The phase speciation and estuarine behavior of monomethyl mercury (MeHg) were determined in surface waters of the San Francisco Bay estuary in September-October 2000 (low flow)and March 2001 (high flow). Colloidally associated MeHg was isolated using a cross-flow ultrafiltration technique with a nominal molecular weight cutoff of I kDa. Filter-passing MeHg was 57 +/- 18% of the MeHg in unfiltered water in the fall and 39 +/- 12% in the spring. Colloidal MeHg averaged 34 +/- 11% of the filter passing MeHg in the fall and 56 +/- 15% in the spring. Significantly higher particle-water partition coefficients were observed between colloidal and dissolved MeHg (log K-C = 5.6 +/- 0.3, n = 21) compared with those between particulate and dissolved MeHg (log K-P = 4.9 +/- 0.5, n = 21), which suggests that MeHg is preferentially associated with colloidal material. Strong correlations of MeHg with organic carbon content in the filter-passing, colloidal, and dissolved fractions confirmed the importance of organic matter in the MeHg cycle. Both absolute and relative (as a percentage of Hg) MeHg concentrations were highest in the river water end-member under both flow-regimes, which suggests that riverborne MeHg is the major source of MeHg introduced to the estuary. A nonconservative estuarine mixing model suggests that significant amounts of colloidal and dissolved MeHg are removed in the estuary under both flow regimes, standing in marked contrast to Hg, which had a source within the estuary under the low flow condition.