Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds

The replacement of oxygen within a chloroformate ester (ROCOCl) by sulfur can lead to a chlorothioformate (RSCOCl), a chlorothionoformate (ROCSCl), or a chlorodithioformate (RSCSCl). Phenyl chloroformate (PhOCOCl) reacts over the full range of solvents usually included in Grunwald-Winstein equation studies of solvolysis by an addition-elimination (A-E) pathway. At the other extreme, phenyl chlorodithioformate (PhSCSCl) reacts across the range by an ionization pathway. The phenyl chlorothioformate (PhSCOCl) and phenyl chlorothionoformate (PhOCSCl) react at remarkably similar rates in a given solvent and there is a dichotomy of behavior with the A-E pathway favored in solvents such as ethanol-water and the ionization mechanism favored in aqueous solvents rich in fluoroalcohol. Alkyl esters behave similarly but with increased tendency to ionization as the alkyl group goes from 1° to 2° to 3°. N,N-Disubstituted carbamoyl halides favor the ionization pathway as do also the considerably faster reacting thiocarbamoyl chlorides. The tendency towards ionization increases as, within the three contributing structures of the resonance hybrid for the formed cation, the atoms carrying positive charge (other than the central carbon) change from oxygen to sulfur to nitrogen, consistent with the relative stabilities of species with positive charge on these atoms.     

Observations on the changes in nitrate concentrations along streams in seven upland moorland catchments in Northeast Scotland

River water has been sampled under baseflow conditions in both summer and winter at c. 250-m intervals along the length of each of seven rivers in northeast Scotland, and the nitrate contents have been determined. The resultant data have been examined in the context of the nitrogen saturation hypothesis. Capacity of the catchment soils to retain nitrate was generally minimal in winter. Although biological uptake of nitrate was evident in summer, in the upper part of each catchment substantial nitrate leaching still occurred. The phenomenon was most marked in water draining from hill peats, except where these were conspicuously waterlogged. The results are discussed in the context of possible nitrogen saturation effects on upper catchment slopes.     

Contribution of trace metals from atmospheric deposition to stormwater runoff in a small impervious urban catchment

The contribution of atmospheric deposition to emissions of trace metals in stormwater runoff was investigated by quantifying wet and dry deposition fluxes and stormwater discharges within a small, highly impervious urban catchment in Los Angeles. At the beginning of the dry season in spring 2003, dry deposition measurements of chromium, copper, lead, nickel, and zinc were made monthly for 1 year. Stormwater runoff and wet deposition samples also were collected, and loading estimates of total annual deposition (wet+dry) were compared with annual stormwater loads. Wet deposition contributed 1-10% of the total deposition inside the catchment, indicating the dominance of dry deposition in semi-arid regions such as Los Angeles. Based on the ratio of total deposition to stormwater, atmospheric deposition potentially accounted for as much as 57-100% of the total trace metal loads in stormwater within the study area. Despite potential bias attributable to processes that were not quantified in this study (e.g., resuspension out of the catchment or sequestration within the catchment), these results demonstrate atmospheric deposition represents an important source of trace metals in stormwater to waterbodies near urban centers.     

伊拉克某油田注水站设计方案优化

伊拉克鲁迈拉油田CP00注水站设计规模为1 000 m3/h,注水压力为20 MPa。该注水站的设计方案及优化考虑了安全、环保、节能、节省投资等因素。重点介绍了CP00内向注水泵喂水的方案选择及设计优化,以及整体工艺流程的设计。