Acute ecotoxicological effects of Hg(CN)2 in Danio rerio (zebrafish).

Artisanal and small-scale gold mining (ASGM) is the largest source of anthropogenic Hg emissions on the planet. In addition, Hg-contaminated tailings are often reprocessed with sodium cyanide (NaCN) to extract the residual gold remaining in the material. This leads to the formation of mercury cyanide (Hg(CN)2) complexes, which are often discharged in untreated form into local drainages, leading to large amounts of free cyanide being released. However, data on mercury-cyanide interactions are scarce. In this study, we investigated the impact of cyanide and Hg bioavailability in zebrafish when added as Hg(CN)2. Different concentrations of Hg(CN)2 and NaCN were used, leading to an LC50 of 0.53 mg.L-1 for NaCN and 0.16 mg.L-1 for Hg(CN)2. Analyzing free cyanide concentrations in aquarium water, >40% dissociation was observed for NaCN and about 5% for Hg(CN)2. The accumulation of total Hg (THg) in the brain, gills, muscle and kidney was quantified. All fish exposed to Hg(CN)2 had higher THg levels than their controls and kidney was the tissue with higher Hg(CN)2 accumulation. Histological effects on the kidney and gills of both cyanides in D. rerio tissues were investigated, suggesting renal alterations in fish exposed to Hg(CN)2 and showing hyperplasia in the gills of animals exposed to NaCN and Hg(CN)2. The results alert to the risks of the presence of these complexes in aquatic environments.

Reaction of Cyanide with Hg0-Contaminated Gold Mining Tailings Produces Soluble Mercuric Cyanide Complexes.

Elemental mercury (Hg0) contamination in artisanal and small-scale gold mining (ASGM) communities is widespread, and Hg0-contaminated tailings are often reprocessed with cyanide (-CN) to extract residual gold remaining after amalgamation. Hg0 reacts with -CN under aerobic conditions to produce Hg(CN)42- and other Hg(CN)nn-2 complexes. The production of solvated Hg(CN)nn-2 complexes increases upon agitation in the presence of synthetic and authentic Hg0-contaminated tailings that aid in dispersing the Hg0, increasing its reactive surface area. Adult rats were exposed to various concentrations of Hg(CN)2, and accumulation in organs and tissues was quantified using direct mercury analysis. The primary site of Hg(CN)2 accumulation was the kidney, although accumulation was also detected in the liver, spleen, and blood. Little accumulation was observed in the brain, suggesting that Hg(CN)2 complexes do not cross the blood-brain barrier. Renal tissue was particularly sensitive to the effects of Hg(CN)2, with pathological changes observed at low concentrations. Hg(CN)2 complexes are handled by mammalian systems in a manner similar to other inorganic species of Hg, yet appear to be more toxic to organ systems. The findings from this study are the first to show that Hg(CN)2 complexes are highly stable complexes that can lead to cellular injury and death in mammalian organ systems.

Cyanide Contamination of the Puyango-Tumbes River Caused by Artisanal Gold Mining in Portovelo-Zaruma, Ecuador.

PURPOSE OF REVIEW: To examine cyanide (CN-) contamination of a large river in southeastern Ecuador that has been severely impacted by the indiscriminate discharge of untreated gold processing effluents. RECENT FINDINGS: Poor environmental stewardship of cyanide (CN-) use by 87 gold processing centers in Portovelo-Zaruma in southern Ecuador to leach residual gold from Hg-contaminated tailings has resulted in high CN- contamination of the Puyango-Tumbes River downstream from the centers. Free CN- concentrations were high in river surface waters for 50 km below the processing plants, with the highest concentration 9088 times above the CCME standard of 5 µg/L and 1136 times above the 24-h LC50 concentration of 40 µg/L free CN- for some fish species. Due to cyanidation of mercury-contaminated tailings, the formation of Hg-CN complexes is a grave concern, as these complexes have been shown to be highly bioavailable. Preliminary tests conducted in a laboratory using bioassays with Danio rerio sp. and varying concentrations of synthetic Hg(CN)2 salt have shown significant THg bioaccumulation in muscle and kidney fish tissues exposed to concentrations >0.12 mg/L. Furthermore, low MeHg results in fish tissues demonstrated little occurrence of methylation and that the bulk of the total mercury content was in the form of inorganic mercury. Although construction of a communal tailings facility (CTF) in Portovelo is a positive development to reduce riverine pollution, the requirement to truck tailings up to the CTF likely results in inadequate compliance of environmental regulations that are poorly enforced.

Mercury isotopic signatures of tailings from artisanal and small-scale gold mining (ASGM) in southwestern Ecuador.

Artisanal and small-scale gold mining (ASGM) is currently one of the largest anthropogenic sources of mercury (Hg) to the atmosphere and a significant source to downstream terrestrial aquatic systems. Given the potential toxicity of Hg when it is released to aquatic ecosystems, both scientific and regulatory communities have interest in the development of tools and methods for understanding the fate and transport of Hg in the environment. Although Hg isotopes are applied extensively to trace other anthropogenic point sources of Hg in aquatic ecosystems, few studies have used isotopic analyses to investigate the downstream impacts of ASGM. Furthermore, these studies are currently limited by relatively sparse Hg isotopic analyses on ASGM materials. In this study, ASGM samples from Portovelo-Zaruma (Ecuador), representing various stages of the processing of low-grade gold-bearing ores, were analyzed for Hg concentrations and stable isotope ratios. These data were used to assess the isotopic variability of the ASGM endmember and confirm the results of prior isotopic analyses of ASGM materials and downstream sediments from Portovelo-Zaruma. While the Hg concentrations of the ASGM samples varied significantly, isotopic analyses revealed a limited range of signatures that was characterized by relatively heavy mass-dependent fractionation (MDF) with little to no significant mass-independent fractionation (MIF). The signatures of ASGM samples analyzed in this study matched well with previously reported ASGM samples from Portovelo-Zaruma as well as downstream sediments (for up to 120 km). Furthermore, the overall Hg isotopic compositions of potential ASGM endmembers are distinct from typical compositions observed in freshwater ecosystems (e.g., from soil erosion, atmospheric deposition), allowing Hg isotopes to be a powerful tool in tracing downstream Hg contamination from ASGM.

Training artisanal miners: A proposed framework with performance evaluation indicators.

Worldwide, approximately 30 million people depend directly on artisanal mining of many different minerals to provide for themselves and their families. However, poverty and a lack of education and training keep artisanal miners trapped in a cycle of rudimentary practices, which generate both environmental and health impacts. As the needs and motivations of artisanal miners are often ignored, previous attempts to deliver training projects have resulted in little sustained success. A successful training project for artisanal miners should be site-specific, including implementation of a thorough evaluation plan to monitor progress of the project's initiatives through established indicators. Frequently, training projects are restricted to the specifications of the funding donor, instead of designing initiatives that adequately reflect the realities of the context in which the training will take place. Furthermore, it is imperative that any training project uses a bottom-up approach that incorporates knowledge garnered from the successes and mistakes of previous projects. In this study, after analysis of previous and current training efforts, the attributes of a successful training project were outlined, including the importance of training champions within artisanal miner communities, drawing effectively on government support, and providing simple, affordable and profitable techniques to improve productivity and reduce environmental impacts. In addition, a framework with performance indicators was mapped out to show how a successful training project could be designed, implemented, monitored and evaluated, including the need to incorporate inclusive consultation, cultural sensitivity and consistently applied protocols into every step of the project. Instead of instructing practitioners on what the training should cover, the framework outlines how a training project's design can be informed by the needs of a particular mining sector. Ultimately, this kind of framework can serve as a template for practitioners working in diverse sectors around the world.

An investigation of mercury sources in the Puyango-Tumbes River: Using stable Hg isotopes to characterize transboundary Hg pollution.

Mercury (Hg) concentrations and stable isotopes along with other trace metals were examined in environmental samples from Ecuador and Peru's shared Puyango-Tumbes River in order to determine the extent to which artisanal- and small-scale gold mining (ASGM) in Portovelo-Zaruma, Ecuador contributes to Hg pollution in the downstream aquatic ecosystem. Prior studies investigated the relationship between ASGM activities and downstream Hg pollution relying primarily on Hg concentration data. In this study, Hg isotopes revealed an isotopically heavy Hg signature with negligible mass independent fractionation (MIF) in downstream sediments, which was consistent with the signature observed in the ASGM source endmember. This signature was traced as far as ∼120 km downstream of Portovelo-Zaruma, demonstrating that Hg stable isotopes can be used as a tool to fingerprint and trace sources of Hg over vast distances in freshwater environments. The success of Hg isotopes as a source tracer in fresh waters is largely due to the particle-reactive nature of Hg. Furthermore, the magnitude and extent of downstream Hg, lead, copper and zinc contamination coupled with the Hg isotopes suggest that it is unlikely that the smaller artisanal-scale activities, which do not use cyanidation, are responsible for the pollution. More likely it is the scale of ores processed and the cyanide leaching, which can release other metals and enhance Hg transport, used during small-scale gold mining that is responsible. Thus, although artisanal- and small-scale gold mining occur in tandem in Portovelo-Zaruma, a distinction should be made between these two activities.

Evidence of transboundary mercury and other pollutants in the Puyango-Tumbes River basin, Ecuador-Peru.

In Portovelo in southern Ecuador, 87 gold processing centers along the Puyango-Tumbes River produce an estimated 6 tonnes of gold per annum using a combination of mercury amalgamation and/or cyanidation and processing poly-metallic ores. We analysed total Hg, Hg isotopes, total arsenic, cadmium, copper, lead and zinc in water and sediment along the Puyango in 2012-2014. The highest total mercury (THg) concentrations in sediments were found within a 40 km stretch downriver from the processing plants, with levels varying between 0.78-30.8 mg kg-1 during the dry season and 1.80-70.7 mg kg-1 during the wet season, with most concentrations above the CCME (Canadian Council of Ministers of the Environment) Probable Effect Level (PEL) of 0.5 mg kg-1. Data from mercury isotopic analyses support the conclusion that mercury use during gold processing in Portovelo is the source of Hg pollution found downstream in the Tumbes Delta in Peru, 160 km away. The majority of the water and sediment samples collected from the Puyango-Tumbes River had elevated concentrations of, arsenic, cadmium, copper, lead and zinc exceeding the CCME thresholds for the Protection of Aquatic Life. At monitoring points immediately below the processing plants, total dissolved concentrations of these metals exceeded the thresholds by 156-3567 times in surface waters and by 19-740 times in sediment. The results illustrate a significant transboundary pollution problem involving Hg and other toxic metals, amplified by the fact that the Puyango-Tumbes River is the only available water source in the semi-arid region of northern Peru.

Cyanidation of Mercury-Contaminated Tailings: Potential Health Effects and Environmental Justice.

There is a variety of health and environmental issues associated with artisanal and small-scale gold mining (ASGM), which includes concerns regarding mercury pollution. In many countries, intervention programs and policies emphasized the importance of reducing mercury use by focusing on viable alternative methods to amalgamation that may include a transition to cyanidation. ASGM communities that now employ a combination of both methods may be increasing health and environmental risks by using mercury-contaminated tailings in the cyanidation process. This review provides a current overview of mercury and cyanide use in ASGM including the dangers of centralized processing centers that lack best practices. The combination of amalgamation and cyanidation has the potential to adversely affect many ASGM communities around the world and necessitates additional investigations to determine environmental and health impacts.

Mercury contamination from artisanal gold mining in Antioquia, Colombia: The world's highest per capita mercury pollution.

The artisanal gold mining sector in Colombia has 200,000 miners officially producing 30tonnes Au/a. In the Northeast of the Department of Antioquia, there are 17 mining towns and between 15,000 and 30,000 artisanal gold miners. Guerrillas and paramilitary activities in the rural areas of Antioquia pushed miners to bring their gold ores to the towns to be processed in Processing Centers or entables. These Centers operate in the urban areas amalgamating the whole ore, i.e. without previous concentration, and later burn gold amalgam without any filtering/condensing system. Based on mercury mass balance in 15 entables, 50% of the mercury added to small ball mills (cocos) is lost: 46% with tailings and 4% when amalgam is burned. In just 5 cities of Antioquia, with a total of 150,000 inhabitants: Segovia, Remedios, Zaragoza, El Bagre, and Nechí, there are 323 entables producing 10-20tonnes Au/a. Considering the average levels of mercury consumption estimated by mass balance and interviews of entables owners, the mercury consumed (and lost) in these 5 municipalities must be around 93tonnes/a. Urban air mercury levels range from 300ng Hg/m(3) (background) to 1million ng Hg/m(3) (inside gold shops) with 10,000ng Hg/m(3) being common in residential areas. The WHO limit for public exposure is 1000ng/m(3). The total mercury release/emissions to the Colombian environment can be as high as 150tonnes/a giving this country the shameful first position as the world's largest mercury polluter per capita from artisanal gold mining. One necessary government intervention is to cut the supply of mercury to the entables. In 2009, eleven companies in Colombia legally imported 130tonnes of metallic mercury, much of it flowing to artisanal gold mines. Entables must be removed from urban centers and technical assistance is badly needed to improve their technology and reduce emissions.

Using performance indicators to evaluate an environmental education program in artisanal gold mining communities in the Brazilian Amazon.

The Tapajos River Basin in the Brazilian Amazon is the location of one of the largest concentrations of artisanal and small-scale miners in the world. Today, 40,000 miners produce 8 t of gold annum(-1) and at least double this amount of mercury is released into the environment. This region was selected under the Global Mercury Project, a United Nations program that aims to reduce the environmental and health impacts caused by mercury through the application of cleaner technologies and increased awareness. A group of educators provided support to miners, training 4200 people in 141 mining locations. The effectiveness of this training was evaluated based on 20 performance indicators. After 120 days of training, an absolute improvement of approximately 29% had been achieved. As a result of this training, it is estimated that annual mercury emissions in Tapajos have been reduced by 1762 kg or around 10% of the total mercury released in the region.

Socioeconomic consequences of mercury use and pollution.

In the past, human activities often resulted in mercury releases to the biosphere with little consideration of undesirable consequences for the health of humans and wildlife. This paper outlines the pathways through which humans and wildlife are exposed to mercury. Fish consumption is the major route of exposure to methylmercury. Humans can also receive toxic doses of mercury through inhalation of elevated concentrations of gaseous elemental mercury. We propose that any effective strategy for reducing mercury exposures requires an examination of the complete life cycle of mercury. This paper examines the life cycle of mercury from a global perspective and then identifies several approaches to measuring the benefits of reducing mercury exposure, policy options for reducing Hg emissions, possible exposure reduction mechanisms, and issues associated with mercury risk assessment and communication for different populations.

Mercury reduction in Munhena, Mozambique: homemade solutions and the social context for change.

The health and environmental impacts of artisanal gold mining are of growing concern in Munhena, Mozambique, where more than 12,000 people are involved in such activities. Gold is extracted using mercury amalgamation, posing a considerable threat to human and environmental health. A pilot project ascertained the feasibility of reducing mercury use and emissions by promoting control measures utilizing local resources. Retorts were fabricated with local materials. Training workshops introduced the homemade retorts, and a portable mercury monitor revealed effective mercury reduction. Barriers to widespread technology adoption include poverty, lack of knowledge and trust, and the free supply of mercury from private gold buyers. Homemade retorts are inexpensive and effective, and miners could benefit by building community amalgamation centers. The government could play a greater role in gold purchasing to reduce mercury pollution.

Mercury contamination in fish from gold mining areas in Indonesia and human health risk assessment.

This study investigates the effects on fish and assesses human health hazards from mercury released in two gold mining areas in Indonesia: Tatelu (North Sulawesi Province) and Galangan (Katingan District, Central Kalimatan Province). In Tatelu, 154 fish specimens of 10 freshwater species were collected, as well as five marine species from the fish market. The mean concentration of total mercury in muscles of freshwater fish from this area was 0.58+/-0.44 microg/g, with more than 45% of fish having Hg levels above the WHO guideline for human consumption of 0.5 microg/g. In Galangan, where 263 fish specimens of 25 species were collected, the total mercury in muscles averaged 0.25+/-0.69 microg/g. Excluding data from flooded open pits in sub-area P4, mean Hg levels in fish from Galangan were 2 to 4 times lower than 0.5 microg/g, while fewer than 10% of fish from Galangan exceeded WHO guidelines. The Hazard Quotient (HQ) was applied to both areas to determine the threat of MeHg exposure for communities in both areas. The HQ is a risk assessment indicator which defines the ratio of exposure level to a single substance in relation to a reference dose. Samples from Tatelu (excluding marine species) had an HQ above one, while those from Galangan resulted in values of 2.4 for the whole area and 9.9 for sub-area P4, pointing to potentially harmful fish consumption for the local population. By using the single-compartment model to estimate mercury levels in blood and hair from daily intake dose, sub-area P4 showed the highest levels, higher than the upper limit guideline for pregnant women, but still lower than threshold levels associated with observed clinical effects.