稳定氯同位素地球化学研究进展

地球卤素元素含量相对稀少,相对而言氯为最常见的卤素元素。氯是一种挥发性元素,具有强烈的亲水性。自然界氯两个稳定同位素³⁵Cl和³⁷Cl,其相对丰度分别为75.76%和24.24%。文章综述了氯在各个地质储库的特征、稳定氯同位素分馏的控制因素以及氯同位素的地质应用三大方面的研究进展。地球主要储库中蒸发岩、海水、岩浆岩、沉积物、变质岩、地幔的氯同位素组成分别为-0.5‰~+0.8‰、0.00±0.05‰、-1.12‰~+0.79‰、-3.0‰~+2.0‰、-3.6‰~0、-1.9‰~+7.2‰。地外(月球、火星及其他小行星4-Vesta)氯同位素组成变化范围分别为-4‰~+81.1‰、-5.6‰~+8.6‰、-3.8‰~+7.7‰。相对地球上氯同位素(δ³⁷Cl)的变化范围(-14‰~+16‰),月球和火星δ³⁷Cl的变化范围可达-5.6‰~+81‰,表明挥发分氯在地内和地外迁移循环过程中有显著不同同位素分馏主控机制。已经探明氯同位素分馏受控于物理过程(如扩散、离子过滤、沉淀溶解作用、火山作用)和化学作用(如水岩作用、变质作用,尤其是蛇纹石化作用)等。扩散作用、淋滤作用和火山作用富集重同位素,沉淀作用结晶盐δ³⁷Cl先减小后上升,而蛇纹石化过程中多种因素共同影响。与其他指标结合,氯同位素地球化学可用于有效指示钾盐矿床远景区,评估示踪地下水的来源和演化路径、示踪污染物源区和量化生物修复、探究矿化流体来源、指示行星演化岩浆海洋脱气等过程。     

37 ka以来日本海沉积物有机质碳和氮稳定同位素变化及其古海洋学意义

海洋沉积物有机质碳氮稳定同位素(δ¹³C、δ¹⁵N)广泛用于有机质来源示踪、古生产力和古海洋环境重建。日本海沉积物δ¹³C和δ¹⁵N值一个显著特征是在末次冰盛期(LGM)同步负偏,但是对这一现象产生的原因以及他们的演化过程的认识仍然存在明显不足。在本研究中,我们详细调查了37 ka以来日本海中部LV53-23-1岩心沉积物δ¹³C和δ¹⁵N演化历史。结果显示,沉积物δ¹³C和δ¹⁵N分别介于-26.3‰至-22.5‰和1.6‰至6.1‰,低值出现在LGM(26.5~17 ka)暗色层状泥发育时期,指示较强的陆源输入贡献。在Heinrich冰阶1时期(17~14.5 ka),δ¹³C和δ¹⁵N快速正偏,表明日本海海洋环境发生了明显的转换,对应于对马海峡淹没及对马暖流入侵。14.5 ka之后,沉积物δ¹⁵N值恢复到5‰,与开阔大洋海水硝酸盐的δ¹⁵N值近似。我们采用二端员混合模型粗略地估算了有机质来源的相对贡献。LGM时期陆源有机质贡献介于65%至80%,14.5 ka以后海源有机质贡献介于60%至80%。除了增加的陆源有机质贡献以外,LGM时期沉积物δ¹⁵N亏损还涉及如下过程:(1)较高的含Fe沙尘供给提高日本海表层海洋生物固氮效率;(2)缺氧环境盛行减弱成岩作用对沉积物δ¹⁵N影响。37 ka以来,日本海沉积物δ¹³C和δ¹⁵N变化与有机质来源、营养盐的供给、表层生产力和沉积物氧化还原条件相关,实际受海平面和全球气候制约。     

俄罗斯极地乌拉尔硬玉岩成因矿物学研究

俯冲带是壳-幔物质循环的重要场所,硬玉岩可以记录这一循环过程。文中总结了俄罗斯极地乌拉尔硬玉岩的研究进展。硬玉岩呈脉状或透镜状产在蛇纹石化的方辉橄榄岩中,主要由硬玉和绿辉石组成。根据结构和颜色,硬玉可识别出两个世代。硬玉韵律环带发育,含有H₂O和CH₄流体包裹体,显示从流体中结晶的特征。硬玉岩中的锆石为热液锆石,锆石稀土元素中La_N/Yb_N=0.001~0.01,Lu_N/Gd_N=10~83,Ce/Ce^*=2.8~72,显示正异常,δEu=0.53~1.02,类似于岩浆锆石。锆石的¹⁷⁶Hf/¹⁷⁷Hf=0.282 708~0.283 017,ε_Hf(t)=+6~+17,类似于N-MORB的Hf同位素组成,锆石δ¹⁸O组成为5.03‰~6.04‰,平均δ¹⁸O为(5.45±0.11)‰,类似于岩浆热液和地幔的氧同位素组成。这可能反映了锆石是被俯冲带流体从途经火成岩中捕获的或者形成锆石的流体与寄主岩(方辉橄榄岩)达到了平衡。硬玉岩稀土元素配分模式近平坦或轻稀土元素略显富集,La_N/Yb_N比值为0.82~2.42,δEu为1.2~1.6,显示正异常,这与寄主岩稀土元素配分模式相似。富集Sr、Ba、Zr、Hf,Nb为负异常,与岛弧岩浆特征类似。(⁸⁷Sr/⁸⁶Sr)_t为0.703 400~0.703 519(t=368 Ma),变化较小,与古海水差别明显;ε_Nd(t)值为+0.77~+5.61,变化较大,与寄主岩(方辉橄榄岩)的Nd同位素组成类似,但不同于海水及沉积物的Nd同位素组成,表明硬玉岩的物质来源与寄主岩有明显继承关系,海水与沉积物的贡献不是主要的。矿物学和岩石学证据支持极地乌拉尔的硬玉岩主要是俯冲带流体与橄榄岩相互作用后并在其中结晶的产物。     

铜同位素示踪覆盖区地表土壤的异常来源初探:以福建罗卜岭隐伏铜钼矿床为例

地表微细粒土壤地球化学测量是国内研究较多的深穿透地球化学方法之一,判断地表异常与深部隐伏矿体的关系是未来该方法广泛应用的理论基础。以已知的隐伏矿床——紫金山罗卜岭铜钼矿床为研究对象,利用铜同位素示踪覆盖区地表土壤的异常来源。结果显示:(1)矿石单矿物的δ⁶⁵Cu变化范围较小(-0.04‰~0.56‰),指示较高的成矿温度(250~300 ℃);钻孔由深至浅,矿石的δ⁶⁵Cu值具有明显升高的趋势,符合斑岩型成矿系统早期至晚期铜同位素的变化特征,流体分馏是造成不同阶段形成的矿石铜同位素存在差异的主要原因。(2)背景区地表土壤铜含量的平均值(59.4 μg/g)显著低于异常区(131.0 μg/g)。背景区土壤δ⁶⁵Cu变化范围为-1.94‰~-0.82‰,平均值为-1.38‰;异常区土壤δ⁶⁵Cu变化范围为-5.01‰~1.05‰,平均值为-1.40‰,背景区和异常区铜同位素组成相差不大。(3)本次利用铜同位素组成判别地表介质铜异常来源的效果不理想,可能因为矿石本身的铜同位素组成存在差异,地表土壤本身的铜同位素信息覆盖了来自深部与隐伏铜矿体有关的信息,或从深部原生环境迁移至地表氧化环境的过程中,因氧化还原反应发生了铜同位素的分馏。     

内蒙古大井铜锡多金属矿床矿石中Cu-S同位素特征及成矿预测

内蒙古大井铜锡多金属矿床是大兴安岭成矿带代表性矿床之一,矿区位于内蒙古东部林西县境内,成矿地质条件良好。矿床矿石中同位素特征及与成矿的关系研究薄弱。本文通过对矿体中黄铜矿Cu同位素,黄铜矿、黄铁矿S同位素和Pb同位素的研究表明:黄铜矿δ⁶⁵Cu 值总体范围为 -0.46‰+0.32‰,平均值为0 ‰,2σ误差平均值约为0.03‰;黄铜矿、黄铁矿δ³⁴S值总体范围为 +0.076 ‰+3.00‰,平均值为+1.83‰,且δ³⁴S值分散程度也较小,整体较均一,属于岩浆硫的同位素特征;Pb同位素数据整体变化很小,具体为²⁰⁶Pb/²⁰⁴Pb=18.29118.353,²⁰⁷Pb/²⁰⁴Pb =15.50115.574,²⁰⁸Pb/²⁰⁴Pb =38.05138.265。结合区域前人的研究表明,大井矿Cu同位素的变化是由于硫化物-岩浆分异过程导致,大井矿矿石黄铜矿δ⁶⁵Cu的变化可能指示了矿化阶段成矿硫化物的演化方向,δ⁶⁵Cu逐渐降低的方向可能存在隐伏矿体,研究区域东部生产区域与外围预测未生产区域具有一致的Cu同位素特征,Cu同位素证据表明大井矿外围预测区可能存在深部隐伏矿体。     

南秦岭柞水—山阳矿集区夏家店金矿床黄铁矿微量元素和氢、氧、硫同位素对矿床成因的制约

为了研究柞水—山阳矿集区夏家店金矿床成因,采用LA-ICP-MS和LA-MC-ICP-MS技术分析夏家店金矿床矿体及围岩样品中黄铁矿原位微量元素及氢、氧、硫同位素组成特征。结果表明,该矿床黄铁矿的Co/Ni 比值为0.11~0.76,说明其与沉积作用有关。矿石中黄铁矿的δ³⁴S值(-9.40‰~7.16‰)与围岩碳质板岩的δ³⁴S值(-8.84‰~10.64‰)接近,黄铁矿的δ³⁴S均值(2.47‰)基本落在岩浆硫的范围内,指示矿石硫可能由地层硫和岩浆硫混合而成。氢、氧同位素测试结果表明,夏家店矿床成矿流体可能主要来自岩浆水,成矿后期有大气降水的加入。综合矿床地质特征、成矿温度、金赋存状态等特征和黄铁矿微量元素、硫同位素组成可知,夏家店金矿床属于卡林型金矿,其成矿流体主要来自岩浆水,成矿后期有大气降水加入;其成矿物质是由深部岩浆与地层混合而成。     

浑善达克沙地碱湖表层沉积物的粒度、沉积有机质变化特征与指示意义

本文选择浑善达克沙地南缘濒临干涸的碱湖为研究对象,综合分析湖泊及流域表层沉积物的粒度、总有机碳(TOC)及其同位素(δ¹³C_TOC)指标的空间分布特征及环境指示意义。结果表明,湖泊水域区及滩地区的黏土与粉砂组分含量高,TOC含量多低于1%,而东缘的盐生草甸砂组增加,同时TOC含量升高至10.75%;δ¹³C_TOC值表现为从西向东,即水域区(-24.88‰)、滩地区(-25.17‰)、盐生草甸(-27.93‰)呈逐渐偏负的趋势。水域区表层沉积物粒度端员组分分析表明,粗粒端员(近源风成组分及洪积组分)含量的增加指示湖泊退缩及流域植被退化;水域区低TOC指示水生植物基本消失,陆源C₃植物成为湖泊沉积物有机质的主要来源,控制了δ¹³C_TOC的波动。当湖泊彻底干涸,裸露滩地的粒度初始以细粒组分(黏土、粉砂)为主,而后强烈的风蚀作用将富盐细粒带走,沉积物的粒度变粗,盐度降低,盐生植被入侵。此后沉积物的TOC含量显著增加,而δ¹³C_TOC值逐渐偏负可能与上覆盐生植被演替过程中C₃植物生物量增加有关。因此,乌日图音淖尔现代沉积过程及机理的研究,加深了对浑善达克沙地碱湖干涸过程中沉积及生态演化过程的认识,也为古环境的重建提供了重要依据。     

冲绳海槽MIS6期以来底栖有孔虫碳氧同位素特征及其古海洋指示意义

基于AMS ¹⁴C年龄和底栖有孔虫氧同位素建立的地层年代框架,重点探讨了冲绳海槽中北部CSHC-15孔MIS6期以来(约200 ka)底栖有孔虫δ¹³C特征及其古海洋指示意义。结果显示,冰期-间冰期表层初级生产力和有机质通量的变化是导致底栖有孔虫δ¹³C值在MIS4和MIS6期负偏而在MIS1、MIS3和MIS5期正偏的主要原因。MIS2期的底栖有孔虫δ¹³C正偏,指示了NPIW侵入冲绳海槽,导致通风性加强,底层水呈弱氧化状态。甲烷渗漏引发的甲烷厌氧氧化作用(AOM)是导致CSHC-15孔底栖有孔虫在MIS4期碳同位素大幅负偏的原因。     

稳定氯同位素在水环境地球科学中的研究进展

氯元素广泛分布于地表水体和沉积物中,并在地表圈层之间进行迁移和转化等生物地球化学循环.氯元素有两种稳定同位素:35Cl和37Cl,其相对含量分别为35Cl=75.153%和37Cl=24.147%.氯离子在地表环境中通常没有价态变化,既不发生引起键能明显变化的氧化还原反应,也不明显参与生物作用,因此氯离子不会因元素迁移形态转变而改变同位素组成.但是,自然界中氯同位素37Cl和35Cl间存在较大的相对质量差,氯在蒸发结晶、离子扩散、渗透和对流混合等水体迁移过程中35Cl和37Cl的运移速度因其质量差而有所不同,致使氯同位素发生分馏[1].在蒸发沉积作用过程中,因37Cl相对35Cl有较大的键结合能,而优先进入固相(盐类沉积物)中.相对于其它轻稳定同位素(H、O、C)而言,稳定氯同位素的分馏并不明显,自然界中δ37Cl为-14‰～16‰,但大气圈、水圈和岩石圈的氯同位素组成大多集中在-2‰～2‰.近年来,氯同位素测定方法的改进大大提高了测试精度和准确度,使得氯同位素得以广泛应用于对蒸发盐、地下水体的演化、海水入侵、矿床形成过程中的成矿流体作用、氯代有机溶剂的分馏机理、人工合成与自然降解的有机物示踪等方面的研究[2～10].     

塔里木北缘震旦纪—寒武纪转折期碳同位素漂移事件及成因机制

震旦纪—寒武纪转折期是地球演化的关键节点,这一时期的碳-氧同位素记录在塔里木保留完整却关注较少。选取苏盖特布拉克露头震旦系与寒武系交界地层实测采样,并开展了古生物、镜下鉴定、碳同位素漂移事件的综合分析,探讨了N1(BACE)、P1(ZHUCE)等碳同位素漂移事件的成因机制。样品的δ¹³C_carb和δ¹⁸O_carb相关系数(R²=0.05)、δ¹⁸O_carb和Mn/Sr相关系数(R²=0.09)及岩石学特征表明,后期成岩改造并未导致碳-氧同位素的显著分馏,原始碳同位素特征得以基本保留。由下至上,在该剖面识别出P-1事件(δ¹³C_carb峰值1.9‰2.4‰)、N1事件(-6.8‰-10.3‰)、P1事件(1.4‰4.1‰)、N2a-c事件(-0.4‰-2.8‰)、P2a-c事件(0.2‰0.6‰)和N3事件(-3.4‰)。综合碳同位素演化特征与古生物、年代学数据,确认了玉尔吐斯组底部硅质页岩与奇格布拉克组顶部藻云岩的分界面为塔里木震旦系与寒武系的分界线,并实现了该露头与老林、肖滩、三峡、西伯利亚、阿曼和摩洛哥剖面的地层对比。分析认为,塔里木北缘震旦纪—寒武纪转折期的碳漂移事件,更多受控于古海洋氧气含量变化引起的固碳率f_org的波动。玉尔吐斯组早期海侵背景下的大规模缺氧事件导致的初级生产力和固碳率降低,是N1负漂移事件(BACE)的主因;随后海退中氧气含量的增加引起生产力重建和固碳率增加,形成了P1正漂移事件(ZHUCE)。这一成果性认识有助于塔里木盆地寒武纪古环境研究与深层超深层油气远景资源评价。     

硼同位素分馏的实验理论认识和矿床地球化学研究进展

硼是一种中等挥发性元素,具有¹¹B和¹⁰B两个稳定同位素。两个同位素间高达10%的相对质量差使其在地质过程中引起高达-70‰至+75‰的硼同位素变化。硼在自然界主要与氧键合形成三配位(BO₃)和四配位(BO₄)结构,因而¹¹B和¹⁰B间同位素分馏主要受控于三配体(BO₃)和四面体(BO₄)间配分。本文综述了低温和高温地质过程的硼同位素分馏的理论和实验研究进展。在溶液中B(OH)₃和${B(OH)^{-}_{4}}$间硼同位素分馏受pH和热力学p-T条件控制,实验和理论表征获得常温常压条件下的B(OH)₃和$B(OH)^{-}_{4}$间同位素分馏系数(α_3-4)变化范围为1.019 4至1.033 3。低温条件下矿物(如碳酸盐、黏土矿物(蒙脱石和伊利石)、针铁矿、水锰矿、硼酸盐)与溶液间硼同位素分馏行为除了受p-T-pH影响外,矿物表面吸附引起的分馏效应十分显著。在中高温过程(蒙脱石伊利石化、富硼电气石和白云母矿物与热液流体,以及硅酸盐熔体与流体)中硼同位素分馏行为受到硼配位构型、化学成分以及物理化学条件的控制。随着硼同位素分馏机理研究的深入以及越来越完善的地质储库硼同位素端员特征表征,硼同位素地球化学指标可以灵敏示踪成矿物质来源、探究成矿作用与成因模式和重建成矿过程物理化学条件。目前矿床硼同位素地球化学研究的难点在于实现不同赋存相(如流体、矿物和熔体)中硼配位键合结构和硼同位素组成的精细化表征。     

Neo-Proterozoic rift-related syenites (Northern Damara Belt, Namibia): Geochemical and Nd–Sr–Pb–O isotope constraints for mantle sources and petrogenesis

Major element, trace element and Nd–Sr–Pb–O isotope data for a suite of Neo-Proterozic, pre-orogenic, rift-related syenites from the Northern Damara orogen (Namibia) constrain their sources and petrogenesis. New U–Pb ages obtained on euhdreal titanite of inferred magmatic origin constrain the age of intrusion of the Lofdal and Oas syenites to ca. 750 Ma compatible with previous high-precision zircon analyses from the Oas complex. Major rock types from Lofdal and Oas are mildly sodic nepheline-normative and quartz-normative syenites and were primarily generated by fractional crystallization from a mantle-derived alkaline magma. Primitive samples from Lofdal and Oas show depletion of Rb, K and Th relative to Ba and Nb together with variable negative anomalies of P and Ti on a primitive mantle-normalized diagram. Evolved samples from Oas develop significant negative Ba, Sr, P and Ti anomalies and positive U and Th anomalies mainly as a function of crystal fractionation processes. The lack of a pronounced negative Nb anomaly in samples from Lofdal suggests that involvement of a crustal component is negligible. For the nepheline-normative samples from Lofdal, the unradiogenic Sr and radiogenic Nd isotope composition and low δ¹⁸O values suggest derivation of these samples from a moderately depleted lithospheric upper mantle with crustal-like U/Pb ratios (⁸⁷Sr/⁸⁶Sr: 0.7031–0.7035, ε Nd: ca. + 1, δ¹⁸O: 7‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.58–15.60). Primitive samples of the Oas quartz-normative syenites have identical isotope characteristics (⁸⁷Sr/⁸⁶Sr: 0.7034, ε Nd: ca. + 1, δ¹⁸O: 6.5‰, ²⁰⁶Pb/²⁰⁴Pb: ca.18.00, ²⁰⁷Pb/²⁰⁴Pb: 15.59) whereas more differentiated samples have higher ⁸⁷Sr/⁸⁶Sr ratios (0.709–0.714), slightly higher δ¹⁸O values (7.0–7.1‰), less radiogenic ε Nd values (− 1.1 to − 1.4) and more radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios up to 18.27. These features together with model calculations using Sr–Nd–Pb isotopes suggest modification of a primary syenite magma by combined AFC processes involving ancient continental crust. In this case, high Nb abundances of the parental syenite liquid prevent the development of significant negative Nb anomalies that may be expected due to interaction with continental crust.     

铷同位素分析方法及研究进展

Rb作为一个具有中度挥发性、流体活动性、在岩浆过程中呈不相容性的碱金属元素,能为各种地质过程和物质源区提供制约;同时,⁸⁷Rb是放射性母体,Rb-Sr定年体系在确定长时间尺度的地质体年龄方面也有广泛的应用。传统研究认为特定地质年代下Rb同位素比值(⁸⁷Rb/⁸⁵Rb)是一个定值,但随着分离纯化方法的改进和质谱分析精度的提高,高精度Rb同位素组成得以测定,其结果显示,不同地质样品存在明显的Rb同位素组成的差异,意味着地质过程中存在Rb同位素的分馏。Rb同位素分馏能否为示踪Rb的地质过程提供更多有用信息,是否会对传统Rb-Sr定年体系产生影响,这些基础性的问题目前仍然没有答案。要回答这些问题,首先需要了解不同地质储库的Rb同位素组成,发现不同地质过程中的Rb同位素分馏,探讨其发生的控制机制。然而,这方面的研究目前还非常欠缺。文章回顾了近20年来国际上地球科学领域中的Rb同位素已有的研究,包括技术方法、分馏机理等各个方面,在此基础上对其研究前景进行展望,主要包括:(1)总结了Rb同位素组成测定的化学纯化及仪器测量方法,并对其优缺点进行点评,同时指出谨慎的化学前处理方法及质谱测定流程是获得高精度Rb同位素组成结果的基本前提;(2)收集了现有的地外样品Rb同位素组成数据,简述了Rb同位素在宇宙化学中的应用研究成果,指出Rb作为一个中度挥发性元素,对太阳系行星的吸积和演化过程具有重要的指示意义;(3)对Rb同位素在地质过程中潜在广阔的应用前景进行展望,例如完善经典的Rb-Sr定年体系,限定壳幔及地壳内部的分异过程,制约大陆硅酸盐岩风化,以及揭示超大型Rb矿的形成机制。     

基于连续流同位素质谱的地下水无机物氯稳定同位素测试方法及影响因素研究

氯稳定同位素作为示踪剂,能指示水体演化和探索地质环境变化,在地球科学领域具有广泛的应用前景.连续流同位素质谱法(CF-IRMS)具有样品用量少和灵敏度高的优点,被广泛应用于氯等稳定同位素的测试.氯甲烷作为一种易挥发的气体,在反应过程及测试管路中容易逸出,造成样品损失.如何减少反应及测试过程中氯甲烷的流失,实现氯甲烷的分...     

陕西旬阳泗人沟铅锌矿床地质及S、Pb同位素地球化学特征

陕西旬阳泗人沟铅锌矿床位于南秦岭褶皱系之大羊山复向斜南翼,赋存在上志留统水洞沟组第二岩性段的粉砂质千枚岩中。矿体受控于层间破碎带和劈理带,呈层状、似层状、透镜状产出。矿石矿物以闪锌矿、方铅矿、黄铁矿、磁黄铁矿和黄铜矿为主;矿石结构主要为它形-半自形粒状集合体结构、交代结构和固溶体分离结构;矿石构造主要为块状、条带状、浸染状和细脉状。激光剥蚀多接收等离子体质谱原位S同位素组成分析结果显示,矿石硫化物的硫同位素组成比较稳定,样品的δ³⁴S值主要介于0.17‰~2.03‰之间,具有塔式分布特征,反映硫主要源于地幔和深部地壳,也有少量地层硫参与。9件矿石硫化物样品的²⁰⁶Pb/²⁰⁴Pb值为17.198~18.213,平均17.845;²⁰⁷Pb/²⁰⁴Pb值为15.564~15.627,平均15.610; ²⁰⁸Pb/²⁰⁴Pb值为37.982~38.471,平均38.206;反映铅同位素总体较稳定,变化范围较小,铅同位素主要源于上地壳,也有少量地幔铅参与。综合矿床地质、地球化学特征,认为泗人沟铅锌矿床成因类型属于后生热液充填交代型。     

Isotopic equilibrium/disequilibrium in granites, metasedimentary rocks and migmatites (Damara orogen, Namibia)—a consequence of polymetamorphism and melting

The overwhelming part of the continental crust in the high-grade part of the Damara orogen of Namibia consists of S-type granites, metasedimentary rocks and migmatites. At Oetmoed (central Damara orogen) two different S-type granites occur. Their negative ε_Nd values (− 3.3 to − 5.9), moderately high initial ⁸⁷Sr/⁸⁶Sr ratios (0.714–0.731), moderately high ²⁰⁶Pb/²⁰⁴Pb (18.21–18.70) and ²⁰⁸Pb/²⁰⁴Pb (37.74–37.89) isotope ratios suggest that they originated by melting of mainly mid-Proterozoic metasedimentary material. Metasedimentary country rocks have initial ε_Nd of − 4.2 to − 5.6, initial ⁸⁷Sr/⁸⁶Sr of 0.718–0.725, ²⁰⁶Pb/²⁰⁴Pb ratios of 18.32–18.69 and ²⁰⁸Pb/²⁰⁴Pb ratios of 37.91–38.45 compatible with their variation in Rb/Sr, U/Pb and Th/Pb ratios. Some migmatites and residual metasedimentary xenoliths tend to have more variable ε_Nd values (initial ε_Nd: − 4.2 to − 7.1), initial Sr isotope ratios (⁸⁷Sr/⁸⁶Sr: 0.708–0.735) and less radiogenic ²⁰⁶Pb/²⁰⁴Pb (18.22–18.53) and ²⁰⁸Pb/²⁰⁴Pb (37.78–38.10) isotope compositions than the metasedimentary rocks. On a Rb–Sr isochron plot the metasedimentary rocks and various migmatites plot on a straight line that corresponds to an age of c. 550 Ma which is interpreted to indicate major fractionation of the Rb–Sr system at that time. However, initial ⁸⁷Sr/⁸⁶Sr ratios of the melanosomes of the stromatic migmatites (calculated for their U–Pb monazite and Sm–Nd garnet ages of c. 510 Ma) are more radiogenic (⁸⁷Sr/⁸⁶Sr: 0.725) than those obtained on their corresponding leucosomes (⁸⁷Sr/⁸⁶Sr: 0.718) implying disequilibrium conditions during migmatization that have not lead to complete homogenization of the Rb–Sr system. However, the leucosomes have similar Nd isotope characteristics than the inferred residues (melanosomes) indicating the robustness of the Sm–Nd isotope system during high-grade metamorphism and melting. On a Rb–Sr isochron plot residual metasedimentary xenoliths show residual slopes of c. 66 Ma (calculated for an U–Pb monazite age of 470 Ma) again indicating major fractionation of Rb/Sr at c. 540 Ma. However, at 540 Ma, these xenoliths have unradiogenic Sr isotope compositions of c. 0.7052, indicating depleted metasedimentary sources at depth. Based on the distinct Pb isotope composition of the metasedimentary rocks and S-type granites, metasedimentary rocks similar to the country rocks are unlikely sources for the S-type granites. Moreover, a combination of Sr, Nd, Pb and O isotopes favours a three-component mixing model (metasedimentary rocks, altered volcanogenic material, meta-igneous crust) that may explain the isotopic variabilty of the granites. The mid-crustal origin of the different types of granite emphasises the importance of recycling and reprocessing of pre-existing differentiated material and precludes a direct mantle contribution during the petrogenesis of the orogenic granites in the central Damara orogen of Namibia.     

Mantle heterogeneity and crustal recycling in Archean granite-greenstone belts: Evidence from Nd isotopes and trace elements in the Rainy Lake area, Superior Province, Ontario, Canada

The 2685–2752 Ma old granite-greenstone crust in the Rainy Lake area, Ontario, consists of metaigneous and metasedimentary rocks that range in composition from tholeiite to monzogranite and include anorthosite, trachyandesite, monzodiorite and high-silica rhyodacite. Major element, rare earth and other trace element data are the basis for modelling the formation of the crust by melting of large-ionlithophile element enriched and unenriched mantle, by melting of basalt at mantle to crustal levels and by melting of monzodiorite and tonalite at crustal levels.

All metaigneous rocks lie on a ¹⁴³Nd/¹⁴⁴Nd vs. ¹⁴⁷Sm/¹⁴⁴Nd isochron with an age of 2737 ±42 Ma and an initial ¹⁴³Nd/¹⁴⁴Nd of 0.509178 ±33 (ε_Nd = +1.9). This age is consistent with U-Pb zircon ages, which suggests the Nd isotopic system has been unaffected since the crust-forming events. The positive initial ε_Nd's are further evidence for time-averaged depletion in Sm/Nd relative to CHUR for the Archean mantle. The similarity of the initial Nd isotopic composition for both mantle-derived and crustally-derived rocks suggests rapid recycling of crustal components, which were previously derived from depleted mantle sources.

Initial ¹⁴³Nd/¹⁴⁴Nd ratios on individual rocks range from ε_Nd = +3.3 to ε_Nd = −0.4. Younger granitoids have lower ε_Nd values (+1.5 to −0.1) relative to tholeiites and monzodiorites crystallized from mantle-derived melts (+3.3 to +1.0). Thus, incorporation of slightly older crust (ca. 100–200 Ma) in some of the granitoid source areas is possible. Mantle-derived rocks form an isochron of 2764 ±58 Ma that represents a minimum age for enrichment processes in the mantle sources for the Rainy Lake area. Consideration of data from the Abitibi belt suggests such enrichment processes in the mantle may have preceded crust-forming events in a wide area of the Superior Province, perhaps by as much as 50–70 Ma.     

The mineral isotope composition of two Precambrian carbonatite complexes from the Kola Alkaline Province – Alteration versus primary magmatic signatures

We investigated the isotope composition (O, C, Sr, Nd, Pb) in mineral separates of the two Precambrian carbonatite complexes Tiksheozero (1.98 Ga) and Siilinjärvi (2.61 Ga) from the Karelian–Kola region in order to obtain information on Precambrian mantle heterogeneity. All isotope systems yield a large range of variations. The combination of cathodoluminescence imaging with stable and radiogenic isotopes on the same samples and mineral separates indicates various processes that caused shifts in isotope systems. Primary isotope signatures are preserved in most calcites (O, C, Sr, Pb), apatites (O, Sr, Nd), amphiboles (O), magnetites (O), and whole rocks (Sr, Nd).

The primary igneous C and O isotope composition is different for both complexes (Tiksheozero: δ¹³C = − 5.0‰, δ¹⁸O = 6.9‰; Siilinjärvi: δ¹³C = − 3.7‰, δ¹⁸O = 7.4‰) but very uniform and requires homogenization of both carbon and oxygen in the carbonatite melt. The lowest Sr isotope ratios of our carbonates and apatites from the Archaean Siilinjärvi (0.70137) and the Palaeoproterozoic Tiksheozero (0.70228) complexes are in the range of bulk silicate earth (BSE). Positive ε_Nd values of the two carbonatites point to very early Archaean enrichment of Sm/Nd in the Fennoscandian mantle. No HIMU components could be detected in the two complexes, whereas Tiksheozero carbonatites give the first indication of Palaeoproterozoic U depletion for Fennoscandia.

Sub-solidus exchange processes with water during emplacement and cooling of carbonatites caused an increase in the oxygen isotope composition of some carbonates and probably also an increase of their ⁸⁷Sr/⁸⁶Sr ratio. A larger increase of initial Sr isotope ratios was found in carbonatized silicic rocks compared to carbonatite bodies. The Svecofennian metamorphic overprint (1.9–1.7 Ga) caused reset of Rb/Sr (mainly mica) and Pb/Pb (mainly apatite) isochron systems.