维苏威和武尔卡诺火山碎屑物中磷灰石挥发组分的研究

磷灰石中挥发分的类质同象替换可以反映其结晶时岩浆体系的成分特点。采用扫描电镜、能谱、电子探针、X射线单晶晶胞参数测定和红外、拉曼光谱,对维苏威和武尔卡诺火山碎屑物中磷灰石进行了初步研究,发现其Ca、P位置上不出现替换,主要替换形成于通道位置上。武尔卡诺磷灰石低硫富Cl,晶胞参数c/a值很小,在低压高温下形成;而维苏威磷灰石含硫稍多,通道离子主要由OH-F组成,形成于压力较大、温度较低的环境,Cl趋向于在早期喷发物中富集,而F则趋向于在晚期喷发物中富集。     

镉-钙羟基磷灰石固溶体晶须的液相合成及其晶体化学与热力学研究

通过XRD、FT—IR和SEM等方法对采用液相化学反应法合成的镉-钙羟基磷灰石（cadmium—calcium hydroxyapatite,Cd—CaHap）连续固溶体进行分析,结果表明：Cd—CaHap中没有杂质相存在,是纯的固溶体晶须。它们的晶胞参数a和c、晶胞体积V随Cd离子替换量x（原子百分数）的增加呈线性减小,线性方程分别为：a=0．94727—9．159×10^-5x（R=0．9847）;c=0．688682．070×10^-4X（R=0．9815）;V=0．5357—2．74×10^-4X（R=0．9925）。随Cd离子含量的增加,固溶体的标准摩尔生成焓呈线性增加：△fH=46．53402x-13316．31257（R=0．99998）。摩尔混合焓△mH曲线的非对称性则说明替换后的Cd离子在磷灰石结构中可能存在着优先占位的倾向。     

磷灰石结构替换的研究进展

综述了作为重要环境矿物材料的磷灰石在钙位、四面体位和结构通道位置上类质同象替换的研究进展，讨论了替换离子的结构占位、替换形式和机理，并就替换对这种矿物在环境治理领域应用的影响进行了简要评述。     

苏鲁三清阁榴辉岩中柯石英的发现及其地质意义探讨

在苏鲁三清阁多硅白云母榴辉岩中发现了柯石英包体,该榴辉岩与超高压含菱镁矿大理岩共生。石榴石中存在的柯石英残晶和多晶石英假相包体表明榴辉岩的变质压力超过2.8 GPa。运用石榴石–单斜辉石Fe2+–Mg温度计和多硅白云母压力计估算结果表明,矿物核部的平衡压力为3.1～3.5 GPa（T ＝650～689℃）,边部的平衡压力为2.9~3.3 GPa（T＝652～671℃）。与石榴石伴生的绿辉石普遍发育石英出溶结构。在磷灰石中观察到金属硫化物出溶体。磷灰石富含OH,F,Cl和S等挥发份,这些挥发性组分的深循环对地壳和地幔之间的相互作用研究具有重要意义。通过磷灰石,苏鲁—大别俯冲带能够将大量（～80 000 Mt）OH,F和Cl携带到地幔深处。     

岩浆型磷灰石结构四面体替换特征的标型意义

根据文献中列了的５６个产于碳酸岩－碱性岩磷灰石的成分数据，讨论了这些岩浆型磷灰石结构四面体替换特征的标型意义，并定义出四面体替换指数，（ＴＳＩ＝（Ｓｉ＋ＳＣ）／Ｐ，单位晶胞原子数百分比），以区别侵入相碳酸岩磷灰石，喷发相碳酸岩磷灰石和碱性岩磷灰石：ＩＡＰ的ＴＳＩ为０－６．９，平均３．６２，仅少量Ｃ进入Ｔ位置；     

藏西北多龙矿集区拿若斑岩铜（金）矿床磷灰石矿物学特征及地质意义

拿若矿床目前是藏西北阿里地区改则县多龙矿集区第三大斑岩铜（金）矿床,前人开展了系统的成岩成矿年代学、成矿地质背景等研究,但空间蚀变分带和岩浆演化过程等方面研究较为薄弱。本文以拿若矿床磷灰石作为研究对象,在大量钻孔科研编录的基础上,开展了磷灰石矿物学和矿物化学研究,探讨拿若矿床磷灰石矿物彩色阴极发光特征与蚀变分带的耦合关系,揭示含矿岩浆演化期次及氧化还原状态。磷灰石彩色阴极发光特征显示,拿若矿床磷灰石彩色阴极发光（CL）特征主要表现为黄褐色、绿色—亮黄色和灰黑色,分别对应未蚀变、钾化蚀变和绢英岩化蚀变环境,磷灰石彩色CL特征与其所处蚀变环境的关系验证了本文重新厘定的拿若矿床斑岩系统“双钾化带”空间蚀变分带结构。磷灰石电子探针（EPMA）主量元素测试结果显示,磷灰石的CaO = 53. 5%~56. 5%,P2O5 = 39. 5%~42%,F = 1. 26%~3. 24%,Cl = 0. 01%~1. 99%,SO3 = 0~1. 28%,由此计算的XF= 0. 68~1. 76,XCl = 0. 001~0. 58,XOH = 0. 21~1. 05。不同类型、阶段的磷灰石挥发分（F、Cl、OH）、SO3等变化趋势反映了拿若矿床岩浆—热液演化过程发生了气体饱和流体出溶金属沉淀的过程,并揭示了成矿岩浆高氧逸度的性质。此外,环带状岩浆磷灰石反映了隐爆角砾岩系统发育了三期次岩浆作用,并指示了第I、III期岩浆活动具有更高氧逸度特征,与成矿关系更加密切。因此,本文认为在复杂造山带发育的多期次岩浆热液叠加型斑岩铜矿床中,磷灰石在辅助厘定蚀变类型和反演岩浆—热液演化过程中具有重要的价值。     

在我国广西发现的钡毒铁石

1989年我们在广西德保矿区发现了钡毒铁石，其化学成分为（％）：BaO8．45，Fe2O335．10，As2O538．15，K2O0．14，Al2O30．07，H2O 18．48，总量为100．38。其理想矿物分子式为Ba0.5Fe4（AsO4）。（OH）4·7H2O，与德国产出的钡毒铁石的矿物分子式［BaFe4（AsO4）3（OH）5·5H2O］有一定的差异，是毒铁石［KFe4（AsO4）3（OH）4·7H2O］的钡端员矿物。该矿物是黄绿色、浅黄色，立方体晶形，硬度H=3，实测比重D=3．00，N=l．724～l．731，均质性，常见光性异常。粉晶X射线分析主要衍射强线（um）为：O．805（200）（99），0．563（220）（23），0．399（400）（47），O．326（422）（100），0284（44O）（73），0．241（542）（33），0．178（841）（23），等轴晶系，空间群为P43m，晶胞参数a=1．603nm。     

辉石中(2n 1)×0.45um宽度堆垛的结构观察与模型推导

在斜顽辉石加温产物中观察到1．35和2．25um宽度堆垛，前者属单斜晶系。这些（2n＋1）×0．45um宽度堆垛可以由辉石的Si－O链错排引起。按单斜辉石或斜方辉石的Si（A）、Si（B）链结构数据所计算的1．35um堆垛，多属单斜晶系，晶胞参数范围是a＝1．357～1．420，b＝0．886，c＝0．516nm，β＝96．1°～108．3°；当斜方辉石的Si－O链作Si（A）Si（B）St（B′）排列时，1．35um堆垛应为斜方晶系。计算的2．25um堆垛的晶胞参数是a＝2．255，b＝0．886，c＝0．516nm，β＝73．8°。     

藏西北多龙矿集区拿若斑岩铜（金）矿床磷灰石矿物学特征及地质意义

拿若矿床目前是藏西北改则县多龙矿集区第三大斑岩型铜（金）矿床,前人开展了系统的成岩成矿年代学、成矿地质背景等研究,但空间蚀变分带和岩浆演化过程等方面研究较为薄弱。笔者等以拿若矿床磷灰石作为研究对象,在大量钻孔科研编录的基础上,开展了磷灰石矿物学和矿物化学研究,探讨拿若矿床磷灰石矿物彩色阴极发光特征与蚀变分带的耦合关系,揭示含矿岩浆演化期次及氧化还原状态。磷灰石彩色阴极发光特征显示,拿若矿床磷灰石彩色阴极发光（CL）特征主要表现为黄褐色、绿色—亮黄色和灰黑色,分别对应未蚀变、钾化蚀变和绢英岩化蚀变环境,磷灰石彩色CL特征与其所处蚀变环境的关系验证了笔者等重新厘定的拿若矿床斑岩系统“双钾化带”空间蚀变分带结构。磷灰石电子探针（EPMA）主量元素测试结果显示,磷灰石的CaO = 53. 5%~56. 5%,P2O5 = 39. 5%~42%,F = 1. 26%~3. 24%,Cl = 0. 01%~1. 99%,SO3 = 0~1. 28%,由此计算的XF = 0. 68~1. 76,XCl = 0. 001~0. 58,XOH = 0. 21~1. 05。不同类型、阶段的磷灰石挥发分（F、Cl、OH）、SO3等成分含量变化趋势反映了拿若矿床岩浆—热液演化过程发生了气体饱和流体出溶金属沉淀的过程,并揭示了成矿岩浆高氧逸度的性质。此外,环带状岩浆磷灰石反映了隐爆角砾岩系统发育了三期次岩浆作用,并指示了第I、III期岩浆活动具有更高氧逸度特征,与成矿关系更加密切。因此,笔者等认为在多期次岩浆热液叠加型斑岩铜矿床中,磷灰石在辅助厘定蚀变类型和反演岩浆—热液演化过程中具有重要的价值。     

江西省铜厂斑岩铜矿磷灰石世代和成分特征研究

对德兴铜矿区的铜厂斑岩铜矿中出现的岩浆成因和热液成因磷灰石进行了对比研究。在铜厂,除含矿斑岩体中含有磷灰石以外,成矿早期蚀变(钾化)与主矿化期蚀变(石英-绿泥石-绢云母化)也形成了磷灰石。电子探针分析结果表明三期磷灰石成分差异显著,岩浆期磷灰石的主要特征是富S和Si,钾化期磷灰石的主要特征是富Mn和Fe,主矿化期磷灰石与早期磷灰石的主要差别在于其较高的S含量、F含量和较低的Cl含量;岩浆期、钾化期和主矿化期磷灰石的Cl/F比值依次降低,这反映了流体和岩浆Cl/F比值的演化趋势。岩浆Cl/F比值的降低可能由岩浆的析气作用以及Cl和F在岩浆和流体中的分配系数不同所致。S在岩浆期磷灰石和主矿化期磷灰石中均作为P的替位阳离子存在,但在两期磷灰石中替位机制不同,P-S替位的电荷平衡离子分别为Si和Na。在三期磷灰石中,主矿化期磷灰石S含量最高,而Cl含量显著低于岩浆期和钾化期磷灰石,这表明在主矿化期,Cu-S配合物可能是比Cu-Cl配合物更重要的金属搬运形式。     

Apatite Chlorine Concentration Measurements by LA‐ICP‐MS

Apatite incorporates variable and significant amounts of halogens (mainly F and Cl) in its crystal structure, which can be used to determine the initial F and Cl concentrations of magmas. The amount of chlorine in the apatite lattice also exerts an important compositional control on the degree of fission‐track annealing. Chlorine measurements in apatite have conventionally required electron probe microanalysis (EPMA). Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) is increasingly used in apatite fission‐track dating to determine U concentrations and also in simultaneous U‐Pb dating and trace element measurements of apatite. Apatite Cl measurements by ICP‐MS would remove the need for EPMA but the high (12.97 eV) first ionisation potential makes analysis challenging. Apatite Cl data were acquired using two analytical set‐ups: a Resonetics M‐50 193 nm ArF Excimer laser coupled to an Agilent 7700× quadrupole ICP‐MS (using a 26 μm spot with an 8 Hz repetition rate) and a Photon Machines Analyte Excite 193 nm ArF Excimer laser coupled to a Thermo Scientific iCAP Qc (using a 30 μm spot with a 4 Hz repetition rate). Chlorine concentrations were determined by LA‐ICP‐MS (1140 analyses in total) for nineteen apatite occurrences, and there is a comprehensive EPMA Cl and F data set for 13 of the apatite samples. The apatite sample suite includes different compositions representative of the range likely to be encountered in natural apatites, along with extreme variants including two end‐member chlorapatites. Between twenty‐six and thirty‐nine isotopes were determined in each apatite sample corresponding to a typical analytical protocol for integrated apatite fission track (U and Cl contents) and U‐Pb dating, along with REE and trace element measurements. ³⁵Cl backgrounds (present mainly in the argon gas) were ~ 45–65 kcps in the first set‐up and ~ 4 kcps in the second set‐up. ³⁵Cl background‐corrected signals ranged from ~ 0 cps in end‐member fluorapatite to up to ~ 90 kcps in end‐member chlorapatite. Use of a collision cell in both analytical set‐ups decreased the low mass sensitivity by approximately an order of magnitude without improving the ³⁵Cl signal‐to‐background ratio. A minor Ca isotope was used as the internal standard to correct for drift in instrument sensitivity and variations in ablation volume during sessions. The ³⁵Cl/⁴³Ca values for each apatite (10–20 analyses each) when plotted against the EPMA Cl concentrations yield excellently constrained calibration relationships, demonstrating the suitability of the analytical protocol and that routine apatite Cl measurements by ICP‐MS are achievable.     

Geochemie des Apatits in Tiefengesteinen am Beispiel des Odenwaldes

Summary The apatite in various igneous rocks (from quartzmonzonitic to gabbroic composition) in one and the same area of differentiation was geochemically examined. The samples were taken from 24 different localities in the Odenwald (Germany) and the thin sections were determined petrographically with a point counter. 25 kg of each sample were dressed and the apatite separated from the heavy mineral concentrates. The pure apatite was analysed quantitative chemically. The variable components of the apatite are represented diagrammatically as functions of the rockchemistry, the physical- and the X-ray constants and their relationships are discussed. The following relations were established: The F-content of magmatic apatites increases in the acidic rocks without showing a stringent lawfulness to the rockchemistry. F remains in all apatites, compared with Cl, OR and 0, alwavs in predominance.With increase in the content of F the refractive index, as well as the lattice constants of the apatites, decrease.The Cl-content of magmatic apatites increases towards the basic rocks, but here too it remains much less than the amount of F. Further more all other statements refering to F can be applied to Cl, but with opposite meaning.A comparison of the chemical analyses of apatites from the newer literature and these of the author reveals in all probability that there is only a limited miscibility between F- and Cl-apatites. The limit being 20 atom per cent Cl. The relation of F : Cl as 1:1 in some apatites might be attributed to an orderly arranged state of the F- and Cl-apatites.OH behaves in a similar manner as Cl, except that the results have wider dispersion effect.According to the chemical equivalence calculations there is generally a small excess of cations. This means that Oxygen must fill up free halogen-places in the lattice.The content of SiO₂ of the apatites shows an increasing tendency towards in the basic rocks and the content of P₂O₅ a decreasing one.The contents of the rare earths of magmatic apatites increase in acidic rocks and only those ones with even numbers (with the exception of La) appear.Only apatites from rocks with metamorphic characteristics had an amount of SO₃.By means of a comparison between the exploit of apatite and P₂O₅-contents of the rocks can be supposed with probability that the principal quantity of the P₂O₅ in the magmatic rocks is not bound to the apatite but to the silicates. This supposition will shortly be further examined.The relative increasing of the intensity of the line (0002) and (0004) in the X-ray-graphs (X-ray-goniometer) in the F-rich apatites suggests a better (0001)-cleavage as in the Cl-rich apatites. This observation can be explained easily with the different structures of the F- and the Cl-apatites.     

Partitioning behavior of chlorine and fluorine in the system apatite-silicate melt-fluid

The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of D_Cl^apatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ∼3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing D_Cl^apatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes “saturated” in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which D_Cl^apatite/melt and D_Cl^fluid/melt begin to increase also depends on composition. The experiments reveal that D_F^apatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so D_F^apatite/melt is constant for a wide range of composition.The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.     

Chlorine in phosphorites and bone phosphate from oceanic and marine deposits

The content, distribution patterns, and occurrence forms of Cl in phosphorites and bone phosphate from the ocean bottom, as well as in a set of samples from the land, are studied. The total Cl content ranges from 0.05 to 4.25% in phosphorites and from 2.48 to 2.75% in recent phosphate-bearing sediments. Recent phosphorites are enriched in Cl relative to ancient ones. The bound Cl content (not extractable by washing), which increases with lithification, ranges from 0.17 to 0.60% in oceanic and land phosphorites and from 0.02% to 1.30% in the bone phosphate. The Na content in most samples is higher relative to NaCl due to its incorporation into the crystal lattice of apatite. However, the opposite relationship is observed in some samples, indicating a partial Cl incorporation into the anion complex of phosphate. The behavior of Cl in phosphorites from the present-day ocean bottom is controlled by early diagenetic processes, whereas the role of weathering, catagenesis, and hydrogeological factors may be crucial for phosphorites on continents.Translated from Litologiya i Poleznye Iskopaemye, No. 1, 2005, pp. 65–77.Original Russian Text Copyright © 2005 by Baturin.     

新疆阿尔泰可可托海伟晶岩型稀有金属矿床中磷灰石地球化学特征及意义

磷灰石可以记录和保存岩浆和热液活动的信息。可可托海伟晶岩型稀有金属矿床磷灰石发育,为研究该矿床伟晶岩成岩成矿过程提供了优良的条件。已有对可可托海伟晶岩型稀有金属矿床磷灰石的研究集中在其稀土元素特征,较少讨论其对伟晶岩成岩成矿过程的制约。本文选取可可托海伟晶岩型稀有金属矿床富矿伟晶岩脉(3号脉)和相对贫矿伟晶岩脉(1号、2b号和3a号脉)中的磷灰石作为研究对象,进行磷灰石岩相学和地球化学研究。岩相学分析表明,磷灰石主要与钠长石、石英、白云母、锰铝榴石等伴生。EPMA分析显示,磷灰石F含量为3.67%～4.41%,Cl含量小于0.67%,较低的Cl含量表明伟晶岩熔体出溶的流体Cl含量较低;大部分磷灰石MnO含量为4.67%～8.71%,但2b号脉磷灰石MnO含量变化较大(1.23%～14.28%),这是由于2b号脉磷灰石具有分带结构,暗示其遭受后期热液作用,促使磷灰石溶解-再沉淀,导致MnO含量发生较大变化。LA-ICP-MS分析显示,贫矿伟晶岩脉磷灰石的稀土元素含量较低(180×10~(-6));相反,富矿伟晶岩脉磷灰石的稀土元素含量较高( 700×10~(-6)),并具有明显的四分组效应(TE_(1-3)平均值为1.7)。1号脉和3a号脉磷灰石均显示轻稀土元素富集,反映其形成过程中有含Cl热液的参与。3号脉磷灰石显示强烈Eu负异常和Ce正异常,而2b号脉磷灰石显示强烈Ce负异常和中等Eu负异常,这种Eu、Ce异常的差异可能与岩浆-热液阶段大量流体出溶密切相关。磷灰石的沉淀将导致热液中HF含量的降低,促使磷灰石周围铌钽矿结晶和Nb、Ta进入磷灰石中。可见,在伟晶岩形成过程中,磷灰石并非保持稳定,其分带结构和主微量成分变化记录了后期热液活动,暗示后期热液活动对伟晶岩的成矿具有重要作用。     

铁碎片与人体活组织之间的长期相互作用

一铁碎片被意外植入人体内,并在体内呆了16 a。该碎片经历了显著的形态和化学变化。铁碎片的表面呈现葡萄状或者鲕粒状。碎片转化为铁的氧化物和氢氧化物以及钙的磷酸盐(可能为磷灰石)。在碎片中确认出Fe、O、P、Ca、Cl、Na、K和Mg等元素。从边缘到核心,Fe含量增加,P和Ca含量减少。碎片从人身体内吸附了Ca、P、O、Cl、Na和K。研究表明,磷灰石或者其他钙的磷酸盐能够在人体里保持稳定达16 a。然而,钙的磷酸盐与铁的氧化物或者氢氧化物混合,可能还不足以坚固到与骨头结合。本研究也表明,铁或者含铁合金在人体内不够稳定。     

S-rich apatite-hosted glass inclusions in xenoliths from La Palma: constraints on the volatile partitioning in evolved alkaline magmas

The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO₃ (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce₂O₃. Sulfur is incorporated in apatite via several independent exchange reactions involving (P⁵⁺, Ca²⁺) vs. (S⁶⁺, Si⁴⁺, Na⁺, and Ce³⁺). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from <0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO₃ (sulfate-saturated systems). The chlorine partition coefficients (D_Cl^{apatite/glass}) range from 0.4 to 1.3 (average D_Cl^{apatite/glass} = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions D_F^{apatite/glass} decreases from 35 to 3. However, most of our data display a high partition coefficient (~30) close to D_F^{apatite/glass} determined experimentally in felsic rock. D_S^{apatite/glass} decreases from 9.1 to 2.9 with increasing SO₃ in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (>0.2 wt% SO₃). D_S^{apatite/glass} is only slightly dependent on the melt composition and can be expressed as: SO_{3 apatite} (wt%) = 0.157 * ln SO_{3 glass} (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and haüyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of haüyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.     

A tephrochronologic method based on apatite trace-element chemistry

Geochemical correlation of ash-fall beds with conventional tephrochronologic methods is not feasible when original glass composition is altered. Thus, alternative correlation methods may be required. Initial studies of heavily altered Paleozoic tephra (K-bentonites) have suggested the potential for employing trace-element concentrations in apatite as ash-fall bed discriminators. To further test the utility of apatite trace-element tephrochronology, we analyzed apatite phenocrysts from unaltered volcanic rocks with an electron microprobe: nine samples from rocks erupted during the Quaternary and one sample from a rock erupted during the Paleogene. The resulting apatite trace-element data provide unique bed discriminators despite within-crystal variability. Each of the volcanic rocks studied possesses unique trends in Mg, Cl, Mn, Fe, Ce and Y concentrations in apatite. The results from this study establish an important tephrochronologic method that can be applied to nearly all portions of the Phanerozoic stratigraphic record and greatly assist development of an advanced timescale. In addition to establishing a fingerprint for a particular eruption, apatite chemistry provides useful information about the source magma.     

Mineralogy and Mineral Chemistry of the Cretaceous Duolong Gold‐Rich Porphyry Copper Deposit in the Bangongco Arc,Northern Tibet

The Early Cretaceous Duolong gold‐rich porphyry copper deposit is a newly discovered deposit with proven 5.38 Mt Cu resources of 0.72% Cu and 41 t gold of 0.23 g t^?1 in northern Tibet. Granodiorite porphyry and quartz diorite porphyrite are the main ore‐bearing porphyries. A wide range of hydrothermal alteration associated with these porphyries is divided into potassic, argillic and propylitic zones from the ore‐bearing porphyry center outward and upward. In the hydrothermal alteration zones, secondary albite (91.5–99.7% Ab) occurs along the rim of plagioclase phenocryst and fissures. Secondary K‐feldspar (75.1–96.9% Or) replaces plagioclase phenocryst and matrix or occurs in veinlets. Biotite occurs mainly as matrix and veinlet in addition to phenocryst in the potassic zone. The biotite are Mg‐rich and formed under a highly oxidized condition at temperatures ranging from 400°C to 430°C. All the biotites are absent in F, and have high Cl content (0.19–0.26%), with log (X_Cl/X_OH) values of ?2.74 to ?2.88 and IV (Cl) values of ?3.48 to ?3.35, suggesting a significant role of chloride complexes (CuCl₂^‐ and AuCl₂^‐) in transporting and precipitating copper and gold. Chlorites are present in all alteration zones and correspond mainly to pycnochlorite. They have similar Fe/(Fe+Mg), Mn/(Mn+Mg) ratios, and a formation temperature range of 280–360°C. However, the formation temperature of chlorite in the quartz‐gypsum‐carbonate‐chlorite vein is between 190°C and 220°C, indicating that it may have resulted from a later stage of hydrothermal activity. Fe³⁺/Fe²⁺ ratios of chlorites have negative correlation with Al^IV, suggesting oxygen fugacity of fluids increases with decreasing temperature. Apatite mineral inclusions in the biotite phenocrysts show high SO₃ content (0.44–0.82%) and high Cl content (1–1.37%), indicating the host magma had a high oxidation state and was enriched in S and Cl. The highest Cl content of apatite in the propylitic zone may have resulted from pressure decrease, and the lowest Cl content of apatite in the argillic zone may have been caused by a low Cl content in the fluids. The low concentration of SO₃ content in the hydrothermal apatite compared to the magmatic one may have resulted from the decrease of oxygen fugacity and S content in the hydrothermal fluid, which are caused by the abundant precipitation of magnetite.