多环芳烃的零阶价分子连接性指数与正-辛醇/水分配系数

本文建立了准确预测多环芳烃(PAHs)及其烷基衍生物的正-辛醇/水分配系数(Kow)模型。模型表明PAHs的分配性质可用零阶价分子连接性指数(~°x~v)描述,~°x~v数值与PAHs的logKow成正比。应用本模型可以预测大范围PAHs的logKow值。     

Detection of polycyclic aromatic hydrocarbons using a high performance-single particle aerosol mass spectrometer

The real-time detection of the mixing states of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs in ambient particles is of great significance for analyzing the source, aging process, and health effects of PAHs and nitro-PAHs; yet there is still few effective technology to achieve this type of detection. In this study, 11 types of PAH and nitro-PAH standard samples were analyzed using a high performance-single particle aerosol mass spectrometer (HP-SPAMS) in lab studies. The identification principles ‘parent ions’ and ‘mass-to-charge (m/z) = 77’ of each compound were obtained in this study. It was found that different laser energies did not affect the identification of the parent ions. The comparative experiments of ambient atmospheric particles, cooking and biomass burning emitted particles with and without the addition of PAHs were conducted and ruled out the interferences from primary and secondary organics on the identification of PAHs. Besides, the reliability of the characteristic ions extraction method was evaluated through the comparative study of similarity algorithm and deep learning algorithm. In addition, the real PAH-containing particles from vehicle exhaust emissions and ambient particles were also analyzed. This study improves the ability of single particle mass spectrometry technology to detect PAHs and nitro-PAHs, and HP-SPAMS was superior to SPAMS for detecting single particles containing PAHs and nitro-PAHs. This study provides support for subsequent ambient observations to identify the characteristic spectrum of single particles containing PAHs and nitro-PAHs.     

Uptake and accumulation of phenanthrene and pyrene in spiked soils by Ryegrass(Lolium perenne L.)

Phytoremediation has long been recognized as a cost-effective method for the removal of polycyclic aromatic hydrocarbons （PAHs） from soil. A study was conducted to investigate the uptake and accumulation of PAHs in root and shoot of Lolium perenne L. Pot experiments were conducted with series of concentrations of 3.31-378.37 mg/kg for phenanthrene and those of 4.22-365.38 mg/kg for pyrene in a greenhouse. The results showed that both ryegrass roots and shoots did take up PAHs from spiked soils, and generally increased with increasing concentrations of PAH in soil. Bioconcentration factors（BCFs） of phenanthrene by shoots and roots were 0.24- 4.25 and 0.17-2.12 for the same treatment. BCFs of pyrene by shoots were 0.20-1.5, except for 4.06 in 4.32 mg/kg treatment, much lower than BCFs of pyrene by roots （0.58-2.28）. BCFs of phenanthrene and pyrene tended to decrease with increasing concentrations of phenanthrene and pyrene in soil. Direct uptake and accumulation of these compounds by Lolium perenne L. was very low compared with the other loss pathways, which meant that plant-promoted microbial biodegradation might be the main contribution to plant-enhanced removal of phenanthrene and pyrene in soil. However, the presence of Lolium perenne L. significantly enhanced the removal of phenanthrene and pyrene in spiked soil. At the end of 60 d experiment, the extractable concentrations of phenanthrene and pyrene were lower in planted soil than in non-planted soil, about 83.24%-91.98% of phenanthrene and 68.53%-84.10% of pyrene were removed from soils, respectively. The results indicated that the removal of PAHs in contaminated soils was a feasible approach by using Lolium perenne L.     

Development of a continuously stirred flow cell for investigating sorption mass transfer

This paper introduces a new reversible-flow design for a continuously stirred reactor used to study sorption mass transfer in soil and solvent systems. The stirred reactor has potential advantages over conventional packed column or batch reactors because it isolates intraparticle sorption rate limitations from advective-dispersive transport, yet allows changes to flux through the reactor for analysis of sorption kinetics under dynamic conditions. Previously, stirred reactors have often failed due to clogging of sediment on the effluent frit. The reverse-flow backwashing design allows longer life and higher confidence in maintaining mixed conditions than previous designs. Mass transfer 'rate coefficients estimated from stirred and column experiments are compared; both techniques produced results consistent with a published correlation. The data also show that fitted sorption mass transfer coefficients can be strongly dependent on the choice of equilibrium partition coefficient (i.e. batch or first-moment derived values), and that the conventional two-site sorption kinetics model fails to accurately predict sorption mass transfer in the presence of changing solvent velocity through the reactor.     

Phytoremediation of polyaromatic hydrocarbons, anilines and phenols

Phytoremediation technologies based on the combined action of plants and the microbial communities that they support within the rhizosphere hold promise in the remediation of land and waterways contaminated with hydrocarbons but they have not yet been adopted in large-scale remediation strategies. In this review plant and microbial degradative capacities, viewed as a continuum, have been dissected in order to identify where bottle-necks and limitations exist. Phenols, anilines and polyaromatic hydrocarbons (PAHs) were selected as the target classes of molecule for consideration, in part because of their common patterns of distribution, but also because of the urgent need to develop techniques to overcome their toxicity to human health. Depending on the chemical and physical properties of the pollutant, the emerging picture suggests that plants will draw pollutants including PAHs into the plant rhizosphere to varying extents via the transpiration stream. Mycorrhizosphere-bacteria and -fungi may play a crucial role in establishing plants in degraded ecosystems. Within the rhizosphere, microbial degradative activities prevail in order to extract energy and carbon skeletons from the pollutants for microbial cell growth. There has been little systematic analysis of the changing dynamics of pollutant degradation within the rhizosphere; however, the importance of plants in supplying oxygen and nutrients to the rhizosphere via fine roots, and of the beneficial effect of microorganisms on plant root growth is stressed. In addition to their role in supporting rhizospheric degradative activities, plants may possess a limited capacity to transport some of the more mobile pollutants into roots and shoots via fine roots. In those situations where uptake does occur (i.e. only limited microbial activity in the rhizosphere) there is good evidence that the pollutant may be metabolised. However, plant uptake is frequently associated with the inhibition of plant growth and an increasing tendency to oxidant stress. Pollutant tolerance seems to correlate with the ability to deposit large quantities of pollutant metabolites in the 'bound' residue fraction of plant cell walls compared to the vacuole. In this regard, particular attention is paid to the activities of peroxidases, laccases, cytochromes P450, glucosyltransferases and ABC transporters. However, despite the seemingly large diversity of these proteins, direct proof of their participation in the metabolism of industrial aromatic pollutants is surprisingly scarce and little is known about their control in the overall metabolic scheme. Little is known about the bioavailability of bound metabolites; however, there may be a need to prevent their movement into wildlife food chains. In this regard, the application to harvested plants of composting techniques based on the degradative capacity of white-rot fungi merits attention.     

A PCE groundwater plume discharging to a river: influence of the streambed and near-river zone on contaminant distributions

An investigation of a tetrachloroethene (PCE) groundwater plume originating at a dry cleaning facility on a sand aquifer and discharging to a river showed that the near-river zone strongly modified the distribution, concentration, and composition of the plume prior to discharging into the surface water. The plume, streambed concentration, and hydrogeology were extensively characterized using the Waterloo profiler, mini-profiler, conventional and driveable multilevel samplers (MLS), Ground Penetrating Radar (GPR) surveys, streambed temperature mapping (to identify discharge zones), drivepoint piezometers, and soil coring and testing. The plume observed in the shallow streambed deposits was significantly different from what would have been predicted based on the characteristics of the upgradient plume. Spatial and temporal variations in the plume entering the near-river zone contributed to the complex contaminant distribution observed in the streambed where concentrations varied by factors of 100 to 5000 over lateral distances of less than 1 to 3.5 m. Low hydraulic conductivity semi-confining deposits and geological heterogeneities at depth below the streambed controlled the pattern of groundwater discharge through the streambed and influenced where the plume discharged into the river (even causing the plume to spread out over the full width of the streambed at some locations). The most important effect of the near-river zone on the plume was the extensive anaerobic biodegradation that occurred in the top 2.5 m of the streambed, even though essentially no biodegradation of the PCE plume was observed in the upgradient aquifer. Approximately 54% of the area of the plume in the streambed consisted solely of PCE transformation products, primarily cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC). High concentrations in the interstitial water of the streambed did not correspond to high groundwater-discharge zones, but instead occurred in low discharge zones and are likely sorbed or retarded remnants of past high-concentration plume discharges. The high-concentration areas (up to 5529 microg/l of total volatile organics) in the streambed are of ecological concern and represent potential adverse exposure locations for benthic and hyporheic zone aquatic life, but the effect of these exposures on the overall health of the river has yet to be determined. Even if the upgradient source of PCE is remediated and additional PCE is prevented from reaching the streambed, the high-concentration deposits in the streambed will likely take decades to hundreds of years to flush completely clean under natural conditions because these areas have low vertical groundwater flow velocities and high retardation factors. Despite high concentrations of contaminants in the streambed, PCE was detected in the surface water only rarely due to rapid dilution in the river and no cDCE or VC was detected. Neither the sampling of surface water nor the sampling of the groundwater from the aquifer immediately adjacent to the river gave an accurate indication of the high concentrations of PCE biodegradation products present in the streambed. Sampling of the interstitial water of the shallow streambed deposits is necessary to accurately characterize the nature of plumes discharging to rivers.     

Trimethylbenzoic acids as metabolite signatures in the biogeochemical evolution of an aquifer contaminated with jet fuel hydrocarbons

Evolution of trimethylbenzoic acids in the KC-135 aquifer at the former Wurtsmith Air Force Base (WAFB), Oscoda, MI was examined to determine the functionality of trimethylbenzoic acids as key metabolite signatures in the biogeochemical evolution of an aquifer contaminated with JP-4 fuel hydrocarbons. Changes in the composition of trimethylbenzoic acids and the distribution and concentration profiles exhibited by 2,4,6- and 2,3,5-trimethylbenzoic acids temporally and between multilevel wells reflect processes indicative of an actively evolving contaminant plume. The concentration levels of trimethylbenzoic acids were 3-10 orders higher than their tetramethylbenzene precursors, a condition attributed to slow metabolite turnover under sulfidogenic conditions. The observed degradation of tetramethylbenzenes into trimethylbenzoic acids obviates the use of these alkylbenzenes as non-labile tracers for other degradable aromatic hydrocarbons, but provides rare field evidence on the range of high molecular weight alkylbenzenes and isomeric assemblages amenable to anaerobic degradation in situ. The coupling of actual tetramethylbenzene loss with trimethylbenzoic acid production and the general decline in the concentrations of these compounds demonstrate the role of microbially mediated processes in the natural attenuation of hydrocarbons and may be a key indicator in the overall rate of hydrocarbon degradation and the biogeochemical evolution of the KC-135 aquifer.     

白腐菌对芳香族化合物的降解途径

白腐菌 (Whiterotfungi)是目前所发现的对芳香族化合物有很强降解能力的一类微生物。本文探讨了降解芳香族化合物的白腐菌种及其代谢化合物的主要类型 ,分析了对不同化合物的不同代谢途径 ,同时展望了其应用前景     

人工湿地处理系统中多环芳烃的行为

采用Oasis HLB柱固相萃取的前处理技术,以气相色谱质谱联用仪(GC/MS)的分析方法,对我国北方永定河上游黑土洼人工湿地中多环芳烃污染的特征以及分布规律进行了研究.结果表明,该湿地系统以低环数多环芳烃污染为主,其中浓度最高的是菲和蒽,未检出高环数(5环、6环)多环芳烃.通过比较进水和出水的浓度,湿地系统总体上不能有效去除进水中的多环芳烃.但是比较不同工艺单元进出水浓度,复氧、植物根系及微生物等均影响到多环芳烃的去除效果,去除率在28%～65%之间.     

人工湿地处理系统中多环芳烃的行为

采用Oasis HLB柱固相萃取的前处理技术,以气相色谱质谱联用仪（GC/MS）的分析方法,对我国北方永定河上游黑土洼人工湿地中多环芳烃污染的特征以及分布规律进行了研究.结果表明,该湿地系统以低环数多环芳烃污染为主,其中浓度最高的是菲和蒽,未检出高环数（5环、6环）多环芳烃.通过比较进水和出水的浓度,湿地系统总体上不能有效去除进水中的多环芳烃.但是比较不同工艺单元进出水浓度,复氧、植物根系及微生物等均影响到多环芳烃的去除效果,去除率在28%～65%之间.