Ultrahigh resolution mass spectrometric differentiation of dissolved organic matter isolated by coupled reverse osmosis-electrodialysis from various major oceanic water masses

• A broad range of oceanic DOM, isolated by RO/ED, was analyzed by FTICR-MS.
• A high percentage of molecular signatures were common to all samples.
• Pacific and Atlantic surface waters were enriched in high H/C molecular formulas.
• North Pacific deep waters were enriched in high O/C molecular formulas.
• North Pacific subtropical gyre waters were enriched in photo-refractory DOM.

A high-recovery technique of dissolved organic matter (DOM) isolation – reverse osmosis coupled with electrodialysis (RO/ED) – was used to isolate DOM from the North Atlantic Senegal-Mauritanian upwelling area surface water (5 m), North Atlantic oxygen minimum water (415 m) and deep water (3000 m), North Pacific subtropical gyre surface water (5 m), and North Pacific intermediate water (674 m) and deep water (3500 m). Samples were characterized by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry with electrospray ionization (ESI FTICR-MS). RO/ED isolated DOM samples share a significant number of common formulas accounting for 54–79% of formulas in each sample. Total dissolved carbohydrate (TCHO) concentrations in RO/ED isolated DOM were specifically measured using a colorimetric method, and were found to have higher contribution to DOC than estimated by FTICR-MS data. Percentages of TCHO-C in DOC are in the range of 3.7–19.6% in all samples, with the North Pacific deep (3500 m) water having the lowest % and the North Atlantic upwelling core surface water having the highest %. Principal component analysis (PCA) using the relative magnitudes of MS peaks facilitated identification of specific peaks that are enriched in different samples. Peaks enriched in surface samples have higher H/C values than peaks enriched in deep samples, in both the North Atlantic DOM and the North Pacific DOM. This enrichment pattern is likely due to the selective photo-degradation of aromatic compounds and the bio-production of aliphatic and carbohydrate-like compounds in surface waters, and the selective bio-degradation of aliphatic and carbohydrate-like compounds with increasing depth. In further support of a photo-degraded signature for DOM in surface waters, photo-resistant and photo-produced molecular formulas were present in the highest numbers in the surface North Pacific subtropical gyre DOM. Peaks enriched in the North Pacific intermediate and deep DOM have significantly higher O/C values than the North Atlantic oxygen minimum layer and deep DOM, for both CHO formula compounds and CHON formula compounds. This difference in O/C values observed for the deep Pacific vs. Atlantic suggests oxidation of DOM, possibly via microbial activity during the ageing of DOM or the preferential remineralization of DOM from sinking particles at depth in the Pacific.