Development of a highly sensitive extractive spectrophotometric method for the determination of nickel(II) from environmental matrices using N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone

Nickel(II) reacts with N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone (ECCT) and forms a yellow colored complex, which was extracted into n-butanol from sodium acetate and acetic acid buffer at pH 6.0. The absorbance value of the Ni(II)-ECCT complex was measured at different intervals of time at 400nm, to ascertain the time stability of the complex. The extraction of the complex into the solvent was instantaneous and stable for more than 72h. The system obeyed Beer's law in the concentration range of 1.2-5.6mugml(-1) of nickel(II), with an excellent linearity and a correlation coefficient of 0.999. The molar absorptivity and Sandell's sensitivity of the extracted species were found to be 1.114x10(4)Lmol(-1)cm(-1) and 5.29x10(-3)mugcm(-2) at 400nm, respectively. Hence, a detailed study of the extraction of nickel(II) with ECCT has been undertaken with a view to developing a rapid and sensitive extractive spectrophotometric method for the determination of nickel(II) when present alone or in the presence of diverse ions which are usually associated with nickel(II) in environmental matrices like soil and industrial effluents. Various standard alloy samples (CM 247 LC, IN 718, BCS 233, 266, 253 and 251) have been tested for the determination of nickel for the purpose of validation of the present method. The results of the proposed method are comparable with those from atomic absorption spectrometry and were found to be in good agreement.     

Comparison of 85Kr and 3H Apparent Ground‐Water Ages for Source Water Vulnerability in the Collyer River Catchment,Maine1

Abstract: Apparent ground‐water ages as determined by the noble gas isotope ⁸⁵Kr and the water isotope ³H are compared. Refined gas extraction methodology at the wellhead permits efficient collection of Kr for ⁸⁵Kr isotope enrichment. ⁸⁵Kr isochrones elucidate areas of much younger ground‐water ages than ³H. Declining ³H activities in the catchment prevent its correlation with the youngest measured ⁸⁵Kr ages. Source water for most drinking water supplies in the Collyer River catchment is recharged within 40 years BP (2004). Mean‐age (τ) transport modeling suggests uncertainty of ground‐water ages is greatest in the central basin area.     

Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe(VI) systems

The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO₂ suspension under UV illumination has been investigated using oxygen (O₂) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O₂ for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO₂–UV–O₂ system, while in contrast phthalic acid was found to be the main intermediate product in the TiO₂–UV–Fe(VI) system. These findings indicate that DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO₂–UV–O₂ reaction system and an unknown radical species (most likely an iron–oxo species) is suspected to exist in the TiO₂–UV–Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO₂–UV–O₂ and TiO₂–UV–Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO₂–UV–O₂ reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO₂–UV–Fe(VI) reaction systems attack the alkyl chain of DMP.     

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.     

不同母质发育的水稻土中铁、锰对甲烷排放的影响

盆栽结果表明,不同土壤类型铁、锰含量的差异是造成不同土壤类型间甲烷排放量差异甚大的重要因素之一。土壤中铁、锰通过对土壤氧化还原电位及根膜形成的影响而影响甲烷的排放。     

大气光化学烟雾反应机理比较(Ⅰ)O3和NOx的比较

在相同初始和排放条件下,对四种应用较广的光化学烟雾反应机理(CB4-99,RADM2,RACM,SAPRC99)进行了比较.研究发现对于O3,在低VOCs/NOx时,四种机理模拟结果相关较小,平均相对标准偏差为7%,在高VOCs/NOx时,平均相对标准偏差为26%,差距较大;对于NOx,多数情况下RACM和RADM2的模拟结果较高,CB4-99和SAPRC99的模拟值偏低,其原因主要来源于不同机理中O3的生成对NOx及VOCs的敏感性不同而造成的.在用模式模拟O3和NOx时,应特别注意机理不同而带来的模拟结果差异.     

“MMA”技术路线在太湖蓝藻水华监测中的应用

通过对3S技术整合,提出"MMA"技术路线应用于蓝藻水华监测,包括监测、测绘、分析等关键步骤。对太湖蓝藻水华研究结果表明,总体规律一致,但又有所差异。一方面,太湖蓝藻密度(CBD)、叶绿素a(Chl-a)及水华频率分布图结果均呈现"西高东低"的空间分布规律;另一方面,太湖湖心区CBD和Chl-a浓度亦较高,而遥感监测后的水华频率图显示为无水华或频率小于1%。故应参照"MMA"技术路线,综合应用3S技术,并核验比对,弥补单项技术存在的不足,全面真实反映藻类水华情况。"MMA"技术路线既适用于水华监测,亦可推广至其他环境监测工作。     

气质联用法测固定污染源中三氟甲烷、四氟甲烷、六氟乙烷和六氟化硫

建立了固定污染源排气中三氟甲烷、四氟甲烷、六氟乙烷和六氟化硫的采样和气质联用分析方法,检出限分别为0.06、0.15、0.21、0.71 mg/m3,精密度在3.2%以下,相关系数大于0.999 6,并对浙江省内2家典型企业排放的温室气体进行了监测,实际样品监测结果表明,该方法能够满足废气中4种温室气体的监测要求。     

基于3G网络平台的环保移动执法系统构建

从当前环保现场执法所面临的手段落后、执法尺度不一等实际问题出发,构建了一套依托于3G无线通信平台的移动执法系统。该系统采用先进的网络通讯技术,借助执法终端PDA手机,可实现在执法现场实时查询环保动、静态信息,录入、打印检查笔录及执法表单等功能,实现环保监察部门统一执法、规范执法流程、提高执法效率的最终目标。     

臭氧前体物排放清单相关模型及应用

欧美等国家对于O_3污染的研究开展较早,已建立较成熟的O_3污染生成、扩散及空气质量等模型。文章主要介绍评述了美国环保局推荐使用的计算O_3前体物的相关模型(MOVES、NONROAD、SMOKE、EMFAC和EDMS),从基本原理和功能、污染源类型、研究尺度、所需参数等方面对比分析各模型的特点和适用范围,并综述其国内外研究应用情况;讨论了中国在这些模型的使用方面应该注意的问题,如加强开展模型计算结果验证和基础实验获得本土化的模型参数,以及中国开发的相关模型的优势和适用性等。