Description: The sea surface microlayer (SML) is the uppermost layer of the water column that links the ocean and atmosphere. It accumulates a variety of biogenic surface-active and buoyant substances, including gelatinous material, such as transparent exopolymer particles (TEP) and Coomassie stainable particles (CSP), potentially affecting air–sea exchange processes. Here, we studied the influence of the annual cycle of phytoplankton production on organic matter (OM) accumulation in the SML relative to the subsurface water (SSW). Sampling was performed monthly from April 2012 to November 2013 at the Boknis Eck Time Series Station (Baltic Sea). For SML sampling, we used the Garrett screen, while SSW samples were collected by Niskin bottles at 1 m depth. Samples were analyzed for carbohydrates, amino acids, TEP, CSP, chlorophyll a (SSW only) and bacterial abundance. Our data showed that the SML reflected the SSW during most parts of the year, with changes mainly responding to bloom formation and decay. OM composition during phytoplankton blooms clearly differed from periods of higher bacterial abundance. Of all components investigated, only the enrichment of total carbohydrates in the SML was inversely related to the wind speed indicating that wind-driven mixing also affected the accumulation of OM in the SML during our study.

Description: A mesocosm experiment was conducted to investigate the impact of rising fCO2 on the build-up and decline of organic matter during coastal phytoplankton blooms. Five mesocosms (∼38 m³ each) were deployed in the Baltic Sea during spring (2009) and enriched with CO2 to yield a gradient of 355–862 µatm. Mesocosms were nutrient fertilized initially to induce phytoplankton bloom development. Changes in particulate and dissolved organic matter concentrations, including dissolved high-molecular weight (〉1 kDa) combined carbohydrates, dissolved free and combined amino acids as well as transparent exopolymer particles (TEP), were monitored over 21 days together with bacterial abundance, and hydrolytic extracellular enzyme activities. Overall, organic matter followed well-known bloom dynamics in all CO2 treatments alike. At high fCO2, higher ΔPOC:ΔPON during bloom rise, and higher TEP concentrations during bloom peak, suggested preferential accumulation of carbon-rich components. TEP concentration at bloom peak was significantly related to subsequent sedimentation of particulate organic matter. Bacterial abundance increased during the bloom and was highest at high fCO2. We conclude that increasing fCO2 supports production and exudation of carbon-rich components, enhancing particle aggregation and settling, but also providing substrate and attachment sites for bacteria. More labile organic carbon and higher bacterial abundance can increase rates of oxygen consumption and may intensify the already high risk of oxygen depletion in coastal seas in the future.

Description: To investigate the combined effect of temperature and light availability on organic matter production and degradation during a winter/spring phytoplankton bloom in Kiel Bight, we conducted a mesocosm study applying two temperature regimes, ambient (T + 0) and plus 6°C (T + 6) and three irradiance levels. Rising temperature accelerated the onset of the phytoplankton bloom, while light intensity played only a minor role for the timing and bloom development. Maximum build-up of chlorophyll a and particulate organic carbon were ∼20% lower at T + 6 compared with T + 0, probably caused by a combination of elevated heterotrophic processes and enhanced sedimentation during the bloom. The latter is supported by increased TEP concentrations at T + 6 (TEP/POC 0.18 mol C/mol C) compared with T + 0 (0.11 mol C/mol C) during bloom conditions, which may have promoted cell aggregation and sinking. Dissolved organic carbon concentrations increased more rapidly at elevated temperature. For a warmer future ocean, we can hence expect two counteracting mechanisms controlling organic matter flow during phytoplankton blooms: (1) enhanced processing of organic matter via the microbial loop resulting in a faster recycling and (2) depending on the dominating phytoplankton species, enhanced TEP formation resulting in increased particle aggregation and thus export of carbon and nutrients.

Description: Highlights: • Activity of Arctic bacterioplankton in summer is regulated by concentration and composition of organic matter. • Bacterial production in Fram Strait is significantly related to concentrations of total amino acids. • Bacterioplankton in Polar Water show enhanced enzymatic hydrolysis of combined carbohydrates compared to Atlantic Water. Abstract The bacterial turnover of organic matter was investigated in Fram Strait at 79°N. Both Atlantic Water (AW) inflow and exported Polar Water (PW) were sampled along a transect from Spitsbergen to the eastern Greenland shelf during a late successional stage of the main annual phytoplankton bloom in summer. AW showed higher concentrations of amino acids than PW, while organic matter in PW was enriched in combined carbohydrates. Bacterial growth and degradation activity in AW and PW were related to compositional differences of organic matter. Bacterial production and leucine-aminopeptidase along the transect were significantly correlated with concentrations of amino acids. Activity ratios between the extracellular enzymes β-glucosidase and leucine-aminopeptidase indicate the hydrolysis potential for polysaccharides relative to proteins. Along the transect, these ratios showed a higher hydrolysis potential for polysaccharides relative to proteins in PW than in AW, thus reflecting the differences in organic matter composition between the water masses. Q10 values for bacterial production ranged from 2.4 (± 0.8) to 6.0 (± 6.8), while those for extracellular enzymes showed a broader range of 1.5 (± 0.5) to 23.3 (± 11.8). Our results show that in addition to low seawater temperature also organic matter availability contributes to the regulation of bacterial growth and enzymatic activity in the Arctic Ocean.

Description: Highlights: • Elemental C:N:P variations of organic matter are simulated at monitoring site BY15. • No N2 fixation needed to explain observed PO4PO4 and pCO2pCO2 levels after spring bloom. • Model features relevance of DOP production and remineralization for N2 fixation. • Model estimates of annual N2 fixation are View the MathML source297±24mmolNm-2a-1. • Model estimates of annual total production are View the MathML source14.16±0.71molCm-2a-1. Abstract: For most marine ecosystems the growth of diazotrophic cyanobacteria and the associated amount of nitrogen fixation are regulated by the availability of phosphorus. The intensity of summer blooms of nitrogen (N2) fixing algae in the Baltic Sea is assumed to be determinable from a surplus of dissolved inorganic phosphorus (DIP) that remains after the spring bloom has ended. But this surplus DIP concentration is observed to continuously decrease at times when no appreciable nitrogen fixation is measured. This peculiarity is currently discussed and has afforded different model interpretations for the Baltic Sea. In our study we propose a dynamical model solution that explains these observations with variations of the elemental carbon-to-nitrogen-to-phosphorus (C:N:P) ratio during distinct periods of organic matter production and remineralization. The biogeochemical model resolves seasonal C, N and P fluxes with depth at the Baltic Sea monitoring site BY15, based on three assumptions: (1) DIP is utilized by algae though not needed for immediate growth, (2) the uptake of dissolved inorganic nitrogen (DIN) is hampered when the algae׳s phosphorus (P) quota is low, and (3) carbon assimilation continues at times of nutrient depletion. Model results describe observed temporal variations of DIN, DIP and chlorophyll-a concentrations along with partial pressure of carbon dioxide (pCO2)(pCO2). In contrast to other model studies, our solution does not require N2 fixation to occur shortly after the spring bloom to explain DIP drawdown and pCO2pCO2 levels. Model estimates of annual N2 fixation are View the MathML source297±24mmolNm-2a-1. Estimates of total production are View the MathML source14200±700mmolCm-2a-1, View the MathML source1400±70mmolNm-2a-1, and View the MathML source114±5mmolPm-2a-1 for the upper 50 m. The models C, N and P fluxes disclose preferential remineralization of P and of organic N that was introduced via N2 fixation. Our results are in support of the idea that P uptake by phytoplankton during the spring bloom contributes to the consecutive availability of labile dissolved organic phosphorus (LDOP). The LDOP is retained within upper layers and its remineralization affects algal growth in summer, during periods of noticeable N2 fixation.

Description: Highlights: • Coagulation efficiency of the coccolithophorid Emiliania huxleyi was determined with Couette flow devices. • Higher coagulation efficiencies of cells were observed at lower growth rates. • Coagulation efficiency increases with the extracellular polysaccharides fraction. Abstract: Coagulation of small particles results in the formation of larger aggregates that play an important role in the biological pump, moving carbon and other elements from the surface to the deep ocean and seafloor. In this study, we estimated the efficiency of particle coagulation of the coccolithophore Emiliania huxleyi at different growth rates using Couette flow devices at a natural shear rate. To determine the impacts of chemical and biological factors involved in aggregate formation, we investigated how variance in organic matter composition, and in particular the presence of extracellular polysaccharides (EP), including transparent exopolymer particles (TEP) and acidic polysaccharides attached to the coccolith surface, affect the coagulation efficiency (α). When E. huxleyi was grown in a chemostat at different growth rates, coagulation efficiency increased from ~ 0.40 to 1 as cell growth rates declined and nutrients became more limited. With declining growth rate the concentration of EP and the number of detached coccoliths increased. Overall a close correlation between coagulation efficiency of E. huxleyi and the ratio of EP to total particle volume was observed. The minimum value of α of ~ 0.4 determined during this study is higher than estimates published for other phytoplankton cells, and may be related to the presence of EP attached to coccoliths. Based on our findings, we suggest that E. huxleyi is more prone to form aggregates, particularly during the decline of blooms, when increased production of EP and enhanced shedding of coccoliths coincide. This may be one explanation for why blooms of E. huxleyi play an important role in the biological carbon pump, efficiently enhancing the vertical flux of particles, as has been suggested by sediment trap studies.

Description: A method is described to simultaneously determine the neutral, amino, and acidic sugar content of combined carbohydrates in high molecular weight (HMW, 〉 1 kDa) dissolved organic matter and in particles from seawater samples. Monomeric sugars are determined after acid hydrolysis and neutralization through acid evaporation using high performance anion exchange chromatography (HPAEC) coupled with pulsed amperometric detection (PAD). The separation of sugars during chromatography is achieved in two steps, an isocratic elution (18 mM NaOH) followed by a gradient course of two mobile eluent phases (NaOH and CH3COONa). HPAEC-PAD has previously been applied to measure neutral and amino sugars in marine samples. Since salt anions interfere with the measurement, some of the earlier studies used ion exchange resins for seawater desalting. Thereby, variable losses of neutral and amino sugars, and the complete removal of acidic sugars have been reported. Here, we show that desalting by membrane dialysis (1 kDa) is an efficient alternative to ion exchange resins and yields recoveries of 〉 90% for HMW carbohydrates. We conducted several tests to determine the accuracy and reproducibility of the method. Sugar concentrations determined with our protocol were compared to results obtained with the colorimetric TPTZ-method, and with earlier HPAEC-PAD protocols using cation/ anion exchange resins. Applications of our protocol to field samples indicated that acidic sugars can comprise a substantial fraction (30-50%) of HMW dissolved carbohydrates in seawater. The simultaneous analysis of the three classes of sugars appears promising to detect a larger fraction of marine combined carbohydrates, and thus to improve our understanding of organic matter cycling in the ocean.

Description: The abundance of transparent exopolymer particles (TEP) was determined in the northeast Atlantic Ocean (40–55°N, ∼20°W) during several cruises from June to November 1996. An accumulation of TEP in the water column was observed at bloom and post-bloom sites along a 20°W transect in June/July (maximum concentration: 124 μg Gum Xanthan equivalents (Xeq.) l−1), but concentrations were uniformly low (mean concentration: 28.5±10.2 μg Xeq. l−1) during autumn at the BIOTRANS site (47°N, 20°W). TEP concentrations in the open northeast Atlantic were considerably lower than previously published values from coastal sites. However, during June/July TEP:Chl a (weight/weight) ratios were comparable to values at coastal seas. It is suggested that phytoplankton production modulates TEP concentration in the open ocean as it does in coastal systems. TEP contributed significantly to the organic carbon pool as derived from the ratio TEP-C:POC, in summer (mean percentage: 17±7.5; w/w), as well as in autumn (mean percentage: 18±11, w/w). The potential influence of TEP on particle coagulation rates in the northeast Atlantic was assessed from estimates of their influence on particle stickiness and on particle volume concentrations. This indicated that TEP may be essential for initiating particle aggregation at low biomass concentrations, typical for open ocean sites.

Description: Incubation experiments with natural phytoplankton revealed a relationship between CO2 concentration and the production of transparent exopolymer particles (TEP), with TEP production being linearly related to theoretical CO2 uptake rates.

Description: The termination of diatom spring blooms in temperate waters has been connected with the formation and subsequent rapid sedimentation of aggregates. According to coagulation theory, the rate of aggregate formation depends on the probability of particle collision and on the efficiency with which two particles adhere once they have collided (stickiness). During this study, the variation in particle stickiness was determined over the decline of a diatom bloom using the Couette Chamber assay with low shear (G = 0.86 s–1). A mixed diatom population, dominated by Skeletonema costatum, was sampled during the spring bloom in the Baltic Sea and incubated in the laboratory for 18 days. Measurements of diatom species composition, transparent exopolymer particles (TEP) and bulk particle abundance, as well as chemical and biological variables, were conducted in order to reveal the determinants of coagulation efficiency. The investigation showed that an increase in TEP concentration relative to conventional particles at the decline of the bloom significantly enhanced apparent coagulation efficiencies. High proportions of TEP led to apparent values of stickiness 〉1, which indicates that collision rates can be substantially underestimated when the stickiness parameter α is calculated on the basis of conventional particle counting only, e.g. with the Coulter Counter. A new stickiness parameter, α′, was therefore estimated based on the combined volume fractions of TEP and conventional particles. The problems of stickiness measurements are discussed and the role of TEP in coagulation processes is emphasized.