The factors controlling the accumulation of mercury in fish are poorly
understood. The oft invoked lipid solubility of MMHg is an inadequate
explanation because inorganic Hg complexes, which are not bioaccumula
ted, are as lipid soluble as their MMHg analogs and, unlike other hydr
ophobic compounds, MMHg in fish resides in protein rather than fat tis
sue. We show that passive uptake of the lipophilic complexes (primaril
y HgCl2, and CH3HgCl) results in high concentrations of both inorganic
and MMHg in phytoplankton. However, differences in partitioning withi
n phytoplankton cells between inorganic mercury - which is principally
membrane bound - and MMHg - which accumulates in the cytoplasm - lead
to a greater assimilation of MMHg during zooplankton grazing. Most of
the discrimination between inorganic and MMHg thus occurs during trop
hic transfer while the major enrichment factor is between water and ph
ytoplankton. As a result, MMHg concentrations in fish are ultimately d
etermined by water chemistry which controls MMHg speciation and uptake
at the base of the food chain.