The Paleoclimatic Variation Records of Carbonate and Iron Oxides in the Weinan Loess Section

The contents and distributions of CaCO3,Fe2O3.FeO and free Fe2O3 in the Weinan loess section of Shaanxi Province of China were investigated through dense sampling.The results show that the contents of CaCO3 and the ration of Fe2O3/FeO may be chosen as proxy in dices for the precipitation and temperature changes in the formation time of the strata,respectively.According to these geochemical indices,six stages of plaeoclimate evolution are proposed in this region since 142 ka B.P.,and secondary climate changes are discussed as well based on the curves of geochemical indices.     

REE Geochemical Evolution and Its Significance of Early Precambrian Metamorphic Terrain,Wuyang,Henan

The supracrustal rocks of the Wuyang metamorphic terrain are divided into the Zhao anzhuang,Tieshanmiao and Yangshuwan Formations.These three Formations were dated at 3000-2550Ma,2550-2300Ma and 2300-2200Ma,respectively.∑REE and La/Yb)n of the Zhao anzhuang Formation volcanic rocks are obviously higher than those of the Tiesanmiao Formation equivalents,suggesting a sedimentary gap(2550 Ma boundary)between these two formations,The Zhao‘anzhuang Formation is older than the Tieshanmiao Formation.The sediments of these two Formations show no obvious differences in REE and are generally characterized by low ∑REE and positive Eu anomalies.On the contrary,the sediments of the Yangshuwan Formation are characterized by high ∑REE and negative Eu anomalies.Detailed discussions demonstrate that the Yangshuwan Formation was deposited in an oxidizing environment whereas the other two formations were formed in a reducing environment.At the end of the evolution of the Tieshanmiao Formation about 2300 Ma ago,the sedimentary environment was transformed from reducing to oxidizing .On the basis of the SHAB (soft/hard acid and base)theory,an oxidation-reduction model for sedimentary REE evolution has been established .It is proposed that the mantle tends to become gradually depleted in REE.especially in LREE,and the indices ∑REE and La/Yb) n of mantle-dervived volcanic rocks also tend to become lower and lower.     

黄土剖面中古气候变化的地球化学记录

作者通过对陕西洛川黄土剖面中碳酸盐总量、氧化物比值和元素演化周期性的分析，讨论了黄土高原地区２．４Ｍａ以来古气候的演化模式。对渭南黄土剖面高密度连续采集的样品，着重分析了ＣａＣＯ_３、Ｆｅ₂Ｏ_３／ＦｅＯ值和有机碳的高分辨记录。指出它们的变化彼此同步(但趋势不尽相同)，与黄土一古土壤系列变化一致，井与深海沉积物氧同位素可进行良好的对比。它们综合反映了该区１３４５００年来有五次万年级的暖湿(或凉湿)一冷干的气候波动，其中各期又有若干次级的小颤动。它们的变化与季风影响强弱程度明显有关。     

Analytical Model for the Palaeoenvironmental Evolution of the Nihewan Beds

In this paper, the evolutional characteristics of palaeoclimate and oxidation-reduction conditions as well asacidity-alkalinity environment are discussed by means of the step-regression, cluster, optimal partitioning andcorrelation analyses of CaCO_3, C / P_2O_5, Fe~(2+) / Fe~(3+), pH and Eh values, taking the Xiaodukou section in theNihewan basin as an example. The CaCO_3, C / P_2O_5 and pH were calculated respectively using the optimalpartitioning method. Thus five cold zones and six warm zones as well as five reduction and six oxidation zoneswere distinguished. Then the inductive method was used to produce four numerical groups: 8.10, 8.3-8.4,8.6-8.7 and 8.9-8,97. The above-mentioned results are respectively based on CaCO_3 content, C/P_2O_5 andpH values. From Fig. 3, Tables 1 and 2 it can be seen that the Nihewan Beds were formed mainly under a re-duction and slightly alkaline environment of cold climate, with pH values of 8.3-8.4. Fig. 3 shows that bed 35is approximately near the boundary between the Brunhes and Matuyama polarity epochs, 0.73 Ma in age; bed26 is roughly near the Jaramillo event (base), 0.97 Ma in age; bed 18 coincides roughly with themagnetostratigraphic boundary of 2.00 Ma (?). Bed 13 may be the Pleistocene-Pliocene boundary, 2.48 Ma inage. Thus geochemical zones Ⅰ, Ⅱ, Ⅲ and Ⅳ include respectively cold zones 1; 2 and 3; 4; and 5.     

合肥下蜀土地球化学特征及其古气候意义

合肥地处长江中下游北岸,下蜀黄土广泛分布,通过对合肥地区BK2钻孔剖面岩性、氧化物含量及其地球化学风化参数的分析,研究合肥地区风成沉积物地球化学元素特征及其气候变化规律。结果表明:野外钻孔岩芯剖面显示地层较好连续性,结合年龄数据划分了该孔的第四纪沉积框架,Qh底界为1.20 m,Qp3底界为5 m,5~35.10 m属Qp2中晚期地层;合肥下蜀土主要化学成分（SiO₂+Al₂O₃+Fe₂O₃）的平均含量之和达88.99%,这种显著的富硅铝铁现象表明了该区气候较为湿润;化学风化程度较强,下蜀土的CIA平均值及其脱Ca、Na、K的程度均大于洛川黄土,说明其堆积期古气候比同期堆积的洛川气候温湿,较宣城干凉,与南京、镇江气候较为接近;近0.5 Ma以来总体经历由湿热-干冷的变化,大致可分为35~14.50 m、14.50~4.50 m、4.50~1.20 m和1.20~0 m四个阶段,气候变化由温暖湿润-温暖偏干-冷凉偏干-温暖湿润,显示了区内更新世中晚期以来的气候变迁具有全球一致性特征。      

Climatic sub-cycles recorded by the fourth paleosol layer at Luochuan on the Loess Plateau

The Chinese loess–paleosol succession, deep-sea sedimentary sequences and ice cores are the three types of paleoclimatic records. Measurements were made of the ancient climatic proxies of magnetic susceptibility, median diameter of grain size and content >40 μm, and the CaCO₃ content of samples collected at 1 cm depth intervals in the fourth paleosol layer of the Luochuan loess-paleosol section on the Chinese Loess Plateau. Wavelet analysis of the data identified cycles of climate change, which were compared to the marine δ¹⁸O record of SPECMAP. The results showed that: (1) when the fourth paleosol layer was forming, the paleoclimate was relatively stable but five extreme climatic events were identifiable as occurring around 408, 381, 376, 368 and 361 kaBP; (2) two of these regional events differed from the global trend; (3) during marine isotope stage (MIS)11, the fourth paleosol layer of the Luochuan loess section recorded a regional quasi-19 ka climatic sub-cycle and (4) this sub-cycle was also reflected globally in the SPECMAP data indicating that, during MIS11, this sub-cycle was regionally and globally synchronized.     

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt,Xinjiang (NW China)

The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al₂O₃ and TiO₂, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al₂O₃ (<3 wt%), TiO₂ (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al₂O₃ (>3 wt%), TiO₂, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu¹_PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu¹_PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe³⁺/(Fe³⁺/Fe²⁺) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ¹³C_V-PDB (−4.0‰ to −6.6‰) and δ¹⁸O_V-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ¹³C_V-PDB = −0.8‰ to + 3.1‰ and δ¹⁸O_V-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu¹_PAAS and δ¹³C_V-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO₂, with the deeper water, from which the carbonate facies BIF formed, depleted in δ¹³C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe²⁺-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe²⁺-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.     

Composition and age of Sariolian volcanites of the Vermas formation in Northern Karelia

During this work, the composition of Sariolian volcanites of the Vermas formationin the Karelian region was studied and the U-Pb age of these rocks was first obtained (SHRIMP-II). In composition these volcanites are andesites and andesite-basalts, as well as, to a lesser extent, trachyandesites and trachyandesitobasalts of the calc-alkaline series. Due to porphyroblast crystallization, widely manifested in this region volcanites are enriched in TiO₂, Al₂O₃, Fe₂O_3total, K₂O, Rb, Cs, Zr, Hf, Y, Nb, Cr, V, Th and REE (primarily La and Ce). Rocks of the Vermas formation formed in the Paleoproterozoic (2412 ± 17 Ma) and were transformed as a result of the Svecofennian metamorphism in the interval of 1970 ± 15 Ma. The source of the melt and inherited zircons with the age of 2630–2760 Ma can be crustal material with the ancient Sm-Nd model age (3–3.1 Ga).     

Hydrothermal Cu-Ni-Au-Ag mineralization in a granodiorite sill north of Cradock, Republic of South Africa

An undulating sheet-like granodiorite body is intrusive into sedimentary rocks and dolerite of the Karoo Supergroup north of Cradock. The top of this sheet, where in contact with dolerite, is characterised by the presence of graphite containing nodules of sedimentary origin, and by sulphide-arsenide mineralization. REE and other geochemical evidence indicate that the granodiorite and the ore-bearing horizon are genetically related, but the latter is more altered by hydrothermal fluids. Similarities in REE distribution patterns also imply very little assimilation of sedimentary material. The granodiorite displays plume-like features signifying that the material was plastic or semi-molten when segregation of the plume-like features took place. The Ni-mineralisation in the ore-bearing horizon is not linked to the MgO or Fe₂O₃ of the granodiorite or of the ore-bearing zone, and is regarded as a separate event of hydrothermal origin. Received: 26 July 1996 / Accepted: 17 March 1997     

Mobility Sequence of Chemical Elements During Loess Weathering—Pedogenesis,Weinan,Shaanxi Province,China

The distribution of chemical elements in the Weinan loess section shows that: (1) carbonate is the critical constituent affecting loess chemistry. The leaching of carbonates may cause “apparent” enrichment of some other constituents. (2) CaCO₃, SiO₂, FeO, MgO, K₂O and Na₂O are mobile while Al₂O₃, Fe₂O₃ and TiO₂ are inert components. The mobility sequence may follow the order of CaCO₃>FeO>MgO>Na₂O>K₂O>SiO₂>Al₂O₃>TiO₂>Fe₂O₃. (3) No obvious migration is noticed of iron, except changes in valence and forms, during the pedogenic process. Little iron has been supplied to paleosol from precipitation. (4) Carbonates and, to a lesser extent, iron are most sensitive to, and can be therefore used as good indicators of, environmental changes. This research project was financially supported by the National Natural Science Foundation of China (Grant No. 49672137).     

微生物碳酸盐岩沉积特征研究——以四川盆地高磨地区灯影组为例

四川盆地震旦系灯影组属于新元古界最后一套地层,也是四川盆地第一套沉积岩盖层。岩性以质纯色浅的白云岩为主,并且经历了多期复杂的成岩作用,因此其沉积环境始终是研究的难点和争议的焦点。本文以盆地周缘的野外剖面、钻井岩心、测井资料及分析化验等资料为基础,以岩石学、沉积学和石油地质学等理论为指导,并结合现代叠层石沉积特征,对灯影组岩石学特征、沉积环境进行了综合分析。研究表明:1灯影组的岩石类型可分为3个亚类和12个微类,其中贫藻段主要由晶粒云岩、凝块状云岩、粒屑云岩等组成,通常发育于一个完整沉积旋回的早—中期;富藻段主要由层纹状云岩、叠层状云岩、泡沫状云岩组成,通常形成于一个沉积旋回中—晚期;2四川盆地灯影组沉积相主要为浅水局限台地相,可细分为藻丘、颗粒滩、台坪、潟湖4个亚相。研究区以藻丘亚相为主,藻丘可进一步细分为丘基、丘核、丘盖3个微相;3优质储层受相控特征明显,台内颗粒滩相和藻丘相储集物性最好,尤其是两者叠合形成的"丘滩复合体"。总之,四川盆地震旦系灯影组的天然气勘探将围绕着微生物岩展开。     

Petrology and geochemistry of late archaean granitoids in the northern part of Eastern Dharwar Craton,Southern India: Implications for transitional geodynamic setting

The results of field, petrographic and geochemical work of the granitoids of Hutti-Gurgunta area in the northern part of Eastern Dharwar Craton (EDC) is presented in this paper. This crustal section comprises polyphase banded to foliated TTG gneisses, middle amphibolite facies Gurgunta schist belt and upper greenschist facies Hutti schist belt and abundant granite plutons. The focus of the present study is mainly on basement TTG gneisses and a granite pluton (∼ 240 sq km areal extent), to discuss crustal accretion processes including changing petrogenetic mechanism and geodynamic setting. The TTGs contain quartz, plagioclase, lesser K-feldspar and hornblende with minor biotite while the granite contain quartz, plagioclase, K-feldspar and hornblende. Late stage alteration (chloritisation, sericitisation and epidotisation) is wide spread in the entire area. A huge synplutonic mafic body which is dioritic to meladioritic in composition injects the granite and displays all stages of progressive mixing and hybridization. The studied TTGs and granite show distinct major and trace element patterns. The TTGs are characterized by higher SiO₂, high Al₂O₃, and Na₂O, low TiO₂, Mg#, CaO, K₂O and LILE, and HFS elements compared to granite. TTGs define strong trondhjemite trend whilst granite shows calc-alkaline trend. However, both TTGs and granite show characteristics of Phanerozoic high-silica adakites. The granite also shows characteristics of transitional TTGs in its high LILE, and progressive increase in K₂O with differentiation. Both TTGs and granite define linear to sub-linear trends on variation diagrams. The TTGs show moderate total REE contents with fractionated REE patterns (La/Yb_N =17.73–61.73) and slight positive or without any significant Eu anomaly implying little amount of amphibole or plagioclase in residual liquid. On the other hand, the granite displays poor to moderate fractionation of REE patterns (La/Yb_N = 9.06–67.21) without any significant Eu anomaly. The TTGs have been interpreted to be produced by low-K basaltic slab melting at shallow depth, whereas the granite pluton has been formed by slab melting at depth and these melts interacted with peridotite mantle wedge. Such changing petrogenetic mechanisms and geodynamic conditions explain increase in the contents of MgO, CaO, Ni and Cr from 2700 Ma to 2500 Ma granitoids in the EDC.     

Pelagic records from the Equatorial Ninetyeast Ridge and significant environmental events during the past 3.5 Ma

This paper presents pelagic records of planktic foraminifera, as well as data of stable isotope stratigraphy and carbonate stratigraphy since 3.5 Ma B.P. from site ODP758 in the Ninetyeast Ridge of the Indian Ocean. Based on these data, manifestations and related mechanisms of major tectonic and environmental events such as the rapid uplift of the Himalaya Mountains, “middle Pleistocene climatic transition” and “mid-Brunhes dissolution event” in the region are discussed. According to the analysis and comparison of various indices and changes in terms of foraminifera assemblage, paleotemperature, paleosalinity and themocline from site ODP758, the authors deduce that the paleoclimatic changes might correlate with the mid-Pleistocene transition at 1.4–1.7 Ma B.P. The changes of CaCO₃, mass accumulation rates (MAR) of CaCO₃ and non- CaCO₃ MAR indicate that the loaded terrigenous sediments increased at 1.7 Ma, which is in agreement with the uplift history of the Qinghai-Tibet plateau as shown by the available data. The last two changes coincide with the uplift of the Qinghai-Tibet plateau, hence they are called “Qinghai-Tibet movement” (1.7 Ma), and the “Kunlun-Yellow River movement” (1.2–0.6 Ma). The changes of the CaCO₃ content, coarse fraction (> 150 μm) content and planktonic foraminifera biostratigraphy show that strong dissolution of abyssal CaCO₃ occurred in the study region during 0.5–0.4 Ma. The event was consistent with the “mid-Brunhes dissolution event” in the sedimentary records of the Atlantic Ocean, Pacific Ocean, Indian Ocean and Nansha sea area of the South China Sea. __________ Translated from Geological Bulletin of China, 2007, 26(12): 1627–1632 [译自: 地质通报]     

Evolution and REE geochemistry of Huangsha-Tieshanlong ore-bearing granite

Our studies show that the granite bodies (γ ₅ ^{2 − 1} and γ ₅ ³ ) which constitute the Huangsha-Tieshanlong composite granitic intrusion in Jiangxi are characterized by their similarities in mineral assemblage, petrochemistry, trace element and REE distribution pattern. The values of ΣREE, ΣLREE, ΣHREE, ΣCe/ΣY, δEu and La/Yb apparently decrease from γ ₅ ^{2 − 1a} to γ ₅ ^{2 − 1b} , γ ₅ ³ and γ ₅ ³ . It is shown that the early Yenshanian W(Ta, Nb)-bearing granite (γ ₅ ^{2 − 1} ) and late Yenshanian Ta, Nb-bearing granite (γ ₅ ³ ) may have been derived from the differentiation and evolution of granitic magmas due to repeated remelting of the crust and their earlier and later intrusion. Although the earlier (γ ₅ ^{2 − 1b} and later (γ ₅ ³ ) albitized Ta, Nb-bearing granites show some obvious differences in REE content, their δEu values and La/Yb ratios are similar to each other. Therefore, it may be concluded that the early and late Ta, Nb-bearing granites were derived from a congenetic magma.     

REE-, Zr-, and Th-rich titanite and associated accessory minerals from a kersantite in the Frankenwald, Germany

Summary The mineral chemistry of a Variscan lamprophyre (kersantite) from the Frankenwald, Germany, has been investigated by electron microprobe. This potassic, Si-saturated, mafic rock contains an assemblage of different generations of titanite and allanite-(Ce), Th-rich zircon, and metamict REE–Ti–Zr–Th silicates. The primary ferroan-ceroan titanite contains unusually high contents of REE₂O₃ (max. (ΣLa to Sm)+Y = 36.8 oxide wt.%), ZrO₂ (max. 5.4 wt.%), and ThO₂ (max. 3.1 wt.%). Its empirical formula averages to (Ca_0.31 La_0.17 Ce_0.30 Pr_0.03 Nd_0.08 Sm_0.01 Y_0.01 Fe²⁺_0.06 Th_0.02 Mn_0.01)_Σ1.00 (Ti_0.60 Fe²⁺_0.22 Al_0.06 Zr_0.07 Mg_0.04 Nb_0.01)_Σ1.00 O_1.00(Si_0.93 Al_0.07)_Σ1.00 O₄. Element correlations reveal operation of the complex substitution Ca²⁺+Ti⁴⁺+Th⁴⁺ ⇔ REE³⁺+Al³⁺+Zr⁴⁺. In comparison to allanite-(Ce), ferroan-ceroan titanite preferentially incorporated the LREE and Th. This finding is inconsistent with previous experimental studies and suggests that both minerals are not cogenetic. High Zr contents in titanite, usually known only from Si-undersaturated alkaline rocks, and the predominance of Fe²⁺ suggest that the ferroan-ceroan titanite crystallized from an alkali-rich, low-fO₂ residual melt.     

Fine-Grained Aluminosiliciclastic Rocks of the Middle Riphean Stratotype Section in the Southern Urals: Formation Conditions,Composition and Provenance Evolution

General trends of the formation of Middle Riphean fine-grained aluminosiliciclastic rocks in the Bashkir Meganticlinorium are considered. It is shown that Yurmatinian shales do not contain any significant pyroclastic admixture. Judging from the relatively constant Th/Cr ratio throughout the Yurmatinian section, the tectonic regime in the study territory during the early Middle Riphean is suggested to be rather stable. The main paleoclimatic indices and indicators of the pelitic material maturity (CIA, CIW, IVC, PIA, and Ce/Y) suggest that paleodrainage systems in the early Middle Riphean were dominated by humid climate that gave way to the arid or semiarid type in the middle Yurmatinian. The low Mo/Mn ratio and some other indicators of redox conditions in shales from all Yurmatinian lithostratigraphic units show that no explicit reducing conditions existed in the basin during the early Middle Riphean. The shales were characterized by the increase in K₂O/Al₂O₃ ratio, gradual enrichment in REE, and growth of LREE/HREE and La_N/Yb_N ratios toward the middle Yurmatinian, indicating the gain of an appreciable amount of slightly weathered arkosic aluminosiliciclastic material in the sedimentary basin about 1220–1200 Ma ago. The REE distribution and the UCC- and AUC-normalized shale compositions suggest that the eroded upper crust was compositionally close to the UCC. The occurrence of mafic and ultramafic rocks is also inferred. Data points of Yurmatinian shales plotted in the Cr–Ni, Eu/Eu*–Gd_N/Yb_N, and (La/YB)_N–Yb_N diagrams are localized between the fields of Upper Archean and post-Archean rocks or within the latter field. Hence, post-Archean igneous and metamorphic complexes prevailed in paleodrainage systems of the early Middle Riphean. This is also confirmed by the model Nd ages.     

Microanalysis of Fe3+/ΣFe in oxide and silicate minerals by investigation of electron energy-loss near-edge structures (ELNES) at the Fe M 2,3 edge

The Fe M _2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe₃(Al_1–xFe_x)₂[SiO₄]₃ and andradite-skiagite (Fe_1–xCa_x)₃Fe₂[SiO₄]₃), pyroxenes (acmite-hedenbergite (Ca_1–xNa_x)(Fe²⁺ _1−xFe³⁺ _x)Si₂O₆), and spinels (magnetite-hercynite Fe(Al_1–xFe_x)₂O₄) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission electron microscope (TEM). The Fe M _2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge feature varies depending on Fe³⁺/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship between Fe³⁺/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M _2,3 edge is observed. Since the partial cross sections of the Fe M _2,3 edges are some orders of magnitude higher than those of the Fe L _2,3 edges, the Fe M _2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated by Fe M _2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that shows different edge shapes consistent with variations in the Fe³⁺/ΣFe ratio over distances on the order of 100 nm. Received: 14 April 1998 / Revised, accepted: 8 March 1999     

Premetamorphic lateritisation in Proterozoic metabasites of Rogaland,SW Norway

Heterogeneous layers of granulite facies metamorphic basites of the Proterozoic supracrustal Faurefjell Formation in Rogaland, S.W. Norway, display an extreme chemical variation. Within a single layer the bulk chemical composition gradually changes from approximately basaltic in basic granulites to alumina-iron-rich in granofelses. Component-ratios and composition-volume relations indicate open-system chemical reactions mainly involving the extraction of silica. Apparent enrichment in Fe, Ti, P, Al, Zr, Ni, Co, Zn, Y, Nb, Hf and REE and variations in resulting metamorphic mineral assemblages are related to premetamorphic progressive lateritisation of a basaltic protolith. The weathering generated a continuous chemical suite from SiO₂=48 wt%, Fe₂O₃=10 wt% and Al₂O₃=19 wt% in the basic granulites to 14 wt%, 40 wt% and 25 wt% in the Fe-Al granofelses. Metasomatism during diagenesis and during (very) high-grade metamorphism (1200–900 Ma) further perturbed the concentrations of relatively mobile elements Ca, Mg, K, Rb, Sr, Ba, Na and Li in the laterites without affecting the transition metal ratios. In particular, the REE did not fractionate differentially during the supracrustal and metasomatic alteration.     

扬子地块西缘峨山新元古代A2型花岗闪长岩的成因及构造意义

在扬子地块西缘出露有大量的新元古代岩浆岩,这些岩石对于重建罗迪尼亚超大陆有着重要的意义。本文对云南峨山岩体的花岗闪长岩和似斑状黑云母二长花岗岩开展了详细的岩石学、岩石地球化学和年代学研究,结果表明,似斑状黑云母二长花岗岩侵位于826.6±2.5 Ma,而花岗闪长岩有着较年轻的结晶年龄818.3±2.8 Ma,花岗闪长岩比似斑状黑云母二长花岗岩有着更低的SiO₂含量,但是更高的Al₂O₃、MgO、Fe₂O₃、TiO₂和P₂O₅含量。在稀土元素配分曲线和微量元素蛛网图上,两种岩性呈现出相似的特征,都是具有右倾的稀土元素配分样式,呈现出Eu负异常,相对于大离子亲石元素（LILEs）更亏损高场强元素（HFSEs）。似斑状黑云母二长花岗岩富集Nd同位素组分,而花岗闪长岩与之有着相似的Nd同位素值。地球化学数据显示可能的岩石学成因是变质火成岩源区在826 Ma时发生部分熔融形成了峨山似斑状黑云母二长花岗岩并且残留下来了一个麻粒岩化的源区;麻粒岩源区在818 Ma时再次发生部分熔融形成了具有A型属性的峨山花岗闪长岩。结合前人的数据和本文的研究,认为扬子西缘在新元古代时期是一个活动大陆边缘,而华南地块当时在罗迪尼亚的位置更可能是在边缘而不是中心。     

Bioavailability of arsenic in the soil horizon: a laboratory column study

Groundwater contaminated with arsenic (As), when extensively used for irrigation, causes potentially long-term detrimental effects to surface soils. Such contamination can also directly affect human health when irrigated crops, such as rice, vegetable and fruits, are used for human consumption. Therefore, an understanding of the leaching behavior of As in surface soils is of high importance, because such behavior may increase the bioavailability of As in the soil horizon. In this study, we have investigated the role of phosphate ions in leaching and bioavailability of As in the soil horizon, where drinking groundwater contains elevated levels of As (≥50 μg/L). Soil and groundwater samples were characterized in the laboratory and measured for physical and chemical constituents. The soils are generally neutral to slightly alkaline in character (pH range 7.5–8.1) with low to moderate levels of free Fe₂O₃, Al₂O₃, CaCO₃, organic carbon, and clay content. The measured electrical conductivity (mean 599 μS/cm) of the soils demonstrates their non-saline nature. The Eh values (range −37 to −151 mV) of the groundwater indicate anoxic condition with low to moderate levels of bicarbonate (range 100–630 mg/L) and phosphate (range 0.002–4.0 mg/L). The arsenic content (range 50–690 μg/L; mean 321 μg/L) in groundwater has exceeded both WHO recommended guideline values (10 μg/L) and the National safe drinking water limit (50 μg/L). Regression analyses demonstrate that the bioavailability of As in the soil horizon is mainly controlled by the composition of free Fe₂O₃ and CaCO₃ content of the soils. However, application of P could increase bioavailability of As in the soil horizon and become available to plants for uptake.