Persistence of methyl <Emphasis Type="Italic">tertiary</Emphasis> butyl ether (MTBE) against metabolism by Danish vegetation

BACKGROUND: Methyl tertiary butyl ether (MTBE) is the second most highly produced industrial chemical in the US and a frequent groundwater pollutant. At the same time, MTBE is quite persistent to biotic and abiotic decomposition. The goal of this study was to find plant species that could degrade MTBE and might be used in phytoremediation. METHODS: Excised roots and leaves (0.3 g) from more than 24 Danish plant species out of 15 families were kept in glass vessels with 25 ml spiked aqueous solution for 2 to 4 days. MTBE concentrations were 1 to 5 mg/L. Samples were taken directly from the solution with a needle and injected to a purge and trap unit. MTBE and the main metabolite, TBA, were measured by GC/FID. RESULTS AND DISCUSSION: Solutions with roots of poplar (Populus robusta) and a willow hybrid (Salix viminalis x schwerinii) produced TBA in trace amounts, probably stemming from bacteria. Significant MTBE reduction (> 10%) was not observed in any of the tests. Leaves from none of the species (trees, grasses and herbs) reduced the concentration of MTBE in the solution and no TBA, nor any other known metabolite of MTBE, was detected. CONCLUSION: It was not possible to find plants capable of efficiently degrading MTBE. This gives rise to the conclusion that plants probably cannot degrade MTBE at all, or only very slowly. RECOMMENDATIONS AND OUTLOOK: For phytoremediation projects, this has, as consequence, that the volatilization by plants (except with genetically engineered plants) is the only relevant removal process for MTBE. For risk assessment of MTBE, degradation by the plant empire is not a relevant sink process.     

Bioavailability of cyanide in the different environmental compartments

Introduction C yanide, a strong ligand capable of com plexing w ith virtually any heavy m etals, had its beginning in m etallurgical operations in N ew Zealand over a century ago. The basic m echanism for cyanide leaching technique w as defined as the fol…     

Uptake of Tributyltin into Willow Trees

BACKGROUND: Organotins have been used world-wide as antifoulants in ship paints. Repeatedly, severe effects on aquatic species have resulted. The use of organotins for this purpose was ruled out, and dumping of contaminated harbor sludge into the sea was prohibited. Land-based dumping is seen as an alternative. OBJECTIVE: This study investigates sorption, uptake and translocation of tributyltin (TBT) to willow trees in order to evaluate phytoremediation as treatment option. The study considers the influence of pH on the plant uptake of organotins. EXPERIMENTAL SET-UP: Chemicals investigated were the weak base tributyltin chloride (TBTCl) and the neutral tributyltin hydride (TBTH). Organotins were extracted from solution and plant material with toluene, and analyzed as tin by AAS with graphite oven. The pH in solution varied from pH 4 to pH 7. The sorption to living and dead roots, stems and leaves was measured in shaking experiments. The uptake into intact trees was measured at nominal levels of 1 and 10 mg TBT/l for TBTH and TBTCl at low and high pH. RESULTS: The sorption to roots and leaves dropped for dead tissue, but did not vary much with pH. The sorption to stems increased for dead stems and with pH. The solubility of TBTCl in water was below 10 mg/l and lowest at pH 4. Concentrations of TBTCl and TBTH in solutions with trees dropped rapidly to low values. Highest TBT contents in trees were found in roots and lower stems. The concentrations followed the concentrations in solution. The pH had only a small effect on the plant uptake of TBTCl, and no effect on the uptake of TBTH. No effective translocation to higher stems or leaves was found. DISCUSSION: An ion trap mechanism that accumulates the weak base TBTCl in the xylem sap of plants and leads to upward translocation could not be detected. Neither TBTCl at low or high pH, nor the neutral lipophilic chemical TBTH, were translocated effectively to leaves. The TBT+ cation sorbed strongly to plant tissue. The exact mechanism for the strong sorption of the cation is unknown, but similar effects have been observed for algae, liposomes and isolated biomembranes. CONCLUSIONS: Both the uptake of the neutral TBTH and the uptake of the neutral molecule form of TBTCl into willows was as is to be expected from theory. The cation TBT+ showed an unexpected behavior which has been observed before. No ion trap occurs, and the phytoextraction of TBT is not feasible. OUTLOOK: Planting trees, or other appropriate vegetation, could have a beneficial remediation effect by aeration of the TBT-contaminated soil or sludge. In a follow-up paper, the toxicity of TBT to willow trees will be described.     

Phytotoxicity of Cyanide to Weeping Willow Trees

Background Cyanide is found predominantly in industrial effluents generated by metallurgical operations. It is an extremely toxic compound, so that problems and catastrophic accidents have recently occurred all around the globe. The goal of this study was to determine the toxicity of cyanide to a Chinese willow species, and to determine the removal capacity. Methods The toxicity of potassium cyanide (KCN) to weeping willow trees (Salix babylonica L.) was tested. The normalized, relative transpiration of the plants was used to determine the phytotoxicity of cyanide. The cyanide removal capacity of weeping willows was also determined. Results and Discussion In hydroponic solution, no chlorosis of leaves and only a small reduction in normalized relative transpiration was observed when weeping willows were exposed to low doses of cyanide (&#61601;&#61660;&#61472;0.93 mg CN/L). Severe signs of toxicity were found for the treatment groups exposed to higher doses of cyanide (&#61601;&#61661;&#61472;9.3 mg CN/L). Weeping willows grown in sandy soils survived the entire period (216 hours) without any toxic effect when irrigated with low doses of cyanide (3.72 mg CN/L). High doses of cyanide (&#61601;&#61661;&#61472;18.6 mg CN/L) in irrigation water were fatal for the weeping willows within 216 hours. EC50 values for a 50% inhibition of the transpiration of the trees were estimated to be between 3.27 and 8.23 mg CN/L, depending on the duration of the exposure. Conclusions The results obtained for the Chinese willow species Salix babylonica were very similar to those obtained for the European species S. viminalis in earlier studies. Phytotoxic effects were only found at high doses of cyanide. A large proportion of applied cyanide was removed from the contaminated media in the presence of weeping willows. This gives rise to the conclusion that the metabolism of cyanide by weeping willows is possible. Recommendations and Outlook Cyanide elimination with trees seems to be a feasible option for cleaning soils and water contaminated with cyanide. A full-scale treatment has been installed in Denmark. For phytoremediation projects in China, weeping willow could be a suitable species. The tree can tolerate and remove cyanide, and it is a native Chinese species. Besides, the tree is of outstanding beauty and is planted as a common park tree in many parts of the world.     

Toxicity of tributyltin to willow trees

BACKGROUND: Tributyltin is an organotin compound, used as an antifouling agent in ship paint, with heavy impact on the marine environment. Contaminated dredged harbor sludge is now dumped on land. The toxicity of tributyltin (TBT) to trees has not yet been quantified. Eventually, a vegetation cover on the dumped sludge could be established for the purpose of non-food cash crop production and phytoremediation. METHODS: The phytotoxicity of tributyltin chloride (TBTCl) and tributyltin hydride (TBTH) was measured at pH 4 and at pH 7 using the willow tree transpiration test. Different pH levels of the nutrient solutions were achieved by adding ammonium salt (low pH) or nitrate (high pH) as nitrogen source. RESULTS AND DISCUSSION: At low pH (pH 4), all trees showed symptoms of poor health. Transpiration decreased at concentrations above or equal to 0.1 mg TBTCl/l and 1 mg TBTH/L. The TBT toxicity was more pronounced at pH 7. The trees survived even the highest dose of 10 mg/l TBTCl or TBTH, although their growth and transpiration was strongly reduced. CONCLUSION: In contrast to other organisms, TBTCl and TBTH were less toxic to higher plants. RECOMMENDATIONS AND OUTLOOK: The toxicity of TBT is no hindrance for establishing vegetation on TBT-contaminated sludge. Phytoremediation and cash crop production could be possible with suitable plants.     

Metabolic responses of weeping willows to selenate and selenite

Goal, Scope and Background Selenium (Se) is one of the most widely distributed elements of the earth’s crust at low concentrations. The extensive use of Se-containing chemicals due to anthropogenic activities has increased the ecological risk to environmental compartments. Plants, under unfavorable environmental conditions, often increase the formation of reactive oxygen species (ROS), and consequently plant antioxidant enzymatic systems have been proposed to be important in plant stress tolerance. The goal of this study was to find out the metabolic responses of plants to Se, to provide quantitative information whether exogenous Se has a beneficial role in plants, and to investigate the potential of vegetation management of Se for potential phytoremediation. Material and Methods Pre-rooted plants of weeping willows (Salix babylonica L.) were grown hydroponically in growth chambers and treated with Na₂SeO₄ or Na₂SeO₃ at 24.0 ± 1°C for 168 h. Five different treatment concentrations were used, ranging from 0.44 to 8.72 mg Se/L for the treatments exposed to SeO₄²⁻ and from 0.50 to 10.0 mg Se/L for the treatments exposed to SeO₃²⁻, respectively. Transpiration rates, soluble protein contents and antioxidative enzyme activities of the plants were monitored to evaluate toxicity from exogenous Se exposure. At the end of the study, total Se in the hydroponic solution was analyzed by hydride generation-atomic fluorescence spectrometry (HG-AFS). Results Both chemical forms of Se at low concentrations showed growth-promoting effects on plants. A significant decrease of transpiration rates and of soluble protein contents of plants was observed at higher Se concentrations after 168 h of exposure. Measurable change of superoxide dismutases (SOD) activity in leaves was only detected under high Se treatments. Catalase (CAT) activity was significantly affected by the Se application. Slight change of peroxidase (POD) activity was measured in all treatments, whereas significant inhibition of POD activity was detected for the plants exposed to SeO₃²⁻ of 10.0 mg Se/L. Se-induced stress appeared in all treatments, thus resulting in measurable increase of glutathione peroxidase (GSH-Px) activity of the plants. Although both chemical forms of Se were taken up by weeping willows efficiently, their uptake rates were different. Discussion Of all measured parameters, POD and CAT activities in leaves were noted the most sensitive indicator for the plants exposed to SeO₄²⁻ and SeO₃²⁻, respectively. Deleterious effects on plant physiological functions due to Se application were not observed over 168 h of exposure. This is largely due to the fact that well-established antioxidant enzymatic systems in plants and higher activities of GSH-Px largely reduced the negative effects on plants; SeO₃²⁻ caused much more severe stress to plants than SeO₄²⁻ at higher Se application rates. The uptake mechanisms between the two chemical species were quite different. Conclusions Neither visible toxic symptoms nor metabolic lesions were observed at low concentrations of Se, probably due to the effective established enzymatic systems in weeping willows. All selected parameters for toxicity determination were significantly correlated to Se application, but metabolic responses of plants to SeO₄²⁻ and SeO₃²⁻ were quite different. GSH-Px in leaves was probably the principle enzyme responsible for stress reduction from Se exposure. Due to their different chemical properties, weeping willows showed a faster uptake rate for SeO₄²⁻ than for SeO₃²⁻. Recommendations Exogenous Se has a beneficial role in plants and vegetation management of Se is a potential remediation strategy in cleaning up Se-contaminated sites. Further investigation on the biochemical mechanism of Se metabolism will provide insight to the specific interactions between Se and plants on the molecular level. Perspectives Weeping willow has a sound potential for phytoremediation of Se-contaminated sediment and groundwater because the tree is not only tolerant to Se but also uptakes chemical species from the environment.