Physical behaviors of the iron-fertilized patch in SEEDS II

Sulfur hexafluoride (SF₆) tracer release experiments were carried out to trace the iron-fertilized water mass during the iron-fertilization experiments in the western North Pacific of Subarctic Pacific Iron Experiment for Ecosystem Dynamics Study II (SEEDS II) in 2004. A solution of Fe and SF₆ tracer was released into the surface mixed layer over an 8×8 km area, and the fertilized patch was traced by onboard SF₆ analysis for 12 days during each experiment. A Lagrangian frame of reference was maintained by the use of a drogued GPS buoy released at the center of the patch to reduce the advection effect on observations. The patch moved along the contour of sea-surface height (SSH) of a clockwise mesoscale eddy for 4 days after release. Then strong easterly winds dragged the patch across the contour of SSH. The patch behavior was affected by both the mesoscale eddy and surface winds. Apparent horizontal diffusivities were determined by the change of the distribution of SF₆ concentrations. The averaged apparent horizontal diffusivity was about 49 m² s⁻¹ during SEEDS II. It was larger than the one in SEEDS. Mixed-layer depth (MLD) was 8.5–18 m during SEEDS, and 12–33 m during SEEDS II. The larger horizontal diffusivity and deeper MLD in SEEDS II were disadvantages to maintain a high iron concentration in the surface layer compared to SEEDS. Temporal change of the MLD corresponded to the temporal change of chlorophyll-a concentration. Temporal change in the surface MLD was also important for the response of phytoplankton by iron fertilization.     

Did dilution limit the phytoplankton response to iron addition in HNLCLSi sub-Antarctic waters during the SAGE experiment?

An in situ iron addition experiment (SAGE) was carried out in high-nitrate low-chlorophyll low-silicic acid (HNLCLSi) sub-Antarctic surface waters south-east of New Zealand. In contrast to other iron addition experiments, the phytoplankton response was minor, with a doubling of biomass relative to surrounding waters, with the temporal trends in dissolved iron and macronutrients instead dominated by physical factors such as mixing and dilution. The initial increase in patch surface area indicated a lateral dilution rate of 0.125 d⁻¹, with a second estimate from a model of the decline in peak SF₆ concentration yielding a higher lateral dilution rate of 0.16-0.25 d⁻¹. The model was tested on the SOIREE SF₆ dataset and provided a lateral dilution of 0.07 d⁻¹, consistent with previous published estimates. MODIS ocean colour images showed elevated chlorophyll coincident with the SF₆ patch on day 10 and 12, and an elevated chlorophyll filament at the SAGE experiment location 3-4 days after ship departure, which provided additional lateral dilution estimates of 0.19 and 0.128 d⁻¹. Dissolved iron at the patch centre declined by 85% within two days of the initial infusion, of which dilution accounted for 50-65%; it also decreased rapidly after the 2nd and 3rd infusions but remained elevated after the fourth infusion. Despite decreases in nitrate and silicic acid from day 7 and 10, respectively, the final nutrient concentrations in the patch exceeded the initial concentrations due to supply from lateral intrusion and mixed-layer deepening. The low Si:N loss ratio suggested that the observed limited response to iron was primarily by non-siliceous phytoplankton. Algal growth rate exceeded the minimum dilution rate during two periods (days 3-6 and 10-14), and coincided with net chlorophyll accumulation. However, as the ratio of algal growth to dilution was the lowest reported for an iron addition experiment, dilution was clearly a significant factor in the SAGE experiment recording the lowest phytoplankton response to mesoscale iron addition.     

Distribution of Trace Bioelements in the Subarctic North Pacific Ocean and the Bering Sea (the R/V Hakuho Maru Cruise KH-97-2)

A column concentration-high resolution inductively coupled plasma mass spectrometry (ICP-MS) determination was applied to measure the total dissolved concentrations of Fe, Co, Ni, Cu and Zn in seawater collected from the subarctic North Pacific (~45°N) and the Bering Sea in July–September 1997. Total adsorbable Mn was determined on board by column electrolysis preconcentration and chemiluminescence detection. The vertical profiles for Fe, Ni and Zn were nutrient-like. The deep water concentration of Fe was ~0.5 nM in the northeast Pacific (18°-140°W) and increased to ~1 nM in the northwest Pacific (161°E) and ~2 nM in the Bering Sea (57°N, 180°E). The deep water concentrations for Ni and Zn in the Bering Sea were also 1.3–2 times higher than in the North Pacific. The profiles for Co and Cu were examined in the subarctic North Pacific, and results obtained were consistent with previous reports. There was a significant correlation between the concentrations of Co and Mn except for surface mixed layer. The profiles for total adsorbable Mn were similar to the reported profiles for total dissolvable Mn. The deep water concentration of Mn in the Bering Sea was also 4 times higher than in the North Pacific. Iron and zinc were depleted in surface water of the subarctic North Pacific. The relationship between these trace elements and nutrients suggests that these elements could be a limiting factor of phytoplankton productivity. In the Bering Sea, surface water contained ~0.3 nM of Fe. The Zn concentration, which was less than the detection limit in surface water, increased at shallower depths (~30 m) compared with the subarctic North Pacific. These results imply a higher flux of Fe and Zn to surface water in the Bering Sea. This in turn may cause the ecosystem in the Bering Sea characterized by a dominance of diatoms and high regenerated production.     

Concentration and Regeneration of Cd in the Japan Sea Proper Water

The concentration level of cadmium (Cd) and the regeneration related to phosphate (PO₄) were examined at two stations (CM10, CM12) in the eastern Japan Basin in July 1998. The observed Cd concentrations were around 0.2–0.3 nM and 0.5–0.6 nM in the surface and deep layers (Japan Sea Proper Water; JSPW), respectively; the concentration of Cd in the JSPW was much lower than that in the Pacific deep water, which is attributed to its specific formation system (which driven by the winter convection of the surface layer within the Japan Sea, thereafter descending to the deep layer) connected with the relatively active vertical mixing in the Japan Sea. A plot of Cd against PO₄ showed good linearity with positive y-intercept values, suggesting that the excess Cd was apparently not available in the biogeochemical cycle. The molecular ratios of consumed O₂ to regenerated Cd and PO₄ in the JSPW were 688,000, 140 and 881,000, 146 for CM10 and CM12, respectively, and a lower preformed Cd concentration (around 0.37 nM) was also estimated in the JSPW, different from that of the North Pacific deep water (613,000 for Cd, 170 for PO₄, and 0.64 nM of preformed Cd).     

Comparison of Time-Dependent Tracer Ages in the Western North Pacific: Oceanic Background Levels of (SF6, CFC-11, CFC-12 and CFC-113

To verify the actual usefulness of time-dependent tracer dating techniques in the ocean, we simultaneously obtained two cross sections of sulfur hexafluoride (SF₆) and chlrofluoromethanes (CFC-11, trichlorofluoromethane; CFC-12, dichloro-difluromethane; CFC-113, trichlorotrifluoroethane) in the western North Pacific in 1998. The vertical distribution patterns of SF₆ and CFC-113 were similar in shape to those of CFC-11 and CFC-12. Maximum penetration depths of SF₆ and CFC-113 remained around 800 m in the subpolar region and 400 m in the tropical region, while the maximum penetration depths of CFC-11 and CFC-12 were still found below 1000 m depth. We also found all maximum contents of these tracers around 26.6−26.8σ_θ with a gradual decrease southward. This suggested that a new subsurface water mass in the subpolar region spread out over the entire North Pacific, which agrees closely with previous studies based on the salinity minimum. Moreover, we compared the tracer ages (the elapsed period of a water mass from when the water mass left from the ocean surface) using ten time-dependent tracer dating techniques, CFC-11, CFC-12, CFC-113, SF₆, CFC-11/CFC-12, CFC-113/CFC-11, CFC-113/CFC-12, SF₆/CFC-11, SF₆/CFC-12 and SF₆/CFC-113. This quantitative evaluation of multiple tracer dating techniques in the ocean was the first confirmation of its usefulness based on the observational data on the ocean basin-wide scale. We conclude that SF₆/CFC-11, SF₆/CFC-12, SF₆/CFC-113 and SF₆ dating techniques would be the most promising tools for determining the age of water mass not only just for the past several decades but for the future, too. This revised version was published online in July 2006 with corrections to the Cover Date.     

Responses of DMS in the seawater and atmosphere to iron enrichment in the subarctic western North Pacific (SEEDS-II)

Simultaneous measurements of dimethylsulfide (DMS) in the seawater and atmosphere were conducted during SEEDS-II to investigate the responses of DMS to iron (Fe) fertilization in the subarctic North Pacific. No significant increases in the seawater DMS (DMSw) concentration were observed inside the fertilized patch compared to those outside the patch, while particulate dimethylsulfoniopropionate (DMSPp) concentration inside the patch increased 2-fold compared to those outside the patch in the phytoplankton bloom of major DMSP producers such as prasinophytes, cryptophytes, diatoms and prymnesiophytes. In the decline phase of the bloom, maximum DMSw was observed both inside the patch (ca. 6.2 nM) and outside the patch (ca. 9.3 nM). In this period, increases in mesozooplankton and decreases in the DMSP producers (prymnesiophytes and diatoms) were observed both sides of the patch, but larger inside the patch than outside the patch. Large decreases in the DMSPp inside the patch, which was probably related to the large increases in mesozooplankton inside the patch, did not result in increases in the DMSw concentration. Considering biological and nonbiological parameters, we discussed these results, although they could not be completely explained. Unfortunately, the impact of Fe fertilization on the atmospheric DMS (DMSa) concentration was not detected due to no significant changes in DMSw. However, it is noted that DMSa concentrations were dependent on the sea–air DMS flux in the air from higher latitudes and/or the Eurasian continent, though the DMS flux was a minor role to the budget of DMSw. Therefore if DMSw were significantly changed by Fe fertilization, DMSa might be affected through changes in the sea-air flux in this condition.     

Behaviors of dissolved and particulate Co,Ni, Cu,Zn, Cd and Pb during a mesoscale Fe-enrichment experiment (SEEDS II) in the western North Pacific

During mesoscale Fe enrichment (SEEDS II) in the western North Pacific ocean, we investigated dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb in seawater from both field observation and shipboard bottle incubation of a natural phytoplankton assemblage with Fe addition. Before the Fe enrichment, strong correlations between dissolved trace metals (Ni, Zn and Cd) and PO₄³⁻, and between particulate trace metals (Ni, Zn and Cd) and chlorophyll-a were obtained, suggesting that biogeochemical cycles mainly control the distributions of Ni, Zn and Cd in the study area. Average concentrations of dissolved Co, Ni, Cu, Zn, Cd and Pb in the surface mixed layer (0–20 m) were 70 pM, 4.9, 2.1, 1.6, 0.48 nM and 52 pM, respectively, and those for the particulate species were 1.7 pM, 0.052, 0.094, 0.46, 0.037 nM and 5.2 pM, respectively. After Fe enrichment, chlorophyll-a increased 3 fold (up to 3 μg L⁻¹) during developing phases of the bloom (<12 days). Mesozooplankton biomass also increased. Particulate Co, Ni, Cu and Cd inside the patch hinted at an increase in the concentrations, but there were no analytically significant differences between concentrations inside and outside the patch. The bottle incubation with Fe addition (1 nM) showed an increase in chlorophyll-a (8.9 μg L⁻¹) and raised the particulate fraction up to 3–45% for all the metals, accompanying changes in Si/P, Zn/P and Cd/P. These results suggest that Fe addition lead to changes in biogeochemical cycling of trace metals. The comparison between the mesoscale Fe enrichment and the bottle incubation experiment suggests that although Fe was a limiting factor for the growth of phytoplankton, the enhanced biomass of mesozooplankton also limited the growth of phytoplankton and the transformation of trace metal speciation during the mesoscale Fe enrichment. Sediment trap data and the elemental ratios taken up by phytoplankton suggest that export loss was another reason that no detectable change in the concentrations of particulate trace metals was observed during the mesoscale Fe enrichment.     

Improved Method for Calculating Anthropogenic CO2 in the Upper Layer of the North Pacific Subtropical Gyre along 175°E

Seawater samples were collected in the North Pacific along 175°E during a cruise of the Northwest Pacific Carbon Cycle Study (NOPACCS) program in 1994. Many properties related to the carbonate system were analyzed. By using well-known ratios to correct for chemical changes in seawater, the CO₂ concentration at a given depth was back calculated to its initial concentration at the time when the water left the surface in winter. We estimated sea-surface CO₂ and titration alkalinity (TA) in present-day winter, from which we evaluated the degree of air-sea CO₂ disequilibrium in winter was. Using a correction factor for air-sea CO₂ disequilibrium in winter, we reconstructed sea-surface CO₂ in pre-industrial times. The difference between the back-calculated initial CO₂ and sea-surface CO₂ in pre-industrial times should correspond to anthropgenic CO₂ input. Although the mixing of different water masses may cause systematic error in the calculation, we found that the nonlinear effect induced by the mixing of different water masses was negligible in the upper layer of the North Pacific subtropical gyre along 175°E. The results of our improved method of assessing the distribution of anthropogenic CO₂ in that region show marked differences from those obtained using the previous back-calculation method.     

Iron-induced alterations of bacterial DMSP metabolism in the western subarctic Pacific during SEEDS-II

The effect of added iron on bacterial cycling of the climate-active gas dimethylsulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) was tested during the second Subarctic Pacific Iron Experiment for Ecosystem Dynamics Study (SEEDS II) from 19 July to 21 August 2004 aboard the R/V Hakuho-Maru. The study area in the northwest Pacific Ocean (48°N 165°E) was enriched with Fe and the conservative tracer, SF₆, allowing the fertilized patch to be tracked. Microbial DMSP cycling rates were determined in the surface mixed layer (5 m) during incubations using the ³⁵S-DMSP technique. The addition of iron resulted in a 4-fold increase in concentrations of chlorophyll a (chl a) within the surface mixed layer (5 m depth), and the length of the sampling period allowed the observation of both bloom and post-bloom conditions. Inside the fertilized patch, the alleviation of resource limitation gave rise to the concurrent increase in bacterial abundance and production. Changes in the phytoplankton community within the Fe-enriched patch translated into a sustained decrease in chl a-normalized particulate DMSP (DMSP_p) concentrations, suggesting a preferential stimulation of the growth of DMSP_p-poor phytoplankton species. Despite short-lived peaks of DMSP_p within the Fe-enriched area, concentrations of DMSP_p generally remained stable during the entire sampling period inside and outside the fertilized patch. During the Fe-induced bloom, microbial DMSP-sulfur (DMSP-S) assimilation efficiency increased 2.6-fold inside the Fe-enriched area, which indicated that as bacterial production increased, a greater proportion of DMSP-S was assimilated and possibly diverted away from the bacterial cleavage pathway (i.e. production of DMS). Our results suggest that iron-induced stimulation of weak DMSP_p-producers and DMSP-assimilating bacteria may diminish the potential production of DMS and thus limit its flux towards the atmosphere over the subarctic Pacific Ocean.     

An in situ iron-enrichment experiment in the western subarctic Pacific (SEEDS): Introduction and summary

To test the iron hypothesis in the subarctic Pacific Ocean, an in situ iron-enrichment experiment (SEEDS) was performed in the western subarctic gyre in July–August 2001. About 350 kg of iron (as acidic iron sulfate) and 0.48 mol of the inert chemical tracer sulfur hexafluoride were introduced into a 10-m deep surface mixed layer over an 80 km² area. This single iron infusion raised dissolved iron levels to 2.9 nM initially. Dissolved iron concentrations rapidly decreased after the infusion, but levels remained close to 0.15 nM even at the end of the 14-day experimental period. During SEEDS there were iron-mediated increases in chlorophyll a concentrations (up to 20 μg l⁻¹), primary production rates, biomass and photosynthetic energy conversion efficiency relative to waters outside the iron-enriched patch. The rapid and very high accumulation of phytoplankton biomass in response to the iron addition appeared to be partly attributable to shallow mixed-layer depth and moderate water temperature in the western subarctic Pacific. However, the main reason was a floristic shift to fast-growing centric diatom Chaetoceros debilis, unlike the previous iron-enrichment experiments in the equatorial Pacific and the Southern Ocean, in both of which iron stimulated the growth of pennate diatoms. The iron-mediated blooming of diatoms resulted in a marked consumption of macronutrients and drawdown of pCO₂. Biological and physiological measurements indicate that phytoplankton growth in the patch became both light- and iron-limited, making phytoplankton biomass relatively constant after day 9. The increase in microzooplankton grazing rate after day 9 also influenced the net growth rate of phytoplankton. There was no significant increase in the export flux of carbon to depth during the 14-day occupation of the experimental site. The export flux between day 4 and day 13 was estimated to be only 13% of the integrated primary production in the iron-enriched patch. The major part of the carbon fixed by the diatom bloom remained in the surface mixed layer as biogenic particulate matter. Our findings support the hypothesis that iron limits phytoplankton growth and biomass in a ‘bottom up’ manner in this area, but the fate of algal carbon remains unknown.     

Discharge and surface plume measurements during manganese nodule mining tests in the north equatorial pacific

Rates, concentrations, and composition of mining discharge and the size and structure of the ensuing surface plumes were examined during North Pacific tests of scaled manganese nodule mining systems. Discharge was composed principally of bottom water and pelagic silts and clays, although nodule fragments with diameters less than 1 mm were also discharged at widely varying rates. Average flow rates of the discharge varied from 95 to 160 litres/s, with the solid fraction varying from 550 to approximately 2000g/s. The plume, as determined by particulate concentrations in excess of ambient oceanic conditions, extended approximately 5 km from the mining ship and had a width of about 1 km. Fe and Mn signatures allowed detection of the plume nearly 35 km from the source. The plume provided evidence of settling more rapidly than expected of silt and clay-size particles: a mean settling velocity of 6 × 10^?2 cm/s for the particulates in the plume and a mixed layer vertical turbulent eddy diffusivity of 1 × 10^?2m²/s have been inferred from the data. Field and laboratory data together suggest that the rapid settling was due to flocculation of the discharge particulates.     

Dissolved iron(III) speciation in the high latitude North Atlantic Ocean

On voyages in the Iceland Basin in 2007 and 2009, we observed low (ca. 0.1 nM) total dissolved iron concentrations [dFe] in surface waters (<150 m), which increased with depth to ca. 0.2–0.9 nM. The surface water [dFe] was low due to low atmospheric Fe inputs combined with biological uptake, with Fe regeneration from microbial degradation of settling biogenic particles supplying dFe at depth. The organic ligand concentrations [L_T] in the surface waters ranged between 0.4 and 0.5 nM, with conditional stability constants (log K′_FeL) between 22.6 and 22.7. Furthermore, [L_T] was in excess of [dFe] throughout the water column, and dFe was therefore largely complexed by organic ligands (>99%). The ratio of [L_T]/[dFe] was used to analyse trends in Fe speciation. Enhanced and variable [L_T]/[dFe] ratios ranging between 1.6 and 5.8 were observed in surface waters; the ratio decreased with depth to a more constant [L_T]/[dFe] ratio in deep waters. In the Iceland Basin and Rockall Trough, enhanced [L_T]/[dFe] ratios in surface waters resulted from decreases in [dFe], likely reflecting the conditions of Fe limitation of the phytoplankton community in the surface waters of the Iceland Basin and the high productivity in the Rockall Trough.Below the surface mixed layer, the observed increase in [dFe] resulted in a decrease of the [L_T]/[dFe] ratios (1.2–2.6) with depth. This indicated that the Fe binding ligand sites became occupied and even almost saturated at enhanced [dFe] in the deeper waters. Furthermore, our results showed a quasi-steady state in deep waters between dissolved organic Fe ligands and dFe, reflecting a balance between Fe removal by scavenging and Fe supply by remineralisation of biogenic particles with stabilisation through ligands.     

Export Production in the Subarctic North Pacific over the Last 800 kyrs: No Evidence for Iron Fertilization?

The subarctic North Pacific is a high nitrate-low chlorophyll (HNLC) region, where phytoplankton growth rates, especially those of diatoms, are enhanced when micronutrient Fe is added. Accordingly, it has been suggested that glacial Fe-laden dust might have increased primary production in this region. This paper reviews published palaeoceanographic records of export production over the last 800 kyrs from the open North Pacific (north of ∼35°N). We find different patterns of export production change over time in the various domains of the North Pacific (NW and NE subarctic gyres, the marginal seas and the transition zone). However, there is no compelling evidence for an overall increase in productivity during glacials in the subarctic region, challenging the paradigm that dust-born Fe fertilization of this region has contributed to the glacial draw down of atmospheric CO₂. Potential reasons for the lack of increased glacial export production include the possibility that Fe-fertilization rapidly drives the ecosystem towards limitation by another nutrient. This effect would have been exacerbated by an even more stable mixed layer compared to today. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Western North Pacific Playing a Key Role in Global Biogeochemical Fluxes

The oceanic biogeochemical fluxes in the North Pacific, especially its northwestern part, are discussed to prove their importance on a global scale. First, the air-sea exchange processes of chemical substances are considered quantitatively. The topics discussed are sea salt particles transported to land, sporadic transport of soil dust to the ocean and its role in the marine ecosystem, the larger gas transfer velocity of CO₂ indicating the effect of bubbles, and DMS and greenhouse gases other than CO₂. Next, chemical tracers are utilized to reveal the water circulation systems in the region, which are the Pacific Deep Water including its vertical eddy diffusivity, the North Pacific Intermediate Water and the Japan Sea Deep Water. Thirdly, the particulate transport process of chemical substances through the water column is clarified by analyzing the distribution of insoluble radionuclides and the results obtained from sediment trap experiments. Fourthly, the northern North Pacific is characterized by stating the site decomposing organic matter and Si playing a key role in the marine ecosystem. Both are induced by the upwelled Pacific Deep Water. Fifthly, the oceanic CO₂ system related to global warming is presented by clarifying the distribution of anthropogenic CO₂ in the western North Pacific, and roles of the upwelled Pacific Deep Water and the continental shelf zone in the absorption of atmospheric CO₂. Finally, Mn and other chemical substances in sediments are discussed as recorders of the early diagenesis and indicators of low biological productivity during glacial ages in the northwestern North Pacific. It is concluded that the western North Pacific is characterized mainly by the Pacific Deep Water bringing nutrients to the northern North Pacific, located at the exit of the global deep water circulation and, therefore, the region plays a key role in the global biogeochemical fluxes. This revised version was published online in August 2006 with corrections to the Cover Date.     

Responses of phytoplankton and heterotrophic bacteria in the northwest subarctic Pacific to in situ iron fertilization as estimated by HPLC pigment analysis and flow cytometry

To verify the hypothesis that the growth of phytoplankton in the Western Subarctic Gyre (WSG), which is located in the northwest subarctic Pacific, is suppressed by low iron (Fe) availability, an in situ Fe fertilization experiment was carried out in the summer of 2001. Changes over time in the abundance and community structure of phytoplankton were examined inside and outside an Fe patch using phytoplankton pigment markers analyzed by high-performance liquid chromatography (HPLC) and flow cytometry (FCM). In addition, the abundance of heterotrophic bacteria was also investigated by FCM. The chlorophyll a concentration was initially ca. 0.9 μg l⁻¹ in the surface mixed layer where diatoms and chlorophyll b-containing green algae (prasinophytes and chlorophytes) were predominant in the chlorophyll biomass. After the iron enrichment, the chlorophyll a concentration increased up to 9.1 μg l⁻¹ in the upper 10 m inside the Fe patch on Day 13. At the same time, the concentration of fucoxanthin (a diatom marker) increased 45-fold in the Fe patch, and diatoms accounted for a maximum 69% of the chlorophyll biomass. This result was consistent with a microscopic observation showing that the diatom Chaetoceros debilis had bloomed inside the Fe patch. However, chlorophyllide a concentrations also increased in the Fe patch with time, and reached a maximum of 2.2 μg l⁻¹ at 5 m depth on Day 13, suggesting that a marked abundance of senescent algal cells existed at the end of the experiment. The concentration of peridinin (a dinoflagellate marker) also reached a maximum 24-fold, and dinoflagellates had contributed significantly (>15%) to the chlorophyll biomass inside the Fe patch by the end of the experiment. Concentrations of 19′-hexanoyloxyfucoxanthin (a prymnesiophyte marker), 19′-butanoyloxyfucoxanthin (a pelagophyte marker), and alloxanthin (a cryptophyte marker) were only incremented a few-fold increment inside the Fe patch. On the contrary, chlorophyll b concentration reduced to almost half of the initial level in the upper 10 m water column inside the Fe patch at the end of the experiment. A decrease with time in the abundance of eukaryotic ultraphytoplankton (<ca. 5 μm in size), in which chlorophyll b-containing green algae were possibly included was also observed by FCM. Overall, our results indicate that Fe supply can dramatically alter the abundance and community structure of phytoplankton in the WSG. On the other hand, cell density of heterotrophic bacteria inside the Fe patch was maximum at only ca. 1.5-fold higher than that outside the Fe patch. This indicates that heterotrophic bacteria abundance was little respondent to the Fe enrichment.     

Relationship between Cd and PO4 in the Subtropical Sea near the Ryukyu Islands

The relationship between dissolved cadmium (Cd) and phosphate (PO₄) was examined at three stations in the subtropical area near the Ryukyu Islands in May 1999. Preformed PO₄ was obtained using the Redfield ratio in order to separate the surface water and the other layers in this study area. Almost 0 μM (−0.043 μM to 0.094 μM) was estimated in the layers above 300 m and 250 m at Sts. 1 and 3 and at St. 2, respectively. Up to these depths, water was considered to be uniform, and these layers were defined as the surface water in this study area. In the surface water, the slopes of the regression lines of the Cd-PO₄ plot were 0.162, 0.156, and 0.226 (nM/μM) at Sts. 1, 2, and 3, respectively, and these values were much closer to the estimated regenerated ratio of Cd to PO₄ from the Apparent Oxygen Utilization (AOU)-Cd/PO₄ plots, which was 0.197 (nM/μM) in this study area. Below surface layers, the slopes of the Cd-PO₄ plot changed to 0.371, 0.352, and 0.362 (nM//μM) at Sts. 1, 2, and 3, respectively. In the relationships between Cd and PO₄, clear deviations or kinks were observed at three stations at a PO₄ concentration of approximately 0.2 μM in the plot, which was attributable to the discontinuity of surface water and the other layers across the North Pacific subtropical mode water. In studies of the interaction between surface water and biogenic particles concerning the Cd/PO₄ ratio, separate analyses of seawater (surface water and the other layers) should be carried out to obtain the individual surface water ratio because the Cd/PO₄ ratio in the surface water is expected to differ from that of the underlying water. Furthermore, the biological fractionation of these constituents is based on the surface water ratio. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preformed Cd and PO4 and the relationship between the two elements in the northwestern Pacific and the Okhotsk Sea

Preformed Cd and PO₄ were investigated in the northwestern Pacific (Station CM05) and the Okhotsk Sea (Station CM06), and the relationship between the two elements was examined. At CM05, from the apparent oxygen utilization (AOU)–Cd and PO₄ plot, the different molecular ratios of consumed O₂ to regenerated Cd and PO₄ were calculated to be 254,000 (Cd) and 96 (PO₄) for the shallow layer (30–99 m) and 613,000 (Cd) and 170 (PO₄) for the deep layer (below the oxygen minimum layer), which suggested the preferential remineralization of Cd and PO₄ in the shallow layer. At CM06, regeneration ratios of O₂/Cd, PO₄ were obtained only in the shallow layer (29–124 m) as 227,000 (Cd) and 75 (PO₄). The calculated preformed Cd and PO₄ concentrations in the shallow layer were 0.59 nM of Cd and 1.6 μM of PO₄ at CM05 and 0.35 nM of Cd and 0.95 μM of PO₄ at CM06. These concentrations were much higher than those (close to 0) in the low-latitude area, which was attributable to the supply of these constituents from deep water by the strong winter convection. In the deep layer, at CM05, preformed concentrations were 0.64 nM of Cd and 1.4 μM of PO₄. Preformed PO₄ generally agreed with previously reported values in the Pacific, which suggested that the concentrations of the initial PO₄ in the deep water were preserved as preformed through the movement to the northwestern Pacific. On the other hand, obtained preformed Cd in the northwestern Pacific deep water showed a somewhat higher value than that in the southwest Pacific. The possibility of the terrestrial input and remineralization of Cd by CaCO₃ dissolution during the northward movement was considered. A plot of Cd and PO₄ showed a linear relationship with slopes of 0.34 and 0.40 (nM/μM) at CM05 and CM06, respectively, which generally agreed with the reported values in the North Pacific.     

Seasonal variability of dissolved oxygen,percent oxygen saturation,and apparent oxygen utilization in the Atlantic and Pacific Oceans

Using objectively analyzed seasonal fields of dissolved oxygen content, percent oxygen saturation, and apparent oxygen utilization (AOU), we describe the large-scale seasonal variability of oxygen for the Atlantic and Pacific Oceans in the upper 400 m. The winter minus summer basin zonal averages of AOU reveal a two-layer feature in both the Atlantic and the Pacific, for both hemispheres. Biological activity and seasonal stratification in the summer give the upper 50–75 m of the water column in each basin a lower AOU in summer than winter. Greater mixing of upper ocean waters in winter gives the 75–400 m layer lower AOU values in that season. The basin integral seasonal volumes of oxygen for both the North Atlantic and the North Pacific mirror what is occurring in the atmosphere, indicating that there is a seasonal flux of oxygen across the air–sea interface. Winter total O₂ volume in the ocean is above the annual mean; the summer volume is below. Larger seasonal differences in the total O₂ content are observed in the North Atlantic Ocean than the North Pacific Ocean. A seasonal net outgassing (SNO) of 8.3×10¹⁴ moles O₂ is calculated from basin means, which is 25% higher than previous results.     

Remote effects of mixed layer development on ocean acidification in the subsurface layers of the North Pacific

Using the outputs of projections under the highest emission scenario of the representative concentration pathways performed by Earth system models (ESMs), we evaluate the ocean acidification rates of subsurface layers of the western North Pacific, where the strongest sink of atmospheric CO₂ is found in the mid-latitudes. The low potential vorticity water mass called the North Pacific Subtropical Mode Water (STMW) shows large dissolved inorganic carbon (DIC) concentration increase, and is advected southwestward, so that, in the sea to the south of Japan, DIC concentration increases and ocean acidification occurs faster than in adjacent regions. In the STMW of the Izu-Ogasawara region, the ocean acidification occurs with a pH decrease of ~0.004 year^?1 , a much higher rate than the previously estimated global average (0.0023 year^?1), so that the pH decreases by 0.3–0.4 during the twenty-first century and the saturation state of calcite (Ω_Ca) decreases from ~4.8 down to ~2.4. We find that the ESMs with a deeper mixed layer in the Kuroshio Extension region show a larger increase in DIC concentration within the Izu-Ogasawara region and within the Ryukyu Islands region. Comparing model results with the mixed layer depth obtained from the Argo dataset, we estimate that DIC concentration at a depth of ~200 m increases by 1.4–1.6 μmol kg^?1 year^?1 in the Izu-Ogasawara region and by 1.1–1.4 μmol kg^?1 year^?1 in the Ryukyu Islands region toward the end of this century.     

Surface layer mixing during the SAGE ocean fertilization experiment

Vessel-based observations of the oceanic surface layer during the 14-day 2004 SAGE ocean fertilization experiment were conducted using ADCP, CTD and temperature microstructure in a frame of reference moving with a patch of injected SF₆ tracer. During the experiment the mixed layer depth z_mld ranged between 50 and 80 m, with several re-stratifying events that brought z_mld up to less than 40 m. These re-stratifying events were not directly attributable to local surface-down development of stratification and were more likely associated with horizontal variation in density structure. Comparison between the CTD and a one-dimensional model confirmed that the SAGE experiment was governed by 3-d processes. A new method for estimating z_mld was developed that incorporates a component that is proportional to density gradient. This highlighted the need for well-conditioned near-surface data which are not always available from vessel-based survey CTD profiles. A centred-displacement scale, L_c, equivalent to the Thorpe lengthscale, reached a maximum of 20 m, with the eddy-centroid located at around 40 m depth. Temperature gradient microstructure-derived estimates of the vertical turbulent eddy diffusivity of scalar (temperature) material yielded bin-averaged values around 10⁻³ m² s⁻¹ in the pycnocline rising to over 10⁻² m² s⁻¹ higher in the surface layer. This suggests transport rates of nitrate and silicate at the base of the surface layer generate mixed layer increases of the order of 38 and 13 mmol/m²/day, respectively, during SAGE. However, the variability in measured vertical transport processes highlights the importance of transient events like wind mixing and horizontal intrusions.