Comparison of reductive accumulation of Re and Os in seawater-sediment systems

In order to understand the fractionation of Re and Os in marine environments, their removal from artificial seawater to Tokyo Bay sediments is studied using a multitracer technique. The chemical processes of the removal of Re and Os are also estimated based on their speciation analyses by X-ray absorption fine structure (XAFS) spectroscopy. The partitioning experiments, which use the multitracer technique, provide information on Re and Os regarding (i) their distributions between artificial seawater-sediment systems, (ii) their complexation with humic acid, and (iii) their carriers in sediments. In addition, XAFS spectroscopy provides direct information on the chemical states of Re and Os in the sediments.In an artificial seawater-sediment system containing a multitracer, Re is removed from the artificial seawater only under a reducing environment. The speciation of Re by X-ray absorption near-edge structure (XANES) suggests that the majority of Re remains as in the artificial seawater even under highly reducing conditions, during laboratory time scale (about 2 weeks). Moreover, XANES simulation shows that some Re exists at a lower oxidation state, such as ReO₂, in the reducing sediment. These results can be explained by the slow kinetics of the reaction which is similar to those suggested by previous geochemical studies.In contrast, Os is readily removed from the artificial seawater into sediments under various redox conditions. Even under oxic conditions, a large fraction of Os is removed from the artificial seawater to sediments without organic matter. Based on the Os XANES study, it is confirmed that the oxidation states of Os incorporated in the reducing sediment and oxic sediment are trivalent and tetravalent, respectively. Sequential extraction suggests that the main carrier of Os in the organic-rich sediment is either ferromanganese oxides or organic matter, and that the Os in these two fractions may correspond to hydrolyzed insoluble Os species and Os species interacting with organic matter, at lower valence, respectively. The results of distribution study of Os in the absence and presence of humic acid (HA) also imply that Os assumes more than one chemical species, and a small fraction of Os may interact with HA in the experimental system. Meanwhile, extended X-ray absorption fine structure (EXAFS) confirms that the first neighboring atom of Os in the reducing sediment is oxygen. If Os(VIII) is the main dissolved species in seawater, as is expected thermodynamically, reductive removal may control the enrichment of Os in the sediment. Osmium, which is removed as Os(IV), is reduced further to Os(III) by a diagenetic process and may be complexed with organic matter in the reducing sediment.The results of the removal behaviors of Re and Os obtained in the current study show that Re can be removed from the artificial seawater only under highly reducing conditions within 2 weeks, but Os removal from the artificial seawater can be found under various redox conditions. Thus, a high ¹⁸⁷Re/¹⁸⁸Os ratio can occur only in reducing sediments, such as black shales. The high¹⁸⁷Re/¹⁸⁸Os ratio, in turn, makes black shales suitable for Re-Os dating. In contrast, authigenic sediments (and minerals) under oxic environments can enrich Os, but since Re is not distributed to the sediments under oxic conditions, this will cause a much lower ¹⁸⁷Re/¹⁸⁸Os ratio than that of seawater. The Os isotope system of these materials can be used as a paleo-marine environmental tracer since the ¹⁸⁷Os/¹⁸⁸Os ratio cannot grow significantly due to its extremely low ¹⁸⁷Re/¹⁸⁸Os ratio.     

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.     

Mantle heterogeneity beneath the southern Mid-Atlantic Ridge: trace element evidence for contamination of ambient asthenospheric mantle

We report new trace element data for an extensive suite of quench basalt glasses dredged from the southern Mid-Atlantic Ridge (MAR) between 40°S and 52.5°S. Ratios between highly incompatible trace elements are strongly correlated and indicate a systematic distribution of incompatible element enriched mid-ocean ridge basalt (MORB) (E-type: Zr/Nb=5.9-19, Y/Nb=0.9-8.4, (La/Sm)_n=1.0-2.9) and incompatible element depleted MORB (N-type: Zr/Nb=30-69, Y/Nb=11-29, (La/Sm)_n=0.48-0.79) along this section of the southern MAR. A notable feature of N-type MORB from the region is the higher than usual Ba/Nb (4-9), La/Nb (1.2-2.4) and primitive mantle normalised K/Nb ratios (>1). Ba/Nb ratios in E-type MORB samples from 47.5 to 49°S are especially elevated (>10). The occurrence and geographic distribution of E-type MORB along this section of the southern MAR can be correlated with the ridge-centred Shona and off-axis Discovery mantle plumes. In conjunction with published isotope data for a subset of the same sample suite [Douglass et al., J. Geophys. Res. 104 (1999) 2941], a model is developed whereby prior to the breakup of Gondwana and the opening of the South Atlantic Ocean, the underlying asthenospheric mantle was locally contaminated by fluids/melts rising from the major Mesozoic subduction zone along the south-southwest boundary of Gondwana, leaving a subduction zone geochemical imprint (elevated (K/Nb)_n and ⁸⁷Sr/⁸⁶Sr ratios, decreased ¹⁴³Nd/¹⁴⁴Nd ratios). Subsequent impingement of three major mantle plume heads (Tristan/Gough, Discovery, Shona) resulted in heating and thermal erosion of the lowermost subcontinental lithosphere and dispersal into the convecting asthenospheric mantle. With the opening of the ocean basin, continued plume upwelling led to plume-ridge interactions and mixing between geochemically enriched mantle derived from the Shona and Discovery mantle plumes, material derived from delamination of the subcontinental lithosphere, and mildly subduction zone contaminated depleted asthenospheric mantle.     

中国东部富钾埃达克岩成因的实验约束

Adakite在地球化学上具明显特征的火山岩和深成花岗岩类岩石，见于洋内岛孤环境和大陆孤，如安底斯孤。在洋内岛孤，由热的消减的大洋岩石圈熔融形成（叫做“板片熔融”），而在大陆孤，熔融曾发生在构造或岩浆加厚的下地壳底（叫做“下地壳熔融”）。在这两种产状环境中，adakite的鲜明地球化学特征被认为是起因子，一种不同程度含水的变质基性原岩在足够深度上的部分熔融，这里的足够深度是指可使石榴子石在残余结晶组合（即石榴角闪石和/或榴辉石的残余）中保持稳定的深度。“原始”或“母”adakite熔体一旦形成，便可能在其向上运移和侵位上地壳期间受到同化作用（或是地幔，或是大陆物质）和结晶分异作用的改造。中国东部晚中生代（早中白垩世，160-110Ma）的adakite,与见于同一地区和其它地方的钠质adakite相比，通常富含钾(K2O)和其它大离子亲石元素（如Ba,Th,U），有较低的Na2O/K2O比值（-1.0-1.1）,类似于玄武岩在石榴角闪岩-榴辉岩相含水熔融实验中所产生adakite熔体，要么是由洋壳板片熔融所形成，要么是由不同成分的玄武质下地壳原岩部分熔融所形成。尽管有些成分差异，它们的总体化学特征仍然可将中国东部的富钾花岗岩类岩石定均adakite。我们把这些富钾的adakite的独特化学行特征，归因于成分来源的特殊性，或adakite母岩浆遭受了同化混染和结晶分异(AFC)作用的改造。虽然中国东部与消减带环境明显不同这一点表明，那里的adakite可由板块底部侵位的（岩浆加厚的）镁铁质下地壳部分熔融所形成，但燕山运动期间中国东部存在“平坦”俯冲的地球动力学环境是可能被排除的。     

Concentrations of 222 Rn, Its Short-Lived Daughters And 212 Pb And Their Ratios Under Complex Atmospheric Conditions And Topography

Atmospheric activity concentrations of ²¹²Pb and short-lived ²²²Rndaughters, together with meteorological elements, have been observed continuously atthree sites at Kamisaibara Village in Japan. In addition, atmospheric activity concentrationof ²²²Rn, equilibrium-equivalent concentration of ²²²Rn and conditionsof the lower atmosphere were observed for three intensive observation periods at Akawase,one of the three sites in Kamisaibara Village. The equilibrium-equivalent concentration of²²²Rn is almost the same as the atmospheric activity concentration of short-lived²²²Rn daughters.The activity concentrations of ²¹²Pb and the short-lived ²²²Rn daughtersand their ratio were low in the daytime owing to convective mixing, and high at nightowing to the surface-based inversion during periods of no precipitation. Their variationshave several patterns corresponding to the scale of the drainage wind or weak mixing.Mechanical mixing due to strong winds through both day and night during the first andsecond observation periods made the atmospheric activity concentrations of ²¹²Pb and the short-lived ²²²Rn daughters continuously low. However, their ratios werecontinuously high during the first period yet continuously low during the second period.This difference can be explained by the effect ofextraction of ²²⁰Rn and ²²²Rndue to strong winds and snow cover. There were also cases in which the ratio of theatmospheric activity concentration of ²¹²Pb to that of the short-lived ²²²Rndaughters at night was equal to or less than the ratio in the daytime. Thisinverse trend, asin the periods of no precipitation mentioned above, is considered to be due to near-neutralconditions on these nights.We find a difference in the ratio of the equilibrium-equivalent concentration of²²²Rn (the activity concentration of short-lived ²²²Rn daughters) tothe activity concentration of ²²²Rn during the first observation period and thatduring the second. The difference can be explained by snow cover on the ground. Wealso find differences among the ratios of the activity concentration of the short-lived²²²Rn daughters to that of ²²²Rn during the three observation periods.These differences can be explained by the submergence of paddy fields.