Size distribution of condensed aromatic rings in various soil humic acids

Condensed aromatic rings are important skeletal components with regard to the recalcitrant nature of humic acids (HAs) in the environment. However, they have not been extensively studied. The relative content and composition (size distribution) of condensed aromatic rings in HAs were obtained from various soils subjected to transmission electron microscopy (TEM) and X-ray diffraction (XRD) profile analysis. In the XRD profiles of all the HAs, the 11 band that was derived from the carbon layer planes was clearly observed. Analysis of the 11 band indicated that the size of the carbon layer planes in HAs ranged from 0.48-1.68 nm, corresponding to 4- to 37-ring condensed aromatic structures. The contents of the total and larger carbon layer planes were larger in HAs with darker color and larger aromatic carbon content. At the same time, the carbon layer planes in HAs were smaller than those in a carbon black reference (from 0.24 to >3.66 nm). In the TEM analysis, fringes observed in HAs were less distinct and less ordered than those in carbon black, which was in agreement with the XRD result.     

Effect of iron enrichment on the dynamics of transparent exopolymer particles in the western subarctic Pacific

Dynamics of transparent exopolymer particles (TEP) was studied during the first in situ iron-enrichment experiment conducted in the western subarctic Pacific in July–August 2001, with the goal of evaluating the contribution of TEP to vertical flux as a result of increased primary production following iron enrichment in open ocean ecosystems. Subsequent to the enhancement of phytoplankton production, we observed increase in TEP concentration in the surface layer and sedimentation of organic matter beneath it. Vertical profiles of TEP, chlorophyll a (Chl a) and particulate organic carbon (POC) were obtained from six depths between 5 and 70 m, from a station each located inside and outside the enriched patch. TEP and total mass flux were estimated from the floating sediment traps deployed at 200 m depth. Chl a and TEP concentrations outside the patch varied from 0.2 to 1.9 μg L⁻¹ and 40–60 μg XG equiv. L⁻¹, respectively. Inside the patch, Chl a increased drastically from day 7 reaching the peak of 19.2 μg L⁻¹ on day 13, which coincided with the TEP peak of 189 μg XG equiv. L⁻¹. TEP flux in the sediment trap increased from 41 to 88 mg XG equiv. m⁻² d⁻¹, with 8–14% contribution of TEP to total mass flux. This forms the basic data set on ambient concentrations of TEP in the western subarctic Pacific, and evaluation of the effect of iron enrichment on TEP.     

Type IIIb radio bursts: 80 MHz source position and theoretical model

We present Culgoora spectrograph and radioheliograph observations as well as a model of type IIIb bursts; the latter are defined as chains of striae of slow or no frequency drift, the chain as a whole drifting like a normal type III burst.The 80 MHz source positions are studied for a group of IIIb bursts, a IIIb precursor and harmonic pairs of 1:2 frequency ratio. It is found that the IIIb position may vary in a IIIb group. No significant difference was found between the source positions of a IIIb precursor and the following III burst. For one event we found that the fundamental IIIb burst showed a high degree of circular polarization (46%), while its second harmonic, a normal type III burst, was unpolarized.We suggest that the main cause for the striae in type IIIb bursts is the existence of filamentary, density irregularities along the path of the electron stream. The denser filaments initially reduce the value of the density gradient along the electrons' path and thereby enhance their emissions over a small range of plasma frequencies. If the radio emission from the filaments dominates the emission from the ambient rarified plasma, striae appear in the spectrum and a type IIIb burst results. This condition is more easily satisfied at the fundamental frequency and for electron streams of relatively high density.Radiophysics Publication RPP 1758, October, 1974, (2nd version).On leave from the Dept. of Astronomy, University of Tokyo, Tokyo, Japan.On leave from the Dept. of Astronomy, Cairo University, Cairo, Egypt.     

Deep convection seesaw controlled by freshwater transport through the Denmark Strait

Observations of deep ocean temperature and salinity in the Labrador and Greenland Seas indicate that there is negative correlation between the activities of deep convection in these two sites. A previous study suggests that this negative correlation is controlled by the North Atlantic Oscillation (NAO). In this study, we discuss this deep convection seesaw by using a coupled atmosphere and ocean general circulation model. In this simulation, the deep convection is realistically simulated in both the Labrador and Greenland Seas and their negative correlation is also recognized. Regression of sea level pressure to wintertime mixed layer depth in the Labrador Sea reveals strong correlation between the convection and the NAO as previous studies suggest, but a significant portion of their variability is not correlated. On the other hand, the convection in the Greenland Sea is not directly related to the NAO, and its variability is in phase with changes in the freshwater budget in the GIN Seas. The deep convection seesaw found in the model is controlled by freshwater transport through the Denmark Strait. When this transport is larger, more freshwater flows to the Labrador Sea and less to the Greenland Sea. This leads to lower upper-ocean surface salinity in the Labrador Sea and higher salinity in the Greenland Sea, which produces negative correlation between these two deep convective activities. The deep convection seesaw observed in the recent decades could be interpreted as induced by the changes in the freshwater transport through the Denmark Strait, whose role has not been discussed so far.     

Landslide risk evaluation and hazard zoning for rapid and long-travel landslides in urban development areas

Risk evaluation for earthquake-induced rapid and long-travel landslides in densely populated urban areas is currently the most important disaster mitigation task in landslide-threatened areas throughout the world. The research achievements of the IPL M-101 APERITIF project were applied to two urban areas in megacities of Japan. One site is in the upper slope of the Nikawa landslide site where previous movements were triggered by the 1995 Hyogoken-Nambu earthquake. During detailed investigation, the slope was found to be at risk from a rapid and long-travel landslide induced by sliding surface liquefaction by earthquakes similar in scale to the 1995 event. A new plan to prevent the occurrence of this phenomenon was proposed and the plan was implemented. Another area is the Tama residential area near Tokyo. A set of field and laboratory investigations including laser scanner, geological drilling and ring-shear tests showed that there was a risk of sliding surface liquefaction for both sites. A geotechnical computer simulation (Rapid/LS) using the quantitative data obtained in the study allowed urban landslide hazard zoning to be made at individual street level.     

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.     

Depositional Age of a Fossil Whale Bone from São Paulo Ridge,South Atlantic Ocean,Based on Os Isotope Stratigraphy of a Ferromanganese Crust

Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (¹⁸⁷Os/¹⁸⁸Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. ¹⁸⁷Os/¹⁸⁸Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.     

Variation of dissolved organic matter and fluorescence characteristics before,during and after phytoplankton bloom

The variation of dissolved organic matter (DOM) and fluorescence characteristics during the phytoplankton bloom were investigated in Yashima Bay, at the eastern part of the Seto Inland Sea, Japan. We found significant accumulations of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), chromophoric dissolved organic matter (CDOM) fluorescence, and UV₂₆₀ during the phytoplankton bloom period in 2005, although lower accumulations of DOC and DON and only increases of CDOM fluorescence were observed during the bloom period in 2006. Little or no correlation between DOM and phytoplankton abundance might be due to the composition of DOM, which is a complex mixture of organic materials. The 3D-EEM results revealed that the DOM produced around the phytoplankton bloom period contained tyrosine, tryptophan, and humic-like substances. Our results showed that the occurrence of phytoplankton bloom contributed to the production of DOM in coastal water but the DOM accumulation depended on the type of phytoplankton bloom, the phytoplankton species in particular. From our results, we concluded that phytoplankton have a great role in the dynamics of DOM as a producer in a coastal environment.     

A Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.