New insights on ecosystem mercury cycling revealed by stable isotopes of mercury in water flowing from a headwater peatland catchment

Stable isotope compositions of mercury (Hg) were measured in the outlet stream and in soil cores at different landscape positions in a 9.7-ha boreal upland-peatland catchment. An acidic permanganate/persulfate digestion procedure was validated for water samples with high dissolved organic matter (DOM) concentrations through Hg spike addition analysis. We report a relatively large variation in mass-dependent fractionation (δ202Hg; from −2.12 to −1.32‰) and a smaller, but significant, variation of mass-independent fractionation (Δ199Hg; from −0.35 to −0.12‰) during two years of sampling with streamflow varying from 0.003 to 7.8 L s–1. Large variations in δ202Hg occurred only during low streamflow (<0.6 L s–1), which suggest that under high streamflow conditions a peatland lagg zone between the bog (3.0 ha) and uplands (6.7 ha) becomes the dominant source of Hg in downstream waters. Further, a binary mixing model showed that except for the spring snowmelt period, Hg in streamwater from the catchment was main...