Trace element geochemistry of the Lower Cambrian black rock series from northwestern Hunan, South China

Samples of black rock series collected from the Lower Cambrian Niutitang Formation, northwestern Hunan Province, China, were analyzed for trace elements.The trace element geochemical characteristics of the ore layer (high enrichments of Ni, Mo, V, U, Cu, Pb, Zn, Cd, Tl and Ba; high U/Th ratios and LREE-enriched patterns with positive Eu and Y anomalies) support the assumption that the Ni-Mo polymetallic layer is of submarine hydrothermal origin.High field strength elements (HFSE) and lithophile elements such as Nb, Ta, Zr, Hf, Li, Be, Rb, Cs, Th and Sc are remarkably higher in the upper unit than those in the lower unit of the Niutitang Formation.These features may reflect that hydrothermal contributions were diminished, and terrigenous constituents were increased in the sediments of the upper unit of the Niutitang Formation.     

Elemental composition in the sediments of the Yangtze and the Yellow Rivers and their tracing implication

Elemental compositions in the surface sediments of the Yangtze River and the Yellow River are quite different. The Yangtze River' s sediment is rich in K, Fe, Mg, Al and most of trace elements, and its elemental composition show remarkable spatial variations, whereas the Yellow River s sediment has higher contents of Ca, Na, Sr, Ba, Zr and Hf, and the elemental composition remains relatively stable. The ratios of some elements are also different in the sediments of the two rivers. The elemental composition of the Yangtze River sediment results from widely distributed igneous rocks and complicated source rocks and strong chemical weathering in the Yangtze River catchment basin, while the main provenance of the Yellow River sediment is the Loess Plateau which has dominant influence on the elemental composition, and the intense physical weathering is another controlling factor. The elements such as Cu, Zn, Sc, Ti, Fe, V, Ni, Cr, Co, Li and element ratios such as La/Sc, La/Co, Th/Co, Ti/Zr and Zr/Y can be used as the tracers to distinguish the Yangtze River sediment from the Yellow River s. The tracers can be used in the study of the mixing and distribution of the substances of the two rivers matters in coastal zones of China.     

皮秒Nd:YAG激光对生物金属纯Ti和Ti–13Nb–13Zr合金的表面改性

The effects of picosecond Nd:YAG laser irradiation on chemical and morphological surface characteristics of the commercially pure titanium and Ti–13Nb–13Zr alloy in air and argon atmospheres were studied under different laser output energy values. During the interaction of laser irradiation with the investigated materials, a part of the energy was absorbed on the target surface, influencing surface modifications. Laser beam interaction with the target surface resulted in various morphological alterations, resulting in crater formation and the presence of microcracks and hydrodynamic structures. Moreover, different chemical changes were induced on the target materials’ surfaces, resulting in the titanium oxide formation in the irradiation-affected area and consequently increasing the irradiation energy absorption. Given the high energy absorption at the site of interaction, the dimensions of the surface damaged area increased. Consequently, surface roughness increased. The appearance of surface oxides also led to the increased material hardness in the surface-modified area. Observed chemical and morphological changes were pronounced after laser irradiation of the Ti–13Nb–13Zr alloy surface.     

Surface modifications of biometallic commercially pure Ti and Ti–13Nb–13Zr alloy by picosecond Nd:YAG laser

The effects of picosecond Nd:YAG laser irradiation on chemical and morphological surface characteristics of the commercially pure titanium and Ti–13 Nb–13 Zr alloy in air and argon atmospheres were studied under different laser output energy values. During the interaction of laser irradiation with the investigated materials, a part of the energy was absorbed on the target surface, influencing surface modifications.Laser beam interaction with the target surface resulted in various morphological alterations, resulting in crater formation and the presence of microcracks and hydrodynamic structures. Moreover, different chemical changes were induced on the target materials' surfaces, resulting in the titanium oxide formation in the irradiation-affected area and consequently increasing the irradiation energy absorption. Given the high energy absorption at the site of interaction, the dimensions of the surface damaged area increased. Consequently, surface roughness increased.The appearance of surface oxides also led to the increased material hardness in the surface-modified area. Observed chemical and morphological changes were pronounced after laser irradiation of the Ti–13 Nb–13 Zr alloy surface.     

Does chemical index of alteration （CIA） reflect silicate weathering and monsoonal climate in the Changjiang River basin？

Chemical weathering of continental silicates significantly influences global climate change,earth surface processes,material cy-cling and oceanic chemical composition.How to quantitatively reconstruct chemical weathering history has become an important issue in global change research.Chemical index of alteration(CIA) has been widely used as a quantitative indicator for estimating the degree of silicate weathering.However,its method of calculation and the limitations of its application are not well understood.In this study,we calculated CIA values from suspended particulate matter collected from the mainstream and major tributaries of the Changjiang River.The values yielded considerable variations at different temporal and spatial scales.The average CIA values increased from the upper to middle-lower reaches,and were lower in the suspended samples taken during the flood than in the dry season.The spatial variation in the CIA is predominantly controlled by basinal monsoon climate.In contrast,the temporal varia-tion in the Changjiang River basin is controlled mainly by the changing provenance of suspended samples in relation to the shift of the precipitation zone.The CIA probably indicates the integrated weathering history in the river basin,and thus,cannot be used as a reliable proxy of instantaneous chemical weathering.Furthermore,the calculation method and hydrodynamic sorting also influence the CIA values.Therefore,caution should be taken when using the CIA as a proxy for studying chemical weathering from different regions.     

Variations of geochemical compositions and the paleoclimatic significance of a loess-soil sequence from Garzê County of western Sichuan Province, China

The West Sichuan Plateau is located in the southeast margin of the Tibetan Plateau, where the climate is mainly influenced by the Indian southwest summer monsoon and the Tibetan Plateau monsoon. In this study, detailed geochemical analysis has been carried out on Ganzisi loess-paleosol sequence in Ganzê County of western Sichuan Province. The results indicate that Ganzê loess and paleosol have experienced the incipient stage of chemical weathering in dust source regions, characterized by the decomposition of plagioclase which caused the depletion of mobile elements Na and Ca. The post-depositional chemical weathering is characterized by carbonate dissolution and oxidation of Fe2＋. The variations of some geochemical indexes （such as CIA values, Na/K and Fe2＋/ Fe3＋ ratios） in Ganzisi loess-paleosol sequence indicate a gradually decreased chemical weathering intensity in the dust source regions and deposition areas since 1.15 Ma BP consistent with the general increase of global ice volume, reflecting that the arid trend since 1.15 Ma BP in the southeast Tibetan Plateau is a regional response to the global climate change. The geochemical indexes in this section also reveal an obvious drying step occurred at about 250 ka BP in this region. We interpret this drying step as a result of decreased influence of the Indian southwest summer monsoon. This decrease in monsoon moisture is probably attributable to the uplift of the southeast margin of the Tibetan Plateau at about 250 ka BP.     

Discovery of the Early Paleozoic post-collisional granites in northern margin of the Erguna massif and its geological significance

The Luoguhe intrusion, located in Mohe County, Heilongjiang Province, is mainly composed of monzogranite, quartz diorite and granodiorite, with minor diorite, tonalite, quartz monzodiorite, quartz monzonite, syenogranite and alkali-feldspar granite. The intrusion can be divided into two iithological units, i.e. quartz diorite and monzogranite units, with affinities to high-K caic-alkaline series. The quartz diorite unit （SiO2： 54.79%-58.30%, Na2O/CaO： 0.79-1.53 and Shand index： 0.77-0.82） belongs to metaluminous rocks. And the monzogranite unit （SiO2： 65.29%-66.45%, Na2O/CaO： 1.73-3.43 and Shand index 〈1.05） can be considered as weakly peraluminous rocks. The intrusion is characterized by high REE abundance （∑REE = 180.2-344.3μg/g）, medium-strong negative Eu anomalies （δEu = 0.33-0.82）, weak REE fractionation [（La/Yb）N = 4.12-10.45], enrichments in Rb, Th, U, K, La, Ce, Nd, Hf, Zr and Sm, but strong depletions of Ba, Nb, Ta, Sr, P and Ti. These characteristics of major, REE and trace elements indicate that the intrusion was formed in a transitional tectonic setting from compressionai to extensional regime, which can be classified as post-collisional granitoids. SHRIMP U-Pb zircon analyses yield ages of 517±9 and 504±8 Ma for the quartz diorite and monzogranite units, respectively. The discovery of Early Paleozoic post-collisionai granites in the northern margin of the Erguna massif indicates that the northern branch of Paleo-Asian Ocean between Siberian plate and Erguna massif was closed in the Early Paleozoic and the Salair orogeny ended ca. 500 Ma ago.     

Caledonian reworking of Paleoproterozoic basement in the Cathaysia Block: Constraints from zircon U-Pb dating,Hf isotopes and trace elements

A combined study of zircon U-Pb dating, Hf isotopes and trace elements has been carried out for granodioritic neosomes of migmatites from the Tianjingping area in northwestern Fujian Province. Zircons are characterized by zoning, higher Th/U ratios （mostly≥0.1）, HREE enrichment, and positive Ce and negative Eu anomalies, and show features similar to magmatic or anatectic zircons. Apparent ^206Pb/^238U ages for the zircons are 447±2 Ma （95 % conf., MSWD=0.88）, corresponding to a Caledonian event. εHf（t） values are -13.3 to -9.7, indicating a crustal source. Two-stage Hf model ages are 1.7 to 1.9 Ga, suggesting that protolith of the migmates was probably formed in the Paleoproterozoic. The granodioritic neosomes have the characteristics of peraluminous calc-alkaline granite, and their REE patterns and trace elements spidergrams show features of middle to upper crustal rocks. Together with previous studies, we conclude that the protolith of the Cathaysia basement in the Tianjingping area was likely formed in the middle-late Paleoproterozoic and experienced partial melting during the Caledonian period. The recognition of Caledonian reworking of the Paleoproterozoic basement in the Cathaysia Block provides a new insight into the tectonic evolution of the Cathaysia Block in the Caledonian period and the interaction between the Cathaysia Block and the Yangtze Block.     

Spatiotemporal variations of Zr/Rb ratio in three last interglacial paleosol profiles across the Chinese Loess Plateau and its implications for climatic interpretation

The ratio of Zirconium to Rubidium （Zr/Rb） is suggested to be a better proxy for the East Asian winter monsoon strength than the widely-used grain size distribution. The rationale for the Zr/Rb proxy relies on the following assumptions： （1） Grain size fractionating characteristics during eolian dust transport should be archived in the Zr/Rb ratio records and this assumption is based on the premise that Zr is preferentially enriched in coarser grain size fraction while Rb tend to be enriched in finer grain size fraction; and （2） post-depositional weathering does not change the Zr/Rb ratio due to the immobility of these two elements. To examine these two assumptions, three last interglacial paleosols （S1） from Dingxi, Tianshui and Lantian, along a NW-SE transect across the Chinese Loess Plateau, were geo- chemically investigated. Our results show that the Rb concentration exhibits an increasing trend along the NW-SE transect both in the paleosol （S1） and the measured portions of the loess units （L1 and L2）, being supportive to the assumption that Rb is enriched in the fine particles. But we also found that Rb loss did occur to some extent in the three profiles, contradicting to the presumption of Rb immobility during pedogenic processes. The Zr concentration exhibits an expected decreasing trend in the measured portions of the loess units and an unexpected increasing trend in the paleosol along the NW-SE transect. Moreover, the ratios of Zirconium to Hafnium （Zr/Hf） show different variation patterns between interglacial and glacial, implying that Zr-bearing minerals and their resident grain size fractions are probably not identical during interglacial and glacial. Thus, the assumption that Zr is enriched in coarse grain size fraction can no longer hold. We conclude that the final Zr/Rb value is not only dependent on grain size sorting processes but also on post-depositional alteration and source prove- nance. Under enhanced chemical weathering, especially when chemical index of alterat     

The evidence of Sm-Nd isochron age for the early Paleozoic ophiolite in Mangya area, Altun Mountains

The REE patterns of the basic volcanic rocks in Mangya area, Altun, are slight rich in LREE with (La/Ya)-N=1.69-3.20, (La/Sm)-N=1.37-1.87, other trace element ratios of the rocks are Th/Ta≈1 (for a few samples greater than 1.5), Nb/Y=0.34-0.62, Ti/Y=310-443 (on the average: 381), Ti/V=37-62, Zr/Nb=9.4-12.4, Sr/Rb=12-80 (on the average: 37), and Nb/Th=7.7-16.8. These features are similar to that of E-MORE or OIB. The ε Nd(t) value, being 3.95- 4.12, shows that the source of the volcanic rocks is derived from depleted asthenosphere mantle mixed with materials from enriched mantle. These, together with the information of geological setting and rock assemblages, indicate that the basic volcanic rocks are of ophiolite. The Sm-Nd isotope ages for the eight basic volcanic rock samples construct a straight line with good correlation, and the calculated isochron age is (481.3±53) Ma. Besides, the eight calculated ε Nd(t) and model ages are close to each other, which suggests that they are homologous, so the isochron is not a mixed line. In the meantime, the isochron age ((481.3±53) Ma) is lower than the model ages (T DM=1 004-1 534 Ma) of the samples, suggeting that the isochron age represents the formation age of the basic volcanic rocks and the ophiolite belt in Mangya area, Altun is formed in the early Paleozoic (Cambrian-Ordovician). In spite of the greater uncertainty of the age, it is still reliable because it is consistent with the age constrained by the regional strata.     

Zircon U-Pb age and Hf isotope of Quanyishang A-type granite in Yichang: signification for the Yangtze continental cratonization in Paleoproterozoic

Zircon U-Pb age and Hf isotope, and major and trace element compositions were reported for granite at Quanyishang, which intruded into the Kongling complex in Yichang, Hubei Province. The results show that the Quanyishang granite is rich in silicon and alkalis but poor in calcium and magnesium, and displays enrichment in Ga, Y, Zr, Nb but depletion in Sr and Ba, exhibiting the post-orogenic A-type affinity. 90% zircons from the granite are concordant, and give a middle Paleoproterozoic magmatic crystallization age (mean 1854 Ma). Initial Hf isotope ratios (176Hf/177Hf)i of the middle Paleoproterozoic zircons range from 0.280863 to 0.281134 and they have negative eHf(t) values with a minimum of -26.3. These zircons give the depleted mantle model ages (TDM) of 2.9―3.3 Ga (mean 3.0 Ga), and the average crustal model ages (Tcrust) of 3.6―4.2 Ga (mean 3.8 Ga). A Mesoarchean grain with 207Pb/206Pb age of 2859 Ma has a slightly high TDM (3.4 Ga) but similar Tcrust (3.8 Ga) to the Paleoproterozoic zircons. All these data suggest that the source materials of the Quanyishang A-type granite are unusually old, at least ≥2.9 Ga (even Eoarchean). The event of crustal remelting, which resulted in the formation of the Quanyishang granite in the middle Paleoproterozoic, recorded the cratonization of the Yangtze conti-nent. The process may have relation to the extension and collapse of the deep crust with Archean ages, in response to the transition stage of the assembly and breakup of the Columbia supercontinent.     

Microstructural evolution in Al–Zn–Mg–Cu–Sc–Zr alloys during short-time homogenization

Microstructural evolution in a new kind of aluminum(Al) alloy with the chemical composition of Al–8.82Zn–2.08Mg– 0.80Cu–0.31Sc–0.3Zr was investigated. It is found that the secondary phase Mg Zn2 is completely dissolved into the matrix during a short homogenization treatment(470°C, 1 h), while the primary phase Al3(Sc,Zr) remains stable. This is due to Sc and Zr additions into the Al alloy, high Zn/Mg mass ratio, and low Cu content. The experimental findings fit well with the results calculated by the homogenization diffusion kinetics equation. The alloy shows an excellent mechanical performance after the short homogenization process followed by hot-extrusion and T6 treatment. Consequently, a good combination of low energy consumption and favorable mechanical properties is obtained.     

Microstructural evolution in Al-Zn-Mg-Cu-Sc-Zr alloys during short-time homogenization

Microstructural evolution in a new kind of aluminum (Al) alloy with the chemical composition of Al-8.82Zn-2.08Mg-0.80Cu-0.31Sc-0.3Zr was investigated. It is found that the secondary phase MgZn₂ is completely dissolved into the matrix during a short homogenization treatment (470℃, 1 h), while the primary phase Al₃(Sc,Zr) remains stable. This is due to Sc and Zr additions into the Al alloy, high Zn/Mg mass ratio, and low Cu content. The experimental findings fit well with the results calculated by the homogenization diffusion kinetics equation. The alloy shows an excellent mechanical performance after the short homogenization process followed by hot-extrusion and T6 treatment. Consequently, a good combination of low energy consumption and favorable mechanical properties is obtained.     

Trace element characteristics in the diopsides of peridotite xenoliths: a laser ablation-inductively coupled plasma-mass spectrometry study

Among the various xenoliths entrained by the Cenozoic Hannuoba basalts, peridotite is the most abundant one. The trace elements of the diopsides from the peridotite xenoliths were analysed by LA-ICP-MS. The overall depletion and some heterogeneity of the continental mantle beneath northern North China Craton were indicated by the characteristics of the trace elements. The ∑REE amount in diopside correlates with the Cr/(Cr+Al) ratio of diopside which is indicative of xenolith's partial melting degree. As the peridotite hosts and pyroxenite veins show similar REE distribution patterns, the composite xenoliths are probably formed by mantle deformation, rather than by the late metasomatism of mantle fluids/melts.     

U-Pb zircon dating of Early Paleozoic gabbro from the Nantinghe ophiolite in the Changning-Menglian suture zone and its geological implication

The Nantinghe ophiolite is located in the northern part of the Changning-Menglian suture zone in southeast Tibet. It is composed of meta-peridotite, cumulative gabbro, meta-gabbro, plagioclase amphibolite and meta-basalt. Zircon U-Pb dating of the cumulative gabbro gives concordant ages of 473.0±3.8 Ma and 443.6±4.0 Ma respectively, indicating the early and late episodes of mafic magmatisms during the Paleo-Tethys oceanic rifting. The 16 LA-ICPMS zircon U-Pb analyses of meta-gabbro yield a weight mean age of 439±2.4Ma. The gabbro shows relatively low contents of SiO2 (46.46%-52.11%), TiO2 (0.96%-1.14%) and K2O (0.48%-0.75%). Its trace element distribution patterns are partly similar to those of the mid-ocean ridge basalts, and part is depleted in high field strength elements such as Nb, Ta, Zr, Hf and Ti. These features suggest that the mafic rocks were probably formed in a MORB-like or backarc rift basin setting. The zircon U-Pb age of gabbro is consistent with a late crystallization age of the cumulative gabbro from the Nantinghe ophiolite, suggesting that the Paleo-Tethys oceanic basin was opened during 444-439 Ma, possibly as a backarc basin. It is the first precise age which defines the formation time of the early Paleozoic ophiolite in the Changning-Menglian suture zone. These geochronological and geochemical characteristics of the Nantinghe ophiolite are consistent with those from the Guoganjianianshan and Taoxinghu of the Longmu Co-Shuanghu suture in the Qiangtang region. Thus, we suggest that the both Changning-Menglian and Longmu Co-Shuanghu sutures were probably transformed from the relic oceanic crust of the uniform Paleo-Tethys, which likely represents the original and main Paleo-Tethys oceanic basin.     

Os isotopic evidence for a carbonaceous chondritic mantle source for the Nagqu ophiolite from Tibet and its implications

Early-crystallizing chromian spinel(Cr-spinel) in the Nagqu ophiolite has high Os and low Re contents,and it is resistant to alteration during serpentinization,weathering and metamorphism.The chemical composition of primitive magma is preserved in Cr-spinel,which makes it suitable for determining the initial Os-isotope composition of the mantle source.This study presents Cr-spinel Os isotopes and zircon U-Pb ages for cumulate dunite and gabbro,respectively,in the same cumulate section of the ophiolite at Nagqu in Tibet.The results shed light on the formation and evolution of lithospheric mantle.The Nagqu ophiolite is located in the central part of the Bangong-Nujiang suture zone.It is a remnant of the Neotethyan oceanic crust,and contains cumulate dunite and gabbro.Zircon from the gabbro yielded a weighted mean 206 Pb/238 U age of 183.7±1 Ma.Cr-spinel exhibits Os values of 0.2 to 0.3,suggesting that the mantle source for the dunite is similar to that of carbonaceous chondrites.Thus,the Tibetan lithosphere is primarily a relic of Tethyan oceanic lithosphere,which has formed by the transformation of the normal asthenospheric mantle in the Mesozoic.This is the first study to combine the spinel Os isotopes with accurate zircon U-Pb ages to constrain the geochemical characteristics of the mantle source for the ophiolite.     

REE geochemistry of suspended sediments from the rivers around the Yellow Sea and provenance indicators

Rare earth element (REE) compositions of the suspended sediments from the rivers around the Yellow Sea were different in that Korean river sediments (Han, Keum and Yeongsan Rivers) yield stronger fractionations than Chinese river sediments (Changjiang, Huanghe and Yalujiang), shown by obvious enrichments of LREE (light rare earth element) relative to UCC (upper continental crust).Variations of source rock compositions in the drainage basins are responsible for the differences of REE compositions between the river sediments. REE fractionation parameters including (La/Yb)ucc and (Gd/Yb)ucc as well as the ratios of La/Sc and Th/Sc can be treated as proper proxies for identifying the Chinese river sediments from those Korean river matters, and furthermore, for studying the provenances and paleoenvironmental changes of the marginal seas of China.     

Morphologic characteristics and growth interface stability of nano-micron FeS2 whiskers

Micromorphology is further studied on the basis of our previous researches concerned with the nano-micron FeS2 whisker. There are obvious differences in the intensive degree, diameter and micro- morphology among the FeS2 whiskers growing in different stages. From the early to late stage, the intensive degree increases, the diameter decreases, and the surface micro-morphology changes following the regularity： protrusive nodulation → coarse → smooth → flat. According to the theory of crystal growth, the geological setting and processes of whisker formation, we discuss the stability and evolution of crystal growth interface of FeS2 whisker occurring in Gengzhuang gold deposit （Shanxi Province, China）. The results suggest that the negative temperature gradient and the supercooling appear in the early stage of the whisker growth, whereas the positive temperature gradient of reposeful state appears in the late stage. In the whisker growth stage, the component concentration changes through the three stages： severely nonhomogeneous in the early stage, relatively homogeneous in the middle stage, more homogeneous in the late stage. The general changing process of the interfacial state is from unstable to stable. Micromorphology of FeS2 whisker in Gengzhuang is the result of synergism of temperature, component concentration and stability of crystal interface phase in hydrothermal system. The micromorphology not only reflects the physical and chemical characteristics of the hydrothermal system during the whisker growth, but also indicates the stability characteristics of the interface phase and records the changing process of the whisker growth.     

Luminescence chronology of ＂Old Red Sand＂ in Jinjiang and its implications for optical dating of sediments in South China

A weathered deposit in South China is widespread on the coastal areas of Fujian and Guangdong provinces, China. This deposit consists of slightly cemented, medium- to fine-grained sands, and is characterized by its colors of red, brown red, light reddish brown or dark yellowish orange, and is usually called ＂Old Red Sand＂. The uncertainty in its formation age has been a major obstacle to the study of this type of deposit. In this paper, optically stimulated luminescence （OSL） techniques were used to date the ＂Old Red Sand＂ sediments from Jinjiang, Fujian Province, China. The effect of the geochemical behavior of uranium and thorium in sediment during chemical weathering on estimation of annual dose was investigated. The results show that the change in annual dose due to weathering poses a major problem for the optical dating of such weathered sediments. The optical dating of these weathered deposits will produce erroneous ages if average annual dose during burial cannot be correctly estimated. For the profiles studied, the OSL dates obtained on samples from the upper part do not represent the burial age of the samples. It is highly likely that they are underestimated due mainly to the accumulated radioactive elements as a result of chemical weathering. It is concluded that changes in annual dose due to chemical weathering must be considered when dating similar sediments in South China. With a detailed analysis of the OSL dating results, the chronology of the marine terraces in this area was suggested. The lowest terrace was formed at -3.5 ka and the second terrace was dated to -74 ka. The age of the highest terrace may not be established accurately, but is inferred to be older than the apparent OSL date of -77 ka and so is the Paleolithic artifacts from it.     

Delamination and destruction of the North China Craton

This article presents an overview on recent developments in studies of chemical and physical processes of lithospheric delamination with respect to destruction of the North China Craton. It is emphasized that the pyroxenite source resulting from interaction between eclogite-derived melt and peridotite is a direct consequence of delamination. The pyroxenite source thus formed has unique mineralogical and geochemical features, which characterize Mesozoic basalts of the North China Craton. Melt-peridotite interaction played an important role in refertilization of cratonic lithospheric mantle, leading to density increase, weakening and final destabilization of the North China Craton. The nature of the melt is the key to distinguish mechanisms of destructing this craton.