Potential source and diagenetic signatures of oceanic dissolved and particulate organic matter as distinguished by lipid biomarker distributions

Potential biogenic sources of ultrafiltered dissolved and suspended particulate organic matter (UDOM and POM, respectively) from the Sargasso Sea (SS) and North Central Pacific (NCP) Ocean were investigated using lipid biomarker compounds. Organic carbon (OC) concentrations were ~ 20–40 times greater in UDOM than POM and decreased with depth. However, total OC-normalized lipid concentrations were 2–3 orders of magnitude higher in POM than in UDOM. Particulate total lipids decreased 3–10-fold with depth, compared to 10–20% for dissolved total lipids. Total fatty acids (FA), the most abundant lipids, showed similar patterns as total lipids, comprising ~ 62–88% of the total lipids analyzed in UDOM and ~ 57–84% in POM.FA were dominated by straight-chain saturated compounds followed by monounsaturated, polyunsaturated, and branched FA. Polyunsaturated FA were enriched in POM vs. UDOM and in surface vs. deep waters for both UDOM and POM, likely reflecting the algal origins and greater reactivity of surface-derived materials. In both UDOM and POM, sterols of planktonic origin dominated, including cholest-5-en-3β-ol (C₂₇Δ⁵), 24-methylcholesta-5,24(28)E-dien-3β-ol (C₂₈Δ^5,24(28)) and 24-ethylcholest-5-3β-ol (C₂₉Δ⁵), with varying contributions from cholesta-5,22E-3β-ol (C₂₇Δ^5,22), 24-methylcholesta-5,22E-3β-ol (C₂₈Δ^5,22) and 24-ethylcholesta-5,22E-3β-ol (C₂₉Δ^5,22).Factor analysis of lipid biomarkers showed major differences between the UDOM and POM pools and for each pool as a function of depth, but not between the SS and NCP. While UDOM and POM biomarkers were both dominated by autochthonous sources, differences between the two pools suggest potential effects from some combination of source and diagenetic factors. The lipid biomarker data are further evaluated relative to previous studies of radiocarbon (¹⁴C) and elemental (C:N:P) characteristics of UDOM and POM in the SS and NCP.     

Determination of particulate organic carbon (POC) in seawater: The relative methodological importance of artificial gains and losses in two glass-fiber-filter-based techniques

Particulate matter in aquatic systems is an important vehicle for the transport of particulate organic carbon (POC). Its accurate measurement is of central importance for the understanding of marine carbon cycling. Previous work has shown that GF/F-filter-based bottle-sample-derived concentration estimates of POC are generally close to or higher than large-volume in-situ-pump-derived values (and in some rare cases in subzero waters are up to two orders of magnitude higher). To further investigate this phenomenon, water samples from the surface and mid-water Northeast Atlantic and the Baltic Sea were analyzed. Our data support a bias of POC concentration estimates caused by adsorption of nitrogen-rich dissolved organic material onto GF/F filters. For surface-ocean samples the mass per unit area of exposed filter and composition of adsorbed material depended on the filtered volume. Amounts of adsorbed OC were enhanced in the surface ocean (typically 0.5 μmol cm^− 2 of exposed filter) as compared to the deep ocean (typically 0.2 μmol cm^− 2 of exposed filter). These dependencies should be taken into account for future POC methodologies. Bottle/pump differences of samples that were not corrected for adsorption were higher in the deep ocean than in the surface ocean. This discrepancy increased in summer. It is shown that POC concentration estimates that were not corrected for adsorption depend not only on the filtered volume, true POC concentration and mass of adsorbed OC, but also on the filter area. However, in all cases we studied, correction for adsorption was important, but not sufficient, to explain bottle/pump differences. Artificial formation of filterable particles and/or processes leading to filterable material being lost from and/or missed by sample-processing procedures must be considered. It can be deduced that the maximum amounts of POC and particulate organic nitrogen (PON) that can be artificially formed per liter of filtered ocean water are  3–4 μM OC (5–10% of dissolved OC) and  0.2–0.5 μM ON (2–10% of dissolved ON), respectively. The relative sensitivities of bottle and pump procedures, and of surface- and deep-ocean material, to artificial particle formation and the missing/losing of material are evaluated. As present procedures do not exist to correct for all possible biasing effects due to artificial particle formation and/or miss/loss of filterable material, uncertainties of filtration-based estimates of POC concentrations need further testing. The challenge now is to further constrain the magnitude of the biasing effects that add to the adsorption effect to reduce the uncertainties of estimates of POC concentrations, inventories and fluxes in the ocean.     

Production of chromophoric dissolved organic matter by Sargasso Sea microbes

Time series of chromophoric dissolved organic matter (CDOM) light absorption coefficients indicate a local origin for a large fraction of the CDOM in the upper water column of the Sargasso Sea. In the present study, we demonstrate that CDOM is produced in bacterial culture experiments using Sargasso Sea water and naturally occurring microbial assemblages. Seawater cultures were prepared and grown at in situ temperatures in the dark for periods of weeks. Selected cultures were treated with amendments including inorganic nutrients, glucose, phytoplankton exudates, and zooplankton excretia. In all experiments, when bacterial biomass increased, CDOM increased during the first week of the experiment, followed by a decrease over a longer period of time. Cultures amended with both glucose and inorganic nitrogen and phosphorus produced more CDOM than controls or cultures amended with glucose or inorganic nutrients alone. However, when complex DOM substrates (derived from phytoplankton or zooplankton cultures) were added to seawater cultures, there was a net accumulation of CDOM over the course of the experiments. These data suggest that, in addition to microbial growth, the quality of the substrate plays an important role in net CDOM production. ‘New’ CDOM produced in culture was spectroscopically similar to CDOM appearing below the surface during summer stratification. The results of the present study support a new paradigm for CDOM in the open ocean, which allows for local origin and significant dynamics. Appreciation of CDOM dynamics will, in turn, add to our understanding of microbial productivity, photochemical rate processes, and ultraviolet radiation availability in the global ocean.     

Black carbon in marine particulate organic carbon: Inputs and cycling of highly recalcitrant organic carbon in the Gulf of Maine

To increase our understanding of the roles of black carbon (BC), a highly sorptive and recalcitrant material, we measured BC concentrations and fluxes in marine particulate organic carbon (POC) out of the water column in the Gulf of Maine (GoM), a representative coastal area downwind of important BC sources of the Northeastern United States. Concentrations ranged from < 0.1 to 16 μg/L in the spring and late summer, typically contributing between 1 and 20% of the POC. Water-column export fluxes were near 10 g_BC/m²∙yr. These observations suggest that (a) up to 50% of the “molecularly uncharacterized” POC in this region's seawater is combustion-derived BC, and (b) the “bioavailabilities” of hydrophobic pollutants like polycyclic aromatic hydrocarbons (PAHs) would be influenced substantially by sorption to BC. The observed BC spatial distributions imply that a large part of the BC was carried offshore by wind and that much of it is accumulated in the coastal sediments. On a global scale, these results suggest the GoM and other coastal areas with similar BC loadings accumulate significant amounts of highly recalcitrant organic carbon that remineralizes on geological time scales in the world's oceans.     

Sources and transport of dissolved and particulate organic carbon in the Mississippi River estuary and adjacent coastal waters of the northern Gulf of Mexico

Dissolved organic carbon (DOC), stable carbon isotopic (δ¹³C) compositions of DOC and particulate organic carbon (POC), and elemental C/N ratios of POC were measured for samples collected from the lower Mississippi and Atchafalaya rivers and adjacent coastal waters in the northern Gulf of Mexico during the low flow season in June 2000 and high flow season in April 2001. These isotopic and C/N results combined with DOC measurements were used to assess the sources and transport of terrestrial organic matter from the Mississippi and Atchafalaya rivers to the coastal region in the northern Gulf of Mexico. δ¹³C values of both POC (−23.8‰ to −26.8‰) and DOC (−25.0‰ to −29.0‰) carried by the two rivers were more depleted than the values measured for the samples collected in the offshore waters. Strong seasonal variations in δ¹³C distributions were observed for both POC and DOC in the surface waters of the region. Fresh water discharge and horizontal mixing played important roles in the distribution and transport of terrestrial POC and DOC offshore. Our results indicate that both POC and DOC exhibited non-conservative behavior during the mixing especially in the mid-salinity range. Based on a simple two end-member mixing model, the comparison of the measured DOC-δ¹³C with the calculated conservative isotopic mixing curve indicated that there was a significant in situ production of marine-derived DOC in the mid- to high-salinity waters consistent with our in situ chlorophyll-a measurements. Our DOC-δ¹³C data suggest that a removal of terrestrial DOC mainly occurred in the high-salinity (>25) waters during the mixing. Our study indicates that the mid- to high- (10–30) salinity range was the most dynamic zone for organic carbon transport and cycling in the Mississippi River estuary. Variability in isotopic and elemental compositions along with variability in DOC and POC concentrations suggest that autochthonous production, bacterial utilization, and photo-oxidation could all play important roles in regulating and removing terrestrial DOC in the northern Gulf of Mexico and further study of these individual processes is warranted.     

Seasonal and spatial distribution of particulate organic matter (POM) in the Chukchi and Beaufort Seas

As part of the Western Arctic Shelf–Basin Interactions (SBI) project, the production and fate of organic carbon and nitrogen from the Chukchi and Beaufort Sea shelves were investigated during spring (5 May–15 June) and summer (15 July–25 August) cruises in 2002. Seasonal observations of suspended particulate organic carbon (POC) and nitrogen (PON) and large-particle (>53 μm) size class suggest that there was a large accumulation of carbon (C) and nitrogen (N) between spring and summer in the surface mixed layer due to high phytoplankton productivity. Considerable organic matter appeared to be transported from the shelf into the Arctic Ocean basin in an elevated POC and PON layer at the top of the upper halocline. Seasonal changes in the molar carbon:nitrogen (C:N) ratio of the suspended particulate organic matter (POM) pool reflect a change in the quality of the organic material that was present and presumably being exported to the sediment and to Arctic Ocean waters adjacent to the Chukchi and Beaufort Sea shelves. In spring, low particulate C:N ratios (<6; i.e., N rich) were observed in nitrate-replete surface waters. By the summer, localized high particulate C:N ratios (>9; i.e., N-poor) were observed in nitrate-depleted surface waters. Low POC and inorganic nutrient concentrations observed in the surface layer suggest that rates of primary, new and export production are low in the Canada Basin region of the Arctic Ocean.     

The satellite reversion of dissolved organic carbon (DOC) based on the analysis of the mixing behavior of DOC and colored dissolved organic matter: the East China Sea as an example

The retrieval of dissolved organic carbon (DOC) distribution by remote sensing is mainly based on the empirical relationship of DOC concentration and colored dissolved organic matter (CDOM) concentration in many literatures. To investigate the nature of this relationship, the distributions and mixing behaviors of DOC and CDOM are reviewed in the world’s major estuaries and bays. It is found that, generally, the CDOM concentration is well correlated with the salinity in most estuaries, while DOC usually shows a nonconservative behavior which leads to a weak correlation between the DOC concentration and the CDOM concentration. To establish a good satellite reversion of the DOC concentration, the East China Sea(ECS) was taken as an example, and the mixing behavior of DOC and CDOM as well as the influence of biogeochemical processes were analyzed except for the physical mixing process with the data from late autumn (November, 2010) and winter (December, 2009) cruises. In the two ECS cruises, the CDOM concentration was found to be tightly correlated with the salinity, influenced little by the photochemical or biological processes. The data from the winter cruise show that DOC followed a conservative mixing along the salinity gradient, while in the late autumn cruise it was significantly affected by the biological activities, resulting in a poor correlation between the DOC and the CDOM. Accordingly, an improved DOC algorithm (CSDM) was proposed: when the biological influence was significant (Chl a greater than 0.8 μg/dm3 ), DOC was retrieved by the conservative and biological model, and if the conservative mixing was dominant (Chl a less than 0.8 μg/dm3 ), the direct DOC concentration and CDOM concentration relationship was used. Based on the proposed algorithm, a reasonable DOC distribution for the ECS from satellite was obtained in this study, and the proposed method can be applied to the other large river-dominant marginal sea.     

Seasonal trends in the abundance, composition and bioavailability of particulate and dissolved organic matter in the Chukchi/Beaufort Seas and western Canada Basin

The objectives of this study were to investigate the seasonality, abundance, sources and bioreactivity of organic matter in the water column of the western Arctic Ocean. The concentrations of particulate and dissolved amino acids and amino sugars, as well as bulk properties of particulate and dissolved organic matter (DOM), were measured in shelf, slope and basin waters collected during the spring and summer of 2002. Particulate organic matter concentrations in shelf waters increased by a factor of 10 between spring and summer. Dissolved organic carbon (DOC) and nitrogen (DON) concentrations exhibited only minor seasonal variations, whereas dissolved amino acid concentrations doubled between spring and summer, and dissolved amino sugars increased by 31% in shelf waters of the Chukchi and Beaufort Seas. Concentrations of DOC did not exhibit a significant seasonal change in surface waters of the Canada Basin, but dissolved amino acid concentrations increased by 45% between spring and summer. No significant seasonal differences were detected in the concentration or composition of DOM in waters below 100 m in depth. Concentrations of particulate and dissolved amino acids and amino sugars were strongly correlated with chlorophyll-a, indicating a plankton source of freshly produced organic matter. The amino acid and amino sugar compositions of freshly produced DOM indicated that a large portion of this material is bioavailable. While freshly produced DOM was found to be relatively bioreactive, preformed DOM in the Arctic appears to be less bioreactive but similar in degradation state to average DOM in the Atlantic and Pacific. These data demonstrate substantial summer production of POM and DOM on the Chukchi and Beaufort shelves that is available for utilization in shelf waters and export to the Canada Basin.     

A method to measure the isotopic (C) composition of dissolved organic carbon using a high temperature combustion instrument

The stable isotopes of dissolved organic carbon (DOC) are a powerful tool for distinguishing sources and inputs of organic matter in aquatic systems. While several methods exist to perform these analyses, no labs routinely utilize a high temperature combustion (HTC) instrument. Advantages of HTC instruments include rapid analysis, small sample volumes and minimal sample preparation, making them the favored devices for most routine oceanic DOC concentration measurements. We developed a stable carbon DOC method based around an HTC system. This method has the benefit of a simple setup, requiring neither vacuum nor high pressures. The main drawback of the method is a significant blank, requiring careful accounting of all blank sources for accurate isotopic and concentration values. We present here a series of experiments to determine the magnitude, source and isotopic composition of the HTC blank. Over time, the blank is very stable at  20 ng of carbon with a δ¹³C of − 18.1‰ vs. VPDB. The similarity of the isotopic composition of the blank and seawater samples makes corrections relatively minor. The precision of the method was determined by oxidizing organic standards with a wide isotopic and concentration range (− 9‰ to − 39‰; 18 μM to 124 μM). Analysis of seawater samples demonstrates the accuracy for low concentration, high salinity samples. The overall error on the measurement is approximately ± 0.8‰.     

The relationship between chromophoric dissolved organic matter and dissolved organic carbon in the European Atlantic coastal area and in the West Mediterranean Sea (Gulf of Lions)

The absorption coefficient of chromophoric dissolved organic matter (aCDOM) has been found to be correlated with fluorescence emission (excitation at 355 nm). In the coastal European Atlantic area and in the Western Mediterranean Sea (Gulf of Lions), a significant statistical dependence has been found between aCDOM and fluorescence with dissolved organic carbon (DOC) concentration. The relationship shows that, in the river plume areas (Rhine in the North Sea and Rhône in the Gulf of Lions), a consistent fraction of DOC (from 40% to 60% of the average of the DOC measured) is non-absorbing in visible light range, where the dissolved organic matter (DOM) is typically absorbent. In comparison, in the open sea, apparently not affected by the continental inputs, the entire DOC belongs to the chromophoric DOM whose specific absorption is lower (5 to 10 times) than that found in the river plume areas.     

Measurements of dissolved organic carbon (DOC) in sea water by high temperature combustion method

Dissolved organic carbon (DOC) is the largest organic carbon reservoir in sea water and plays an imporrant role in the marine carbon cycle and other biogeochemical processes in the ocean. Accurate and precise determinalion of the bOC concentration in sea water is thus a prerequisite for any interpretation of DOC biogeochemistry. A key factor in analytical quality control is an accurate determination of the blank. The assessment and distinction of DOC blanks are essential for the precise measurements of oceanic DOC. The total DOC blank includes instrument and water blanks in the high temperature catalytic oxidation (HTCO) method. DOC can be measured accurately using the HTCO method only when the instrument blank is correctly distinguished from the total DOC blank and corrected in the sample measurements. Low DOC blanks can be achieved by extensive conditioning of new catalysts and the whole instrument system, whereas instrument blanks can be quantified by subtracting the water blank from the total DOC blank. We have been able to produce low carbon nanopure water [≤2μmol/dm³(C)] and have a low instrumental blank [< 5-6 μmol/dm³(C)] when using the HTCO method. Results of concentrations and distributions of DOC in the Gulf of Mexico and the North Atlantic are oceanographically consistent. Results from DOC measurements on samples from the international DOC methods comparison program further confirmed our low values of both nenopure water and the instrument blank.     

Deep sea circulation of particulate organic carbon in the Japan Sea

Seasonal and spatial variations of particulate organic carbon (POC) flux were observed with sediment traps at three sites in the Japan Sea (western and eastern Japan Basin and Yamato Basin). In order to investigate the transport processes of POC, radiocarbon (¹⁴C) measurements were also carried out. Annual mean POC flux at 1 km depth was 30.7 mg m⁻²day⁻¹ in the western Japan Basin, 12.0 mg m⁻²day⁻¹ in the eastern Japan Basin and 23.8 mg m⁻²day⁻¹ in the Yamato Basin. At all stations, notably higher POC flux was observed in spring (March–May), indicating biological production and rapid sinking of POC in this season. Sinking POC in the high flux season showed modern Δ¹⁴C values (>0‰) and aged POC (Δ¹⁴C < −40‰) was observed in winter (December–January). The Δ¹⁴C values in sinking POC were negatively correlated with aluminum concentration, indicating that Δ¹⁴C is strongly related to the lateral supply of lithogenic materials. The Δ¹⁴C values also showed correlations with excess manganese (Mn_xs) concentrations in sinking particles. The Δ¹⁴C-Mn_xs relationship suggested that (1) the majority of the aged POC was advected by bottom currents and incorporated into sinking particles, and (2) some of the aged POC might be supplied from the sea surface at the trap site as part of terrestrial POC. From the difference in the Δ¹⁴C-Mn_xs relationships between the Japan Basin and the Yamato Basin, we consider that basin-scale transport processes of POC occur in the Japan Sea.     

Characterization of chromophoric dissolved organic matter (CDOM) in the Baltic Sea by excitation emission matrix fluorescence spectroscopy

Chromophoric dissolved organic matter (CDOM) is the major light absorber in the Baltic Sea. In this study, excitation emission matrix (EEM) fluorescence spectra and UV–visible absorption spectra of CDOM are reported as a function of salinity. Samples from different locations and over different seasons were collected during four cruises in 2002 and 2003 in the Baltic Sea in both Pomeranian Bay and the Gulf of Gdansk. Absorption by CDOM decreased with increased distance from the riverine source and reached a relatively stable absorption background in the open sea. Regression analysis showed that fluorescence intensity was linearly related to absorption by CDOM at 375 nm and a_CDOM(375) absorption coefficients were inversely related to salinity. Analysis of CDOM-EEM spectra indicated that a change in composition of CDOM occurred along the salinity gradient in the Baltic Sea. Analysis of percent contribution of respective fluorophore groups to the total intensity of EEM spectra indicated that the fluorescence peaks associated with terrestrial humic components of the CDOM and total integrated fluorescence decreased with decreasing CDOM absorption. In contrast, the protein-like fraction of CDOM decreased to a lesser degree than the others. Analysis of the percent contribution of fluorescence peak intensities to the total fluorescence along the salinity gradient showed that the contribution of protein-like fluorophores increased from 2.6% to 5.1% in the high-salinity region of the transect. Fluorescence and absorption changes observed in the Baltic Sea were similar to those observed in similar transects that have been sampled elsewhere, e.g. in European estuaries, Gulf of Mexico, Mid-Atlantic Bight and the Cape Fear River plume in the South Atlantic Bight, although the changes in the Baltic Sea occurred over a much smaller salinity gradient.     

Deep-sea terrigenous organic carbon transfer and accumulation: Impact of sea-level variations and sedimentation processes off the Ogooue River (Gabon)

Sedimentary, isotopic and bulk geochemical proxies measured in sediment samples of five gravity cores collected in the distal part of the Ogooue turbidite system (around 4000 m-depth) were used to develop a conceptual model to describe the accumulation of terrigenous organic matter (OM) during the last 200,000 yrs BP in the eastern part of the Gulf of Guinea. This model takes into account the influence of the different depositional processes (turbiditic vs hemipelagic sedimentation), geomorphological features and sea-level variations.Total organic carbon (TOC) and the stable organic carbon isotopes of the OM (δ¹³C) variability follow the highstand/lowstand (interglacial/glacial) cyclicity with a very low accumulation rate of terrigenous OM during periods of high sea-level and higher accumulation rate during period of low sea-level. A sea-level of 80–120 m below present day seems to favor the transfer of terrigenous sediments to the deep offshore environment through the turbidite system and thanks to the connection of the canyons heads with the river system presently located at the shelf edge at −120 m water depth.In this system, terrigenous OM matter delivered by the river accumulate in the sediments via two main processes. Indeed, a part of the terrigenous OM settles in combination with the finest particles forming hemipelagites, while another part, formed of very well preserved land plant debris, is transported and deposited far offshore with turbidity currents. The proportion of terrigenous OM accumulated due to turbidity currents is important as it can represent more than 70% of the carbon accumulated during sea-level lowstand. Moreover, terrigenous OM seems to preferentially accumulate in the levees and the lobes of the system notably due to the higher frequency of organic-rich turbidites.This study demonstrates that gravity flows, influenced by the sea-level variations, can significantly affect the terrigenous OM budget of the deep offshore Atlantic margins and that channel-levee complexes as well as turbidite lobes can be regarded as good sink for terrestrial organic carbon. These processes should be taken into consideration in the context of source rocks exploration but also for the estimation of the general carbon accumulation in ocean sediment.