Use of principal component analysis to profile temporal and spatial variations of chlorinated solvent concentration in groundwater

This work aims at evaluating spatial distribution patterns of concentration variations for chlorinated solvents in groundwater, based on principal component analysis and geographic information system (GIS) tools. The study investigates long-time series of chlorinated solvent concentrations in groundwater measured for 18 contaminated industrial sites. The characterization of contaminant plumes and delineation of pollutant sources are essential for choosing appropriate monitoring and remediation strategies, as contaminated groundwaters are characterized by complex patterns of spatial and temporal concentration variability, with wide unpredictable fluctuations over time. The present work describes the results of a new exploratory statistical method called the Variability Index Method (VIM) applied to environmental data to assess the performance of using concentration variations as molecular tracers to reveal aquifer dynamics, industrial impacts, and point sources for contamination plumes. The application of this method provides a useful assessment of controls over contaminant concentration variations as well as support for remediation techniques.     

Identification of key parameters controlling dissolved oxygen migration and attenuation in fractured crystalline rocks

In the crystalline rocks of the Canadian Shield, geochemical conditions are currently reducing at depths of 500-1000 m. However, during future glacial periods, altered hydrologic conditions could potentially result in enhanced recharge of glacial melt water containing a relatively high concentration of dissolved oxygen (O2). It is therefore of interest to investigate the physical and geochemical processes, including naturally-occurring redox reactions, that may control O2 ingress. In this study, the reactive transport code MIN3P is used in combination with 2k factorial analyses to identify the most important parameters controlling oxygen migration and attenuation in fractured crystalline rocks. Scenarios considered are based on simplified conceptual models that include a single vertical fracture, or a fracture zone, contained within a rock matrix that extends from the ground surface to a depth of 500 m. Consistent with field observations, Fe(II)-bearing minerals are present in the fractures (i.e. chlorite) and the rock matrix (biotite and small quantities of pyrite). For the parameter ranges investigated, results indicate that for the single fracture case, the most influential factors controlling dissolved O2 ingress are flow velocity in the fracture, fracture aperture, and the biotite reaction rate in the rock matrix. The most important parameters for the fracture zone simulations are flow velocity in the individual fractures, pO2 in the recharge water, biotite reaction rate, and to a lesser degree the abundance and reactivity of chlorite in the fracture zone, and the fracture zone width. These parameters should therefore receive increased consideration during site characterization, and in the formulation of site-specific models intended to predict O2 behavior in crystalline rocks.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

机体细胞镉摄入离子转运通道研究进展

镉是人体非必需金属离子,长期镉暴露易引发镉中毒。机体内没有负责镉转运的特定载体,镉可通过必需金属离子转运载体进入机体细胞。机体内能够转运镉的载体有多种,主要包括铁的转运载体二价金属离子转运蛋白1(DMT1)、钙离子通道(电压门控钙通道(VGCC)、瞬时感受器电位(TRP)和钙库调控的钙通道(SOC))以及锌铁调控蛋白ZIP家族中的ZIP8和ZIP14等,且不同的机体细胞镉吸收所需转运载体不同。转运载体对镉离子的转运符合米氏方程,不同载体调节镉吸收的米氏常数Km值不同。机体细胞镉的吸收是个复杂的过程,通常存在着多种转运载体的交互作用,机体细胞可根据环境变化而选择镉的转运载体。对镉的生理毒性,以及细胞镉吸收常用的转运载体类型加以阐述,并分析了不同机体细胞镉吸收的可能转运载体,以期为后续探究机体细胞镉吸收具体分子机制提供理论指导。     

城市污泥-磷石膏陶粒的制备条件及性能分析

以城市污水处理厂剩余污泥和磷酸生产废渣磷石膏为原料制备多孔陶粒,考察不同配比、烧结温度及烧结时间对多孔陶粒堆积密度、吸水率及盐酸可溶率的影响。结果表明:在污泥与磷石膏混合比1∶4、烧结温度1 050℃、烧结时间15 min的条件下,可制得堆积密度为685.78 kg/m~3、吸水率27.34%、盐酸可溶率11.38%的陶粒,该陶粒内部含有丰富的膨胀气孔,可用作水处理滤料或建材骨料。     

2016—2017年武汉市城区大气PM2.5污染特征及来源解析

利用2016年1月至2017年9月湖北省环境监测中心站大气复合污染自动监测站的在线监测数据,对武汉市城区PM_2.5的污染特征及主要来源进行解析。结果表明,武汉市城区PM_2.5质量浓度呈现出明显的季节差异,季节变化规律为冬季>春季>秋季>夏季。水溶性离子的主要成分SO₄^2-、NO₃^-和NH₄⁺占总离子质量浓度的82.0%。PM_2.5中阴离子相对阳离子较为亏损,颗粒整体呈碱性。夏季气态污染物的氧化程度较高且SO₂较NO₂氧化程度高。后向轨迹分析结果表明,区域传输是武汉市PM_2.5的一个重要来源,在4个典型重污染阶段,武汉市分别受到局地、东北、西北及西南方向气团传输的影响。PMF模型解析出武汉市PM_2.5五大主要来源及平均贡献率：扬尘22.0%、机动车排放27.7%、二次气溶胶21.6%、重油燃烧14.9%和生物质燃烧13.8%。     

常州市臭氧污染传输路径和潜在源区

利用NCEP全球再分析资料和HYSPLIT4模式,计算了2013—2015年常州市臭氧(O_3)超标日的气流后向轨迹。结合聚类分析方法和常州市PM2.5、PM10、SO2、NO2、O_3数据,分析了O_3超标日不同类型气团来源对各污染物浓度的影响,并利用引入权重因子后的潜在污染源贡献函数分析了影响常州市O_3超标的潜在污染源区分布特征。结果表明:常州市O_3超标期间易受到东南和西南方向气流影响,其中从东海和黄海途经浙江东北部、上海、江苏南部等地的东南气流占比达50%以上。自内陆途经黄山-湖州-宜兴到常州的气流对应的O_3平均质量浓度最高,为116μg/m3。自山东经枣庄-宿迁-淮安-泰州-苏州-无锡到常州的气流对应的O_3平均质量浓度最低,为78μg/m3,但该气流对应的SO2和NO2平均值为各聚类中的最高。影响常州市O_3的潜在污染源区主要在常州周边200 km以内的区域,且集中在从南京至上海的长江下游沿线区域和杭州湾区域;其中太湖湖区为重点污染源源区之一。O_3超标日影响常州NO2的潜在污染源区主要集中在江苏南部、浙江东北部和上海3个区域,太湖周边的常州、无锡、苏州和湖州等几个临近城市为潜在的重点污染源区。与影响常州O_3的WPSCF高值区相比,影响NO2的高值区分布范围更大、距离更远。影响常州O_3的潜在污染源区分布,与长江三角洲地区人为源大气污染物的高排放区域较为一致,说明长江三角洲地区的O_3污染与本区域的人为源大气污染物排放有着极为密切的关联。     

海口市臭氧污染特征

基于2013—2015年海口市4个空气质量自动监测站点数据,结合气象资料,分析了海口市O_3的污染特征。结果表明:海口市O_3总体优良,优良天数比例为99.4%,污染天数均为轻度污染;在良和污染天数中,O_3作为首要污染物的天数占40%,超过其他5项污染物占比。海口市10月O_3浓度最高。O_3月均浓度与温度呈负相关关系,同时与风向有密切关系:5—8月气温较高,以南风为主,O_3浓度较低;1月北风频率较高,易受外来污染传输作用,O_3浓度相对较高。O_3超标日以东北风为主,日变化并未呈现单峰型特征,12:00—22:00时段O_3浓度在10%范围内小幅变化。台风外围型和北方冷高压底部型是造成海口市O_3超标的2类典型天气形势。     

精细化工固定源废气采样时机的选择探讨

以某医药企业某产品生产过程为实例,综合各工段生产步骤、时间、废气产生情况及估算的污染物浓度等因素,绘制各污染因子排放规律图,从而确定各污染因子排放浓度(排放量)最大的1 h为最佳采样时机。