Effect of divalent cations on the kinetics of Fe(III) complexation by organic ligands in natural waters

We have investigated the kinetics of Fe(III) complexation by several organic ligands including fulvic acid, citrate and ethylenediaminetetraacetic acid (EDTA). Particular attention was given to examination of the effect of competitive divalent cations (Me: Ca²⁺ and Mg²⁺) at concentrations typical of seawater on the complexation rate. All experiments were conducted in 0.5 M NaCl solution buffered with 2 mM bicarbonate at pH 8.0 in the absence and presence of Me (25 μM-250 mM). The rate constants of complex formation determined by using the competitive ligand (5-sulfosalicylic acid) method combined with visible spectrophotometry ranged from 3.3 × 10⁴ to 3.2 × 10⁶ M⁻¹ s⁻¹. The mechanism of complexation was then examined based on a kinetic model. When EDTA was used as a ligand, Me at concentrations comparable to the ligand markedly retarded the rate of iron complex formation due to the predominance of an adjunctive pathway (where iron-ligand complex is formed via direct association of iron to Me-ligand complex). In contrast, the competing effect of Me on iron complexation by citrate and fulvic acid was observed only when the Me concentration was in excess of the ligand by more than a factor of 10-1000. The kinetic model suggests that iron complexation by fulvic acid occurs predominantly via a disjunctive pathway (where iron complexation by ligand occurs after dissociation of Me from Me-ligand complex) at concentrations of divalent cations and natural organic matter typical of natural waters including seawater and freshwater.     

Gravity and S-wave modelling across the Jan Mayen Ridge,North Atlantic; implications for crustal lithology

The horizontal components from fourteen Ocean Bottom Seismometers deployed along four profiles focused along the western margin of the Jan Mayen microcontinent, North Atlantic, have been modelled with regard to S-waves, based on P-wave models obtained earlier. The seismic models have furthermore been constrained by 2D gravity modelling. High V _p/V _s-ratios (2.3–7.9) within the Cenozoic sedimentary section are attributed to significant porosities, whereas V _p/V _s-ratios in the order of 1.9–2.2 for the Mesozoic and Paleozoic sedimentary rocks indicate shale-dominated lithology throughout the area. The eastern side of the Jan Mayen Ridge is interpreted as a passive, volcanic margin, based on relatively high crustal V _p/V _s-ratios (1.9), whereas lower V _p/V _s-ratios (1.75–1.8) suggest the presence of intermediate composition crust and non-volcanic margin on the western side of the ridge. In the westernmost part of the Jan Mayen Basin, slightly increased upper mantle V _p/V _s-ratios may indicate some degree of serpentization of upper mantle peridotites.     

Precise Positioning of Ocean Bottom Seismometer by Using Acoustic Transponder and CTD

We have obtained precise estimates of the position of Ocean Bottom Seismometers (OBS) on the sea bottom. Such estimates are usually uncertain due to their free falling deployment. This uncertainty is small enough, or is correctable, with OBS spacing of more than 10 km usually employed in crustal studies. But, for example, if the spacing is only 200 m for OBS reflection studies, estimates of the position with an accuracy of the order of 10 m or more is required.The determination was carried out with the slant range data, ship position data and a 1D acoustic velocity structure calculated from Conductivity–Temperature–Depth (CTD) data, if they are available. The slant range data were obtained by an acoustic transponder system designed for the sinker releasing of the OBS or travel time data of direct water wave arrivals by airgun shooting. The ship position data was obtained by a single GPS or DGPS. The method of calculation was similar to those used for earthquake hypocenter determination.The results indicate that the accuracy of determined OBS positions is enough for present OBS experiments, which becomes order of 1 m by using the DGPS and of less than 10 m by using the single GPS, if we measure the distance from several positions at the sea surface by using a transponder system which is not designed for the precise ranging. The geometry of calling positions is most important to determine the OBS position, even if we use the data with larger error, such as the direct water wave arrival data. The 1D acoustic velocity structure should be required for the correct depth of the OBS. Although it is rare that we use a CTD, even an empirical velocity structure works well.     

Changes in the lower limit of mountain permafrost between 1973 and 2004 in the Khumbu Himal, the Nepal Himalayas

Because the Khumbu Himal of the Nepal Himalayas lacks long-term climate records from weather stations, mountain permafrost degradation serves as an important indicator of climate warming. In 1973, the permafrost lower limit was estimated to be 5200–5300 m above sea level (ASL) on southern-aspect slopes in this region. Using ground-temperature measurements, we examined the mountain permafrost lower limit on slopes with the same aspect in 2004. The results indicate that the permafrost lower limit was 5400–5500 m ASL in 2004. The permafrost lower limit was estimated to be 5400 to 5500 m on slopes with a southern aspect in the Khumbu Himal in 1991 using seismic reflection soundings. Thus, it is possible that the permafrost lower limit has risen 100–300 m between 1973 and 1991, followed by a stable limit of 5400 to 5500 m over the last decade. An increase in mean annual air temperature of approximately 0.2 to 0.4 °C from the 1970s to the 1990s has indicated a rise in the permafrost lower limit of 40 to 80 m at the Tibetan Plateau. The rise in the mountain permafrost lower limit in the Khumbu Himal exceeds that of the Tibetan Plateau, suggesting the possibility of greater climate warming in the Khumbu Himal.     

Estrogenic activity in sediments contaminated by nonylphenol in Tokyo Bay (Japan) evaluated by vitellogenin induction in male mummichogs (Fundulus heteroclitus)

Estrogenic activity was determined in sediments collected from Tokyo Bay. Sampling was performed at five stations including the site near the sewage treatment plant. The most estrogenic sediment collected near the sewage treatment plant was fractionated into ten fractions using normal-phase high-performance liquid chromatography. Chemical analysis was carried out for each fraction and nonylphenol (NP, 20,700 ng g⁻¹ dry wt) was detected at a higher concentration than estron (2.39 ng g⁻¹ dry wt) and 17β-estradiol (<0.7 ng g⁻¹ dry wt). Furthermore, each fraction was administered to male mummichogs (Fundulus heteroclitus), and vitellogenin (Vtg) was measured after two weeks. The induction of Vtg was observed; this estrogenic potency could be attributed to the NP content in this fraction. This is the first report to suggest that the high NP concentration in the sediments from Tokyo Bay has the potential to induce Vtg in wild fish.     

Compaction and fragmentation of porous gypsum targets from low-velocity impacts

We performed low-velocity impact experiments of gypsum spheres with porosity ranging from 0 to 61% and diameter ranging from 25 to 83 mm. The impact velocity was from 0.2 to 22 m/s. The target was an iron plate. The outcome of gypsum spheres with porosity 31-61% was different from those of non-porous ice [Higa M., Arakawa, M., Maeno, N., 1996. Planet. Space Sci. 44, 917-925; Higa M., Arakawa, M., Maeno, N., 1998. Icarus 133, 310-320] and non-porous gypsum. In between the intact and fragmentation modes, the outcome of the non-porous ice and gypsum was crack growth at the impact point. However, the outcome of the porous gypsum was compaction. We found that the restitution coefficients of the porous gypsum spheres were all in a similar range, in spite of the difference of the porosity and size at impact velocities up to about 10 m/s where they begin to be fragmented in pieces. Moreover, there is not a large difference between the restitution coefficient of porous and non-porous gypsum. These results collectively indicate that restitution coefficient of gypsum spheres of cm-size is not strongly dependent upon the porosity and compaction process.     

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.     

The Southern Westerlies during the last glacial maximum in PMIP2 simulations

The Southern Hemisphere westerly winds are an important component of the climate system at hemispheric and global scales. Variations in their intensity and latitudinal position through an ice-age cycle have been proposed as important drivers of global climate change due to their influence on deep-ocean circulation and changes in atmospheric CO₂. The position, intensity, and associated climatology of the southern westerlies during the last glacial maximum (LGM), however, is still poorly understood from empirical and modelling standpoints. Here we analyse the behaviour of the southern westerlies during the LGM using four coupled ocean-atmosphere simulations carried out by the Palaeoclimate Modelling Intercomparison Project Phase 2 (PMIP2). We analysed the atmospheric circulation by direct inspection of the winds and by using a cyclone tracking software to indicate storm tracks. The models suggest that changes were most significant during winter and over the Pacific ocean. For this season and region, three out four models indicate decreased wind intensities at the near surface as well as in the upper troposphere. Although the LGM atmosphere is colder and the equator to pole surface temperature gradient generally increases, the tropospheric temperature gradients actually decrease, explaining the weaker circulation. We evaluated the atmospheric influence on the Southern Ocean by examining the effect of wind stress on the Ekman pumping. Again, three of the models indicate decreased upwelling in a latitudinal band over the Southern Ocean. All models indicate a drier LGM than at present with a clear decrease in precipitation south of 40°S over the oceans. We identify important differences in precipitation anomalies over the land masses at regional scale, including a drier climate over New Zealand and wetter over NW Patagonia.     

A heating process of Kuchi-erabu-jima volcano,Japan, as inferred from geomagnetic field variations and electrical structure

Since August 2000, we have recorded the total intensity of the geomagnetic field at the summit area of Kuchi-erabu-jima volcano, where phreatic eruptions have repeatedly occurred. A time series analysis has shown that the variations in the geomagnetic field since 2001 have a strong relationship to an increase in volcanic activity. These variations indicate thermal demagnetization of the subsurface around the presently active crater. The demagnetization source for the early variations, until summer 2002, was estimated at about 200 m below sea level. For the variations since 2003, the source was modeled on the basis of the expansion of a uniformly magnetized ellipsoid. The modeling result showed that the source is located at 300 m above sea level beneath the crater. We carried out an audio-frequency magnetotelluric survey with the aim of obtaining a relation between the demagnetization source and the shallow structure of the volcano. A two-dimensional inversion applied to the data detected two good conductors, a shallow thin one which is restricted to a region around the summit area, while the other extends over the edifice at depths between 200 and 800 m. These conductors are regarded as clay-rich layers with low permeability, which were assumed to be generated through hydrothermal alteration. The demagnetization source for the early variations was possibly located at the lower part of the deep conductor and the source after 2003 lies between the two conductors, where groundwater is considered to be abundant. Based on these results, as well as on seismological, geodetic, and geochemical information, we propose a heating process of the Kuchi-erabu-jima volcano. In the initial stage, high-temperature volcanic gases supplied from the deep-seated magma remained temporarily at the level around the lower part of the less permeable deep conductor since the ascent path had not yet been established. Then, when the pathway developed as a result of repeated earthquakes, it became possible for a massive flux of volcanic gases to ascend through the conductor. The high temperature gases reached the aquifer located above the conductor and the heat was efficiently transported to the surrounding rocks through the groundwater. As a consequence, an abrupt increase of the gas flux and diffusion of the heat through the aquifer occurred and the high-temperature zone expanded. Since the high-temperature zone is located beneath another conductor, which acts as caprock, we assume that the energy of the phreatic explosion is accumulated there.     

Preliminary report on the activity at Unzen Volcano (Japan), November 1990-November 1991: Dacite lava domes and pyroclastic flows

The eruption of Unzen Volcano commenced on 17 November 1990. Phreatic and phreatomagmatic eruptions occurred by early May 1991. No large-scale explosive eruptions preceded the extrusion of lava domes. Lava domes appeared in a summit crater on 20 May 1991, and they grew on the steep slope of Mt. Fugen at Unzen Volcano. Rockfalls from the margins of the domes frequently generated pyroclastic flows. Major pyroclastic flows occurred on 3 June, 8 June, and 15 September 1991. The 3 June pyroclastic flow killed forty-three persons. Many of the pyroclastic flows seem to have resulted from the simple rockfalls, except one flow on 8 June, which was accompanied by an explosion from the crater. Many of the rockfalls that generated pyroclastic flows were witnessed. As of November 1991. Unzen Volcano was still active with a nearly constant magma-supply rate of about 0.3 × 10⁶ m³/d. The total magma output exceeded 45 × 10⁶ m³ by the beginning of November 1991. The volume of the lava domes is more than 23 × 10⁶ m³.