Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates,nicotianamine, and phytosiderophore,and new Fe isotopic measurements in higher plants

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ～3‰ (⁵⁶Fe/⁵⁴Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ～1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate₂ and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ⁵⁶Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.     

Geochemical study of the redistribution of elements in soil—I. Evaluation of degree of weathering of transported soil materials by distribution of major elements among the particle size fractions and soil extract

Sixteen alluvial and terrace soils from Japan and Thailand were separated into six fractions ; an amorphous sesquioxide and combined organic matter fraction, crystalline sesquioxides, clay, silt, fine sand and coarse sand. Content of ten major and minor elements in these six fractions was analyzed; SiO₂, A1₂O₃, Fe₂O₃, MgO, CaO, K₂O, TiO₂, Rb₂O and SrO were determined by X-ray fluorescence spectrometry, and Na₂O was determined by neutron activation analysis. The clay, silt, fine sand and coarse sand mineralogy were estimated semi-quantitatively by X-ray diffraction methods.We propose three indices of geochemical maturity for the soils and test their usefulness as measures of the degree of weathering. Three concomitant factors are proposed to measure the relative resistate, hydrolyzate and oxidate nature of the major elements in the soils.     

Seasonal Variation of Stratification in the Gulf of Thailand

Intensive hydrographic observations were carried out in the western part of the Gulf of Thailand and the east coastal sea of Peninsular Malaysia in September 1995 and April–May 1996. The characteristics of seasonal variation of oceanic condition in that area are discussed basis of an analysis of observed water temperature, salinity and density distributions in these cruises and NAGA cruises (Yanagi and Takao, 1998a). Stratification is most developed in March–May mainly due to large sea surface heating and weak sea surface wind, which weakened until September–October, vanishing in December–January. The horizontal distribution of bottom cold, saline and heavy water masses, which are found during the stratified season, is governed by the tidal mixing and the water depth. Water exchange between the Gulf of Thailand and the South China Sea becomes large in March–May due to a coupled effect of the intensified estuarine circulation and the Ekman transport by the southwest monsoon. This revised version was published online in August 2006 with corrections to the Cover Date.     

The reversible effect of temperature on the chemical composition of interstitial water of marine sediment

The reversibility of the temperature effect on the chemical composition of interstitial waters of three deep-sea sediment samples was examined between 2 and 25°C for Cl, Na, K, Mg, Ca, Si, B, Mn and alkalinity. When the temperature of sediment samples was returned from 25°C to the initial value of 2°C, most chemical species gave nearly their initial concentrations. However, for alkalinity and in one case for magnesium, it took another three to four hours to reach their initial concentrations.     

Origin of theAbiki phenomenon (a kind of seiche) in Nagasaki Bay

Large oscillations of water level in Nagasaki Bay are calledAbiki and are most frequently observed in winter. The largestAbiki recorded in the past 20 years at the tide station at Nagasaki occurred on March 31, 1979. Simultaneously, a distinct atmospheric pressure disturbance of solitary type with an amplitude of about 3 mb was recorded at several neighbouring stations in Kyûshû, which indicated the pressure disturbance probably travelled eastward with an average speed of about 110 km h^–1.The quantitative relation between this pressure disturbance and notable seiches observed in Nagasaki Bay is examined by means of numerical simulation, and it is confirmed that the exceptionally large range of oscillations in the bay, which reached 278 cm at the tide station, was indeed produced by this travelling pressure disturbance.The leading part of shallow water waves induced by the atmospheric pressure disturbance was amplified up to about 10 cm in amplitude, over the broad continental shelf region off China, because of near resonant coupling to the pressure disturbance. After leaving this continental shelf region, the amplified water wave converged into the shelf region (Gotô Nada) surrounded by the north-western coast of Kyûshû and the Gotô Islands and excited eigenoscillations on the shelf. A train of waves thus formed with a period of about 35 min entered Nagasaki Bay and was resonantly amplified at periods of 36 min and 23 min which are the eigen periods of the bay. Besides resonance, the combined effects of shoaling and reflection inside Nagasaki Bay also enhanced the amplification.     

Sulfate reduction and sulfur fixation in sediment of a historically meromictic lake,Lake Suigetsu,Japan

Vertical distributions of sulfate, hydrogen sulfide, and iron (II) concentrations in interstitial waters and of sulfur content in sediment have been studied in a sediment core (73 cm long) from a meromictic lake, Lake Suigetsu, which changed from fresh-water to brackish conditions in 1664 A.D. The diatom assemblage of the sediment has also been analyzed. A boundary between high (>1.5%) and low (<0.2%) sulfur contents is found at a depth of 52 cm in the core. In the high sulfur layer (above 52 cm), the maximum sulfur content is 6.8% at 35 to 37 cm. The diatom assemblage, however, indicates that the boundary between fresh-water and brackish sediments lies at 40 cm. The hydrogen sulfide and iron (II) profiles in the interstitial waters indicate a sink for these chemical species near a depth of 40 cm. The discrepancy between the chemically-defined boundary at 52 cm and the paleontologically-defined boundary at 40 cm seems to be due to the downward migration of hydrogen sulfide and deposition of iron sulfide after the lake became brackish.     

Diagenetic deposition of manganese in sediment of a historically meromictic lake,Lake Suigetsu,Japan

Vertical profiles of manganese concentration in interstitial waters and of manganese and iron contents in five chemically-separated fractions of sediments have been studied in a sediment core (73 cm long) from a meromictic lake, Lake Suigetsu, which changed from freshwater to brackish conditions in 1664 A.D. The interstitial waters show a minimum manganese concentration of 0.13 ppm near a depth of 10 cm and a maximum of 26 ppm near 65 cm in the core. A predominant amount of manganese, up to 0.17%, is found in the hydrogen peroxide-soluble fraction of sediments in layers above a depth of 52 cm. It is suggested that the manganese is included in stable iron sulfides such as pyrite. Manganese, which diffuses upward from the lower layer, is thought to be deposited along with stable iron sulfide during diagenetic formation of the latter near a depth of 10 cm in the core.     

Radial Speed Evolution of Interplanetary Coronal Mass Ejections During Solar Cycle 23

We report radial-speed evolution of interplanetary coronal mass ejections (ICMEs) detected by the Large Angle and Spectrometric Coronagraph onboard the Solar and Heliospheric Observatory (SOHO/LASCO), interplanetary scintillation (IPS) at 327 MHz, and in-situ observations. We analyze solar-wind disturbance factor (g-value) data derived from IPS observations during 1997?–?2009 covering nearly the whole period of Solar Cycle 23. By comparing observations from SOHO/LASCO, IPS, and in situ, we identify 39 ICMEs that could be analyzed carefully. Here, we define two speeds [V _SOHO and V _bg], which are the initial speed of the ICME and the speed of the background solar wind, respectively. Examinations of these speeds yield the following results: i) Fast ICMEs (with V _SOHO?V _bg>500 km?s^?1) rapidly decelerate, moderate ICMEs (with 0 km?s^?1≤V _SOHO?V _bg≤500 km?s^?1) show either gradually decelerating or uniform motion, and slow ICMEs (with V _SOHO?V _bg<0 km?s^?1) accelerate. The radial speeds converge on the speed of the background solar wind during their outward propagation. We subsequently find; ii) both the acceleration and the deceleration are nearly complete by 0.79±0.04 AU, and those are ended when the ICMEs reach a 480±21 km?s^?1. iii) For ICMEs with (V _SOHO?V _bg)≥0 km?s^?1, i.e. fast and moderate ICMEs, a linear equation a=?γ ₁(V?V _bg) with γ ₁=6.58±0.23×10^?6 s^?1 is more appropriate than a quadratic equation a=?γ ₂(V?V _bg)|V?V _bg| to describe their kinematics, where γ ₁ and γ ₂ are coefficients, and a and V are the acceleration and speed of ICMEs, respectively, because the χ ² for the linear equation satisfies the statistical significance level of 0.05, while the quadratic one does not. These results support the assumption that the radial motion of ICMEs is governed by a drag force due to interaction with the background solar wind. These findings also suggest that ICMEs propagating faster than the background solar wind are controlled mainly by the hydrodynamic Stokes drag.     

Nuclear field shift effect as a possible cause of Te isotopic anomalies in the early solar system—An alternative explanation of Fehr et al. (2006 and 2009)

Abstract— We explore the possibility that Te isotopic anomalies measured in Ca‐Al‐rich inclusions (Fehr et al. 2009) and in leachates of carbonaceous chondrites (Fehr et al. 2006) may be due to mass‐independent effects controlled by nuclear field shift rather than to nucleosynthetic processes. Fehr et al.'s spectrum of mass‐independent anomalies of Te isotopes shows a smooth correlation with mass number and nuclear charge distribution. Ratios of even to odd isotopes, as the ¹²⁵Te/¹²⁶Te ratio used by these authors for normalization are particularly prone to nuclear field shift effects. We show that the alternative normalization of isotopic ratios to ¹³⁰Te/¹²⁶Te strongly reduces the trend of isotopic fractionation with mass number, leaving only ¹²⁵Te as truly anomalous. For both normalizations (¹²⁵Te/¹²⁶Te and ¹³⁰Te/¹²⁶Te), Fehr et al.'s results fit the theory of Bigeleisen (1996), which suggests that the nuclear field shift effect can potentially account for the observed Te isotope abundances, as an alternative to nucleosynthetic processes. We propose that these mass‐independent effects may be acquired during accretion of sulfides from the solar nebula.     

Tidal Mixing in the Kuril Straits and Its Impact on Ventilation in the North Pacific Ocean

A numerical study using a 3-D nonhydrostatic model has been applied to baroclinic processes generated by the K ₁ tidal flow in and around the Kuril Straits. The result shows that large-amplitude unsteady lee waves are generated and cause intense diapycnal mixing all along the Kuril Island Chain to levels of a maximum diapycnal diffusivity exceeding 10³ cm²s⁻¹. Significant water transformation by the vigorous mixing in shallow regions produces the distinct density and potential vorticity (PV) fronts along the Island Chain. The pinched-off eddies that arise and move away from the fronts have the ability to transport a large amount of mixed water (∼14 Sv) to the offshore regions, roughly half being directed to the North Pacific. These features are consistent with recent satellite imagery and in-situ observations, suggesting that diapycnal mixing within the vicinity of the Kuril Islands has a greater impact than was previously supposed on the Okhotsk Sea and the North Pacific. To examine this influence of tidal processes at the Kurils on circulations in the neighboring two basins, another numerical experiment was conducted using an ocean general circulation model with inclusion of tidal mixing along the islands, which gives a better representation of the Okhotsk Sea Mode Water than in the case without the tidal mixing. This is mainly attributed to the added effect of a significant upward salt flux into the surface layer due to tidal mixing in the Kuril Straits, which is subsequently transported to the interior region of the Okhotsk Sea. With a saline flux into the surface layer, cooling in winter in the northern part of the Okhotsk Sea can produce heavier water and thus enhance subduction, which is capable of reproducing a realistic Okhotsk Sea Mode Water. The associated low PV flux from the Kuril Straits to the open North Pacific excites the 2nd baroclinic-mode Kelvin and Rossby waves in addition to the 1st mode. Interestingly, the meridional overturning in the North Pacific is strengthened as a result of the dynamical adjustment caused by these waves, leading to a more realistic reproduction of the North Pacific Intermediate Water (NPIW) than in the case without tidal mixing. Accordingly, the joint effect of tidally-induced transport and transformation dominating in the Kuril Straits and subsequent eddy-transport is considered to play an important role in the ventilation of both the Okhotsk Sea and the North Pacific Ocean. This revised version was published online in July 2006 with corrections to the Cover Date.