城镇区土壤中Hg环境地球化学异常查证及评价新思路

城镇区重金属元素异常查证及评价是目前开展的平原区多目标地球化学调查工作中亟待解决的问题.在Hg环境地球化学异常查证及评价研究中发现,在城镇及其周边土壤Hg异常内普遍存在着辰砂,而且辰砂的产出位置与Hg异常的空间分布位置基本吻合.该成果为Hg异常查证及其生态效应评价等提供了新的思路.     

平原区城市及周边Hg异常土壤中辰砂的发现及其特征

在我国东部平原区城市及其周边土壤Hg异常查证过程中首次发现辰砂，对其矿物学特征进行了研究，并就辰砂分布与土壤Hg异常的空间对应关系、辰砂的含量与Hg异常土壤中Hg含量间的相关性等问题进行了探讨。结果表明，辰砂是Hg异常土壤中Hg的一种主要存在形式。这一发现对研究和评价Hg异常土壤的生态环境效应具有重要的理论和实用价值。     

城镇及其周边土壤重金属元素异常成因机理

普遍出现在城镇及其周边地区土壤中的重金属元素异常受到广泛关注,但是目前对此类异常的生态危害还没有明确的结论,原因之一是对异常的成因机理缺乏深入研究和客观认识。这里研究结果发现,城镇周边地区的土壤重金属元素异常,与燃煤(或金属矿石选冶)过程中释放出的“微球粒“物质和黄铁矿、磁铁矿等重矿物具有成因联系,因此为确认此类异常的成因机理提供了证据,对异常的生态效应评价以及预警预测研究具有直接意义。     

北京市土壤Hg污染的区域生态地球化学评价

城市土壤Hg异常/污染是中国普遍存在的重大生态环境问题。文章对北京市近1000km2范围内的地表土壤、壤中气、大气干湿沉降、大气颗粒物、大气中的Hg含量水平和空间分布模式进行了系统研究,查明北京地表土壤Hg平均含量为0.41mg/kg,大气干湿沉降物中的Hg平均含量为0.194mg/kg,壤中气Hg的平均含量为559.65ng/m3,大气颗粒物PM10和PM2.5中的Hg含量分别为0.59和0.67ng/m3,大气中的Hg平均含量为3.13ng/m3。北京市自2000年起实现了由燃煤转变为燃气的减排措施,导致干湿沉降物中的Hg沉降通量显著减少,2006年大气干湿沉降物中Hg的沉降通量1.837mg·m-2·a-1,北京市城区(近1000km2)Hg全年沉降为1837kg,空气中总Hg浓度由1998年的8.3~24.7ng/m3下降到2006年的3.13ng/m3,大气颗粒物中Hg含量由2003年的1.18ng/m3下降到2006年的0.59ng/m3(PM10)和0.67ng/m3(PM2.5),表明北京市煤改气减排措施的实施显著改善了大气环境质量。通过对土壤中Hg的存在形式研究,发现土壤中有硫化物(辰砂)及各种Hg盐(HgCl2)的含Hg矿物,Hg也可以各种吸附方式或壤中气方式存在。研究证实北京壤中气Hg与大气Hg存在显著的相关性(n=131,R=0.267,p<0.01),表明壤中气Hg是大气Hg的重要来源之一。利用2005年地表土壤总Hg与Hg释放速率的线性方程估算,土壤Hg平均释放速率为102.42ng·m-2·h-1,2005年土壤释放进大气的Hg通量为936.70kg。在查明土壤中存在大量辰砂矿物的同时,还分布有大量具有高温熔融特征的金属微球粒和玻璃质微球粒,证明燃煤和冶金烟尘是地表土壤Hg的主要来源。土壤中Hg、S、pH和辰砂颗粒浓度在空间上的高度耦合性表明,碱性条件下,土壤中高含量的S和Hg是辰砂形成的重要原因。按国家土壤环境质量标准,北京市I级土壤Hg环境质量的面积为176km2,Ⅱ级为808km2,Ⅲ级为24km2,超Ⅲ为36km2。Ⅲ级、超Ⅲ级主要分布在二环路以内的中心城区。城南(长安街为界)大气Hg环境质量明显优于城北,在北四、北五环之间的部分地区,大气颗粒Hg的环境质量为Ⅲ级或超Ⅲ级。在地表土壤Hg含量较高的中心城区,居民每天因呼吸摄入的Hg高达364ng,对人体健康构成潜在风险。根据我国"十一五"规划中每年实现10%节能减排的目标,对北京市未来50年土壤Hg含量的时空演变趋势预测,预测2050年北京因干湿沉降带来的Hg输入量为16.03kg,地表土壤释放Hg的输出量为37.36kg,明显大于Hg的输入通量,土壤Hg的环境质量将得到根本改善。预测到2040年Ⅲ级土壤Hg环境质量的区域将完全消失,到2060年以Ⅰ级土壤为主。     

城市汞污染土壤中Hg的形态特征

介绍了我国13个城市及其周边地区汞污染土壤中汞的形态特征研究成果。通过对汞污染土壤化学分析、形态分析、热释汞研究、重矿物研究发现,我国城市汞污染土壤中HgS是Hg的主要存在形态,13城市汞污染土壤重矿物研究中辰砂的大量出现及其含量与分布特征也进一步佐证了这一结论。汞污染土壤中汞污染程度越高,HgS含量越高,辰砂出现几率越大,且含量越高。该成果对我国汞污染调查研究和汞污染土壤生态地球化学环境评价具有重要的理论价值和实际意义。     

苏州西部土壤汞分布特征及成因

在收集以往自然重砂测量、土壤测量资料的基础上,结合1∶5万土壤地球化学调查,进行苏州西部土壤中汞的分布特征及成因解析。结果表明,研究区土壤中Hg含量变化范围较大,介于0.023～5.012 mg/kg之间,平均值高达0.386 mg/kg,远高于苏州地区表层土壤及太湖水网平原表层土壤Hg含量平均值,土壤汞污染比较严重。区内辰砂矿物与土壤中Hg的空间分布具有较高的耦合性,与区内断裂构造、矿床分布有关,表明区内土壤中的汞、辰砂分布是多金属矿成生作用的产物,人类活动的影响不大。     

我国平原区土壤地球化学异常成因研究

我国平原地区土壤地球化学异常普遍存在,但是目前对这些异常的成因缺乏系统认识。这里以长春和南京地区的Hg、Cd异常试验研究结果为例,利用元素相关关系法,对此进行了系统研究。结果表明,城镇及其周边地区的土壤地球化学异常,异常组分叠加量表现出表层累积型特点,此类异常的成因与人类活动有关。分布在河流沿岸的土壤地球化学异常,在垂向上,异常组分叠加量表现出了连续型分布特点,且异常组分含量主要受土壤物质组成的控制,此类异常是在河流沉积物自然沉积过程中形成的。     

城镇周边和江河沿岸土壤中Hg和Cd存在形式解析与生态风险评估

受人类活动和自然作用双重影响,土壤中重金属元素异常普遍存在,其中尤以城镇周边的Hg异常和大江河沿岸区域Cd异常最为典型。近年来,通常采用化学分步提取的方式,探讨土壤水溶态、离子交换态、有机态、铁锰氧化物态等形态中Hg、Cd等重金属元素含量的状况,进而分析其生态效应,但对土壤中Hg、Cd等重金属元素的自然存在形式缺乏深入探讨。本文以Hg、Cd两元素为重点,选择我国代表性城市和地区,采集城镇周边Hg异常区和江河沿岸Cd异常区的土壤样品,采用王水溶样原子荧光光谱法(AFS)测定Hg含量,采用盐酸-硝酸-氢氟酸-高氯酸溶样电感耦合等离子体质谱法(ICP-MS)测定Cd含量,同时配合其他相关实验手段,对Hg、Cd的自然存在形式进行解析;并以水稻中Hg、Cd含量为依据对Hg、Cd的生态效应进行了评价。结果表明:长春、南京、漳州和广州等城镇周边土壤Hg异常区Hg主体以硫化物形式存在,而且至少有一部分是以辰砂矿物形式存在,由此决定了土壤中Hg有效态在Hg全量中所占比例较小,土壤中Hg平均含量达到500μg/kg时,水稻籽实中Hg含量超过无公害食品标准的比例为3.4%,生态效应不甚敏感;长江、珠江等江河沿岸区域Cd异常区内Cd主要呈黏土吸附形式存在,由此导致50%左右的Cd以有效态形式存在,在土壤Cd全量中所占比例较大,当土壤中Cd平均含量达到1000μg/kg时,水稻籽实中Cd含量超过无公害食品标准的比例为43%,生态效应敏感。由此揭示出土壤中Hg、Cd等重金属元素生态效应敏感程度更直接地受到自然存在形式的影响。以辰砂矿物形式存在的Hg呈现"惰性",不容易被农作物吸收,故生态效应不敏感;以黏土矿物吸附形式存在的Cd活动性更强,容易被农作物吸收,故生态效应敏感。Hg、Cd等重金属元素被农作物乃至人体吸收后,其存在形式及其转化特性是评估该元素是否存在生态风险的关键。     

贵州玉屏县土壤Hg、Cd元素异常查证方法及其成因分析

通过贵州省玉屏县耕地质量地球化学调查评价工作,发现该县部分区域耕地土壤中Hg、Cd元素含量超过国家土壤环境质量三级标准值,达到严格管控范围,出现高值异常,分别形成汞、镉两个异常区。进一步查清异常区特征及其异常源,对该区土壤质量的评价和农业种植结构调整具有实际指导意义。本文采用横向剖面法、垂向剖面法、地质剖面法等三种方法相结合开展异常查证及成因分析。经综合分析得知:汞异常区位于北东向新晃-玉屏深大断裂带上及其附近,异常源为区内的汞矿化点,其经强风化成土后残留原地或有较小的迁移而形成汞异常。镉异常区位于近东西向太阳山断层附近,其异常源为寒武系下统"黑色岩系"地层和区内铅锌矿化点,其"黑色岩系"地层中富含Cd元素和铅锌矿化点中伴生的镉矿物是引起镉异常的直接因素。     

城镇地区土壤中汞的累加量及其存在形式

以长春、南京的土壤汞异常和东营研究区的区域地球化学调查资料为例,采用元素相关关系法首先确定土壤中汞的基准值,在此基础上确定汞的累加量,取得了满意的结果。进一步的研究结果表明,汞的累加与土壤中出现的辰砂具有一定关系。     

Distribution and speciation of mercury in soil in the area of an ancient mercury ore roasting site,Frbejžene trate (Idrija area,Slovenia)

In the initial period of mining activities in the Idrija basin (the16^th and the first half of the17^th centuries), Hg ore processing was performed at various small-scale roasting sites in the woods surrounding Idrija, by roasting ore in earthen vessels. The recovery rate of this method was very low; about half of Hg was lost, causing soil contamination and considerable amounts of waste material that could potentially leach Hg into the surrounding environment. The main aims of present geochemical study were to determine the contents, vertical distribution and speciation of Hg in soils at the roasting site at Frbej?ene trate in order to verify the extreme pollution of ancient Hg ore roasting sites in the Idrija area and to establish their significance in the wider spatial contamination of soils and aquatic systems. Soil sampling was performed at the area of the former roasting site. The organic matter-rich surface soil layer (SOM) and underlying mineral soil were sampled at 63 sampling locations. Mercury speciation was performed using Hg thermo-desorption-AAS to distinguish cinnabar from potentially bioavailable forms. The results indicate extremely high Hg concentrations with a maximum of 37,000 mg/kg in SOM and 19,900 mg/kg in mineral soil. The established Hg median in soil was 370 mg/kg and in SOM 96.3 mg/kg. Spatial distributions of Hg in SOM and soil showed very high Hg contents in the central area and decreased rapidly with distance. The results of Hg thermo-desorption measurements indicated the presence of cinnabar (HgS) and Hg bound to organic or mineral soil matter. A significant portion (35–40%) of Hg in the investigated soil and SOM samples was comprised of non-cinnabar compounds, which are potentially bioavailable. It has been shown that soils contain high amounts of potentially transformable non-cinnabar Hg, which is available for surface leaching and runoff into the surrounding environment. Therefore, contaminated soils and roasted residues at the studied area are important for persistent Hg release into the aquatic ecosystem.     

Discovery of Cinnabar in Soils in Hg Anomalous Zones in City and Town Areas and Their Surroundings and Its Significance

As a result of systematic study on heavy minerals in soils at city and town areas and their surroundings,cinnabar was discovered for the first time in areas of Hg anomalies in China, and it was found that the distribution of cinnabar was basically coincident in scope with that of Hg anomalies, showing that Hg anomalies were‘closely related to cinnabar. This finding provides a theoretical basis for a verification of Hg anomalies in soils in city and town areas and their surroundings, as well as evaluation of its ecological effects, and is significant to revealing the occurrence modes and origin of Hg in soils.     

土壤中Hg离子地球化学行为模拟实验 ——以山西的典型土壤为例

土壤样品分别采于山西省大同、太原和临汾3个地区。实验分成吸附解吸实验和运移实验2个部分。其中吸附实验分成砂粒土壤和粘粒土壤2个粒级分别进行。结果表明：3种土壤对Hg的吸附量随着加入Hg离子溶液浓度的增加而增加。用4种吸附模式来拟合3种土样对Hg的吸附可以得出,Freundlich模式和Langmuir模式能较好地拟合3种土壤对Hg吸附的实验数据。3种土壤对Hg都有一定的吸持固定作用。解吸率由大到小依次为大同土壤〉临汾土壤〉太原土壤。当Hg^2＋的浓度为300mg/L时,Hg在大同土壤中的穿透速率最快,在太原土壤中穿透速率最慢。从而得出Hg^2＋在壤质砂土中运移速度最快、在粉壤土中运移速度最慢的结论。     

Environmental impact of ancient small-scale mercury ore processing at Pšenk on soil (Idrija area, Slovenia)

The Idrija mine was the second largest Hg mine in the world surpassed only by the Almaden mine in Spain. It has been estimated that almost 145,000 tons of Hg was produced during operation (1490-1995) of the mine. In the first decade of Hg mining in Idrija the ore was roasted in piles; after that it was roasted for 150 years, until 1652, in earthen vessels at various sites in the woods around Idrija. Pšenk is one out of 21 localities of ancient roasting sites established on the hills surrounding Idrija and one of the largest localities of roasting vessel fragments. The unique way of roasting very rich Hg ore at this site has resulted in soil contamination and considerable amounts of waste material that potentially leach Hg into the surrounding environment. The main aim of this study was to determine the distribution and the forms of Hg in contaminated soils in order to evaluate potential environmental risk. Detailed soil sampling was performed on 37,800 m² area to establish the extent of Hg pollution and to investigate Hg transformations and transport characteristics through the 400 a-long period. A total of 156 soil (0-15 cm and 15-30 cm) and SOM (soil organic matter) samples were collected from 73 sampling points. Three soil profiles were sampled to determine vertical distribution of Hg. The main Hg phases were determined by the Hg-thermo-desorption technique. The measured Hg contents in soil samples in the study area vary from 5.5 to almost 9000 mg/kg with a median of 200 mg/kg. In SOM, Hg contents range from 1.4 to 4200 mg/kg with a median of 20 mg/kg. Extremely high Hg contents were found in soil profiles where the metal reaches 37,020 mg/kg. In general, Hg concentrations in all three profiles show a gradual decrease with depth with the minimum values between 140 mg/kg and 1080 mg/kg. The Hg-thermo-desorption curves indicate the presence of Hg in the form of cinnabar and that of Hg bound to organic or mineral soil matter. The distribution of Hg species in soil and SOM samples show almost equal distribution of cinnabar and non-cinnabar Hg compounds. The non-cinnabar fraction shows a little increase with depth, but cinnabar represents a high portion of total Hg (about 40%). Large amounts of potentially mobile and transformable non-cinnabar Hg compounds exist at the roasting site, which are potentially bioavailable.     

Physical partitioning of mercury in till: an example from central British Columbia, Canada

The physical partitioning of Hg into different grain size fractions of till is predominantly controlled by the primary bedrock mineralogy, the distance of glacial transport, and the relative stability of cinnabar (HgS) in the soil weathering environment. At sites located short distances down-ice from bedrock cinnabar mineralization, the highest Hg concentrations in unoxidized till were measured in the sand- and granule-sized fractions reflecting the abundance of cinnabar in those size ranges. Similar partitioning was measured in oxidized till as cinnabar was found to be relatively resistant to postglacial weathering. Discrete clay-sized cinnabar grains obtained from the unoxidized till were viewed under the scanning electron microscope and suggest that the terminal grade of cinnabar is in the clay-sized range. In till collected from areas barren of cinnabar mineralization, the highest Hg levels were found in the clay-sized fraction which is attributed to the high adsorption of Hg by clay minerals.