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Particulate mercury (Hg)

Bulk and low molecular weight (LMW) (<1 kDa) water-extractable carbon were collected from fresh and microbially degraded wheat straw (Triticum aestivum L.) and crimson clover (Trifolium incarnatum L.) residues to monitor early-stage humification over an 8-wk incubation. Copper complexation parameters were determined for both bulk and LMW water-extractable C for both plant materials in a separate 1-wk incubation. Humification progressed through increasing molar absorptivity (A285) and phenolic and total acidity (TA), and through an increase in average molecular size and degree of polymerization as determined by ultrafiltration and changes in fluorescence peak locations. Such dynamic transformations demonstrate that while humification is a bulk property, with C breakdown and stabilization occurring simultaneously and continuously in soil, its early stages can be effectively monitored for fresh plant residues. Significant changes consistently occurred during the first 7 d of the incubation and were more pronounced for LMW fractions than bulk extracts. For both residues, water-extractable C extracted initially and following a 7-d incubation desorbed and complexed 0.11 to 0.55 mmol resin-bound Cu g(-1) C. Low molecular weight water-extractable C generated the higher values within this range, and values increased consistently following incubation. Potential concerns regarding LMW soluble Cu complexes include percolation through soils or runoff into adjacent water bodies as well as effects on plant root development.

To assess the lability of porewater and sediment solid-phase mercury (Hg), mercapto-substituted siloxane gels were deployed within the sediments of the Penobscot estuary in Maine. Gel deployments occurred in time series and at discrete sediment depths. A sediment distribution coefficient (K(D)) was estimated by modeling the resultant gel Hg uptake. For deployments > 1 day, depth-averaged gel Hg uptake was significantly greater at depth (Zone B 6-20 cm) than in the vicinity of the sediment-water interface (Zone A 0-5 cm), with uptake ultimately reaching 16.7 +/- 4.9 ng Hg g(-1) gel versus 35.5 +/- 3.8 ng Hg g(-1) gel for Zone A versus Zone B, respectively. For Zone A, a simple diffusive model adequately describes gel mass flux, suggesting that Hg repartitioning from the solid phase does not generate a net Hg source term within the time frame of gel deployment. For Zone B, model-determined values of K(D) (K(D) = 25-75) were considerably smaller than literature values typically based on total sediment Hg concentration. The magnitude of the modeled K(D) suggests that it is a small fraction of total sediment-sequestered Hg that is likely sensitive, via interaction with porewater ligands, to the presence of an external sink. These observations of low general Hg reactivity suggest that the net porewater Hg pool may be properly defined as a function of porewater ligand production. Such a definition highlights the importance of microbially mediated diagenesis in controlling Hg cycling within estuarine sediments.