A simple guideline to apply excitation-emission matrix spectroscopy(EEMs)for the characterization of dissolved organic matter(DOM)in anoxic marine sediments

Marine sediments represent a major carbon reservoir on Earth.Dissolved organic matter(DOM)in pore waters accumulates products and intermediates of carbon cycling in sediments.The application of excitation-emission matrix spectroscopy(EEMs)in the analysis of subseafloor DOM samples is largely unexplored due to the redox-sensitive matrix of anoxic pore water.Therefore,this study aims to investigate the interference caused by the matrix on EEMs and propose a guideline to prepare pore water samples from anoxic marine sediments.The parameters determined by fluorescence spectra include 3D-index derived from EEMs after parallel factor analysis(PARAFAC),fluorescence index(FI)(contribution of terrigenous DOM),biological index(BIX)and humification index(HIX)derived from 2D emission spectra.First,we investigated the impacts of extensively-presented ions as typical electron acceptors,which are utilized by anaerobic microbes and stratified in marine sediments:Fe(II),Fe(III),Mn(II)and sulfide in anoxic pore water resulted in biases of fluorescent signals.We proposed threshold concentrations of these ions when the interference on EEMs occurred.Effective removal of sulfide from sulfide-rich samples could be achieved by flushing with N_(2)for 2 min.Second,the tests based on DOM standard were further verified using pristine samples from marine sediments.There was a significant change in the fluorescence spectra of DOM in anoxic sediments from the Rhône Delta.This study demonstrated that the change was caused by oxidation of the matrix rather than the intrinsic alteration of DOM.It was confirmed by extracted DOM via both EEMs analysis and Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR-MS).Slight oxidation of sulfur-containing compounds(e.g.,sulfhydryl)and polyphenol-like compounds occurred.Finally,a sample preparation sequence is proposed for pore water from anoxic sediments.This method enables measurement with small volumes of the sample(e.g.,50µL in this study)and ensures reliable data without the interference of the redox-sensitive matrix.This study provides access to the rapid analysis of DOM composition in marine sediments and can potentially open a window into examining the carbon cycling of the marine deep biosphere.

离子排斥色谱用于厌氧消化处理的水中脂肪族羧酸的分析(英文)

The analysis of seven aliphatic carboxylic acids(formic,acetic,propionic,iso-butyric,n-butyric,iso-valeric and n-valeric acid) in anaerobic digestion process waters for biogas production was examined by ion-exclusion chromatography with dilute acidic eluents(benzoic acid,perfluorobutyric acid(PFBA) and sulfuric acid) and non-suppressed conductivity/ultraviolet(UV) detection.The columns used were a styrene/divinylbenzene-based strongly acidic cation-exchange resin column(TSKgel SCX) and a polymethacrylate-based weakly acidic cation-exchange resin column(TSKgel Super IC-A/C).Good separation was performed on the TSKgel SCX in shorter retention times.For the TSKgel Super IC-A/C,peak shape of the acids was sharp and symmetrical in spite of longer retention times.In addition,the mutual separation of the acids was good except for iso-and n-butyric acids.The better separation and good detection was achieved by using the two columns(TSKgel SCX and TSKgel Super IC-A/C connected in series),lower concentrations of PFBA and sulfuric acid as eluents,non-suppressed conductivity detection and UV detection at 210 nm.This analysis was applied to anaerobic digestion process waters.The chromatograms with conductivity detection were relatively simpler compared with those of UV detection.The use of two columns with different selectivities for the aliphatic carboxylic acids and the two detection modes was effective for the determination and identification of the analytes in anaerobic digestion process waters containing complex matrices.