Formation of Zn–Ca phyllomanganate nanoparticles in grass roots

It is now well established that a number of terrestrial and aquatic microorganisms have the capacity to oxidize and precipitate Mn as phyllomanganate. However, this biomineralization has never been shown to occur in plant tissues, nor has the structure of a natural Mn(IV) biooxide been characterized in detail. We show that the graminaceous plant Festuca rubra (red fescue) produces a Zn-rich phyllomanganate with constant Zn:Mn and Ca:Mn atomic ratios (0.46 and 0.38, respectively) when grown on a contaminated sediment. This new phase is so far the Zn-richest manganate known to form in nature (chalcophanite has a Zn:Mn ratio of 0.33) and has no synthetic equivalent. Visual examination of root fragments under a microscope shows black precipitates about ten to several tens of microns in size, and their imaging with backscattered and secondary electrons demonstrates that they are located in the root epidermis. In situ measurements by Mn and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) with a micro-focused beam can be quantitatively described by a single-phase model consisting of Mn(IV) octahedral layers with 22% vacant sites capped with tetrahedral and octahedral Zn in proportions of 3:1. The layer charge deficit is also partly balanced by interlayer Mn and Ca. Diffracting crystallites have a domain radius of 33 Å in the ab plane and contain only 1.2 layers (8.6 Å) on average. Since this biogenic Mn oxide consists mostly of isolated layers, basal 00l reflections are essentially absent despite its lamellar structure. Individual Mn layers are probably held together in the Mn–Zn precipitates by stabilizing organic molecules. Zinc biomineralization by plants likely is a defense mechanism against toxicity induced by excess concentrations of this metal in the rhizosphere.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: I. Effect of hydraulic retention time

Sulfate-reducing passive bioreactors have proved to be an effective technology for the treatment of acid mine drainage (AMD) contaminated waters over relatively short periods of time (1–5 a). However, long-term efficiency can be limited by several factors including problems related to the hydraulic properties of the reactive mixture. In this study, the effect of two hydraulic retention times (HRTs) of 7.3 d and 10 d on the performance of passive bioreactors was evaluated over an 11-month period for the treatment of a highly contaminated AMD. Evolution of the porosity and hydraulic conductivity of the reactive mixture was also evaluated during the 15-month operation of two bioreactors. Results indicated that bioreactors were effective at both HRTs for increasing the pH and alkalinity of contaminated water and for SO₄ and metal removal (60–82% for Fe and up to 99.9% for Cd, Ni and Zn). Although the quality of treated effluent was significantly improved with the 10 d HRT compared to the 7.3 d HRT, results showed that the higher HRT reduced the porosity and the permeability of the reactive mixture which might lead to hydraulic related problems and, eventually, to limited efficiency in long-term operation compared to a shorter HRT. The choice of HRT for a passive bioreactor must therefore consider both the desired quality of treated effluent and the potential for deterioration of hydraulic properties in the reactive mixture.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

Diel Patterns in Chlorophyll <Emphasis Type="Italic">a</Emphasis> Specific Absorption Coefficient and Absorption Efficiency Factor of Picoplankton

Diel patterns in the chlorophyll a specific absorption coefficient of surface picoplankton, a*_pico (γ) (m²·[mg chlorophyll a]⁻¹), were studied at 7 stations under daily cycle of in situ light condition in the western subarctic Pacific and Japan Sea. All the data were normalized by dividing the anomaly with daily averaged a*_pico (γ). Opposite diel patterns were observed for the normalized a*_pico (443) and a*_pico (675) with maximum toward dawn or dusk and minimum toward midday at 4 stations under low-irradiance (LI) conditions and vice versa at 3 stations under high-irradiance (HI) conditions. The absorption efficiency factors at red absorption peak, Q _a (675), were determined by reconstruction with intracellular chlorophyll a concentration and cell diameter. The normalized Q _a (675) also showed diel pattern with maximum toward midday and minimum toward dawn or dusk under LI. The diel pattern in a*_pico (675) and Q _a (675) were primarily caused by changes in intracellular chlorophyll a concentration due to photoadaptation under LI. The diel pattern in a*_pico (443) was influenced by pigmentation, as recognized by blue to red ratio [a*_pico (443)/a*_pico (675)] under HI. This study proposed that the opposite diel pattern in a*_pico (γ) might occur for a wide range of algal species. The results presented here have important consequences for the interpretation of diel variations in optical properties observed in the open ocean.     

CO<Subscript>2</Subscript> Flux Measurements over the Sea Surface by Eddy Correlation and Aerodynamic Techniques

The measurements of the vertical transport of CO₂ were carried out over the Sea of Japan using the specially designed pier of Kyoto University on September 20 to 22, 2000. CO₂ fluxes were measured by the eddy correlation and aerodynamic techniques. Both techniques showed comparable CO₂ fluxes during sea breeze conditions: −0.001 to −0.08 mg m⁻²s⁻¹ with the mean of −0.05 mg m⁻²s⁻¹. This means that the measuring site satisfies the fetch requirement for meteorological observations under sea breeze conditions. Moreover, the eddy diffusivity coefficient used in the aerodynamic technique is found to be consistent with the coefficient used in the eddy correlation technique. The present result leads us to conclude that the aerodynamic technique may be applicable to underway CO₂ flux measurements over the ocean and may be used in place of the bulk technique. The important point is the need to maintain a measuring accuracy of CO₂ concentration difference of the order of 0.1 ppmv on the research vessels or the buoys.     

Long-Term Investigation of Spatio-Temporal Variations in Faunal Composition and Species Richness of Megabenthos in Ise Bay,Central Japan

Based on our long-term data from megabenthos sampling from 1993 to 2002 in Ise Bay, central Japan, we examined spatio-temporal variations in taxon composition, species richness and its distribution of megabenthos in the bay in relation to the occurrence of the oxygen-poor water (i.e. oxygen content less than 3 ppm) in bottom waters of the bay. A total of 261 species were identified including 6 cnidarians, 1 tentaculate, 5 annelids, 71 molluscs, 72 crustaceans, 16 echinoderms, 12 urochordates and 78 pisces. Of the most abundant 10 megabenthos species, the following 4 species of echinoderms made up more than the half of megabenthos biomass: Luidia quinaria, Echinocardium cordatum, Asterias amurensis and Astropecten scoparius. Species richness of megabenthos varied significantly between seasons and among stations. The severity and period of occurrence of the oxygen-poor water developing every summer play an important role in determining spatial distributions of species richness in the bay.     

Relationship between Salinity and Nutrients in the Subsurface Layer in the Suruga Bay

We investigated the water structure and nutrient distribution in the Suruga Bay from April 2000 to July 2002, especially the Offshore Water, which occupies a large part of the bay. The maximum salinity in the upper 200 m varied between 34.49 and 34.71, indicating a temporal change in the influence of Kuroshio Water on the Offshore Water. Seasonal variation in nutrient concentrations was largest from surface to 50 m. On the other hand, the variance in nutrient concentrations within each season was largest in the subsurface layer of 100–300 m in spring, summer and fall. In the Offshore Water, the change of nutrients was negatively correlated with that of salinity in each season. This suggests that an increasing intrusion of saline water brings about a lower nutrient concentration in the Offshore Water. Likewise, negative correlations were observed between the change of the maximum salinity and chlorophyll a (Δ [chl.a-int])/nutrients integrated in the upper 200 m. Δ[chl.a-int] was significantly correlated with the changes of nitrate and phosphorus, but there were no significant correlations between Δ[chl.a-int] and the change of silicate. These results suggest that the concentrations of chlorophyll a and nutrients in the Offshore Water were decreased due to the increasing intrusion of Kuroshio Water. The Offshore Water is likely to be related to the regulation of primary production by nitrate.     

Drag Coefficient,Dynamic Roughness and Reference Wind Speed

Surface waves are the roughness element of the ocean surface. The parameterization of the drag coefficient of the ocean surface is simplified by referencing to wind speed at an elevation proportional to the characteristic wavelength. The dynamic roughness is analytically related to the drag coefficient. Under the assumption of fetch limited wave growth condition, various empirical functions of the dynamic roughness can be converted to equivalent expressions for comparison. For datasets covering a wide range of the dimensionless frequency (inverse wave age), it is important to account for the variable rate of wave development at different wave ages. As a result, the dependence of the Charnock parameter on wave age is nonmonotonic. Finally, the analysis presented here suggests that the significant wave steepness is a sensitive property of the ocean surface and a single variable normalization of the dynamic roughness using a wavelength or wave height parameter actually produces more robust functions than bi-variable normalizations using wave height and wave slope.     

Seasonal and Spatial Variations of Total Mass Flux around Coral Reefs in the Southern Ryukyus,Japan

Total mass flux, size distribution of sediment particles and some chemical components such as total carbon (TC), total nitrogen (TN) and calcium carbonate (CaCO₃) were monitored monthly using a multi-cup sediment traps at seven coral reef sites (6 reef flat and 1 reef slope) of the Marine Protected Areas around Ishigaki, Kohama, Kuroshima and Iriomote Islands in the southern Ryukyus, Japan from September 2000 to September 2001. The size distribution of trapped sediments revealed mostly uni-modal fine sand to mud in the reef flat and gravelly to coarse sand in the reef slope. The total mass flux ranged between 0.54 to 872 gm⁻²d⁻¹, and showed a pronounced seasonality (high in summer-autumn and low in spring) at each site, which was consistent with the rainfall and typhoon regime. Exceptionally high values were observed on the reef slope (Iriomote) in February–March 2001 (1533 gm⁻²d⁻¹) owing to a large amount of bottom sediment re-suspension. On the reef flat (Todoroki South and North; Ishigaki), values obtained in July–August 2001 (872 gm⁻²d⁻¹) and August–September 2001 (800 gm^{− 2}d⁻¹) indicate the high terrestrial discharge from Todoroki River. Trapped sediment particles consist of CaCO₃ (1.2–27.1%) and a non-carbonate fraction (98.8–72.9%), which contains total carbon (4.9–26%), carbonate carbon (CO₂-C) (0.2–3.1%) and non-carbonate carbon (NC-C) (7.9–25.6%). Total nitrogen content was in the range 0.02–0.48%. TN is contained mainly in the carbonate fraction and NC-C may be contained in the non-carbonate fraction. The low TN/OC ratio of the trapped sediments suggests that they were mostly of terrestrial origin and that both fractions migrated. The high total mass flux derived from Todoroki River exceeded the threshold at which a lethal effect on coral community is caused. The results stress the importance of conducting seasonal studies of sedimentation over more than one year and at more than one location in south Japan coral reef ecosystems to gain an understanding of the processes controlling the total mass fluxes and their nutrients content, also to develop an awareness of how to prevent the damage of coral reef ecosystems and, if it does occur, to allow mitigation measures to be undertaken.     

Influence of Current Width Variation on the Annual Mean Transport of the East Sakhalin Current: A Simple Model

Recent observations suggest that the annual mean southward transport of the East Sakhalin Current (ESC) is significantly larger than the annual mean Sverdrup transport. Motivated by this observational result, transport of a western boundary current has been investigated using a simple numerical model with a western slope. This transport is defined as the instantaneous barotropic transport integrated from the western boundary to the offshore point where the barotropic velocity vanishes. The model, forced by seasonally varying wind stress, exhibits an annual mean of the western boundary current transport that is larger than that of the Sverdrup transport, as observed. The southward transport from October to March in the model nearly equals the instantaneous Sverdrup transport, while the southward transport from April to September decreases slowly. Although the Sverdrup transport in July vanishes, the southward transport in summer nearly maintains the annual mean Sverdrup transport, because the barotropic Rossby wave cannot intrude on the western slope. This summer transport causes the larger annual mean. Although there are some uncertainties in the estimation of the Sverdrup transport in the Sea of Okhotsk, the seasonal variation of the southward transport in the model is qualitatively similar to the observations.