Linking optical and molecular signatures of dissolved organic matter in the Mediterranean Sea

Original research paperDissolved organic matter (DOM) plays a key role in global biogeochemical cycles and experiences changes in molecular composition as it undergoes processing. In the semi-closed basins of the oligotrophic Mediterranean Sea, these gradual molecular modifications can be observed in close proximity. In order to extend the spatial resolution of information on DOM molecular composition available from ultrahigh resolution mass spectrometry in this area, we relate this data to optical (fluorescence and absorption spectroscopy) measurements. Covariance between molecular formulae signal intensities and carbon-specific fluorescence intensities was examined by means of Spearman’s rank correlations. Fifty two per cent of the assigned molecular formulae were associated with at least one optical parameter, accounting for 70% of the total mass spectrum signal intensity. Furthermore, we obtained significant multiple linear regressions between optical and intensity-weighted molecular indices. The resulting regression equations were used to estimate molecular parameters such as the double bond equivalent, degradation state and occurrence of unsaturated aliphatic compounds from optical measurements. The statistical linkages between DOM molecular and optical properties illustrate that the simple, rapid and cost-efficient optical spectroscopic measurements provide valuable proxy information on the molecular composition of open ocean marine DOM.y the project HOTMIX (grant number CTM2011-30010-C02-MAR) and the project FERMIO (MINECO, CTM2014-57334-JIN), both co-financed with FEDER fundsVersión del editor2,92

Dissolved Organic Matter (DOM) in the open Mediterranean Sea. I. Basin-Wide distribution and drivers of chromophoric DOM

Original research articleChromophoric dissolved organic matter (CDOM) in the open Mediterranean Sea (MedSea) is barely documented, remaining the basin–wide patterns in intermediate and deep waters still enigmatic. Here, full–depth distributions of CDOM absorption coefficients and spectral slopes recorded during the HOTMIX 2014 cruise are presented and their respective environmental drivers resolved. General Additive Models (GAMs) in surface waters and Optimum MultiParameter (OMP) water mass analysis in deep waters were applied. In the surface, apparent oxygen utilisation (AOU), a proxy to cumulative net community respiration, explained most of the variability of dissolved organic carbon (DOC) and the absorption coefficient at 254 nm (a254), whereas the absorption coefficient at 325 nm (a325), and the spectral slopes were mostly explained by potential temperature, a proxy to stratification and solar radiation, indicating that both water column stability and photobleaching may drive the variability of the UV–A absorbing CDOM components. In deep waters, the effect of water mass mixing and basin–scale mineralization were discerned from local mineralization processes. Water mass mixing and basin–scale mineralization contributed more substantially to explain the variability of DOC, a254 and a325 (82–91%) than the variability of the spectral slopes (35–64%). Local mineralization processes indicate that DOC and CDOM play a more relevant role in the carbon cycle in the Eastern (EastMed) than in the Western (WestMed) Mediterranean: whereas DOC contributed to 66 ± 10% of the oxygen demand in the EastMed, it represented only 24 ± 4% in the WestMed. Independently of basins and layers, a254 revealed as an excellent proxy to the concentration of DOC in the MedSea. Also, the unexpected inverse relationship of a325 with AOU indicates that the consumption of the UV–A absorbing CDOM fraction prevails over their productionSpanish Ministry of Education and Culture, Spanish Ministry of Economy and Competitiviness, FEDER, CSIC, University of GranadaVersión del editor3,26

Turnover time of fluorescent dissolved organic matter in the dark global ocean

Research articleMarine dissolved organic matter (DOM) is one of the largest reservoirs of reduced carbon on Earth. In the dark ocean (4200 m), most of this carbon is refractory DOM. This refractory DOM, largely produced during microbial mineralization of organic matter, includes humic-like substances generated in situ and detectable by fluorescence spectroscopy. Here we show two ubiquitous humic-like fluorophores with turnover times of 435±41 and 610±55 years, which persist significantly longer than the B350 years that the dark global ocean takes to renew. In parallel, decay of a tyrosine-like fluorophore with a turnover time of 379±103 years is also detected. We propose the use of DOM fluorescence to study the cycling of resistant DOM that is preserved at centennial timescales and could represent a mechanism of carbon sequestration (humic-like fraction) and the decaying DOM injected into the dark global ocean, where it decreases at centennial timescales (tyrosine-like fraction).Versión del editor10,015

Dissolved organic matter (DOM) in the open Mediterranean Sea. II: Basin-wide distribution and drivers of fluorescent DOM

Research articleFluorescent dissolved organic matter (FDOM) in the Mediterranean Sea was analysed by excitation–emission matrix (EEM) spectroscopy and parallel factor (PARAFAC) analysis during the cruise HOTMIX 2014. A 4–component model, including 3 humic–like and 1 protein–like compounds, was obtained. To decipher the environmental factors that dictate the distributions of these components, we run generalized additive models (GAMs) in the epipelagic layer and an optimum multiparametric (OMP) water masses analysis in the meso– and bathypelagic layers. In the epipelagic layer, apparent oxygen utilization (AOU) and temperature presented the most significant effects on the variability of the marine humic-like peak M fluorescence, suggesting that its distribution was controlled by the net community respiration of organic matter and photobleaching. On the contrary, the variability of the soil humic-like peak E and the protein–like peak T fluorescence was explained mainly by the prokaryotic heterotrophic abundance, which decreased eastwards. In the meso– and bathypelagic layers, water mass mixing and basin–scale mineralization processes explained >72% and 63% of the humic–like and protein–like fluorescence variability, respectively. When analysing the two basins separately, the OMP model offered a better explanation of the distribution of fluorescence in the eastern Mediterranean Sea, as expected from the reduced biological activity in this ultra–oligotrophic basin. Furthermore, while western Mediterranean deep waters display the usual trend in the global ocean (increase of humic–like fluorescence and decrease of protein–like fluorescence with higher AOU values), the eastern Mediterranean deep waters presented an opposite trend. Different initial fluorescence intensities of the water masses that mix in the eastern basin, with Adriatic and Aegean origins, seem to be behind this contrasting pattern. The analysis of the transect–scale mineralization processes corroborate this hypothesis, suggesting a production of humic–like and a consumption of protein–like fluorescence in parallel with water mass ageing. Remarkably, the transect–scale variability of the chromophoric dissolved organic matter (CDOM) absorbing at the excitation wavelength of the humic–like peak M indicates an unexpected loss with increasing AOU, which suggests that the consumption of the non–fluorescent fraction of CDOM absorbing at that wavelength exceeded the production of the fluorescent fraction observed hereProject HOTMIX (reference CTM2011–30010–C02 01–MAR and 02–MAR), co–financed with FEDER funds (re ference BES–2012–056175) ; the project MODMED from CSIC (PIE, 201730E020) and the project FERMIO (MINECO, CTM2014–57334–JIN), co–financed with FEDER fundsVersión del editor3,26

Empirical leucine-to-carbon conversion factors for estimating heterothrophic bacterial production in surface waters of the world oceans

Comunicación oralBacterial biomass production is a key parameter for evaluating the role of bacterioplankton in ocean carbon cycling. However, bacterial production cannot be directly measured and is typically estimated from the incorporation rates of radiolabelled leucine. The conversion of leucine uptake rates into bacterial carbon production rates requires the use of conversion factors (CFs) which must be empirically determined. Despite the empirical leucine-to-carbon CFs vary widely across environments very little is known about its potential controlling factors. We conducted a set of 10 surface seawater cultures experiments where the growth of the natural bacterial assemblage was promoted by filtration (removal of grazers) or by both filtration and dilution. Sampling stations were located between 30 ºN and 30 ºS, including the Atlantic, Pacific and Indian oceans. CFs varied from 0.13 to 1.47 Kg C mol Leu-1, being higher in the filtrated than in the filtrated and diluted treatment. The abundance of picocyanobacteria explained 60% of the observed variability. Our results further suggest that the composition of bacterioplankton, as assessed by ARISA fingerprinting, may partially explain the observed variation in CFs

Sample dilution and bacterial community composition influence empirical leucine-to-carbon conversion factors in surface waters of the world's oceans

Research articleThe transformation of leucine incorporation into prokaryotic carbon production rates requires the use of either theoretical or empirically determined conversion factors. Empirical leucine-to-carbon conversion factors (eCFs) vary widely across environments, and little is known about their potential controlling factors. We conducted 10 surface seawater manipulation experiments across the world’s oceans, where the growth of the natural prokaryotic assemblages was promoted by filtration (i.e. removal of grazers; F treatment) or filtration combined with dilution (i.e. relieving also resource competition; FD treatment). The impact of sunlight exposure was also evaluated in the FD treatments, and we did not find a significant effect on the eCFs. The eCFs varied from 0.09 to 1.47 kg C mol Leu-1 and were significantly lower in the filtered and diluted (FD) than in the filtered (F) treatments. Also, changes in bacterial community composition during the incubations, as assessed by Automated Ribosomal Intergenic Spacer Analysis (ARISA), were stronger in the FD than in the F treatments, as compared to unmanipulated controls. Thus, we discourage the common procedure of diluting samples (in addition to filtration) for eCFs determination. The eCFs in the filtered treatment were negatively correlated with the initial chlorophyll a concentration, picocyanobacterial abundance (mostly Prochlorococcus) and the percentage of heterotrophic prokaryotes with high nucleic acid content (%HNA). The latter two variables explained 80% of the eCFs variability in the F treatment, supporting the view that both Prochlorococcus and HNA prokaryotes incorporate leucine in substantial amounts although resulting into relatively low carbon production rates in the oligotrophic ocean.En prensa3,829