Surface Dissolved Organic Carbon Research Articles

Sensitivity of Steady State, Deep Ocean Dissolved Organic Carbon to Surface Boundary Conditions

AbstractWe use the transport matrices of a data‐constrained circulation model to efficiently compute the steady state distribution of the deep ocean dissolved organic carbon (DOC) at a 1° horizontal resolution by propagating the surface DOC boundary conditions into the ocean interior. An equivalent simulation in the traditional forward modeling approach would be prohibitively computationally expensive. Our model simulates the total DOC as the sum of two DOC pools, the refractory and the semi‐labile. The model is able to simulate the large‐scale features of the deep ocean DOC without local sources or sinks of DOC in the ocean interior. The deep ocean DOC in the model is sensitive to the preformed DOC concentrations in the formation sites of deep and bottom waters, where observations are lacking. Furthermore, our model experiments indicate that the deep Atlantic DOC gradient is sensitive to the mixing of deep waters with different concentrations of preformed refractory DOC, the transport of semi‐labile DOC from the surface North Atlantic, and the decay rate of semi‐labile DOC. These, combined with the observation that much of the deep ocean DOC gradient is in the Atlantic, suggests that the semi‐labile DOC may be an important component of the deep Atlantic DOC. Finally, we show that DOC export depends substantially on the depth level where it is evaluated.

Distribution and Dynamics of Dissolved Organic Matter in the Changjiang Estuary and Adjacent Sea

AbstractLarge, river‐dominated estuaries provide important land‐ocean interfaces for biogenic element fluxes that impact global marine biogeochemistry. However, the reactivity and fate of dissolved organic matter (DOM) in this dynamic region remain not well understood. In this study, three cruises were conducted in February, May, and July 2017 in the Changjiang Estuary and adjacent sea (CEAS). Incubation experiments to determine photochemically and/or biologically mediated degradation of terrigenous and marine DOM were performed. Dissolved organic carbon (DOC), chromophoric DOM (CDOM) absorption, and total dissolved amino acids (TDAAs) were measured. DOM photodegradation and transformation were indicated by the CDOM spectral slope (S275−295) and diagenetic state by DOC‐normalized yields of TDAA [TDAA (%DOC)]. From the river to the open sea, DOC showed non‐conservative mixing and was rapidly removed in low salinity areas. Photodegradation, biodegradation, and photoenhanced biodegradation are important DOC removal mechanisms and exhibit specific responses depending on DOC source and composition. Terrigenous DOM is vulnerable to photodegradation, while marine DOM experiences rapid biodegradation. Contrary to DOC, TDAA (%DOC) increased from the river to the nearshore and then decreased toward the open sea, indicating the contribution of fresh marine plankton production. A box model showed that the annual DOC removal of CEAS was 2.6 ± 1.9 × 106 tons. Seaward increase of ammonium (NH4‐N) was observed in the CEAS; photoammonification, biomineralization of autochthonous and allochthonous DOM are potential NH4‐N regeneration mechanisms. A model was developed to calculate surface DOC concentrations based on CDOM absorption coefficients allowing high‐resolution monitoring of DOC in the CEAS.

Enhanced Biodegradation of Dissolved Organic Carbon in the Western Boundary Kuroshio Current When Intruded to the Marginal South China Sea

AbstractThe advective supply of allochthonous dissolved organic carbon (DOC) from open ocean to marginal seas through western boundary current intrusion influences the regional carbon inventory and microbial activities. However, there is limited observation about this process and its biogeochemical impacts on marginal seas. In this study, we investigated the biodegradation of allochthonous DOC carried by the intrusion of the Kuroshio Current into South China Sea (SCS). Using an isopycnal mixing model, the exchange and biodegradation processes of Kuroshio‐intruded DOC were quantified. We estimated that approximately 10% of the surface DOC was remineralized due to the enhanced biodegradation in the SCS. This result was supported by the on‐deck bioassay experiments that were conducted under different environmental contexts. The results of modeling and on‐deck incubations indicate that DOC biodegradation was enhanced by the sharp gradient of environment factors, including nutrients supply, microbial species, and bio‐lability of DOC in the frontal zone during the surface water mass mixing. The amount of carbon released from the enhanced DOC degradation by Kuroshio intrusion was estimated to be approximately equal to 8.6 Tg C yr−1. Concomitantly, the amount of nitrogen released could contribute 0.19–0.70 mmol N m−2 d−1 to the surface of SCS which is comparable to the total supply from deeper water and nitrogen fixation in surface waters. This study suggests that the enhanced biodegradation of DOC during the western boundary currents intrusion could serve as an important sink of oceanic DOC, and thus provide an additional nutrient source to marginal seas.

Modeling Terrestrial Dissolved Organic Carbon Loading to Western Arctic Rivers.

The mobilization and land‐to‐ocean transfer of dissolved organic carbon (DOC) in Arctic watersheds is intricately linked with the region's climate and water cycle, and furthermore at risk of changes from climate warming and associated impacts. This study quantifies model‐simulated estimates of runoff, surface and active layer leachate DOC concentrations and loadings to western Arctic rivers, specifically for basins that drain into coastal waters between and including the Yukon and Mackenzie Rivers. Model validation leverages data from other field measurements, synthesis studies, and modeling efforts. The simulations effectively quantify DOC leaching in surface and subsurface runoff and broadly capture the seasonal cycle in DOC concentration and mass loadings reported from other studies that use river‐based measurements. A marked east‐west gradient in simulated spring and summer DOC concentrations of 24 drainage basins on the North Slope of Alaska is captured by the modeling, consistent with independent data derived from river sampling. Simulated loadings for the Mackenzie and Yukon show reasonable agreement with estimates of DOC export for annual totals and four of the six seasonal comparisons. Nearly equivalent loading occurs to rivers which drain north to the Beaufort Sea and west to the Bering and Chukchi Seas. The modeling framework provides a basis for understanding carbon export to coastal waters and for assessing impacts of hydrological cycle intensification and permafrost thaw with ongoing warming in the Arctic.

Increasing freshwater and dissolved organic carbon flows to Northwest Alaska’s Elson lagoon

Manifestations of climate change in the Arctic are numerous and include hydrological cycle intensification and permafrost thaw, both expected as a result of atmospheric and surface warming. Across the terrestrial Arctic dissolved organic carbon (DOC) entrained in arctic rivers may be providing a carbon subsidy to coastal food webs. Yet, data from field sampling is too often of limited duration to confidently ascertain impacts of climate change on freshwater and DOC flows to coastal waters. This study applies numerical modeling to investigate trends in freshwater and DOC exports from land to Elson Lagoon in Northwest Alaska over the period 1981–2020. While the modeling approach has limitations, the results point to significant increases in freshwater and DOC exports to the lagoon over the past four decades. The model simulation reveals significant increases in surface, subsurface (suprapermafrost), and total freshwater exports. Significant increases are also noted in surface and subsurface DOC production and export, influenced by warming soils and associated active-layer thickening. The largest changes in subsurface components are noted in September, which has experienced a ∼50% increase in DOC export emanating from suprapermafrost flow. Direct coastal suprapermafrost freshwater and DOC exports in late summer more than doubled between the first and last five years of the simulation period, with a large anomaly in September 2019 representing a more than fourfold increase over September direct coastal export during the early 1980s. These trends highlight the need for dedicated measurement programs that will enable improved understanding of climate change impacts on coastal zone processes in this data sparse region of Northwest Alaska.

Response of methane emissions to litter input manipulation in a temperate freshwater marsh, Northeast China

The photograph of the field experiment of different litter input manipulations in situ and the treatment effects on CH 4 fluxes during observations in 2015 and 2016. Abbreviations: NL, no aboveground litter; DL, double litter; CK, control; AR, standing litter removal. • We conducted a two seasons litter input manipulation experiment in a freshwater marsh. • Litter input manipulations obviously affected CH 4 emission and surface DOC contents. • Litter removal induced higher soil temperature, DOC content and CH 4 emission. • The abundance of methanogens in surface soil relied on the ways of litter manipulation. Plant litter plays an important role in regulating CH 4 emission in wetland ecosystems. Our knowledge of the impacts of plant litter on CH 4 budget is important for understanding the response and feedbacks of wetland ecosystems to climate warming. Nevertheless, the effects of plant litter on CH 4 emission and temperature sensitivity (Q 10 ) are not clear under the background of global change. In this study, a field litter inputs manipulation experiment with four treatments including no aboveground litter (NL), standing litter removal (AR), doubled litter input (DL) and controls (CK) was conducted to study the effects of litter manipulations on CH 4 emission in a seasonal inundated freshwater marsh over two growing seasons of 2015 and 2016 in the Sanjiang Plain, Northeast China. Results showed that CH 4 emission was significantly associated with altered litter input over the observation period. Compared with CK, the cumulative CH 4 emission increased by 105.83%, 42.20% and 42.50% for NL, AR and DL treatments, respectively, in 2015, and the values were 199.04%, 115.55% and 17.55%, in 2016. Variances of CH 4 emission were more sensitive to litter removal effects. Altered litter input also significantly affected the dissolved organic carbon (DOC) concentration ([DOC]) in surface pore water. DL and CK treatments with lower soil temperature had lower [DOC] than litter removal treatments of NL and AR. The abundance of methanogens among the four treatments exhibited synchronous change with DOC over the observation period. The Q 10 values of CH 4 emission didn’t show consistent changing patterns with those of DOC among different litter input treatments, which was probably due to the different temperature sensitivity of dominant methanogen types. Due to its great effects on soil microclimate, substrate availability and the concomitant variation in temperature sensitivity, our results highlighted that plant litter effects should be incorporated into the current process-based CH 4 biogeochemical models to predict future CH 4 fluxes from natural wetlands under the background of global change.

Seasonality of Dissolved Organic Carbon in the Upper Northeast Pacific Ocean

AbstractFrom seasonal cruises in the NE Pacific Ocean during 2017, we (1) determined dissolved organic carbon concentrations; (2) calculated net community production (NCP) from nitrate drawdown; and (3) established relationships between NCP and seasonal dissolved organic carbon (DOC) accumulation in the upper 75 m. The fraction of NCP that accumulated as DOC, hereafter referred to as the net dissolved production ratio, was calculated for several stations during spring and summer. The net dissolved production ratio was about 0.26 at the oceanic station Ocean Station Papa during different seasons and years. Using nitrate concentration profiles obtained from Bio‐Argo floats during 2009–2018 operating near Ocean Station Papa, we calculated NCP at high temporal resolution and then applied the 0.26 constant in order to (4) estimate DOC variability for the 9‐year period. We found strong seasonality near Ocean Station Papa, with NCP maxima during summers ranging from 0.3 to 2.9 mol C/m2 and surface DOC concentrations estimated from 56 μmol/kg in winters to 73 μmol/kg in summers. There was a 10‐fold interannual variability in the seasonally accumulated inventory of DOC, ranging from 0.078 to 0.75 mol C/m2. This study reinforces the value of deploying floats equipped with chemical sensors in order to better understand marine biogeochemical cycles, especially when high resolution data cannot be obtained otherwise. Given that ~26% of NCP accumulates as DOC in the central Gulf of Alaska, the remaining balance of ~74% is available for export as sinking biogenic particles.

The composition and distribution of semi-labile dissolved organic matter across the southwest Pacific

Abstract. The distribution and dynamics of dissolved organic carbon (DOC) and dissolved combined neutral sugars (DCNS) were studied across an increasing oligotrophic gradient (18 to 22∘ S latitude) in the tropical South Pacific Ocean, spanning from the Melanesian Archipelago (MA) area to the western part of the South Pacific gyre (WGY), in austral summer as a part of the OUTPACE project. Our results show that DOC and DCNS concentrations exhibited no statistical differences between the MA and WGY areas (0–200 m: 47–81 µM C for DOC and 0.2-4.2 µM C for DCNS). However, due to a deepening of the euphotic zone, a deeper penetration of DOC was noticeable at 150 m of depth at the WGY area. Excess DOC (DOCEX) was determined as the difference between surface and deep-sea DOC values, and euphotic zone integrated stocks of both DOC and DOCEX were higher in the WGY than the MA area. Considering DOCEX as representative of semi-labile DOC (DOCSL), its residence time was calculated as the ratio of DOCSL to bacterial carbon demand (BCD). This residence time was 176±43 days (n=3) in the WGY area, about 3 times longer than in the MA area (Tr=51±13 days, n=8), suggesting an accumulation of semi-labile dissolved organic matter (DOM) in the surface waters of WGY. Average epipelagic (0–200 m) DCNS yields (DCNS × DOC−1) based on volumetric data were roughly similar in both areas, accounting for ∼2.8 % of DOC. DCNS exhibited a longer residence time in WGY (Tr=91±41 days, n=3) than in MA (Tr=31±10 days, n=8), further suggesting that this DCNS pool persists longer in the surface waters of the WGY. The accumulation of DOCEX in the surface waters of WGY is probably due to very slow bacterial degradation due to nutrient and/or energy limitation of heterotrophic prokaryotes, indicating that biologically produced DOC can be stored in the euphotic layer of the South Pacific gyre for a long period.

Distribution of dissolved organic carbon in the Bay of Bengal: Influence of sediment discharge, fresh water flux, and productivity

Abstract Dissolved organic carbon (DOC) plays an important role in the oceanic carbon cycle , with its distribution and variation primarily controlled by in situ productivity. The vertical and spatial distribution of DOC measured during two cruises has been investigated to decipher the processes controlling DOC in the Bay of Bengal (BoB). The terrestrial DOC flux to the BoB constitutes a significant fraction of the total DOC and has implications for the carbon budget of the northern Indian Ocean. High concentrations of DOC were observed in the northern BoB, which is primarily due to high flux of terrestrially derived fresh water from various rivers draining to the BoB. Compared to surface DOC concentration of the world oceans, BoB surface water generally has a higher DOC concentration (75–100 μM), which can be attributed to the high DOC content of the riverine flux. Stratification of surface water helps to maintain DOC content due to inhibited vertical mixing in the BoB as a result of the fresh water lens. High subsurface DOC concentration is due to the remineralisation of biogenic sinking particles brought along with the sediments. Subsurface DOC concentrations in the BoB exhibit a conspicuous decreasing trend southwards due to reduced influence of riverine biogenic flux. This study demonstrates that the average contribution of apparent oxygen utilization (AOU) to the DOC remineralisation in the BoB was ~18%.

Seasonal Dynamics of Dissolved Organic Carbon Under Complex Circulation Schemes on a Large Continental Shelf: The Northern South China Sea

AbstractWe examined the distribution and seasonality of dissolved organic carbon (DOC) based on a large data set collected from the northern South China Sea (NSCS) shelf under complex circulation schemes influenced by river plume, coastal upwelling, and downwelling. The highest surface values of ∼117 μmol L−1 were observed nearshore in summer suggesting high DOC supplies from the river inputs, whereas the lowest surface values of ∼62 μmol L−1 were on the outer shelf in winter due to entrainment of DOC‐poor subsurface water under strengthened vertical mixing. While the summer coastal upwelling brought lower DOC from offshore depth to the nearshore surface, the winter coastal downwelling delivered higher surface DOC to the midshelf deep waters from the inner shelf fueled by the China Coastal Current (CCC) transporting relatively high DOC from the East China Sea to the NSCS. The intensified winter downwelling generated a cross‐shelf DOC transport of 3.1 × 1012 g C over a large shelf area, which induced a significant depression of the NSCS DOC inventory in winter relative to in autumn. In addition to the variable physical controls, net biological production of DOC was semiquantified in both the river plume (2.8 ± 3.0 μmol L−1) and coastal upwelling (3.1 ± 1.3 μmol L−1) in summer. We demonstrated that the NSCS shelf had various origins of DOC including riverine inputs, inter‐shelf transport and in situ production. Via cross‐shelf transport, the accumulated DOC would be exported to and stored in the deep ocean, suggesting that continental shelves are a potentially effective carbon sink.

Long Term Trends and Dynamics of Dissolved Organic Carbon (DOC) in a Subtropical Reservoir Basin

This study evaluates the long term trends and seasonal patterns of dissolved organic carbon (DOC) concentration in the Fei-Tsui Reservoir basin in Northern Taiwan during the period of 2000 to 2015. The non-parametric seasonal Mann-Kendall test was conducted to identify the trends of DOC and its potential drivers (e.g., temperature, runoff, atmospheric acid deposition and stream water chemistry). The monthly tributaries and water surface DOC concentrations in Fei-Tsui Reservoir had showed strong temporal and seasonal variability. The sulfate (SO4) concentration had exhibited statistically significant decreasing trend over a period of 16 years. The decreasing trends of anions (SO4 and NO3) and base cations (Ca and Mg) as well as increasing trends of pH and acidification index (ACI) in Fei-Tsui Reservoir and streams indicated recovery from acidification. However, there was no significant annual trend in DOC concentration of Fei-Tsui Reservoir and streams. Significant positive correlation was obtained between DOC and trophic state index of Fei-Tsui Reservoir. The results suggested that DOC concentration at the water surface of Fei-Tsui Reservoir was mainly driven by the re-oligotrophication and temperature effects rather than a decrease in atmospheric sulfur deposition. Stream DOC concentration was largely determined by the temporal variability in temperature and rainfall. We concluded that climatic and hydrological factors are the dominant drivers for stream DOC dynamics in the study.

Tracing high time-resolution fluctuations in dissolved organic carbon using satellite and buoy observations: Case study in Lake Taihu, China

Field measurements of dissolved organic carbon (DOC) concentration and remote-sensing reflectance were conducted to develop a regional, empirical red-blue algorithm to retrieve surface DOC from Geostationary Ocean Color Imager (GOCI) data for Lake Taihu, China. The auxiliary data (in-situ observations of the optical properties and water quality, buoy measurements of hydrodynamic data and water chemical parameters) were used to investigate the spatial and temporal variations in DOC. GOCI was shown to be capable of successfully obtaining hourly variations in DOC, with a root mean square error percentage (RMSP) of 17.29% (RMSE=0.69mg/L) for the match-up data. The GOCI-derived DOC in Lake Taihu confirms that the highest DOC concentration is in northwest Lake Taihu, followed by Meiliang Bay, Gonghu Bay and northeast Lake Taihu. Hourly DOC variation is significant and presents a different trend for each lake segment due to the variety of influencing factors. Discharge of DOC from surrounding rivers is an important factor to the variation of DOC in northeast Lake Taihu. However, organic products of algae will be the primary contributor to DOC when algal bloom occurred. During the period of algal bloom, high DOC levels in Lake Taihu can lead to hypoxia when coupled with high temperatures and low disturbance.

Sources, Distributions, and Dynamics of Dissolved Organic Matter in the Canada and Makarov Basins

A comprehensive survey of dissolved organic carbon (DOC) and chromophoric dissolved organic matter (CDOM) was conducted in the Canada and Makarov Basins and adjacent seas during 2010-2012 to investigate the dynamics of dissolved organic matter (DOM) in the Arctic Ocean. Sources and distributions of DOM in polar surface waters were very heterogeneous and closely linked to hydrological conditions. Canada Basin surface waters had relatively low DOC concentrations (69±6 µmol L-1), CDOM absorption (a325: 0.32±0.07 m-1) and CDOM-derived lignin phenols (3±0.4 nmol L-1) and high spectral slope values (S275-295: 31.7±2.3 µm-1), indicating minor terrigenous inputs and evidence of photochemical alteration in the Beaufort Gyre. By contrast, surface waters of the Makarov Basin had elevated DOC (108±9 µmol L-1) and lignin phenol concentrations (15±3 nmol L-1), high a325 values (1.36±0.18 m-1) and low S275-295 values (22.8±0.8 µm-1), indicating pronounced Siberian river inputs associated with the Transpolar Drift and minor photochemical alteration. Observations near the Mendeleev Plain suggested limited interactions of the Transpolar Drift with Canada Basin waters, a scenario favoring export of Arctic DOM to the North Atlantic. The influence of sea-ice melt on DOM was region-dependent, resulting in an increase (Beaufort Sea), a decrease (Bering-Chukchi Seas), and negligible change (deep basins) in surface DOC concentrations and a325 values. Halocline structures differed between basins, and the Canada Basin upper halocline and Makarov Basin halocline were comparable in their average DOC (65-70 µmol L-1) and lignin phenol concentrations (3-4 nmol L-1) and S275-295 values (22.9-23.7 µm-1). Deep-water DOC concentrations decreased by 6-8 µmol L-1 with increasing depth, water mass age, nutrient concentrations, and apparent oxygen utilization. Maximal estimates of DOC degradation rates (0.036-0.039 µmol L-1 yr-1) in the deep Arctic were lower than those in other ocean basins, possibly due to low water temperatures. DOC concentrations in bottom waters (>2500 m; 46±2 µmol L-1) of the Canada and Makarov Basins were slightly lower than those reported for deep waters of the Eurasian Basin and Nordic Seas. Elevated a325 values (by 10-20%) were observed near the seafloor, indicating biological activity in Arctic basin sediments.

Linked changes in marine dissolved organic carbon molecular size and radiocarbon age

AbstractMarine dissolved organic carbon (DOC) is a major global carbon reservoir, yet its cycling remains poorly understood. Previous work suggests that DOC molecular size and chemical composition can significantly affect its bioavailability. Thus, DOC size and composition may control DOC cycling and radiocarbon age (via Δ14C). Here we show that DOC molecular size is correlated to DOC Δ14C in the Pacific Ocean. Our results, based on a series of increasing molecular size fractions from three depths in the Pacific, show increasing DOC Δ14C with increasing molecular size. We use a size‐age distribution model to predict the DOC and Δ14C of ultrafiltered DOC. The model predicts both large and small surface DOC with high Δ14C and a narrow range (200–500 Da) of low Δ14C DOC. Deep model offsets suggest different size distributions and/or Δ14C sources at 670–915 m. Our results suggest that molecular size and composition are linked to DOC reactivity and storage in the ocean.

A decade of weekly dissolved organic carbon values in the coastal upwelling of the NW Spain (Atlantic Galician Rías)

Dissolved organic carbon (DOC) was measured weekly in five coastal upwelling Galician rías (Ría de Vigo, Ría de Pontevedra, Ría de Arousa, Ría de Muros and Ría de Ares–Betanzos) and the first decadal DOC series was examined in these rías. The temporal variability of DOC was assessed by considering biweekly values at 10 oceanographic stations for the decade 2002–2011. Seasonal variability in surface DOC concentrations was observed, with higher values (101±8μmolL−1; average±STD) during the accumulation period (DOCb; May–October) in all inner and outer stations. During the rest of the year (DOCc; November–April) surface DOC concentrations decreased to 88±6μmolL−1. The temporal distribution of DOC and temperature were comparable, with a marked seasonal variability, suggesting that the temperature was the main proxy for DOC. The average decadal seasonal increase in surface DOC (ΔDOCs=DOCb−DOCc) was between 7 and 18μmolL−1 for all stations. The interannual variability of surface DOC ranged between 0 and 18μmolL−1; 0 and 11% of the average DOC of each station. Decadal DOC trends were slightly positive in middle-inner areas of the Rías Baixas (Ría de Vigo, Ría de Pontevedra, Ría de Arousa and Ría de Muros) in agreement with positive temperature trends. The outer area of the Rías Baixas showed positive DOC trends in the stations of Ría de Vigo and Ría de Arousa and negative DOC trends in the stations of Ría de Pontevedra and Ría de Muros, although temperature presented positive trends in these four stations. The Ría de Ares–Betanzos exhibited negative trends in DOC and temperature.

An improved algorithm for remotely sensing marine dissolved organic carbon: Climatology in the northern South China Sea shelf-sea and adjacent waters

By using field in situ observations, data from the NOMAD database, and remotely sensed data from MODIS-Aqua, an improved algorithm has been developed for estimating the surface concentrations of dissolved organic carbon (DOC) in the Northern South China Sea Shelf-sea (NoSoCS) and adjacent waters through a combination of the remotely sensed sea-surface temperature (SST) and the absorption coefficient of colored dissolved organic matter (CDOM). Unlike previously reported algorithms, which were based on only one of these two parameters, this algorithm does not require seasonal tuning and is applicable to both coastal and pelagic waters. The uncertainty in the remotely sensed concentrations of DOC is about ±4–10µM. The climatological distributions of the satellite-derived surface DOC in the NoSoCS and adjacent waters between 2002 and 2012 followed a general trend of increasing concentrations landward, from about 58 and 73μM in the open South China Sea (SCS) in January and July, respectively, to >100μM at the mouth of the Pearl River. The intra-annual changes in the monthly average concentration of DOC in the NoSoCS follow a distinct seasonal cycle, with the lowest and highest concentrations, 56μM and 75μM, in February and July, respectively. The seasonal cycle of DOC was in phase with that of SST but out of phase with that of primary production, suggesting that biological activity was not likely its primary control. Instead, it was consistent with the entrainment of the cold and less DOC-rich sub-surface water in the surface water by enhanced vertical mixing during winter, and the high inflow of organic-rich river water to the NoSoCS in summer. Sub-regionally, lower concentrations of DOC were found in the known upwelling zones in the NoSoCS, where vertical mixing was enhanced. In the inner shelf, the effect of riverine input was indicated by higher concentrations of DOC in the plume of water at the mouth of the Pearl River. This work represents the first attempt to characterize the regional distribution of surface concentration of DOC in the NoSoCS and adjacent waters.

A physically based framework for modeling the organic fractionation of sea spray aerosol from bubble film Langmuir equilibria

Abstract. The presence of a large fraction of organic matter in primary sea spray aerosol (SSA) can strongly affect its cloud condensation nuclei activity and interactions with marine clouds. Global climate models require new parameterizations of the SSA composition in order to improve the representation of these processes. Existing proposals for such a parameterization use remotely sensed chlorophyll a concentrations as a proxy for the biogenic contribution to the aerosol. However, both observations and theoretical considerations suggest that existing relationships with chlorophyll a, derived from observations at only a few locations, may not be representative for all ocean regions. We introduce a novel framework for parameterizing the fractionation of marine organic matter into SSA based on a competitive Langmuir adsorption equilibrium at bubble surfaces. Marine organic matter is partitioned into classes with differing molecular weights, surface excesses, and Langmuir adsorption parameters. The classes include a lipid-like mixture associated with labile dissolved organic carbon (DOC), a polysaccharide-like mixture associated primarily with semilabile DOC, a protein-like mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture. Box model calculations have been performed for several cases of organic adsorption to illustrate the underlying concepts. We then apply the framework to output from a global marine biogeochemistry model, by partitioning total dissolved organic carbon into several classes of macromolecules. Each class is represented by model compounds with physical and chemical properties based on existing laboratory data. This allows us to globally map the predicted organic mass fraction of the nascent submicron sea spray aerosol. Predicted relationships between chlorophyll a and organic fraction are similar to existing empirical parameterizations, but can vary between biologically productive and nonproductive regions, and seasonally within a given region. Major uncertainties include the bubble film thickness at bursting, and the variability of organic surfactant activity in the ocean, which is poorly constrained. In addition, polysaccharides may enter the aerosol more efficiently than Langmuir adsorption would suggest. Potential mechanisms for enrichment of polysaccharides in sea spray include the formation of marine colloidal particles that may be more efficiently swept up by rising bubbles, and cooperative adsorption of polysaccharides with proteins or lipids. These processes may make important contributions to the aerosol, but are not included here. This organic fractionation framework is an initial step towards a closer linking of ocean biogeochemistry and aerosol chemical composition in Earth system models. Future work should focus on improving constraints on model parameters through new laboratory experiments or through empirical fitting to observed relationships in the real ocean and atmosphere, as well as on atmospheric implications of the variable composition of organic matter in sea spray.

Annual benthic metabolism and organic carbon fluxes in a semi-enclosed Mediterranean bay dominated by the macroalgae Caulerpa prolifera

Coastal areas play an important role on carbon cycling. Elucidating the dynamics on the production, transport and fate of organic carbon is relevant to gain a better understanding of the role coastal areas play in the global carbon budget. Here, we assess the metabolic status and associated organic carbon fluxes of a semi-enclosed Mediterranean bay supporting a meadow of Caulerpa prolifera. We test whether the EDOC pool is a significant component of the organic carbon pool and associated fluxes in this ecosystem. The Bay of Portocolom was in net metabolic balance on a yearly basis, but heterotrophic during the summer months. Community respiration (CR) was positively correlated to C. prolifera biomass, while net community production (NCP) had a negative correlation. The benthic compartment represented, on average, 72.6 ± 5.2 % of CR and 86.8 ± 4.5 % of gross primary production (GPP). Dissolved organic carbon (DOC) production peaked in summer and was always positive, with the incubations performed in the dark almost doubling the flux of those performed in the light. Exchangeable dissolved organic carbon (EDOC), however, oscillated between production and uptake, being completely recycled within the system and representing around 14% of the DOC flux. The pools of bottom and surface DOC were high for an oligotrophic environment, and were positively correlated to the pool of EDOC. Thus, despite being in metabolic balance, this ecosystem acted as a conduit for organic carbon (OC), as it is able to export OC to adjacent areas derived from allochtonous inputs during heterotrophic conditions. These inputs likely come from groundwater discharge, human activity in the watershed, delivered to the sediments through the high capacity of C. prolifera to remove particles from the water column, and from the air-water exchange of EDOC, demonstrating that these communities are a major contributor to the cycling of OC in coastal embayments.

Estimating dissolved organic carbon inventories in the East China Sea using remote‐sensing data

AbstractThe coastal ocean is characterized by a high dissolved organic carbon (DOC) concentration due to large terrestrial inputs and high primary production. Monitoring the dynamic variation of DOC inventories in coastal oceans provide more information on carbon flux, but is very challenging in practice. We propose a method of estimating DOC inventories in the East China Sea (ECS) by integrating the surface DOC distribution with a vertical model of the DOC profile via satellite data. Surface DOC concentration was retrieved from satellite‐derived chromophoric dissolved organic matter and chlorophyll concentration. Two vertical DOC profile models (uniform model and stratified model) were established based on water‐density profiles, and the usage of these two models was corresponded to water mass classification determined by a water mass index. The average bias of the satellite‐derived DOC inventory, in the euphotic layer was 23.8% in spring, 24.8% in autumn and 14.7% in winter, and in the water column was 15.6% in spring, 12.3% in autumn, and 10.2% in winter. The total satellite‐derived DOC inventory integrated in the water column was about 31.84, 31.96, 28.59, and 31.18 Tg in four seasons in the ECS (5.84 × 105 km2). Sensitivity analysis indicated that the remote‐sensing method of estimating DOC inventory is stable and reliable. The available long‐term and large‐scale satellite‐derived DOC inventories in marginal sea would provide us basic information on carbon cycle, and the difference between the seasonal DOC inventories would help to understand the DOC export and relative biogeochemical processes in the ECS.

Effects of soot deposition on particle dynamics and microbial processes in marine surface waters

AbstractLarge amounts of soot are continuously deposited on the global ocean. Even though significant concentrations of soot particles are found in marine waters, the effects of these aerosols on ocean ecosystems are currently unknown. Using a combination of in situ and experimental data, and results from an atmospheric transport model, we show that the deposition of soot particles from an oil‐fired power plant impacted biogeochemical properties and the functioning of the pelagic ecosystem in tropical oligotrophic oceanic waters off New Caledonia. Deposition was followed by a major increase in the volume concentration of suspended particles, a change in the particle size spectra that resulted from a stimulation of aggregation processes, a 5% decrease in the concentration of dissolved organic carbon (DOC), a decreases of 33 and 23% in viral and free bacterial abundances, respectively, and a factor ~2 increase in the activity of particle‐attached bacteria suggesting that soot introduced in the system favored bacterial growth. These patterns were confirmed by experiments with natural seawater conducted with both soot aerosols collected in the study area and standard diesel soot. The data suggest a strong impact of soot deposition on ocean surface particles, DOC, and microbial processes, at least near emission hot spots.