No abstract

Untargeted molecular analyses of complex mixtures are relevant for many fields of research, including geochemistry, pharmacology, and medicine. Ultrahigh-resolution mass spectrometry is one of the most powerful tools in this context. The availability of open scripts and online tools for specific data processing steps such as noise removal or molecular formula assignment is growing, but an integrative tool where all crucial steps are reproducibly evaluated and documented is lacking. We developed a novel, server-based tool (ICBM-OCEAN, Institute for Chemistry and Biology of the Marine Environment, Oldenburg−complex molecular mixtures, evaluation & analysis) that integrates published and novel approaches for standardized processing of ultrahigh-resolution mass spectrometry data of complex molecular mixtures. Different from published approaches, we offer diagnostic and validation tools for all relevant steps. Among other features, we included objective and reproducible reduction of noise and systematic errors, spectra recalibration and alignment, and identification of likeliest molecular formulas. With 15 chemical elements, the tool offers high flexibility in formula attribution. Alignment of mass spectra among different samples prior to molecular formula assignment improves mass error and facilitates molecular formula confirmation with the help of isotopologues. The online tool and the detailed instruction manual are freely accessible at www.icbm.de/icbm-ocean.

No 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.