Implications of the serpentine phase transition on the behaviour of beryllium and lithium-boron of subducted ultramafic rocks

The Totalp-Platta-Malenco ophiolites in the Eastern Central Alps offer a unique opportunity to study the behaviour of Li, Be and B in ultramafic rocks in response to serpentinization and to progressive Alpine metamorphism. These units represent the remnants of a former ocean-continent transition that was intensely serpentinized during exposure on the Jurassic seafloor of the Ligurian Tethys. From north to the south, three isograd reactions (lizardite⇒antigorite+brucite;lizardite+talc⇒antigorite;lizardite+tremolite⇒antigorite+diopside) have been used to quantify the evolution of the light element content of metamorphic minerals. We determined the Li, Be and B concentrations in major silicate minerals from the ultramafic bodies of Totalp, Platta and Malenco by secondary ion mass spectrometry. Mantle minerals have Be concentrations (e.g. <0.001-0.009 μg/g in olivine) similar to the metamorphic minerals that replace them (e.g. <0.001-0.016 μg/g in serpentine). The mantle signature of Be is thus neither erased during seafloor alteration nor by progressive metamorphism from prehnite-pumpellyite to epidote-amphibolite facies. In contrast, the Li and B inventories of metamorphic minerals are related to the lizardite-to-antigorite transition. Both elements display higher concentrations in the low-temperature serpentine polymorph lizardite (max. 156 μg/g Li, max. 318 μg/g B) than in antigorite (max. 0.11 μg/g Li, max. 12 μg/g B). Calculated average B/Li ratios for lizardite (∼1395) and antigorite (∼115) indicate that Li fractionates from B during the lizardite-to-antigorite transition during prograde metamorphism in ultramafic rocks. In subduction zones, this signature is likely to be recorded in the B-rich nature of forearc fluids.Relative to oceanic mantle the Be content of mantle clinopyroxene is much higher, but similar to Be values from mantle xenoliths and subduction-related peridotite massifs. These data support previous hypothesis that the mantle rocks from the Eastern Central Alps have a subcontinental origin. We conclude that Be behaves conservatively during subduction metamorphism of ultramafic rocks, at least at low-temperature, and thus retains the fingerprint of ancient subduction-related igneous events in mantle peridotites.     

Site occupation and electric field gradient in acentric neptunite-measurements and evaluations concerning powder- and single crystal – Mössbauer spectroscopy and x-ray diffractometry

Mössbauer measurements on neptunite (KNa₂Li(Fe,Mn,Mg)₂Ti₂Si₈O₂₄) at 400?K reveal the distribution of Fe-ions on the crystallographic sites in agreement with neutron diffraction results published elsewhere. Even the previously postulated small amount of Fe-ions on the Ti(2) site has been detected, combined with a charge transfer which is in agreement with optical absorption investigations by other authors. A qualitative site occupation model is able to explain the different features of our observations. Single crystal Mössbauer measurements with the k-vector of incident γ-rays parallel to the crystallographic b-axis (space group Cc) of neptunite at different temperatures yield the angle β between the main component of the electric field gradient (EFG), V _zz and b. This angle is in close accordance with a calculated value of β for the Fe(1) position from electron density maps. The latter also reveal an absolute value of V _zz which is in satisfactory agreement with V _zz derived from Mössbauer spectroscopy.     

Inducing mineral precipitation in groundwater by addition of phosphate

Background

Induced precipitation of phosphate minerals to scavenge trace elements from groundwater is a potential remediation approach for contaminated aquifers. The success of engineered precipitation schemes depends on the particular phases generated, their rates of formation, and their long term stability. The purpose of this study was to examine the precipitation of calcium phosphate minerals under conditions representative of a natural groundwater. Because microorganisms are present in groundwater, and because some proposed schemes for phosphate mineral precipitation rely on stimulation of native microbial populations, we also tested the effect of bacterial cells (initial densities of 10⁵ and 10⁷ mL^-1) added to the precipitation medium. In addition, we tested the effect of a trace mixture of propionic, isovaleric, formic and butyric acids (total concentration 0.035 mM).

Results

The general progression of mineral precipitation was similar under all of the study conditions, with initial formation of amorphous calcium phosphate, and transformation to poorly crystalline hydroxylapatite (HAP) within one week. The presence of the bacterial cells appeared to delay precipitation, although by the end of the experiments the overall extent of precipitation was similar for all treatments. The stoichiometry of the final precipitates as well as Rietveld structure refinement using x-ray diffraction data indicated that the presence of organic acids and bacterial cells resulted in an increasing a and decreasing c lattice parameter, with the higher concentration of cells resulting in the greatest distortion. Uptake of Sr into the solids was decreased in the treatments with cells and organic acids, compared to the control.

Conclusions

Our results suggest that the minerals formed initially during an engineered precipitation application for trace element sequestration may not be the ones that control long-term immobilization of the contaminants. In addition, the presence of bacterial cells appears to be associated with delayed HAP precipitation, changes in the lattice parameters, and reduced incorporation of trace elements as compared to cell-free systems. Schemes to remediate groundwater contaminated with trace metals that are based on enhanced phosphate mineral precipitation may need to account for these phenomena, particularly if the remediation approach relies on enhancement of in situ microbial populations.     

超基性岩中锆石年龄的特征和意义——以西南天山UHP蛇纹岩中锆石U-Pb年龄为例

超基性岩本身难以生长锆石的特性,使得研究其中的锆石需要特别谨慎。超基性岩中的锆石虽然具有多解性,但是锆石也携带了很多演化信息。产出不同地质背景的超基性岩,其中的锆石特征不同。本文总结现有的研究实例表明:(1)经历高温高压变质作用的石榴橄榄岩通常通过交代作用获得锆石,且锆石能够记录峰期变质时代,其中的继承锆石较少,可能在高温高压条件下,继承锆石发生分解重结晶;(2)大洋蛇绿岩型超基性岩和地幔岩捕掳体中通常具有年龄分布很广的锆石年龄特征,锆石年龄峰值通常与区域上构造事件相吻合,为捕掳晶锆石。接下来本文以西南天山超高压(UHP)蛇纹岩为例,对其锆石年龄进行解释。西南天山蛇纹岩为经历过超高压变质作用的大洋蛇绿岩型超基性岩,2个蛇纹岩样品中锆石的阴极发光图像分析和SIMS U-Pb定年分析结果显示,西南天山UHP蛇纹岩中的锆石包含捕掳晶锆石和变质锆石,捕掳晶锆石的年龄为2.1~1.0Ga,对应该区变泥质岩中碎屑锆石记录的年龄峰值。409~537Ma可能代表了蛇纹岩原岩结晶时代。区域上的变质压力峰期年龄(~320Ma)在蛇纹岩中没有记录,仅有1颗锆石记录了309±5Ma的近峰期时代。270~155Ma的退变质时代在西南天山蛇纹岩中出现较广,这与榴辉岩中出现的退变年龄相吻合,代表了折返过程中较为普遍的后期热液事件。基于对超基性岩中锆石特征的初步了解,结合西南天山蛇纹岩的研究实例,认为通过研究锆石的年代学,结合锆石矿物化学、包体矿物学、同位素地球化学等特征,不仅可以提供年代学信息,还可以对超基性岩的来源和演化过程进行解析。     

Coupling of oceanic and continental crust during Eocene eclogite-facies metamorphism: evidence from the Monte Rosa nappe,western Alps

High precision U–Pb geochronology of rutile from quartz–carbonate–white mica–rutile veins that are hosted within eclogite and schist of the Monte Rosa nappe, western Alps, Italy, indicate that the Monte Rosa nappe was at eclogite-facies metamorphic conditions at 42.6 ± 0.6 Ma. The sample area [Indren glacier, Furgg zone; Dal Piaz (2001) Geology of the Monte Rosa massif: historical review and personal comments. SMPM] consists of eclogite boudins that are exposed inside a south-plunging overturned synform within micaceous schist. Associated with the eclogite and schist are quartz–carbonate–white mica–rutile veins that formed in tension cracks in the eclogite and along the contact between eclogite and surrounding schist. Intrusion of the veins at about 42.6 Ma occurred at eclogite-facies metamorphic conditions (480–570°C, >1.3–1.4 GPa) based on textural relations, oxygen isotope thermometry, and geothermobarometry. The timing of eclogite-facies metamorphism in the Monte Rosa nappe determined in this study is identical to that of the Gran Paradiso nappe [Meffan-Main et al. (2004) J Metamorphic Geol 22:261–281], confirming that these two units have shared the same Alpine metamorphic history. Furthermore, the Gran Paradiso and Monte Rosa nappes underwent eclogite-facies metamorphism within the same time interval as the structurally overlying Zermatt-Saas ophiolite [∼50–40 Ma; e.g., Amato et al. (1999) Earth Planet Sci Lett 171:425–438; Mayer et al. (1999) Eur Union Geosci 10:809 (abstract); Lapen et al. (2003) Earth Planet Sci Lett 215:57–72]. The nearly identical P–T–t histories of the Gran Paradiso, Monte Rosa, and Zermatt-Saas units suggest that these units shared a common Alpine tectonic and metamorphic history. The close spatial and temporal associations between high pressure (HP) ophiolite and continental crust during Alpine orogeny indicates that the HP internal basement nappes in the western Alps may have played a key role in exhumation and preservation of the ophiolitic rocks through buoyancy-driven uplift. Coupling of oceanic and continental crust may therefore be critical in preventing permanent loss of oceanic crust to the mantle.     

Vertical migration of municipal wastewater in deep injection well systems,South Florida,USA

Deep well injection is widely used in South Florida, USA for wastewater disposal largely because of the presence of an injection zone (“boulder zone” of Floridan Aquifer System) that is capable of accepting very large quantities of fluids, in some wells over 75,000 m³/day. The greatest potential risk to public health associated with deep injection wells in South Florida is vertical migration of wastewater, containing pathogenic microorganisms and pollutants, into brackish-water aquifer zones that are being used for alternative water-supply projects such as aquifer storage and recovery. Upwards migration of municipal wastewater has occurred in a minority of South Florida injection systems. The results of solute-transport modeling using the SEAWAT program indicate that the measured vertical hydraulic conductivities of the rock matrix would allow for only minimal vertical migration. Fracturing at some sites increased the equivalent average vertical hydraulic conductivity of confining zone strata by approximately four orders of magnitude and allowed for vertical migration rates of up 80 m/year. Even where vertical migration was rapid, the documented transit times are likely long enough for the inactivation of pathogenic microorganisms.     

Heterogeneous shock-induced thermal radiation in minerals

A 500 channel optical imaging intensifying and spectral digital recording system is used to record the shock-induced radiation emitted from 406 to 821 nm from transparent minerals during the time interval that a shock wave propagates through the sample. Initial results obtained for single crystals of gypsum, calcite and halite in the 30 to 40 GPa (300 to 400 kbar) pressure range demonstrate greybody emission spectra corresponding to temperatures in the 3,000 to 4,000 K range and emissivities ranging from 0.003 to 0.02. In the case of gypsum and calcite, distinctive line spectra, are superimposed on the thermal radiation. The observed color temperatures are a factor of 2 to 10 greater than the Hugoniot temperature, calculable on the basis of continuum thermodynamics and equation of state models for the shock states achieved in the three minerals. These observed high temperatures are believed to be real. We conclude that we are detecting a large number of closed spaced high temperature shear-band regions immediately behind the shock front. A shear instability model, such as proposed independently by Grady (1977, 1980), Ananin et al. (1974), and Horie (1980), in which small zones of highly deforming and melted material are produced which are the source of the detected thermal radiation and have a fractional effective area approximately numerically equal to the measured emissivity, can be used to predict an effective emissivity of 0.0065 directly behind the shock front. If shear band instability arises from viscous flow processes, Grady's model and mineral thermal properties yield for the shocked mineral viscosities values in the range of 10⁹ to 10¹⁵ P immediately behind the shock front.     

Economic development,technological change,and the new international economic order

This paper examines dimensions of technological change and selected relationships between new technology and the process of economic development within the general framework of the New International Economic Order. Concepts discussed include economic growth and development, structural change, technological change, innovations, the transfer of technology, and appropriate technology. The relationships between these concepts are described and their significance with regard to the economic development of lesser-developed countries is assessed.     

The lateral and vertical reflectance and petrological variation of a heat-affected bituminous coal seam from southeastern British Columbia, Canada

Thermally altered pods of coal of very high rank have been observed in a high-volatile-bituminous coal seam in the eastern side of Eagle Mountain, Elk Valley Coalfield, British Columbia. Rank changes have been measured over a strike distance of 7.5 m from 1.24% to 7.1% R_{o max}, corresponding to a rank gradient of 0.78% R_om⁻¹.Petrologically, unaltered to extremely altered vitrinite showing nongranular (basic) anisotropy, mosaic-textured liptinite and pyrolytic carbon are the most abundant components. The limited presence of mosaic on vitrinite is an indication that the coal seam may have been weathered prior to being heat-affected.Evidence points to localized temperatures as high as 1,000°C, which could have been caused by a lightning strike. The eastern side of Eagle Mountain has experienced higher temperatures than the western side, and it appears that the heat ‘front’ and zone of alteration have an irregular pattern, pointing to saturation of parts of the coal seam by water.Four types of pyrolytic carbon having distinct morphology, anisotrophy and optical path with increasing temperature were observed. Reflectance of pyrolytic carbon falls within the zone of heat-affected coals, whereas the optical path of heat-affected Seam 15 samples is different from that of fresh coal with increasing rank.Finally, the reflectance of vitrinite in heat-affected coal is higher than the reflectance of vitrinite in carbonaceous shale in the Seam 15 section.     

Thermoelastic stress due to a rectangular heat source in a semi-infinite medium. Presentation of an analytical solution

The thermoelastic response due to a time-dependent rectangular heat source in a semi-infinite medium is analyzed. The problem originates from studies of nuclear waste repositories in rock. Canisters containing heat-emitting nuclear waste are deposited over a large rectangular area deep below the ground surface. The solution for a time-dependent heat source is obtained from the corresponding instantaneous heat source by superposition. The thermoelastic problem for the instantaneous rectangular heat source in a infinite surrounding is solved exactly. An important step is the introduction of so-called quadrantal heat sources. The solution for the rectangle is obtained from four quadrantal solutions. The solution for the quadrantal heat source depends on the three dimelasionless coordinates only. Time occurs in the scale factors only. The condition of zero normal and shear stresses at the ground surface is fulfilled by using a mirror heat source and a boundary solution. The boundary solution accounts for the residual normal stress at the ground surface. Using a Hertzian potential, a surprisingly simple solution is obtained. The final analytical solution is quite tractable considering the complexity of the initial problem. The solution may be used to test numerical models for coupled thermoelastic processes. It may also be used in more detailed numerical simulations of the process near the heat sources as boundary conditions to account for the three-dimensional global process.