华北南缘中元古界高山河群碎屑锆石U-Pb年代学及其地质意义

为了探讨华北板块南缘中元古代沉积地层的时代归属和物质来源、区域古地理格局和大地构造特征,对豫西灵宝福地地区的高山河群进行碎屑锆石U-Pb年代学和锆石微量元素特征研究。获得的高山河群年龄最小(年轻)的单颗碎屑锆石207Pb/206Pb年龄值为1685±39 Ma,从而限制了高山河群最早沉积年龄不早于1700 Ma。结合上覆的龙家园组年代学标定(1594±12 Ma),将高山河群的形成年代限定为1700—1600 Ma,即中元古代长城纪的中晚期,属国际地质年表的"固结纪"。高山河群中碎屑锆石207Pb/206Pb年龄范围为1685—2751 Ma,呈现1850 Ma、2150 Ma、2300 Ma和2500 Ma共4个年龄峰值,对应于华北克拉通古元古代重要的地质事件,并且高山河群以1850 Ma和2500 Ma峰值年龄段的地质体为主要的物源区。根据高山河群与云梦山组碎屑锆石年龄频率对比,推测在豫西地区西侧存在以往报道较少的年龄为2500 Ma的地质体。根据熊耳群火山岩及其对应锆石的地球化学特征和熊耳期盆地动力学性质,并结合高山河群沉积相特征和沉积盆地构造属性,认为熊耳群形成于与"岛弧"共生的拉张性质的弧后盆地地区,而其上覆的高山河群为弧后盆地靠近大陆一侧的具有被动大陆边缘性质的滨浅海沉积。     

华北南缘中元古界高山河群碎屑锆石U-Pb年代学及其地质意义*

为了探讨华北板块南缘中元古代沉积地层的时代归属和物质来源、区域古地理格局和大地构造特征,对豫西灵宝福地地区的高山河群进行碎屑锆石U-Pb年代学和锆石微量元素特征研究。获得的高山河群年龄最小(年轻)的单颗碎屑锆石 ²⁰⁷Pb/²⁰⁶Pb 年龄值为1685±39 Ma,从而限制了高山河群最早沉积年龄不早于1700 Ma。结合上覆的龙家园组年代学标定(1594±12 Ma),将高山河群的形成年代限定为1700—1600 Ma,即中元古代长城纪的中晚期,属国际地质年表的“固结纪”。高山河群中碎屑锆石 ²⁰⁷Pb/²⁰⁶Pb 年龄范围为1685—2751 Ma,呈现1850 Ma、2150 Ma、2300 Ma和2500 Ma共4个年龄峰值,对应于华北克拉通古元古代重要的地质事件,并且高山河群以1850 Ma和2500 Ma峰值年龄段的地质体为主要的物源区。根据高山河群与云梦山组碎屑锆石年龄频率对比,推测在豫西地区西侧存在以往报道较少的年龄为2500 Ma的地质体。根据熊耳群火山岩及其对应锆石的地球化学特征和熊耳期盆地动力学性质,并结合高山河群沉积相特征和沉积盆地构造属性,认为熊耳群形成于与“岛弧”共生的拉张性质的弧后盆地地区,而其上覆的高山河群为弧后盆地靠近大陆一侧的具有被动大陆边缘性质的滨浅海沉积。     

豫西汝阳群、洛峪群碎屑锆石年代学特征及其地质意义

华北克拉通南缘"豫陕裂陷槽"发育大量中—新元古代地层,其中汝阳群和洛峪群分布于渑池—确山地层小区,其形成时代一直存有争议.本文针对汝阳群和洛峪群沉积岩进行了系统的碎屑锆石年代学研究工作,结合地层发育和岩石组合分析,为建立华北克拉通南缘中—新元古代地层框架提供依据.根据云梦山组下部碎屑锆石中获得年轻锆石年龄平均值1723.6 Ma,结合前人从洛峪群凝灰岩夹层中获得的年代学资料(1611±8 Ma、1640±16 Ma、1638±9 Ma、1634±10 Ma),将汝阳群-洛峪群的沉积时限限定在1720～1600 Ma之间.本文所采集的云梦山组、白草坪组和崔庄组样品中碎屑锆石207Pb/206Pb年龄分别在2657～1739 Ma、2712～1780 Ma和2654～1819 Ma之间,说明三个组沉积物质主要来源于古元古代地质体,部分为新太古代地质体.鲁山地区发育的新太古代—古元古代的太华杂岩,登封地区发育的新太古代登封群以及古元古代嵩山群和花岗质岩石等,均可为中—新元古代沉积岩提供物源.豫西地区汝阳群-洛峪群碎屑锆石中～2.7 Ga、～2.5 Ga、2.1～2.0 Ga和1.85～1.8 Ga的年龄谱峰值分别对应华北克拉通早前寒武纪发生地壳生长、克拉通化、裂谷和造山等重要地质事件.越来越多资料显示华北克拉通在2.2～2.0Ga时期存在强烈的岩浆活动,豫西地区～2.1 Ga的岩浆作用也逐渐被识别出来.     

华北克拉通南缘中-新元古代沉积演化:以豫西地区黄连垛组和董家组为例

华北克拉通(华北)南缘中元古代早期熊耳群火山活动之后,在渑池-确山地区发育了一套中-新元古代沉积(汝阳群、洛峪群、黄连垛组、董家组以及罗圈组和东坡组),记录了该时期沉积-构造演化过程。通过该区碎屑锆石和洛峪群顶部凝灰岩年龄的约束,将汝阳群-洛峪群的沉积时代基本限定于约1750～1600Ma,导致洛峪群由中元古界上部或新元古界下划到中元古界长城系。因此,在现有的地层年代格架下,需要重新对该区中-新元古代沉积演化进行讨论。本文通过对洛峪口组上覆黄连垛组和董家组沉积环境和物源分析,同时借助古生界辛集组源区分析的约束,揭示华北南缘中-新元古代沉积-构造演化。沉积环境分析显示,黄连垛组沉积初期发育了河口湾沉积环境。伴随海侵扩大,在下汤地区沉积了潮上带长石石英砂岩与泥质粉砂岩,而叶县地区发育了潮间带泥晶白云岩。晚期下汤和叶县地区发育潮下带泥晶白云岩与含硅质条带白云岩。董家组与下伏黄连垛组为平行不整合接触,董家组沉积初期为陆源碎屑物质供给充分的滨海相,在下汤和叶县地区沉积底部细砾岩及长石石英砂岩。随后,两个地区发育潮坪相长石石英砂岩与泥质粉砂岩,在顶部沉积了局限台地钙质泥岩。黄连垛组在豫西下汤和叶县地区沉积于河口湾-潮坪沉积环境,整体表现为自南向北的海进序列,而董家组总体上沉积于局限海盆的滨浅海-潮坪环境。由于下伏汝阳群-洛峪群分别沉积在河流-滨海-潮坪和浅海-滨海-潮坪环境,黄连垛组和董家组指示其沉积时期盆地产生收缩。碎屑锆石定年结果显示,黄连垛组和董家组碎屑锆石年龄主要峰值为1800Ma、2250Ma、2350Ma、2650Ma,两者物源均为华北克拉通。但下汤地区早古生界辛集组碎屑锆石显示主要峰值年龄为1850Ma、2500Ma、2200Ma、2700Ma,其次为1200Ma。结合华北克拉通发育大量的中元古代末期到新元古代碎屑锆石以及南缘中元古界官道口群和新元古界栾川群沉积特征,黄连垛组和董家组代表的局限盆地(海盆)沉积可能构成了该时期盆地的边缘相,期间伴随的抬升和盆地中心迁移可能与同期大地构造演化密切相关。     

华北克拉通南缘官道口群和洛峪群的年代学研究新进展——来自凝灰岩SHRIMP锆石U-Pb年龄的新证据

华北克拉通南缘结晶基底之上广泛发育中-新元古代(1800～542Ma)盖层岩系,但由于缺少精确的同位素年龄数据,其地层划分和对比方案一直存在较大的争议。本次工作在河南省栾川县龙家园组底部和下部各发现了一套凝灰岩,进而获得了1594±12Ma和1541±8Ma的SHRIMP锆石U-Pb年龄,首次精确标定了该地区龙家园组的形成时限,该组底界的时代接近1600Ma。龙家园组沉积时代为中元古代蓟县纪最早期;在河南省汝阳、汝州、鲁山地区的洛峪口组凝灰岩中获得了1596±7Ma、1596±15Ma、1608±17Ma和1620±16Ma的SHRIMP锆石U-Pb年龄,进一步精确标定了洛峪口组的形成时代,洛峪口组形成于长城纪的末期。结合汝阳群云梦山组碎屑锆石U-Pb年龄结果,汝阳群-洛峪群的形成时限约为1700～1600Ma。官道口群应是汝阳群之后的地层系统,而不是早前认为的与之同期的地层。     

华北克拉通西南缘汝阳群沉积时代及其地质意义：来自碎屑锆石U-Pb年龄的证据

汝阳群分布在华北克拉通西南缘,位于河南-陕西-山西交界地区,主要为一套未变质的碎屑岩及碳酸盐岩地层,不整合于熊耳群火山岩系之上,其上被洛峪群整合覆盖。长期以来,其地质时代一直存有较大的争议。本文通过对汝阳群下部白草坪组4个石英砂岩样品中的碎屑锆石进行LA-ICP-MS U-Pb年龄测定,获得的²⁰⁷Pb/²⁰⁶Pb年龄分布范围为3 000～1 800 Ma,主要集中在2 600～2 400 Ma之间(约占67%),年龄主峰值为2 550～2 500 Ma,说明其沉积物质主要来源于新太古代末以及古元古代的地质体。其中,最年轻锆石的²⁰⁷Pb/²⁰⁶Pb谐和年龄值分别为1 817±22 Ma、1 838±23 Ma、1 924±17 Ma和1 829±28 Ma,说明汝阳群沉积时代不老于1 800 Ma,与其上覆洛峪群中近期获得1 611±8 Ma的年龄相吻合,因此其形成时代应为中元古代早期。     

华北克拉通南缘洛峪群-汝阳群属于中元古界长城系——河南汝州洛峪口组层凝灰岩锆石LA—MC-ICPMSU—Pb年龄的直接约束

运用LA—MC—ICPMS方法,对河南汝州阳坡村附近洛峪口组中部层凝灰岩夹层开展了锆石U-Pb同位素年代学研究,获得了1611±8Ma的高精度年龄。这一年龄第一次精确标定了该地区洛峪口组的形成时限,并显示该组顶界应接近1600Ma。由于洛峪口组位于华北克拉通南缘原划归“新元古界青白口系”洛峪群的最顶部,洛峪群又覆于“中元古界蓟县系”汝阳群之上,因此,这一新的年代学进展实际上同时也将洛峪群和汝阳群都下压到了中元古界长城系,并将洛峪群顶界限定为该地区长城系与蓟县系分界。结合区域资料,特别是熊耳群（下伏于汝阳群）火山岩近年来的年代学标定（多集中于1750～1780Ma）,可初步将该地区汝阳群一洛峪群的形成年代限定为1750～1600Ma之间,对应于国际固结纪（Statherian。1800～1600Ma）即中国长城纪中晚期。华北南缘洛峪口组形成年龄的直接约束及相关地层划分的重新厘定,为中元古代华北克拉通南北缘的准确对比及其与哥伦比亚超大陆关系、早期生命演化等重大地学命题提供了新的重要的年代学证据。     

华北克拉通南缘洛峪群-汝阳群属于中元古界长城系——河南汝州洛峪口组层凝灰岩锆石LA—MC-ICPMSU—Pb年龄的直接约束

运用LA—MC—ICPMS方法,对河南汝州阳坡村附近洛峪口组中部层凝灰岩夹层开展了锆石U-Pb同位素年代学研究,获得了1611±8Ma的高精度年龄。这一年龄第一次精确标定了该地区洛峪口组的形成时限,并显示该组顶界应接近1600Ma。由于洛峪口组位于华北克拉通南缘原划归“新元古界青白口系”洛峪群的最顶部,洛峪群又覆于“中元古界蓟县系”汝阳群之上,因此,这一新的年代学进展实际上同时也将洛峪群和汝阳群都下压到了中元古界长城系,并将洛峪群顶界限定为该地区长城系与蓟县系分界。结合区域资料,特别是熊耳群（下伏于汝阳群）火山岩近年来的年代学标定（多集中于1750～1780Ma）,可初步将该地区汝阳群一洛峪群的形成年代限定为1750～1600Ma之间,对应于国际固结纪（Statherian。1800～1600Ma）即中国长城纪中晚期。华北南缘洛峪口组形成年龄的直接约束及相关地层划分的重新厘定,为中元古代华北克拉通南北缘的准确对比及其与哥伦比亚超大陆关系、早期生命演化等重大地学命题提供了新的重要的年代学证据。     

华北南缘高山河组和云梦山组中解体的次火山岩:锆石U-Pb定年

华北南缘中元古代熊耳群之上中–新元古代官道口群高山河组和汝阳群云梦山组中发育疑似火山岩的"夹层",前人试图确定这套地层的年代,但一直没有取得实质性进展。本文研究发现这套"火山岩"与围岩并非沉积接触,而是侵入基底变质岩系的次火山岩。运用LA-ICP-MS法进行锆石U-Pb同位素定年,首次获得了栾川地区侵入高山河组的次粗安岩的206Pb/238U年龄为162±1 Ma,舞钢地区侵入云梦山组的次玄武安山岩的206Pb/238U年龄为165±2 Ma。这些结果表明这些中–晚侏罗世次火山岩应从官道口群高山河组和汝阳群云梦山组地层中解体出来,为华北南缘中–晚侏罗世构造岩浆作用的产物,而非古老的中–新元古代官道口群和汝阳群的沉积地层。同时为确立华北南缘存在燕山早期的火山岩浆活动,及其相关的陆内伸展构造事件提供了关键的年代学制约。     

朝鲜平南盆地古元古界-下古生界沉积岩碎屑锆石年龄谱对比及意义

中朝古陆(华北古陆)平南盆地面积~25000km~2,位于朝鲜半岛中部,发育从中元古界到下古生界地层,但经历了低级变质作用(绿片岩相及以下)。变质基底岩石中有一套角闪岩相-麻粒岩相的变质的古元古界地层。本文根据盆地不同时代沉积岩碎屑锆石/变质锆石U-Pb LA-ICP MS年龄数据讨论沉积源区的变化,并对区域演化进行制约。甑山群/杂岩为盆地基底岩系,变质砂岩样品中碎屑锆石出现ca.2500~2100Ma的年龄峰值。另外,36.5亿年的碎屑锆石是朝鲜迄今发现的最古老碎屑锆石;夕线榴片麻岩样品记录了~1850Ma(1859±9Ma)的变质年龄;推测甑山群沉积于ca.2100~1900Ma,变质于1850 Ma。黄海群局限分布于朝鲜半岛中部,碎屑锆石年龄谱显示~1850 Ma的峰值,可见~1250 Ma的年龄,推测对应物源为古元古代基底岩浆岩和变质岩系;结合其上覆直岘群的沉积时代,推测地层沉积于ca.1250~1000Ma。直岘群是平南盆地分布最广的地层之一,底部长峰组样品显示明显的~1850Ma的峰值,而其上第二个和第三个组则显示明显的ca.1400~1600Ma和ca.1000~1200 Ma年龄峰值,~1850 Ma年龄很少;推测直岘群开始沉积时,物源主体是盆地基底岩系,但之后出现大量中元古代物质;推测其沉积时代为ca.1000~900Ma。黄州群有~1850Ma和~2500Ma的峰值,另外,还有较少的ca.1000~1200Ma及1400~1600 Ma年龄,表明沉积物源主体仍是基底岩系,可能有中新元古代沉积岩(黄州群-直岘群)的再沉积。这些沉积岩碎屑锆石年龄峰值与辽东和山东半岛沉积地层相似,并且中新元古代地层中均有大量1000~1200Ma及1400~1600Ma的物质,推测可能来自华北古陆之外,如圣弗朗西斯科克拉通。     

Trace-element composition of hydrothermal zircon and the alteration of Hadean zircon from the Jack Hills,Australia

Hydrothermal zircon can be used to date fluid-infiltration events and water/rock interaction. At the Boggy Plain zoned pluton (BPZP), eastern Australia, hydrothermal zircon occurs with hydrothermal scheelite, molybdenite, thorite and rutile in incipiently altered aplite and monzogranite. The hydrothermal zircon is texturally distinct from magmatic zircon in the same rocks, occurring as murky-brown translucent 20–50 μm-thick mantles on magmatic cores and less commonly as individual crystals. The hydrothermal mantles are internally textureless in back-scatter electron and cathodoluminescence images whereas magmatic zircon is oscillatory zoned. The age of the hydrothermal zircon is indistinguishable from magmatic zircon, indicating precipitation from a fluid evolved from the magma during the final stages of crystallization. Despite indistinguishable U-Pb isotopic compositions, the trace-element compositions of the hydrothermal and magmatic zircon are distinct. Hydrothermal zircon is enriched in all measured trace-elements relative to magmatic zircon in the same rock, including V, Ti, Nb, Hf, Sc, Mn, U, Y, Th and the rare-earth elements (REE). Chondrite-normalized REE abundances form two distinct pattern groupings: type-1 (magmatic) patterns increase steeply from La to Lu and have Ce and Eu anomalies—these are patterns typical for unaltered magmatic zircon in continental crust rock types; type-2 (hydrothermal) patterns generally have higher abundances of the REE, flatter light-REE patterns [(Sm/La)_N = 1.5–4.4 vs. 22–110 for magmatic zircon] and smaller Ce anomalies (Ce/Ce* = 1.8–3.5 vs. 32–49 for magmatic zircon). Type-2 patterns have also been described for hydrothermally-altered zircon from the Gabel Hamradom granite, Egypt, and a granitic dyke from the Acasta Gneiss Complex, Canada.Hadean (∼4.5–4.0 Ga) zircon from the Jack Hills, Western Australia, have variable normalized REE patterns. In particular, the oldest piece of Earth—zircon crystal W74/2-36 (dated at 4.4 Ga)—contains both type-1 and type-2 patterns on a 50 μm scale, a phenomenon not yet reported for unaltered magmatic zircon. In the context of documented magmatic and hydrothermal zircon compositions from constrained samples from the BPZP and the literature, the type-2 patterns in crystal W74/2-36 and other Jack Hills Hadean (JHH) zircon are interpreted as hydrothermally-altered magmatic compositions. An alteration scenario, constrained by isotope and trace-element data, as well as α-decay event calculations, involving fluid/zircon cation and oxygen isotope exchange within partially metamict zones and minor dissolution/reprecipitation, may have occurred episodically for some JHH zircon and at ∼4.27 Ga for zircon W74/2-36. Type-2 compositions in JHH zircon are interpreted to represent localized exchange with a light-REE-bearing, high δ¹⁸O (∼6–10‰ or higher) fluid. Thus, a complex explanation involving “permanent” liquid water oceans, large-scale water/rock interaction and plate tectonics in the very early Archean is not necessary as the zircon textures and compositions are simply explained by exchange between partially metamict zircon and a low volume ephemeral fluid.     

Ti in zircon from the Boggy Plain zoned pluton: implications for zircon petrology and Hadean tectonics

The understanding of zircon crystallization, and of the Ti-in-zircon thermometer, has been enhanced by Ti concentration measurements of zircon from a small, concentrically zoned pluton in south-eastern Australia, the Boggy Plain zoned pluton (BPZP). Zircon crystals from rocks ranging in composition from gabbro to aplite were analysed for U–Th–Pb dating and Ti concentrations by an ion microprobe. Geochronological data yield a ²⁰⁶Pb/²³⁸U age of 417.2 ± 2.0 Ma (95% confidence) and demonstrate the presence of older inherited or xenocrystic zircon. Titanium measurements (n = 158) yield a mean Ti concentration of 11.7 ± 6.1 ppm (2SD) which corresponds to a mean crystallization temperature of 790°C for an α-TiO₂ = 0.74 (estimated using mineral equilibria), or 760°C for an α-TiO₂ = 1.0. Apparent zircon crystallization temperatures are similar in all intrusive phases, although the gabbro yields slightly higher values, indicating that crystallization occurred at the same temperature in all rock types. This finding is consistent with previous work on the BPZP, which indicates that liquid–crystal sorting (crystal fractionation) was the dominant control on chemical differentiation, and that late, differentiated liquids were similar in composition for all rock types. A simple forward model approximately predicts the range of crystallization temperatures, but not the shape of the distributions, due to sampling biases and complexities in the cooling and crystallization history of the pluton. The distribution of Ti concentrations has a mode at a higher Ti (higher temperature) than the sample set of Hadean detrital zircon. This is consistent with the hypothesis that the skew to low-T in the Hadean dataset is due to the presence of zircon that crystallized from wet anatectic melts.     

Metamorphic zircon formation by solid-state recrystallization of protolith igneous zircon

Protolith zircon in high‐grade metagranitoids from Queensland, Australia, partially recrystallized during granulite‐grade metamorphism. We describe the zircon in detail using integrated cathodoluminescence, U–Pb isotope, trace element and electron backscatter diffraction pattern (EBSP) analyses. Primary igneous oscillatory zoning is partially modified or obliterated in areas within single crystals, but is well preserved in other areas. A variety of secondary internal structures are observed, with large areas of transgressive recrystallized zircon usually dominant. Associated with these areas are recrystallization margins, interpreted to be recrystallization fronts, that have conformable boundaries with transgressive recrystallized areas, but contrasting cathodoluminescence and trace element chemistry. Trace element analyses of primary and secondary structures provide compelling evidence for closed‐system solid‐state recrystallization. By this process, trace elements in the protolith zircon are purged during recrystallization and partitioned between the enriched recrystallization front and depleted recrystallized areas. However, recrystallization is not always efficient, often leaving a ‘memory’ of the protolith trace element and isotopic composition. This results in the measurement of ‘mixed’ U–Pb isotope ages. Nonetheless, the age of metamorphism has been determined. A correlation between apparent age and Th/U ratio is indicative of incomplete re‐setting by partial recrystallization. Recrystallization is shown to probably not significantly affect Lu–Hf ages. Recrystallization has been determined by textural and trace element analysis and EBSP data not to have proceeded by sub‐grain rotation or local dissolution/re‐precipitation, but probably by grain‐boundary migration and defect diffusion. The formation of metamorphic zircon by solid‐state recrystallization is probably common to high‐grade terranes worldwide. The recognition of this process of formation is essential for correct interpretation of zircon‐derived U–Pb ages and subsequent tectonic models.     

Crystallization thermometers for zircon and rutile

Zircon and rutile are common accessory minerals whose essential structural constituents, Zr, Ti, and Si can replace one another to a limited extent. Here we present the combined results of high pressure–temperature experiments and analyses of natural zircons and rutile crystals that reveal systematic changes with temperature in the uptake of Ti in zircon and Zr in rutile. Detailed calibrations of the temperature dependencies are presented as two geothermometers—Ti content of zircon and Zr content of rutile—that may find wide application in crustal petrology. Synthetic zircons were crystallized in the presence of rutile at 1–2 GPa and 1,025–1,450°C from both silicate melts and hydrothermal solutions, and the resulting crystals were analyzed for Ti by electron microprobe (EMP). To augment and extend the experimental results, zircons hosted by five natural rocks of well-constrained but diverse origin (0.7–3 GPa; 580–1,070°C) were analyzed for Ti, in most cases by ion microprobe (IMP). The combined experimental and natural results define a log-linear dependence of equilibrium Ti content (expressed in ppm by weight) upon reciprocal temperature:

锆石裂变径迹年龄和逐层蒸发法铅年龄测定对比研究

本文阐述了颗粒锆石裂变径迹法及双带源逐层蒸发法的方法原理，对取自美国菲什（Fish）峡谷凝灰岩中的锆石裂变径迹年龄国际标准样及取自香港花岗岩中锆石的两种年龄结果进行了对比，并分析了它们年龄差异的原因，认为铅年龄代表锆石的结晶年龄，而裂变径迹表观年龄代表岩体的冷却年龄或最后一次热事件的年代。开展不同方法的对比研究，可以得到更多的信息，以期更好地探讨研究区的演化历史。     

大别山北部卢镇关群变质火山岩和共生变质的花岗岩全岩和锆石氧同位素、锆石U-Pb年代学研究

分布在大别山北部的卢镇关群火山岩和共生的花岗岩类形成在新元古代.2个卢镇关群变质流纹岩SIMS锆石U-Pb给出了757Ma岩浆结晶年龄,3个变质花岗岩给出了757 ～ 770Ma岩浆结晶年龄.全岩氧同位素分析表明它们经受了地表流体参与交代蚀变作用.锆石SIMS氧同位素分析表明少量锆石边部存在岩浆期后的氧同位素改造,然而锆石的氧同位素的改造部分没有明显的U-Pb重置,因此,地表流体参与交代蚀变作用时间无法通过锆石的U-Pb年龄来测定,只能限定在757Ma以后.研究样品中存在δ18O值2.8‰～4.0‰岩浆锆石,它们从低δ18O岩浆中结晶而来.低δ18O岩浆是早期地表流体参与交代蚀变岩石再熔融的产物,从这个意义上说,早于770Ma的地表流体参与的蚀变应该存在.这些时间上的证据表明卢镇关群火山岩和共生的花岗岩类记录了早于770 ～ 757 Ma之后地表流体参与交代蚀变,这从时间上看,岩石发生的地表流体参与的蚀变与扬子地台上新元古代冰川事件不能简单的关联在一起.     

Si diffusion in zircon

Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO₂ and ³⁰Si-enriched SiO₂ in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. ³⁰Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction ³⁰Si(p,γ)³¹P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol⁻¹/RT) m² s⁻¹ for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol⁻¹/RT) m² s⁻¹]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D _Zr < D _Si << D _{O, dry} < D _{O, ‘wet’}.     

Li diffusion in zircon

Diffusion of Li under anhydrous conditions at 1 atm and under fluid-present elevated pressure (1.0–1.2 GPa) conditions has been measured in natural zircon. The source of diffusant for 1-atm experiments was ground natural spodumene, which was sealed under vacuum in silica glass capsules with polished slabs of zircon. An experiment using a Dy-bearing source was also conducted to evaluate possible rate-limiting effects on Li diffusion of slow-diffusing REE⁺³ that might provide charge balance. Diffusion experiments performed in the presence of H₂O–CO₂ fluid were run in a piston–cylinder apparatus, using a source consisting of a powdered mixture of spodumene, quartz and zircon with oxalic acid added to produce H₂O–CO₂ fluid. Nuclear reaction analysis (NRA) with the resonant nuclear reaction ⁷Li(p,γ)⁸Be was used to measure diffusion profiles for the experiments. The following Arrhenius parameters were obtained for Li diffusion normal to the c-axis over the temperature range 703–1.151°C at 1 atm for experiments run with the spodumene source:

锆石微量元素的理论基础及其应用研究进展

锆石是地质学研究中最重要的副矿物,其分布广泛、物理、化学性质稳定,记录了结晶时的年龄、温度、氧逸度以及O-Hf-Si-Zr-Li等多元同位素和微量元素信息,被广泛运用于地球科学的研究中。近年来,随着分析技术的发展,研究者在获取锆石年龄的同时也获取了大量锆石微量元素数据,这些数据的积累推动着研究者对锆石微量元素理论研究的不断深入,并取得了一系列重要进展,如发现锆石微量元素组成受锆石本身的晶格特点主导,符合晶格应变模型和类质同象替代机制;发现锆石微量元素组成受到熔体成分演化影响,锆石结晶时的熔体微量元素组成往往不等同于全岩;发现锆石内部的微量元素不均一特征(矿物包裹体、热点、蜕晶化作用等)可能会严重影响锆石的微量元素组成,继而建立了"干净锆石"的判别指标和筛选机制。此外,锆石微量元素的应用研究也取得了长足进展,研究者们不断尝试通过各类锆石微量元素指标、图解、分配系数,识别母岩浆物理化学性质、反演母岩浆组成,大大推动了锆石微量元素在示踪岩浆源区和岩浆过程中的应用。然而,由于锆石微量元素组成受控于多种因素,使得锆石微量元素在实际应用当中常常面临着多解性问题、重叠问题和分配系数的选择问题,在一定程度上影响了锆石微量元素应用研究的可靠性。未来的锆石微量元素研究将不满足于使用传统的低维指标和图解以及分配系数,而将在充分吸收传统方法精华的基础上,从海量数据与更高的维度中寻找元素之间相关性,基于热力学定律揭示新原理,基于更高空间分辨率揭示动力学因素的影响,从数据驱动和理论驱动的全新视角下深入揭示隐藏在锆石微量元素中的信息。