Use of hardwood and sulfurized-hardwood biochars as amendments to floodplain soil from South River, VA, USA: Impacts of drying-rewetting on Hg removal

Abstract

Periodic flooding and drying conditions in floodplains affect the mobility and bioavailability of Hg in aquatic sediments and surrounding soils. Sulfurized materials have been recently proposed as Hg sorbents due to their high affinity to bind Hg, while sulfurizing organic matter may enhance methylmercury (MeHg) production, offsetting the beneficial aspects of these materials. This study evaluated hardwood biochar (OAK) and sulfurized-hardwood biochar (MOAK) as soil amendments for controlling Hg release in a contaminated floodplain soil under conditions representative of periodic flooding and drying in microcosm experiments in three stages: (1) wet biochar amended-systems with river water in an anoxic environment up to 200 d; (2) dry selected reaction vessels in an oxic environment for 90 d; (3) rewet such vessels with river water in an anoxic environment for 90 d. In Stage 1, greater Hg removal (17-98% for unfiltered total Hg (THg) and 47-99% for 0.45-μm THg) and lower MeHg concentrations (<20 ng L^-1) were observed in MOAK-amended systems (10%MOAKs). In Stage 3, release of Hg in 10%MOAKs was eight-fold lower than in soil controls (SedCTRs), while increases in aqueous (up to 21 ng L^-1) and solid (up to 88 ng g^-1) MeHg concentrations were observed. The increases in MeHg corresponded to elevated aqueous concentrations of Mn, Fe, SO₄^2-, and HS^- in Stage 3. Results of S K-edge X-ray absorption near edge structure (XANES) analysis suggest oxidation of S in Stage 2 and formation of polysulfur in Stage 3. Results of pyrosequencing analysis indicate sulfate-reducing bacteria (SRB) became abundant in Stage 3 in 10%MOAKs. The shifts in biogeochemical conditions in 10%MOAKs in Stage 3 may increase the bioavailability of Hg to methylating bacteria. The results suggest limited impacts on Hg removal during drying and rewetting, while changes in biogeochemical conditions may affect MeHg production in sulfurized biochar-amended systems.

Keywords: Dissimilatory Mn(IV) reduction; Fe(III) and SO(4)(2−) reduction; Hg HERFD-XAS; Methyl mercury production; S K-edge XANES; S disproportionation.