Theoretical study on the chemical properties of polybrominated diphenyl ethers

Density functional theory calculations at the B3LYP/6-31+G(d) and B3LYP/aug-cc-pVDZ levels were performed to obtain the equilibrium structures, thermodynamic properties, and electron affinities (EA) of 14 polybrominated diphenyl ether (PBDE) congeners in the gas phase. All congeners except for those of symmetric BDE are found to have two or more conformational isomers. The optimized geometries of the most stable conformational isomers are in agreement with recently published X-ray crystallographic data. The thermodynamic properties of the congeners with a given number of bromine substitutions are strongly dependent on the substitution pattern, whereas the EA values also depend on the number of bromine substitutions. The vertical electron affinities (EA(Ver)) calculated for the selected BDE congeners at the B3LYP/aug-cc-pVDZ level are all positive except for di-BDEs, and are correlated with the initial reductive debromination rate constants obtained recently [Keum, Y.-S., Li, Q.X., 2005. Reductive debromination of polybrominated diphenyl ethers by zerovalent iron. Environ. Sci. Technol. 39, 2280]. All adiabatic electron affinities (EA(Ada)) are positive, and suggest that the BDE congeners act as electron acceptors when reacting with receptors in living cells. The calculated EA(Ada) values differ considerably from those of EA(Ver) because of the large geometrical relaxation from the neutral to the anionic BDE congeners, highlighted by the lengthening of a C-Br bond. The elongated C-Br bond, which occurs at the alpha position, is directly involved in the debromination of n-bromodiphenyl to (n-1)-bromodiphenyl ethers in the reductive debromination experiments.     

Pedological characteristics of Mn mine tailings and metal accumulation by native plants

In southern China revegetation and ecological restoration of many abandoned Mn tailings has become a major concern. To determine the major constraints for plant establishment and evaluate the feasibility of remediation, a comparative study was conducted on Mn tailings and rhizosphere soils at the boundary of the tailings pond. Both tailings and rhizosphere soils had neutral to slightly alkaline pH and normal electrical conductivity. They were both enriched with organic matter (6.8-9.2%), total N (1.77-5.94 g kg(-1)), available P (41.78-73.83 mg kg(-1)) and K (146.7-906.9 mg kg(-1)), suggesting the tailings were a nutrient rich substrate for revegetation. Mn tailings were clay textured, while rhizosphere soils were silty loam or clay loam. The compaction and anoxic nature of Mn tailings were considered to be the major constraints for plant establishment. Total Mn (31903 mg kg(-1)), Cd (119 mg kg(-1)), Cu (126 mg kg(-1)) and Zn (2490 mg kg(-1)) in tailings were all at phytotoxic levels, but did not differ significantly from those in rhizosphere soils. In both tailings and rhizosphere soils, percentages of water- and DTPA-extractable metals were less than 1% and 2% of the total metal pools, respectively. Sequential extraction revealed that the majority of Mn, Cu and Zn were associated with the residual fraction, while the majority of Cd occurred as Fe-Mn oxides. The natural succession of plants around Mn tailings formed a distinctive metal-tolerant plant community, mainly comprising nine species such as Cynodon dactylon and Humulus scandens and so on. All species studied could be good candidates for revegetation of Mn tailings.     

Characterization of subsoil heterogeneity, estimation of grain size distribution and hydraulic conductivity at the Krauthausen test site using Cone Penetration Test

A Cone Penetration Test (CPT) survey with a high spatial resolution was performed in order to investigate the stratigraphy as well as the spatial variability of various soil properties of the Krauthausen test site. Analyses of the CPT measurements showed the subsurface to be dominated by a planar layered structure. Variogram analysis of the various CPT parameters disclosed that within each layer the soil properties have an anisotropic spatial correlation structure. A correlation analysis of the measured CPT data and co-located grain size distributions from soil samples was performed. Since the correlation coefficients were greater equal to 0.7, a reliable empirical relationship between the data sets could be developed. Based on this empirical relationship grain size distributions were estimated at CPT locations. The statistical processing of estimated and measured grain size distributions with respect to their spatial correlation structure disclosed good agreement between the data sets. The estimated grain size distributions from CPT data were used to estimate the hydraulic conductivity in the aquifer. The results provide detailed information of the spatial heterogeneity of the hydraulic conductivity at Krauthausen test site. The validation of these results, using a prior investigation of hydraulic conductivity statistics, suggests the CPT a fast and inexpensive tool for the estimation of three dimensional hydraulic conductivity fields with sufficient accuracy.     

The ozone productivity of n-propyl bromide: Part 2--An exception to the Maximum Incremental Reactivity Scale

In an earlier paper the ozone-forming potential of n-propyl bromide (NPB) was studied with a new methodology designed to address issues associated with a marginal smog-forming compound. However, the U.S. Environmental Protection Agency (EPA) subsequently revised its policy and now recommends using the Maximum Incremental Reactivity (MIR) scale to rank the ozone-forming potential of all volatile organic compounds (VOCs), including those of marginal ozone productivity. Nevertheless, EPA contemplated exceptions to the box-model-derived MIR scale by allowing use of photochemical grid-model simulations for case specific reactivity assessments. The California Air Resources Board (CARB) also uses the MIR scale and CARB has a Reactivity Scientific Advisory Committee that can consider exceptions to the MIR scale. In this study, grid-model simulations that were recommended by EPA are used to evaluate the incremental ozone impacts of NPB using an update to the chemical mechanism developed in an earlier paper. New methods of analysis of the grid-model output are further developed here to quantify the relative reactivities between NPB and ethane over a wide range of conditions. The new grid-model-based analyses show that NPB is significantly different and generally less in ozone-forming potential (i.e., reactivity) than predicted by the box-model-based MIR scale relative to ethane, EPA's "bright-line" test for non-VOC status. Although NPB has low reactivity compared to typical VOCs on any scale, the new grid-model analyses developed here show that NPB is far less reactive (and even has negative reactivity) compared to the reactivity predicted by the MIR scale.     

Effects of suburban land use on phosphorus fractions and speciation in the Upper Peruque Creek, Eastern Missouri

This field study was conducted to explore the spatial and seasonal changes in total phosphorus and fraction distribution in relation to land uses. Water samples were collected biweekly at four sampling locations, which represented different potential phosphorus sources along the Upper Peruque Creek in Eastern Missouri. Total phosphorus concentrations of > 0.8 mg/L appeared sporadically at site 2, downstream of a small community, with an average of 0.82 +/- 0.14 mg/L in fall. Particulate phosphorus accounted for approximately 80% of total phosphorus at all sampling sites, except for site 2, where approximately 50 to 75% of dissolved phosphorus was often observed. Approximately 71 and 85% of total phosphorus in the sediment was in the form of iron (III) phosphate at the headwaters and downstream sites, respectively; 29 and 15% was in the form of phytic acid at the two sites. Land uses affect the total phosphorus concentration and alternate phosphorus fraction and speciation in the creek.     

Relationship between atmospheric pollution processes and synoptic pressure patterns in northern China

The air pollution index (API) sequences in 10 cities in northern China and the synoptic pressure patterns during autumn and winter from 2002 to 2006 were analyzed with diagnostic and statistical methods. The results showed that the air qualities in northern China had a prominent correlation with the pressure systems. It revealed that (a) the increasing phase of API was associated with high pressure and the successive low pressure, (b) the preceding part of front (i.e. the retral part of low pressure) was associated with the maximum of API values during a cycle of air pollution process, (c) the pressure systems with high gradient led to the decrease of API, and (d) the synoptic pressure patterns and their evolvements were the main causes of regional air pollution processes. These relations can be used to analyze the variation characteristics and mechanism of regional atmosphere pollution process, and provide important basis for the qualitative prediction, control, and management of regional air pollution problems.     

Effects of a zeolite-selective catalytic reduction system on comprehensive emissions from a heavy-duty diesel engine

The effects of a zeolite urea-selective catalytic reduction (SCR) aftertreatment system on a comprehensive spectrum of chemical species from diesel engine emissions were investigated in this study. Representative samples were collected with a newly developed source dilution sampling system after an aging process designed to simulate atmospheric dilution and cooling conditions. Samples were analyzed with established procedures and compared between the measurements taken from a baseline heavy-duty diesel engine and also from the same engine equipped with the exhaust aftertreatment system. The results have shown significant reductions for nitrogen oxides (NOx), carbon monoxide, total hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and organic carbon (OC) emissions. Additionally, less significant yet notable reductions were observed for particulate matter mass and metals emissions. Furthermore, the production of new species was not observed with the addition of the zeolite urea-SCR system joined with a downstream oxidation catalyst.     

高效降氰菌群的构建及降解特性

从筛选到的降氰菌中构建出了优于单一菌种降氰活性的复配菌群CNR.研究了该复合菌群的生长条件,探讨了温度、pH、接种量、氰化物初始浓度及降解时间等因素对CNR降氰的影响.研究表明,复配菌群CNR适应碱性环境,可降解高浓度氰化物(CN-11 000 mg/L),并对金属氰化物和脂肪族腈具有极强的降解能力.在有氧、pH 11、33 ℃和接种量10%条件下.含CN-11 000 ng/L培养液经60 h降解后,CN-1浓度降为0.49 mg/L,降氰率高达99.96%,达到国家一级排放标准.