rate of 2,4-D could be greatly improved as the concentration of hydrogen peroxide increased. However, the efficiency of 2,4-D photodecay was retarded if the concentration of H2O2 was overdosed, because the excess hydrogen peroxide consumes the hydroxyl radicals (HO*) in the solution, resulting in a much weaker oxidant HO2*. The decay of 2,4-D was also pH dependent. A ranking of acid (highest), base (middle) and neutral (lowest) was observed owing to the property change of reactants and the shifting of dominant mechanisms among photolysis, photohydrolysis and chemical oxidation. Two mathematical models were proposed to predict the quantum yield for various [H2O2]/[2,4-D] ratios and initial pH levels, in which very good correlation was found for the ranges of regular application.     

Beta-cyclodextrin(beta-CD) influence on the biotoxicities of substituted benzene compounds and pesticide intermediates

The acute toxicities of 19 substituted benzene compounds and intermediates of pesticides to Photobacterium phosphoreum in beta-CD aqueous solution (5 g/L) were studied and compared with those in water through luminescent bacteria toxicity test, and 15min-EC50 values were obtained. The presence of beta-CD significantly reduce biotoxicities of the low-polarity compounds, while for the higher-polarity compounds, such effect was slight. The differences of biotoxicities were correlated with Log10Kow (octanol/water partition coefficients). A significant linear relationship was obtained with some abnormal data picked out. Some explanations concerning molecular structure of chemicals as well as beta-CD were given for the relationship.     

Visible injury responses

During a five year experiment on the causes of forest disease, symptoms of visible injury and pest infestations in trees treated with various air pollutants in open-top chambers were observed. Though the long-term experiment was originally not intended to include such investigations, insect infestation and some discoloration of the trees (Beech, Fagus sylvatica; Fir, Abies alba; Spruce, Picea abies) could not be avoided. Abundance and size of some of the insects were measured after two years and at the end of the experiment. Because it was unknown when the first infestation in the chambers occurred, quantitative investigations of the population size provided little information. Visible injury on leaves and needles was infrequent in general. When it occurred, it appeared to be caused by at least three stress factors. However, three different types of symptoms on beech and fir could be attributed mainly to air pollutants. These symptoms consisted of two types of foliar necrosis and browning in beech and needle tip chlorosis in fir. These symptoms have been observed under certain conditions in the German forests. The spruce clone used, however, developed no injuries which could be connected definitely to treatment effects.     

Assessing the recovery of lakes in southeastern Canada from the effects of acidic deposition

Reductions in North American sulfur dioxide (SO2) emissions promoted expectations that aquatic ecosystems in southeastern Canada would soon recover from acidification. Only lakes located near smelters that have dramatically reduced emissions approach this expectation. Lakes in the Atlantic provinces, Quebec and Ontario affected only by long-range sources show a general decline in sulfate (SO4(2-)) concentrations, but with a relatively smaller compensating increase in pH or alkalinity. Several factors may contribute to the constrained (or most likely delayed) acidity response: declining base cation concentrations, drought-induced mobilization of SO4(2-), damaged internal alkalinity generation mechanisms, and perhaps increasing nitrate or organic anion levels. Monitoring to detect biological recovery in southeastern Canada is extremely limited, but where it occurs, there is little evidence of recovery outside of the Sudbury/Killarney area. Both the occurrence of Atlantic salmon in Nova Scotia rivers and the breeding success of Common Loons in Ontario lakes are in fact declining although factors beyond acidification also play a role. Chemical and biological models predict that much greater SO2 emission reductions than those presently required by legislation will be needed to promote widespread chemical and latterly, biological recovery. It may be unrealistic to expect that pre-industrial chemical and biological conditions can ever be reestablished in many lakes of southeastern Canada.     

Sustainable watershed management: an international multi-watershed case study

Global freshwater resources are being increasingly polluted and depleted, threatening sustainable development and human and ecosystem health. Utilizing case studies from 4 different watersheds in the United States, Japan, Switzerland, and Brazil, this paper identifies the most relevant sustainability deficits and derives general vectors for more sustainable water management. As a consequence of the demographic and economic developments experienced in the last few decades, each watershed has suffered declines in water quality, streamflow and biotic resources. However, the extent and the cultural perception of these water-related problems vary substantially in the different watersheds, leading to specific water-management strategies. In industrialized countries, exemplified by the US, Switzerland, and Japan, these strategies have primarily consisted of finance- and energy-intensive technologies, allowing these countries to meet water requirements while minimizing human health risks. But, from a sustainability point of view, such strategies, relying on limited natural resources, are not long-term solutions. For newly industrialized countries such as Brazil, expensive technologies for water management are often not economically feasible, thus limiting the extent to which newly industrialized and developing countries can utilize the expertise offered by the industrialized world. Sustainable water management has to be achieved by a common learning process involving industrialized, newly industrialized, and developing countries, following general sustainability guidelines as exemplified in this paper.