The mobilization of mercury and dissolved organic carbon (DOC) during snowmelt often accounts for a major fraction of the annual loads. We studied the role of hydrological connectivity of riparian wetlands and upland/wetland transition zones to surface waters on the mobilization of Hg and DOC in Fishing Brook, a headwater of the Adirondack Mountains, New York. Stream water total mercury (THg) concentrations varied strongly (mean = 2.25 ± 0.5 ng L⁻¹), and the two snowmelt seasons contributed 40% (2007) and 48% (2008) of the annual load. Methyl mercury (MeHg) concentrations ranged up to 0.26 ng L⁻¹, and showed an inverse log relationship with discharge. TOPMODEL‐simulated saturated area corresponded well with wetland areas, and the application of a flow algorithm based elevation‐above‐creek approach suggests that most wetlands become well connected during high flow. The dynamics of simulated saturated area and soil storage deficit were able to explain a large part of the variation of THg concentrations (r² = 0.53 to 0.72). In contrast, the simulations were not able to explain DOC variations and DOC and THg concentrations were not correlated. These results indicate that all three constituents, THg, MeHg, and DOC, follow different patterns at the outlet: (1) the mobilization of THg is primarily controlled by the saturation state of the catchment, (2) the dilution of MeHg suggests flushing from a supply limited pool, and (3) DOC dynamics follow a pattern different from THg dynamics, which likely results from differing gain and/or loss processes for THg and/or DOC within the Fishing Brook catchment.