Modification of fluid inclusions in quartz by deviatoric stress. II: experimentally induced changes in inclusion volume and composition

Fluid inclusions in quartz are known to modify their densities during shear deformation. Modifications of chemical composition are also suspected. However, such changes have not been experimentally demonstrated, their mechanisms remain unexplained, and no criteria are available to assess whether deformed inclusions preserve information on paleofluid properties. To address these issues, quartz crystals containing natural CO₂–H₂O–NaCl fluid inclusions have been experimentally subjected to compressive deviatoric stresses of 90–250 MPa at 700°C and ~600 MPa confining pressure. The resulting microcracking of the inclusions leads to expansion by up to 20%, producing low fluid densities that bear no relation to physical conditions outside the sample. Nevertheless, the chemical composition of the precursor inclusions is preserved. With time the microcracks heal and form swarms of tiny satellite inclusions with a wide range of densities, the highest reflecting the value of the maximum principle stress, σ ₁. These new inclusions lose H₂O via diffusion, thereby passively increasing their salt and gas contents, and triggering plastic deformation of the surrounding quartz via H₂O-weakening. Using microstructural criteria to identify the characteristic types of modified inclusions, both the pre-deformation fluid composition and syn-deformation maximum stress on the host mineral can be derived from microthermometric analysis and thermodynamic modelling.     

Modification of fluid inclusions in quartz by deviatoric stress I: experimentally induced changes in inclusion shapes and microstructures

Fluid inclusions in quartz are known to modify their shapes and microstructures (textures) during weak plastic deformation. However, such changes have not been experimentally demonstrated and criteria are not available to relate them to paleostress conditions. To address these issues, quartz crystals containing natural CO₂–H₂O–NaCl fluid inclusions have been experimentally subjected to compressive deviatoric stresses of 90–250 MPa at 700°C and ~600 MPa confining pressure. Strains of up to 1% cause the inclusions to develop irregular shapes and to generate microcracks in crystallographic planes oriented subperpendicular to the major compression axis, σ ₁. The uniform alignment of the microcracks imparts a planar fabric to the samples. The microcracks heal and form swarms of tiny satellite inclusions. These new inclusions lose H₂O by diffusion, thereby triggering plastic deformation of the surrounding quartz via H₂O-weakening. Consequently, the quartz samples deform plastically only in domains originally rich in inclusions. This study shows that fluid inclusions deformed by deviatoric stresses may indeed record information on paleostress orientations and that they play a key role in facilitating crystal-plastic deformation of quartz.     

Synthetic fluid inclusions - VII. Re-equilibration of fluid inclusions in quartz during laboratory-simulated metamorphic burial and uplift

ABSTRACT P-T conditions inferred from fluid inclusions in metamorphic rocks often disagree with the values predicted from mineral equilibria calculations. These observations suggest that inclusions formed during early stages of regional metamorphism continue to re-equilibrate during burial and subsequent uplift in response to differential pressure. P-T conditions accompanying burial and uplift were experimentally simulated by initially forming pure H₂O inclusions in quartz at elevated temperatures and pressures, and then re-equilibrating the inclusions in the presence of a 20 wt% NaCl solution such that final confining pressures ranged from 5 kbar above to 4 kbar below the initial internal pressure of the inclusions at the temperature of re-equilibration. In all samples re-equilibrated at confining pressures below the internal pressure, some inclusions were formed that had compositions of 20 wt% NaCl and densities in accord with the final P-T conditions. Additionally, some inclusions were observed to contain fluids of intermediate salinities (between 0 and 20 wt% NaCl). Densities of these inclusions were also consistent with formation at the re-equilibration P-T conditions. The remainder of the fluid inclusions observed in these samples contained pure H₂O and their homogenization temperatures corresponded to densities intermediate between the initial and final P-T conditions. In short-term experiments (7 days) where the initial internal overpressure exceeded 1 kbar, no inclusions were found that contained the original density and none were found to have totally re-equilibrated. Instead, most H₂O inclusions re-equilibrated until their internal pressures were between ∼750 and 1500 bars above the confining pressure, regardless of the initial pressure differential. In a long-term experiment (52 days), inclusions re-equilibrated at a lower confining pressure than the initial internal pressure displayed homogenization temperatures corresponding to a range in final internal pressures between 0 kbar (i.e. total re-equilibration) and 1.2 kbar above the confining pressure. In experiments where the confining pressure during re-equilibration exceeded the initial internal pressure, densities of pure H₂O inclusions increased to values intermediate between the initial and final P-T conditions. Additionally, these inclusions were generally surrounded by a three-dimensional halo of smaller inclusions, also of intermediate density, resulting in a texture similar to that previously ascribed to decrepitation from internal overpressure. In extreme cases where confining pressures were 4–5 kbar above the initial pressure, the parent inclusion almost completely closed leaving only the three-dimensional array of small (5 μm) inclusions, the outline of which may be several times the volume of the original inclusion. Groups of such inclusions closely resemble textures commonly observed in medium- to high-grade metamorphic rocks. Inclusions containing 10 and 42 wt% NaCl solutions trapped at 600 °c and 3 kbar were re-equilibrated at 600 °c and 1 kbar for 5 days in dry argon to evaluate the importance of H₂O diffusion as a mechanism of lowering the inclusion bulk density. Salinities of re-equilibrated inclusions obtained from freezing point depressions and halite dissolution temperatures indicate that original compositions were preserved. Density changes similar to those previously described were noted in these experiments, in inclusions showing no visible microfractures. Therefore, density variations observed in inclusions in this study, re-equilibrated under rapid deformation conditions, are considered to result from a change in the inclusion volume, without significant loss of contents by diffusion or leakage.     

Synthetic fluid inclusions. XV. TEM investigation of plastic flow associated with reequilibration of fluid inclusions in natural quartz

The nature and abundance of dislocations in quartz surrounding fluid inclusions were studied to obtain a better understanding of processes associated with fluid inclusion reequilibration. Synthetic fluid inclusions containing 10 wt% NaCl aqueous solution were formed in three samples at 700 °C and 5 kbar. One of the samples was quenched along an isochore to serve as a reference sample. The other two samples were quenched along a P-T path that generated internal pressures in excess of the confining pressure. The two samples were held at the final reequilibration P-T conditions of 625 °C and 2 kbar for 30 and 180 days, respectively. Following the experiments, microstructures associated with fluid inclusions were examined with the TEM. Quartz in healed fractures in the reference sample that was quenched isochorically shows a moderate dislocation activity. Quartz adjacent to reequilibrated fluid inclusions in the other two samples, however, showed a marked increase in dislocation activity compared to the un-reequilibrated sample. Deformation of the inclusion walls occurred anisotropically by expansion of mobile dislocations in their slip systems. Dislocation expansion was controlled by glide in the rhombohedral planes {1 0 1 1} that was restricted to narrow zones (≤3 μm) in the immediate vicinity of the fluid inclusion walls outside of the healed fracture plane. These plastic zones were observed after both short term (30 days) and long term (180 days) experiments and are attributed to hydrolytic weakening of quartz around fluid inclusions owing to diffusion of water into the quartz matrix during the experiment. The close spatial association of submicroscopic water bubbles with dislocations, and the rarity of water bubbles in the reference sample, show clearly that in both the 30 and 180 day experiments reequilibration involves water loss from the fluid inclusions. Our results indicate that synthetic fluid inclusions in this study recover (chemically and volumetrically), even at relatively fast experimental loading rates, such that internal stresses never reach the point of brittle failure. The driving force for fluid inclusion deformation involves two related mechanisms: plastic deformation of hydrolytically weakened wet quartz in the healed fracture, and water leakage associated with preexisting and strain-induced dislocations. Received: 5 May 1998 / Accepted: 10 February 2000     

主应力方向和偏应力比对TJ-1模拟月壤各向异性的影响

采用空心圆柱扭剪仪对干燥TJ-1模拟月壤试样进行了应力主轴固定的定向剪切试验及不同偏应力比时主应力方向的纯旋转试验。从应力-应变关系角度出发,研究主应力方向、偏应力比对其各向异性的影响,并探讨了上述因素对TJ-1模拟月壤非共轴性的影响。试验结果表明：主应力方向和偏应力比对TJ-1模拟月壤的各向异性均有显著影响;应力主轴旋转引起的非共轴现象比定向剪切时明显,且偏应力比较小时非共轴角随应力主轴旋转呈先减小后增加的趋势,偏应力比较大时非共轴角一直减小直至试样破坏时非共轴现象消失。上述成果可弥补干砂试样非共轴领域的研究空白,并可望为将来月球上基础设施的修建提供技术支持。     

Some effects of tectonic recrystallisation on fluid inclusions in vein quartz

Filling temperature data obtained from tectonic vein quartz varies according to the state of intracrystalline deformation. Strain free domains within grains exhibit abundant primary fluid inclusions, from which internally consistent temperatures are recorded. The onset of optical features associated with intracrystalline deformation by dislocation creep is accompanied by a decrease in the number of fluid inclusions and an increase of filling temperatures. At higher states of strain tectonic recrystallisation, evidenced by the formation of new subgrains, leads to the complete destruction of inclusion arrays. Empty cavities are swept out of the new grains during recrystallisation, into subgrain walls. Heterogeneous deformation of vein quartz at the intracrystalline level may be due in part to selective hydrolytic weakening in areas where fluid inclusions have leaked and thereby increased the structural water content.     

Quantitative trace element analysis of single fluid inclusions by proton-induced X-ray emission (PIXE): application to fluid inclusions in hydrothermal quartz

Single fluid inclusion analogues with known elemental composition and regular shape were analyzed for trace element contents by particle-induced X-ray emission (PIXE)—a nondestructive method for the analysis of single fluid inclusions—to evaluate the accuracy and detection limits of this type of analysis. Elements with concentrations of 10 to 1000 ppm were measured with average estimated relative error of ±7%. For natural fluid inclusions with 30 μm radius and 20 μm depth in quartz, the total analytical errors were estimated to be ±40% relative for Ca, ±16% for Fe, ±13% for Zn, ±12% for Sr, and ±11% for Br and Rb, by considering uncertainties in microscopic measurements of inclusion depths. Detection limits of 4 to 46 ppm for elements of mass numbers 25-50 were achieved for analyses of a spherical fluid inclusion with 30 μm radius and 20 μm depth in quartz, at an integrated charge of 1.0 μC. The trace element compositions of single fluid inclusions in a hydrothermal quartz crystal were also determined. The elemental concentrations in the inclusions varied widely: 0.2-9 wt.% for Ca and Fe, 300-8000 ppm for Mn and Zn, 40-3000 ppm for Cu, 100-4000 ppm for Br, Rb, Sr, and Pb, and less than 100 ppm for Ge. Elemental concentrations of secondary fluid inclusions on the same trail varied over an order of magnitude, even though all these inclusions were formed from the same fluid. Elemental concentrations in inclusions on the same trail are positively correlated with each other, except for Cu and Rb. Ratios of almost all elements in the inclusions on the trail were essentially unchanged; thus, the elemental ratios can provide original information on trace element compositions of a hydrothermal fluid.     

Synthetic fluid inclusions - VI. Quantitative evaluation of the decrepitation behaviour of fluid inclusions in quartz at one atmosphere confining pressure

ABSTRACT The decrepitation behaviour of fluid inclusions in quartz at one atmosphere confining pressure has been evaluated using pure H₂O synthetic inclusions formed by healing fractures in natural quartz. Three different modes of non-elastic deformation, referred to as stretching, leakage or partial decrepitation, and total decrepitation have been observed. The internal pressure required to initiate non-elastic deformation is inversely related to inclusion size according to the equation: internal pressure (kbar) = 4.26 D^-0.423 where D is the inclusion diameter in microns. Regularly shaped inclusions require a higher internal pressure to initiate non-elastic deformation than do irregularly shaped inclusions of similar size. Heating inclusions through the α/β quartz inversion results in mechanical instability in the quartz crystal and leads to mass decrepitation of inclusions owing to structural mismatches generated by pressure gradients in the quartz around each inclusion. Long-term heating experiments (∼2 years) suggest that the internal pressure required to initiate non-elastic deformation does not decrease significantly with time and indicates that short-lived thermal fluctuations in natural systems should not alter the inclusion density and homogenization temperature. Inclusions that do exhibit decreased density (higher homogenization temperature) are, however, always accompanied by a change in shape from irregular to that of a negative crystal. Observations of this study are consistent with elasticity theory related to fracture generation and propagation around inclusions in minerals. These results indicate that an inclusion will not be influenced by a neighbouring inclusion, or other defect in the host phase, as long as the distance between the two is >2–4 diameters of the larger of the two inclusions.     

中国大陆科学钻探（CCSD）高压超高压变质岩中石英脉流体包裹体初步研究

初步的岩相学和冷热台显微测温表明，CCSDHP—UHP岩石中石英脉和后期碳酸盐脉中含有3种流体包裹体：盐水溶液(NaCl-H2O)包裹体(Ⅰ类)、NaCl-CaCl2-H20(Ⅱ类)和N2-CH4纯气相(Ⅲ类)包裹体，其中Ⅰ类盐水溶液包裹体可进一步分为中高盐度盐水溶液包裹体(Ia)、中等盐度盐水溶液包裹体(Ib)和低盐度盐水溶液包裹体(Ic)，而Ⅲ类为CCSD中首次发现：Ia、Ib和Ⅱ型流体包裹体主要以原生或假次生形式赋存在榴辉岩的石英脉或石英颗粒中，在角闪岩相的片麻岩及其石英脉中均未观察到，显示它们可能主要被捕获于榴辉岩的减压重结晶或退变质阶段，而Ic型包裹体分布广泛，表明其主体可能是在超高压变质岩折返过程的最晚阶段捕获的；N2-CH4纯气相包裹体均为原生包裹体，主要呈孤立和小群状与Ia和Ib类包裹体分布于榴辉岩中条带状石英脉中，可能主要是在高压-超高压榴辉岩相变质条件下被捕获的；CCSD榴辉岩中石英脉的主体形成于板块折返有关的减压重结晶和退变质，而片麻岩中石英脉则主要来源于角闪岩相及其后期退变质作用；榴辉岩和片麻岩中石英脉流体包裹体的组成和地球化学特征存在明显区别，但它们各自相似于其寄主岩石中的石英颗粒中包裹体，说明CCSD中HP—UHP岩石在板块折返过程中释放出的变质流体没有经过大规模的迁移。     

Metamorphic reactions between fluid inclusions and mineral hosts. I. Progress of the reaction calcite+quartz=wollastonite+CO2 in natural wollastonite-hosted fluid inclusions

 At the Bufa del Diente contact-metamorphic aureole, brine infiltration through metachert layers embedded in limestones produced thick wollastonite rims, according to Cc+Qz=Wo+CO₂. Fluid inclusions trapped in recrystallized quartz hosts include: (1) high salinity four phase inclusions [Th(V-L)=460–573° C; Td(salts)=350–400° C; (Na+K)_Cleq=64–73 wt%; X _{CO 2}≤0.02]; (2) low density vapour-rich CO₂-bearing inclusions [Th(L-V)≈500±100° C; X _{CO 2}=0.22–0.44; X _NaCl≤0.01], corresponding to densities of 0.27± 0.05 gcm⁻³. Petrographical observations, phase compositions and densities show that the two fluids were simultaneously trapped in the solvus of the H₂O-CO₂-salts system at 500–600° C and 700±200 bars. The low density fluid was generated during brine infiltration at the solvus via the wollastonite producing reaction. Identical fluid types were also trapped as inclusion populations in wollastonite hosts 3 cm adjacent to quartz crystals. At room temperature, both fluid types additionally contain one quartz and one calcite crystal, generated by the back-reaction Wo+CO₂=Cc+Qz of the host with the CO₂-proportion of the fluid during retrogression. All of the CO₂ was removed from the fluid. On heating in the microstage, the reaction progress of the prograde reaction was estimated via volume loss of the calcites. In vapour-rich fluids, 50% progress is reached at 490–530° C; 80% at 520–560° C; and 100% at 540–590° C, the latter representing the trapping temperatures of the original fluid at the two fluid solvus. The progress is volume controlled. With knowledge of compositions and densities from unmodified inclusions in quartz and using the equation of state of Duan et al. (1995) for H₂O-CO₂-NaCl, along with f _{CO 2}-values extracted from it, the reaction progress curve was recalculated in the P-T-X-space. The calculated progress curve passes through the two fluid solvus up to 380° C/210 bars, continues in the one fluid field and meets the solvus again at trapping conditions. The P-T slope is steep, most of the reaction occurs above 450° C and there is high correspondence between calculated and measured reaction progress. We emphasize that with the exception of quartz, back-reactions between inclusion fluids and mineral hosts is a common process. For almost any prograde metamorphic mineral that was formed by a devolatilization reaction and that trapped the equilibrium fluid or any peak metamorphic fluid as an inclusion, a fluid-host back-reaction exists which must occur somewhere along the retrograde path. Such retrograde reactions may cause drastic changes in density and composition of the fluid. In most cases, however, evidence of the evolving mineral assemblages is not given for they might form submicroscopical layers at the inclusion walls. Received: 15 March 1995 / Accepted: 1 June 1995     

等应力比平面应变试验中主应力转换的研究

土的平面应变是岩土工程中常见的状态,其中零应变方向的主应力是十分复杂的。承德中密砂等应力比平面应变试验结果表明,平面应变状态下零应变方向的主应力在不同条件下可能是大主应力、中主应力或者小主应力。利用由等应力比三轴压缩试验确定的切线泊松比,可以合理地预测等应力比平面应变试验中零应变方向主应力的转换过程,这一认识对于一些实际工程问题的分析具有一定的意义。     

中主应力与大主应力方向角对软黏土排水变形特性影响

为研究中主应力系数和大主应力方向角对各向异性软黏土变形特性的影响,利用GDS空心圆柱扭剪仪对温州原状软黏土进行了一系列不同中主应力系数和大主应力方向角的排水定向剪切试验。试验过程中在大主应力方向角和中主应力系数不变的条件下,逐渐增加剪应力直至试样破坏。分析了中主应力系数和大主应力方向角对温州原状土偏应力与大主应变关系、体应变、中主应变和小主应变与大主应变关系的影响。试验结果表明：试样的应力-应变关系在中主应力系数和大主应力方向角不同时表现出明显的各向异性。当中主应力系数为0.00和1.00时,大主应力方向角对应力-应变关系的影响较小;而当中主应力系数为0.50时,应力-应变关系中的割线剪切模量随大主应力方向角变化明显。当大主应力方向角为30°时,随着中主应力系数从0.00增加到0.50,中主应变由压缩状态变为拉伸状态;当大主应力方向角为45°时,随着中主应力系数从0.00增加到1.00,中主应变由压缩状态变为拉伸状态。     

Characteristics and Applications of Fluid Inclusions in the Eogene System of the Biyang Depression—I.A Fluid Inclusion Study

Presented in this paper are the rypes,salinities,homogenization temperatures and organic components of fluid inclusions formed at the four stages of diagenetic authigenesis in the Eogene of the Biyang Depression.The results of cooling experiments on fluid inclusions were used to determine the fluid system and composition of saline aqueous solution in each of the stages .The homogenization temperatures of saline aqueous solution inclusions and hydrocarbon organic inclu-sions have been corrected by two approaches ,and the trapping temperatures and pressures of fluid inclusions at each of the stages have been obtained.This strdy has shed light on the physicochemistry and evolution of diagenetic fluids.The diagentic fluid system is a system which was transformed from a chloride-bearing to a carbonate-bearing system along with the diagenic evolu-tion.The decrease of diagenetic temperature at Stage III of diagenetic authigenesis suggests that the depression would have experiences uplifting at that time.The fluorescent characteristics of fluid inclusions indicate the varieties of organic components in fluid inclusions both in time and in space.     

大主应力方向及中主应力系数对重塑黄土小应变刚度特性影响试验研究

利用配备高精度应变传感器的空心圆柱扭剪仪对重塑黄土开展了一系列定向剪切试验,剪切过程中保持平均主应力p、大主应力方向角? 以及中主应力系数b不变。共完成了包括3组不同大主应力方向角和1组不同中主应力系数的4组试验,共21个试样。对定向剪切条件下重塑粉土的应力-应变-强度以及小应变（<0.1%）刚度特性进行了研究,分析了不同大主应力方向角及中主应力系数的影响。试验研究结果表明,重塑黄土存在显著的强度各向异性特性,沿? =0°方向的强度最大,而最小强度方向因中主应力系数的不同而不同。? =0°时,b=0.25的强度最大,此时试样接近平面应变条件。小应变条件下重塑黄土的剪切刚度也因剪切时?和b的不同而不同,剪应变小于0.02%和大于2%时,刚度基本保持不变,初始剪切刚度很大,当剪应变大于0.02%后,随着剪应变的增加而迅速衰减,衰减曲线可以采用指数函数进行较好的拟合。     

Synthetic fluid inclusions in natural quartz. III. Determination of phase equilibrium properties in the system H2O-NaCl to 1000°C and 1500 bars

Phase equilibria in the system H₂O-NaCl have been determined to 1000°C and 1500 bars using synthetic fluid inclusions formed by healing fractures in inclusion-free Brazilian quartz in the presence of the two coexisting, immiscible H₂O-NaCl fluids at various temperatures and pressures. Petrographic and microthermometric analyses indicate that the inclusions trapped one or the other of the two fluids present, or mixtures of the two. Salinities of the two coexisting phases were obtained from heating and freezing studies on those inclusions which trapped only a single, homogeneous fluid phase.Results of the present study are consistent with previously published data on the H₂O-NaCl system at lower temperatures and pressures, and indicate that the two-phase field extends well into the P-T range of most shallow magmatic-hydrothermal activity. As a consequence, chloride brines exsolved from many epizonal plutons during the process of “second-boiling” should immediately separate into a high-salinity liquid phase and a lower salinity vapor phase and produce coexisting halite-bearing and vapor-rich fluid inclusions. This observation is consistent with results of numerous fluid inclusion studies of ore deposits associated with shallow intrusions, particularly the porphyry copper deposits, in which halite-bearing and coexisting vapor-rich inclusions are commonly associated with the earliest stages of magmatic-hydrothermal activity.     

The Na/K ratio of fluid inclusions in pegmatitic quartz and its genetic implications. A study by neutron activation analysis

Samples of quartz and its fluid inclusions (f.i.) from Black Hills pegmatites and from graphic granites were analyzed for Na, K, Rb and Cs by neutron activation analysis. The Na/K ratios of the whole quartz and its f.i. seem unrelated. The spatial locations for six samples from the Helen Beryl pegmatite were known. The Na/K ratios of their f.i. are mainly a function of their vertical positions in the pegmatite. The ratios of the central-core quartz f.i. seemingly indicate a much higher temperature than those closer to the upper wall. This is consistent with the theory of pegmatite genesis by Jahns & Burnham. The f.i. of quartz from two graphic granites give very different Na/K ratios, seemingly related to differences in their formation history.     

Syndeformational fluid trapping in quartz: determining the pressure-temperature conditions of deformation from fluid inclusions and the formation of pure CO2 fluid inclusions during grain-boundary migration

Abstract Observations and microthermometric data on fluid inclusions from a terrane that underwent deformation following peak metamorphic conditions show that grain-boundary migration recrystallization favours the entrapment of carbonic inclusions whereas microfracturing during brittle deformation favours the infiltration and eventual entrapment of aqueous fluids. Our results imply that pure CO₂ fluid inclusions in metamorphic rocks are likely to be the residue of deformation-recrystallization process rather than representing a primary metamorphic fluid.
Where the temperature of deformation can be deduced by other means, the densities of fluid inclusions trapped during recrystallization, which we call recrystallization-primary fluid inclusions, can be used to constrain the ambient pressure during deformation. Using these constraints, the data imply that the post-metamorphic Hercynian exhumation in Sardinia brought rocks at 300° C to within 3km of the surface. This conclusion is similar to that described for the rapidly uplifted Southern Alps in New Zealand.