Mercury speciation, transformation, and transportation in soils, atmospheric flux, and implications for risk management : a critical review

Mercury (Hg) is a potentially harmful trace element in the environment and one of the World Health Organization's foremost chemicals of concern. The threat posed by Hg contaminated soils to humans is pervasive, with an estimated 86 Gg of anthropogenic Hg pollution accumulated in surface soils worldwide. This review critically examines both recent advances and remaining knowledge gaps with respect to cycling of mercury in the soil environment, to aid the assessment and management of risks caused by Hg contamination. Included in this review are factors affecting Hg release from soil to the atmosphere, including how rainfall events drive gaseous elemental mercury (GEM) flux from soils of low Hg content, and how ambient conditions such as atmospheric O3 concentration play a significant role. Mercury contaminated soils constitute complex systems where many interdependent factors, including the amount and composition of soil organic matter and clays, oxidized minerals (e.g. Fe oxides), reduced elements (e.g. S2−), as well as soil pH and redox conditions affect Hg forms and transformation. Speciation influences the extent and rate of Hg subsurface transportation, which has often been assumed insignificant. Nano-sized Hg particles as well as soluble Hg complexes play important roles in soil Hg mobility, availability, and methylation. Finally, implications for human health and suggested research directions are put forward, where there is significant potential to improve remedial actions by accounting for Hg speciation and transportation factors

Chlor-alkali industrial contamination and riverine transport of mercury: Distribution and partitioning of mercury between water, suspended matter, and bottom sediment of the Thur River, France

Total dissolved and total particulate Hg mass balances were estimated during one hydrological period (July 2001–June 2002) in the Thur River basin, which is heavily polluted by chlor-alkali industrial activity. The seasonal variations of the Hg dynamics in the aquatic environment were assessed using total Hg concentrations in bottom sediment and suspended matter, and total and reactive dissolved Hg concentrations in the water. The impact of the chlor-alkali plant (CAP) remains the largest concern for Hg contamination of this river system. Upstream from the CAP, the Hg partitioning between dissolved and particulate phases was principally controlled by the dissolved fraction due to snow melting during spring high flow, while during low flow, Hg was primarily adsorbed onto particulates. Downstream from the CAP, the Hg partitioning is controlled by the concentration of dissolved organic and inorganic ligands and by the total suspended sediment (TSS) concentrations. Nevertheless, the particulate fluxes were five times higher than the dissolved ones. Most of the total annual flux of Hg supplied by the CAP to the river is transported to the outlet of the catchment (total Hg flux: 70 lg m2 a1). Downstream from the CAP, the bottom sediment, mainly composed of coarse sediment (>63 lm) and depleted in organic matter, has a weak capacity to trap Hg in the river channel and the stock of Hg is low (4 mg m2) showing that the residence time of Hg in this river is short

Impact of mercury atmospheric deposition on soils and streams in a mountainous catchment (Vosges, France) polluted by chlor-alkali industrial activity: The important trapping role of the organic matter

Total atmospheric Hg contamination in a French mountainous catchment upstream from a chlor-alkali industrial site was assessed using Hg concentrations in the deepest soil horizon, in the stream bottom sediments, in river waters and in bryophytes. The natural background level of Hg content deriving from rock weathering was estimated to 32 ng g1 in the deepest soil layers. The soils appear to be Hg contaminated in two stages: atmospheric deposition and leaching through the soil profiles of Hg-organic matter complexes. The Hg enrichment factor (EFHgSc) which could be calculated by normalization to a conservative element like Sc, allows to estimate the major contribution (63% to 95%) of the atmospheric inputs, even in the upper part of the basin. This contribution may be attributed to diffuse regional atmospheric deposition of Hg and is mainly due to the geographic location of the chlor-alkali plant. This study shows for the first time that the mercury enrichment is proportional to the carbon content indicating that most of the atmospheric mercury deposition is trapped by the organic matter contained in the soils and in the stream sediments. The Hg stock in the soils of the upper catchment and the soil erosion contribution to the riverine Hg fluxes are estimated for the first time and allow to assess the Hg residence time. It indicates that Hg is trapped in the soils of such a polluted catchment for probably several thousand years

Fission modes of mercury isotopes

Background: Recent experiments on beta-delayed fission in the mercury-lead region and the discovery of asym- metric fission in 180 Hg [1] have stimulated theoretical interest in the mechanism of fission in heavy nuclei. Purpose: We study fission modes and fusion valleys in 180 Hg and 198 Hg to reveal the role of shell effects in pre-scission region and explain the experimentally observed fragment mass asymmetry and its variation with A. Methods: We use the self-consistent nuclear density functional theory employing Skyrme and Gogny energy density functionals. Results: The potential energy surfaces in multi-dimensional space of collective coordinates, including elongation, triaxiality, reflection-asymmetry, and necking, are calculated for 180 Hg and 198 Hg. The asymmetric fission valleys - well separated from fusion valleys associated with nearly spherical fragments - are found in in both cases. The density distributions at scission configurations are studied and related to the experimentally observed mass splits. Conclusions: The energy density functionals SkM\ast and D1S give a very consistent description of the fission process in 180 Hg and 198 Hg. We predict a transition from asymmetric fission in 180 Hg towards more symmetric distribution of fission fragments in 198 Hg. For 180 Hg, both models yield 100 Ru/80 Kr as the most probable split. For 198 Hg, the most likely split is 108 Ru/90 Kr in HFB-D1S and 110 Ru/88 Kr in HFB-SkM\ast.Comment: 6 pages, 5 figures, to be published in Physical Review

Shape evolution and the role of intruder configurations in Hg isotopes within the interacting boson model based on a Gogny energy density functional

The interacting boson model with configuration mixing, with parameters derived from the self-consistent mean-field calculation employing the microscopic Gogny energy density functional, is applied to the systematic analysis of the low-lying structure in Hg isotopes. Excitation energies, electromagnetic transition rates, deformation properties, and ground-state properties of the $^{172-204}$Hg nuclei are obtained by mapping the microscopic deformation energy surface onto the equivalent IBM Hamiltonian in the boson condensate. These results point to the overall systematic trend of the transition from the near spherical vibrational state in lower-mass Hg nuclei close to $^{172}$Hg, onset of intruder prolate configuration as well as the manifest prolate-oblate shape coexistence around the mid-shell nucleus $^{184}$Hg, weakly oblate deformed structure beyond $^{190}$Hg up to the spherical vibrational structure toward the near semi-magic nucleus $^{204}$Hg, as observed experimentally. The quality of the present method in the description of the complex shape dynamics in Hg isotopes is examined.Comment: 19 pages, 14 figures, revised version including new results and discussions, title changed, accepted for publication in Phys. Rev.

Terrestrial organic matter biomarkers as tracers of Hg sources in lake sediments

Terrestrial organic matter (TOM) plays a key role in mercury (Hg) dynamics between watersheds and lakes. In this study we attempts to determine the role of TOM source and quality and not only quantity, in the fate and transport of total Hg (T-Hg) to boreal lakes. Integrating the watershed complexity is a daunting task. Within the scope of this project, we characterized this organic matter at a molecular level in order to determine Hg transfer conditions to the sediments. We sampled ten lakes in the Quebec boreal forest. In each lake, we took a sediment core at the deepest point in addition to analyzing T-Hg and a set of terrigenous biomarkers in recent sediments. Our results show no relationship between TOM quantity and T-Hg concentration in lake sediments. However, [T-Hg] variation is well explained by the increase of 3,5Bd/V ratios (R2 = 0.84; p\0.0002) and the decrease of C/V ratios (R2 = 0.5; p\0.0227). Our study shows that TOM source and quality are determinant for Hg loadings in lake sediments. More precisely, increasing TOM derived from humified soil horizons explains most of Hg level variation within sediments

Echocardiography during submaximal isometric exercise in children with repaired coarctation of the aorta compared with controls

Objective Patients with repaired coarctation (RCoA) remain at higher risk of cardiac dysfunction, initially often only detected during exercise. In this study, haemodynamics of isometric handgrip (HG) and bicycle ergometry (BE) were compared in patients with RCoA and matched controls (MCs). Methods Case-control study of 19 children with RCoA (mean age 12.9 +/- 2.3 years; mean age of repair 7 months) compared with 20 MC. HG with echocardiography followed by BE was performed in both groups. Results During HG (blood pressure) BP increased from 114 +/- 11/64 +/- 4 mm Hg to 132 +/- 14/79 +/- 7 mm Hg, without significant differences. During HG as well as BE, HR increased less in patients with RCoA. There were no significant differences in (left ventricle) LV dimensions or LV mass. The RCoA group had diastolic dysfunction: both at rest and during HG they had significantly higher transmitral E and A velocities and lower tissue Doppler E' and A' velocities. E/E' was higher, reaching statistical significance during HG (p<0001). Conventional parameters of systolic function (FS and EF) were similar at rest and HG. More sensitive tissue Doppler S' was significantly lower at rest in CoA subjects (5.1 +/- 1.5 cm/s vs 6.5 +/- 1 +/- 1 cm/s; p<0.01), decreasing further during HG by 5% in the CoA group (NS) while unchanged in controls. Conclusions We provide first evidence that HG with echocardiography is feasible, easy and patient-friendly. A decreased systolic (tissue Doppler) and impaired diastolic LV function was measured in the RCoA group, a difference that tended to increase during HG

Thermal stability of Hg1-xMnxTe compound semiconductors

The thermal behaviour of Hg1-xMnxTe single crystals is investigated by means of the RBS/channeling technique. The stoichiometry parameter x ranges from 0.08 to 0.2. An important release of Hg atoms is observed after annealing in hydrogen atmosphere at 240 °C for 10 min. Backscattering spectra for crystals with x = 0.2 revealed quite a sharp Hg edge proceeding towards greater depth with increasing annealing temperature, the shallower region being completely depleted of Hg. Somewhat different behaviour is noticed for samples with x < 0.1. Although the Hg edge is also observed, the intensity of the Hg portion of the spectra diminishes with increasing annealing temperature or time. The latter effect is also observed for all samples after the second and further annealings. The examination by means of the optical microscopy reveals the presence of small cracks and pits which are apparently formed upon annealing. The Hg release through the crack walls is therefore responsible for the lowering of the Hg portion in the backscattering spectra

Synthesis and characterization of a new nanosorbent based on functionalized magnetic nanoparticles and its use in the determination of mercury by FI-CV-ETAAS

In this work, a new chelating sorbent which employs 1,5-bis(di-2-pyridil)methylene thiocarbohydrazide as the functional group and magnetic nanoparticles (MNPs) as its support (DPTH-MNP) was synthetized and characterized. The MNPs were prepared by coprecipitation of Fe+2 and Fe+3 with NH3 and then coated with silica in order to easily bind the support and the functionalizing molecule. The aim of the synthesis of this material is applying it as a solid-phase extracting agent and evaluating its potential for the extraction and pre-concentration of trace amounts of analytes present in biological and environmental samples with on-line methods. The MNPs’ magnetic core would allow overcoming the usual backpressure problems that happen in solid-phase extraction methods thanks to the possibility of immobilizing the MNPs by applying an external magnetic field. From the study of its adsorption capacity toward metal ions, mercury and antimony were the most retained. Thus, a flow injection solid phase extraction and cold vapor generation method for mercury determination based on the use of this new chelating nanosorbent was optimized. The greatest efforts were put into the reactor design to minimize compaction and loss of nanosorbent. The knotted reactor shown in Figure 1 was chosen as the best. Then, chemical and flow variables were optimized by Central composite designs (CCDs). The method developed has showed to be useful for the automatic pre-concentration and determination of mercury in environmental and biological samples. The determination was performed using electrothermal atomic absorption spectrometry (ETAAS). Under the optimum conditions, pH 5 and 120 s preconcentration time, the enrichment factor was 5.33; the detection limit (3σ) was 7.8 ng L-1; the determination limit (10σ) was 99 ng L-1; and the precisions (calculated for 10 replicate determinations at a 1 and 5 µg L-1 standards) were 1.7 and 1.9 % (RSD), respectively. Two linear calibration graphs were obtained, from the determination limits to 10 µg L-1 and from 10 to at least 50 µg L-1. From the comparison with other similar methods found in the bibliography, the detection limit and precisions calculated with our method were better. In order to evaluate the accurate and applicability of the method, the analysis of five certified samples LGC 6016 estuarine water, TMDA 54.4 fortified lake water, SRM 2976 mussel tissue, TORT-1 lobster hepatopancreas and DOLT-1 dogfish liver by standard addition and external calibration, were addressed. The results showed good agreement between the certified values, or added amounts of mercury, and the found concentrations. The method was successfully applied to the determination of mercury in sea-water samples collected in the Málaga Bay.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Mercury sources and bioavailability in lakes located in the mining district of Chibougamau, eastern Canada

The presence of Hg in the fish of the lakes from the Cu–Zn–Au mining region of Chibougamau (Canada) represents a serious source of concern for the health of local sports and subsistence fishers. This study focuses on identifying the origin of Hg present in the sediments of lakes with mine wastes stored in tailing facilities located on their shores. In addition to C/N ratios and determination of total Hg, Methyl Hg and other metals, a series of lignin biomarkers were used to contrast the history of the mining contamination with the nature and the intensity of terrigenous organic matter (TOM) inputs from the watersheds to the sampled lakes. It appears that sediments located nearest to mine tailings are as expected most enriched in total Hg and other metals (Cu, As, Al, Fe, Pb). Nevertheless, the presence of only small amounts of refractory TOM in these contaminated sediments could explain why only a very small fraction of Hg is found as Methyl Hg. In sediments with little or no impact by mining activities, a relationship was observed between logging activities in the lake watershed and increased TOM derived from inorganic gymnosperms soils horizons and increased Hg transport to the lakes. Nevertheless, it appears that the additional TOM transported to logged lakes is refractory enough not to promote high levels of Methyl Hg. The highest fractions of Methyl Hg relative to total Hg in lake sediments of the studied area were thus observed in relatively pristine environments where least degraded TOM is brought from the watersheds