The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

Experimental constraints on the effects of pressure and H2O on the fractional crystallization of high-Mg island arc basalt

H₂O-undersaturated melting experiments of synthesized basalt (SiO₂ = 50.7 wt.%, MgO = 8.3 wt.%, Mg# = 60) were conducted at fO₂ corresponding to NNO+1 and NNO−1 to clarify the effects of pressure (2–7 kbar) and H₂O on fractional crystallization in island arcs. H₂O content was ranged from nominally anhydrous to 4.4 wt.%. Differentiation trends, namely the liquid lines of descent, change sensitively according to pressure-H₂O relations. Tholeiitic differentiation trends are reproduced with H₂O ≤ ∼2 wt.% in primary magma. With such quantities of H₂O, fractional crystallization is controlled by olivine + plagioclase at 2 kbar. Increasing the pressure from 2 to ≥4 kbar induces early crystallization of orthopyroxene instead of olivine and therefore SiO₂ enrichment in the residual melts is suppressed. Increasing H₂O (≥ ∼2 wt.% in primary magma) stabilizes clinopyroxene relative to orthopyroxene and/or magnetite. Although the phase relations and proportions strongly depend on fO₂ and H₂O content, differentiation trends are always calc-alkaline.     

Generation of random waves in time-dependent extended mild-slope equations using a source function method

We develop techniques of numerical wave generation in the time-dependent extended mild-slope equations of Suh et al. [1997. Time-dependent equations for wave propagation on rapidly varying topography. Coastal Engineering 32, 91–117] and Lee et al. [2003. Extended mild-slope equation for random waves. Coastal Engineering 48, 277–287] for random waves using a source function method. Numerical results for both regular and irregular waves in one and two horizontal dimensions show that the wave heights and the frequency spectra are properly reproduced. The waves that pass through the wave generation region do not cause any numerical disturbances, showing usefulness of the source function method in avoiding re-reflection problems at the offshore boundary.     

A community-wide intercomparison exercise for the determination of dissolved iron in seawater

The first large-scale international intercomparison of analytical methods for the determination of dissolved iron in seawater was carried out between October 2000 and December 2002. The exercise was conducted as a rigorously “blind” comparison of 7 analytical techniques by 24 international laboratories. The comparison was based on a large volume (700 L), filtered surface seawater sample collected from the South Atlantic Ocean (the “IRONAGES” sample), which was acidified, mixed and bottled at sea. Two 1-L sample bottles were sent to each participant. Integrity and blindness were achieved by having the experiment designed and carried out by a small team, and overseen by an independent data manager. Storage, homogeneity and time-series stability experiments conducted over 2.5 years showed that inter-bottle variability of the IRONAGES sample was good (< 7%), although there was a decrease in iron concentration in the bottles over time (0.8–0.5 nM) before a stable value was observed. This raises questions over the suitability of sample acidification and storage.     

Factors involved in growth plasticity of cockles Cerastoderma edule (L.), identified by field survey and transplant experiments

In Arcachon Bay, a macrotidal coastal lagoon in southwest France, growth rates of cockles Cerastoderma edule (L.) differ greatly between locations. Sampling of populations at different tidal levels showed that the mean shell length was significantly and positively correlated with immersion time, whereas no correlation was found with population density and microphytobenthos biomass. Transplants of cockles between two intertidal sites were used to examine the relative importance of habitat and site of origin for growth rate and condition index. Artifacts due to manipulation were assessed, i.e. the impact of enclosures on growth, conditon index and mortality. During a 5-mo reciprocal transplant experiment, growth rates of the transplanted cockles and the cockles already present were similar, whereas the sites of origin did not affect growth rate. Condition index, however, displayed significant differences in relation to both transplant and origin sites. During a further 6-mo experiment in which cockles were transplanted from one site to four new sites, growth was mainly influenced by tidal level. These results indicate that net growth started when cockles were immersed 30% of the time. It is concluded that, on the scale of Arcachon Bay (156 km²), differences in growth and condition between cockle populations are largely phenotypic. Tidal level (i.e. food supply and emersion stress) accounts for most of these differences, but the existence of genetically or physiologically different populations cannot be excluded.     

Numerical study of enhanced energy dissipation near a seamount

Using a two-dimensional primitive equation model, we examine nonlinear responses of a semidiurnal tidal flow impinging on a seamount with a background Garrett-Munk-like (GM-like) internal wavefield. It is found that horizontally elongated pancake-like structures of high vertical wavenumber near-inertial current shear are created both in the near-field (the region over the slope of the seamount) and far-field (the region over the flat bottom of the ocean). An important distinction is that the high vertical wavenumber near-inertial current shear is amplified only at mid-latitudes in the far-field (owing to a parametric subharmonic instability (PSI)), whereas it is amplified both at mid-and high-latitudes (above the latitude where PSI can occur) in the near-field. In order to clarify the generating mechanism for the strong shear in the near-field, additional numerical experiments are carried out with the GM-like background internal waves removed. The experiments show that the strong shear is also created, indicating that it is not caused by the interaction between the background GM-like internal waves and the semidiurnal internal tides. One possible explanation is proposed for the amplification of high vertical wavenumber near-inertial current shear in the near-field where tide residual flow resulting from tide-topography interaction plays an important role in transferring energy from high-mode internal tides to near-inertial internal waves.     

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.     

Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean

Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 10¹³ relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.     

深海资料浮标体及系泊系统的阻力试验研究

本文结合国家“七五”重点科技攻关项目“深海资料浮标”研制而进行浮标体和系泊系统的各种阻力试验研究，试验成果已直接应用于深海资料浮标系泊系统设计。实践表明本文介绍的各种阻力试验结果是可靠的。     

Primary production in the eastern tropical Pacific: A review

The eastern tropical Pacific includes 28 million km² of ocean between 23.5°N and S and Central/South America and 140°W, and contains the eastern and equatorial branches of the north and South Pacific subtropical gyres plus two equatorial and two coastal countercurrents. Spatial patterns of primary production are in general determined by supply of macronutrients (nitrate, phosphate) from below the thermocline. Where the thermocline is shallow and intersects the lighted euphotic zone, biological production is enhanced. In the eastern tropical Pacific thermocline depth is controlled by three interrelated processes: a basin-scale east/west thermocline tilt, a basin-scale thermocline shoaling at the gyre margins, and local wind-driven upwelling. These processes regulate supply of nutrient-rich subsurface waters to the euphotic zone, and on their basis we have divided the eastern tropical Pacific into seven main regions. Primary production and its physical and chemical controls are described for each.Enhanced rates of macronutrient supply maintains levels of primary production in the eastern tropical Pacific above those of the oligotrophic subtropical gyres to the north and south. On the other hand lack of the micronutrient iron limits phytoplankton growth (and nitrogen fixation) over large portions of the open-ocean eastern tropical Pacific, depressing rates of primary production and resulting in the so-called high nitrate-low chlorophyll condition. Very high rates of primary production can occur in those coastal areas where both macronutrients and iron are supplied in abundance to surface waters. In these eutrophic coastal areas large phytoplankton cells dominate; conversely, in the open-ocean small cells are dominant. In a ‘shadow zone’ between the subtropical gyres with limited subsurface ventilation, enough production sinks and decays to produce anoxic and denitrified waters which spread beneath very large parts of the eastern tropical Pacific.Seasonal cycles are weak over much of the open-ocean eastern tropical Pacific, although several eutrophic coastal areas do exhibit substantial seasonality. The ENSO fluctuation, however, is an exceedingly important source of interannual variability in this region. El Niño in general results in a depressed thermocline and thus reduced rates of macronutrient supply and primary production. The multi-decadal PDO is likely also an important source of variability, with the ‘El Viejo’ phase of the PDO resulting in warmer and lower nutrient and productivity conditions similar to El Niño.On average the eastern tropical Pacific is moderately productive and, relative to Pacific and global means, its productivity and area are roughly equivalent. For example, it occupies about 18% of the Pacific Ocean by area and accounts for 22–23% of its productivity. Similarly, it occupies about 9% of the global ocean and accounts for 10% of its productivity. While representative, these average values obscure very substantial spatial and temporal variability that characterizes the dynamics of this tropical ocean.