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This study traces dissolved organic matter (DOM) in different water masses of the Arctic Ocean and its effect on the distributions of trace elements (TEs; Fe, Cu, Mn, Ni, Zn, Cd) using fluorescent properties of DOM and the terrigenous biomarker lignin. The Nansen, Amundsen, and Makarov Basins were characterized by the influence of Atlantic water and the fluvial discharge of the Siberian rivers with high concentrations of terrigenous DOM (tDOM). The Canada Basin and the Chukchi Sea were characterized by Pacific water, modified through contact with productive shelf sediments with elevated levels of marine DOM. Within the surface layer of the Beaufort Gyre, meteoric water (river water and precipitation) was characterized by low concentrations of lignin and terrigenous DOM fluorescence proxies as DOM is removed during freezing. High-resolution in situ fluorescence profiles revealed that DOM distribution closely followed isopycnals, indicating the strong influence of sea-ice formation and melt, which was also reflected in strong correlations between DOM fluorescence and brine contributions. The relationship of DOM and hydrography to TEs showed that terrigenous and marine DOM were likely carriers of dissolved Fe, Ni, Cu from the Eurasian shelves into the central Arctic Ocean. Chukchi shelf sediments were important sources of dCd, dZn, and dNi, as well as marine ligands that bind and carry these TEs offshore within the upper halocline (UHC) in the Canada Basin. Our data suggest that tDOM components represent stronger ligands relative to marine DOM components, potentially facilitating the long-range transport of TE to the North Atlantic. Key Points Dissolved Organic Matter (DOM) distribution in the Arctic Ocean is largely controlled by sea ice formation and melt processes DOM distribution in the Arctic Ocean reveals its potential as a tracer for halocline formation and freshwater source assignments Terrigenous and marine DOM are carriers of trace elements from shelves to the open Arctic Ocean, but terrigenous DOM represent stronger ligands

Here we provide compelling evidence that deep particle export enhanced dissolved organic carbon (DOC) concentrations beneath the Pacific’s Subarctic Front (SA, ∼42°N) and Northern Subtropical Front (NST, ∼34°N). We report three main findings: First, deep export of subjectively small particles (128–512 μm) was apparent throughout the frontal zone in which the SA resides. However, export of large particles was specifically associated with the SA, rather than the entire frontal zone, and appeared to exclusively transfer DOC into the bathypelagic water column. Second, a similar DOC enrichment existed beneath the NST, though this signal was curiously not accompanied by observable particles (>128 μm). We conclude that export occurring previously in winter left this DOC behind as a residue, though the associated particles were no longer present by spring. Third, the presence of strong hydrographic fronts was not the only control on export that resulted in these unique DOC distributions. Deep export and DOC enrichment was also controlled by latitude-specific biogeochemical and hydrographic conditions, such as depth of the nutricline and seasonal mixed layer shoaling. Given these observations, the fronts within the transitional region of the North Pacific are clearly special locations for deep carbon sequestration and for providing uncommon DOC enrichment that ultimately supports the deep microbial community.

Marine polymer gels play a critical role in regulating ocean basin scale biogeochemical dynamics. This brief review introduces the crucial role of marine gels as a source of aerosol particles and cloud condensation nuclei (CCN) in cloud formation processes, emphasizing Arctic marine microgels. We review the gel’s composition and relation to aerosols, their emergent properties, and physico-chemical processes that explain their change in size spectra, specifically in relation to aerosols and CCN. Understanding organic aerosols and CCN in this context provides clear benefits to quantifying the role of marine nanogel/microgel in microphysical processes leading to cloud formation. This review emphasizes the DOC-marine gel/aerosolized gel-cloud link, critical to developing accurate climate models.

International audience; The goal of the EXport Processes in the Ocean from RemoTe Sensing (EXPORTS) field campaign is to develop a predictive understanding of the export, fate, and carbon cycle impacts of global ocean net primary production. To accomplish this goal, observations of export flux pathways, plankton community composition, food web processes, and optical, physical, and biogeochemical (BGC) properties are needed over a range of ecosystem states. Here we introduce the first EXPORTS field deployment to Ocean Station Papa in the Northeast Pacific Ocean during summer of 2018, providing context for other papers in this special collection. The experiment was conducted with two ships: a Process Ship, focused on ecological rates, BGC fluxes, temporal changes in food web, and BGC and optical properties, that followed an instrumented Lagrangian float; and a Survey Ship that sampled BGC and optical properties in spatial patterns around the Process Ship. An array of autonomous underwater assets provided measurements over a range of spatial and temporal scales, and partnering programs and remote sensing observations provided additional observational context. The oceanographic setting was typical of late-summer conditions at Ocean Station Papa: a shallow mixed layer, strong vertical and weak horizontal gradients in hydrographic properties, sluggish sub-inertial currents, elevated macronutrient concentrations and low phytoplankton abundances. Although nutrient concentrations were consistent with previous observations, mixed layer chlorophyll was lower than typically observed, resulting in a deeper euphotic zone. Analyses of surface layer temperature and salinity found three distinct surface water types, allowing for diagnosis of whether observed changes were spatial or temporal. The 2018 EXPORTS field deployment is among the most comprehensive biological pump studies ever conducted. A second deployment to the North Atlantic Ocean occurred in spring 2021, which will be followed by focused work on data synthesis and modeling using the entire EXPORTS data set.

The ocean contains a large reservoir of dissolved organic matter (DOM) that persists for millennia. Both the very dilute concentrations of individual DOM molecules and intrinsic recalcitrance to microbial decay imparted by molecular structure are suggested mechanisms for this long residence time. Here, we report an experiment comparing the responses of surface and deep prokaryotes to DOM isolated and enriched by solid‐phase extraction from surface and deep waters of the subtropical North Atlantic Ocean. Extracts from both depths were qualitatively characterized as biologically recalcitrant given their similarly high C : N ratios of 26. Surface prokaryotes measurably drew down extracted dissolved organic carbon (DOC) concentrations, but the drawdown was only 4% of the initial enriched DOC concentration regardless of enrichment level or depth. Deep microbes, in contrast, did not cause observable changes in DOC concentrations. Surface and deep prokaryotes had similar temperature‐normalized growth responses to extracts from each depth. Biological indicators (e.g., kinetics) suggest that prokaryotes were less efficient at catalyzing surface than deep DOM (catalytic efficiencies of 0.003–0.005 vs. 0.02–0.03 h−1, respectively). These values indicate qualitative differences in extracted DOM from the two depths, perhaps suggesting a variable nature of the refractory DOC depending on depth. Moreover, only a small portion of the extracted DOM was biologically utilizable, regardless of concentration factor or depth, and essentially only a small fraction of it was incorporated into biomass. Microbial selection against substrates that meet modest energy but no growth demands may be a factor contributing to the long‐term stability of marine DOM.

The bioavailability of organic matter (OM) to marine heterotrophic bacterioplankton is determined by both the chemical composition of OM and the microbial community composition. In the current study, changes in OM bioavailability were identified at Ocean Station Papa as part of the 2018 Export Processes in the Ocean from Remote Sensing (EXPORTS) field study. Removal rates of carbon (C) in controlled experiments were significantly correlated with the initial composition of total hydrolyzable amino acids, and C removal rates were high when the amino acid degradation index suggested a more labile composition. Carbon remineralization rates averaged 0.19 ± 0.08 μmol C L–1 d–1 over 6–10 days while bacterial growth efficiencies averaged 31 ± 7%. Amino acid composition and tandem mass spectrometry analysis of compound classes also revealed transformations to a more degraded OM composition during experiments. There was a log2-fold increase in the relative abundances of 16S rDNA-resolved bacterioplankton taxa in most experiments by members of the Methylophilaceae family (OM43 genus) and KI89A order. Additionally, when OM was more bioavailable, relative abundances increased by at least threefold for the classes Bacteroidetes (Flavobacteriaceae NS2b genus), Alphaproteobacteria (Rhodobacteraceae Sulfitobacter genus), and Gammaproteobacteria (Alteromonadales and Ectothiorhodospiraceae orders). Our data suggest that a diverse group of bacterioplankton was responsible for removing organic carbon and altering the OM composition to a more degraded state. Elevated community diversity, as inferred from the Shannon–Wiener H index, may have contributed to relatively high growth efficiencies by the bacterioplankton. The data presented here shed light on the interconnections between OM bioavailability and key bacterioplankton taxa for the degradation of marine OM.

The interseasonal and interannual variability of total organic carbon (TOC) was assessed in the deep northeastern Pacific Ocean, an area characterized by high primary production and organic matter export. Samples were collected from throughout the deeper water column (>250 m) seasonally in 2017 and 2018 along the Line P transect, as well as one distribution of dissolved organic carbon (DOC) in spring 2018. High heterogeneity was observed in TOC concentrations at depths greater than 1000 meters, both within seasons (concentration differences of ~2-6 µmol kg-1) and across seasons (~2-12 µmol kg-1), coinciding with changes in fluorescence in the overlying waters. Such observations suggest that biogenic particles sinking from the upper ocean are seasonally delivering observable TOC to depth. The presence of these particles also appeared to contribute to the DOC pool, as suggested by differences in the TOC and DOC distributions in spring 2018. Seasonal TOC net accumulation and removal rates differed between the years: 0.5 and 2.1 µmol kg-1 day-1 (accumulation) and 0.6 and 2.1 µmol kg-1 day-1 (removal) for 2017 and 2018, respectively. The rate estimates indicated that introduction of organic carbon to the bathypelagic occurred at approximately the same rate as removal post-bloom, demonstrating the efficient removal of seasonally-produced organic carbon. High abundances of gelatinous zooplankton in spring 2018, supported by higher abundances of phytoplankton, enhanced the export of organic carbon to the bathypelagic zone during the seasonal bloom, resulting in localized TOC concentrations up to 148 µmol kg-1 in the bathypelagic. These results indicate high variability in bathypelagic TOC concentrations at high latitude, unlike oligotrophic systems.

Data from GEOTRACES cruises GN01 (HLY1502) and GN04 (PS94) have been archived at the Biological & Chemical Oceanography Data Management Office (BCO-DMO; https://www.bco-dmo.org/deployment/638807) and PANGAEA (https://www.pangaea.de/?q=PS94&f.campaign%5B%5D=PS94) websites, respectively. The inorganic carbon data are available at the NOAA Ocean Carbon Data System (OCADS ; doi :10.3334/CDIAC/OTG.CLIVAR_ARC01_33HQ20150809). In addition to these national data archives, the data used in this paper is available as a supplementary downloadable excel file; International audience; A major surface circulation feature of the Arctic Ocean is the Transpolar Drift (TPD), a current that transports river‐influenced shelf water from the Laptev and East Siberian Seas toward the center of the basin and Fram Strait. In 2015, the international GEOTRACES program included a high‐resolution pan‐Arctic survey of carbon, nutrients, and a suite of trace elements and isotopes (TEIs). The cruises bisected the TPD at two locations in the central basin, which were defined by maxima in meteoric water and dissolved organic carbon concentrations that spanned 600 km horizontally and ~25‐50 m vertically. Dissolved TEIs such as Fe, Co, Ni, Cu, Hg, Nd, and Th, which are generally particle‐reactive but can be complexed by organic matter, were observed at concentrations much higher than expected for the open ocean setting. Other trace element concentrations such as Al, V, Ga, and Pb were lower than expected due to scavenging over the productive East Siberian and Laptev shelf seas. Using a combination of radionuclide tracers and ice drift modeling, the transport rate for the core of the TPD was estimated at 0.9 ± 0.4 Sv (106 m3 s‐1). This rate was used to derive the mass flux for TEIs that were enriched in the TPD, revealing the importance of lateral transport in supplying materials beneath the ice to the central Arctic Ocean and potentially to the North Atlantic Ocean via Fram Strait. Continued intensification of the Arctic hydrologic cycle and permafrost degradation will likely lead to an increase in the flux of TEIs into the Arctic Ocean.

Antarctica's continental shelves generate the densest waters in the world and are responsible for the formation of Antarctic Bottom Water (AABW), a water mass with the potential to sequester carbon in the deep ocean for millennia. One such form of marine carbon is dissolved organic carbon (DOC), the ocean's largest standing stock of reduced carbon. In this study, we quantify DOC enrichment in dense shelf waters (DSW) in the Ross Sea and assess the potential for DOC to be sequestered from Antarctic shelves into AABW. We find that Ross Sea DSW is enriched in DOC by ∼7 μmol kg−1 relative to the incoming source waters (initial conditions), which is primarily caused by vertical mixing. The total DOC excess in DSW suggests that 4.0 ± 0.6 Tg DOC yr−1 is exported off the shelf. However, this exported fraction does not appear to persist in newly formed AABW and is likely remineralized, sequestering this carbon as TCO2 in the deep ocean.

The phytoplankton bloom in the Ross Sea is the largest in spatial extent and one of the most productive in Antarctica, yet the fate of the summer bloom remains poorly understood. Here we present carbon system data from the first biogeochemical process cruise to be conducted in both the western and central Ross Sea during late summer (February–March 2013). Using one-dimensional carbon budgets, we found evidence for substantial positive net community production (425 ± 204 mmol C m−2 d−1) during the late summer in Terra Nova Bay (TNB) of the western Ross Sea, which was rapidly exported to below 200 m. In addition, seasonally integrated carbon export was higher in diatom-dominated TNB (7.3 ± 0.9 mol C m−2) compared to the Phaeocystis antarctica-dominated central Ross Sea (3.4 ± 0.8 mol C m−2). Substantial late summer productivity and export may be a widespread phenomenon in Antarctic coastal regions that is not accounted for in regional carbon models.

In this study, the abundance of transparent exopolymer particles (TEP) is examined across a surface water gradient of organic carbon from a phytoplankton bloom region in the western North Atlantic to oligotrophic waters in the Sargasso Sea, including a coastal region sampled near Cape Cod. TEP are macrogels that reach up to millimeters in size and abiotically assemble from dissolved acidic polysaccharides secreted by phytoplankton. Due to their great stickiness, TEP self aggregate and also form aggregates with non-TEP particulate organic carbon (POC). Aggregation enhances ballasting, thereby mutually facilitating export and subsequent sedimentation of both TEP and POC, increasing the efficiency of the biological pump. Here, four distinct regions with varying chlorophyll a concentrations, temperature, and salinity were sampled in the upper column, at the surface, and from the sea surface microlayer (SML). While TEP in seawater shows no correlation to chlorophyll a, nutrients, or total organic carbon (TOC) concentration, a strong correlation exists between TEP and TOC in the SML; and concentrations of both variables are inversely proportional to surface productivity as indicated by chlorophyll a concentrations. As open ocean regions show greater enrichments of TEP and TOC in the SML compared to the coastal region, we suggest that the role of the SML in organic carbon cycling is dependent on regional biogeochemistry and productivity. We hypothesize that a lower abundance of particles in oligotrophic regions compared to bloom regions limits TEP export by sinking, thus increasing the residence time of TEP in the upper water column and the SML.

The Ross Sea plays a major role in the transfer of organic carbon from the surface into the deep sea due to the combination of high seasonal productivity and Antarctic bottom water formation. Here we present a particle inventory of the Ross Sea based on a combined deployment of a video particle profiler (VPP) and a high-resolution digital holographic microscope (DIHM). Long-distance (100 s of kilometers) and short-distance (10 s of kilometers) sections showed high variability of particle distributions that co-varied with the density structure of the water column. Particle export was apparent at sites of locally weakened pycnoclines, likely an indirect effect of nutrient mixing into the surface layer and local blooms that lead to export. Particle volume abundances at 200–300 m depth were highly correlated with particle volume abundances in the upper mixed layer (

The transport of dissolved organic matter (DOM) across the land-ocean-aquatic-continuum (LOAC), from freshwater to the ocean, is an important yet poorly understood component of the global carbon budget. Exploring and quantifying this flux is a significant challenge given the complexities of DOM cycling across these contrasting environments. We developed a new model, UniDOM, that unifies concepts, state variables and parameterisations of DOM turnover across the LOAC. Terrigenous DOM is divided into two pools, T1 (strongly-UV-absorbing) and T2 (non- or weakly-UV-absorbing), that exhibit contrasting responses to microbial consumption, photooxidation and flocculation. Data are presented to show that these pools are amenable to routine measurement based on specific UV absorbance (SUVA). In addition, an autochtonous DOM pool is defined to account for aquatic DOM production. A novel aspect of UniDOM is that rates of photooxidation and microbial turnover are parameterised as an inverse function of DOM age. Model results, which indicate that ~ 5% of the DOM originating in streams may penetrate into the open ocean, are sensitive to this parameterisation, as well as rates assigned to turnover of freshly-produced DOM. The predicted contribution of flocculation to DOM turnover is remarkably low, although a mechanistic representation of this process in UniDOM was considered unachievable because of the complexities involved. Our work highlights the need for ongoing research into the mechanistic understanding and rates of photooxidation, microbial consumption and flocculation of DOM across the different environments of the LOAC, along with the development of models based on unified concepts and parameterisations.

12 pages, 5 figures, 2 tables, Most dissolved organic carbon (DOC) sequestered in the deep ocean has residence times of decades to thousands of years, with clear implications for climate regulation, though some net removal is typically observed with increasing water mass age. Here, a high‐quality‐high‐resolution data set has allowed us to identify net additions of recalcitrant DOC in specific water masses of the deep South Atlantic. Overall, the South Atlantic is a net source of recalcitrant DOC, adding 0.027 ± 0.019 Pg C/year, while the North Atlantic is a net sink that removes 0.298 ± 0.141 Pg C/year. We find that the balance of addition/removal of recalcitrant DOC depends not only on the origin but also on the temperature, age, and depth of the water masses that circulate and mix in the Atlantic Ocean. Future changes in the water mass composition and circulation patterns due to climate change would eventually affect that balance, altering the carbon cycle, C. R.‐C. was supported by a Juan de la Cierva‐ Incorporación Postdoctoral Fellowship (IJCI‐2015‐23357) from the Spanish “Ministerio de Economía y Competitividad” and XAA‐S by the Spanish MINECO Grant CTM2015‐ 69392‐C3‐2‐R. Data collection on U.S. CLIVAR sections and involvement by C. R.‐C. and D. A. H. were supported by U.S. NSF OCE1436748

Optical instruments can rapidly determine numbers and characteristics of water column particles with high sensitivity. Here we show the usefulness of optically assessed total particle volume below the main pycnocline to estimate carbon export in two systems: the open subarctic North Atlantic and the Ross Sea, Antarctica. Both regions exhibit seasonally high phytoplankton production and efficient export (i.e., a strong biological pump). Total particle volumes in the mesopelagic (200–300 m) were significantly correlated with those in the overlying surface mixed layer (50–60 m), indicating that most particles at depth reflect export from the surface. This connectivity, however, is modulated by the physical structure of the water column and by particle type (e.g., the presence of colonies of the haptophyte Phaeocystis Antarctica versus diatoms). Evidence from both regions show that a strong pycnocline can delay or may even prevent particles from settling to deeper layers, which then succumb to disintegration, and microbial and zooplankton consumption. Strong katabatic winds in the Ross Sea may deepen the mixed layer, causing a rapid transfer of particles to mesopelagic depths through the mixed-layer pump. Independent estimates of seasonally integrated export production in the Ross Sea, based on upper water column carbon mass balance, were significantly correlated (in the order of shared variance) with (1) total particle volumes from images, (2) particulate organic carbon, and (3) chlorophyll fluorescence, all recorded at a depth range of 200–300 m. Carbon export was not significantly correlated with particle abundance measured by a Coulter counter at the same depth range. Measuring total particle volume below the primary pycnocline is therefore a useful approach to estimate carbon export at least in regions characterized by seasonally high particle export.

Marine dissolved organic matter (DOM) contains one of the largest exchangeable organic carbon pools on Earth. Riverine input represents an important source of DOM to the oceans, yet much remains to be learned about the fate of the DOM linking terrestrial to oceanic carbon cycles through rivers at the global scale. Here we use ultrahigh-resolution mass spectrometry to identify 184 molecular formulae that are indicators of riverine inputs (referred to as t-Peaks) and to track their distribution in the deep North Atlantic and North Pacific Oceans. The t-Peaks were found to be enriched in the Amazon River, to be highly correlated with known tracers of terrigenous input, and to be observed in all samples from four different rivers characterized by vastly different landscapes and vegetation coverage spanning equatorial (Amazon and Congo), subtropical (Altamaha), and Arctic (Kolyma) regions. Their distribution reveals that terrigenous organic matter is injected into the deep ocean by the global meridional overturning circulation, indicating that a fraction of the terrigenous DOM introduced by rivers contributes to the DOM pool observed in the deep ocean and to the storage of terrigenous organic carbon. This novel molecular approach can be used to further constrain the transfer of DOM from land to sea, especially considering that Fourier transform ion cyclotron resonance mass spectrometer analysis is becoming increasingly frequent in studies characterizing the molecular composition of DOM in lakes, rivers, and the ocean.

The global ocean contains a massive reservoir (662 ± 32 Pg C) of dissolved organic carbon (DOC), and its dynamics, particularly in the deepest zones, are only slowly being understood. DOC in the deep ocean is ubiquitously low in concentration (~35 to 48 µmol kg−1) and aged (4000 to 6000 years), persisting for multiple meridional overturning circulations. Deep waters relatively enriched in DOC form in the North Atlantic, migrate to the Southern Ocean to mix with waters from Antarctic shelves and the deep Pacific and Indian Oceans, in turn forming the voluminous waters of the Circumpolar Deep Water. Here we seek evidence for local (autochthonous) versus distant (allochthonous) processes in determining the distribution of DOC in the deep Southern Ocean. Prior analyses on DOC in the deep Southern Ocean have conflicted, describing both conservative and nonconservative traits: the deep DOC field has been reported as uniform in distribution, yet local inputs have been suggested as quantitatively important. We use multiple approaches (multiple linear regression, mass transport, and mass balance calculations) with data from Climate Variability and Predictability Repeat Hydrography sections to evaluate the system. We find that DOC concentrations in the deep Southern Ocean largely reflect the conservative mixing of the several deep waters entering the system from the north. Mass balance suggests that the relatively depleted DOC radiocarbon content in the deep Southern Ocean is a conserved property as well. These analyses advance our understanding of the controls on the DOC reservoir of the Southern Ocean.

To understand controls on the production and remineralization of recalcitrant dissolved organic carbon (DOC) produced in association with positive net community production (NCP), we simulated upwelling systems of different intensities by combining and incubating whole seawater collected from different depths in the Florida Strait (27°N, ∼79°W). The natural microbial communities in the treatments grew under controlled light and temperature for 15 days (i.e., the autotrophic phase); they were subsequently incubated for 35 days in the dark heterotrophic phase. We analyzed the phytoplankton composition and pigment fluorescence intensity during the light phase, and dissolved organic and inorganic variables during both phases. Initial high or low availability of inorganic nutrients controlled phytoplankton growth and the magnitude of NCP. In the strong upwelling treatment with higher initial inorganic nutrients, 25% of NCP accumulated as DOC after 15 days, however, this material was in turn fully remineralized during the dark phase. In contrast, low nutrients in the weak upwelling treatment limited the magnitude of NCP and accumulated DOC, which represented 11% of NCP. Surprisingly, most of this fraction resisted microbial remineralization in the dark phase, suggesting that upwellings of different intensities affect the quality of dissolved organic matter produced, thereby affecting the timing and location of its remineralization and, hence, its prospects for export to the deep ocean.

The global ocean contains a massive reservoir of dissolved organic carbon (DOC), rivaling the atmosphere's pool of CO2. The most recalcitrant fractions have mean radiocarbon ages of similar to 4,000years in the Atlantic to similar to 6,000years in the Pacific. Knowing the radiocarbon signatures of DOC and the molecular composition of dissolved organic matter (DOM) is crucial to develop understanding of the persistence and lifetime of the DOC pool. In this research, we collected samples from the deep North Pacific in August 2013 (aboard the RV Melville) to couple the Delta C-14 content of solid-phase-extracted DOM (Delta C-14-SPE-DOM) with its molecular composition in the ocean's oldest deep waters. We find that deep waters in this region held a mean Delta C-14-SPE-DOM value of -554 +/- 9 (similar to 6,400(14)Cyears), substantially more depleted than that in the deep Atlantic, which held a mean Delta C-14-SPE-DOM value of -445 +/- 5. While we find a more degraded molecular composition of DOM in the deep Pacific than the deep Atlantic, the molecular formulae within the Island of Stability (Lechtenfeld et al., 2014, ), are largely retained. These results imply that a fraction of deep DOM is resistant to removal and present in both the deep Atlantic and Pacific Oceans.

The composition and photochemical transformations of dissolved organic matter (DOM) in the northern North Pacific Ocean were investigated at the molecular level using ultrahigh resolution mass spectrometry and geochemical tracers. Analyses included vertical profiles and experiments in which deep sea DOM was exposed to sunlight and incubated in the dark. The composition of the deep sea DOM was found to be approximately uniform and enriched with highly unsaturated compounds, with highly aromatic compounds, and with polycyclic aromatics. Surface DOM had a significantly different composition, being enriched with both highly unsaturated and with unsaturated aliphatic compounds potentially due to the addition of photodegradation products and phytoplankton inputs. Deep sea DOM composition is transformed by photoreactions, becoming more similar to surface DOM. The influence of photochemistry extends beyond the photic zone, presumably because of vertical export of DOM previously modified at the surface.

Vertical distributions of dissolved organic carbon (DOC) were determined in different seasons in the southern Adriatic and Tyrrhenian Seas to study the role of stratification in DOC patterns. These two seas are located at similar latitude but differ in extents of vertical stratification. Stratification affects DOC dynamics in both basins, but with interesting differences. In the Tyrrhenian Sea, where the upper water column was stratified during all cruises, DOC showed high surface layer values without substantial seasonality. By contrast, in the southern Adriatic Sea, the seasonal cycle of stratification forced opposite trends in the 0–50 m and 50–800 m stocks, with DOC removal from the upper 50 m associated with DOC increase below 50 m. Regarding DOC export via deep water formation in the southern Adriatic Sea, we estimate that 0.19 Tg C yr−1 was exported to the 50–800 m layer by convective overturn, while 0.85–1.19 Tg C yr−1 was sequestered below 1000 m due to a continental shelf pump mechanism. We hypothesize that enhanced stratification associated with a warmer ocean could further increase DOC concentrations in the mixed layer, changing the role of DOC in the oceanic carbon cycle.

[1] The global ocean holds one of Earth's major carbon reservoirs as dissolved organic matter (662 ± 32 PgC). Most of this material (>95%) is termed refractory dissolved organic carbon (RDOC) as Williams and Druffel (1987) found it to be old relative to the circulation time of the ocean. While RDOC within the modern ocean is thus perceived as vast and only slowly renewed, its mobilization has been implicated by Sexton et al. (2011) to explain Earth's transient warming events (i.e., hyperthermals) of the Paleocene and Eocene epochs (65–34 million years ago). Assessing this proposed function of RDOC as a rapidly (~5–10 kyr) exchangeable carbon reservoir is presently limited by insufficient knowledge of the responsible processes. Here we investigate the dynamics of RDOC in the deep Pacific Ocean, previously characterized by concentration gradients thought to be established by slow but systematic RDOC removal with circulation and aging of the water masses. We demonstrate that RDOC is instead conserved during much of its circulation, but that there exist localized sinks in the deep, far North Pacific and at mid depth in the subtropical South Pacific. Water mass mixing into these sink regions creates the observed RDOC gradients. Together, the Pacific sinks remove 7–29% of the 43 Tg RDOC added to the deep global ocean each year with overturning circulation, and point to an important but still unidentified control on the RDOC inventory of deep marine systems.

Bacteria and archaea in the dark ocean (>200 m) comprise 0.3–1.3 billion tons of actively cycled marine carbon. Many of these microorganisms have the genetic potential to fix inorganic carbon (autotrophs) or assimilate single-carbon compounds (methylotrophs). We identified the functions of autotrophic and methylotrophic microorganisms in a vent plume at Axial Seamount, where hydrothermal activity provides a biogeochemical hot spot for carbon fixation in the dark ocean. Free-living members of the SUP05/Arctic96BD-19 clade of marine gamma-proteobacterial sulfur oxidizers (GSOs) are distributed throughout the northeastern Pacific Ocean and dominated hydrothermal plume waters at Axial Seamount. Marine GSOs expressed proteins for sulfur oxidation (adenosine phosphosulfate reductase, sox (sulfur oxidizing system), dissimilatory sulfite reductase and ATP sulfurylase), carbon fixation (ribulose-1,5-bisphosphate carboxylase oxygenase (RuBisCO)), aerobic respiration (cytochrome c oxidase) and nitrogen regulation (PII). Methylotrophs and iron oxidizers were also active in plume waters and expressed key proteins for methane oxidation and inorganic carbon fixation (particulate methane monooxygenase/methanol dehydrogenase and RuBisCO, respectively). Proteomic data suggest that free-living sulfur oxidizers and methylotrophs are among the dominant primary producers in vent plume waters in the northeastern Pacific Ocean.

[1] Dissolved organic carbon (DOC), nitrogen (DON), and phosphorus (DOP) were measured monthly at the CARIACO Time Series station (10°30′N, 64°40′W) in the southeastern Caribbean Sea between 2005 and 2012. Marked seasonal variability in DOC concentrations was observed, with lower values (~66 µM) in the upper water column ( 350 m, DOC concentrations were 56 ± 4.7 µM, roughly 10 µM higher than those in the Caribbean Sea over the same depth range. DON and DOP showed similar vertical profiles to that of DOC, with higher concentrations (6.8 ± 1.2 µM N and 0.15 ±0.09 µM P) in the upper water column and invariant, lower concentrations at depth (4.8 ± 1.6 µM N and 0.10 ± 0.08 µM P). Wind-driven advection of surface DOC out of the Cariaco Basin was estimated to support a net export ~15 Gmol C yr−1 into the Caribbean Sea; this rate is comparable to the flux of settling particulate organic carbon to depths >275 m within the basin.

[1] The allochthonous supply of dissolved organic nitrogen (DON) from gyre margins into the interior of the ocean’s oligotrophic subtropical gyres potentially provides an important source of new N to gyre surface waters, thus sustaining export production. This process requires that a fraction of the transported DON be available to euphotic zone photoautotroph communities via mineralization. In this study, we investigated the biological and physical controls on the distribution and fate of DON within global ocean surface waters. Inputs of nitrate to the euphotic zone at upwelling zones fuel net accumulation of a DON pool that appears to resist rapid microbial remineralization, allowing subsequent advective transport into the subtropical gyres. Zonal gradients in DON concentrations across these gyres imply a DON sink in the surface layer. Assessment of the physical dynamics of gyre circulation and winter mixing revealed a pathway for DON removal from the mixed layer via vertical transport to the deep euphotic zone, which establishes the observed zonal gradients. Incubation experiments from the Florida Straits indicated surface-accumulated DON was largely resistant (over a few months) to utilization by the extant surface bacterioplankton community. In contrast, this same material was remineralized three times more rapidly when exposed to upper mesopelagic bacterioplankton. These results suggest the primary fate of surface DON to be removal via vertical mixing and subsequent mineralization below the mixed layer, implying a limited role for direct DON support of gyre export production from the surface layer. DON may contribute to export production at the eastern edges of the subtropical gyres, but only after its mineralization within the deep euphotic zone.

Biogeochemical studies show that the surface waters of the subtropical North Atlantic are highly phosphorus (P) stressed. Human activity may exacerbate phosphorus stress by enhancing atmospheric nitrogen (N) deposition and raising N/P ratios in deposition. However, the magnitude of this effect is unclear, in part, because atmospherically deposited phosphorus sources are not well known, particularly the contribution from organic phosphorus. Here we report measurements of phosphorus in aerosols and wet deposition at Miami and Barbados. African dust is the major aerosol P source at both Miami and Barbados, containing ~880 ppm total phosphorus and ~70 ppm soluble reactive phosphorus (SRP). Organic compounds contribute, on average, 28%–44% of soluble phosphorus in precipitation. Because of dust transport seasonality, phosphorus inputs to the North Atlantic are expected to be highly variable with 2–10 times more P deposition during summer than winter. Pollution is also an important contributor to total and soluble phosphorus in Miami aerosols and deposition. Estimated SRP deposition in Barbados and Miami is 0.21 and 0.13 µmol m−2 d−1 phosphorus, respectively. Inorganic nitrogen in excess of Redfield ratio expectations in deposition was very different between the sites, totaling 21–30 and 127–132 µmol m−2 d−1 nitrogen in Barbados and Miami, respectively; the high deposition rates at Miami are linked to pollutants. Including soluble organic nitrogen and phosphorus halved the estimates of excess nitrogen in Barbados wet deposition. Thus, the organic phosphorus fraction is important in the assessment of the magnitude of biogeochemical change of the North Atlantic caused by atmospheric deposition.

Little is known about the distribution and dynamics of dissolved organic nitrogen (DON) within Arctic Ocean surface waters, though seasonal inputs from both rivers and marine phytoplankton production are likely important. Here we combine multiple datasets to provide the first quasi-synoptic view of DON concentrations in the summertime Arctic Ocean Polar Surface Layer (PSL) and western Arctic shelves, and infer controlling processes. Distributions indicate inputs of DON by Arctic rivers followed by net consumption of up to 70% of this terrigenous material across the resulting salinity gradients over time scales of years. Coupling of DON losses to PSL residence times indicates first order decay constants (λ) of 0.15 ± 0.07 yr− 1 and 0.08 ± 0.01 yr− 1 for terrigenous DON in the eastern and western Arctic systems, respectively. Riverine delivery of both inorganic and organic nitrogen have only a minor (