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: 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: Two cruises were conducted after the diatom spring bloom in the northern Bay of Biscay (2006, 2007), to assess the contribution of combined carbohydrates to organic carbon partitioning. Partitioning of total organic carbon (TOC) into particulate organic carbon (POC) and dissolved organic carbon (DOC) differed between the two years, particularly for depths above 60 m, and was related to the vernal development of the system: a post spring-bloom system in 2007, and a more stratified summer system with higher coccolithophore abundance in 2006. In general, contribution of POC to TOC ranged between 4% and 28% and decreased with depth. Concentration of high-molecular-weight (HMW;〉1 kDa) dissolved combined carbohydrates (dCCHO) ranged from 0.6 to 1.4 μmol L−1 and contributed between 4% and 11% to DOC. Concentration of particulate combined carbohydrates (pCCHO) varied between 0.03 and 1.3 μmol L−1. A high contribution of pCCHO to POC was observed in 2007, i.e. 22–60% C compared to 3–10% C in 2006, and coincided with a higher abundance of transparent exopolymer particles (TEP). TEP accounted for 0.4–2.0 μmol C L−1 in 2007 and 0.5–1.5 μmol C L−1 in 2006. Above 60 m, differences in contribution of TEP-C to POC were most pronounced yielding 15.4±3.0% in 2007 compared to relatively low 4.8±1.4%, in 2006. TEP-C could explain about 60% in 2007 and about 40% of pCCHO-C in 2006. Hence, TEP were identified as a substantial component of pCCHO and POC, particularly in the wake of the spring bloom. Molecular composition of CCHO, i.e. HMW−dCCHO+pCCHO, revealed little difference between the years but strong variation over depth. Uronic acids (URA) were identified as a major component of CCHO (20–40%). Our study indicates that the distribution and composition of CCHO in surface seawater are determined by biogeochemical processes on a seasonal scale. A better knowledge of CCHO cycling and molecular signature has therefore a high potential for a better tracing of carbon dynamics in shelf sea ecosystems. Highlights: ► Role of combined carbohydrates for DOC–POC partitioning assessed (Bay of Biscay). ► TEP comprised substantial carbon fraction of particulate carbohydrates. ► Molecular composition of polysaccharides revealed organic matter diagenesis. ► Uronic acids comprised 20–40% of total and dissolved combined carbohydrates.

Description: The sea surface microlayer (SML) covers more than 70% of the Earth’s surface and is the boundary layer interface between the ocean and the atmosphere. This important biogeochemical and ecological system is critical to a diverse range of Earth system processes, including the synthesis, transformation and cycling of organic material, and the air–sea exchange of gases, particles and aerosols. In this review we discuss the SML paradigm, taking into account physicochemical and biological characteristics that define SML structure and function. These include enrichments in biogenic molecules such as carbohydrates, lipids and proteinaceous material that contribute to organic carbon cycling, distinct microbial assemblages that participate in air–sea gas exchange, the generation of climate-active aerosols and the accumulation of anthropogenic pollutants with potentially serious implications for the health of the ocean. Characteristically large physical, chemical and biological gradients thus separate the SML from the underlying water and the available evidence implies that the SML retains its integrity over wide ranging environmental conditions. In support of this we present previously unpublished time series data on bacterioneuston composition and SML surfactant activity immediately following physical SML disruption; these imply timescales of the order of minutes for the reestablishment of the SML following disruption. A progressive approach to understanding the SML and hence its role in global biogeochemistry can only be achieved by considering as an integrated whole, all the key components of this complex environment. Highlights ► The sea surface microlayer is a biogenic film layer at the air-ocean interface. ► Distinct microbial assemblages have defining roles in microlayer functions. ► The sea surface microlayer is fundamentally involved in air-ocean transfer. ► The sea surface microlayer is linked to aerosol production. ► The sea surface microlayer is reservoir of pollutants.

Description: The present study investigates the combined effect of phosphorous limitation, elevated partial pressure of CO2 (pCO2) and temperature on a calcifying strain of Emiliania huxleyi (PML B92/11) by means of a fully controlled continuous culture facility. Two levels of phosphorous limitation were consecutively applied by renewal of culture media (N:P=26) at dilution rates (D) of 0.3 d−1 and 0.1 d−1. CO2 and temperature conditions were 300, 550 and 900 μatm pCO2 at 14 °C and 900 μatm pCO2 at 18 °C. In general, the steady state cell density and particulate organic carbon (POC) production increased with pCO2, yielding significantly higher concentrations in cultures grown at 900 μatm pCO2 compared to 300 and 550 μatm pCO2. At 900 μatm pCO2, elevation of temperature as expected for a greenhouse ocean, further increased cell densities and POC concentrations. In contrast to POC concentration, C-quotas (pmol C cell−1) were similar at D=0.3 d−1 in all cultures. At D=0.1 d−1, a reduction of C-quotas by up to 15% was observed in the 900 μatm pCO2 at 18 °C culture. As a result of growth rate reduction, POC:PON:POP ratios deviated strongly from the Redfield ratio, primarily due to an increase in POC. Ratios of particulate inorganic and organic carbon (PIC:POC) ranged from 0.14 to 0.18 at D=0.3 d−1, and from 0.11 to 0.17 at D=0.1 d−1, with variations primarily induced by the changes in POC. At D=0.1 d−1, cell volume was reduced by up to 22% in cultures grown at 900 μatm pCO2. Our results indicate that changes in pCO2, temperature and phosphorus supply affect cell density, POC concentration and size of E. huxleyi (PML B92/11) to varying degrees, and will likely impact bloom development as well as biogeochemical cycling in a greenhouse ocean.

Description: This study investigates the turnover of polysaccharides by heterotrophic bacterioplankton in the northern Bay of Biscay, a productive marine system on the continental margin of the temperate Atlantic Ocean. Bacterial biomass production (BBP) near the surface ranged from 0.5 to 25.7 nmol C L−1 h−1 during small phytoplankton blooms in May and June that occurred after the main spring bloom. A direct relationship between BBP and total polysaccharides strongly suggests the dependence of bacterial growth on the availability of semi-labile organic matter. Concentrations of combined glucose as well as rate constants of extracellular glucosidase activity and glucose uptake were determined to estimate the actual carbon fluxes from bacterial polysaccharide turnover. Results reveal that the degradation of polysaccharides in the upper 100 m of the water column sustained a glucose flux of 15.2–32.3 mg C m−2 d−1 that was available for bacterial consumption. The mean turnover time for polysaccharides was 170 and 165 days for α- and β-glycosidic linked polymers, respectively. Incorporation of free glucose supported 0.4–19.6% of BBP. The availability of nitrate plus nitrite (NOx) was identified as one factor increasing bacterial incorporation of glucose in most samples. Our results demonstrate that the bacterial recycling of polysaccharides generated a significant flux of organic carbon in microbial food-webs and biogeochemical processes.

Description: Primary production (PP), calcification (CAL), bacterial production (BP) and dark community respiration (DCR) were measured along with a set of various biogeochemical variables, in early June 2006, at several stations at the shelf break of the northern Bay of Biscay. The cruise was carried out after the main spring diatom bloom that, based on the analysis of a time-series of remotely sensed chlorophyll-a (Chl-a), peaked in mid-April. Remotely sensed sea surface temperature (SST) indicated the occurrence of enhanced vertical mixing (due to internal tides) at the continental slope, while adjacent waters on the continental shelf were stratified, as confirmed by vertical profiles of temperature acquired during the cruise. The surface layer of the stratified water masses (on the continental shelf) was depleted of inorganic nutrients. Dissolved silicate (DSi) levels probably did not allow significant diatom development. We hypothesize that mixing at the continental slope allowed the injection of inorganic nutrients that triggered the blooming of mixed phytoplanktonic communities dominated by coccolithophores (Emiliania huxleyi) that were favoured with regards to diatoms due to the low DSi levels. Based on this conceptual frame, we used an indicator of vertical stratification to classify the different sampled stations, and to reconstruct the possible evolution of the bloom from the onset at the continental slope (triggered by vertical mixing) through its development as the water mass was advected on-shelf and stratified. We also established a carbon mass balance at each station by integrating in the photic layer PP, CAL and DCR. This allowed computation at each station of the contribution of PP, CAL and DCR to CO2 fluxes in the photic layer, and how they changed from one station to another along the sequence of bloom development (as traced by the stratification indicator). This also showed a shift from net autotrophy to net heterotrophy as the water mass aged (stratified), and suggested the importance of extracellular production of carbon to sustain the bacterial demand in the photic and aphotic layers.

Description: An experimental study was conducted to test the effects of projected sea surface warming (according to the IPPC scenarios) on the accumulation and composition of dissolved organic matter (DOM) during marine phytoplankton blooms in cold seas (〈4°C). Eight mesocosms (∼1400 L) were filled with natural seawater, and two replicate mesocosms each were incubated by raising temperature by +0, +2, +4 and +6°C, respectively. The enclosed water was initially fertilized with inorganic nutrients to induce the development of phytoplankton blooms, which were then dominated by diatoms. Over a 4-week period, dissolved combined carbohydrates (DCCHO) and dissolved amino acids (DAA) were determined as major components of freshly produced, labile to semi-labile DOM. In all mesocosms, the increase in DCCHO concentration occurred sharply after the peak of chlorophyll a concentration, when nutrients became depleted. Rising temperature resulted in an earlier, faster and higher accumulation of DCCHO and of combined glucose predominantly. DCCHO yielded a maximum percentage of 35, 40, 49 and 59% of total combined carbohydrates in the +0, +2, +4 and +6°C treatments, respectively. Accumulation of DAA occurred more continuously and at an average rate of 0.79 ± 0.20 nmol L−1 h−1, but was not affected by rising temperature. Owing to the higher accumulation of DCCHO, the C:N ratio of DOM increased strongly during the course of the bloom, with higher ratios in the warmer treatments. Our study suggests that warming increases the extracellular release of carbohydrates from phytoplankton and, therefore, may affect the bottom-up control of the microbial loop in cold seas in the future.