Distribution and speciation of mercury in surface water in Wanshan Hg-mined areas, Guizhou Province, China

Mercury as a toxic element poses environmental concerns, especially in historically Hg-mined districts. The Wanshan Hg mine located in the eastern part of Guizhou Province, southwestern China, ranks the largest Hg-producing district in China. Mining at Wanshan was initiated in 221 B.C., but ceased in 2001. Approximately 22000 tons of Hg, 6000 tons of cinnabar and large quantities of mine-wastes had been produced at Wanshan. Significant quantities of calcines, which were piled irregularly near the old mine processing sites and retorts, continue to impact the local environments in the Wanshan area. In this study, a regional contamination of mercury in surface waters collected from the Meizixi, Dashuixi, Huandao and Gaolouping rivers, whose upstreams or branches originate from the hilly karstic area and receive drainage arising from the calcines, was investigated by determining all Hg species in a base-flow and a flood-flow season. Reactive, dissolved, particulate, and total Hg concentrations in surface water varied from 0.60 to 400 ng/L, 11 to 430 ng/L, 1.4 to 9210 ng/L, and 15 to 9260 ng/L, respectively. Total methylmercury in water samples ranges from 0.31 to 25 ng/L. The concentrations of total Hg and particulate Hg in water samples collected during the flood season are higher than those in the base-flow season, whereas, the concentrations of dissolved and reactive Hg are lower with the peak values observed in water samples collected in the base-flow season. A strong positive correlation between total Hg and particulate Hg is noticed in the water samples collected from Hg-mined areas with the proportion higher than 80%.     

万山汞矿区稻田土壤生物有效性汞的提取方法

土壤中汞的生物有效性是决定土壤汞污染和农作物汞富集的重要指标。然而,采用不同提取方法所得到的有效态汞含量存在差异。为探索适用于汞矿区稻田土壤生物有效性汞的提取方法,研究对比了4种提取剂(超纯水、0.005 mol/L DTPA混合液、0.1 mol/L CaCl2和0.1 mol/L HCl)对万山汞矿区内两条典型河流沿岸稻田土壤生物有效态汞的测定结果。结果表明,万山汞矿区稻田土壤总汞含量均值为(12.7±0.42)mg/kg,超标率为93%。土壤生物有效态汞含量较低,4种试剂提取的有效态汞占总汞比例依次为0.005%、0.018%、0.003%和0.036%;超纯水提取的土壤生物有效态汞与稻田土壤、水稻根和茎的总汞浓度显著相关,表明超纯水提取方法最适用于测定万山汞矿区稻田土壤的生物有效态汞。本研究可为评估土壤汞污染风险提供技术和数据参考。     

Multielemental contents of foodstuffs from the Wanshan (China) mercury mining area and the potential health risks

Potentially harmful element contamination from mining and smelting raises concerns due to possible health risks. For most people, diet is the main route of exposure to potentially harmful elements, so determination of the concentrations of these elements in foodstuffs and assessment of their possible risk for humans via dietary intake is very important. This study was designed to investigate the concentrations of different elements, including Hg, Pb, Cd, Mn and Se in foodstuffs and to estimate the potential health risk of these elements via consumption of polluted foodstuffs in the Wanshan Hg mine area, Guizhou province, SW China. The multielemental concentrations were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The target hazard quotient (THQ) and hazard index (HI) were calculated to evaluate the potential health risk from individual and combined potentially harmful elements due to dietary intake. The average contents of Hg, Pb, Cd, Mn and Se in the most frequently consumed foodstuffs were: 31, 248, 121, 1035 and 32 μg/kg respectively. Among them, Cd and Hg were the most important contributors to potentially harmful elements contamination in Wanshan. Eight of 10 kinds of vegetables were contaminated to various levels by different elements but the samples of rice, pork, radish and potato were below the stipulated limits for toxic elements. In this study, the average dietary intakes of Hg, Pb, Cd, Mn, Se by an adult man of 60 kg living in Wanshan were: 27, 167, 86, 1061, 42 μg/day, respectively. The HIs for multielement dietary intake was 3.11, with the relative contributions of Hg, Pb, Cd, Mn and Se being 22.3%, 24.3%, 45.0%, 3.9% and 4.4%, respectively, which indicated that consumption of food poses a potential health risk. Vegetables were found to be the main source of potentially harmful element dietary intake.     

The geochemical characteristics of mine-waste calcines and runoff from the Wanshan mercury mine,Guizhou, China

Mercury and other geochemical parameters were measured in mine-waste calcines, stream sediments and surface waters from the Wanshan Hg district in the Guizhou Province of China to evaluate adverse effects of Hg to the surrounding environment. Wanshan ore is dominantly cinnabar, and lacks other sulfide minerals and as a result, heavy metals other than Hg are rare in the calcines and mine-water runoff. Host rocks in the Wanshan area are dominantly carbonates, which upon weathering, produces alkaline-water runoff. Surface waters emanating from calcine piles have water pH varying from 10.6 to 11.8, contain high EC values, and variable major element geochemistries. Dissolved Hg concentration decreases from 300 to 1900 ng/l in mine water to 72 ng/l in stream water collected significantly downstream from the mine. High concentrations of Hg in mine-waste calcines and alkaline surface water are the major threats to the surrounding environment. Alkalinity is also naturally attenuated downstream from the Wanshan mine. However, erosion and transport of Hg in sediment and water and highly alkaline mine-water runoff, may adversely affect sediment, aquatic and biological columns downstream from the Wanshan mine area.     

Mercury pollution from artisanal mercury mining in Tongren, Guizhou, China

Concentrations of total Hg (T-Hg) were measured in mine waste, stream water, soil and moss samples collected from the Tongren area, Guizhou, China to identify potential Hg contamination to local environments, which has resulted from artisanal Hg mining. Mine waste contained high T-Hg concentrations, ranging from 1.8 to 900 mg/kg. High concentrations of Hg were also found in the leachates of mine waste, confirming that mine waste contains significant water-soluble Hg compounds. Total Hg distribution patterns in soil profiles showed that top soil is contaminated with Hg, which has been derived from atmospheric deposition. Data suggest that organic matter plays an important role in the binding and transport of Hg in soil. Elevated T-Hg concentrations (5.9–44 mg/kg) in moss samples suggest that atmospheric deposition is the dominant source of Hg to local terrestrial ecosystems. Concentrations of T-Hg were highly elevated in stream water samples, varying from 92 to 2300 ng/L. Particulate Hg in water constituted a large proportion of the T-Hg and played a major role in Hg transport. Methyl–Hg (Me–Hg) concentrations in the water samples was as high as 7.9 ng/L. Data indicate that Hg contamination is dominantly from artisanal Hg mining in the study area, but the extent of Hg contamination is dependent on the mining history and the scale of artisanal Hg mining.     

Total gaseous mercury emissions from mercury-enriched soil in Guizhou, China

Guizhou is located in the Circum-Pacific Global Mercuriferous Belt, and mercury concentrations in soil in this area are enriched. In-situ total gaseous mercury （TGM） exchange fluxes between air and soil surface were intensively measured at four sampling sites in Guiyang from 21 May to 16 June, 2003, and five sites in the Lanmuchang mercury mining area in December 2002 and May 2003, respectively. The in-situ Hg flux measurement was conducted with a dynamic flux chamber （DFC） of quartz. Overall, net emissions were obtained from all sampling sites. Soil mercury concentration and solar radiation have been proved to be the two most important parameters to control mercury emissions from soil. Meanwhile, rain events can enhance mercury emission rate significantly.     

Mercury emission from the indigenous mercury smelting in Wuchuan mercury mining areas, Guizhou Province, China

Mercury smelting is one of the important anthropogenic atmospheric mercury emission sources. Small-scale mercury smelting activities with indigenous method which is considered illegal and forbidden by local government always extensively existed in the Wuchuan area, northeastern Guizhou Province, China. Because of the simple processes without any environmental protection, a large amount of mercury vapor released to the ambient air during the processing of cinnabar roasting. By determining mercury concentrations in mercury ore and smelting slag samples, a mass balance method was used to calculate mercury emission factors and annual mercury emission from indigenous mercury smelting in Wuchuan mercury mining areas, Guizhou Province, China. The mercury emission factors ranged from 6.9% to 32.1% with the recovery from 78.4% to 93.6% and the annual mercury emission was up to 3.7-9.6 metric tons. The results highlighted that the indigenous mercury smelting was one of the most important anthropogenic atmospheric mercury emission sources in this region.     

Selenium speciation,distribution, and transport in a river catchment affected by mercury mining and smelting in Wanshan,China

Selenium (Se) is an important co-existing elemental component of the mineral matrix of mercury (Hg) ore deposits. The hazards associated with Se contamination of the aquatic ecosystems in Hg mining areas; however, are often overlooked by environmental researchers due to a preoccupation with Hg. Selenium may also pose a long-term risk to the local ecosystem, and further complicate the situation as Se may also play an important antagonistic role against Hg. Furthermore, most studies on Se pollution have focused only on total Se, whereas the toxicity, bioavailability, and bioaccumulation of Se in aquatic ecosystems is primarily determined by its site-specific individual species. In this study, the concentrations of total Se, inorganic Se (tetravalent and hexavalent), and organic Se were determined in water samples collected from 41 typical sites selected in rivers, tributaries, and springs in Wanshan, China, where Hg and Se co-occur due to historic Hg mining and retorting activities. Se concentrations were observed to decrease with distance from mine-waste calcines, which indicated that mine-waste calcines may be significant sources of the elevated Se in the rivers, especially in downstream areas within 8 km from the mine-waste calcines. The concentration of total aqueous Se throughout the study area was highly variable (3.8 ± 6.0 μg L⁻¹) and on average was one order of magnitude greater than that in natural river systems worldwide (0.1–0.3 μg L⁻¹). The majority of the Se was hexavalent (3.1 ± 4.9 μg L⁻¹; 65%), followed by tetravalent (0.53 ± 0.86 μg L⁻¹; 15%) and organic forms (0.85 ± 1.5 μg L⁻¹; 20%), possibly due to the generally alkaline conditions. Se concentrations in some sampling sites exceeded certain recommended limit of values. However, the existing criteria for Se in aquatic system are mainly based on total Se and the recommended limit of values in different countries or organizations are inconsistent with one another. Therefore, the need to consider Se speciation rather than only total Se is highlighted for future studies.     

Mercury and methylmercury in riparian soil,sediments, mine-waste calcines,and moss from abandoned Hg mines in east Guizhou province,southwestern China

Concentrations of total Hg and methylmercury (MMHg) in riparian soil, mine-waste calcine, sediment, and moss samples collected from abandoned Hg mines in Wanshan district, Guizhou province, China, were measured to show regional dispersion of Hg-contamination. High total Hg and MMHg concentrations obtained in riparian soils from mined areas, ranged from 5.1 to 790 mg kg⁻¹ and 0.13 to 15 ng g⁻¹, respectively. However, total Hg and MMHg concentrations in the soils collected from control sites were significantly lower varying from 0.1 to 1.2 mg kg⁻¹ and 0.10 to 1.6 ng g⁻¹, respectively. Total Hg and MMHg concentrations in sediments varied from 90 to 930 mg kg⁻¹ and 3.0 to 20 ng g⁻¹, respectively. Total Hg concentrations in mine-waste calcines were highly elevated ranging from 5.7 to 4400 mg kg⁻¹, but MMHg concentrations were generally low ranging from 0.17 to 1.1 ng g⁻¹. Similar to the high Hg concentrations in soil and sediments, moss samples collected from rocks ranged from 1.0 to 95 mg kg⁻¹ in total Hg and from 0.21 to 20 ng g⁻¹ in MMHg. Elevated Hg concentrations in mosses suggest that atmospheric deposition might be an important pathway of Hg to the local terrestrial system. Moreover, the spatial distribution patterns of Hg contamination in the local environment suggest derivation from historic Hg mining sites in the Wanshan area.     

Concentration,distribution and bioaccumulation of mercury in the Xunyang mercury mining area,Shaanxi Province,China

Samples of surface water, soil, sediment and plants from the Xunyang Hg mining area in Shaanxi Province, China, were analyzed to assess the effects of the Hg mining activities on the environment. The results show that: (1) the mining activities are sources of Hg to the environment surrounding the mine; (2) the environment, especially riverbeds in the Xunyang area, is contaminated with Hg and (3) Hg accumulation in cabbage leaves, the main vegetable for the local residents, is high, reaching concentrations that are 6–540 times higher than the maximum Hg concentration recommended for edible plants in China. Action should be taken to remediate contaminated sites, manage waste discharges and reduce the exposure of Hg to local residents by issuing advisories against consuming agricultural products grown in the area, which are contaminated with Hg.     

贵州开阳磷矿区崩塌及其防治

开阳磷矿区被称为地质灾害的博物馆,区内地质灾害灾种齐全,滑坡、崩塌、泥石流、地面塌陷、地裂缝等地质灾害广泛分布,山体崩塌是区内分布最广的地质灾害之一。文章通过对开阳磷矿区山体崩塌地质灾害的地质背景、采矿活动的调查和分析,得出开阳磷矿区山体崩塌地质灾害形成的基本条件是区内的特殊地形地貌及断裂构造,地下磷矿开采是主要诱因;统计了各矿段崩塌体的分布特征及其危害对象;选取区内典型崩塌体,利用极射赤平投影法定性分析崩塌体的稳定性,分析得出崩塌体是不稳定的;提出了采用井下充填采矿,遏制区内崩塌的进一步发展,并结合生态移民工程、锚固与防护工程、切割爆破清除危岩体等综合治理方法。     

Environmental Geochemistry of Heavy Metal Contaminants in Soil and Stream Sediment in Panzhihua Mining and Smelting Area,Southwestern China

Mining and smelting activities are the main causes for the increasing pollution of heavy metals in soil, Water body and stream sediment. An environmental geochemical investiga-tion was carried out in and around the Panzhihua mining and smelting area to determine the ex-tent of chemical contamination in soil and sediment. The main objective of this study was to in-vestigate the environmental geochemistry of Ti, V, Cr, Mn, Cu, Pb, Zn and As in soil andsediment and to assess the degree of pollution in the study area. The data of heavy metal con-centrations reveal that soils and sediments in the area have been slightly contaminated. Geo-chemical maps of Igeo of each heavy metal show that the contaminated sites are located in V-Ti-magnetite sloping and smelting, gangues dam. The pollution sources of the selected elementscome mainly from dusts resultant from mining activities and other three-waste-effluents. The areaneeds to be monitored regularly for trace metal, especially heavy metal enrichment.     

矿山水土污染与防治对策研究

矿山水土环境污染是采矿活动引发的主要环境地质问题之一。我国矿山数量众多,水土污染比较普遍,尤以金属矿山最为严重,矿山水土污染防治是今后开展国土空间生态保护修复的重要内容。基于全国矿山地质环境摸底调查成果资料,对矿业活动不同阶段的水土污染风险以及不同矿山的水土污染类型、特征和污染物迁移演化规律等进行了研究。分析指出:矿业活动过程包括勘探、建矿、开采、洗选、冶炼等多个阶段,而水土污染风险贯穿于矿业活动全过程,不同阶段的污染风险不同;矿产资源开发造成的水土污染物类型、特征因开采的矿产类型不同而不同,呈现出特征污染物与矿体母岩的高度相关性;矿山及其周边污染物的迁移作用受污染物自身的物理化学性质和外界环境条件的影响,在矿山长期持续开采条件下矿山水土污染物存在累积效应,而矿产资源集中开采区的污染物扩散表现出叠加效应。通过对某典型水土环境污染案例的分析研究,初步证实了上述推断。根据我国矿山水土环境污染多发性和复杂性的特点,建议今后开展矿山水土污染防治工作应区分不同类型矿山、不同地质环境条件、不同污染物特征、不同污染程度,采取分类施策、系统修复、标本兼治的对策,以实现矿山环境明显改善。     

黔中典型喀斯特地区土壤水分时空特性分析

土壤水分是岩溶山区植被恢复和生态环境建设的关键性限制因素.利用黔中喀斯特普定石漠化研究基地的采样分析数据,用回归模型分析了不同利用类型(坡面、洼地)0～50cm土壤水分的动态变化规律;探讨了土壤水分空间变化的影响因子.结果表明,坡面和洼地土壤水分呈现弱变异特征,其中坡面土壤水分变异程度相对较大,变程分别是30.4～24.5和30.4～26.2.在剖面上,两者的垂直变异趋势大致相反,坡面土壤水分变异系数随土层的加深而增大;而洼地由于受外界自然条件的干扰相对较小,变异系数随着土层深度的增加而减小,而且其中的不同土地利用类型都是在40～50cm处达到最小.研究显示,植被覆盖度提高后土壤总体上朝着有利于水分保蓄和植被恢复的方向转变.     

Effect of acid mine drainage on a karst basin: a case study on the high-As coal mining area in Guizhou province,China

Acid mine drainage (AMD) is a common pollution in mining areas due to the oxidation of pyrite and associated sulfide minerals at mines, tailings and mine dumps. Elevated metals (Fe, Mn, Al) and metalloids (As, Hg) in AMD would deteriorate the local aquatic environment and influence the water supply. A carbonate basin with deposits of high-arsenic coal in Xingren County, southwestern China, was chosen to study the behavior of As and other chemical constituents along a river receiving AMD. Heavy metals (Fe, Mn) and major ions such as (Ca²⁺, Mg²⁺, Cl⁻, SO₄ ²⁻) in surface water, and As in sediment and surface water were analyzed. It was found that high concentrations of SO₄ ²⁻ (1,324–7,560 mg/L) and Fe (369–1,472 mg/L) in surface water were mainly controlled by the interactions between water and rocks such as the oxidation of pyrite in the local coal seams, precipitation and adsorption of iron minerals. Although ubiquitous carbonate minerals in the bedrock and the riverbeds, low pH (<3) water was maintained until 2 km downstream from the AMD source due to the Fe(hydro)oxide minerals coating on the surface of carbonate minerals to restrain the neutralization of acidic water. Moreover, the formation of Fe(hydro)oxide precipitations absorbed As was dominated the attenuation of As from water to sediment. Whereas, the dilution also played an important role in decrease of As in river water.     

淮南采煤沉陷区土壤中汞的时空分布特征

以淮南采煤沉陷区土壤为研究对象,测试分析了样品中汞的含量,结合土壤pH值、有机质含量特征,探讨了采煤沉陷区土壤中汞的时空分布特征。结果表明：与未沉陷区土壤相比,沉陷区土壤有机质破坏严重,最高下降了46%;采煤沉陷区土壤中汞的含量为0.013~0.050 mg/kg,平均值为0.027 mg/kg,69.7%的采样点超过了淮南市土壤背景值;沉陷8 a后土壤汞含量最高,为0.033 mg/kg,是未沉陷土壤汞含量的1.74倍,且随着沉陷时间的增加,土壤中汞存在富集趋势;水稻土壤汞富集能力最高,高于玉米和大豆土壤;在垂直剖面上,汞含量由表层向下依次降低;且汞与pH值表现出显著负相关,有机质与汞显著正相关。     

贵州典型喀斯特区土壤地球化学特征研究

以贵州花溪党武、遵义虾子和安龙木咱3个地区的土壤为主要研究对象,从地球化学的角度研究其土壤中相关矿物元素的含量、元素在岩-土剖面中的迁移富集特征及其风化成土系数,综合表征出研究区土壤的农业地质环境特征,并对其矿物营养元素环境质量做出初步评价。研究结果表明,石灰土中矿物营养元素的淋溶较为强烈,有10种左右元素的含量低于中国或世界土壤化学组成中值,具体表现为纯的碳酸盐岩所发育的土壤中矿物营养元素的含量较少,而安龙木咱地区由于其成土母质为白云质灰岩,且所处地质环境易于汇集周边淋溶出来的营养元素,使得其土壤矿物营养元素环境质量好于其余两地,三地土壤中营养元素达标率分别为73.7%（安龙木咱）、63.1%（遵义虾子）和68.4%（花溪党武）。总体而言,碳酸盐岩风化成土作用缓慢,土层较薄,土壤营养元素含量不足,需要施用相应的矿物肥料。      

我国主要磷矿、硫铁矿集中开采区水土污染现状分析

我国化工矿山地质环境保护工作有序进行,为全面掌握磷矿、硫铁矿矿产资源集中开采区水土环境质量现状,保障资源、经济与环境的可持续发展,为矿山地质环境保护提供基础资料,通过开展我国主要磷矿、硫铁矿集中开采区矿山地质环境调查,对采集调查区的水土样品进行了测试分析,综合评价磷硫矿山集中开采区水土环境质量,针对存在的水土污染问题提出治理对策及建议,促进化工矿山企业的可持续发展。     

Hydrochemistry of geothermal water in Tianshui and adjacent area, Gansu province, China

A geochemical study on thermal water has been carried out in Tianshui and its adjacent area, Gansu province, China. Chemical and isotopic contents were employed in the investigation on the origin and evolution of thermal water and the evaluation of reservoir temperature in the geothermal systems. Thermal waters in Wushan and Tianshui are characterized by outlet temperatures from 15 to 38°C and low TDS (226?C255?mg/L), defined as bicarbonate water. Its origin may be attributed to the interaction between meteoric rain, biotite plagioclase gneiss and carbonate reservoir rocks. In contrast, thermal waters in Tongwei and Qingshui have higher outlet temperatures of 25?C54.2°C and a moderate TDS of 915?C1,793?mg/L, regarded as sulfate waters. These sulfate waters may arise from the interaction between meteoric water, granite and amphogneiss. Isotopic data presented here suggest that thermal waters in the study area have a meteoric origin without being significantly effected by water?Crock isotope exchange. Chemical geothermometry indicates the existence of a deep geothermal reservoir of low-to-medium enthalpy (70?C111°C) in the Tianshui study area.     

贵州省万山区耕地土壤硒元素分布特征与相关性分析

硒是环境中重要的生命元素,缺硒和硒过剩都将引起生物及人体的不良反应。本文以贵州省万山区耕地土壤为研究对象,通过系统采样及化验分析耕地土壤硒含量,结果发现万山区耕地土壤硒含量在005801 mg/kg,平均值为050 mg/kg,总体上达到富硒区标准,富硒土壤面积2278万亩,占万山区耕地总面积的7743%,硒元素高值区分布在万山区东部的熬寨乡。同时,对影响万山区耕地土壤硒元素含量的相关性进行研究,得知影响土壤硒含量的主要因素是成土母岩、土壤类型,土地利用方式,土壤硒含量只与Hg、Cd、Mo、SOM呈弱相关性,与其余元素均无相关性。本研究成果对万山区土地合理规划利用,富硒产业的科学发展具有重要价值。