Cédric G. Fichot

Pan-Arctic distributions of continental runoff in the Arctic Ocean

Continental runoff is a major source of freshwater, nutrients and terrigenous material to the Arctic Ocean. As such, it influences water column stratification, light attenuation, surface heating, gas exchange, biological productivity and carbon sequestration. Increasing river discharge and thawing permafrost suggest that the impacts of continental runoff on these processes are changing. Here, a new optical proxy was developed and implemented with remote sensing to determine the first pan-Arctic distribution of terrigenous dissolved organic matter (tDOM) and continental runoff in the surface Arctic Ocean. Retrospective analyses revealed connections between the routing of North American runoff and the recent freshening of the Canada Basin, and indicated a correspondence between climate-driven changes in river discharge and tDOM inventories in the Kara Sea. By facilitating the real-time, synoptic monitoring of tDOM and freshwater runoff in surface polar waters, this novel approach will help understand the manifestations of climate change in this remote region.

The fate of terrigenous dissolved organic carbon in a river‐influenced ocean margin

The mineralization of terrigenous dissolved organic carbon (tDOC) discharged by rivers can impact nutrient and trace metal cycling, biological productivity, net ecosystem metabolism, and air-sea CO2 exchange in ocean margins. However, the extreme heterogeneity of river-influenced ocean margins represents a major challenge for quantitative assessments of tDOC transformations and thereby obscures the role of tDOC in biogeochemical cycles. Here a lignin-based optical proxy for tDOC and a shelf-wide mass balance approach were used to quantitatively assess the fate of tDOC discharged from the Mississippi-Atchafalaya River System (M-ARS) to the Louisiana shelf. The mass balance revealed that ~40% of the tDOC discharged by the M-ARS during March 2009–2010 was mineralized to CO2 on the Louisiana shelf, with two thirds of the mineralization taking place in the mixed layer. A strong seasonality in tDOC mineralization was observed, with mineralization rates severalfold higher during summer than during winter. Independent assessments of specific mineralization processes indicated biomineralization accounted for ~94% of the tDOC mineralization on an annual basis and suggest that photochemical transformations of tDOC enhanced biomineralization by ~50% in the mixed layer. Direct photomineralization accounted for a relatively small fraction (~6%) of the tDOC mineralization on an annual basis. This quantitative assessment directly confirms that ocean margins are major sinks of the tDOC discharged by rivers and indicates that tDOC mineralization rates in the shelf mixed layer are sufficiently large to influence whether the Louisiana shelf is a net sink or source of atmospheric CO2.

Pulsed, cross-shelf export of terrigenous dissolved organic carbon to the Gulf of Mexico

The export of terrigenous dissolved organic carbon (tDOC) and other river-borne material across the continental shelf boundary has important ramifications for biological productivity and the cycling of continentally derived bioelements in the ocean. Recent studies revealed the 275–295 nm spectral slope coefficient of chromophoric dissolved organic matter (CDOM), S275–295, is a reliable tracer for terrigenous dissolved organic carbon (tDOC) in river-influenced ocean margins. Here an empirical algorithm for the accurate retrieval of S275–295 from ocean color was developed and validated using in situ optical properties collected seasonally in the northern Gulf of Mexico. This study also demonstrated S275–295 is a robust proxy for tDOC concentration in this environment, thereby providing a means to derive surface tDOC concentrations on synoptic scales and in quasi-real time using remote sensing. The resulting tDOC-algorithm was implemented using Aqua-MODIS in a retrospective analysis of surface tDOC concentrations over the northern Gulf of Mexico between July 2002 and June 2013. Large pulses of tDOC were observed in continental-slope surface waters off the Mississippi River delta, indicating cross-shelf export of tDOC was sporadic and exhibited considerable interannual variability. Favorable winds following an anomalously high discharge from the Mississippi-Atchafalaya river system always coincided with a major export event, and in general, cross-shelf export was enhanced during years of anomalously high discharge. The tDOC-algorithm will find applicability in the assessment of future climate- and human-induced changes in tDOC export, in biogeochemical models of the continental shelf, and in the validation of high-resolution coastal models of buoyancy-driven shelf circulation.

Predicting Dissolved Lignin Phenol Concentrations in the Coastal Ocean from Chromophoric Dissolved Organic Matter (CDOM) Absorption Coefficients

Dissolved lignin is a well-established biomarker of terrigenous dissolved organic matter (DOM) in the ocean, and a chromophoric component of DOM. Although evidence suggests there is a strong linkage between lignin concentrations and chromophoric DOM (CDOM) absorption coefficients in coastal waters, the characteristics of this linkage and the existence of a relationship that is applicable across coastal oceans remain unclear. Here, 421 paired measurements of dissolved lignin concentrations (sum of 9 lignin phenols) and CDOM absorption coefficients (ag(λ)) were used to examine their relationship along the river-ocean continuum (0-37 salinity) and across contrasting coastal oceans (sub-tropical, temperate, high-latitude). Overall, lignin concentrations spanned four orders of magnitude and revealed a strong, non-linear relationship with ag(λ). The characteristics of the relationship (shape, wavelength dependency, lignin-composition dependency) and evidence from degradation indicators were all consistent with lignin being an important driver of CDOM variability in coastal oceans, and suggested physical mixing and long-term photodegradation were important in shaping the relationship. These observations were used to develop two simple empirical models for estimating lignin concentrations from ag(λ) with a +/- 20% error relative to measured values. The models are expected to be applicable in most coastal oceans influenced by terrigenous inputs.

Dark production of carbon monoxide (CO) from dissolved organic matter in the St. Lawrence estuarine system Implication for the global coastal and blue water CO budgets

We investigated the thermal (dark) production of carbon monoxide (CO) from dissolved organic matter (DOM) in the water column of the St. Lawrence estuarine system in spring 2007. The production rate, Q(co), decreased seaward horizontally and downward vertically. Q(co) exhibited a positive, linear correlation with the abundance of chromophoric dissolved organic matter (CDOM). Terrestrial DOM was more efficient at producing CO than marine DOM. The temperature dependence of Q(co) can be characterized by the Arrhenius equation with the activation energies of freshwater samples being higher than those of salty samples. Q(co) remained relatively constant between pH 4-6, increased slowly between pH 6-8 and then rapidly with further rising pH. Ionic strength and iron chemistry had little influence on Q(co). An empirical equation, describing Q(co) as a function of CDOM abundance, temperature, pH, and salinity, was established to evaluate CO dark production in the global coastal waters (depth 200 m). Both the coastal and global dark source strengths are significant compared to the corresponding photochemical CO source strengths (coastal: similar to 2.9 Tg CO-C a(-1); global: similar to 50 Tg CO-C a(-1)). Steady state deepwater CO concentrations inferred from Q(co) and microbial CO uptake rates are < 0.1 nmol L-1.

DMS dynamics in the most oligotrophic subtropical zones of the global ocean

The influences of physico-chemical and biological processes on dimethylsulfide (DMS) dynamics in the most oligotrophic subtropical zones of the global ocean were investigated. As metrics for the dynamics of DMS and the so-called ‘summer DMS paradox’ of elevated summer concentrations when surface chlorophyll a (Chl) and particulate organic carbon (POC) levels are lowest, we used the DMS-to-Chl and DMS-to-POC ratios in the context of three independent and complementary approaches. Firstly, field observations of environmental variables (such as the solar radiation dose, phosphorus limitation of phytoplankton and bacterial growth) were used alongside discrete DMS, Chl and POC estimates extracted from global climatologies (i.e., a ‘station based’ approach). We then used monthly climatological data for DMS, Chl, and POC averaged over the biogeographic province wherein a given oligotrophic subtropical zone resides (i.e., a ‘province based’ approach). Finally we employed sensitivity experiments with a new DMS module coupled to the ocean general circulation and biogeochemistry model PISCES to examine the influence of various processes in governing DMS dynamics in oligotrophic regions (i.e., a ‘model based’ approach). We find that the ‘station based’ and ‘province based’ approaches yield markedly different results. Interestingly, the ‘province based’ approach suggests the presence of a ‘summer DMS paradox’ in most all of the oligotrophic regions we studied. In contrast, the ‘station based’ approach suggests that the ‘summer DMS paradox’ is only present in the Sargasso Sea and eastern Mediterranean. Overall, we found the regional differences in the absolute and relative concentrations of DMS between 5 of the most oligotrophic regions of the world’s oceans were better accounted for by their nutrient dynamics (specifically phosphorus limitation) than by physical factors often invoked, e.g., the solar radiation dose. Our ‘model based’ experiments suggest that it is the limitation of phytoplankton/bacterial production and bacterial consumption of DMS by pervasive phosphorus limitation that is responsible for the ‘summer DMS paradox’.

Linkages among fluorescent dissolved organic matter, dissolved amino acids and lignin-derived phenols in a river-influenced ocean margin

Excitation emission matrix (EEM) fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC) is commonly used to investigate the dynamics of dissolved organic matter (DOM). However, a lack of direct comparisons with known biomolecules makes it difficult to substantiate the molecular composition of specific fluorescent components. Here, coincident surface-water measurements of EEMs, dissolved lignin, and total dissolved amino acid (TDAA) acquired in the northern Gulf of Mexico were used to investigate the relationships between specific fluorescent components and DOM biomolecules. Two terrestrial humic-like components identified by EEM-PARAFAC using samples obtained from river to offshore waters were strongly linearly correlated with dissolved lignin concentrations. In addition, changes in terrestrial humic-like abundance were correlated with those in lignin phenol composition, suggesting such components are largely derived from lignin and its alteration products. By applying EEM-PARAFAC to offshore samples, two protein-like components were obtained. The tryptophan-like component was strongly correlated with TDAA concentrations, corroborating the suggested protein/peptide origin of this component. The ratios of tryptophan-like component to tyrosine-like component or dissolved organic carbon (DOC) concentrations were also correlated with DOC-normalized yields of TDAA, suggesting these proxies are useful indicators of the bioavailability of DOM in marine waters of the studied ecosystem.

Sources and Transformations of Dissolved Lignin Phenols and Chromophoric Dissolved Organic Matter in Otsuchi Bay, Japan

Dissolved lignin phenols and optical properties of dissolved organic matter (DOM) were measured to investigate the sources and transformations of terrigenous DOM (tDOM) in Otsuchi Bay, Japan. Three rivers discharge into the bay, and relatively high values of syringyl:vanillyl phenols (0.73 ± 0.07) and cinnamyl:vanillyl phenols (0.33 ± 0.10) indicated large contributions of non-woody angiosperm tissues to lignin and tDOM. The physical mixing of river and seawater played an important role in controlling the concentrations and distributions of lignin phenols and chromophoric DOM (CDOM) optical properties in the bay. Lignin phenol concentrations and the CDOM absorption coefficient at 350 nm, a(350), were strongly correlated in river and bay waters. Measurements of lignin phenols and CDOM in bay waters indicated a variety of photochemical and biological transformations of tDOM, including oxidation reactions, photobleaching and a decrease in molecular weight. Photodegradation and biodegradation of lignin and CDOM were investigated in decomposition experiments with river water and native microbial assemblages exposed to natural sunlight or kept in the dark. There was a rapid and substantial removal of lignin phenols and CDOM during the first few days in the light treatment, indicating transformations of tDOM and CDOM can occur soon after discharge of buoyant river water into the bay. The removal of lignin phenols was slightly greater in the dark (34%) than in the light (30%) during the remaining 59 days of the incubation. Comparison of the light and dark treatments indicated biodegradation was responsible for 67% of total lignin phenol removal during the 62-day incubation exposed to natural sunlight, indicating biodegradation is a dominant removal process in Otsuchi Bay.