Provenance of Miocene sandstones in northern Iraq: constraints from framework petrography,bulk-rock geochemistry and mineral chemistry

Modal analysis, bulk-rock geochemistry and phase chemistry of sandstones of the Miocene Fat'ha and Injana formations, northern Iraq, show that the clastics were derived from heterogeneous sources that include basic igneous and metamorphic rocks as well as older sedimentary rocks. The sandstones are generally carbonate-rich lithic arenites. Their geochemistry supports the petrographic results and indicates that they are all Fe-rich, lithic or quartz arkosic sandstones. According to geochemical data, garnets are derived from metamorphic sources, hornblende is of igneous origin, and clinopyroxenes, are produced by basic igneous rocks. Epidote is most probably to be a product of disintegration of metamorphic rocks, essentially, metamorphosed igneous rocks. Rutile geochemistry implies low-grade metamorphic and basic to ultrabasic igneous sources. Chemical composition of chromian spinels indicates that they are derived from Alpine-type peridotite. The ophiolitic-radiolarite belts of Taurus-Zagros as well as the uplifted Cretaceous and Paleocene strata of north and northeastern Iraq are likely to be the major source of clastics to the Fat'ha–Injana basin, a foreland basin formed as a result of the continental Arabian and Turkish/Iranian plates collision.     

滇东北矿集区茂租铅锌矿床热液白云石稀土元素特征

茂租铅锌矿床位于扬子地台西南缘,是滇东北矿集区内的一个大型矿床,矿体呈似层状产于震旦系灯影组白云岩中。矿石矿物以闪锌矿为主,次为方铅矿。脉石矿物主要为白云石、萤石和方解石。矿床的矿化蚀变分带明显,从围岩到矿体,矿化蚀变分带分别为:斑点状白云石化带、脉状白云石化带、星点状矿化带、细脉浸染状矿化带和矿体。白云石是该矿床的重要脉石矿物,除了震旦系灯影组的微晶-细晶白云石外,与成矿热液活动有关的白云石主要有斑点状白云石、脉状白云石和团块状白云石。文章对茂租铅锌矿床3种热液白云石及围岩灯影组白云岩的稀土元素地球化学特征进行了对比研究。结果表明:3种热液白云石与灯影组白云岩的稀土元素配分模式比较接近,总体上具有稀土元素总量低、轻稀土元素富集和Ce元素负异常的特征,这些相似的稀土元素特征表明3种蚀变白云石与围岩之间存在着成因联系。灯影组白云岩ΣREE含量较低,具有Eu元素负异常,而脉状和团块状热液白云石具有明显的Eu元素正异常,反映了存在较高温度的流体活动,热液蚀变白云岩是由高温热液流体形成。斑点状热液白云石Eu元素异常不太明显,可能是由于蚀变强度较弱,继承了原岩Eu元素负异常的特征。团块状白云石ΣREE和w(Y)、w(Sm)较高,表明有其他REE富集流体的加入。3种热液白云石是由高温流体形成,流体主要来源于地层,并有其他富含REE流体加入。     

川东北飞仙关组白云岩的主要类型、地球化学特征和白云化机制

四川盆地东北部蕴藏有丰富的烃类资源,三叠系飞仙关组的白云岩是最主要的储层和产层,这使得飞仙关组白云岩成为人们近年来高度关注的对象.按照结构,我们可以将飞仙关组白云岩分为三种端元类型:微晶白云岩、具原始结构的粒屑白云岩和结晶白云岩,在一个向上变浅的剖面旋回中,这三种白云岩分别位于旋回的顶部、上部和中下部.微晶白云岩和具原始结构的粒屑白云岩具有较高的锰含量和较低的包裹体均一化温度,白云化流体的δ~(18O) 值(从白云石的包裹体均一化温度和δ~(18O) 值反演,以下同)介于大气水和海水之间,反映这类白云岩形成于有大气水参与的相对开放的沉积-成岩环境中,蒸发泵作用(对于微晶白云岩)和混合水作用(对于具原始结构的粒屑白云岩)可能是其主要的形成机制;结晶白云岩(表现为好储层)具有很低的锰含量和较高的包裹体均一化温度,白云化流体的δ~(18O) 值显著高于早三叠世海水,表明这类白云岩形成于相对封闭的埋藏成岩环境,白云化流体具较高的温度和盐度,但到目前为止,还没有一个已有模式可以较好地解释这类白云岩的成因.     

Origin of Dinantian zebra dolomites south of the Brabant-Wales Massif, Belgium

Zebra dolomites, characterized by a repetition of dark grey (a) and light (b) coloured dolomite sheets building up abbabba-sequences, occur in Dinantian strata from deep boreholes (> 2000 m) south of the Brabant-Wales Massif in Belgium. These zebra dolomite sequences are several tens of metres thick. The dark grey dolomite sheets (a) consist of non-planar crystals, 80–150 μm in diameter. These crystals display a mottled red–orange luminescence and are interpreted to be replacive in origin. The white dolomite sheets (b) consist of coarse crystalline nonplanar b₁ dolomite, which evolves outwards into transparent saddle shaped b₂ dolomite. The b₁ dolomites possess a mottled red–orange luminescence similar to the a dolomites, while the saddle shaped b₂ rims display red to dark brown luminescent-zones. The b₁ dolomites are possibly partly replacive and partly cavity filling. Their b₂ rims display criteria typical for a cement origin. Locally, cavities exist between two succeeding white dolomite sheets. These cavities make up ≈5% of the zebra rocks and are locally filled by saddle shaped ankerite and/or xenomorphic ferroan calcite. Geochemical and fluid inclusion data (T_h ≈ 120 °C) indicate a burial diagenetic origin for these zebra dolomites. The a and b₁ dolomites are characterized by similar geochemical compositions and fluid inclusion data pointing toward a related origin. To explain the development of the zebra textures, suprahydrostatic pressures in conjunction with late Variscan tectonic compression are invoked. A model involving dolomitizing fluids expelled during the Variscan orogeny is proposed. An overpressured system is also invoked to explain the important porosity development, the creation of centimetre-scale subvertical displacements of the zebra pattern and the microfractures affecting the b₁–b₂ dolomite crystals.     

Nickel geochemistry of a Philippine laterite examined by bulk and microprobe synchrotron analyses

The Ni geochemistry of limonite and saprolite laterite ores from Pujada in the Philippines has been investigated using a mixture of laboratory and synchrotron techniques. Nickel laterite profiles are typically composed of complicated mineral assemblages, with Ni being distributed heterogeneously at the micron scale, and thus a high degree of spatial resolution is required for analysis. This study represents the first such analysis of Philippine laterite ores. Synchrotron bulk and microprobe X-ray absorption spectroscopy (XAS), comprising both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies, together with synchrotron microprobe X-ray fluorescence microscopy (XFM) and diffraction (XRD) have been applied to provide quantitative analysis of the mineral components and Ni speciation.Synchrotron microprobe EXAFS spectroscopy suggests that the limonite Ni is associated with phyllomanganate via adsorption onto the Mn oxide layers and substitution for Mn within these layers. Laboratory scanning electron microscopy, coupled to electron dispersive spectroscopy analyses, indicates that Ni is also associated with concentrated Fe containing particles and this is further confirmed by synchrotron bulk and microprobe investigation. Linear combination fitting of the bulk EXAFS limonite data suggests 60 ± 15% of the Ni is associated with phyllomanganate, with the predominant fraction adsorbed above vacancies in the MnO₆ layers with the remainder being substituted for Mn within these layers. The remaining 40 ± 10% of the Ni in the limonite ore is incorporated into goethite through replacement of the Fe. In the saprolite ore, 90 ± 23% of the Ni is associated with a serpentine mineral, most likely lizardite, as a replacement for Mg. The remaining Ni is found within phyllomanganate adsorbed above vacancies in the MnO₆ layers.     

Origin and emplacement of the Higher Himalayan Leucogranite in the eastern Himalaya: Constraints from geochemistry and mineral chemistry

The Higher Himalayan Leucogranites (HHLG) intruded into the high grade rocks of the Higher Himalayan Crystallines (HHC) in western Arunachal Pradesh, eastern Himalaya, yield distinctive field data, petrography, geochemical and mineral chemistry data. The HHLG mostly occur as sill like bodies of limited thickness and lateral extent within the HHC. The Arunachal HHLG are characterized by the presence of two micas; normative corundum; high contents of SiO₂ (67–78 wt.%), Al₂O₃ (13–18 wt.%), A/CNK (0.98–1.44) and Rb (154–412 ppm); low contents of CaO (0.33–1.91 wt.%) and Sr (19–171 ppm), and a high ratio of FeO_(tot)/MgO in biotite (2.54–4.82). These distinctive features, along with their strong depletion in high field strength elements (HFSE), suggest their affinity to peraluminous S-type granite generated by the partial melting of crustal material. Since the HHLG associated with high grade rocks of HHC and lack of basaltic magmatism, strongly suggests that the high grade rocks of HHC might represent the melt source and HHLG are product of pure crustal melt without any contamination of mantle material. Geothermobarometric estimations and mineral assemblages of the HHC metapelites confirm that the HHLG were probably generated in the middle crust (～20 km) and the produced melts intruded the HHC in the form of sills/dykes.     

柴北缘果可山岩体的岩浆混合作用:来自岩相学、矿物学和地球化学证据

青海南山岩浆岩带沿柴达木盆地和西秦岭造山带北缘分布,主要由与古特提斯洋俯冲-碰撞相关的晚二叠世-三叠纪花岗岩组成。本文对柴北缘东段果可山石英闪长岩及其中镁铁质微粒包体开展岩相学、矿物学、地球化学和Sr-Nd同位素综合研究及成因约束,为探究壳-幔相互作用提供新信息。LA-ICP-MS锆石U-Pb定年结果显示,果可山石英闪长岩与镁铁质包体形成于～247Ma。石英闪长岩属中钾钙碱性I型花岗岩,具有中等K_2O含量(1.43%～2.18%)和高Mg~#值(48.9～52.4),还表现出富集轻稀土元素、大离子亲石元素(如U、K、Pb),亏损重稀土元素和高场强元素(如Nb、Ta、Ti)和弱Eu负异常特征(Eu/Eu~*=0.71～0.85)。Sr-Nd同位素组成和矿物不平衡结构(如斜长石韵律环带和突变环带及角闪石包裹黑云母)表明,石英闪长岩主要源自镁铁质下地壳部分熔融并伴有富集地幔来源镁铁质组分的参与。镁铁质微粒包体呈椭球状,发育冷凝边和特殊的显微结构(如针状磷灰石、斜长石反环带和斜长石含刀刃状角闪石),具有更低的SiO 2含量(56.68%～59.28%)、更高的ε#Nd(t)和Mg值(58.5～62.2)以及更平坦的稀土配分曲线,暗示果可山镁铁质包体和寄主花岗岩是由源自遭受俯冲交代地幔的镁铁质岩浆与古老下地壳(古元古代晚期)来源的长英质岩浆不同比例混合形成的。结合前人对区域沉积学和构造解析研究结果,本文认为青海南山早-中三叠世岩浆活动与古特提斯洋向北俯冲诱发的幔源岩浆底侵和岩浆混合作用有关。     

Origin of the northern Indus Fan and Murray Ridge, Northern Arabian Sea: interpretation from seismic and magnetic imaging

The nature and origin of the sediments and crust of the Murray Ridge System and northern Indus Fan are discussed. The uppermost unit consists of Middle Miocene to recent channel–levee complexes typical of submarine fans. This unit is underlain by a second unit composed of hemipelagic to pelagic sediments deposited during the drift phase after the break-up of India–Seychelles–Africa. A predrift sequence of assumed Mesozoic age occurring only as observed above basement ridges is composed of highly consolidated rocks. Different types of the acoustic basement were detected, which reflection seismic pattern, magnetic anomalies and gravity field modeling indicate to be of continental character. The continental crust is extremely thinned in the northern Indus Fan, lacking a typical block-faulted structure. The Indian continent–ocean transition is marked on single MCS profiles by sequences of seaward-dipping reflectors (SDR). In the northwestern Arabian Sea, the Indian plate margin is characterized by several phases of volcanism and deformation revealed from interpretation of multichannel seismic profiles and magnetic anomalies. From this study, thinned continental crust spreads between the northern Murray Ridge System and India underneath the northern Indus Fan.     

Geochemistry and Origin of Layers in Single Manganese Nodule from the Philippine Sea and Manganese Nodules from Offshore Minami-Torishima,Western Pacific

Layers from one manganese nodule dredged from the Philippine Sea(16°56'N, 129°48'E; water depth, 5700 m) and 45 bulk nodules from offshore Minami-Torishima Island, Japan(23°3'N, 153°22'E; water depth, 1200 m) were analyzed chemically and their origin is discussed based on geochemical constraints. In general, Cu, Ni, Zn and Mo tend to increase with increasing Mn content, while Co, Pb, Ba, V, Sc, Th, and the rare earth elements(REEs) show less variation with increasing Mn content. Nodule 42 H from the Philippine Sea has an average Mn/Fe ratio close to 1 and shows a positive Ce anomaly, suggesting a predominant hydrogenous origin. Profiles of 230Th230 ex and Thex/232 Th ratios in the outer ~0.3 mm of nodule 42 H indicate a steady growth rate of ~1.7 mm/Myr. Nodule E30 from offshore Minami-Torishima is characterized by lower Mn, Fe, Mn/Fe(0.53) and Mo/V(0.2) ratios but higher P and Cu/Ni(0.31) ratio relative to other nodules from that area. The Ce content of E30 is unusually low(82 ppm) when compared with other nodules from the area and it is the only nodule analyzed with a negative Ce anomaly(-0.64). Based on the geochemical data we suggest that most nodules from offshore Minami-Torishima are primarily of hydrogenous origin except E30, which is dominated by hydrothermal input, and E45, which has about a 35% hydrothermal contribution.     

Organic Geochemistry of Lead—Zinc Polymetallic Dposits,Northern Guangdong

The characters of organic matter in rocks and ores in the Fankou and Dabaoshan deposits are systematically studied with regard to their implications for mineralization.The results show that kerogens in this area faaa mainly into the plutonism field in Van Krevelen‘s diagram.Reflectivity of the organic substance was measured to be 3.06%(Fankou)and 1.67%(Dabaoshan),corresponding to the paleo-geotemperatures of 232℃ and 184℃ respectively.The same types of porphyrins and hydrocarbons were recognized in the rocks and ores and hydrocarbon-bearing inclusions are widespread in quartz and calcite,particularly in Dabaoshan,It is thought that the orgain matter must have played a critical role in diagenesis and metallization in these deposits and that the hydrothermal solution was most likely to be the type of water-oil hot brine.     

北武夷铜钹山花岗质火山-侵入杂岩岩石地球化学

北武夷东部山前铜钹山出露一套花岗质火山-侵入杂岩,具高硅、富碱、过铝、铁镁含量低及富Rb、Th、Ce、LREE,贫Nb、Hf、Yb、Y,δEu变化较大等特点.区内花岗岩类与酸性中酸性火山岩在时间、空间和成岩物质来源具一致性,主要形成于晚燕山造山后期构造回返的类裂谷拉张环境中.该套杂岩是由于壳幔作用促使钙碱性岩浆活动的残留源区再次部分熔融,并有幔源物质混入其中,产生高钾钙碱性和橄榄安粗质花岗岩浆结晶分异形成.     

Sedimentology,geochemistry, and biota of Volgian carbonaceous sequences in the northern part of the central Russian Sea (Kostroma region)

Lithological, geochemical, stratigraphic, and paleoecological features of carbonaceous sediments in the Late Jurassic Volgian Basin of the East European Platform (Kostroma region) are considered. The shalebearing sequence studied is characterized by greater sedimentological completeness as compared with its stratotype sections in the Middle Volga region (Gorodishche, Kashpir). Stratigraphic position and stratigraphy of the shale-bearing sequence, as well as the distribution of biota in different sedimentation settings, are specified. It is shown that Volgian sediments show a distinct cyclic structure. The lower and upper elements of cyclites consist of high-carbonaceous shales and clayey-calcareous sediments, respectively, separated by transitional varieties. Bioturbation structures in different rocks are discussed. Microcomponent composition and pyrolytic parameters of organic matter, as well as distribution of chemical elements in the lithologically variable sediments are analyzed. Possible reasons responsible for the appearance of cyclicity and accumulation of organicrich sediments are discussed.     

Petrography and geochemistry of early-stage, fine- and medium-crystalline dolomites in the Middle Devonian Presqu'ile Barrier at Pine Point, Canada

The petrography and geochemistry of fine- and medium-crystalline dolomites of the Middle Devonian Presqu’ile barrier at Pine Point (Western Canada Sedimentary Basin) are different from those of previously published coarse-crystalline and saddle dolomites that are associated with late-stage hydrothermal fluids. Fine-crystalline dolomite consists of subhedral to euhedral crystals, ranging from 5 to 25 μm (mean 8 μm). The dolomite interbedded with evaporitic anhydrites that occur in the back-barrier facies in the Elk Point Basin. Fine-crystalline dolomite has δ¹⁸Ο values between ?1·6 to –3·8‰ PDB and ⁸⁷Sr/⁸⁶Sr ratios from 0·7079–0·7081, consistent with derivation from Middle Devonian seawater. Its Sr concentrations (55–225 p.p.m., mean 105 p.p.m.) follow a similar trend to modern Little Bahama seawater dolomites. Its rare earth element (REE) patterns are similar to those of the limestone precursors. These data suggest that this fine-crystalline dolomite formed from Middle Devonian seawater at or just below the sea floor. Medium-crystalline dolomite in the Presqu’ile barrier is composed of anhedral to subhedral crystals (150–250 μm, mean 200 μm), some of which have clear rims toward the pore centres. This dolomite occurs mostly in the southern lower part of the barrier. Medium-crystalline dolomite has δ¹⁸O values between ?3·7 to ?9·4‰ PDB (mean ?5·9‰ PDB) and ⁸⁷Sr/⁸⁶Sr ratios from 0·7081–0·7087 (mean 0·7084); Sr concentrations from 30 to 79 p.p.m. (mean 50 p.p.m.) and Mn content from 50 to 253 p.p.m. (mean 161 p.p.m.); and negative Ce anomalies compared with those of marine limestones. The medium-crystalline dolomite may have formed either (1) during shallow burial at slightly elevated temperatures (35–40 °C) from fluids derived from burial compaction, or, more likely (2) soon after deposition of the precursor sediments by Middle Devonian seawater derived from the Elk Point Basin. These results indicate that dolomitization in the Middle Devonian Presqu’ile barrier occurred in at least two stages during evolution of the Western Canada Sedimentary Basin. The geochemistry of earlier formed dolomites may have been modified if the earlier formed dolomites were porous and permeable and water/rock ratios were large during neomorphism.     

Organic geochemistry of Amynteo lignite deposit,northern Greece: a Multi-analytical approach

Several lignite samples were collected from boreholes of the Amynteo opencast lignite mine, northern Greece. Organic geochemical characteristics were investigated with the help of various analytical techniques, comprising Gas Chromatography (GC) and Gas-chromatography-Mass Spectrometry (GC-MS), Fourier Transform Infrared Spectroscopy (FTIR), solid-state Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR) spectroscopy, petrographical measurements as well as determination of bulk parameters. In the low rank (Rr = 0.21%) Amynteo lignites, huminite is the most abundant maceral group, inertinite has relatively low percentages and liptinite concentrations are rather high. Carbon Preference Index (CPI) reveals the predominance of odd-numbered, long-chained aliphatic hydro-carbons, which is related to a higher terrestrial plant input. The Pr/Ph ratio suggests that reducing conditions were persistent during peatification. Gymnosperm biomarkers such as isoprimarane, abietane, phyllocladane and sandaracopimarane, as well as angiosperm indicators (lupane) and hopanoid compounds with bacterial origin were identified. Analyses of the aromatic fractions revealed the presence of naphthalene, alkyl benzenes and phenols, pyrene, cadalene, cadinane, fluoranthene and dibenzofurane. Based on the FTIR analysis, aliphatic and oxygen containing structures were prevailed over the aromatic moieties. The intensity of the mineral bands was preferentially increased in the FTIR spectra of insoluble material. According to NMR analysis, the aliphatic carbons (0–50 ppm) have higher proportions comparing to aromatic carbons (100–160 ppm). The aromaticity fraction is low (fa = 0.32), as expected for these low rank coals. The presence of free organic radicals and Fe³⁺ and Mn²⁺ paramagnetic ions was revealed by EPR. In summary, the combined application of complementary analytical techniques allowed a deep inside into the geochemical characteristics of Amynteo lignites.     

粤北笋洞花岗岩的形成时代、地球化学特征与成因

笋洞花岗岩体是粤北贵东复式花岗岩体的一个重要组成部分。锆石U-Pb年龄为189.1±0.7Ma,是燕山早期岩浆活动产物。该岩体的主要元素显示富硅、富碱、强过铝质和低 CaO/Na_2O比值等特征;微量元素方面,富集Rb,Th,U,Ce,Sm,Y,亏损 Ba,Sr,P,Ti;LREE轻微富集(LREE/HREE=6.6～8.8,(La/Yb)_N=6.44～10.74),Eu亏损明显(δEu=0.14～0.31);它具有低的ε_(Nd)(t)(-11.4～-9.3),高的δ~(18)O(10.2～12.7‰)、(~(87)Sr/~(86)Sr);(0.72949～0.74923)、~(206)Pb/~(204)Pb(18.180～18.488)、~(207)Pb/~(204)Pb(15.655～15.661)和古老的Nd模式年龄(1762～1933Ma)。上述这些特征表明,笋洞岩体属于典型的壳源型花岗岩,是在地壳伸展-减薄的构造背景下,通过以泥质成分为主的古-中元古代变质沉积岩部分熔融的方式形成。     

Mineralogy,chemistry, and grain size composition of recent sediments in the northern Tyrrhenian Sea: Contribution to the study of sediment transport and distribution

As a contribution to an environmental study on Tuscany's marine shelf, textural, mineralogical, and chemical characteristics of recent sediments in the northern Tyrrhenian Sea between Elba Island and Livorno have been analyzed. The data provide clear information on sediment sources and movement patterns. The main sediment source appears to be the Cecina River; very subordinate is the contribution of the Fine River. As to sediment movement patterns, the surveyed basin appears to be divided into two subbasins: (1) a greater, southern subbasin, bounded by Tuscany mainland, Elba Island and Elba Ridge, and Capraia Isle, and Vada Shoals; and (2) a smaller, northern subbasin, enclosed between Vada Shoals and Meloria Shoals (off Livorno port).In the former the coarse-grade Cecina River sediments are transported southward along most of the mainland coast by littoral drift and coastal current; a northward flowing countercurrent seems to be active only in the southernmost part. Silts and clays are distributed in concentric belts around basin's central part, being transported mainly by slow circular water movements. In the marginal western zone, very little terrigenous influx is coupled with a high biologic productivity, and biogenic debris sedimentation prevails there.In the northern subbasin the sediment contribution from Fine River is more appreciable. Here the environmental energies are very low and the coarse sediments are restricted to a few small pocket beaches where they are deposited by local creeks. Most of the subbasin area is occupied by sapropelitic muds, again distributed by slow small-scale gyres.     

新疆恰尔墩巴斯希铁-铜-金矿矿床地质研究

新疆恰尔墩巴斯希铁-铜-金矿床中磁铁矿化和铜矿化与中基性侵入岩体密切相关。磁铁矿化在辉长岩体与中基性火山岩的内外接触带发育,由内带的磁铁矿+透辉石组合变化到外带的磁铁矿+石英+钙铁榴石+方解石组合。辉长岩和闪长岩的轻、重稀土元素分异明显〔(La/Yb)N为3.19～7.81〕,富集大离子亲石元素,亏损Nb、Ta,具岛弧岩浆岩特征。辉长岩氧逸度较高,明显富钾。铜矿化主要集中于闪长岩体的外接触带,大部分铜矿化充填在热液角砾岩中。可划分出4个铜矿化阶段:①钠长石-石英阶段;②黄铜矿-黄铁矿-自然金-绢云母-石英阶段;③黄铜矿-黄铁矿-绿帘石-葡萄石阶段;④闪锌矿-方铅矿-石英-方解石阶段。自然金主要出现在糜棱岩化之后的黄铁矿-石英脉中。     

Schorlomite: a discussion of the crystal chemistry, formula, and inter-species boundaries

Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe²⁺ and Mg in the octahedrally coordinated Y site, and Fe³⁺, Al and Fe²⁺ in the tetrahedrally coordinated Z site. Substitutions Ti⁴⁺Fe³⁺Fe³⁺_–1Si_–1 and Ti⁴⁺Al³⁺Fe³⁺_–1Si_–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe²⁺ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe²⁺ contents) for the presence of ^[6]Ti³⁺ or ^[4]Ti⁴⁺ in schorlomite. The simplified general formula of schorlomite can be written as Ca₃Ti⁴⁺₂[Si_3-x(Fe³⁺,Al,Fe²⁺)_xO₁₂], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti⁴⁺ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe³⁺, Fe²⁺ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of ^[6]Ti⁴⁺, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: (^[6]Ti⁴⁺–^[6]Fe²⁺–^[6]Mg²⁺– ^[8]Na⁺)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca₃Fe³⁺₂Si₃O₁₂), morimotoite (Ca₃Fe²⁺TiSi₃O₁₂), and Ca₃MgTiSi₃O₁₂. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.

Cyrilovite from Italy: Structure and crystal chemistry

Summary The crystal structure of the cyrilovite from Bosa, Sardinia, Italy, a new locality for this rare mineral, has been refined in the P 4₁2₁2 space group to aR value of 0.053 for 907 observed reflections. The structure consists of sheets of Fe³⁺-centered octahedra sharing vertices to form a square net, in the center of which the 8-fold coordinated Na+ ion is located. The Na-Fe-O sheets are linked together by P0₄ distorted tetrahedra and by hydrogen bonds. The unit-cell parameters (a = 7.313 (2) Å,c = 19.315 (3) Å, V = 1033.0 (4) Å3,c/a 2.641) are substantially greater than those of wardite, the other endmember of the solid solution series. The chemistry is close to the end-member, but shows a limited solid solution of Al for Fe, and of Ca for Na; the latter may imply a yet poorly known possibility of vacancies in the 8-fold coordinated sites. The IR spectra show the presence of AI substituting for Fe³⁺ in the form of additional weak bands.[

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Cyrilovit aus Italien:Struktur und kristallchemie

Zusammenfassung Die Kristallstruktur von Cyrilovit aus Bosa, Sardinien, Italien - einem neuen Fundort dieses seltenen Minerals - wurde in Raumgruppe P 4₁2₁2 auf einen R-Wert von 0,053 für 907 beobachtete Reflexe verfeinert. Die Struktur besteht aus Schichten; Oktaeder mit Fe³⁺ als Zentralatom werden über Ecken zu einem quadratischen Netz verknüpft, wobei in der Mitte ein 8-koordiniertes Na+-Ion liegt. Die Na-Fe-O-Schichten werden durch verzerrte PO₄-Tetraeder und durch Wasserstoffbrückenbindungen verknüpft. Die Gitterparametera = 7,313 (2) Å,c = 19,315 (3) Å,V = 1033,0 (4) Å3,c/a = 2,641) sind wesentlich größer als jene des Wardits, dem zweiten Endglied dieser Mischkristallreihe. Die chemische Zusammensetzung kommt dem Endglied nahe, zeigt jedoch einen geringfügigen Ersatz von AI für Fe bzw. von Ca für Na; letzterer dürfte auf die bisher nur wenig beachtete Möglichkeit von Leerstellen in der 8-koordinierten Position hindeuten. Das IR-Spektrum zeigt aufgrund zusätzlicher schwacher Banden das Vorliegen des Ersatzes von Al für Fe³⁺.

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With 3 Figures     

The geochemistry of the Dunedin Volcano: Strontium isotope chemistry

The isotopic composition of strontium has been determined for samples from the alkaline lavas of the Dunedin Volcano covering the range basalt, basanite, intermediate compositions, phonolite and quartz normative trachyte. The basaltic, intermediate and phonolitic rocks appear to be comagmatic and have similar low initial Sr⁸⁷/Sr⁸⁶ ratios around 0.7030, comparable with those of other alkaline provinces. The quartz normative trachytes have initial ratios significantly higher than those of the other rocks (0.7040) although their age is comparable. Contamination by sea water or crustal material could explain the higher initial ratios of the trachytes but it does not account for important features of their chemistry. It is suggested that the trachytes formed by partial melting involving an alkali feldspar-rich portion of older igneous rocks. Rb-Sr ages obtained are comparable with published K-Ar dates. The Rb-Sr age for the trachytes is 14.± 7 m.y. and the other alkali-enriched rocks give ages ranging within the limits of 14.4 to 12.0 m.y.