汞同位素自然库存研究进展

汞同位素自然库存作为对汞污染源进行准确示踪的基础,对其进行完善仍是汞同位素研究领域的工作重点。汞存在7种稳定同位素且兼具质量分馏和非质量分馏效应,通过汞同位素对污染源、汞迁移转化过程进行示踪成为理想途径。库存数据作为汞同位素研究的基础,借助多道接收电感耦合等离子质谱仪(MC-ICPMS)对汞同位素进行精确测试,汞同位素库存研究领域取得了显著成果。表现如下:自然界不同库存汞同位素数据库已经初步建立;不同环境汞同位素组成差异显著且同一环境下不同样品同位素组成也各不相同,对其形成机理有了初步认知;依据汞同位素在不同环境的分馏特点及不同库存同位素组成特征,研究者开始对汞污染源进行示踪探索并取得了成功;自然界一些涉及汞迁移、转化的过程,同位素分馏特征已被掌握,特别是奇数非质量分馏的典型过程(光致还原、吸附)已被用于判别汞的地球化学迁移转化过程。涉及煤火的表生态汞的迁移转化是复杂的,部分汞具有二次释放特性,其中汞同位素产生的分馏效应无疑使通过同位素研究对汞污染源进行准确示踪变得困难,因此涉及煤火的表生态汞地球化学特征可作为汞同位素研究领域的一个新的方向。     

小浪底水库鱼体和沉积物中汞稳定同位素组成特征

使用多接收器电感耦合等离子体质谱仪(MC-ICP-MS)测定了小浪底水库鱼体和沉积物中汞同位素的组成.结果显示,小浪底水库鱼体具有偏负的δ~(202)Hg和偏正的Δ~(199)Hg(δ~(202)Hg:-0.26‰±0.30‰;Δ~(199)Hg:0.79‰±0.08‰),而沉积物比鱼体具有更加偏负的δ~(202)Hg和趋近于0值的Δ~(199)Hg(δ~(202)Hg:-1.48‰±0.38‰;Δ~(199)Hg:0.01‰±0.02‰).与以往的研究相比,小浪底水库鱼体内汞同位素特征与淡水水库区域鱼体中类似,而Δ~(199)Hg/Δ~(201)Hg的比值为1.22,表明小浪底水库鱼体内汞的非质量分馏主要是甲基汞的光化学降解产生的;沉积物的同位素特征表明其受到了人为源排放的影响.鱼体内δ15N数据表明在营养转移的过程中会发生质量分馏,但不会发生非质量分馏.     

亚热带与温带森林小流域生态系统汞的生物地球化学循环及其同位素分馏

汞是通过大气进行长距离传输的全球污染物,引起国际社会和学术界高度关注.陆地森林生态系统是全球物质循环最为活跃的地方,但其对全球汞的生物地球化学循环影响的认识还不清楚.同时,森林生态系统汞的生物地球化学循环过程可能对全球大气汞同位素组成产生重要的影响,但目前这两方面的研究还非常缺乏,制约了对全球尺度汞的生物地球化学循环深化规律的把握.本课题组拟在我国温带和亚热带选择3个森林小流域,首先系统开展森林小流域汞的质量平衡研究工作,深入刻画森林流域汞的生物地球化学演化规律,在此基础上开展流域汞的生物地球化学循环过程中汞同位素的分馏特征研究,最终建立流域尺度森林系统汞及其同位素的生物地球化学模型.该项目将极大推进对森林流域尺度汞的生物地球化学循环的认识,探讨森林生态系统与大气汞交换过程对全球尺度汞生物地球化学循环和对大气汞同位素组成的影响,为最终建立基于汞同位素的全球汞生物地球化学循环模型提供基础数据.     

内蒙古自治区原煤中汞含量分布及燃煤大气汞排放量估算

燃煤汞排放是主要的人为大气汞排放源,且煤炭消耗量巨大,全球因燃煤向大气排放的汞量已不容忽视[1].我国作为世界能源消费大国,现今及今后50年仍将以煤炭燃烧作为主要的能源[2].内蒙古自治区地区煤炭资源储量极其丰富,煤炭预测资源总量约为1.4万亿吨,位居全国第二.因此,确定内蒙古自治区原煤中汞含量及空间分布、估算各行业燃煤大气汞排放量对于完善我国煤炭汞资料、评估燃煤汞排放的环境风险具有重要指导意义.1材料和方法根据内蒙古自治区地区煤矿分布情况,在赤峰、大雁、霍林河、锡林郭勒旗、鄂尔多斯、榆林(内蒙和陕西交界处)、伊     

燃煤电厂固体废弃物中汞分布特征及排放量估算

采用湿法消解,原子荧光光谱法测定了5个燃煤电站入炉煤、粉煤灰、炉渣和脱硫石膏中汞的含量,分析探讨了汞在燃煤及不同固体废物中的分布特征.采用质量平衡模型(MB)、修正因子模型(EMF)和烟气计算模型(FC)分别对以上电站的汞排放量进行了估算,并对不同方法得到的排放量进行了对比.研究结果显示,3种方法所得汞排放量结果差距明显,亟需建立更加完善的燃煤电站汞污染排放模型.     

淮南燃煤电厂汞分配、富集与释放通量

汞是一种环境有害元素,燃煤汞排放业已成为当今中国最主要的汞污染源.有效的汞减排政策的制定需要准确了解煤中汞在煤炭燃烧过程中的分配规律及富集模式.本研究针对淮南燃煤电厂的原煤、飞灰、脱硫石膏和脱硫废水进行分析,研究发现,灰渣中的汞含量最低(9.8—27 ng·g~(-1)),其相对于原煤汞(约450 ng·g~(-1))的富集系数一般小于2.1%;飞灰中汞的含量相对较高(121—700 ng·g~(-1)),其富集系数介于9%—54%;而脱硫石膏中汞的浓度最高(1489—4589 ng·g~(-1)).通过物料平衡原理,计算出汞在各个燃煤产物中的分配如下:底灰占1%;飞灰占24%—32%;脱硫石膏及废渣液占7%—22%;大气排放占54%—64%.静电除尘器的脱汞效率为24%—32%,接近世界平均值;而脱硫装置的脱汞效率较低,为10%—29%.根据本研究的汞释放系数(0.24—0.29 g Hg·t~(-1)coal),计算出该电厂在2003—2010年的汞排放通量为1.8—7.3 t.本研究认为燃烧前原煤汞脱除,以及加大对现有脱硫装置的改造能够有效降低大气汞排放.     

陡河水库鱼体汞的生物积累初探

为了解陡河燃煤电厂大气汞释放对毗邻的陡河水库水生生态系统中鱼体汞含量、生物积累和放大等的影响,本研究采集陡河水库野生鱼、虾和螺蛳,分别测定了鱼样等生物样品中的总汞和甲基汞,并对部分代表性样品测定稳定碳氮同位素比值。鱼汞分布特征和δ13C‰和δ15N‰同位素比值分布特征显示:鱼体(鲜样)中总汞和甲基汞平均含量分别为56.4±26.7和15.5±8.4 ng·g-1,总汞含量最高的是杂食性的白条鱼为133 ng·g-1。不同食性的鱼体δ13C和δ15N稳定同位素值变化范围分别为-28.1‰~-24.4‰和12.0‰~16.1‰,Log10[Hg]与δ15N的线性相关斜率值为负值。以上结果表明:陡河水库鱼体汞总体偏低,没有发现高生物积累和生物放大,其主要原因在于陡河水库水环境中汞含量较低,且陡河水库靠近市区,过度捕捞使可以捕获的鱼样种类和数量偏少,且鱼龄较低。     

农田土壤中汞的吸附分配行为研究

汞是环境中毒性最强的重金属之一,由于具有持久性、长距离迁移性和生物累积性被列为全球性污染物。土壤是汞重要的源和汇,在汞的生物地球化学循环中发挥关键作用,其理化性质可以显著影响汞的吸附分配行为。本文基于采自全国各地的131份农业土壤样品考察了汞(Hg2+)在土壤中的吸附分配行为,测定了Hg2+的固液分配系数(Kd),并探讨其与p H、有机质(OM)、粒度组成、溶解性有机质(DOM)和总硫等土壤理化性质的关系。利用逐步多元线性回归的方法分析发现旱地土壤对汞Kd的主要影响因素是DOM和土壤粒度,而水田的主要影响因素是总硫。通过淹水实验,进一步探究了土壤氧化还原对Hg2+分配的影响。研究发现,旱地土壤中,大部分土壤在淹水30 d后Kd呈明显增大趋势,继续淹水至60 d的Kd表现为稳定或下降的趋势;大部分水田土壤在淹水条件下Kd未表现出增大的趋势,且随淹水时间呈稳定或下降的趋势。     

淮南市电厂和炉渣中汞的分布规律

汞是煤中潜在毒害微量元素中关注最多的元素之一,而燃煤是大气中汞的重要来源,2005年美国环保局(EPA)首次公布了洁净空气中汞的标准,对电厂燃煤过程中汞的排放进行了限制,同时,对燃煤过程中汞排放量的限制将是发展洁净煤技术和环境保护的重要内容之一.     

环境中汞微生物转化研究进展

汞(Hg)污染是全球最为关注的环境问题之一.Hg的不同形态之间毒性差异大,其以有机形态存在的甲基汞(MeHg)具有强神经毒性,且能在生物体内富集,具有很强的健康与生态风险.环境中不同形态的Hg可以在生物与非生物作用下进行转化,特别是微生物在一定条件下驱动着Hg的甲基化、去甲基化、还原与氧化,从而影响Hg的移动性和生物有效性.因此,理解微生物参与Hg转化的特征与机制对人体健康和生态环境都有着重要的意义.已有不少研究报道了Hg的微生物转化过程,但缺乏一个系统的总结与归纳.本文综述了关于Hg微生物甲基化、去甲基化、还原和氧化的最新研究进展,重点讨论Hg甲基化微生物类群,分析了微生物对Hg的甲基化和还原机制,以及影响Hg甲基化过程的主要环境因子,并提出未来关于Hg微生物转化的研究方向与重点.     

Human hair mercury levels in the Wanshan mercury mining area,Guizhou Province,China

The total mercury (T-Hg) and methyl mercury (Me-Hg) concentrations in the hair were measured to evaluate mercury (Hg) exposure for the residents in Da-shui-xi Village (DSX) and Xia-chang-xi Village (XCX) in the Wanshan Hg mining area, Guizhou Province, Southwestern China. The mean concentrations in the hair of DSX residents were 5.5 ± 2.7 μg/g and 1.9 ± 0.9 μg/g for T-Hg and Me-Hg, respectively. The concentrations in the hair of XCX residents were 3.3 ± 1.4 μg/g and 1.2 ± 0.5 μg/g for T-Hg and Me-Hg, respectively. Hair Me-Hg concentrations were significantly correlated to T-Hg (r = 0.42, P < 0.01) in the two sites; on average, hair Me-Hg concentration accounted for 40 and 44% of T-Hg for DSX and XCX residents, respectively. Age has no obvious correlation with hair Hg and the hair Hg levels showed a significant gender difference, with higher T-Hg and Me-Hg concentrations in the hair from males than females. The rice collected from the two sites showed high levels of T-Hg and Me-Hg concentration. The results indicated a certain Hg exposure for the residents in DSX and XCX in the Wanshan Hg mining area.     

Quantification and fractionation of mercury in soils from the Chatian mercury mining deposit,southwestern China

Contents of total Hg and Hg fraction, organic matter, pH, grain size and chemical composition were measured to investigate the pollution characteristics and binding behavior of Hg in soils collected from the Chatian Hg mining deposit (CMD), southwestern China. The average concentration of Hg concentration in the CMD soils was 155 and 1,315 times higher than that in control soils and Chinese soils, respectively, suggesting that the CMD soils were heavily contaminated by the element. The finding was confirmed by Müller geoaccumulation index assessment with 75% very seriously polluted, 6.25% highly to very highly polluted and 18.75% moderately to highly polluted. Hg sources in the region were natural and anthropogenic: in addition to the pedogenic process and original geochemical situation, human mining–refining activities have also seriously impacted the redistribution of Hg in soils, especially in paddy soils. Based on the BCR protocol, soil Hg was divided into exchangeable (EXC), amorphous Fe–Mn oxides (AFe–MnOX), organic-crystalline iron oxides (OM-CFe) and residual (RES) fraction. The average percentage of the four fractions in the CMD followed the trend: RES (85.77%) > OM-CFe (12.44%) > AFe–MnOX (0.93%) ≥ EXC (0.86%), suggesting that the majority proportion of soil Hg in the study area remained of residual form inside the soil mineral matrix. However, their concentrations and percentages significantly varied among different locations and land use types. Soil physico-chemical parameters were key factors affecting the presence of Hg fraction. Generally, Hg fraction concentrations were positively correlated with the sand contents and soil pH values, which was presumably due to the basic anthropogenic input of Hg-containing materials and their similarity to sand in physical characteristics. However, organic matter caused adsorption–fixation and reduction–volatilization to coexist, which had opposite effects on Hg concentrations in soil, consequently exhibiting its dual nature.     

Environmental contamination and risk assessment of mercury from a historic mercury mine located in southwestern China

A field survey of mercury pollution in environmental media and human hair samples obtained from residents living in the area surrounding the Chatian mercury mine (CMM) of southwestern China was conducted to evaluate the health risks of mercury to local residents. The results showed that mine waste, and tailings in particular, contained high levels of mercury and that the maximum mercury concentration was 88.50 μg g^?1. Elevated mercury levels were also found in local surface water, paddy soil, and paddy grain, which may cause severe health problems. The mercury concentration of hair samples from the inhabitants of the CMM exceeded 1.0 μg g^?1, which is the limit recommended by the US EPA. Mercury concentrations in paddy soil were positively correlated with mercury concentrations in paddy roots, stalks, and paddy grains, which suggested that paddy soil was the major source of mercury in paddy plant tissue. The average daily dose (ADD) of mercury for local adults and preschool children via oral exposure reached 0.241 and 0.624 μg kg^?1 body weight per day, respectively, which is approaching or exceeds the provisional tolerable daily intake. Among the three oral exposure routes, the greatest contributor to the ADD of mercury was the ingestion of rice grain. Open-stacked mine tailings have resulted in heavy mercury contamination in the surrounding soil, and the depth of appreciable soil mercury concentrations exceeded 100 cm.     

Atmospheric mercury at mediterranean coastal stations

Mercury in air has been measured at five coastal Mediterranean sites, involving measurements in Spain, France, Italy, Slovenia and Israel. Four two-weeks long measurements campaigns were performed at the five sites. The measurements were carried out during autumn 2003 and winter, spring and summer 2004. Total gaseous mercury/elemental gaseous mercury, particulate mercury and divalent gaseous mercury were measured in parallel at the five sites. The activities constituted a subtask of the EU funded MERCYMS research project, which also included Mediterranean Sea cruises where both mercury in air and water were measured. The result from an evaluation of all the coastal air data is presented. Mercury concentrations from the different sites are compared with similar data obtained in northern Europe and elsewhere. The result shows that the background concentration of mercury in Mediterranean coastal air is lower than earlier anticipated. Background concentrations of TGM, RGM and TPM corresponded to 1.75–1.80 ng m⁻³, 1–13 and 3–23 pg m⁻³, respectively. The measurements also showed that the mercury concentration occasionally can be very high in some areas due to local anthropogenic emissions. It is proposed that diurnal variation in RGM concentrations observed during situation with nocturnal inversion merely is an effect of meteorology rather than due to local photochemistry.     

断裂带中汞的地球化学特征

汞是揭示构造活动及强震孕育机制的重要化学示踪元素.研究断裂带中汞及其同位素,可以示踪地震断裂带汞异常来源、汞的迁移路径,从而揭示流体在地震孕育中的作用.本文总结了汞的观测技术,断裂带岩石、土壤和地下水中汞的特征,概述了汞同位素技术在深部断裂带研究中的进展,以及汞在地震监测和活断层探测方面的应用.断裂带中汞的研究,将有助于厘清汞-深部流体-构造活动-地震的可能关系及其机制,对提升汞在地震监测预测中的研究水平具有重要的理论意义和应用价值.     

Removal of elemental mercury by KI-impregnated clay

This study described the use of clay impregnated by KI in gas phase elemental mercury (Hg^o) removal in flue gas. The effects of KI loading, temperature, O₂, SO₂ and H₂O on Hg^o removal were investigated using a fixed bed reactor. The Hg^o removal efficiency of KI-clay with 3% KI loading could maintain at a high level (approximately 80 %) after 3 h. The KI-clay demonstrated to be a potential adsorbent for Hg^o removal when compared with activated carbon based adsorbent. O₂ was found to be an important factor in improving the Hg^o removal. O₂ was demonstrated to assist the transfer of KI to I₂ on the surface of KI-clay, which could react with Hg^o directly. NO and SO₂ could slightly improve Hg^o removal, while H₂O inhibited it greatly. The results indicated that after adsorption, most of the mercury escaped from the surface again. Some of the mercury may have been oxidized as it left the surface. The results demonstrated that the chemical reaction primarily occurred between KI and mercury on the surface of the KI-clay.     

Speciation of mercury in South African coals

Total mercury (Hg_TOT) concentrations were determined by inductively coupled plasma mass spectrometry (ICP MS) for South African Highveld coals. The distribution of Hg in coals was investigated using a four-stage sequential leaching protocol and isotope dilution/gas chromatography coupled to ICP MS (ID-GC-ICP MS). The results show that Hg_TOT ranged from 144 to 303?µg?kg^?1 with a mean of 199?±?26?µg?kg^?1, while Hg_TOT leached from coals using different solvents ranged between 103 and 310?µg?kg^?1 (mean: 218?±?60?µg?kg^?1). Hg leaching rates of 53–78% were achieved in crushed coals. Hg⁰, Hg²⁺, and CH₃Hg⁺ were identified in all coals. CH₃Hg⁺ in studied coals ranged between 0.1 and 0.4 (mean: 0.2) µg?kg^?1. GC ICP MS chromatograms also showed unknown Hg peaks which were identified as other organomercury species such as ethylmercury. Modes of occurrence of Hg in coals were variable with the organic-bound (37–40%) and the sulfide-bound (37–39%) being the dominant mercury forms. Increasing the HCl concentration in the used protocol increased the amount of Hg leached (16%) during this step.     

类芬顿试剂吸收去除气态元素汞

实验初步研究了类芬顿试剂为吸收剂对气态元素汞的脱除性能,考察了铁盐种类、pH、初始汞浓度、反应温度、卤素离子、甲酸添加量等因素对类芬顿试剂脱除气态元素汞性能的影响.结果表明,在pH 3.5条件下,以氯化铁为催化剂时,气态元素汞的脱除效率为76.4%;添加250μg.mL-1Cl-、150μg.mL-1Br-或5.0μg.mL-1甲酸均可以显著提高类芬顿反应体系对气态元素汞的脱除效果,最高脱除效率可达95%以上.     

Source attribution for mercury deposition with an updated atmospheric mercury emission inventory in the Pearl River Delta Region,China

Estimated anthropogenic Hg emission was 11.9 tons in Pearl River Delta for 2014. Quantifying contributions of emission sources helps to provide control strategies. More attentions should be paid to Hg deposition around the large point sources. Power plant, industrial source and waste incinerator were priorities for control. A coordinated regional Hg emission control was important for controlling pollution. We used CMAQ-Hg to simulate mercury pollution and identify main sources in the Pearl River Delta (PRD) with updated local emission inventory and latest regional and global emissions. The total anthropogenic mercury emissions in the PRD for 2014 were 11,939.6 kg. Power plants and industrial boilers were dominant sectors, responsible for 29.4 and 22.7%. We first compared model predictions and observations and the results showed a good performance. Then five scenarios with power plants (PP), municipal solid waste incineration (MSWI), industrial point sources (IP), natural sources (NAT), and boundary conditions (BCs) zeroed out separately were simulated and compared with the base case. BCs was responsible for over 30% of annual average mercury concentration and total deposition while NAT contributed around 15%. Among the anthropogenic sources, IP (22.9%) was dominant with a contribution over 20.0% and PP (18.9%) and MSWI (11.2%) ranked second and third. Results also showed that power plants were the most important emission sources in the central PRD, where the ultra-low emission for thermal power units need to be strengthened. In the northern and western PRD, cement and metal productions were priorities for mercury control. The fast growth of municipal solid waste incineration were also a key factor in the core areas. In addition, a coordinated regional mercury emission control was important for effectively controlling pollution. In the future, mercury emissions will decrease as control measures are strengthened, more attention should be paid to mercury deposition around the large point sources as high levels of pollution are observed.     

施肥及种植作物对汞污染土壤中微生物生态的修复

以中性紫色土为材料，通过向土壤添加氯化汞的模拟培养试验、施肥试验以及作物栽培试验，研究了汞对土壤中微生物区系和重要微生物生理群繁育的毒害效应。结果表明，向土壤中添加HgCl2，总体上抑制了细菌、真菌、放线菌及氨化细菌的繁育，硝化细菌、自生固氮菌、纤维素降解菌在一定质量分数范围内被汞刺激增长，在另一定质量分数段则被汞抑制。施肥和栽种作物削弱了汞对微生物的毒害，使土壤微生物生态得到一定程度的修复，说明利用农业措施修复汞污染的土壤是可行的。栽种作物时，汞对微生物的抑制效应受到掩蔽，作物产量和植株体内汞含量是汞污染程度的良好指标。以微生物和植物对汞污染的反应，基本一致的HgCl2危害质量分数指标是5mg．kg^-1。