Cosmogenic effects on Li/Li, B/B, and W/W in CAIs from carbonaceous chondrites

This study focuses on cosmogenic effects on lithium, boron, and tungsten isotopes in CAIs from carbonaceous chondrites. The results for lithium isotopes have been used to properly correct experimental data obtained by Chaussidon et al. (2006a) for Allende CAI 3529-41 for cosmogenic contributions. After proper correction, the new inferred ratios slightly but systematically differ from the original ones, indicating that the original study slightly overestimated the cosmogenic corrections. A statistical interpretation of the data indicates that there is a non-linear correlation between ⁷Li/⁶Li and ⁹Be/⁶Li that might be interpreted as a disturbed isochron. For boron isotopes, the data obtained here confirm that cosmogenic corrections on the ¹⁰Be-¹⁰B dating system are indeed very minor and can in most cases be neglected. However, a statistical interpretation of the data demonstrates that the type of the fitting procedure used can significantly change the results. It is demonstrated that a fitting procedure using the uncertainties as weights gives a slope about 50% shallower compared to the slope obtained using a non-weighted fitting procedure (for the same data). Such a difference can be wrongly interpreted as an age difference of about one half-life. The modeled results for tungsten isotopes clearly demonstrate that cosmic-ray effects might be of importance for samples having high Ta/W ratios due to thermal neutron capture on ¹⁸¹Ta to form ¹⁸²W. This effect does not increase the scatter of the data around the isochron but increases the slope of the isochron and therefore gives too old formation ages for the studied CAIs. Consequently, a proper handling of cosmic-ray induced shifts is necessary for high precision ¹⁸²Hf-¹⁸²W dating studies.     

Concentrations,sources, and losses of H2O,CO2, and S in Kilauean basalt

Basaltic glasses included in olivine phenocrysts from Kilauea volcano contain concentrations of H₂O, CO₂, and S similar to glassy Kilauean basalt dredged from the deep sea floor and greater than vesicular, subaerial Kilauean basalt. Our result contrasts with earlier reports that inclusions of basaltic glass in phenocrysts have little or no H₂O and large ratios of $\text{CO}{}_2\text{H}{}_2\text{O}$. Our analysed inclusions of glass are larger than 100 micrometers thick and similar in chemical composition to the host glass surrounding the olivine crystals indicating that the trapped melts are representative of the bulk liquid from which the crystals grew. Crystallization of about 2–8% of olivine from the melts after they were trapped is indicated by slight departures from the experimentally established equilibrium distribution of Mg and Fe between olivine and liquid. The measured concentrations of CO₂ correspond to phenocryst crystallization pressures of about 1.3 kbar for a subaerial basalt and about 5 kbar for a submarine basalt, consistent with geophysical models of Kilauea volcano. The compositions of volcanic gas predicted from our analyses are consistent with restored compositions of actual Kilauean gases. The rate of sulfur emission predicted from our analyses is greater than the sulfur dioxide emission rate observed during repose, but probably consistent with total degassing including eruptive episodes. The concentrations of H₂O, K₂O, Cl, and P in parental Kilauean basalt can be derived from upper mantle phlogopitic mica, pargasitic amphibole and apatite with compositions close to those of natural primary minerals in ultramafic xenoliths from continental kimberlites, or solely from apatite and phlogopitic mica with $\text{H}{}_2\text{O}\text{K}{}_2\text{O}$ near 0.47 ± 0.03, slightly higher than the range of values reported. The amounts of phlogopitic mica and pargasitic amphibole contributing volatiles to Kilauean tholeiite is about 10 percent by mass of the parental liquid, or about 5% if the source does not include amphibole. In view of an estimated 20% of partial melting of mantle source rock to produce Kilauean tholeiites, there may be about 2 weight percent of mica plus amphibole in part of the mantle beneath Kilauea, or about 1 weight percent of phlogopitic mica if amphibole is absent.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts and aqueous solutions—II. The network modifying effects of Mg2+ , K+, Na+, Li+, H+, OH−, F−, Cl−, H2O,CO2 and H3O+ on silicate polymers

The effect of the group IA and VIIA ions, as well as Mg²⁺, and the molecules H₂O, CO₂, H₃O⁺ and OH^? on the energy of the Si-O bond in a H₆Si₂O₇ cluster has been calculated using semiempirical molecular orbital calculations (CNDO/2). Three types of elementary processes, i.e. substitution, addition, and polymerization reactions have been used to interpret data on the dynamic viscosity, surface tension and surface charge, hydrolytic weakening, diffusivity, conductivity, freezing point depression, and degree of polymerization of silicates in melts, glasses, and aqueous solutions. As a test of our calculational procedure, observed X-ray emission spectra of binary alkali silicate glasses were compared with calculated electronic spectra. The well known bondlength variations between the bridging bond [Si-O(br)] and the non-bridging bond [Si-O(nbr)] in alkali silicates are shown to be due to the propagation of oscillating bond-energy patterns through the silica framework. A kinetic interpretation of some results of our calculations is given in terms of the Bell-Evans-Polanyi reaction principle.     

Mg,Ca and O18O16 exchange in the sediment-pore water system,hole 149, DSDP

The diagenesis and geochemical evolution of deep-sea sediments are controlled by the interaction between sediments and their associated pore waters. With increasing depth, the pore water of Hole 149 (DSDP) exhibits a strong depletion in Mg and a corresponding enrichment in Ca, while the alkalinity remains relatively constant. Dissolved SiO₂ is nearly constant in the upper 100 m of sediment, but is highly enriched in the deepest pore waters. The pore waters exhibit a depletion in K with increasing depth, and $\text{O}{}^{18}\text{O}{}^{16}$ pore water ratios also decrease.The sediment section has three zones of sedimentary regimes with increasing depth in the drill hole: an upper 100 m section of detrital clays, a middle section enriched in calc-akalic volcanics which have undergone submarine weathering to a smectite phase, and a lower section of siliceous ooze which still has a diagenetic smectite phase. The quartz-feldspar ratios and $\text{O}{}^{18}\text{O}{}^{16}$ composition of the silicate phases are in agreement with these interpretations.The submarine weathering of volcanics to a smectite can account for the observed pore water gradients. Volcanics release Ca and Mg to the pore waters causing the alkalinity values to increase. Smectite is formed, depletes the pore waters in Mg and O¹⁸ and causes the alkalinity to decrease. The net reaction allows for the observed relationship between pore water Ca and Mg gradients with little net change in alkalinity. Given the abundance of volcanics in many deep-sea sediments, especially in lower sections which often form near ridge crests, the submarine formation of smectite may be an additional oceanic Mg sink which has not yet been fully considered.     

The lanthanide tetrad effect and its correlation with K/Rb,Eu/Eu1, Sr/Eu,Y/Ho,and Zr/Hf of evolving peraluminous granite suites

Lanthanide tetrad effects are often observed in REE patterns of more highly evolved Variscan peraluminous granites of mid-eastern Germany (Central Erzgebirge, Western Erzgebirge, Fichtelgebirge, and Northern Oberpfalz). The degree of the tetrad effect (TE_1,3) is estimated and plotted vs. K/Rb, Sr/Eu, Eu/Eu1, Y/Ho, and Zr/Hf. The diagrams reveal that the tetrad effect develops parallel to granite evolution, and significant tetrad effects are strictly confined to highly differentiated samples. Mineral fractionation as a cause for the tetrad effect is not supported by a calculated Rayleigh fractionation, which also could not explain the fractionation trends of Sr/Eu and Eu/Eu1. The strong decrease of Eu concentrations in highly evolved rocks suggests that Eu fractionates between the residual melt and a coexisting aqueous high-temperature fluid. Mineral fractionation as a reason for the tetrad effect is even more unlikely as REE patterns of accessory minerals display similar tetrad effects as the respective host rocks. The accessory minerals inherit the REE signature of the melt and do not contribute to the bulk-rock tetrad effect via mineral fractionation. These results point in summary to significant changes of element fractionation behavior in highly evolved granitic melts: ionic radius and charge, which commonly control the element distribution between mineral and melt, are no longer the exclusive control. The tetrad effect and the highly fractionated trace element ratios of Y/Ho and Zr/Hf indicate a trace element behavior that is similar to that in aqueous systems in which chemical complexation is of significant influence. This distinct trace element behavior and the common features of magmatic-hydrothermal alteration suggest the increasing importance of an aqueous-like fluid system during the final stages of granite crystallization. The positive correlation of TE_1,3 with bulk-rock fluorine contents hints at the importance of REE fluorine complexation in generating the tetrad effect. As the evolution of a REE pattern with tetrad effect (M-type) implies the removal of a respective mirroring REE pattern (W-type), the tetrad effect identifies open system conditions during granite crystallization.     

Seawater nutrient and carbonate ion concentrations recorded as P/Ca, Ba/Ca, and U/Ca in the deep-sea coral Desmophyllum dianthus

As paleoceanographic archives, deep sea coral skeletons offer the potential for high temporal resolution and precise absolute dating, but have not been fully investigated for geochemical reconstructions of past ocean conditions. Here we assess the utility of skeletal P/Ca, Ba/Ca and U/Ca in the deep sea coral D. dianthus as proxies of dissolved phosphate (remineralized at shallow depths), dissolved barium (trace element with silicate-type distribution) and carbonate ion concentrations, respectively. Measurements of these proxies in globally distributed D. dianthus specimens show clear dependence on corresponding seawater properties. Linear regression fits of mean coral Element/Ca ratios against seawater properties yield the equations: P/Ca_coral (μmol/mol) = (0.6 ± 0.1) P/Ca_sw(μmol/mol) - (23 ± 18), R² = 0.6, n = 16 and Ba/Ca_coral(μmol/mol) = (1.4 ± 0.3) Ba/Ca_sw(μmol/mol) + (0 ± 2), R² = 0.6, n = 17; no significant relationship is observed between the residuals of each regression and seawater temperature, salinity, pressure, pH or carbonate ion concentrations, suggesting that these variables were not significant secondary dependencies of these proxies. Four D. dianthus specimens growing at locations with Ω_arag ? 0.6 displayed markedly depleted P/Ca compared to the regression based on the remaining samples, a behavior attributed to an undersaturation effect. These corals were excluded from the calibration. Coral U/Ca correlates with seawater carbonate ion: U/Ca_coral(μmol/mol) = (−0.016 ± 0.003) (μmol/kg) + (3.2 ± 0.3), R² = 0.6, n = 17. The residuals of the U/Ca calibration are not significantly related to temperature, salinity, or pressure. Scatter about the linear calibration lines is attributed to imperfect spatial-temporal matches between the selected globally distributed specimens and available water column chemical data, and potentially to unresolved additional effects. The uncertainties of these initial proxy calibration regressions predict that dissolved phosphate could be reconstructed to ±0.4 μmol/kg (for 1.3-1.9 μmol/kg phosphate), and dissolved Ba to ±19 nmol/kg (for 41-82 nmol/kg Ba_sw). Carbonate ion concentration derived from U/Ca has an uncertainty of ±31μmol/kg (for ). The effect of microskeletal variability on P/Ca, Ba/Ca, and U/Ca was also assessed, with emphasis on centers of calcification, Fe-Mn phases, and external contaminants. Overall, the results show strong potential for reconstructing aspects of water mass mixing and biogeochemical processes in intermediate and deep waters using fossil deep-sea corals.     

Corrensite and mixed-layer chlorite/corrensite in metabasalt from northern Taiwan: TEM/AEM,EMPA, XRD,and optical studies

Many chloritic minerals in low-grade metamorphic or hydrothermally altered mafic rocks exhibit abnormal optical properties, expand slightly upon glycolation (expandable chlorite) and/or have excess Al^VI relative to Al^IV, as well as significant Ca, K and Na contents. Chloritic minerals with these properties fill vesicles and interstitial void space in low-grade metabasalt from northern Taiwan and have been studied with a combination of TEM/AEM, EMPA, XRD, and optical microscopy. The chloritic minerals include corrensite, which is an ordered 1:1 mixed-layer chlorite/smectite, and expandable chlorite, which is shown to be a mixed-layer chlorite/corrensite. Corrensite and some mixed-layer chlorite/corrensite occur as rims of vesicles and other cavities, while later-formed mixed-layer chlorite/corrensite occupies the vesicle cores. The TEM observations show that the mixed-layer chlorite/corrensite has ca. 20%, and the corrensite has ca. 50% expandable smectite-like layers, consistent with XRD observations and with their abnormal optical properties. The AEM analyses show that high Si and Ca contents, high Al^VI/Al^IV and low Fe^VI/(Fe+Mg)^VI ratios of chlorites are correlated with interstratification of corrensite (or smectite-like) layers in chlorite. The AEM analyses obtained from 200–500 Å thick packets of nearly pure corrensite or chlorite layers always show that corrensite has low Al^IV/Si^IV and low Fe^VI/(Fe+Mg)^VI, while chlorite has high Al^IV/Si^IV and high Fe^VI/(Fe+Mg)^VI. This implies that the trioctahedral smectite-like component of corrensite has significantly lower Al^IV/Si^IV and Fe^VI/(Fe+Mg)^VI. The ratios of Fe^VI/(Fe+Mg)^VI and Al^IV/Si^IV thus decrease in the order chlorite, corrensite, smectite. The proportions of corrensite (or smectite-like) layers relative to chlorite layers in low-grade rocks are inferred to be controlled principally by Fe/Mg ratio in the fluid or the bulk rock and by temperature. Compositional variations of chlorites in low-grade rocks, which appear to correlate with temperature or metamorphic grade, more likely reflect variable proportions of mixed-layered components. The assemblages of trioctahedral phyllosilicates tend to occur as intergrown discrete phases, such as chlorite-corrensite, corrensite-smectite, or chlorite-corrensite-smectite. A model for the corrensite crystal structure suggests that corrensite should be treated as a unique phase rather than as a 1:1 ordered mixed-layer chlorite/smectite.     

滇西腾冲更新世粗面安山岩Ar-Ar年代学、地球化学特征及其构造意义

腾冲芒棒地区广泛发育新近纪以来的火山岩,本文首次对该区粗面安山岩进行的高精度40Ar/39Ar同位素定年,其坪年龄分别为2.1±0.1Ma和2.0±0.1Ma,代表其喷溢时代为早更新世。岩石地球化学特征研究显示,粗面安山岩属高钾钙碱性系列,富集大离子亲石元素、亏损高场强元素,具有弧火山岩与大陆板内火山岩的双重属性,推测其形成于后造山环境。综合研究表明,腾冲地块更新世火山岩的形成与印度-欧亚板块俯冲-碰撞造山隆升后的伸展垮塌、富集地幔部分熔融作用密切相关,而印支陆块向东南逃逸以及腾冲弧形走滑断裂带(龙川江断裂带、大盈江断裂带)的活化促使了该期火山岩的喷发与侵位。     

Regional differences in plant-soil mercury relations in Equisetum, Plantago and Taraxacum

The mercury contents of Equisetum, Plantago and Taraxacum growing in the Prince George area of British Columbia varied with soil mercury level. In contrast, mercury in the same plant species growing around Mount St. Helens was soil-concentration independent. Both regions are mercury-rich, but the former is relatively thermally inactive at present. It is suggested that both populations limit their tissue mercury levels to about 100–500 ppb but that those around Mount St. Helens, where soil levels remain moderate, equilibrate tissues with atmospheric mercury from the volcano, whereas those in British Columbia depend more upon biovolatilization as a partial control process.     

Sources, degassing, and contamination of CO2, H2O, He, Ne, and Ar in basaltic glasses from Kolbeinsey Ridge, North Atlantic

New volatile data (CO₂, H₂O, He, Ne, and Ar) are presented for 24 submarine basaltic glasses from the Kolbeinsey Ridge, Tjörnes Fracture Zone and Mohns Ridge, North Atlantic. Low CO₂ and He contents indicate that magmas were strongly outgassed with the extent of degassing increasing toward the south, as expected from shallower ridge depths. Ne and Ar are significantly more abundant in the southernmost glasses than predicted for degassed melt. The strong atmospheric isotopic signal associated with this excess Ne and Ar suggests syn- or posteruptive contamination by air. Degassing, by itself, cannot generate the large variations in δ¹³C values of dissolved CO₂ or coupled CO₂-Ar variations. This suggests that δ¹³C values were also affected by some other processes, most probably melt-crust interaction. Modelling indicates that degassing had a negligible influence on water owing to its higher solubility in basaltic melt than the other volatiles. Low H₂O contents in the glasses reflect melting of a mantle source that is not water-rich relative to the source of N-MORB.Before eruption, Kolbeinsey Ridge melts contained ∼400 ppm CO₂ with δ¹³C of −6‰, 0.1 to 0.35 wt.% H₂O, ³He/⁴He ∼11 R_A, and CO₂/³He of ∼2 × 10⁹. We model restored volatile characteristics and find homogeneous compositions in the source of Kolbeinsey Ridge magmas. Relative to the MORB-source, He and Ne are mildly fractionated while the ⁴⁰Ar/³⁶Ar may be low. The ³He/⁴He ratios in Tjörnes Fracture Zone glasses are slightly higher (13.6 R_A) than on Kolbeinsey Ridge, suggesting a greater contribution of Icelandic mantle from the south, but the lack of ³He/⁴He variation along the Kolbeinsey Ridge is inconsistent with active dispersal of Icelandic mantle beyond the Tjörnes Fracture Zone.     

Mg/Ca, Sr/Ca, and stable isotopes in modern and Holocene Protothaca staminea shells from a northern California coastal upwelling region

This study explores the potential of intertidal Protothaca staminea shells as high-resolution geochemical archives of environmental change in a coastal upwelling region. Mg/Ca and Sr/Ca ratios were analyzed by excimer laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) at sub-weekly temporal resolution in shells growing ∼1 mm per month. Growth patterns of a modern P. staminea shell from Humboldt Bay, California, collected in December 1999 made it possible to infer a lifespan from 1993 to 1998. Growth hiatuses in the shell may have excluded records of extreme events. Mg/Ca ratios appeared to be partly controlled by water temperature; the correlation coefficient between temperature and Mg/Ca was r = 0.71 in one of four growth increments. Significant year-to-year differences in the sensitivity of Mg/Ca to temperature in P. staminea could not be explained, however. Sr/Ca ratios appeared to be more closely related to shell growth rate. Oxygen isotopes, measured at 2-week temporal resolution in the same shell, did not show a clear relation to local temperature in summer, possibly because temperatures were higher and less variable at the King Salmon mudflat, where the shell was collected, than in the main channel of Humboldt Bay, where water properties were monitored. Negative shell δ¹³C values (<−0.5‰) marked spring and summer coastal upwelling events.The Mg contents of P. staminea midden shells dated to ∼3 ka and ∼9 ka were significantly lower than in the modern shell. This may have resulted from degradation of a Mg-rich shell organic matrix and precluded quantitative interpretation of the older high-resolution records. Elevated δ¹³C values in the ∼3 ka shell suggested that the individual grew in highly productive or stratified environment, such as a shallow coastal embayment or lagoon.     

The Growth of Estuarine Resources (Zostera marina, Mercenaria mercenaria, Crassostrea virginica, Argopecten irradians, Cyprinodon variegatus) in Response to Nutrient Loading and Enhanced Suspension Feeding by Adult Shellfish

While many coastal ecosystems previously supported high densities of seagrass and abundant bivalves, the impacts of overfishing, eutrophication, harmful algal blooms, and habitat loss have collectively contributed to the decline of these important resources. Despite improvements in wastewater treatment in some watersheds and subsequent reduced nutrient loading to neighboring estuaries, seagrass and bivalve populations in these locations have generally not recovered. We performed three mesocosm experiments to simultaneously examine the contrasting effects of nutrient loading and historic suspension-feeding bivalve densities on the growth of eelgrass (Zostera marina), juvenile bivalves (northern quahogs, Mercenaria mercenaria; eastern oysters, Crassostrea virginica; and bay scallops, Argopecten irradians), and juvenile planktivorous fish (sheepshead minnow, Cyprinodon variegatus). High nutrient loading rates led to significantly higher phytoplankton (chlorophyll a) levels in all experiments, significantly increased growth of juvenile bivalves relative to controls with lower nutrient loading rates in two experiments, and significantly reduced the growth of eelgrass in one experiment. The filtration provided by adult suspension feeders (M. mercenaria and C. virginica) significantly decreased phytoplankton levels in all experiments, significantly increased light penetration and the growth of eelgrass in one experiment, and significantly decreased the growth of juvenile bivalves and fish in two experiments, all relative to controls with no filtration from adult suspension feeders. These results demonstrate that an appropriate level of nutrient loading can have a positive effect on some estuarine resources and that bivalve filtration can mediate the effects of nutrient loading to the benefit or detriment of different estuarine resources. Future ecosystem-based approaches will need to simultaneously account for anthropogenic nutrient loading and bivalve restoration to successfully manage estuarine resources.     

地下水中高锰酸盐指数和硝酸根铵根稳定性研究

高锰酸盐指数(CODMn)、硝酸根(NO-3)、铵根(NH+4)是判断水体是否受到三氮污染的重要指标。对于测定这三个指标的水样保存方式和时间,地质行业标准和国内外主要国家标准间存在明显差异。地质行业标准规定地下水样品原水室温保存,CODMn和NH+4在3天内测定;NO-3在20天内测定;国家标准和美国标准推荐样品硫酸酸化,避光或冷藏保存,在2~7天内完成CODMn和NO-3和1~7天内完成NH+4测试。为了分析各类标准在样品保存要求上的差异对检测结果的影响,确保检测数据能真实地反映水体污染状况,找寻简便的保存方式,本文在广州地区采集地下水,按照地质行业标准与国家标准进行处理和保存,并在不同时间段对三个指标进行测试。分析验证结果表明:地质行业标准与国家和美国标准关于水样的保存方法均非常可靠。地质行业标准主要针对静态地下水,保存方法相对宽松;国家标准和美国标准适用范围除了地下水,还包括动态的地表水和废水,采样对象成分更为复杂,更不稳定,更容易受外界影响发生变化,故保存条件高于地质标准。在广州地区,采用原水室温避光保存水样,CODMn、NH+4保存时间可为5天,NO-3保存时间可为30天;采用酸化水室温保存水样,CODMn、NO-3和NH+4保存时间可长达30天。这两种方式均比地质行业标准和国家标准推荐的有效时间长,且原水和酸化水室温保存方式相对于冷藏保存方式更为方便。本文提出,如果采集的水样能方便、快速送达实验室,可采用原水保存;如果不能在短时间内送达实验室检测,可采用硫酸酸化保存。     

Structure, thermodynamics, and diffusion in CaAl2Si2O8 liquid from first-principles molecular dynamics

We have performed first-principles molecular dynamics simulations of CaAl₂Si₂O₈ (anorthite) liquid at pressures up to 120 GPa and temperatures of 3000, 4000 and 6000 K. At the lowest degrees of compression the liquid is seen to accommodate changes in density through decreasing the abundance of 3- and 4-membered rings, while increases in coordination of network forming cations take effect at somewhat higher degrees of compression. Results are fit to a fundamental thermodynamic relation with 4th order finite strain and 1st order thermal variable expansions. Upon compression by a factor of two, the Grüneisen parameter (γ) is found to increase continuously from 0.35 to 1.10. Weak temperature dependence in γ is thermodynamically consistent with a slight decrease in isochoric heat capacity (C_V), for which values of between 4.4 and 5.2 Nk_B are obtained, depending on the temperature. Pressure and temperature dependence of self-diffusivities is found to be well represented by an Arrhenius relation, except at 3000 K and pressures lower than 5 GPa, where self-diffusivities of Si, Al, and O increase with pressure. Analysis of the lifetimes of individual coordination species reveals that this phenomenon arises due to the disproportionately high stability of 4-fold coordinated Si, and to a lesser extent 4-fold coordinated Al. Our results represent a marked improvement in accuracy and reliability in describing the physics of CaAl₂Si₂O₈ liquid at deep mantle pressures, pointing the way to a general thermodynamic model of melts at extreme pressures and temperatures relevant to planetary-scale magma oceans and deep mantle partial melting.     

Annular seismicity structures and the March 11, 2011, earthquake (Mw = 9.0) in Northeast Japan

The characteristics of seismicity prior to the series of eight very strong earthquakes (M _w = 7.0–9.0) in Northeast Japan are discussed. Ring seismicity structures that appeared prior to all eight events in two depth ranges of 0–33 and 34–70 km are identified. The epicenters of the main shocks were located near areas of crossing or touching of shallow and deep rings. It was shown that the sizes of shallow rings and threshold magnitudes corresponding to seismicity rings grow with the energy of the main shocks. It was noted that the prognosis with respect to the place and magnitude of the catastrophic earthquake on March 11, 2011, had been made before it based on the data obtained prior to July 1, 2009. Use of the new data obtained prior to March 10, 2011, enabled us to specify this prognosis significantly. We obtained correlation dependences of threshold magnitudes on the energy of the main shocks (with a high correlation coefficients). It was shown that the duration of the period for seismicity rings to emerge in the considered region nearly did not depend on magnitude. The nature of annular structures and the possibility of application of their parameters for prognosis of strong earthquakes were discussed.     

Solubility of cassiterite in evolved granitic melts: effect of T, fO2, and additional volatiles

The aim of this experimental study was to determine the solubility of cassiterite in natural topaz- and cassiterite-bearing granite melts at temperatures close to the solidus. Profiles of Sn concentrations at glass–crystal (SnO₂) interface were determined following the method of (Harrison, T.M., Watson, E.B., 1983. Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content. Contributions to Mineralogy and Petrology 84, 66–72). The cassiterite concentration calculated at the SnO₂–glass interface is the SnO₂ solubility. Experiments were performed at 700–850 °C and 2 kbar using a natural F-bearing peraluminous granitic melt with 2.8 wt.% normative corundum. Slightly H₂O-undersaturated to H₂O-saturated melt compositions were chosen in order to minimize the loss of Sn to the noble element capsule walls. At the nickel–nickel oxide assemblage (Ni–NiO) oxygen fugacity buffer, the solubility of cassiterite in melts containing 1.12 wt.% F increases from 0.32 to 1.20 wt.% SnO₂ with an increasing temperature from 700 to 850 °C. At the Ni–NiO buffer and a given corundum content, SnO₂ solubility increases by 10% to 20% relative to an increase of F from 0 to 1.12 wt.%. SnO₂ solubility increases by 20% relative to increasing Cl content from 0 to 0.37 wt.% in synthetic granitic melts at 850 °C. We show that Cl is at least as important as F in controlling SnO₂ solubility in evolved peraluminous melts at oxygen fugacities close to the Ni–NiO buffer. In addition to the strong effects of temperature and fO₂ on SnO₂ solubility, an additional controlling parameter is the amount of excess Al (corundum content). At Ni–NiO and 850 °C, SnO₂ solubility increases from 0.47 to 1.10 wt.% SnO₂ as the normative corundum content increases from 0.1 to 2.8 wt.%. At oxidizing conditions (Ni–NiO +2 to +3), Sn is mainly incorporated as Sn⁴⁺ and the effect of excess Al seems to be significantly weaker than at reducing conditions.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—I. Electronic structure of H6Si2O7, H6AlSiO71−, and H6Al2O72−

As part of a study of the effect of geologically common network modifiers on polymerization in silicate melts, glasses, and silica-rich aqueous solutions, we have studied the energies, electronic structures, and inferred chemical properties of ^IVT-O-^IVT linkages in the tetrahedral dimers H₆,Si₂O₇, H₆AlSiO₇^1?, and H₆Al₂O₇^2? using semi-empirical molecular orbital theory (CNDO/2). Our results indicate that the electron donating character of the bridging oxygen, O(br), linking two tetrahedra increases with increasing T-O(br) bond length but decreases with decreasing T-O(br)-T angles and increasing O-T-O(br) angles. This increase or decrease of the donor character of O(br) coincides with an increase or decrease of the affinity of O(br) for hard acceptors. The calculated electronic structure for the H₆Si₂O₇ molecule is compared with the observed X-ray emission, absorption, and photoelectron spectra of quartz and vitreous silica; the reasonable match between calculated and observed oxygen Kα emission spectra of vitreous silica supports our assertion that non-bonded O(br) electron density energetically at the top of the valence band controls the chemical reactivity of ^IVT-O-^IVT linkages in polymerized tetrahedral environments.     

Producing/contesting whiteness: rebellion, anti-slavery and enslavement in Barbados, 1816

The increasing attention paid by geographers to white identities represents a welcome corrective to research on race and ethnicity that focused on non-white subjectivities and promises to deconstruct the purportedly `normal' or `unremarkable' status often afforded to whiteness. Such work is a vital part of a critical geographical agenda. This paper seeks to contribute to such an agenda by responding to Bonnett [Area 29 (1997) 193, White Identities: Historical and International Perspectives, Prentice Hall, 2000] call for a historical geographical engagement with `white studies'. To do so, it begins by considering how such a critical geography might be spatially and theoretically framed. It then introduces a specific context for such an engagement--the revolt of 1816 by enslaved people of African origin in the British Caribbean colony of Barbados. Reading this not as a single event but as a locus of multiple and conflicting narrations, each linked to particular assertions and contestations of whiteness, the paper argues that geographies of white identities must emphasise struggles between `white' subjects, as well as the role of subaltern acts and representations in white racialisation. This is important if postcolonial, and therefore critical, geographies of white identities are to be produced.     

Molecular H2O in armenite, BaCa2Al6Si9O30·2H2O, and epididymite, Na2Be2Si6O15·H2O: Heat capacity, entropy and local-bonding behavior of confined H2O in microporous silicates

Armenite, ideal formula BaCa₂Al₆Si₉O₃₀·2H₂O, and its dehydrated analog BaCa₂Al₆Si₉O₃₀ and epididymite, ideal formula Na₂Be₂Si₆O₁₅·H₂O, and its dehydrated analog Na₂Be₂Si₆O₁₅ were studied by low-temperature relaxation calorimetry between 5 and 300 K to determine the heat capacity, C_p, behavior of their confined H₂O. Differential thermal analysis and thermogravimetry measurements, FTIR spectroscopy, electron microprobe analysis and powder Rietveld refinements were undertaken to characterize the phases and the local environment around the H₂O molecule.The determined structural formula for armenite is Ba_0.88(0.01)Ca_1.99(0.02)Na_0.04(0.01)Al_5.89(0.03)Si_9.12(0.02)O₃₀·2H₂O and for epididymite Na_1.88(0.03)K_0.05(0.004)Na_0.01(0.004)Be_2.02(0.008)Si_6.00(0.01)O₁₅·H₂O. The infrared (IR) spectra give information on the nature of the H₂O molecules in the natural phases via their H₂O stretching and bending vibrations, which in the case of epididymite only could be assigned. The powder X-ray diffraction data show that armenite and its dehydrated analog have similar structures, whereas in the case of epididymite there are structural differences between the natural and dehydrated phases. This is also reflected in the lattice IR mode behavior, as observed for the natural phases and the H₂O-free phases. The standard entropy at 298 K for armenite is S° = 795.7 ± 6.2 J/mol K and its dehydrated analog is S° = 737.0 ± 6.2 J/mol K. For epididymite S° = 425.7 ± 4.1 J/mol K was obtained and its dehydrated analog has S° = 372.5 ± 5.0 J/mol K. The heat capacity and entropy of dehydration at 298 K are Δ = 3.4 J/mol K and ΔS^rxn = 319.1 J/mol K and Δ = −14.3 J/mol K and ΔS^rxn = 135.7 J/mol K for armenite and epididymite, respectively. The H₂O molecules in both phases appear to be ordered. They are held in place via an ion-dipole interaction between the H₂O molecule and a Ca cation in the case of armenite and a Na cation in epididymite and through hydrogen-bonding between the H₂O molecule and oxygen atoms of the respective silicate frameworks. Of the three different H₂O phases ice, liquid water and steam, the C_p behavior of confined H₂O in both armenite and epididymite is most similar to that of ice, but there are differences between the two silicates and from the C_p behavior of ice. Hydrogen-bonding behavior and its relation to the entropy of confined H₂O at 298 K is analyzed for various microporous silicates.The entropy of confined H₂O at 298 K in various silicates increases approximately linearly with increasing average wavenumber of the OH-stretching vibrations. The interpretation is that decreased hydrogen-bonding strength between a H₂O molecule and the silicate framework, as well as weak ion-dipole interactions, results in increased entropy of H₂O. This results in increased amplitudes of external H₂O vibrations, especially translations of the molecule, and they contribute strongly to the entropy of confined H₂O at T < 298 K.