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.     

Dissolved iron(II) in the Pacific Ocean: Measurements from the PO2 and P16N CLIVAR/CO2 repeat hydrography expeditions

The redox speciation of dissolved iron in seawater was evaluated at 121 locations in the Pacific Ocean at depths of 15-1000 m, using the method of luminol chemiluminescence. The results indicate that reduced iron, Fe(II), is ubiquitous in surface seawater with a relatively consistent pattern of occurrence. Surface maxima were present in most profiles, with median concentrations of 25-30 pM representing 12-14% of the total dissolved iron. Concentrations decreased monotonically with depth to<12 pM within the upper euphotic zone. This pattern was observed during both day and nighttime sampling events, which suggests that non-photochemical production mechanisms can produce photochemical-like signatures. Further, if theoretical rates of Fe(II) oxidation are applicable to the open ocean, then the employed sampling methods precluded assessment of photochemically-produced Fe(II), regardless of ambient light conditions. For this and other reasons, the concentrations reported here for the upper water column likely represent lower limits of labile iron concentration, and suggest that dissolved iron may be more available for uptake than previously believed. Deeper in the water column, Fe(II) was also frequently detected, though it constituted a small fraction of the total dissolved iron. Possible source mechanisms at these depths include thermal (dark) reduction of Fe(III) organic complexes or remineralization of sinking biogenic particles containing Fe(II). In the northern Philippine Sea between the Japanese coast and the Izu-Bonin volcanic arc system, Fe(II) concentrations were found to be atypically high, possibly because of high atmospheric dust deposition near the surface and transport of sediment-derived iron at depth.     

Silver in the subarctic northeast Pacific Ocean: Explaining the basin scale distribution of silver

Five vertical profiles of silver (Ag) in the subarctic northeast Pacific are presented. Dissolved (< 0.2 μm) Ag concentrations within the surface mixed layer range from 6–25 pM, with the highest observed values at the most coastal site. Elevated Ag concentrations at this station are most likely attributable to the estuarine circulation in the Juan de Fuca Strait. One open-ocean station (P20) exhibited a strong surface Ag maximum. The station was located at the edge of a Haida eddy which raises the possibility that such eddies transport Ag seaward from the coastal zone. Ag concentrations in the deep waters ranged from 60–80 pM. These measurements are consistent with other recent Ag data collected in the Pacific. Ag profiles throughout the Pacific Ocean yield a strong positive correlation between Ag concentration and dissolved silicic acid concentration. However, Ag is depleted relative to silicic acid at intermediate depths where dissolved O₂ concentrations are low, implying a possible removal of Ag from oxygen-depleted waters by scavenging and/or precipitation.     

Organic complexation of iron in the Southern Ocean

The chemical speciation of iron was determined in the Southern Ocean along a transect from 48 to 70°S at 20°E. Dissolved iron concentrations were low at 0.1–0.6 nM, with average concentrations of 0.25±0.13 nM. Organic iron complexing ligands were found to occur in excess of the dissolved iron concentration at 0.72±0.23 nM (equivalent to an excess of 0.5 nM), with a complex stability of log K_FeL′=22.1±0.5 (on the basis of Fe³⁺ and L′). Ligand concentrations were higher in the upper water column (top 200 m) suggesting in situ production by microorganisms, and less at the surface consistent with photochemical breakdown. Our data are consistent with the presence of stable organic iron-complexing ligands in deep global ocean waters at a background level of ∼0.7 nM. It has been suggested that this might help stabilise iron at levels of ∼0.7 nM in deep ocean waters. However, much lower iron concentrations in the waters of the Southern Ocean suggest that these ligands do not prevent the removal of iron (by scavenging or biological uptake) to well below the concentration of these ligands. Scavenging reactions are probably inhibited by such ligand competition, so it is likely that biological uptake is the chief cause for the further removal of iron to these low levels in waters that suffer from very low iron inputs.     

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.     

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.     

Reduced iron associated with secondary nitrite maxima in the Arabian Sea

Dissolved iron and Fe(II) were measured in the oxygen minimum zone (OMZ) of the Arabian Sea in September 2004. The OMZ is a well-demarcated feature characterized by high rates of denitrification, and a deep nitrite maximum coinciding with oxygen levels below 1 μmol L⁻¹. This zone is significantly enriched in dissolved Fe relative to overlying and underlying waters and up to 50% of the dissolved Fe is present as Fe(II). The maxima in Fe(II) are at the same depth as the deep nitrite maxima, centered around 200–250 m. They coincide with a local maximum in total dissolved Fe, suggesting that Fe accumulates at this depth because of the greater solubility of Fe(II) over Fe(III). Fe(II) is thermodynamically unstable even at submicromolar oxygen levels, so active biological reduction is the most plausible source. To our knowledge, this is the first report of a potential link between Fe reduction, elevated dissolved Fe concentrations, and nitrite accumulation within an OMZ. Denitrification has a high Fe requirement associated with the metalloenzymes for nitrate and nitrite reduction, so in situ redox cycling of Fe has important implications for the nitrogen cycle.     

Production and air–sea flux of halomethanes in the western subarctic Pacific in relation to phytoplankton pigment concentrations during the iron fertilization experiment (SEEDS II)

Iron could play a key role in controlling phytoplankton biomass and productivity in high-nutrient, low-chlorophyll regions. As a part of the iron fertilization experiment carried out in the western subarctic Pacific from July to August 2004 (Subarctic Pacific iron Experiment for Ecosystem Dynamics Study II—SEEDS II), we analysed the concentrations of trace gases in the seawater for 12 d following iron fertilization. The mean concentrations of chlorophyll a in the mixed layer (5–30 m depth) increased from 0.94 to 2.81 μg L^–1 for 8 d in the iron patch. The mean concentrations of methyl bromide (CH₃Br; 5–30 m depth) increased from 6.4 to 13.4 pmol L^–1 for 11 d; the in-patch concentration increased relative to the out-patch concentration. A linear correlation was observed between the concentrations of 19′-hexanoyloxyfucoxanthin, which is a biomarker of several prymnesiophytes, and CH₃Br in the seawater. After fertilization, the air–sea flux of CH₃Br inside the patch changed from influx to efflux from the ocean. There was no clear evidence for the increase in saturation anomaly of methyl chloride (CH₃Cl) due to iron fertilization. Furthermore, CH₃Cl fluxes did not show a tendency to increase after fertilization of the patch. In contrast to CH₃Br, no change was observed in the concentrations of bromoform (in-patch day 11 and out-patch day 11: 1.7 and 1.7 pmol L^–1), dibromomethane (2.1 and 2.2 pmol L^–1), and dibromochloromethane (1.0 and 1.2 pmol L^–1, respectively). The concentration of isoprene, which is known to have a relationship with chlorophyll a, did not change in this study. The responses of trace gases during SEEDS II differed from the previous findings (in situ iron enrichment experiment—EisenEx, Southern Ocean iron experiment—SOFeX, and Subarctic Ecosystem Response to Iron Enrichment Study—SERIES). Thus, in order to estimate the concomitant effect of iron fertilization on the climate, it is important to assess the induction of biological activity and the distributions/air–sea fluxes of trace gases by iron addition.     

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.     

Size-fractionated biological iron and carbon uptake along a coastal to offshore transect in the NE Pacific

Iron has been shown to limit phytoplankton growth in high-nutrient low-chlorophyll (HNLC) regions such as the NE subarctic Pacific. We report size-fractionated Fe-uptake rates by the entire plankton community in short (6–8 h) light and dark incubations along an E–W transect from P04 (a coastal ocean station) to OSP (an open-ocean HNLC station) during August–September 1997. Size-fractionated primary productivity and chl a were measured to monitor algal Fe : C uptake ratios and Fe-uptake relative to phytoplankton biomass. The >5.0 μm size-class, which consisted mostly of large diatoms, had the highest Fe-uptake rate at nearshore stations (P04 and P8), but Fe-uptake rates for this size class decreased despite increases in biomass and primary productivity when transecting westwards to HNLC waters. Fe-uptake rates of the small size class (0.2–1.0 μm, including heterotrophic bacteria and autotrophs) were inversely related to the >5.0 μm size-class uptake rates, in that stations with high dissolved Fe (DFe) concentrations had relatively low uptake rates compared to those in the low-Fe offshore region. The 1.0–5.0 μm size-class Fe-uptake rates were low, relatively invariant along the transect, and differed little between light and dark incubations. Dark Fe-uptake rates averaged 10–20% less than those in the light for the >5.0 μm size class. Dark uptake rates however, were higher than light uptake rates for the 0.2–1.0 μm size class at all stations. Fe : C uptake ratios were high for all size classes at P04, but decreased as DFe concentrations decreased offshore. The prokaryote-dominated 0.2–1.0 μm size class had the highest Fe : C uptake ratios at all stations. These data suggest that prokaryotic organisms make an important contribution to biological Fe uptake in this region. Our experiments support the results of previous culture work, suggesting higher Fe : C ratios in coastal phytoplankton compared to open-ocean species, and demonstrate that light can have a large effect on Fe partitioning between size classes in subarctic Pacific HNLC waters.     

Deep-water circulation at low latitudes in the western North Pacific

Full-depth conductivity-temperature-depth-oxygen profiler (CTDO₂) data at low latitudes in the western North Pacific in winter 1999 were analyzed with water-mass analysis and geostrophic calculations. The result shows that the deep circulation carrying the Lower Circumpolar Water (LCPW) bifurcates into eastern and western branch currents after entering the Central Pacific Basin. LCPW colder than 0.98°C is carried by the eastern branch current, while warmer LCPW is carried mainly by the western branch current. The eastern branch current flows northward in the Central Pacific Basin, supplying water above 0.94°C through narrow gaps into an isolated deep valley in the Melanesian Basin, and then passes the Mid-Pacific Seamounts between 162°10′E and 170°10′E at 18°20′N, not only through the Wake Island Passage but also through the western passages. Except near bottom, dissolved oxygen of LCPW decreases greatly in the northern Central Pacific Basin, probably by mixing with the North Pacific Deep Water (NPDW). The western branch current flows northwestward over the lower Solomon Rise in the Melanesian Basin and proceeds westward between 10°40′N and 12°20′N at 150°E in the East Mariana Basin with volume transport of 4.1 Sv (1 Sv=10⁶ m³ s⁻¹). The current turns north, west of 150°E, and bifurcates around 14°N, south of the Magellan Seamounts, where dissolved oxygen decreases sharply by mixing with NPDW. Half of the current turns east, crosses 150°E at 14–15°N, and proceeds northward primarily between 152°E and 156°E at 18°20′N toward the Northwest Pacific Basin (2.1 Sv). The other half flows northward west of 150°E and passes 18°20′N just east of the Mariana Trench (2.2 Sv). It is reversed by a block of topography, proceeds southward along the Mariana Trench, then detours around the south end of the trench, and proceeds eastward along the Caroline Seamounts to the Solomon Rise, partly flowing into the West Mariana and East Caroline Basins. A deep western boundary current at 2000–3000 m depth above LCPW (10.0 Sv) closes to the coast than the deep circulation. The major part of it (8.5 Sv) turns cyclonic around the upper Solomon Rise from the Melanesian Basin and proceeds along the southern boundary of the East Caroline Basin. Nearly half of it proceeds northward in the western East Caroline Basin, joins the current from the east, then passes the northern channel, and mostly enters the West Caroline Basin (4.6 Sv), while another half enters this basin from the southern side (>3.8 Sv). The remaining western boundary current (1.5 Sv) flows over the middle and lower Solomon Rise, proceeds westward, then is divided by the Caroline Seamounts into southern (0.9 Sv) and northern (0.5 Sv) branches. The southern branch current joins that from the south in the East Caroline Basin, as noted above. The northern branch current proceeds along the Caroline Seamounts and enters the West Mariana Basin.     

Spatial and seasonal evolution of dissolved oxygen and nutrients in the Southern Levantine Basin (Eastern Mediterranean Sea): chemical characterization of the water masses and inferences on the N : P ratios

The spatial and seasonal variability of nutrients and dissolved oxygen concentrations as well as the chemical characterization of the different water masses of the Southern Levantine Basin were determined in detail. In summer, the upper 150 m of the water body was stratified and the cross basin distribution of dissolved oxygen and nutrients was fairly constant. Surficial waters were saturated with dissolved oxygen, and a shallow oxygen maximum (oversaturated) was present at about 80 m depth. Oversaturation was attributed mainly to the physical process of rapid capping and trapping of oxygen in the Atlantic water (AW) mass, with only 28% of the excess oxygen originating from biological production. Nutrient concentrations were very low and showed an increase in the intermediate levels, coupled with a decrease in oxygen. The winter cross-section distribution showed an upper mixed layer of 100 m, with dissolved oxygen and nutrient concentrations fairly constant across the basin. The concentration of nitrate was higher than in summer, while phosphate was slightly lower and silicic acid similar. In winter, the influence of the physical features (gyres) could be detected up to the surface, and in summer they were detected by the chemical properties in the 150–600 m layer. In the transition layer between the Levantine intermediate water (LIW) and the deep water (DW) (400–700 m) there was a gradual decrease in dissolved oxygen and an increase in nutrient concentrations eastwards. The DW showed no seasonal variation, only spatial variability: dissolved oxygen decreased and silicic acid increased eastwards. No differences were found in nitrate and phosphate concentrations between the DW in the western and eastern provinces, indicating the oxidation of organic matter poor in N and P.N : P ratios in the upper water masses were seasonally dependent. The largest variation was found in the Levantine surface water (LSW), from an average of 52 in winter to 5 in summer. It is hypothesized that the gradual decrease from winter to summer values was due mainly to preferential atmospheric input of N in winter and P in summer, together with biological consumption and differential regeneration of N and P. In the DW, the N : P ratios were constant throughout the year (25.2±2.7, n=567), and higher than Redfield's ratio. It was speculated that the high N : P ratio in the DW was a result of oxidation of particulate organic matter deficient in P.The winter wet atmospheric input of N provided 12% of new N to the LSW. Average new production for the Southern Levantine Basin was estimated from the new N as 4.75 g C m⁻² yr⁻¹. The dry atmospheric contribution of P was estimated to significantly increase the P pool in the LSW. Dry deposition is not evenly distributed and occurs in episodic and localized events, which may have a large effect on productivity in the short periods when deposition occurs.There have been recently reported changes in the deep thermohaline circulation of the Eastern Mediterranean, with main contribution of the Aegean Sea as a source of DW. The data presented here can serve as a reference for assessing future changes in the chemical composition of the water masses in the Southern Levantine.     

Spatial and temporal variability of POC in the northeast Subarctic Pacific

Particulate organic carbon (POC) concentrations from 0 to 1000 m were quantified in size-fractionated particulate matter samples obtained by the multiple unit large volume in situ filtration system (MULVFS) in 1996 and 1997 along the 1600 km long “line P” transect from continental slope waters near southern Vancouver Island to Ocean Station PAPA (OSP, 50°N, 145°W). Regression of in situ POC vs. beam attenuation coefficient, c, from a simultaneously deployed 1-m pathlength SeaTech transmissometer gave slope, intercept and r² values of 6.15±0.19×10⁻⁵ m⁻¹ (nmol C l⁻¹)⁻¹, 0.363±0.003 m⁻¹, and 0.951 (n=145), respectively. This result agreed within several percent of calibrations obtained from two 2600-km-long transects of the equatorial Pacific in 1992 (Bishop, 1999). Data from other, more frequently deployed transmissometers were standardized against the 1-m instrument, and the combined optical data set was used to document POC variability at finer spatial and temporal scales than could be sampled directly using either conventional water bottle casts or MULVFS. Published bottle POC vs. c relationships show much more variability and remain problematic. Along the line P transect in the salinity-stratified upper 100 m, POC isolines shoaled from winter to summer in concert with seasonal stratification. At the same time, POC was progressively enriched in subeuphotic zone waters to depths greater than 500 m. Near-surface POC fields sampled in the winter time showed strong temporal POC variability over time scales of days as well as between years. POC concentrations at OSP in February 1996 were higher than those found at any other time of year. Less variability was found along line P in other seasons. In May 1996, kilometer-scale spatial variability of POC at OSP was small; dawn vs. dusk variations of c were used to calculate 0–100 m POC turnover times shorter than 6 d. Calculations also suggest that 25–50% of primary productivity was expressed as dissolved organic carbon at OSP in May 1996.     

Vertical and horizontal extension of the oxygen minimum zone in the eastern South Pacific Ocean

Recent hydrographic measurements within the eastern South Pacific (1999–2001) were combined with vertically high-resolution data from the World Ocean Circulation Experiment, high-resolution profiles and bottle casts from the World Ocean Database 2001, and the World Ocean Atlas 2001 in order to evaluate the vertical and horizontal extension of the oxygen minimum zone (<20 μmol kg⁻¹). These new calculations estimate the total area and volume of the oxygen minimum zone to be 9.82±3.60×10⁶ km² and 2.18±0.66×10⁶ km³, respectively. The oxygen minimum zone is thickest (>600 m) off Peru between 5 and 13°S and to about 1000 km offshore. Its upper boundary is shallowest (<150 m) off Peru, shoaling towards the coast and extending well into the euphotic zone in some places. Offshore, the thickness and meridional extent of the oxygen minimum zone decrease until it finally vanishes at 140°W between 2° and 8°S. Moving southward along the coast of South America, the zonal extension of the oxygen minimum zone gradually diminishes from 3000 km (15°S) to 1200 km (20°S) and then to 25 km (30°S); only a thin band is detected at ∼37°S off Concepción, Chile. Simultaneously, the oxygen minimum zone's maximum thickness decreases from 300 m (20°S) to less than 50 m (south of 30°S). The spatial distribution of Ekman suction velocity and oxygen minimum zone thickness correlate well, especially in the core. Off Chile, the eastern South Pacific Intermediate Water mass introduces increased vertical stability into the upper water column, complicating ventilation of the oxygen minimum zone from above. In addition, oxygen-enriched Antarctic Intermediate Water clashes with the oxygen minimum zone at around 30°S, causing a pronounced sub-surface oxygen front. The new estimates of vertical and horizontal oxygen minimum zone distribution in the eastern South Pacific complement the global quantification of naturally hypoxic continental margins by Helly and Levin [2004. Global distribution of naturally occurring marine hypoxia on continental margins. Deep-Sea Research I 51, 1159–1168] and provide new baseline data useful for studies on the role of oxygen in the degradation of organic matter in the water column and the related implications for biogeochemical cycles. Coastal upwelling zones along the eastern Pacific combine with general circulation to provide a mechanism that allows renewal of upper Pacific Deep Water, the most oxygen-poor and oldest water mass of the world oceans.     

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.     

Volume transport and distribution of deep circulation at 165°W in the North Pacific

We conducted full-depth hydrographic observations between 8°50′ and 44°30′N at 165°W in 2003 and analyzed the data together with those from the World Ocean Circulation Experiment and the World Ocean Database, clarifying the water characteristics and deep circulation in the Central and Northeast Pacific Basins. The deep-water characteristics at depths greater than approximately 2000 dbar at 165°W differ among three regions demarcated by the Hawaiian Ridge at around 24°N and the Mendocino Fracture Zone at 37°N: the southern region (10–24°N), central region (24–37°N), and northern region (north of 37°N). Deep water at temperatures below 1.15 °C and depths greater than 4000 dbar is highly stratified in the southern region, weakly stratified in the central region, and largely uniform in the northern region. Among the three regions, near-bottom water immediately east of Clarion Passage in the southern region is coldest (θ<0.90 °C), most saline (S>34.70), highest in dissolved oxygen (O₂>4.2 ml l^?1), and lowest in silica (Si<135 μmol kg^?1). These characteristics of the deep water reflect transport of Lower Circumpolar Deep Water (LCDW) due to a branch current south of the Wake–Necker Ridge that is separated from the eastern branch current of the deep circulation immediately north of 10°N in the Central Pacific Basin. The branch current south of the Wake–Necker Ridge carries LCDW of θ<1.05 °C with a volume transport of 3.7 Sv (1 Sv=10⁶ m³ s^?1) into the Northeast Pacific Basin through Horizon and Clarion Passages, mainly through the latter (～3.1 Sv). A small amount of the LCDW flows northward at the western boundary of the Northeast Pacific Basin, joins the branch of deep circulation from the Main Gap of the Emperor Seamounts Chain, and forms an eastward current along the Mendocino Fracture Zone with volume transport of nearly 1 Sv. If this volume transport is typical, a major portion of the LCDW (～3 Sv) carried by the branch current south of the Wake–Necker and Hawaiian Ridges may spread in the southern part of the Northeast Pacific Basin. In the northern region at 165°W, silica maxima are found near the bottom and at 2200 dbar; the minimum between the double maxima occurs at a depth of approximately 4000 dbar (θ～1.15 °C). The geostrophic current north of 39°N in the upper deep layer between 1.15 and 2.2 °C, with reference to the 1.15 °C isotherm, has a westward volume transport of 1.6 Sv at 39–44°30′N, carrying silica-rich North Pacific Deep Water from the northeastern region of the Northeast Pacific Basin to the Northwest Pacific Basin.     

A segment-scale survey of the Broken Spur hydrothermal plume

We conducted a segment-scale hydrothermal plume survey of the Broken Spur segment, 29°00-20′N, Mid-Atlantic Ridge (MAR). The purpose of the study was to identify the distribution of sources of venting throughout the segment as part of a larger study of hydrothermal fluxes. Evidence from plume particle concentrations (as deduced from in situ nephelometer data) and total dissolvable Mn (TDMn) analyses (from discrete water samples) indicated a restricted source of venting close to the segment centre, coincident with the previously known vent-site. No other pronounced plume signals were observed outside an area bounded by 29°07.5–12.5′N and 43°10–12′W, representing less than 10% of the >300 km² of deep water (>2600 m) within the segment. In addition, however, low-level (<2 nmol l^-1) deepwater TDMn concentrations reveal a pervasive enrichment throughout the segment of ⩾0.15 nmol l^-1. For the 4×1011 m³ of deepwater within the Broken Spur segment, this corresponds to a standing crop of 6×10⁴ mol of hydrothermal Mn. Future studies of long-term current flow will allow the flux of dissolved Mn out of the segment to be established and will investigate the partitioning of its source, between high temperature and axial diffuse flow.     

Deep-circulation current through the Main Gap of the Emperor Seamounts Chain in the North Pacific

The deep-circulation current in the North Pacific carries lower circumpolar deep water (LCDW), which is characterized by high dissolved oxygen and low echo intensity of reflected sound pulses. Using the characteristics of LCDW, we examined a branch current of the deep circulation passing through the Main Gap of the Emperor Seamounts Chain (ESC) by analyzing conductivity temperature depth profiler (CTD) data and data of velocity and echo intensity from a lowered acoustic Doppler current profiler (LADCP), which were obtained along 170°E immediately west of the ESC, along 180°W and 175°W over the northern slope of the Hess Rise, and along 165°W. The velocity and water characteristics showed that the eastern branch current of the deep circulation, which has penetrated into the Northwest Pacific Basin (NWPB) through Wake Island Passage, bifurcates around 30°N, 170°E in the NWPB into the westward main stream and a northward branch current, and that the latter current proceeds along the western side of the ESC and passes through the Main Gap of the ESC, flowing eastward. The current in the Main Gap at 170°E flows southeastward with eastward velocity cores around 4000 dbar and at depths greater than 4800 dbar centered at 5400 dbar. The current in the deeper core is stronger and reaches a maximum velocity of approximately 10 cm s^?1. The eastward current in the Main Gap enters the Northeast Pacific Basin (NEPB) and flows eastward along the northern slope of the Hess Rise. As the current flows downstream, the characteristics of LCDW carried by the current are diluted gradually. To the east of the Hess Rise, the branch current joins another branch current of the deep circulation from the south carrying less-modified LCDW. As a result, LCDW carried from the Main Gap is renewed by mixing with the less-modified LCDW coming from the south. Carrying the mixed LCDW, the confluence flows eastward south of 37°N at 165°W toward the northeastern region of the NEPB, where the LCDW overturns and changes to North Pacific Deep Water (NPDW). NPDW is probably carried by the westward current in the upper deep layer north of 37°N at 165°W.     

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.     

Occurrence and turnover of DMSP and DMS in deep waters of the Ross Sea,Antarctica

High concentrations of the phytoplankton metabolite dimethylsulfoniopropionate (DMSP) and its degradation product dimethylsulfide (DMS) are associated with blooms of Phaeocystis antarctica in the Ross Sea, Antarctica. Episodic and rapid vertical export of Phaeocystis biomass to deep water has been reported for the Ross Sea, therefore we examined the distribution and microbial consumption rates of DMSP and DMS throughout the sub-euphotic water column. Total DMSP (dissolved+particulate; DMSPt) was present at 0.5–22 nM at depths between 70 and 690 m during both the early bloom (November) and the late bloom (January). Sub-euphotic peaks of DMSP were sometimes associated with mid-water temperature maxima, and elevated DMSP below 70 m was found mainly in water masses characterized as Modified Circumpolar Deep Water or Antarctic Shelf Water. Overall, 50–94% of the integrated water-column DMSPt was found below the euphotic zone. At one station during the early bloom, local maxima of DMSPt (14 nM) and DMS (20 nM) were observed between 113 and 240 m and these maxima corresponded with high chlorophyll a concentrations, P. antarctica cell numbers, and Fv/Fm (the quantum yield of photosystem II). During the late bloom, a sub-euphotic maximum of DMSPt (15.8 nM) at 250 m cooccurred with peaks of chlorophyll a concentration, DMSP lyase activity, bacterial production and dissolved DMSP consumption rates. DMSP turnover contributed ～12% of the bacterial carbon demand between 200 and 400 m. DMS concentrations peaked at 286 m but the maximum concentration (0.42 nM) was far lower than observed during the early bloom, probably because of relatively rapid biological consumption of DMS (1–3 turnovers per day) which, in turn, contributed to elevated dissolved dimethylsulfoxide (DMSO) concentrations. Relatively stable DMSPt distributions at some sites suggest that rapid sinking of Phaeocystis biomass is probably not the major mechanism responsible for mesopelagic DMSP accumulations. Rather, subduction of near-surface water masses, lateral advective transport or trapping of slowly sinking P. antarctica biomass in intermediate water masses are more likely mechanisms. We found that a culture of P. antarctica maintained cellular integrity during 34 days of darkness, therefore the presence of intact cells (and DMSP) at depth can be explained even under a slow sinking/advection scenario. Whatever the mechanism, the large pools of DMSP and DMS below the euphotic zone suggest that export exerts a control on potential DMS emission from the surface waters of the Ross Sea.