Synthesis of polychlorinated biphenyls (PCBs) using the Suzuki-coupling

An improved synthesis of polychlorinated biphenyls (PCBs) utilizing a palladium-catalyzed cross-coupling reaction (Suzuki-coupling) is described. The coupling of (chlorinated) aryl boronic acids 1-3 with bromochlorobenzenes 4 using the standard conditions of the Suzuki-coupling gave the desired PCB congeners 5-7 in good to excellent yields. The self-coupling product of the aryl boronic acids is the major impurity of this reaction. 3,4,5-trichlorophenyl derivatives such as 10 can be synthesized by coupling of an aryl boronic acid with the corresponding bromochloroaniline 8. The approach offers the advantage of high selectivity and good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.     

Hydroxyl radical scavenging role of chloride and bicarbonate ions in the H2O2/UV process

Simultaneous effect of inorganic anions, such as chloride and bicarbonate ions, on the scavenging of hydroxyl radicals (HO*) in the H2O2/UV process is the focus of this paper. The model compound of n-chlorobutane (BuCl) was used as the probe of HO*. By changing the pH conditions (2-9) and the concentrations of NaCl (0.25-2500 mM) and NaHCO3 (25 mM), the variation of HO* concentrations and the rate of H2O2 decomposition were compared. In general, the BuCl and H2O2 follow closely the first-order reaction within the first 10 and 40 min, respectively. In the presence of chloride alone at the pH range of 2-6, the HO* concentration in the reaction mixture increases with the increase of pH, and the HO* concentration at pH = 6 is 100 times of that at pH = 2. Including bicarbonate species in the solution, the peak HO* concentration was found at a certain pH, which shifts from 4, 5, to 5-7, as the molar ratios of chloride/bicarbonate species increase from 1 to 100. In addition, without bicarbonate species HO* concentration decreases significantly with increasing chloride concentration but remained rather unchanged beyond 1250 mM. In contrast, the HO* scavenging in the presence of bicarbonate species became relatively significant only when the chloride concentration reached beyond 250 mM. Throughout all experiments of different water quality conditions, the H2O2 decomposition rate remains rather unchanged.     

Comparison among air pollutants, meteorological conditions and some chemical parameters in the transplanted lichen Usnea amblyoclada

The response of Usnea amblyoclada (Müll. Arg.) Zahlbr. to real concentrations of atmospheric pollutants measured by two automatic monitoring stations, was studied in Córdoba City, Argentina. The influence of different weather conditions on the biomonitor's response was also assessed. The concentration of chlorophyll a, chlorophyll b, hydroperoxy-conjugated dienes, and malondialdehyde were quantified in lichen thalli collected from a clean area and in transplanted thalli after 1 month of exposure in an urban area, from April to October, 1996. The dry weight/fresh weight, chlorophyll b/chlorophyll a and phaeophytin a/chlorophyll a ratios were also calculated. Data sets were evaluated by two-way analysis of variance and correlation analysis. It was observed that hydroperoxy-conjugated dienes, malondialdehyde, chlorophylls, and pigment degradation increase during winter-time, when higher levels of suspended particles, non-methane hydrocarbons, hydrogen sulfide and ozone were also measured. These findings would be connected mainly with meteorological conditions, as most pollutants did not exceed prescribed threshold levels.     

Monitoring laboratory-scale bioventing using synchronous scan fluorescence spectroscopy: analysis of the vapor phase

Bioventing is an improved method of soil remediation that is being used with increasing frequency. In this paper, we refine techniques to measure the progress of petroleum hydrocarbon decomposition by monitoring vapor phase composition with synchronous scan fluorescence spectroscopy (SSFS). Analysis of the vapor phase has advantages compared to standard extraction techniques that require extensive sample handling and clean up. For comparison, hydrocarbon contamination in the soil was measured by analysis of Soxhlet extractions with gas chromatography-mass spectrometry (GC-MS). Comparison of the GC-MS and SSFS data showed that changes in hydrocarbon composition measured in the vapor phase provide an accurate measure of decomposition reactions taking place in the soil.     

Critical remarks on the use of terrestrial moss (Hylocomium splendens and Pleurozium schreberi) for monitoring of airborne pollution

Duplicate samples of the two terrestrial moss species Hylocomium splendens and Pleurozium schreberi, which are widely used to monitor airborne heavy metal pollution, have been collected from eight catchments spread over a 1,500,000 km2 area in northern Europe. These were analysed for a total of 38 elements by inductively coupled plasma-mass spectrometry, inductively coupled plasma-atomic emission spectrometry and cold vapour-atomic absorption spectometry techniques. Results show that the moss species can be combined without interspecies calibration for regional mapping purposes. For the majority of elements the observed within-catchment variation is large--big composite samples over a large area should thus be collected when moss is to be used for monitoring purposes. For the majority of elements the input of dust governs moss chemistry. For a reliable 'contamination' signal over a sizeable area a major source is needed. Some elements show a dependence on climate/vegetation zone. In coastal areas the input of marine aerosols will alter the chemical signal obtained from moss samples.     

津巴布韦因西扎地区的菲拉布斯河床开采:小型人工采矿的可持续性发展模式

河床开采计划位于因西扎地区的菲拉布斯小镇附近,地处津巴布韦西南部的布拉瓦约东南方大约 100公里的地方 .1990年代中期,这个示范工程由已故的 Jurgen G. Voss教授和他的"津巴布韦大学采矿工程与冶金学系"的工作人员发起,资金支持则由德国技术援助集团 (GTZ)提供 .     

Rapid degradation of butachlor in wheat rhizosphere soil

The degradative characteristics of butachlor in non-rhizosphere, wheat rhizosphere, and inoculated rhizosphere soils were measured. The rate constants for the degradation of butachlor in non-rhizosphere, rhizosphere, and inoculated rhizosphere soils were measured to be 0.0385, 0.0902, 0.1091 at 1 mg/kg, 0.0348, 0.0629, 0.2355 at 10 mg/kg, and 0.0299, 0.0386, 0.0642 at 100 mg/kg, respectively. The corresponding half-lives for butachlor in the soils were calculated to be 18.0, 7.7, 6.3 days at 1 mg/kg, 19.9, 11.0, 2.9 days at 10 mg/kg, and 23.2, 18.0, 10.8 days at 100 mg/kg, respectively. The experimental results show that the degradation of butachlor can be enhanced greatly in wheat rhizosphere, and especially in the rhizosphere inoculated with the bacterial community designated HD which is capable of degrading butachlor. It could be concluded that rhizosphere soil inoculated with microorganisms-degrading target herbicides is a useful pathway to achieve rapid degradation of the herbicides in soil.     

Assessing chronic toxicity of bisphenol A to larvae of the African clawed frog (Xenopus laevis) in a flow-through exposure system

A number of currently used industrial chemicals are estrogenic, and therefore have potential to disrupt sexual differentiation in vertebrate wildlife during critical developmental windows. We assessed the effect of larval exposure to bisphenol A (BPA) on growth, development and sexual differentiation of the gonad in the African Clawed frog, Xenopus laevis. Larvae were maintained in flow-through conditions at 22 +/- 1 degrees C and exposed to BPA at mean measured concentrations of 0.83, 2.1, 9.5, 23.8, 100, and 497 microg/l, from developmental stages 43/45-66 (completion of metamorphosis). Each test concentration, plus dilution water control (DWC) and positive control (17beta-estradiol (E2), 2.7 microg/l) employed four replicate test vessels with 40 larvae per tank. Individual froglets were removed from test vessels upon reaching stage 66, and the study was terminated at 90 days. Froglets were dissected and sex was determined by inspection of gross gonadal morphology. Test concentrations of BPA had no effect on survival, growth, developmental stage distributions at exposure days 32 and 62, or mean time to completion of metamorphosis, compared to DWC. Analysis of post-metamorphic sex ratio, determined by gross gonadal morphology, indicated no significant deviations from expected (50:50) sex ratio, in DWC or any BPA test concentration. In contrast, exposure of larvae to (E2) resulted in feminisation, with sex ratio deviating significantly (31% male, replicates pooled). Exposure to BPA in the concentration range 0.83-497 microg/l in flow-through conditions had no observable effect on larval growth, development or sexual differentiation (as determined by gross gonadal morphology) in this study.     

Spatial and temporal organic and heavy metal pollution at Mai Po Marshes Nature Reserve,Hong Kong

An intensive monthly sampling of water and sediments from 12 sites over 8 months covering wet and dry seasons at Mai Po Marshes Nature Reserve was conducted during June 1997-February 1998. Major organic (C, N and P) and heavy metal pollutants (Cd, Cr, Cu, Ni, Pb, Zn) water and sediment samples were examined. The results showed that Mai Po Marshes were severely polluted by organic matter and heavy metals, and the water from Deep Bay appeared to be the source of pollution. Up to 13-55% chance that the sediments of Mai Po Marshes were classified as moderately to seriously metal contaminated materials, according to the guideline set by Hong Kong Government. Empirical models describing organic matter and heavy metal spatial and seasonal dynamics in the water and sediments were formulated, based on data analysis. During wet season (June-October), more than 58% variations of total P can be explained by ortho-P in water, while ammonia-N explained up to 90% variations of total Kjeldahl nitrogen in water. Throughout the whole sampling period (June-February), there were significant correlations (p<0.01) between total organic C in water. pH in the sediments and salinity in water appeared to be important factors determining heavy metal mobility in sediments, while potential metal release from the sediments is a concern when any oxidizing processes such as flooding or dredging are imposed on sediments.     

Summary of regulatory/policy/economic issues related to nitrogen

This is a summary of the two presentations from the session that dealt with the regulatory, policy and economic issues related to nitrogen compounds and the need to reduce their emissions. The papers were presented by Ronald Evans and Jan Willem Erisman. Information on ecological impacts of nitrogen species and atmospheric relationships are presented in other papers in this special issue. This summary provides an overview of the discussions from the above presentations.