Variations in dissolved organic matter chemistry on a vertical scale in the eastern Indian Ocean

Abstract

Oceans cover approximately 71% of the Earth's surface area, which is why some people refer to the Earth as a large water sphere. Marine dissolved organic matter (DOM) constitutes the main carbon pool for biogeochemical cycles and plays an important role in global carbon dynamics. Here, the molecular composition and component characteristics of surface (5 m), deep chlorophyll maximum (DCM), and deep (2000 m) layer DOM in the eastern Indian Ocean (EIO) were investigated using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and three-dimensional fluorescence spectroscopy. Thousands of individual DOM formulas (approximately 3716-6986 formulas) were detected at 100-700 Da, showing a Gaussian distribution. The elements carbon (C), hydrogen (H), oxygen (O), nitrogen (N) and sulfur (S) were detected and constituted four formula classes in solid-phase extracted marine DOM samples. Furthermore, the order of the percent intensity of the formulas was CHO > CHNO > CHOS > CHNOS. Carboxylic-rich alicyclic molecule (CRAM) compounds, as part of recalcitrant DOM (RDOM), were detected at 61.32%-78.77% (by intensity). In addition, the concept of islands of stability (IOS, approximately 3.99%-11.22%) has been proposed in this study, representing the most stable components in the marine environment. Such molecular formulas as described above probably contribute to increased RDOM content in the EIO and potentially reflect enhanced accumulation or sequestration of RDOM in the deep layer. The variation in the spectroscopic indices (FI, β/α, BIX, and HIX) and fluorescent components (C1 to C4) with depth indicates a shift from protein-like to humic-like components, leading to gradual aging of the water column. In brief, this study relies on data from marine DOM in the EIO to provide a molecular and chemical background for global models of marine DOM production, transformation and sequestration.

Keywords: Carboxylic-rich alicyclic molecules (CRAMs); Dissolved organic matter (DOM); Fluorescent components; Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS); Recalcitrant DOM (RDOM); Spectroscopic indices.