华北克拉通新生代玄武岩携带的地幔橄榄岩Fe同位素地球化学及含金云母地幔岩岩石学研究

In recent years, thanks to the improvement of analytical methods and the use of MC-ICP-MS, Fe isotope can be measured precisely. Fe isotope shows considerable variation both in biological and inorganic processes (from low T to high T) in nature, Therefore, Fe isotope has become one of the exciting frontier sciences and has favorable prospects of the application to the geosciences and life sciences. Based on a comprehensive review of available references in the related field, this study focuses on the development of techniques for high-precision measurement of iron isotope using MC-ICP-MS, and application of the techniques developed to study the Fe isotopes as well as major and trace element compositions of minerals (Ol, Opx, Cpx and Sp) from spinel peridotitic xenoliths from Cenozoic alkaline basalts to investigate Fe isotopic features of the lithospheric mantle beneath the North China Craton. The minerals from these xenoliths are similar to those off-cratonic peridotites world-wide, but are remarkably different from those on-cratonic peridotites and clinopyroxenes from these spinel lherzolites exhibit two types of chondrite-normalized REE patterns i.e. LREE-depleted and flat or spoon-shaped. It is noted that total abundances of REE in clinopyroxenes from these peridotites show a broad negative correlation with Cr# numbers of Cpx and Sp. The Fe isotope results show that the spinel peridotitic xenoliths have small but distinguishable Fe isotopic variations in minerals (generally Ol < Opx < Cpx) and samples, and the isotopic range in spinel is relatively large. Positive linear relationship with the ε57Fecpx/ε57Feopx ratio close to one unit has been observed between Fe isotopes of coexistent Opx and Cpx, indicating that the Cpx and Opx have generally reached Fe isotopic equilibrium. However, Fe isotopes between the Ol and Sp show apparent disequilibrium. The broadly negative correlation between mineral Fe isotopes and oxygen fugacity (fo2), metasomatic indexes such as spinel Cr#, (La/Yb) N and (La/Sm) N ratios of clinopyroxenes suggest that Fe isotopic variations in different minerals and peridotites were probably produced by melt-peridotite interaction. This study further confirms the previous observation that the lithospheric mantle has distinguishable and heterogeneous Fe isotopic variations at a scale of xenoliths. Mantle metasomatism that induces the interaction of the lithospheric mantle peridotite with metasomatic agent is a most potential mechanism for the Fe isotope fractionation in mantle peridotites. Therefore, Fe isotope could be a new and powerful tool to probe the evolution of the lithospheric mantle. We also report mineral compositions, clinopyroxene trace element concentrations and Sr-Nd isotopes for newly-discovered phlogopite-bearing spinel lherzolite and olivine clinopyroxenite xenoliths from three different localities （Hannuoba, Hebei Province; Jining Sangyitang, Inner Mongolia; Hebi, Henan Province）of the North China Craton. Systematic comparisons with phlogopite-free spinel lherzolite xenolith from the same locality reveals that the phlogopite-bearing peridotitic xenoliths have relatively higher Al2O3, CaO, Na2O, K2O, TiO2 contents and lower MgO contents than those phogopite-free counterparts. The former also has higher LREE concentrations, but relatively less radiogenic Sr-Nd isotopic ratios. This demonstrates that mantle metasomatism can not only enrich the basaltic components and trace element concentrations, but also make a decrease in Mg# of the peridotites and olivines and a relative depletion in Sr-Nd isotopes. 87Rb/86Sr-87Sr/86Sr isochrons of the phlogopite-bearing xenoliths indicate that mantle metasomatism happened in the Mesozoic and/or Cenozoic time. The metasomatic agent was derived from the asthenosphere. The result also manifests that the widespread similarity of the geochemical features such as major and trace elements and isotopic compositions in the Cenozoic lithospheric mantle beneath the North China Craton to those “oceanic” lithospheric mantle could be as a result of the ubiquitous presence of the interaction between the old refractory peridotites and the infiltrated asthenospheric melt, rather than the actually newly-accreted lithospheric mantle.

北大别黄土岭麻粒岩变质演化：对大别造山带演化进程的指示意义

Granulites from Huangtuling in the North Dabie metamorphic core complex in eastern China preserve rare mineralogical and mineral chemical evidence for multistage metamorphism related to Paleoproterozoic metamorphic processes, Triassic continental subduction-collision and Cretaceous collapse of the Dabieshan Orogen. Six stages of metamorphism are established, based on detailed mineralogical and petrological studies: (I) amphibolite facies (6.3–7.0 kbar, 520–550 °C); (II) high-pressure/high-temperature granulite facies (12–15.5 kbar, 920–980 °C); (III) cooling and decompression (4.8–6.0 kbar, 630-700 °C); (IV) medium-pressure granulite facies (7.7–9.0 kbar, 690–790 °C); (V) low-pressure/high-temperature granulite facies (4.0–4.7 kbar, 860–920 °C); (VI) retrograde greenschist facies overprint (1–2 kbar, 340–370 °C). The P–T history derived in this study and existing geochronological data indicate that the Huangtuling granulite records two cycles of orogenic crustal thickening events. The earlier three stages of metamorphism define a clockwise P–T path, implying crustal thickening and thinning events, possibly related to the assembly and breakup of the Columbia Supercontinent ca. 2000 Ma. Stage IV metamorphism indicates another crustal thickening event, which is attributed to the Triassic subduction/collision between the Yangtze and Sino–Korean Cratons. The dry lower crustal granulite persisted metastable during the Triassic subduction/collision due to lack of hydrous fluid and deformation. Stage V metamorphism records the Cretaceous collapse of the Dabieshan Orogen，possibly due to asthenosphere upwelling or removal of the lithospheric mantle resulting in heating of the granulite and partial melting of the North Dabie metamorphic core complex. Comparison of the Huangtuling granulite in North Dabie and the high-pressure (HP)–ultrahigh-pressure (UHP) metamorphic rocks in South Dabie indicates that the subducted upper (South Dabie) and lower (North Dabie) continental crusts underwent contrasting tectonometamorphic evolution during continental subduction–collision and orogenic collapse. High-pressure granulites are generally characterized by the absence of orthopyroxene. However, the Huangtuling felsic granulite rarely preserves the high-pressure granulite facies assemblage of garnet + orthopyroxene + biotite + plagioclase + K-feldspar + quartz. To investigate the effects of bulk rock composition on the stability of orthopyroxene-bearing, high-pressure granulite facies assemblages in the NCKFMASHTO (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3) system, we constructed a series of P–T–X pseudosections based on the melt-reintegrated composition of the Huangtuling felsic high-pressure granulite. Our calculations demonstrate that the orthopyroxene-bearing, high-pressure granulite facies assemblages are restricted to low XAl [Al2O3/(Na2O + CaO + K2O + FeO + MgO + Al2O3) < 0.35, mole proportion] or high XMg [MgO/(MgO + FeO) > 0.85] felsic–metapelitic rock types. Our study also reveals that the XAl values in the residual felsic–metapelitic, high-pressure granulites could be significantly reduced by a high proportion of melt loss. We suggest that orthopyroxene-bearing high-pressure granulites occur in residual overthickened crustal basement under continental subduction–collision zones and arc–continent collision belts.

班公湖带多不杂超大型富金斑岩铜矿床的成岩成矿年代学、岩石学及高氧化岩浆¬流体-成矿作用

Duobuza copper deposit, newly discovered typical gold-rich porphyry copper deposit with superlarge potential, is located in the Tiegelong Mesozoic tectonic -magmatic arc of the southern edge of Qiangtang block and the northern margin of Bangonghu-Nujiang suture. Quartz diorite porphyrite and grandiorite porphyry, occurred in stock, are the main ore-bearing porphyries. As the emplacement of porphyry stock, a wide range of hydrothermal alteration has developed. Within the framework of the ore district, abundant hydrothermal magnetite developed, and the relationship between precipitation of copper and gold and hydrothermal magnetite seems much close. Correspondingly, a series of veinlets and network veinlets occurred in all alteration zones. Therefore, systematic research on such a superlarge high-grade Duobuza gold-rich porphyry copper deposit can fully revealed the metallogenic characteristics of gold-rich porphyry copper deposits in this region, establish metallogenetic model and prospecting criteria, and has important practical significance on the promotion of regional exploration. In addition, this research on it can enrich metallogenic theory of strong oxidation magma-fluid to gold-rich porphyry copper deposit, and will be helpful to understand the metallogenic characteristics in early of subduction of Gangdese arc stages and its entire evolution history of the Qinghai-Tibet Plateau, the temporal and spatial distribution of ore deposits and their geodynamics settings. Northern ore body of Duobuza copper deposit have been controlled with width (north-south) about 100 ~ 400 m, length (east-west) about 1400 m, dip of 200 °, angle of dip 65 °~ 80 °. And controlled resource amount is of 2.7 million tons Cu with grade 0.94% and 13 tons Au with 0.21g/tAu. Overall features of ore body are large scale, higher grade copper, gold-rich. Ore occurred in the body of granodiotite porphyry and quartz diorite porphyrite and its contact zone with wall rock. Through the detailed mapping and field work studies, some typies of alteration are identificated as follows: albitization, biotititation, sericitization, silication, epidotization, chloritization, carbonatization, illitization, kaolinization and so on. The range of alteration is more than 10km2. Wall alteration zone can be divided into potassic alteration, moderate argillization alteration, argillization, illite-hydromuscovite or propylitization from ore-bearing porphyry center outwards, but phyllic alteration has not well developed and only sericite-quartz veins occurred in local area. Moreover, micro-fracture is development in ore district , and correspondingly a series of veinlets are development as follows: biotite vein (EB type), K-feldspar-biotite-chalcopyrite-quartz vein, magnetite-antinolite-K-feldspar vein, quartz-chalcopyrite-magnetite veins (A-type), quartz-magnetite-biotite-K-feldspar vein, chalcopyrite veinlets in potassic alteration zone; (2) chalcopyrite occurring in the center vein–quartz vein (B type), chalcopyrite veinlets, chalcopyrite-gypsum vein in intermediate argillization alteration; (3) chalcopyrite- pyrite-quartz vein, pyrite-quartz vein, chalcopyrite-gypsum veins, quartz-gypsum- molybdenite-chalcopyrite vein in argillization alteration; (4) gypsum veins, quartz-(molybdenite)-chalcopyrite vein, quartz-pyrite vein, gypsum- chalcopyrite vein, potassium feldspar veinlets, Carbonate veins, quartz-magnetite veins in the wall rock. In short, various veins are very abundant within the framework of the ore district. The results of electronic probe microscopy analysis (EMPA) indicate that Albite (Ab 91.5~99.7%) occurred along the rim of plagioclase phenocryst and fracture, and respresents the earliest stages of alteration. K-feldspar (Or 75.1~96.9%) altered plagioclase phenocryst and matrix or formed secondary potassium feldspar veinlets. Secondary biotite occurred mainly in phenocryst, matrix and veinlets, belong to magnesium-rich biotite formed under the conditions of high-oxidation magma- hydrothermal. Chloritization developed in all alteration zones and alterd iron- magnesium minerals such as biotite and hornblende and then formed chlorite veinlets. As the temperature rises, Si in the tetrahedral site of chlorite decreased, and chlorite component evolved from diabantite to ripiolite. The consistent 280℃~360℃ of formation temperature hinted that chlorite formed on the same temperature range in all alteration zones. However, formation temperature range of chlorite from the gypsum-carbonate-chlorite vein was 190℃~220℃, and it may be the product of the latest stage of hydrothermal activity. The closely relationship between biotite and rutile indicate that most of rutiles are precipitated in the process of biotite alteration and recrystallization. In addition, the V2O3 concentration of rutile from ore body in Duobuza gold-rich porphyry copper deposit is >0.4％, indicate that V concentration in rutile has important significance on marking main ore body of porphyry copper deposit. Apatites from Duobuza deposit all are F-rich. And apatite in the wall rock contained low MnO content and relatively high FeO content, which may due to the basaltic composition of the wall rocks. The MnO in apatite from altered porphyry show a strong positive correlation with FeO. In addition, Cl/F ratio of apatite from wall rock was highest, followed by the potassic alteration zone and potassic alteration zone overprinted by moderate argillization alteration was the lowest. SO2 in Apatite are in the scope of 0 to 0.66%, biotite in the apatite has the highest SO2, followed by the potassic alteration zone, potassic alteration zone overprinted by moderate argillization alteration, and the lowest in the surrounding rocks, which may be caused by the decrease of oxygen fugacity of hydrothermal fluid and S exhaust by sulfide precipitation in potassic alteration. Magnetite in the wall rock have higher Cr2O3 and lower Al2O3 features compared with altered porphyry, this may be due to basalt wall rock generally has high Cr content. And magnetites have higher TiO2 content in potassic alteration than moderate argillization alteration overprinted by potassic alteration, argillization and wall rock, suggested that its formation temperature in potassic alteration was the highest among them. The ore minerals mainly are chalcopyrite and bornite, and Au contents of chalcopyrite, bornite, and pyrite are similar with chalcopyrite slightly higher. The Eu* negative anomaly of disseminated chalcopyrite was relatively lower than chalcopyrite in veinlets. Within a drill hole, the Eu* negative anomaly of disseminated chalcopyrite was gradually larger from bottom to top. Magnetite has the same distribution model, with obvious negative Eu* abnormal, and ΣREE in great changes. The gypsum has the highest ΣREE content and the obvious negative anomaly, and biotite obviously has the Eu* abnormal. Based on the petrographic and geochemical characteristics, five series of magmatic rocks can be broadly classified; they are volcanic rocks of the normal island arc, high-Nb basaltic rocks, adakites, altered porphyry and diorite. The Sr, Nd, Hf isotopes and geochemistry of various series of magmatic rock show that they may be the result of mixing between basic magma and various degrees of acid magma coming from lower crust melted by high temperature basic underplating from partial melting of the subduction sediment melt metasomatic mantle wedge. Furthermore S isotope and Pb isotope of the sulfide, ore-bearing porphyries and volcanic rocks indicated ore-forming source is the mantle wedge metasomatied by subduction sediment melt. Oxygen fugacity of magma estimated by Fe2O3/FeO of whole rock and zircon Ce4+/Ce3+ indicated that the oxidation of basalt-andesitic rocks is higher than ore-forming porphyry, and might imply high-oxidation characteristics of underplated basic magma. Its high oxidative mechanism is likely mantle sources metasomatied by subduction sediment magma, including water and Fe3+. And such high oxidation of basaltic magma is conducive to the mantle of sulfides in the effective access to melt. And the An component of dark part within plagioclase phenocryst zoning belong to bytownite (An 74%), and its may be a result of magma composition changes refreshment by basaltic magma injection. SHRIMP zircon U-Pb and LA-ICP-MS zircon U-Pb geochronology study showed that the intrusions and volcanic rocks from Duobuza porphyry copper deposit belong to early Cretaceous magma series (126~105Ma). The magma evolution series are as follows: the earliest diorite and diorite porphyrite → ore-bearing porphyry and barren grandiorite porphyry →basaltic andesite → diorite porphyrite → andesite → basaltic andesite, and magma component shows a evolution trend from intermediate to intermediate-acid to basic. Based on the field evidences, the formation age of high-Nb basalt may be the latest. The Ar-Ar geochronology of altered secondary biotite, K-feldspar and sericite shows that the main mineralization lasting a interval of about 4 Ma, the duration limit of whole magma-hydrothermal evolution of about 6 Ma, and possibly such a long duration limit may result in the formation of Duobuza super-large copper deposit. Moreover, tectonic diagram and trace element geochemistry of volcanic rocks and diorite from Duobuza porphyry copper deposit confirm that it formed in a continental margin arc environment. Zircon U-Pb age of volcanic rocks and porphyry fall in the range of 105~121Ma, and Duobuza porphyry copper deposit locating in the north of the Bangonghu- Nujiang suture zone, suggested that Neo-Tethys ocean still subducted northward at least early Cretaceous, and its closure time should be later than 105 Ma. Three major inclusion types and ten subtypes are distinguished from quartz phenocrysts and various quartz veins. Vapor generally coexisting with brine inclusions, suggest that fluid boiling may be the main ore-forming mechanism. Raman spectrums of fluid inclusions display that the content of vapor and liquid inclusion mainly contain water, and vapor occasionally contain a little CO2. In addition, the component of liquid inclusions mainly include Cl-, SO42-, Na+, K+, a small amount of Ca2+, F-; and Cl- and Na+ show good correlation. Vapor mainly contains water, a small amount of CO2, CH4 and C2H6 and so on. The daughter minerals identified by Laman spectroscopy and SEM include gypsum, chalcopyrite, halite, sylvite, rutile, potassium feldspar, Fe-Mn-chloride and other minerals, and ore-forming fluid belong to a complex hydrothermal system containing H2O-NaCl-KClFeCl2CaCl2. H and O isotopic analysis of quartz phenocryst, vein quartz, magnetite, chlorite and gypsum from all alteration zones show that the ore-forming fluid of Duobuza gold-rich porphyry copper deposit consisted mainly of magmatic water, without addition of meteric water. Duobuza gold-rich porphyry copper deposit formed by the primary magmatic fluid (600-950C), which has high oxidation, ultra-high salinity and metallogenic element-rich, exsolution direct from the magma, and it is representative of the typical orthomagmatic end member of the porphyry continuum. Moreover, the fluid evolution model of Duobuza gold-rich porphyry copper deposit has been established. Furthermore, two key factors for formation of large Au-rich porphyry copper deposit have been summed up, which are ore-forming fluids earlier separated from magma and high oxidation magma-mineralization fluid system.

中国北方中新世风尘物质来源及古气候的地球化学指示

The most prominent tectonic and environmental events during the Cenozoic in Asia are the uplift of the Himalaya-Tibetan plateau, aridification in the Asian interior, and onset of the Asian monsoons. These caused more humid conditions in southeastern China and the formation of inland deserts in northwestern China. The 22 Ma eolian deposits in northern China provide an excellent terrestrial record relative to the above environmental events. Up to date, many studies have focused on the geochemical characters of the late Mio-Pleistocene eolian deposits, however, the geochemical characteristics of the Miocene loess and soils is still much less known. In this study, the elemental and Sr-Nd isotopic compositions of the eolian deposits from the Qinan (from 22.0 to 6.2 Ma) and the Xifeng (from 3.5 Ma until now) loess-soil sections were analyzed to examine the grain size effects on the element concentrations and the implications about the dust origin and climate. The main results are as follows: 1. The contents of Si, Na, Zr and Sr are higher in the coarser fractions while Ti and Nb have the highest contents in the 2-8 μm fractions. Al, Fe, Mg, K, Mn, Rb, Cu, Ga, Zn, V, Cr, Ni, LOI have clear relationships with grain-size, more abundant in the fine fraction while non significant relationship is observed for Y. Based on these features, we suggest that K2O/Al2O3 ratio can be used to address the dust provenance, and that VR (Vogt ratio = (Al2O3+K2O)/(MgO+CaO+Na2O)) can be used as a chemical weathering proxy for the Miocene eolian deposits because of their relative independence on the grain size. Meanwhile, SiO2/Al2O3 molar ratio is a best geochemical indicator of original eolian grain size, as suggested in earlier studies. 2. Analyses on the Sr and Nd isotope composition of the last glacial loess samples (L1) and comparison with the data from the deserts in northern China suggest that that Taklimakan desert is unlikely to be the main source region of the eolian dust. In contrast, these data suggest greater contributions of the Tengger, Badain Jaran and Qaidam deserts to the eolian dust during the last glacial cycle. Since the geochemical compositions (major, trace, REE and Sr, Nd isotope) of loess samples for the past 22 Ma are broadly similar with the samples from L1, these data trend to suggest relatively stable and insignificant changes of dust sources over the past 22 Ma. 3. Chemical weathering is stronger for Miocene paleosol samples than for the Plio-Pleistocene ones, showing warmer/more humid climatic conditions with a stronger summer monsoon in the Miocene. However, chemical weathering is typical of Ca-Na removal stage, suggesting a climate range from semiarid to subhumid conditions. These support the notion about the formation of a semi-arid to semi-humid monsoonal regime by the early Miocene, as is consistent with earlier studies.

泥河湾盆地大长梁剖面岩石磁学和环境磁学研究

The fluvio-lacustrine sequence in the Nihewan Basin is an important archive of late Pliocene-Pleistocene climate and environment changes in temperate northern China, which provides excellent sources of early human settlements in high latitude East Asia. The recent years have witnessed a considerable progress in the paleomagnetic dating of its stratigraphy, which has notably increased our understanding of a series of important issues such as the early human occupation in the Old World, the infilling history of the Nihewan Basin, and the chronological sequence of the Nihewan faunas. Up to now, the long-term paleoenvironmental changes directly retrieved from this basin, which might influence the evolution and expansion of early humans in the Nihewan Basin, are still poorly constrained, although several paleoclimatic records have been retrieved from this area. In this study, a combined mineral-magnetic and geochemical investigation was carried out on the fluvio-lacustrine sequence from the Dachangliang section at the eastern margin of the basin in order to reveal its rock magnetic and environmental magnetic characteristics and its implications for early human evolution in East Asia. The major findings and conclusions are listed as the following: First, there is an increased cooling coupled with an intensified aridification recorded in the fluvio-lacustrine sequence of the Dachangliang section. The cooling is related to an up-section decrease in propensity to chemical weathering as inferred from an increase in low-field susceptibility after cycling to 700 °C. Close to 700 °C, reacting chlorite is providing the iron source for newly formed very fine-grained ferrimagnetic minerals which enhances the susceptibility signal. The reactivity of chlorite after annealing at temperatures above 600 °C is documented with X-ray diffraction. Second, degrees of chemical weathering in the Nihewan Basin are further estimated by clay mineralogy (i.e. chlorite and illite contents and chlorite/illite ratio) and a series of major element proxies (i.e. Na2O/Al2O3 versus K2O/Al2O3 diagram, Al2O3-(CaO + Na2O)-K2O ternary diagram (A-CN-K), chemical index of alteration (CIA), (CaO + Na2O + MgO)/TiO2, (CaO + Na2O + MgO + K2O)/(TiO2 + Al2O3), CaO/Al2O3 and CaO/TiO2). The up-section decrease in propensity to chemical weathering suggested by the aforementioned rock mangetic measurement is further confirmed by these geochemical analyses. Combining the chemical weathering records from the Nihewan Basin, Chinese Loess Plateau, South China Sea and eastern China, we find that the consecutive decreasing trend in chemical weathering intensity during the late Cenozoic is ubiquitous across China. This pattern may result from a long-term decreasing East Asian summer monsoon and increasing East Asian winter monsoon, and thus a consecutive increasing of aridification and cooling in Asia during the Quaternary. Furthermore, the chemical weathering intensity increased from South China to North China during the Quaternary, in line with the decreasing East Asian summer monsoon and increasing East Asian winter monsoon and thus the gradually intensified aridification and cooling from South China to North China. Third, a combined mineral-magnetic and geochemical investigation provides evidences that the large-amplitude alterations of concentration of magnetic minerals mainly result from preservation/dissolution cycles of detrital magnetic minerals in alternately oxic and anoxic depositional environments. The preservation/dissolution model implies that the high-magnetic and low-magnetic cycles of this sedimentary sequence represent glacial and interglacial climate cycles, respectively. This contribute significnatly to our understanding of the link between climate and magnetic properties. Finally, the paleoclimatic implications of these rock magnetic and geochemical characteristics significantly increase our understanding of the general setting of early humans in high northern latitude in East Asia. We propose that the cold and dry climate may have contributed significantly to the expansion and adaptation of early humans, rather than bringing hardship, as is often thought. The relationship between magnetic properties and climate possibly provides valuable information on the climatic context of the Paleolithic sites in the basin, especially whether the occupation occurred during an interglacial or glacial period.

特提斯喜马拉雅带晚白垩世-始新世沉积源区分析及其构造意义

Tethyan Himalayan Sequence (THS) is located at the frontier of the India-Asia collision zone, which can preserve critical information about collision. This paper reports detailed petrology, geochemistry, spinels electron microprobe data, and in situ U-Pb ages and Lu-Hf isotopic data on detrital zircons from the late Cretaceous to early Eocene strata in Gyantze and Gamba area, south Tibet that provide important constraints on the early tectonic evolution of the India-Asia collision. In Gyantze, the lithic arkose in Zongzhuo mélange is characterized by, SiO2 =80.4%, Al2O3=8.6%, Na2O=1.6%, K2O=1.1%, LaN/YbN=8.90, and εNd (0) =-10.27. Spinels compositions are characterized by low TiO2 (generally <0.1%) and a Cr number mainly between 70 and 80. The largest population of detrital zircons is within the 73-169Ma range with high εHf (t) and > 500 Ma with complex εHf (t) values. The lithic arkose in Rilang conglomerate is characterized by, SiO2 =56.5%, Al2O3=15.6%, Na2O=4.7%, K2O=0.6%, LaN/YbN=5.00-5.29, and εNd (0) =1.92. Spinels of 2006T98 display high TiO2 (generally >0.2%) and a Cr number mainly between 70 and 85, other spinels are characterized by low TiO2 (generally <0.2%) and a Cr number mainly between 60 and 90. The largest population of detrital zircons is within 90-146 Ma range with high εHf (t). The lithic arkose in Jiachala formation is characterized by, SiO2 =64.6%, Al2O3=12.1%, Na2O=1.9%, K2O=1.8%, LaN/YbN=7.73-9.13, and εNd (0) =-5.52~-8.43. Spinels in the Jiachala formation have low TiO2 (generally <0.2%) and a Cr number between 39 and 88. Detrital zircons have a wide range of age distribution of 82-3165Ma with complex εHf (t). In Gamba, The quartze sandstone in Jidula formation is characterized by, SiO2=97.4%, Al2O3=0.9%, Na2O=0.03%, K2O=0.18%, LaN/YbN=18.70-21.684, and εNd (0) between -13.1~-7.4. While the lithic arkose in Zhepure formation is characterized by, SiO2=68.4%, Al2O3=7.3%, Na2O=1.15%, K2O=0.52%, LaN/YbN=6.09-8.99, and εNd(0)=-5.8~-6.3. Based on our geochemical analysis, spinles electron microprobe data, U–Pb ages and Hf isotope data for detrital zircons of the late Cretaceous-Eocene strata in Gyantze and Gamba, southern Tibet, the following major conclusions can be drawn: 1. In Gyantze, the Zongzhuo mélange was mainly derived from accretionary prism/THS of continental slop and Gangdese arc. Rilang conglomerate was totally from Gangdese arc. The Jiachala formation was derived from THS, suture zone and Gangdese arc. 2. In Gamba, the Jidula formation was from India craton, while the Zhepure formation was derived from THS, suture zone and Gangdese arc. 3. The deposite of Zongzhuo mélange and Rilang conglomerate (73-55Ma) marks the collision between India and Asia. 4. Late Paleocene-Eocene tectonic evolution is consistent with foreland basin system.

广西凭祥英安岩的化学风化作用研究

利用薄片观察、X射线粉晶衍射分析和化学分析方法研究了广西凭祥英安岩风化剖面的形成作用。风化作用初期,母岩中微量黄铁矿的氧化分解导致方解石与绿泥石的迅速分解;风化中期形成了大量的高岭石、伊利石、蒙脱石和蛭石;风化作用高级阶段以高岭石、石英和氧化铁矿物的富集为特征,但仍然存在少量蒙脱石、伊利石和蛭石。风化剖面的部分层段显示出与剖面其他部分明显不同的地球化学特征,即Na的富集和K的亏损。在Al2O3-(CaO+Na2O)-K2O三角图上,风化中期这些层段明显偏离了正常的风化趋势。矿物学和微形貌的研究表明,造成偏离的原因是古地下水引起的正长石的钠长石化作用。

贵州老万场金矿床红土化作用及对金赋存状态的制约

红土的矿物成分、硅酸盐成分和化学蚀变指数(CIA)特征表明，贵州老万场红土化过程经历了粘土化、铝土矿化、铁化三种化学风化作用；地球化学上属早期红土化作用阶段。风化过程中K2O、Na2O、CaO相对于Al2O3的淋失量很高，显示较强的化学蚀变作用。红土剖面中成矿元素Au、As、Sb含量变化很大。Au通常为40～4551ng／g；Sb普遍小于0．1％；As通常为0．n％，最高1．8％。它们普遍高于大厂层硅质岩中相应成矿元素的含量。红土化过程中，Au、As的富集与Fe的富集作用有明显的关系，并与红土剖面中相对还原的部位有关，而sb则在相对氧化的环境中聚集。红土剖面中稀土元素含量普遍较高，轻重稀土元素之比通常小于10，稀土元素分布模式非常相似，与大厂层稀土元素特征有明显差别。微量元素图解显示红土剖面中的大离子亲石元素、不相容元素与大厂层也有明显的不同。成矿元素问的差异性也很明显，表明大厂层岩石可能并不为老万场红土层的发育提供直接的物质来源，红土层的发育似乎与后期第四系的冲积物、洪积物有关。成矿物质也可能不与大厂层直接有关。带能谱的透射电镜(TEM-EDX)观察表明金的存在形式多样，虽然金主要以浑圆状的自然金颗粒产出，但也可以被针铁矿(含砷针铁矿)、石英硅质吸附，或被伊利石等吸附。显示红土化过程中铁还原作用对金富集的重要性。

贵州赫章土法炼锌导致的土壤重金属污染特征及微生物生态效应

贵州省赫章县妈姑镇新关寨附近的土法炼锌不仅导致植被的破坏，而且使附近土壤中重金属有不同程度的积累，Zn达到162.23-877.88mg/kg,Pb为37.24-305.56mg/kg,Cd为0.50-16.43mg/kg，大大超过了当地的土壤背景值；而且重金属含量（特别是Pb和Zn含量）与土壤中的Fe2O3和Al2O3有极显著的正相关关系，显示土壤中铁氧化物和粘土矿物对重金属的固定作用。化学形态研究表明，Pb和Zn在土壤中主要表现为铁锰氧化物结合态与残渣态，而Cd的情况与Pb和Zn完全相反，其形态以可交换态为主。本区土壤微生物生物量（用含碳量表示）较低，仅为57.00-388.00μg/g，而且与土壤重金属间有显著的负相关关系，特别是与Zn的相关系数高达-0.7801，反映出重金属对微生物的毒害作用。Biolog测试结果表明，土壤微生物群落结构间没有明显的差别；土壤微生物DNA经PCR（聚合酶链式反应）和DGGE（变性梯度胶电泳）反应后的基因片段非常一致，反映出不同程度的重金属污染并没有导致土壤微生物群落结构的改变和基因损伤，另一方面也表明，土壤本身有强烈的固定重金属能力，抵御了重金属对土壤生物的进一步毒害。

贵州赫章土法炼锌导致的重金属积累

贵州省赫章县的土法炼锌不仅导致植被的破坏，而且使附近土壤和溪流沉积物中重金属有不同程度的积累，土壤中w(Pb)达到37．24×lO^-6～30100×lO^-6，w(Zn)为162．23×lO^-6～31625×lO^6。，w(Cd)为O．50×lO^-6～113×lO^-6，大大超过了当地的土壤背景值；沉积物中w(Pb)达到325．00×lO^-6～21850×lO^-6，w(Zn)为1250．00×10^-6～30425×10^-6，w(Cd)为25×10^-6～97×10^-6。土壤和沉积物中Pb、Zn含量与Al2O3有极显著的正相关性；土壤中重金属Pb、压含量与A12O3有极显著的正相关性，而沉积物中Pb、压含量与Al2O3则没有相关性。土壤和沉积物中铁矿物(铁氧化物和氢氧化物)对重金属的强烈固定作用。连续提取法对化学形态研究表明，Pb、办在土壤中主要表现为铁锰氧化物结合态与残渣态，而在沉积物中则主要为碳酸盐结合态、残渣态和铁锰氧化物结合态。土壤中可交换态Pb、压所占的比例很小，但其绝对含量变化较大，w(Pb)从最低2．75×lO^-6到最高310．4l×l0^-6，w(Zn)4．94×lO^-6～321．10×lO^-6。沉积物中w(Pb)7．42×lO^-6～98．9l×lO^-6;w(zn))9．97×lO^-6～72．67×lO^-6。土壤中重金属Pb、压的有效性程度明显高于溪流沉积物，对生态环境的潜在危害更大.

贵州老万场金矿成矿物质来源的研究

硅酸盐成分研究表明老万场红土化过程经历了粘土化、铝土矿化、铁化三种化学风化作用;风化中化学蚀变较强,K2O、Na2O、CaO 相对于Al2O3 的淋失量很高。在红土剖面上成矿元素的含量变化很大。相关性分析表明,红土化过程中,Au、As 的富集与脱硅富铝化程度关系不大,而与铁的富集有明显的关系;Au、As 的富集与相对还原的环境有关,而Sb 则在相对氧化的环境中易于聚集。可能反映了红土剖面中潜水面下部附近相对还原的环境Au、As 易于富集。大厂层样品和老万场红土剖面样品在成矿元素(Au、As、Sb) 含量、稀土元素含量、轻重稀土比值、配分曲线上以及微量元素特征包括大离子亲石元素、不相容元素上的较大差异,显示了红土层的发育与大厂层岩石有较大的差别,暗示它们物质来源上的一定差异性。

贵州修文小山坝铝土矿中稀土元素地球化学特征

前人已经积累了大量贵州铝土矿的研究成果,但关于铝土矿与其中稀土元素的关系至今不清。本研究以修文小山坝铝土矿为例,通过ICP-MS分析测试,研究了矿石和围岩的稀土元素组成。结果表明,矿石中稀土配分模式为轻稀土富集向右倾斜型,具明显Eu负异常,与下寒武统娄山关群含泥质白云岩稀土特征参数和配分模式相似,指出该矿床成矿物质来源以下寒武统娄山关群含泥质白云岩为主,在相对氧化环境下经风化作用成矿。矿床中稀土元素主要富集于矿体及其周围,与Al2O3含量具正相关关系。矿石中稀土元素含量大多达到或超过综合利用标准,具有巨大的潜在经济价值。

陆相热水沉积成因硅质岩与超大型锗矿床的成因—— 以临沧锗矿床为例

临沧锗矿床的硅质岩中存在大量的热水沉积构造和植物化石, 该硅质岩富SiO2 , 低TiO 2和Al2O3, Al/(Al+Fe+Mn)比值平均为0.010, 明显富集Ge, Sb, As, W; 其次Cs, U, Mo和Tl有不同程度的富集, 稀土总量一般小于1 μg/g, 最大2.324 μg/g , 相对富集LREE; δ Eu为0.452 ~ 5.141, δ Ce为 0.997 ~ 1.174; 稀土元素北美页岩标准化模式呈平坦状或向左倾斜; 氧同位素组成与热泉硅华类似. 上述特征表明本区硅质岩属陆相热水沉积成因. 硅质岩作为中寨锗矿体的顶板或夹层, 在空间上与锗矿体紧密接触. 硅质岩中含锗5.6 ~ 360 μg/g, 平均78 μg/g. 靠近硅质岩的煤中锗含量明显升高. 随着煤中锗含量的不断升高, 含矿煤的特征微量元素比值及稀土元素的球粒陨石标准化分配模式与硅质岩越来越相似. 临沧锗矿床煤中锗可能主要由与煤层形成近同时的、以热水成因硅质岩为标志的热水活动带入.

渔塘坝硒矿硅质岩的地球化学特征及成因

渔塘坝硒矿床是目前我国发现含硒量（8590×10^-6）最高的小型独立硒矿床，其赋矿岩石主要为硅质岩，且发育程度较高。早二叠世晚期的黑色碳质硅质岩系，是区内的赋矿层位，它局限于特定的沉积相位，即碳酸盐合地海盆浅部沼泽（藻沼）环境沉积的黑色碳质硅质岩相带，硒矿化层和这套碳质硅质岩相带密切相关，其矿化相带呈NW向展布。硅质岩的SiO2含量变化较大（64.2%-94.85％），平均为75.9%;Fe2O3、Fe2O3、FeO、MnO、TiO2、Al2O3和MgO等含量相对，与其它热水成因硅质岩相近；硅质岩富含As、Sb、Fe和Ag，而贫Cu、Co和Ni；在Al-Fe-(Cu+Co+Ni)三角图、U-Th相关图和P2O3-Y相关图上的投影特征，也同样显示出硅质岩的热水成因特征。另本区硅质岩中的Cr含量较大，且（Fe+Mn）/Ti的比值为6.34，这表明硅质岩在成因上还可能和二叠纪峨眉山玄武岩喷发的火山作用有一定的联系。

高岭石热转变产物^29Si、^27Al魔角旋转核磁共振研究

运用魔角旋转核磁共振结合红外光谱及X射线衍射等手段，研究了苏州高岭石的560－1600℃热转变产物，主要获得以下结论：（1）高岭石－偏高岭石－莫来石的转变系列的确存在结构上的连续性。其转变经历了几个阶段；脱羟阶段（400－600℃），偏高岭石阶段（600－800℃），相分离阶段（800－1100℃），莫来石阶段（1100－1600℃）。（2）莫来石形成过程没有出现Al2O3的大量分凝，但存在SiO2的分凝。（3）偏高岭石－莫来石转变过程的中间相为Al-Si尖晶石和准莫来石。（4）引起1000℃放热反应的主要因素是准莫来石的形成。