Carbon and contaminant trace metal biogeochemistry in surficial organic-rich terrestrial systems

Abstract

Peats and organic-rich soils are a key part of the global carbon (C) cycle due to their sequestration and storage of atmospheric C as organic matter. Atmospheric deposition as a result of human activities has led to increased inventories of lead (Pb) and mercury (Hg) in UK peats and organic-rich soils. Ombrotrophic peat bogs, which receive all their nutrients and pollutants from the atmosphere, provide a historic record of Pb and Hg deposition within their solid phase. Organic-rich forest soil systems can also act as sinks for anthropogenic Pb but vertical transport of Pb can distort these temporal records. The long-term outlook may, however, be affected by processes which lead to decomposition of organic matter e.g. drying out of peatlands and soils due to climatic change, since these may release Pb into the aqueous phase and volatile Hg to the atmosphere. The associations and speciation of Pb and Hg within peats and organic-rich soils are not well understood but are key to understanding both the potential for release of these pollutants into other environmental compartments and the risks to ecosystems and human health posed by such a release. Investigation of 4 sites in central Scotland showed that, depending on vertical depth, ~40-99% of Pb in ombrotrophic peat was in association with large (0.22 μm – 100 kDa) humic molecules. Near-surface regions where intact plant material had not yet undergone complete humification showed the lowest proportion of Pb-humic association. Historical Pb deposition was retained to similar degrees across each site with recorded inventories to 1986 of 0.340-0.561 g m-2. However, perturbation of the 206Pb/207Pb isotope ratio profile at Glentress forest indicated that limited migration of petrol-sourced Pb may be occurring. Similarly, perturbation of the 210Pb profile at Auchencorth Moss, in addition to discrepancies in the apparent time period in which peak Pb deposition occurred, indicated that Pb may also be subject to migration within this ombrotrophic system. With respect to Hg, between-site differences in speciation were observed. For example, Hg2+ represented <25% of the total Hg species in the top 10 cm of solid phase ombrotrophic peat but >50% of the total in forest soil. In contrast, aqueous phase Hg was entirely in the inorganic form across all sites. The occurrence of a solid phase [Hg] peak in layers corresponding to the ~1955 height of coal burning, in addition to the narrow range of peatland Hg inventories to 1950 (2.20-3.23 g m-2) provide evidence that Hg deposition records may be maintained in organic-rich systems to a greater degree than previously assumed. Differences observed in the associations of Pb and the speciation of Hg between the surface vegetation of ombrotrophic bogs and the underlying peat suggests that plants play an integral role in the biogeochemical behavior and sequestration of Pb and Hg in these terrestrial systems.