ALBERT

Description: This paper proposes improved guidelines for dissolved organic matter (DOM) isolation by solid phase extraction (SPE) with a styrene-divinylbenzene copolymer (PPL) sorbent, which has become an established method for the isolation of DOM from natural waters, because of its ease of application and appreciable carbon recovery. Suwannee River water was selected to systematically study the effects of critical SPE variables such as loading mass, concentration, flow rate, and up-scaling on the extraction selectivity of the PPL sorbent. High-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and proton nuclear magnetic resonance (H-1 NMR) spectroscopy were performed to interpret the DOM chemical space of eluates, as well as permeates and-wash liquids with molecular resolution. Up to 89% dissolved organic carbon (DOC) recovery was obtained with a DOC/PPL mass ratio of 1:800 at a DOC concentration of 20 mg/L. With the 0 application of larger loading volumes, low proportions of highly oxygenated compounds were retained on the PPL sorbent. The effects of the flow rate on the extraction selectivity of the sorbent were marginal. Up-scaling had a limited effect on the extraction selectivity with the exception of increased self-esterification with a methanol solvent, resulting in methyl ester groups. Furthermore, the SPE/PPL extract exhibited highly authentic characteristics in comparison with original water and reverse osmosis samples. These findings will be useful for reproducibly isolating DOM with representative molecular compositions from various sources and concentrations and minimizing potential inconsistencies among interlaboratory comparative studies.

Description: Large Arctic rivers discharge significant amounts of dissolved organic matter (DOM) into the Arctic Ocean. We sampled natural waters of the Lena River, the Buor-Khaya Bay (Laptev Sea), permafrost melt water creeks, ice complex melt water creeks and a lake. The goal of this study was to characterize the molecular DOM composition with respect to different water bodies within the Lena Delta. We aimed at an identification of source-specific DOM molecular markers and their relative contribution to DOM of different origin. The molecular characterization was performed for solid-phase extracted DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Average dissolved organic carbon concentrations in the original samples were 490 ± 75 µmol C L−1 for riverine and bay samples and 399 ± 115 µmol C L−1 for permafrost melt water creeks. Average TDN concentrations were elevated in the permafrost melt waters (19.7 ± 7.1 µmol N L−1) in comparison to the river and the bay (both 13.2 ± 2.6 µmol N L−1). FT-ICR MS and statistical tools demonstrated that the origin of DOM in the Lena Delta was systematically reflected in its molecular composition. Magnitude weighted parameters calculated from MS data (O/Cwa, H/Cwa, C/Nwa) highlighted preliminary sample discrimination. The highest H/Cwa of 1.315 was found for DOM in melt water creeks in comparison to 1.281 for river and 1.230 for the bay samples. In the bay samples we observed a higher fraction of oxygen-rich components which was reflected in an O/Cwa ratio of 0.445 in comparison to 0.425 and 0.427 in the river and creeks, respectively. From the southernmost location to the bay a relative depletion of nitrogenous molecular markers and an enrichment of oxidized DOM components occurred. The highest contribution of nitrogenous components was indicative for creeks reflected in a C/Nwa of 104 in comparison to 143 and 176 in the river and bay, respectively. These observations were studied on a molecular formula level using principal component and indicator value analyses. The results showed systematic differences with respect to water origin and constitute an important basis for a better mechanistic understanding of DOM transformations in the changing Arctic rivers.

Description: Marine bacteria are the main consumers of the organic matter and largely control 〈sub〉2〈/sub〉 and CO〈sub〉2〈/sub〉 budgets in the ocean. The present increase in anthropogenic O〈sub〉2〈/sub〉 emissions is constantly decreasing seawater pH. This ocean acidification is expected to affect enzymatic hydrolysis of organic compounds with so-far unknown consequences for microbial physiology, organic matter cycling and marine biogeochemistry. We studied the effect of ocean acidification on a natural plankton community during a large-scale mesocosm study in the Raunefjord (Norway). We determined the concentration and composition of dissolved organic matter, in particular combined carbohydrates and amino acid, as well as marine gel particles, bacterial growth and enzymatic rates of organic matter hydrolysis. Dissolved organic carbon concentrations were increasing over time in all treatments while dissolved organic nitrogen concentrations remained stable. We observed higher protein hydrolysis rates, gel particle concentrations, and bacterial cell numbers in the low pH treatments. We conclude that ocean acidification may favor bacterial growth and degradation activities and therewith potentially change organic matter composition and cycling in the future ocean.

Description: 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.

Description: Large Arctic rivers discharge significant amounts of dissolved organic matter (DOM) into the Arctic Ocean. We sampled natural waters of the Lena River, the Buor-Khaya Bay (Laptev Sea), permafrost melt water creeks, ice complex melt water creeks and a lake. The goal of this study was to characterize the molecular DOM composition with respect to different water bodies within the Lena Delta. We aimed at an identification of source-specific DOM molecular markers and their relative contribution to DOM of different origin. The molecular characterization was performed for solid-phase extracted DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Average dissolved organic carbon concentrations in the original samples were 490±75 µmol C/L for riverine and bay samples and 399±115 µmol C/L for permafrost melt water creeks. Average TDN concentrations were elevated in the permafrost melt waters (19.7±7.1 µmol N/L) in comparison to the river and the bay (both 13.2±2.6 µmol N/L). FT-ICR MS and statistical tools demonstrated that the origin of DOM in the Lena Delta was systematically reflected in its molecular composition. Magnitude weighted parameters calculated from MS data (O/Cwa, H/Cwa, C/Nwa) highlighted preliminary sample discrimination. The highest H/Cwa of 1.315 was found for DOM in melt water creeks in comparison to 1.281 for river and 1.230 for the bay samples. In the bay samples we observed a higher fraction of oxygen-rich components which was reflected in an O/Cwa ratio of 0.445 in comparison to 0.425 and 0.427 in the river and creeks, respectively. From the southernmost location to the bay a relative depletion of nitrogenous molecular markers and an enrichment of oxidized DOM components occurred. The highest contribution of nitrogenous components was indicative for creeks reflected in a C/Nwa of 104 in comparison to 143 and 176 in the river and bay, respectively. These observations were studied on a molecular formula level using principal component and indicator value analyses. The results showed systematic differences with respect to water origin and constitute an important basis for a better mechanistic understanding of DOM transformations in the changing Arctic rivers.