Dataset Information

Molecular Fractionation of Dissolved Organic Matter in a Shallow Subterranean Estuary: The Role of the Iron Curtain.

ABSTRACT: Iron that precipitates under aerobic conditions in natural aquatic systems scavenges dissolved organic matter (DOM) from solution. Subterranean estuaries (STEs) are of major importance for land-ocean biogeochemical fluxes. Their specific redox boundaries, coined the "iron curtain" due to the abundance of precipitated iron(III) (oxy)hydroxides, are hot spots for the removal and redissolution of iron, associated nutrients, and DOM. We used ultra-high-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to molecularly characterize the iron-coagulating fractions of 32 groundwater and seawater DOM samples along a salinity gradient from a shallow STE on Spiekeroog Island, North Sea, Germany, and linked our findings to trace metal and nutrient concentrations. We found systematic iron coagulation of large (>450 Da), oxygen-rich, and highly aromatic DOM molecules of terrestrial origin. The extent of coagulation increased with growing terrestrial influence along the salinity gradient. Our study is the first to show that the iron curtain may be capable of retaining terrigenous DOM fractions in marine sediments. We hypothesize that the iron curtain serves as an inorganic modulator for the supply of DOM from groundwaters to the sea, and that the STE has the potential to act as a temporal storage or even sink for terrigenous aromatic DOM compounds.

SUBMITTER: Linkhorst A

PROVIDER: S-EPMC5299545 | biostudies-literature | 2017 Feb

REPOSITORIES: biostudies-literature

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Molecular Fractionation of Dissolved Organic Matter in a Shallow Subterranean Estuary: The Role of the Iron Curtain.

Linkhorst Annika A Dittmar Thorsten T Waska Hannelore H

Environmental science & technology 20170119 3

Iron that precipitates under aerobic conditions in natural aquatic systems scavenges dissolved organic matter (DOM) from solution. Subterranean estuaries (STEs) are of major importance for land-ocean biogeochemical fluxes. Their specific redox boundaries, coined the "iron curtain" due to the abundance of precipitated iron(III) (oxy)hydroxides, are hot spots for the removal and redissolution of iron, associated nutrients, and DOM. We used ultra-high-resolution electrospray ionization Fourier tran ...[more]

PMID: 27976873

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Project description:Dissolved organic matter (DOM) is ubiquitous in natural waters and plays a central role in the biogeochemistry in riverine, estuarine and marine environments. This study quantifies and characterizes solid-phase extractable DOM and trace element complexation at different salinities in the Weser and Elbe River, northern Germany, and the North Sea. Dissolved organic carbon (DOC), total dissolved nitrogen (TDN), Co and Cu concentrations were analyzed in original water samples. Solid-phase extracted (SPE) water samples were analyzed for DOC (DOCSPE), dissolved organic nitrogen (DONSPE), sulfur (DOSSPE) and trace metal (51V, 52Cr, 59Co, 60Ni, 63Cu, 75As) concentrations. Additionally, different pre-treatment conditions (acidification vs. non-acidification prior to SPE) were tested. In agreement with previous studies, acidification led to generally higher recoveries for DOM and trace metals. Overall, higher DOM and trace metal concentrations and subsequently higher complexation of trace metals with carbon and sulfur-containing organic complexes were found in riverine compared to marine samples. With increasing salinity, the concentrations of DOM decreased due to estuarine mixing. However, the slightly lower relative decrease of both, DOCSPE and DONSPE (~77%) compared to DOSSPE (~86%) suggests slightly faster removal processes for DOSSPE. A similar distribution of trace metal and carbon and sulfur containing DOM concentrations with salinity indicates complexation of trace metals with organic ligands. This is further supported by an increase in Co and Cu concentration after oxidation of organic complexes by UV treatment. Additionally, the complexation of metals with organic ligands (analyzed by comparing metal/DOCSPE and metal/DOSSPE ratios) decreased in the order Cu > As > Ni > Cr > Co and thus followed the Irving-Williams order. Differences in riverine and marine trace metal containing DOMSPE are summarized by their average molar ratios of (C107N4P0.013S1)1000V0.05Cr0.33Co0.19Ni0.39Cu3.41As0.47 in the riverine endmember and (C163N7P0.055S1)1000V0.05Cr0.47Co0.16Ni0.07Cu4.05As0.58 in the marine endmember.

Project description:Analyzing the molecular composition change of dissolved organic matter (DOM) during transportation in estuaries can enhance our understanding of the fate of DOM. However, the impact of hydrologic conditions resulting from large river plumes on the DOM cycle are less explored, and previous studies were insufficient to capture the molecular fate that occur during the transportation process. In this study, we used a range of bulk and optical techniques, as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), to determine the concentration and characteristics of DOM along two trajectories of downstream plumes of diluted water of the Yangtze (Changjiang) River estuary (YRE) during the high discharge season. These two plumes situated along the route of the summer Changjiang diluted water (CDW) have been identified and named CDW-North (CDW-N) and CDW-South (CDW-S), respectively. Despite having the same riverine end-member origin, the turbidity zone in YRE significantly modifies the molecular characteristics and composition of DOM. The results of FT-ICR MS indicated a spatial variation of DOM composition in the coastal zone of the two plumes. The relative intensities of the CHO, CHOS, and CHONS compounds are negatively correlated with salinity. In addition, the coastal zones of both CDW-N and CDW-S are characterized by more autochthonous DOM sources. More CHON compounds in CDW-N are probably due to the production of autochthonous DOM in offshore waters. The activity of phytoplankton increased the surface dissolved oxygen level of CDW-N in the coastal zone. However, the hypoxic zone formed at the bottom of the CDW-N due to microbial degradation of organic matter and may further benefit the preservation of CHON compounds. Our study emphasizes that the characteristics and composition of the estuarine DOM can be significantly shaped by distinct large river plumes. Furthermore, using FT-ICR MS in combination with complementary techniques can better assist in identifying the sources and transformation mechanisms of estuarine DOM in large river plume-affected systems and provide more valuable insights into the role of DOM in the estuarine biogeochemical cycle.

Dataset Information

Molecular Fractionation of Dissolved Organic Matter in a Shallow Subterranean Estuary: The Role of the Iron Curtain.

Publications

Molecular Fractionation of Dissolved Organic Matter in a Shallow Subterranean Estuary: The Role of the Iron Curtain.

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