Importance of ultraviolet radiation in the photodemethylation of methylmercury in freshwater ecosystems.

Environmental science & technology

PubMedID: 19731664

Lehnherr I, St Louis VL. Importance of ultraviolet radiation in the photodemethylation of methylmercury in freshwater ecosystems. Environ Sci Technol. 2009;43(15):5692-8.
Photodemethylation (PD) is thought to be the most important biogeochemical sink of methylmercury (MeHg) in freshwater lakes. However, we possess little mechanistic knowledge of this important biogeochemical process with regard to, for instance, the role of ultraviolet (UV) radiation versus visible light in mediating MeHg PD. This information is critical to correctly model MeHg PD at the whole-lake level, since wavelengths in the UV and visible regions of the solar spectrum are attenuated at very different rates in the water column of lakes. Furthermore, the established methodology for quantifying MeHg PD requires the addition of a MeHg spike, which often increases the concentration of ambient MeHg by 1 to 2 orders of magnitude; however, the assumption that the MeHg spike behaves like ambient MeHg has never been verified. We quantified MeHg PD rates using an isotopically enriched Me199Hg tracer added to lake waters already containing high concentrations of ambient MeHg, allowing us to simultaneously monitor the decomposition rate of the spike and ambient MeHg. Experiments were conducted at the Experimental Lakes Area to quantify the first-order rate constant (k(pd)) of MeHg PD in samples exposed to (1) full solar radiation, (2) UV-A and visible light (i.e., with UV-B blocked), or (3) visible light only. We demonstrate for the first time that the use of a MeHg spike to quantify PD rates is appropriate since spike and ambient MeHg-both in samples with and without a spike of Me199Hg--are photodemethylated at the same rate. We also show that rates of MeHg PD are reduced by an order of magnitude in the absence of UV radiation and that to correctly model MeHg PD at the whole-lake scale, both UV and visible light mediated MeHg PD rates must be independently calculated using the light-specific rate constants (k(pd-UWB), k(pd.UVA), k(pd-VIS)). By examining modeled a real MeHg PD fluxes, we observed that UV radiation accounts for 58% and 79% of MeHg PD activity in a clear and colored lake, respectively. Finally, we demonstrate that correcting k(pd-overall) for the attenuation of solar radiation by Teflon bottles, which are normally used for MeHg PD experiments, increases the measured value of 3.69 x 10(-3) m2 E(-1) to 4.41 x 10(-3) m2 E(-1).