Molecular transformation and degradation of refractory dissolved organic matter in the Atlantic and Southern Ocean

More than 90% of the global ocean dissolved organic carbon (DOC) is refractory, has an average age of 4,000–6,000 years and a lifespan from months to millennia. The fraction of dissolved organic matter (DOM) that is resistant to degradation is a long-term buffer in the global carbon cycle but its chemical composition, structure, and biochemical formation and degradation mechanisms are still unresolved. We have compiled the most comprehensive molecular data set of 197 Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analyses from solid-phase extracted marine DOM covering two major oceans, the Atlantic sector of the Southern Ocean and the East Atlantic Ocean (ranging from 50° N to 70° S). Molecular trends and radiocarbon dating of 34 DOM samples (comprising Δ14C values from -229 to -495‰) were combined to model an integrated degradation rate for bulk DOC resulting in a predicted age of >24 ka for the most persistent DOM fraction. First order kinetic degradation rates for 1,557 mass peaks indicate that numerous DOM molecules cycle on timescales much longer than the turnover of the bulk DOC pool (estimated residence times of >100 ka) and the range of validity of radiocarbon dating. Changes in elemental composition were determined by assigning molecular formulae to the detected mass peaks. The combination of residence times with molecular information enabled modelling of the average elemental composition of the slowest degrading fraction of the DOM pool. In our dataset, a group of 361 molecular formulae represented the most stable composition in the oceanic environment (“island of stability”). These most persistent compounds encompass only a narrow range of the elemental ratios H/C (average of 1.17 ± 0.13), and O/C (average of 0.52 ± 0.10) and molecular masses (360 ± 28 and 497 ± 51 Da). In the Weddell Sea DOC concentrations in the surface waters were low (46.3 ± 3.3 μM) while the organic radiocarbon was significantly more depleted than that of the East Atlantic, indicating average surface water DOM ages of 4,920 ± 180 a. These results are in accordance with a highly degraded DOM in the Weddell Sea surface water as also shown by the molecular degradation index IDEG obtained from FT-ICR MS data. Further, we identified 339 molecular formulae which probably contribute to an increased DOC concentration in the Southern Ocean and potentially reflect an accumulation or enhanced sequestration of refractory DOC in the Weddell Sea. These results will contribute to a better understanding of the persistent nature of marine DOM and its role as an oceanic carbon buffer in a changing climate

On the relation between organic and inorganic carbon in the Weddell Sea

Carbon cycling in the Weddell Sea was investigated during the ANT X/7 cruise with 'FS Polarstern' Dec. 1992 - Jan. 1993. Samples were taken on a cross section from Kapp Norvegia to Joinville Island, and on a section from the Larsen Ice Shelf to the north-east. The following quantities were measured: total carbon dioxide (TCO2), fluorescence from humic substances and total organic carbon. The distribution of TCO2 was strongly positively correlated to the time elapsed since the various water masses were last ventilated. In general, humic substance fluorescence was positively correlated with TCO2, with the exception of the productive part of the western Weddell Sea, where the correlation was negative in the surface mixed layer. The increased fluorescence at the surface is suggested to be a result of biological production. The distribution of total organic carbon showed less structure, since this quantity includes a particulate component, which is subject to dispersion processes different from those of the dissolved components TCO2 and humic substances. The mean total organic carbon concentration below the surface mixed layer was 50 µmol l1. At some stations, a steep maximum around 2000 m depth was observed. This was interpreted to result from mass sinking of phytoplankton blooms. Total organic carbon had a maximum in surface water and, at some stations also a second subsurface maximum. In the Warm Deep Water, TCO2 and fluorescence had their maximum values, while total organic carbon tended to be low. In low productivity surface water in the eastern part of the Kapp Norvegia - Joinville Island section, the lowest fluorescence was found. Surface water is eventually formed from Warm Deep Water, which had the highest fluorescence values, and therefore it is concluded that humic substances were removed in situ from surface water. In the central area of the Weddell Sea, TCO2 and fluorescence showed their highest Warm Deep Water maxima, while total organic carbon was low. The Warm Deep Water in this area, close to the axis of the Weddell Gyre, is part of the so-called Central Intermediate Water which circulates for a long time within the Gyre. Reduced total organic carbon, which coincides with the most pronounced Central Intermediate Water characteristics, and high TCO2 can thus both be accounted for by continued degradation of organic matter in this water mass. The associated fluorescence maximum implies that humic substances are also produced during mineralisation. Recently formed bottom water, by contrast, could be seen as patches of low TCO2, low fluorescence and high total organic carbon along the western slope of the Weddell Sea

Complexation of aluminum with DNA.

The extent of complexation of aluminum(III) with DNA (Calf thymus, Sigma type I) was estimated by means of two experimental techniques: potentiometric titration with a fluoride selective indicator electrode and dialysis followed by aluminum determination by graphite furnace AAS. Both types of experiments indicate that aluminum(III) is bound to DNA. The data are treated by assuming an ion exchange reaction with the phosphate diester groups. Using Rt to denote the concentration of these groups the values of log [AlMn-3R]/(Rt-3[AlMn-3R])[Al3+] decrease from approx. 7.6 to 5.6 when the concentration of sodium chloride is increased from 1 to 100 mM. In the pH range 4.5-5.5 the ion exchange constant increases approximately 0.5 log units. Dialysis gives lower values for the complex formation constant than potentiometry

Using fluorescence to characterize dissolved organic matter in Antarctic sea ice brines

Sea ice plays a dynamic role in the air‐sea exchange of CO2. In addition to abiotic inorganic carbon fluxes, an active microbial community produces and remineralizes organic carbon, which can accumulate in sea ice brines as dissolved organic matter (DOM). In this study, the characteristics of DOM fluorescence in Antarctic sea ice brines from the western Weddell Sea were investigated. Two humic‐like components were identified, which were identical to those previously found to accumulate in the deep ocean and represent refractory material. Three amino‐acid‐like signals were found, one of which was unique to the brines and another that was spectrally very similar to tryptophan and found both in seawater and in brine samples. The tryptophan‐like fluorescence in the brines exhibited intensities higher than could be explained by conservative behavior during the freezing of seawater. Its fluorescence was correlated with the accumulation of nitrogen‐rich DOM to concentrations up to 900 mmol L−1 as dissolved organic carbon (DOC) and, thus, potentially represented proteins released by ice organisms. A second, nitrogen‐poor DOM fraction also accumulated in the brines to concentrations up to 200 mmol L−1 but was not correlated with any of the fluorescence signals identified. Because of the high C:N ratio and lack of fluorescence, this material is thought to represent extracellular polymeric substances, which consist primarily of polysaccharides. The clear grouping of the DOM pool into either proteinaceous or carbohydrate‐dominated material indicates that the production and accumulation of these two subpools of DOM in sea ice brines is, to some extent, decoupled