大别-苏鲁造山带高级变质岩中锆石微区U，Th和Pb化学组成特征统计

对大别-苏鲁造山带27个高级变质岩(以榴辉岩和片麻岩为主)中锆石进行了337次微区离子探针U.Th和Pb测定和U-Pb年龄研究。根据测定点年龄的不同，可以把变质岩中锆石分成三种不同成因区域，一是变质岩原岩(继承)锆石区域，它遭受了不同程度的变质重结晶作用，其^206Pb/^238U年龄值大于277Ma；二是三叠纪高压.超高压变质阶段形成的变质锆石区域，其年龄限定为273-184Ma；三是碰撞造山变质作用后形成的锆石区域，其年龄小于148Ma。对三种类型锆石中U，Th和Pb特征分析发现：片麻岩锆石中U的含量是榴辉岩类锆石中U的丰度的两倍，片麻岩类和榴辉岩类锆石中Th的丰度大致相近。各类岩石变质阶段形成的变质锆石和原岩锆石区域相比，U含量有升有降，而Th含量则大幅下降，下降幅度一般在2-10倍，高者可达20-30倍以上。除石榴石橄榄岩外，各类岩石变质锆石中区域的Th/U比都小于0.1，这是判断高压-超高压变质成因锆石的极重要化学指标。大别山超高压变质阶段后形成的锆石的Th/U比多数类似于其原岩锆石，少数接近变质锆石，说明白垩纪后期热扰动对变质岩中已存在的锆石的影响如同岩浆结晶过程。各类岩石中锆石Pb的含量变化比较复杂，Pb-U正相关性表明锆石中普通铅含量很低，绝大部分为放射成因铅。     

Fractionation of U,Th, Ra and Pb from boreal forest soils by sequential extractions

To determine the mobility of natural radionuclides in boreal forest soil, a five-step sequential extraction procedure was carried out on soil samples taken from various depths down to 3 m on Olkiluoto Island, Finland, where there are plans to construct a spent nuclear fuel disposal repository in the bedrock. The extracted fractions studied were exchangeable, acid-soluble, reducible, oxidizable and tightly bound. It was found that the extractability of most of the radionuclides studied was dependent on the sample grain size and depth. All the elements were concentrated in the smallest grain size samples (<0.063 mm). The extraction behaviour of Th, however, did not vary with sample depth, and only about 10% of the Th was extracted by the time of the final extraction step. Stable Pb and ²¹⁰Pb, as well as Ba and Ra concentrations were strongly correlated in the extractions. Radium and Ba were leached more readily than the other elements; approximately 17% of the total Ra was found in the first fraction extracted, representing exchangeable ions. Uranium was more mobile in the topsoil horizons than in the lower horizons. In the topsoil samples, an average of 51% of the extractable U was leached in the second extraction step, representing the elements soluble in weak acids, whereas only 13% of the U in the subsoil samples was extracted in this step. This is probably due to changes in soil redox conditions lower down the soil profile. The extraction behaviour of Pb and Fe also suggests the presence of more reducing conditions in the deeper soil horizons, because the percentage of extractable Pb and Fe in the oxidizable fraction increased with sample depth.     

Zircon U–Pb ages and Hf isotope compositions of migmatites from the North Qinling terrane and their geological implications

Migmatites are predominant in the North Qinling (NQ) orogen, but their formation ages are poorly constrained. This paper presents a combined study of cathodoluminescence imaging, U–Pb age, trace element and Hf isotopes of zircon in migmatites from the NQ unit. In the migmatites, most zircon grains occur as new, homogeneous crystals, while some are present as overgrowth rims around inherited cores. Morphological and trace element features suggest that the zircon crystals are metamorphic and formed during partial melting. The inherited cores have oscillatory zoning and yield U–Pb ages of c. 900 Ma, representing their protolith ages. The early Neoproterozoic protoliths probably formed in an active continental margin, being a response to the assembly of the supercontinent Rodinia. The migmatite zircon yields Hf model ages of 1911 ± 20 to 990 ± 22 Ma, indicating that the protoliths were derived from reworking of Palaeoproterozoic to Neoproterozoic crustal materials. The anatexis zircon yields formation ages ranging from 455 ± 5 to 420 ± 4 Ma, with a peak at c. 435 Ma. Combined with previous results, we suggest that the migmatization of the NQ terrane occurred at c. 455–400 Ma. The migmatization was c. 50 Ma later than the c. 490 Ma ultra‐high‐P (UHP) metamorphism, indicating that they occurred in two independent tectonic events. By contrast, the migmatization was coeval with the granulite facies metamorphism and the granitic magmatism in the NQ unit, which collectively argue for their formation due to the northward subduction of the Shangdan Ocean. UHP rocks were distributed mainly along the northern margin and occasionally in the inner part of the NQ unit, indicating that they were exhumed along the northern edge and detached from the basement by the subsequent migmatization process.     

安徽女山橄榄岩包体的氧同位素比值和微量元素组成：地幔交代作用

1本文的研究对象是9个来自安徽女山新生代玄武岩的橄榄岩包体,利用激光氟化技术系统分析了橄榄石、单斜辉石和斜方辉石的氧同位素比值;利用LA-ICPMS技术分析了单斜辉石的微量元素组成,结果显示,女山橄榄岩存在辉石与橄榄石之间的氧同位素不平衡分馏现象,其中△Cpx-O1^18O（=δ^18OCpx-δ^18OO1））出现低至-0．5‰的负值;合角闪石包体中的单斜辉石明显富集大离子亲石元素（LILE,如Sr、Th、LREE）和亏损高场强元素（HFSE,如Nb、Zr、Ti）,氧同位素的数据表明,女山上地幔曾经经历过俯冲洋壳流体参与的交代作用,根据单斜辉石和橄榄石之间氧同位素分馏值△Cpx-O1^18O与包体形成深度之间的负相关性,提出了一个“上升＋缓冲”的流体交代模型,虽然微量元素特征也表明女山上地慢受到过地壳流体的影响,但是氧同位素的不平衡分馏和LILE的富集／HFSE的亏损并不是同步的,对这种现象的可能解释是：引起氧同位素不平衡分馏的交代作用和造成女山单斜辉石微量元素特征的交代作用不是同一期的,即女山上地幔曾经发生过至少2次交代事件.     

New constraints on elemental and Pb and Nd isotope compositions of South American and Southern African aerosol sources to the South Atlantic Ocean

Improving the geochemical database available for characterising potential natural and anthropogenic aerosol sources from South America and Southern Africa is a critical precondition for studies aimed at understanding trace metal controls on the marine biogeochemical cycles of the South Atlantic Ocean. We here present new elemental and isotopic data for a wide range of sample types from South America and Southern Africa that are potentially important aerosol sources. This includes road dust from Buenos Aires and lichen samples from Johannesburg, soil dust from Patagonia, volcanic ash from the Andean volcanic belt, and aerosol samples from São Paulo. All samples were investigated for major (Al, Ca, Fe, Mg, Na, K, Mn) and trace element (Cd, Co, Cr, Cu, Ni, Pb, REE, Sc, Th, Y, V, Zn) concentrations and Nd and Pb isotopic compositions. We show that diagrams of ²⁰⁸Pb/²⁰⁷Pb vs. ε_Nd, ²⁰⁸Pb/²⁰⁷Pb vs. Pb/Al, 1/[Pb], Zn/Al, Cd/Al, Cu/Al, and ε_Nd vs. Pb/Al, and 1/[Nd] are best suited to separate South American and South African source regions as well as natural and anthropogenic sources. A subset of samples from Patagonia and the Andes was additionally subjected to separation of a fine (<5?μm) fraction and compared to the composition of the bulk sample. We show that differences in the geochemical signature of bulk samples between individual regions and source types are significantly larger than between grain sizes. Jointly, these findings present an important step forward towards a quantitative assessment of aeolian trace metal inputs to the South Atlantic Ocean.     

中国大陆岩石圈地幔镍-钴-铂族元素组成及其成矿意义: 地幔捕虏体证据

镍、钴和铂族元素（PGEs,Platinum group elements）是我国紧缺的关键金属,它们作为亲铁元素主要储存在地核和地幔中。幔源岩浆作用能否超常富集镍、钴和铂族成矿在一定程度上取决于地幔源区这些元素的组成与富集程度,地幔捕虏体可揭示中国大陆岩石圈地幔镍、钴和铂族元素的组成与含量。本文总结了中国华北克拉通、华南克拉通和中亚造山带东部等主要构造单元地幔捕虏体中镍、钴和铂族元素的组成与含量,认为：（1）华北和华南克拉通岩石圈地幔镍、钴和铂族元素原始含量较高,高于原始地幔,且随深度增加而增加,是镍、钴和铂族元素成矿岩浆的有利地幔源区;（2）镍、钴和铂族元素以纳米原子团簇、合金或硫化物等形式赋存、运移与富集;（3）不同构造单元岩石圈地幔镍、钴和铂族元素的富集程度不同;（4）岩石圈地幔镍、钴和铂族元素含量从元古代到新生代有所降低,意味着该区存在镍、钴和铂族元素抽取的岩浆事件,故其成矿潜力巨大。

     

Constraining late stage melt-peridotite interaction in the lithospheric mantle of southern Ethiopia: evidence from lithium elemental and isotopic compositions

Mineralogy and Petrology - Lithium (Li) elemental and isotopic compositions for mineral separates of coexisting olivine, orthopyroxene and clinopyroxene of mantle xenoliths from the Quaternary...     

苏皖地区幔源橄榄岩捕瞄虏体的锇同位素组成、模式年龄及其意义

苏皖地区发育的新生代玄武岩中富含地幔橄榄岩捕虏体，测定了25个橄榄岩全岩的锇同位素组成。结果表明大部分样品呈亏损特征,187Os/188Os=0.119～0.129.Os同位素比值与主量成分之间有显著的相关性.采用187Os/188Os-Al2O3代用等时线方法,由截距得到初始值(187Os/188Os)0=0.109,在对流地幔的187Os/188Os比值演化线上获得模式年龄t=2.5(±0.1)Ga,为晚太古-早元古代。用样品组中最低的锇同位素组成,即187Os/188Os=0.119,计算Re亏损模式年龄,t=1.2Ga,为中元古代。表明苏皖地区新生代玄武岩中的地幔橄榄岩捕虏体具有古老的形成年龄,它们是经过显生宙减薄作用后的残余地幔的碎片。大陆岩石圈地幔的古老形成年龄与上覆地壳克拉通的古老稳定年龄相耦合。     

Source indicators of humic substances and proto-kerogen. Stable isotope ratios,elemental compositions and electron spin resonance spectra

Stable isotope ratios of C, N and H, elemental compositions and electron spin resonance (ESR) data of humic acids and proto-kerogens from twelve widely varying sampling locations are presented. Humic acids and proto-kerogens from algal sources are more aliphatic and higher in N than those from higher plant sources. Oxygen content appears to represent a measure of maturation, even in Recent sediments and S content may reflect redox conditions in the environment of deposition. The ESR data indicate that the transformation of humic substances to proto-kerogens in Recent sediments is accompanied by an increase in aromatic character. A combination of δ¹³C and $\text{H}\text{C}$ ratio may be a simple but reliable source indicator which allows differentiation of marine-derived from terrestrially-derived organic matter. The δ¹⁵N values are useful indicators of nitrogen nutrient source. Deuterium/hydrogen isotope ratios appear to reflect variations in meteoric waters and are not reliable source indicators.     

Source contamination and mantle heterogeneity in the genesis of Italian potassic and ultrapotassic volcanic rocks: Sr–Nd–Pb isotope data from Roman Province and Southern Tuscany

Summary The Tyrrhenian border of the Italian peninsula has been the site of intense magmatism from Pliocene to recent times. Although calc-alkaline, potassic and ultrapotassic volcanism overlaps in space and time, a decrease of alkaline character in time and space (southward) is observed. Alkaline ultrapotassic and potassic volcanic rocks are characterised by variable enrichment in K and incompatible elements, coupled with consistently high LILE/HFSE values, similar to those of calc-alkaline volcanic rocks from the nearby Aeolian arc. On the basis of mineralogy and major and trace element chemistry two different arrays can be recognised among primitive rocks; a silica saturated trend, which resulted in formation of leucite-free mafic rocks, and a silica undersaturated trend, charactrerised by leucite-bearing rocks. Initial ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd values of Italian ultrapotassic and potassic mafic rocks range from 0.70506 to 0.71672 and from 0.51173 to 0.51273, respectively. ²⁰⁶Pb/²⁰⁴Pb values range between 18.50 and 19.15, ²⁰⁷Pb/²⁰⁴Pb values range between 15.63 and 15.70, and ²⁰⁸Pb/²⁰⁴Pb values range between 38.35 and 39.20. The general ε_Sr vs. ε_Nd array, along with crustal lead isotopic values, clearly indicates that a continental crustal component has played an important role in the genesis of these magmas. The main question is where this continental crustal component has been acquired by the magmas. Volcanological and petrologic data indicate continental crustal contamination to be a leading process along with fractional crystallisation and magma mixing. Considering, however, only the samples thought to represent primary magmas, which have been in equilibrium with their mantle source, a clearer picture emerges. A large variation of ε_Sr vs. ε_Nd is still observed, with ε_Sr from −2 to +180 and ε_Nd from + 2 to −12. A bifurcation of this array is observed in the samples that plot in the lower right quadrant, with mafic leucite-bearing Roman Province rocks buffered at ε_Sr = + 100 whereas the mafic leucite-free potassic and ultrapotassic rocks point to strongly radiogenic Sr compositions. We may argue that mafic leucite-bearing Roman Province rocks point to ε_Sr and ε_Nd values similar to those of Miocene carbonate sediments whereas mafic leucite-free potassic and ultrapotassic rocks point to a silicate upper crust end-member. Lead isotopes plot well inside the field of island arcs, overlapping the values of pelagic sediments as well, but bifurcation between the samples north and south of Rome is observed. The main characteristic for the mantle source of Italian potassic and ultrapotassic magmas is the clear upper crustal signature acquired prior to partial melting through metasomatic agents released by the subducted slab. In addition, one lithospheric mantle source in the north and an asthenospheric mantle source, pointing to an HIMU reservoir, in the south were recognised. The chemical and isotopic differences observed between the northern and southern sectors of the magmatic region were possibly due to the presence of a carbonate-rich component in the crustal enriching agent in the south. One crustal component might have been generated by melting of silicate metasedimentary rocks or sediments from an ancient subducted slab. The second one might reflect the activity of mostly CO₂-rich fluid released more recently by the incipient subduction of carbonate sedimentary rocks. Received February 16, 2000; revised version accepted September 6, 2001     

Aliphatic and diterpenoid hydrocarbons and their individual carbon isotope compositions in coals from the Liaohe Basin, China

Abundant tricyclic diterpanes (i.e., pimarane, dehydroabietane and simonellite) and tetracyclic diterpanes (e.g., phyllocladane) were detected in coal samples from the third member of the Shahejie Formation, Lower-Eogene, Liaohe Basin, China. Gas chromatography–isotope ratio mass spectrometry (GC–IRMS) analyses show that the carbon isotopic composition of terrigenous tricyclic and tetracyclic diterpenoid hydrocarbons are about 4–6‰ enriched in ¹³C compared to n-alkanes in the same samples. In addition, the pimaranes and phyllocladane have comparatively narrow stable carbon isotopic compositions among the different samples, with a slightly wider range in δ¹³C compositions for the abietanes (i.e., abietane, dehydroabietane and simonellite). The n-alkanes and triterpenoids reflect the δ¹³C compositions of higher plant wax.     

夏日哈木超大型镍矿I号岩体地幔源区性质和硫化物熔离过程：来自橄榄石成分、亲铜元素和硫同位素的约束

夏日哈木超大型镍矿I号岩体的地幔源区目前仍存在软流圈、大陆下岩石圈地幔和辉石岩地幔三种不同认识。本次研究通过对该岩体西段新近发现的隐伏矿体ZK3109钻孔中斜方辉石岩和浸染状矿石中的橄榄石进行原位成分分析,识别地幔源区性质,并结合硫化物原位S同位素和全岩亲铜元素组成,探讨硫化物熔离过程。样品中橄榄石均具有较低的Mn/Zn比值(基本小于13.5),而且斜方辉石岩中橄榄石具有较低的100×Mn/Fe比值(基本小于1.35),指示岩体源区有辉石岩地幔组分加入,与前人根据硫化物矿体富Ni特征的推测一致。橄榄石低Ca(小于300.00×10^-6)、高Li(平均9.83×10^-6)以及Sc与Ni正相关指示辉石岩地幔组分可能是俯冲洋壳物质交代大陆下岩石圈地幔的产物。另一方面,斜方辉石岩中橄榄石Ni、Fo值均与Co负相关且全岩S和铂族元素(PGE)相关性不明显,说明浅部岩浆房硫化物熔离发生在斜方辉石岩形成之后。浸染状矿石中橄榄石Co和Ni正相关且全岩S和PGE正相关,暗示橄榄石成分受控于硫化物熔离。样品中镍黄铁矿、磁黄铁矿和黄铜矿δ³⁴...     

Multiple mantle metasomatism beneath the Leizhou Peninsula,South China: evidence from elemental and Sr-Nd-Pb-Hf isotope geochemistry of the late Cenozoic volcanic rocks

ABSTRACT

We analysed whole-rock major and trace elements and Sr-Nd-Pb-Hf isotopes of the late Cenozoic volcanic rocks in the Leizhou Peninsula, South China to investigate their mantle source characteristics. These volcanic rocks, collected from Jiujiang, Tianyang and Huoju areas of the Leizhou Peninsula, are characterized by incompatible element enrichment but variable isotopic depletion. The volcanic rocks from Jiujiang and Tianyang show prominent primitive-mantle-normalized positive Nb, Ta and Sr anomalies and depleted Sr-Nd-Pb-Hf isotope compositions, whereas those from Huoju show slight positive to negative Nb and Ta anomalies, a prominent positive Pb anomaly, and more enriched Sr-Nd-Pb-Hf isotope compositions. Two types of mantle metasomatism are required to explain the geochemical characteristics of these rocks. The Jiujiang and Tianyang samples were largely derived from a mantle source metasomatized recently by a low-F melt. Such low-F melt is generated within the asthenospheric mantle, which is enriched in volatiles and incompatible elements with positive Sr anomaly and depleted Sr-Nd-Pb-Hf isotope compositions. The Huoju samples were largely derived from a mantle source metasomatized by recycled upper continental crust material. These two types of mantle metasomatism beneath the Leizhou Peninsula are consistent with trace element characteristics of mantle mineralogy (e.g. clinopyroxene vs. amphibole), which reflects source evolution in space and time (e.g. tectonic setting change).     

An Acetic Acid‐Based Extraction Protocol for the Recovery of U,Th and Pb from Calcium Carbonates for U‐(Th)‐Pb Geochronology

A new method for the simultaneous recovery of U, Th and Pb from ca. 0.5 g calcium carbonate samples for the purpose of U‐(Th)‐Pb geochronometry is presented. The protocol employs ion‐exchange chromatography. Standard anion exchange resin (AG 1‐X8 100–200 mesh) was used as the static phase, and 90% acetic acid was used as the mobile phase to elute the unwanted matrix components; dilute nitric acid was used to elute the U, Th and Pb. Blanks of 1.8 pg Th, 6.4 pg Pb and 8.4 pg U were obtained. The protocol was evaluated by determining the isotopic composition of U‐Th‐Pb separates obtained from an in‐house reference material (prepared from a natural speleothem) by MC‐ICP‐MS. An independently dated speleothem was also reanalysed. Based on these tests, the extraction protocol had an acceptable blank and produced a Pb separate sufficiently free of matrix‐induced instrumental biases to be appropriate for U‐Th‐Pb chronology.     

238U, 232Th profiling and U-series isotope analysis of fossil teeth by laser ablation-ICPMS

U and Th concentration profiles in fossil hominid and faunal teeth have been measured by laser ablation ICPMS. These profiles record diverse modes of U and Th uptake, particularly within enamel, that can be broadly related to the state of sample preservation. Observed U profiles are in general inconsistent with existing diffusion–adsorption models developed for U-uptake in bone and teeth. Where the models appear applicable, calculated diffusion rates are several orders of magnitude smaller than previous estimates. Laser ablation ICPMS offers a means of rapidly characterizing U and Th distributions in the enamel and dentine components of teeth as a precursor to ESR and U-series dating. In particular, it should allow the identification of teeth (and also bone) samples that have simple U-uptake histories and are amenable to precise dating by time-consuming and expensive Th–U and Pa–U TIMS techniques. We also demonstrated the use of laser ablation ICPMS to measure U-series isotopes in dentine and enamel samples with relatively high U concentrations (>20 ppm). These results, obtained using a quadrupole ICPMS, illustrate significant promise for in situ U-series isotope analysis, particularly when combined with the greater sensitivity and multi-collection capabilities of new sector ICPMS instrumentation. The latter may permit precise isotope ratio measurements on samples containing only a few ppm of U.     

Identification of contamination in a lake sediment core using Hg and Pb isotopic compositions,Lake Ballinger,Washington, USA

Concentrations and isotopic compositions of Hg and Pb were measured in a sediment core collected from Lake Ballinger, near Seattle, Washington, USA. Lake Ballinger has been affected by input of metal contaminants emitted from the Tacoma smelter, which operated from 1887 to 1986 and was located about 53 km south of the lake. Concentrations and loadings of Hg and Pb in Lake Ballinger increased by as much as three orders of magnitude during the period of smelting as compared to the pre-smelting period. Concentrations and loadings of Hg and Pb then decreased by about 55% and 75%, respectively, after smelting ended. Isotopic compositions of Hg changed considerably during the period of smelting (δ²⁰²Hg = −2.29‰ to −0.38‰, mean −1.23‰, n = 9) compared to the pre-smelting period (δ²⁰²Hg = −2.91‰ to −2.50‰, mean −2.75‰, n = 4). Variations were also observed in ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb isotopic compositions during these periods. Data for Δ¹⁹⁹Hg and Δ²⁰¹Hg indicate mass independent fractionation (MIF) of Hg isotopes in Lake Ballinger sediment during the smelting and post-smelting period and suggest MIF in the ore smelted, during the smelting process, or chemical modification at some point in the past. Negative values for Δ¹⁹⁹Hg and Δ²⁰¹Hg for the pre-smelting period are similar to those previously reported for soil, peat, and lichen, likely suggesting some component of atmospheric Hg. Variations in the concentrations and isotopic compositions of Hg and Pb were useful in tracing contaminant sources and the understanding of the depositional history of sedimentation in Lake Ballinger.     

The origin and evolution of chondrites recorded in the elemental and isotopic compositions of their macromolecular organic matter

Extraterrestrial organic matter in meteorites potentially retains a unique record of synthesis and chemical/thermal modification by parent body, nebular and even presolar processes. In a survey of the elemental and isotopic compositions of insoluble organic matter (IOM) from 75 carbonaceous, ordinary and enstatite chondrites, we find dramatic variations within and between chondrite classes. There is no evidence that these variations correlate with the time and/or location of chondrite formation, or with any primary petrologic or bulk compositional features that are associated with nebular processes (e.g., chondrule and volatile trace element abundances). Nor is there evidence for the formation of the IOM by Fischer-Tropsch-Type synthesis in the nebula or in the parent bodies. The elemental variations are consistent with thermal maturation and/or oxidation of a common precursor. For reasons that are unclear, there are large variations in isotopic composition within and between chondrite classes that do not correlate in a simple way with elemental composition or petrologic type. Nevertheless, because of the pattern of elemental variations with petrologic type and the lack of any correlation with the primary features of the chondrite classes, at present the most likely explanation is that all IOM compositional variations are the result of parent body processing of a common precursor. If correct, the range of isotopic compositions within and between chondrite classes implies that the IOM is composed of several isotopically distinct components whose relative stability varied with parent body conditions. The most primitive IOM is found in the CR chondrites and Bells (CM2). Isotopically, the IOM from these meteorites resembles the IOM in interplanetary dust particles. Chemically, their IOM resembles the CHON particles of comet Halley. Despite the large isotopic anomalies in the IOM from these meteorites, it is uncertain whether the IOM formed in the interstellar medium or the outer Solar System, although the former is preferred here.     

Assessing the origin of old apparent ages derived by Pb stepwise leaching of vein-hosted epidote from Mount Isa,northwest Queensland,Australia

Epidote metasomatism affected large areas of tholeiitic metabasalts of the ~1,780 Ma Eastern Creek Volcanics in the Western Fold Belt of the Proterozoic Mount Isa inlier. Hydrothermal epidote generally occurs in quartz veins parallel to or boudinaged within the dominant S₂ fabrics which formed during the regional metamorphic peak at ~1,570 Ma associated with the Isan orogeny. Previously published stable isotopic and halogen data suggest that the fluids responsible for epidote formation are metamorphic in origin (with an evaporitic component). Application of the Pb stepwise leaching technique to the epidote does not separate radiogenic Pb⁴⁺ and common Pb²⁺, generating little spread in ²⁰⁶Pb/²⁰⁴Pb (between 16.0 and 30.5). The causes for this relatively low range are twofold: There is little radiogenic Pb in the epidotes (the most radiogenic steps account for <1 % of Pb released) and both Pb²⁺ and uranogenic Pb⁴⁺ substitute into the same site in the epidote crystal lattice. Consequently, age regressions using the Pb stepwise leaching data give ages between 150 and 1,500 myrs older than the host rocks and over 450 myrs older than the thermal metamorphic peak. These old ages are attributed to chemical inheritance from the host metabasalts, via radiogenic Pb release by breakdown of phases such as zircon, monazite, titanomagnetite, and ilmenite during metamorphism. This idea is supported by trace element data and chrondrite-normalized rare earth element patterns that are similar to both the metabasalts and epidotes (except for a variable Eu anomaly in the latter). Relatively high fO₂ during vein formation (Fe³⁺ dominates in the epidote crystal lattice) would allow the incorporation of Th⁴⁺ and exclusion of U⁶⁺ and would explain elevated Th/U ratios (up to 12) in epidote compared with the host metabasalts. Non-incorporation of U would explain the relatively low U/Pb ratios and non-radiogenic character of the epidote. This process may provide a source of metal for the small U deposits around Mount Isa and may also suggest a relationship between U mineralization and regional Cu mobilization during the Isan orogeny. Our work suggests that non-conventional geochronometers should be used only if additional geological information and geochemical data (e.g., mineral chemistry, trace elements) are available to evaluate any resulting age calculations.     

Fluid-rock interaction during progressive migration of carbonatitic fluids, derived from small-scale trace element and Sr, Pb isotope distribution in hydrothermal fluorite

Associated with the Cretaceous Okorusu carbonatite complex (Namibia) is a hydrothermal fluorite mineralization hosted in Pan-African country rock marbles, which resulted from fluid-rock reaction between the marbles and orthomagmatic, carbonatitic fluids expelled from the carbonatite. Yellow fluorite I was deposited in veins up to 5 cm away from the wallrock contact, followed by purple and colorless fluorite II, smoky quartz and barite, a Mn-rich crust on early calcite, and pure calcite. This clear-cut sequence of mineral growth allows an investigation into fluid-rock interaction processes between the marble and the migrating carbonatitic fluid, and element fractionation patterns between the fluid and subsequent hydrothermal precipitates.Fluorite I shows a progressive change in color from dark yellow to colorless with purple laminations over time of deposition. Subsequent fluorite I precipitates show an increase in Ca, and a continuous decrease in F, Sr, REE, Y, Th, U and Pb contents. The ratios (Eu/Eu*)_cn, Th/Pb and U/Pb increase whereas Y/Ho, Th/U and (La/Yb)_cn decrease. The Sr-isotopic composition remains constant at ⁸⁷Sr/⁸⁶Sr = 0.70456-0.70459, but with varying, highly radiogenic Pb (²⁰⁶Pb/²⁰⁴Pb = 32-190, ²³⁸U/²⁰⁴Pb = 7-63). Fluorite II has ⁸⁷Sr/⁸⁶Sr = 0.70454-0.70459, ²⁰⁶Pb/²⁰⁴Pb = 18.349, and ²⁰⁷Pb/²⁰⁴Pb = 15.600, and a chemical composition similar to youngest fluorite I. The Mn-rich crust on early calcite accumulated REE, Ba, Pb, Zr, Cs, Th and U, developing into pure calcite with a prominent negative Ce anomaly and successively more radiogenic Sr. The calculated degrees of fluid-rock interaction, f = weight fraction of fluid/(fluid + marble), decrease from fluorite I and most fluorite II (f = 0.5) to calcite (f = 0.2-0.3) and hydrothermal quartz (f ? 0.1). A crush-leach experiment for fluid inclusions in the hydrothermal quartz yielded a Rb-Sr isochron age of 103 ± 12 Ma. Crush-leach analysis for the carbonatitic fluid trapped in the wallrock yielded a trend from the fluid leachate to the host quartz (²⁰⁶Pb/²⁰⁴Pb = 18.224 and 18.602, ²⁰⁷Pb/²⁰⁴Pb = 15.616 and 15.636, respectively) extending from carbonatite towards crustal rocks.Calculated trace element distribution coefficients fluorite/fluid are below unity throughout, and increase from La to Yb. Elements largely excluded from fluorite (Ba, Pb, LREE relative to HREE) were incorporated later into the Mn-rich crust on calcite. The trace element patterns of the hydrothermal minerals are related to changing aCO₂ and aF⁻ in the fluid during continued fluid-marble reaction. A predominance of carbonate over fluoride complexing in the fluid as reactions proceeded controlled the Y/Ho, Th/U and REE patterns in the fluid and the crystallizing phases. Deviations from these trends indicate discontinuous processes of fluid-rock reaction.