Optimised Ferrozine Micro‐Method for the Determination of Ferrous and Ferric Iron in Rocks and Minerals

The ferrozine wet chemical method was optimised for the determination of the total iron content and speciation in small geological samples. The ferrozine micro‐method involves dissolution by a mixture of HF and H₂SO₄ followed by spectrophotometric analysis using the complexing agent ferrozine. The method was tested for twenty‐one replicates of eight rock RMs using test portions of 5–14 mg and containing 0.37–5.45 mg total Fe and more than 0.29 mg Fe(II). The optimised ferrozine method was accurate to within 0.23% m/m FeO and 0.34% m/m total Fe, which compares favourably to other wet chemical methods.     

Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials

Geochemical studies of geological samples require the precise determination of their major and trace element contents and, when measured, of their isotopic compositions. It is now commonly accepted that the accuracy and precision of geochemical analyses are best estimated by the concomitant analysis of international reference materials run as unknown samples. Although the composition of a wide selection of basalts is relatively well constrained, this is far from being the case for sedimentary materials. We present here a comprehensive set of major and trace element data as well as Nd, Hf, Sr and Pb isotopic compositions for thirteen commonly used international reference materials – eight magmatic rocks (BHVO‐2, BR, BE‐N, BR 24, AGV‐1, BIR‐1, UB‐N, RGM‐1) and five sediments (JLk‐1, JSd‐1, JSd‐2, JSd‐3, LKSD‐1). We determined the concentrations of over forty elements in the magmatic rocks together with Sr, Nd, Hf and Pb isotopic compositions. Our trace element results were both accurate (difference ≤ 3%) and precise (reproducibility at 1s ≤ 3%) and the isotopic results were very similar to other published values. In contrast, we observed a significant chemical and isotopic variability in the sedimentary materials, which we attribute to mineral heterogeneities in the powders. Despite the limitation imposed by this heterogeneity, our work presents a complete set of data determined with a precision not yet achieved in the literature for sedimentary material. We also provide the first Nd, Hf and Pb isotopic measurements for the five sediments, which are commonly used by the geochemical community. Our study of both basalt and sediment reference materials represents a comprehensive and self‐consistent set of geochemical data and can therefore be considered as a reference database for the community.     

Non‐Matrix‐Matched Calibration for the Multi‐Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA‐ICP‐MS: A Comparison with Nanosecond Lasers

LA‐ICP‐MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non‐matrix‐matched calibration. We therefore investigated matrix‐related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP‐213) laser. The ion intensity of the 200 nm fs laser ablation was much lower than that of the 213 nm Nd:YAG laser, because the ablation rate was a factor of about 30 lower. Our experiments did not show significant matrix dependency with the 200 nm fs laser. Therefore, a non‐matrix‐matched calibration for the multi‐element analysis of quite different matrices could be performed. This is demonstrated with analytical results from twenty‐two international synthetic silicate glass, geological glass, mineral, phosphate and carbonate reference materials. Calibration was performed with the certified NIST SRM 610 glass, exclusively. Within overall analytical uncertainties, the 200 nm fs LA‐ICP‐MS data agreed with available reference values.     

The Potassium‐Argon Laser Experiment (KArLE): In Situ Geochronology for Planetary Robotic Missions

Geochronology is a fundamental measurement for planetary samples, providing global and solar system context for the conditions prevailing on the planet at the time of major geological events. The potassium (K)‐Argon (Ar) laser experiment (KArLE) will make in situ noble gas geochronology measurements aboard planetary robotic missions such as rovers and landers. Laser‐induced breakdown spectroscopy (LIBS) is used to measure the K abundance in a sample and to release its noble gases; the evolved Ar is measured by mass spectrometry, and relative K content is related to absolute Ar abundance by sample mass, determined by optical measurement of the ablated volume. This approach allows K and Ar to be measured on identical volumes multiple times to create an isochron, which improves the age determination and reveals irregularities in the rock if they exist. The KArLE technique measures a whole‐rock K‐Ar age with 10% uncertainty or better for rocks 2 Ga or older, sufficient to resolve the absolute age of many planetary samples. The LIBS–mass spectrometry approach is attractive because the analytical components have been flight‐proven, do not require further technical development and provide essential measurements (complete elemental abundance, evolved volatile analysis, micro‐imaging) as well as in situ geochronology.     

Elemental Concentrations of Stream Sediments in Southern China

Over 3 million samples were collected from southern China at a density of 1–2 stream sediment samples per square kilometre as part of the Regional Geochemistry National Reconnaissance (RGNR) programme of China initiated in the late 1970s. Approximately 5244 composite samples of stream sediments from twelve provinces of southern China were prepared from the original RGNR samples collected from a territory with an area of 2300000 km² at a density of one composite sample per 1:50000 map sheet (about 400 km²). Seventy‐six elements were determined by the geoanalysis laboratory of Henan Province (platinum‐group elements) and by the Institute of Geophysical and Geochemical Exploration (IGGE) laboratory for the remainder. Internal quality and external quality control methods were applied to ensure that the analytical data were comparable. Statistics were used to derive the mean and background values and indicate the average concentrations of the seventy‐six elements. Comparisons were made against the mean values obtained from stream sediments, floodplain sediments, overall sediments and overall soils of the entire territory of China. The concentrations of Hg, Cd, rare earth elements and 24 other elements were higher than their background for the whole of China. In contrast, the concentration of Na₂O, CaO, Ba and Sr were lower in the stream sediments in southern China than their whole China background.     

Effects of the Chemical Compositions of Salars de Uyuni and Atacama Brines on Lithium Concentration during Evaporation

During Li recovery from salar brines, Li concentration is typically increased to about 60,000 mg L^?1 by evaporation. We investigated the concentration changes of Li, Na, K, Mg, Cl, SO₄, and B during evaporation of both natural Uyuni and artificial Atacama brines. The Uyuni brine exhibited a maximum Li concentration of 6810 mg L^?1 at 31 days of evaporation, at which point the majority of the Na and K in the brine was removed. The Li concentration decreased with further evaporation due to precipitation as Li₂SO₄, such that the level at the 56 day mark was approximately 4130 mg L^?1. In contrast, the artificial Atacama brine showed no pronounced Li precipitation, even after 54 days, at which point the Li concentration was 21,800 mg L^?1. The initial concentrations of Na and K in the Atacama brine were higher than those in the Uyuni brine, and the Atacama solution still retained K after 54 days of evaporation. The order of precipitation of cation species during the evaporation of both brines was: Na, followed by K, Mg, and Li. Thus, Li precipitation in the Atacama brine might be prevented due to the more favored precipitations of Na and K, such that significant Li removal did not occur in this brine.     

Provenance of metasedimentary rocks of the Western Pernambuco-Alagoas Domain: Contribution to understand the crustal evolution of southern Borborema Province

The Borborema Province is a complex neoproterozoic orogen in northeastern Brazil, made of a mosaic of fault-bounded terrains and several metassedimentary sequences. In the present work, new zircon U–Pb provenance data for metasedimentary rocks in the Western Pernambuco-Alagoas Domain, southern part of the Province, are reported. Detrital zircon ages range from Archean to Neoproterozoic. Three samples of the Cabrobó Complex were investigated: (i) sillimanite-kyanite-garnet-biotite schist, which presented mostly Ediacaran and Cryogenian detrital zircon ages (youngest zircon at ca. 554 Ma) indicating erosion of neoproterozoic sources, (ii) garnet-biotite schist, which has a dominant Tonian/Stenian population, a less abundant Cryogenian (youngest zircon age at ca. 643 Ma) as well as Paleoproterozoic and Archean zircon grains, and (iii) tourmaline-muscovite quartzite, which contains detrital zircon varying in age between ca. 2.08 Ga and 1.57 Ga, and an abundant population close to the Meso/Paleoproterozoic boundary, possibly associated with the erosion of rocks formed during the Statherian taphrogenesis, known in the central part of the São Francisco Craton as well as in other areas of the Borborema Province. Two samples of the Riacho Seco Metasedimentary Complex were also investigated: (i) a biotite schist with a dominant population presenting ages mostly between 2.3 and 2.7 Ga (youngest zircon age at ca. 2023 Ma) and (ii) a magnetite-biotite-muscovite quartzite, having detrital zircon grains with ages ranging between ca. 1.9 and 2.7 Ga. The sedimentary rocks of the Riacho Seco Complex may have their origin related to the erosion of sources within the São Francisco Craton. The data for the Riacho Seco metasedimentary rocks, however, are not conclusive with respect to the depositional age of the original sedimentary rocks. The sequence might represent exposure of an old (Paleoproterozoic) sedimentary pile or, alternatively, it comprises a neoproterozoic passive margin sequence, with the original sediments derived from the erosion of the cratonic areas to the south.     

南美玻利维亚重点盆地油气地质特征和勘探潜力评价

基于对玻利维亚区域构造演化与沉积充填特征的分析,研究盆地烃源岩、储集层及盖层等油气成藏地质条件的差异,分析盆地勘探潜力。玻利维亚境内发育查科、贝尼和马德雷德迪奥斯等3个重点盆地,均是在前寒武系基底基础上发育起来的叠合盆地,盆内依次充填了古生代克拉通边缘海相沉积层序、三叠纪-白垩纪裂谷期海相-海陆过渡沉积层序和晚白垩世至今前陆陆相沉积层序。油气成藏地质条件综合对比分析认为,3个盆地均发育泥盆系主力烃源岩,储集层以泥盆系-石炭系和白垩系砂岩为主,发育古生界泥岩和碳酸盐岩及古近系泥岩等多套区域盖层。成熟烃源岩主要分布在冲断带和前渊区,油气必须通过垂向和侧向运移才能聚集成藏,具有晚期生烃、晚期成藏的特点。马德雷德迪奥斯盆地前渊-斜坡带低幅构造圈闭和地层圈闭、查科盆地和贝尼盆地逆冲褶皱带构造圈闭是主要的勘探目标。