云南兰坪富锶文石的振动光谱特征

为进一步研究富锶文石的晶体结构、颜色成因和矿物成因，采用振动光谱、EMPA和SEM对富锶文石进行了测试和分析。红外光谱、拉曼光谱测试分析表明，由于富锶文石存在着锶与钙的类质同像现象，其红外光谱和拉曼光谱中CO3^2-的v1、v2、v3、v4种振动模式波数介于文石和碳酸锶矿之间，与文石、碳酸锶矿等文石型碳酸盐振动光谱特征一致，并且文石的v4存在分裂峰。EMPA面扫描发现Ca^2 、Sr^2 的分布与富锶文石内部环带的分布存在一致性。由于CuO含量较少，分布规律不明显。SEM分析发现在环带之间存在空隙，各环带中富锶文石结晶程度和晶体表面特征不一，不同颜色和形态的环带反复生长。生长过程中，流体成分中各种元素的含量、温度和压力的变化造成不同颜色环带的形成，反映了该富锶文石是经过不同时期沉积形成的。     

等轴锶钛石在我国的首次发现

笔者于1985—1986年,对华北地区岩浆岩型磷灰石矿床进行研究时,在山西省临县紫金山的钛榴霞石正长斑岩中,发现了与苏联的达乌松矿（Tausonite）相似的矿物,即等轴锶钛石。该矿物在我国的首次发现,对这一地区碱性岩的矿物学和岩石学研究无疑是很有意义的。本区等轴锶钛石一般为淡棕色,呈立方体或不规则柱状,折射率N=1.977±0.002,比重为4.66,均质体,个别具光性异常并呈环带构造,晶胞参数a0=3.905A,空间群Pm3m,晶胞体积v=59.55A。本文重点对该矿物的地质产状、矿物共生组合、物理性质与光学性质、矿物化学成分及X射线分析进行了研究。笔者认为本区等轴锶钛石是富钛富碱贫硅的碱性岩浆中早期结晶的产物。     

富锶文石的发现及其研究

富锶文石是文石的变种,其化学式为(Ca,Sr)CO3。二轴晶,负光性,2▽=9,折光率Ng=1.6620,Nm=1.6561,Np=1.5168,D=3.34,H=3.75,比磁化系数为0.32×10-6CGSMcm3/g。矿物为白色,透明,呈细小晶粒状或砂糖状集合体。易溶于稀盐酸。斜方晶系,晶胞参数a=4.61,b=7.89,c=5.78。矿物产于内蒙古白云鄂博铁、铌、稀土矿床的脉状含铌、稀土白云石碳酸盐岩中,在自然界中产出含锶如此之高的变种是罕见的。该矿物的发现对研究碳酸盐矿物中钙、锶元素类质同象置换机理和晶体光学均具有一定的学术意义。     

冀东迁滦地区沉积变质型铁矿床变质作用程度：来自石榴子石的制约

石榴子石是冀东地区沉积变质铁矿中常见的变质矿物之一。本文采集迁安-滦县地区代表性铁矿中含有石榴子石的岩石样品,对其石榴子石进行电子探针和X-射线粉晶衍射分析,得出司马地区为角闪岩相,杏山-黄柏峪一带为角闪岩-麻粒岩相,水厂-大石河地区为麻粒岩相,这与前人对迁滦地区用主要矿物共生组合等来研究变质相的结论相一致;同时迁滦地区沉积变质铁矿中石榴子石的端元组分和晶胞参数a0随变质程度的增加呈规律性变化: 司马地区的铁铝榴石+钙铝榴石→杏山-黄柏峪一带的铁铝榴石→水厂-大石河一带铁铝榴石+镁铝榴石,其晶胞参数a0值逐渐减小。因此在沉积变质型铁矿床中,变质矿物石榴子石的化学成分及晶胞参数特征对不同地区的变质程度具有示踪意义。     

钍石的新变种——铅钍石

铅钍石是钍石的新变种，属首次发现。其ＰｂＯ含量达９．０４％，由此引起其性质的变化，如比重、硬度、折光率和晶胞参数均小于铀钍石，并可根据红外吸收谱判断铅钍石的变生程度。     

土壤锶地球化学特征及土壤富锶标准探讨——以河南固始史河一带为例

锶是生物有机体内必需的微量元素之一,具有改善骨代谢、增强骨质强度,预防龋齿、“三高”和心血管疾病,有益肝细胞的增殖和胆红素代谢等作用。富锶土壤作为新的优势地质资源,逐渐受到重视,多个地方推出富锶农产品。目前对土壤中锶的地球化学特征研究较少,也无土壤富锶含量标准,这些严重制约了富锶生态农业的发展。研究区在河南固始史河一带,分析归纳不同成因、不同类型土壤中锶的含量特征及空间的分布规律,研究土壤锶形态及与其他元素相关性,总结土壤中锶地球化学特征。并对土壤富锶含量进行探讨,推荐提出富锶土壤锶含量标准：表层土壤中Sr含量≥205 mg/kg。并以此标准对固始史河一带土壤富锶资源进行评价,圈定绿色无公害食品富锶耕地236.3 km²,优选建立富锶特色农业示范区,助力地方美丽乡村建设。     

结构矿物学的新成果

五、无水碳酸盐矿物结构中阳离子有序—无序问题本文讨论与CaCO_3的各种同质多相变体(方解石、文石、球方解石)结构相关的无水碳酸盐矿物.近年来,在我国找到了几乎所有的已知的这类矿物,并且发现了几种新矿物(黄河矿、氟碳钸钡矿、中华镁矿、大青山矿)和新变种(富锶的文石、富锶的本斯顿石、富镍的菱镁矿(河西矿).对这些矿物都作过X射线研究,测定了钡解石、大青山矿、黄河矿、氟碳钸钡矿、碳钸钠石、Doverite的晶     

浙江诸暨地开石矿床中的磷铝锶石及其成因探讨

报道了赋存于上侏罗系蚀变凝灰岩型地开石矿床中的磷铝锶石矿物。它的含量不到３％。通过氢氟酸溶蚀，富集了磷铝锶石。用ＸＲＤ和ＩＲ研究了磷铝锶石的矿物学特征，并获得了良好ＩＲ图谱。磷铝锶石矿物具有特征的３４７５ｃｍ－１和３０７０ｃｍ－１ＯＨ吸收峰可区别于其他同族矿物。这种磷铝锶石形成于成岩作用后期，晚于地开石。     

金顶氧化铅锌矿石中镉的赋存状态

云南省兰坪县金顶矿床是目前我国已发现的最大铅锌矿床,在世界上已发现的大型铅锌矿床中名列第四。兰坪氧化铅锌矿石中,除铅锌外,还含有硫、镉、铊、银、锶、钡等多种有益组份。其中镉含量高达0.15％,同时也是一个大型镉矿床。因此。查明矿石中镉的赋存状态,对矿床的综合评价和矿产的综合利用,都是十分必要的。兰坪矿区分为北场、架崖山、峰子山、西坡,南厂和白草坪等六个矿段。昆明冶金研究所和云南省地矿局实验室曾在该区做了大量工作,本文在此基础上。研究了以锌为主的、储量最大的北场矿段氧化铅锌矿石中镉的赋存状态,并与架崖山矿段进行了比较。     

新疆库鲁克塔格兴地塔格群中石榴石的矿物学特征研究

通过电子探针测试和X射线粉晶衍射分析,对新疆库鲁克塔格兴地塔格群中红色石榴石样品的矿物学特征进行了研究。电子探针测试结果显示,不同变质期次形成的石榴石,铁铝榴石端员组分均由核部到边部逐渐增加,锰铝榴石均由核部向边缘逐渐减少,镁铝榴石由核部到边部逐渐增加,钙质系列石榴石总含量很低且变化稳定。研究表明,兴地塔格群石榴石由核部至边缘生长温度整体上升,形成压力基本稳定,石榴石形成环境的变质程度逐渐提高。根据X射线粉晶衍射数据计算出石榴石的晶胞参数较理论值大,是由Ca2+、Mn2+两种大半径离子对Fe2+的置换数目多于小半径Mg2+对Fe2+的置换引起的。     

海水珍珠微结构棱柱层的新认识

棱柱层是珍珠层微结构中与珍珠质层明显不同的结构单元。运用XRD、IR显微镜和偏光显微镜对我国优劣海水珍珠层微结构——棱柱层进行微区测试研究，结果发现海水珍珠微结构棱柱层不是以往认为的仅由方解石组成，而是有各种形态的文石棱柱，文石与方解石共同组成的棱柱。珍珠质量与棱柱体层的厚度及空间分布有密切关系，而并非完全是以往认为的文石含量越高海水珍珠质量就越好。     

New interpretations of Great Salt Lake ooids and of ancient non-skeletal carbonate mineralogy

Earlier interpretations of textural alteration affecting Great Salt Lake ooids have greatly influenced concepts of ooid diagenesis. Scanning electron microscope study shows, however, that the coarse radial aragonite rays are depositional, that no recrystallization of pellet cores has occurred, and that Great Salt Lake ooids have not suffered noticeable diagenesis. As suggested by Kahle (1974), radial texture in ancient calcitic ooids is probably mainly original, not diagenetic. Retention of such fine textures has been attributed to organic matter (since found to be equivalent in modern skeletal and non-skeletal grains) or to paramorphic replacement (proposed for non-skeletal grains whose original aragonite mineralogy was only inferred from modern analogs). Pleistocene ooids known to have been aragonite alter like aragonite shells to coarse neomorphic calcite, often with aragonite relics. The striking uniformity of that coarse texture in neomorphic calcite replacing known skeletal aragonites throughout the geologic record has been noted for over 100 years. In contrast, Mississippian ooids retain fine texture as do calcite layers of coexisting gastropods, but unlike the strongly altered aragonite layers of these same gastropods. Therefore, inferences of original aragonitic mineralogy of ancient non-skeletal carbonate grains (including muds) which are now calcite but retain fine texture appear unwarranted, as do assumptions of differential diagenetic behaviour of ancient aragonitic skeletal and non-skeletal grains. Accordingly, modern depositional environments of marine ooids and carbonate muds must be rejected as chemically unrepresentative of comparable ancient environments. It is inferred that ancient non-skeletal carbonates were originally predominantly or exclusively calcite because of an earlier lower oceanic Mg/Ca ratio (<2/1) which altered progressively to values favouring aragonite (modern Mg/Ca value = 5/1). Major influencing factors are: selective removal of calcium by planktonic foraminifers and coccolithophorids since Jurassic-Cretaceous time and by abundant younger, Mg-poor aragonite skeletons and an erratic trend toward decreasing dolomite formation (decreasing removal of oceanic Mg). The change to aragonite dominance over calcite for non-skeletal carbonates was probably during early to middle Cenozoic time.     

Botryoidal aragonite and its diagenesis

Botryoidal aragonite is a spectacular growth-form occurring as mamelons, up to 100 mm in diameter. Three examples of this particular carbonate cement have been discovered in two distinct areas: in New Caledonia, small-scale mamelons have been recognized within Pleistocene reefal terraces at Ouvea, an Island of the Loyalty archipelago, and in the Red Sea, large-scale mamelons of botryoidal aragonite exist within Pleistocene reefal terraces along the Um Gheig region of the Egyptian Coast. In addition, a similar botryoidal cement, partly dolomitized but exhibiting aragonite relics, occurs within a Miocene reef in the same region. Mamelons of botryoidal aragonite are isolated and/or coalescent but grow only on fixed substrates. They occur within cavities of varied origin. Their fabrics are characterized by fans of elongate euhedral crystals of aragonite fibres. Botryoidal aragonite can be preceded or followed by other types of cements or internal sediment. Despite similar mineralogy, petrography and ultrastructure, there are differences between the fabrics of the Pleistocene botryoids from the Red Sea and Ouvea and the Miocene botryoids from the Red Sea. The former are of submarine origin as confirmed by the strontium content (8500–10,500 ppm) and isotopic composition (δ¹⁸O between -0.10 and +0.19% PDB). The latter, related to a Miocene karst, are rich in strontium (average 13,600 ppm), and have an isotopic composition (average δ¹⁸O -10.50% PDB) indicative of non-marine precipitation. Diagenesis of these botryoidal aragonites consists of slight dissolution for Pleistocene botryoids and mineralogical transformation for the Miocene botryoids. The latter exhibit the diagenetic sequence aragonite → calcite → dolomite. The aragonite to calcite transformation is a dissolution-reprecipitation process, the void distribution and size influencing the distribution and the size of the replacement calcite crystals.     

The solubility of aragonite in seawater—I. Effect of pH and water chemistry at one atmosphere

The effect of water chemistry on the solubility of aragonite in seawater has been defined experimentally as a series of apparent solubility products measured with respect to pH at one atmosphere.The dominant control of the apparent solubility product of aragonite is the carbonate ion concentration, and this is primarily a function of pH. In the light of this fact, we have reconciled our data with 81 other reported values of aragonite solubility by simply examining the water chemistry of the waters in which they were determined.     

Aragonite and magnesite in eclogites from the Jæren nappe,SW Norway: disequilibrium in the system CaCO3–MgCO3 and petrological implications

Eclogites from the Jæren nappe in the Caledonian orogenic belt of SW Norway contain aragonite, magnesite and dolomite in quartz‐rich layers. The carbonates comprise composite grains that occur interstitially between phases of the eclogite facies assemblage: garnet + omphacite + zoisite + clinozoisite + quartz + apatite + rutile ± dolomite ± kyanite ± phengite. Pressure and temperature conditions for the main eclogite stage are estimated to be 2.3–2.8 GPa and 585–655 °C. Published ultrahigh pressure (UHP) experiments on CaO‐, MgO‐ and CO₂‐bearing systems have shown that equilibrium assemblages of aragonite and magnesite form as a result of dolomite breakdown at pressures >5 GPa. As a result, recognition of magnesite and aragonite in eclogite facies rocks has been used as an indicator for UHP conditions. However, petrological testing showed that the samples studied here have not experienced such conditions. Aragonite and magnesite show disequilibrium textures that indicate replacement of magnesite by aragonite. This process is inferred to have occurred via a coupled dissolution–precipitation reaction. The formation of aragonite is constrained to eclogite facies conditions, which implies that the studied rocks have experienced metasomatic, reactive fluid flow during their residence at high pressure (HP) conditions. During decompression, the bimineralic carbonate aggregates were overgrown by rims of dolomite, which partially reacted with aragonite to form Mg‐calcite. The well‐preserved carbonate assemblages and textures observed in the studied samples provide a detailed record of the reaction series that affected the rocks during and after their residence at P–T conditions near the coesite stability field. Recognition of the HP mechanism of magnesite replacement by aragonite provides new insight into metasomatic processes that occur in subduction zones and illustrates how fluids facilitate HP carbonate reactions that do not occur in dry systems at otherwise identical physiochemical conditions. This study documents that caution is warranted in interpreting aragonite‐magnesite associations in eclogite facies rocks as evidence for UHP metamorphic conditions.     

Primary aragonite and high‐Mg calcite in the late Cambrian (Furongian). Potential evidence from marine carbonates in Oman

Transient aragonite seas occurred in the early Cambrian but several models suggest the late Cambrian was a time of calcite seas. Here, evidence is presented from the Andam Group, Huqf High, Oman (Gondwana) that suggests a transient Furongian (late Cambrian) aragonite sea, characterized by the precipitation of aragonite and high‐Mg calcite ooids and aragonite isopachous, fibrous, cements. Stable carbon isotope data suggest that precipitation occurred just before and during the SPICE (Steptoean Positive Carbonate Isotope Excursion). Aragonite and high‐Mg calcite precipitation can be accounted for if mMg:Ca ratios were around 1.2 given the very high atmospheric CO₂ at that time and if precipitation occurred in warm waters associated with the SPICE. This, together with reported occurrences of early Furongian aragonite ooids from various locations in North America (Laurentia), suggests that aragonite and high‐Mg calcite precipitation from seawater may have been more than just a local phenomenon.     

Variation in production,input and preservation of metastable calcium carbonate off Somalia during the last 90,000 years

To improve our understanding of the Late Pleistocene and Holocene carbonate system of the western Arabian Sea a high-resolution sedimentary record off Somalia has been analysed. The 15.26-m-long piston core 905 comprises a complete record of the last 90,000 years. We have measured concentrations of carbonate minerals, i.e., aragonite, calcite, Mg-calcite, and element ratios (Sr/Ca) together with pteropod counts and an estimation of the preservation state of pteropod shells to trace temporal changes in carbonate production and preservation.The Sr/Ca ratio shows strong similarities to the aragonite percentage and the δ¹⁸O record of the planktic foraminifer Neogloboquadrina dutertrei. High Sr/Ca ratios together with fragments of corals found in the coarse fraction indicate that most of the aragonite is of shallow water origin (high-Sr aragonite) and pteropods contribute much less than expected. High resuspensional input of shallow-marine aragonite occurs during sea-level highstands (interglacials) and low input during lowstands (glacials).The Mg-calcite concentration record resembles the whole pteropod abundance and pteropod shell preservation records confirming the use of Mg-calcite in combination with pteropod preservation proxies to reconstruct past fluctuations in carbonate dissolution. Preservation of aragonite and Mg-calcite increases during stadials, H-equivalents, YD and late Marine Isotope Stage (MIS) 3. During late MIS 5/early MIS 4 and in the Late Holocene absence of few pteropods as well as low Mg-calcite weight percentages point to strong dissolution of aragonite and Mg-calcite.     

文石石笋发生矿物重结晶的影响因素及其古气候意义

洞穴沉积物—石笋已成为研究岩溶区环境气候变化历史的重要载体。在我国湘西地区,某些洞穴石笋原始沉积多为不稳定的文石矿物,极易发生重结晶,可能使石笋中相关化学元素含量最终偏离原生矿物的特征,限制了文石石笋某些代用指标在古气候研究中的应用。文章以前人研究成果为基础,总结梳理了文石石笋发生重结晶的影响因素及其对石笋记录古气候的影响:（1）石笋剖面特征、XRD结果、显微镜观察和地球化学元素特征等可作为石笋发生重结晶的判别依据;（2）洞穴滴水和石笋孔隙水饱和度、文石晶体缺陷和晶体之间的方解石胶结物以及岩溶水体中Mg2+浓度等均会影响文石石笋的矿物转变;（3）在文石向方解石转变过程中,石笋铀含量会有一定程度的流失,可导致放射性铀系定年的异常或年代倒序;（4）矿物重结晶可导致δ18O、δ13C及石笋微量元素浓度（或比值）等指标发生改变,其变化特征因洞穴而异,从而影响其作为环境指示器的可靠性;（5）湖南龙山惹迷洞石笋（RM2）发生了不均一的矿物重结晶,自顶部至20.3 cm以放射状为主,20.3 cm至底部主要为糖粒状,并结合年代结果发现文石重结晶对石笋铀系定年产生了影响,而重结晶作用对该石笋其他指标的影响还有待进一步研究。      

Quantitative aspects of Mn-activated cathodoluminescence of natural and synthetic aragonite

The cathodoluminescence analyses of the trigonal carbonates calcite and dolomite have been applied intensively in sedimentary petrology for a long time and the properties of these minerals are well-known, but much less attention has been paid to aragonite. In this study, the cathodoluminescence behaviour and the trace element composition of natural and synthetic aragonite have been studied employing trace element analyses (proton induced X-ray emission) and luminescence spectroscopy. Aragonite doped with Mn²⁺ has been synthesized in a NH₄⁺–Mg²⁺–Ca²⁺–Cl⁻ solution in contact with a CO₂–H₂O–NH₃ atmosphere. The low effective distribution coefficients indicate a rapid growth of the crystals of millimetre size which occurred within hours or days. The natural aragonite samples contain Mn, Fe and Sr in different concentrations. The Mn-bearing aragonites exhibit a bright green luminescence which is caused by a strong emission band at 575 nm with a half-width of about 84 nm. The luminescence intensity shows a strong positive correlation with Mn in aragonite when Fe and Mn do not exceed 2000 p.p.m. The intensity is depressed if the concentration of these elements exceeds the critical values. In the shell of a recent Unio sp., the luminescence intensity deviates from the linear correlation, although the trace element contents are not too high; this is probably an effect of quenching by organic material between the crystallites of the biogenic aragonite.     

Aragonitische Lumachellen im bituminösen Wealden des Emslandes

In the Wealden beds of the Dalum oil pool (NW-Germany), cycles of the following composition have been deposited especially on synsedimentary uplifts: Bituminous shales (at the base) — shales with cyrena layers — cyrena coquinas (at the top). The cyrena and gastropod shells are preserved in aragonite, if they are embedded in shale or surrounded by oil, which stopped the diagenesis. Water saturated coquinae, poor in clay, are always calcitisated. As a consequence, the transformation aragonite → calcite should have been performed by solution and recrystallisation. Only in aragonitic shells, organic structures are visible by fluorescence microscopy. In the bituminous shales, admixtures of Mg-calcite have been preserved sporadically.