Reference Materials in Geoanalytical Research -Review for 2004 and 2005

This review gives an overview of the use and development of reference materials of geochemical and environmental interest in the literature of the years 2004 and 2005. In these years the performance of existing methods has been improved and new geochemical applications using new techniques have been developed. Accordingly, there was an increasing need for new reference materials, especially for in situ microanalysis and for precise stable isotope measurements. In addition, there was a notable trend for further characterisation of existing reference materials, mainly for the platinum-group elements. This review focuses on five topics: reference materials for platinum-group elements, reference glasses for in situ microanalysis, zircon reference materials, isotopic reference materials, and the development and certification of reference materials.     

Variscan to eo-Alpine events recorded in European lower-crust zircons sampled from the French Massif Central and Corsica, France

Ion-microprobe U–Pb zircon dating of lower-crust metasedimentary granulite are reported on samples from two localities in Europe in order to determine (a) how this environment recorded the Variscan and eo-Alpine events, and (b) whether the transition between the two orogenic cycles was continuous or separated by a gap. The samples come from enclaves hosted by Miocene volcanoes at Bournac in the French Massif Central, and from the granulitic metasedimentary basement of the Alpine Santa Lucia nappe in Corsica, on the South European paleomargin of the Ligurian branch of the Tethys Sea. The zircon ages from Bournac range between 630 and 430 Ma and between 380 and 150 Ma with a major frequency peak at 285 Ma; the zircons older than 430 Ma are interpreted as detrital, whereas those younger than 380 Ma are considered to have formed by metamorphic processes after burial in the lower crust. Zircon ages from Santa Lucia range from to 356 to 157 Ma, with exception of one inherited Archean grain, and are interpreted like the younger Bournac zircons as having been formed by metamorphic processes.

In a granulite metamorphic environment, as opposed to an anatectic environment, new zircon growth can occur in the solid state. Once Zr has been incorporated into zircon, however, it is difficult to remobilize without dissolution; thus Zr available for new zircon growth must result from the breakdown of Zr-bearing minerals during prograde and/or retrograde events. In this light, the U–Pb zircon-age probability curves are interpreted as markers for major tectonometamorphic events, as suggested by the close correspondence between peaks in the curve and geological events recorded in the upper-crust, such as magma emplacement and basin subsidence.

Evidence of a tectonometamorphic gap between the Variscan and Alpine orogeneses is provided by the Santa Lucia zircon-age probability curve, which reveals a probable interlude during the Variscan–Alpine transition between 240 and 210 Ma. Here, the peak at 240 Ma is interpreted as the very beginning of crustal extension and the low at 210 Ma as a period of quiescence prior to the formation of an active margin and oceanization.     

Metal sources of the Navan carbonate-hosted base metal deposit, Ireland: Nd and Sr isotope evidence for deep hydrothermal convection

Nd and Sr isotope analyses are presented for gangue mineral samples from the giant carbonate-hosted Navan Zn–Pb deposit, Ireland, and for rocks from which Navan metals may have been derived. Analysis of gangue minerals spanning the Navan paragenetic sequence reveals systematic evolution in the composition of the mineralising fluid. Early fluid represented by replacive dolomite exhibits the lowest initial ⁸⁷Sr/⁸⁶Sr ratio (0.7083–0.7086), closest to that of the host limestone and to Lower Carboniferous seawater, and the highest ¹⁴³Nd/¹⁴⁴Nd ratio (0.51161–0.51176). Later generations of dolomite, barite and calcite, which encompass sulphide precipitation, have higher initial ⁸⁷Sr/⁸⁶Sr ratios (maximum 0.7105) and lower initial ¹⁴³Nd/¹⁴⁴Nd ratios (minimum 0.51157). All samples have initial Nd isotope ratios that are too low to have been acquired only from the host limestone. Drill core samples of presumed Ordovician volcanic and sedimentary rocks from beneath the Navan orebody have ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr ratios at the time of mineralisation of 0.51184–0.51217 and 0.7086–0.7138, respectively. The data are interpreted to indicate mixing of sulphide-rich, limestone-buffered brine, with a metal-bearing hydrothermal fluid, which had passed through sub-Carboniferous rocks, consistent with published fluid inclusion and S isotope data. The ¹⁴³Nd/¹⁴⁴Nd ratio of this basement-derived fluid is too low to have been imparted by flow through the Devonian Old Red Sandstone, as required in models of regional fluid flow in response to Hercynian uplift. Irrespective of whether such regional fluid flow occurred, the hydrothermal Nd must have been derived from sub-Devonian rocks. These conclusions broadly support the hydrothermal convection cell model in which brines, ultimately of surface origin, penetrated to a depth of several kilometres, leaching metals from the rocks through which they passed. The data also support increasing depth of penetration of convection cells with time. Metals were subsequently precipitated in carbonate rocks at sites of mixing with cooler, sulphide-rich fluids. However, comparison of the Navan hydrothermal gangue Nd–Sr isotope data with data from Lower Palaeozoic rocks strongly suggests that the latter cannot alone account for the “basement” signature. As the Navan deposit lies immediately north of the Iapetus Suture, this suggests that the Laurentian margin includes Precambrian basement.     

Post-depositional 137Cs Mobility in the Sediments of Three Shallow Coastal Lagoons, SW England

We present ¹³⁷Cs profiles for three low lying coastal lagoons in Southwest England that show a decline in activity with sediment depth. ¹³⁷Cs inventories are lower than expected by comparison with local reference inventories despite the fact that sampling was undertaken in the deep-water zone of each lake where sediment and ¹³⁷Cs focusing would be expected. At all three locations, lake sediment ⁷Be and unsupported ²¹⁰Pb (²¹⁰Pb_un) inventories are not significantly lower than the local reference inventory. ¹³⁷Cs inventories in the study cores range from 38 to 95% of local reference inventories. The standing water level and mud: water interface at two sites are below maximum tide level and, at all three sites, salinity increases significantly in the water columns between low and high tide and in the pore waters of the underlying sediments. We suggest that the difference in hydrostatic pressure between sea level and standing water levels in the lagoons forces salt water up through the sediment column and that monovalent cations (especially Na⁺ and K⁺) replace ¹³⁷Cs on exchange sites leading to the upward migration and loss of ¹³⁷Cs. Rising sea levels may therefore contribute to remobilisation and release of ¹³⁷Cs to the aquatic environment from the sediments of coastal lagoons.     

Lead, zinc, and antimony contamination of the Rio Chilco-Rio Tupiza drainage system, Southern Bolivia

An intense, but localized rainfall event in February 2003, led to the severe erosion and failure of a tailings disposal impoundment at the Abarόa Antimony Mine in southern Bolivia. The failure released approximately 5,500 m³ of contaminated tailings into the Rio Chilco-Rio Tupiza drainage system. The impacts of the event on sediment quality are examined and compared to contamination resulting from historic mining operations in the headwaters of the basin. Of primary concern are contaminated floodplain soils located along downstream reaches of the Rio Tupiza which were found to contain lead (Pb), zinc (Zn), and antimony (Sb) concentrations that locally exceed Canadian, German, and Dutch guidelines for agricultural use. Spatial patterns in sediment-borne trace metal concentrations, combined with Pb isotopic data, indicate that Pb, Zn, and Sb are derived from three tributary basins draining the Abarόa, Chilcobija, and Tatasi-Portugalete mining districts. Downstream of each tributary, geographical patterns in trace metal concentrations reflect local geomorphic changes throughout the drainage system. Trace metal concentrations within the Rio Chilco decrease rapidly downstream as a result of dilution by uncontaminated sediments and storage of metal enriched particles (e.g., sulfide minerals) in the channel bed as a result of ongoing aggradation. Storage in the floodplains is limited. These processes significantly reduced the dispersal and, thus, the relative environmental affects of tailings eroded from the Abarόa Mine during the 2003 flood. In contrast, storage of Pb, Zn, and Sb in floodplains along the Rio Tupiza is significant, the majority of which is derived from historic mining operations, particularly mining within the Tatasi-Portugalete district.     

Early Cretaceous U–Pb zircon ages for the Copiapó plutonic complex and implications for the IOCG mineralization at Candelaria, Atacama Region, Chile

Four of the major plutons in the vicinity of the Candelaria mine (470 Mt at 0.95% Cu, 0.22 g/t Au, 3.1 g/t Ag) and a dike–sill system exposed in the Candelaria open pit have been dated with the U–Pb zircon method. The new geochronological data indicate that dacite magmatism around 123 Ma preceded the crystallization of hornblende diorite (Khd) at 118 ± 1 Ma, quartz–monzonite porphyry (Kqm) at 116.3 ± 0.4 Ma, monzodiorite (Kmd) at 115.5 ± 0.4 Ma, and tonalite (Kt) at 110.7 ± 0.4 Ma. The new ages of the plutons are consistent with field relationships regarding the relative timing of emplacement. Plutonism temporally overlaps with the iron oxide Cu–Au mineralization (Re–Os molybdenite ages at ∼115 Ma) and silicate alteration (ages mainly from 114 to 116 and 110 to 112 Ma) in the Candelaria–Punta del Cobre district. The dated dacite porphyry and hornblende diorite intrusions preceded the ore formation. A genetic link of the metallic mineralization with the quartz–monzonite porphyry and/or the monzodiorite is likely. Both of these metaluminous, shoshonitic (high-K) intrusions could have provided energy and contributed fluids, metals, and sulfur to the hydrothermal system that caused the iron oxide Cu–Au mineralization. The age of the tonalite at 110.7 Ma falls in the same range as the late alteration at 110 to 112 Ma. Tonalite emplacement may have sustained existing or driven newly developed hydrothermal cells that caused this late alteration or modified ⁴⁰Ar/³⁹Ar and K/Ar systematic in some areas.     

华南下寒武统镍钼矿层中铜铅锌矿物的发现及意义

华南扬子地块是我国古热水沉积成矿作用最为发育的地区之一,其热水沉积特性最早引起我国学者的关注。华南下寒武统黑色岩系中赋存多个与热水沉积成矿作用相关的大型、超大型重晶石矿床与N i-Mo-U-V多金属富集层。进一步研究分布在华南扬子地块黑色岩系中的金属、非金属矿床成因及其地球化学特征,对认识华南乃至全球晚震旦—早寒武世生物与环境演化有着十分重要的意义。本文对华南下寒武统镍-钼富集层矿石进行电子探针研究,识别出黄铜矿、黝铜矿等铜的独立矿物;闪锌矿等锌的独立矿物;方铅矿、白铅矿等铅的独立矿物。研究表明,在镍-钼矿石中这些矿物的发现为镍-钼矿层是热水沉积作用产物提供了直接的矿物学证据。     

Early Proterozoic syn-and postcollision granites in the northern part of the Baikal fold area

Early Proterozoic granitoids are of a limited occurrence in the Baikal fold area being confined here exclusively to an arcuate belt delineating the outer contour of Baikalides, where rocks of the Early Precambrian basement are exposed. Geochronological and geochemical study of the Kevakta granite massif and Nichatka complex showed that their origin was related with different stages of geological evolution of the Baikal fold area that progressed in diverse geodynamic environments. The Nichatka complex of syncollision granites was emplaced 1908 ± 5 Ma ago, when the Aldan-Olekma microplate collided with the Nechera terrane. Granites of the Kevakta massif (1846 ± 8 Ma) belong to the South Siberian postcollision magmatic belt that developed since ～1.9 Ga during successive accretion of microplates, continental blocks and island arcs to the Siberian craton. In age and other characteristics, these granites sharply differ from granitoids of the Chuya complex they have been formerly attributed to. Accordingly, it is suggested to divide the former association of granitoids into the Chuya complex proper of diorite-granodiorite association ～2.02 Ga old (Neymark et al., 1998) with geochemical characteristics of island-arc granitoids and the Chuya-Kodar complex of postcollision S-type granitoids 1.85 Ga old. The Early Proterozoic evolution of the Baikal fold area and junction zone with Aldan shield lasted about 170 m.y. that is comparable with development periods of analogous structures in other regions of the world.     

Zircon LA-ICP-MS U-Pb age, Ce^4＋/Ce^3＋ ratios and the geochemical features of the Machangqing complex associated with copper deposit

1IntroductionQuite a number of porphyry copper deposits havebeen found in the Cenozoic alkali-intrusions along theJinshajiang-Ailaoshan-Red River fault zone,whichconstitute the Cenozoic ore belt in China.The Cenozo-ic alkali-intrusive rocks are similar in…     

Detrital Zircon of 4100 Ma in Quartzite in Burang, Tibet

A detrital zircon aged 4.1 Ga is discovered by the SHRIMP U-Pb method in a quartzite in Burang County, western Tibet. This is presently the oldest single-grain detrital zircon in China. The Th-U ratios of the two testing points of the 〉4.0 Ga zircon are between 0.76 and 0.86, indicating their magmatic origin. This discovery has offered an important age for investigating the geological evolution of the Qinghai-Tibet Plateau.