环境样品的热解-溶液吸收预处理及其汞同位素组成的测定

利用多道接收电感耦合等离子体质谱仪(MC-ICP-MS)可实现汞同位素的高精度测定,但对样品预处理的要求很高。目前,液态、固态、气态环境样品的预处理方式不一,存在一定的系统误差。该研究旨在尽可能统一各状态样品的预处理步骤。先将各样品中的不同形态汞富集转化为固体可吸附态,令其吸附在固态载体上,包括:采用金柱富集气体样品中的气态单质汞;以吹扫-金柱捕集法富集液体样品中的溶解气态汞和总汞;用膜过滤法收集大气中的颗粒态汞。最后以管式炉热解定量固态样品,采用高氧化效率的酸性高锰酸钾混合溶液吸收热解产生的Hg~0并氧化为Hg~(2+),保存于溶液中供MC-ICP-MS测定。优化了气体流速、吸收液体积及高锰酸钾浓度等参数,考察了方法空白、回收率及精密度等指标,并将建立的方法应用于大气气态单质汞、大气颗粒态汞、溶解气态汞、雨水总汞和土壤总汞等样品中汞同位素的分析。     

大气活性气态汞采样和分析方法

改进了利用镀KCl扩散管采集大气活性气态汞分析方法。实验证明：在450℃条件下加热10min被扩散管捕获的活性气态汞会被热解出。该法最低检出限为3pg，具有成本低、分析方法简单、省时及采样管能多次使用等优点。     

洗选过程对宁武煤中汞迁移和热释放的影响特性

采用逐级化学提取和热分析方法,选取宁武煤田某洗煤厂原煤及洗选产物为研究对象,在汞质量平衡基础上对煤中汞赋存形态进行分类并验证,进而考察了洗选过程对煤中汞迁移行为和热释放的影响特性。结果表明,洗选过程在降低原煤灰分和硫分含量的同时也改变了汞的富集规律,引起了汞的重新分配;样品中汞元素与灰分和硫含量之间的线性相关性分别为0.89和0.99,原煤中汞主要以无机结合态存在,其迁移行为受控于无机矿物质迁移,洗选后矸石总汞绝对含量较原煤增加了322.8%,而精煤汞含量降低至原煤的40%,汞脱除率达到56.4%;洗煤产物中汞富集程度的差异与其在原煤中赋存形态密切相关,其中,矸石中硫化物结合态汞的占比高达56.6%,而精煤和煤泥中有机结合态汞较原煤中均有所提高;相同温度下汞在煤泥中释放率最大,矸石中最小,所有样品中汞至650℃均接近完全析出;煤中汞热释放特性也与其赋存形态密切相关,不同热解温度段汞热释放行为由煤中汞的固有赋存形态所决定,其中,有机结合态汞随有机质分解在300℃已大量逸出,而硫化物结合态汞分解温度主要为400-600℃。     

直接进样-冷原子吸收分光光度法测定大气颗粒物中汞的含量

<正>大气中汞的来源主要有自然源和人为源,自然源包括土壤、水体、植被、森林火灾、火山爆发等,人为源包括化石燃料燃烧、金属冶炼、水泥制造等^[1-2]。据统计,全球每年向大气中排放汞的总量为5 000 t, 其中4 000 t来自人为排放。大气中的汞可以通过皮肤和呼吸进入人体,并且对神经系统造成危害^[3]。大气中的汞按照物理化学特性分类,一般可被分为气态元素汞、活性气态汞和颗粒态汞3种形态。     

森林生态系统汞的生物地球化学过程

森林系统占全球陆地总面积的31%,是全球生物地球化学循环最活跃的地区之一。认识森林系统汞的生物地球化学过程对确立大气-森林系统汞的相关归趋,及进一步定量分析全球汞的生物地球化学循环过程至关重要。然而,当前森林系统在全球大气汞的循环中的角色认识还不清楚,即无法确定森林系统是大气汞的汇还是源。本文基于森林系统汞的质量平衡、土壤汞的累积过程及汞的同位素地球化学的研究,阐述了当前关于汞在全球森林生态系统多介质间汞的相互耦合作用过程及其迁移转化规律的认识。在此基础上,针对当前森林系统汞的生物地球化学过程研究的关键科学问题,提出了未来该领域的研究重点和方向。     

环境汞污染

由于特殊的物理化学性质和强的毒性,汞已经成为全球关注的污染物.本文对目前大气汞的来源、汞在大气中的形态分布及在全球大气分布的特点和汞在大气中的迁移转化规律等方面进行了详细地介绍,提出了大气汞研究的展望.评述了近年来水生生态系统汞的生物地球化学循环研究领域的新进展及存在问题,提出了对汞甲基化机理认识的研究要进一步加强的观点.对汞矿开采和混汞法炼金区环境汞污染及对居民健康的危害研究进展进行了详细地评述,指出矿区居民汞暴露的主要途径.最后,本文还总结了目前人体暴露不同形态汞对人体健康影响的最新进展.     

沉积物样品中痕量元素汞的形态分析研究进展

归纳总结了沉积物中汞形态分析研究进展,内容包括沉积物汞的赋存形态,样品的预处理和不同形态汞的原子光谱法、色谱法、电感耦合等离子体质谱法及联用技术等分析方法,指出了存在的问题和未来的发展方向。     

煤中汞赋存形态及其热解时析出规律研究

利用程序升温热解反应系统,研究了煤中不同形态汞的析出温度,通过积分各析出温度下汞的总析出量来分析各赋存形态的汞所占比例,同时研究了添加CaCl2后抑制煤热解过程中汞析出的机理。结果表明,实验所选煤中汞主要存在三种赋存形态,其析出温度点分别在220、300和400℃;其中,300℃析出的汞所占比例最高,为54.18%,从析出温度分析该部分汞主要以HgS的形式赋存。添加CaCl2对第一和第三赋存形态的汞析出具有抑制作用,改变了其析出温度,对第二赋存形态的汞析出几乎无影响,添加后使得汞析出温度更为集中;抑制析出的主要原因是氧化吸附,添加CaCl2对汞总析出量基本无影响。     

两种煤在热解过程中汞的析出和形态分布实验研究

在程序升温热解反应系统上,研究了大同煤和宝日希勒煤在N2气氛下热解过程中汞析出及形态分布规律。实验结果表明,温度是影响煤热解过程中汞释放的主要因素。煤中汞释放率随着温度的升高而明显升高,当热解温度为600℃时,煤中汞已基本逸出,汞释放率在92%以上。元素汞(Hg0)是气态汞释放的主要形态,随着热解温度的升高,大同煤释放的元素汞在气态汞中的质量分数先增加后减小,而宝日希勒煤中元素汞的质量分数逐渐降低。随着停留时间的延长,煤中汞释放率和元素汞的质量分数都呈增加趋势,宝日希勒煤的增幅较大同煤更为显著。较高的加热速率促进了煤中汞的释放,同时也在一定程度上提高了氧化汞的质量分数,其中宝日希勒煤的氧化汞增幅明显大于大同煤,达19.5%。     

煤中汞赋存形态及其热解时析出规律研究

利用程序升温热解反应系统,研究了煤中不同形态汞的析出温度,通过积分各析出温度下汞的总析出量来分析各赋存形态的汞所占比例,同时研究了添加CaCl₂后抑制煤热解过程中汞析出的机理。结果表明,实验所选煤中汞主要存在三种赋存形态,其析出温度点分别在220、300和400 ℃;其中,300 ℃析出的汞所占比例最高,为54.18%,从析出温度分析该部分汞主要以HgS的形式赋存。添加CaCl₂对第一和第三赋存形态的汞析出具有抑制作用,改变了其析出温度,对第二赋存形态的汞析出几乎无影响,添加后使得汞析出温度更为集中;抑制析出的主要原因是氧化吸附,添加CaCl₂对汞总析出量基本无影响。     

Measurement techniques for mercury species in ambient air

This review critically evaluates the measurement methodologies most commonly employed for the analysis of the various forms of mercury (Hg) in air. Emphasis is given to the three most common forms of mercury in air [i.e. gaseous elemental mercury (GEM, Hg⁰), reactive gaseous mercury (RGM), and particle-bound mercury (Hg_p)]. Moreover, we also briefly describe methods dealing with gas-phase analysis of organic mercury species (e.g., mostly methyl mercury), as they are also reported to be present in air on rare occasions. To begin with, we describe the approaches to sampling airborne mercury species and associated sample-treatment strategies. We evaluate both conventional and emerging alternative detection techniques for different mercury forms with respect to their applicability in airborne mercury analysis. We also discuss the artifacts and the biases associated with analysis of different mercury species. Finally, the review summarizes current methodological developments for the determination of mercury in air and highlights future prospects for improvements.     

Measurements of atmospheric mercury with high time resolution: Recent applications in environmental research and monitoring

In the past five years automated high time-resolution measurements of mercury species in ambient air have promoted remarkable progress in the understanding of the spatial distribution, short-term variability, and fate of this priority pollutant in the lower troposphere. Examples show the wide range of possible applications of these techniques in environmental research and monitoring. Presented applications of measurement methods for total gaseous mercury (TGM) include long-term monitoring of atmospheric mercury at a coastal station, simultaneous measurements during a south-to-north transect measurement campaign covering a distance of approximately 800 km, the operation on board of a research aircraft, and the quantification of mercury emissions from naturally enriched surface soils. First results obtained with a new method for the determination of reactive gaseous mercury (RGM) are presented. Typical background concentrations of TGM are between 1.5 and 2 ng m(-3) in the lower troposphere. Concentrations of RGM have been determined at a rural site in Germany between 2 and 35 pg m(-3). Flux measurements over naturally enriched surface soils in the Western U.S.A. have revealed emission fluxes of up to 200 ng Hg m(-1) h(-1) under dry conditions.     

Evaluation and applications of a gaseous mercuric chloride source

In this study, a diffusion-type device for generating gaseous mercuric chloride (HgCl₂) was systematically evaluated and applied to validate the annular denuder method for sampling gaseous HgCl₂ species in a synthetic gas stream. The results show that it takes at least 48 h for the system to reach a steady-state condition after the diffusion cell reaches the temperature set-point and the carrier gas is activated. The primary Hg species from the source was proven to be HgCl₂. In the temperature range from –5.00 to 11.80 °C, the Hg emission rates from the source vary from 1.8 to 14.2 pg min^–1. It is shown that, under the experimental conditions examined, KCl-coated annular quartz denuders designed for ambient reactive gaseous mercury (RGM) collection could quantitatively collect HgCl₂. It is also demonstrated that the impactors used to remove coarse airborne particulate matter could lead to a loss of up to one third of the HgCl₂ in the gas stream.     

On-line coupling of sequential injection lab-on-valve to differential pulse anodic stripping voltammetry for determination of Pb in water samples

Sequential injection lab-on-valve (LOV) was first proposed for analyzing ultra-trace amounts of Pb using differential pulse anodic stripping voltammetry (DPASV) with a miniaturized electrochemical flow cell fabricated in the LOV unit. Deposition and stripping processes took place between the renewable mercury film carbon paste electrode and sample solution, the peak current was employed as the basis of quantification. The mercury film displayed a long-term stability and reproducibility for at least 50 cycles before next renewal, the properties of integrated miniature LOV unit not only enhanced the automation of the analysis procedure but also declined sample/reagent consumption. Potential factors that affect the present procedure were investigated in detail, i.e., deposition potential, deposition time, electrode renewable procedure and the volume of sample solution. The practical applicability of the present procedure was demonstrated by determination of Pb in environmental water samples.     

Calorimetric studies of solid wastes,sewage sludge,wastewaters and their effects on soil biodegradation processes

Calorimetric studies of solid wastes, sewage sludge, wastewaters and their environmental effects focus on three main research areas. The first research area involves determination of selected thermal and physical parameters characterizing the above substances, such as specific heat, thermal conductivity and others. The second area covers processes of total or gradual destruction of the examined substances at a fixed composition of the gaseous phase. The methods applied in this case enable to determine the heat of combustion or the calorific value of the analyzed material, as well as changes in the rate of heat production, measured by differential scanning calorimetry (DSC). The third area of calorimetric studies covers microbial calorimetry as a method for non-destructive monitoring of organic matter biodegradation in order to measure the kinetic and thermodynamic parameters of the investigated processes, i.e., wastewater treatment, composting and decomposition of organic soil matter, as well as to determine the stability of wastes. This paper describes, based on available literature data, the major directions of investigations, using different calorimetric methods, of solid wastes, sewage sludge and wastewaters and additionally their effects on soil microbial processes. The paper also presents the selected calorimetric studies and analyses the biodegradation kinetics of organic wastewaters and glucose decomposition in the presence of phosphogypsum in different soils.     

The role of sample collection method and the bias between different standard matrices in the determination of volatile organic compounds in air

This study was undertaken to assess the relative bias between two types of sampling methods for volatile organic compounds (VOCs), i.e., sorbent tube vs. bag sampling methods and between different standard phases. For the purpose of this comparative study, gaseous standards containing three major aromatic VOCs (benzene, toluene, and xylene—commonly called BTX) were analyzed by thermo-desorption gas chromatography (TD-GC) with flame ionization detector. According to our findings, the relative response of target compounds can be smaller in the bag method than in the tube method. Although the relative bias varies with the sample transfer conditions for the TD, the mean slope values of the former are smaller by up to 20% relative to the latter, possibly due to sorptive loss on the bag sampler. In addition, the effects of different standard matrices (i.e. liquid and gas phases) were also examined using the sorbent tube method. The results indicated that the slope values of the gas-phase standard were smaller by half (about 43–56%) than the liquid-phase standard. Consequently, information concerning the extent of relative bias between sampling methods (e.g., bag and tube) or standard matrices (e.g., gas and liquid) should be considered as one of the key factors in TD applications.     

Investigation of mercury speciation in lichens.

Epiphytic lichens have long been considered to be reliable bioindicators of air pollution. In the present study only one lichen species, Hypogymnia physodes (L.) Nyl., was chosen; this species is very often used for biomonitoring in Europe. Total mercury and methylmercury were determined in lichens taken from various polluted and unpolluted locations in Slovenia, including a mercury mining area around Idrija. Additionally, total gaseous mercury in air was also determined at several sampling points.     

Screening of potential sites for undeclared nuclear facilities in environmental monitoring for nuclear proliferation

The sensitivity of environmental sampling and analysis for the estimated atmospheric concentrations of radionuclides in effluents from clandestine nuclear facilities may require many sampling sites and exorbitant costs to monitor such large areas. An assessment has been made of the key factors necessary to support the operation of a nuclear facility, e.g., the existence of a nearby transportation network, main electrical power supply, and population centers. Screening, the subject of this paper, evaluates how cartographic data and satellite imagery can be used to identify areas most capable of supporting undeclared nuclear operations. As a result, large geographical areas can be eliminated from environmental monitoring and sampling. This leads to reduced costs, a reduction in the number of sampling sites required, and a reduction in the overall level of effort required to accomplish effective environmental monitoring. The screening methodology and techniques are described and examples given.