土壤中汞存在形式的研究

本文运用部分连续萃取不同地球化学相的化学分析方法，对高汞区，人为汞污染区和背景参考区五个采样点土壤样品的七种汞形态进行了分析，研究表明，人为汞污染和地质作用都会造成土壤中汞的富集，但这两类土壤中汞的相态分布有明显的差别。     

Farmland mercury contamination in the vicinity of an organic chemical factory in Guizhou,China

This study assesses the level of contamination of Hg in farmland soils along the irrigating channel downstream from Guizhou Organic Chemical Factory （GOCF）, where metallic mercury is used as a catalyst to produce acetic acid. The total input of mercury into the environment, as announced by GOCF, is 140 t in the past 30 years （1971-2000）. Sampling sites were chosen based on the distance from the source of pollution--the chemical factory. A total of 39 samples were collected from the study area and analyzed for total mercury concentrations and methyl mercury concentrations. The characteristics of vertical and horizontal distributions of total mercury and methyl mercury in the study area （farmland） are described in this paper. Much attention was paid to the transformation of inorganic Hg into organic mercury species in soils as well. The results showed that the farmland has been heavily contaminated by Hg. Land cultivation activity, land utilization style and distance from the pollution source could be the dominant factors controlling the distribution of THg and MeHg. It is observed that active transformation of inorganic Hg into organic mercury species （MeHg） usually takes place in paddy soils.     

贵州万山汞矿区稻田土壤汞的分布及污染特征

受历史汞矿开采活动影响,万山汞矿区稻田遭受了严重的汞污染。为了查明万山汞矿区稻田土壤的汞污染现状以及评估其环境质量改善情况,系统采集了受汞矿区影响的五条主干河流沿岸稻田土壤进行汞含量分析,评价总汞和甲基汞污染程度及其生态风险,并与2008年以来该区域稻田土壤汞数据进行对比。结果表明,研究区稻田土壤的总汞含量为0.21~207 mg/kg,几何平均值为(4.26±4.83)mg/kg;甲基汞含量为0.42~13μg/kg,几何平均值为(1.81±1.93)μg/kg。59%的稻田土壤处于重度汞污染,75%的稻田土壤存在极强的汞潜在生态风险。与已往数据相比,稻田土壤汞含量在2012年后呈下降趋势,基本反映了当地汞防治措施的执行效果。为了避免稻田土壤汞污染引起的安全健康风险,今后应采取除污染源治理以外的土壤修复措施或风险管控措施。     

陕西潼关金矿区农田土壤Hg污染的环境效应

以潼关金矿区农田土壤Hg污染区的小麦、蔬菜、水果中的Hg含量为重点研究对象,与尚未污染的农田土壤区进行对比,研究土壤Hg污染的农作物效应.评价区小麦样本Hg的超标率为78.57%,小麦Hg超标与土壤Hg污染的关系明显.评价区萝卜样本超标率为40%,叶菜、西红柿、苹果、红薯中样本超标率均为100%,对照区果蔬类也全部超标,但明显低于评价区.评价区农作物Hg超标倍数从大到小依次为:青菜＞油麦菜＞萝卜叶＞西红柿＞苹果＞红薯＞小麦＞萝卜.土壤Hg污染的环境效应极为严重,矿区环境污染防治刻不容缓.     

湖南洞庭湖地区土壤中Hg的来源

Hg污染已成为全球性的环境问题,尤其是Hg对土壤的污染,因其具有隐蔽性、不可逆性和长期性的特点,对陆生生态系统构成潜在的巨大威胁,因此查明土壤中Hg的来源非常重要。运用生态地球化学填图的指导思想,对湖南洞庭湖地区土壤剖面分析和成土过程研究后发现,表层土壤中Hg含量的高低与成土母质中Hg的含量有很好的对应性,成土过程对土壤中Hg的含量也有显著的影响。     

江苏省土壤重金属分布特征与污染源初步研究

以24 186个表层土壤(0～20 cm)和6 127个深层土壤(150～200 cm)样品之Cd、Hg、Pb、As等含量数据为基础,研究了江苏全省土壤环境的重金属分布与主要污染特征.结果表明.全省自然土壤环境与人为活动土壤环境的重金属元素分布都不均匀,但人为活动土壤环境中的不均衡程度远高于自然土壤环境:全省农田中有1.02%的土壤受到Cd、Hg、Pb等8种重金属的严重污染,苏州市、无锡市土壤环境被重金属污染的程度相对严重;工业化、城市化进程中的人为活动及自然地质作用都是引起江苏局部土壤重金属污染的重要原因,自然成因的重金属污染土壤多呈面状、多元素、低强度、双层污染等特点,从而与人为成因的重金属污染土壤有所区别.     

福建沿海地区表层土壤矿物分布特征及地质和环境意义

对福建沿海地区表层土壤矿物组分、含量、组合以及分布特征进行了分析研究。结果表明,不同地质背景形成的土壤其重矿物组成具有复杂性、一致性和差异性;不同的土壤类型其矿物组合可以较好地反映土壤与成土母岩的内在成因关系;不同沉积环境下形成的土壤矿物组成受外力影响具有一定的分选性;平原区土壤中汞、砷等元素的区域性高异常则与土壤中辰砂、雄黄矿物存在有关。     

中国汞的地球化学空间分布特征

20世纪80年代以来中国积累了岩石、土壤和水系沉积物中的大量可靠的汞分析数据和图件,为分析汞的地球化学空间分布特征提供了依据.从空间分布上看,从中国北部到南部,从西部到东部,土壤和水系沉积物中汞的含量背景值逐渐增高,汞在以干旱荒漠区、半干旱荒漠区、黄土地区和高寒山区为主的西部和北部呈低背景,在东部的森林沼泽区和半湿润低山丘陵区为中等背景,在南部的湿润低山丘陵区、热带雨林区和高山峡谷区为高背景,尤其在以云南东南部、贵州、广西西部、湖南西部岩溶区为中心的低温成矿域内,无论岩石、土壤还是水系沉积物,汞含量背景值达到最高.一般情况下,岩石、土壤和水系沉积物之间的汞含量具有继承性,在地理空间分布上呈明显的对栽应关系,并且土壤和水系沉积物之间的汞含量具有相近性,土壤和水系沉积物较岩石更为富集汞.     

Review: evaporation of mercury from soils. An integration and synthesis of current knowledge

 Understanding the mechanisms of mercury evaporation from soil to the atmosphere is necessary for tracing the fate of mercury in the biological environment and for assessing potential health effects and the impact of anthropogenic mercury emissions on the environment. In this article an integrating overview of the current knowledge of the mechanisms of mercury evaporation is presented. Abiological and biological formation of Hg(0) and/or (CH₃)₂Hg in the uppermost soil layers are the rate limiting processes of mercury evaporation from soils in background areas; the evaporation rate in background areas is probably strongly influenced by deposited airborne mercury. The evaporation rate limiting factors in mercury enriched mineralized areas with large fractions of total mercury being volatile mercury species (relative to background soil in the non-mineralized vicinity) meteorological variations and the transport characteristics of soils for volatile mercury species. Mercury evaporation rates from background soils are usually <0.2 μg·m^–2·h^–1 and significantly smaller than from mercury-enriched mineralized areas. Received: 20 November 1995 / Accepted: 24 July 1996     

Mercury mobility and bioavailability in soil from contaminated area

The mobility and bioavailability of mercury in the soil from the area near a plant using elemental mercury for manufacturing thermometers, areometers, glass energy switches and other articles made of technical glass has been evaluated. Mercury has been determined by sequential extraction method and with additional thermo desorption stage to determine elemental mercury. The procedure of sequential extraction involves five subsequent stages performed with the solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH and aqua regia. The mean concentration of total mercury in soil was 147 ± 107 μg g⁻¹ dry mass (range 62–393), and the fractionation revealed that mercury was mainly bound to sulfides 56 ± 8% (range 45–66), one of the most biounavailable and immobile species of mercury in the environment. The fractions that brought lower contribution to the total mercury content were semi-mobile humic matter 22 ± 9% (range 11–34) and elemental mercury 17 ± 5% (range 8–23). The contributions brought by the highly mobile and toxic organomercury compounds were still lower 2.3 ± 2.7% (range 0.01–6.5). The lowest contributions brought the acid-soluble mercury 1.5 ± 1.3% (range 0.1–3.5) and water-soluble mercury 1.0 ± 0.3% (range 0.6–1.7). The surface layer of soil (0–20 cm) was characterized by higher mercury concentrations than that of the subsurface soil (60–80 cm), but the fractional contributions were comparable. The comparison of mercury fractionation results obtained in this study for highly polluted soils with results of fractionation of uncontaminated or moderately contaminated samples of soil and sediments had not shown significant statistical differences; however, in the last samples elemental mercury is usually present at very low concentrations. On the basis of obtained correlation coefficients it seems that elemental mercury soils from “Areometer” plant are contaminated; the main transformation is its vaporization to atmosphere and oxidation to divalent mercury, probably mainly mediated by organic matter, and next bound to humic matter and sulfides.     

广州市黄埔港区土壤中汞的形态分析及分布特征

采用化学浸提技术对广州市黄埔港区土壤中的汞进行形态分析,通过实验确定了可交换态汞(包括水溶性汞)、盐酸溶汞、元素汞、腐殖酸结合态汞、有机质结合态汞、硫化汞、残渣态汞的浸提条件,探讨了各种形态汞在表层及总量在垂直方向上的分布特征。分析结果表明,广州市黄埔港区土壤中汞以比较稳定的形态存在,活动态约占6%。总汞含量随深度增加而降低,总汞在垂直方向中的含量差异在一定程度上反映出汞受人为污染的影响情况。     

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。     

Mercury concentration in some calcareous soils of western Iran with a focus on pedological evolution and weathering process

The aim of this study was to evaluate total mercury concentration and its lithogenic and exogenic fractions in some calcareous soils of western Iran, where water contamination and bioaccumulation of mercury have been reported in the bottomland’s reservoir. In particular, we investigated soil physico-chemical properties and weathering conditions related to lithogenic and exogenic fractions of mercury for two groups of calcareous soils with a known comparative pedological evolution and weathering condition that was evident in the presence or absence of underlying layers of accumulated clay. Our results showed that the total mercury content of the studied soils ranged from 45.40 to 830.36 with a mean of 486.81 μg kg^?1. Furthermore, calculation of mercury fractions revealed that lithogenic and exogenic fractions vary slightly according to the three reference elements (Fe, U and Nb) used in the calculations for the two groups of studied soils. The results also illustrated that most of the mercury content is of exogenic origin; therefore, total mercury variations are closely related to the content of exogenic mercury, while the lithogenic fraction exhibited no relationship with total mercury concentration. Moreover, application of the weathering indexes of Parker and the CaO/ZrO₂ molar ratio supported the dependence of lithogenic mercury accumulation on weathering intensity in the studied calcareous soils. However, the significance of this relationship is stronger for more weathered calcareous soils; in such cases, fine-particle fractions are more developed, which encourages carrier phases such as organic materials and iron oxyhydroxides to become involved in more efficient fixation of mercury. Nevertheless, the formation of underlying layers of accumulated clay, i.e. argillic horizons, may restrain fixation of exogenic mercury by limiting its atmospheric input.     

Comparison of Methods for Determining Specific-surface Area of Fine-grained Soils

Characteristics of fine-grained soils primarily depend on their specific-surface area and hence, reliable determination of this parameter is essential. In this context, researchers have employed quite sophisticated instruments (viz., a BET surface area analyzer, the mercury intrusion porosimetry, internal reflectance spectroscopy, X-Ray diffraction and gas pycnometer etc.) and methodologies (viz., sorption of Methylene Blue dye, Ethylene Glycol Monoethyl Ether and p-Nitrophenol) to determine specific-surface area of these soils. However, most of these methodologies are found to be quite tedious, cost and time intensive. Apart from this, the results obtained are contentious due to the inherent limitations associated with either the instruments employed or the basic assumptions made for computing the specific-surface area of the soil. Hence, it becomes mandatory to evaluate the efficiency of these methodologies for determining specific-surface area of fine-grained soils. With this in view, different types of soils were considered in this study and their specific-surface area was determined, by following different methodologies, and the results were evaluated critically. In addition, attempts were made to develop relationships between the basic properties of fine-grained soils (viz., liquid limit, cation-exchange capacity, activity, and free swell index) and the specific-surface area. These relationships will be of immense help to the practicing engineers and research fraternity.     

Comparative analysis of heavy metal concentration in secondary treated wastewater irrigated soils cultivated by different crops

The use of treated urban wastewater for irrigation is a relatively recent innovation in Botswana and knowledge is still limited on its impact on soil heavy metal levels. The aim of this study is to analyze and compare heavy metal concentration in secondary wastewater irrigated soils being cultivated to different crops: olive, maize, spinach and tomato in the Glen Valley near Gaborone City, Botswana. The studied crop plots have been cultivated continuously under treated wastewater irrigation for at least 3 years. Most crop farms have sandy loam, loamy sand soils. Based on food and agriculture organization, heavy metal threshold values for crop production have been studied. Results showed that the wastewater irrigated soils in the Glen Valley have higher cadmium, nickel and copper than desirable levels, while the levels of mercury, lead and zinc are lower than the maximum threshold values recommended for crop production. The control sites show that the soils are naturally high in some of these heavy metals (e.g copper, zinc, nickel) and that crop cultivation under wastewater irrigation has actually lowered the heavy metal content. Comparing between the crops, mercury and cadmium levels are highest in soils under maize and decline linearly from maize to spinach to olive to tomato and control site. By contrast, concentrations of the other metals are at their lowest in maize and then increase from maize to spinach to olive to tomato and to control site.     

Importance of vegetation type for mercury sequestration in the northern Swedish mire, Rödmossamyran

Even if mires have proven to be relatively reliable archives over the temporal trends in atmospheric mercury deposition, there are large discrepancies between sites regarding the magnitude of the anthropogenic contribution to the global mercury cycle. A number of studies have also revealed significant differences in mercury accumulation within the same mire area. This raises the question of which factors, other than mercury deposition, affect the sequestration of this element in peat. One such factor could be vegetation type, which has the potential to affect both interception and retention of mercury. In order to assess how small-scale differences in vegetation type can affect mercury sequestration we sampled peat and living plants along three transects on a northern Swedish mire. The mire has two distinctly different vegetation types, the central part consists of an open area dominated by Sphagnum whereas the surrounding fen, in addition to Sphagnum mosses, has an understory of ericaceous shrubs and a sparse pine cover. A few main patterns can be observed in our data; (1) Both peat and Sphagnum-mosses have higher mercury content (both concentration and inventory) in the pine-covered fen compared to the open Sphagnum area (100% and 71% higher for peat and plants, respectively). These differences clearly exceed the 33% difference observed for lead-210, which is considered as a good analogue for atmospheric mercury deposition. (2) The differences in mercury concentration between peat profiles within a single vegetation type can largely be attributed to differences in peat decomposition. (3) When growing side by side in the open Sphagnum area, the moss species Sphagnum subsecundum has significantly higher mercury concentrations compared to S. centrale (24 ± 3 and 18 ± 2 ng Hg g⁻¹, respectively). Based on these observations we suggest that species composition, vegetation type and decomposition can affect the mercury sequestration in a peat record, and that any changes in these properties over time, or space, have the potential to modify the mercury deposition signal recorded in the peat.     

贵州省独山半坡锑矿地球化学特征及深部找矿预测

半坡锑矿床是典型的断裂控矿,热液充填型矿床.文章阐述了半坡锑矿区的水系沉积物、土壤及岩石地球化学特征,总结了半坡断层常微量元素及热释汞量的分布分配特点,研究了蚀变过程中元素的迁移、富集规律.从地物化条件探讨了深部找矿前景.     

A study of the soil geochemistry of the Platreef in the Bushveld Complex, South Africa

A study of the soil profiles in the central Transvaal showed that in most areas a thick top layer of transported soils is present. Since this transported horizon has moved for considerable distances and because mixing took place in the process, the use of soil geochemistry in the search for hidden ore bodies tends to yield erratic results. In the present investigation an attempt was made to use volatile elements such as Hg, As, S and C as CO₂ as geochemical indicator elements and to establish whether epigenetic haloes of these elements are imprinted on the transported soils. The geochemical behaviour of these elements are compared with elements such as Ni, Co, Cu and Fe, which would tend to migrate with the transported soil.The geochemical study was done on the Platreef in the Bushveld Complex, north of Potgietersrus. The Platreef consists of a stratified horizon which contains appreciable amounts of chalcopyrite, pyrrhotite, pentlandite and platinum-group elements. Four traverses across the ore body were investigated and the results indicate that in cases where the soil cover is relatively thin, approximately 1 to 2 metres, all the elements studied can be used to locate the ore body. Those traverses where the soil cover is thicker and where transported soils are definitely present, only mercury yields significant anomalies, while siderophile elements give erratic and poor results. The mercury anomalies are usually not displaced and even tend to delineate mineralized sub-zones of the Platreef.Arsenic, sulphur and carbon measured as total CO₂, also give erratic results in the cases where a thick soil cover is present. The fact that arsenic tends to be fixed relatively easily in soils, either in laterite particles or in surface limestone, apparently is the prime reason for its erratic behaviour. The results indicate that both S and C would yield unsatisfactory results if these elements are measured as total S and C in the soils. The use of gas species may be more successful.A surprising but consistent result, was the tendency for mercury to be concentrated in the soils above faults, which intersect the ore body at depth. The behaviour of mercury in soils taken along the strike of a fault indicated that a logarithmic relationship exists between the mercury concentration in the soil and the depth of the ore body.     

贵州喀斯特地区生态环境恶化的人为因素分析

贵州是喀斯特强烈发育的省区。由于人类活动的影响，近年来贵州喀斯特地区的生态环境出现了日益恶化的趋势，严重影响可持续发展甚至西部大开发战略的顺利实施。本阐述了喀斯地区生态环境恶化的现状，深入探讨了人为因素对喀斯特地区生态环境恶化的影响，为防止喀斯特地区生态环境进一步恶化提供科学依据。     

Mercury and mercury compounds in surface air, soil gas, soils and rocks

Secondary mercury dispersion haloes were detected and defined above sulphide mineralization by in-situ mercury in soil gas measurements. The meteorological factors controlling the concentration of mercury in soil gas were investigated by long-term experiments. Different mercury compounds in soils and rocks have been determined by a thermal destruction technique. In areas with sulphide mineralization, adsorbed mercury, HgCl₂, HgS, HgSO₄ and organically fixed mercury are the most important mercury compounds. The concentrations, transport and secondary formation of mercury and its compounds is controlled by: (1) the content of organic matter, Fe-oxides/hydroxides and clay minerals of the soils; and (2) the composition of the underlying rocks.The occurrence of mercury-sulphur compounds indicates the topographic influence on down-slope dispersion and the direction of inclination of the ore body. HgS and HgSO₄ are the dominant mercury compounds in the ore; in the bedrock, mercury occurs mainly as adsorbed mercury.