Longitudinal and Vertical Variations of Dissolved Labile Phosphoric Monoesters and Diesters in the Subtropical North Pacific

The labile fraction of dissolved organic phosphorus (DOP) – predominantly consisting of phosphoric esters – is an important microbial P source in the subtropical oligotrophic ocean. However, unlike phosphate, knowledge for labile DOP is still limited due to the scarcity of broad and intensive observations. In this study, we examined the concentrations and size-fractionated hydrolysis rates of labile phosphoric monoesters and diesters along a >10,000 km longitudinal transect in the North Pacific (23°N; upper 200-m layer). Depth-integrated monoesters decreased westward with a maximum difference of fivefold. Vertical profiles of monoesters in the eastern and western basins showed decreasing and increasing trends with depth, respectively. The monoester-depleted shallow layer of the western basin was associated with phosphate depletion and monoesterase activity was predominant in the large size fraction (>0.8 μm), suggesting that monoesters are significant P sources particularly for large microbes. In contrast, diester concentrations were generally lower than monoester concentrations and showed no obvious horizontal or vertical variation in the study area. Despite the unclear distribution pattern of diesters, diesterase activity in the particulate fraction (>0.2 μm) increased in the phosphate-depleted shallow layer of the western basin, suggesting that the targeted diesters in the assay were also important microbial P sources. Diesterase activities in the dissolved fraction (<0.2 μm) were not correlated with ambient phosphate concentrations; however, cell-free diesterase likely played a key role in P cycling, as dissolved diesterase activities were substantially higher than those in the particulate fraction. The horizontal and vertical variability of labile monoesters in the subtropical North Pacific were therefore predominantly regulated by P stress in particularly large microbes, whereas the distributions of labile diesters and diesterase activities were generally independent of microbial P stress, indicating a more complex regulation of diesters to that of monoesters.

Impact of snow deposition on major and trace element concentrations and fluxes in surface waters of Western Siberian Lowland

Towards a better understanding of chemical composition of snow and its impact on surface water hydrochemistry in poorly studied Western Siberia Lowland (WSL), dissolved (melted snow) and particulate (> 0.45 μm) fractions of snow were sampled in February 2014 across a 1700-km latitudinal gradient (c.a. 56.5 to 68° N) in essentially pristine regions. Concentration of dissolved Fe, Co, Cu, As, La, increased by a factor of 2 to 5 north of 63° N. The pH, Ca, Mg, Sr, Mo and U dissolved concentration in snow water increased with the increase in concentration of particulate fraction (PF), which was also correlated with the increase in calcite and dolomite proportion in the mineral fraction, suggesting an enrichment of meltwater by these elements during dissolution of carbonate minerals. The concentrations of Al, Fe, Pb, La and other insoluble elements in

Spectroscopic detection of a ubiquitous dissolved pigment degradation product in subsurface waters of the global ocean

Measurements of light absorption by chromophoric dissolved organic matter (CDOM) from subsurface waters of the tropical Atlantic and Pacific Oceans showed a distinct absorption shoulder at 410–415 nm. This indicates an underlying absorption of a pigment whose occurrence is partly correlated with the apparent oxygen utilization (AOU) but also found in the deep chlorophyll maximum. A similar absorption maximum at ~415 nm was also found in the particulate fraction of samples taken below the surface mixing layer and is usually attributed to absorption by respiratory pigments of heterotrophic unicellular organisms. In our study, fluorescence measurements of pre-concentrated dissolved organic matter (DOM) samples from 200–6000 m confirmed a previous study suggesting that the absorption at ~415 nm was related to fluorescence at 650 nm in the oxygen minimum zone. The absorption characteristics of this fluorophore was examined by fluorescence emission/excitation analysis and showed a clear excitation maximum at 415 nm that could be linked to the absorption shoulder in the CDOM spectra. The spectral characteristics of the substance found in the dissolved and particulate fraction did not match with those of chlorophyll a degradation products (as found in a sample from the sea surface) but can be explained by the occurrence of porphyrin pigments from either heterotrophs or autotrophs. Combining the observations of the fluorescence and the 415-nm absorption shoulder suggests that there are high concentrations of a pigment degradation product in subsurface DOM of all major oceans. Most pronouncedly we found this signal in the deep chlorophyll maximum and the oxygen minimum zone of tropical regions. The origin, chemical nature, turnover rate, and fate of this molecule is so far unknown.

Indications for a ubiquitous dissolved pigment degradation product in subsurface waters of the global ocean

Measurements of light absorption by chromophoric dissolved organic matter (CDOM) from sub-surface waters of the tropical Atlantic and Pacific showed a distinct absorption shoulder at 410–415 nm, indicating an underlying absorption of a pigment. A similar absorption maximum at ~410 nm was also found in the particulate fraction and is usually attributed to absorption by respiratory pigments of heterotrophic unicellular organisms. The CDOM absorption shoulder was described earlier in the Indian Ocean at 600 m depth and was related to a "deep red fluorescence" found in the same depth, i.e. in the oxygen minimum zone (Breves et al., 2003; Broenkow et al., 1983). In our study, fluorescence measurements of pre-concentrated DOM samples confirmed that the absorption at ~410 nm was related to a specific fluorescence at 650 nm. The absorption characteristic of this specific fluorophor was examined by fluorescence emission/excitation analysis and this showed a clear excitation maximum at 415 nm (in methanol) that can explain the absorption shoulder in the CDOM spectra. The spectral characteristics of the substance found in the dissolved and particulate fraction did not match with those of chlorophyll a degradation products (as found in a sample from the sea surface) but can be explained by the occurrence of respiratory pigments from heterotrophs. Combining the observations of the "deep red fluorescence" and the 410 nm-absorption shoulder suggests that there are high concentrations of a pigment degradation product (cytochrome c) in DOM of all major oceans. Most pronouncedly we found this signal in the deep chlorophyll maximum and the oxygen minimum zone of tropical regions. The origin, chemical nature, turn-over rate, and fate of this molecule is so far unknown.