The accumulation of dissolved organic matter (DOM) at the air-sea interface
is controlled by dynamic physical processes at the boundary between ocean
and atmosphere. Much of the DOM concentrated in the surface microlayer is t
hought to be protein or glycoprotein. Enzymatic hydrolysis of these and oth
er biopolymers is an important step in the microbial uptake of dissolved an
d particulate organic matter in many aquatic environments. We employed a se
nsitive fluorescence technique to investigate differences between extracell
ular enzymatic peptide hydrolysis in the sea surface microlayer and corresp
onding subsurface water from Stony Brook Harbor, NY. We separated the micro
layer from its underlying water and thus measured hydrolysis potential rath
er than an in-situ process. Peptide turnover was always faster in the micro
layer than in subsurface waters. This was confirmed by allowing a new surfa
ce film to form on subsurface water; hydrolysis was still faster in the new
surface film. In a year-long study, we found the relative difference betwe
en turnover times in the surface film and subsurface waters to vary greatly
with season. While rate constants of peptide hydrolysis were generally hig
her in both microlayer and bulk water samples in spring/summer than in fall
/winter, the difference in activity between the two environments was greate
st in winter. Enhanced hydrolysis in the sea surface microlayer is likely d
ue to the greater concentrations of DOM in the microlayer. Seasonal changes
in distribution of hydrolytic activity between surface film and subsurface
water probably reflect seasonal variation in the mechanisms of DOM enrichm
ent, which depend On water temperature, substance and energy fluxes across
the water-air boundary; activity of aquatic organisms and other seasonal va
riables. (C) 2001 Elsevier Science B.V. All rights reserved.