The emergent wetland and littoral components of the land-water zone are functionally coupled by the amounts and types of dissolved organic matter that are released, processed, transported to, and then further processed within the recipient waters. Operational couplings and integrations in freshwater ecosystems occur along physical and metabolic gradients of a number of scales from micrometer to kilometer dimensions. The operation and turnover of the microbial communities, largely associated with surfaces, generate the metabolic foundations for material fluxes along larger-scale gradients.Because of the predominance of small, shallow freshwater bodies, most dissolved organic carbon (DOC) of lacustrine and riverine ecosystems is derived from photosynthesis of higher plants and microflora associated with detritus, including sediments, and is only augmented by photosynthesis of phytoplankton. As the dissolved organic compounds generated in the wetland and littoral interface regions move toward the open-water regions of the ecosystems, partial utilization effects a selective increase in organic recalcitrance. Even though DOC from allochthonous and from interface sources is more recalcitrant than that produced by planktonic microflora, decomposition of the much larger interface quantities imported to the pelagic zone dominates ecosystem decomposition. The observed high sustained productivity of the land-water interface zone results from extensive recycling of essential resources (nutrients, inorganic carbon) and conservation mechanisms. On the average in lakes and streams, greater than 90 percent of the decomposition in the ecosystem is by bacteria utilizing DOM from non-pelagic sources of primary productivity. In addition to direct mineralization of DOC from non-pelagic sources, many of the organic compounds function indirectly to influence metabolism. New evidence is presented to demonstrate formation of complexes between humic and fulvic organic acids and extracellular enzymes. These complexes inhibit enzyme activity and can be transported within the ecosystem. The complex can be decoupled by mild ultraviolet photolysis with regeneration of enzyme activity in displaced locations.