Atomic selectivity in dissociative electron attachment to dihalobenzenes.

We investigated electron attachment to three dihalobenzene molecules, bromochlorobenzene (BCB), bromoiodobenzene (BIB) and chloroiodobenzene (CIB), by molecular beam photoelectron spectroscopy. The most prominent product of electron attachment in the anion mass spectra was the atomic fragment of the less electronegative halogen of the two, i.e., Br(-) for BCB and I(-) for BIB and CIB. Photoelectron spectroscopy and ab initio calculations suggested that the approaching electron prefers to attack the less electronegative atom, a seemingly counterintuitive finding but consistent with the mass spectrometric result. For the iodine-containing species BIB and CIB, the photoelectron spectrum consists of bands from both the molecular anion and atomic I(-), the latter of which is produced by photodissociation of the former. Molecular orbital analysis revealed that a large degree of orbital energy reordering takes place upon electron attachment. These phenomena were shown to be readily explained by simple molecular orbital theory and the electronegativity of the halogen atoms.

Spatial And Temporal Trends Of Organic Pollutants In Vegetation From Remote And Rural Areas.

Persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) used in agricultural, industrial, and domestic applications are widely distributed and bioaccumulate in food webs, causing adverse effects to the biosphere. A review of published data for 1977-2015 for a wide range of vegetation around the globe indicates an extensive load of pollutants in vegetation. On a global perspective, the accumulation of POPs and PAHs in vegetation depends on the industrialization history across continents and distance to emission sources, beyond organism type and climatic variables. International regulations initially reduced the concentrations of POPs in vegetation in rural areas, but concentrations of HCB, HCHs, and DDTs at remote sites did not decrease or even increased over time, pointing to a remobilization of POPs from source areas to remote sites. The concentrations of compounds currently in use, PBDEs and PAHs, are still increasing in vegetation. Differential congener specific accumulation is mostly determined by continent-in accordance to the different regulations of HCHs, PCBs and PBDEs in different countries-and by plant type (PAHs). These results support a concerning general accumulation of toxic pollutants in most ecosystems of the globe that for some compounds is still far from being mitigated in the near future.

Metabolism and toxicity of hydrochlorofluorocarbons: current knowledge and needs for the future.

Hydrochlorofluorocarbons (HCFCs) are being developed as replacements for chlorofluorocarbons (CFCs) that deplete stratospheric ozone. The depletion of stratospheric ozone may increase the intensity of ultraviolet radiation at the earth's surface, which may be associated with global, adverse human health effects. The greater tropospheric lability of HCFCs, which is due to the presence of C-H bonds, reduces HCFC migration to the stratosphere; HCFCs should, therefore, cause less depletion of stratospheric ozone than CFCs. HCFCs under development include HCFC-22 (chlorodifluoromethane), HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HCFC-132b (1,2-dichloro-1,1-difluoroethane), HCFC-134a (1,1,1,2-tetrafluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane, and HCFC-142b (1-chloro-1,1-difluoroethane). With the exception of HCFC-22, which is already in use, the metabolism and toxicity of HCFCs have not been studied in detail. By analogy to chlorinated ethanes, predictions can be made about the possible metabolism of HCFCs, but there are insufficient data available to predict rates of metabolism. Although most HCFCs appear to show low acute toxicity, some HCFCs are mutagenic in the Ames test. Hence, future research on HCFCs should include studies on the in vivo and in vitro metabolism of HCFCs as well as on their toxicity in in vivo and in vitro systems.