The influence of radical architecture on cadmium bioaccumulation in the black mangrove, Avicennia germinans L

Two groups of Avicennia germinans plants with differences in the radical architecture were exposed under hydroponic conditions to 95ppm of cadmium (Cd) for a period of 24h. Later, Cd concentration in roots, stems and leaves was determined by graphite furnace atomic absorption spectrophotometry. Our results showed that, for both groups of plants, the roots accumulated higher concentration of Cd as compared to stems and leaves, though, the plants of group B displayed enhanced radical architecture, better growth performance, and lower Cd concentration as compared to plants of group A. In contrast, low values of leaves/roots Cd transportation index, and bioaccumulation factor were found in plants of group B. These results suggest that the higher radical architecture developed in plants of group B might better adjust the uptake of Cd as a result of an integrated network of multiple response processes for instances, production of organic acids, antioxidative replay, cell-wall lignification and/or suberization. Further studies will be focused in understanding the role of the radical system in mangrove plants with the rhizosphere activation and root adsorption to soil Cd under natural conditions.     

Comparison of organochlorine compound concentrations in colostrum and mature milk

Human breast milk represents the best choice for the nutrition of infants. It is often used for monitoring human exposures to environmental chemicals. Uniquely suited to meet human biological needs, breast milk composition, especially fat content, changes significantly with time from delivery. With the aim to compare the concentration of organochlorine compounds (OCs) in colostrum versus mature milk, we obtained samples of fourth-fifth day postpartum milk (colostrum) and day-14 postpartum milk (mature milk) from 12 women enrolled in the project "Early Childhood Development and PCB Exposure in Slovakia". The concentrations of selected organochlorine pesticides and congeners of polychlorinated biphenyls (PCBs) were measured using gas chromatography with electron capture detection and reported on lipid adjusted basis. No significant differences were found between organochlorine levels in colostrum and those in mature milk samples. A very close correlation was found between the concentrations of organochlorine compounds in colostrum and mature milk (Spearman correlation coefficient r=0.94-0.98 for PCBs, and r=0.85-0.99 for organochlorine pesticides, p<0.001 for all compounds). The present study concludes that the use of colostrum samples provides a close estimate of the child's exposure to OCs in the early neonatal period and demonstrates that, despite the lower fat content, colostrum specimens are adequate to conduct OC analyses.     

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol in supercritical water

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol (o-CP) in supercritical water (SCW) were studied in this paper under the conditions of 450 degrees C and 25 MPa. Experimental results indicated that the dechlorination of o-CP can be accelerated significantly by all alkalis investigated. The dechlorination of o-CP proceeded mainly via two pathways: hydrodechlorination and hydrolysis. Both of the two pathways can be promoted by alkalis, and the dechlorination of o-CP can be accelerated by both the cations and hydroxide ion dissociated from alkalis. The overall dechlorination of o-CP can be accelerated by cations via promoting the hydrodechlorination pathway, while, hydroxide ion via promoting the hydrolysis pathway. In addition, the hydrodechlorination can be accelerated faster by sodium alkalis than that by potassium ones, while, the hydrolysis can be promoted faster by potassium alkalis. This difference may be caused by the different charge density between potassium ion and sodium ion, and the different solubility and dissociation constant between potassium alkalis and sodium alkalis in SCW. Dechlorination of o-CP with addition of alkalis prior to supercritical water oxidation (SCWO) process not only can avoid the reactor corrosion caused by the generated hydrochloric acid in direct SCWO of o-CP, but also can reduce the formation of toxic chlorinated byproducts compared with direct SCWO process or SCWO of o-CP with addition of alkali.     

Oxidation of trichloroethene over metal oxide catalysts: kinetic studies and correlation with adsorption properties

The performance of bulk chromium oxide is compared with that of a Mn commercial catalyst for the deep oxidation of trichloroethene (1000-2500ppmv, 55h(-1) space velocity) in air, in dry and wet (20000ppm of H(2)O) conditions, in terms of activity, selectivity and stability. Chromium oxide was found to be more active (on a catalyst weight basis), however its activity decreases continuously with time on stream. The presence of water increases its stability, the Mn catalyst showing the opposite behaviour. The effect of water on the Cr catalyst can be explained according to the Deacon equilibrium, as the presence of water tends to decrease the Cl(2) concentration, assumed to be responsible of the catalyst deactivation. Regarding to the selectivity, the Mn catalyst yields C(2)Cl(4), CCl(4) and CHCl(3) as organochlorinated by-products, whereas chromium oxide produces only trace amounts of CCl(4). Simple power-law kinetics expressions (first-order for Mn and zero-order for Cr) provide fairly good fits for the evolution of the conversion with the temperature. Furthermore, the kinetic behaviour of chromium oxide can be represented with a Langmuir-Hinshelwood model taking into account the chlorine inhibitory effect.     

HPLC-MSn and GC-MS methods to study sunlight and UV-lamp degradations of 1-amino-5-naphthalene sulfonate

HPLC-DAD, HPLC-MS/MS, GC-MS and spectrophotometric methods are employed to investigate the degradation process of sodium 1-amino-5-naphthalene sulfonate (1A5NS) aqueous solutions, when exposed to sunlight and UV-lamp (254 nm) irradiations. Experimental results show that both sunlight and 254 nm UV-lamp irradiations destroy the chemical and give rise to major degradation products, characterised by the same m/z ratios. Degradation times are lower for sunlight irradiation, for which a t(1/2) value of 137.4 min has been evaluated, in comparison with the value of t(1/2) of 26.8 min, observed for UV-lamp irradiation. The degradation pathway and the structures of the degradation products are proposed.     

QSARs for the toxicity of polychlorinated dibenzofurans through DFT-calculated descriptors of polarizabilities, hyperpolarizabilities and hyper-order electric moments

DFT-B3LYP method with 6-31G(**) basis set was employed to fully optimize the electronic structures of 135 polychlorinated dibenzofurans and parent compound, namely dibenzofuran. It was demonstrated that polarizability anisotropy and mean polarizability could change sensitively and systematically with chlorine number and substitution pattern. And new quantitative structure-activity relationships (QSARs) focused on the binding affinities of aryl hydrocarbon receptor (AhR), aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD) induction potencies of PCDFs were developed. It was concluded that polarizability anisotropy in conjunction with hyperpolarizabilties and hyper-order electric moments, e.g. octupole moments could well interpret the variation of toxicity of different congeners and dispersion interaction should be the leading form among various interactions. Although the terms of hyperpolarizabilities and hyper-order electric moments were not the same significant ones as polarizability anisotropy, the long-range interactions characterized by them should not be ignored in explaining the toxicity.     

The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999

Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.     

Evaluation of nitrification inhibitor 3,4-dimethyl pyrazole phosphate on nitrogen leaching in undisturbed soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors (NI) as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, the efficacy of the new NI, 3,4-dimethyl pyrazole phosphate (DMPP), was tested under simulated high-risk leaching situations in two types of undisturbed soil columns. The results showed that the accumulative leaching losses of soil nitrate under treatment of urea with 1.0% DMPP, from columns of silt loam soil and heavy clay soil, were 66.8% and 69.5% lower than those soil columns tested with regular urea application within the 60 days observation, respectively. However, the losses of ammonium leaching were reversely increased 9.7% and 6.7% under the former treatment than the latter one. Application of regular urea with 1.0% DMPP addition can reduce about 59.3%-63.1% of total losses of inorganic nitrogen via leaching. The application of DMPP to urea had stimulated the inhibition effects of DMPP on the ammonium nitrification process in the soil up to 60 days. It is proposed that the DMPP could be used as an effective NI to control inorganic N leaching losses, minimizing the risk of nitrate pollution in shallow groundwater.     

Atrazine sorption and fate in a Ultisol from humid tropical Brazil

This study combined laboratory based microcosm systems as well as field experiments to evaluate the mobility of atrazine on a Ultisol under humid tropical conditions in Brazil. Results from sorption experiments fit to the Freundlich isotherm model [K(f) 0.99 mg kg(-1)/(mg l(-1))(1/n)], and indicate a low sorption capacity for atrazine in this soil and consequently large potential for movement by leaching and runoff. Microcosm systems using (14)C-atrazine to trace the fate of the applied herbicide, showed that 0.33% of the atrazine was volatilized, 0.25% mineralized and 6.89% was recorded in the leachate. After 60 d in the microcosms, 75% of the (14)C remained in the upper 5 cm soil layer indicating atrazine or its metabolites remained close to the soil surface. In field experiments, after 60 d, only 5% of the atrazine applied was recovered in the upper soil layers. In the field experiments atrazine was detected at a depth of 50 cm indicating leaching. Simulating tropical rain in field experiments resulted in 2.1% loss of atrazine in runoff of which 0.5% was adsorbed onto transported soil particles and 1.6% was in solution. Atrazine runoff was greatest two days after herbicide application and decreased 10 fold after 15 d. The use of atrazine on Ultisols, in the humid tropics, constitutes a threat to water quality, causing surface water and ground water pollution.     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.