Tin and mercury

This chapter contains sections titled: Introduction Geogenic Occurrence Sources of Soil Contamination Chemical Behaviour in Soils Risks from Tin and Mercury in Soils References

Abatement of mercury pollution in the small-scale gold mining industry: Restructuring the policy and research agendas

This paper critiques contemporary research and policy approaches taken toward the analysis and abatement of mercury pollution in the small-scale gold mining sector. Unmonitored releases of mercury from gold amalgamation have caused considerable environmental contamination and human health complications in rural reaches of sub-Saharan Africa, Latin America and Asia. Whilst these problems have caught the attention of the scientific community over the past 15-20 years, the research that has since been undertaken has failed to identify appropriate mitigation measures, and has done little to advance understanding of why contamination persists. Moreover, the strategies used to educate operators about the impacts of acute mercury exposure, and the technologies implemented to prevent farther pollution, have been marginally effective at best. The mercury pollution problem will not be resolved until governments and donor agencies commit to carrying out research aimed at improving understanding of the dynamics of small scale gold mining communities. Acquisition of this knowledge is the key to designing and implementing appropriate support and abatement measures. (c) 2005 Elsevier B.V. All rights reserved.

Improving awareness of mercury pollution in small-scale gold mining communities: Challenges and ways forward in rural Ghana

This paper critiques the approach taken by the Ghanaian Government to address mercury pollution in the artisanal and small-scale gold mining sector. Unmonitored releases of mercury-used in the gold-amalgamation process-have caused numerous environmental complications throughout rural Ghana. Certain policy, technological and educational initiatives taken to address the mounting problem, however, have proved marginally effective at best, having been designed and implemented without careful analysis of mine community dynamics, the organization of activities, operators' needs and local geological conditions. Marked improvements can only be achieved in this area through increased government-initiated dialogue with the now-ostracized illegal galamsey mining community; introducing simple, cost-effective techniques for the reduction of mercury emissions; and effecting government-sponsored participatory training exercises as mediums for communicating information about appropriate technologies and the environment. (c) 2006 Elsevier Inc. All rights reserved.

Mercury: An agent of poverty in Ghana's small-scale gold-mining sector?

There is consensus worldwide that the artisanal and small-scale mining (ASM) sector is comprised of individuals who are trapped in a vicious cycle of poverty, lacking the necessary financial and technological means to improve their standards of living. Minimal work, however, has been undertaken to identify the very factors behind miners' plight, which inevitably vary from country to country. This paper uses a case study of Ghana to argue that an increased dependence upon mercury for amalgamation In artisanal gold-mining communities is one such-albeit overlooked-"agent of poverty". There is mounting empirical evidence which suggests that dealings with the monoponistic middlemen who supply mercury, purchases of costly medicines to remedy ailments caused by mercury poisoning, and a lack of appropriate safeguards and alternatives to amalgamation, are preventing gold miners from improving their practices and livelihoods. The solution to the problem lies in breaking this cycle of dependency, which can be achieved by providing miners with robust support services, mercury-free technologies and education. (c) 2006 Elsevier Ltd. All rights reserved.

Challenges with minimising mercury pollution in the small-scale gold mining sector: Experiences from the Guianas

This paper examines the barriers to mitigating mercury pollution at small-scale gold mines in the Guianas (Guyana, French Guiana and Suriname), and prescribes recommendations for overcoming these obstacles. Whilst considerable attention has been paid to analysing the environmental impacts of operations in the region, minimal research has been undertaken to identify appropriate policy and educational initiatives for addressing the mounting mercury problem. Findings from recent fieldwork and selected interviews with operators from Guyanese and Surinamese gold mining regions reveal that legislative incapacity, the region's varied industry policy stances, various technological problems, and low environmental awareness on the part of communities are impeding efforts to facilitate improved mercury management at small-scale gold mines in the Guianas. Marked improvements can be achieved, however, if legislation, particularly that pertaining to mercury, is harmonised in the region; educational seminars continue to be held in important mining districts; and additional outlets for disseminating environmental equipment and mercury-free technologies are provided.

Stereochemically non-rigid helical mercury(II) complexes

Reactions of the 1: 2 condensate (L) of benzil dihydrazone and 2-acetylpyridine with Hg(ClO4)(2) center dot xH(2)O and HgI2 yield yellow [HgL2](ClO4)(2) (1) and HgLI2 (2), respectively. Homoleptic 1 is a 8-coordinate double helical complex with a Hg(II)N-8 core crystallising in the space group Pbca with cell dimensions: a = 16.2250(3), b = 20.9563(7), c = 31.9886(11) angstrom. Complex 2 is a 4-coordinate single helical complex having a Hg(II)N2I2 core crystallising in the space group P2(1)/n with cell dimensions a = 9.8011(3), b = 17.6736(6), c = 16.7123(6) angstrom and b = 95.760(3). In complex 1, the N-donor ligand L uses all of its binding sites to act as tetradentate. On the other hand, it acts as a bidentate N-donor ligand in 2 giving rise to a dangling part. From variable temperature H-1 NMR studies both the complexes are found to be stereochemically non-rigid in solution. In the case of 2, the solution process involves wrapping up of the dangling part of L around the metal. (C) 2008 Elsevier B.V. All rights reserved.

Homogeneous and heterogeneous reactions of atmospheric mercury(II) with sulfur(IV)

Atmospheric models suggest that the reduction of Hg(II) to Hg(O) by S(W) prolongs the residence time of mercury. The redox reaction was investigated both in the aqueous phase (where the reductant is sulfite) and on particulate matter (where the reductant in SO2(g)). In both cases, one of the ultimate products is HgS. A mechanism is proposed involving formation of Hg(O) followed by mercury-induced disproportionation of SO2.

The polychaete worm Nereis diversicolor increases mercury lability and methylation in intertidal mudflats

The polychaete worm Nereis diversicolor engineers its environment by creating oxygenated burrows in anoxic intertidal sediments. The authors carried out a laboratory microcosm experiment to test the impact of polychaete burrowing and feeding activity on the lability and methylation of mercury in sediments from the Bay of Fundy, Canada. The concentration of labile inorganic mercury and methylmercury in burrow walls was elevated compared to worm-free sediments. Mucus secretions and organic detritus in worm burrows increased labile mercury concentrations. Worms decreased sulfide concentrations, which increased Hg bioavailability to sulfate-reducing bacteria and increased methylmercury concentrations in burrow linings. Because the walls of polychaete burrows have a greater interaction with organisms, and the overlying water, the concentrations of mercury and methylmercury they contain is more toxicologically relevant to the base of a coastal food web than bulk samples. The authors recommend that researchers examining Hg in marine environments account for sediment dwelling invertebrate activity to more fully assess mercury bioavailability.

Mercury and methylmercury bioaccumulation by polychaete worms is governed by both feeding ecology and mercury bioavailability in coastal mudflats

Polychaete worms are abundant in many mudflats but their importance to coastal food web Hg biomagnification is not known. We sampled sediments and polychaete worms from mudflats in the Bay of Fundy to investigate the bioaccumulation of mercury (Hg) and methylmercury (MeHg) in the coastal invertebrate food web. Hg concentrations in the sediments were low (<20 μg kg−1). Labile Hg (methanol/KOH sediment extraction) in surface sediments (0–1 cm) was positively correlated with Hg bioaccumulation by surface sediment-ingesting polychaetes but, surprisingly, there was a negative correlation between δ15N (i.e. trophic level) and THg bioaccumulation factors in polychaete worms. Worms feeding on deeper sediments contained the greatest MeHg concentrations (69.6 μg kg−1). Polychaetes are an important vector for Hg biomagnification to the coastal avian food web. This research demonstrates that feeding depth and method of feeding are more important than trophic position or sediment Hg concentrations for predicting Hg bioaccumulation.

Modeling the photo-oxidation of dissolved organic matter by ultraviolet radiation in freshwater lakes: implications for mercury bioavailability

Uncertainties in projected ultraviolet (UV) radiation may lead to future increases in UV irradiation of freshwater lakes. Because dissolved organic carbon (DOC) is the main binding phase for mercury (Hg) in freshwater lakes, an increase in DOC photo-oxidation may affect Hg speciation and bioavailability. We quantified the effect of DOC concentration on the rate of abiotic DOC photo-oxidation for five lakes (DOC = 3.27–12.3 mg L−1) in Kejimkujik National Park, Canada. Samples were irradiated with UV-A or UV-B radiation over a 72-h period. UV-B radiation was found to be 2.36 times more efficient at photo-oxidizing DOC than UV-A, with energy-normalized rates of dissolved inorganic carbon (DIC) production ranging from 3.8 × 10−5 to 1.1 × 10−4 mg L−1 J−1 for UV-A, and from 6.0 × 10−5 to 3.1 × 10−4 mg L−1 J−1 for UV-B. Energy normalized rates of DIC production were positively correlated with DOC concentrations. Diffuse integrated attenuation coefficients were quantified in situ (UV-A Kd = 0.056–0.180 J cm−1; UV-B Kd = 0.015–0.165 J cm−1) and a quantitative depth-integrated model for yearly DIC photo-production in each lake was developed. The model predicts that, UV-A produces between 3.2 and 100 times more DIC (1521–2851 mg m−2 year−1) than UV-B radiation (29.17–746.7 mg m−2 year−1). Future increases in UV radiation may increase DIC production and increase Hg bioavailability in low DOC lakes to a greater extent than in high DOC lakes.

Effects of coastal managed retreat on mercury biogeochemistry

We investigated the impact of managed retreat on mercury (Hg) biogeochemistry at a site subject to diffuse contamination with Hg. We collected sediment cores from an area of land behind a dyke one year before and one year after it was intentionally breached. These sediments were compared to those of an adjacent mudflat and a salt marsh. The concentration of total mercury (THg) in the sediment doubled after the dyke was breached due to the deposition of fresh sediment that had a smaller particle size, and higher pH. The concentration of methylmercury (MeHg) was 27% lower in the sediments after the dyke was breached. We conclude that coastal flooding during managed retreat of coastal flood defences at this site has not increased the risk of Hg methylation or bioavailability during the first year. As the sediment becomes vegetated, increased activity of Hg-methylating bacteria may accelerate Hg-methylation rate.

Calixarene and Resorcarene Based Receptors: From Structural and Thermodynamic Studies to the Synthesis of a New Mercury(II) Selective Material

Materials used in current technological approaches for the removal of mercury lack selectivity. Given that this is one of the main features of supramolecular chemistry, receptors based on calix[4]arene and calix[4]resorcarene containing functional groups able to interact selectively with polluting ions while discriminating against biologically essential ones were designed. Thus two receptors, a partially functionalized calix[4]arene derivative, namely, 5,11,17,23-tetra-tert-butyl [25-27-bis(diethyl thiophosphate amino)dihydroxy] calix[4]arene (1) and a fully functionalized calix[4]resorcarene, 4,6,10,12,16,18,22,24-diethyl thiophosphate calix[4]resorcarene (2) are introduced. Mercury(II) was the identified target due to the environmental and health problems associated with its presence in water Thus following the synthesis and characterization of 1 and 2 in solution ((1)HNMR) and in the solid state (X-ray crystallography) the sequence of experimental events leading to cation complexation studies in acetonitrile and methanol ((1)H NMR, conductance, potentiometric, and calorimetric measurements) with the aim of assessing their behavior as mercury selective receptors are described. The cation selectivity pattern observed in acetonitrile follows the sequence Hg(II) > Cu(II) > Ag(I). In methanol 1 is also selective for Hg(II) relative to Ag(I) but no interaction takes place between this receptor and Cu(II) in this solvent. Based on previous results and experimental facts shown in this paper, it is concluded that the complexation observed with Cu(II) in acetonitrile occurs through the acetonitrile-receptor adduct rather than through the free ligand. Receptor 2 has an enhanced capacity for uptaking Hg(II) but forms metalate complexes with Cu(II). These studies in solution guided the inmobilization of receptor 1 into a silica support to produce a new and recyclable material for the removal of Hg(II) from water. An assessment on its capacity to extract this cation from water relative to Cu(II) and Ag (I) shows that the cation selectivity pattern of the inmobilized receptor is the same as that observed for the free receptor in methanol. These findings demonstrate that fundamental studies play a critical role in the selection of the receptor to be attached to silicates as well as in the reaction medium used for the synthesis of the new decontaminating agent.

Development of a sequential injection-square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h(-1). Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 mu L s(-1). For a concentration range between 0.010 and 0.25 mg L(-1), the current (i(p), mu A) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L(-1)): ip = (-20.5 +/- 0.3) Cparaquat -(0.02 +/- 0.03). The limits of detection and quantification were 2.0 and 7.0 mu g L(-1), respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.