Speleothem preservation and diagenesis in South African hominin sites implications for paleoenvironments and geochronology

Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ¹³C values of the primary and secondary calcites range from +6 to −9‰ and δ¹⁸O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ¹³C and relatively invariant δ¹⁸O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO₂ during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C₃ and C₄ vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.     

Partitioning of trace elements between rutile and silicate melts: Implications for subduction zones

Mineral/melt trace element partition coefficients were determined for rutile (TiO₂) for a large number of trace elements (Zr, Hf, Nb, Ta, V, Co, Cu, Zn, Sr, REE, Cr, Sb, W, U, Th). Whilst the high field strength elements (Zr, Hf, Nb, Ta) are compatible in rutile, other studied trace elements are incompatible (Sr, Th, REE). In all experiments we found D_Ta > D_Nb, D_Hf > D_Zr and D_U > D_Th. Partition coefficients for some polyvalent elements (Sb, W, and Co) were sensitive to oxygen fugacity. Melt composition exerts a strong influence on HFSE partition coefficients. With increasing polymerization of the melt, rutile/melt partition coefficients for the high field strength elements Zr, Hf, Nb and Ta increase about an order of magnitude. However, D_Nb/D_Ta and D_Hf/D_Zr are not significantly affected by melt composition. Because D_U ? D_Th, partial melting of rutile-bearing eclogite in subducted lithosphere may cause excesses of ²³⁰Th over ²³⁸U in some island arc lavas, whereas dehydration of subducted lithosphere may cause excesses of ²³⁸U over ²³⁰Th. From our partitioning results we infer partition coefficients for protactinium (Pa) which we predict to be much lower than previously anticipated. Contrary to previous studies, our data imply that rutile should not significantly influence observed ²³¹Pa-²³⁵U disequilibria in certain volcanic rocks.     

Geochemistry of the trace elements and rare-earth elements at the boundary between Cambrian Series 2 and Series 3 at Jianshan, South China: Paleoenvironmental and stratigraphic implications

The Jianshan section in Jianhe County,Guizhou Province,is a very important auxiliary section to the candidate stratotype at the boundary between Cambrian Series 2 and Series 3.Twenty four samples collected from the Jianshan section of the Kaili Formation were analyzed for the concentrations of trace element and rare-earth elements(REEs) by inductively coupled plasma mass spectrometry.The trace element and REE geochemical characteristics of the Kaili Formation at the Jianshan section show that trace element composition and REE distribution patterns across the section are covariant.Notably,at 44 m above the base of the Kaili Formation,most trace element contents and REEs concentrations are lower than those values observed below 44 m.Above 44 m,an increasing trend in the concentration of both trace elements and REEs is observed.These geochemical data indicate important,but subtle,changes at the 44 m horizon.If this is,in fact,verified by work in progress,geochemical criteria can provide additional supports for defining the top surface of Cambrian Series 2,especially in sections where Oryctocephalus indicus is absent.Trace element ratios,specifically Ni/Co,V/Cr,V/(Ni+V) and Th/U as well as Ce and Eu anomalies indicate that the sedimentary environment of the Kaili Formation at the Jianshan section was oxidizing,that benthic redox conditions were less oxic,and may have been influenced by freshwater as compared to the Balang area.Moreover,the Eu anomalies observed in the Kaili Formation are similar to the negative Eu anomalies observed in post-Archean sedimentary rocks,and reveal fluctuations in oxygen content from the bottom to the top of the Kaili Formation.     

Solid sedimentation rates history of the Southern African continental margins: Implications for the uplift history of the South African Plateau

The Cretaceous and Cenozoic fill of the continental margins of southern Africa (South‐East Atlantic and Agulhas Margins) contains a continuous record of sediment supplied from the South African Plateau (SAP) for the past 134 million years. Estimates of solid sediment volumes deposited offshore were calculated from isopach maps and extrapolated vertical cross‐sections derived from a large amount of industrial geophysical data. Solid phase volumes and accumulation rates were calculated for six epochs: Lower Cretaceous (134–113 Ma), Mid Cretaceous (113–93.5 Ma), Upper Cretaceous (93.5–81 and 81–66 Ma), Palaeogene (66–25 Ma), Neogene (25–0 Ma). Our new compilation demonstrates the existence of two periods of elevated flux. The most important one occurs in the late Cretaceous (93.5–66 Ma) and was synchronous with an acceleration of onshore denudation as shown by thermochronometric data. After a period of extremely low accumulation rate, the second phase of elevated flux started in the Oligocene (~30–25 Ma) until present‐day. From these observations we suggest that the main phase of uplift of the SAP took place during the Upper Cretaceous. Two mechanisms, namely uplift caused by lithospheric delamination or by dynamic topography caused by the continent moving over the African Superplume, are viable explanations for our observations. The more recent and lower amplitude episode of enhanced accumulation rates is likely to correspond to a second period of uplift, potentially associated with the onset of uplift and extension along the East African Rift System.     

Ozonation of triterpenoids: Implications for early diagenesis of biomarkers in oxic environments

This study examines the fate of commonly found organic natural products under exposure to ozone to simulate early oxic diagenesis. The model compounds β-amyrin, lupenone and friedelin have been investigated by ozonation in the presence of water. The transformation products were identified or proposed based on their fragmentation patterns in mass spectra. The double bonds located at the isopropenyl group of lupenone and ring C of β-amyrin are the main reaction sites in the ozonation reaction. The major products identified from the ozonation of β-amyrin are β-amyrone, 12,13-epoxyoleanan-3β-ol, 11-oxo-olean-12-en-3β-ol, 12-oxo-oleanan-3β-ol. In addition, 8,14-seco-12-oxo-olean-14-en-3β-ol, 8,14-seco-12-oxo-olean-13-en-3β-ol and 8,14-seco-oleana-3,12-dione, generated from the bond cleavage between C-8 to C-14 of 12-oxo-oleanan-3β-ol and 12-oxo-oleanan-3-one, respectively, have also been detected. 22,29,30-trisnorlup-18(19)-en-3-one, 22,29,30-trisnorlupan-3-one, 22,29,30-trisnorlupana-3,19-dione, 22,29,30-trisnorlupana-3,12-dione, lupeol, lup-22(29)-en-3-on-29-ol, 22,29-epoxylupan-3-one, lupan-3-on-29-al, lupan-3-on-29-ol and 19,22-epoxylupan-3-one are the major products from the ozonation of lupenone. No transformation product was detected for friedelin, probably due to its stability to ozonation.     

Implications of sea-level rise for overwash enhancement at South Portugal

Overwash is one of the most prominent hazards affecting coastal zones, and the associated consequences are expected to increase because of both sea-level rise and intensification of coastal occupation. This study used a 23-year data set of wave heights and tide-surge levels to define return periods of overwash potential for current and future sea-level conditions, namely 2055 and 2100, at two sites from South Portugal. A relevant intensification of both frequency and magnitude of the overwash is expected to occur by mid-century if adaptation measures are not taken and further aggravated by 2100. Current overwash levels with a return period of 100-years can reach a return period lower than 20-years by 2055 and 10-years by 2100. However, these values are rather variable from site to site, highlighting the urgency to develop detailed local studies to identify climate change impacts along coastal sectors, based on validated equations and long-term time series. These could be easily carried by replicating and adapting the here proposed methodology to sandy coasts worldwide. Understating the impact that climate change (namely sea-level rise) may have at the local level is key to contribute to effective management plans that include adaptation measures to minimize risks associated with coastal floods.

     

南天山萨瓦亚尔顿金矿床稀土微量元素特征及其成因意义

萨瓦亚尔顿金矿位于新疆乌恰县的南天山构造带中,是我国20世纪90年代发现的第一例“穆龙套型”金矿.矿床形成于印支期,矿化与石英脉密切相关,显示了与穆龙套金矿的相似性.成矿流体演化经历了早期高温无矿化石英阶段,中期中低温矿化石英阶段,晚期低温碳酸盐脉阶段.早期无矿石英的稀土及微量元素含量均低于矿化石英.矿化石英包体中流体的稀土元素配分模式显示较一致的轻稀土富集和Eu正异常,指示流体中较高的钙离子或相对还原环境;流体中Pb含量较高,而蚀变强烈的围岩则显示出明显的Ca和Pb流失,这表明成矿流体可能部分来源于与围岩发生交代作用的蚀变流体,矿质沉淀可能与流体混合作用相关.早期石英包体中流体的稀土和微量元素含量较低则指示早期阶段可能未发生流体混合.萨瓦亚尔顿Ⅳ号矿脉为最大矿带,其含矿石英包体中流体微量元素一般高于其它矿脉石英,可能显示较强的流体混合及成矿作用.Ⅱ号矿脉在流体稀土及微量元素含量上显示与Ⅳ脉更为相似.萨瓦亚尔顿金矿稀土微量元素研究表明围岩组分可能为成矿流体主要来源之一,而流体混合则为成矿重要机制,这与前期流体包裹体及同位素研究结论一致,也符合造山型金矿的一般特征.     

Tin-bearing minerals at the Furong tin deposit,South China: Implications for tin mineralization

It remains poorly constrained whether remobilization of Sn from granites and prograde skarns plays an essential role in forming economic (skarn-type) tin mineralization. Using both electron probe microanalysis and laser ablation–inductively coupled plasma–mass spectrometry methods, in-situ Sn contents, as well as major elements, were analyzed for numerous silicates and magnetite from fresh granite, altered granite, and skarn at the large Furong Sn deposit (530,000 t Sn @ 0.8% Sn) in the Nanling Range, South China. Hornblende and biotite in fresh granite are the main Sn-bearing phases (Sn = 44–321 ppm), while plagioclase and K-feldspar are poor in Sn (< 5 ppm). In altered granite, tin is hosted mainly by hydrothermal muscovite (299–583 ppm) replacing plagioclase, but rarely by chlorite (mostly <10 ppm) replacing hornblende and biotite. In contrast, most silicates (garnet, diopside, vesuvianite, pargasite and epidote) and magnetite from tin skarn are Sn-rich (47–44,241 ppm), except for Sn-poor phlogopite and scapolite (< 10 ppm). In particular, garnet, pargasite, and epidote reach tin concentrations in the percent range. Tin generally enters the stannous silicates and magnetite through substitutions for octahedral Al^vi and Fe³⁺. Comparisons of Sn contents between magmatic and hydrothermal minerals in granite, prograde and retrograde minerals related to tin skarn indicate that remobilization of Sn from granite and prograde skarn is not a pre-requisite to form tin mineralization.     

Mineralogical and geochemical controls on the release of trace elements from slag produced by base- and precious-metal smelting at abandoned mine sites

Slag collected from smelter sites associated with historic base-metal mines contains elevated concentrations of trace elements such as Cu, Zn and Pb. Weathering of slag piles, many of which were deposited along stream banks, potentially may release these trace elements into the environment. Slags were sampled from the Ely and Elizabeth mines in the Vermont copper belt, from the copper Basin mining district at Ducktown, Tennessee and from the Clayton silver mine in the Bayhorse mining district, Idaho, in the USA. Primary phases in the slags include: olivine-group minerals, glass, spinels, sulfide minerals and native metals for Vermont samples; glass, sulfide minerals and native metals for the Ducktown sample; and olivine-group minerals, clinopyroxenes, spinels, sulfide minerals, native metals and other unidentified metallic compounds for Clayton slag. Olivine-group minerals and pyroxenes are dominantly fayalitic and hedenbergitic in composition, respectively and contain up to 1.25 wt.% ZnO. Spinel minerals range between magnetite and hercynite in composition and contain Zn (up to 2.07 wt.% ZnO), Ti (up to 4.25 wt.% TiO₂) and Cr (up to 1.39 wt.% Cr₂O₃). Cobalt, Ni, Cu, As, Ag, Sb and Pb occur in the glass phase, sulfides, metallic phases and unidentified metallic compounds. Bulk slag trace-element chemistry shows that the metals of the Vermont and Tennessee slags are dominated by Cu (1900–13,500 mg/kg) and Zn (2310–10,200 mg/kg), whereas the Clayton slag is dominated by Pb (63,000 mg/kg), Zn (19,700 mg/kg), Cu (7550 mg/kg), As (555 mg/kg), Sn (363 mg/kg) and Ag (200 mg/kg). Laboratory-based leach tests indicate metals can be released under simulated natural conditions. Leachates from most slags were found to contain elevated concentrations of Cu and Zn (up to 1800 and 470 μg/l, respectively), well in excess of the acute toxicity guidelines for aquatic life. For the Idaho slag, the concentration of Pb in the leachate (11,000 μg/l) is also in excess of the acute toxicity guideline. Geochemical modeling of the leachate chemistry suggests that leachates from the Vermont, Tennessee and Clayton slags are saturated with amorphous silica and Al hydroxide. Therefore, the dissolution of silicate and oxide phases, the oxidation of sulfide phases, as well as the precipitation of secondary phases may control the composition of leachate from slags. The presence of secondary minerals on slag deposits in the field is evidence that these materials are reactive. The petrographic data and results of leaching tests from this study indicate slag may be a source of potentially toxic metals at abandoned mine sites.     

Variations in trapping temperatures and trace elements in peridotite-suite inclusions from African diamonds: evidence for two inclusion suites,and implications for lithosphere stratigraphy

The proton microprobe has been used to measure the trace element contents of Cr-pyrope, olivine and orthopyroxene inclusion (DI) in>60 diamonds from southern Africa, and in concentrate garnets from the host kimberlites. Olivine inclusions show a negative correlation of Ca with Fo content, but olivines coexisting with very subcalcic garnets are anomously depleted in Ca relative to Fo. The maximum and median values of Ti, Zn, Ga, Zr and Y in DI garnets decrease as Ca decreases relative to Cr, consistent with increasing depletion by removal of silicate melts. However, the most subcalcic garnets are anomously enriched in Sr (and LREE). The contrasting depletion in Zr, Y, Ti etc. and enrichment in Sr is not consistent with a single-stage depletion event. The extreme Ca depletion of the most subcalcic garnets and their coexisting olivines, and the Sr enrichment, are interpreted as the result of metasomatism by a carbonatitic fluid following depletion. Trapping temperatures of garnet DI, estimated by nickel thermometry range from 950 to > 1500°C. Most DI with T>1200°C are lherzolitic, rather than subcalcic. In most pipes studied, the trapping T of DI garnets is higher than the T range of equivalent garnets from concentrates. The high Ts are interpreted as reflecting the formation of diamonds during short-lived thermal pulses, followed by cooling toward a conductive geotherm. The T distribution of calcic and subcalcic garnets in concentrates from kimberlites suggests that lherzolite and harzburgite are intimately intermixed over the depth range 150–180 km beneath the Kalahari craton. The abundance of calcic garnets with T>1200°C suggests the presence of significant amounts of lherzolite at greater depths. This deeper lherzolite may be associated with eclogite, and may be the source region for some high-T lherzolitic DI garnets.     

Rare earth elements of seep carbonates: Indication for redox variations and microbiological processes at modern seep sites

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (ΣREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the ΣREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that ΣREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.     

Paleo-ocean chemistry records in marine opal: Implications for fluxes of trace elements, cosmogenic nuclides (Be and Al), and biological productivity

Here, we provide evidence suggesting that marine (diatom) opal contains not only a high fidelity record of dissolved oceanic concentrations of cosmic ray-produced radionuclides, ¹⁰Be and ²⁶Al, but also a record of temporal variations in a large number of trace elements such as Ti, Fe, Zn and Mn. This finding is derived from measurements in purified biogenic opal that can be separated from detrital materials using a newly developed technique based on surface charge characteristics. Initial results from a sediment core taken near the present-day position of the Antarctic Polar Front (ODP Site 1093) show dramatic changes in the intrinsic concentrations of, Be, Al, Ti, Fe, Mn and Zn in the opal assemblages during the past ∼140 kyr BP. The results imply appreciable climatically controlled fluctuations in the level of bioreactive trace elements. The time series of total Be, Al, Ti, Fe and ¹⁰Be in the sediment core are all well correlated with each other and with dust records in the polar ice cores. The observations suggest that a significant flux of these trace metals to oceans is contributed by the aeolian dust, in this case, presumably from the Patagonia. This observation also allows determination of fluxes of dust-contributed ¹⁰Be to the Antarctica ice sheets. However, our data show that the relationships among the various metals are not perfectly linear. During periods of higher dissolved concentrations of trace elements (indicated by Fe and Ti) the relative concentrations of bioreactive elements, Be, Al, Mn and Zn are decreased. By contrast, the Fe/Zn and Fe/Mn ratios decrease significantly during each transition from cold to warm periods. The relative behavior could be consistent with any of the following processes: (i) enhanced biological productivity due to greater supply of the bioreactive elements (e.g. Zn) during cold periods (ii) increased biological and inorganic scavenging of particle active elements (e.g. Be and Al) during early interglacial periods (iii) differential uptake/removal of the metals by the various diatom taxa whose relative productivity or growth rate changes with large scale climate. In any case, with one sedimentary phase and in single sedimentary sections, we now have the potential to compare directly a proxy for aeolian input of micronutrients (e.g. Fe or Ti), with a proxy for production (e.g. ²⁶Al/Al ratios). We expect that studies of the temporal records of trace elements and cosmogenic nuclides in contrasting regions of upwelling and productivity, which exhibit different sensitivities to global climate fluctuations and micronutrient inputs, would lead to a direct and comprehensive test of ideas such as the hypothesis of iron control of atmospheric carbon dioxide [Martin, J.H., 1990. Glacial-interglacial CO₂ change: the iron hypothesis. Paleoceanography5, 1-13]. Our present data from a single site do not show that increases in dissolved Fe concentrations, per se, were responsible for increased biological productivity. However, a much clearer picture of the effect of increased dust fluxes should emerge when we have data for trace elements and the cosmogenic nuclides, ¹⁰Be and ²⁶Al from various oceanic provinces.     

白云鄂博碳酸岩墙的稀土和微量元素地球化学及对其成因的启示

根据矿物组成白云鄂博矿区的碳酸岩岩可墙可分为白云石型、白云石－方解石共存型和方解石型三种类型。REE和微量元素地球化学表明，这三类碳酸岩岩墙为碳酸岩浆演化不同阶段的产物，白云石型和白云石－方解石共存型对应于早期岩浆阶段，其（La/Nd)n、(La/Yb)n比值随稀土总量的增加而增大，方解石型则对应于碳酸岩浆演化的晚期热液阶段，其稀土总量明显富集，但其（La/Nd)n、(La/Y)n和（La/Yb)n比值随稀土总量的增加却有减小的趋势，热液阶段也是白云鄂博稀土矿化的主要阶段。     

Particulate trace metal speciation in stream sediments and relationships with grain size: Implications for geochemical exploration

Sediment samples were collected from streambeds in an undisturbed watershed in eastern Quebec (Gaspé Peninsula). Two sampling sites were located on a stream draining an area of known mineralization (Cu, Pb, Zn) and two on a control stream. The sediment samples were separated into 8 distinct size classes in the 850 μm to <1 μm size range by wet sieving, gravity sedimentation or centrifugation. Each sediment subsample was then subjected to a sequential extraction procedure designed to partition the particulate heavy metals into five fractions: (1) exchangeable; (2) specifically adsorbed or bound to carbonates; (3) bound to Fe-Mn oxides; (4) bound to organic matter; (5) residual. The following metals were analyzed in each extract: Cu, Pb, Zn; Fe, Mn.Comparison of samples from the mineralized area with control samples revealed the expected increase in total concentrations for Cu, Pb and Zn. Non-detrital metals were mainly associated with Fe oxides (specifically adsorbed; occluded) and with organic matter or resistant sulfides. For a given sample, variation of trace metal levels in fractions 2 and 3 with grain size reflected changes in the available quantities of the inorganic scavenging phase (FeOx/MnOx); normalization with respect to Fe and Mn content in fraction 3 greatly reduced the apparent dependency on grain size.The results of this study suggest that a single reducing extraction (NH₂OH.HCl) could be used advantageously to detect anomalies in routine geochemical surveys. A second leaching step with acidified H₂O₂ could also be included, as the trace metal concentrations in fraction 4, normalized with respect to organic carbon content, also showed high {anomaly/background} ratios.     

The Concentration of the Platinum-Group Elements in South African Komatiites: Implications for Mantle Sources, Melting Regime and PGE Fractionation during Crystallization

We have analysed 18 samples of komatiite from five consecutivelava flows of the Komati Formation at Spinifex Creek, BarbertonMountain Land. Our samples include massive komatiite, varioustypes of spinifex-textured komatiite, and flow-top breccias.The rocks have low platinum-group element (PGE) contents andPd/Ir ratios relative to komatiites from elsewhere, at 0·45–2ppb Os, 1–1·4 ppb Ir, <1–5 ppb Ru, 0·33–0·79ppb Rh, 1·7–6 ppb Pt, 1·6–6·1ppb Pd, and Pd/Ir 3·3. Pt/Pd ratios are c. 1·1.Platinum-group elements are depleted relative to Cu (Cu/Pd =15 300). They display a tendency to increase in the less magnesiansamples, suggesting that the magmas were S-undersaturated uponeruption and that all PGE were incompatible with respect tocrystallizing olivine. Komatiites from the Westonaria Formationof the Ventersdorp Supergroup and the Roodekrans Complex nearJohannesburg have broadly similar PGE patterns and concentrationsto the Komati rocks, suggesting that the PGE contents of SouthAfrican ultrabasic magmas are controlled by similar processesduring partial mantle melting and low-P magmatic crystallization.Most workers believe that the Barberton komatiites formed byrelatively moderate-degree batch melting of the mantle at highpressure. Based on the concentration of Zr in the Komati samples,we estimate that the degree of partial melting was between 26and 33%. We suggest that the low PGE contents and Pd/Ir ratiosof all analysed South African komatiites are the result of sulphideshaving been retained in the mantle source during partial melting.The difference in Pd/Ir between our samples and Al-undepletedkomatiites from elsewhere further suggests that the PGE arefractionated during progressive partial melting of the mantle.Thus, our data are in agreement with other recent studies showingthat the PGE are hosted by different phases in the mantle, withPd being concentrated by interstitial Cu-rich sulphide, andthe IPGE (Os, Ir, Ru) and Rh resting in monosulphide solid solutionincluded within silicates. Pt is possibly controlled by a discreterefractory phase, as Pt/Pd ratios of most komatiites worldwideare sub-chondritic. KEY WORDS: platinum-group elements; komatiites; Barberton; mantle melting; South Africa     

Relationships between major and trace elements during weathering processes in a sedimentary context: Implications for the nature of source rocks in Douala,Littoral Cameroon

In Douala (Littoral Cameroon), the Cretaceous to Quaternary formation composed of marine to continental sediments are covered by ferrallitic soils. These sediments and soils have high contents of SiO₂ (≥70.0 wt%), intermediate contents of Al₂O₃ (11.6–28.4 wt%), Fe₂O₃ (0.00–20.5 wt%) and TiO₂ (0.04–4.08 wt%), while K₂O (≤0.18 wt%), Na₂O (≤0.04 wt%), MgO (≤0.14 wt%) and CaO (≤0.02 wt%) are very low to extremely low. Apart from silica, major oxides and trace elements (REE included) are more concentrated in the fine fraction (<62.5 μm) whose proportions of phyllosilicates and heavy minerals are significant. The close co-associations between Zr, Hf, Th and ∑REE in this fraction suggest that REE distribution is controlled by monazite and zircon. CIA values indicate intense weathering. Weathering products are characterized by the association Al₂O₃ and Ga in kaolinite; the strong correlation between Fe₂O₃ and V in hematite and goethite; the affinity of TiO₂ with HFSE (Hf, Nb, Th, Y and Zr) in heavy minerals. The ICV values suggest mature sediments. The PCI indicates a well-drained environment whereas U/Th and V/Cr ratios imply oxic conditions. La/Sc, La/Co, Th/Cr, Th/Sc and Eu/Eu* elemental ratios suggest a source with felsic components. Discrimination diagrams are consistent with the felsic source. The REE patterns of some High-K granite and granodiorite of the Congo Craton resemble those of the samples, indicating that they derive from similar source rocks.     

安徽省东源斑岩型钨矿床白钨矿原位微量元素特征及其指示意义

新兴的白钨矿面扫描技术对于解释矿物微量元素特征具有重要的指示意义。文章选择皖南地区东源斑岩型钨矿床中白钨矿为研究对象,利用面扫描和阴极发光图像技术对矿物微区结构和原位微量元素特征进行系统研究。分析结果显示,白钨矿具有核边结构且微量元素特征具有明显的分带性,同一白钨矿颗粒核部亏损Mo、Nb、Ta元素,富集REEs,而边部相反。在此基础上,文章通过系统的白钨矿单点微量元素分析,反演了成矿流体性质和演化过程,提出东源钨矿床成矿流体氧逸度逐渐增高,成矿流体富集F挥发分且F含量逐渐增加,成矿物质很可能有幔源组分加入。通过白钨矿面扫描和阴极发光图像查明矿物微区结构,进而开展了白钨矿微区微量元素单点分析,有可能对成矿流体和矿质来源作出合理的解释。     

造山型金矿床黄铁矿微量元素对成矿机制的指示

黄铁矿作为重要的金属硫化物,在各类金矿床中广泛产出,其微量元素特征被广泛应用于成矿流体物理化学性质的反演、成矿过程和矿床成因的限定。造山型金矿床作为全球金资源的主要提供者,其黄铁矿微量元素被广泛研究,但多局限于矿床个例的精细解剖与应用,缺乏对已有数据的综合统计分析。为此,本文广泛收集了前人发表的67个造山型金矿床黄铁矿微量元素数据4092组,开展了相关的数据统计分析,以此揭示造山型金矿床的成矿流体特征及其成矿机制。分析结果表明,造山型金矿床中黄铁矿Co/Ni比值(0.2~1.5)暗示了其流体以变质流体来源为主;但少部分样品具有低Cu/Zr和高Ni、Cr的特征,表明其成矿流体也可能与幔源流体相关;根据黄铁矿Se温度计算出的造山型金矿床的成矿温度峰值接近或高于350℃,这与前人认为该类矿床的成矿温度(200~350℃)有所差异,说明在低Se条件下这种温度计的计算结果具有不确定性;造山型金矿的黄铁矿Te含量(0.320×10^-6~7.07×10^-6)以及Cu/Au比值(1.3~60.2)表明流体在迁移过程主要处于还原环境。此外,造山型金矿中黄铁矿的As/Sb、Ag/Co比值表明流体沸腾是Au沉淀的主要机制,Se/Te和Se/Ge比值则表明流体与大气降水的混合对于这类矿床的Au沉淀也起到了重要作用;而其黄铁矿的高孔隙度以及Au与低熔点亲铜元素的弱相关性表明造山型金矿中赋存的不可见金需要通过溶解再沉淀过程来实现其Au的活化迁移和再富集。本文黄铁矿微量元素大数据分析结果表明造山型金矿床的成矿机制并非由单一因素控制,且其流体来源多样,这一发现对于造山型金矿床的矿产勘查具有一定的指示意义。