Luminescence spectra of chabazite-Ca,a zeolite mineral

Chabazite-Ca deposited on dacite laccolith from Osódi Hill, Dunabogdány, Hungary, exhibited bluish-white luminescence under ultraviolet (UV) light. The photoluminescence (PL) and optical excitation spectra of chabazite-Ca were obtained at 300 K. The PL spectrum under 300-nm excitation consists of (1) a Ce³⁺ band with a peak at 340 nm, (2) a broad main band with a peak at 453 nm and (3) five narrow bands at 592, 616, 650, 700 and 734 nm due to Eu³⁺. The main band is spread over the entire visible-wavelength region. The excitation spectrum obtained by monitoring green luminescence at 520 nm consists of a band at wavelengths shorter than 200 nm and an extremely broad band with a peak at 385 nm. The extremely broad band is spread over not only the UV region but also the blue region. The features of PL and excitation spectra suggest that the origin of bluish-white luminescence is luminescent organic matter incorporated into chabazite-Ca crystals during growth.     

Fine structure in photoluminescence spectrum of S<Subscript>2</Subscript><Superscript>−</Superscript> center in sodalite

The photoluminescence and excitation spectra of sodalites from Greenland, Canada and Xinjiang (China) are observed at 300 and 10 K in detail. The features of the emission and excitation spectra of the orange-yellow fluorescence of these sodalites are independent of the locality. The emission spectra at 300 and 10 K consist of a broad band with a series of peaks and a maximum peak at 648 and 645.9 nm, respectively. The excitation spectra obtained by monitoring the orange-yellow fluorescence at 300 and 10 K consist of a main band with a peak at 392 nm. The luminescence efficiency of the heat-treated sodalite from Xinjiang is about seven times as high as that of untreated natural sodalite. The emission spectrum of the S₂ ⁻ center in sodalite at 10 K consists of a band with a clearly resolved structure with a series of maxima spaced about 560 cm⁻¹ (20–25 nm) apart. Each narrow band at 10 K shows a fine structure consisting of a small peak due to the stretching vibration of the isotopic species of ³²S³⁴S⁻, a main peak due to that of the isotopic species of ³²S₂ ⁻ and five peaks due to phonon sidebands of the main peak.     

Photoluminescence properties of anthophyllite

The photoluminescence (PL) spectra, optical excitation spectra and PL decay curves of anthophyllite from Canada were obtained at 300 and 10 K. The MnO content in the sample, determined using an electron probe microanalyzer, was high at 5.77 wt%. In the PL spectra obtained under 410-nm excitation, bright red bands with peaks at 651 and 659 nm were observed at 300 and 10 K, respectively. The origin of the red luminescence was ascribed to Mn²⁺ in anthophyllite from the analysis of the excitation spectra and PL decay times of 6.1–6.6 ms. In the PL spectra obtained under 240-nm excitation at 300 K, a small violet band with a peak at 398 nm was observed. On the violet band at 10 K, a vibronic structure was observed. The origin of the violet luminescence was attributed to a minor impurity in anthophyllite.     

Optical spectroscopic study of synthetic NaScSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–CaNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxenes at normal and high pressures

Six synthetic NaScSi₂O₆–CaNiSi₂O₆ pyroxenes were studied by optical absorption spectroscopy. Five of them of intermediate (Na_1−x , Ca _x )(Sc_1−x , Ni _x )Si₂O₆ compositions show spectra typical of Ni²⁺ in octahedral coordination, more precise Ni²⁺ at the M1 site of the pyroxene structure. The common feature of all spectra is three broad absorption bands with maxima around 8,000, 13,000 and 24,000 cm⁻¹ assigned to ³ A _2g → ³ T _2g, ³ A _2g → ³ T _1g and →³ T _1g (³ P) electronic spin-allowed transitions of ^VINi²⁺. A weak narrow peak at ∼14,400 cm⁻¹ is assigned to the spin-forbidden ³ A _2g → ¹ T _2g (¹ D) transition of Ni²⁺. Under pressure the spin-allowed bands shift to higher energies and change in intensity. The octahedral compression modulus, calculated from the shift of the ³ A _2g → ³ T _2g band in the (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆ pyroxene is evaluated as 85±20 GPa. The Racah parameter B of Ni²⁺(M1) is found gradually changing from ∼919 cm⁻¹ at ambient pressure to ∼890 cm⁻¹ at 6.18 GPa. The Ni end-member pyroxene [(Ca_0.93 Ni_0.07)NiSi₂O₆] has a spectrum different from all others. In addition to the above mentioned bands of Ni²⁺(M1) it displays several new relatively intense and broad extra bands, which were attributed to electronic transitions of Ni²⁺ at the M2 site. In difference to CaO₈ polyhedron geometry of an eightfold coordination, Ni²⁺(M2)O₈ polyhedra are assumed to be relatively large distorted octahedra. Due to different distortions and different compressibilities of the M1 and M2 sites the Ni²⁺(M1)- and Ni²⁺(M2)-bands display rather different pressure-induced behaviors, becoming more resolved in the high-pressure spectra than in that measured at atmospheric pressure. The octahedral compression modulus of Ni²⁺(M1) in this end-member pyroxene is evaluated as 150 ± 25 GPa, which is noticeably larger than in Ni_0.3 pyroxene. This is due to a smaller size and, thus, a stiffer character of Ni²⁺(M1)O₆ octahedron in the (Ca_0.93Ni_0.07)NiSi₂O₆ pyroxene compared to (Na_0.7Ca_0.3)(Sc_0.7Ni_0.3)Si₂O₆.

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     

Yellow fluorescence from baghdadite and synthetic Ca3(Zr,Ti)Si2O9

Baghdadite from Fuka, Okayama Prefecture, Japan shows a bright yellow fluorescence under UV (Hg 253.7 nm) excitation. The photoluminescence (PL) spectrum at 300 K consists of one large band near 580 nm and two small UV bands at 318 and 397 nm. The optical excitation spectrum of the bright yellow fluorescence consists of two bands near 220 and 250 nm. The temperature dependence of the PL intensity exhibits linear thermal quenching. To reveal the origin of the bright yellow fluorescence from baghdadite, powder Ca₃(Zr,Ti)Si₂O₉ crystals are synthesized. Synthetic Ca₃(Zr,Ti)Si₂O₉ shows luminescence spectra similar to those of baghdadite, and the intensity of the yellow fluorescence is markedly increased by titanium addition. The origin of the bright yellow fluorescence from baghdadite is ascribed to the existence of titanium.     

Luminescence centers in anhydrite,barite, celestite and their synthesized analogs

The intrinsic luminescence center (LC) of SO ₄ ^2? appears at 360 nm in all types of sulfates, but is absent in sulfates with large quantities of impurities. Three nonequivalent Gd³⁺ LC have been observed in luminescence spectra of anhydrite. Gd³⁺, Ce³⁺ O ₂ ^? LC were established in celestite. Photoluminescence (PL) bands in the sulfates were assigned as follows: the band at 460 nm is related to Eu²⁺ (a connection with Al³⁺ or donor-acceptor pair is possible also) in sulfates of Ca and Ba; bands at 520 nm and 590 nm are related to VO₄, MoO₄ and TiO₄ substituting SO₄; the band at 660 nm is assigned to Ti³⁺ X-ray luminescence (XL) band at 620 nm is assigned to Ag⁺.     

Natural fluorite emitting yellow fluorescence under UV light

Many mineralogists believe that fluorite emits violet fluorescence under UV light, but a special fluorite from Japan emits yellow fluorescence under UV light. The analysis by inductively coupled plasma-mass spectrometry (ICP-MS) shows that this fluorite includes high concentrations of Dy together with various rare-earth (RE) impurities other than Pm and Eu. Photoluminescence (PL) emission and excitation spectra of the fluorite are investigated at 10, 80 and 300 K. The origin of yellow fluorescence is attributed to the electronic transition within Dy³⁺. Profiles of the PL and excitation spectra depend on the excitation wavelength and on the observation wavelength, respectively. The obtained spectra are ascribed to the RE ions Ce³⁺, Sm³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Sm²⁺ and Yb²⁺ in the fluorite. In natural fluorite, the low concentration of Eu enables us to observe the bright fluorescence characteristic of trivalent RE ions, instead of the bluish violet fluorescence due to Eu²⁺.     

Chromium and vanadium impurities in natural green euclase and their relation to the color

Natural specimens of green gemological euclase (chemical formula BeAlSiO₄(OH)) from Brazil were investigated by electron paramagnetic resonance (EPR) and optical absorption. In addition to iron-related EPR spectra, analyzed recently in blue and colorless euclase, chromium and vanadium-related EPR spectra were also detected in green euclase. Their role as color causing centers is discussed. The results indicate that Cr³⁺ ions substitute for Al³⁺ ions in the euclase structure. The EPR rotation patterns of Cr³⁺ with electron spin S = 3/2 were analyzed with monoclinic spin Hamiltonian leading to the parameters of g _xx , g _yy and g _zz equal to 2.018, 2.001 and 1.956 and electronic fine structure parameters of D = −8.27 GHz and E = 1.11 GHz, respectively, with high asymmetry ratio E/D = 0.13. For the vanadium-related EPR spectra the situation is different. It is concluded that vanadium is incorporated as the vanadyl radical VO²⁺ with electron spin S = 1/2 with nearly axial spin Hamiltonian parameters g_zz = 1.9447, g _xx  = 1.9740 g _yy  = 1.9669 and axial hyperfine interactions due to the nuclear spin I = 7/2 of the ⁵¹V isotope leading to A _zz  = 502 MHz, A _xx  = 150 MHz and A _yy  = 163 MHz. The green color of euclase is caused by two strong broad absorption bands centered at 17,185 and 24,345 cm⁻¹ which are attributed to the ⁴A_2g → ⁴T_2g, ⁴T_1g transitions of Cr³⁺, respectively. Vanadyl radicals may introduce some absorption bands centered in the near infrared with tail extending into the visible spectral range.     

Photoluminescence properties of thenardite from Ai-Ding Salt Lake,Xinjiang, China

The photoluminescence (PL) spectra, excitation spectra, and PL decay curves of natural, heat-treated, and γ-ray-irradiated thenardites from Ai-Ding Salt Lake, Xinjiang, China, were studied. The natural thenardite under 300 nm excitation showed milk-white luminescence, and the PL spectrum consisted of an extremely broad band with a peak located at approximately 509 nm, spreading over a wide range of UV and visible wavelengths. The excitation spectra, obtained by monitoring the luminescence at 530 nm, consisted of a broad band with a peak located at approximately 235 nm and a flat band spreading over a wide range of UV and visible wavelengths. The PL decay curve of natural thenardite consisted of a fast-decay component with a lifetime of less than 0.1 μs and a slow-decay component with a half-decay time of approximately 0.4 s. The heat treatment of thenardite at 900°C for 20 min reduced the luminescence efficiency to 1/100. The γ-ray irradiation of thenardite reduced the luminescence efficiency to approximately half.     

内蒙古阿拉善地区绿色戈壁玛瑙的宝石学特征与致色成因研究

内蒙古阿拉善地区经历数亿年的地质活动,产出颜色丰富且结构致密的戈壁玛瑙。通过常规宝石学测试、偏光显微镜及扫描电镜观察、X射线粉晶衍射、电子探针、红外光谱及紫外-可见光-近红外分光光度计等测试分析方法对绿色戈壁玛瑙的宝石矿物学特征及致色成因进行了深入研究。肉眼观察,阿拉善绿色玛瑙呈深绿色至褐绿色,微透明至不透明,相对密度、折射率、摩氏硬度等均符合石英质玉石的特点。偏光显微镜观察,绿鳞石富集于表层,并向内部呈放射状生长;方解石与石英均为隐晶质结构。扫描电镜观察,绿鳞石呈颗粒状分布于石英及方解石之间。X射线衍射分析结果表明,绿色戈壁玛瑙的物相组成主要为石英、方解石和绿鳞石。电子探针分析结果表明绿鳞石的主要化学组成为SiO₂、FeO、Al₂O₃、K₂O和MgO。红外光谱分析也显示存在绿鳞石对应基团的特征峰。表层绿鳞石在紫外-可见光-近红外分光光度计下显示出Fe²⁺与Fe³⁺的特征光谱,Fe²⁺与Fe³⁺之间的电荷转移是其...     

The stability of primary alluaudites in granitic pegmatites: an experimental investigation of the Na2(Mn2−2x Fe1+2x )(PO4)3 system

In order to assess the geothermometric potential of the Na₂(Mn_2−2x Fe_1+2x )(PO₄)₃ system (x = 0–1), which represents the compositions of natural weakly oxidized alluaudites, we performed hydrothermal experiments between 400 and 800°C, at 1 kbar, under an oxygen fugacity (f(O₂)) controlled by the Ni–NiO (NNO), Fe₂O₃–Fe₃O₄ (HM), Cu₂O–CuO (CT), and Fe–Fe₃O₄ (MI) buffers. When f(O₂) is controlled by NNO, single-phase alluaudites crystallize at 400 and 500°C, whereas the association alluaudite + marićite appears between 500 and 700°C. The limit between these two fields corresponds to the maximum temperature that can be reached by alluaudites in granitic pegmatites, because marićite has never been observed in these geological environments. Because alluaudites are very sensitive to variations of oxygen fugacity, the field of hagendorfite, Na₂MnFe²⁺Fe³⁺(PO₄)₃, has been positioned in the f(O₂)–T diagram, and provides a tool that can be used to estimate the oxygen fugacity conditions that prevailed in granitic pegmatites during the crystallization of this phosphate.     

Laser-induced time-resolved luminescence spectroscopy of minerals: a powerful tool for studying the nature of emission centres

The paper summarises new data and results referring to the characterization of the nature of luminescence centres in minerals that were published during the last 8 years. Besides well-established luminescence centres, such as Mn²⁺, Fe³⁺, Cr³⁺, divalent and trivalent rare-earth elements, S₂ ^?, and Pb²⁺, several other centres were proposed and substantiated, such as Mn³⁺, Mn⁴⁺, V²⁺, Ni²⁺, Pb⁺, Mn³⁺, Sb³⁺, Tl⁺, and radiation-induced centres. Also, a relatively new type of luminescence excitation mechanism is discussed briefly, namely plasma-induced luminescence. Here, the emission takes place when the matrix, where the formation of plasma is caused by irradiation with a beam of laser light, is capable to luminescence and contains luminescence centres.     

Electronic absorption and luminescence spectroscopic studies of kyanite single crystals: differentiation between excitation of FeTi charge transfer and Cr3+ dd transitions

A selected set of five different kyanite samples was analysed by electron microprobe and found to contain chromium between <0.001 and 0.055 per formula unit (pfu). Polarized electronic absorption spectroscopy on oriented single crystals, R₁, R₂-sharp line luminescence and spectra of excitation of λ₃- and λ₄-components of R₁-line of Cr³⁺-emission had the following results: (1) The Fe²⁺–Ti⁴⁺ charge transfer in c-parallel chains of edge connected M(1) and M(2) octahedra shows up in the electronic absorption spectra as an almost exclusively c(||Z′)-polarized, very strong and broad band at 16000 cm⁻¹ if <, in this case the only band in the spectrum, and at an invariably lower energy of 15400 cm⁻¹ in crystals with  ≥ . The energy difference is explained by an expansion of the O_f–O_k, and O_b–O_m edges, by which the M(1) and M(2) octahedra are interconnected (Burnham 1963), when Cr³⁺ substitutes for Al compared to the chromium-free case. (2) The Cr³⁺ is proven in two greatly differing crystal fields a and b, giving rise to two sets of bands, derived from the well known dd transitions of Cr^{3+ 4}A_2g→⁴T_2g(F)(I), →⁴T_1g(F)(II), and →⁴T_1g(P)(III). Band energies in the two sets a and b, as obtained by absorption, A, and excitation, E, agree well: I: 17300(a, A), 17200(a, E), 16000(b, A), 16200(b, E); II: 24800(a, A), 24400(a, E); 22300(b, A), 22200(b, E); III: 28800(b,A) cm⁻¹. Evaluation of crystal field parameters from the bands in the electronic spectra yield Dq(a)=1730 cm⁻¹, Dq(b)=1600 cm⁻¹, B(a)=790 cm⁻¹, B(b)=620 cm⁻¹ (errors ca. ±10 cm⁻¹), again in agreement with values extracted from the λ³, λ⁴ excitation spectra. The CF-values of set a are close to those typical of Cr³⁺ substituting for Al in octahedra of other silicate minerals without constitutional OH⁻ as for sapphirine, mantle garnets or beryl, and are, therefore, interpreted as caused by Cr³⁺ substituting for Al in some or all of the M(1) to M(4) octaheda of the kyanite structure, which are crystallographically different but close in their mean Al–O distances, ranging from 1.896 to 1.919 A (Burnham 1963), and slight degrees of distortion. Hence, band set a originates from substitutive Cr³⁺ in the kyanite structural matrix. The CF-data of Cr³⁺ type b, expecially B, resemble those of Cr³⁺ in oxides, especially of corundum type solid solutions or eskolaite. This may be interpreted by the assumption that a fraction of the total chromium contents might be allocated in a precursor of a corundum type exsolution. Received: 3 January 1997 / Revised, accepted: 2 May 1997     

Laser-induced time-resolved luminescence of tugtupite,sodalite and hackmanite

We have interpreted a number of luminescence centers in natural tugtupite Na₈Al₂Be₂Si₈O₂₄Cl₂, sodalite Na₈Al₆Si₆O₂₄C₂ and hackmanite Na₈Al₆Si₆O₂₄(Cl₂,S) by use of laser-induced time-resolved luminescence spectroscopy. The main new results are the following: Fe³⁺, Mn²⁺, Eu²⁺, Ce³⁺, mercury type (potentially Pb²⁺, Tl⁺, Sn²⁺ and/or Sb³⁺), radiation induced luminescence centers; several types of S₂ ⁻ centers. Spectral shift connected with the presence of luminescence centers, which are detected together with S₂ ⁻ centers and impossible to resolve with continuous wave luminescence spectroscopy, is the possible reason for spectral diversity of S₂ ⁻ luminescence centers presented in different publications.     

Experimental Study on the Solubility of Cr^2 in Olivine,Orthopyroxene and Spinel Solid Solutions

Experiments have been performed on the system MgO-SiO2-Cr-O at 0-2.88 GPa and 1100-1450℃,focusing on the stability of Cr^2 in olivine(O1),orthopyroxene(Opx) and spinel(Sp) and its partitioning between these phases.Analytical reagent grade chemicals,MgO,SiO2,Cr2O3.and Cr were used to make starting mixtures.Excess Cr(50%) was then added in these mixtures to ensure that the resultant phases were in equilibrium with the metal Cr.Flux of BaO B2O3(%) was added for facilitating experimental equilibrium and crystal growth.Cr was used as capsule material.All phases in the product were identified by X-ray and analyzed by electron microprobe,The contents of CrO in the different phases(O1,Opx and Sp)were calculated according to stoichiometry.The obtained results of calculation indicate that Cr^3 in Ol and Opx is negligible.The experimental results show;(a) with increasing temperature and decreasing pressure,Cr^2 solubility in Ol,Opx and Sp increases;(b) with in creasing temperature,the partitioning coefficient of Mg and Cr^2 between Ol and Opx decreases,that between Opx and Sp increases,and that between Ol and Sp remains almost unchanged;(c) the effect of pressure on all partitioning coefficients is negligible.     

A theoretical study of the absorption spectra of Pb+ and Pb3+ in site K+ of microcline: application to the color of amazonite

The blue-green color of amazonite has been assigned by various authors to ions Pb⁺ (6 s)² (6 p) and/or Pb³⁺ (6 s) in site of K⁺ of microcline. Owing to the complex which forms between the ion Pb³⁺ and the lone pairs of the oxygen atoms surrounding it, the peripheral electron of Pb³⁺ passes on the levels (6 p) of the latter, which results in a great similarity of the spectra of Pb⁺ and Pb³⁺ in amazonite (the transition energies are multiplied by a factor greater than 1), whereas, in the isolated state, these spectra are completely different from one another. An analytical development of the crystal field around a site K⁺ is established. Under the effect of the crystal field, the transition ² P _1/2→² P _3/2 (6 p) is split into two double transitions. The lower transition only falls in the visible domain (1.6–1.8 eV for Pb⁺), the second in U−V. The green color would arise from the ion Pb⁺, whereas the blue one would be attributed to the ion Pb³⁺. Received: 23 January 1997 / Revised, accepted: 10 September 1997     

Oxidative Ce3+ sequestration by fungal manganese oxides with an associated Mn(II) oxidase activity

Sequestration of Ce³⁺ by biogenic manganese oxides (BMOs) formed by a Mn(II)-oxidizing fungus, Acremonium strictum strain KR21-2, was examined at pH 6.0. In anaerobic Ce³⁺ solution, newly formed BMOs exhibited stoichiometric Ce³⁺ oxidation, where the molar ratio of Ce³⁺ sequestered (Ce_seq) relative to Mn²⁺ released (Mn_rel) was maintained at approximately two throughout the reaction. A similar Ce³⁺ sequestration trend was observed in anaerobic treatment of BMOs in which the associated Mn(II) oxidase was completely inactivated by heating at 85 °C for 1 h or by adding 50 mM NaN₃. Aerobic Ce³⁺ treatment of newly formed BMO (enzymatically active) resulted in excessive Ce³⁺ sequestration over Mn²⁺ release, yielding Ce_seq/Mn_rel > 200, whereas heated or poisoned BMOs released a significant amount of Mn²⁺ with lower Ce³⁺ sequestration efficiency. Consequently, self-regeneration by the Mn(II) oxidase in newly formed BMO effectively suppressed Mn²⁺ release and enhanced oxidative Ce³⁺ sequestration under aerobic conditions. Repeated treatments of heated or poisoned BMOs under aerobic conditions confirmed that oxidative Ce³⁺ sequestration continued even after most Mn oxide was released from the solid phase, indicating auto-catalytic Ce³⁺ oxidation at the solid phase produced through primary Ce³⁺ oxidation by BMO. From X-ray diffraction analysis, the resultant solid phases formed through Ce³⁺ oxidation by BMO under both aerobic and anaerobic conditions consisted of cerianite with crystal sizes of 5.00–7.23 Å. Such nano-sized CeO₂ (CeO_2,BMO) showed faster auto-catalytic Ce³⁺ oxidation than that on well-crystalized cerianite under aerobic conditions, where the normalized pseudo-first order rate constants for auto-catalytic Ce³⁺ oxidation on CeO_2,BMO was two orders of magnitude higher. Consequently, we concluded that Ce³⁺ contact with BMOs sequesters Ce³⁺ through two oxidation paths: primary Ce³⁺ oxidation by BMOs produces nano-sized crystalline cerianite, and subsequent auto-catalytic Ce³⁺ oxidation efficiently occurs using dissolved oxygen as the oxidizing agent. Pretreatment of newly formed BMOs with La³⁺ solution resulted in decreased rate constants for primary Ce³⁺ oxidation by BMO due to site blocking by La³⁺ sorption. The results presented herein increase our understanding of the role of BMO in oxidative Ce³⁺ sequestration process(es) through enzymatic and abiotic paths in natural environments and provide supporting evidence for the potential application of BMOs towards the recovery of Ce³⁺ from contaminated waters.     

Reliability of experimental partition coefficients in carbonate systems: Evidence for inhomogeneous distribution of impurity cations

Electron spin resonance (ESR) spectroscopy, thermal analysis and X-ray diffraction (XRD) analysis are used to study the mode of incorporation of a wide range of impurity ions (up to 1% Ni²⁺, Sr²⁺, Cd²⁺, Mg²⁺, Cu²⁺, Fe²⁺, Zn²⁺, Pb²⁺, Mn²⁺ and Ba²⁺) in calcites synthesised in aqueous solutions. It is shown that when certain impurity ions are incorporated in these calcites they become concentrated, together with other trace elements such as Mn²⁺, into hitherto unsuspected trace phases. The important conclusion is drawn that unless the scavenging of trace elements by these phases can be avoided or corrected for, any calcite—liquid partition coefficients measured may have limited significance. ESR spectroscopy has revealed the intense strain common in calcites grown by different methods, whilst thermal analysis suggested that such strain may significantly alter the thermodynamic properties of these calcites. ESR spectroscopic analysis of aragonites synthesised by methods previously reported in the literature has revealed the common occurrence of trace calcite at concentrations below the XRD detection limit and proves the tendency of this calcite to scavenge trace Mn. Using ESR spectroscopy to monitor trace calcite levels and structural imperfections in synthetic aragonites, the urea hydrolysis technique is modified to provide a method for the synthesis of high-purity strain-free aragonite available for experimental studies.     

He+ ion implantation and electron irradiation effects on cathodoluminescence of plagioclase

Cathodoluminescence (CL) spectra of unirradiated, He⁺ ion-implanted and electron-irradiated plagioclase minerals contain the following emission bands: (1) below 300 nm due to Pb²⁺, (2) at ~320 and ~350 nm to Ce³⁺, (3) at 380–420 nm to Eu²⁺, Ti⁴⁺ and/or Al–O^?–Al/Ti defects, (4) at 560–580 nm to Mn²⁺ and (5) at 720–760 nm to Fe³⁺. During the implantation of He⁺ ion, much of their energy may be dissipated by partial destruction and strain of the feldspar framework, resulting in quenching of CL. Deconvolution of CL spectra acquired from albite and oligoclase reveals an emission component at 1.86 eV (666 nm) assigned to a radiation-induced defect center associated with Na⁺ atoms. As its intensity increases with radiation dose, this emission component has potential for geodosimetry and geochronometry. Electron irradiation causes Na⁺ migration in plagioclase, and then a considerable reduction in intensity of emissions assigned to impurity centers, which is responsible for an alteration in the energy state or a decrease in luminescence efficiency following the change of activation energy. Emission intensity at 1.86 eV positively correlates with electron irradiation time for unimplanted and He⁺ ion-implanted albite and oligoclase, but negatively for the implanted albite above 1.07 × 10^?4 C/cm². It implies that radiation halo produced by α-particles should not be measured using CL spectroscopy to estimate β radiation dose on albite in the high radiation level.