Enhanced extracellular enzymatic peptide hydrolysis in the sea-surface microlayer

Abstract

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 thought to be protein or glycoprotein. Enzymatic hydrolysis of these and other biopolymers is an important step in the microbial uptake of dissolved and particulate organic matter in many aquatic environments. We employed a sensitive fluorescence technique to investigate differences between extracellular enzymatic peptide hydrolysis in the sea surface microlayer and corresponding subsurface water from Stony Brook Harbor, NY. We separated the microlayer from its underlying water and thus measured hydrolysis potential rather than an in-situ process. Peptide turnover was always faster in the microlayer than in subsurface waters. This was confirmed by allowing a new surface 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 between turnover times in the surface film and subsurface waters to vary greatly with season. While rate constants of peptide hydrolysis were generally higher in both microlayer and bulk water samples in spring/summer than in fall/winter, the difference in activity between the two environments was greatest in winter. Enhanced hydrolysis in the sea surface microlayer is likely due 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 enrichment, which depend on water temperature, substance and energy fluxes across the water–air boundary, activity of aquatic organisms and other seasonal variables.