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 (0.93 mg CN/L). Severe signs of toxicity were found for the treatment groups exposed to higher doses of cyanide (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 (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.     

Quantification of bacterial lipopolysaccharides (endotoxin) by GC-MS determination of 3-hydroxy fatty acids

A GC-MS method for the quantification of bacterial lipopolysaccharides (LPS, endotoxin) is presented. After hydrolytic cleavage of 3-hydroxy fatty acids (3-OH FAs) from the lipid A region of LPS, derivatisation of both the hydroxyl and the carboxyl group was performed in one step with a mixture of methyl-bis(trifluoracetamide)(MBTFA) and N-methyl-N-(tert-butyldimethylsilyl)trifluoracetamide (MTBSTFA). Using GC-MS in the EI mode with selected ion monitoring (SIM) for analysis, baseline separation of 3-OH FAs (and of possibly interfering 2-OH FAs) was achieved. The sensitivity of the method (LOD 7-50 pg/injection for the different 3-OH FAs investigated) allows for the efficient quantification of LPS in occupational and environmental samples. Degradation of 3-OH FAs as well as of their derivatives during sample preparation and GC-MS separation as a possible source of errors in analytical methods based on 3-OH FA determination is reported for the first time. Thermal elimination of water from the underivatised 3-OH FAs and of trifluoroacetic acid from the derivatives was identified as the cause of degradation. The resulting alpha,beta-unsaturated compounds showing the same mass spectra as the 3-OH FA derivatives were detected as more or less prominent satellite peaks. By using alkaline instead of acidic hydrolysis and cool on-column instead of split/splitless injection, elimination was reduced to an acceptable level.     

Plant uptake and transport models for neutral and ionic chemicals

BACKGROUND: Models for predicting uptake and transport of chemicals in plants are applied in pesticide design, risk assessment, and environmental biotechnology. OBJECTIVE: This review considers the theoretical basics of the most popular models, and discusses what they have in common. The line is drawn between models for neutral compounds, and models for weak and strong electrolytes. MAIN FEATURES: Neutral Compounds. Neutral compounds undergo only very few processes inside plants (lipophilic interactions, metabolism), in contrast to weak electrolytes. The models developed for neutral compounds are widely applied in the risk assessment of environmental contaminants, but are not of much use for weak electrolytes, such as pesticides. Weak electrolytes. A very important process for weak electrolytes is the 'ion trap', which traps chemicals that dissociate inside plant cells. This is considered in the popular models of Kleier, Satchivi and Briggs. Other relevant processes for electrolytes are electrophilic interactions, speciation and complex formation. None of the currently used models considers these processes. CONCLUSIONS: The accuracy of models for neutral compounds is satisfactory, but the prediction of electrolyte behavior inside plants is still quite difficult due to gaps in knowledge.     

Diffusive boundary layer development above a sediment-water interface.

A model to estimate the entry length to a fully developed diffusive boundary layer above a sediment bed, such as those found in lakes, reservoirs, rivers, and estuaries, is presented. The model is used to determine how the length of a sediment bed in mass-transfer experiments influences the measured vertical diffusive flux at the sediment-water interface. A nondimensional local mass flux is introduced in the form of a Sherwood number (Sh) and expressed as a function of both the distance from the leading edge of the sediment bed (x) and the Schmidt number (Sc). Similarly, a mean Sherwood number (Sh(ave)) for a sediment bed of length (L) is introduced. The diffusive boundary layer grows with distance, and its thickness depends on the Schmidt number (i.e., the diffusive boundary layer gets thicker and develops more quickly as the Schmidt number decreases). For Schmidt numbers greater than or equal to 100, the diffusive boundary layer begins to develop slowly but is fully developed when the nondimensional horizontal coordinate (x+) is approximately 1000. The Sherwood number is largest (i.e., infinity) near the leading edge of the sediment bed (i.e., at x = 0), decreases as the distance from the bed increases, and, finally, approaches a constant value for a fully developed diffusive boundary layer (Sh(infinity)). In this paper, the distance to a fully developed diffusive boundary layer (L99) and the required length of a sediment bed are related explicitly to Sc, sheer velocity (U*), and the relative errors of local or average Sherwood numbers (Sh or Sh(ave), respectively) against the Sherwood number for the fully developed diffusive boundary layer (Sh(infinity)). The lengths L99 and L decrease as the Schmidt number increases and become independent of the Schmidt number when Sc is greater than 1000. A longer sediment bed is needed when the shear velocity or the Schmidt number is small (e.g., L99 and L approximately 1.0 m and 8.0 m, respectively, for Sc = 500, U* = 0.1 cm/s, and a 3% acceptable error). Experimental studies may not be able to meet these requirements and an adjustment of measured mass-transfer rates at a sediment-water interface may be necessary. The magnitude of that adjustment is up to 50%. Its dependence on the Schmidt number, shear velocity, and bed length is given in this paper.     

Oxidative degradation of 2,4-xylidine by photosensitization with 2,4,6-triphenylpyrylium: homogeneous and heterogeneous catalysis

The possibility of using zeolites containing the 2,4,6-triphenylpyrylium cation as photocatalysts for the degradation of pollutants has been tested on aqueous xylidine (2,4-dimethylaniline) solutions as models for contaminated wastewaters. The influence of the photocatalyst and substrate concentrations on xylidine oxidation has been investigated in homogeneous solution, by performing a series of experiments chosen according to the experimental design methodology (Doehlert uniform array). The empirical models and the corresponding response surfaces obtained from data analysis have been used for simulating and predicting degradation efficiency. The results have shown that conversion increases with increasing amounts of photocatalyst and decreasing concentration of the model pollutant. The fluorescence of 2,4,6-triphenylpyrylium was quenched by xylidine with a rate constant k(q) of 3.1x10(9)M(-1)s(-1). This result suggests a direct electron transfer between the excited pyrylium salt and xylidine. Because of the limited stability of the photocatalyst in homogeneous media, a pyrylium containing Y-zeolite has been tested for the photocatalytic oxidation of xylidine under heterogeneous conditions. The results suggest that the supported catalyst has a much improved stability and that xylidine oxidation rates remain nearly constant during the whole reaction time. An additional advantage of the pyrylium containing zeolite photocatalyst is that it can be recycled and used for further experiments.     

Neue horizonte für die chemie

Zusammenfassung  Der Begriff ‘nachhaltige Entwicklung’ wird auf seine Bedeutung und Anwendung in der Chemie am Beispiel der organischen Synthesechemie exemplarisch diskutiert. Ein Rückblick auf die Geschichte der Chemie macht die Notwendigkeit einer Weiterentwicklung im Rahmen der Konzepte der Nachhaltigkeit deutlich: nach dem Zeitalter des Steinkohlenteers und des Erd?ls in den beiden vorigen Jahrhunderten steht in diesem Jahrhundert die Suche nach neuen Rohstoffen und die Verminderung des globalen ?kotoxikologischen Gefahrenpotenzials an. Kritische Reflexion ist notwendig, damit der Begriff Nachhaltigkeit nicht zum Schlagwort verkommt. Deswegen muss auf der Ebene des Forschungshandelns ebenso angesetzt werden, wie auf derjenigen ihrer Reflexion hinsichtlich der Einordnung chemisch-wissenschaftlicher Forschungsarbeit in die gesellschaftlichen und politischen Zusammenh?nge. Neben neuer Synthesewege bedarf es der Formulierung von Kriterien für Entscheidungsfindungen.      

Efficient adsorption of the mycotoxins zearalenone and T-2 toxin on a modified yeast glucan

1,3-Beta-D-glucan derived from baker's yeast was chemically modified in two steps yielding crosslinked carboxymethyl glucan as the sodium salt (2). After cation exchange with hexadecyltrimethylammonium chloride, a hydrophobic adsorbent (3) was obtained which showed an excellent binding of the estrogenic mycotoxin zearalenone with a maximum adsorption of up to 183 mg/g. Compound 3 additionally showed a relatively high adsorption capacity for the trichothecene T-2 toxin of at least 10 mg/g. Starting from 2, various derivatives were prepared by cation exchange using quaternary ammonium salts bearing substituents besides methyl from four to 18 carbon atoms. The adsorption of T-2 toxin on these derivatives were compared with compound 3 leading to the conclusion that 3 is the best adsorbent of all investigated tetraalkylammonium-modified derivatives of 2.     

2003, das Jahr der Chemie

Ohne Zusammenfassung     

Removal of cyanide by woody plants

Hydrogen cyanide is a high volume production chemical that causes severe environmental problems. The toxicity of potassium cyanide (KCN) to basket willow trees (Salix viminalis) was tested. In aqueous solution, 2 mg CN l(-1) as KCN depressed the transpiration after 72 h about 50%. Trees exposed to 0.4 mg CN l(-1) in aqueous solution showed initially a depression of transpiration, but recovered. Doses of 8 and 20 mg CN l(-1) in aqueous solution were quickly mortal to the trees. At the end of the test, almost all cyanide had disappeared from the solutions. Levels of cyanide in plants were related to the toxicity, with no elevated levels of cyanide in plants exposed to 0.4 mg CN l(-1). Willows grown in sand survived 423.5 h irrigation with 20 mg CN l(-1). Willows grown in sand irrigated with 50 mg CN l(-1) died within a few days. The roots of the surviving willows were able to consume about 10 mg CN kg fresh weight(-1)h(-1). Vascular plants possess the enzymes beta-cyanoalanine synthase and beta-cyanoalanine hydrolase, which convert free cyanide to the amino acid asparagine. The in vivo capacity of woody plants (willow, poplar, elder, rose, birch) to remove cyanide was evaluated. Tests were performed with detached leaves and roots in KCN solutions of different concentrations. The highest removal capacity was obtained for basket willow hybrids (Salix viminalis x schwerinii). The Michaelis-Menten kinetics was determined. Realistic values of the half-saturation constant, K(M), were between 0.6 and 1.7 mg CN l(-1); the maximum metabolic capacity, v(max), was around 9.3 mg CN kg fresh weight(-1)h(-1). The removal of cyanide by plants might be useful in phytoremediation and treatment of wastewater from gold mining.