What Is the Molecular Weight of "High" Molecular Weight Dissolved Organic Matter?

The use of ultrafiltration to isolate high molecular weight dissolved organic matter (HMWDOM) from seawater is a fundamental tool in the environmental organic chemist's toolbox. Yet, important characteristics of HMWDOM relevant to its origin and cycling, such as its molecular weight distribution, remain poorly defined. We used diffusion-ordered NMR spectroscopy coupled with mixed-mode chromatography to separate and characterize two major components of marine HMWDOM: acylpolysaccharides (APS) and high molecular weight humic substances (HS). The molecular weights (MWs) of APS and HS both fell within distinct, narrow envelopes; 2.0-16 kDa for APS and 0.9-6.5 kDa for HS. In water samples from the North Pacific Ocean the average MW of both components decreased with depth through the mesopelagic. However, the minimum MW of APS was >2 kDa, well above the molecular weight cutoff of the ultrafilter, suggesting APS removal processes below 2 kDa are highly efficient. The MW distribution of APS shows only small variations with depth, while the MW distribution of HS narrowed due to removal of HMW components. Despite the narrowing of the MW distribution, the concentration of HS did not decrease with depth between 15 and 915 m. This suggests that HMW HS produced in surface waters was either degraded into lower MW compounds without significant remineralization, or that HMW HS was remineralized but replaced by an additional source of HS in the mesopelagic ocean. Based on these results, we propose potential pathways for the production and removal of these major components of HMWDOM.