Mercury balance in amalgamation in artisanal and small-scale gold mining: identifying strategies for reducing environmental pollution in Portovelo-Zaruma,Ecuador

The gold ore mined by artisanal and small-scale miners in Portovelo-Zaruma, Ecuador, is processed in custom mills. Miners can choose between Chilean-mill processing centers, where the ore is ground, concentrated and amalgamated, or “Chancha” Centers, where the whole ore is amalgamated. By weighing mercury before and after all unit operations involved in the amalgamation process, it was possible to determine mercury losses. Analyses in eight centers indicated that 51–59% of mercury introduced into the amalgamation process is recovered when miners squeeze the excess mercury. Around 29% of total mercury is lost when miners burn amalgam and gold is melted, and 15% is lost with the tailings. When only gravity concentrates are amalgamated, 1.4% of mercury entering the process is lost with tailings, whereas 29.5% is lost when the whole ore is amalgamated. Approximately 1.5 tonnes/annum of mercury is released in Portovelo-Zaruma, from which 70% is evaporated and 30% is released with tailings. Mercury-contaminated tailings are leached with cyanide in agitated tanks. A large majority of the processing centers dispose the final tailings with mercury and cyanide into the Calera River and Amarillo River. Mercury dissolved with cyanide likely becomes more bioavailable than metallic mercury. A campaign for reducing mercury emissions must focus on the use of individual retorts – mercury pollution control devices – and the elimination of whole ore amalgamation.     

Origin and consumption of mercury in small-scale gold mining

Mercury (Hg) is used by small-scale gold miners in more than 50 developing countries, where the accompanied releases affect human health and the environment. The objectives of this paper are to summarize present use of Hg in artisanal and small-scale mining (ASM) worldwide, reveal the origin of part of the Hg used by the gold miners, and propose appropriate actions to reduce the resulting Hg emissions. Significant releases of mercury are associated with inefficient amalgamation techniques. Releases are estimated to range from 800 to 1000 tonne/annum. Of this total, approximately 200–250 tonne of Hg are released in China, 100–150 tonne in Indonesia, and 10–30 tonne each in Bolivia, Brazil, Colombia, Peru, Philippines, Venezuela and Zimbabwe. Mercury usually enters these countries legally – typically imported from countries in the European Union – although in some cases and in some years (e.g., Indonesia, Venezuela, etc.), the reported imports of Hg are far below estimated consumption. Meanwhile, the EU, while gradually replacing Hg products and processes with more environmentally benign alternatives, paradoxically continues to produce virgin Hg at government-owned mines, further exacerbating a general global oversupply of Hg – evident from its historically low market price. Political leadership is needed to avoid the transfer of excess Hg, and related health and environmental risks from the EU to third countries. Otherwise, the present situation will continue or even worsen, with no oversight or control of the global Hg trade in which the transfer of excess EU Hg to artisanal miners is favoured by low Hg prices relative to gold prices.     

中国非燃煤大气汞排放量估算

本研究根据各种非燃煤大气汞排放源的活动水平和排放因子,估算了1995～2003年中国分省非燃煤大气汞的排放量。2003年中国非燃煤大气汞排放量为393t,比燃煤汞排放多137t。在非燃煤大气汞排放中,84%来自有色金属冶炼,其中锌冶炼、铅冶炼、铜冶炼和黄金冶炼分别占总排放的51%、18%、4%和11%。Hg0、Hg2+和HgP在中国非燃煤大气汞排放中所占比例分别为77%、18%和5%。中国非燃煤汞排放在各地区间有较大差异,排放量超过30t?a-1的省区包括湖南、河南和云南,排放强度超过1t?km-2的省区包括上海、湖南、河南、辽宁和广东,这些地区的主要汞排放源为有色金属冶炼和生活垃圾焚烧。1995～2003年中国非燃煤大气汞排放的年均增长率为9%,其中生活垃圾焚烧排放的年均增长率最高,达到42%。     

中国燃煤汞排放清单的初步建立

建立中国分省燃煤汞排放清单,对于研究汞的大气化学转化、迁移和沉降,制定中国汞污染控制对策具有重要意义.本研究按经济部门、燃料类型、燃烧方式和污染控制技术将排放源划分为65种不同类型,根据各类型的煤炭消费量、燃料汞含量和汞排放因子计算汞排放量,最终建立了分省燃煤汞排放清单.用2组原煤汞含量数据资料计算的2000年中国燃煤大气汞排放量分别为161.6 t和219.5 t,其中绝大部分汞排放来自工业、电力和生活消费,分别占46%、35%和14%.Hg⁰、Hg²⁺和Hg_p在中国燃煤大气汞排放中所占的比例分别为16%、61%和23%.中国燃煤汞排放在各地区间有较大差异,排放量较大的省份有河南、山西、河北、辽宁和江苏,均超过10t/a.     

Distribution of mercury and methylmercury in river water and sediment of typical manganese mining area

Manganese (Mn) ores contain substantial concentrations of mercury (Hg), and mining and smelting of Mn ores can bring Hg into the surrounding aquatic environment through atmospheric deposition, leaching of electrolytic Mn residue and Mn gangue dump. However, limited is known that how these processes influence the environmental behaviors of Hg in waterbody. Therefore, the seasonal distribution and existing form of Hg in water and sediment in one Mn ore area in Xiushan County, Chongqing were investigated. Our results showed that the mean Hg and methylmercury (MeHg) concentrations in water (n=35) were 5.8 ± 4.6 ng/L and 0.22 ± 0.14 ng/L, respectively. The mean Hg concentrations in retained riverbed and fluvial bank sediment (n=35) were 0.74 ± 0.26 mg/kg and 0.63 ± 0.27 mg/kg, respectively (the mean MeHg concentrations were 0.64 ± 0.40 µg/kg and 0.51 ± 0.30 µg/kg, respectively). It indicated that the mining and smelting of Mn ores were the main sources of anthropogenic Hg, and Mn may inhibit Hg methylation in rivers in Mn ore areas. Mercury in the bound to iron/ Mn (Fe/Mn) oxides of low crystallinity fraction (Hg-OX) accounted for 4.01% and 5.25% of the total Hg concentrations in the retained riverbed and fluvial bank sediment, respectively. The amount of Hg bound to Fe/Mn oxides in sediment increased significantly due to the manganese mining activities in the investigated area. Therefore, it could be hypothesized that high Hg concentrations in river sediment in Mn mining areas are closely related to high Mn concentration in sediment.     

Total mercury in wild fish in Guizhou reservoirs, China

The health hazard of mercury (Hg) compounds is internationally recognized, and the main pathways for methylmercury (MeHg) intake in humans are through consumption of food, especially fish. Given the large releases of Hg to the environment in China, combined with the fast development of hydropower, this issue deserves attention. Provided similar mobilization pathways of Hg in China as seen in reservoirs in North America and Europe one should expect increased Hg contamination in relation to future hydropower reservoir construction in this country. This study presents total Hg (THg) concentrations in wild fish from six Guizhou reservoirs, China. The THg concentrations in fish were generally low despite high background levels in the bedrock and depositions from local point sources. The over all mean ± SD concentration of THg was (0.066 ± 0.078) μg/g (n = 235). After adjusting for among-reservoir variation in THg, there were significant differences in THg among functional groups of the fish, assumed to re?ect trophic levels. Predicted THg- concentration ratios, retrieved from a mixed linear model, between the functional groups were 9:4:4:1 for carnivorous, omnivorous, planktivorous and herbivorous fish. This result indicated that MeHg accumulation may prevail even under circumstances with short food chains as in this Chinese water system. No fish exceeded recommended maximum THg limit for human consumption set by World Health Organization and the Standardization Administration of China (0.5 μg/g fish wet weight (ww)). Only six fish (2.5%) exceeded the maximum THg limit set by US Environmental Protection Agency (0.3 μg/g fish ww).     

中国燃煤汞排放量估算

研究了中国煤炭的汞含量及主要用煤行业燃煤汞排放因子．结合有关统计资料计算了我国各行业和各地区燃煤汞的排放量．全国煤炭的平均汞含量为0.22mg/kg ,主要燃煤行业中大气汞排放因子为64.0 ％ ～78.2 ％ ．1995年全国燃煤共排放汞302.9t,其中向大气中排汞量为213.8t,排入灰渣及产品中的汞为89.07t.1978（1995 年全国燃煤大气汞排放量的年平均增长速度为4.8 ％ ,累积排汞量为2493.8t ;北京、上海、天津等超大城市排汞强度较高;燃煤汞排放是中国面临的重要环境问题．     

Mill leaching: a viable substitute for mercury amalgamation in the artisanal gold mining sector?

Artisanal small-scale gold miners (ASM) occasionally employ whole ore amalgamation by adding mercury into ball mills to recover gold. In this process, 25–30% of the mercury added is lost to the environment. It is also inefficient less than 30% of gold is recovered. Amalgamation, followed by cyanidation, has been observed at many artisanal mining sites. This combination poses additional environmental and health consequences. Tests with ore samples from Talawaan, North Sulawesi, Indonesia indicate the possibility of replacing mercury by cyanidation in the ball mill, reaching gold extraction of 93% in 6 h of leaching. The gold in the Indonesian ore sample is fine and less than 8% of gold recovery was obtained with gravity concentration of the ore ground 80% below 0.25 mm, which is a reasonably fine grain size for artisanal gold operations. Replacing mercury addition with cyanidation in ball mills was implemented in one artisanal gold mining operation in Portovelo, Ecuador, achieving 95% of gold extraction in 8 h of mill leaching. This technique demonstrated a drastic improvement in gold recovery. It was found to be a simple, inexpensive technique well accepted by local miners. The results from laboratory and field tests are promising; however a thorough investigation into the socio-economic and environmental aspects of this presented alternative must be conducted prior to introduction.     

Mercury-free gold mining technologies: possibilities for adoption in the Guianas

The rudimentary nature of small-scale gold mining activities often generates a legacy of extensive degradation and deplorable social conditions, both during and after activities have ceased. Small-scale mining usually involves the extraction of secondary gold from placer deposits (alluvial, colluvial or elluvial), which can be liberated and treated using gravity methods. In the Guianas, the most popular form of small-scale gold mining is referred to as “land dredging”, a combination of hydraulicking and suction dredging. This method requires application of large volumes of water for both mining and mineral processing; in most cases, there are no containment structures for the waste tailings generated. Mercury, a dangerous pollutant, is the preferred method employed by small-scale miners for gold recovery. Gold extraction using mercury is comprised of the following four stages: (1) amalgamation, (2) separation of amalgamation, (3) removal of excess mercury, and (4) burning of the remaining amalgam to produce a gold sponge. Mercury can be released into the environment at each stage, which makes the promotion of mercury-free alternatives imperative.Technical alternatives for small-scale gold mining, however, must be thoroughly evaluated, pre-tested, modified accordingly and successfully transferred. Moreover, technology must be inexpensive, relatively simple and easy to adapt, while allowing a rapid rate of return. WWF-Guianas is working with the regulatory agencies and other relevant stakeholders of the Guianas to reduce the environmental footprints caused by small-scale mining. The major aspects of this program are to develop the capacity and regulatory mechanisms within the local government, to promote mercury-free technology, and monitor mercury in the environment. This paper reviews the alternative technologies being investigated by the WWF-Guianas for use in the small-scale gold mining industry.     

城市管道煤气生产中汞的分布特征

采用二次金汞齐 -冷原子吸收光谱法对贵阳市城市民用管道煤气中汞含量进行了测定。对煤气生产中使用的洗精煤及生产过程中产生的化学产品焦碳、煤焦油、焦炉煤气脱硫洗涤物硫浆中汞含量和分布进行了初步研究。管道煤气中汞的含量低于方法检测限 0 .0 5ng/m3,低于贵阳市大气中汞含量。在原煤转化为城市管道煤气过程中 ,原煤的洗选过程脱除了 70 %的汞 ;焦碳中汞含量占洗精煤汞含量的 1 1 .4 % ;焦油中汞含量占洗精煤中汞的 1 2 .6 % ;硫浆的生成过程脱除了煤气生产用洗精煤中 50 %的汞。     

中国燃煤电厂汞的物质流向与汞排放研究

为研究中国燃煤电厂中汞的去向,基于2010年中国各省份燃煤中的汞含量、燃煤消耗量、燃煤电厂大气污染控制设备的安装比例以及粉煤灰、脱硫石膏的二次利用方式,计算了我国燃煤电厂2010年向大气、水体、土壤中排放汞的量.2010年我国电厂燃煤共输入汞271.7t (147.1~403.6t).煤炭在电厂燃烧一次排放到大气中的汞为101.3t (44.0~167.1t),进入燃煤副产物、水体的汞分别为167.4t (84.3~266.3t),3.0t (1.2~5.0t).燃煤副产物二次利用过程向大气排放的汞为32.7t (12.5~56.1t),进入土壤中的汞为58.6t (33.6~103.9t),还有76.1t (30.3~108.6t)汞留在了产品中.结果表明,粉煤灰用于水泥生产和粉煤灰制砖是副产物向大气中二次排放的重要源,分别占总二次排放量的81.7%和15.3%.     

污灌区稻田汞污染特征及健康风险评价

选择天津北排污河灌区作为研究区域,调查了土壤和水稻总汞和甲基汞的含量及分布特征,评估污灌区稻米食用汞暴露风险,并对污灌区土壤-稻米甲基汞的影响因素进行了初步分析.结果表明,1.调查的29个污灌区稻田,土壤总汞含量为(367.04 ± 129.36) μg/kg,显著高于区域土壤Hg背景值73 μg/kg,甲基汞含量为(0.87 ± 0.77) μg/kg;水稻各部位总汞含量依次为稻叶 > 稻根 > 稻茎 > 稻米,稻米总汞含量为(12.80 ± 5.14) μg/kg,甲基汞含量依次为稻米 > 稻根 > 稻茎 > 稻叶,稻米对甲基汞具有很强的富集能力,甲基汞含量为(2.09 ± 1.20) μg/kg,甲基化率均值超过10%.污灌区稻米总汞每周摄入量为0.068~1.25μg/(kg·bw),甲基汞每周摄入量为0.0095~0.49μg/(kg·bw),污灌区稻米总汞及甲基汞暴露对居民健康风险总体仍在安全阈值内,但个别汞污染较严重地块甲基汞暴露风险值得高度关注.土壤甲基汞含量仅与土壤总汞含量及黏粒含量的相关性达到显著性水平,稻米甲基汞含量与土壤总汞含量、土壤甲基汞含量、稻米总汞含量及黏粒含量的相关性达到显著性水平.     

管道煤气生产中汞的分布

为了解城市管道煤气生产中可能存在的汞污染,对贵阳市管道煤气及煤气生产所使用的洗精煤、煤气生产过程中产生的化学产品焦碳、焦油及焦炉煤气脱硫洗涤物硫浆中汞的含量和分布进行了研究。研究发现,管道煤气中汞的含量低于二次金汞齐-冷原子吸收光谱法检测限0.05ng/m3,较贵阳市城区大气汞的含量还低。在原煤转化为城市管道煤气过程中,煤中的汞在煤气生产的各个环节都有不同程度的脱除:其中原煤的洗选过程是最主要的脱汞过程,约75%左右的汞在该过程中被脱除;焦碳中汞含量占洗精煤汞含量的14.1%;煤焦油中汞含量占洗精煤中汞的15.5%;硫浆的生成过程则脱除了煤气生产用洗精煤中51%的汞。     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

汞的环境地球化学研究进展

介绍了目前对环境样品中总汞及其各形态未的分析方法以及大气和水生生态系统中汞的研究进展，并指出，燃煤、汞齐法采金和人造水库等引起的环境汞污染问题以及汞在热带地区水生生态系统中的迁移转化规律等是目前的研究热点。     

Strategies for reducing the environmental impact of reprocessing mercury-contaminated tailings in the artisanal and small-scale gold mining sector: insights from Tapajos River Basin,Brazil

Worldwide, the environmental impacts of artisanal and small-scale gold mining (ASGM) are extensive. Annual losses from mercury, which is used to amalgamate gold, are in the range of 1000 tonnes, and at advanced sites, there is the additional threat of cyanide contamination.Recent developments in The Brazilian Amazon, an area populated by 200,000 small-scale gold miners, have the potential to reduce these impacts considerably. In the locality of Garimpo Ouro Roxo, miners are presently using amalgamation and cyanidation in vat-leaching. Each cycle typically recovers 50% of the gold and lasts 20 days (per tank), consuming around 3300 kg NaCN/month. A new process has been developed and implemented in a pilot plant in this area, involving gravity concentration followed by cyanidation in a ball mill. Concentrate leaching is conducted with a PVC capsule filled with activated carbon inserted in the cyanide solution in the mill. The cycle takes less than 24 h and recovers up to 98% of the gold in the concentrate. The main advantages of wide adoption of this method, apart from a reduced gold recovery cycle and improved recovery, include possible phase out of amalgamation altogether, and marked reductions in cyanide consumption (from current 22,000 kg–980 kg annually).     

影响大气汞化学过程的敏感因子分析

为了分析汞在大气中的化学行为,在一个化学模式中加入汞的气相、气液平衡和液相反应,模拟大气汞及其化合物的演变规律,并分析了气象因子(云、光解率、温度)和化学因子(气态O3、H2O2、HO2、OH和气态零价汞Hg0(g))的初始体积分数对各形态汞及其化合物浓度和Hg0(g)转化率的影响.模拟结果表明,在中等大气污染条件下,Hg0(g)的每小时平均转化率为2.91%.敏感性试验结果表明,云量、光解率、温度、O3和Hg0(g)的初始体积分数对不同形态汞的影响较为显著.云量的增加、光解率的增加、臭氧初始体积分数的升高,各形态汞的平衡时间缩短,除气态氧化汞和一价汞离子外,其他形态汞的平衡浓度均会降低,Hg0(g)的转化率增加.温度增加将抑制Hg0(g)的转化.Hg0(g)的初始体积分数增加,各形态汞的浓度升高,但其平均转化率没有显著变化.不同因子对汞化学过程的相对作用对区域或全球大气汞的环境模拟具有指导意义.     

两次金汞齐-冷原子荧光光谱法测定大气中的痕量气态总汞

建立了两次金汞齐-冷原子荧光光谱法(CVAFS)测定大气中痕量气态总汞(TGM)的方法。研究表明:本方法的绝对检出限为2 pg;当以0.2~0.4 L·min-1 采样速度,采集12~48 h时,采样效率> 99%,精密度为9.63%;样品经2次循环加热分析,热解吸效率> 99%。这种分析方法还可以运用到其他环境样品痕量汞的测定。     

三峡库区长寿湖水体不同形态汞的空间分布特征

以三峡库区长寿湖为调查对象,采用网格法均匀设点采样分析,并基于Arc GIS地统计模块,研究了长寿湖水体不同形态汞浓度及其空间分布特征.结果表明,长寿湖表层水总汞浓度变化范围为0.50~3.78 ng·L-1,平均值为1.51 ng·L-1;总甲基汞浓度变化范围为0.10~0.75 ng·L-1,平均值为0.23 ng·L-1.表层水体各形态汞的块金效应值分别为总汞50.65%、溶解态汞49.80%、颗粒态汞29.94%和活性汞26.95%,具有中等程度空间自相关性,表明在空间分布上一方面受水体内在属性的影响,另一方面也与渔业养殖、工业活动、农业耕种等人为外源输入干扰因素有关.表层水体溶解态甲基汞块金效应值3.49%,小于25%,表现很强的空间自相关性,其分布主要受到水体内在环境因素等的控制.各采样点水体总甲基汞占总汞的比例均较高,均达到淡水湖泊和河流中总甲基汞占总汞的质量分数上限值30%,暗示长寿湖水体内在环境条件利于汞的甲基化.     

Methylmercury and sulfate-reducing bacteria in mangrove sediments from Jiulong River Estuary, China

Estuaries are important sites for mercury (Hg) methylation, with sulfate-reducing bacteria (SRB) thought to be the main Hg methylators. Distributions of total mercury (THg) and methylmercury (MeHg) in mangrove sediment and sediment core from Jiulong River Estuary Provincial Mangrove Reserve, China were determined and the possible mechanisms of Hg methylation and their controlling factors in mangrove sediments were investigated. Microbiological and geochemical parameters were also determined. Results showed that SRB constitute a small fraction of total bacteria (TB) in both surface sediments and the profile of sediments. The content of THg, MeHg, TB, and SRB were (350 150) ng/g, (0.47 0.11) ng/g, (1.4 1011 4.1 109) cfu/g dry weight (dw), and (5.0 106 2.7 106) cfu/g dw in surficial sediments, respectively, and (240 24) ng/g, (0.30 0.15) ng/g, (1.9 1011 4.2 1010) cfu/g dw, and (1.3 106 2.0 106) cfu/g dw in sediment core, respectively. Results showed that THg, MeHg, TB, MeHg/THg, salinity and total sulfur (TS) increased with depth, but total organic matter (TOM), SRB, and pH decreased with depth. Concentrations of MeHg in sediments showed significant positive correlation with THg, salinity, TS, and MeHg/THg, and significant negative correlation with SRB, TOM, and pH. It was concluded that other microbes, rather than SRB, may also act as main Hg methylators in mangrove sediments.