Distribution, partitioning and fluxes of dissolved and particulate organic C, N and P in the eastern North Pacific and Southern Oceans

Concurrent distributions of dissolved and suspended particulate organic carbon (DOC and POC_susp), nitrogen (DON and PON_susp) and phosphorus (DOP and POP_susp), and of suspended particulate inorganic phosphorus (PIP_susp), are presented for the open ocean water column. Samples were collected along a three-station transect from the upper continental slope to the abyssal plain in the eastern North Pacific and from a single station in the Southern Ocean. The elemental composition of surface sedimentary organic matter (SOM) was also measured at each location, and sinking particulate organic matter (POM_sink) was measured with moored sediment traps over a 110-d period at the abyssal site in the eastern North Pacific only. In addition to elemental compositions, C : N, C : P and N : P ratios were also calculated. Surface and deep ocean concentrations of dissolved organic matter (DOM) and inorganic nutrients between the two sites displayed distinct differences, although suspended POM (POM_susp) concentrations were similar. Concentrations of DOM and POM_susp displayed unique C, N and P distributions, with POM_susp concentrations generally about 1–2 orders of magnitude less than the corresponding DOM concentrations. These differences were likely influenced by different biogeochemical factors: whereas the dissolved constituents may have been influenced more by the physical regime of the study site, suspended particulate matter may have been controlled to a greater extent by biological and chemical alteration. Up to 80% of total particulate P in POM_susp, POM_sink and SOM consisted of PIP. For all organic matter pools measured, elemental ratios reveal that organic P is preferentially remineralized over organic C and organic N at both sites. Increases in C : P and N : P ratios with depth were also observed for DOM at both sites, suggesting that DOP is also preferentially degraded over C and N as a function of depth. A simple one-dimensional vertical eddy diffusion model was applied to estimate the contributions of dissolved and suspended particulate organic C, N and P fluxes from the upper mixed layer into the permanent thermocline. Estimated vertical DOM fluxes were 28–63% of the total organic matter fluxes; POM_susp and POM_sink fluxes were 8–20 and 28–52% of the total.     

Stocks and dynamics of dissolved and particulate organic matter in the southern Ross Sea, Antarctica

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 μM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 μM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO₃ concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DIC_equiv). The fraction of DIC_equiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DIC_equiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as “semi-labile” DOM. The “semi-labile” pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.     

Spring distribution of dissolved organic matter in a system encompassing the Northeast Water Polynya: Implications for early-season sources and sinks

This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.     

Simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation: conditions for precise shipboard measurements

Appropriate conditions have been achieved for the accurate, rapid, and highly precise shipboard simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation. A nitrogen-specific Antek 705D chemiluminescence detector and a CO₂-specific LiCor Li6252 IRGA have been coupled in-series with a Shimadzu TOC-5000 organic carbon analyser. Precision of both simultaneous measurements is ≤1.5%, i.e. ±1 μmol C l⁻¹ and ±0.3 μmol N l⁻¹, respectively. Quality of analysis is not compromised by vibrations associated with ocean going research vessels.     

Remineralization and accumulation of organic carbon and nitrogen in marine sediments of eutrophic bays: the case of the Bay of Concepcion, Chile

The Bay of Concepcion (36°40′S; 73°02′W) is a semi-enclosed and shallow embayment in which biogeochemical processes are seasonally coupled to coastal upwelling during the austral spring and summer. The nutrient cycle in the bay is complex due to the combined effects of a pronounced O₂ minimum layer and high nutrient concentrations both originating from subsurface equatorial water during coastal upwelling and a rapid rate of sediment nutrient recycling. The sediments are characterized by a high content of organic matter mainly due to the extremely high rates of phytoplankton production and deposition. During the upwelling period, a black flocculent layer frequently covers the sediment–water interface in the inner part of the bay where an extensive mat of Beggiatoa spp. develops. Three approaches are used to analyse the extent to which the benthic system recycles or retains nutrients at two stations, located at the centre (station C, St. C) and mouth (station B, St. B) of the bay for a 1-year period (March 1996–1997): (1) estimation of C and N remineralization rates based on SO₄²⁻ reduction measurements, (2) calculation of C and N turnover rates using a diagenetic model applied to total organic carbon and total nitrogen vertical distributions and, (3) construction of C and N budgets from direct measurements of sedimentation (from a sediment trap) and estimates of the C and N burial rates. Depth-integrated SO₄²⁻ reduction rates varied between 3.4 (winter) and 25.5 (summer) mmol m⁻² d⁻¹. Estimated C and N oxidation rates ranged between 7.9 and 87.8 mol C m⁻² yr⁻¹ and between 0.9 and 6.9 mol N m⁻² yr⁻¹, respectively. Each approach yielded minor differences in the C and N remineralization rates (and also minor differences between both studied stations), except when the kinetic model was applied to C and N distribution without including the presence of the flocculent layer. The rates of carbon oxidation and sulphate reduction were considerably higher than in other coastal sediments with similar depositional regime. The C and N burial rates were 2.23 and 0.21 (St. C) and 1.30 and 0.09 (St. B) mol m⁻² yr⁻¹, respectively. The C/N ratio of the buried fraction was ca. 10.6 at St. C and 14.4 at St. B. Because the observed differences in burial rates could not be ascribed to distinctive depositional (both stations have similar sediment accumulation rates) and oceanographic (similar O₂ concentration and hydrography) conditions, differences may be due to in part spatial heterogeneity in the supply of organic matter. The degree of preservation of organic matter as plankton detritus and nitrogen accumulating bacterial biomass associated with Beggiatoa spp. at St. C may also be involved.     

Altimeter-derived surface circulation in the large–scale NE Pacific Gyres. : Part 1. seasonal variability

The seasonal variability of sea surface height (SSH) and currents are defined by analysis of altimeter data in the NE Pacific Ocean over the region from Central America to the Alaska Gyre. The results help to clarify questions about the timing of seasonal maxima in the boundary currents. As explained below, the long-term temporal mean of the SSH values must be removed at each spatial point to remove the temporally invariant (and large) signal caused by the marine geoid. We refer to the resulting SSH values, which contain all of the temporal variations, as the ‘residual’ SSH. Our main findings are:

1. The maximum surface velocities around the boundaries of the cyclonic Alaska Gyre (the Alaska Current and the Alaska Stream) occur in winter, at the same time that the equatorward California Current is weakest or reversed (forming the poleward Davidson Current); the maximum surface velocities in the California Current occur in summer. These seasonal maxima are coincident with the large-scale atmospheric wind forcing over each region.

2. Most of the seasonal variability occurs as strong residuals in alongshore surface currents around the boundaries of the NE Pacific basin, directly connecting the boundaries of the subpolar gyre, the subtropical gyre and the Equatorial Current System.

3. Seasonal variability in the surface velocities of the eastward North Pacific Current (West Wind Drift) is weak in comparison to seasonal changes in the surface currents along the boundaries.

4. There is an initial appearance next to the coast and offshore migration of seasonal highs and lows in SSH, alongshore velocity and eddy kinetic energy (EKE) in the Alaska Gyre, similar to the previously-described seasonal offshore migration in the California Current.

5. The seasonal development of high SSH and poleward current residuals next to the coast appear first off Central America and mainland Mexico in May–June, prior to their appearance in the southern part of the California Current in July–August and their eventual spread around the entire basin in November–December. Similarly, low SSH and equatorward transport residuals appear first off Central America and Mexico in January–February before spreading farther north in spring and summer.

6. The maximum values of EKE occur when each of the boundary currents are maximum.

Dynamics of carbohydrates in the Norwegian Sea inferred from monthly profiles collected during 3 years at 66°N, 2°E

Water samples were collected monthly for 3 years at 66°N, 2°E in the Norwegian Sea, 250 nautical miles off the Norwegian coast. Concentrations of mono- and polysaccharides were measured with the 2,4,6-tripyridyl-s-triazine (TPTZ) spectroscopic method. Total dissolved carbohydrates varied from 3.4 to 28.2 μM C of all samples and the ratio of carbohydrate to dissolved organic C (DOC) varied from an average of 14% at 0–25 m depth to 11% at 800–2000 m depth. This indicates that dissolved carbohydrates were a significant constituent of DOC in the Norwegian Sea. Polysaccharides varied from 0.4 to 21.5 μM C and monosaccharides from 0.7 to 11.7 μM C at all depths. The level of monosaccharides was relatively constant at 2.8–3.2 μM C below the euphotic zone, whereas polysaccharides showed more varying concentrations. Dissolved carbohydrates accumulated during the productive season, reaching maximum concentrations during summer although interannual differences were observed. A significant positive correlation between Chl a and soluble carbohydrate was found in one growing season with nutrient analyses. Average values for total carbohydrates were highest in the surface – 0 to 25 m – with 13.3 μM C and decreased to 8.4 μM C at 800–2000 m depth. The ratio of monosaccharides to polysaccharides exhibited a marked seasonal variation, increased from January to a maximum in June of 1.1, and declined to 0.5 in July.     

A nitrate and silicate budget in the equatorial Pacific Ocean: a coupled physical–biological model study

A coupled physical–biological model was developed to simulate the low-silicate, high-nitrate, and low-chlorophyll (LSHNLC) conditions in the equatorial Pacific Ocean and used to compute a detailed budget in the Wyrtki box (5°N–5°S, 180–90°W) for the major sources and cycling of nitrogen and silicon in the equatorial Pacific. With the incorporation of biogenic silicon dissolution, NH₄ regeneration from organic nitrogen and nitrification of ammonia in the model, we show that silicon recycling in the upper ocean is less efficient than nitrogen. As the major source of nutrients to the equatorial Pacific, the Equatorial Undercurrent provides slightly less Si(OH)₄ than NO₃ to the upwelling zone, which is defined as 2.5°N–2.5°S. As a result, the equatorial upwelling supplies less Si(OH)₄ than NO₃ into the euphotic zone in the Wyrtki box, having a Si/N supply ratio of about 0.85 (2.5 vs. 2.96 mmolm⁻² day⁻¹). More Si(OH)₄ than NO₃ is taken up with a Si/N ratio of 1.17 (2.72 vs. 2.33 mmolm⁻² day⁻¹) within the euphotic zone. The difference between upwelling supply and biological uptake is balanced by nutrient regeneration and horizontal advection. Excluding regeneration, the net silicate and nitrate uptakes are nearly equal (1.76 vs. 1.84 mmolm⁻² day⁻¹). However, biogenic silica export production is slightly higher than organic nitrogen (1.74 vs. 1.59 mmolm⁻² day⁻¹) following a 1.1 Si/N ratio. In the central equatorial Pacific, low silicate concentrations limit diatom growth; therefore non-diatom new production accounts for most of the new production. Higher silicate supply in the east maintains elevated diatom growth rates and new production associated with diatoms dominate upwelling zone. In contrast, the new production associated with small phytoplankton is nearly constant or decreases eastward along the equator. The total new production has a higher rate in the east than in the west, following the pattern of surface silicate. This suggests that silicate regulates the diatom production, total new production, and thereby carbon cycle in this area. The modeled mean primary production is 48.4 mmolCm⁻² day⁻¹, representing the lower end of direct field measurements, while new production is 15.0 mmolCm⁻² day⁻¹, which compares well with previous estimates.     

The influence of a mature cyclonic eddy on particle export in the lee of Hawaii

Mesoscale eddies may enhance primary production (PP) in the open ocean by bringing nutrient-rich deep waters into the euphotic zone, potentially leading to increased transport of particles to depth. This hypothesis remains controversial, however, due to a paucity of direct particle export measurements. In this study, we investigated particle dynamics using ²³⁴Th–²³⁸U disequilibria within a mesoscale cold-core eddy, Cyclone Opal, which formed in the lee of the Hawaiian Islands. ²³⁴Th samples were collected along two transects across Cyclone Opal as well as during a time-series within the eddy core during a decaying diatom bloom. Particulate carbon (PC), particulate nitrogen (PN) and biogenic silica (bSiO₂) fluxes at 150 m varied spatially and temporally within the eddy and strongly depended on the ²³⁴Th model formulation used (e.g., steady state versus non-steady state, inclusion of upwelling, etc.). Particle fluxes estimated from a steady state model assuming an upwelling rate of 2 m day⁻¹ yielded the best fit to sediment-trap data. These ²³⁴Th-derived particle fluxes ranged from 332±14 to 1719±53 μmol C m⁻² day⁻¹, 27±3 to 114±12 μmol N m⁻² day⁻¹, and 33±20 to 309±73 μmol Si m⁻² day⁻¹. Although PP rates within Cyclone Opal were elevated by a factor of 2–3, PC and PN fluxes were the same, within error, inside and outside of Cyclone Opal. The ratio of PC export to PP remained surprisingly low at <0.03 and similar to those measured in surrounding waters. In contrast, bSiO₂ fluxes within the eddy core were three times higher. Detailed analyses of ²³⁴Th depth profiles consistently showed excess ²³⁴Th at 100–175 m, associated with the remineralization and possible accumulation of suspended and dissolved organic matter from the surface. We suggest that strong microzooplankton grazing facilitated particulate organic matter recycling and resulted in the export of empty diatom frustules. Thus, while eddies may increase PP, they do not necessarily increase PC and PN export to deep waters. This may be a general characteristic of wind-driven cyclonic eddies of the North Pacific Subtropical Gyre and suggests that eddies may preferentially act as a silica pump, thereby playing an important role in promoting silicic-acid limitation in the region.     

Variability in plankton community structure, metabolism, and vertical carbon fluxes along an upwelling filament (Cape Juby, NW Africa)

The variability in dissolved and particulate organic matter, plankton biomass, community structure and metabolism, and vertical carbon fluxes were studied at four stations (D₁–D₄), placed along a coastal-offshore gradient of an upwelling filament developed near Cape Juby (NW Africa). The filament was revealed as a complex and variable system in terms of its hydrological structure and distribution of biological properties. An offshore shift from large to small phytoplankton cells, as well as from higher to lower autotrophic biomass, was not paralleled by a similar gradient in particulate (POC) or dissolved (DOC) organic carbon. Rather, stations in the central part of the filament (D₂ and D₃) presented the highest organic matter concentrations. Autotrophic carbon (POC_Chl) accounted for 53% (onshore station, D₁) to 27% (offshore station, D₄) of total POC (assuming a carbon to chlorophyll ratio of 50), from which nano- and pico-phytoplankton biomasses (POC_{A < 10 μm}) represented 14% (D₁) to 79% (D₄) of POC_Chl. The biomass of small hetrotrophs (POC_{H < 10 μm}) was equivalent to POC_{A < 10 μm}, except at D₁, where small autotrophs were less abundant. Dark community respiration (R_d) in the euphotic zone was in general high, almost equivalent to gross production (P_g), but decreasing offshore (D₁–D₄, from 108 to 41 mmol C m⁻² d⁻¹). POC sedimentation rates (POC_sed) below the euphotic zone ranged from 17 to 6 mmol C m⁻² d⁻¹. Only at D₄ was a positive carbon balance observed: P_g−(R_d + POC_sed) = 42 mmol C m⁻² d⁻¹. Compared to other filament studies from the NE Atlantic coast, the Cape Juby filament presented lower sedimentation rates and higher respiration rates with respect to gross production. We suggest that this is caused by the recirculation of the filament water, induced by the presence of an associated cyclonic eddy, acting as a trapping mechanism for organic matter. The export capacity of the Cape Juby filament therefore would be constrained to the frequency of the interactions of the filament with island-induced eddies.     

Laboratory study of nitrogen and phosphorus remineralization during the decomposition of coastal plankton and seston

The decomposition of cultured marine phytoplankton (Skeletonema costatum) and natural estuarine seston from Narragansett Bay, RI, was studied at two temperatures (8°C and 18°C) in bottles containing sterile bay-water (30‰) and in bay-water with micro-organisms small enough to pass through a glass fibre filter (nominally < 1μ). About 50% of the particulate organic nitrogen (PON) and particulate phosphorus (PP) was immediately released to the water in dissolved organic forms from both types of organic matter. Comparison of changes in the dissolved organic nitrogen (DON) fraction in the sterile and non-sterile systems indicated that nearly all of the DON initially released was subsequently remineralized. Ammonification proceeded only in non-sterile bay-water. 20–25% of the PP was converted to dissolved inorganic-P (DIP) fraction after only 7 h in both sterile and non-sterile bay-water. Following autolytic releases of DON, DOP and DIP the initial rates of N and P remineralization were temperature dependent: Q₁₀ values for PON and PP decay during first phase of microbially mediated decomposition ranged from 1·3 to 6·4. Rates of remineralization then slowed so that about equal amounts of nutrients were remineralized (45–50% of the N and 57–60% of the P in the phytoplankton and 60–63% of the N and 36–60% of the P in the natural seston) after 30 days storage at either temperature. During 30 days of decomposition in non-sterile seawater the N/P ratios in the dissolved inorganic fractions converged on the ratios of total-N/total-P initially present in the bottles. Kinetic analysis of the decay of total organic-N (TON) and total organic-P (TOP) in the non-sterile systems and analysis of similar sets found in the literature showed that the initial stages of the decomposition of N and P from planktonic POM in vitro could be modelled as the sequential decay, at first-order rates, of two particulate fractions. The first, more labile, fraction comprised about 60% of the particulate N and P. First-order rate constants (−k, base e) for decomposition during the 1st and 2nd phases were 0·02 to 0·2 day⁻¹ and 0·003 to 0·02 day⁻¹, respectively. The decay rates are far too slow to account for the ‘rapid in situ recycling’ of nutrients needed to support phytoplankton production when other means of nutrient resupply (by advection, fixation, rainfall, etc.) are very low.     

Dissolved Iodate and Total Iodine During an Extreme Hypoxic Event in the Southern Benguela System

Dissolved iodate and total iodine were studied in St Helena Bay, South Africa, during a period of acute hypoxia, following upwelling off Cape Columbine. Despite the generally high concentrations of chlorophyll α (10–30 mg m⁻³) total iodine concentration was essentially constant in the main part of the Bay, and similar to that found elsewhere in the oceans. Occasional, lower concentrations of total iodine (0·28 to 0·42 μM) were found with exceptionally high chlorophyll α concentrations (500 mg m⁻³) in shallow waters. In contrast, iodate was found to be reduced to iodide at both the surface and the bottom of the Bay. The implications of these changes are discussed, given that the surface waters reflect sustained eutrophication while the bottom waters are hypoxic as a result of the organic-rich sediment from the waters above.     

Stoichiometry of the net ecosystem metabolism in a coastal inlet affected by upwelling. The Ría de Arousa (NW Spain)

The net uptake of inorganic carbon and nitrogen, phosphate and silicate and the net production of dissolved oxygen and organic carbon, nitrogen and phosphorus have been examined in the Ría de Arousa, a large coastal embayment in the NW Iberian upwelling system. Fluxes and net budgets were estimated with a non-stationary 2-D box model [Rosón, G., Álvarez-Salgado, X.A., Pérez, F.F., 1997. A non-stationary box-model to determine residual flows in a partially mixed estuary, based on both thermoline properties. Application to the Ría de Arousa (NW Spain). Estuarine, Coastal Shelf Sci., 44, 249–262] and the distributions of the different species acquired twice a week between May and October 1989 [Rosón, G., Pérez, F.F., Álvarez-Salgado, X.A., Figueiras, F.G., 1995. Variation of both thermohaline and chemical properties in an estuarine upwelling ecosystem: Ría de Arousa: 1. Time Evolution. Estuarine, Coastal Shelf Sci., 41, 195–213]. High N/P and N/Si net uptake ratios of 21 and 3.2 were observed during the upwelling season. The rapid recycling of phosphorus compared to nitrogen and the recurrent succession from pioneer diatoms (Si/N1) to red-tide forming species (Si/N=0) following the periodic upwelling pulses are the reasons behind the observed ratios. The molar ratios of dissolved oxygen production to inorganic carbon (−1.48) and nitrogen uptake (−10.2) during the upwelling season agree with the Redfield stoichiometry. On the contrary, net nutrient regeneration occurred with N/P, N/Si and O₂/C ratios of 7.4, 1.0 and −1.02 during an intense autumn downwelling event. These low ratios are due to the release of an excess of phosphate, silicate and CO₂ from the sediments. Conversely, the production of inorganic nitrogen is associated to the consumption of dissolved oxygen following a Redfield ratio of −10.0. Whereas the C/N ratio of the suspended organic matter produced during the upwelling season and consumed during the autumn downwelling event is 6.3–6.7, the N/P ratio changes from 11 during the upwelling season to 15 during the autumn downwelling. About 1/5 of the dissolved oxygen produced during the upwelling season and consumed during the autumn downwelling is delivered to and came from the atmosphere, respectively. Despite the C/N/P/O₂ ratios differ from the Redfield values, the high correlation between nutrient salts consumption and dissolved oxygen production (r²=0.74–0.86) allow to estimate an average net ecosystem production (NEP) from the individual elements. The 3–4 d time-scale variability of the average NEP depends on the 2-week periodicity of upwelling pulses, the heat exchange across the sea surface and the stability of the water column. As much as 70% of the total variability can be explained with a linear combination of these parameters.     

Lipid biomarkers and bacterial lipase activities as indicators of organic matter and bacterial dynamics in contrasted regimes at the DYFAMED site, NW Mediterranean

This study investigated the relationships between dissolved organic matter (DOM) composition and bacterial dynamics on short time scale during spring mesotrophic (March 2003) and summer oligotrophic (June 2003) regimes, in a 0–500 m depth water column with almost no advection, at the DYFAMED site, NW Mediterranean. DOM was characterized by analyzing dissolved organic carbon (DOC), colored dissolved organic matter (CDOM) and lipid class biotracers. Bacterial dynamic was assessed through the measurement of in situ bacterial lipase activity, abundance, production and bacterial community structure. We made the assumption that by coupling the ambient concentration of hydrolysable acyl-lipids with the measurement of their in situ bacterial hydrolysis rates (i.e. the free fatty acids release rate) would provide new insights about bacterial response to change in environmental conditions. The seasonal transition from spring to summer was accompanied by a significant accumulation of excess DOC (+5 μM) (ANOVA, p<0.05, n=8) in the upper layer (0–50 m). In this layer, the free fatty acids release rate to the bacterial carbon demand (BCD) ratio increased from 0.6±0.3 in March to 1.3±1.0 in June (ANOVA, p<0.05, n=8) showing that more uncoupling between the hydrolysis of the acyl-lipids and the BCD occurred during the evolution of the season, and that free fatty acids contributed to the excess DOC. The increase of lipolysis index and CDOM absorbance (from 0.24±0.17 to 0.39±0.13 and from 0.076±0.039 to 0.144±0.068; ANOVA, p<0.05, n=8, respectively), and the higher contribution of triglycerides, wax esters and phospholipids (from <5% to 12–31%) to the lipid pool reflected the change in the DOM quality. In addition to a strong increase of bacterial lipase activity per cell (51.4±29.4–418.3±290.6 Ag C cell⁻¹ h⁻¹), a significant percentage of ribotypes (39%) was different between spring and summer in the deep chlorophyll maximum (DCM) layer in particular, suggesting a shift in the bacterial community structure due to the different trophic conditions. At both seasons, in the chlorophyll layers, diel variations of DOM and bacterial parameters reflected a better bioavailability and/or DOM utilization by bacteria at night (the ratio of free fatty acids release rate to bacterial carbon demand decreased), most likely related to the zooplankton trophic behaviour. In mesotrophic conditions, such day/night pattern was driving changes in the bacterial community structure. In more oligotrophic period, diel variations in bacterial community structure were depth dependent in relation to the strong summer stratification.     

Seasonal dynamics of inorganic nutrients and phytoplankton biomass in the NW Alboran Sea

The seasonal dynamics of inorganic nutrients and phytoplankton biomass (chlorophyll a), and its relation with hydrological features, was studied in the NW Alboran Sea during four cruises conducted in February, April, July and October 2002. In the upper layers, the seasonal pattern of nutrient concentrations and their molar ratios (N:Si:P) was greatly influenced by hydrological conditions. The higher nutrient concentrations were observed during the spring cruise (2.54 μM NO₃⁻, 0.21 μM PO₄³⁻ and 1.55 μM Si(OH)₄, on average), coinciding with the increase of salinity due to upwelling induced by westerlies. The lowest nutrient concentrations were observed during summer (<0.54 μM NO₃⁻, 0.13 μM PO₄³⁻ and 0.75 μM Si(OH)₄, on average), when the lower salinities were detected. Nutrient molar ratios (N:Si:P) followed the same seasonal pattern as nutrient distribution. During all the cruises, the ratio N:P in the top 20 m was lower than 16:1, indicating a NO₃⁻ deficiency relative to PO₄³⁻. The N:P ratio increased with depth, reaching values higher than 16:1 in the deeper layers (200–300 m). The N:Si ratio in the top 20 m was lower than 1:1, excepting during spring when N:Si ratios higher than 1:1 were observed in some stations due to the upwelling event. The N:Si ratio increased with depth, showing a maximum at 50–100 m (>1.5:1), which indicates a shift towards Si-deficiency in these layers. The Si:P ratio was much lower than 16:1 throughout the water column during the four cruises. In general, the spatial and seasonal variation of phytoplankton biomass showed a strong coupling with hydrological and chemical fields. The higher chlorophyll a concentrations at the depth of the chlorophyll maximum were found in April (2.57 mg m⁻³ on average), while the lowest phytoplankton biomass corresponded to the winter cruise (0.74 mg m⁻³ on average). The low nitrate concentrations together with the low N:P ratios found in the upper layers (top 20 m) during the winter, summer and autumn cruises suggest that N-limitation could occur in these layers during great part of the year. However, N-limitation during the spring cruise was temporally overcome by nutrient enrichment caused by an intense wind-driven upwelling event.     

Abundance, size distribution, and stable carbon and nitrogen isotopic compositions of marine organic matter isolated by tangential-flow ultrafiltration

Tangential-flow ultrafiltration was used to isolate particulate and high-molecular-weight dissolved material from seawater collected at various depths and geographic regions of the Pacific and Atlantic Oceans. Ultrafiltration proved to be a relatively fast and efficient method for the isolation of hundreds of milligrams of material. Optical and electron microscopy of the isolated materials revealed that relatively fragile materials were recovered intact. Depth-weighted results of the size distribution of organic matter in seawater indicated that ˜ 75% of marine organic carbon was low-molecular-weight (LMW) dissolved organic carbon (< 1 nm), ˜ 24% was high-molecular-weight (HMW) dissolved organic carbon (1–100 nm), and ˜ 1% was particulate organic carbon (> 100 nm). The distribution of carbon in surface water was shifted to greater relative abundances of larger size fractions, suggesting a diagenetic sequence from macromolecular material to small refractory molecules. The average C:N ratios of particulate organic matter (POM) and HMW dissolved organic matter (DOM) were 7.7 and 16.7, respectively. Differences in C:N ratios between POM and HMW DOM were large and invariant with depth and geographic region, indicating that the aggregation of HMW DOM to form POM must be of minor significance to overall carbon dynamics. The stable carbon isotope composition (δ¹³C) of POM averaged −22.7%. in surface water and −25.2%. in subsurface water. Several possible explanations for the observed isotopic shift with depth were explored, but we were unable to discern the cause. The δ¹³C of HMW DOM samples was relatively constant and averaged −21.7%., indicating a predominantly marine origin for this material. The δ¹⁵N values of POM were highly variable (5.8–15.4%.), and the availability of nitrate in surface waters appeared to be the major factor influencing δ¹⁵N values in the equatorial Pacific. In the upwelling region nitrate concentrations were relatively high and δ¹⁵N values of POM were low, whereas to the north and south of the upwelling nitrate concentrations were low and δ¹⁵N values were high. The δ¹⁵N values of HMW DOM reflected the same trends observed in the POM fraction and provided the first such evidence for biological cycling of dissolved organic nitrogen (DON). Using the observed δ¹⁵N values and an estimate of meridional advection velocity, we estimated a turnover time of 0.3 to 0.5% day⁻¹ for HMW DON. These results suggest a major role for DON in the upper ocean nitrogen cycle.     

Analysis of marine DOC using a dry combustion method

As part of a continuing effort to verify and improve measurements of marine dissolved organic carbon (DOC), we combusted dried sea salts + adhered organic matter to assay DOC concentrations in representative samples from the Atlantic and Pacific oceans. Combustions were performed overnight at 580 °C in sealed tubes, and oxidation of organic materials occurred via a novel mechanism, thermal sulfate reduction: 2H₂SO₄ + CH₂O → 2SO₂ + 3H₂O + CO₂Measured DOC concentrations ranged from 43 to 114 μM C, with highest values observed in inshore surface samples from Woods Hole Harbor, and lowest values observed in twelve deep offshore Atlantic and Pacific waters. Stable carbon isotope values determined for all samples were near − 22%., consistent with a predominantly marine phytoplankton origin for DOC. A seasonal study in Woods Hole Harbor showed no significant temporal trend in nearshore DOC concentrations. Problems associated with sample storage and contamination during drying steps prevented highly precise (± 1 μM) DOC concentration determinations; however, an improved drying and measurement system is outlined (Appendix A) for possible future dry-combustion studies of DOC concentrations.     

Photochemical production of ammonium and transformation of dissolved organic matter in the Baltic Sea

The release of ammonium from the photochemical degradation of dissolved organic matter (DOM) has been proposed by earlier studies as a potentially important remineralisation pathway for refractory organic nitrogen. In this study the photochemical production of ammonium from Baltic Sea DOM was assessed in the laboratory. Filtered samples from the Bothnian Bay, the Gulf of Finland and the Arkona Sea were exposed to UVA light at environmentally relevant levels, and the developments in ammonium concentrations, light absorption, fluorescence and molecular size distribution were followed. The exposures resulted in a decrease in DOM absorption and loss of the larger sized fraction of DOM. Analysis of the fluorescence properties of DOM using parallel factor analysis (PARAFAC) identified 6 independent components. Five components decreased in intensity as a result of the UVA exposures. One component was produced as a result of the exposures and represents labile photoproducts derived from terrestrial DOM. The characteristics of DOM in samples from the Bothnian Bay and Gulf of Finland were similar and dominated by terrestrially derived material. The DOM from the Arkona Sea was more autochthonous in character. Photoammonification differed depending on the composition of DOM. Calculated photoammonification rates in surface waters varied between 121 and 382 μmol NH₄⁺ L^− 1 d^− 1. Estimated areal daily production rates ranged between 37 and 237 μmol NH₄⁺ m^− 2 d^− 1, which are comparable to atmospheric deposition rates and suggest that photochemical remineralisation of organic nitrogen may be a significant source of bioavailable nitrogen to surface waters during summer months with high irradiance and low inorganic nitrogen concentrations.     

The distribution of particulate organic carbon and nitrogen in some surface waters of the World Ocean

Data is presented for the concentrations of organic carbon and nitrogen, and C:N ratios, in marine particulate matter, and for POC and PN, from surface waters collected in the northeastern Atlantic, South Atlantic, Indian Ocean and China Sea.The organic carbon content of this particulate matter varies between 4.6% and 29.9%, and has an average of 17.8%. The average organic carbon content of particulate matter from the various oceans decreases in the order: Northeastern Atlantic > South Atlantic > Indian Ocean > China Sea.The nitrogen content of the particulate matter varies between 1.0% and 3.9%, with an average of 2.2%, and in general follows the same trend as that of organic carbon.C:N ratios vary between 5.1 and 10.6, and have an average of 7.9.The POC contents of the oceanic waters vary between 6.6 and 211 μg/l, with an average of 52 μg/l. The concentrations in the surface waters decrease in the following order: Northeastern Atlantic τ China Sea > South Atlantic > Indian Ocean.The concentrations, and compositions, of particulate matter from various coastal localities are given for comparison with the oceanic values.