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).     

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.     

Variation in the Cadmium Concentration Related to Phosphate in the Surface Layer of the Equatorial Pacific

Variation in the cadmium (Cd) concentration related to phosphate (PO₄) in the surface layer (0–150 m) of the equatorial Pacific (175°E, 170°W, and 160°W) was investigated in January of 2001 and 2002. A plot of Cd against PO₄ from 0 to 150 m showed good linearity, and plotted points shifted in the direction of the origin along the regression line from 2001 to 2002. The variation of the Cd concentration in the surface layer was attributed to biological uptake-regeneration, the variation of subsurface water concentration, and the upwelling effect at each station in connection with the El Nino phenomenon.     

Trace metals (Co,Ni, Cu,Cd, and Pb) in the southern East/Japan Sea

Total dissolvable metals (Co, Ni, Cu, Cd, and Pb) in both surface waters and the water columns were acquired in the southern East/Japan Sea during a cruise around the Ulleung Basin in June 2001 to understand the spatial distributions of the metals. Concentrations in offshore surface waters were found to be Co 60 ± 12 pM, Ni 2.16 ± 0.25 nM, Cu 1.85 ± 0.55 nM, Cd 0.134 ± 0.018 nM, and Pb 155 ± 40 pM. Spatial distributions in surface waters showed that metal levels were generally enhanced at coastal sites in both Korea and Japan, where the metal distributions indicated complex patterns due to inputs, biogeochemical processes, and physical factors including upwelling. The Co distributions in the water columns seemed to be influenced predominantly by surface and bottom inputs, scavenged rather than regenerated at depth. For Cd, there was generally good agreement between the Cd and PO₄ depth distributions, in agreement with the literature. The Cd/PO₄ ratio from the water columns was found to be 0.133–0.203, lower than that in other marginal seas (e.g. the East/South China Seas and the Philippine Sea) of the western Pacific Ocean; this might be a result of the fast ventilation rate in this sea. The vertical Pb profile showed typical scavenged-type behavior with a surface maximum and deep minimum. From a comparison of inputs from the atmosphere and the Tsushima Warm Current, atmospheric deposition is substantial enough that it cannot be ignored, and its role in metal cycling is more significant in the offshore zone.     

Relationship between cadmium and phosphate in the northwest Pacific Ocean

The relationship between Cd and PO₄ in the Kuroshio and Oyashio regions and the Okhotsk Sea was examined. The resultant equations are as follows: Cd (ng l^–1)=37.0 PO₄ (M)+2.6; Cd(ng l^–1)=32.1 PO₄ (M)+1.2 and Cd (ng l^–1)=34.1 PO₄ (M)+7.9, respectively. These results are in good agreement with previously reported studies, and indicate that during removal from surface waters to deeper waters by biological assimilation and regeneration in deeper waters Cd and PO₄ maintain the same ratio in the open ocean. The relationship between Cd and PO₄ in coastal waters, however, differed from that in the open ocean.     

Cadmium and phosphate in coastal Antarctic seawater: Implications for Southern Ocean nutrient cycling

Cadmium is a biologically important trace metal that co-varies with phosphate (PO₄³⁻ or Dissolved Inorganic Phosphate, DIP) in seawater. However, the exact nature of Cd uptake mechanisms and the relationship with phosphate and other nutrients in global oceans remain elusive. Here, we present a time series study of Cd and PO₄³⁻ from coastal Antarctic seawater, showing that Cd co-varies with macronutrients during times of high biological activity even under nutrient and trace metal replete conditions. Our data imply that Cd/PO₄³⁻ in coastal surface Antarctic seawater is higher than open ocean areas. Furthermore, the sinking of some proportion of this high Cd/PO₄³⁻ water into Antarctic Bottom Water, followed by mixing into Circumpolar Deep Water, impacts Southern Ocean preformed nutrient and trace metal composition. A simple model of endmember water mass mixing with a particle fractionation of Cd/P (α_Cd–P) determined by the local environment can be used to account for the Cd/PO₄³⁻ relationship in different parts of the ocean. The high Cd/PO₄³⁻ of the coastal water is a consequence of two factors: the high input from terrestrial and continental shelf sediments and changes in biological fractionation with respect to P during uptake of Cd in regions of high Fe and Zn. This implies that the Cd/PO₄³⁻ ratio of the Southern Ocean will vary on glacial–interglacial timescales as the proportion of deep water originating on the continental shelves of the Weddell Sea is reduced during glaciations because the ice shelf is pinned at the edge of the continental shelf. There could also be variations in biological fractionation of Cd/P in the surface waters of the Southern Ocean on these timescales as a result of changes in atmospheric inputs of trace metals. Further variations in the relationship between Cd and PO₄³⁻ in seawater arise from changes in population structure and community requirements for macro- and micronutrients.     

Cadmium, copper and nickel distributions at four stations in the eastern central and south Atlantic

Distributions of cadmium, copper and nickel at four stations in the eastern part of the Atlantic Ocean from 30 ° S to 34 ° N are described based on analytical results from three laboratories. The Cd and Ni profiles show nutrient-like distributions with concentrations in the deep waters increasing from north to south. Copper profiles all show gradual increases from surface to bottom with the highest concentrations occurring near bottom on the most northerly station.Variations in the deep-water Cd and Ni concentrations can be understood in terms of mixing of southern source waters with high concentrations with lower concentration northern source waters. The deep-water Cu distributions indicate a significant near-bottom source to the northern end of the section.Cadmium vs. phosphate relationships show features that result from both regeneration and mixing. Higher Cd:PO₄ ratios are seen in the southern source waters than in the northern waters, thus discounting the suggestion that the inflection in the global Cd:PO₄ relationship at PO₄ ≈ 1.3 μM originates in the southern ocean. Differential regeneration of Cd and PO₄ is seen through the equatorial oxygen minimum.     

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.     

Rates of C,N, P and Si recycling and denitrification at the US Mid-Atlantic continental slope depocenter

Benthic fluxes of O₂, titration alkalinity (TA), total inorganic carbon (TIC), Ca²⁺, NO₃⁻, NH₄⁺, PO₄³⁻, and Si(OH)₄ were measured by in situ benthic flux chamber incubations at 13 locations on the North Carolina continental slope. The majority of measurements were made at water depths of approximately 700–850 m, in the previously identified upper slope depocenter. This region is characterized by extremely high organic matter deposition rates and near saturation bottom water oxygen concentrations. Measured benthic fluxes of TA are reasonably correlated with O₂ benthic fluxes. Because bottom waters are supersaturated with respect to calcite and aragonite at these shallow water depths, these results demonstrate the importance of metabolically driven dissolution in this region. Subtraction of the calcium carbonate dissolution contributions from the TIC benthic fluxes suggests rates of organic matter remineralization ranging from 0.97 to 3.9 mol C m⁻² yr⁻¹ at the depocenter sites, a factor of 3–10 greater than estimated for the adjacent continental rise and upper slope areas. Because biological primary production in the overlying waters does not follow this pattern, these extremely high values are most likely supported by lateral inputs of highly reactive organic matter. Mass balance calculations indicate that despite the oxygenated bottom water conditions, 68% of the organic nitrogen released during organic matter remineralization processes is ultimately denitrified. The release of PO₄³⁻ from the depocenter sediments is equivalent to or larger than that predicted from the remineralization of Redfield organic matter. This implies either that PO₄³⁻ is preferentially released in this setting and that the accumulating sediments must be depleted in PO₄³⁻ relative to organic carbon or that another, non-organic, phase is contributing PO₄³⁻ to the system. The molar ratio of the Si benthic flux and organic carbon remineralization rate ranges from 0.30 to 0.86. This is significantly greater than the ratio reported for most pelagic diatoms. Possible reasons for this high ratio include the deposition of benthic diatoms that may have a larger Si : C ratio than pelagic diatoms, the near-bottom lateral input of partially reworked organic matter that may have an elevated Si : C ratio relative to fresh diatoms, preferential loss of carbon in sinking particulates or the release of Si from non-opaline materials.     

The fluorescence of dissolved organic matter in seawater

A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO₃⁻, PO₄³⁻) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.     

Spatial and temporal variability of the ratios between the nitrate and phosphate concentrations in the Sea of Okhotsk

The relation between the nitrate and phosphate concentrations in the Sea of Okhotsk and the bordering waters of the Pacific Ocean were studied. The surveys were carried out in the autumn, spring, and summer of 2001–2002. For the deepwater part of the sea, the relation [NO^? ₃] = ((14.88 ± 0.07) × [PO^3? ₄] ? 5.46 ± 0.17) was found. The coefficients in the equation given are statistically different from those in the similar equation for the Pacific waters: [NO^? ₃] = (16.05 ± 0.15) × [PO^3? ₄]-(7.23 ± 0.36). In the northern part of the sea; on the shelf; in the slope area; and, especially, in the deep waters of the TINRO Depression, the linear dependence between the phosphate and nitrate concentrations was distorted. This feature was described in terms of nitrate deficiency. The maximum values of this deficiency were found in the near-bottom waters. The principal processes that might cause the nitrate deficiency were considered: the difference in the oxidation rates of the nitrogen and phosphorus organic compounds, the matter transfer between the continent and the sea, the different efficiency of the biogenic burial of nitrogen and phosphorus in the bottom sediments, and the denitrification in the upper layer of the bottom sediments. It was shown that the most probable cause of the nitrate deficiency was the denitrification. The loss of inorganic nitrogen owing to the supply of the waters of the Sea of Okhotsk to the Pacific Ocean was estimated as ～2.5 × 10¹¹ mol N/year.     

Nutrient distributions in baroclinic eddies of the oligotrophic North Atlantic and inferred impacts on biology

High-sensitivity (nanomolar) techniques for nitrate and phosphate were applied to study nutrient patterns in the euphotic zone of mesoscale eddies in the Sargasso Sea during the EDDIES project. Surface concentrations of nitrate plus nitrite (DNN) and phosphate (DIP) were found in the range of 1–20 nM with substantial spatial variability in the eddies, with resulting mean N:P molar ratios of 2.1. Chlorophyll biomass was well correlated with DNN but not DIP in the upper euphotic zone, suggesting N-limitation of marine phytoplankton at this time of year. Within the upper 140 m, the water column experienced a transition from a P-enriched (relative to Redfield ratio) shallow layer to a N-enriched deep layer, which may suggest downward transport and subsequent remineralization of high N/P biogenic products presumably originating from N₂ fixation. Chlorophyll biomass in the deep chlorophyll maximum of eddies was found to be tightly related to eddy–induced variability in major nutrients (N, P, Si) and nutrient stoichiometry, suggesting that the impact of eddies on biology is through control of nutrient availability. Because the eddies were likely to be in various phases of development (different degrees of both biological and physical maturity), full interpretation of eddy data and dynamics will require better coverage of a full eddy life cycle.     

Oxygen Utilization and Organic Carbon Remineralization in the Upper Water Column of the Pacific Ocean

As a part of the JGOFS synthesis and modeling project, researchers have been working to synthesize the WOCE/JGOFS/DOE/NOAA global CO₂ survey data to better understand carbon cycling processes in the oceans. Working with international investigators we have compiled a Pacific Ocean data set with over 35,000 unique samples analyzed for at least two carbon species, oxygen, nutrients, chlorofluorocarbon (CFC) tracers, and hydrographic parameters. We use these data here to estimate in-situ oxygen utilization rates (OUR) and organic carbon remineralization rates within the upper water column of the Pacific Ocean. OURs are derived from the observed apparent oxygen utilization (AOU) and the water age estimates based on CFCs in the upper water and natural radiocarbon in deep waters. The rates are generally highest just below the euphotic zone and decrease with depth to values that are much lower and nearly constant in water deeper than 1200 m. OURs ranged from about 0.02–10 μmol kg⁻¹yr⁻¹ in the upper water masses from about 100–1000 m, and averaged = 0.10 μmol kg⁻¹yr⁻¹ in deep waters below 1200 m. The OUR data can be used to directly estimate organic carbon remineralization rates using the C:O Redfield ratio given in Anderson and Sarmiento (1994). When these rates are integrated we obtain an estimate of 5.3 ± 1 Pg C yr⁻¹ for the remineralization of organic carbon in the upper water column of the Pacific Ocean. This revised version was published online in July 2006 with corrections to the Cover Date.     

Trace metals in the Western Pacific: temporal and spatial variability in the concentrations of Cd, Cu, Mn and Ni

Profiles of total dissolvable Cd, Cu, Mn and Ni are reported for samples collected from the southwest Pacific in 1989, from the western equatorial Pacific along 155°E at 5°S, 0° and 5°N in 1990 and 1993, and along the equator from 143°E to 152°E and in the Bismarck Sea in 1997 and 2000. Profiles of Cd along 155°E in 1990 and along the equator were essentially the same but, in 1993, Cd values at 5°N were higher by a factor of about 1.5–2 than at 5°S over the depth range 500–1500 m. Similar, but less pronounced, differences were observed for PO₄ and Ni. Cd and Ni were both strongly correlated with PO₄, and an even stronger correlation was found between Ni and Cd. The concentration of Ni did not fall below ≈2 nmolkg⁻¹, even in the nitrate-depleted waters of the western equatorial Pacific, where primary production is strongly dependent on recycled nitrogen (mainly ammonia and urea). It is proposed that this residual Ni is not bioavailable and that Ni could be biolimiting, since the metabolism of urea requires the nickel-containing enzyme urease. The impact of the Sepik River on Cd, Cu and Ni concentrations was small but elevated concentrations of Mn were observed near the Sepik River and close to the coast suggesting that the rivers and sediments on the north coast of New Guinea are a significant local source of Mn to the Bismarck Sea. Simple mass balance calculations show that the elevated levels of Mn observed in the Equatorial Undercurrent cannot be due to input from the rivers of New Guinea and they were attributed to the trapping of particulate matter due to strong current shear. A strong hydrothermal source of Mn was observed in the central Bismarck Sea.     

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.     

Fractionation during remineralization of organic matter in the ocean

Remineralization ratios (–O₂:P, C_org.:P, N:P) in the ocean are estimated from ocean tracer data using a new approach, which takes into account the effects of local exchange across neutral surfaces. This approach is applied to temperature, salinity, phosphate, nitrate, dissolved oxygen, alkalinity, and dissolved inorganic carbon data from the low- and mid-latitude Pacific, Indian, and South Atlantic Oceans. The consideration of local exchange effects tends to reduce the –O₂:P and C_org.:P remineralization estimates above 1500 m compared to earlier estimates. Below 1500 m, exchange effects can be neglected (except in the South Atlantic) and earlier estimates appear robust. In the deep South Atlantic, the consideration of these effects leads to increased –O₂:P and C_org.:P remineralization ratio estimates, bringing them more in line with the robust deep ocean estimates. For reasonable, open ocean mixing coefficient values and several choices for phosphate remineralization rate profiles, –O₂:P (C_org.:P) remineralization ratios in the ocean increase from about 140 (100) at 750 m depth to about 170 (130) at 1500 m and remain so deeper down. Such an increase down through the upper ocean thermocline implies significant fractionation during remineralization of organic matter—nutrients are released higher in the water column than inorganic carbon. These results also argue for a –O₂:P (C_org.:P) uptake ratio in new production of about 140–150 (100–110). N:P remineralization ratios decrease from about 15 at 750 m to about 12 at 1500–2000 m. This may reflect a “true” N:P remineralization (and uptake) ratio of about 16, modified by denitrification.These results imply that applications of derived, quasi-conservative tracers, based on the assumption of constant remineralization ratios, may be subject to significant error for depths less than 1500 m. In addition, present Ocean General Circulation Models of the natural carbon cycle in the ocean–atmosphere system assume remineralization to occur without fractionation but have problems simulating observed, pre-industrial levels of atmospheric pCO₂, given observed ocean inventories of alkalinity and dissolved inorganic carbon. Implementation of uptake and (depth-dependent) remineralization ratios estimated here would likely reduce this problem considerably. Furthermore, calculations with a simple global carbon cycle model show that fractionation in the modern ocean, as estimated in the present work, has reduced atmospheric pCO₂ by more than 20 ppm below the level it would have had without fractionation.     

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.     

Excess CO2 and pHexcess in the Intermediate Water Layer of the Northwestern Pacific

Excess CO₂ and pH_excess showing an increase in dissolved inorganic carbon and a decrease in pH from the beginning of the industrial epoch (middle of the 19th century) until the present time have been calculated in the intermediate water layer of the northwestern Pacific and the Okhotsk Sea. It is concluded that: (1) The Kuril Basin (Okhotsk Sea) and the Bussol' Strait areas are characterized by the greatest concentrations of excess CO₂ at isopycnal surfaces due to the processes of formation and transformation of intermediate water mass. (2) The largest difference in excess CO₂ concentration between the Okhotsk Sea and the western subarctic Pacific (about 8 µmol/kg) is found at the = 27.0. (3) The difference in excess CO₂ between the western subarctic Pacific and subtropical regions is significant only in the upper part of the intermediate water layer ( = 26.7–27.0). (4) About 10% of the excess CO₂ accumulation in the subtropical north Pacific is determined by water exchange with the subarctic Pacific and the Okhotsk Sea.     

Particulate Flux and Cd/P Ratio of Particulate Material in the Pacific Ocean

Time-series Mark 7 sediment traps were deployed at three stations at 0°N, 13°N and 48°N along 175°E to investigate seasonal and spatial variations of particulate material flux. Chemical analysis of particulate material was performed for four major chemical components, viz. opal, CaCO₃, organic material and clay minerals, Cd and P in the particulate material were also determined. We discuss the characteristics of particulate material at each site and the transportation of Cd and P to deep water by the particulate material. The total mass fluxes and variation of fluxes at each site reflect oceanographic conditions, such as biological productivity and kind of major planktonic organisms. At the northern site, large mass fluxes with a spring bloom and high ratios of opal are characteristic. Relatively small mass fluxes with high ratios of CaCO₃ are distinct, and dissolution of CaCO₃ due to sinking is recognized in the middle latitude and 0°N sites. The larger flux at the lower trap than the upper trap at the equatorial site suggests influence by lateral transport in the deep water. Distinctive decreasing Cd/P ratio and CaCO₃ concentrations in the particulate material with increasing depth suggests that the change of Cd/P ratio in the intermediate and deep water occurs through the dissolution of CaCO₃. The dissolved Cd/P ratios in the deep water are proportional to the age of the deep water in the Atlantic but not in the Pacific. This is explained by the difference of kinds of particulate material transporting Cd and P in the deep water between the oceans. That is, the major planktonic organisms are planktons of CaCO₃ tests in the Atlantic Ocean and diatoms of opal tests in the North Pacific Ocean.     

Interstitial water chemistry of villefranche bay sediments: Trace metal diagenesis

Pore water aliquots were taken with an in situ close interval sampler: the “Peeper”.We report here the pore water concentration profiles of TCO₂, SO₄, TH₂S, Ca and the trace metals Mn, Cu, Pb, Cd and Cr from sediments of a relatively polluted area, the Villefranche Bay, on the French Riviera (close to Nice).We investigated the major ion concentrations in order to establish geochemical mass balances of organic matter oxidation. ΔTCO₂/ΔSO₄ was <−2.0, reflecting the precipitation of calcite as confirmed by the calcium profile. Reduction of sulfate led to increasing sulfide concentrations with depth.Trace metal interstitial water concentrations decreased from 63 to 5 nM, 18 to 4 nM and 6.6 to less than 2 nM for Cu, Pb and Cr, respectively. Cd showed a different pattern with top and deep values of 0.7 nM and a minimum of 0.27 nM.Thermodynamic calculations were performed which suggest the potential formation of mineral phases such as sulfides.