Hydrothermal-derived black carbon as a source of recalcitrant dissolved organic carbon in the ocean.

Deep-sea hydrothermal vents are a possible source of thermogenic dissolved black carbon (DBC), which is a component of recalcitrant dissolved organic carbon, but little is known about the distribution of hydrothermal DBC in the deep ocean. Here, we show basin-scale distributions of DBC along two transects in the eastern Pacific Ocean, which are located outside the jet-like hydrothermal plumes from the East Pacific Rise. The DBC concentration in the deep waters did not show a strong linear relationship with apparent oxygen utilization (AOU), as previously observed in the central and western Pacific Ocean. Deviations in DBC concentration from the DBC-AOU relationship observed in the central and western Pacific Ocean were quantified. The deviation was linearly correlated with excess 3He, a tracer for hydrothermal input, indicating that a fraction of the DBC in the deep ocean is transported long distances from hydrothermal systems.

Fate of dissolved black carbon in the deep Pacific Ocean.

Black carbon (BC), a byproduct of biomass and fossil fuel combustion, may impact the climate because it can be stored on Earth's surface for centuries to millennia. Dissolved BC (DBC) occurs ubiquitously in the ocean. However, the DBC cycle in the ocean has not been well constrained. Here, we show the basin-scale distribution of DBC in the Pacific Ocean and find that the DBC concentrations in the deep Pacific Ocean decrease along with deep-ocean meridional circulation. The DBC concentration is negatively correlated with apparent oxygen utilization, a proxy of the integrated flux of sinking particles, in the deep Pacific Ocean, implying that DBC is removed from the deep ocean to abyssal sediments through sorption onto sinking particles. The burial flux of BC to abyssal sediments is estimated to be 0.040-0.085 PgC yr-1, corresponding to 1.5-3.3% of the anthropogenic CO2 uptake by the ocean.

Eco-engineering approaches for ocean negative carbon emission.

The goal of achieving carbon neutrality in the next 30-40 years is approaching worldwide consensus and requires coordinated efforts to combat the increasing threat of climate change. Two main sets of actions have been proposed to address this grand goal. One is to reduce anthropogenic CO2 emissions to the atmosphere, and the other is to increase carbon sinks or negative emissions, i.e., removing CO2 from the atmosphere. Here we advocate eco-engineering approaches for ocean negative carbon emission (ONCE), aiming to enhance carbon sinks in the marine environment. An international program is being established to promote coordinated efforts in developing ONCE-relevant strategies and methodologies, taking into consideration ecological/biogeochemical processes and mechanisms related to different forms of carbon (inorganic/organic, biotic/abiotic, particulate/dissolved) for sequestration. We focus on marine ecosystem-based approaches and pay special attention to mechanisms that require transformative research, including those elucidating interactions between the biological pump (BP), the microbial carbon pump (MCP), and microbially induced carbonate precipitation (MICP). Eutrophic estuaries, hypoxic and anoxic waters, coral reef ecosystems, as well as aquaculture areas are particularly considered in the context of efforts to increase their capacity as carbon sinks. ONCE approaches are thus expected to be beneficial for both carbon sequestration and alleviation of environmental stresses.

Relationships between dissolved black carbon and dissolved organic matter in streams.

Black carbon (BC) is a pyrolyzed product derived from incomplete combustion. A major fraction of BC produced by landscape fires is initially deposited onto onsite soils. Atmospheric deposition of soot is known to be an important source of soil BC, especially in watersheds that are not affected by landscape fires. The transport of the dissolved fraction of oxidized BC in soil, defined as dissolved black carbon (DBC), to streams is considered one of the important loss pathways of BC in soil, but the mechanism is not well documented. We measured the quantity and quality of DBC, determined by a benzenepolycarboxylic acid method, and the quantitative and qualitative parameters of bulk dissolved organic matter (DOM) in streams in Hokkaido, northern Japan, whose catchments were not affected by landscape fire for at least 110 years. DBC with relatively low polycondensed signatures occurred in the streams, irrespective of differences in watershed characteristics and seasons, suggesting that atmospheric deposition of soot into the catchment is probably a major source of stream DBC. The DBC concentration was linearly related to the dissolved organic carbon (DOC) concentration, irrespective of the differences in watershed characteristics and seasons. Furthermore, the polycondensation degree of DBC was observed to correlate with the qualitative parameters of bulk DOM. Such quantitative and qualitative relationships between DBC and bulk DOM imply that the transfer mechanism from soils to streams of soot-derived polycondensed DBC is linked with that of higher plant-derived, high-molecular-weight aromatic DOM.

Evaluation of the Production of Dissolved Organic Matter by Three Marine Bacterial Strains.

A large part of marine dissolved organic matter (DOM) is considered to be recalcitrant DOM (RDOM) produced by marine bacteria. However, it is still unclear whether differences in bacterial species and/or physiology control the efficiency of RDOM production. Here, batch culture experiments with glucose as the sole carbon source were carried out using three model marine bacterial strains, namely, Alteromonas macleodii (Alt), Vibrio splendidus (Vib), and Phaeobacter gallaeciensis (Pha). Dissolved organic carbon (DOC) concentrations drastically decreased during the exponential growth phases of these bacteria due to the consumption of glucose. The efficiency of bacterial DOC production at the end of incubation was largely different among the strains and was higher for Vib (20%) than for the other two strains (Alt, 4%; Pha, 6%). All strains produced fluorescent DOM (FDOM), including humic-like FDOM which is considered as recalcitrant component in the ocean, even though the composition of bacterial FDOM was also different among the strains. The efficiency of humic-like FDOM production during the exponential growth phase was different among the bacterial strains; that is, Pha produced humic-like FDOM efficiently compared with the other two species. The efficiency of humic-like FDOM production with mineralization of organic matter was lower during the exponential growth phase than during the stationary phase of Alt and Pha. Four processes for the production of bacterially derived recalcitrant humic-like FDOM are suggested from this study: (1) production during active growing (in all strains), (2) production with the reutilization of bacterial DOM (Alt), (3) production with the consumption of cellular materials (Pha), and (4) release from lysis (Vib). Our results suggest that bacterial species and physiology can regulate RDOM production and accumulation in the ocean.

New index of organic mass enrichment in sea spray aerosols linked with senescent status in marine phytoplankton.

Linking the amount of organic matter (OM) in sea spray aerosols (SSAs) to biological processes in ocean surface is essential for understanding marine aerosol formation and their potential to affect cloud formation. To date, chlorophyll (Chl) a concentration has been widely used as a surrogate for surface phytoplankton biomass or productivity to predict the relative abundance of OM in SSAs (OMSSA). Here we show a new index to present OMSSA using concentrations of Chl a and chlorophyllide (Chllide) a, which is a breakdown product of Chl a and has been used as a biomarker of senescent algal cells. The index was compared with submicrometer OMSSA, based on surface seawater and aerosol samples obtained during the pre-bloom in the western subarctic Pacific. Our results showed that the OMSSA was highly correlated with this unique index, suggesting that the OMSSA was closely linked with senescent algal cells and/or cell lysis. Furthermore, the hygroscopicity parameters κ derived from water-extracted SSA samples implied a reduction in the SSA hygroscopicity with increasing senescent status of phytoplankton. The index can represent OMSSA on a timescale of a day during the pre-bloom period, which should be further examined over different oceanic regions.

Subpolar marginal seas fuel the North Pacific through the intermediate water at the termination of the global ocean circulation.

The mechanism by which nutrients in the deep ocean are uplifted to maintain nutrient-rich surface waters in the subarctic Pacific has not been properly described. The iron (Fe) supply processes that control biological production in the nutrient-rich waters are also still under debate. Here, we report the processes that determine the chemical properties of intermediate water and the uplift of Fe and nutrients to the main thermocline, which eventually maintains surface biological productivity. Extremely nutrient-rich water is pooled in intermediate water (26.8 to 27.6 σθ) in the western subarctic area, especially in the Bering Sea basin. Increases of two to four orders in the upward turbulent fluxes of nutrients were observed around the marginal sea island chains, indicating that nutrients are uplifted to the surface and are returned to the subarctic intermediate nutrient pool as sinking particles through the biological production and microbial degradation of organic substances. This nutrient circulation coupled with the dissolved Fe in upper-intermediate water (26.6 to 27.0 σθ) derived from the Okhotsk Sea evidently constructs an area that has one of the largest biological CO2 drawdowns in the world ocean. These results highlight the pivotal roles of the marginal seas and the formation of intermediate water at the end of the ocean conveyor belt.

Shelf humic substances as carriers for basin-scale iron transport in the North Pacific.

Iron is one of the key elements controlling phytoplankton growth in large areas of the global ocean. Aeolian dust has traditionally been considered the major external source of iron in the North Pacific. Recent studies have indicated that sedimentary iron from the shelf region of the Sea of Okhotsk has a strong impact on the iron distribution in the North Pacific, while the mechanism supporting its long-distance transport remains poorly understood. Here, we report that refractory shelf humic substances, which complex and carry dissolved iron, are transported conservatively at least 4000 km from the shallow sediments of the Sea of Okhotsk to the subtropical North Pacific with the circulation of intermediate water. This result indicates that shelf humic substances are probably one of the key factors shaping the distribution of dissolved iron in the ocean interior.

Endothelial Insulin Resistance of Freshly Isolated Arterial Endothelial Cells From Radial Sheaths in Patients With Suspected Coronary Artery Disease.

Background Endothelial insulin resistance is insulin-insensitivity in the vascular endothelium and can be observed in experimental models. This study aimed to investigate endothelial insulin resistance in patients with suspected coronary artery disease. To this end, a novel method of obtaining freshly isolated arterial endothelial cells from a radial catheter sheath was developed. Methods and Results Freshly isolated arterial endothelial cells were retrieved from catheter sheaths placed in radial arteries for coronary angiography (n=69, patient age 64±12 years). The endothelial cells were divided into groups for incubation with or without insulin, vascular endothelial growth factor, or acetylcholine. The intensity of phosphorylated endothelial nitric oxide synthase at Ser1177 (p- eNOS ) was quantified by immunofluorescence microscopy. The percentage increase of insulin-induced phosphorylated endothelial nitric oxide synthase correlated negatively with derivatives of reactive oxygen metabolites, an oxidative stress test ( r=-0.348, n=53, P=0.011), E/E', an index of left ventricular diastolic dysfunction in Doppler echocardiography (ρ=-0.374, n=49, P=0.008), and log-transformed brain natriuretic peptide ( r=-0.266, n=62, P=0.037). Furthermore, percentage increase of insulin-induced p- eNOS was an independent factor for the cardio-ankle vascular index (standardized coefficient ß=-0.293, n=42, P=0.021) in the multivariate regression analysis of adaptive least absolute shrinkage and selection operator. Conclusions Our results suggested that endothelial insulin resistance is associated with oxidative stress, left ventricular diastolic dysfunction, heart failure, and arterial stiffness.

Chemical transfer of dissolved organic matter from surface seawater to sea spray water-soluble organic aerosol in the marine atmosphere.

It is critical to understand how variations in chemical composition in surface seawater (SSW) affect the chemistry of marine atmospheric aerosols. We investigated the sea-to-air transfer of dissolved organic carbon (DOC) via cruise measurements of both ambient aerosols and SSW in the Oyashio and its coastal regions, the western subarctic Pacific during early spring. Sea spray aerosols (SSAs) were selected based on the stable carbon isotope ratio of water-soluble organic carbon (WSOC) (δ13CWSOC) and concentrations of glucose as a molecular tracer in marine aerosols together with local surface wind speed data. For both SSA and SSW samples, excitation-emission matrices were obtained to examine the transfer of fluorescent organic material. We found that the ratios of fluorescence intensity of humic-like and protein-like substances in the submicrometer SSAs were significantly larger than those in the bulk SSW (~63%). This ratio was also larger for the supermicrometer SSAs than for the SSW. The results suggest significant decomposition of protein-like DOC on a timescale of <12-24 h and/or preferential production of humic-like substances in the atmospheric aerosols regardless of the particle size. This study provides unique insights into the complex transfer of DOC from the ocean surface to the atmosphere.

Production and Reutilization of Fluorescent Dissolved Organic Matter by a Marine Bacterial Strain, Alteromonas macleodii.

The recalcitrant fraction of marine dissolved organic matter (DOM) plays an important role in carbon storage on the earth's surface. Bacterial production of recalcitrant DOM (RDOM) has been proposed as a carbon sequestration process. It is still unclear whether bacterial physiology can affect RDOM production. In this study, we conducted a batch culture using the marine bacterial isolate Alteromonas macleodii, a ubiquitous gammaproteobacterium, to evaluate the linkage between bacterial growth and DOM production. Glucose (1 mmol C L-1) was used as the sole carbon source, and the bacterial number, the DOM concentration in terms of carbon, and the excitation-emission matrices (EEMs) of DOM were monitored during the 168-h incubation. The incubation period was partitioned into the exponential growth (0-24 h) and stationary phases (24-168 h) based on the growth curve. Although the DOM concentration decreased during the exponential growth phase due to glucose consumption, it remained stable during the stationary phase, corresponding to approximately 4% of the initial glucose in terms of carbon. Distinct fluorophores were not evident in the EEMs at the beginning of the incubation, but DOM produced by the strain exhibited five fluorescent peaks during exponential growth. Two fluorescent peaks were similar to protein-like fluorophores, while the others could be categorized as humic-like fluorophores. All fluorophores increased during the exponential growth phase. The tryptophan-like fluorophore decreased during the stationary phase, suggesting that the strain reused the large exopolymer. The tyrosine-like fluorophore seemed to be stable during the stationary phase, implying that the production of tyrosine-containing small peptides through the degradation of exopolymers was correlated with the reutilization of the tyrosine-like fluorophore. Two humic-like fluorophores that showed emission maxima at the longer wavelength (525 nm) increased during the stationary phase, while the other humic-like fluorophore, which had a shorter emission wavelength (400 nm) and was categorized as recalcitrant, was stable. These humic-like fluorophore behaviors during incubation indicated that the composition of bacterial humic-like fluorophores, which were unavailable to the strain, differed between growth phases. Our results suggest that bacterial physiology can affect RDOM production and accumulation in the ocean interior.

The conservative behavior of dissolved organic carbon in surface waters of the southern Chukchi Sea, Arctic Ocean, during early summer.

The spatial distribution of dissolved organic carbon (DOC) concentrations and the optical properties of dissolved organic matter (DOM) determined by ultraviolet-visible absorbance and fluorescence spectroscopy were measured in surface waters of the southern Chukchi Sea, western Arctic Ocean, during the early summer of 2013. Neither the DOC concentration nor the optical parameters of the DOM correlated with salinity. Principal component analysis using the DOM optical parameters clearly separated the DOM sources. A significant linear relationship was evident between the DOC and the principal component score for specific water masses, indicating that a high DOC level was related to a terrigenous source, whereas a low DOC level was related to a marine source. Relationships between the DOC and the principal component scores of the surface waters of the southern Chukchi Sea implied that the major factor controlling the distribution of DOC concentrations was the mixing of plural water masses rather than local production and degradation.

Fluorescent water-soluble organic aerosols in the High Arctic atmosphere.

Organic aerosols are ubiquitous in the earth's atmosphere. They have been extensively studied in urban, rural and marine environments. However, little is known about the fluorescence properties of water-soluble organic carbon (WSOC) or their transport to and distribution in the polar regions. Here, we present evidence that fluorescent WSOC is a substantial component of High Arctic aerosols. The ratios of fluorescence intensity of protein-like peak to humic-like peak generally increased from dark winter to early summer, indicating an enhanced contribution of protein-like organics from the ocean to Arctic aerosols after the polar sunrise. Such a seasonal pattern is in agreement with an increase of stable carbon isotope ratios of total carbon (δCTC) from -26.8‰ to -22.5‰. Our results suggest that Arctic aerosols are derived from a combination of the long-range transport of terrestrial organics and local sea-to-air emission of marine organics, with an estimated contribution from the latter of 8.7-77% (mean 45%).

Laterally spreading iron, humic-like dissolved organic matter and nutrients in cold, dense subsurface water of the Arctic Ocean.

The location and magnitude of oceanic iron sources remain uncertain owing to a scarcity of data, particularly in the Arctic Ocean. The formation of cold, dense water in the subsurface layer of the western Arctic Ocean is a key process in the lateral transport of iron, macronutrients, and other chemical constituents. Here, we present iron, humic-like fluorescent dissolved organic matter, and nutrient concentration data in waters above the continental slope and shelf and along two transects across the shelf-basin interface in the western Arctic Ocean. We detected high concentrations in shelf bottom waters and in a plume that extended in the subsurface cold dense water of the halocline layer in slope and basin regions. At σθ = 26.5, dissolved Fe, humic-like fluorescence intensity, and nutrient maxima coincided with N* minima (large negative values of N* indicate significant denitrification within shelf sediments). These results suggest that these constituents are supplied from the shelf sediments and then transported laterally to basin regions. Humic dissolved organic matter probably plays the most important role in the subsurface maxima and lateral transport of dissolved Fe in the halocline layer as natural Fe-binding organic ligand.

Accumulation of humic-like fluorescent dissolved organic matter in the Japan Sea.

Major fraction of marine dissolved organic matter (DOM) is biologically recalcitrant, however, the accumulation mechanism of recalcitrant DOM has not been fully understood. Here, we examine the distributions of humic-like fluorescent DOM, factions of recalcitrant DOM, and the level of apparent oxygen utilization in the Japan Sea. We find linear relationships between these parameters for the deep water (>200 m) of the Japan Sea, suggesting that fluorescent DOM is produced in situ in the Japan Sea. Furthermore, we find that the amount of fluorescent DOM at a given apparent oxygen utilization is greater in the deep water of the Japan Sea than it is in the North Pacific, where the highest level of fluorescent DOM in the open ocean was previously observed. We conclude that the repeated renewal of the deep water contributes to the accumulation of fluorescent DOM in the interior of the Japan Sea.

Fluorescence characteristics of size-fractionated dissolved organic matter: implications for a molecular assembly based structure?

Surface freshwater samples from Everglades National Park, Florida, were used to investigate the size distributions of natural dissolved organic matter (DOM) and associated fluorescence characteristics along the molecular weight continuum. Samples were fractionated using size exclusion chromatography (SEC) and characterized by spectroscopic means, in particular Excitation-Emission Matrix fluorescence modeled with parallel factor analysis (EEM-PARAFAC). Most of the eight components obtained from PARAFAC modeling were broadly distributed across the DOM molecular weight range, and the optical properties of the eight size fractions for all samples studied were quite consistent among each other. Humic-like components presented a similar distribution in all the samples, with enrichment in the middle molecular weight range. Some variability in the relative distribution of the different humic-like components was observed among the different size fractions and among samples. The protein like fluorescence, although also generally present in all fractions, was more variable but generally enriched in the highest and lowest molecular weight fractions. These observations are in agreement with the hypothesis of a supramolecular structure for DOM, and suggest that DOM fluorescence characteristics may be controlled by molecular assemblies with similar optical properties, distributed along the molecular weight continuum. This study highlights the importance of studying the molecular structure of DOM on a molecular size distribution perspective, which may have important implications in understanding the environmental dynamics such materials.

Dissolved black carbon in grassland streams: is there an effect of recent fire history?

While the existence of black carbon as part of dissolved organic matter (DOM) has been confirmed, quantitative determinations of dissolved black carbon (DBC) in freshwater ecosystem and information on factors controlling its concentration are scarce. In this study, stream surface water samples from a series of watersheds subject to different burn frequencies in Konza Prairie (Kansas, USA) were collected in order to determine if recent fire history has a noticeable effect on DBC concentration. The DBC levels detected ranged from 0.04 to 0.11 mg L(-1), accounting for ca. 3.32±0.51% of dissolved organic carbon (DOC). No correlation was found between DBC concentration and neither fire frequency nor time since last burn. We suggest that limited DBC flux is related to high burning efficiency, possibly greater export during periods of high discharge and/or the continuous export of DBC over long time scales. A linear correlation between DOC and DBC concentrations was observed, suggesting the export mechanisms determining DOC and DBC concentrations are likely coupled. The potential influence of fire history was less than the influence of other factors controlling the DOC and DBC dynamics in this ecosystem. Assuming similar conditions and processes apply in grasslands elsewhere, extrapolation to a global scale would suggest a global grasslands flux of DBC on the order of 0.14 Mt carbon year(-1).

Photo-dissolution of flocculent, detrital material in aquatic environments: contributions to the dissolved organic matter pool.

This study shows that light exposure of flocculent material (floc) from the Florida Coastal Everglades (FCE) results in significant dissolved organic matter (DOM) generation through photo-dissolution processes. Floc was collected at two sites along the Shark River Slough (SRS) and irradiated with artificial sunlight. The DOM generated was characterized using elemental analysis and excitation emission matrix fluorescence coupled with parallel factor analysis. To investigate the seasonal variations of DOM photo-generation from floc, this experiment was performed in typical dry (April) and wet (October) seasons for the FCE. Our results show that the dissolved organic carbon (DOC) for samples incubated under dark conditions displayed a relatively small increase, suggesting that microbial processes and/or leaching might be minor processes in comparison to photo-dissolution for the generation of DOM from floc. On the other hand, DOC increased substantially (as much as 259 mgC gC(-1)) for samples exposed to artificial sunlight, indicating the release of DOM through photo-induced alterations of floc. The fluorescence intensity of both humic-like and protein-like components also increased with light exposure. Terrestrial humic-like components were found to be the main contributors (up to 70%) to the chromophoric DOM (CDOM) pool, while protein-like components comprised a relatively small percentage (up to 16%) of the total CDOM. Simultaneously to the generation of DOC, both total dissolved nitrogen and soluble reactive phosphorus also increased substantially during the photo-incubation period. Thus, the photo-dissolution of floc can be an important source of DOM to the FCE environment, with the potential to influence nutrient dynamics in this system.