Review of Rare Earths and Fluid-Rock Interaction

As demonstrated by a great amount of geologic and experimental evidences, RE of rock systems may be mobilized during fluid-rock interaction when solutions are rich in F -, Cl -, CO 3 2-, HCO 3 -, CO 2, HPO 4 2-, HS -, S 2-, SO 4 2-, though little has been known about the mobilizing mechanism of these anions or ligands. The fractionation of RE resulted from hydrothermal alterations, i. e., fluid-rock interactions, are distinctive. One set of field data implies the preferential mobility of the LRE, while another set of field observations demonstrates the dominant mobilization of the HRE, and some theoretical prediction is not consistent with the field evidence. The Eu anomalies caused by fluid-rock interaction are complex and compelling explanation is not available due to inadequate experimental approaches. To know the exact behavior of RE during fluid-rock interaction and to solve the contradiction between some theoretical predictions and field observations, the following works remain to be done: (1) experimental investigations of RE mobility and fractionation as a function of fluid chemistry, e.g., the activity of F -, Cl -, CO 3 2-, HCO 3 -, CO 2, HPO 4 2-, HS -, S 2-, SO 4 2-, etc.; (2) experimental determination of RE mobility and fractionation as a function of T, P, pH, E h and water/rock ratios; (3) investigation of the mechanism and the controlling factors of RE partitioning between hydrothermal minerals and fluids. It was demonstrated that RE mobility is a potentially useful method for exploration.

Subduction channel fluid-rock interaction:Indications from rutile-quartz veins within eclogite from the Yuka terrane,North Qaidam orogen

High-pressure(HP)or ultrahigh-pressure(UHP)rutile-quartz veins that form at mantle depths due to fluid-rock interaction can be used to trace the properties and behavior of natural fluids in subduction zones.To explore the fluid flow and the associated element mobility during deep subduction and exhumation of the continental crust,we investigated the major and trace elements of Ti-rich minerals.Additionally,U–Pb dating,trace element contents,and Lu–Hf isotopic composition of zircon grains in the UHP eclogite and associated rutile-quartz veins were examined in the North Qaidam UHP metamorphic belt,Yuka terrane.The zircon grains in the rutile-quartz veins have unzoned or weak oscillatory zonings,and show low Th/U ratios,steep chondrite-normalized patterns of heavy rare earth elements(HREEs),and insignificant negative Eu anomalies,indicating their growth in metamorphic fluids.These zircon grains formed in 431
3 Ma,which is consistent with the 432
2 Ma age of the host eclogite.As for the zircons in the rutile-quartz veins,they showed steep HREE patterns on one hand,and were different from the zircons present in the host eclogite on the other.This demonstrates that their formation might have been related to the breakdown of the early stage of garnet,which corresponds to the abundance of fluids during the early exhumation stage.The core-rim profile analyses of rutile recorded a two-stage rutile growth across a large rutile grain;the rutile core has higher Nb,Ta,W,and Zr contents and lower Nb/Ta ratios than the rim,indicating that the rutile domains grew in different metamorphic fluids from the core towards the rim.The significant enrichment of high field strength elements(HFSEs)in the rutile core suggests that the peak fluids have high solubility and transportation capacity of these HFSEs.Furthermore,variations in the Nb vs.Cr trends in rutile indicate a connection of rutile to mafic protolith.The zircon grains from both the rutile-quartz veins and the host eclogite have similar Hf isotopic compositions,indicating that the vein-forming fluids are internally derived from the host eclogite.These fluids accumulated in the subduction channel and were triggered by local dehydration of the deeply subducted eclogite during the early exhumation conditions.

Behaviors of Rare Earths during Fluid-Rock Interaction and Its Significance of Geochemistry

Rare earths in ores, altered and unaltered sericite phyllite, altered and unaltered dacite porphyry were determined in order to examine behaviors of rare earths in hydrothermal alteration associating with ore-forming processes of Yinshan deposit. It is not sufficient to show the mobility only by the absolute abundance of trace elements changes before and after alteration. This can simply result from dilution or concentration if other elements are added to or removed from the rock. As shown by that in Yinshan deposit, less than 20% of the increment of RE was caused by the 'condensed' of leaching some of major elements (e.g. Si, Na) from the rock. The principal factor which should be responsible for the higher contents of RE in altered rock is the addition of RE into the rock by hydrothermal fluids. Eu is selectively leached from the altered sericite phyllite by a mild acidity and reducing fluid which is characterized by much lower LRE/HRE ratio and a large positive Eu anomaly. A major effect on the RE patterns is the tendency to develop relatively flatter chondrite-normalized patterns. The RE characteristics may be used to distinguish between small and large ore bodies at a later stage of exploration.

Mineralogical and Geochemical Evidence of Fluid-rock Interaction at the Shallow Crustal Level in Koyna Seismogenic Region, Maharashtra, India: Impact and Implications

The Koyna region of Maharashtra located in the western part of the~65 Myr old Deccan traps province,overlying the Neoarchean cratonic granitoid basement of peninsular India,has been experiencing recurring seismicity since 1962 after the impoundment of the Shivajisagar Reservoir behind the Koyna Dam.

Discrimination Study on Fluid-Rock Interaction Between Metallogenic and Non-Metallogenic Sections in a Shear Zone

Discriminations in a local chemical, fluidal, mechanical and thermal processes in a shear zone will lead to metallogenic differentiation in a local section. This paper, based on the general geological setting of the Shibangou gold deposit in Xixia, Henan, deals with petrological and petrochemical samples of altered rocks in the metallogenic section and of mylonites in the non\|metallogenic section of a selected shear zone. The discriminations in fluid\|rock interaction and petrological mass balance between altered rocks near the orebody and mylonites in the shear zone are discussed as well. The results show that the petrological volume of altered rocks in the metallogenic section of the shear zone is almost always dilatant and the mylonite volume in the non\|metallogenic section is almost always lost. Major elements in altered rocks from the metallogenic section and in mylonites from the non\|metallogenic section always show a tendency of being enriched and depleted, respectively. Fluid\|rock ratios in the mylonites (Nu=\{93.68-468.40\}) are larger than those of the altered rocks (Nc\+s\-\{(Ⅳ)\}=\{36.11-216.67\}). The gain and loss of major and trace elements from the altered rocks and mylonites in the shear zone are a composite process to be imported and exported by percolating fluids as well as of the loss and dilatancy of rock volume.

注热化学流体吞吐解除岩石储层反凝析伤害评价

为长期有效解除凝析气藏反凝析带来的储层伤害,提出了一种注热化学流体吞吐解除凝析油堵塞孔喉的新方法。针对致密砂岩、碳酸盐岩和页岩3类岩石,开展了注热化学流体吞吐岩心驱油实验,评价了热化学流体解除凝析油堵塞的可行性,并基于核磁共振技术分析了吞吐前后3类岩石微观孔隙结构的变化特征,明确了热化学流体解除反凝析伤害机理。实验结果表明,热化学流体(NH_(4)Cl和NaNO_(2))在乙酸溶液催化下能够迅速释放大量气体和蒸汽,提高岩心压力和温度,降低原油黏度,使凝析油由液态转变为气态,减小渗流阻力。致密砂岩、碳酸盐岩和页岩岩心注热化学流体吞吐累积凝析油采出程度分别为65.7%,73.9%和46.3%。其中,致密砂岩和碳酸盐岩岩心仅需2轮吞吐即可有效清除55.5%和67.6%的凝析油堵塞。而页岩岩心需要延长焖井时间及增加吞吐次数方能提高凝析油的采出程度。热化学流体吞吐后,致密砂岩、碳酸盐岩和页岩岩心平均孔径分别由0.37,1.04和0.0021μm增大至0.84,2.04和0.0058μm。热化学流体吞吐效果是注CH_(4)吞吐和注甲醇吞吐效果的1.85和1.32倍。

基于孔裂隙储层弹性参数频散衰减机理的有限元数值模拟

饱含流体孔隙裂隙储层介质的弹性参数频变特性常应用于地震勘探和储层评价中。针对传统有效介质理论不准确及计算精度不高的问题,该研究推导了适用于孔隙弹性储层的Biot固结方程;为了研究模型介质渗透率、流体类型和黏度等参数对频变弹性参数的影响机理,开发了相应的有限元数值模拟流程,用于计算由波致流引起的地震波速度频散及衰减。模拟结果表明:1)与现有岩石物理理论模型对比,该数值模拟方法在宽频段模拟一维/二维孔隙裂隙介质的适用性更好;2)渗透率、流体黏度以及流体饱和模式作为岩心重要的物性表征,显著影响地震波弹性响应,渗透率增大,特征频率右移;黏度增大,特征频率左移;水包气模型相对于油包气模型衰减峰值较大,特征频率略高。综上所述,该研究为深入理解地震波在孔裂隙储层中的传播特性提供了准确的预测方法,有助于揭示储层的非均质性和孔隙结构,提高勘探精度和储层评价的可靠性,对储层预测与流体识别的岩石物理解释具有重要的指导意义。

降雨入渗对防军隧道浅埋小净距段围岩稳定性的影响

为控制降雨入渗对浅埋小净距隧道围岩稳定性的影响,以义东高速公路防军隧道为依托,基于流固耦合理论和水土特征曲线,采用MIDAS GTS NX有限元软件建立浅埋小净距隧道数值模型,对雨季施工时的土体孔隙水压力、围岩变形特征和边仰坡安全系数展开分析。结果表明:随着降雨入渗的持续,围岩及边仰坡土体基质吸力逐渐减小,其土体抗剪强度也随之降低,稳定性变差。经过7 d累积降雨,孔隙水压力增大趋势逐渐放缓,围岩变形达到最大值,工况1的拱顶沉降增大了21.48%,且边仰坡安全系数小于1,处于失稳状态。洞口段采取加固和排水措施来控制围岩的稳定性,边仰坡的安全系数较加固前提升了17.27%,取得了良好的效果,保证了隧道后期的安全施工。

藏南中成明赛和浅成马扎拉金矿床成矿异同:来自地质和硫化物原位微量元素、硫同位素约束

特提斯喜马拉雅带地处青藏高原南部,是产于青藏高原大陆碰撞背景的新生代金成矿省,然而其赋存的造山型金矿床分布零散,且不同构造层次造山型金矿床(如中成、浅成)的蚀变矿化、流体组成和成矿过程缺乏系统对比。本文通过详细对比特提斯喜马拉雅东段中成明赛金矿和浅成马扎拉金(锑)矿床蚀变矿化、硫化物结构、原位微量元素和硫同位素组成,探讨其成矿过程、成矿流体组成及控制因素。两矿床均赋存于侏罗系板岩和凝灰岩夹层中,板岩中蚀变弱,沿层理发育浸染状黄铁矿-铁白云石-绢云母-石英;而凝灰岩夹层蚀变强,长石和黑云母等矿物已蚀变为铁白云石、绿泥石和绢云母等,并发育大量浸染状自形-半自形黄铁矿和毒砂。板岩中黄铁矿(明赛:Py sa;马扎拉:Py sb)结构均较为均一,且Au(平均为0.33×10^(-6))等微量元素含量低,δ^(34)S值变化较大(Py sa:8.12‰~15.6‰;Py sb:-24.3‰~3.36‰)且与侏罗系地层δ^(34)S值相吻合。明赛凝灰岩中黄铁矿(Py va)发育富砷同心环带,具较高的Au(平均含量为14.3×10-6)、As含量,而马扎拉凝灰岩中黄铁矿(Py vb)发育不规则核-边结构且富Au(平均含量为3.8×10-6)、Cu、Pb、Sb。两矿床凝灰岩中黄铁矿和毒砂的δ^(34)S值相似(Py va平均值为2.7‰、毒砂为2.4‰;Py vb平均值为3.2‰、毒砂为3.2‰),与藏南造山型金矿中黄铁矿δ^(34)S值一致。上述两个矿床板岩中黄铁矿贫金且硫同位素组成差异较大,可能为成矿流体与含不同沉积黄铁矿围岩反应所致;而凝灰岩中的黄铁矿富金且与毒砂具有相似的硫同位素组成,可归因于同源流体与相同围岩发生均一化水岩反应。本次研究表明藏南地区广泛分布的凝灰岩是形成造山型金矿的有利岩性,研究区不同构造层次的造山型金矿具相似物质源区,成矿系统差异性受控于不同水岩反应过程。

斑岩铜矿蚀变分带与成矿机制:玉龙矿床水-岩反应热力学平衡模拟例析

蚀变分带和成矿机制的准确厘定是建立斑岩成矿模型与找矿预测的关键。本文以新生代金沙江-哀牢山成矿带的玉龙斑岩铜矿为例,通过质量作用定律(LMA)和吉布斯自由能最小化模型(GEM),构建含矿热液与斑岩侵入体的pH-f O 2相图和动态传输模型,以揭示蚀变分带成因和金属成矿机制。LMA与GEM结果显示初始成矿流体pH值为4.7,logf_(O2)=-23.0(ΔFMQ=+2.7),且溶解Cu含量为1138×10^(-6),Mo为1.2×10^(-6)。研究表明,当该酸性及强氧化性流体流入二长花岗斑岩体时,在温度为450~360℃范围内,代表钾硅酸盐化蚀变的钾长石、黑云母、硬石膏、赤铁矿和磁铁矿的矿物逐渐沉淀,且与钾硅酸盐化蚀变相关流体具有较高pH值(5.0~7.0)和氧逸度(ΔFMQ=+2.9~+3.6)特征;当温度在360~320℃范围时,代表青磐岩化蚀变阶段的典型矿物如绿帘石、铁绿泥石和斜绿泥石等逐渐形成,流体pH值(5.0~6.4)和氧逸度(ΔFMQ=+1.1)均有所下降;当温度进一步从320℃下降到200℃时,流体pH值(5.0~5.7)进一步小幅下降,而氧逸度则(ΔFMQ=+1.7)略有回升,在此期间,绢云母和方解石等开始沉淀并形成典型的绢英岩化蚀变。此外,以HMoO_(4)^(-)和MoO_(4)^(2-)为载体的Mo在狭窄高温区间(450~370℃)内沉淀,而以CuCl(CuCl_(4)^(3-)、CuCl_(2)^(-)、CuCl)为主要载体的Cu则在在中、高温(450~300℃)范围中沉淀。通过利用LMA反演及GEM正演相结合定量化地刻画了玉龙斑岩铜矿水岩反应过程,由此揭示了斑岩矿床蚀变分带是逐渐冷却的单一岩浆热液与斑岩体不断反应的结果,且不同温度窗口对应着钾硅酸盐化(450~360℃)、青磐岩化(360~320℃)和绢英岩化(320~200℃)蚀变矿物的形成,故含矿流体温度的快速下降可能是玉龙铜矿蚀变叠加的重要因素。此外,Cu、Mo络合离子溶解度对温度变化的差异响应,导致了Mo矿化主要发育于靠近斑岩体的高温区域,而Cu则以网脉状-浸染状叠加到Mo矿化之上,并广泛分布于斑岩体周边的高-中温区域。

基于储层砂岩孔隙结构的地震岩石物理模型

在实验室内对新疆车排子地区春光油田沙湾组储层砂岩样品进行了系统地震岩石物理实验,在确定储层砂岩中不同孔隙类型组成条件下,基于非接触模型综合考虑储层砂岩孔隙度以及孔隙形状对于干燥岩石骨架弹性性质的影响,并利用实验结果对模型参数进行标定进而建立表征目标储层岩石骨架地震弹性性质的岩石物理模型,模型结果与实验结果吻合良好。依据实验及模型结果,利用喷射流作用模型替代传统Gassmann方程进行流体替换,同样能够较好地对超声频率实验结果进行解释。

Hydrogen and oxygen isotope studies of metamorphic fluid-rock interactions in the Dabie Mountains

Hydrogen and oxygen isotope studies were carried out on mineral separates from high to ultrahigh pressure metamorphic rocks at Huangzhen and Shuanghe in the eastern Dabie Mountains, East China. The δ 18O values of eelogites cover a wide range of-5‰ to+9‰, but the δD values of micas fall within a narrow range of -85‰ to -70‰. Both equilibrium and disequilibrium oxygen isotope fractionations were observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some eclogite samples. The δ 18O values of -5‰ to -1‰ for some of the eclogites represent the oxygen isotope compositions of their protoliths which underwent meteoric water-rock interaction prior to plate subduction. The preservation of oxygen isotope heterogeneity in the eclogites implies a channelized flow of fluids during progressive metamorphism caused by rapid subduetion. Retrograde metamorphism has caused oxygen and hydrogen isotope disequilibria between some of the minerals, but the

辽河坳陷清水洼陷古近系沙河街组深层烃源岩特征及油气成藏模式

通过有机碳、岩石热解、氯仿沥青“A”、饱和烃色谱-质谱和流体包裹体等的分析,对辽河坳陷清水洼陷古近系沙河街组深层烃源岩特征和油气成藏模式进行了详细研究。研究结果表明:(1)辽河坳陷清水洼陷古近系沙河街组深层烃源岩主要发育在E2s32亚段、E2s33亚段和E2s4段,其中E2s32亚段Ⅱ小层泥岩最为发育,主要为深灰色厚层泥岩,整体厚度约170 m。(2)研究区深层烃源岩总有机碳质量分数平均可达1.60%,生烃潜量平均值为2.82 mg/g;有机质类型以Ⅱ1—Ⅲ型为主,主要为浮游植物与高等植物混合贡献,为弱氧化—弱还原的湖相咸水沉积环境;烃源岩有机质丰度为0.5%~1.5%,普遍达到大量生烃阶段,部分已达到高成熟演化阶段。(3)研究区深层烃源岩在距今38 Ma时进入生油窗,距今20 Ma时开始生成天然气;流体包裹体显示研究区存在2期油气充注,分别为38~26 Ma和20 Ma~现今,与生烃演化史匹配。

碳酸盐岩地层漏失规律研究

碳酸盐岩在沉积/成岩过程中由于受到化学溶蚀作用,发育包括溶孔、溶洞和裂缝在内的多种类型漏失通道,导致漏失成为安全高效钻井的首要挑战。以S油田N组巨厚碳酸盐岩地层为研究对象,综合测井和录井解释成果,建立了溶孔、溶洞和裂缝不同类型的等效物理模型。通过采用将离散裂缝嵌入变渗透率基质中的方法建立钻井液漏失流-固耦合数学模型,并采用有限元方法进行求解,系统对比分析不同漏失通道条件下的钻井液漏速和漏量的变化特征,以及钻井液参数对漏失的影响。研究结果表明,漏失通道类型是影响漏失的主控因素,漏失程度与溶洞渗透率大小成正相关,且易引发失反性漏失。裂缝宽度和溶蚀半径也对漏速和漏量影响较大,但二者存在阈值,当达到一定极限时漏速和漏量趋于平缓。漏失通道组合越复杂,漏失越严重。钻井液密度与漏失程度成正相关。建立的数值模型可为溶孔-溶洞-裂缝型碳酸盐岩漏失规律理论研究提供新的思路,为安全高效钻井提供理论支持。

页岩层系不同岩矿组合试样渗透率变化规律差异及其机理分析

页岩地层垂向岩矿组合变化大,页岩气开采需要对储层进行大规模人工水力压裂改造。笔者等基于样品的全岩X-射线衍射分析,通过对不同岩矿组合的3块页岩试样进行流—固耦合物理模拟实验,获得了3点认识,反映了不同岩矿成分的页岩在不同条件微裂缝与渗透率的变化特征,以及碳酸盐矿物含量高时的影响。这一实验对于研究页岩储层在压裂过程中的变化具有探索性,对于页岩气生产具有重要的参考意义。

高阻地层HDIL阵列感应影响因素分析与校正方法

近年来,四川盆地川中深层灯影组和龙王庙组天然气勘探中越来越多地使用油基泥浆,使得裸眼井电阻率测井只能选择阵列感应仪器。该地区目的层致密碳酸盐岩普遍表现为中高电阻率,典型气层的电阻率一般在500Ω·m以上甚至高达2000Ω·m,使得测量电导率的感应测井仪器接收的信号弱,叠加深层高温等因素的影响,采集的信号常出现负值,软件聚焦处理结果常出现平头现象,不能用于储层识别和气层评价。采用有限元模拟算法,分析泥浆电阻率、侵入半径及原状地层电阻率等单因素对阵列感应测井响应的影响规律,明确了各环境因素对感应测量信号的影响规律。结果表明,地层与泥浆电阻率对比度对测量信号有明显影响,当对比度接近于1时,各子阵列的误差较小,而侵入深度是另一个重要影响因素。总体上,较长源距的子阵列受各种因素的影响相对较小。针对实际资料的特点,提出一种基于Archie公式的原始电导率信号约束校正方法,对约束校正后的数据再开展软件聚焦,其结果得到明显改善。

Fluid-rock interaction and mass balance of deformed rock in deformation——Taking the Eritx tectonic zone,northern Xinjiang

The Irtish techonic zone,as an example,is presented to study fluid-rock interactions duringoverthrusting the deformation process at the depth of middle-lower earth crust.The results show that therewere compicuous fluid actions in the meantime of deformation and many deformational and differentialmicrostructures related to fluid-rock interactions provided direct evidence of fluid actions.Fluid,as a mediumof mass transfer,played an important role in the loss and getting of chemical compositions in deformed rocksduring tectono-dynamic lithogeneous processes in which rock alterations from protolith（volcanics）throughmylonite to migmatite and finally to migmatitic granite took place.The loss and getting of chemicalcompositions can he calculated by means of major and trace elements.Using the calculated results andSiO2 solubility,the calculation fluid（mass）/rock（volume）ratio is 103-105g fluid/m3 rock.The possible fluidresources are dehydration reactions of pore water and mineral water within protoliths（marine mid-acidvolcanics）and foodwaU rocks during tectono-rise pressure and temperature processes.The fluid flow migratedfrom deep to shallow positions of the earth crust along the large-scale thrusting fault,penetrative cleavage,andS-C foliation.Fluid mass transportation resulted in chemical composition alterations in deformed rocks.Within overthrusting zone under the compressive orogenic background,the major mechanism of masstransportation is infiltration or advection in the open system.

鄂尔多斯盆地南缘上奥陶统赵老峪组岩石磁学研究

利用古地磁学手段定量约束华北板块早古生代古地理位置可为原特提斯造山作用及华北板块与冈瓦纳大陆的亲缘性研究提供重要科学依据。但华北板块早古生代以来经历了多期构造运动,其西部鄂尔多斯盆地含丰富油气资源,后期构造运动和油气运移均可能导致其早古生代地层遭受重磁化影响。对鄂尔多斯盆地南缘富平地区上奥陶统赵老峪组灰岩、凝灰岩样品进行了系统岩相学、岩石磁学及逐步退磁研究,包括光学显微镜鉴定实验、扫描电镜(SEM)实验、能谱分析(EDS)实验、饱和等温剩磁(SIRM)实验、三轴等温热退磁实验、磁化率随温度变化(κ-T)实验、磁滞回线实验、一阶反转曲线(FORC)实验、系统热退磁实验以及热-交混合退磁实验,探讨了各类岩石的主要载磁矿物及其是否具备记录原生剩磁信息的潜能。结果表明:灰岩及凝灰岩样品的主要载磁矿物为磁铁矿、磁黄铁矿和(或)胶黄铁矿,部分样品还含少量赤铁矿(含杂质)和针铁矿,矿物颗粒的磁畴类型同时含有SD(单畴)和MD(多畴)两种。结合岩相学及退磁实验结果认为这些主要载磁矿物可能是与后期流体作用(有机质成熟及运移等)有关的次生矿物,其携带的剩磁信号不能直接用于约束板块早古生代古地理位置,或可用于约束鄂尔多斯盆地南缘下古生界油气运移成藏过程。