绿柱石中铁离子的晶格占位及致色作用

绿柱石族宝石颜色丰富,一直是市场上重要的宝石品种。几十年来,国内外学者对不同颜色绿柱石的致色机理及改色工艺开展了广泛的研究。铁离子作为重要的致色过渡金属离子之一,其价态调控是绿柱石改色工艺的关键,所以铁离子的价态、晶格占位和对应的致色作用也一直是绿柱石研究的焦点。铁离子被认为可能存在于绿柱石中的铝氧八面体Al³⁺格位、硅氧四面体Si⁴⁺格位、铍氧四面体Be²⁺格位、结构通道2a或2b位和晶格间隙6g位等位置,是蓝、绿或黄等颜色绿柱石的主要致色元素。本文通过对绿柱石的晶体结构、铁离子的核外电子排布和晶格占位等方面文献资料的梳理及综合分析,认为Fe²⁺和Fe³⁺分别对蓝色和黄色绿柱石的呈色起着主导作用。当Fe²⁺和Fe³⁺处于晶格中不同位置时致色作用的具体差异,仍有待于进一步研究。     

白垩纪大洋红层的致色机制及成因研究

为了查明白垩纪大洋红层的致色矿物及其赋存状态,并探讨白垩纪大洋红层可能的制约因素及成因模式,本文以中国西藏床得剖面红色页岩、意大利Vispi Quarry剖面红色灰岩以及北大西洋ODP1049C孔12X岩芯段Aptian-Albian期高频旋回红色泥灰岩为研究对象,对各剖面(或岩芯)中的红色和非红色样品分别进行了X射线衍射和漫反射光谱测试,同时对配制的含赤铁矿的标样进行了同样的测试。测试结果表明,无论是红色页岩、红色灰岩,还是红色泥灰岩,赤铁矿都是主要的致色矿物,其中西藏床得剖面红色页岩由结晶较好的碎屑状赤铁矿和结晶较差的细分散状的赤铁矿共同致色。在意大利Vispi Quarry剖面红色泥岩中,结晶程度相近的赤铁矿是唯一的致色铁氧化物,而在ODP1049C孔红色泥灰岩中,结晶差的赤铁矿和针铁矿的出现是泥灰岩呈红色的矿物学根源。赤铁矿的形成主要受铁的来源、沉积时的氧化还原条件以及成岩作用的影响,这些因素也成为制约红层形成的关键因素。本课题组在多年研究的基础上,结合前人研究成果进一步从矿物学的角度深化了大洋红层的成因模式。     

软玉子料黑皮和褐皮的致色物测试

黑皮、褐皮是软玉子料的常见皮色。文章通过岩石薄片、电子探针、差热分析等多种手段测试,综合判定软玉子料的褐皮是含褐铁矿所致,黑皮是含褐铁矿加有机质所致,这为软玉子料鉴定提供了依据,对子料成因研究也有重要意义。     

天然金珍珠和染色金珍珠的致色因素和鉴定分析方法研究进展

金属离子、卟啉和类胡萝卜素是天然金珍珠的主要致色成分,有机染料是染色金珍珠的致色成分。鉴定天然金珍珠和染色金珍珠的主要手段有常规观察检测、紫外可见吸收光谱法、拉曼光谱法、荧光光谱等。本文结合天然金珍珠的致色成分和染色金珍珠的染色方法,对两类金珍珠的鉴定技术作了评述,认为常规观察检测是十分必要的,染色珍珠颜色分布不均匀,在孔眼内或表面破损处可看到染料的沉淀浓集;紫外可见吸收光谱法是目前较为常用的鉴定方法,天然金珍珠主要吸收峰位于350~360 nm,而染色金珍珠则出现明显的410~450 nm谱峰;应用拉曼光谱法鉴定可获得天然金珍珠在275 cm-1明显的特征峰,而染色金珍珠出现强的荧光背景峰;应用荧光光谱法鉴定金黄色天然珍珠在376 nm处光激发时谱峰是以472 nm为中心,而染色珍珠在372 nm处受光激发时谱峰位于436 nm。这些鉴定方法仍然在实验验证阶段,进一步优化和开发新的测试手段则是今后重要的发展方向。     

晚古生代古亚洲洋俯冲作用:来自珲春前山镁铁质侵入岩的年代学和地球化学记录

珲春地区前山镁铁质侵入岩主要由橄榄辉长岩、苏长岩和辉长闪长岩组成,形成年龄273±2Ma,为早二叠世侵入岩。该岩体显示出岛弧拉斑玄武岩的元素地球化学特征,弱富集LREE且正Eu(Eu/Eu*=1.05～1.44)异常的REE配分模式,在不相容元素中富集大离子亲石元素(LILE)如Ba和Sr,亏损高场强元素(HFSE)(La/Nb=2.8～4.8;Zr/Sm=8.0～22.5),与起源于流体交代地幔楔部分熔融的岛弧低钾拉斑玄武岩类似。在同位素特征上低放射成因Sr,高放射成因Nd和Hf(87Sr/86Sr(i)=0.70295～0.70375;εNd(t)=+4.5～+6.4;εHf(t)=+9.6～+14.6),反映其来源于同位素组成亏损的交代地幔。结合区域地质背景,我们认为前山镁铁质岩形成于晚古生代期间古亚洲洋向华北板块的俯冲作用背景,其亏损Nb-Ta、Zr-Hf及Hf-Nd同位素解耦特点说明该岩体最有可能来源于俯冲流体交代的地幔楔。     

水温突降-缓升型的响应机理之冷水下渗学说的研究——以重庆北温泉水Fe3+、Mn2+对汶川地震的响应为例

深井水温观测在中国已经开展了20多年,但目前对于水温响应机理的研究还不充分.而且利用温泉水对水温响应机理研究甚少.本文在2008年5月12日汶川8.0级地震前后,即2008年5月1日至7月4日,对重庆北温泉水(距震中约400 km)进行采样监测,发现泉水水温水量发生较大变化:震后水温下降了1℃:海拔相对较高的BWQ-2、BWQ-3、BWQ-4相继断流,监测点BWQ-1的水量增加了15 L/s;与此同时.各泉点Fe~(3+)、Mn~(2+)浓度于地震当日成倍增长,随后逐渐减小,7月4日时浓度与5月1日相当.重庆北温泉位于四川盆地东部边缘地带,受汶川地震强烈影响导致冷水下渗作用,海拔相对较高而温度较低的温泉水改道,并有其他来自裂隙或者地表的低温水汇入温泉含水层,Fe~(3+)、Mn~(2+)浓度的变化从水化学上印证了冷水下渗学说.     

额尔古纳地块新元古代岩浆作用与微陆块构造属性:来自侵入岩锆石U-Pb年代学、地球化学和Hf同位素的制约

对额尔古纳地块新元古代花岗岩进行了锆石LA-ICP-MS U-Pb年代学、岩石地球化学和锆石Hf同位素研究,以便对其新元古代岩浆作用历史与微陆块构造属性给予制约.所测花岗质岩石中锆石的CL图像特征和Th/U比值(0.17~1.46) 显示其为岩浆成因.测年结果并结合前人定年结果,可以判定额尔古纳地块上至少存在~929 Ma、~887 Ma、~850 Ma、~819 Ma、~792 Ma、~764 Ma和~738 Ma岩浆事件.岩石地球化学特征显示,~887 Ma花岗岩为一套后碰撞花岗岩类;而850~737 Ma花岗质岩石整体上属于A-型花岗岩,也有部分岩体(漠河、阿木尔、碧水和室韦岩体)显示I-型花岗岩特征.锆石Hf同位素特征反映这些花岗岩的源区既有中-新元古代(T_DM2=884~1 563 Ma)新增生地壳物质的部分熔融,同时伴有少量古老地壳物质的混染,也有残留的古老中基性下地壳物质的部分熔融.综合研究区新元古代侵入岩的地球化学特征,同时对比新元古代全球构造热事件,认为额尔古纳地块上新元古代岩浆活动记录了Rodinia超大陆形成和演化过程中的地壳响应:927~880 Ma的岩浆作用应是Rodinia超大陆汇聚造山的产物;而850~737 Ma的岩浆作用应是对Rodinia超大陆快速裂解的记录.通过岩浆事件对比发现,额尔古纳地块与邻近的西伯利亚南缘微陆块(如中蒙古地块和图瓦地块)具有亲缘性,而与塔里木板块和华南板块至少在新元古代岩浆活动上具有一定的相似性,而明显区别于华北板块和西伯利亚板块.      

阿尔泰造山带晚古生代高温变质作用与塔里木地幔柱活动的成因联系:来自泥质和镁铁质麻粒岩的证据

阿尔泰造山带是中亚造山带(CAOB)的重要组成部分,在其南缘出露有高温泥质和镁铁质麻粒岩,确定其P-T轨迹对于理解阿尔泰造山带南缘在晚古生代的构造演化历史具有重要意义。通过对该区乌恰沟泥质和镁铁质麻粒岩样品精细的岩相学观察,显示其变质矿物组合分别为石榴石+堇青石+黑云母+斜长石+石英+磁铁矿+钛铁矿±斜方辉石±尖晶石±钾长石,斜方辉石+单斜辉石+角闪石+黑云母+斜长石+钾长石+石英+钛铁矿+磁铁矿。使用传统温压计和平均温压计算方法对其变质峰期及峰期后的P-T条件进行了计算,并利用Thermocalc软件对其中两个泥质麻粒岩进行了P-T视剖面图模拟,确定了其峰期变质条件为770~865℃和3.0~5.1kbar,并得到了两条峰期后近等压冷却(IBC)的P-T演化轨迹。这样近等压冷却的P-T轨迹表明高温变质作用可能发生于一个总体伸展的大地构造背景之下。已有年代学数据支持该区高温变质事件发生于二叠纪(270~280Ma),与塔里木地幔柱活动的时间(~275Ma)高度一致。这说明阿尔泰二叠纪高温变质事件可能与塔里木地幔柱有着密切的成因联系。因此,我们认为二叠纪地幔柱活动引起的幔源岩浆底侵和加热可能提供了阿尔泰南缘高温-超高温变质作用所需的热源。     

拉萨地块东南缘晚白垩世高温变质作用及其地质意义:来自石英出溶金红石的证据和锆石U-Pb定年

文中对拉萨地块东南缘林芝杂岩中的含榴斜长角闪岩进行了详细的岩相学研究和锆石U-Pb定年。岩相学观察表明,含榴斜长角闪岩经历了峰期麻粒岩相变质和角闪岩相退变质作用。峰期麻粒岩相矿物组合为石榴子石+高Ti角闪石+紫苏辉石+斜长石+石英+金红石,其中的石榴子石、石英和角闪石中含有大量金红石出溶体,说明这些矿物的初始成分具有高Ti含量。角闪岩相退变质矿物组合为低Ti角闪石+斜长石+斜黝帘石+石英+金红石。利用Ti在石英中的含量(TitaniQ)温度计计算得到峰期麻粒岩相变质温度为803～924℃,后期角闪岩相退变质温度为555～732℃。样品中的锆石具有明显的核边结构,核部为典型岩浆型锆石,具有高的Th/U值,强烈富集HREE,明显的正Ce异常和负Eu异常,206Pb/238U年龄为(89.3±0.6)Ma,代表含榴斜长角闪岩原岩结晶年龄。锆石边部呈无环带结构,同核部相比,具有低的Th/U值,低的M-HREE和弱的Eu负异常,为变质峰期生长的锆石,206Pb/238U年龄为(81.1±0.8)Ma,代表麻粒岩相峰期变质年龄。我们认为约81Ma高温麻粒岩相变质作用可能与洋中脊俯冲造成的板片窗导致的软流圈上涌有关。     

三角洲前缘亚相致密砂岩储层的成岩作用与有利成岩相带:以鄂尔多斯盆地子洲气田山_2~3段砂岩为例

致密砂岩储层成岩作用复杂,成岩相分布表现出明显的差异性。以物性、铸体薄片、扫描电镜、X衍射、高压压汞等测试数据为基础,对鄂尔多斯盆地东部子洲气田山32段砂岩的成岩作用和成岩相进行了研究。结果表明:岩性以石英砂岩为主,岩屑含量自西向东表现出增加趋势;残余粒间孔、溶蚀孔和晶间孔为主要孔隙类型;压实压溶作用使原生粒间孔大量损失;胶结作用对储集空间具有双重影响,但整体使物性变差;溶解作用对石英砂岩和岩屑石英砂岩的影响不同,对石英砂岩的溶蚀程度更高;综合多项成岩阶段划分指标,子洲气田山32段砂岩已进入晚成岩B期,部分指标进入C期;参考多项定性和定量参数,划分出6种成岩相,分布于水下分流河道厚砂体中的石英加大粒间孔-溶蚀孔相是最有利的成岩相带,石英加大粒间孔-晶间孔相和粘土杂基充填晶间孔-溶蚀孔相次之,成岩相的平面分布受沉积微相和碎屑组分变化影响明显。     

An EPR study of Mn2+ and Fe3+ in dolomites

Electron paramagnetic resonance (EPR) measurements on dolomites from 9 different localities revealed contents of Mn²⁺ on two axial sites in all of them. The center with largerzero-field splitting (ZFS) was always present in much higher concentrations, except for a sample from Oberdorf it amounted to 95 percent or more of the total. This dolomite was the only one with a considerable content of Fe³⁺ on one axial site, almost certainly substituting for Mg²⁺. With X-ray irradiation the concentration of Fe³⁺ increased by about 30 percent showing that at least some of the divalent iron also substitutes for Mg. The ZFSs for Fe³⁺ and Mn²⁺ with larger ZFS increase with decreasing temperature in the same manner. The previous assignment of this Mn²⁺ to Mg sites is thus confirmed. An almost regular increase of the trigonal distortions at the divalent ions in different carbonates with increasing ionic radius is indicated by their crystal structure data. The very small ZFS for Mn²⁺ on Ca sites in dolomite must thus result from a strong local relaxation in the direction of a more regular octahedral arrangement. It is difficult to explain the different distribution ratios of Mn²⁺ on Ca and Mg sites with differences in growth and/or annealing temperatures alone. Thus different supply of Mg²⁺ and Ca²⁺ in the growth solutions may also contribute.     

Time-resolved luminescence of Fe3+ and Mn2+ ions in hydrous volcanic glasses

 Time-resolved luminescence spectra of natural and synthetic hydrous volcanic glasses with different colors and different Fe, Mn, and H₂O content were measured, and the implications for the glass structure are discussed. Three luminescence ranges are observed at about 380–460, 500–560, and 700–760 nm. The very short-living (lifetimes less than 40 ns) blue band (380–460 nm) is most probably due to the ⁴T₂(⁴D) →⁶A₁(⁶S) and ⁴A₁(⁴G) →⁶A₁(⁶S) ligand field transitions of Fe³⁺. The green luminescence (500–560 nm) arises from the Mn²⁺ transition ⁴T₁(⁴G) →⁶A₁(⁶S). It shows weak vibronic structure, short lifetimes less than 250 μs, and indicates that Mn²⁺ is tetrahedrally coordinated, occupying sites with similar distortions and ion–oxygen interactions in all samples studied. The red luminescence (700–760 nm) arising from the ⁴T₁(⁴G) →⁶A₁(⁶S) transition of Fe³⁺ has much longer lifetimes of the order of several ms, and indicates that ferric iron is also mainly tetrahedrally coordinated. Increasing the total water content of the glasses leads to quenching of the red luminescence and decrease of the distortions of the Fe³⁺ polyhedra. Received: 30 July 2001 / Accepted: 15 November 2001     

四川旺苍志留系鲕粒灰岩特征及地质意义

近期在川西北旺苍地区早志留世南江组中首次发现了鲕粒灰岩.它们多以10 cm左右的薄层夹持在页岩或粉砂质泥岩中, 沉积相分析显示该段地层总体应属于均斜缓坡沉积体系.说明这些鲕粒是由异地搬运而来, 在旺苍附近可能会存在相当规模的鲕粒滩.在显微镜下可观察到, 其中的鲕粒类别单一, 鲕粒紧密排列, 并呈现一定程度的压缩变形, 局部壳层呈锯齿状, 也指示这些鲕粒曾经历过高能分选和搬运, 以及压实成岩作用等.氧碳同位素测试显示, 这些鲕粒灰岩沉积时的古温度大体为25~31 ℃, 表明早志留世的上扬子地台应处于中低纬度干热或温暖的古气候带.除去古气候及古地理学方面的意义, 当前鲕粒灰岩的发现还为该区油气勘探提供了重要的储层信息.      

The role of Fe2+ and Fe3+ in synthetic Fe-substituted tetrahedrite

Summary Tetrahedrites with the composition between Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ were synthesized at 457 °C and 500 °C from the elements and carefully studied by Mössbauer spectroscopy of⁵⁷Fe. Between Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ iron is predominantly ferric. Between Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ iron is predominantly ferrous and occupies the tetrahedral M1-sites.

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Zusammenfassung Die Rolle von Fe²⁺ und Fe³⁺ in synthetischen Tetraedriten mit Fe-Substitution Tetraedrite mit einer Zusammensetzung zwischen Cu₁₂Sb₄S₁₃ and Cu₁₀Fe₂Sb₄S₁₃ wurden bei 457 °C und 500 °C aus den Elementen synthetisiert und sorgfdltig mit Mössbauer-Spektroskopie von⁵⁷Fe untersucht. Zwischen Cu₁₂Sb₄S₁₃ and Cu₁₁Fe₁Sb₄S₁₃ ist Eisen überwiegend dreiwertig. Zwischen Cu₁₁Fe₁Sb₄S₁₃ and Cu₁₁Fe₂Sb₄S₁₃ ist Eisen überwiegend zweiwertig und besetzt die tetraedrisch koordinierten M1-Plätze.

     

Electrochemical Evidence for Pentasulfide Complexes with Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+

A series of stable pentasulfide complexes of the common base metals, Mn, Fe, Co, Ni, Cu and Zn exist in aqueous solutions at ambient temperatures. Pure sodium pentasulfide was prepared and reacted with the divalent cations of Mn, Fe, Co, Ni, Cu and Zn in aqueous solution at ambient temperature. The S52- complexes were found to exist as determined by voltammetric methods.Pentasulfide complexes with compositions assigned as [M(1-S5)] and [M2(- S5)]2+ occur for Mn, Fe, Co and Ni where only one terminal S atom in the S52- binds to one metal (1 = mono-dentate ligand or M-S-S-S-S-S, = ligand bridging two metal centers or M-S-S-S-S-S-M). Conditional stability constants are similar for all four metals with log 1 between 5.3 and 5.7 and log 2 between 11.0 and 11.6. The constants for these pentasulfide complexes are similar to the tetrasulfide complexes and are approximately 0.4–0.8 log units higher than for comparable bisulfide complexes [M(SH)]+ as expected based on the higher nucleophilicity of S52- compared to HS-. Voltammetric results indicate that these are labile complexes.As with the bisulfide and tetrasulfide complexes, Zn(II) and Cu(II) are chemically distinct from the other metals. Zn(II) reacts with pentasulfide to form a stable monomeric pentasulfide chelate, [Zn(1-S5)] with log = 8.7. Cu(II) reacts with pentasulfide to form a complex with the probable stoichiometry [Cu(S5)]2 with log estimated to be 20.2. As with the other four metals, these complexes are comparable with the tetrasulfide complexes. Discrete voltammetric peaks are observed for these complexes and indicate they are electrochemically inert to dissociation. Reactions of Zn(II) and Cu(II) also lead to significant breakup of the polysulfide.The relative strength of the complexes is Cu > Zn > Mn, Fe, Co, Ni. Cu displaces Zn from [Zn(1- S5)] and both Cu and Zn displace Mn, Fe, Co and Ni from their pentasulfide complexes.     

The distribution of Fe2+ and Fe3+ in iron-bearing tourmalines: A Mössbauer study

Summary Room-temperature Mössbauer spectra of five iron-bearing tourmalines were measured and analyzed. The Fe²⁺/Fe³⁺ ratio and the iron occupancy of the Y and Z positions could be assigned to all samples, with the help of two previously well characterized samples, from Mexico and Madagascar. Ferric or ferrous ions or both partially occupy the Z as well as the Y octahedra. This fact of observation is interpreted as the chemical response, during crystal growth, to the requirement of size matching for the edge-sharing Y and Z oxygen octahedra. It accounts for the inexistence of solid solution between the Mg and (Li, Al) tourmalines.

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Die Verteilung von Fe²⁺ und Fe³⁺ in eisenhaltigen Turmalinen: Eine Mössbauer-Untersuchung

Zusammenfassung Mössbauer-Spektren von fünf eisenhaltigen Turmalinen wurden gemessen und analysiert. Das Verhältnis Fe²⁺/Fe³⁺ und die Eisenverteilung konnten mit Hilfe von zwei gut identifizierten Turmalin-Kristallen von Mexiko und Madagascar für die Y-und Z-Lagen aller Exemplare bestimmt werden. Zweiwertiges sowie dreiwertiges Eisen findet sich sowohl in der Z-als auch in der Y-Lage. Da sich die Y-und Z-Oktaeder in einer gemeinsamen Kante treffen, wird diese Beobachtung als chemische Antwort des Kristalles auf die erforderte Größenanpassung der Y-und Z-Oktaeder während seines Wachstums erklärt. Die Abwesenheit der festen Lösung zwischen Dravit und Elbait kann somit erklärt werden.

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With 4 Figures     

Sign of the magnetic coupling of Fe2+ and Fe3+ in biotite

Mössbauer spectra of biotite at 4 K are reported. The biotite crystals were oriented with the c-axis parallel to the γ-ray direction and some spectra were recorded with external magnetic fields of 40 kOe applied at right angles to the c-axis. Decrease of the magnetic-hyperfine field of both Fe²⁺ and Fe³⁺ ions on application of the external field shows that both Fe³⁺-Fe³⁺ pairs and Fe²⁺-Fe²⁺ pairs are coupled ferromagnetically.     

重庆桃花赤铁矿地质特征与成矿规律分析

桃花赤铁矿位于川东褶皱带与川湘凹陷的过渡带,矿区出露一套以砂岩、泥岩、灰岩为主的沉积层。上泥盆统黄家蹬组(D3h)为桃花赤铁矿的赋矿地层,矿体呈层状、似层状、透镜状分布于黄家蹬组上部,矿体与顶底板围岩界线清楚。黄家蹬组含Fe1和Fe2两层矿体,其中Fe1矿体无工业价值,Fe2矿体为矿区主矿体(层厚1.07m～5.89m)。矿区矿石为高磷、低杂质、较低品位酸性鲕状赤铁矿矿石,矿石因含泥质不同而呈紫红色或暗紫色,发育条带状构造和块状构造。依据矿床地质特征分析,桃花赤铁矿的分布主要受岩相古地理影响,矿体产出形态受褶皱构造控制。桃花赤铁矿属渝东鄂西"宁乡式"铁矿成矿区的西延部分,矿区泥盆系中统云台观组(D2y)和泥盆系上统黄家蹬(D3h)为一套海进过程中形成的滨海相沉积序列,矿体分布于细砂岩、粉砂岩、粉砂质页岩向页岩或碳酸盐岩过渡的层位。湿热气候和邻近海盆是形成赤铁矿矿的有利古环境,古海盆周围的古陆风化碎屑物是成矿的物质来源。矿区及其外围上泥盆统地层分布区是宁乡式赤铁矿的找矿远景区,褶皱是良好的构造找矿标志。     

High pressure single-crystal synthesis, structure and compressibility of the garnet Mn2+ 3Mn3+ 2[SiO4]3

Single crystals of the garnet Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ and coesite were synthesised from MnO₂-SiO₂ oxide mixtures at 1000°C and 9 GPa in a multianvil press. The crystal structure of the garnet [space group Ia3¯d, a=11.801(2) Å] was refined at room temperature and 100 K from single-crystal X-ray data to R1=2.36% and R1=2.71%, respectively. In contrast to tetragonal Ca₃Mn³⁺ ₂[GeO₄]₃ (space group I4₁/a), the high-pressure garnet is cubic and does not display an ordered Jahn-Teller distortion of octahedral Mn³⁺. A disordered Jahn-Teller distortion either dynamic or static is evidenced by unusual high anisotropic displacement parameters. The room temperature structure is characterised by following bond lengths: Si-O=1.636(4) Å (tetrahedron), Mn³⁺-O=1.995 (4) Å (octahedron), Mn²⁺-O=2.280(5) and 2.409(4) Å (dodecahedron). The cubic structure was preserved upon cooling to 100 K [a=11.788(2) Å] and upon compressing up to 11.8 GPa in a diamond-anvil cell. Pressure variation of the unit cell parameter expressed by a third-order Birch-Murnaghan equation of state led to a bulk modulus K ₀=151.6(8) GPa and its pressure derivatives K′=6.38(19). The peak positions of the Raman spectrum recorded for Mn²⁺ ₃Mn³⁺ ₂[SiO₄]₃ were assigned based on a calderite Mn²⁺ ₃Fe³⁺ ₂[SiO₄]₃ model extrapolated from andradite and grossular literature data.     

Evidence for absorption by exchange-coupled Fe2+-Fe3+ pairs in the near infra-red spectra of minerals

Reduction of Fe³⁺ to Fe²⁺ by heating in hydrogen reduces the absorbance of the bands at 9,000 and 13,800 cm^?1 in the E ⊥ c spectrum of tourmaline, and the 9,000 and 11,000 cm^?1 bands in the E ∥ (001) spectrum of biotite. This behaviour is consistent with the presumed d-d origin of these bands (which seems well established) only if they gain much of their intensity from exchange-coupling with neighbouring Fe³⁺ ions. Intensification of spin-forbidden bands in sapphire by Fe³⁺-Fe³⁺ exchange-coupling was recognized by Ferguson and Fielding (1971, 1972), but exchange-coupling has not previously been thought to intensify spin-allowed d-d bands. Spin-allowed exchange-coupled bands resulting from Fe²⁺-Fe³⁺ pairs have features in common with both normal single ion d-d bands, which they resemble in energy, width and pressure dependence, and Fe²⁺+Fe³⁺→Fe³⁺+Fe²⁺ charge transfer bands, which they resemble in temperature-, heat treatment-, composition-, and polarization-dependence. Distinction between normal d-d, charge transfer, and pair d-d absorptions is thus complicated, and criteria for assigning these bands are discussed. Spin-allowed exchange-coupled pair bands should be sought in the spectra of transition metal clusters (trimers and polymers as well as pairs may be involved) whenever geometry favours their origin. It is possible that the bands near 10,000 and 11,500 cm^?1 in blue sapphire, and at about 5,000 cm^?1 in titanian garnets are of this type, but many other examples are likely to occur. Exchange-coupling may involve ions other than Fe³⁺ (e.g., Mn²⁺, also d ⁵), although Fe²⁺-Fe²⁺ coupling is unlikely to be important at laboratory temperatures.