The chemical speciation of iron in the north-east Atlantic Ocean

The distribution of dissolved iron and its chemical speciation (organic complexation and redox speciation) were studied in the northeastern Atlantic Ocean along 23°W between 37 and 42°N at depths between 0 and 2000 m, and in the upper-water column (upper 200 m) at two stations further east at 45°N10°W and 40°N17°W in the early spring of 1998. The iron speciation data are here combined with phytoplankton data to suggest cyanobacteria as a possible source for the iron binding ligands. The organic Fe-binding ligand concentrations were greater than that of dissolved iron by a factor of 1.5–5, thus maintaining iron in solution at levels well above it solubility. The water column distribution of the organic ligand indicates in-situ production of organic ligands by the plankton (consisting mainly of the cyanobacteria Synechococcus sp.) in the euphotic layer and a remineralisation from sinking biogenic particles in deeper waters. Fe(II) concentrations varied from below the detection limit (<0.1 nM) up to 0.55 nM but represented only a minor fraction of 0% to occasionally 35% of the dissolved iron throughout the water column. The water column distribution of the Fe(II) suggests biologically mediated production in the deep waters and photochemical production in the euphotic layer. Although there was no evidence of iron limitation in these waters, the aeolian iron input probably contributed to a shift in the phytoplankton assemblage towards increased Synechococcus growth.     

Atmospheric iron deposition and sea-surface dissolved iron concentrations in the eastern Atlantic Ocean

Atmospheric iron and underway sea-surface dissolved (<0.2 μm) iron (DFe) concentrations were investigated along a north–south transect in the eastern Atlantic Ocean (27°N/16°W–19°S/5°E). Fe concentrations in aerosols and dry deposition fluxes of soluble Fe were at least two orders of magnitude higher in the Saharan dust plume than at the equator or at the extreme south of the transect. A weaker source of atmospheric Fe was also observed in the South Atlantic, possibly originating in southern Africa via the north-easterly outflow of the Angolan plume. Estimations of total atmospheric deposition fluxes (dry plus wet) of soluble Fe suggested that wet deposition dominated in the intertropical convergence zone, due to the very high amount of precipitation and to the fact that a substantial part of Fe was delivered in dissolved form. On the other hand, dry deposition dominated in the other regions of the transect (73–97%), where rainfall rates were much lower. Underway sea-surface DFe concentrations ranged 0.02–1.1 nM. Such low values (0.02 nM) are reported for the first time in the Atlantic Ocean and may be (co)-limiting for primary production. A significant correlation (Spearman's rho=0.862, p<0.01) was observed between mean DFe concentrations and total atmospheric deposition fluxes, confirming the importance of atmospheric deposition on the iron cycle in the Atlantic. Residence time of DFe in the surface waters relative to atmospheric inputs were estimated in the northern part of our study area (17±8 to 28±16 d). These values confirmed the rapid removal of Fe from the surface waters, possibly by colloidal aggregation.     

Community respiration/production and bacterial activity in the upper water column of the central Arctic Ocean

Community metabolism (respiration and production) and bacterial activity were assessed in the upper water column of the central Arctic Ocean during the SHEBA/JOIS ice camp experiment, October 1997–September 1998. In the upper 50 m, decrease in integrated dissolved oxygen (DO) stocks over a period of 124 d in mid-winter suggested a respiration rate of ∼3.3 nM O₂ h⁻¹ and a carbon demand of ∼4.5 gC m⁻². Increase in 0–50 m integrated stocks of DO during summer implied a net community production of ∼20 gC m⁻². Community respiration rates were directly measured via rate of decrease in DO in whole seawater during 72-h dark incubation experiments. Incubation-based respiration rates were on average 3-fold lower during winter (11.0±10.6 nM O₂ h⁻¹) compared to summer (35.3±24.8 nM O₂ h⁻¹). Bacterial heterotrophic activity responded strongly, without noticeable lag, to phytoplankton growth. Rate of leucine incorporation by bacteria (a proxy for protein synthesis and cell growth) increased ∼10-fold, and the cell-specific rate of leucine incorporation ∼5-fold, from winter to summer. Rates of production of bacterial biomass in the upper 50 m were, however, low compared to other oceanic regions, averaging 0.52±0.47 ngC l⁻¹ h⁻¹ during winter and 5.1±3.1 ngC l⁻¹ h⁻¹ during summer. Total carbon demand based on respiration experiments averaged 2.4±2.3 mgC m⁻³ d⁻¹ in winter and 7.8±5.5 mgC m⁻³ d⁻¹ in summer. Estimated bacterial carbon demand based on bacterial productivity and an assumed 10% gross growth efficiency was much lower, averaging about 0.12±0.12 mgC m⁻³ d⁻¹ in winter and 1.3±0.7 mgC m⁻³ d⁻¹ in summer. Our estimates of bacterial activity during summer were an order of magnitude less than rates reported from a summer 1994 study in the central Arctic Ocean, implying significant inter-annual variability of microbial processes in this region.     

Vertical distributions of dissolved organic carbon and nitrogen in the Southern Ocean

Detailed vertical profiles of dissolved organic carbon (DOC), nitrogen (DON) and DOC/DON ratios in the Australian sector of the Southern Ocean (56°–65°S around 140°W transect) were obtained by a high-temperature catalytic oxidation method with a modified Shimadzu TOC-5000 unit. The simultaneous analyses of DOC and total dissolved nitrogen (TDN) gave high precision results (±0.7 μMC and ±0.3 μMN). In surface layers, DOC concentrations were lower (45–55 μM) than those generally obtained from other oceanic environments (60–90 μM). The surface concentrations of DON varied from 4 to 9 μM, but within the range generally reported for other ocean regions. Surface excesses of DOC and DON were calculated against nearly constant subsurface concentrations. A consistent contribution of low C/N ratio (2.7–5.0) was found in the mid-surface layer (30–75 m), suggesting more extensive degradation of carbon-enriched materials and/or enhanced supply of nitrogen-enriched ones.     

Nitrous oxide and methane in the Atlantic Ocean between 50°N and 52°S: Latitudinal distribution and sea-to-air flux

We discuss nitrous oxide (N₂O) and methane (CH₄) distributions in 49 vertical profiles covering the upper ∼300 m of the water column along two ∼13,500 km transects between ∼50°N and ∼52°S during the Atlantic Meridional Transect (AMT) programme (AMT cruises 12 and 13). Vertical N₂O profiles were amenable to analysis on the basis of common features coincident with Longhurst provinces. In contrast, CH₄ showed no such pattern. The most striking feature of the latitudinal depth distributions was a well-defined “plume” of exceptionally high N₂O concentrations coincident with very low levels of CH₄, located between ∼23.5°N and ∼23.5°S; this feature reflects the upwelling of deep waters containing N₂O derived from nitrification, as identified by an analysis of N₂O, apparent oxygen utilization (AOU) and NO₃⁻, and presumably depleted in CH₄ by bacterial oxidation. Sea-to-air emissions fluxes for a region equivalent to ∼42% of the Atlantic Ocean surface area were in the range 0.40–0.68 Tg N₂O yr⁻¹ and 0.81–1.43 Tg CH₄ yr⁻¹. Based on contemporary estimates of the global ocean source strengths of atmospheric N₂O and CH₄, the Atlantic Ocean could account for ∼6–15% and 4–13%, respectively, of these source totals. Given that the Atlantic Ocean accounts for around 20% of the global ocean surface, on unit area basis it appears that the Atlantic may be a slightly weaker source of atmospheric N₂O than other ocean regions but it could make a somewhat larger contribution to marine-derived atmospheric CH₄ than previously thought.     

Primary productivity,differential size fraction and pigment composition responses in two Southern Ocean in situ iron enrichments

Two in situ iron-enrichment experiments were conducted in the Pacific sector of the Southern Ocean during summer 2002 (SOFeX). The “north patch,” established within the Subantarctic Zone (∼56°S), was characterized by high nitrate (∼21 mmol m⁻³) but low silicic acid (2 mmol m⁻³) concentrations. North patch iron enrichment increased chlorophyll (Chl) by 12-fold to 2.1 mg m⁻³ and primary productivity (PP_EU) by 8-fold to 188 mmol C m⁻² d⁻¹. Surprisingly, despite low silicic acid concentrations, diagnostic pigment and size-fraction composition changes indicated an assemblage shift from prymnesiophytes toward diatoms. The “south patch,” poleward of the Southern Boundary of the Antarctic Circumpolar Current (SBACC) (∼66°S), had high concentrations of nitrate (∼27 mmol m⁻³) and silicic acid (64 mmol m⁻³). South patch iron enrichment increased Chl by 9-fold to 3.8 mg m⁻³ and PP_EU 5-fold to 161 mmol C m⁻² d⁻¹ but, notably, did not alter the phytoplankton assemblage from the initial composition of ∼50% diatoms. South patch iron addition also reduced total particulate organic carbon:Chl from ∼300 to 100; enhanced the presence of novel non-photosynthetic, but fluorescent, compounds; and counteracted a decrease in photosynthetic performance as photoperiod decreased. These experiments show unambiguously that in the contemporary, high nitrate Southern Ocean increasing iron supply increases primary productivity, confirming the initial premise of the Martin Iron Hypothesis. However, despite a 5-fold increase in PP_EU under iron-replete conditions in late summer, the effect of iron on annual productivity in the Southern Ocean poleward of the SBACC is limited by seasonal ice coverage and the dark of polar winter.     

Speciation of Fe in the Eastern North Atlantic Ocean

In the Eastern North Atlantic Ocean iron (Fe) speciation was investigated in three size fractions: the dissolvable from unfiltered samples, the dissolved fraction (<0.2 μm) and the fraction smaller than 1000 kDa (<1000 kDa). Fe concentrations were measured by flow injection analysis and the organic Fe complexation by voltammetry. In the research area the water column consisted of North Atlantic Central Water (NACW), below which Mediterranean Overflow Water (MOW) was found with the core between 800 and 1000 m depth. Below 2000 m depth the North Atlantic Deep Water (NADW) proper was recognised. Dissolved Fe and Fe in the <1000 kDa fraction showed a nutrient like profile, depleted at the surface, increasing until 500–1000 m depth below which the concentration remained constant. Fe in unfiltered samples clearly showed the MOW with high concentrations (4 nM) compared to the overlying NACW and the underlying NADW, with 0.9 nM and 2 nM Fe, respectively. By using excess ligand (Excess L) concentrations as parameter we show a potential to bind Fe. The surface mixed layer had the highest excess ligand concentrations in all size fractions due to phytoplankton uptake and possible ligand production. The ratio of Excess L over Fe proved to be a complementary tool in revealing the relative saturation state of the ligands with Fe. In the whole water column, the organic ligands in the larger colloidal fraction (between 0.2 μm and 1000 kDa) were saturated with Fe, whereas those in the smallest fraction (<1000 kDa) were not saturated with Fe, confirming that this fraction was the most reactive one and regulates dissolution and colloid aggregation and scavenging processes. This regulation was remarkably stable with depth since the alpha factor (product of Excess L and K′), expressing the reactivity of the ligands, did not vary and was 10¹³. Whereas, in the NACW and the MOW, the ligands in the particulate (>0.2 μm) fraction were unsaturated with Fe with respect to the dissolved fraction, thus these waters had a scavenging potential.     

Evaluation of the budget for silicic acid in Cascadia Basin deep water

Between 2 and 3 km depth, North Pacific deep waters contain a plume of water with high silicic acid concentrations. The plume extends outward from Cascadia Basin (the Washington Margin), where waters can contain in excess of 200 μM off the coast of Oregon and Washington. To identify the source of the high Si concentrations in Cascadia Basin, we measured silicic acid and germanium concentrations in deep waters, and their fluxes from sediments using incubated cores. The mean flux of silicic acid into bottom waters is 0.81±0.05 mmol/m²-day, and the Ge/Si ratio of this flux is 0.7±0.1 μmol/mol. A box model, incorporating these results with hydrographic data, indicates that (1) no more than 5% of the silicic acid added to Basin deep waters can have a hydrothermal source (either hot or warm seeps), and (2) the total input of silicic acid to Basin deep waters is 0.06±0.02 Tmol/y. This input is nearly all from remineralized biogenic debris and should contribute about 0.5% of the 14 Tmol/y that are estimated to be necessary to maintain the North Pacific plume.     

The distribution and speciation of mercury in the South and equatorial Atlantic

Mercury concentration and speciation were measured in surface and deep ocean waters of the South and equatorial Atlantic. In the surface waters, total Hg was 2.9±1.7 pM on average, with a significant fraction present as reactive Hg (1.7±1.2 pM). The reactive Hg fraction consisted of elemental Hg (Hg°) as the dominant species (1.2±0.8 pM). Measurements in surface waters also showed that Hg partitioned to the “colloidal” phase (0.33±0.28 pM) and was associated with particulate matter (0.1±0.05 pM). No dimethylmercury (DMHg;<0.01 pM) or monomethylmercury (MMHg; <0.05 pM) was detected in mixed layer samples. The highest DMHg concentrations were found in recently formed deep waters – Antarctic Intermediate Water and Antarctic Bottom Water and in the equatorial sub-thermocline region. Higher concentrations of DMHg coincided with higher values of apparent oxygen utilization, indicative of a link between microbial activity and methylated Hg production. The lowest-deep water DMHg concentrations were found in the core of the North Atlantic Deep Water. Incubation experiments on-board demonstrated that light enhanced the decomposition of DMHg, with MMHg as the major product. In deep waters, Hg° was still an important constituent and is likely formed as a decomposition product from MMHg. These results suggest that methylated Hg production occurs primarily in regions of high biological activity, and that ionic Hg is strongly complexed to organic matter (colloidal material) in open ocean surface waters.     

Cu complexation by organic ligands in the sub-arctic NW Pacific and Bering Sea

Cu speciation was characterized at three stations in the sub arctic NW Pacific and Bering Sea using cathodic stripping voltammetry with the competing ligands benzoylacetone and salicylaldoxime. A single ligand model was fit to the titration data, yielding concentrations throughout the water column of ∼3–4 nM, and conditional stability constants ranging from 10^12.7 to 10^14.1, this range being partly due to the choice of competing ligand. Free Cu²⁺ in surface waters was 2–4×10⁻¹⁴ M, in close agreement with values reported by previous workers in the NE Pacific using anodic stripping voltammetry (ASV). However, those results showed that complexation by strong organic ligands becomes unimportant below 200–300 m, while our data indicated Cu is strongly complexed to depths as great as 3000 m. Free Cu²⁺ concentrations in surface waters reported here and in previous work are close to the threshold value where Cu can limit the acquisition of Fe by phytoplankton.     

Dissolved iron distributions in the central region of the Gulf of California,México

We report dissolved iron (Fe_d) concentrations measured in the upper 600 m in the central region of the Gulf of California (GC) under spring conditions. Our results showed the complex nature of Fe cycling within the GC. In the northern region of the study area, surface waters were relatively enriched, with Fe_d concentrations >5.0 nM, which can be partially explained by an atmospheric source. These concentrations are 12 times higher than those found in the adjacent Pacific Ocean. In contrast, Fe_d depth profiles in the southern region did not show any Fe_d surface enrichment (concentrations <1.5 nM) because of particle scavenging and higher stratification of the water-column. The most southern station in our area of study was the most stratified and showed an excess Fe_d and PO₄ with respect to NO₃, conditions favorable for nitrogen fixation. This station also showed the least negative surface value of N* of all stations. However, despite the adequate levels of Fe_d and PO₄ at that location, the surface temperature (22.6 °C) was probably not high enough for diazotrophs to develop. A slight increase in Fe_d levels in intermediate waters at the southern region was associated with the oxygen minimum zone. Finally, our results suggest that remineralization of organic matter is probably the major source of Fe_d in subsurface waters of the GC.     

Iron and mixing affect biological carbon uptake in SOIREE and EisenEx,two Southern Ocean iron fertilisation experiments

This study explores the changes in the surface water fugacity of carbon dioxide (fCO₂) and biological carbon uptake in two Southern Ocean iron fertilisation experiments with different hydrographic regimes. The Southern Ocean Iron Release Experiment (SOIREE) experiment was carried out south of the Antarctic Polar Front (APF) at 61°S, 141°E in February 1999 in a stable hydrographic setting. The EisenEx experiment was conducted in a cyclonic eddy north of the APF at 48°S, 21°E in November 2000 and was characterised by a rapid succession of low to storm-force wind speeds and dynamic hydrographic conditions. The iron additions promoted algal blooms in both studies. They alleviated algal iron limitation during the 13-day SOIREE experiment and probably during the first 12 days of EisenEx. The fCO₂ in surface water decreased at a constant rate of 3.8 μatm day⁻¹ from 4 to 5 days onwards in SOIREE. The fCO₂ reduction was 35 μatm after 13 days. The evolution of surface water fCO₂ in the iron-enriched waters (or ‘patch’) displayed a saw tooth pattern in EisenEx, in response to algal carbon uptake in calm conditions and deep mixing and horizontal dispersion during storms. The maximum fCO₂ reduction was 18–20 μatm after 12 and 21 days with lower values in between. The iron-enriched waters in EisenEx absorbed four times more atmospheric CO₂ than in SOIREE between 5 and 12 days, as a result of stronger winds. The total biological uptake of inorganic carbon across the patch was 1389 ton C (±10%) in SOIREE and 1433 ton C (±27%) in EisenEx after 12 days (1 ton=10⁶ g). This similarity probably reflects the comparable size of the iron additions, as well as algal growth at a similar near-maximum growth rate in these regions. The findings imply that the different mixing regimes had less effect on the overall biological carbon uptake across the iron-enriched waters than suggested by the evolution of fCO₂ in surface water.     

Structure and mechanisms of the Arabian Sea variability during the winter monsoon

In the southern Arabian Sea (between the Equator and 10°N), the shoaling of isotherms at subsurface levels (20 °C isotherm depth is located at ∼90 m) leads to cooling at 100 m by 2–3 °C relative to surrounding waters during the winter monsoon. The annual and interannual variations of this upwelling zone, which we call the Arabian Sea dome (ASD), are studied using results from an eddy-permitting ocean general circulation model in conjunction with hydrography and TOPEX/ERS altimeter data. The ASD first appears in the southeastern Arabian Sea during September–October, maturing during November–December to extend across the entire southern Arabian Sea (along ∼5°N). It begins to weaken in January and dissipates by March in the southwestern Arabian Sea. From the analysis of heat-budget balance terms and a pair of model control experiments, it is shown that the local Ekman upwelling induced by the positive wind-stress curl of the winter monsoon generates the ASD in the southeastern Arabian Sea. The ASD decays due to the weakening of the cyclonic curl of the wind and the westward penetration of warm water from the east (Southern Arabian Sea High). The interannual variation of the ASD is governed by variations in the Ekman upwelling induced by the cyclonic wind-stress curl. Associated with the unusual winds during 1994–1995 and 1997–1998 Indian Ocean dipole (IOD) periods, the ASD failed to develop. In the absence of the ASD during the IOD events, the 20 °C isotherm depth was 20–30 m deeper than normal in the southern Arabian Sea resulting in a temperature increase at 97 m of 4–5 °C. An implication is that the SST evolution in the southern Arabian Sea during the winter monsoon is primarily controlled by advective cooling: the shoaling of isotherms associated with the ASD leads to SST cooling.     

Nutrient gradients in the western North Atlantic Ocean: Relationship to microbial community structure and comparison to patterns in the Pacific Ocean

Studies of nitrogen and phosphorus dynamics in the oligotrophic surface waters of the western North Atlantic Ocean have been constrained because ambient concentrations are typically at or below the detection limits of standard colorometric methods, except during periods of deep vertical mixing. Here we report the application of high-sensitivity analytical methods—determinations of nitrate plus nitrite (N+N) by chemiluminescence and soluble reactive phosphorus (SRP) by the magnesium induced co-precipitation (MAGIC) protocol—to surface waters along a transect from the Sargasso Sea at 26°N through the Gulf Stream at 37°N, including sampling at the JGOFS Bermuda Atlantic Time-series Study (BATS) station. The results were compared with data from the BATS program, and the HOT station in the Pacific Ocean, permitting cross-ecosystem comparisons. Microbial populations were analyzed along the transect, and an attempt was made to interpret their distributions in the context of the measured nutrient concentrations.Surface concentrations of N+N and SRP during the March 1998 transect separated into 3 distinct regions, with the boundaries corresponding roughly to the locations of the BATS station (∼31°N) and the Gulf Stream (∼37°N). Although N+N and SRP co-varied, the [N+N] : [SRP] molar ratios increased systematically from ∼1 to 10 in the southern segment, remained relatively constant at ∼40–50 between 31°N and 37°N, then decreased again systematically to ratios <10 north of the Gulf Stream. Dissolved organic N (DON) and P (DOP) dominated (⩾90%) the total dissolved N (TDN) and P (TDP) pools except in the northern portion of the transect. The [DON] : [DOP] molar ratios were relatively invariant (∼30–60) across the entire transect.Heterotrophic prokaryotes (operationally defined as “bacteria”), Prochlorococcus, Synechococcus, ultra- and nanophytoplankton, cryptophytes, and coccolithophores were enumerated by flow cytometry. The abundance of bacteria was well correlated with the concentration of SRP, and that of the ultra- and nanophytoplankton was well correlated with the concentration of N+N. The only group whose concentration was correlated with temperature was Prochlorococcus, and its abundance was unrelated to the concentrations of nutrients measured at the surface.We combined our transect results with time-series measurements from the BATS site and data from select depth profiles, and contrasted these North Atlantic data sets with time-series of N and P nutrient measurements from a station in the North Pacific subtropical gyre near Hawaii [Hawaii Ocean Time-series (HOT) site]. Two prominent differences are readily observed from this comparison. The [N+N] : [SRP] molar ratios are much less than 16 : 1 during stratified periods in surface waters at the BATS site, as is the case at the HOT site year round. However, following deep winter mixing, this ratio is much higher than 16 : 1 at BATS. Also, SRP concentrations in the upper 100 m at BATS fall in the range 1–10 nM during stratified periods, which is at least one order of magnitude lower than at the HOT site. That two ecosystems with comparable rates of primary and export production would differ so dramatically in their nutrient dynamics is intriguing, and highlights the need for detailed cross ecosystem comparisons.     

Hydrography of chromophoric dissolved organic matter in the North Atlantic

The distribution and optical absorption characteristics of chromophoric dissolved organic matter (CDOM) were systematically investigated along three meridional transects in the North Atlantic Ocean and Caribbean Sea conducted as part of the 2003 US CLIVAR/CO₂ Repeat Hydrography survey. Hydrographic transects covered in aggregate a latitudinal range of 5° to 62° north along longitudes 20°W (line A16N, Leg 1), 52°W (A20), and 66°W (A22). Absorption spectra of filtered seawater samples were collected and analyzed for depths ranging from the surface to ∼6000 m, sampling all the ocean water masses in the western basin of the subtropical North Atlantic and several stations on the North and South American continental slopes. The lowest surface abundances of CDOM (< 0.1 m⁻¹ absorption coefficient at 325 nm) were found in the central subtropical gyres while the highest surface abundances (∼0.7 m⁻¹) were found along the continental shelves and within the subpolar gyre, confirming recent satellite-based assessments of surface CDOM distribution. Within the ocean interior, CDOM abundances were relatively high (0.1–0.2 m⁻¹ absorption coefficient at 325 nm) except in the subtropical mode water, where a local minimum exists due to the subduction of low CDOM surface waters during mode water formation. In the subthermocline water masses of the western basin, changes in CDOM abundance are not correlated with increasing ventilation age as assessed using chlorofluorocarbon (CFC) concentrations and the atmospheric CFC history. But dissolved organic carbon (DOC) mass-specific absorption coefficients of CDOM increase with increasing ventilation age in the deep sea, indicating that CDOM is a refractory component of the DOC pool. The overall CDOM distribution in the North Atlantic reflects the rapid advection and mixing processes of the basin and demonstrates that remineralization in the ocean interior is not a significant sink for CDOM. This supports the potential of CDOM as a tracer of ocean circulation processes for subducted water masses.     

Arsenic and antimony species in surface transects and depth profiles across a frontal zone: The Chatham Rise,New Zealand

Measurements of total dissolved arsenic (As(III+V)) and antimony (Sb(III+V) and their simple methylated species are presented for samples collected from three vertical profiles and along three surface transects in the Chatham Rise region, east of New Zealand. As(III+V) concentrations showed a slight increase with depth (16–17 nM at 25 m to 20 nM at 100 m) whereas Sb(III+V) concentrations were conservative with depth (1.02–1.12 nM). Along the three surface water transects, As(III+V) and Sb(III+V) concentrations showed little variation, with average concentrations of 18±2 and 0.99±0.05 nM, respectively. Inorganic arsenic was not correlated with orthophosphate (r²=0.01). Monomethyl- and dimethyl-arsenic (MMAs, DMAs) concentrations (0.04–0.01 and 0.65–0.07 nM, respectively) decreased with depth, suggesting surface water production by biota and degradation at depth. Along the Chatham Rise transect, DMAs concentrations increased on the Rise (0.65 nM maximum) compared to waters north and south of the Rise (∼0.22 nM). Fluctuation in MMAs concentrations were also seen for water samples collected on the Chatham Rise. Monomethyl-, dimethyl- and trimethyl-antimony (MMSb, DMSb, TMSb) species were detected in water samples collected along all the three surface water transects suggesting surface water production by biota. Concentrations of MMSb, DMSb and TMSb in water samples were fairly constant along all the three surface transects (0.06–0.07, 0.015–0.025 and 0.005–0.015 nM, respectively), showing no significant enrichment on the Chatham Rise. These arsenic and antimony results support the current global view that inorganic As and Sb are conservative and the methyl species are of biological origin.     

A quantitative analysis of sources for summertime phytoplankton variability over 18 years in the South Shetland Islands (Antarctica) region

Eighteen years of summertime hydrographic and chlorophyll-a (Chl-a) data (～2700 stations) from the South Shetland Islands (Antarctica) region show that a “bell-shaped” (unimodal) distribution of phytoplankton biomass results annually when plotted against the inshore to offshore gradient in surface salinity. The maximum for this unimodal Chl-a distribution corresponds with a shallow upper mixed layer (UML) in iron-rich waters that occurs at salinities ～34. Methods of gradient analysis are used to distinguish sources of variability for bloom development among years. The control of phytoplankton biomass is resolved across the salinity gradient that separates the co-limiting conditions of deep UML depths and low-iron concentrations as opposing end-members. Chlorophyll-fluorescence yield data (a proxy for Fe-stress) showed that at salinities ～34, phytoplankton biomass was unlikely to be limited by Fe. Instead, blooming at salinities ～34 (1.3±1 mg Chl-a m^?3) co-varied with shallow UML depths (41±19 m) that occurred as a function of higher UML temperature (1.5±0.5 °C) among years, and is evidence that atmospheric climate variability impacts summertime phytoplankton biomass and production in this Southern Ocean seascape.     

Seasonal dimethylsulfoniopropionate (DMSP) variability in Dona Paula bay

Data on temporal variations of total dimethylsulfoniopropionate (DMSP_t) and the environmental factors that influence DMSP_t concentrations are important in understanding the biogeochemical cycling of organic sulfur compounds. Annual and diurnal variations of DMSP_t were investigated in relation to environmental variables at a fixed station in Dona Paula bay (west coast of India). DMSP concentrations were high in the day and low at night and ranged from 3.69 to 84 nM with a maximum at 17.00 h. The high concentrations of DMSP_t during daytime closely followed that of Chl a concentrations. The DMSP utilizers averaged 0.8 ± 0.3 × 10³ cells l^?1 during night and 0.4 ± 0.1 × 10³ cells l^?1 during the day. The diel variation of DMSP_t was influenced more by biological variables than hydrographic parameters. In the year-round study, the concentrations ranged from 0.69 to 15.8 nM. It was fourfold higher during the southwest monsoon season (13.4 ± 2 nM) and threefold higher during the post-monsoon season (9.96 ± 5 nM) compared to the pre-monsoon season (3.1 ± 1 nM). DMSP_t concentrations showed temporal variability, both during diurnal and annual studies. Diatoms were identified as producers of DMSP in Dona Paula bay. Dinoflagellates also contributed during the non-monsoon seasons. Another factor involved in the variability of DMSP_t was DMSP utilizing bacteria, which ranged from 1 to 10% of the total heterotrophic count.     

Continuous shipboard sampling of gas tension,oxygen and nitrogen

A novel shipboard gas tension device (GTD) that measures total dissolved air pressure in ocean surface waters is described and demonstrated. In addition, an improved method to estimate dissolved N₂ levels from simultaneous measurements of gas tension, dissolved O₂, water temperature, and salinity is described. Other than a flow-through plenum, the shipboard GTD is similar to the previously described moored-mode GTD (McNeil et al., 1995, Deep-Sea Research I 42, 819–826). The plenum has an integrated water-side screen to protect the membrane, and prevent the membrane from flexing in super-saturated near surface waters. The sampling scheme uses a well mixed and thermally insulated 15 L container that is flushed by the ship's seawater intake at a rate of 3–15 L min⁻¹. Dissolved gas sensors are placed inside this container and flushed with a small recirculation pump. Laboratory data that characterize the response of the modified GTD are presented. The modified GTD has a constant, isothermal, characteristic (e-folding) response time of typically 11±2 min at 20 °C. The response time decreases with increasing temperature and varies by ±35% over a temperature range of 5–35 °C. Results of field measurements, collected on the R.V. Brown between New York and Puerto Rico during September 2002, are presented, and provide the first look at co-variability in surface ocean N₂, O₂, and CO₂ levels over horizontal length scales of several kilometers. Dissolved N₂ concentrations decreased by approximately 16% as the ship sailed from the colder northern continental shelf waters, across the Gulf Stream, and into the warmer northwestern Atlantic Ocean. Historical database measurements, buoy time series, and satellite imagery, are used to aid interpretation of the dissolved gas levels.     

Exopolysaccharides produced by bacteria isolated from the pelagic Southern Ocean — Role in Fe binding,chemical reactivity,and bioavailability

As a result of ubiquitous excretion by micro-organisms, extracellular polymeric substances are reported in high concentrations in marine systems. The majority of this material is exopolysaccharide (EPS). Despite previous studies showing that EPS can affect carbon as well as trace metal cycling, little is known about the effect on Fe – a critical nutrient limiting primary productivity in up to 40% of the ocean. Here, we have characterised an EPS purified from bacteria isolated from the pelagic Southern Ocean (Pseudoalteromonas sp.) and investigated its role in Fe chemical speciation, solubility, as well as bioavailability for two keystone Southern Ocean phytoplankton strains. This EPS has an average molecular weight of 4.6 MDa, exhibiting mainly –OH, COO– and –NH₂ functional groups. An asymmetrical flow field-flow fractionation coupled online with UV-spectrophotometer, differential refractive index, and multiangle laser light scattering (aFlFFF-UV-DRI-MALS) demonstrates that this EPS is polydisperse with three, not well resolved, size populations having molar masses in the range from 0.57 to 15.8 MDa. Fe was exclusively associated with the medium size fraction of this EPS and was the most abundant trace metal with 2.2 nM Fe per nM EPS. Only a third of this Fe was chemically labile, and the strength of Fe-EPS complexes increased with equilibration time. 1 nM EPS is efficient to retain Fe in solution, mainly in the colloidal phase (0.02–0.2 μm). Fe bound to the EPS was highly bioavailable (25% as much as for inorganic Fe). Due to combined effect of EPS on Fe solubility and bioavailability, it can increase the residence time of bioavailable Fe in the euphotic zone, therefore possibly sustaining and controlling primary productivity in sensitive oceanic regions, such as the Southern Ocean.