Photochemical transformations of tetrabromobisphenol A and related phenols in water

A method was developed for studies of the phototransformation at UV irradiation of aqueous solutions of tetrabromobisphenol A (TBBPA), tribromobisphenol A (TriBBPA), tetrachlorobisphenol A (TCBPA), 2,4-dichlorophenol at various pHs as well as 2-chlorophenol, 2-bromophenol, 3,4-dichlorophenol and bisphenol A at pH 11. The absorbance spectra of the compounds and the emission spectra of the light-source were determined and used to calculate disappearance quantum yields of the photochemical reactions that were taking place. No major differences between the disappearance quantum yields of TBBPA and TCBPA were observed at pH 10, while the disappearance quantum yield of TriBBPA was approximately two times higher. The rate of decomposition of TBBPA was six times higher at pH 8 than at pH 6. Identification of the degradation products of TBBPA and TriBBPA, by GC-MS analysis and by comparison to synthesised reference compounds, indicated that TBBPA and TriBBPA decompose via different mechanisms. Three isopropylphenol derivatives; 4-isopropyl-2,6-dibromophenol, 4-isopropylene-2,6-dibromophenol and 4-(2-hydroxyisopropyl)-2,6-dibromophenol, were identified as major degradation products of TBBPA while the major degradation product of TriBBPA was tentatively identified as 2-(2,4-cyclopentadienyl)-2-(3,5-dibromo-4-hydroxyphenyl)propane.     

生活在土地上的人们:20世纪全球人口和耕地的变化

本研究评述了20世纪全球耕地分布发生的主要变化.在20世纪,耕地基数大幅度减小,人均耕地从1900年的0.75hm2/人下降到1990年的0.35 hm2/人.     

Fate of 1,2,3,4,6,7,8-heptachlorodibenzofuran and pentachlorophenol during laboratory-scale anaerobic mesophilic sewage sludge digestion

The possibility of the formation of PCDDs and dechlorination of PCDFs during the anaerobic digestion of sewage sludge in laboratory scale digesters was investigated. Digesters were spiked with 1,2,3,4,6,7,8-HpCDF-13C(6) (240 ng/g organic matter (OM)) and pentachlorophenol (PeCP)-13C(6) (24 microg/g OM) and the output sludge monitored for 60 days. No dechlorination or formation of the labelled or native PCDD/Fs was observed. The detectable 1,2,3,4,6,7,8-HpCDF-13C(6) dechlorination yield was 0.0008-1% depending on homologue group and the detectable formation of OCDD yield was 0.00042% PeCP-13C(6). Preferential respiration of other, more bioavailable, substrates is suggested as the most plausible explanation for the lack of dechlorination. Formation of PCDDs from PeCP has been observed in aerobic environments but this study provides further evidence that it is not a precursor for formation during anaerobic digestion.     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

The Future Chemical Evolution of the Aral Sea from 2000 to the Years 2050

The future of Southern Aral Sea water in Kazakhstan, and of the sequence of mineral evaporitic sediments precipitated since the beginning of the present regression from gypsum to bloed-ite (astrakhanite) was studied. A comparison is made with previous regressive deposits discovered earlier in cores by I.V. Rubanov. Absence of mirabilite deposits in sediments of the eastern basin is attributed to deflation processes during the XIVth century AD.     

MODELING THE HYDROLOGIC IMPACTS OF FOREST HARVESTING ON FLORIDA FLATWOODS1

ABSTRACT: The great temporal and spatial variability of pine flat-woods hydrology suggests traditional short-term field methods may not be effective in evaluating the hydrologic effects of forest management. The FLATWOODS model was developed, calibrated and validated specifically for the cypress wetland-pine upland landscape. The model was applied to two typical flatwoods sites in north central Florida. Three harvesting treatments (Wetland Harvesting, Wetland + Upland Harvesting, and Control) under three typical climatic conditions (dry, wet, and normal precipitation years) were simulated to study the potential first-year effects of common forest harvesting activities on flatwoods. Long-term (15 years) simulation was conducted to evaluate the hydrologic impacts at different stages of stand rotation. This simulation study concludes that forest harvesting has substantial effects on hydrology during dry periods and clear cutting of both wetlands and uplands has greater influence on the water regimes than partial harvesting. Compared to hilly regions, forest harvesting in the Florida coastal plains has less impact on water yield.     

The Relationship between the Income Elasticities of Demand and Willingness to Pay

The relationship between income and willingness to pay for collectively provided public/environmental goods is investigated. We show that while the income elasticity of willingness to pay and the ordinary income elasticity of demand are related, knowledge of one is insufficient to determine the magnitude or even the sign of the other. The income elasticity of willingness to pay is influenced by additional factors which are generally unobservable. Examples are provided to illustrate the degree to which the two income elasticities may diverge. Our results indicate that even when goods are demand luxuries they may or may not have income elasticities of willingness to pay which are greater than one.