Karst breakdown mechanisms from observations in the gypsum caves of the Western Ukraine: implications for subsidence hazard assessment

The term karst breakdown is employed in this paper to denote the totality of processes and phenomena of gravitational and/or hydrodynamic destruction of the ceiling of a karst cavity and of the overlying sediments. It refers not only to the existence of a surface subsidence (collapse) feature but, first of all, to the internal (hidden in the subsurface) structures that precede development of a surface form. This study reports and discusses the results of direct mapping and examination of breakdown structures in the gypsum karst of the Western Ukraine, at the level of their origin, i.e., in caves. The accessibility of numerous laterally extensive maze cave systems in the region provided an excellent opportunity for such an approach, which made it possible to examine the relationship between breakdown structures and particular morphogenetic or geological features in caves, and to reveal stages of breakdown development. It is found that breakdown is initiated mainly at specific speleogenetically or geologically weakened localities, which classify into a few distinct types. The majority of breakdowns, which are potent to propagate through the overburden, relate with the outlet cupolas/domepits that represent places where water had discharged out of a cave to the upper aquifer during the period of transverse artesian speleogenesis. Distribution of breakdown structures does not correlate particularly well with the size of the master passages. Several distinct mechanisms of breakdown development are revealed, and most of them proceed in several stages. They are guided by speleogenetic, geological and hydrogeological factors. The study confirms that a speleogenetic approach is indispensable to the understanding of breakdown pre-requisites and mechanisms, as well as for eventual subsidence hazard assessment. Direct observations in caves, aimed both at speleogenetic investigation and breakdown characterization on regional- or site-specific levels, should be employed wherever possible.     

Local tomography and focal mechanisms in the south-western Alps: Comparison of methods and tectonic implications

We investigate how focal solutions and hypocenter locations may depend on the ray tracing algorithm and the strategy of velocity inversion. Using arrival times from a temporary seismological network in the south-western Alps, a local earthquake tomography has been performed by Paul et al. [Paul, A., Cattaneo, M., Thouvenot, F., Spallarossa, D., Béthoux, N., and Fréchet, J., 2001. A three-dimensional crustal velocity model of the south-western Alps from local earthquake tomography. J. Geophys. Res. 106, 19367–19390.] with the method developed by Thurber [Thurber, C.H., 1993. Local earthquake tomography: velocity and Vp/Vs-Theory, in Seismic Tomography: Theory and practice, Iyer, H.M., and Irahara eds., Chapman and Hall, New York, 563–583.]. Another inversion of the same data set is performed here using a different tomography code relying on a shooting paraxial method and cubic interpolation of velocities. The resulting images display the same main features, although Thurber's code appears to be more robust in regions with scarce ray coverage and strong velocity contrasts. Concerning hypocenter location in Piemont units, one major result is the concentration of hypocenters at the boundary between the mantle wedge of the Ivrea body and the European crust. Forty-six focal mechanisms are shown that were computed using both the take-off angles in the minimum 1-D model and in the 3-D velocity structures resulting from the two inversions. The sets of focal solutions are very similar, proving the reliability and the coherency of the focal solutions. The widespread extension in the core of the western Alps is confirmed whereas a few compressive solutions are found east of the Piemont units. These results constrain the sharp change of stress tensor and evidence a decoupling of strain beneath the east of Dora Maira massif up to beneath the north of Argentera massif. On a geodynamical point of view seismicity and focal mechanism distribution are compatible with the present day models published for the western Alps, where the major feature is the lithospheric thickening [Schmid, S.M., and Kissling, E., 2000. The arc of the western Alps in the light of geophysical data on deep crustal structure. Tectonics, 19, 62–85.], implying widespread extension in the core of the western Alps [Sue, C., Thouvenot, F., Fréchet, J., and Tricart, P., 1999. Widespread extension in the core of the western Alps revealed by earthquake analysis. J. Geophys. Res., 104, 25611–25622.]. However the existence of compressive events dealing at depth with the boundary of Ivrea body allows to postulate that this geological structure is still tectonically active. Even if field work has not shown this so far, the Insubric line appears to extend toward the south at depth, as a blind fault, and to play a key role in the dynamics of the south-western Alps.     

Complete chemical analyses of metamorphic hornblendes: implications for normalizations,calculated H2O activities,and thermobarometry

Twenty-two hornblendes separated from amphibolites and granulites of the Grenville Orogen of Ontario have been quantitatively analyzed for major and minor elements by electron microprobe, for FeO/Fe₂O₃ by wet chemistry, and for H₂O by manometric measurement as H₂. Hornblende formulae were calculated on the basis of 24O+OH+Cl+F. Most samples are magnesio-hornblendes, ferroan pargasitic hornblendes and ferroan hastingsitic hornblendes, with weight fractions of Fe³⁺/(Fe²⁺+Fe³⁺) ranging from 0.15 to 0.50. An oxy-amphibole component of 0–25 mol%, with an average value of 17 mol%, is obtained for these complete analyses. When compared with structural formulae determined solely from microprobe data, normalization based on 13=Si+Ti+Al+Fe+Mn+Mg cations provides the best approximation to hornblende formulae calculated from the complete analyses. Less satisfactory agreement is obtained from a normalization scheme based on 15=Si+Ti+Al+Fe+Mn+Mg+Ca, while worst agreement is obtained from normalization to 23 oxygens assuming all Fe is Fe²⁺. No normalization scheme based on microprobe data alone consistently replicates the measured FeO, Fe₂O₃, and H₂O; accurate determination of these values requires complete chemical analysies. Ionic solution models previously have been proposed to evaluate the activity of Ca₂Mg₅Si₈ O₂₂(OH)₂(a _Trem) in hornblende for use in equilibria that constrain the activity of H₂O (a _{H 2}O) in igneous and metamorphic rocks. Application of ionic models to typical hornblendes produces low a _Trem (usually<0.01), consequetly yielding extremely low a _{H 2}O. If an oxy-amphibole component is present, the calculated a _Trem and H₂O is further reduced. An oxy-amphibole component of 25% reduces the calculated H₂O activity and that of any hydroxyl-amphibole component by 50% below that calculated with simplified assumptions regarding X _OH in the hydroxyl site (i.e., X _OH=1, or X _OH=1–X _Cl–X _f). Thus, methods of amphibole normalizations appear to have a substantial effect on calculated amphibole and H₂O activites. Before quantitative hornblende thermobarometry can be calibrated and applied, the amounts of FeO, Fe₂O₃ and H₂O must be measured in order to fully characterize hornblende solid solutions.Contribution No. 478 from the Mineralogical Laboratory, University of Michigan     

Effect of grain growth on cation exchange between dunite and fluid: implications for chemical homogenization in the upper mantle

The effect of grain growth on the cation exchange between synthesized forsterite aggregates (i.e., dunite) and nickel-rich aqueous fluid was evaluated experimentally at 1.2 GPa and 1,200°C. The grain boundary (GB) migration caused nickel enrichment in the area swept by the GBs in a fashion similar to that reported for stable isotope exchange in the quartz aggregates. The progress of the grain growth resulted in an increase in the average nickel concentration in the dunites of up to ~80 times that was calculated for a system having stationary GBs. The overall diffusivity of the nickel along the wet GBs and interconnected fluid networks was found to be 6.5 × 10⁻¹⁹–6.7 × 10⁻¹⁸ m³/s, which is 4–5 orders of magnitude higher than the grain boundary diffusivity in the dry dunite. These results show that the grain growth rate is a fundamental factor in the evaluation of the time scale of chemical homogenization in the upper mantle.     

Epigenetic geochemical dynamics and driving mechanisms of chemical elemental distribution patterns in soil in Southwest China

The Earth's surface is a complex system involving mutual interactions of its many components, including mountains, rivers, forests, farmlands, lakes and grasses. The interaction and mutual feedback of chemical elements in Earths surface layer can drive changes in chemical elemental distribution patterns. In this study, we evaluated the mechanisms and interactions driving the distribution patterns of macroelements, probiotics, halogens and heavy metals in soils in Southwest China, based on a systematic geochemical land-quality survey at a scale of 1250000. The results showed that the parent material determines the natural state of chemical elements in land resources. Epigenetic geochemical dynamics reshapes the distribution patterns of chemical elements in top soil; biogeochemical processes drive the evolutionary trends of land quality; and human activities, such as mining, disrupt the natural evolution of chemical elemental distribution patterns. The establishment of an epigenetic geochemical dynamics theory allows the construction of a framework for understanding the Earths surface layer and promoting technological innovations for the comprehensive geochemical investigation of land resources.     

碱性花岗岩的动力学氧同位素交换和流体流动几何学：交换机制和平流冷却

新疆北部乌仑古塔斯嘎克碱性花岗岩体分为主体相和北部边缘相。条纹长石广泛发育出溶；石英与碱性长石复杂交生。条纹长石的出溶衍生出压应力，造成石英的变形。大部分钠铁闪石是由霓辉石交代形成的。在δ^18O石英-δ^18O条纹长石和δ^18O石英-δ^18O钠铁闪石协变图上，应用耦合的质量传输和动力学限制的同位素交换模型对样品进行了模拟。相对交换速率常数和3个矿物的显微组构特征共同指示，表面反应即溶解-再沉淀和管道扩散是氧同位素交换的主要机制。大气降水从塔斯嘎克碱性花岗岩的北部边缘相住主体相发生了平流渗透。北部边缘相样品的较陡的斜率、以及石英和条纹长石较低的^18O亏损程度，被解释为是由于与同位素组成未演化的短路径大气降水在相对较短的时限内发生氧同位素交换造成的。但是，与同位素组成演化了的长路径大气降水在相对较长的时限内的相互作用，导致了主体样品的较缓的斜率以及石英和条纹长石的较高程度的^18O亏损。对于一个侵入岩体的冷却来说，平流冷却与传导冷却一样重要。     

表生地球化学动力学与中国西南土壤中化学元素分布模式的驱动机制

地球表层是由山水林田湖草等要素构成的互动和互馈的复杂系统,这些要素中化学元素的互动和互馈过程均可驱动化学元素分布模式的变化。本文以系统的1∶25万土地质量地球化学调查数据为基础,讨论了中国西南地区土壤中常量元素、亲生物元素、卤族元素、重金属元素分布模式的驱动机制和互动过程。结果发现成土母质决定了土地资源中化学元素的自然状况,表生地球化学动力学过程重塑了表层土壤中元素分布模式,生物地球化学过程驱动了土地质量的演化趋势,强烈的人类活动(如矿业活动)破坏了元素分布的自然演化规律。表生地球化学动力学理论的提出将引领山水林田湖草生命共同体知识体系构建和土地资源地球化学综合调查技术的革新。     

Dominant simple-shear deformation during peak metamorphism for the lower portion of the Greater Himalayan Sequence in West Nepal: New implications for hybrid channel flow-type mechanisms in the Dolpo region

I conducted new vorticity and deformation temperatures studies to test competing models of the exhumation of the mid-crustal rocks exposed in the Dolpo region (West Nepal). My results indicate that the Main Central Thrust is located ∼5 km structurally below the previous mapped locations. Deformation temperature increasing up structural section from ∼450 °C to ∼650 °C and overlap with peak metamorphic temperature indicating that penetrative shearing was responsible for the exhumation of the GHS occurred at “close” to peak metamorphic conditions. I interpreted the telescoping and the inversion of the paleo-isotherms at the base of the GHS as produced mainly by a sub-simple shearing (Wm = 0.88–1) pervasively distributed through the lower portion of the GHS. My results are consistent with hybrid channel flow-type models where the boundary between lower and upper portions of the GHS, broadly corresponding to the tectonometamorphic discontinuity recently documented in west Nepal, represents the limit between buried material, affected by dominant simple shearing, and exhumed material affected by a general flow dominates by pure shearing. This interpretation is consistent with the recent models suggesting the simultaneous operation of channel flow- and critical wedge-type processes at different structural depth.     

胶东三山岛金矿床黄铁矿As富集机制及其对金成矿作用的指示

胶东是中国最大的金矿集区,其金矿成因目前还存在较大争议.作为最重要的载金矿物,黄铁矿显微结构及元素-同位素组成能够很好地示踪成矿物质来源和成矿过程.利用SEM、EPMA和LA-ICP-MS微区原位分析方法对胶东代表性蚀变岩型金矿—三山岛金矿的黄铁矿开展详细的BSE显微结构以及As含量和S同位素耦合关系研究,发现矿区至少...     

超高压变质岩的塑性流变：显微构造和变形机制

超高压变质岩是大陆深俯冲作用的产物。超高压变质岩在深俯,中和快速折返过程中,经历了长距离地构造搬运和构造力的作用。其构造变形主要集中在韧性剪切带中,并发生强烈地塑性流变。研究超高压变质构造岩的显微构造及其变形机制对于深入了解大陆壳岩石在深俯;中过程中的流变学行为有十分重要的意义。山东仰口的超高压韧性剪切带中榴辉岩质和花岗质糜棱岩记录了超高压变形的历史。在超高压条件下的稳定矿物绿辉石、多硅白云母、兰晶石和钾长石具有不规则波状消光、亚晶界、核幔构造和动态重结晶等显微构造特征,TEM研究揭示了大量的位错构造,表明位错蠕变是其主要的变形机制。在花岗质糜棱岩中,金红石在刚性矿物的压力影中沉积,细粒的石榴石条带平行片理延伸,都说明超高压变形过程中有流体存在,流体助力的物质扩散迁移是又一个重要的变形机制、依据现有的流变学定律估算的流变应力应该在几十兆帕以上。     

Erosion rates on subalpine paleosurfaces in the western Mediterranean by in-situ <Superscript>10</Superscript>Be concentrations in granites: implications for surface processes and long-term landscape evolution in Corsica (France)

A study of erosion rates by in-situ ¹⁰Be concentrations in granites of Miocene high-elevation paleosurfaces in Corsica indicates maximum erosion rates between 8 and 24 mm/kyear. The regional distribution of measured erosion rates indicates that the local climatic conditions, namely precipitation, the petrographic composition of granites, and the degree of brittle deformation govern erosion rates. Chemical erosion dominates even at elevations around 2,000 m in presently subalpine climate conditions. Field evidence indicates that erosion operates by continuous dissolution and/or disintegration to grains (grusification). The erosion rates are relatively high with respect to the preservation of inferred Early Miocene landscapes. We infer temporal burial in the Middle Miocene and significantly lower erosion rates in the Neogene until ∼3 Ma to explain the preservation of paleosurfaces, in line with fission track data. Valley incision rates that are a magnitude higher than erosion rates on summit surfaces result in relief enhancement and long-term isostatic surface uplift. On the other hand, widening and deepening of valleys by cyclic glaciation progressively destroys the summit surface relics.

Lithium isotopic composition of Central American Volcanic Arc lavas: implications for modification of subarc mantle by slab-derived fluids

Li contents and isotopic compositions were determined for a suite of well-characterized basaltic lavas from the Central American Volcanic Arc (CAVA). Variable Li/Y (0.2–0.5), Li/Sc (0.1–0.4), and δ⁶Li values (+2.6 to −7.7‰) attest to significant compositional heterogeneity in the subarc mantle. Within specific arc segments, these parameters correlate strongly with each other and with a number of other constituents (e.g., K, Rb, Ba, B/La, ¹⁰Be/⁹Be, ⁸⁷Sr/⁸⁶Sr, U/Ce, and ²³⁰Th/²³²Th, among others); these correlations are particularly strong for Nicaragua samples. Coupling of this particular set of constituents is best explained in terms of addition of ‘subduction components' to the subarc mantle. Moreover, their selective enrichment with respect to relatively fluid-immobile incompatible elements signifies the dominance of fluid vs. silicate melt transport of slab components to the subarc mantle. Several interesting nuances are revealed by the Li data. First, although Li and B are strongly correlated in both Costa Rica and Nicaragua, there are systematic along-strike variations in Li/B that are consistent with these elements having different ‘fluid release patterns' from subducted slab segments. For example, Li/B is highest in Costa Rica where auxiliary evidence indicates higher subduction zone temperatures; apparently B is preferentially depleted and Li retained in the slab under warmer conditions. The same relations are reflected in Li/¹⁰Be and other subduction tracer systematics, all of which point to larger subduction contributions below Nicaragua. Yet, even Nicaragua lavas vary widely in levels of subduction enrichment. High-Ti basalts from Nejapa are the least enriched and have the highest δ⁶Li (1.4 to 2.6‰); these values are greater than in fresh MORB (ca. −4‰) and are not easily explained by additions of subducted Li because most oceanic crustal rocks and marine sediments have lower δ⁶Li than MORB (with typical values between −8 and −20‰). Thus, it appears the Nejapa data may be representative of isotopically light mantle domains. Relatively light δ⁶Li values in an undepleted spinel lherzolite (+11.3‰) from Zabargad Is. (Red Sea) and in primitive backarc basalts (−1.6 to −0.5‰) from Lau Basin support this conclusion. Considering representative fluid and mantle endmember compositions, the CAVA data are consistent with limited (up to a few percent) additions of slab-derived fluids to a heterogeneous mantle containing variably depleted and enriched domains to form the respective magma sources. In our view, the subarc mantle is heterogeneous on a small scale, but some arc sectors clearly received greater slab inputs than others.     

Muscovite dehydration melting: Reaction mechanisms,microstructures, and implications for anatexis

Dehydration melting of muscovite in metasedimentary sequences is the initially dominant mechanism of granitic melt generation in orogenic hinterlands. In dry (vapour-absent) crust, muscovite reacts with quartz to produce K-feldspar, sillimanite, and monzogranitic melt. When water vapour is present in excess, sillimanite and melt are the primary products of muscovite breakdown, and any K-feldspar produced is due to melt crystallization. Here we document the reaction mechanisms that control nucleation and growth of K-feldspar, sillimanite, and silicate melt in the metamorphic core of the Himalaya, and outline the microstructural criteria used to distinguish peritectic K-feldspar from K-feldspar grains formed during melt crystallization. We have characterized four stages of microstructural evolution in selected psammitic and pelitic samples from the Langtang and Everest regions: (a) K-feldspar nucleates epitaxially on plagioclase while intergrowths of fibrolitic sillimanite and the remaining hydrous melt components replace muscovite. (b) In quartzofeldspathic domains, K-feldspar replaces plagioclase by K⁺–Na⁺ cation exchange, while melt and intergrowths of sillimanite+quartz form in the aluminous domains. (c) At 7–8 vol.% melt generation, the system evolves from a closed to open system and all phases coarsen by up to two orders of magnitude, resulting in large K-feldspar porphyroblasts. (d) Preferential crystallization of residual melt on K-feldspar porphyroblasts and coarsened quartz forms an augen gneiss texture with a monzogranitic-tonalitic matrix that contains intergrowths of sillimanite+tourmaline+muscovite+apatite. Initial poikiloblasts of peritectic K-feldspar trap fine-grained inclusions of quartz and biotite by replacement growth of matrix plagioclase. During subsequent coarsening, peritectic K-feldspar grains overgrow and trap fabric-aligned biotite, resulting in a core to rim coarsening of inclusion size. These microstructural criteria enable a mass balance of peritectic K-feldspar and sillimanite to constrain the amount of free H₂O present during muscovite dehydration. The resulting modal proportion of K-feldspar in the Himalayan metamorphic core requires vapour-absent conditions during muscovite dehydration melting and leucogranite formation, indicating that the generation of large volumes of granitic melts in orogenic belts is not necessarily contingent on an external source of fluids.     

D/H exchange in pure and Cr-doped enstatite: implications for hydrogen diffusivity

The kinetics of hydrogen diffusion in enstatite was studied by hydrogen–deuterium exchange experiments in the range of 1–5,000 bar and 700–850°C using synthetic single crystals of pure and Cr-doped enstatites. The OH- and OD-content in the samples was quantified after each thermal treatment with Fourier transformed infrared spectroscopy. H–D-exchange rates were measured parallel to the three crystallographic axes. In addition, in order to visualize diffusion profiles, OH and OD were mapped for some samples, utilizing synchrotron IR micro-spectroscopy. Hydrogen self-diffusivities derived from D/H exchange experiments at one atmosphere are very similar to the chemical diffusivity of hydrogen in natural Fe-bearing orthopyroxene, which was reported previously (Stalder and Skogby 2003) to exhibit a small, but significant anisotropy (D[001] > D[100] > D[010]). Activation energies are estimated to be 211 (±31) kJ/mol for diffusion parallel [100] and 185 (±28) kJ/mol for diffusion parallel [010]. Lattice diffusion of hydrogen is decelerated by more than one order of magnitude when Cr is dissolved in enstatite. In comparison to the chemical composition, pressure seems to have only a minor influence on hydrogen diffusion. Compared to other minerals in the Earth’s upper mantle, enstatite exhibits the highest activation energy for hydrogen diffusion, suggesting faster diffusion than in other mafic minerals at mantle temperatures, but slower diffusion at crustal conditions. Thus under upper mantle conditions, physical properties that are expected to be influenced by hydrogen mobility, such as electrical conductivity, may in enstatite be more intensely affected by the presence of hydrogen than in other upper mantle minerals.     

Usage of strain and vorticity analyses to interpret large‐scale fold mechanisms along the Sanandaj–Sirjan HP‐LT metamorphic belt,SW Iran

3D finite strain analyses and kinematic vorticity measurements were carried out on the Loghon Anticline within the HP‐LT Sanandaj–Sirjan metamorphic belt (Neyriz area, SW Iran). Rƒ/φ and Fry methods were used on the strain markers (e.g. deformed fossils) to interpret geometric relationships between the fold axis, strain ellipsoid axes and shear zone boundaries. The results indicate the predominance of prolate strain in the anticline. Quantitative kinematic analyses show that the W_k parameter is 0. 67 ± 0. 06 (i.e. pure‐shear dominated non‐coaxial flow). This study quantitatively supports the establishment of a dextral transpressive system, which is responsible for the development of the large‐scale right‐lateral shear zones that strike sub‐parallel to the major folds. Flexural shear combined with regional dextral‐shear is suggested to be the most common mechanism of folding in this area. Copyright © 2011 John Wiley & Sons, Ltd.     

Recent crustal uplift of Precambrian cratons: Key patterns and possible mechanisms

Precambrian cratons cover about 70% of the total continental area. According to a large volume of geomorphological, geological, paleontological, and other data for the Pliocene and Pleistocene, these cratons have experienced a crustal uplift from 100-200 m to 1000-1500 m, commonly called the recent or Neotectonic uplift. Shortening of the Precambrian crust terminated half a billion years ago or earlier, and its uplift could not have been produced by this mechanism. According to the main models of dynamic topography in the mantle, the distribution of displacements at the surface is quite different from that of the Neotectonic movements. According to seismic data, there is no magmatic underplating beneath most of the Precambrian cratons. In most of cratonic areas, the mantle lithosphere is very thick, which makes its recent delamination unlikely. Asthenospheric replacement of the lower part of the mantle lithosphere beneath the Precambrian cratons might have produced only a minor part of their Neotectonic uplifts. Since the above mechanisms cannot explain this phenomenon, the rock expansion in the crustal layer is supposed to be the main cause of the recent uplift of Precambrian cratons. This is supported by the strong lateral nonuniformity of the uplift, which indicates that expansion of rocks took place at a shallow depth. Expansion might have occurred in crustal rocks that emerged from the lower crust into the middle crust with lower pressure and temperature after the denudation of a thick layer of surface rocks. In the dry state, these rocks can remain metastable for a long time. However, rapid metamorphism accompanied by expansion of rocks can be caused by infiltration of hydrous fluids from the mantle. Analysis of phase diagrams for common crustal rocks demonstrates that this mechanism can explain the recent crustal uplift of Precambrian cratons.     

Microstructural observations on natural syntectonic fibrous veins: implications for the growth process

Syntectonic antitaxial and ataxial fibrous veins were investigated using SEM, microprobe, cathodoluminescence (CL) and optical microscopy. In antitaxial calcite veins, fibres and surrounding selvage grew simultaneously, with similar growth rates of crystallographically differently oriented grains. New material precipitated at the vein margin in antitaxial and bi-mineralic ataxial microstructures. Bridges of country rock material formed during vein growth in an initial en-echelon vein system. In our antitaxial and bi-mineralic ataxial samples, the spacing of solid inclusions does not reflect individual crack-seal openings.     

Sub-micron-scale trace-element distributions in natural zircons of known provenance: implications for Ti-in-zircon thermometry

NanoSIMS measurements of Ti, P, Y, Ce, and Hf in zircon separates from the Youngest Toba Tuff, the Bishop Tuff, the Quottoon Igneous Complex, the Sierra Nevada batholith, and an Adirondack migmatite show that micron-scale oscillatory zoning of Ti is common. The zircons we have studied typically display banded concentration gradients, having between 1 and 7 peaks in Ti abundance over length scales of 10–20 μm—the beam diameter commonly used for SIMS trace-element zircon analyses—with amplitudes of up to 4.5 ppm Ti (baseline values are ~1–4 ppm) and widths (measured at half-height) of between ~0.2 and 4 μm. Spatial correlations between concentrations of Ti and other trace elements (P, Y, and Ce) are also common, but variable in character, ranging from oscillatory co-variation of Ti, P, Y, and Ce to cases where only a subset of peaks for a given element is spatially correlated with peaks in Ti. There are also longer length-scale, generally positive correlations among concentrations of Ti, P, Y, and Ce (i.e., gradients on which narrower peaks are superimposed). In contrast, Hf concentrations are either uncorrelated or inversely correlated with these longer length-scale variations in Ti concentrations. The wide range in Ti concentrations over distances of less than 1 μm and the various correlations between Ti concentrations and those of the other analyzed elements suggest that on the micron scale and at temperatures between ~700 and 800 °C, zircon-liquid Ti partitioning is not controlled by bulk or lattice equilibrium. Treating our NanoSIMS Ti ion maps as though they were conventional SIMS analyses (i.e., generating an average Ti concentration for each map), we evaluate the hypothesis that while micron-scale variations in Ti concentrations might be kinetically controlled, when averaged over 100–400 μm², such variations capture the thermal state of the growing zircon. Using these average Ti concentrations, independent petrologic pressure and temperature constraints, estimates of silica and titania activities based on phase assemblages as well as calculations using rhyolite-MELTS, we show that crystallization temperatures predicted by Ti-in-zircon geothermometry generally do not agree with the independently constrained temperatures for the samples.     

Degradation of carbon tetrachloride in a reducing groundwater environment: implications for natural attenuation

Several laboratory experiments have demonstrated degradation of carbon tetrachloride (CT) in groundwater, but there appear to have been no corroborating long-term field studies. Investigations conducted in 1989 and 1999 at an industrial site constructed on an infilled estuarine environment in France provide data over a decade for which CT degradation could be evaluated. A Dense Non-Aqueous Phase Liquid (DNAPL) containing oil and >90% CT that was present in 1989 was absent in the extremely reducing site groundwater in both 1999 and 2000 (average Eh=−170 mV at pH 7, sulfide up to 21 mg l⁻¹, and Fe⁺² up to 3.2 mg l⁻¹). These conditions facilitated dechlorination of CT to chloroform (CF) present at up to 46 mg l⁻¹, and methylene chloride (up to 75 mg l⁻¹). Carbon disulfide (CS₂), a terminal degradation product in reducing environments in laboratory experiments, was present at a mass ratio averaging 2.4:1 CF:CS₂, indicative of abiotic degradation. The lack of detection of the separate phase CT, the ratio of CF:CS₂, the presence of low molecular weight organic acids (i.e., acetate ∼900 mg l⁻¹; citrate 360 mg l⁻¹; and propionate, up to 111 mg l⁻¹) and pyrite in conjunction with excess inorganic Cl in groundwater are all indicators of ongoing degradation of the chlorinated compounds. However, while natural attenuation of chloromethanes may be a viable adjunct to strategies designed to remediate CT in reducing groundwater, its efficacy is hard to quantify in complex field environments where upgradient sources are still present.