Description: Oceans constitute one of the most important reservoirs for mercury. In order to provide a first insight into the concentrations of Hg species in the Atlantic sector of the Southern Ocean a sampling campaign was carried out south of the Polar Front. Water samples taken at discrete depths from the surface down to 300 m at six stations were analysed for total Hg (HgT), methylmercury (MeHg) and other interpretative parameters such as salinity, temperature, dissolved and particulate organic carbon, dissolved oxygen, chlorophyll and inorganic nutrients. Results showed a high spatial variability in the concentrations of HgT and MeHg. HgT (0.93±0.69 ng L−1) and MeHg (0.26±0.12 ng L−1) levels were similar or higher than those reported in previous works in high latitude studies. The highest values were found at a location (−53°, 10°E) south of the South Polar Front, an area of strong gradients caused by the mixing of different water masses. Vertical profiles showed a great variability even for those stations sampled at the same location or an area dominated by the same oceanographic features. A decrease of HgT and a consequent increase in MeHg with depth was observed in some sites, suggesting the occurrence of Hg-methylation process, while at other stations, a concurrent decrease or increase of both mercury species was observed. In spite of these differences, an overall positive correlation between HgT and MeHg was observed. Differences between vertical profiles of Hg species were attributed to favourable environmental conditions for Hg methylation. The highest proportion of MeHg (% of HgT) was observed in sites with low dissolved oxygen or highest estimated remineralization rates. The results obtained in this study show that the Hg distribution and speciation in the Atlantic sector of the SO is comparable (or in some sites higher) to the ones published for the other open ocean regions. However, the concentrations of MeHg in this area are more dependent on the environmental conditions than on the total concentration of Hg present in the water.

Description: A method is presented for the chemical characterization of natural organic matter (NOM). We combined reversed-phase chromatographic separation of NOM with high resolution inductively coupled plasma mass spectrometry. A desolvation technique was used to remove organic solvent derived from the preceding chromatographic separation. We applied our method to solid-phase extracted marine dissolved organic matter samples from South Atlantic and Antarctic surface waters. The method provided a direct and quantitative determination of dissolved organic phosphorus and sulfur in fractions of differing polarity and also allowed simultaneous speciation studies of trace elements. Dissolved organic carbon/phosphorus and carbon/sulfur ratios for the different chromatographic fractions of our two samples ranged between 341–3025 for C/P and 11–1225 for C/S. Differences in elemental distribution between the fractions were attributed to different biochemical environments of the samples. Sulfur was exclusively found in one hydrophilic fraction, while uranium showed a strong affinity to the hydrophobic fractions. Our method was designed to be easily adapted to other separation techniques. The elemental information will deliver valuable information for ultrahigh resolution molecular analyses.

Description: Investigating the biogeochemistry of dissolved organic matter (DOM) requires the synthesis of data from several complementary analytical techniques. The traditional approach to data synthesis is to search for correlations between measurements made on the same sample using different instruments. In contrast, data fusion simultaneously decomposes data from multiple instruments into the underlying shared and unshared components. Here, Advanced Coupled Matrix and Tensor Factorization (ACMTF) was used to identify the molecular fingerprint of DOM fluorescence fractions in Arctic fjords. ACMTF explained 99.84% of the variability with six fully shared components. Individual molecular formulas were linked to multiple fluorescence components and vice versa. Molecular fingerprints differed in diversity and oceanographic patterns, suggesting a link to the biogeochemical sources and diagenetic state of DOM. The fingerprints obtained through ACMTF were more specific compared to traditional correlation analysis and yielded greater compositional insight. Multivariate data fusion aligns extremely complex, heterogeneous DOM data sets and thus facilitates a more holistic understanding of DOM biogeochemistry.

Description: Marine dissolved organic matter (DOM) is an important component of the global carbon cycle, yet its intricate composition and the sea salt matrix pose major challenges for chemical analysis. We introduce a direct injection, reversed-phase liquid chromatography ultrahigh resolution mass spectrometry approach to analyze marine DOM without the need for solid-phase extraction. Effective separation of salt and DOM is achieved with a large chromatographic column and an extended isocratic aqueous step. Postcolumn dilution of the sample flow with buffer-free solvents and implementing a counter gradient reduced salt buildup in the ion source and resulted in excellent repeatability. With this method, over 5,500 unique molecular formulas were detected from just 5.5 nmol carbon in 100 μL of filtered Arctic Ocean seawater. We observed a highly linear detector response for variable sample carbon concentrations and a high robustness against the salt matrix. Compared to solid-phase extracted DOM, our direct injection method demonstrated superior sensitivity for heteroatom-containing DOM. The direct analysis of seawater offers fast and simple sample preparation and avoids fractionation introduced by extraction. The method facilitates studies in environments, where only minimal sample volume is available e.g. in marine sediment pore water, ice cores, or permafrost soil solution. The small volume requirement also supports higher spatial (e.g., in soils) or temporal sample resolution (e.g., in culture experiments). Chromatographic separation adds further chemical information to molecular formulas, enhancing our understanding of marine biogeochemistry, chemodiversity, and ecological processes.