Geochemistry of coral from Papua New Guinea as a proxy for ENSO ocean–atmosphere interactions in the Pacific Warm Pool

A Porites sp. coral growing offshore from the Sepik and Ramu Rivers in equatorial northern Papua New Guinea has yielded an accurate 20-year history (1977–1996) of sea surface temperature (SST), river discharge, and wind-induced mixing of the upper water column. Depressions in average SSTs of about 0.5–1.0 °C (indicated by coral Sr/Ca) and markedly diminished freshwater runoff to the coastal ocean (indicated by coral δ¹⁸O, δ¹³C and UV fluorescence) are evident during the El Niño – Southern Oscillation (ENSO) events of 1982–1983, 1987 and 1991-1993. The perturbations recorded by the coral are in good agreement with changes in instrumental SST and river discharge/precipitation records, which are known to be diagnostic of the response of the Pacific Warm Pool ocean–atmosphere system to El Niño. Consideration of coastal ocean dynamics indicates that the establishment of northwest monsoon winds promotes mixing of near-surface waters to greater depths in the first quarter of most years, making the coral record sensitive to changes in the Asian–Australian monsoon cycle. Sudden cooling of SSTs by 1°C following westerly wind episodes, as indicated by the coral Sr/Ca, is consistent with greater mixing in the upper water column at these times. Furthermore, the coral UV fluorescence and oxygen isotope data indicate minimal contribution of river runoff to surface ocean waters at the beginning of most years, during the time of maximum discharge. This abrupt shift in flood-plume behaviour appears to reflect the duration and magnitude of northwest monsoon winds, which tend to disperse flood plume waters to a greater extent in the water column when wind-mixing is enhanced. Our results suggest that a multi-proxy geochemical approach to the production of long coral records should provide comprehensive reconstructions of tropical paleoclimate processes operating on interannual timescales.     

Combined Trace Element and Pb-Nd-Sr-O Isotope Evidence for Recycled Oceanic Crust (Upper and Lower) in the Iceland Mantle Plume

We present the results of a comprehensive major element, traceelement and Sr–Nd–Pb–O isotopic study of post-glacialvolcanic rocks from the Neovolcanic zones on Iceland. The rocksstudied range in composition from picrites and tholeiites, whichdominate in the main rift systems, to transitional and alkalicbasalts confined to the off-rift and propagating rift systems.There are good correlations of rock types with geochemical enrichmentparameters, such as La/Sm and La/Yb ratios, and with long-termradiogenic tracers, such as Sr–Nd–Pb isotope ratios,indicating a long-lived enrichment/depletion history of thesource region. ⁸⁷Sr/⁸⁶Sr vs ¹⁴³Nd/¹⁴⁴Nd defines a negative array.Pb isotopes define well-correlated positive arrays on both ²⁰⁶Pb/²⁰⁴Pbvs ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb diagrams, indicating mixing ofat least two major components: an enriched component representedby the alkali basalts and a depleted component represented bythe picrites. In combined Sr–Nd–Pb isotopic spacethe individual rift systems define coherent mixing arrays withslightly different compositions. The enriched component hasradiogenic Pb (²⁰⁶Pb/²⁰⁴Pb > 19·3) and very similargeochemistry to HIMU-type ocean island basalts (OIB). We ascribethis endmember to recycling of hydrothermally altered upperbasaltic oceanic crust. The depleted component that is sampledby the picrites has unradiogenic Pb (²⁰⁶Pb/²⁰⁴Pb < 17·8),but geochemical signatures distinct from that of normal mid-oceanridge basalt (N-MORB). Highly depleted tholeiites and picriteshave positive anomalies in mantle-normalized trace element diagramsfor Ba, Sr, and Eu (and in some cases also for K, Ti and P),negative anomalies for Hf and Zr, and low ¹⁸O_olivine values(4·6–5·0) below the normal mantle range.All of these features are internally correlated, and we, therefore,interpret them to reflect source characteristics and attributethem to recycled lower gabbroic oceanic crust. Regional compositionaldifferences exist for the depleted component. In SW Icelandit has distinctly higher Nb/U (68) and more radiogenic ²⁰⁶Pb/²⁰⁴Pbratios (18·28–18·88) compared with the NErift (Nb/U 47; ²⁰⁶Pb/²⁰⁴Pb = 18·07–18·47).These geochemical differences suggest that different packagesof recycled oceanic lithosphere exist beneath each rift. A thirdand minor component with relatively high ⁸⁷Sr/⁸⁶Sr and ²⁰⁷Pb/²⁰⁴Pbis found in a single volcano in SE Iceland (Öræfajökullvolcano), indicating the involvement of recycled sediments inthe source locally. The three plume components form an integralpart of ancient recycled oceanic lithosphere. The slope in theuranogenic Pb diagram indicates a recycling age of about 1·5Ga with time-integrated Th/U ratios of 3·01. Surprisingly,there is little evidence for the involvement of North AtlanticN-MORB source mantle, as would be expected from the interactionof the Iceland plume and the surrounding asthenosphere in formof plume–ridge interaction. The preferential samplingof the enriched and depleted components in the off-rift andmain rift systems, respectively, can be explained by differencesin the geometry of the melting regions. In the off-rift areas,melting columns are truncated deeper and thus are shorter, whichleads to preferential melting of the enriched component, asthis starts melting deeper than the depleted component. In contrast,melting proceeds to shallower depths beneath the main rifts.The longer melting columns also produce significant amountsof melt from the more refractory (lower crustal/lithospheric)component. KEY WORDS: basalts; trace element and Sr, Nd, Pb, O isotope geochemistry; Iceland plume; isotope ratios; oceanic crustal recycling; partial melting; plume–ridge interaction     

Combined Sr isotope and trace element analysis of melt inclusions at sub-ng levels using micro-milling, TIMS and ICPMS

This paper describes a technique, which allows precise and accurate Sr isotope measurement combined with trace element analysis of individual melt inclusions, of sample sizes  1 ng of Sr. The technique involves sampling by micro-milling, chemical dissolution, micro Sr column chemistry, TIMS, and ICPMS analyses. A 10% aliquot of each sample solution is used for trace element analysis by double focusing magnetic sector field ICPMS, while Sr is chemically separated from the remaining 90% and used for ⁸⁷Sr/⁸⁶Sr determinations by TIMS.During the development of the technique outlined above, we documented in detail the potential sources of blank contributions and their magnitude. The average size and Sr isotope composition of our laboratory total procedural blank during this study was 5.4 pg ± 0.3 pg Sr (n = 21) with an ⁸⁷Sr/⁸⁶Sr of 0.7111 ± 0.0002 (2SE, n = 3). The total procedural Rb blank was 1.9 ± 0.7 pg (n = 21). The total procedural blank was found to have minimal effect (< 150 ppm shift) on the ⁸⁷Sr/⁸⁶Sr of sample material containing down to  250 pg Sr. Applying a blank correction allows ‘in house’ standards of this size to be corrected back to within 175 ppm of their accepted values. By applying blank corrections we can confidently measure the Sr isotope composition on sample sizes down to  25 pg Sr to an accuracy better than 400 ppm.The utility of the technique is illustrated by application to a suite of melt inclusions from NW Iceland and their host olivines. It is shown that the effect of a small amount of entrainment of the host olivine during sampling of 50 μm melt inclusions has a negligible effect on the measured Sr isotope and trace element composition. Furthermore, where melt inclusions are < 50 μm it is possible to obtain Sr isotope and trace element data on multiple melt inclusions hosted in a single olivine. This provides similar information to that of the single melt inclusions.     

A new procedure for separating and measuring radiogenic isotopes (U, Th, Pa, Ra, Sr, Nd, Hf) in ice cores

A new method for the radiogenic isotope (U–Th–Pa–Ra, Sr, Nd, Hf) analysis of the soluble and insoluble components found within ice cores is presented. Melting experiments with rock standards in the presence of EDTA indicate that carbonates, as well as silicates, can be buffered sufficiently to preclude dissolution. The use of EDTA allows adsorbing species, such as Th and Hf, to remain in solution during melting thus fully separating the dust (insoluble) and sea salt (soluble) components of the ice after filtration. A new elemental separation scheme for low sample masses, less than 5 mg solid material, utilizes 4 primary ion exchange columns and two “clean-up” columns to fully isolate U, Th, Pa, Ra, Sr, Nd, and Hf while maintaining high yields. Elution schemes measured for USGS rock standards and a Chinese loess are presented to provide a comparison for variable matrix compositions. Mass spectrometer techniques were modified to measure small aliquots of the standards, equivalent to the amounts found in ice core samples, 10 ng and less. A MC-ICPMS was employed for the measurement of U, Th, Pa, Ra, and Hf; results of the experiments show that with ion yields up to 1%, rock standards have errors for ²³⁴U/²³⁸U of 1%, ²³⁰Th/²³²Th of 1.5%, [²²⁸Ra] of 9%, and ¹⁷⁶Hf/¹⁷⁷Hf of 100 ppm. MC-TIMS measurements of Sr and Nd show similar errors for small sample sizes: ⁸⁷Sr/⁸⁶Sr of 50 ppm and ¹⁴³Nd/¹⁴⁴Nd of 80 ppm. This new analytical method increases the number of possible tracers measured from a single sample, reducing separation times and sample consumption, as well as providing the addition of a radiometric clock, U-series, to the traditional suite of isotopic tracers, Sr, Nd, and Hf.     

Geochronological framework and Pb, Sr isotope geochemistry of the Qingchengzi Pb–Zn–Ag–Au orefield, Northeastern China

The Qingchengzi orefield in northeastern China, is a concentration of several Pb–Zn, Ag, and Au ore deposits. A combination of geochronological and Pb, Sr isotopic investigations was conducted. Zircon SHRIMP U–Pb ages of 225.3 ± 1.8 Ma and 184.5 ± 1.6 Ma were obtained for the Xinling and Yaojiagou granites, respectively. By step-dissolution Rb–Sr dating, ages of 221 ± 12 Ma and 138.7 ± 4.1 Ma were obtained for the sphalerite of the Zhenzigou Zn–Pb deposit and pyrargyrite of the Ag ore in the Gaojiabaozi Ag deposit, respectively. Pb isotopic ratios of the Ag ore at Gaojiabaozi (²⁰⁶Pb/²⁰⁴Pb = 18.38 to 18.53) are higher than those of the Pb–Zn ores (²⁰⁶Pb/²⁰⁴Pb = 17.66 to 17.96; Chen et al. [Chen, J.F., Yu, G., Xue, C.J., Qian, H., He, J.F., Xing, Z., Zhang, X., 2005. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone, northeastern China. Science in China Series D 48, 467–476.]). Triassic granites show low Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb = 17.12 to 17.41, ²⁰⁷Pb/²⁰⁴Pb = 15.47 to 15.54, ²⁰⁸Pb/²⁰⁴Pb = 37.51 to 37.89) and metamorphic rocks of the Liaohe Group have high ratios (²⁰⁶Pb/²⁰⁴Pb = 18.20 to 24.28 and 18.32 to 20.06, ²⁰⁷Pb/²⁰⁴Pb = 15.69 to 16.44 and 15.66 to 15.98, ²⁰⁸Pb/²⁰⁴Pb = 37.29 to 38.61 and 38.69 to 40.00 for the marble of the Dashiqiao Formation and schist of the Gaixian Formation, respectively).Magmatic activities at Qingchengzi and in adjacent regions took place in three stages, and each contained several magmatic pulses: ca. 220 to 225 Ma and 211 to 216 Ma in the Triassic; 179 to 185 Ma, 163 to 168 Ma, 155 Ma and 149 Ma in the Jurassic, as well as ca. 140 to 130 Ma in the Early Cretaceous. The Triassic magmatism was part of the Triassic magmatic belt along the northern margin of the North China Craton produced in a post-collisional extensional setting, and granites in it formed by crustal melting induced by mantle magma. The Jurassic and Early Cretaceous magmatism was related to the lithospheric delamination in eastern China. The Triassic is the most important metallogenic stage at Qingchengzi. The Pb–Zn deposits, the Pb–Zn–Ag ore at Gaojiabaozi, and the gold deposits were all formed in this stage. They are temporally and spatially associated with the Triassic magmatic activity. Mineralization is very weak in the Jurassic. Ag ore at Gaojiabaozi was formed in the Early Cretaceous, which is suggested by the young Rb–Sr isochron age, field relations, and significantly different Pb isotopic ratios between the Pb–Zn–Ag and Ag ores. Pb isotopic compositions of the Pb–Zn ores suggest binary mixing for the source of the deposits. The magmatic end-member is the Triassic granites and the other metamorphic rocks of the Liaohe Group. Slightly different proportions of the two end-members, or an involvement of materials from hidden Cretaceous granites with slightly different Pb isotopic ratios, is postulated to interpret the difference of Pb isotopic compositions between the Pb–Zn–(Ag) and Ag ores. Sr isotopic ratios support this conclusion. At the western part of the Qingchengzi orefield, hydrothermal fluid driven by the heat provided by the now exposed Triassic granites deposited ore-forming materials in the low and middle horizons of the marbles of the Dashiqiao Formation near the intrusions to form mesothermal Zn–Pb deposits. In the eastern part, hydrothermal fluids associated with deep, hidden Triassic intrusions moved upward along a regional fault over a long distance and then deposited the ore-forming materials to form epithermal Au and Pb–Zn–Ag ores. Young magmatic activities are all represented by dykes across the entire orefield, suggesting that the corresponding main intrusion bodies are situated in the deep part of the crust. Among these, only intrusions with age of ca. 140 Ma might have released sufficient amounts of fluid to be responsible for the formation of the Ag ore at Gaojiabaozi.Our age results support previous conclusions that sphalerite can provide a reliable Rb–Sr age as long as the fluid inclusion phase is effectively separated from the “sulfide” phase. Our work suggests that the separation can be achieved by a step-resolution technique. Moreover, we suggest that pyrargyrite is a promising mineral for Rb–Sr isochron dating.     

相山铀矿田西部地区深部多金属矿化成矿年代与成矿流体演化:Rb-Sr同位素体系的制约

江西相山铀矿田科学深钻3号孔在深部-700 m发现大量铅锌多金属矿化脉,垂向上呈"上铀下多金属"的分布特征。本文选取深部多金属矿脉主成矿阶段(S3)自形闪锌矿样品6件和不同阶段的毒砂、黄铁矿、方铅矿、方解石等样品12件,以及围岩全岩样品17件,进行了Rb、Sr同位素组成研究。结果表明:(1)由闪锌矿Rb-Sr等时线法确定的相山铀矿田深部多金属矿化形成于121. 0±3. 5Ma,与围岩火山岩存在较大时差,可能与晚于围岩的深部次火山有关。根据穿插关系,多金属矿化略晚于碱性交代铀矿化,但明显早于酸性交代铀矿化;(2)多金属矿化脉体中金属矿物的Rb和Sr含量分别介于0. 041×10~(-6)～1. 38×10-6和2. 35×10-6～23. 11×10-6之间,Sr同位素初始比值(87Sr/86Sr)i变化较大,介于0. 706114～0. 718814之间,平均值为0. 713579,暗示相山铀矿田深部多金属矿化的成矿物质主要来源于地壳。初始流体Sr同位素值(0. 718665)明显高于成矿时赋矿围岩(流纹英安岩为0. 714581,碎斑流纹岩为0. 714417)的Sr同位素组成,表明多金属成矿流体和物质并非来自围岩火山岩;(3)由早到晚阶段的(87Sr/86Sr)i呈明显降低的演化趋势,表明成矿流体演化过程中受到大气降水的不断稀释作用。相山矿田的铀矿和深部多金属矿化同形成于华南中生代板内伸展构造背景。     

藏南冈底斯岩基东段中新世中酸性高Sr/Y比岩浆岩的地球化学特征及成因探讨

藏南冈底斯带广泛发育中新世中酸性高Sr/Y比岩浆岩,对该类型岩石的成因研究可为藏南后碰撞岩浆活动提供良好的记录和约束。通过对冈底斯带东段中酸性岩浆岩进行锆石U-Pb年代学研究表明,该中酸性岩浆岩形成于16～18Ma,为中新世时期;全岩地球化学数据表明岩浆岩具有高SiO_2含量( 64%),高钾富钠,高Sr、低Y和高Sr/Y比,轻稀土富集、重稀土亏损且较平坦的特征,显示出埃达克质岩的地球化学亲缘性;与冈底斯带中段～14Ma埃达克质闪长玢岩脉相比,冈底斯带东段的中新世岩浆岩具有更高的K含量;锆石Hf同位素分析结果表明,中新世中酸性岩浆岩具有正的且变化较大的εHf(t)值(+1. 2～+14. 4);全岩(La/Yb)N值对中新世地壳厚度的估算结果为77～84km,处于壳幔边界处。综合上述数据分析表明,冈底斯带东段中新世中酸性高Sr/Y岩浆岩的成因为拉萨地块加厚下地壳(占主体的新生下地壳+少量古老地壳)的部分熔融,并在源区残留了石榴子石和角闪石,造成熔融的热量来源可能为拉萨地体岩石圈根部拆沉导致的热扰动。     

In Situ U‐Th‐Pb Dating and Sr‐Nd Isotope Analysis of Bastnäsite by LA‐(MC)‐ICP‐MS

Bastnäsite is the end member of a large group of carbonate–fluoride minerals with the common formula (REE) CO₃F·CaCO₃. This group is generally widespread and, despite never occurring in large quantities, represents the major economic light rare earth element (LREE) mineral in deposits related to carbonatite and alkaline intrusions. Since bastnäsite is easily altered and commonly contains inclusions of earlier‐crystallised minerals, in situ analysis is considered the most suitable method to measure its U‐Th‐Pb and Sr‐Nd isotopic compositions. Electron probe microanalysis and laser ablation (multi‐collector) inductively coupled plasma‐mass spectrometry of forty‐six bastnäsite samples from LREE deposits in China, Pakistan, Sweden, Mongolia, USA, Malawi and Madagascar indicate that this mineral typically has high Th and LREE and moderate U and Sr contents. Analysis of an in‐house bastnäsite reference material (K‐9) demonstrated that precise and accurate U‐Th‐Pb ages could be obtained after common Pb correction. Moreover, the Th‐Pb age with its high precision is preferable to the U‐Pb age because most bastnäsites have relatively high Th rather than U contents. These results will have significant implications for understanding the genesis of endogenous ore deposits and formation processes related to metallogenic geochronology research.     

Paleoproterozoic volcanic rocks in the southern margin of the North China Craton,central China:Implications for the Columbia supercontinent

The volcanic rocks of the Xiong'er Group are situated in the southern margin of the North China Craton(NCC).Research on the Xiong er Group is important to understand the tectonic evolution of the NCC and the Columbia supercontinent during the Paleoproterozoic.In this study,to constrain the age of the Xiong'er volcanic rocks and identify its tectonic environment,we report zircon LA-ICP-MS data with Hf isotope,whole-rock major and trace element compositions and Sr-Nd-Pb-Hf isotopes of the volcanic rocks of the Xiong'er Group.The Xiong'er volcanic rocks mainly consist of basaltic andesite,andesite.dacite and rhyolite,with minor basalt.Our new sets of data combined with those from previous studies indicate that Xiong'er volcanism should have lasted from 1827 Ma to 1746 Ma as the major phase of the volcanism.These volcanics have extremely low MgO.Cr and Ni contents,are enriched in LREEs and LILEs but depleted in HFSEs(Nb,Ta,and Ti),similar to arc-related volcanic rocks.They are characterized by negative zircon ε_(Hf)_(t) values of-17.4 to 8.8,whole-rock initial ~(87)Sr/~(86)Sr values of 0.7023 to 0.7177 andε_(Nd)(t) values of-10.9 to 6.4.and Pb isotopes(~(206)Pb/~(204)Pb =14.366-16.431,~(207)Pb/~(204)Pb =15.106-15.371,~(208)Pb/~(204)Pb= 32.455-37.422).The available elemental and Sr-Nd-Pb-Hf isotope data suggest that the Xiong'er volcanic rocks were sourced from a mantle contaminated by continental crust.The volcanic rocks of the Xiong'er Group might have been generated by high-degree partial melting of a lithospheric mantle that was originally modified by oceanic subduction in the Archean.Thus,we suggest that the subduction-modified lithospheric mantle occurred in an extensional setting during the breakup of the Columbia supercontinent in the Late Paleoproterozoic,rather than in an arc setting.     

大陆风化与全球气候变化

:“构造隆升驱动气候变化”的假说是当前解释新生代以来全球气候变冷的主流观点。该假说把新生代以来发生的几个主要现象 ,即全球气候总体上趋冷 ,大气 CO2 浓度下降 ,海洋 87Sr/ 86Sr比值上升 ,以及构造作用引起的大面积隆升等加以有机的联系 ,给以了合理的解释。近几年围绕大陆风化和全球气候变化问题取得了一些新的进展 ,主要是对发源于喜马拉雅山的河流进行研究 ,探讨青藏高原隆起对于大陆风化速率的影响。这些争论主要是有关硅酸盐风化还是碳酸盐风化 ,有机碳的风化与埋藏 ,大陆风化与大气温度 ,大气 CO2 浓度与大气温度等问题。最后介绍了我国研究人员在黄土高原的黄土沉积地层所作的研究工作和取得的成果。