First Multi‐Isotopic (Pb‐Nd‐Sr‐Zn‐Cu‐Fe) Characterisation of Dust Reference Materials (ATD and BCR‐723): A Multi‐Column Chromatographic Method Optimised to Trace Mineral and Anthropogenic Dust Sources

Atmospheric dust is an integral component of the Earth system with major implications for the climate, biosphere and public health. In this context, identifying and quantifying the provenance and the processes generating the various types of dust found in the atmosphere is paramount. Isotopic signatures of Pb, Nd, Sr, Zn, Cu and Fe are commonly used as sensitive geochemical tracers. However, their combined use is limited by the lack of (a) a dedicated chromatographic protocol to separate the six elements of interest for low‐mass samples and (b) specific reference materials for dust. Indeed, our work shows that USGS rock reference materials BHVO‐2, AGV‐2 and G‐2 are not applicable as substitute reference materials for dust. We characterised the isotopic signatures of these six elements in dust reference materials ATD and BCR‐723, representatives of natural and urban environments, respectively. To achieve this, we developed a specific procedure for dust, applicable in the 4–25 mg mass range, to separate the six elements using a multi‐column ion‐exchange chromatographic method and MC‐ICP‐MS measurements.     

Paleoproterozoic juvenile magmatism within the northeastern sector of the São Francisco paleocontinent: Insights from the shoshonitic high Ba–Sr Montezuma granitoids

New,integrated petrographic,mineral chemistry,whole rock geochemical,zircon and titanite UPb geochronology,and zircon Hf isotopic data from the Montezuma granitoids,as well as new geochemical results for its host rocks represented by the Corrego Tingui Complex,provides new insights into the late-to post-collisional evolution of the northeastern Sao Francisco paleocontinent.U-Pb zircon dates from the Montezuma granitoids spread along the Concordia between ca.2.2 Ga to 1.8 Ga and comprise distinct groups.Group I have crystallization ages between ca.2.15 Ga and 2.05 Ga and are interpreted as inherited grains.Group II zircon dates vary from 2.04 Ga to1.9 Ga and corresponds to the crystallization of the Montezuma granitoids,which were constrained at ca.2.03 Ga by the titanite U-Pb age.Inverse age zoning is common within the ca.1.8 Ga Group III zircon ages,being related to fluid isotopic re-setting during the Espinhaco rifiting event.Zircon ε_(Hf)(t) analysis show dominantly positive values for both Group I(-4 to+9) and Ⅱ(-3 to+8) zircons and T_(DM2) model ages of 2.7-2.1 Ga and 2.5-1.95 Ga,respectively.Geochemically,the Montezuma granitoids are weakly peraluminous to metaluminous magnesian granitoids,enriched in LILES and LREE,with high to moderate Mg#and depleted in some of the HFSE.Their lithochemical signature,added to the juvenile signature of both inherited and crystallized zircons,allowed its classification as a shoshonitic high Ba-Sr granitoid related to a late-to post-collisional lithosphere delamination followed by asthenospheric upwelling.In this scenario,the partial melting of the lithospheric mantle interacted with the roots of an accreted juvenile intra-oceanic arc,being these hybrid magma interpreted as the source of the Montezuma granitoids.The Corrego Tingui Complex host rocks are akin to a syn-to late-collisional volcanic arc granitoids originated from the partial melting of ancient crustal rocks.The results presented in this study have revealed the occurrence of juvenile rocks,probably related to an island arc environment,that are exotic in relation to the Paleo-to Neoarchean crust from the Sao Francisco paleocontinent's core.     

滇东南南秧田钨矿床白钨矿原位Sr同位素对成矿的指示

南秧田钨矿床位于滇东南老君山W-Sn矿集区,地处扬子地块和印支地块的结合部位,地质背景复杂并遭受了多期岩浆活动和区域变质事件,其成矿时代和成因一直存在争议。本文对矽卡岩型和长石-石英脉型白钨矿开展了年代学、原位微量元素、Sr同位素研究,分析了两类白钨矿年龄、成因以及物质来源的差异。结果表明,长石-石英脉内与白钨矿共生辉钼矿的Re-Os同位素等时线年龄为151.0±1.3Ma,明显晚于矽卡岩矿体年龄,属于后期成矿事件。矽卡岩型白钨矿的轻稀土富集、重稀土强烈亏损,Eu呈明显负异常(δEu=0.46),∑REE平均含量为65.60μg/g,Mo平均含量为240.16μg/g,Sr平均含量为883.43μg/g;长石-石英脉型白钨矿稀土呈Eu正异常(δEu=2.8)的平坦型,∑REE平均含量为194.40μg/g,Mo平均含量为16.01μg/g,Sr平均含量为129.26μg/g。以上两者微量、稀土元素含量的差别显示它们具有性质明显不同的流体来源,Eu异常指示矽卡岩型白钨矿形成于氧逸度较高的环境,长石-石英脉型白钨矿形成于还原性环境。矽卡岩白钨矿~(87)Sr/~(86)Sr值相对较低,并且比较均一,介于0.71319～0.71491之间,表明成矿流体主要来自岩浆热液;长石-石英脉型白钨矿~(87)Sr/~(86)Sr值较高且变化范围大,介于0.71537～0.72803之间,平均0.72079,呈现出变质流体特征。两种不同类型白钨矿Sr同位素都具有二元混合的特征,显示长石-石英脉型白钨矿对矽卡岩型白钨矿有叠加改造作用,成矿流体与围岩的强烈交代作用是白钨矿形成的关键。     

4A沸石吸附模拟核素Sr,Cs后的组分变化和结构表征

通过4A沸石吸附模拟核素Sr,Cs前后的化学成分分析、X衍射分析和红外光谱分析等手段方法,分析探讨了模拟核紊Sr,Cs在4A沸石的赋存状态,结果表明：4A沸石与模拟核素Sr,Cs之间主要以离子交换的方式发生作用,Sr^2 ,Cs^ 取代4A沸石中的可交换离子Na^ ,占据4A沸石a笼中的6元环和8元环。导致4A沸石的晶胞参数增大,晶格发生畸变。     

In situ Pb and bulk Sr isotope analysis of the Yinchanggou Pb-Zn deposit in Sichuan Province (SW China): Constraints on the origin and evolution of hydrothermal fluids

The Yinchanggou Pb-Zn deposit, located in southwestern Sichuan Province, western Yangtze Block, is stratigraphically controlled by late Ediacaran Dengying Formation and contains >0.3 Mt of metal reserves with 11 wt% Pb + Zn. A principal feature is that this deposit is structurally controlled by normal faults, whereas other typical deposits nearby (e.g. Maozu) are controlled by reverse faults. The origin of the Yinchanggou deposit is still controversial. Ore genetic models, based on conventional whole-rock isotope tracers, favor either sedimentary basin brine, magmatic water or metamorphic fluid sources. Here we use in situ Pb and bulk Sr isotope features of sulfide minerals to constrain the origin and evolution of hydrothermal fluids. The Pb isotope compositions of galena determined by femtosecond LA-MC-ICPMS are as follows: ²⁰⁶Pb/²⁰⁴Pb = 18.17–18.24, ²⁰⁷Pb/²⁰⁴Pb = 15.69–15.71, ²⁰⁸Pb/²⁰⁴Pb = 38.51–38.63. These in situ Pb isotope data overlap with bulk-chemistry Pb isotope compositions of sulfide minerals (²⁰⁶Pb/²⁰⁴Pb = 18.11–18.40, ²⁰⁷Pb/²⁰⁴Pb = 15.66–15.76, ²⁰⁸Pb/²⁰⁴Pb = 38.25–38.88), and both sets of data plotting above the Pb evolution curve of average upper continental crust. Such Pb isotope signatures suggest an upper crustal source of Pb. In addition, the coarse-grained galena in massive ore collected from the deep part has higher ²⁰⁶Pb/²⁰⁴Pb ratios (18.18–18.24) than the fine-grained galena in stockwork ore sampled from the shallow part (²⁰⁶Pb/²⁰⁴Pb = 18.17–18.19), whereas the latter has higher ²⁰⁸Pb/²⁰⁴Pb ratios (38.59–38.63) than the former (²⁰⁸Pb/²⁰⁴Pb = 38.51–38.59). However, both types of galena have the same ²⁰⁷Pb/²⁰⁴Pb ratios (15.69–15.71). This implies two independent Pb sources, and the metal Pb derived from the basement metamorphic rocks was dominant during the early phase of ore formation in the deep part, whereas the ore-hosting sedimentary rocks supplied the majority of metal Pb at the late phase in the shallow part. In addition, sphalerite separated from different levels has initial ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7101 to 0.7130, which are higher than the ore formation age-corrected ⁸⁷Sr/⁸⁶Sr ratios of country sedimentary rocks (⁸⁷Sr/⁸⁶Sr_200 Ma = 0.7083–0.7096), but are significantly lower than those of the ore formation age-corrected basement rocks (⁸⁷Sr/⁸⁶Sr_200 Ma = 0.7243–0.7288). Again, such Sr isotope signatures suggest that the above two Pb sources were involved in ore formation. Hence, the gradually mixing process of mineralizing elements and associated fluids plays a key role in the precipitation of sulfide minerals at the Yinchanggou ore district. Integrating all the evidence, we interpret the Yinchanggou deposit as a strata-bound, normal fault-controlled epigenetic deposit that formed during the late Indosinian. We also propose that the massive ore is formed earlier than the stockwork ore, and the temporal-spatial variations of Pb and Sr isotopes suggest a certain potential of ore prospecting in the deep mining area.     

Early Cretaceous porphyry copper mineralization in Northeast China: the Changfagou example

The Changfagou Cu deposit is a newly discovered porphyry deposit located in the southern Jilin Province of Northeastern China, on the northeastern margin of the North China Craton. To better understand the formation of the Cu deposit, we report the zircon U–Pb and molybdenite Re–Os dating, and Sr-, Nd-, and Hf- isotopic data of the granite porphyry. LA-ICP-MS dating of zircon grains from two mineral zones in the granite porphyry yield ages of 115.7 ± 0.8 and 115.3 ± 0.6 Ma, which is interpreted as the emplacement age of the granite porphyry. The molybdenite Re–Os model ages of 112.5 to 113.8 Ma, an isochron age of 113.3 ± 1.3 Ma, and a weighted mean model age of 113.0 ± 0.7 Ma, which represents the age of the Cu mineralization quite well. The Changfagou granite porphyry samples lack amphibole and muscovite, and are compositionally characterized by high SiO₂, high Na₂O+K₂O, and low P₂O₅, enriched in some Rb, Th, U, and Pb, and depleted in Nb, Ta, Ti, P, and Eu. Mineralogical and geochemical features suggest that the Changfagou granite porphyry samples are slightly peraluminous and are of highly fractionated I-type granitoids. The granitic rocks also have relatively high (⁸⁷Sr/⁸⁶Sr)_i (0.71199 to 0. 71422), and both low εNd(t) (?14.56 to ?13.19) and εHf(t) values (?14.916 to ?8.644), which suggest that Changfagou granite porphyry are derived from mixed sources of crustal and mantle, and diagenesis and mineralization were possibly related to the switch in subduction direction of the Palaeo-Pacific Plate in the late phase of Early Cretaceous.     

Petrogenesis and metallogenic potential of the Jurassic porphyries in the northwest Zhejiang Province,South China: insights from SHRIMP zircon geochronology,geochemistry, and Sr–Nd–Hf isotopes of the Huangbaikeng ore-bearing porphyries

The northwest Zhejiang Province is a key domain for providing deep insight into the crust–mantle interaction and tectonic evolution of the South China block. In this paper, we collect geochemical, geochronological, and isotopic data of the Jurassic porphyries in this region, and investigated the Huangbaikeng ore-bearing porphyry in the Tongcun Mo–Cu deposit, using it as an example to uncover the porphyry petrogenesis and evaluate their metallogenic potential. Two varieties of the Huangbaikeng porphyry were distinguished: the medium- to coarse-grained type and medium- to fine-grained type. Zircon Sensitive High-Resolution Ion Microprobe U–Pb dating indicates that they were emplaced at 161.8 ± 2.8 and 162.7 ± 3.5 Ma, respectively, which are consistent with the molybdenite Re–Os ages of 163.9–161.8 Ma. The inherited zircons age spectrum significantly recorded a series of geological events, for example, assembly and breakup of the Columbia and Rodinia supercontinent, and the Triassic collision of Yangtze and North China blocks. Whole rock Sr–Nd and Jurassic zircon Hf isotopic data yield mostly negative ε_Hf(t) values (0.5 to ?8.4) and ε_Nd(t) values (?0.79 to ?4.82). Besides the Huangbaikeng porphyry, all the Jurassic porphyries in the northwest Zhejiang Province have a wide range of SiO₂ contents (76.78–60.91 wt.%). They do not contain typical aluminous minerals (e.g. cordierite and garnet), and are mainly metaluminous to weakly peraluminous with high Na₂O, low FeO^T/MgO, and Zr + Nb + Ce + Y concentrations in composition. They thus fit the I-type granite definition. Some major and trace elements show strong correlations with SiO₂, possibly indicating extensive fractional crystallization during their magma evolution. Tectonic discriminations imply that these plutons were likely formed in a volcanic arc regime possibly related to subduction of the Palaeo-Pacific plate. Sr–Nd–Hf isotopic data suggest a mixed source of the Mesoproterozoic crust and 30–50% mantle components. Compared with the adjacent Dexing Cu-bearing porphyies, which have more positive ε_Hf(t) and ε_Nd(t) values with more significant mantle components (55–70%), the Jurassic porphyries in the northwest Zhejiang Province probably lack metallogenic potential to form a giant porphyry copper deposit as Dexing.     

Geochemistry of late Palaeozoic granitoids of the Balkhash metallogenic belt,Kazakhstan: implications for crustal growth and tectonic evolution of the Central Asian Orogenic Belt

ABSTRACT

The Balkhash metallogenic belt (BMB) in Kazakhstan is a famous porphyry Cu–Mo metallogenic belt in the Central Asian Orogenic Belt (CAOB). The late Palaeozoic granitoids in the BMB are mainly high-K calc-alkaline and I-type granites, with shoshonite that formed during a late stage. Geochemical analyses and tectonic discrimination reveal a change in the tectonic environment from syn-collision and volcanic arcs during the Carboniferous to post-collision during the Permian. The late Palaeozoic granitoids from the Borly porphyry Cu deposit formed in a classical island-arc environment, and those from the Kounrad and Aktogai porphyry Cu deposits and the Sayak skarn Cu deposit are adakitic. The ε_Nd(t) values for the late Palaeozoic granitoids are between ?5.87 and +5.94, and the ε_Sr(t) values range from ?17.16 to +51.10. The continental crustal growth histories are different on either side of the Central Balkhash fault. On the eastern side, the ε_Nd(t) values of the granitoids from the Aktogai and Sayak deposits are very high, which are characteristic of depleted mantle and suggest that crustal growth occurred during the late Palaeozoic. On the western side, the ε_Nd(t) values of the granitoids from the Borly and Kounrad deposits are slightly low, which suggests the presence of a Neoproterozoic basement and the mixing of crust and mantle during magmatism. The granitoids have initial ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of 18.335–20.993, 15.521–15.732, and 38.287–40.021, respectively, which demonstrate an affinity between the late Palaeozoic magmatism in the BMB and that in the Tianshan, Altai, and Junggar orogens.     

Concentrations of 137Cs, 90Sr, 108m Ag, 239+240 Pu and atom ratio of 240Pu/239Pu in tanner crabs, Chionoecetes japonicus and Chionoecetes opilio collected around Japan

The anthropogenic radionuclides, ¹³⁷Cs, ⁹⁰Sr, ^108mAg, ^239+240Pu, were measured in two Chionoecetes species, red queen crab (Chionoecetes japonicus) and snow crab (Chionoecetes opilio) collected around Japan during 1996–2007. There was no increase in the concentrations of these radionuclides and no large variation of the atom ratio of ²⁴⁰Pu/²³⁹Pu during this research period. These results indicated that the source of the radionuclides was not the radioactive wastes dumped by the former USSR and Russia and originated from past nuclear weapon tests. The higher atom ratio in the crab species than that from global fallout would be contributed by the Pacific Proving Grounds close-in fallout. The variability of the concentration of radionuclides in the crab species would result from the variability of the composition and quantity in the diet. However, the decrease in the concentration of radionuclides with sampling depth would depend on the concentration in the seawater and diet.