Character and environmental lability of cyanobacteria-derived dissolved organic matter

Autotrophic dissolved organic matter (DOM) is central to the carbon biogeochemistry of aquatic systems, and the full complexity of autotrophic DOM has not been extensively studied, particularly by high-resolution mass spectrometry (HRMS). Terrestrial DOM tends to dominate HRMS studies in freshwaters due to the propensity of such compounds to ionize by negative mode electrospray, and possibly also because ionizable DOM produced by autotrophy is decreased to low steady-state concentrations by heterotrophic bacteria. In this study, we investigated the character of DOM produced by the widespread cyanobacteriaMicrocystis aeruginosausing high-pressure liquid chromatography-electrospray ionization-high-resolution mass spectrometry.M. aeruginosaproduced thousands of detectable compounds in axenic culture. These compounds were chromatographically resolved and the majority were assigned to aliphatic formulas with a broad polarity range. We found that the DOM produced byM. aeruginosawas highly susceptible to removal by heterotrophic freshwater bacteria, supporting the hypothesis that this autotroph-derived organic material is highly labile and accordingly only seen at low concentrations in natural settings

Identification of dissolved organic matter size components in freshwater and marine environments

Dissolved organic matter (DOM) in the transition zone from freshwater to marine systems was analyzed with a new approach for parameterizing the size distribution of organic compounds. We used size-exclusion chromatography for molecular size analysis and quantified colored DOM (CDOM) on samples from two coastal environments in the Baltic Sea (Roskilde Fjord, Denmark and Gulf of Gdansk, Poland). We applied a Gaussian decomposition method to identify peaks from the chromatograms, providing information beyond bulk size properties. This approach complements methods where DOM is separated into size classes with pre-defined filtering cutoffs, or methods where chromatograms are used only to infer average molecular weight. With this decomposition method, we extracted between three and five peaks from each chromatogram and clustered these into three size groups. To test the applicability of our method, we linked our decomposed peaks with salinity, a major environmental driver in the freshwater-marine continuum. Our results show that when moving from freshwater to low-salinity coastal waters, the observed steep decrease of apparent molecular weight is mostly due to loss of the high-molecular-weight fraction (HMW; >2 kDa) of CDOM. Furthermore, most of the CDOM absorbance in freshwater originates from HMW DOM, whereas the absorbing moieties are more equally distributed along the smaller size range (<2 kDa) in marine samples.Peer reviewe

The changing carbon cycle of the coastal ocean

The carbon cycle of the coastal ocean is a dynamic component of the global carbon budget. But the diverse sources and sinks of carbon and their complex interactions in these waters remain poorly understood. Here we discuss the sources, exchanges and fates of carbon in the coastal ocean and how anthropogenic activities have altered the carbon cycle. Recent evidence suggests that the coastal ocean may have become a net sink for atmospheric carbon dioxide during post-industrial times. Continued human pressures in coastal zones will probably have an important impact on the future evolution of the coastal ocean's carbon budget

Advances in structure elucidation of small molecules using mass spectrometry

The structural elucidation of small molecules using mass spectrometry plays an important role in modern life sciences and bioanalytical approaches. This review covers different soft and hard ionization techniques and figures of merit for modern mass spectrometers, such as mass resolving power, mass accuracy, isotopic abundance accuracy, accurate mass multiple-stage MS(n) capability, as well as hybrid mass spectrometric and orthogonal chromatographic approaches. The latter part discusses mass spectral data handling strategies, which includes background and noise subtraction, adduct formation and detection, charge state determination, accurate mass measurements, elemental composition determinations, and complex data-dependent setups with ion maps and ion trees. The importance of mass spectral library search algorithms for tandem mass spectra and multiple-stage MS(n) mass spectra as well as mass spectral tree libraries that combine multiple-stage mass spectra are outlined. The successive chapter discusses mass spectral fragmentation pathways, biotransformation reactions and drug metabolism studies, the mass spectral simulation and generation of in silico mass spectra, expert systems for mass spectral interpretation, and the use of computational chemistry to explain gas-phase phenomena. A single chapter discusses data handling for hyphenated approaches including mass spectral deconvolution for clean mass spectra, cheminformatics approaches and structure retention relationships, and retention index predictions for gas and liquid chromatography. The last section reviews the current state of electronic data sharing of mass spectra and discusses the importance of software development for the advancement of structure elucidation of small molecules