Transformation dynamics and reactivity of dissolved and colloidal iron in coastal waters

We have investigated the chemical forms, reactivities and transformation kinetics of Fe(III) species present in coastal water with ion exchange and filtration methods. To simulate coastal water system, a mixture of ferric iron and fulvic acid was added to filtered seawater and incubated for a minute to a week. At each incubation time, the seawater sample was acidified with hydrochloric acid and then applied to anion exchange resin (AER) to separate negatively charged species (such as fulvic acid, its complexes with iron and iron oxyhydroxide coated with fulvic acid) from positively charged inorganic ferric iron (Fe(III)′). By monitoring the acid-induced Fe(III)′ over an hour, it was found that iron complexed by fulvic acid dissociated rapidly to a large extent (86–92% at pH 2), whereas amorphous ferric oxyhydroxide particles associated with fulvic acid (AFO-L) dissociated very slowly with the first-order dissociation rate constants ranging from 6.1 × 10^− 5 for pH 3 to 2.7 × 10^− 4 s^− 1 for pH 2. Therefore, a brief acidification followed by the AER treatment (acidification/AER method) was likely to be able to determine fulvic acid complexes and thus differentiate the complexes from the AFO-L particles (the dissolution of AFO-L was insignificant during the brief acidification). The acidification/AER method coupled with a simple filtration technique suggested that the iron–fulvic acid complexes exist in both the < 0.02 μm and 0.02–0.45 μm size fractions in our coastal water system. The truly dissolved iron (< 0.02 μm) was relatively long-lived with a life-time of 14 days, probably due to the complexation by strong ligands. Such an acid-labile iron may be an important source of bioavailable iron in coastal environments, as a significant relationship between the chemical lability and bioavailability of iron has been well recognised.     

Nonlinear behaviour of scoria soil sediments evaluated from borehole records in eastern Shizuoka prefecture,Japan

We evaluate the non-linear behaviour of soil sediments, analysing five weak and four strong motions observed at depths of 1 m and 28 m, in eastern Shizuoka prefecture, Japan. We identify S-wave velocities and frequency-dependent damping factors by minimizing the residual between observed and theoretical spectral ratios, based on a linear one-dimensional model. We find that S-wave velocities identified from strong motions, whose peak ground acceleration are 440, 210, 176, and 140 cm/s², are significantly smaller than those identified from weak motions. The shear modulus reduction ratios estimated from identified S-wave velocities become clear above an effective shear strain of 10^-4 and agree with laboratory test results below an effective shear strain of 8×10^-4. The differences of damping factors between weak and strong motions are not clear below this effective shear strain, as the laboratory test suggested. The equivalent linear one-dimensional model, with frequency-dependent damping factors, is confirmed to be valid to simulate strong motions at least an effective shear strain of less than 4×10^-4. © 1997 John Wiley & Sons, Ltd.     

Rare earth element measurements and mapping of minerals in the Allende CAI, 7R19‐1, by NanoSIMS ion microprobe

We have established analytical procedures for quantitative rare earth element (REE) measurements by NanoSIMS 50L ion microprobe with 2–10 μm spatial resolution. Measurements are performed by multidetection using energy filtering under several static magnetic field settings. Relative sensitivity factors and REE oxide/REE element secondary ion ratios that we determined for the NanoSIMS match values previously determined for other ion microprobes. REE measurements of 100 ppm REE glass standards yielded reproducibility and accuracy of 0.5–2.5% and 5–15%, respectively. REE measurements of minerals of an Allende type‐A CAI, 7R19‐1, were performed using three different methods: spot analysis, line profile, and imaging. These data are in excellent agreement with previous REE measurements of this inclusion by IMS‐3f ion microprobe. The higher spatial resolution NanoSIMS measurements provide additional insight into the formation process of this CAI and offer a promising new tool for analysis of fine‐grained and complexly zoned materials.     

Tidal transport through the Tsugaru Strait — part I: Characteristics of the major tidal flow and its residual current

The potential role of the tide-induced time-mean flow (the tidal residual current) in determining transport through the Tsugaru Strait (located between the East/Japan Sea and the North Pacific) is investigated using a high-resolution numerical barotropic model. The calculated K₁, O₁, M₂, and S₂ tidal fields agree well with available observational records derived from both tide gauge and current meter measurements in the strait and the adjacent seas. The tidal residual current speed reaches 0.3 ms⁻¹ in two narrow “neck” areas where topographic sills are located. This result suggests that tides should be taken into account in estimating the long-term water mass and nutrient transport through narrow regions between the East/Japan Sea and the North Pacific. An interesting aspect of the tidal residual current field is the prediction of several active eddy zones in which sequences of eddy triplets develop in the vicinity of capes. Our vorticity analysis reveals that the interplay of topographic effects arising from both the headland and the sill around capes plays a critical role in the formation of these triple eddy patterns.     

Estimation of baroclinic tide energy available for deep ocean mixing based on three-dimensional global numerical simulations

The global distributions of the major semidiurnal (M₂ and S₂) and diurnal (K₁ and O₁) baroclinic tide energy are investigated using a hydrostatic sigma-coordinate numerical model. A series of numerical simulations using various horizontal grid spacings of 1/15–1/5° shows that generation of energetic baroclinic tides is restricted over representative prominent topographic features. For example, nearly half of the diurnal (K₁ and O₁) baroclinic tide energy is excited along the western boundary of the North Pacific from the Aleutian Islands down to the Indonesian Archipelago. It is also found that the rate of energy conversion from the barotropic to baroclinic tides is very sensitive to the horizontal grid spacing as well as the resolution of the model bottom topography; the conversion rate integrated over the global ocean increases exponentially as the model grid spacing is reduced. Extrapolating the calculated results in the limit of zero grid spacing yields the estimate of the global conversion rate to be 1105 GW (821, 145, 102, 53 GW for M₂, S₂, K₁, and O₁ tidal constituents, respectively). The amount of baroclinic tide energy dissipated in the open ocean below a depth of 1000 m, in particular, is estimated to be 500–600 GW, which is comparable to the mixing energy estimated by Webb and Suginohara (Nature 409:37, 2001) as needed to sustain the global overturning circulation.     

Compensatory response of the unicellular-calcifying alga <Emphasis Type="Italic">Emiliania huxleyi</Emphasis> (Coccolithophoridales,Haptophyta) to ocean acidification

Ocean acidification damages calcareous organisms, such as calcifying algae, foraminifera, corals, and shells. In this study, we made a device equipped with a Clark-type oxygen electrode and a pH-stat to examine how the most abundant calcifying phytoplankton, the coccolithophorid Emiliania huxleyi, responded to acidification and alkalization of the seawater medium. When E. huxleyi was incubated at pH 8.2, close to oceanic pH, the medium was alkalized during photosynthesis, and the alkalization rate [determined as μmol HCl added (mg Chl)⁻¹ h⁻¹] was identical to the activity of photosynthesis [determined as μmol O₂ evolved (mg Chl)⁻¹ h⁻¹]. When pH was maintained at 7.2 by the pH-stat, alkalization activity was stimulated and exceeded photosynthetic activity, resulting in an increase in the ratio of alkalization to photosynthesis (Alk/PS). On the other hand, no alkalization and photosynthesis were observed at pH 9.2. In contrast, acidification of seawater was observed in the dark because of the release of respiratory CO₂ from cells at pH 8.2–9.2, but not at pH 7.2. When orthophosphate was rapidly depleted within a day in the batch culture, intracellular calcification gradually increased, and both photosynthesis and alkalization decreased gradually. During the period the Alk/PS ratio also decreased gradually. These results indicate that E. huxleyi possesses an ability to compensate for the acidification of seawater when photosynthesis is more actively driven than respiration. These results suggest that the E. huxleyi cells may not be severely damaged by oceanic acidification during photosynthesis because of their homeostatic function to avoid negative effects on cellular activity. Finally, we concluded that E. huxleyi cells possess a buffering ability to reduce acidification effects when photosynthesis is actively driven.     

River Water Pollution in Developed and Developing Countries: Judge and Assessment of Physicochemical Characteristics and Selected Dissolved Metal Concentration

To compare water quality in rivers of developed and developing countries, a study based on physicochemical parameters and dissolved metals levels was conducted. Water samples were collected from selected sites in Dhaka, Bangladesh; Hokkaido and Osaka, Japan; Erdenet, Mongolia and West Java, Indonesia. Analysis of least significant differences revealed that most water quality parameters were within comparable low levels in both developed and developing countries. The dissolved metals concentrations were found to be similar and below those of water standards except for manganese and cadmium at every sampling point, and lead in Erdenet, Mongolia. Some metals showed high enrichment factors in the rivers of Osaka, Japan and Erdenet, Mongolia, indicating accumulation possibility of metals in the river‐bed sediments. High concentrations of dissolved organic carbon, Escherichia coli and dissolved metals suggested greater water pollution in some rivers of developing countries than in the rivers of Japan. Principal component analysis showed strong correlations between “dissolved organic carbon and chemical oxygen demand” and “conductivity and total dissolved solids” at each sampling point, and E. coli, nitrate (NO), nitrite (NO), and pH levels were found to be higher in the rivers of Dhaka and Erdenet. In addition, there were high levels of Al and Zn in West Java, Pb in Erdenet, and Mn, Fe, and Cr in the rivers of Dhaka and Japan. Based on pressures and impacts, it is evident that dissolved metal, organic, and fecal pollution in the rivers of developing countries are in somewhat dreadful condition in comparison with the rivers of developed country.     

Superoxide-mediated Fe(II) formation from organically complexed Fe(III) in coastal waters

Fe(III) complexed by organic ligands (Fe(III)L) is the primary form of dissolved Fe in marine and coastal environments. Superoxide, typically produced in biological and photochemical processes, is one of the reducing agents that contributes to transformation of Fe(III)L to bioavailable, free dissolved Fe(II) (Fe(II)′). In this work, the kinetics of superoxide-mediated Fe(II)′ formation from Fe(III)L in a simulated coastal water system were investigated and a comprehensive kinetic model was developed using citrate and fulvic acid as exemplar Fe-binding ligands. To simulate a coastal environment in laboratory experiments, Fe(III)L samples with various ligand/Fe ratios were incubated for 5 min to 1 week in seawater medium. At each ratio and incubation time, the rate of superoxide-mediated Fe(II)′ formation was determined in the presence of the strong Fe(II) binding ligand ferrozine by spectrophotometrically measuring the ferrous-ferrozine complex generated at a constant concentration of superoxide. The Fe(II)′ formation rate generally decreased with incubation time, as Fe(III)L gradually dissociated to form less reactive Fe(III) oxyhydroxide. However, when the ligand/Fe ratio was sufficiently high, the dissociation of Fe(III)L (and subsequent Fe precipitation) was suppressed and Fe(II)′ was formed at a higher rate. The rate of Fe(II)′ produced during the experiment was explained by the kinetic model. The model confirmed that both the ligand/Fe ratio and incubation time have a significant effect on the pathway via which Fe(II)′ is formed from Fe(III)-fulvic acid complexes.