Nuclear volume effects in kinetic isotope fractionation:A case study of mercury oxidation by chlorine species

It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the effect of the NVE on these kinetic processes is not known.The total fractionations(MDFs+NVEinduced MIFs)of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes.NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages(named the electron density scaling method).Additionally,the NVE-induced kinetic isotope effect(KIE)of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species.Total KIEs for 202 Hg/^(198)Hg ranging from−2.27‰to 0.96‰are obtained.Three anomalous^(202)Hg-enriched KIEs(δ^(202)Hg/^(198)Hg=0.83‰,0.94‰,and 0.96‰,)caused by the NVE are observed,which are quite different from the classical view(i.e.,light isotopes react faster than the heavy ones).The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.

Translocation and distribution of mercury in biomasses from subtropical forest ecosystems:evidence from stable mercury isotopes

To understand its source,distribution,storage,and translocation in the subtropical forest ecosystems,mercury(Hg)concentrations and stable isotopes in forest biomass tissues(foliage,branch,bark,and trunk)were investigated at Ailao Mountain National Nature Reserve,Southwest China.The total Hg(THg)concentrations in the samples show the following trend:mature foliage(57±19 ng g-1)>bark(11±4.0 ng g-1)>branch(5.4±2.5 ng g-1)>trunk(1.6±0.7 ng g-1).Using the measured THg concentrations and the quantity of respective biomasses,the Hg pools in the forest are:wood(60±26μg m-2)>bark(51±18μg m-2)>foliage(41±11μg m-2)>branch(26±8.3μg m-2).The tree biomasses displayed negativeδ202Hg(-1.83‰to-3.84‰)andΔ199Hg(-0.18‰to-0.62‰).The observedΔ200Hg(-0.08‰to 0.04‰)is not significantly from zero.AΔ199Hg/Δ201Hg ratio of 1.05 was found in tree biomasses,suggesting that mercury has undergone Hg(Ⅱ)photoreduction processes.A Hg-isotope based binary mixing model suggests that Hg in the tree biomasses mainly originated from foliage uptake of atmospheric Hg0,constituting 67%,80%,and 77%of Hg in wood,branch,and bark,respectively.Our study sheds new light on the transportation and sources of Hg in the subtropical forest ecosystems.

Mercury isotope constraints on the genesis of late Mesozoic Sb deposits in South China

The late Mesozoic antimony(Sb)mineralization belt in South China hosts a large portion of the world’s Sb reserves.However,the source and mineralization processes of these Sb deposits remain controversial.Here,we measured mercury(Hg)concentrations and isotopic compositions of stibnite in the Banpo Sb-only and Woxi Sbpolymetallic ore deposits,as well as associated rocks in the Yangtze Block in order to constrain the metal sources and ore formation processes in the South China Sb mineralization belt.Stibnite samples from both deposits exhibit significant enrichment in Hg(4.23–50.6 ppm)and have higher δ^(202)Hg values(−0.47‰to 2.03‰)than the studied Precambrian basement rocks(−1.42‰to 0.59‰),Paleozoic sedimentary rocks(−2.40‰to−0.32‰),and other natural Hg reserves(e.g.,marine and continental systems).This indicates that significant mass-dependent fractionation of Hg isotopes occurred during hydrothermal processes.Negative to slightly positive Δ^(199)Hg values of−0.17‰to 0.02‰were obtained for stibnite from the studied deposits,similar to values for the Precambrian basement rocks,but different from those of the Paleozoic sedimentary rocks and data previously reported for mantle materials.This suggests that Precambrian basement rocks were the source of Hg and associated metals.Our data and the tectonic evolution of South China indicate that late Mesozoic asthenospheric upwelling,in response to the Paleo-Pacific oceanic slab foundering,generated heat that drove the circulation of fluids in the basement and crustal basinal rocks.These fluids leached Sb,Hg,and other metals from the Precambrian basement rocks and formed the world-class Sb mineralization belt in South China.

Stable isotope tracers identify sources and transformations of mercury in rice (Oryza sativa L.) growing in a mercury mining area

Methylmercury (MeHg) contaminated rice is a global issue, particularly in mercury-polluted areas, posing a potential threat to human health. The sources and transformations of mercury (Hg) species in rice are critical points that are not yet fully understood. In this study, field experimental pots together with a stable Hg isotope tracing technique were used to provide direct evidence of the sources and transformations of Hg species in rice plants. Enriched inorganic Hg (IHg) isotope (200Hg(NO3)2) was spiked into paddy soils, and the concentrations of inorganic Hg tracer (I200Hg), MeHg tracer (Me200Hg), and ambient Hg species (IHg and MeHg) were measured in the tissues of rice plants and their corresponding soil samples during the rice growing season. Here, we show that, in addition to the atmosphere, the soil is an important source of IHg to rice grains and was previously largely underestimated. We also show that MeHg is formed in paddy soil via microbial IHg methylation, absorbed through the rice root, translocated from the root to above-ground parts, and finally accumulated in rice grains. Although in vivo methylation of IHg in rice plants is unlikely to occur during the rice growing season, we observed in vivo demethylation of MeHg in the above-ground parts of rice plants, possibly via photolytic demethylation. Promoting in vivo demethylation of MeHg may be an effective approach to mitigate MeHg accumulation in rice grains.