Control of Mercury Accumulation And Mobility in a Forest Soil as Indicated by δ13C

Abstract:

Mobility and cycling of mercury (Hg) in soils is important. Hg leaching results in its transport to wetlands, where Hg methylates and bioaccumulates through aquatic food webs. It has been shown that Hg cycle in soil is controlled by organic matter (OM) quantity as well as quality. The latter is indicated by increase of Hg/C ratio as C/N decreases by decomposition. Here we investigate the Hg-C relationship in a temperate forest soil in Hanover, NH, with a focus of examining the control of OM quality on soil Hg accumulation and mobility. We use δ¹³C as an indicator of carbon quality.

 The soil samples from A, B and C horizons were separated into six particle size fractionations from <25 µm to 1 mm. Both the bulk soil and particle size separates were analyzed for Hg concentrations, carbon content (C%), δ¹³C, and Hg partition coefficient (K_d =mg gSoil^–1/mg Lsolution^–1). We found that the bulk Hg concentration decreases significantly with increasing δ¹³C (R²=0.90, p <0.0001), but Hg/C increases with δ¹³C (R²=0.59, p =0.009). Both Hg/C and δ¹³C increase with soil depth, and at a given horizon, they both increase with decreasing particle size. These results indicate that high Hg/C ratios are associated with aged, decomposed, and low quality OM. Mostly likely, this accumulation of Hg in older OM is a result of retention of Hg upon carbon loss during soil respiration. However, the relationship between particle size and Hg/C is significantly different among different horizons; the most prominent relationship occurs at the deepest C horizon. This cross effect of horizon and particle size cannot be explained by normal aging of the OM through decomposition, pointing to mechanisms of changing in Hg bonding characteristics with OM aging or particle aggregation. The measured K_d value decreased with increasing δ¹³C (R²=0.43, p =0.0031), indicating that Hg associated with older OM is more subject to leaching compared to younger, fresher OM. This association can also be partitioned into effects of of both soil horizon and particle size.

This work demonstrates that soil δ¹³C is a useful tool for studying coupled Hg and C cycles in soils. Linking other methods characterizing bonding characteristics of Hg may bring additional insights to accumulation and mobility of Hg in association with changing chemical and physical properties of OM.