Description: Terrestrial dissolved organic matter (DOM) is continuously discharged by rivers into the ocean. The enhanced permafrost thawing and increased arctic river discharges over the last decades have heightened concern about the input of terrestial materials into the Arctic coastal waters. Chromophoric dissolved organic matter (CDOM) is the optically active component of DOM formed by organic compounds that absorb light at both ultraviolet and visible wavelength bands. This DOM fraction has a strong impact in the carbon cycle and other elements mediating photochemical reactions and, hence, modulates light attenuation in the ocean. Therefore, CDOM interferes with satellite estimations of chlorophyll a and primary production. The objective of this work is to analyze the field CDOM data set including: 202 water samples and 18 vertical CDOM fluorescence profiles taken at oceanographic stations carried out during the TRANSDRIFT-XVII expedition to the Laptev Sea, and 15 water samples from the Lena2010 expedition. Thirty satellite images capturing the Laptev Sea region in September 2010 were processed to reveal the spatial distribution of optical parameters in the surface layer and to correlate the field CDOM and turbidity data with remote sensing data. A relationship between salinity, absorption, slopes and CDOM fluorescence was found and conservative CDOM mixing between riverine and marine waters was observed. This implies that strong in situ sources and/or sinks in CDOM concentration are absent. Within the range of salinities from 0 to 22 the spectral slope of the absorption (S) over the wavelength band of absorption coefficients was in the typical range of CDOM of terrestrial origin. Saltier waters with lower CDOM concentration showed high scattering of S. Optical parameters determined by satellite measurements show a significant covariance with the field observations CDOM and salinity observations while turbidity has not shown reliable coincidence. We suggest that the high concentration of CDOM is the reason of the low influence particular matter concentration on the optical properties of the surface water. Linear regressions were obtained between surface CDOM concentrations and satellite parameters helping to trace the spatial distribution of both salinity and CDOM at the sea surface. Anyhow, further investigations are required to develop an algorithm of calculation of CDOM and salinity based on remote sensing data.

Description: Ocean deoxygenation due to climate change may alter redox-sensitive nutrient cycles in the marine environment. The productive eastern tropical North Atlantic (ETNA) upwelling region may be particularly affected when the relatively moderate oxygen minimum zone (OMZ) deoxygenates further and microbially driven nitrogen (N) loss processes are promoted. Consequently, water masses with a low nitrogen to phosphorus (N : P) ratio could reach the euphotic layer, possibly influencing primary production in those waters. Previous mesocosm studies in the oligotrophic Atlantic Ocean identified nitrate availability as a control of primary production, while a possible co-limitation of nitrate and phosphate could not be ruled out. To better understand the impact of changing N : P ratios on primary production and N2 fixation in the ETNA surface ocean, we conducted land-based mesocosm experiments with natural plankton communities and applied a broad range of N : P ratios (2.67–48). Silicic acid was supplied at 15 µmol L−1 in all mesocosms. We monitored nutrient drawdown, biomass accumulation and nitrogen fixation in response to variable nutrient stoichiometry. Our results confirmed nitrate to be the key factor determining primary production. We found that excess phosphate was channeled through particulate organic matter (POP) into the dissolved organic matter (DOP) pool. In mesocosms with low inorganic phosphate availability, DOP was utilized while N2 fixation increased, suggesting a link between those two processes. Interestingly this observation was most pronounced in mesocosms where nitrate was still available, indicating that bioavailable N does not necessarily suppress N2 fixation. We observed a shift from a mixed cyanobacteria–proteobacteria dominated active diazotrophic community towards a diatom-diazotrophic association of the Richelia-Rhizosolenia symbiosis. We hypothesize that a potential change in nutrient stoichiometry in the ETNA might lead to a general shift within the diazotrophic community, potentially influencing primary productivity and carbon export.

Description: Eastern Boundary Upwelling Systems (EBUSs) represent very productive areas in the World Ocean. The major part of organic carbon, fixed by primary producers, is rapidly reworked and utilized by heterotrophic communities, causing water column deoxygenation. The deoxygenation, caused by biological processes, is also promoted by the strong water column stratification and sluggish circulation that are characteristic for EBUSs. Dissolved organic matter (DOM) represents the major pool of organic carbon in the global ocean. Therefore, high concentrations of DOM, accumulated near the surface as result of phytoplankton release may significantly affect the biogeochemical cycles of oxygen (O2) and other elements in and above oxygen minimum zones (OMZs) and vice versa. However, DOM distribution, composition and cycling in EBUSs and adjacent OMZs are largely understudied. This doctoral thesis includes two case studies that address DOM distribution and cycling in these marine systems. The first part of the thesis investigates the distribution, composition and potential effects of DOM supply on O2 in and above the OMZ in the Eastern Tropical South Pacific (ETSP) region off coast of Peru. The second part of the thesis is focused on DOM production and quality in response to OMZ-induced changes in nutrient availability in the euphotic zone of the Eastern Tropical North Pacific (ETNA). Both studies suggest that OMZs and DOM quantity and quality are tightly linked. Thus, in the first study diapycnal fluxes of dissolved organic carbon (DOC) across the oxycline (20-50 m depth) were found to be equal to 144±250 mg DOC m-2day-1, where dissolved hydrolysable amino acids (DHAA) and dissolved carbohydrates (DCHO) contributed ~5% and ~20%, respectively [Manuscript I]. The attenuation of the DOC flux was potentially responsible for ~180% of O2 consumption across the oxycline, while ~40% of O2 attenuation could be explained by consumption of labile (LDOM) and semi labile (SLDOM) DOM. Therefore, it can be concluded that DOM consumption is important in sustaining the upper boundary of OMZ. On the other hand, composition and optical properties of DOM were only moderately related to changes in O2 concentrations. DOM fluorescence revealed a rapid decrease in protein-like DOM and an accumulation of humic-like components at depths, where oxygen concentrations switched from oxygenated to anoxic [Manuscript II]. The rapid utilization of proteinaceous DOM was generally supported by changes in diagenetic state of DOM [Manuscript I]. Herewith, several differences in the bio-availability of LDOM and SLDOM components were discussed in comparison to other areas, where the water column is oxygenated. At depth, anoxic sediments were recognized as an additional DOM source in the OMZ. The distribution of the DOM plume, released by sediments could be traced in high resolution up to the euphotic zone, suggesting a direct link of sediment release and surface productivity [Manuscript II]. In the second study, DOM revealed sensitivity to, both, dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphorus (DIP) concentrations, which may change under low O2 conditions within OMZs due to N-loss processes and sediment DIP release [Manuscript III]. Fresh bioavailable DOM accumulated under high DIN and DIP, while DOM reworking and, therefore, its optical properties were closer linked to DIN concentrations. This study suggests that N-loss processes, occurring within OMZs, as well as future OMZ expansion and intensification may substantially change DOM quality by decreasing ocean color and DOM reworking. The data included in this thesis indicate that DOM is a highly dynamic pool, which is not only influenced by biogeochemical processes, but also affected by physical mixing. Results show that DOM processing co-determines the consumption of O2 and also may reflect changes in elemental cycles. Therefore, the detailed investigation of DOM composition and its relation to production and removal processes may improve our understanding of biogeochemical cycling in and above OMZs.

Description: The eastern tropical South Pacific (ETSP) represents one of the most productive areas in the ocean that is characterized by a pronounced oxygen minimum zone (OMZ). Particulate organic matter (POM) that sinks out of the euphotic zone is supplied to the anoxic sediments and utilized by microbial communities. The degradation of POM is associated with dissolved organic matter (DOM) production and reworking. The release of recalcitrant DOM to the overlying waters may represent an important organic matter escape mechanism from remineralization within sediments but received little attention in OMZ regions so far. Here, we combine measurements of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) with DOM optical properties in the form of chromophoric (CDOM) and fluorescent (FDOM) DOM from pore waters and near-bottom waters of the ETSP off Peru. We evaluate diffusion–driven fluxes and net in situ fluxes of DOC and DON in order to investigate processes affecting DOM cycling at the sediment–water interface along a transect 12° S. To our knowledge, these are the first data for sediment release of DON and pore water CDOM and FDOM for the ETSP off Peru. Pore-water DOC and DON accumulated with increasing sediment depth, suggesting an imbalance between DOM production and remineralization within sediments. High DON accumulation resulted in very low pore water DOC / DON ratios (〉 1) which could be caused by either an "imbalance" in DOC and DON remineralization, or to the presence of an additional nitrogen source. Diffusion driven fluxes of DOC and DON exhibited high spatial variability. They varied from 0.2–0.1 mmol m−2 d−1 to 2.52–1.3 mmol m−2 d−1 and from −0.042–0.02 mmol m−2 d−1 to 3.32–1.7 mmol m−2 d−1, respectively. Generally low net in situ DOC and DON fluxes as well as steepening of spectral slope (S) of CDOM and accumulation of humic-like FDOM at the near-bottom waters over time indicated active microbial DOM utilization at the sediment–water interface, potentially stimulated by nitrate (NO3−) and nitrite (NO2−). The microbial DOC utilization rates, estimated in our study, may be sufficient to support denitrification rates of 0.2–1.4 mmol m−2 d−1, suggesting that sediment release of DOM contributes substantially to nitrogen loss processes in the ETSP off Peru.

Description: The eastern tropical South Pacific (ETSP) hosts the Peruvian upwelling system, which represents one of the most productive areas in the world ocean. High primary production followed by rapid heterotrophic utilization of organic matter supports the formation of one of the most intense oxygen minimum zones (OMZs) in the world ocean, where dissolved oxygen (O2) concentrations reach less than 1 µmol kg−1. The high productivity leads to an accumulation of dissolved organic matter (DOM) in the surface layers that may serve as a substrate for heterotrophic respiration. However, the importance of DOM utilization for O2 respiration in the Peruvian upwelling system in general and for shaping the upper oxycline in particular remains unclear so far. This study reports the first estimates of diapycnal fluxes and supply of O2, dissolved organic carbon (DOC), dissolved organic nitrogen, dissolved hydrolysable amino acids (DHAA) and dissolved combined carbohydrates (DCCHO) for the ETSP off Peru. Diapycnal flux and supply estimates were obtained by combining measured vertical diffusivities and solute concentration gradients. They were analysed together with the molecular composition of DCCHO and DHAA to infer the transport of labile DOM into the upper OMZ and the potential role of DOM utilization for the attenuation of the diapycnal O2 flux that ventilates the OMZ. The observed diapycnal O2 flux (50 mmol O2 m−2 d−1 at maximum) was limited to the upper 80 m of the water column; the O2 supply of ∼1 µmol kg−1 d−1 was comparable to previously published O2 consumption rates for the North and South Pacific OMZs. The diapycnal DOM flux (31 mmol C m−2 d−1 at maximum) was limited to ∼30 m water depth, suggesting that the labile DOM is extensively consumed within the upper part of the shallow oxycline off Peru. The analyses of DCCHO and DHAA composition support this finding, suggesting that DOM undergoes comprehensive remineralization within the upper part of the oxycline, as the DOM within the core of the OMZ was found to be largely altered. Estimated by a simple equation for carbon combustion, aerobic respiration of DCCHO and DHAA, supplied by diapycnal mixing (0.46 µmol kg−1 d−1 at maximum), could account for up to 38 % of the diapycnal O2 supply in the upper oxycline, which suggests that DOM utilization plays a significant role for shaping the upper oxycline in the ETSP.