Colorimetric determination of nanomolar concentrations of ammonium in seawater using solvent extraction

A solvent extraction method for measuring nanomolar concentrations of ammonium in seawater is described. The procedure is based on formation of indophenol in alkaline solution by reaction of phenol, hypochlorite and ammonia using sodium aquopentacyanoferrate as a coupling agent. Indophenol is then concentrated by extraction into n-hexanol at low pH and re-extraction into aqueous alkaline buffer. The concentration of indophenol blue is determined colorimetrically. The molar absorbance is 2.08 × 10⁵ absorbance units per molar NH₄⁺ in seawater with a precision of ± 1.9 nM NH₄⁺ (95% Cl) for concentrations ≤ 50 nanomolar. This represents a 12-fold improvement in sensitivity and a 26-fold improvement in precision over standard aqueous analyses. Calibration curves are linear to at least 2 μM NH₄⁺. Sensitivity in seawater is 97% of that found in deionized distilled water due to a slight salt effect.     

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

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

A chemiluminescent technique for the determination of nanomolar concentrations of nitrate and nitrite in seawater

A chemiluminescent analysis technique for the determination of nanomolar quantities of nitrate, nitrate plus nitrite or nitrite alone in seawater is described. The method depends on the selective reduction of these species to nitric oxide which is then determined by its chemiluminescent reaction with ozone, using a commercial nitrogen oxides analyzer. The necessary equipment is compact and sufficiently sturdy to allow shipboard use. A precision of ±2 nM is claimed with analytical rates of 10–12 samples h^?1, and modifications are discussed to allow doubling the analytical rate.     

Sensitive determination of enzymatically labile dissolved organic phosphorus and its vertical profiles in the oligotrophic western North Pacific and East China Sea

Trace concentrations of labile dissolved organic phosphorus (LDOP) in oligotrophic seawater were measured by use of an enzymatic procedure and a nanomolar phosphate analytical system consisting of a gas-segmented continuous flow analyzer with a liquid waveguide capillary cell. LDOP, defined as DOP hydrolyzed by alkaline phosphatase (AP) from Escherichia coli, was quantified as the difference between the phosphate concentrations of the seawater sample with and without AP treatment. For sensitive measurement of LDOP, we found that phosphate contamination derived from commercially available AP must be corrected, and azide treatment before AP treatment proved effective in removing biological effect that occurs during DOP hydrolysis. Field observations at six stations of the western North Pacific and the East China Sea during the boreal summer revealed that, in the upper 200 m of the water column, LDOP concentrations ranged from the detection limit (3 nM) to 243 nM, and phosphate concentrations ranged from 5 to 374 nM. The spatial distribution patterns of LDOP were similar to those of phosphate. Most of the depth profiles for LDOP and phosphate showed concentrations were extremely low, <25 nM, between the surface and the deep chlorophyll maximum layer (DCML) and increased below the DCML. Strongly depleted LDOP and phosphate above the DCML suggest that LDOP is actively hydrolyzed under phosphate-depleted conditions and utilized by microbes.     

A modified analytical method for the shipboard determination of nanomolar concentrations of orthophosphate in seawater

A method for the determination of nanomolar concentrations of orthophosphate in oligotrophic seawater developed by Liang et al. (2007) has been modified to make it fully feasible for shipboard application and for faster sample throughput with minimized sample volume. The technique is based on the flow injection method with solid phase extraction on a Sep-Pak C18 cartridge and colorimetric detector. The Schlieren effect was minimized by rinsing the cartridge sequentially with 5 mL water and 2 mL 95% ethanol solution. With three micro pumps in parallel, savings of up to 80% in amount of reagents and 25% volume of seawater samples could be achieved in comparison to the previous method. Variation of stopped flow time and sample loading time gave 3 different standard curves, which corresponded to 3 linear ranges within 3.4 and 515 nM. The modified method permits the analysis of samples over a wide range of concentrations, and has been successfully applied to shipboard determination of trace orthophosphate in more than 200 seawater samples during a one-month cruise in the South China Sea. For seawater at concentrations of 20.6, 82.5, 206.2 nM orthophosphate, the relative standard deviations (RSD) (n = 6), determined daily for 6 days on board ship were 4.45%, 4.73% and 6.75%, respectively. Five seawater samples collected in the Station SEATS (South East Asia Time Series Station at 18°N, 116°E) were analyzed using the present method both on board and in a land-based laboratory, as well as with the magnesium hydroxide-induced coprecipitation (MAGIC) method, and showed no significant difference according to the statistical t-test.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3− and SiO2(OH)22−. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH^? was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 ? B ? 0.008 M and 2.5 ? -log[H⁺] ? 11.7, respectively. Within these ranges the formation of SiO(OH)₃^? and SiO₂(OH)₂^2? with formation constants log β_?11(Si(OH)₄ ? SiO(OH)₃^? + H⁺) = ?9.472 ±0.002 and log β_?21(Si(OH)₄ ? SiO₂(OH)₂^2? + 2H⁺) = ?22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with $\text{-}\text{log[H}{}^{\mathrm{+}}\text{] ? 10.7}$ their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

Dimethylsulphide and dimethylsulphoniopropionate in Antarctic sea ice and their release during sea ice melting

This study presents concentrations of dimethylsulphide (DMS) and its precursor compound dimethylsulphoniopropionate (DMSP) in a variety of sea ice and seawater habitats in the Antarctic Sea Ice Zone (ASIZ) during spring and summer. Sixty-two sea ice cores of pack and fast ice were collected from twenty-seven sites across an area of the eastern ASIZ (64°E to 110°E; and the Antarctic coastline north to 62°S). Concentrations of DMS in 81 sections of sea ice ranged from < 0.3 to 75 nM, with an average of 12 nM. DMSP in 60 whole sea ice cores ranged from 25 to 796 nM and showed a negative relationship with ice thickness (y = 125x^− 0.8). Extremely high DMSP concentrations were found in 2 cores of rafted sea ice (2910 and 1110 nM). The relationship of DMSP with ice thickness (excluding rafted ice) suggests that the release of large amounts of DMSP during sea ice melting may occur in discrete areas defined by ice thickness distribution, and may produce ‘hot spots’ of elevated seawater DMS concentration of the order of 100 nM. During early summer across a 500 km transect through melting pack ice, elevated DMS concentrations (range 21–37 nM, mean 31 nM, n = 15) were found in surface seawater. This band of elevated DMS concentration appeared to have been associated with the release of sea ice DMS and DMSP rather than in situ production by an ice edge algal bloom, as chlorophyll a concentrations were relatively low (0.09–0.42 μg l^− 1). During fast ice melting in the area of Davis station, Prydz Bay, sea ice DMSP was released mostly as extracellular DMSP, since intracellular DMSP was negligible in both hyposaline brine (5 ppt) and in a melt water lens (4–5 ppt), while extracellular DMSP concentrations were as high as 149 and 54 nM, respectively in these habitats. DMS in a melt water lens was relatively high at 11 nM. During the ice-free summer in the coastal Davis area, DMS concentrations in surface seawater were highest immediately following breakout of the fast ice cover in late December (range 5–14 nM), and then remained at relatively low concentrations through to late February (< 0.3–6 nM). These measurements support the view that the melting of Antarctic sea ice produces elevated seawater DMS due to release of sea ice DMS and DMSP.     

A highly sensitive and large concentration range colorimetric continuous flow analysis for ammonium concentration

A continuous flow method for the determination of ammonium concentration in seawater from a nanomolar to a micromolar level is described. To prevent spurious peaks derived from salinity difference, a gas-permeable hydrophobic membrane filter was used to separate the manifold into an outgassing section and an indophenol blue reaction section. The indophenol blue reaction section was adopted for colorimetric analysis and is equipped with a 1-m path length liquid capillary cell and a fiber-optic spectrometer, which is able to record the absorbance at multiple wavelengths. The minimum detection limit at wavelength 630 nm is 5.5 ± 1.8 nM, and the calibration curves are linear to at least 2,000 nM. In addition, the minimum detection limit at wavelength 530 nm was 13 ± 5.3 nM, and linear calibration curves were observed until at least 10,000 nM. The slopes of the calibration curves were similar for standards prepared using filtered seawater and ultrapure water. The ammonium concentration of the ultrapure water was similar to those of ion-exchanged water and unfiltered low-nutrient seawater, but was significantly lower than those of filtered seawater and solutions that contained sodium hydroxide. Therefore, ultrapure water is optimal for both blank and standard preparations because of its stable quality and availability. Given its large concentration range and the use of readily available blanks, this method is suitable for the determination of ammonium concentration and helps our understanding of ammonium dynamics in the ocean.     

Interannual variability of Si and N cycles at the time-series station KERFIX between 1990 and 1995 – a 1-D modelling study

Interannual variability of nutrients and plankton cycles were studied at the time-series station KERFIX (50°40′S, 68°25′E) using a 1-D coupled physical-biogeochemical model that is descended from that of Pondaven et al. (1998). At KERFIX, a high half saturation constant for silicic acid uptake (K_Si) and a high Si/N uptake ratio are required to reproduce the Si and N cycles. Although very high in comparison with most data from temperate systems, these values are consistent with K_Si and Si/N uptake ratios measured in the Indian sector of the Southern Ocean. Past and recent finding on the role of light and iron limitation on nutrient consumption ratios might explain these “unusual” silicon uptake kinetic parameters. Comparison of model results with observations show that the model correctly reproduces the observed interannual variability of nutrients and plankton cycles at KERFIX between 1992 and 1995. Characteristic features of this region are a spring phytoplankton bloom of 1.0–1.5 mg Chlorophyll a m⁻³ and a net excess of silicic acid utilisation over that of nitrate. This high silicic acid utilisation leads to low Si concentrations in late summer and subsequent Si limitation of diatom growth. The interannual variability of production of silicon and nitrogen predicted by the model is 1.93±0.04 mol Si m⁻² yr⁻¹ and 1.35±0.07 mol N m⁻² yr⁻¹ (±SD). In parallel, the predicted export is 1.12±0.04 mol Si m⁻² yr⁻¹ and 0.06±0.01 mol N m⁻² yr⁻¹. It is shown that diatoms may contribute significantly to export if diatom sinking is taken into account. An interannual variability of the predicted Si and N cycles is detected. This variability is associated with changes in the mixed layer properties, which have been documented to be linked to the Pacific El Niño Southern Oscillation or displacement of the Polar Front.     

The return of Pacific waters to the upper layers of the central Arctic Ocean

Temperature, salinity, and chemical measurements, including the nutrients silicic acid (Si), nitrate (NO₃), nitrite (NO₂), ammonium (NH₄), and phosphate (PO₄ or P), the oxygen isotopic composition of seawater (δ¹⁸O), and barium (Ba) concentrations were obtained from the central Arctic Ocean along transects radiating from the North Pole in early spring, 2000–2006. Stations that were reoccupied over this time period were grouped into five regions: from Ellesmere Island, (1) north along 70°W and (2) northwest along 90°W; near the North Pole, (3) on the Amundsen Basin flank and (4) directly over the Lomonosov Ridge; (5) through the Makarov Basin along 170–180°W. These regions had been shown by others to have undergone marked changes in water-mass assemblies in the early 1990s, but our time series tracer hydrographic data indicate a partial return of Pacific origin water within the mixed layer and the upper halocline layers beginning in 2003–2004. Back-trajectories derived from satellite-tracked ice buoys for these stations indicate that the upper levels of Pacific water in the central Arctic in 2004–2006 transited westward from the Bering Strait along the Siberian continental slope into the East Siberian Sea before entering the Transpolar Drift Stream (TPD). By 2004, the TPD shifted back from an alignment over the Alpha-Mendeleev Ridge toward the Lomonosov Ridge, as was characteristic prior to the early 1990s. At most stations occupied in 2006, a decrease in the Pacific influence was observed, both in the mixed layer and in the upper halocline, which suggests the Canadian branch of the TPD was shifting back toward North America. Clearly the system is more variable than has been previously appreciated.     

Iron,macronutrients and diatom blooms in the Peru upwelling regime: brown and blue waters of Peru

Surface water transects and vertical profiles for dissolved iron, macronutrients, chlorophyll a (Chl a), and hydrographic data were obtained in the Peru upwelling regime during August and September 2000. The supply of the micronutrient iron, relative to that of the macronutrients nitrate, phosphate and silicic acid, is shown to play a critical role in allowing extensive diatom blooms to develop in the Peru upwelling system. The extremely high-chlorophyll “brown waters of Peru” (with Chl a concentrations between 20 and 45 μg/l) result from massive diatom blooms with maximal photochemical efficiencies (F_v/F_m >0.6) occurring in the iron-rich upwelling region observed over the broad continental shelf off northern and central Peru. The source of the upwelled water in this region is the nutrient-rich subsurface countercurrent in contact with the organic-rich shelf sediments. This subsurface shelf water is suboxic and has extremely high concentrations of dissolved Fe (>50 nM) in the near-bottom waters. In marked contrast, relatively low-chlorophyll “blue waters” (Chl a <2 μg/l) with low concentrations of dissolved Fe (<0.1 nM) and high unutilized macronutrient concentrations are observed in the coastal upwelled waters along the southern coast of Peru and in the offshore regions of the Peru Current. Southern Peru is a region without a wide shelf to serve as a source of iron and, as a result, dissolved Fe concentrations in the near-bottom suboxic waters of this region are an order-of-magnitude lower than observed off northern and central Peru. In addition, the offshore Peru Current is a broad, Fe-limited, high-nitrate, lower than expected chlorophyll region extending hundreds of kilometers offshore into the northeast region of the South Pacific subtropical gyre and northwestward into the South Equatorial Pacific.     

Mesoscale decrease of surface phosphate and associated phytoplankton dynamics in the vicinity of the subtropical South Pacific islands

Surface distributions of nutrients and phytoplankton were investigated in the vicinity of the subtropical South Pacific islands by using a continuous underway system with a highly sensitive nutrient analysis. A total of 17 transects, whose lengths ranged between 42 and 271 km, were sampled for continuous nutrient measurements. The study area was characterized by an overall depletion of nitrate+nitrite (<15 nM), but phosphate varied from 7 to 192 nM. The transects were grouped into 4 patterns according to distribution of phosphate concentrations. In 7 transects, a mesoscale decrease in phosphate occurred, coinciding with an elevation of in vivo chlorophyll fluorescence, which was accompanied by an increase in phytoplankton abundance as revealed by microscopy, flow cytometry, and accessory pigments. This mirror–image relationship between the phosphate concentration and phytoplankton abundance was most apparent on both a 99-km transect east of Tonga, where the phosphate concentration ranged from 17 to 125 nM, and on a 98-km transect west of Fiji, where the phosphate concentration ranged from 23 to 136 nM. Both these transects contained distinct blooms of Trichodesmium in areas with the lowest concentrations of phosphate. In other 2 transects, fluctuations in phosphate concentrations showed no distinct relationship with chlorophyll fluorescence. Other patterns that emerged included consistently high concentrations, ranging from 109 to 192 nM, in 5 transects and consistently low phosphate concentrations, ranging from 7 to 50 nM, in 3 transects. Abundance of Trichodesmium, Prochlorococcus, Synechococcus, and all accessory pigments examined tended to be higher in the low phosphate transects than in the high phosphate ones. In particular, Trichodesmium occurred in low phosphate water (<25 nM). There was no significant relationship between phosphate concentrations and nanoplanktonic unicellular cyanobacteria. Our observations suggest that surface phosphate decreases are associated with phytoplankton utilization of phosphate, and that nitrogen supply from Trichodesmium may contributes to this utilization.     

台湾海峡铀的来源及保守性混合

Seawater samples are collected in the spring of 2013 from the Taiwan Strait for the analysis of uranium(U)concentrations and isotopic compositions using MC-ICP-MS, and the geochemical behavior patterns of U in the Taiwan Strait are then investigated. Average concentrations of individual U isotopes are(3.23±0.14) μg/kg for 238 U,(2.34±0.09)×10~(–2) μg/kg for ~(235)U and(2.05±0.07)×10~(–4) μg/kg for 234 U. Correspondingly, the U isotopic compositions are 155±18 for δ234U and 138±2 for 238U:235U. The U concentrations and isotopic ratios in the Taiwan Strait are similar to those of open ocean seawater, suggesting the dominance of the open ocean input to the strait's U pool.However, river input, as suggested by the slightly lower salinity than that of the open ocean, also affected the U concentrations and isotopic compositions in the strait. From a compilation of U concentrations in the Taiwan Strait and adjacent areas, including the Jiulong Estuary and Zhujiang Estuary, the Xiamen Bay and the northern South China Sea, a strong and significant relationship between U concentration and salinity [U:S; U=(0.093 4±0.002 4)S+(0.092 0±0.061 5)] is revealed, suggesting conservative mixing of U in the Taiwan Strait. To better understand the U geochemistry in the Taiwan Strait, a multiple endmembers mixing model is applied to estimate the contributions of potential sources. The open ocean seawater contributed 69%–95% of U in the Taiwan Strait, with river water approximately 2%, and dust deposition only around 0.13%. Therefore, the model results supported the open ocean input source and the conservative mixing behavior of U derived from the observation of U concentrations and isotopic ratios and U:S ratios. The sediment interstitial water may be an important source of U to the Taiwan Strait with a possible contribution of 3%–29%, consistent with previous investigations based on radium isotopes.However, further investigations are warranted to examine the U concentration in the sediment interstitial water and its input to the overlying seawater in the Taiwan Strait.     

The distribution and preferential biological uptake of cadmium at 6°W in the Southern Ocean

The spatial and temporal distribution of cadmium (Cd) and phosphate in the Southern Ocean are related to biology and hydrography. During a period of 18 days between transects 5/6 and 11, a phytoplankton spring bloom developed in the Polar Frontal region. Upper water Cd concentrations were not depleted and ranged from 0.2 to 0.8 nM at about 10 m depth. These relatively high Cd concentrations are attributed to upwelling of Upper Circumpolar Deep Water (0.5–1.2 nM in the core) in combination with low biological productivity (0.2 to 0.3 mg m⁻³ chlorophyll-a, 0.3 g C m⁻² d⁻¹). Total particulate Cd concentrations at 40 m depth were between 0.02 and 0.14 nM with the maximum in concentration in the Polar Frontal region. Most of the particulate Cd at this depth (85–94%) was detected in the first phase of a sequential chemical leaching treatment which includes adsorbed Cd as well as Cd incorporated in algae. The Polar Frontal region was characterized by minima in Cd concentration and Cd/phosphate ratio of seawater at both transects; values were the lowest at transect 11 after development of the spring bloom which was dominated by diatoms. This decreasing Cd/phosphate ratio in seawater during spring bloom development was attributed to preferential Cd gross uptake which more than compensated the process of preferential Cd recycling. Within the Upper Circumpolar Deep Water, Cd showed a maximum in concentration similar to that of the major nutrients. Both the Cd concentration and the Cd/phosphate ratio of the deeper water increased in southern direction, from 0.4 to 0.7 nM and from 0.2 to 0.3 nM/μM, respectively. Antarctic Intermediate Water has a Cd concentration of 0.21 nM with a Cd/phosphate ratio of 0.10 nM/μM. In Antarctic Bottom Water, Cd concentrations ranged from 0.60 to 0.82 nM.     

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.     

Short-term variations in trace metal concentrations in the baltic

Baltic surface water was sampled at a fixed position at intervals of a few hours. The trace metal concentrations were measured by graphite furnace AAS after extraction. The mean concentrations found were (ng l^?1): Cd, 30 ± 2.7; Cu, 800 ± 48; Fe, 358 ± 165; Ni, 820 ± 49; Pb, 16 ± 4.5; Zn, 900 ± 160. The variability in the trace metal concentrations is of the same order of magnitude as the precision of the method. Thus, no spatial variations in trace metal concentrations were found.     

Accumulation of Zn,Cu and Cd by crabs and barnacles

The crab Carcinus maenas (L.) and the barnacle Elminius modestus Darwin were exposed to a range of dissolved concentrations of Zn, Cu and Cd for 21 days in artificial seawater. Accumulation of Zn and Cu by crabs has been interpreted in terms of the presence of a regulation mechanism to maintain constant body concentrations (83·2 ± 19·4 μg Zn g^?1 dry wt.; 39·8 ± 9·8 μg Cu g^?1 dry wt.) under varying external dissolved metal levels, until a threshold dissolved metal concentration (c. 400 μg Zn l^?1; c. 170 μg Cu l^?1) beyond which net accumulation of metal begins. Cadium appears to be accumulated by C. maenas at all exposures with no evidence for regulation of body cadmium concentrations. Exposure of E. modestus to Zn, Cu or Cd caused net accumulation of the respective metal in the bodies of the barnacles, with no evidence for regulation of body metal concentrations.     

Factors controlling silicon and nitrogen biogeochemical cycles in high nutrient,low chlorophyll systems (the Southern Ocean and the North Pacific): Comparison with a mesotrophic system (the North Atlantic)

A 1-D coupled physical-biogeochemical model is used to study the seasonal cycles of silicon and nitrogen in two High Nutrient Low Chlorophyll (HNLC) systems, the Antarctic Circumpolar Current (ACC) and the North Pacific Ocean, and a mesotrophic system, the North Atlantic Ocean. The biological model consists of nine compartments (diatoms, nano-flagellates, microzooplankton, mesozooplankton, two types of detritus, nitrate, ammonium and silicic acid) forced by irradiance, temperature, mixing and deep nitrate and silicic acid concentrations. At all sites, nanophytoplankton standing crop variations are low, in spite of variations in primary production, because of a “top–down” control by microzooplankton. Although nanophytoplankton sustain more than 60% of the annual primary production in these areas, their contribution to the export production does not exceed 1% of the total. The differences in the seasonal plankton cycle among these regions come mainly from differences in the dynamics of large phytoplankton (here diatoms). In the ACC, the chlorophyll maximum remains <1.5 mg m⁻³, as an unfavourable light/mixing regime and a likely trace-metal limitation keep diatoms from blooming. In the northeast Pacific, trace-metal limitation seems to keep diatoms from blooming throughout the year. In both these systems, light or iron limitations induce high Si/N uptake ratios. Incidentally these high Si/N uptake ratios lead to a net excess of silicic acid utilization over nitrate, and to a subsequent silicic acid limitation during the summertime. In the North Atlantic, under favourable light/mixing regime and nutrient-replete conditions at the onset of the growing period, diatoms outburst and sustain a bloom >3.5 mg Chl-a m⁻³. Thereafter, mesozooplankton grazing pressure and silicic acid limitation induce the collapse of the chlorophyll maximum and the persistence of lower chlorophyll concentrations in summer. Although the ACC and the North Pacific show HNLC features, they support a high biogenic silica production (1.9 and 1.07 mol Si m⁻² yr⁻¹) and export flux (0.79 and 0.61 mol Si m⁻² yr⁻¹), compared to the North Atlantic (production: 0.23 mol Si m⁻² yr⁻¹, export: 0.12 mol Si m⁻² yr⁻¹). The differences in Si production and export between the HNLC systems and the mesotrophic North Atlantic come from both higher Si concentrations and Si/N uptake ratios in the HNLC areas compared to the North Atlantic. Also, the low dissolution rate of biogenic silica compared to nitrogen degradation rate, and the inhibition of nitrate uptake by ammonium, reinforce the net excess of silicic acid utilization over nitrate. As a result, the model also illustrates the efficiency of the silica pump for the three sites: about 50% of the biogenic silica synthesized in the euphotic layer is exported out of the first 100 m, while only 4–11% of the particulate organic nitrogen escapes recycling in the surface layer.     

Impact of environmental factors on in situ determination of iron in seawater by flow injection analysis

A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (C_p = 2.8 × 10^{− 5}P + 3.4 × 10^{− 2} s nmol^{− 1}, R² = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (C_Θ = 0.009e^0.103Θ, R² = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fe_a (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fe_a (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).     

Dissolution of silica accompanied by oxygen consumption in the bottom layer of Japan’s central Seto Inland Sea in summer

Distribution of silicic acid (Si(OH)₄) in bottom water was investigated in the central Seto Inland Sea under stratified conditions in summer. Water samples were collected at 10 stations on April 24 and 25 and July 7 and 8, 2012. In July, stratification progressed, and a cold water mass (dome) of <20 °C appeared. In response to the cold dome, low oxygen content was observed in the bottom layer of the eastern part of Hiuchi-Nada. In this water mass site, apparent oxygen utilization values calculated from dissolved oxygen (DO) concentrations increased, coinciding with increase of Si(OH)₄ concentrations from April to July. This suggests that increase of Si(OH)₄ [dissolution of biogenic silica (diatom frustules)] was accompanied by DO consumption due to degradation of organic matter such as plankton soft tissue. These findings suggest that a bacterial degradation of the organic matrix that covers diatom frustules could accelerate the dissolution of biogenic silica in bottom water under stratified conditions.