Legacy Mercury Re-emission and Subsurface Migration at Contaminated Sites Constrained by Hg Isotopes and Chemical Speciation.

The re-emission and subsurface migration of legacy mercury (Hg) are not well understood due to limited knowledge of the driving processes. To investigate these processes at a decommissioned chlor-alkali plant, we used mercury stable isotopes and chemical speciation analysis. The isotopic composition of volatilized Hg(0) was lighter compared to the bulk total Hg (THg) pool in salt-sludge and adjacent surface soil with mean ε202HgHg(0)-THg values of -3.29 and -2.35‰, respectively. Hg(0) exhibited dichotomous directions (E199HgHg(0)-THg = 0.17 and -0.16‰) of mass-independent fractionation (MIF) depending on the substrate from which it was emitted. We suggest that the positive MIF enrichment during Hg(0) re-emission from salt-sludge was overall controlled by the photoreduction of Hg(II) primarily ligated by Cl- and/or the evaporation of liquid Hg(0). In contrast, O-bonded Hg(II) species were more important in the adjacent surface soils. The migration of Hg from salt-sludge to subsurface soil associated with selective Hg(II) partitioning and speciation transformation resulted in deep soils depleted in heavy isotopes (δ202Hg = -2.5‰) and slightly enriched in odd isotopes (Δ199Hg = 0.1‰). When tracing sources using Hg isotopes, it is important to exercise caution, particularly when dealing with mobilized Hg, as this fraction represents only a small portion of the sources.

Assessing Mercury Mobility in Sediment of the Union Canal, Scotland, UK by Sequential Extraction and Thermal Desorption.

The mobility of mercury (Hg) was assessed in sediment from the Union Canal, Scotland, UK. Samples collected from the vicinity of a former munitions factory that manufactured mercury fulminate detonators were subjected to sequential extraction followed by cold vapor atomic absorption spectrometry (CVAAS) and direct analysis using thermal desorption (TD). The sequential extraction indicated that > 75% of mercury (up to 429 mg kg-1) was in mobile forms, with < 12% semimobile and < 23% nonmobile species. In the TD method, > 67% of the total Hg content was desorbed in the temperature range 100-250 °C consistent with species weakly attached to the mineral matrix [tentatively identified as an iron (oxy)hydroxide-associated species]. This predominance of mobile mercury species may arise from a lack of association between Hg and either organic matter or sulfur in the sediments. Further investigation of Hg mobilization, transport, and assimilation/biomagnification is required both to determine whether there is a need for remediation of the sediment and to improve understanding of the biogeochemical cycling of Hg in shallow, oxic, freshwater systems.

Simultaneous removal of trace elements from contaminated waters by living Ulva lactuca.

This work shows the capabilities of living seaweed, Ulva lactuca, to remove As, Cd, Pb, Cu, Cr, Hg, Mn and Ni from contaminated waters. Experiments were performed with three algal doses (1.5, 3.0 and 6.0 g L-1, FW), two ionic strengths (salinity 15 and 35), and trace element concentrations corresponding to the maximum allowed values in wastewaters. The highest removals were obtained with the algal dose of 6 g L-1, with efficiencies varying between 48% for As and 98% for Hg, after 24 to 72 h. Salinity showed no effect on the removal efficiency. Overall, Elovich model was the best in describing the kinetics of the process, except for Hg, where pseudo-second-order model performed better. The use of extractions with EDTA (0.001, 0.01 to 0.1 mol L-1) has clarified that most of the Hg (≈98%) and Cr (≈80%) crossed the macroalgae walls, while Ni, Cd and As were retained at the surface (between 60 and 80%). These results support the hypothesis that macroalgae-based technologies may be a viable, cost-effective, and greener option to reduce the rejection of priority hazardous substances in contaminated waters.

Comparative study on metal biosorption by two macroalgae in saline waters: single and ternary systems.

The biosorption capability of two marine macroalgae (green Ulva lactuca and brown Fucus vesiculosus) was evaluated in the removal of toxic metals (Hg, Cd and Pb) from saline waters, under realistic conditions. Results showed that, independently of the contamination scenario tested, both macroalgae have a remarkable capacity to biosorb Hg and Pb. In single-contaminant systems, by using only c.a. 500 mg of non-pre-treated algae biomass (size <200 µm) per litter, it was possible to achieve removal efficiencies between 96 and 99 % for Hg and up to 86 % for Pb. Despite the higher removal of Hg, equilibrium was reached more quickly for Pb (after 8 h). In multi-contaminant systems, macroalgae exhibited a similar selectivity toward the target metals: Hg > Pb> > Cd, although Pb removal by U. lactuca was more inhibited than that achieved by F. vesiculosus. Under the experimental conditions used, none of the macroalgae was effective to remove Cd (maximum removal of 20 %). In all cases, the kinetics of biosorption was mathematically described with success. Globally, it became clear that the studied macroalgae may be part of simple, efficient, and cost-effective water treatment technologies. Nevertheless, Fucus vesiculosus has greater potential, since it always presented higher initial sorption rates and higher removal efficiencies.