Dissolved Black Carbon Facilitates Photoreduction of Hg(II) to Hg(0) and Reduces Mercury Uptake by Lettuce (Lactuca sativa L.)

Here, we investigated the photoreduction of Hg(II) (Hg(NO3)2) mediated by dissolved black carbon (DBC, <0.45 μm size fraction) collected from water extracts of biochar derived by pyrolyzing crop residues (rice, soybean, and peanut). Under simulated sunlight conditions, the presence of 5 mg C/L DBC significantly facilitated the production of Hg(0) from Hg(II) (initially at 10 nmol/L) with a reduction ratio of 73 ± 4% in 5.3 h. Inhibition of photolysis-induced reactive oxygen species by a quencher or removal of dissolved oxygen indicated that Hg(II) was mainly reduced by superoxide anion (O2•–). Reduction by electrons transferred from photoexcited DBC components or by organic free radicals produced from photo-Fenton-like reactions was also proposed to play a role. Contrary to dissolved humic substances, the DBC-mediated photoreduction of Hg(II) led to unique positive mass-independent isotopic fractionation (MIF) of Hg(0) (Δ199Hg = 1.8 ± 0.3‰), which was attributed to the dominance of secondary Hg(II) reduction by O2•–. The leachate from soil amended with rice biochar at 1–5% mass ratios exhibited significantly higher photocatalytic efficiency than that from unamended soil (wherein the reduced Hg(0) increased from 27 ± 1 to 63 ± 2% in maximum), and the efficiency positively correlated with the percentage of amended biochar. Under natural illumination conditions, the total mercury and/or methylmercury uptake by roots, shoots, and leaves of lettuce (Lactuca sativa L.) grown in water extracts of rice biochar-amended soil was consistently lower (up to 70 ± 20%) than that without the biochar amendment. The findings highlight that DBC might play an important and previously unrecognized role in the biogeochemical cycle and the environmental impact of mercury.