A simple protocol is presented for the solid‐phase extraction of dissolved organic matter (SPE‐DOM) from seawater using commercially prepacked cartridges. The method does not require major instrumentation and can be performed in the field. Modified styrene divinyl benzene polymer type sorbents (Varian PPL and ENV) and sorbents of a silica structure bonded with different hydrocarbon chains (Varian C8, C18, C18OH, and C18EWP) were considered. Except for C18OH, which heavily contaminated the samples, none of the sorbents leached significant amounts of dissolved organic carbon (DOC) or nitrogen (DON). Samples from the North Brazil shelf with strong mixing gradients of terrigenous and marine DOM were used to compare the various sorbents. PPL was the most efficient—on average, 62% of DOC was recovered as salt‐free extracts. C18 was found to be most efficient among the silica‐based sorbents, but it showed only two‐thirds of the extraction efficiency of PPL. As indicated by [1H]NMR, C/N, and δ13C analyses, PPL extracted a more representative proportion of DOM than C18. Therefore, PPL was used for comparative studies in the Gulf of Mexico and Antarctica. From brackish marsh and river waters, 65% and 62% of total DOC, respectively, could be extracted. For purely marine DOM in Antarctica and the deep sea, the extraction efficiency was lower (43% on average). The efficiency of the new method to isolate marine DOM is better than or similar to highly laborious methods. A further advantage is the complete desalination of the sample. The isolation of a major DOM fraction, which is salt‐free, offers many possibilities to further characterize DOM by advanced analytical techniques.

Recent progress in Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) has provided extensive molecular mass data for complex natural organic matter (NOM). Structural information can be deduced solely from the molecular masses for ions with extreme molecular element ratios, in particular low H/C ratios, which are abundant in thermally altered NOM (e.g. black carbon). In this communication we propose a general aromaticity index (AI) and two threshold values as unequivocal criteria for the existence of either aromatic (AI > 0.5) or condensed aromatic structures (AI ‡ 0.67) in NOM. AI can be calculated from molecular formulae which are derived from exact molecular masses of naturally occurring compounds containing C, H, O, N, S and P, and is especially useful for substances with aromatic cores and few alkylations. In order to test the validity of our model index, AI is applied to FTICRMS data of a NOM deep-water sample from the Weddell Sea (Antarctica), a fulvic acid standard, and an artificial dataset of all theoretically possible molecular formulae. For graphical evaluation a ternary plot is suggested for four-dimensional data representation. The proposed aromaticity index is a step towards structural identification of NOM and the molecular identification of polyaromatic hydrocarbons in the environment.

For the calculation of the Aromaticity Index (AI) all functional groups that potentially contribute Double Bond Equivalents (DBE) through bonds between carbon and heteroelements are subtracted from the original molecular formula. DBE AI is the DBE of the resulting molecular core, and C AI is the respective number of carbon atoms. AI is the DBE AI to C AI ratio.By mistake, in Eqn. (3), the number of N and P is not adjusted, as done in the correct way in Table 1 (compound d) of the original publication. This error is only relevant for molecular formulae that contain N and P, and in these cases it leads to a slight overestimation of DBE AI and consequently of AI. The corrected Eqn. (3) should read (the corrections are printed in bold red):

Soils, sediments, freshwaters, and marine waters contain natural organic matter (NOM), an exceedingly complex mixture of organic compounds that collectively exhibit a nearly continuous range of properties (size-reactivity continuum). NOM is composed mainly of carbon, hydrogen, and oxygen, with minor contributions from heteroatoms such as nitrogen, sulfur, and phosphorus. Suwannee River fulvic acid (SuwFA) is a fraction of NOM that is relatively depleted in heteroatoms. Ultrahigh resolution Fourier transform ion cyclotron (FTICR) mass spectra of SuwFA reveal several thousand molecular formulas, corresponding in turn to several hundred thousand distinct chemical environments of carbon even without accountancy of isomers. The mass difference deltam among adjoining C,H,O-molecules between and within clusters of nominal mass is inversely related to molecular dissimilarity: any decrease of deltam imposes an ever growing mandatory difference in molecular composition. Molecular formulas that are expected for likely biochemical precursor molecules are notably absent from these spectra, indicating that SuwFA is the product of diagenetic reactions that have altered the major components of biomass beyond the point of recognition. The degree of complexity of SuwFA can be brought into sharp focus through comparison with the theoretical limits of chemical complexity, as constrained and quantized by the fundamentals of chemical binding. The theoretical C,H,O-compositional space denotes the isomer-filtered complement of the entire, very vast space of molecular structures composed solely of carbon, hydrogen, and oxygen. The molecular formulas within SuwFA occupy a sizable proportion of the theoretical C,H,O-compositional space. A 100 percent coverage of the theoretically feasible C,H,O-compositional space by SuwFA molecules is attained throughout a sizable range of mass and H/C and O/C elemental ratios. The substantial differences between (and complementarity of) the SuwFA molecular formulas that are observed using six different modes of ionization (APCI, APPI, and ESI in positive and negative modus) imply considerable selectivity of the ionization process and suggest that the observed mass spectra represent simplified projections of still more complex mixtures.

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Ultrahigh-resolution mass spectrometry via the Fourier transform ion cyclotron resonance technique (FT-ICR-MS) allows the identification of thousands of different molecular formulas in natural organic matter and petroleum samples. Molecular formula assignment from mass data is most critical and time-consuming for these samples, and in many cases, several formulas can be determined for the same molecular mass. Therefore, automated procedures are required for an efficient exploitation of the extensive data sets. Here, we revise statements in a recent publication,1 which might result in a misleading impression about our approach of formula assignment in a previous work. We also summarize and categorize existing procedures for formula assignment. In addition, we propose new techniques, which are suitable to be implemented in automated evaluation software. The homologous series approach is extended toward a building block approach that can be applied as a new exclusion criterion for incorrect formula assignments. The examination of stable isotope ratios of individual molecules in natural organic matter can be applied as an additional and intrinsic evaluation for calculated molecular formulas.

High-performance, non-target, high-resolution organic structural spectroscopy was applied to solid phase extracted marine dissolved organic matter (SPE-DOM) isolated from four different depths in the open South Atlantic Ocean off the Angola coast (3° E, 18° S; Angola Basin) and provided molecular level information with extraordinary coverage and resolution. Sampling was performed at depths of 5 m (Angola Current; near-surface photic zone), 48 m (Angola Current; fluorescence maximum), 200 m (still above Antarctic Intermediate Water, AAIW; upper mesopelagic zone) and 5446 m (North Atlantic Deep Water, NADW; abyssopelagic, ~30 m above seafloor) and produced SPE-DOM with near 40% carbon yield and beneficial nuclear magnetic resonance (NMR) relaxation properties, a crucial prerequisite for the acquisition of NMR spectra with excellent resolution. ¹H and ¹³C NMR spectra of all four marine SPE-DOM showed smooth bulk envelopes, reflecting intrinsic averaging from massive signal overlap, with a few percent of visibly resolved signatures and variable abundances for all major chemical environments. The abundance of singly oxygenated aliphatics and acetate derivatives in ¹H NMR spectra declined from surface to deep marine SPE-DOM, whereas C-based aliphatics and carboxyl-rich alicyclic molecules (CRAM) increased in abundance. Surface SPE-DOM contained fewer methyl esters than all other samples, likely a consequence of direct exposure to sunlight. Integration of ¹³C NMR spectra revealed continual increase of carboxylic acids and ketones from surface to depth, reflecting a progressive oxygenation, with concomitant decline of carbohydrate-related substructures. Aliphatic branching increased with depth, whereas the fraction of oxygenated aliphatics declined for methine, methylene and methyl carbon. Lipids in the oldest SPE-DOM at 5446 m showed a larger share of ethyl groups and methylene carbon than observed in the other samples.

Two-dimensional NMR spectra showed exceptional resolution and depicted resolved molecular signatures in excess of a certain minimum abundance. Classical methyl groups terminating aliphatic chains represented ~15% of total methyl in all samples investigated. A noticeable fraction of methyl (~2%) was bound to olefinic carbon. Methyl ethers were abundant in surface marine SPE-DOM, and the chemical diversity of carbohydrates was larger than that of freshwater and soil DOM.

In all samples, we identified sp²-hybridized carbon chemical environments with discrimination of isolated and conjugated olefins and α,β-unsaturated double bonds. Olefinic proton and carbon atoms were more abundant than aromatic ones; olefinic unsaturation in marine SPE-DOM will be more directly traceable to ultimate biogenic precursors than aromatic unsaturation. The abundance of furan, pyrrol and thiophene derivatives was marginal, whereas benzene derivatives, phenols and six-membered nitrogen heterocycles were prominent; a yet unassigned set of s...

The Arctic icescape is rapidly transforming from a thicker multiyear ice cover to a thinner and largely seasonal first-year ice cover with significant consequences for Arctic primary production. One critical challenge is to understand how productivity will change within the next decades. Recent studies have reported extensive phytoplankton blooms beneath ponded sea ice during summer, indicating that satellite-based Arctic annual primary production estimates may be significantly underestimated. Here we present a unique time-series of a phytoplankton spring bloom observed beneath snow-covered Arctic pack ice. The bloom, dominated by the haptophyte algae Phaeocystis pouchetii, caused near depletion of the surface nitrate inventory and a decline in dissolved inorganic carbon by 16 ± 6 g C m−2. Ocean circulation characteristics in the area indicated that the bloom developed in situ despite the snow-covered sea ice. Leads in the dynamic ice cover provided added sunlight necessary to initiate and sustain the bloom. Phytoplankton blooms beneath snow-covered ice might become more common and widespread in the future Arctic Ocean with frequent lead formation due to thinner and more dynamic sea ice despite projected increases in high-Arctic snowfall. This could alter productivity, marine food webs and carbon sequestration in the Arctic Ocean.