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Sample records for olivines limnpo4 lifepo4

  1. Distinct Configurations of Antisite Defects in Ordered Metal Phosphates: Comparison between LiMnPO4 and LiFePO4

    NASA Astrophysics Data System (ADS)

    Chung, Sung-Yoon; Choi, Si-Young; Lee, Seongsu; Ikuhara, Yuichi

    2012-05-01

    By using a combination of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, ab initio density-functional theory calculations, and neutron powder diffraction techniques, We have found completely different configurations of the antisite exchange defects in LiMnPO4 and LiFePO4, with a random distribution of the exchange pairs without aggregation in the former and with zigzag-type clustering behavior preferred in the latter. Recalling the compositional analogy and identical crystal structure of the two metal phosphates, such unexpectedly distinct arrangement of the same type of point defects is a notable structural aspect.

  2. Enhancing the electrochemical kinetics of high voltage olivine LiMnPO4 by isovalent co-doping.

    PubMed

    Ramar, Vishwanathan; Balaya, Palani

    2013-10-28

    We report here doping of Fe(2+) and/or Mg(2+) in LiMnPO4 cathode material to enhance its lithium storage performance and appraise the effect of doping. For this purpose, LiMn0.9Fe(0.1-x)MgxPO4/C (x = 0 and 0.05) and LiMn0.95Mg0.05PO4/C have been prepared by a ball mill assisted soft template method. These materials were prepared with similar morphology, particle size and carbon content. Amongst them, the isovalent co-doped LiMn0.9Fe0.05Mg0.05PO4/C sample shows better electrochemical performance compared to LiMn0.9Fe0.1PO4/C and LiMn0.95Mg0.05PO4/C samples. For instance, a lithium storage capacity of 159 mA h g(-1) is obtained at 0.1 C for LiMn0.9Fe0.05Mg0.05PO4/C material with a relatively low polarization of ~139 mV. This is in sharp contrast to LiMn0.9Fe0.1PO4/C and LiMn0.95Mg0.05PO4/C which show only 136.8 and 128.4 mA h g(-1) at 0.1 C with the polarization of ~222 and 334 mV respectively. Further, the LiMn0.9Fe0.05Mg0.05PO4/C electrode delivers discharge capacities of 155.8, 141.4, 118.8, 104.6, 81.4 and 51.8 mA h g(-1) at 0.2, 0.5, 1, 2, 5 and 10 C respectively. This electrode material also retains a capacity of 116 mA h g(-1) at 1 C after 200 cycles, which is 96% of its initial capacity. Such improved cycling stability of LiMn0.9Fe0.05Mg0.05PO4/C is attributed to the suppressed Mn dissolution in the electrolyte compared to the other samples. Further, during the Li extraction process, delithiated phases created from the Fe(2+)/Fe(3+) redox reaction (~3.45 V) favor enhanced electrochemical activity of the succeeding Mn(2+)/Mn(3+) redox couples. The fully charged state (4.6 V) contains a partially lithiated phase owing to the presence of electrochemically inactive Mg(2+). The presence of such lithiated phase provides a favourable environment for the subsequent lithium insertion process. We also observe improved electronic conductivity and Li-ion diffusion for the co-doped sample compared to LiMnPO4 doped with either Fe(2+) or Mg(2+) by impedance measurements. The improved storage performance of co-doped LiMnPO4 is thus explained in terms of (i) favorable extraction and insertion reactions and (ii) enhanced transport properties. PMID:24018895

  3. High-performance, nanostructure LiMnPO4/C composites synthesized via one-step solid state reaction

    NASA Astrophysics Data System (ADS)

    Zheng, Jugong; Ni, Liang; Lu, Yanwen; Qin, Cancan; Liu, Panxing; Wu, Tongfu; Tang, Yuefeng; Chen, Yanfeng

    2015-05-01

    LiMnPO4 is proposed as more promising cathode material as LiFePO4, while poor electronic conductivity and Jahn-Teller effects during charge/discharge processes hinder the electrochemical performance. To overcome these problems, one-step solid state reaction method is developed to synthesize LiMnPO4/C composites, which is with nanostructure, high crystallinity and good carbon coating. Manganese oxide sources and calcination temperature are investigated as factors for preparing high-performance LiMnPO4/C for Li-ion batteries. The results show that the LiMnPO4/C composites prepared with mixed manganese oxide deliver a superior initial capacity of 153 mAh g-1 at 0.05 C and high rate performance with discharge capacities of 123 mAh g-1 at 1 C and 103 mAh g-1 at 2 C. And the LiMnPO4/C composites synthesized at 600 C can retain 94% of the initial capacity after 200 cycles at 1 C, revealing a stable cycling stability. Therefore, one-step solid state reaction brings to light the synthesis of high performance LiMnPO4/C cathode materials and is suitable for large scale production.

  4. Electrochemical Performance of Electrophoretically Deposited Nanostructured LiMnPO4-Sucrose Derived Carbon Composite Electrodes for Lithium Ion Batteries.

    PubMed

    Ravi, Soumya P; Praveen, P; Sreelakshmi, K V; Balakrishnan, A; Subramanian, K R V; Shantikumar, V; Lee, Y S; Sivakumar, N

    2015-01-01

    The present study reports an approach by which thin films of sucrose added olivine type LiMnPO4-Ccomposite and pristine LiMnPO4 is made by a technique of electrophoretic co-deposition in which pristine and composite samples were synthesized by a sol-gel route. These thin films with enhanced surface area is used to fabricate cathodes for rechargeable Li ion batteries. XRD confirms phase pure single crystalline orthorhombic structure. Transmission Electron Microscopy (TEM) images shows the carbon coating over LiMnPO4 and the particle size restricted in the nano regime. The presence of sp2 hybridized carbon on LiMnPO4 particles is confirmed by X-ray Photon spectroscopy (XPS). To explore the electrochemical behavior, cyclic voltammetry (CV) and cycling studies were performed. The specific capacity for LiMnPO4-C is found to be increased by 43% in comparison to the pristine LiMnPO4. It also exhibited 86% retention in capacity compared to the pristine LiMnPO4 (52%). The result indicates that a proper carbon coating can significantly improve the electronic conductivity and hence the specific capacity. PMID:26328437

  5. Enhanced thermal safety and high power performance of carbon-coated LiFePO4 olivine cathode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Zaghib, K.; Dub, J.; Dallaire, A.; Galoustov, K.; Guerfi, A.; Ramanathan, M.; Benmayza, A.; Prakash, J.; Mauger, A.; Julien, C. M.

    2012-12-01

    The carbon-coated LiFePO4 Li-ion oxide cathode was studied for its electrochemical, thermal, and safety performance. This electrode exhibited a reversible capacity corresponding to more than 89% of the theoretical capacity when cycled between 2.5 and 4.0 V. Cylindrical 18,650 cells with carbon-coated LiFePO4 also showed good capacity retention at higher discharge rates up to 5C rate with 99.3% coulombic efficiency, implying that the carbon coating improves the electronic conductivity. Hybrid Pulse Power Characterization (HPPC) test performed on LiFePO4 18,650 cell indicated the suitability of this carbon-coated LiFePO4 for high power HEV applications. The heat generation during charge and discharge at 0.5C rate, studied using an Isothermal Microcalorimeter (IMC), indicated cell temperature is maintained in near ambient conditions in the absence of external cooling. Thermal studies were also investigated by Differential Scanning Calorimeter (DSC) and Accelerating Rate Calorimeter (ARC), which showed that LiFePO4 is safer, upon thermal and electrochemical abuse, than the commonly used lithium metal oxide cathodes with layered and spinel structures. Safety tests, such as nail penetration and crush test, were performed on LiFePO4 and LiCoO2 cathode based cells, to investigate on the safety hazards of the cells upon severe physical abuse and damage.

  6. Enhanced Electrochemical Properties of LiMnPO4/C by Glucose-Assisted Polyol Synthesis.

    PubMed

    Song, Jinju; Gim, Jihyeon; Kim, Sungjin; Park, Wangeun; Jo, Jeonggeun; Kim, Jaekook

    2015-08-01

    Carbon-coated nano-sized LiMnPO4/C particles are synthesized by polyol method using low-cost glucose as the carbon source. The X-ray diffraction patterns of the synthesized samples are well indexed to the orthorhombic olivine-LiMnPO4 structure. The morphology studies using FE-SEM and HR-TEM images clearly illustrate thin layered carbon coatings on LiMnPO4 particles of sizes ranging between 50~100 nm. The LiMnPO4/C particles delivers an initial discharge capacity of 151 mA h g-1 at a current density of 1.6 mA g-1 in the voltage range of 2.5-4.3 V with impressive capacity retentions. PMID:26369197

  7. Structural and Electrochemical Characterization of Pure LiFePO 4 and Nanocomposite C- LiFePO 4 Cathodes for Lithium Ion Rechargeable Batteries

    DOE PAGESBeta

    Kumar, Arun; Thomas, R.; Karan, N. K.; Saavedra-Arias, J. J.; Singh, M. K.; Majumder, S. B.; Tomar, M. S.; Katiyar, R. S.

    2009-01-01

    Pure limore » thium iron phosphate ( LiFePO 4 ) and carbon-coated LiFePO 4 (C- LiFePO 4 ) cathode materials were synthesized for Li-ion batteries. Structural and electrochemical properties of these materials were compared. X-ray diffraction revealed orthorhombic olivine structure. Micro-Raman scattering analysis indicates amorphous carbon, and TEM micrographs show carbon coating on LiFePO 4 particles. Ex situ Raman spectrum of C- LiFePO 4 at various stages of charging and discharging showed reversibility upon electrochemical cycling. The cyclic voltammograms of LiFePO 4 and C- LiFePO 4 showed only a pair of peaks corresponding to the anodic and cathodic reactions. The first discharge capacities were 63, 43, and 13 mAh/g for C/5, C/3, and C/2, respectively for LiFePO 4 where as in case of C- LiFePO 4 that were 163, 144, 118, and 70 mAh/g for C/5, C/3, C/2, and 1C, respectively. The capacity retention of pure LiFePO 4 was 69% after 25 cycles where as that of C- LiFePO 4 was around 97% after 50 cycles. These results indicate that the capacity and the rate capability improved significantly upon carbon coating.« less

  8. Cycling stability and degradation mechanism of LiMnPO4 based electrodes

    NASA Astrophysics Data System (ADS)

    Moskon, J.; Pivko, M.; Jerman, I.; Tchernychova, E.; Logar, N. Zabukovec; Zorko, M.; Selih, V. S.; Dominko, R.; Gaberscek, M.

    2016-01-01

    Long term stability of LiMnPO4 particles with a crystallite size between ∼20 and 50 nm covered with a dense native carbon coating (14 wt.%) is demonstrated. More than 500 cycles at a rate of C/20, in the potential window of 2.7-4.5 V and a temperature of 55 °C were achieved. During most of the cycling the average capacity decay was less than 0.06% per cycle. After about 500 cycles a sudden capacity drop was observed. Degradation processes in various stages of cycling were thoroughly examined using a range of techniques. Severe surface film formation, manganese dissolution and degradation of LixMnPO4 accompanied by formation of Li4P2O7 were clearly identified. The good long term stability seems to be due to dense, protective carbon coating. Decomposition is most likely initiated at local defects in the microstructure of pyrolytic carbon coating around LiMnPO4 particles. In addition to known degradation mechanisms of LiMnPO4 we observed pronounced gradual amorphization of the olivine crystallites during long-term cycling at 55 °C. Finally, changes in morphology of the carbon black additive after prolonged cycling are reported and commented.

  9. Hyperfine fields at the Li site in LiFePO(4)-type olivine materials for lithium rechargeable batteries: a (7)Li MAS NMR and SQUID study.

    PubMed

    Tucker, Michael C; Doeff, Marca M; Richardson, Thomas J; Fiones, Rita; Cairns, Elton J; Reimer, Jeffrey A

    2002-04-17

    The (7)Li NMR isotropic shift for olivine LiMPO(4) (M = Fe, Mn, Co, Ni) is assigned to hyperfine coupling between the (7)Li nucleus and the transition metal unpaired electrons on the basis of the Curie-Weiss temperature dependence of the shift. The hyperfine shift arises from a linear combination of Li-O-M through-bond interactions wherein the unpaired A' electrons contribute a negative shift and the unpaired A' ' electrons contribute a positive shift. The hyperfine coupling constant is determined for each composition. PMID:11942811

  10. Analysis of the size effect of LiMnPO4 particles on the battery properties by using STEM-EELS

    NASA Astrophysics Data System (ADS)

    Yoshida, J.; Stark, M.; Holzbock, J.; Hsing, N.; Nakanishi, S.; Iba, H.; Abe, H.; Naito, M.

    2013-03-01

    The LiMnPO4 cathode material is a good candidate for rechargeable lithium ion batteries because of high voltage (4.1 V), high thermal stability and no toxicity. However, the rate performance of this material is extremely low when compared to the conventional LiMO2 (M = Ni or Co) or LiFePO4. In this study, the primary particle size was reduced by a hydrothermal synthesis, and we obtained LiMnPO4 particles with sizes less than 40 nm. The sample exhibited an excellent rate capacity, which was 136 mAh g-1 at 5 C and 120 mAh g-1 at 10 C. We also revealed the effect of the LiMnPO4 particle size on the battery by introducing STEM-EELS, which was expected to allow for the direct microscopic observation of the lithium state in the particles during the charge-discharge process. With the EELS analysis, it was clarified that the lithium diffusion distance from the inside to the surface of the primary particles had to be reduced down to about 20 nm to achieve the high rate performance.

  11. The influence of temperature on a nutty-cake structural material: LiMn1-xFexPO4 composite with LiFePO4 core and carbon outer layer for lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Huo, Zhen-Qing; Cui, Yu-Ting; Wang, Dan; Dong, Yue; Chen, Li

    2014-01-01

    The extremely low electronic conductivity, slow ion diffusion kinetics, and the Jahn-Teller effect of LiMnPO4 limit its electrochemical performance. In this work, a nutty-cake structural C-LiMn1-xFexPO4-LiFePO4 cathode material is synthesized by hydrothermal method and further calcined at different temperatures. The influence of calcination temperature on the electrochemical behavior is investigated by X-ray diffractometer, scanning electron microscope, field-emission high-resolution transmission electron microscope, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy and charge-discharge tests. And the performance of C-LiMn1-xFexPO4-LiFePO4 materials has a relationship with its crystal structure. The well-crystallized Sample-600 calcined at 600 C shows the smallest charge transfer resistance, the largest lithium ion diffusion coefficient (DLi) and the best cycling stability. The discharge capacity of Sample-600 holds around 112 mAh g-1 after the 3rd cycle at 0.1 C rate. The performances improvement of C-LiMn1-xFexPO4-LiFePO4 material can be mainly attributed to the iron diffusion from the LiFePO4 core to the outer LiMnPO4 layer under appropriate calcination temperature.

  12. Three-Dimensional LiMnPO4·Li3V2(PO4)3/C Nanocomposite as a Bicontinuous Cathode for High-Rate and Long-Life Lithium-Ion Batteries.

    PubMed

    Luo, Yanzhu; Xu, Xu; Zhang, Yuxiang; Pi, Yuqiang; Yan, Mengyu; Wei, Qiulong; Tian, Xiaocong; Mai, Liqiang

    2015-08-12

    Olivine-type LiMnPO4 has been extensively studied as a high-energy density cathode material for lithium-ion batteries. To improve both the ionic and electronic conductivities of LiMnPO4, a series of carbon-decorated LiMnPO4·Li3V2(PO4)3 nanocomposites are synthesized by a facile sol-gel method combined with the conventional solid-state method. The optimized composite presents a three-dimensional hierarchical structure with active nanoparticles well-embedded in a conductive carbon matrix. The combination of the nanoscale carbon coating and the microscale carbon network could provide a more active site for electrochemical reaction, as well as a highly conductive network for both electron and lithium-ion transportation. When cycled at 20 C, an initial specific capacity of 103 mA h g(-1) can be obtained and the capacity retention reaches 68% after 3000 cycles, corresponding to a capacity fading of 0.013% per cycle. The stable capacity and excellent rate capability make this carbon-decorated LiMnPO4·Li3V2(PO4)3 nanocomposite a promising cathode for lithium-ion batteries. PMID:26196544

  13. Crystal orientation tuning of LiFePO4 nanoplates for high rate lithium battery cathode materials.

    PubMed

    Wang, Li; He, Xiangming; Sun, Wenting; Wang, Jianlong; Li, Yadong; Fan, Shoushan

    2012-11-14

    We report the crystal orientation tuning of LiFePO(4) nanoplates for high rate lithium battery cathode materials. Olivine LiFePO(4) nanoplates can be easily prepared by glycol-based solvothermal process, and the largest crystallographic facet of the LiFePO(4) nanoplates, as well as so-caused electrochemical performances, can be tuned by the mixing procedure of starting materials. LiFePO(4) nanoplates with crystal orientation along the ac facet and bc facet present similar reversible capacities of around 160 mAh g(-1) at 0.1, 0.5, and 1 C-rates but quite different ones at high C-rates. The former delivers 156 mAh g(-1) and 148 mAh g(-1) at 5 C-rate and 10 C-rate, respectively, while the latter delivers 132 mAh g(-1) and only 28 mAh g(-1) at 5 C-rate and 10 C-rate, respectively, demonstrating that the crystal orientation plays important role for the performance of LiFePO(4) nanoplates. This paves a facile way to prepare high performance LiFePO(4) nanoplate cathode material for lithium ion batteries. PMID:23074971

  14. Electrical conductivity studies of graphene wrapped nanocrystalline LiMnPO4 composite

    NASA Astrophysics Data System (ADS)

    Cheruku, Rajesh; D, Surya Bhaskaram; Govindaraj, G.; Vijayan, Lakshmi

    2015-06-01

    Nanocrystalline LiMnPO4 material was synthesized by template free sucrose assisted hydrothermal method. The material possesses the orthorhombic crystal structure with Pnma, space group having four formula units. The GO was prepared by the hummer's method and it was reduced graphene oxide (rGO) with hydrazine hydrate in the presence of nitrogen atmosphere. LiMnPO4 material was wrapped by the rGO to increase its conductivity. The structural characterization was accomplished through X-ray diffraction, FT-IR and Raman spectroscopy. Morphology was identified by the SEM, Electrical characterization was done through impedance spectroscopy and the results were reported.

  15. Synthesis of a LiFePO4/C cathode material by using a high-energy nano mill

    NASA Astrophysics Data System (ADS)

    Islam, Mobinul; Yoon, Man-Soon; Ur, Soon-Chul

    2015-07-01

    Olivine lithium iron phosphate (LiFePO4) is a promising cathode material for Li-ion battery. A temperature around 700 - 800 ? is generally required to prepare LiFePO4 powder with good crystallinity. The LiFePO4 materials are synthesized via a solid-state method by using a highenergy nano mill (HENM). The conventional ball-milling process is also conducted for the same material for a comparative study. The effect of the precursor's mixing processes on the synthesis temperature of LiFePO4 is investigated in this study. The required reaction temperature of LiFePO4 is 432 ? for the HENM process and 480 ? for the ball-mill process as found from the differential scanning calorimetry (DSC) results. The HENM process improves the reaction activity and the homogeneity of the materials used throughout process and lowers the reaction temperature as compared with the conventional ball-mill process. The milled powders are characterized by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The sample synthesized by using the HENM process exhibits a discharge capacity of 136 mAhg -1 at 0.1 C rate. The results in this study indicate that the HENM process is a substantial and promising process for LiFePO4 cathode preparation owing to its short fabrication time and ability to improve the reaction condition. A HENM can be used to promote formation of LiFePO4 at lower temperatures.

  16. Synthesis of LiyMnSiOx and LiMnPO4 nanostructures

    NASA Astrophysics Data System (ADS)

    Milke, Bettina; Strauch, Peter; Antonietti, Markus; Giordano, Cristina

    2009-09-01

    Nanosized LiyMnSiOx and LiMnPO4 have been synthesized by a hydrothermal route. Simply by changing parameters such as metal precursors and/or template, high surface area LiyMnSiOx with different morphology and sizes were prepared, in particular hollow spheres and plate-like nanoparticles, however with poorly developed crystallinity. In the case of LiMnPO4, highly crystalline nanocrystals were prepared.Nanosized LiyMnSiOx and LiMnPO4 have been synthesized by a hydrothermal route. Simply by changing parameters such as metal precursors and/or template, high surface area LiyMnSiOx with different morphology and sizes were prepared, in particular hollow spheres and plate-like nanoparticles, however with poorly developed crystallinity. In the case of LiMnPO4, highly crystalline nanocrystals were prepared. Electronic supplementary information (ESI) available: FT-IR spectra of LiyMnSiOx prepared with different silica sources and different metal precursors; particles size distributions of LiyMnSiOx in the form of hollow spheres and plate-like nanoparticles; ICP technical details. See DOI: 10.1039/b9nr00149b

  17. Rapid Polyol-Assisted Microwave Synthesis of Nanocrystalline LiFePO4/C Cathode for Lithium-Ion Batteries.

    PubMed

    Paul, Baboo Joseph; Gim, Jihyeon; Baek, Sora; Kang, Jungwon; Song, Jinju; Kim, Sungjin; Kim, Jaekook

    2015-08-01

    Nanocrystalline LiFePO4/C has been synthesized under a very short period of time (90 sec) using a polyol-assisted microwave heating synthesis technique. The X-ray diffraction (XRD) data indicates that the rapidly synthesized materials correspond to phase pure olivine. Post-annealing of the as-prepared sample at 600 C in argon atmosphere yields highly crystalline LiFePO4/C. The morphology of the samples studied using scanning electron microscopy (SEM) reveals the presence of secondary particles formed from aggregation of primary particles in the range of 30-50 nm. Transmission electron microscopy (TEM) images reveal a thin carbon layer coating on the surface of the primary particle. The charge/discharge studies indicate that the as-prepared and annealed LiFePO4/C samples delivered initial discharge capacities of 126 and 160 mA h g-1, respectively, with good capacity retentions at 0.05 mA cm-2 current densities. The post-annealing process indeed improves the crystallinity of the LiFePO4 nanocrystals, which enhances the electrode performance of LiFePO4/C. PMID:26369219

  18. First-principles studies of Mg-doped LiFePO4 for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Shi, Siqi; Zhang, Hua; Mei, Wai-Ning; Liu, Aifang; Lim, Khoon-Cheng

    2010-03-01

    We investigate the formation energy, crystal parameters and electronic properties of Mg-doped (Li site and Fe site) lithium iron orthophosphate (LiFePO4) by using the first-principles calculations. We noticed that the Mg ions are much more easier to be doped on Fe site than Li site. Comparing with the pure LiFePO4, we found the band gap of Mg-doped LiFePO4 is a little narrower than that of the pure one, indicating that the enhancement of the electronic conductivity upon doping is likely. Furthermore, we discovered that Mg doped on the Fe site causes the bond length to change, which is consistent with our experimental data. The reduction of the Mg-O bond length favors the formation of Li^+ diffusion channels, hence improves the ionic dynamic properties of the olivine LiFePO4. Mg-doped LiFePO4 has bigger electricity peak area that the pure one, which is an indication of improved ionic diffusion.

  19. Temperature Dependence of Aliovalent-vanadium Doping in LiFePO4 Cathodes

    SciTech Connect

    Harrison, Katharine L; Bridges, Craig A; Paranthaman, Mariappan Parans; Idrobo Tapia, Juan C; Manthiram, Arumugam; Goodenough, J. B.; Segre, C; Katsoudas, John; Maroni, V. A.

    2013-01-01

    Vanadium-doped olivine LiFePO4 cathode materials have been synthesized by a novel low-temperature microwave-assisted solvothermal (MW-ST) method at 300 oC. Based on chemical and powder neutron/X-ray diffraction analysis, the compositions of the synthesized materials were found to be LiFe1-3x/2Vx x/2PO4 (0 x 0.2) with the presence of a small number of lithium vacancies charge-compensated by V4+, not Fe3+, leading to an average oxidation state of ~ 3.2+ for vanadium. Heating the pristine 15 % V-doped sample in inert or reducing atmospheres led to a loss of vanadium from the olivine lattice with the concomitant formation of a Li3V2(PO4)3 impurity phase; after phase segregation, a partially V-doped olivine phase remained. For comparison, V-doped samples were also synthesized by conventional ball milling and heating, but only ~ 10 % V could be accommodated in the olivine lattice in agreement with previous studies. The higher degree of doping realized with the MW-ST samples demonstrates the temperature dependence of the aliovalent-vanadium doping in LiFePO4.

  20. Characterization of the carbon coating onto LiFePO4 particles used in lithium batteries

    NASA Astrophysics Data System (ADS)

    Julien, C. M.; Zaghib, K.; Mauger, A.; Massot, M.; Ait-Salah, A.; Selmane, M.; Gendron, F.

    2006-09-01

    While nanosized ferromagnetic particles could poison the performance of the Li batteries containing phospho-olivine, the carbon-film coating the LiFePO4 particles has a beneficial effect on cycling life of the cells. In this paper, we present the properties of the carbon layer deposited at the surface of the LiFePO4 grains. Characteristics of the carbon layer are analyzed using scanning electron microscopy, high-resolution transmission scanning electron microscopy, Fourier transform infrared, and Raman scattering (RS) spectroscopy. The carbon deposit characterized by RS spectroscopy is hydrogenated with very small hydrogen/carbon ratio, so that it belongs to the family of the amorphous graphitic carbon. The carbon deposit is similar to that obtained by pyrolysis technique at high temperature. It is expected to have the same properties (small hardness, high electronic conductivity) that favor both the Li diffusion from the LiFePO4 bulk and the charge-discharge rate of the cell. A model for the Li-ion transport throughout the coating is given.

  1. Reaction mechanism and influence of the experimental variables for solvothermal synthesized LiMnPO4 nanoplates

    NASA Astrophysics Data System (ADS)

    Zhu, Kunlei; Zhang, Wenxuan; Du, Jiangyong; Liu, Xiaoyan; Tian, Jianhua; Ma, Huanmei; Liu, Shengzhong; Shan, Zhongqiang

    2015-12-01

    Plate-like LiMnPO4 nanomaterial for Li-ion batteries is synthesised successfully via a facile solvothermal process in mixed water-diethylene glycol (DEG) solvents at 190 °C for 3 h. Experimental variables, including reaction time, reaction temperature and reactant mole ratio, are discussed in detail. A tentative reaction mechanism is proposed on the basis of the time dependent trials. It is found that, with the increase of reaction temperature, the formation of LiMnPO4 phase is accelerated and the reaction for synthesizing LiMnPO4 can be finished in a shorter time. Studies on the effect of reactant mole ratio further support the proposed mechanism. The electrochemical properties of obtained LiMnPO4 are examined after a carbon coating process. Electrochemical tests show that the obtained LiMnPO4 at 190 °C for 3 h exhibits better electrochemical performances than the LiMnPO4 synthesized at 170 °C for 4.5 h or 150 °C for 6 h. It is clear that an improved electrochemical performance can be obtained with the increase of reaction temperature and the decrease of reaction time. This result provides us thoughts and guidance to optimize the reaction conditions by harmonizing the reaction temperature and reaction time, which is beneficial for the practical application.

  2. A polyethylene glycol-assisted carbothermal reduction method to synthesize LiFePO4 using industrial raw materials

    NASA Astrophysics Data System (ADS)

    Fey, George Ting-Kuo; Huang, Kai-Pin; Kao, Hsien-Ming; Li, Wen-Hsien

    2011-03-01

    Olivine LiFePO4 is synthesized by a carbothermal reduction method (CTR) using industrial raw materials with polyethylene glycol (PEG) as a reductive agent and carbon source. A required amount of acetone is added to the starting materials for the ball milling process and the precursor is sintered at 973 K for 8 h to form crystalline phase LiFePO4. The structure and morphology of the LiFePO4/C composite samples have been characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, differential scanning calorimetry and magnetic susceptibility. Electrochemical measurements show that the LiFePO4/C composite cathode delivers an initial discharge capacity of 150 mAh g-1 at a 0.2C-rate between 4.0 and 2.8 V, and almost no capacity loss is observed for up to 50 cycles. Remarkably, the cell can sustain a 30C-rate between 4.6 and 2.0 V, and this rate capability is equivalent to charge or discharge in 2 min. The simple technique, low-cost starting materials, and excellent electrochemical performance make this process easier to commercialize than other synthesized methods.

  3. Direct formation of LiFePO4/graphene composite via microwave-assisted polyol process

    NASA Astrophysics Data System (ADS)

    Lim, Jinsub; Gim, Jihyeon; Song, Jinju; Nguyen, Dang Thanh; Kim, Sungjin; Jo, Jeonggeun; Mathew, Vinod; Kim, Jaekook

    2016-02-01

    The present study reports on the direct synthesis of LiFePO4 nanoparticles and graphene nanosheets to form a composite cathode (LFP/GNs) in a one-step microwave-assisted polyol reaction. The polyol reaction induced by microwave irradiation for a few minutes produces nanocrystalline LFP and graphene nanosheets simultaneously from lithium, iron and phosphorus and carbon (5 wt% of graphite oxide) sources, respectively, used as starting precursors. Powder X-ray diffraction (XRD), electron microscopy, and atomic force microscopy (AFM) studies on microwave-reacted sample obtained using just graphite oxide confirms the formation of graphene nanosheets separately. Whereas, electron microscopy studies on the LFP/GNs composite reveals that olivine nanoparticles of average sizes ranging between 5 and 20 nm are well-dispersed on the graphene nanosheets. Electrochemical measurements reveal that the LiFePO4/GNs nanocomposite cathodes registered enhanced discharge capacities (79 and 108 mAh g-1 for the as-prepared and annealed composite cathodes, respectively) at 32 C rates with good capacity retention capabilities. The AC impedance measurements confirm that the enhanced cathode properties of the LFP/GNs nanocomposite are ascribed to the improved electronic conductivity of the graphene nanosheets and the nano-sized particles. The slightly better electrochemical properties of the annealed LFP/GNs are attributed to its higher crystallinity.

  4. Effects of Ag-embedment on electronic and ionic conductivities of LiMnPO4 and its performance as a cathode for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lee, Kug-Seung; Lee, Kyung Jae; Kang, Yun Sik; Shin, Tae Joo; Sung, Yung-Eun; Ahn, Docheon

    2015-08-01

    An Ag-embedded LiMnPO4 (LMP) cathode was synthesized by solid-state reaction using a 1 wt% Ag precursor. Structure, morphology, and electrical conductivity studies of Ag-embedded LMP were performed by high resolution powder X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and four probe measurements. An Ag nanoparticle (~26 nm) surrounded by several olivine crystallites within a single particle dramatically improved the overall electrical conductivity of LMP by four orders of magnitude relative to that of pristine LMP, playing roles as conducting bridges among LMP crystallites as well as particles. Rietveld analysis confirmed structural variations related to the modification of atomic bond lengths of Mn-O, P-O, and Li-O coordination due to Ag-embedment and thereby leads to facile Li ion diffusion in LMP. Consequently, although a small amount of Ag was included, the Ag-embedded LMP cathode exhibited outstanding electrochemical performances (92 mA h g-1 at 10 C) versus lithium.An Ag-embedded LiMnPO4 (LMP) cathode was synthesized by solid-state reaction using a 1 wt% Ag precursor. Structure, morphology, and electrical conductivity studies of Ag-embedded LMP were performed by high resolution powder X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and four probe measurements. An Ag nanoparticle (~26 nm) surrounded by several olivine crystallites within a single particle dramatically improved the overall electrical conductivity of LMP by four orders of magnitude relative to that of pristine LMP, playing roles as conducting bridges among LMP crystallites as well as particles. Rietveld analysis confirmed structural variations related to the modification of atomic bond lengths of Mn-O, P-O, and Li-O coordination due to Ag-embedment and thereby leads to facile Li ion diffusion in LMP. Consequently, although a small amount of Ag was included, the Ag-embedded LMP cathode exhibited outstanding electrochemical performances (92 mA h g-1 at 10 C) versus lithium. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00933b

  5. Enhanced rate performance of LiFePO4/C by co-doping titanium and vanadium

    NASA Astrophysics Data System (ADS)

    Long, Yun-Fei; Su, Jing; Cui, Xiao-Ru; Lv, Xiao-Yan; Wen, Yan-Xuan

    2015-10-01

    V and Ti co-doped LiFePO4/C composites were synthesized by a wet milling assisted carbothermal reduction technology. The structure, morphology and electrochemical performance of the samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), magnetic susceptibility, positron annihilation lifetime spectra (PAS), scanning electron microscope (SEM), charge/discharge tests, electrochemical impedance spectroscopy (EIS) and cyclic voltammograms (CV). The results showed that the V and Ti co-doped samples kept the olivine structure of LiFePO4, but the synergistic effects between V3+ and Ti4+ in the lattice can increase the disorder degree of the lattice and create Li+ vacancies in LiFePO4/C, thus improve electronic conductivity and Li+ diffusion coefficient. LiV0.069Ti0.025Fe0.905PO4/C delivers an initial discharge capacity of 144.1mAhg-1 with a capacity retention ratio of 99.4%, 96.3% and 93.6% after 100, 200 and 300 cycles at 10C, respectively. Remarkably, it still gives a high discharge capacity of 124.8mAhg-1 even at a high rate of 20C.

  6. Single-crystal growth of LiMnPO 4 by the floating-zone method

    NASA Astrophysics Data System (ADS)

    Wizent, Nadja; Behr, Gnter; Lipps, Ferdinand; Hellmann, Ingo; Klingeler, Rdiger; Kataev, Vladislav; Lser, Wolfgang; Sato, Norio; Bchner, Bernd

    2009-02-01

    LiMnPO 4 crystals with orthorhombic Pnma crystal structure containing large grains have been grown successfully for the first time by the traveling-solvent floating-zone technique under elevated argon pressure. The grains achieve sizes of about 3 mm 210 mm and display an orange transparent color. During the growth process, the traveling zone is continuously enriched with PO 4- and Li-ions, due to the self-adjustment of the liquid zone, which hinders grain selection and leads to constitutional supercooling with the formation of a secondary phase in a later stage of the process. Magnetic measurements performed on oriented cuboids reveal antiferromagnetic ordering of the Mn 2+-ions below TN?34 K. The c-axis is the easy magnetic axis.

  7. High-capacity cathodes for lithium-ion batteries from nanostructured LiFePO4 synthesized by highly-flexible and scalable flame spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Hamid, N. A.; Wennig, S.; Hardt, S.; Heinzel, A.; Schulz, C.; Wiggers, H.

    2012-10-01

    Olivine, LiFePO4 is a promising cathode material for lithium-ion batteries due to its low cost, environmental acceptability and high stability. Its low electric conductivity prevented it for a long time from being used in large-scale applications. Decreasing its particle size along with carbon coating significantly improves electronic conductivity and lithium diffusion. With respect to the controlled formation of very small particles with large specific surface, gas-phase synthesis opens an economic and flexible route towards high-quality battery materials. Amorphous FePO4 was synthesized as precursor material for LiFePO4 by flame spray pyrolysis of a solution of iron acetylacetonate and tributyl phosphate in toluene. The pristine FePO4 with a specific surface from 126-218 m2 g-1 was post-processed to LiFePO4/C composite material via a solid-state reaction using Li2CO3 and glucose. The final olivine LiFePO4/C particles still showed a large specific surface of 24 m2 g-1 and were characterized using X-ray diffraction (XRD), electron microscopy, X-ray photoelectron spectrocopy (XPS) and elemental analysis. Electrochemical investigations of the final LiFePO4/C composites show reversible capacities of more than 145 mAh g-1 (about 115 mAh g-1 with respect to the total coating mass). The material supports high drain rates at 16 C while delivering 40 mAh g-1 and causes excellent cycle stability.

  8. Synthesis, non-isothermal kinetic and thermodynamic studies of the formation of LiMnPO4 from NH4MnPO4H2O precursor

    NASA Astrophysics Data System (ADS)

    Sronsri, Chuchai; Noisong, Pittayagorn; Danvirutai, Chanaiporn

    2014-06-01

    NH4MnPO4H2O was successfully synthesized by precipitating method. The LiMnPO4 was successfully generated through solid state reaction between synthesized NH4MnPO4H2O precursor and Li2CO3. The morphologies were observed to depend on the reaction temperatures. The thermal decomposition of NH4MnPO4H2O and the formation process of LiMnPO4 were confirmed by TG/DTG/DTA, FTIR, AAS/AES, XRD and SEM methods. The average crystallite size of NH4MnPO4H2O, Mn2P2O7 and LiMnPO4 were found to be around 51.2, 44.9 and 48.1 nm, respectively. The non-isothermal kinetic parameters (kinetic triplet: E?, A, g(?)) of the formation process of LiMnPO4 were evaluated from TG data by using Ozawa-Flynn-Wall and Kissinger-Akahira-Sunose methods. The iterative methods of both equations were carried out to determine the exact values of E?. The Coats-Redfern equation and kinetic compensation effects were successfully applied to confirm the activation energy and the most probable mechanism functions of the formation of LiMnPO4. The thermodynamic functions (?H?, ?S?, ?G?) of the transition state complexes of the formation of LiMnPO4 were calculated from the kinetic parameters for the first time.

  9. Effects of Nb-doped on the structure and electrochemical performance of LiFePO4/C composites

    NASA Astrophysics Data System (ADS)

    Ma, Zhipeng; Shao, Guangjie; Wang, Guiling; Zhang, Ying; Du, Jianping

    2014-02-01

    The olivine-type niobium doping Li1-xNbxFePO4/C (x=0, 0.005, 0.010, 0.015, 0.025) cathode materials were synthesized via a two-step ball milling solid state reaction. The effects of Nb doping were charactered by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and galvanostatic charge-discharge. It is found that Nb doping enlarges the interplanar distance of crystal plane parallel to [0 1 0] direction in LiFePO4. In other words, it widens the one dimensional diffusion channels of Li+ along the [0 1 0] direction. Electrochemical test results indicate that the Li0.99Nb0.01FePO4/C composite exhibits the best electrochemical performance with initial special discharge capacity of 139.3 mA h g-1 at 1 C rate. The present synthesis route is promising in making the solid state reaction method more practical for preparation of the LiFePO4 material.

  10. The influence of improved carbon coating layer with nanometer-sized CeO2 interconnector on the enhanced electrochemical performance of LiMnPO4

    NASA Astrophysics Data System (ADS)

    Chen, Fang-Jie; Tao, Fen; Wang, Chun-Mei; Zhang, Wen-Long; Chen, Li

    2015-07-01

    The CeO2/C hybrid coated LiMnPO4 composites are prepared via a simple and effective wet chemical process followed by heat treatment at 550 °C. The nanometer-sized CeO2 acts as an interconnector in carbon network, and its influence on the electrochemical performance is investigated in detail. The 0.25 wt.% CeO2-modified LiMnPO4/C (sample-0.25) exhibits the highest discharge capacity and the best cycle life, which can deliver an initial capacity of 139.9 mAh g-1 at 0.1C and still retain a reversible capacity of 120.4 mAh g-1 after 50 cycles (capacity retention of 86.1%). While for pristine LiMnPO4/C (sample-0), only 94.4 mAh g-1 can be obtained at the 50th cycle, corresponding to 72.9% of its initial discharge capacity (129.5 mAh g-1). Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) results confirm that an integrated and hybrid CeO2/C coating layer is formed on LiMnPO4 surface and its existence has no influence on the structure of LiMnPO4. The reason for the improved electrochemical properties of the CeO2-modified LiMnPO4/C composites has also been studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements.

  11. Lithium-Ion Insertion Kinetics of Na-Doped LiFePO4 as Cathode Materials for Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zhu, Yan-Rong; Zhang, Rui; Deng, Li; Yi, Ting-Feng; Ye, Ming-Fu; Yao, Jin-Han; Dai, Chang-Song

    2015-03-01

    Na-doped Li1- x Na x FePO4 ( x = 0, 0.05, 0.1, and 0.2) materials were synthesized by a simple high-temperature solid-state method. The structure, morphology, and kinetic performances of the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). XRD indicates that all samples are in accordance with the standard LiFePO4 with olivine structure. SEM reveals that the particle size of all samples is about 1 to 2 m. CV exhibits that Na doping obviously improves the reversibility and dynamic behaviors of lithium intercalation and deintercalation. EIS shows that Na doping decreases the charge transfer resistance of LiFePO4 and improves the lithium diffusion coefficients. It can be concluded that Na doping results in lower electrode polarization and higher lithium-ion diffusion coefficient, which can effectively improve the kinetic performance of LiFePO4.

  12. Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X. S.

    2013-12-01

    In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg2+ doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg2+ doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li+ diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg2+ doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of ``cushion'' as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability.In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg2+ doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg2+ doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li+ diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg2+ doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of ``cushion'' as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr04611g

  13. Solid Solution Phases in the Olivine-Type LiMnPO4/MnPO4 System

    SciTech Connect

    Chen, Guoying; Richardson, Thomas J.

    2009-04-07

    Nonstoichiometry is reported in the LiMnPO{sub 4}/MnPO{sub 4} system for the first time. As lithium is removed from crystalline LiMnPO{sub 4} by chemical or electrochemical methods, the resulting two phase mixture consists of stoichiometric LiMnPO{sub 4} and a delithiated phase, Li{sub y}MnPO{sub 4}, whose lattice parameters depend upon the global extent of delithiation and on the crystalline domain size of the delithiated phase. This behavior is reproduced during electrochemical insertion of lithium. Again, no evidence for nonstoichiometry was found in the vicinity of LiMnPO{sub 4}. Attempts to create single phase solid solutions by heating mixtures of the two phases failed due to the thermal instability of Li{sub y}MnPO{sub 4}.

  14. Mesoporous carbon-coated LiFePO4 nanocrystals co-modified with graphene and Mg2+ doping as superior cathode materials for lithium ion batteries.

    PubMed

    Wang, Bo; Xu, Binghui; Liu, Tiefeng; Liu, Peng; Guo, Chenfeng; Wang, Shuo; Wang, Qiuming; Xiong, Zhigang; Wang, Dianlong; Zhao, X S

    2014-01-21

    In this work, mesoporous carbon-coated LiFePO4 nanocrystals further co-modified with graphene and Mg(2+) doping (G/LFMP) were synthesized by a modified rheological phase method to improve the speed of lithium storage as well as cycling stability. The mesoporous structure of LiFePO4 nanocrystals was designed and realized by introducing the bead milling technique, which assisted in forming sucrose-pyrolytic carbon nanoparticles as the template for generating mesopores. For comparison purposes, samples modified only with graphene (G/LFP) or Mg(2+) doping (LFMP) as well as pure LiFePO4 (LFP) were also prepared and investigated. Microscopic observation and nitrogen sorption analysis have revealed the mesoporous morphologies of the as-prepared composites. X-ray diffraction (XRD) and Rietveld refinement data demonstrated that the Mg-doped LiFePO4 is a single olivine-type phase and well crystallized with shortened Fe-O and P-O bonds and a lengthened Li-O bond, resulting in an enhanced Li(+) diffusion velocity. Electrochemical properties have also been investigated after assembling coin cells with the as-prepared composites as the cathode active materials. Remarkably, the G/LFMP composite has exhibited the best electrochemical properties, including fast lithium storage performance and excellent cycle stability. That is because the modification of graphene provided active sites for nuclei, restricted the in situ crystallite growth, increased the electronic conductivity and reduced the interface reaction current density, while, Mg(2+) doping improved the intrinsically electronic and ionic transfer properties of LFP crystals. Moreover, in the G/LFMP composite, the graphene component plays the role of "cushion" as it could quickly realize capacity response, buffering the impact to LFMP under the conditions of high-rate charging or discharging, which results in a pre-eminent rate capability and cycling stability. PMID:24287590

  15. Electrochemical performance of patterned LiFePO4 nano-electrode with a pristine amorphous layer

    NASA Astrophysics Data System (ADS)

    Wang, Mao; Zhang, Wei; Liu, Yihang; Yang, Yong; Wang, Chunsheng; Wang, Yuan

    2014-04-01

    A patterned LiFePO4 nanorod with a pristine amorphous LiFePO4 surface layer was fabricated by controlling the temperature gradient from the interior to the exterior layer in high-temperature annealing process through designing hierarchical multilayer electrode structure. The three dimensional patterned LiFePO4 nanorods were prepared using tobacco mosaic virus nanoforest arrays. The results indicate that the nano-electrodes nearly reached the theoretical capacity at a very low C rate even without conductive coatings. The amorphous LiFePO4 can fast transport the Li-ion to inside crystal LiFePO4, thus enhancing the rate capability.

  16. Effect of conductive additives in LiFePO4 cathode for lithium-ion batteries

    SciTech Connect

    Shim, J.; Guerfi, A.; Zaghib, K.; Striebel, K.A.

    2003-11-25

    The electrochemical properties of LiFePO4 cathodes with different carbon contents were studied to find out the role of carbon as conductive additive. LiFePO4 cathodes containing from 0 percent to 12 percent of conductive additive (carbon black or mixture of carbon black and graphite) were cycled at different C rates. The capacity of LiFePO4 cathode increased, as conductive additive content increased. Carbon increased the utilization of active material and the electrical conductivity of electrode, but decreased volumetric capacity of electrode.

  17. Dispersion, agglomeration, and gelation of LiFePO4 in water-based slurry

    NASA Astrophysics Data System (ADS)

    Tsai, Feng-Yen; Jhang, Jia-Hao; Hsieh, Han-Wei; Li, Chia-Chen

    2016-04-01

    The gelation of commercially available lithium iron phosphate (LiFePO4) in water-based slurry and its corresponding mechanism are studied. Based on surface chemistry analyses using zeta potential measurements and Fourier transform infrared spectroscopy, it is found that the key factor that causes LiFePO4 gelation in the aqueous slurry is the quality of the surface carbon coating on powder. When the surface carbon exhibits functional derivatives, such as carboxyl, hydroxyl, and carbonyl polar functional groups, LiFePO4 tends to form a three-dimensional, gel-like structure via hydrogen bonding. Moreover, the presence of the derivatives reduces the amount of conduction-favorable sp2-bonded carbon to LiFePO4, resulting in an electric resistance increase of the as-prepared electrode and the deterioration of the specific capacity of the as-constructed cell.

  18. Enhanced electrochemical performances of LiFePO4/C by surface modification with Sn nanoparticles

    NASA Astrophysics Data System (ADS)

    Lin, Yingbin; Lin, Ying; Zhou, Ting; Zhao, Guiying; Huang, Yandan; Huang, Zhigao

    2013-03-01

    The surface of LiFePO4/C cathode material is coated with nano-sized Sn via a simple electroless deposition (ED) process, and the effects of the Sn-coating on the electrochemical performances of LiFePO4/C are investigated systematically by the charge/discharge testing, cyclic voltammograms and AC impedance spectroscopy, respectively. In comparison with the pristine LiFePO4/C, the Sn-coated LiFePO4/C exhibits higher capacity, better cyclability and higher rate capability in a wide operation temperature range. An analysis of the electrochemical measurements reveals that Sn-coated LiFePO4/C has good electric contact among particles, much lower charge-transfer resistances and higher lithium diffusion rate, especially at low temperature. In addition, the Sn-coating layer protects the active materials from chemical attack by HF and thus suppresses the dissolution of Fe from LiFePO4 in the LiPF6 based electrolyte.

  19. Unlocking the energy capabilities of micron-sized LiFePO4

    PubMed Central

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

    2015-01-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a ‘carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations. PMID:26235395

  20. Unlocking the energy capabilities of micron-sized LiFePO4

    NASA Astrophysics Data System (ADS)

    Guo, Limin; Zhang, Yelong; Wang, Jiawei; Ma, Lipo; Ma, Shunchao; Zhang, Yantao; Wang, Erkang; Bi, Yujing; Wang, Deyu; McKee, William C.; Xu, Ye; Chen, Jitao; Zhang, Qinghua; Nan, Cewen; Gu, Lin; Bruce, Peter G.; Peng, Zhangquan

    2015-08-01

    Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a `carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.

  1. Storage and Effective Migration of Li-Ion for Defected ?-LiFePO4 Phase Nanocrystals.

    PubMed

    Guo, Hua; Song, Xiaohe; Zhuo, Zengqing; Hu, Jiangtao; Liu, Tongchao; Duan, Yandong; Zheng, Jiaxin; Chen, Zonghai; Yang, Wanli; Amine, Khalil; Pan, Feng

    2016-01-13

    Lithium iron phosphate, a widely used cathode material, crystallizes typically in olivine-type phase, ?-LiFePO4 (?LFP). However, the new phase ?-LiFePO4 (?LFP), which can be transformed from ?LFP under high temperature and pressure, is originally almost electrochemically inactive with no capacity for Li-ion battery, because the Li-ions are stored in the tetrahedral [LiO4] with very high activation barrier for migration and the one-dimensional (1D) migration channels for Li-ion diffusion in ?LFP disappear, while the Fe ions in the ?-phase are oriented similar to the 1D arrangement instead. In this work, using experimental studies combined with density functional theory calculations, we demonstrate that ?LFP can be activated with creation of effective paths of Li-ion migration by optimized disordering. Thus, the new phase of ?LFP cathode achieved a capacity of 128 mAh g(-1) at a rate of 0.1 C (1C = 170 mA g(-1)) with extraordinary cycling performance that 94.5% of the initial capacity retains after 1000 cycles at 1 C. The activation mechanism can be attributed to that the induced disorder (such as FeLiLiFe antisite defects, crystal distortion, and amorphous domains) creates new lithium migration passages, which free the captive stored lithium atoms and facilitate their intercalation/deintercalation from the cathode. Such materials activated by disorder are promising candidate cathodes for lithium batteries, and the related mechanism of storage and effective migration of Li-ions also provides new clues for future design of disordered-electrode materials with high capacity and high energy density. PMID:26632008

  2. Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes.

    PubMed

    Chen, Lin; Dilena, Enrico; Paolella, Andrea; Bertoni, Giovanni; Ansaldo, Alberto; Colombo, Massimo; Marras, Sergio; Scrosati, Bruno; Manna, Liberato; Monaco, Simone

    2016-02-17

    LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g(-1)) and working voltage (4.1 V vs Li(+)/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g(-1) at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g(-1). The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times. PMID:26799094

  3. Relevance of LiPF6 as Etching Agent of LiMnPO4 Colloidal Nanocrystals for High Rate Performing Li-ion Battery Cathodes

    PubMed Central

    2016-01-01

    LiMnPO4 is an attractive cathode material for the next-generation high power Li-ion batteries, due to its high theoretical specific capacity (170 mA h g–1) and working voltage (4.1 V vs Li+/Li). However, two main drawbacks prevent the practical use of LiMnPO4: its low electronic conductivity and the limited lithium diffusion rate, which are responsible for the poor rate capability of the cathode. The electronic resistance is usually lowered by coating the particles with carbon, while the use of nanosize particles can alleviate the issues associated with poor ionic conductivity. It is therefore of primary importance to develop a synthetic route to LiMnPO4 nanocrystals (NCs) with controlled size and coated with a highly conductive carbon layer. We report here an effective surface etching process (using LiPF6) on colloidally synthesized LiMnPO4 NCs that makes the NCs dispersible in the aqueous glucose solution used as carbon source for the carbon coating step. Also, it is likely that the improved exposure of the NC surface to glucose facilitates the formation of a conductive carbon layer that is in intimate contact with the inorganic core, resulting in a high electronic conductivity of the electrode, as observed by us. The carbon coated etched LiMnPO4-based electrode exhibited a specific capacity of 118 mA h g–1 at 1C, with a stable cycling performance and a capacity retention of 92% after 120 cycles at different C-rates. The delivered capacities were higher than those of electrodes based on not etched carbon coated NCs, which never exceeded 30 mA h g–1. The rate capability here reported for the carbon coated etched LiMnPO4 nanocrystals represents an important result, taking into account that in the electrode formulation 80% wt is made of the active material and the adopted charge protocol is based on reasonable fast charge times. PMID:26799094

  4. Enhanced rate performance of multiwalled carbon nanotube encrusted olivine type composite cathode material using polyol technique

    NASA Astrophysics Data System (ADS)

    Muruganantham, R.; Sivakumar, M.; Subadevi, R.

    2015-12-01

    Olivine type multi-walled carbon nanotube encrusted LiFePO4/C composites have been prepared using economic and energy efficient simple polyol technique without any subsequent heat treatment. The prepared material has an olivine type orthorhombic phase. Also, the iron oxidation state is 2+, which is identified by X-ray diffraction and X-ray photoelectron spectroscopy. It is possible to attain the discharge capacity almost close to theoretical capacity of LiFePO4 as in high temperature methods with ∼100% coulombic efficiency. The specific surface area has been increased upon encrusting multi walled carbon nano tube on LiFePO4/C, which results in enhanced reversible capacity upto 166 mAh g-1 at C/10. Also, it exhibits 89 mAh g-1 even at 30 C rate. This is due to the formation of conductive networks by carbon nanotube, and excellent attachment of LiFePO4/C composite particles on multi-walled carbon nanotube, which induced the kinetics during intercalation/deintercalation process. Multi-walled carbon nanotube acts as the electro-conductive filler on the LiFePO4 surface. The direct addition of MWCNT would result better performances than blending the MWCNT with LiFePO4/C.

  5. Impacts of different polymer binders on electrochemical properties of LiFePO4 cathode

    NASA Astrophysics Data System (ADS)

    Nguyen, Van Hiep; Wang, Wan Lin; Jin, En Mei; Gu, Hal-Bon

    2013-10-01

    Impacts of different polymer binders (PVdF, PAA and PMMA) on electrochemical performance of the LiFePO4 cathode in Li-ion batteries are investigated. From CV result, the voltage between redox peaks of the LiFePO4 with PVdF, PAA and PMMA binders are 0.26, 0.20 and 0.23 V, respectively. The current of the LiFePO4 with PMMA binder shows the highest value of 1.4 mA. The apparent diffusion coefficient of the LiFePO4 with PVdF, PAA and PMMA binders is 8.30 10-12, 2.57 10-11 and 9.13 10-11 cm2 s-1, respectively. The discharge capacities of the LiFePO4 with PVdF, PAA and PMMA binders are 106, 143 and 154 mAh g-1 at an initial cycle, respectively. FE-SEM studies clearly demonstrate that plate-like PAA and PMMA coating on the electrodes form a protective film, which may decrease the amount of the deposits, thus decreasing crack and crystallization on the electrode surface. Achieved results indicate that PVdF, PAA and PMMA binders show better properties than the traditional one, especially PMMA one.

  6. Carbon Surface Layers on a High-Rate LiFePO4

    SciTech Connect

    Gabrisch, Heike; Wilcox, James D.; Doeff, Marca M.

    2005-09-06

    Transmission electron microscopy (TEM) was used to image particles of a high-rate LiFePO4 sample containing a small amount of in situ carbon. The particle morphology is highly irregular, with a wide size distribution. Nevertheless, coatings, varying from about 5-10 nm in thickness, could readily be detected on surfaces of particles as well as on edges of agglomerates. Elemental mapping using Energy Filtered TEM (EFTEM) indicates that these very thin surface layers are composed of carbon. These observations have important implications for the design of high-rate LiFePO4 materials in which, ideally, a minimal amount of carbon coating is used.

  7. Dynamic study of sub-micro sized LiFePO4 cathodes by in-situ tender X-ray absorption near edge structure

    NASA Astrophysics Data System (ADS)

    Wang, Dongniu; Wang, Huixin; Yang, Jinli; Zhou, Jigang; Hu, Yongfeng; Xiao, Qunfeng; Fang, Haitao; Sham, Tsun-Kong

    2016-01-01

    Olivine-type phosphates (LiMPO4, M = Fe, Mn, Co) are promising cathode materials for lithium-ion batteries that are generally accepted to follow first order equilibrium phase transformations. Herein, the phase transformation dynamics of sub-micro sized LiFePO4 particles with limited rate capability at a low current density of 0.14 C was investigated. An in-situ X-ray Absorption Near Edge Structure (XANES) measurement was conducted at the Fe and P K-edge for the dynamic studies upon lithiation and delithiation. Fe K-edge XANES spectra demonstrate that not only lithium-rich intermediate phase LixFePO4 (x = 0.6-0.75), but also lithium-poor intermediate phase LiyFePO4 (y = 0.1-0.25) exist during the charge and discharge, respectively. Furthermore, during charge and discharge, a fluctuation of the FePO4 and LiFePO4 fractions obtained by liner combination fitting around the imaginary phase fractions followed Faraday's law and the equilibrium first-order two-phase transformation versus reaction time is present, respectively. The charging and discharging process has a reversible phase transformation dynamics with symmetric structural evolution routes. P K-edge XANES spectra reveal an enrichment of PF6-1 anions at the surface of the electrode during charging.

  8. Conductive surface modification of LiFePO4 with nitrogen doped carbon layers for lithium-ion batteries

    SciTech Connect

    Yoon, Sukeun; Liao, Chen; Sun, Xiao-Guang; Bridges, Craig A; Unocic, Raymond R; Nanda, Jagjit; Dai, Sheng; Paranthaman, Mariappan Parans

    2012-01-01

    The LiFePO4 rod surface modified with nitrogen doped carbon layer has been prepared using hydrothermal processing followed by post-annealing in the presence of an ionic liquid. The coated LiFePO4 rod exhibits good capacity retention and high rate capability as the nitrogen doped carbon improves conductivity and prevents aggregation of the rod during cycling.

  9. Hierarchical LiFePO4 with a controllable growth of the (010) facet for lithium-ion batteries

    PubMed Central

    Guo, Binbin; Ruan, Hongcheng; Zheng, Cheng; Fei, Hailong; Wei, Mingdeng

    2013-01-01

    Hierarchically structured LiFePO4 was successfully synthesized by ionic liquid solvothermal method. These hierarchically structured LiFePO4 samples were constructed from nanostructured platelets with their (010) facets mainly exposed. To the best of our knowledge, facet control of a hierarchical LiFePO4 crystal has not been reported yet. Based on a series of experimental results, a tentative mechanism for the formation of these hierarchical structures was proposed. After these hierarchically structured LiFePO4 samples were coated with a thin carbon layer and used as cathode materials for lithium-ion batteries, they exhibited excellent high-rate discharge capability and cycling stability. For instance, a capacity of 95% can be maintained for the LiFePO4 sample at a rate as high as 20 C, even after 1000 cycles. PMID:24071818

  10. Porous LiFePO4/C microspheres as high-power cathode materials for lithium ion batteries.

    PubMed

    Sun, Bing; Wang, Ying; Wang, Bei; Kim, Hyun-Soo; Kim, Woo-Seong; Wang, Guoxiu

    2013-05-01

    Porous LiFePO4/C microspheres were synthesized by a novel hydrothermal reaction combined with high-temperature calcinations. The morphology of the prepared material was investigated by field-emission scanning electron microscopy. Porous microspheres with diameters around 1-3 microm were obtained, which consisting of primary LiFePO4 nanoparticles. The electrochemical performances of the as-prepared LiFePO4 microspheres were evaluated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge cycling. The carbon coated LiFePO4 microspheres showed lower polarization, higher rate capability, and better cycling stability than that of pristine LiFePO4 microspheres, indicating the potential application as the cathode material for high-power lithium ion batteries. PMID:23858922

  11. LiFePO4 - 3D carbon nanofiber composites as cathode materials for Li-ions batteries

    NASA Astrophysics Data System (ADS)

    Dimesso, L.; Spanheimer, C.; Jaegermann, W.; Zhang, Y.; Yarin, A. L.

    2012-03-01

    The characterization of carbon nanofiber 3D nonwovens, prepared by electrospinning process, coated with olivine structured lithium iron phosphate is reported. The LiFePO4 as cathode material for lithium ion batteries was prepared by a Pechini-assisted reversed polyol process. The coating has been successfully performed on carbon nanofiber 3D nonwovens by soaking in aqueous solution containing lithium, iron salts and phosphates at 70 C for 2-4 h. After drying-out, the composites were annealed at 600 C for 5 h under nitrogen. The surface investigation of the prepared composites showed a uniform coating of the carbon nonwoven nanofibers as well as the formation of cauliflower-like crystalline structures which are uniformly distributed all over the surface area of the carbon nanofibers. The electrochemical measurements on the composites showed good performances delivering a discharge specific capacity of 156 mAhg- 1 at a discharging rate of C/25 and 152 mAhg- 1 at a discharging rate of C/10 at room temperature.

  12. Chemically grafted carbon-coated LiFePO4 using diazonium chemistry

    NASA Astrophysics Data System (ADS)

    Delaporte, Nicolas; Perea, Alexis; Amin, Ruhul; Zaghib, Karim; Blanger, Daniel

    2015-04-01

    The effect of surface functionalization of aminophenyl and bromophenyl groups on carbon-coated LiFePO4 and the electrochemical properties of composite electrode containing these materials are reported. The functionalization was performed by spontaneous reduction of the corresponding in situ generated diazonium ions. The resulting chemically grafted LiFePO4/C materials were characterized by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) to confirm the presence of the surface organic species. XRD analyses indicated the cathode material was partially oxidized. Thermogravimetric and elemental analyses revealed the loading of grafted molecules was between 0.2 and 1.1 wt.% depending on the reaction conditions. Interestingly, the electrochemical performances of the modified LiFePO4/C are not adversely affected by the presence of either aminophenyl and bromophenyl groups at the carbon surface, and in fact the grafted LiFePO4/C displayed slightly superior discharge capacity at the highest C rate investigated for a low loading of organic molecules.

  13. Can Vanadium Be Substituted into LiFePO4

    SciTech Connect

    Omenya F.; Nam K.; Chernova N.A.; Upreti S.; Zavalij P.Y.; Nam K.-W.; Yang X.-Q.; Whittingham M.S.

    2011-11-08

    Vanadium is shown to substitute for iron in the olivine LiFePO{sub 4} up to at least 10 mol %, when the synthesis is carried out at 550 C. In the solid solution LiFe{sub 1-3y/2}V{sub y}PO{sub 4}, the a and b lattice parameters and cell volume decrease with increasing vanadium content, while the c lattice parameter increases slightly. However, when the synthesis is performed at 650 C, a NASICON phase, Li{sub 3}V{sub 2}(PO{sub 4}){sub 3}, is also formed, showing that solid solution is a function of the synthesis temperature. X-ray absorption near-edge structure indicates vanadium is in the 3+ oxidation state and in an octahedral environment. Magnetic studies reveal a shift of the antiferromagnetic ordering transition toward lower temperatures with increasing vanadium substitution, confirming solid solution formation. The addition of vanadium enhances the electrochemical performance of the materials especially at high current densities.

  14. The development of low cost LiFePO4-based high power lithium-ion batteries

    SciTech Connect

    Shim, Joongpyo; Sierra, Azucena; Striebel, Kathryn A.

    2003-11-25

    The cycling performance of low-cost LiFePO4-based high-power lithium-ion cells was investigated and the components were analyzed after cycling to determine capacity fade mechanisms. Pouch type LiFePO4/natural graphite cells were assembled and evaluated by constant C/2 cycling, pulse-power and impedance measurements. From post-test electrochemical analysis after cycling, active materials, LiFePO4 and natural graphite, showed no degradation structurally or electrochemically. The main reasons for the capacity fade of cell were lithium inventory loss by side reaction and possible lithium deposition on the anode.

  15. Investigation of charge transfer kinetics of Li-Intercalation in LiFePO4

    NASA Astrophysics Data System (ADS)

    Heubner, C.; Schneider, M.; Michaelis, A.

    2015-08-01

    Recent studies point out contradictions between classical Butler-Volmer kinetics and the charge transfer kinetics of lithium intercalation in host materials. In this work the charge transfer kinetics of lithium intercalation in LiFePO4 are investigated using current controlled electrochemical impedance spectroscopy with varying amplitudes. The results point out a significant impact of ohmic and diffusion contributions to the total overpotential which is normally extracted from constant current charging - discharging experiments to determine Tafel-plots, exchange currents and charge transfer coefficients. By the accurate separation of the activation overpotential from the total overpotential the authors are able to show that the charge transfer kinetics of lithium intercalation in LiFePO4 perfectly obey the Butler-Volmer equation.

  16. Optimized Operating Range for Large-Format LiFePO4/Graphite Batteries

    SciTech Connect

    Jiang, Jiuchun; Shi, Wei; Zheng, Jianming; Zuo, Pengjian; Xiao, Jie; Chen, Xilin; Xu, Wu; Zhang, Jiguang

    2014-06-01

    e investigated the long-term cycling performance of large format 20Ah LiFePO4/graphite batteries when they are cycled in various state-of-charge (SOC) ranges. It is found that batteries cycled in the medium SOC range (ca. 20~80% SOC) exhibit superior cycling stability than batteries cycled at both ends (0-20% or 80-100%) of the SOC even though the capcity utilized in the medium SOC range is three times as large as those cycled at both ends of the SOC. Several non-destructive techniques, including a voltage interruption approach, model-based parameter identification, electrode impedance spectra analysis, ?Q/?V analysis, and entropy change test, were used to investigate the performance of LiFePO4/graphite batteries within different SOC ranges. The results reveal that batteries at the ends of SOC exhibit much higher polarization impedance than those at the medium SOC range. These results can be attributed to the significant structural change of cathode and anode materials as revealed by the large entropy change within these ranges. The direct correlation between the polarization impedance and the cycle life of the batteries provides an effective methodology for battery management systems to control and prolong the cycle life of LiFePO4/graphite and other batteries.

  17. Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation

    PubMed Central

    Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin; Shukla, Alpesh K.; DellAnna, Rossana; Tyliszczak, Tolek; Chen, Guoying; Andrews, Joy C.; Richardson, Thomas J.; Kostecki, Robert; Cabana, Jordi

    2013-01-01

    The chemical phase distribution in hydrothermally grown micrometric single crystals LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe K- and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures. PMID:23745016

  18. Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation.

    PubMed

    Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin; Shukla, Alpesh K; Dell'anna, Rossana; Tyliszczak, Tolek; Chen, Guoying; Andrews, Joy C; Richardson, Thomas J; Kostecki, Robert; Cabana, Jordi

    2013-05-14

    The chemical phase distribution in hydrothermally grown micrometric single crystals LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe K- and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures. PMID:23745016

  19. Monodisperse porous LiFePO4 microspheres for a high power Li-ion battery cathode.

    PubMed

    Sun, Chunwen; Rajasekhara, Shreyas; Goodenough, John B; Zhou, Feng

    2011-02-23

    A novel solvothermal approach combined with high-temperature calcinations was developed to synthesize on a large scale LiFePO(4) microspheres consisting of nanoplates or nanoparticles with an open three-dimensional (3D) porous microstructure. These micro/nanostructured LiFePO(4) microspheres have a high tap density and, as electrodes, show excellent rate capability and cycle stability. PMID:21268579

  20. Electrical relaxation studies of olivine type nanocrystalline LiMPO4 (M=Ni, Mn and Co) materials

    NASA Astrophysics Data System (ADS)

    Cheruku, Rajesh; Kruthika, G.; Govindaraj, G.; Vijayan, Lakshmi

    2015-11-01

    The olivine type LiMPO4 (M=Ni, Mn and Co) materials were synthesized by solution combustion technique using glycine as fuel. The structural characterizations were explored to confirm the phase formation of materials. The scanning electron microscope was used to identify the morphology of olivine materials. The local structure and chemical bonding between MO6 octahedral and (PO4)3-tetrahedral groups were probed by Raman spectroscopy. Grain and grain boundaries were contributed for ion relaxation and dc conduction in olivine materials. Two orders of enhancement in ionic conductivity was observed in these olivine materials than the reported value. Among all the explored olivine samples, LiMnPO4 showed highest enhancement in conductivity due to weak Li-O bonding and largest unit cell volume.

  1. Enhanced electrochemical performance in LiFePO4/graphene nanocomposite cathode material for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Dhindsa, Kulwinder; Mandal, B.; Lin, M. W.; Nazri, M.; Vaishnava, P.; Naik, V.; Nazri, G. A.; Naik, R.; Zhou, Z. X.

    2012-02-01

    We synthesized LiFePO4/graphene nano-composite employing a sol-gel method, where graphene oxide solution was added to the LiFePO4 precursors during the synthesis. Electrical measurement reveals that the addition of 10% graphene (by weight) to LiFePO4 increases its conductivity by 5 orders of magnitude. SEM images of the composite show that the material consists of LiFePO4 nanoparticles (with a mean particle size 50 nm) homogeneously mixed with graphene sheets; the latter provides a three-dimensional conducting network for Li+ ion and electron transport. A large specific capacity of 170 mAh/g was observed at a discharge rate of C/2. To further increase the conductivity and inhibit particle size growth of LiFePO4 (thus to increase the rate capacity), we coated the nanoparticles with a thin carbon layer by adding 0.25M lauric acid as precursor in addition to graphene oxide during the synthesis. The respective roles of graphene and lauric-acid-induced carbon coating in the specific capacity and charge-discharge rate of the LiFePO4 cathode material will be discussed.

  2. The influence of reduced graphene oxide on electrical conductivity of LiFePO4-based composite as cathode material

    NASA Astrophysics Data System (ADS)

    Arifin, Muhammad; Aimon, Akfiny Hasdi; Winata, Toto; Abdullah, Mikrajuddin; Iskandar, Ferry

    2016-02-01

    LiFePO4 is fascinating cathode active materials for Li-ion batteries application because of their high electrochemical performance such as a stable voltage at 3.45 V and high specific capacity at 170 mAh.g-1. However, their low intrinsic electronic conductivity and low ionic diffusion are still the hindrance for their further application on Li-ion batteries. Therefore, the efforts to improve their conductivity are very important to elevate their prospecting application as cathode materials. Herein, we reported preparation of additional of reduced Graphene Oxide (rGO) into LiFePO4-based composite via hydrothermal method and the influence of rGO on electrical conductivity of LiFePO4-based composite by varying mass of rGO in composition. Vibration of LiFePO4-based composite was detected on Fourier Transform Infrared Spectroscopy (FTIR) spectra, while single phase of LiFePO4 nanocrystal was observed on X-Ray Diffraction (XRD) pattern, it furthermore, Scanning Electron Microscopy (SEM) images showed that rGO was distributed around LiFePO4-based composite. Finally, the 4-point probe measurement result confirmed that the optimum electrical conductivity is in additional 2 wt% rGO for range 1 to 2 wt% rGO.

  3. A high performance hybrid battery based on aluminum anode and LiFePO4 cathode.

    PubMed

    Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Fang, Youxing; Bridges, Craig A; Paranthaman, M Parans; Dai, Sheng; Brown, Gilbert M

    2016-01-28

    A novel hybrid battery utilizing an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl3) (EMImCl-AlCl3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. The hybrid ion battery delivers an initial high capacity of 160 mA h g(-1) at a current rate of C/5. It also shows good rate capability and cycling performance. PMID:26666453

  4. A high performance hybrid battery based on aluminum anode and LiFePO4 cathode

    DOE PAGESBeta

    Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Bridges, Craig A.; Paranthaman, Mariappan Parans; Dai, Sheng; Brown, Gilbert M.

    2016-01-01

    A unique battery hybrid utilizes an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl 3) (EMImCl-AlCl 3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. This hybrid ion battery delivers an initial high capacity of 160 mAh g-1 at a current rate of C/5. It also shows good rate capability and cycling performance.

  5. Novel rapid synthesis method of LiFePO4/C cathode material by high-frequency induction heating

    NASA Astrophysics Data System (ADS)

    Uchida, Satoshi; Yamagata, Masaki; Ishikawa, Masashi

    2013-12-01

    We propose a novel low-cost synthesis method of a LiFePO4/C composite with excellent battery performances that combine high-frequency induction heating with carbothermal reduction. Our method uses a very inexpensive Fe2O3 as a Fe source. The LiFePO4/C is synthesized in far less time (within a few minutes) at 900 C than in a conventional method. Although the initially synthesized LiFePO4/C (LFP-120) contains such over-reduction impurities as Fe2P or Fe3P, optimized LiFePO4/C (LFP-90) containing no impurities is obtained by adjusting the heating time. Moreover, the primary particle size of the LFP-90 is sufficiently small to achieve fast Li-ion diffusion. The cathode containing LFP-90 has good charge-discharge rate performance and shows discharge capacities of 153.3 and 100.1 mAh g-1 at 1/10 and 10C-rates. The cathode with LFP-90 has excellent cycle stability and shows no degradation after high-rate charge-discharge tests. Our method reasonably reduces the manufacturing cost of LiFePO4/C.

  6. Electrochemical and kinetic studies of ultrafast laser structured LiFePO4 electrodes

    NASA Astrophysics Data System (ADS)

    Mangang, M.; Gotcu-Freis, P.; Seifert, H. J.; Pfleging, W.

    2015-03-01

    Due to a growing demand of cost-efficient lithium-ion batteries with an increased energy and power density as well as an increased life-time, the focus is set on intercalation cathode materials like LiFePO4. It has a high practical capacity, is environmentally friendly and has low material costs. However, its low electrical conductivity and low ionic diffusivity are major drawbacks for its use in electrochemical storage devices or electric vehicles. By adding conductive agents, the electrical conductivity can be enhanced. By increasing the surface of the cathode material which is in direct contact with the liquid electrolyte the lithium-ion diffusion kinetics can be improved. A new approach to increase the surface of the active material without changing the active particle packing density or the weight proportion of carbon black is the laser-assisted generation of 3D surface structures in electrode materials. In this work, ultrafast laser radiation was used to create a defined surface structure in LiFePO4 electrodes. It was shown that by using ultrashort laser pulses instead of nanosecond laser pulses, the ablation efficiency could be significantly increased. Furthermore, melting and debris formation were reduced. To investigate the diffusion kinetics, electrochemical methods such as cyclic voltammetry and galvanostatic intermittent titration technique were applied. It could be shown that due to a laser generated 3D structure, the lithium-ion diffusion kinetic, the capacity retention and cell life-time can be significantly improved.

  7. Ab-initio Calculation of the XANES of Lithium Phosphates and LiFePO4

    NASA Astrophysics Data System (ADS)

    Yiu, Y. M.; Yang, Songlan; Wang, Dongniu; Sun, Xueliang; Sham, T. K.

    2013-04-01

    Lithium iron phosphate has been regarded as a promising cathode material for the next generation lithium ion batteries due to its high specific capacity, superior thermal and cyclic stability [1]. In this study, the XANES (X-ray Absorption Near Edge Structure) spectra of lithium iron phosphate and lithium phosphates of various compositions at the Li K, P L3,2, Fe M3,2 and O K-edges have been simulated self-consistently using ab-initio calculations based on multiple scattering theory (the FEFF9 code) and DFT (Density Functional Theory, the Wien2k code). The lithium phosphates under investigation include LiFePO4, ?-Li3PO4, Li4P2O7 and LiPO3. The calculated spectra are compared to the experimental XANES recorded in total electron yield (TEY) and fluorescence yield (FLY). This work was carried out to assess the XANES of possible phases presented in LiFePO4 based Li ion battery applications [2].

  8. Tailored surface structure of LiFePO4/C nanofibers by phosphidation and their electrochemical superiority for lithium rechargeable batteries.

    PubMed

    Lee, Yoon Cheol; Han, Dong-Wook; Park, Mihui; Jo, Mi Ru; Kang, Seung Ho; Lee, Ju Kyung; Kang, Yong-Mook

    2014-06-25

    We offer a brand new strategy for enhancing Li ion transport at the surface of LiFePO4/C nanofibers through noble Li ion conducting pathways built along reduced carbon webs by phosphorus. Pristine LiFePO4/C nanofibers composed of 1-dimensional (1D) LiFePO4 nanofibers with thick carbon coating layers on the surfaces of the nanofibers were prepared by the electrospinning technique. These dense and thick carbon layers prevented not only electrolyte penetration into the inner LiFePO4 nanofibers but also facile Li ion transport at the electrode/electrolyte interface. In contrast, the existing strong interactions between the carbon and oxygen atoms on the surface of the pristine LiFePO4/C nanofibers were weakened or partly broken by the adhesion of phosphorus, thereby improving Li ion migration through the thick carbon layers on the surfaces of the LiFePO4 nanofibers. As a result, the phosphidated LiFePO4/C nanofibers have a higher initial discharge capacity and a greatly improved rate capability when compared with pristine LiFePO4/C nanofibers. Our findings of high Li ion transport induced by phosphidation can be widely applied to other carbon-coated electrode materials. PMID:24786736

  9. Experimental and numerical study of phase transition of LiFePO 4 material in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Siddique, Md Noor E. Alam

    Phase transition behavior of LiFePO4 material has been studied in this work. During electrochemical charge/discharge processes, LiFePO 4 transforms into FePO4 and this electrochemically driven phase transition of the two-phase system results in a potential plateau in a battery discharge curve. Besides, battery performance, especially under high rates, depends critically on this two-phase transition. However, this phase transition mechanism in the LiFePO4 crystal structure has yet not been understood in details. Developing better understanding is essential for designing high performing, safe and stable batteries. Currently available phase transition models for LiFePO4, such as the classical `core-shrinking model' and recently the `domino cascade model', have shed lights on the phase transition mechanism, however, with somewhat contradicting conclusions. The former predicted a continuous phase transition between LiFePO4 and FePO4 within an individual particle. In contrast, the latter, based on the fact of anisotropic diffusion of Li, provided a microscopically heterogeneous picture of phase transition: phase transition is abrupt, and de-lithiated and lithiated particles co-exist in a battery electrode. To achieve a better understanding of the two-phase transition phenomena, two specially designed sophisticated methods, i.e., in-situ Raman spectroscopy and in-situ X-ray Diffraction (XRD), have been developed in this work. The particle level phase transition of LiFePO4 was probed in the in-situ Raman study. Under slow-rate discharge/charge, it was found that the particles were either fully transformed or untransformed indicating that the phase transition in LiFePO4 material was not uniform at the particle level. Electronic conductivity and local electrode microstructure determined the preferred sequence of phase transition of the particles. This study also revealed that non-equilibrium phase transition occurred as a result of delayed phase transition. The in-situ XRD study attempted to investigate the bulk level phase transition behavior of LiFePO4 and was conducted at four different discharge rates. Analysis of the high-resolution diffraction patterns showed a gradual and continuous change in phase transition. Again, a delayed phase transition was observed at high-rate discharge due to the non-equilibrium pathway. From both in-situ Raman and in-situ XRD experiments, only two stoichiometric compounds (LiFePO4 and FePO4) was detected, indicating that during electrochemical charge/discharge processes once Li ion de-intercalates/intercalates, it immediately forms the end-members and no intermediate compounds exist. Particle size and morphology of LiFePO4 were also studied using numerical models in the phase transition behavior. At a slow discharge rate, plate shaped particles showed higher capacity than spherical particles and the opposite trend was observed at high discharge rates above some critical discharge rates. Big particles and high discharge rates induced non-equilibrium phase transition in the LiFePO4 particles which expands the miscibility gap between the end-members and gave sharp narrow two-phase interfaces.

  10. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

    NASA Astrophysics Data System (ADS)

    Jena, Ajit; Nanda, B. R. K.

    2016-01-01

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3?. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator.

  11. Water based processing of LiFePO4/C cathode material for Li-ion batteries utilizing freeze granulation

    NASA Astrophysics Data System (ADS)

    Orlenius, J.; Lyckfeldt, O.; Kasvayee, K. A.; Johander, P.

    2012-09-01

    A water based solid state synthesis of LiFePO4 has been conducted by utilizing freeze granulation. Various processing conditions were tested and achieved powder properties were characterized by density, XRD, specific surface area, carbon content, conductivity and SEM. Freeze granulation, a novel method for precursor preparation was shown to be an effective method to provide high degree of homogeneity prior to calcination and high ultimate yield of pure LiFePO4. Cathodes were manufactured by water based as well as NMP system based tape casting. A commercial LiFePO4/C powder was also characterized and used to manufacture cathodes as comparison in this study. Charge cycling tests showed promising results with high capacity and long term stability, well in the range of what the commercial powder provided. Post-milling of calcined powder prior to paste preparation for tape casting tended, however, to retard the capacity owing to disturbed carbon distribution and loss of conductivity of the LiFePO4/C. In comparison with the solvent system for cathode manufacturing, the water based system gave similar cell performance, illustrating the possibility to apply a more environmentally sustainable processing of Li-battery cells.

  12. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity

    PubMed Central

    Jena, Ajit; Nanda, B. R. K.

    2016-01-01

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)3−. The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator. PMID:26791249

  13. Unconventional Magnetism and Band Gap Formation in LiFePO4: Consequence of Polyanion Induced Non-planarity.

    PubMed

    Jena, Ajit; Nanda, B R K

    2016-01-01

    Oxygen plays a critical role in strongly correlated transition metal oxides as crystal field effect is one of the key factors that determine the degree of localization of the valence d/f states. Based on the localization, a set of conventional mechanisms such as Mott-Hubbard, Charge-transfer and Slater were formulated to explain the antiferromagnetic and insulating (AFI) phenomena in many of these correlated systems. From the case study on LiFePO4, through density-functional calculations, we demonstrate that none of these mechanisms are strictly applicable to explain the AFI behavior when the transition metal oxides have polyanions such as (PO4)(3-). The symmetry-lowering of the metal-oxygen complex, to stabilize the polyanion, creates an asymmetric crystal field for d/f states. In LiFePO4 this field creates completely non-degenerate Fe-d states which, with negligible p-d and d-d covalent interactions, become atomically localized to ensure a gap at the Fermi level. Due to large exchange splitting, high spin state is favored and an antiferromagnetic configuration is stabilized. For the prototype LiFePO4, independent electron approximation is good enough to obtain the AFI ground state. Inclusion of additional correlation measures like Hubbard U simply amplifies the gap and therefore LiFePO4 can be preferably called as weakly coupled Mott insulator. PMID:26791249

  14. Electrochemical performance of LiFePO4 cylinder cell battery

    NASA Astrophysics Data System (ADS)

    Honggowiranto, Wagiyo; Sudaryanto, Kartini, Evvy; Purwanto, Agus

    2016-02-01

    A study on the electrochemical performance of LiFePO4 based cylinder cell battery has been done. The measurements have been carried out using cyclic voltametry (CV), charge-discharge (CD), and electrochemical impedance spectroscopy (EIS). The CV profiles showed that the battery exhibited anodic (charge) peak and chatodic (discharge) peak when scanned between 2.5 and 4.2V at various scan rate of 1 to 0.05 mV/s. The CD result showed that the battery capacity was 700 mAh exhibited excellent capacity retention with efficiency was about 100% after 100 cycles. From EIS measurement, it was also observed that the battery resistance decreased with the state of charge.

  15. Two-dimensional electrochemical-thermal coupled modeling of cylindrical LiFePO4 batteries

    NASA Astrophysics Data System (ADS)

    Xu, Meng; Zhang, Zhuqian; Wang, Xia; Jia, Li; Yang, Lixin

    2014-06-01

    The distributions of potential and reaction rates in a lithium ion battery during discharge process have great influences on the battery thermal characteristics. A two-dimensional electrochemical-thermal model has been developed for a cylindrical LiFePO4 battery by coupling the mass, charge, and energy conservations as well as the cell electrochemical kinetics. The model also includes battery current collecting tabs. The modeling results are validated for both the electrochemical performance and thermal behavior during galvanostatic discharge process. The modeling results agree well with the experimental data. The placement of the positive and the negative current collecting tabs on the cylindrical battery was found to have a significant effect on the distributions of its potential and local reaction rates, which therefore affect heat generation rates, and thus the distribution of the temperature within the battery.

  16. Characterization of LiFePO4 cathode by addition of graphene for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Honggowiranto, Wagiyo; Kartini, Evvy

    2016-02-01

    The improvement of LiFePO4 (LFP) cathode performance has been performed by addition of Graphene (LFP+Graphene). The cathode was prepared from the active material with 5 wt % graphene and 10 wt % polyvinylidene fluoride in an n-methyl pyrrolidone solvent. Another cathode material used only 5% artificial graphite for comparison (LFP+Graphite). The crystal structure, microstructure, electronic conductivity, electrochemical impedance spectroscopy (EIS) of the cathodes were characterized by X-ray diffraction, SEM, and Impedance spectroscopy, respectively. Two half cell coin batteries were assembled using a lithium metal as an anode and LiPf6 as an electrolyte, and two cathodes (LFP+Graphene) and (LFP+Graphite). Charge discharge performance of battery was characterized by Battery analyser (BTS 8). The electronic conductivity of cathode with grapheme increased of about one order magnitude compared with the only cathode with graphite, namely from 1.97E-7S/cm (LFP+Graphite) to 1.92E-6S/cm (LFP+Graphene). The charge-discharge capacity after 10th cycles of LiFePO4 with graphene decreased of about 0.68% from 114.3 mAh/g to113.1 mAh/g, while LFP with graphite decreased of about 2.84% from 110.2 mAh/g to 107.1 mAh, at 0.1C-rates. It could be concluded that the addition of graphene has increased the ionic conductivity, and improved performance of the LFP lithium ion battery, such as higher capacity and better efficiency.

  17. Li-Ion Batteries from LiFePO4 Cathode and Anatase/Graphene Composite Anode for Stationary Energy Storage

    SciTech Connect

    Choi, Daiwon; Wang, Donghai; Viswanathan, Vilayanur V.; Bae, In-Tae; Wang, Wei; Nie, Zimin; Zhang, Jiguang; Graff, Gordon L.; Liu, Jun; Yang, Zhenguo; Duong, Tien Q.

    2009-11-06

    Li-ion batteries based on LiFePO4 cathode and anatase TiO2/graphene anode were investigated for possible stationary energy storage application. Fine-structured LiFePO4 was synthesized by novel molten surfactant approach. Anatase TiO2/graphene nanocomposite was prepared via self assembly method. The full cell that operated at flat 1.6V demonstrated negligible fade after more than 700 cycles. The LiFePO4/TiO2 combination Li-ion battery is inexpensive, environmentally benign, safe and stable. Therefore, it can be practically applied as stationary energy storage for renewable power sources.

  18. Li-ion Batteries: Ultralong Lifespan and Ultrafast Li Storage: Single-Crystal LiFePO4 Nanomeshes (Small 4/2016).

    PubMed

    Zhang, Yan; Zhang, Hui Juan; Feng, Yang Yang; Fang, Ling; Wang, Yu

    2016-01-01

    A low crystal mismatch strategy to fabricate novel LiFePO4 nanomeshes is presented by Y. Wang and co-workers on page 516. The LiFePO4 nanomesh is characterized by numerous advantages, such as mesoporous structure, enhanced structural integrity, and a shortened Li ion diffusion pathway along the [010] direction. Furthermore, the obtained LiFePO4 nanomesh can be applied in lithium ion batteries as an excellent cathode for fast extraction-insertion of lithium ions and exhibits outstanding electrochemical performance. PMID:26797531

  19. Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation.

    PubMed

    Liu, Xiaosong; Wang, Yung Jui; Barbiellini, Bernardo; Hafiz, Hasnain; Basak, Susmita; Liu, Jun; Richardson, Thomas; Shu, Guojiun; Chou, Fangcheng; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Moritz, Brian; Devereaux, Thomas P; Qiao, Ruimin; Chuang, Yi-De; Bansil, Arun; Hussain, Zahid; Yang, Wanli

    2015-10-21

    LiFePO4 is a battery cathode material with high safety standards due to its unique electronic structure. We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4 nanoparticles and single crystals. The results clearly show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. We focus on the energy configurations of the occupied states of LiFePO4 and the unoccupied states of FePO4, which are the critical states where electrons are removed and injected during the charge and discharge process, respectively. In LiFePO4, the soft X-ray emission spectroscopy shows that, due to the Coulomb repulsion effect, the occupied Fe-3d states with the minority spin sit close to the Fermi level. In FePO4, the soft X-ray absorption and hard X-ray Raman spectroscopy show that the unoccupied Fe-3d states again sit close to the Fermi level. These critical 3d electron state configurations are consistent with the calculations based on modified Becke and Johnson potentials GGA+U (MBJGGA+U) framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes. PMID:26388021

  20. Nanoscale LiFePO4 and Li4Ti5O12 for High Rate Li-ion Batteries

    SciTech Connect

    Jaiswal, A.; Horne, C.R.; Chang, O.; Zhang, W.; Kong, W.; Wang, E.; Chern, T.; Doeff, M. M.

    2009-08-04

    The electrochemical performances of nanoscale LiFePO4 and Li4Ti5O12 materials are described in this communication. The nanomaterials were synthesized by pyrolysis of an aerosol precursor. Both compositions required moderate heat-treatment to become electrochemically active. LiFePO4 nanoparticles were coated with a uniform, 2-4 nm thick carbon-coating using an organic precursor in the heat treatment step and showed high tap density of 1.24 g/cm3, in spite of 50-100 nm particle size and 2.9 wtpercent carbon content. Li4Ti5O12 nanoparticles were between 50-200 nm in size and showed tap density of 0.8 g/cm3. The nanomaterials were tested both in half cell configurations against Li-metal and also in LiFePO4/Li4Ti5O12 full cells. Nano-LiFePO4 showed high discharge rate capability with values of 150 and 138 mAh/g at C/25 and 5C, respectively, after constant C/25 charges. Nano-Li4Ti5O12 also showed high charge capability with values of 148 and 138 mAh/g at C/25 and 5C, respectively, after constant C/25 discharges; the discharge (lithiation) capability was comparatively slower. LiFePO4/Li4Ti5O12 full cells deliver charge/discharge capacity values of 150 and 122 mAh/g at C/5 and 5C, respectively.

  1. Optimization of reaction condition for solid-state synthesis of LiFePO 4-C composite cathodes

    NASA Astrophysics Data System (ADS)

    Zhang, S. S.; Allen, J. L.; Xu, K.; Jow, T. R.

    We optimized synthesis condition of LiFePO 4-C composites by solid-state reaction of LiH 2PO 4 and FeC 2O 4·2H 2O in the presence of carbon powder. The preparation was conducted under a N 2 flow through two heating steps. First, the starting materials were thoroughly mixed in a stoichiometric ratio and decomposed at 350-380 °C to form the precursor. Second, the resulting precursor was heated at a high temperature to form the crystalline phase LiFePO 4. For formation of the precursor, the optimized temperature was 350 °C for LiFePO 4 and 380 °C for LiFePO 4-C composites, respectively. For formation of crystalline phase composites, the optimized condition was to heat the precursor in a pelletized form at 800 °C for 5 h, and the optimized content of carbon was 3-10 wt.%. In composites, the carbon not only increases the rate capability, but also enhances capacity stability. We found that capacity of the composites increases with specific surface area of carbon. The best result was observed from a composite made of 8.7 wt.% of black pearls BP 2000 having a specific surface area of 1500 m 2 g -1. At room temperature and low current rate (0.02 C), such a composite shows a specific capacity of 159 mAh g -1. Electrochemical properties and cycling performance of the optimized composite also were evaluated.

  2. Anomalous magnetic structure and spin dynamics in magnetoelectric LiFePO4

    DOE PAGESBeta

    Toft-Petersen, Rasmus; Reehuis, Manfred; Jensen, Thomas B. S.; Andersen, Niels H.; Li, Jiying; Le, Manh Duc; Laver, Mark; Niedermayer, Christof; Klemke, Bastian; Lefmann, Kim; et al

    2015-07-06

    We report significant details of the magnetic structure and spin dynamics of LiFePO4 obtained by single-crystal neutron scattering. Our results confirm a previously reported collinear rotation of the spins away from the principal b axis, and they determine that the rotation is toward the a axis. In addition, we find a significant spin-canting component along c. Furthermore, the possible causes of these components are discussed, and their significance for the magnetoelectric effect is analyzed. Inelastic neutron scattering along the three principal directions reveals a highly anisotropic hard plane consistent with earlier susceptibility measurements. While using a spin Hamiltonian, we showmore » that the spin dimensionality is intermediate between XY- and Ising-like, with an easy b axis and a hard c axis. As a result, it is shown that both next-nearest neighbor exchange couplings in the bc plane are in competition with the strongest nearest neighbor coupling.« less

  3. Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model

    NASA Astrophysics Data System (ADS)

    Delmas, C.; Maccario, M.; Croguennec, L.; Le Cras, F.; Weill, F.

    2008-08-01

    Lithium iron phosphate is one of the most promising positive-electrode materials for the next generation of lithium-ion batteries that will be used in electric and plug-in hybrid vehicles. Lithium deintercalation (intercalation) proceeds through a two-phase reaction between compositions very close to LiFePO4 and FePO4. As both endmember phases are very poor ionic and electronic conductors, it is difficult to understand the intercalation mechanism at the microscopic scale. Here, we report a characterization of electrochemically deintercalated nanomaterials by X-ray diffraction and electron microscopy that shows the coexistence of fully intercalated and fully deintercalated individual particles. This result indicates that the growth reaction is considerably faster than its nucleation. The reaction mechanism is described by a `domino-cascade model' and is explained by the existence of structural constraints occurring just at the reaction interface: the minimization of the elastic energy enhances the deintercalation (intercalation) process that occurs as a wave moving through the entire crystal. This model opens new perspectives in the search for new electrode materials even with poor ionic and electronic conductivities.

  4. Phase boundary propagation in large LiFePO4 single crystals on delithiation.

    PubMed

    Weichert, Katja; Sigle, Wilfried; van Aken, Peter A; Jamnik, Janez; Zhu, Changbao; Amin, Ruhul; Acartrk, Tolga; Starke, Ulrich; Maier, Joachim

    2012-02-15

    Large single crystals of LiFePO(4) have been chemically delithiated. The relevance of chemical oxidation in comparison with electrochemical delithiation is discussed. Analyses of the Li content and profiles were done by electron energy loss spectroscopy and secondary ion mass spectrometry. The propagation of the FePO(4) phase growing on the surface of the large single crystal was followed by in situ optical microscopy as a function of time. The kinetics were evaluated in terms of linear irreversible thermodynamics and found to be characterized by an induction period followed by parabolic growth behavior of the FePO(4) phase indicating transport control. The growth rate was shown to depend on the crystallographic orientation. Scanning electron microscopy images showed cracks and a high porosity of the FePO(4) layer due to the significant changes in the molar volumes. The transport was found to be greatly enhanced by the porosity and crack formation and hence greatly enhanced over pure bulk transport, a result which is supposed to be very relevant for battery research if coarse-grained powder is used. PMID:22191608

  5. Excellent temperature performance of spherical LiFePO4/C composites modified with composite carbon and metal oxides.

    PubMed

    Zhang, Bao; Zeng, Tao; Zhang, Jiafeng; Peng, Chunli; Zheng, Junchao; Chen, Guomin

    2014-01-01

    Nanosized spherical LiFePO4/C composite was synthesized from nanosized spherical FePO4 2H2O, Li2C2O4, aluminum oxide, titanium oxide, oxalic acid, and sucrose by binary sintering process. The phases and morphologies of LiFePO4/C were characterized using SEM, TEM, CV, EIS, EDS, and EDX as well as charging and discharging measurements. The results showed that the as-prepared LiFePO4/C composite with good conductive webs from nanosized spherical FePO4 2H2O exhibits excellent electrochemical performances, delivering an initial discharge capacity of 161.7?mAhg(-1) at a 0.1?C rate, 152.4?mAhg(-1) at a 1?C rate and 131.7?mAhg(-1) at a 5?C rate, and the capacity retention of 99.1%, 98.7%, and 95.8%, respectively, after 50 cycles. Meanwhile, the high and low temperature performance is excellent for 18650 battery, maintaining capacity retention of 101.7%, 95.0%, 88.3%, and 79.3% at 55C, 0C, -10C, and -20C by comparison withthat of room temperature (25C) at the 0.5 C rate over a voltage range of 2.2?V to 3.6?V, respectively. PMID:24526888

  6. Role of PO4 tetrahedron in LiFePO4 and FePO4 system.

    PubMed

    Zeng, Yuewu

    2015-06-01

    Using high resolution transmission electron microscopy with image simulation and Fourier analysis, the Li1- x FePO4 (x < 0.01), Li1- x FePO4 (x ∼ 0.5), and FePO4 particles, prepared by charging or discharging the 053048 electrochemical cells (thickness: 5 mm, width: 30 mm, height: 48 mm) and dismantled inside an Ar-filled dry box, were investigated. The high resolution images reveal: (1) the solid solution of Li1- x FePO4 (x < 0.01) contains some missing Li ions leading PO4 group distorted around M1 tunnel of the unit cell; (2) the texture of the particles of Li1- x FePO4 (x ∼0.5) has homogeneously distributed compositional domains of LiFePO4 and FePO4 resulting from spinodal decomposition which promote Li ion easily getting into the particle due to uphill diffusion, (3) the particles of FePO4 formed in charging have heavily distorted lattice and contain some isolated LiFePO4 , (4) interface between LiFePO4 and FePO4 and between amorphous and crystal region provides the lattice distortion of small polarons. PMID:25846750

  7. Excellent Temperature Performance of Spherical LiFePO4/C Composites Modified with Composite Carbon and Metal Oxides

    PubMed Central

    Zhang, Bao; Zeng, Tao; Zhang, Jiafeng; Peng, Chunli; Zheng, Junchao; Chen, Guomin

    2014-01-01

    Nanosized spherical LiFePO4/C composite was synthesized from nanosized spherical FePO42H2O, Li2C2O4, aluminum oxide, titanium oxide, oxalic acid, and sucrose by binary sintering process. The phases and morphologies of LiFePO4/C were characterized using SEM, TEM, CV, EIS, EDS, and EDX as well as charging and discharging measurements. The results showed that the as-prepared LiFePO4/C composite with good conductive webs from nanosized spherical FePO42H2O exhibits excellent electrochemical performances, delivering an initial discharge capacity of 161.7?mAhg?1 at a 0.1?C rate, 152.4?mAhg?1 at a 1?C rate and 131.7?mAhg?1 at a 5?C rate, and the capacity retention of 99.1%, 98.7%, and 95.8%, respectively, after 50 cycles. Meanwhile, the high and low temperature performance is excellent for 18650 battery, maintaining capacity retention of 101.7%, 95.0%, 88.3%, and 79.3% at 55C, 0C, ?10C, and ?20C by comparison withthat of room temperature (25C) at the 0.5 C rate over a voltage range of 2.2?V to 3.6?V, respectively. PMID:24526888

  8. A synthesis of LiFePO4 starting from FePO4 under reducing atmosphere

    NASA Astrophysics Data System (ADS)

    Prosini, Pier Paolo; Cento, Cinzia; Masci, Amedeo; Carewska, Maria; Gislon, Paola

    2014-06-01

    A fast and easy way to produce LiFePO4 starting from FePO4, used as iron and phosphorus source, is proposed. 5% hydrogen is employed as a reducing agent and various compounds containing lithium as lithiation agents. The selected lithiation agents included: LiCl, CH3COOLi, LiOH, Li2S, LiH, and Li2CO3. Solid state synthesis is used for the LiFePO4 preparation and the so obtained materials are structurally characterized by XRD. The materials are used to fabricate composite electrode and their specific capacity is evaluated by low rate galvanostatic charge/discharge cycles (C/10 rate). Among the various lithium salts, the acetate give rise to the LiFePO4 with the best electrochemical performance. The morphology of this material is further investigated by SEM microscopy and the specific capacity is evaluated as a function of the discharge rate and the cycle number.

  9. Aluminium-doped LiFePO4 single crystals. Part I. Growth, characterization and total conductivity.

    PubMed

    Amin, Ruhul; Lin, Chengtian; Maier, Joachim

    2008-06-28

    Single crystals of Al-doped LiFePO4 (1% Al) were grown by an optical floating zone technique. After cleaving from the as-grown ingot they exhibited a blackish-green color. The grown crystals have been characterized by the Laue X-ray technique, single-crystal and powder X-ray diffraction. Phase composition has been determined by chemical analysis to be Li0.985+/-0.009Fe0.984+/-0.12Al0.0126PO3.993+/-0.06. Secondary ion beam spectroscopy (SIMS) indicates a homogeneous distribution of doped Al in the single crystal block. The total conductivities are shown to be electronic conductivities and have been measured along different directions with the help of the cell Ti/LiFe(Al)PO4/Ti. The samples exhibit effectively two-dimensional electronic conductivities along b- and c-directions similar as in pure LiFePO4. This decrease of conductivity on Al-doping compared with undoped crystals is in agreement with our previous conclusion of p-type conductivity of LiFePO4. Unlike nominally pure material not only the association of holes with lithium vacancies plays an important role but also purely ionic association. PMID:18548157

  10. X-ray Diffraction and Polarized X-ray Absorption Study of Single Crystal LiFePO4

    NASA Astrophysics Data System (ADS)

    Liang, Gan; Benson, Ron; Li, Jiying; Vaknin, David; Croft, Mark

    2006-10-01

    Large size LiFePO4 single crystals have been grown by standard flux growth technique with the LiCl as the flux. Single crystal x-ray diffraction (XRD) and synchrotron polarized x-ray absorption spectroscopy (XAS) measurements have been performed on the crystals. The XRD measurements were performed at T = 293 K using Mo K? radiation (? = 0.7107) to a resolution corresponding to sin?/? = 0.6486 -1, with 2?max = 54.9 . A total number of 1330 reflections were processed with 350 unique data. The obtained crystal structure data were the following: lithium iron (II) phosphate, LiFePO4, orthorhombic, space group Pnma, lattice constants: a = 10.3172 (11) , b = 6.0096(8) , c = 4.6775 (4) , Z = 4, formula weight: 157.76, density: 3.613, ? = 55.562 cm-1. The bond lengths between Fe and O and between P and O were obtained. The polarized XAS was performed at the Fe K-edge with the x-ray E-vector along the a-, b-, and c-axis. The XAS results show that the Fe ions in the LiFePO4 single crystals are divalent. We also observed a big shift in both the energies of the pre-edge 1s -> 3d transition feature and the main edge when the polarization direction of the E-vector changes from along a-axis to along c-axis.

  11. Synthesis, characterization and vibrational spectroscopic study of Co, Mg co-doped LiMnPO4

    NASA Astrophysics Data System (ADS)

    Sronsri, Chuchai; Noisong, Pittayagorn; Danvirutai, Chanaiporn

    2016-01-01

    The isostructural olivine-like LiM(II)PO4 compounds [M(II) = Mn, Mn0.9Co0.1, Mn0.8Co0.1Mg0.1] were successfully generated through the solid state reaction from the synthesized NH4M(II)PO4• H2O precursors. The TG/DTG/DTA, AAS/AES, FTIR and XRD methods were employed to confirm both NH4M(II)PO4• H2O and LiM(II)PO4 compounds. Their morphologies were studied by SEM method. The shift of two theta angle of XRD to higher values was observed in metal doping compounds, which indicate the formation of the single phase of isodivalent doping of Co2 + and Mg2 + ions according to the change in the lattice parameters and cell volumes. Their infrared spectra are reported and discussed with respect to the normal vibrations of NH4+, PO43 -, P2O74 - and H2O molecules using factor group analysis. The correlation field splitting analysis of PO43 - in NH4M(II)PO4• H2O (orthorhombic system, Pmn21, C2v7 and Z = 2, [(3 × 5) - 6] × 2 = 18 internal modes) symbolized as Td - Cs - C2v7 suggested the number of vibrational modes to be: ΓVib = A1(6) + A2(3) + B1(6) + B2(3) and A1(6) + A2(3) + B1(3) + B2(6) for zx and yz plane respectively. While, LiM(II)PO4 crystallizes in the orthorhombic system the space group Pnma (D2h16), Z = 4 and the site symmetry of PO43 - is Cs. The correlation field splitting of type Td - Cs - D2h16 were reported in relation to [(3 × 5) - 6] × 4 = 36 internal modes for PO43 - unit in the structure.

  12. A simple and novel Si surface modification on LiFePO4@C electrode and its suppression of degradation of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Wenyu; Zhuang, Zhenyuan; Chen, Xiang; Zou, Mingzhong; Zhao, Guiying; Feng, Qian; Li, Jiaxin; Lin, Yingbin; Huang, Zhigao

    2015-12-01

    A simple and novel surface modification device of the electrodes based on the ultrasonic spray technique was set up, which is considered to have the enormous prospect of industrial application due to its simpleness and high efficiency. Then, the nano-sized Si nanoparticles were deposited uniformly on the LiFePO4@C electrodes. In comparison with pristine LiFePO4@C electrode, the surface modification of the nano-sized Si with crystalline Si core and amorphous Si shell on the electrode surface exhibits less coarsening degree, higher rate capability, better cyclicity at high charge/discharge rate, especially at elevated temperature. Moreover, Raman spectra of LiFePO4@C, LiFePO4@C/Si electrodes before cycles and after 100 cycles at 1 C and 60 C were measured. It is found that the FePO4 and ?-Fe2O3 phases exist in LiFePO4@C after 100 cycles. On the contrary, there hardly exists the FePO4 and ?-Fe2O3 phases, which means that the nano Si surface modification suppresses the degradation of lithium ion batteries. At last, the schematic and phenomenological resistance models of LiFePO4@C electrode modified by the nano-sized silicon particles have been suggested, which is responsible for the enhancement of the electrochemical performances after nano-sized Si surface modification.

  13. LiFePO4 nanoparticles enveloped in freestanding sandwich-like graphitized carbon sheets as enhanced remarkable lithium-ion battery cathode

    NASA Astrophysics Data System (ADS)

    Zhang, Yan; Zhang, Huijuan; Li, Xiao; Xu, Haitao; Wang, Yu

    2016-04-01

    A novel nanostructure where LiFePO4 nanoparticles are enveloped in sandwich-like carbon sheets as an enhanced cathode in lithium-ion batteries has successfully been synthesized for the first time. Compared to previous carbon-based nanocomposites, the achieved sandwich-like LiFePO4 nanocomposites exhibit totally different architecture, in which LiFePO4 nanoparticles are tightly entrapped between two carbon layers, instead of being anchored on the carbon sheet surfaces. In other words, the achieved sandwich-like LiFePO4 nanocomposite carbon layers are actually freestanding and can be operated and separated from each other. This is a great breakthrough in the design and synthesis of carbon-based functional materials. The obtained sandwich-like LiFePO4 nanocomposites present excellent electrochemical performance, which is rationally ascribed to the superb and unique structure and architecture. Of particular note is that the freestanding sandwich-like LiFePO4 nanocomposites exhibit enhanced cyclability and rate capability. At a high current density of 0.1 A g‑1, a stable specific capacity of approximately 168.5 mAh g‑1 can be delivered over 1000 cycles, and when the charge–discharge rates increase to 0.6, 2, 5 and 10 A g‑1, the specific capacities still survive at 149, 129, 114 and 91 mAh g‑1, respectively. Meanwhile, the sandwiched nanocomposite demonstrates a significantly improved low-temperature electrochemical energy storage performance. With respect to the excellent Li storage performance, and facility and reliability of production, the freestanding sandwich-like LiFePO4 nanocomposites are reasonably believed to have a great potential for multiple electrochemical energy storage applications.

  14. LiFePO4 nanoparticles enveloped in freestanding sandwich-like graphitized carbon sheets as enhanced remarkable lithium-ion battery cathode.

    PubMed

    Zhang, Yan; Zhang, Huijuan; Li, Xiao; Xu, Haitao; Wang, Yu

    2016-04-15

    A novel nanostructure where LiFePO4 nanoparticles are enveloped in sandwich-like carbon sheets as an enhanced cathode in lithium-ion batteries has successfully been synthesized for the first time. Compared to previous carbon-based nanocomposites, the achieved sandwich-like LiFePO4 nanocomposites exhibit totally different architecture, in which LiFePO4 nanoparticles are tightly entrapped between two carbon layers, instead of being anchored on the carbon sheet surfaces. In other words, the achieved sandwich-like LiFePO4 nanocomposite carbon layers are actually freestanding and can be operated and separated from each other. This is a great breakthrough in the design and synthesis of carbon-based functional materials. The obtained sandwich-like LiFePO4 nanocomposites present excellent electrochemical performance, which is rationally ascribed to the superb and unique structure and architecture. Of particular note is that the freestanding sandwich-like LiFePO4 nanocomposites exhibit enhanced cyclability and rate capability. At a high current density of 0.1 A g(-1), a stable specific capacity of approximately 168.5 mAh g(-1) can be delivered over 1000 cycles, and when the charge-discharge rates increase to 0.6, 2, 5 and 10 A g(-1), the specific capacities still survive at 149, 129, 114 and 91 mAh g(-1), respectively. Meanwhile, the sandwiched nanocomposite demonstrates a significantly improved low-temperature electrochemical energy storage performance. With respect to the excellent Li storage performance, and facility and reliability of production, the freestanding sandwich-like LiFePO4 nanocomposites are reasonably believed to have a great potential for multiple electrochemical energy storage applications. PMID:26934516

  15. Etched colloidal LiFePO4 nanoplatelets toward high-rate capable Li-ion battery electrodes.

    PubMed

    Paolella, Andrea; Bertoni, Giovanni; Marras, Sergio; Dilena, Enrico; Colombo, Massimo; Prato, Mirko; Riedinger, Andreas; Povia, Mauro; Ansaldo, Alberto; Zaghib, Karim; Manna, Liberato; George, Chandramohan

    2014-12-10

    LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently "plagued" by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ? 155 mAh/g, ? 135 mAh/g, and ? 125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ? 70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ? 30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries. PMID:25372361

  16. Reversible chemical delithiation/lithiation of LiFePO4: towards a redox flow lithium-ion battery.

    PubMed

    Huang, Qizhao; Li, Hong; Grtzel, Michael; Wang, Qing

    2013-02-14

    Reversible chemical delithiation/lithiation of LiFePO(4) was successfully demonstrated using ferrocene derivatives, based on which a novel energy storage system--the redox flow lithium-ion battery (RFLB), was devised by integrating the operation flexibility of a redox flow battery and high energy density of a lithium-ion battery. Distinct from the recent semi-solid lithium rechargeable flow battery, the energy storage materials of RFLB stored in separate energy tanks remain stationary upon operation, giving us a fresh perspective on building large-scale energy storage systems with higher energy density and improved safety. PMID:23262995

  17. Synthesis of the LiFePO4/C core-shell nanocomposite using a nano-FePO4/polythiophene as an iron source

    NASA Astrophysics Data System (ADS)

    Liu, Jing; Yang, Guiling; Zhang, Xianfa; Wang, Jiawei; Wang, Rongshun

    2012-01-01

    For the first time, a LiFePO4/C core-shell nanocomposite has been synthesized using a nano-FePO4/polythiophene (PTh) as an iron source. With this method, the PTh is in situ polymerized to restrain the growth of FePO4 particles, and the typical size of FePO4/PTh particles is in the range of 20-50 nm. The optimized LiFePO4/C nanocomposite is synthesized at 750 C using 40% citric acid. The prepared LiFePO4 particles show a typical size of 50-100 nm and they are fully coated by carbon of 2-4 nm thickness. The LiFePO4/C core-shell nanocomposite gives an improved high electronic conductivity and a good electrochemical behavior at high rates. Thus, this novel method is an effective and facile strategy to improve the rate performance of the LiFePO4 cathode.

  18. Long-term cycle stability at a high current for nanocrystalline LiFePO4 coated with a conductive polymer

    NASA Astrophysics Data System (ADS)

    Dinh, Hung-Cuong; Lim, Hanjo; Park, Ki Dong; Yeo, In-Hyeong; Kang, Yongku; Mho, Sun-il

    2013-03-01

    Highly uniform hierarchical-microstructured LiFePO4 particles with dumbbell- and donut-shape and individual LiFePO4 nanocrystals were prepared by a hydrothermal method utilizing citric acid or a triblock copolymer (Pluronic P123) as a surfactant. The cathode composed of the individual nanocrystalline LiFePO4 particles exhibited higher specific capacity than the cathodes composed of the hierarchically assembled microparticles. Coating a conductive polymer, poly-3,4-ethylenedioxythiophene (PEDOT), on the surface of LiFePO4 particles improved the battery performances such as large specific capacities, high rate capability and an improved cycle stability. The nanocrystalline LiFePO4 particles coated with PEDOT (20 wt%) exhibited the highest discharge capacities of 175 and 136 mAh g-1 for the first battery cycle and 163 and 128 mAh g-1 after 500 battery cycles, with a degradation rate of 6-7%, at the rates of 1 and 10 C, respectively.

  19. Influence of memory effect on the state-of-charge estimation of large-format Li-ion batteries based on LiFePO4 cathode

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Wang, Jiulin; Zheng, Jianming; Jiang, Jiuchun; Viswanathan, Vilayanur; Zhang, Ji-Guang

    2016-04-01

    In this work, we systematically investigated the influence of the memory effect of LiFePO4 cathodes in large-format full batteries. The electrochemical performance of the electrodes used in these batteries was also investigated separately in half-cells to reveal their intrinsic properties. We noticed that the memory effect of LiFePO4/graphite cells depends not only on the maximum state of charge reached during the memory writing process, but is also affected by the depth of discharge reached during the memory writing process. In addition, the voltage deviation in a LiFePO4/graphite full battery is more complex than in a LiFePO4/Li half-cell, especially for a large-format battery, which exhibits a significant current variation in the region near its terminals. Therefore, the memory effect should be taken into account in advanced battery management systems to further extend the long-term cycling stabilities of Li-ion batteries using LiFePO4 cathodes.

  20. In situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates for superior Li-ion battery cathodes.

    PubMed

    Ma, Zhipeng; Fan, Yuqian; Shao, Guangjie; Wang, Guiling; Song, Jianjun; Liu, Tingting

    2015-02-01

    The low electronic conductivity and one-dimensional diffusion channel along the b axis for Li ions are two major obstacles to achieving high power density of LiFePO4 material. Coating carbon with excellent conductivity on the tailored LiFePO4 nanoparticles therefore plays an important role for efficient charge and mass transport within this material. We report here the in situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates with highly oriented (010) facets by introducing ferrocene as a catalyst during thermal treatment. The as-obtained material exhibits superior performances for Li-ion batteries at high rate (100 C) and low temperature (-20 C), mainly because of fast electron transport through the graphitic carbon layer and efficient Li(+)-ion diffusion through the thin nanoplates. PMID:25584530

  1. Li-Ion Battery with LiFePO4 Cathode and Li4Ti5O12 Anode for Stationary Energy Storage

    SciTech Connect

    Wang, Wei; Choi, Daiwon; Yang, Zhenguo

    2013-01-01

    i-ion batteries based on commercially available LiFePO4 cathode and Li4Ti5O12 anode were investigated for potential stationary energy storage applications. The full cell that operated at flat 1.85V demonstrated stable cycling for 200 cycles followed by a rapid fade. A significant improvement in cycling stability was achieved via Ketjen black coating of the cathode. A Li-ion full cell with Ketjen black modified LiFePO4 cathode and an unmodified Li4Ti5O12 anode exhibited negligible fade after more than 1200 cycles with a capacity of ~130mAh/g. The improved stability, along with its cost-effectiveness, environmentally benignity and safety, make the LiFePO4/ Li4Ti5O12 Li-ion battery a promising option of storing renewable energy.

  2. Enhancement of electrochemical behavior of nanostructured LiFePO4/Carbon cathode material with excess Li

    NASA Astrophysics Data System (ADS)

    Bazzi, K.; Nazri, M.; Naik, V. M.; Garg, V. K.; Oliveira, A. C.; Vaishnava, P. P.; Nazri, G. A.; Naik, R.

    2016-02-01

    We have synthesized carbon coated LiFePO4 (C-LiFePO4) and C-Li1.05FePO4 with 5 mol% excess Li via sol-gel method using oleic acid as a source of carbon for enhancing electronic conductivity and reducing the average particle size. Although the phase purity of the crystalline samples was confirmed by x-ray diffraction (XRD), the 57Fe Mössbauer spectroscopy analyses show the presence of ferric impurity phases in both stoichiometric and non-stoichiometric C-LiFePO4 samples. Transmission electron microscopy measurements show nanosized C-LiFePO4 particles uniformly covered with carbon, with average particle size reduced from ∼100 nm to ∼50 nm when excess lithium is used. Electrochemical measurements indicate a lower charge transfer resistance and better electrochemical performance for C-Li1.05FePO4 compared to that of C-LiFePO4. The aim of this work is to systematically analyze the nature of impurities formed during synthesis of LiFePO4 cathode material, and their impact on electrochemical performance. The correlation between the morphology, charge transfer resistance, diffusion coefficient and electrochemical performance of C-LiFePO4 and C- Li1.05FePO4 cathode materials are discussed.

  3. Space matters: Li+ conduction versus strain effect at FePO4/LiFePO4 interface

    NASA Astrophysics Data System (ADS)

    Lv, Weiqiang; Niu, Yinghua; Jian, Xian; Zhang, Kelvin H. L.; Wang, Wei; Zhao, Jiyun; Wang, Zhiming; Yang, Weiqing; He, Weidong

    2016-02-01

    FePO4/LiFePO4 (FP/LFP) interfacial strain, giving rise to substantial variation in interfacial energy and lattice volume, is inevitable in the (de)lithiation process of LiFePO4, a prototype of Li ion battery cathodes. Extensive theoretical and experimental research has been focused on the effect of lattice strain energy on FP/LFP interface propagation orientation and cyclic stability of the electrode. However, the essential effect of strain induced lattice distortion on Li+ transport at the FP/LFP interface is typically overlooked. In this report, a coherent interface model is derived to evaluate quantitatively the correlation between FP/LFP lattice distortion and Li+ conduction. The results illustrate that the effect of lattice strain on Li+ conduction depends strongly on FP/LFP interface orientations. Lattice strain induces a 90% decrease of Li+ conductivity in ac-plane oriented (de)lithiation at room temperature. The opposite effect of lattice strain on delithiation and lithiation for ab- and bc-orientations is elucidated. In addition, the effect of lattice strain tends to be more pronounced at a lower working temperature. This study provides an efficient platform to comprehend and manipulate Li+ conduction in the charge and discharge of lithium ion batteries, the large-scale application of which is frequently challenged by limited in-cell ion conduction.

  4. Double Carbon Nano Coating of LiFePO4 Cathode Material for High Performance of Lithium Ion Batteries.

    PubMed

    Ding, Yan-Hong; Huang, Guo-Long; Li, Huan-Huan; Xie, Hai-Ming; Sun, Hai-Zhu; Zhang, Jing-Ping

    2015-12-01

    Double carbon-coated LiFePO4 (D-LiFePO4/C) composite with sphere-like structure was synthesized through combination of co-precipitation and solid-state methods. Cetyl-trimethyl-ammonium bromide (CTAB) and citric acid served as two kinds of carbon sources in sequence. SEM images demonstrated that double carbon coating had certain influence on the morphology. The thickness of carbon coating on D-LiFePO4/C was about 1.7 nm and the content of carbon was 2.48 wt%, according to HRTEM and TG analysis. The electrochemical impedance spectroscopy analysis indicated that the D-LiFePO4/C composite presented the charge-transfer resistance of 68 ? and Li ion diffusion coefficient of 2.68 x 10(-13) cm2 S(-1), while the single carbon-coated LiFePO4 (S-LiFePO4/C) exhibited 135.5? and 4.03 x 10(-14) cm2 S(-1). Especially, the prepared D-LiFePO4/C electrode showed discharge capacities of 102.9 (10C) and 87.1 (20C) mA h g(-1), respectively, with almost no capacity lost after 400 cycles at 10C, which were much better than those of S-LiFePO4/C composite. PMID:26682389

  5. Impact of carbon structure and morphology on the electrochemical performance of LiFePO4/C composites

    SciTech Connect

    Doeff, Marca M.; Doeff, Marca M.; Wilcox, James D.; Yu, Rong; Aumentado, Albert; Marcinek, Marek; Kostecki, Robert

    2007-09-19

    The electrochemical performance of LiFePO4/C composites in lithium cells is closely correlated to pressed pellet conductivities measured by AC impedance methods. These composite conductivities are a strong function not only of the amount of carbon but of its structure and distribution. Ideally, the amount of carbon in composites should be minimal (less than about 2 wtpercent) so as not to decrease the energy density unduly. This is particularly important for plug-in hybrid electric vehicle applications (PHEVs) where both high power and moderate energy density are required. Optimization of the carbon structure, particularly the sp2/sp3 and disordered/graphene (D/G) ratios, improves the electronic conductivity while minimizing the carbon amount. Manipulation of the carbon structure can be achieved via the use of synthetic additives including ironcontaining graphitization catalysts. Additionally, combustion synthesis techniques allow co-synthesis of LiFePO4 and carbon fibers or nanotubes, which can act as"nanowires" for the conduction of current during cell operation.

  6. Sequential Monte Carlo filter for state estimation of LiFePO4 batteries based on an online updated model

    NASA Astrophysics Data System (ADS)

    Li, Jiahao; Klee Barillas, Joaquin; Guenther, Clemens; Danzer, Michael A.

    2014-02-01

    Battery state monitoring is one of the key techniques in battery management systems e.g. in electric vehicles. An accurate estimation can help to improve the system performance and to prolong the battery remaining useful life. Main challenges for the state estimation for LiFePO4 batteries are the flat characteristic of open-circuit-voltage over battery state of charge (SOC) and the existence of hysteresis phenomena. Classical estimation approaches like Kalman filtering show limitations to handle nonlinear and non-Gaussian error distribution problems. In addition, uncertainties in the battery model parameters must be taken into account to describe the battery degradation. In this paper, a novel model-based method combining a Sequential Monte Carlo filter with adaptive control to determine the cell SOC and its electric impedance is presented. The applicability of this dual estimator is verified using measurement data acquired from a commercial LiFePO4 cell. Due to a better handling of the hysteresis problem, results show the benefits of the proposed method against the estimation with an Extended Kalman filter.

  7. Etched Colloidal LiFePO4 Nanoplatelets toward High-Rate Capable Li-Ion Battery Electrodes

    PubMed Central

    2014-01-01

    LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently “plagued” by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼155 mAh/g, ∼135 mAh/g, and ∼125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries. PMID:25372361

  8. Ink-jet printed porous composite LiFePO4 electrode from aqueous suspension for microbatteries

    NASA Astrophysics Data System (ADS)

    Delannoy, P.-E.; Riou, B.; Brousse, T.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

    2015-08-01

    This work demonstrates ink-jet printed LiFePO4-based composite porous electrodes for microbattery application. As binder and dispersant, we found that aqueous inks with more suitable rheological properties with respect to ink-jet printing are prepared with the low molecular weight poly-acrylic-co-maleic acid copolymer, rather than with the carboxymethyl cellulose standard binder of the lithium-ion technology. The ink-jet printed thin and porous electrode shows very high rate charge/discharge behavior, both in LiPF6/ethylene carbonate-dimethyl carbonate (LP30) and lithium bis(trifluoromethane)sulfonylimide salt (Li-TFSI) in N-methyl-N-propylpyrrolidinium bis(trifluoromethane)suflonylimide ionic liquid (PYR13-TFSI) electrolytes, as well as good cyclability.

  9. Simplified electrochemical multi-particle model for LiFePO4 cathodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Mastali Majdabadi, Mehrdad; Farhad, Siamak; Farkhondeh, Mohammad; Fraser, Roydon A.; Fowler, Michael

    2015-02-01

    A simplified physics-based model is developed to predict the performance of an LiFePO4 cathode at various operating and design conditions. Newman's full-order porous-electrode model is simplified using polynomial approximations for electrolyte variables at the electrode-level while a multi-particle model featuring variable solid-state diffusivity is employed at the particle level. The computational time of this reduced-order model is decreased by almost one order of magnitude compared to the full-order model without sacrificing the accuracy of the results. The model is general and can be used to expedite the simulation of any composite electrode with active-material particles of non-uniform properties (e.g., size, contact resistance, material chemistry etc.). In a broader perspective, this model is of practical value for electric vehicle power train simulations and battery management systems.

  10. Desired crystal oriented LiFePO4 nanoplatelets in situ anchored on a graphene cross-linked conductive network for fast lithium storage

    NASA Astrophysics Data System (ADS)

    Wang, Bo; Liu, Anmin; Abdulla, Wael Al; Wang, Dianlong; Zhao, X. S.

    2015-05-01

    Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a ``platelet-on-sheet'' LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (~56 mA h g-1 at 60 C) and long life cycling stability (~87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (~98% capacity retention over 1000 cycles at 10 C).Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a ``platelet-on-sheet'' LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (~56 mA h g-1 at 60 C) and long life cycling stability (~87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (~98% capacity retention over 1000 cycles at 10 C). Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01831e

  11. Enhanced electrochemical properties of LiFePO4 by Mo-substitution and graphitic carbon-coating via a facile and fast microwave-assisted solid-state reaction.

    PubMed

    Li, Dan; Huang, Yudai; Sharma, Neeraj; Chen, Zhixin; Jia, Dianzeng; Guo, Zaiping

    2012-03-14

    A composite cathode material for lithium ion battery applications, Mo-doped LiFePO(4)/C, is obtained through a facile and fast microwave-assisted synthesis method. Rietveld analysis of LiFePO(4)-based structural models using synchrotron X-ray diffraction data shows that Mo-ions substitute onto the Fe sites and displace Fe-ions to the Li sites. Supervalent Mo(6+) doping can act to introduce Li ion vacancies due to the charge compensation effect and therefore facilitate lithium ion diffusion during charging/discharging. Transmission electron microscope images demonstrate that the pure and doped LiFePO(4) nanoparticles were uniformly covered by an approximately 5 nm thin layer of graphitic carbon. Amorphous carbon on the graphitic carbon-coated pure and doped LiFePO(4) particles forms a three-dimensional (3D) conductive carbon network, effectively improving the conductivity of these materials. The combined effects of Mo-doping and the 3D carbon network dramatically enhance the electrochemical performance of these LiFePO(4) cathodes. In particular, Mo-doped LiFePO(4)/C delivers a reversible capacity of 162 mA h g(-1) at a current of 0.5 C and shows enhanced capacity retention compared to that of undoped LiFePO(4)/C. Moreover, the electrode exhibits excellent rate capability, with an associated high discharge capacity and good electrochemical reversibility. PMID:22311165

  12. Synthesis, characterization and modification of LiFePO4 by doping with platinum and palladium for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Talebi-Esfandarani, Majid

    Lithium iron phosphate (LiFePO4) with features of excellent thermal stability, non-toxicity, low cost and abundance in nature is one of the most promising cathode materials to be used in lithium ion batteries. However, as it suffers from the low electrical conductivity and poor ionic diffusion, it operates only at low charge/discharge current rates. In this thesis, a dual approach of metal doping and carbon coating was employed to solve the aforementioned problem. This work is mainly on the study, for the first time, of the effect of platinum and palladium doping of LiFePO 4 on its physical-chemical properties. The effect of Pt and Pd doping on the LiFePO4 performance as Li-ion cathode will be also shown. Sol-gel and hydrothermal methods were used to synthesize the LiFePO4 and doped-LiFePO4 cathode materials. The prepared materials were characterized using different methods such as XRD (X-ray Diffraction), XPS (X-ray Photoelectron Spectroscopy), SEM (Scanning Electron Microscopy) and BET (Brunauer Emmett Teller). The electrochemical characterization techniques including charge/discharge test, CV (Cyclic Voltammetry), EIS (Electrochemical Impedance Spectroscopy) and cycling were also used. The effects of metals doping on chemical-physical properties, particles sizes, morphology, structure and purity of the electrodes were investigated and their correlation to the electrochemical properties of materials were studied. In the first section, we determine the optimized amount of carbon support and morphology of the particles using SEM which help to obtain LiFePO 4/C cathode material with an excellent electrochemical performance. It was found that when the amount of coated carbon exceeds the optimized value, the discharge capacity of the LiFePO4/C material decreased. This might indicate a low diffusion of the Li+ ions through the carbon layers during the charge/discharge process. On the other hand, for LiFePO4 coated with carbon quantity lower than the optimum value, LiFePO4/C cathode exhibited poor capacity performance due to its low electrical conductivity. Therefore, both the quality and quantity of carbon coating on the surface of LiFePO4 particles are important and only optimized carbon content can lead to a more uniform carbon distribution. Optimized surface area and conductivity, which give high electrochemical performance, can be only achieved if the appropriate carbon content and method of electrode preparation are obtained. In the second part, the effect of doping the LiFePO4/C electrodes with Pt and Pd on the structure, their chemical compositions and electrochemical properties were investigated. The electrodes were prepared using sol-gel method. The chemical composition analysis by XPS of the Pd doped electrodes showed that Pd was detected in the Pd-doped nano composite materials. Also, for Pt doped electrode, Pt was detected in Pt-doped based nano composite materials. Based on the structure and morphology of the non doped and doped electrodes, the results showed that palladium doping facilitated formation of Li 3PO4 impurity in the LiFe0.98Pd0.02PO 4/C and LiFe0.96Pd0.04PO4/C electrodes. Consequently the presence of the Pd in the doped sample reduced the lattice parameters, increased the size of particles and caused their agglomeration. The electrochemical performances of the electrodes showed that their specific capacity decreased when the palladium content increases. Then, the Pd-doped electrodes fabricated using sol-gel method exhibit less discharge capacity than samples of the non-doped LiFePO4/C electrode. The reduction in the level of performance is attributed to several reasons such as the shrinking of the lattice parameters, the formation of Li3PO4 impurity phase, and large particles size. In contrast, for LiFePO4/C doped with Pt using sol-gel method, it was found that the crystallinity and the lattice parameters of LiFe 0.96Pt0.04PO4/C nanocomposite material increased when compared with LiFePO4/C electrode. No impurity was formed in the Pt-doped electrode. In addition, the Pt doped samples exhibited smaller particle sizes (100-200 nm) than the non doped electrode (200-500 nm). More homogeneous and uniform particles were also obtained with LiFe0.96Pt 0.04PO4/C than LiFePO4/C samples. Therefore, platinum doping might provide more space for the diffusion of Li+ ions which facilitates the movement of Li+ ions through the structure of LiFePO4/C material during the redox reactions in the battery, enhancing the discharge capacities. In the third part of this study, LiFe1-xPdxPO 4/C (x = 0.00, 0.02, 0.04) and LiFe0.96Pt0.04PO 4/C nano composite cathode materials were synthesized by a hydrothermal method and the effects of Pd and Pt were examined. The results indicated that the optimized amount of palladium content (0.02%) in the electrode (LiFe 0.98Pd0.02PO4/C) reduced the nano composite particle sizes. This facilitates the Li+ ion diffusion and consequently enhances the reversibility and decreases the charge transfer resistance. The optimized Pd content in the electrode might act as a pillar to prevent the shrinking and collapse of the initial lattice structure. This might support the stabilization of the crystal structure during the intercalation/de-intercalation process of Li+ ions. However, by increasing the palladium content to 4%, the specific capacities decreased due to the Li3PO 4 impurity formation. The presence of such impurity may produce a small surface area for the redox reaction, and causes difficulty of Li+ ion diffusion during the redox electrochemical process. As a result, the optimized palladium doping is helpful in improving the electrochemical performance of LiFePO4/C material. A LiFe0.96Pt0.04PO 4/C based cathode nano material prepared by a hydrothermal method exhibited better performance when compared to the non-doped LiFePO4/C sample. The improvement in the electrochemical performances can be attributed to the combination of the following aspects related to the presence of Pt in the electrode. The platinum element can act as a stabilizing point of the crystal structure during the charge/discharge process. It contributes to the improvement of the redox reaction rate with the increase of the specific surface area of the composite electrode. LiFe0.96Pt0.04PO4/C electrode exhibited homogeneous small particles which might facilitate the Li+ ions diffusion rate. The results show that the chemical and structural properties and electrochemical performances of Pd and Pt doped LiFePO4/C based electrodes to obtain LiFe1-xPdxPO4/C and LiFe1-xPt xPO4/C as Li-ion cathodes are significantly informed by the method of preparation of the materials and the doping element.

  13. The effect of Cr doping on Li ion diffusion in LiFePO4 from first principles investigations and Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Ouyang, C. Y.; Shi, S. Q.; Wang, Z. X.; Li, H.; Huang, X. J.; Chen, L. Q.

    2004-04-01

    Using the adiabatic trajectory method, the migration energy barriers for the migration of Li ions and Cr ions along the one-dimensional diffusion pathway in pure and Cr doped LiFePO4 are obtained from first principles calculations. The results show that while Li ions can diffuse along the diffusion pathway easily, Cr ions do not easily diffuse away from their initial positions. This means that the heavy Cr ions will block the one-dimensional diffusion pathway of the material. Monte Carlo simulations are performed to evaluate the influences of the blocking behaviours on the electrochemical performance of LiFePO4 cathode material for Li ion secondary batteries. The results show that the evaluated capacity is highly sensitive to the amount of the dopant, the size of the super-cell being used for simulation (particle size of the powder cathode material) and the Monte Carlo steps for statistics (charge-discharge current density).

  14. Effects of Particle Size, Electronic Connectivity, and Incoherent Nanoscale Domains on the Sequence of Lithiation in LiFePO4 Porous Electrodes.

    PubMed

    Li, Yiyang; Meyer, Sophie; Lim, Jongwoo; Lee, Sang Chul; Gent, William E; Marchesini, Stefano; Krishnan, Harinarayan; Tyliszczak, Tolek; Shapiro, David; Kilcoyne, Arthur L David; Chueh, William C

    2015-11-01

    High-resolution X-ray microscopy is used to investigate the sequence of lithiation in LiFePO4 porous electrodes. For electrodes with homogeneous interparticle electronic connectivity via the carbon black network, the smaller particles lithiate first. For electrodes with heterogeneous connectivity, the better-connected particles preferentially lithiate. Correlative electron and X-ray microscopy also reveal the presence of incoherent nanodomains that lithiate as if they are separate particles. PMID:26423560

  15. LiFePO4 microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G

    PubMed Central

    2014-01-01

    We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed. PMID:24948896

  16. Electron microscopy investigations of changes in morphology and conductivity of LiFePO4/C electrodes

    NASA Astrophysics Data System (ADS)

    Scipioni, Roberto; Jørgensen, Peter S.; Ngo, Duc-The; Simonsen, Søren B.; Liu, Zhao; Yakal-Kremski, Kyle J.; Wang, Hongqian; Hjelm, Johan; Norby, Poul; Barnett, Scott A.; Jensen, Søren H.

    2016-03-01

    In this work we study the structural degradation of a laboratory Li-ion battery LiFePO4/Carbon Black (LFP/CB) cathode by various electron microscopy techniques including low kV Focused Ion Beam (FIB)/Scanning Electron Microscopy (SEM) 3D tomography. Several changes are observed in FIB/SEM images of fresh and degraded cathodes, including cracks in the LFP particles, secondary disconnected particles, and agglomeration of CB. Low voltage (1 kV) SEM images show that the CB agglomerates have a different brightness than the fresh CB, due to charging effects. This suggests that the electronic conductivity of the CB agglomerates is low compared to that of the fresh CB particles. HRTEM analysis shows that fresh CB particles are quasi crystalline, whereas the LFP/CB interface in the degraded electrode shows amorphous carbon surrounding the LFP particles. The presence of the amorphous carbon is known to impede the electronic conductivity and thereby decreasing percolation in the cathode and reducing the electrode capacity.

  17. Direct view on the phase evolution in individual LiFePO4 nanoparticles during Li-ion battery cycling

    PubMed Central

    Zhang, Xiaoyu; van Hulzen, Martijn; Singh, Deepak P.; Brownrigg, Alex; Wright, Jonathan P.; van Dijk, Niels H.; Wagemaker, Marnix

    2015-01-01

    Phase transitions in Li-ion electrode materials during (dis)charge are decisive for battery performance, limiting high-rate capabilities and playing a crucial role in the cycle life of Li-ion batteries. However, the difficulty to probe the phase nucleation and growth in individual grains is hindering fundamental understanding and progress. Here we use synchrotron microbeam diffraction to disclose the cycling rate-dependent phase transition mechanism within individual particles of LiFePO4, a key Li-ion electrode material. At low (dis)charge rates well-defined nanometer thin plate-shaped domains co-exist and transform much slower and concurrent as compared with the commonly assumed mosaic transformation mechanism. As the (dis)charge rate increases phase boundaries become diffuse speeding up the transformation rates of individual grains. Direct observation of the transformation of individual grains reveals that local current densities significantly differ from what has previously been assumed, giving new insights in the working of Li-ion battery electrodes and their potential improvements. PMID:26395323

  18. State-of-health estimation of LiFePO4/graphite batteries based on a model using differential capacity

    NASA Astrophysics Data System (ADS)

    Torai, Soichiro; Nakagomi, Masaru; Yoshitake, Satoshi; Yamaguchi, Shuichiro; Oyama, Noboru

    2016-02-01

    A model for expressing the differential capacity characteristics of the LiFePO4 (LFP)/graphite battery for the state-of-health (SOH) estimation was proposed. Our model was based on the deformed pseudo-Voigt peak function with several parameters which are directly associated with the phase transition behavior of the active LFP and graphite materials. Charge/discharge cycle tests for accelerated battery fading were performed under a constant high-temperature condition (40 and 45 °C). The SOH estimation was carried out at different fading point of the battery using a part of the responses for the differential capacity versus voltage (dQ/dV vs. V) against the charging process at the rate of C/5 under constant temperature of 25 °C. The changes in the variables of the model with cycling were correlated to the generally mentioned phenomena that the main factors determining the capacity fading of the LFP/graphite battery are the loss of Li+ by a side reaction and that of the active electrode materials. In addition, the robustness related to the charge/discharge history was confirmed, since the memory effect of the LFP/graphite battery, being induced by the previous condition for use, has an influence on the dQ/dV vs. V. The evaluated SOH errors were within ±3%.

  19. Electrochemical Behavior of LiFePO4 Thin Film Prepared by RF Magnetron Sputtering in Li2SO4 Aqueous Electrolyte

    NASA Astrophysics Data System (ADS)

    Wu, Jiaxiong; Cai, Wei; Shang, Guangyi

    2014-01-01

    LiFePO4 films were deposited on Au/Si substrate by radio-frequency magnetron sputtering. The effect of annealing on the crystallization and morphology of LiFePO4 thin film has been investigated. X-ray diffraction revealed that the films through annealing were well crystallized compared with as-deposited films. The surface morphology of the thin film was also observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Electrochemical tests in 1M Li2SO4 showed that the annealed thin film in 500C exhibits larger Li-ion diffusion coefficient (3.46 10-7 cm2s-1) than as-deposited film and powder. Furthermore, cyclic voltammetry demonstrate a well-defined lithium intercalation/deintercalation reaction at around 0.45 V versus SCE (i.e., 3.6 V versus Li+/Li), suggesting that the annealed LiFePO4 thin film is a promising candidate cathode film for lithium microbatteries.

  20. Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

    NASA Astrophysics Data System (ADS)

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novk, Petr

    2015-09-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ~20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4.

  1. Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries.

    PubMed

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novk, Petr

    2015-01-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ?20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4. PMID:26345306

  2. Increasing the Affinity Between Carbon-Coated LiFePO4/C Electrodes and Conventional Organic Electrolyte by Spontaneous Grafting of a Benzene-Trifluoromethylsulfonimide Moiety.

    PubMed

    Delaporte, Nicolas; Perea, Alexis; Lebgue, Estelle; Ladouceur, Sbastien; Zaghib, Karim; Blanger, Daniel

    2015-08-26

    The grafting of benzene-trifluoromethylsulfonimide groups on LiFePO4/C was achieved by spontaneous reduction of in situ generated diazonium ions of the corresponding 4-amino-benzene-trifluoromethylsulfonimide. The diazotization of 4-amino-benzene-trifluoromethylsulfonimide was a slow process that required a high concentration of precursors to promote the spontaneous grafting reaction. Contact angle measurements showed a hydrophilic surface was produced after the reaction that is consistent with grafting of benzene-trifluoromethylsulfonimide groups. Elemental analysis data revealed a 2.1 wt % loading of grafted molecules on the LiFePO4/C powder. Chemical oxidation of the cathode material during the grafting reaction was detected by X-ray diffraction and quantified by inductively coupled plasma atomic emission spectrometry. Surface modification improves the wettability of the cathode material, and better discharge capacities were obtained for modified electrodes at high C-rate. In addition, electrochemical impedance spectroscopy showed the resistance of the modified cathode was lower than that of the bare LiFePO4/C film electrode. Moreover, the modified cathode displayed superior capacity retention after 200 cycles of charge/discharge at 1 C. PMID:26186016

  3. Combined operando X-ray diffraction–electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

    PubMed Central

    Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

    2015-01-01

    Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4. PMID:26345306

  4. Direct evidence of concurrent solid-solution and two-phase reactions and the nonequilibrium structural evolution of LiFePO4.

    PubMed

    Sharma, Neeraj; Guo, Xianwei; Du, Guodong; Guo, Zaiping; Wang, Jiazhou; Wang, Zhaoxiang; Peterson, Vanessa K

    2012-05-01

    Lithium-ion batteries power many portable devices and in the future are likely to play a significant role in sustainable-energy systems for transportation and the electrical grid. LiFePO(4) is a candidate cathode material for second-generation lithium-ion batteries, bringing a high rate capability to this technology. LiFePO(4) functions as a cathode where delithiation occurs via either a solid-solution or a two-phase mechanism, the pathway taken being influenced by sample preparation and electrochemical conditions. The details of the delithiation pathway and the relationship between the two-phase and solid-solution reactions remain controversial. Here we report, using real-time in situ neutron powder diffraction, the simultaneous occurrence of solid-solution and two-phase reactions after deep discharge in nonequilibrium conditions. This work is an example of the experimental investigation of nonequilibrium states in a commercially available LiFePO(4) cathode and reveals the concurrent occurrence of and transition between the solid-solution and two-phase reactions. PMID:22482702

  5. Improvement of electrochemical performance for spherical LiFePO4 via hybrid coated with electron conductive carbon and fast Li ion conductive La0.56Li0.33TiO3

    NASA Astrophysics Data System (ADS)

    Shu, Hongbo; Chen, Manfang; Fu, Yanqing; Yang, Xiukang; Yi, Xin; Bai, Yansong; Liang, Qianqian; Wei, Qiliang; Hu, Benan; Tan, Jinli; Wu, Chun; Zhou, Meng; Wang, Xianyou

    2014-04-01

    The LiFePO4/(C + La0.56Li0.33TiO3) composites with spherical morphology are synthesized for the first time via ammonia assisted hydrothermal method. The structure and electrochemical performance of LiFePO4/(C + La0.56Li0.33TiO3) are investigated by scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), charge/discharge tests and cyclic voltammetry (CV). It has been found that the hybrid coating layer composing of electron conductive C and fast Li ion conductive La0.56Li0.33TiO3 is synchronously deposited on the surface of LiFePO4 microspheres. The hybrid coating layer can be favourable for fast electron and Li+ transport, and avoid HF eroding LiFePO4 in electrolyte, thus improve the electrochemical performance. The initial discharge capacity of LiFePO4/(C + La0.56Li0.33TiO3) is 126.3 mAh g-1, the capacity retention is still as high as 98.3% even after 100 cycles at 5 C. Even at high rate of 30 C, it still reveals a high discharge capacity of 62.3 mAh g-1.

  6. A novel sol-gel method based on FePO4·2H2O to synthesize submicrometer structured LiFePO4/C cathode material

    NASA Astrophysics Data System (ADS)

    Peng, Wenxiu; Jiao, Lifang; Gao, Haiyan; Qi, Zhan; Wang, Qinghong; Du, Hongmei; Si, Yuchang; Wang, Yijing; Yuan, Huatang

    2011-03-01

    Carbon coated LiFePO4/C cathode material is synthesized with a novel sol-gel method, using cheap FePO4·2H2O as both iron and phosphorus sources and oxalic acid (H2C2O4·2H2O) as both complexant and reductant. In H2C2O4 solution, FePO4·2H2O is very simple to form transparent sols without controlling the pH value. Pure submicrometer structured LiFePO4 crystal is obtained with a particle size ranging from 100 to 500 nm, which is also uniformly coated with a carbon layer, about 2.6 nm in thickness. The as-synthesized LiFePO4/C sample exhibits high initial discharge capacity 160.5 mAh g-1 at 0.1 C rate, with a capacity retention of 98.7% after 50th cycle. The material also shows good high-rate discharge performances, about 106 mAh g-1 at 10 C rate. The improved electrochemical properties of as-synthesized LiFePO4/C are ascribed to its submicrometer scale particles and low electrochemical impedance. The sol-gel method may be of great interest in the practical application of LiFePO4/C cathode material.

  7. Understanding the thermal and mechanical stabilities of olivine-type LiMPO4 (M = Fe, Mn) as cathode materials for rechargeable lithium batteries from first principles.

    PubMed

    Xie, Ying; Yu, Hai-Tao; Yi, Ting-Feng; Zhu, Yan-Rong

    2014-03-26

    To elucidate the microscopic origin of the difference behaviors, first-principles calculations were performed to investigate the thermal and mechanical stabilities of LixFePO4 and LixMnPO4. The calculated free energies suggested that LiFePO4 and LiMnPO4 are thermal stable with respect to relevant oxides both in their pristine and fully delithiated states. According to the calculations, it can be identified that the shear deformations are more easier to occur with respect to the volume compressions in LixFePO4 and LixMnPO4, and this phenomenon is related to M-O(I) and M-O(II) bonds. Typically for MnPO4, Li(+) extraction from the host structures further weakens the Mn-O(I) bonds by about 33%, and it thus becomes very brittle. The shear anisotropy (AG) of MnPO4 is abnormally large and has already reached 19.05 %, which is about 6 times as large as that of FePO4. Therefore, shear deformations and dislocations occur easily in MnPO4. Moreover, as the Mn-O(I) bonds in MnPO4 are mainly spread within the {101} and {1?01} crystal planes, the relevant slip systems thus allow the recombination of bonds at the interfaces, leading to the experimentally observed phase transformation. It can be concluded that mechanical reason will play an important role for the poor cycling performance of MnPO4. PMID:24588772

  8. Electronic structure of phospho-olivines LixFePO4 (x=0,1) fromsoft-x-ray-absorption and -emission spectroscopies

    SciTech Connect

    Augustsson, A.; Zhuang, G.V.; Butorin, S.M.; Osorio-Guillen,J.M.; Dong, C.L.; Ahuja, R.; Chang, C.L.; Ross, P.N.; Nordgren, J.; Guo,J.-H.

    2005-07-17

    The electronic structure of the phospho-olivine LixFePO4 wasstudied using soft-x-ray-absorption (XAS) and emission spectroscopies.Characteristic changes in the valence and conduction bands are observedupon delithation of LiFePO4 into FePO4. In LiFePO4, the Fe-3d states arelocalized with little overlap with the O-2p states. Delithiation ofLiFePO4 gives stronger hybridization between Fe-3d states and O-2p statesleading to delocalization of the O-2p states. The Fe L-edge absorptionspectra yield "fingerprints" of the different valence states of Fe inLiFePO4 and FePO4. Resonant soft-x-ray-emission spectroscopy at the Fe Ledge shows strong contributions from resonant inelastic soft x-rayscattering (RIXS), which is described using an ionic picture of the Fe-3dstates. Together the Fe L-edge XAS and RIXS study reveals a bondingcharacter of the Fe 3d-O2p orbitals in FePO4 in contrast to a nonbondingcharacter in LiFePO4.

  9. Olivines and olivine coronas in mesosiderites

    NASA Technical Reports Server (NTRS)

    Nehru, C. E.; Zucker, S. M.; Harlow, G. E.; Prinz, M.

    1980-01-01

    The paper presents a study of olivines and their surrounding coronas in mesosiderites texturally and compositionally using optical and microprobe methods. Olivine composition ranges from Fo(58-92) and shows no consistent pattern of distribution within and between mesosiderites; olivine occurs as large single crystals or as partially recrystallized mineral clasts, except for two lithic clasts. These are Emery and Vaca Muerta, and both are shock-modified olivine orthopyroxenites. Fine-grained coronas surround olivine, except for those in impact-melt group mesosiderites and those without tridymite in their matrices. Coronas consist largely of orthopyroxene, plagioclase, clinopyroxene, chromite, merillite, and ilmenite, and are similar to the matrix, but lack metal and tridymite. Texturally the innermost parts of the corona can be divided into three stages of development: (1) radiating acicular, (2) intermediate, and (3) granular.

  10. A method for state-of-charge estimation of LiFePO4 batteries at dynamic currents and temperatures using particle filter

    NASA Astrophysics Data System (ADS)

    Wang, Yujie; Zhang, Chenbin; Chen, Zonghai

    2015-04-01

    The state-of-charge (SOC) estimation for LiFePO4 batteries is one of the most important issues in battery management system (BMS) on electric vehicles (EVs). Significant temperature changes and drift current noises are inevitable in EVs and cause strong interference in SOC estimation, therefore a SOC-Particle filter (PF) estimator is proposed for SOC estimation. This paper tries to make three contributions: (1) a temperature composed battery model is established based on commercial LiFePO4 cells which can be used for SOC estimation at dynamic temperatures. (2) A capacity retention ratio (CRR) aging model is established based on the real history statistical analysis of the running mileage of the battery on an urban bus. (3) The proposed models are combined with an electrochemical model and the PF method is employed for SOC estimation to eliminate the drift noise effects. Experiments under dynamic current and temperature conditions are designed and performed to verify the accuracy and robustness of the proposed method. The numeral results of the validation experiments have verified that accurate and robust SOC estimation results can be obtained by the proposed method.

  11. Irreversible phase transition between LiFePO4 and FePO4 during high-rate charge-discharge reaction by operando X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Takahashi, Ikuma; Mori, Takuya; Yoshinari, Takahiro; Orikasa, Yuki; Koyama, Yukinori; Murayama, Haruno; Fukuda, Katsutoshi; Hatano, Masaharu; Arai, Hajime; Uchimoto, Yoshiharu; Terai, Takayuki

    2016-03-01

    LiFePO4 is a practically used cathode material for lithium-ion batteries due to a high theoretical capacity, high cycle capability and the high-rate performance. The metastable LixFePO4 (LxFP) phase with an intermediate composition appears in the non-equilibrium state at high-rate condition. However, the formation process of the metastable LxFP phase and its impact to the electrochemical property are still unclear. In order to elucidate these points, we directly observed the phase transition behavior by applying operando XRD during 10C charge-discharge. LxFP phase does not form in charge reaction but preferentially forms in discharge reaction. The phase transition from LxFP to Li-rich phase is less likely to proceed in the end of discharge reaction. The asymmetric phase transition between LiFePO4 and FePO4 results in decreasing the discharge capacity and increasing the irreversible capacity at high-rate conditions.

  12. Direct Observation of Active Material Concentration Gradients and Crystallinity Breakdown in LiFePO4 Electrodes During Charge/Discharge Cycling of Lithium Batteries

    PubMed Central

    2014-01-01

    The phase changes that occur during discharge of an electrode comprised of LiFePO4, carbon, and PTFE binder have been studied in lithium half cells by using X-ray diffraction measurements in reflection geometry. Differences in the state of charge between the front and the back of LiFePO4 electrodes have been visualized. By modifying the X-ray incident angle the depth of penetration of the X-ray beam into the electrode was altered, allowing for the examination of any concentration gradients that were present within the electrode. At high rates of discharge the electrode side facing the current collector underwent limited lithium insertion while the electrode as a whole underwent greater than 50% of discharge. This behavior is consistent with depletion at high rate of the lithium content of the electrolyte contained in the electrode pores. Increases in the diffraction peak widths indicated a breakdown of crystallinity within the active material during cycling even during the relatively short duration of these experiments, which can also be linked to cycling at high rate. PMID:24790684

  13. Insights in the electronic structure and redox reaction energy in LiFePO4 battery material from an accurate Tran-Blaha modified Becke Johnson potential

    NASA Astrophysics Data System (ADS)

    B. Araujo, Rafael; S. de Almeida, J.; Ferreira da Silva, A.; Ahuja, Rajeev

    2015-09-01

    The main goals of this paper are to investigate the accuracy of the Tran-Blaha modified Becke Johnson (TB-mBJ) potential to predict the electronic structure of lithium iron phosphate and the related redox reaction energy with the lithium deintercalation process. The computed electronic structures show that the TB-mBJ method is able to partially localize Fe-3d electrons in LiFePO4 and FePO4 which usually is a problem for the generalized gradient approximation (GGA) due to the self interaction error. The energy band gap is also improved by the TB-mBJ calculations in comparison with the GGA results. It turned out, however, that the redox reaction energy evaluated by the TB-mBJ technique is not in good agreement with the measured one. It is speculated that this disagreement in the computed redox energy and the experimental value is due to the lack of a formal expression to evaluate the exchange and correlation energy. Therefore, the TB-mBJ is an efficient method to improve the prediction of the electronic structures coming form the standard GGA functional in LiFePO4 and FePO4. However, it does not appear to have the same efficiency for evaluating the redox reaction energies for the investigated system.

  14. Particle shapes and surface structures of olivine NaFePO? in comparison to LiFePO?.

    PubMed

    Whiteside, Alexander; Fisher, Craig A J; Parker, Stephen C; Islam, M Saiful

    2014-10-21

    The expansion of batteries into electric vehicle and grid storage applications has driven the development of new battery materials and chemistries, such as olivine phosphate cathodes and sodium-ion batteries. Here we present atomistic simulations of the surfaces of olivine-structured NaFePO4 as a sodium-ion battery cathode, and discuss differences in its morphology compared to the lithium analogue LiFePO4. The calculated equilibrium morphology is mostly isometric in appearance, with (010), (201) and (011) faces dominant. Exposure of the (010) surface is vital because it is normal to the one-dimensional ion-conduction pathway. Platelet and cube-like shapes observed by previous microscopy studies are reproduced by adjusting surface energies. The results indicate that a variety of (nano)particle morphologies can be achieved by tuning surface stabilities, which depend on synthesis methods and solvent conditions, and will be important in optimising electrochemical performance. PMID:25200320

  15. Mixed Salts of LiTFSI and LiBOB for Stable LiFePO4-Based Batteries at Elevated Temperatures

    SciTech Connect

    Chen, Xilin; Xu, Wu; Engelhard, Mark H.; Zheng, Jianming; Zhang, Yaohui; Ding, Fei; Qian, Jiangfeng; Zhang, Jiguang

    2014-01-13

    To achieve stable long-term cycling stability at elevated temperatures, mixed salts of LiTFSI and LiBOB are used to replace LiPF6 salt in non-aqueous electrolytes for LiFePO4-based batteries. It is found that adding LiBOB in LiTFSI-based electrolytes effectively prevents the severe corrosion to Al current collectors that often is observed in LiTFSI-based electrolytes, which have high thermal stability. The cells using LiTFSI-LiBOB-based electrolytes demonstrate superior high temperature (60 ?C) stability and very similar room temperature performance (i.e., cycling stability and rate capability) when compared to cells using the LiPF6-based electrolyte.

  16. Pilot-scale continuous synthesis of a vanadium-doped LiFePO4/C nanocomposite high-rate cathodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Johnson, Ian D.; Lübke, Mechthild; Wu, On Ying; Makwana, Neel M.; Smales, Glen J.; Islam, Husn U.; Dedigama, Rashmi Y.; Gruar, Robert I.; Tighe, Christopher J.; Scanlon, David O.; Corà, Furio; Brett, Dan J. L.; Shearing, Paul R.; Darr, Jawwad A.

    2016-01-01

    A high performance vanadium-doped LiFePO4 (LFP) electrode is synthesized using a continuous hydrothermal method at a production rate of 6 kg per day. The supercritical water reagent rapidly generates core/shell nanoparticles with a thin, continuous carbon coating on the surface of LFP, which aids electron transport dynamics across the particle surface. Vanadium dopant concentration has a profound effect on the performance of LFP, where the composition LiFe0.95V0.05PO4, achieves a specific discharge capacity which is among the highest in the comparable literature (119 mA h g-1 at a discharge rate of 1500 mA g-1). Additionally, a combination of X-ray absorption spectroscopy analysis and hybrid-exchange density functional theory, suggest that vanadium ions replace both phosphorous and iron in the structure, thereby facilitating Li+ diffusion due to Li+ vacancy generation and changes in the crystal structure.

  17. Nanosized LiFePO4-decorated emulsion-templated carbon foam for 3D micro batteries: a study of structure and electrochemical performance

    NASA Astrophysics Data System (ADS)

    Asfaw, Habtom D.; Roberts, Matthew R.; Tai, Cheuk-Wai; Younesi, Reza; Valvo, Mario; Nyholm, Leif; Edström, Kristina

    2014-07-01

    In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium.In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01682c

  18. Effects of vanadium substitution on the cycling performance of olivine cathode materials

    NASA Astrophysics Data System (ADS)

    Chen, Mao-Sung; Wu, She-huang; Pang, Wei Kong

    2013-11-01

    V-substituted LiFePO4 (LiFe1-xVxPO4, 0 ≤ x ≤ 0.10) powders are prepared via a solution method. The compositions, crystalline structure, morphology of the prepared powders are systemically investigated with inductive couple plasma-option emission spectrometry (ICP-OES), synchrotron radiation X-ray diffraction (s-XRD), X-ray Absorption Spectroscopy (XAS) and field emission-transmission electron microscopy (FE-TEM). Results of s-XRD and Rietveld analysis reveal that olivine phase is observed exclusively for LiFe1-xVxPO4 (x ≤ 0.05) samples, whereas a minor amount of monoclinic Li3V2(PO4)3 is detected in the prepared LiFe0.93V0.07PO4 and LiFe0.90V0.10PO4 samples. It is also found that the lattice parameters of olivine structure and average Li-O and M-O (M = Fe or V) bond lengths slightly increase and decrease with the amount of V substitution, recommending an enhanced lithium diffusivity in the structure. Results of XAS study suggest that V ions occupy octahedral sites (4c) of Fe in LiFePO4 structure with valence of 3+, showing good agreement with shortened M-O bonds determined in Rietveld analysis. As a result of V substitution, LiFe1-xVxPO4, (0 ≤ x ≤ 0.10) cathodes exhibit better electrochemical performance, such as discharge capacity, rate capability, and cycling performance at both room and elevated temperatures.

  19. Olivine-rich asteroids, pallasitic olivine and olivine-metal mixtures: Comparisons of reflectance spectra

    NASA Technical Reports Server (NTRS)

    Cloutis, E. A.

    1993-01-01

    The recent acquisition of high resolution 0.3 - 2.6 micron reflectance spectra for a number of olivine-rich asteroids permits the analysis of their surface compositions to be made on the basis of new and existing laboratory spectral data for pallasitic olivines and olivine-metal mixtures. Analysis of the spectral data for the latter has revealed a number of spectral parameters which can be used to constrain olivine and metal abundances, grain sizes, and olivine compositions. The following topics are discussed in greater detail: pallasite olivine spectra, olivine-metal mixture spectra, and olivine-rich asteroid spectra.

  20. Titanium diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Cherniak, Daniele J.; Liang, Yan

    2014-12-01

    Diffusion of Ti has been characterized in natural olivine and synthetic forsterite. Experiments on the natural olivines were run under buffered conditions (IW and NNO), and those on synthetic forsterite were run in air. Titanium diffusion appears relatively insensitive to crystallographic orientation and oxygen fugacity under the range of investigated conditions, and diffusivities are similar for Fe-bearing olivine and forsterite. For Ti diffusion in synthetic forsterite, we obtain the following Arrhenius relation for diffusion over the temperature range 900-1400 °C:

  1. Real-time investigation on the influences of vanadium additives to the structural and chemical state evolutions of LiFePO4 for enhancing the electrochemical performance of lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Hu, Chih-Wei; Chen, Tsan-Yao; Shih, Kai-Sheng; Wu, Pin-Jiun; Su, Hui-Chia; Chiang, Ching-Yu; Huang, An-Feng; Hsieh, Han-Wei; Chang, Chia-Chin; Shew, Bor-Yuan; Lee, Chih-Hao

    2014-12-01

    The influences of adding vanadium to the structure evolution and electrochemical performance of LiFePO4 are systematically investigated by in-situ X-ray powder diffraction and X-ray absorption near edge structure spectroscopy. The results indicate that the addition of a small amount of vanadium (less than at 1%) significantly reduces the formation of non-crystalline (highly disordered) triphylite and remnant heterosite phases in the cathode of battery especially at the rate capability higher than 0.5C. The cycle stability of LiFePO4 cathode with vanadium additive after 80 cycles is improved by 14.9% compared to that without vanadium additive. Such an enhancement could be attributed to the ion diffusion kinetics being improved and inactive triphylite being reduced by the supervalent-vanadium additive in cathode during electrochemical redox cycles.

  2. Electrode Lithiation: Effects of Particle Size, Electronic Connectivity, and Incoherent Nanoscale Domains on the Sequence of Lithiation in LiFePO4 Porous Electrodes (Adv. Mater. 42/2015).

    PubMed

    Li, Yiyang; Meyer, Sophie; Lim, Jongwoo; Lee, Sang Chul; Gent, William E; Marchesini, Stefano; Krishnan, Harinarayan; Tyliszczak, Tolek; Shapiro, David; Kilcoyne, Arthur L David; Chueh, William C

    2015-11-01

    On page 6591, W. Chueh and co-workers use high-resolution X-ray microscopy to study the sequence of lithiation in LiFePO4 battery electrodes and reveal that local electronic connectivity limits the rate capability. For electrodes with homogeneous interparticle electronic connectivity via the carbon black network, the smaller particles lithiate first. For electrodes with heterogeneous connectivity, the better-connected particles preferentially lithiate. PMID:26545179

  3. Entropy change effects on the thermal behavior of a LiFePO4/graphite lithium-ion cell at different states of charge

    NASA Astrophysics Data System (ADS)

    Jalkanen, K.; Aho, T.; Vuorilehto, K.

    2013-12-01

    The enthalpy and entropy changes in a commercial lithium-ion cell were studied by using potentiometric measurements. The experiments were done on the full cell and individually on its electrode materials, LiFePO4 and artificial graphite. The graphite electrode entropy change follows the amount of intercalated lithium, whereas the LFP electrode entropy change is independent of the lithium content. The full cell entropy change behavior can be concluded to originate from the graphite electrode. For the states of charge between 30 and 75%, the full cell entropy change is positive in the discharge direction, causing the cell to absorb heat. Thus when low discharge currents are used, this entropy effect dominates over the irreversible, heat producing losses, and as a result the cell cools down. In the charge direction the entropy change has the same absolute value but is negative in sign. Because of this, the cell produces extra heat in addition to the irreversible heat production, and thus warms up. These phenomena were confirmed in a calorimetric experiment. The thermal behavior results can be utilized in designing the battery pack cooling system and in choosing favorable states of charge for the battery cycling.

  4. Effects of Laser Energy and Wavelength on the Analysis of LiFePO4 Using Laser Assisted Atom Probe Tomography

    SciTech Connect

    Santhanagopalan, Dhamodaran; Schreiber, Daniel K.; Perea, Daniel E.; Martens, Rich; Janssen, Yuri; Kalifah, Peter; Meng, Ying S.

    2015-01-21

    The effects of laser wavelength (355 nm and 532 nm) and laser pulse energy on the quantitative accuracy of atom probe tomography (APT) examinations of LiFePO4 (LFP) are considered. A systematic investigation of ultraviolet (UV, 355 nm) and green (532 nm) laser assisted APT of LFP has revealed distinctly different behaviors. With the use of UV laser the major issue was identified as the preferential loss of oxygen (up to 10 at. %) while other elements (Li, Fe and P) were observed to be close to nominal ratios. Lowering the laser energy per pulse to 1 pJ increased the observed oxygen concentration to near its correct stoichiometry and was well correlated with systematically higher concentrations of 16O2+ ions. This observation supports the premise that lower laser energies lead to a higher probability of oxygen molecule ionization. Conversely, at higher laser energies the resultant lower effective electric field reduces the probability of oxygen molecule ionization. Green laser assisted field evaporation led to the selective loss of Li (~50% deficiency) and correct ratios of the remaining elements, including the oxygen concentration. The loss of Li is explained by selective dc evaporation of lithium between laser pulses and relatively negligible oxygen loss as neutrals during green-laser pulsing. Lastly, plotting of multihit events on a Saxey plot for the straight-flight path data (green laser only) revealed a surprising dynamic recombination process for some molecular ions mid-flight.

  5. On the complex ageing characteristics of high-power LiFePO4/graphite battery cells cycled with high charge and discharge currents

    NASA Astrophysics Data System (ADS)

    Groot, Jens; Swierczynski, Maciej; Stan, Ana Irina; Kær, Søren Knudsen

    2015-07-01

    Li-ion batteries are known to undergo complex ageing processes, where the operating conditions have a profound and non-linear effect on both calendar life and cycle life. This is especially a challenge for the automotive industry, where the requirements on product lifetime and reliability are demanding. The aim of the present work is to quantify the ageing in terms of capacity fade and impedance growth as a function of operating conditions typical to high-power automotive applications; high charge and discharge rate, elevated temperatures and wide state-of-charge windows. The cycle life of 34 power-optimised LiFePO4/graphite cells was quantified by testing with charge and discharge rates between 1 and 4C-rate, temperatures between +23 °C and +53 °C, and a depth-of-discharge of either 100% or 60%. Although all cells show similar ageing pattern in general, the cycle life and the impedance growth is remarkably different for the tested cases. In addition, it is concluded that high charging rates, high temperatures or intensive cycling do not always lead to a shorter cycle life. One specifically interesting finding is that the combination of 1C-rate discharge in combination with 3.75C-rate charging was found to degrade the tested cells more rapidly than a symmetric cycle with 3.75C-rate in both directions.

  6. Thermal modeling of large prismatic LiFePO4/graphite battery. Coupled thermal and heat generation models for characterization and simulation

    NASA Astrophysics Data System (ADS)

    Damay, Nicolas; Forgez, Christophe; Bichat, Marie-Pierre; Friedrich, Guy

    2015-06-01

    This paper deals with the thermal modeling of a large prismatic Li-ion battery (LiFePO4/graphite). A lumped model representing the main thermal phenomena in the cell, in and outside the casing, is hereby proposed. Most of the parameters are determined analytically using physical and geometrical properties. The heat capacity, the internal and the interfacial thermal resistances between the battery and its cooling system are experimentally identified. On the other hand, the heat sources modeling is considered to be one of the most difficult task. In order to overcome this problem, a heat generation model is included. More specifically, the electrical losses are computed thanks to an electrical model which is represented by an equivalent electric circuit. A method is also proposed for parameter determination which is based on a quasi-steady state assumption. It also takes into account the battery heating during characterization which is the temperature variation due to heat generation during current pulses. This temperature variation is estimated thanks to the coupled thermal and heat generation models. The electrical parameters are determined as function of state of charge (SoC), temperature and current. Finally, the proposed coupled models are experimentally validated with a precision of 1 C.

  7. Conformal Coating Strategy Comprising N-doped Carbon and Conventional Graphene for Achieving Ultrahigh Power and Cyclability of LiFePO4.

    PubMed

    Zhang, Kan; Lee, Jeong-Taik; Li, Ping; Kang, Byoungwoo; Kim, Jung Hyun; Yi, Gi-Ra; Park, Jong Hyeok

    2015-10-14

    Surface carbon coating to improve the inherent poor electrical conductivity of lithium iron phosphate (LiFePO4, LFP) has been considered as most efficient strategy. Here, we also report one of the conventional methods for LFP but exhibiting a specific capacity beyond the theoretical value, ultrahigh rate performance, and excellent long-term cyclability: the specific capacity is 171.9 mAh/g (70 ?m-thick electrode with ?10 mg/cm(2) loading mass) at 0.1 C (17 mA/g) and retains 143.7 mAh/g at 10 C (1.7 A/g) and 95.8% of initial capacity at 10 C after 1000 cycles. It was found that the interior conformal N-C coating enhances the intrinsic conductivity of LFP nanorods (LFP NR) and the exterior reduced graphene oxide coating acts as an electrically conducting secondary network to electrically connect the entire electrode. The great electron transport mutually promoted with shorten Li diffusion length on (010) facet exposed LFP NR represents the highest specific capacity value recorded to date at 10 C and ultralong-term cyclability. This conformal carbon coating approach can be a promising strategy for the commercialization of LFP cathode in lithium ion batteries. PMID:26389552

  8. Non-uniform aging of cycled commercial LiFePO4//graphite cylindrical cells revealed by post-mortem analysis

    NASA Astrophysics Data System (ADS)

    Klett, Matilda; Eriksson, Rickard; Groot, Jens; Svens, Pontus; Ciosek Hgstrm, Katarzyna; Lindstrm, Rakel Wreland; Berg, Helena; Gustafson, Torbjrn; Lindbergh, Gran; Edstrm, Kristina

    2014-07-01

    Aging of power-optimized commercial 2.3 Ah cylindrical LiFePO4//graphite cells to be used in hybrid electric vehicle is investigated and compared for three different aging procedures; (i) using a simulated hybrid electric vehicle cycle within a narrow SOC-range, (ii) using a constant-current cycle over a 100% SOC-range, and (iii) stored during three years at 22 C. Postmortem analysis of the cells is performed after full-cell electrochemical characterization and discharge. EIS and capacity measurements are made on different parts of the disassembled cells. Material characterization includes SEM, EDX, HAXPES/XPS and XRD. The most remarkable result is that both cycled cells displayed highly uneven aging primarily of the graphite electrodes, showing large differences between the central parts of the jellyroll compared to the outer parts. The aging variations are identified as differences in capacity and impedance of the graphite electrode, associated with different SEI characteristics. Loss of cyclable lithium is mirrored by a varying degree of lithiation in the positive electrode and electrode slippage. The spatial variation in negative electrode degradation and utilization observed is most likely connected to gradients in temperature and pressure, that can give rise to current density and potential distributions within the jellyroll during cycling.

  9. Experiment and simulation of a LiFePO4 battery pack with a passive thermal management system using composite phase change material and graphite sheets

    NASA Astrophysics Data System (ADS)

    Lin, Chunjing; Xu, Sichuan; Chang, Guofeng; Liu, Jinling

    2015-02-01

    A passive thermal management system (TMS) for LiFePO4 battery modules using phase change material (PCM) as the heat dissipation source to control battery temperature rise is developed. Expanded graphite matrix and graphite sheets are applied to compensate low thermal conductivity of PCM and improve temperature uniformity of the batteries. Constant current discharge and mixed charge-discharge duties were applied on battery modules with and without PCM on a battery thermal characteristics test platform. Experimental results show that PCM cooling significantly reduces the battery temperature rise during short-time intense use. It is also found that temperature uniformity across the module deteriorates with the increasing of both discharge time and current rates. The maximum temperature differences at the end of 1C and 2C-rate discharges are both less than 5 C, indicating a good performance in battery thermal uniformity of the passive TMS. Experiments on warm-keeping performance show that the passive TMS can effectively keep the battery within its optimum operating temperature for a long time during cold weather uses. A three dimensional numerical model of the battery pack with the passive TMS was conducted using ANSYS Fluent. Temperature profiles with respect to discharging time reveal that simulation shows good agreement with experiment at 1C-discharge rate.

  10. Determination of the Lamb-Mssbauer factors of LiFePO 4 and FePO 4 for electrochemical in situ and operando measurements in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Aldon, L.; Perea, A.; Womes, M.; Ionica-Bousquet, C. M.; Jumas, J.-C.

    2010-01-01

    57Fe Mssbauer spectroscopy is a powerful tool to investigate redox reactions during in electrochemical lithium insertion/extraction processes. Electrochemical oxidation of LiFe IIPO 4 (triphylite) in Li-ion batteries results in Fe IIIPO 4 (heterosite). LiFePO 4 was synthesized by solid state reaction at 800 C under Ar flow from Li 2CO 3, FeC 2O 42H 2O and NH 4H 2PO 4 precursors in stoichiometric composition. FePO 4 was prepared from chemical oxidation of LiFePO 4 using bromine as oxidative agent. For both materials a complete 57Fe Mssbauer study as a function of the temperature has been carried out. The Debye temperatures are found to be ?M=336 K for LiFePO 4 and ?M=359 K for FePO 4, leading to Lamb-Mssbauer factors f300 K =0.73 and 0.77, respectively. These data will be useful for a precise estimation of the relative amounts of each species in a mixture.

  11. Surface-orientation-dependent distribution of subsurface cation-exchange defects in olivine-phosphate nanocrystals.

    PubMed

    Chung, Sung-Yoon; Choi, Si-Young; Kim, Tae-Hwan; Lee, Seongsu

    2015-01-27

    Atomic-scale exchange between two different cations of similar size in crystalline oxides is one of the major types of point defects when multiple cations in oxygen interstitials are arrayed in an ordered manner. Although a number of studies have been performed on a variety of Li-intercalation olivine phosphates to determine the distribution of exchange defects in bulk, understanding of the thermodynamic stability of the defects in subsurface regions and its dependency on the crystallographic orientation at the surface has remained elusive. Through a combination of small-angle neutron scattering, atomic-scale direct probing with scanning transmission electron microscopy, and theoretical ab initio calculations, we directly demonstrate that the antisite exchange defects are distributed in a highly anisotropic manner near the surfaces of LiFePO4 crystals. Moreover, a substantial amount of cation exchanges between Li and Fe sites is identified as an energetically favorable configuration in some surface regions, showing excellent agreement with the calculation results of negative defect formation energies. The findings in this study provide insight into developing better ways to avoid degradation of lithium mobility through the surface as well as scientifically notable features regarding the distribution of exchange defects in olivine phosphates. PMID:25565086

  12. Rapid Microwave-Assisted Solvothermal Synthesis of Non-Olivine Cmcm Polymorphs of LiMPO4 (M = Mn, Fe, Co, and Ni) at Low Temperature and Pressure.

    PubMed

    Assat, Gaurav; Manthiram, Arumugam

    2015-10-19

    Lithium transition-metal phosphates, LiMPO4 (M = Mn, Fe, Co, and Ni), have attracted significant research interest over the past two decades as an important class of lithium ion battery cathode materials. However, almost all of the investigations thus far have focused on the olivine polymorph that exists in the orthorhombic Pnma space group. In this study, a distinct orthorhombic but non-olivine polymorph of LiMPO4, described by a Cmcm space group symmetry, has been synthesized with M = Mn, Fe, Co, and Ni. Of these, LiMnPO4 in the Cmcm space group is reported for the first time. A rapid microwave-assisted solvothermal (MW-ST) heating process with tetraethylene glycol (TEG) as the solvent and transition-metal oxalates as precursors facilitates the synthesis of these materials. The peak reaction temperatures and pressures were below 300 C and 30 bar, respectively, which are several orders of magnitude lower than those of the previously reported high-pressure (gigapascals) method. X-ray diffraction (XRD) confirms the crystal structure with the Cmcm space group, and scanning electron micrographs indicate a submicrometer thin platelet-like morphology. The synthesis process conditions have been optimized to obtain impurity-free samples with the correct stoichiometry, as characterized by XRD and inductively coupled plasma-optical emission spectroscopy (ICP-OES). Upon heat treatment to higher temperatures, an irreversible transformation of the metastable Cmcm polymorphs into olivine is observed by XRD and Fourier transform infrared spectroscopy. Although the electrochemical activity of these polymorphs as lithium ion cathodes turns out to be poor, the facile synthesis under mild conditions has permitted easy access to these materials in a nanomorphology, some of which were not even possible before. PMID:26428928

  13. Exogenous Olivine on Vesta

    NASA Astrophysics Data System (ADS)

    Hoffmann, Martin; Nathues, Andreas; Schäfer, Michael; Thangjam, Guneshwar; Le Corre, Lucille; Vishnu, Reddy; Christensen, Ulrich; Mengel, Kurt; Sierks, Holger; Vincent, Jean-Baptist; Cloutis, Edward A.; Russell, Christopher T.; Schäfer, Tanja; Gutierrez-Marques, Pablo; Hall, Ian; Ripken, Joachim; Büttner, Irene

    2014-11-01

    Vesta has conserved an early status of planetary evolution, demonstrated by the global coverage of HED lithology on its surface. Being sufficiently large to retain some material from slow projectiles, but small enough to prevent its complete evaporation during the impacts, this unique environment is ideal for distinction and identification of exogenous material. In particular, the distribution, concentration, and geological context of olivine exposures are poorly consistent with a Vestan mantle origin. Similar arguments are valid for the areas of dark carbonaceous chondrite-like lithology, and a few other features with unusual visual spectral slopes. Most olivine is found close to the large impact craters Bellicia, Arruntia, and Pomponia in the northern hemisphere, whose ejecta sheet is characterized by a mixing trend from an HED lithology to S- or A-type asteroid material. The olivine has diagnostic significance for the extent and duration of differentiation during the early accretion of parent bodies in the asteroid region. Sources for exogenous olivine are available in Vesta’s environment among A- and S-type asteroids. It is not clear, however, if it is derived mainly from achondritic or chondritic sources. On the other hand, the lack of evidence for Vesta’s mantle material implies constraints on its inner structure, e.g. the depth of the crust.

  14. Microbial Weathering of Olivine

    NASA Technical Reports Server (NTRS)

    McKay, D. S.; Longazo, T. G.; Wentworth, S. J.; Southam, G.

    2002-01-01

    Controlled microbial weathering of olivine experiments displays a unique style of nanoetching caused by biofilm attachment to mineral surfaces. We are investigating whether the morphology of biotic nanoetching can be used as a biosignature. Additional information is contained in the original extended abstract.

  15. "Black-colored olivines" in peridotites: dehydrogenation from hydrous olivines

    NASA Astrophysics Data System (ADS)

    Arai, Shoji; Hoshikawa, Chihiro; Miura, Makoto

    2015-04-01

    Fresh olivines that are black to the naked eye are found in some dunites. Peridotites are easily converted to be black in color, when serpentinized, due to production of secondary fine magnetite particles. The dunites that contain fresh but black-colored olivines are usually coarse-grained. These coarse olivine grains are sometimes very heterogeneous in color; the blackish part grades to whitish parts in single grains. The black color is due to homegeneous distribution of minute (< 10 microns) black particles in olivine. They are rod-like or plate-like in shape in thin section, sometimes being aligned under crystallographic control of the host olivine. Olivines are clear and free of these inclusions around primary chromian spinel inclusions or chromian spinel lamellae (Arai, 1978). Raman spectroscopy indicates the minute black particles are magnetite always associated with diopside. It is interesting to note that olivine in mantle peridotites accompanied by the black-colored dunites is totally free of the black inclusions, giving the ordinary colors (pale yellow to whitish) of Mg-rich olivine. It is not likely that the magnetite inclusions formed through secondary oxidation of olivine by invasion of oxygen, which is possible along cracks or grain boundaries. They most probably formed due to dehydrogenation from primary OH-bearing olivines upon cooling. Hydrogen was quickly diffused out from the olivines to leave magnetite and excess silica. The excess silica was possibly combined with a monticellite component to form diopside. The OH-bearing (hydrous) olivines can be precipitated from hydrous magmas, and the hydrous nature of the magma can promote an increase in grain size due to faster diffusion of elements. The minute inclusions of magnetite + diopside is thus an indicator of primary hydrous character of host olivine.

  16. Unfired olivine bricks for TES

    NASA Astrophysics Data System (ADS)

    Whittemore, O. J.

    1982-12-01

    Olivine is particularly useful for TES because of its low cost, high heat storage capacity, no crystallographic inversions, and refractoriness. Olivine TES brick are being produced by adding small amounts of clay, compacting into bricks and firing at 1200 C or higher. An olivine composition which could be compacted into dense bricks, and simply dried or cured at low temperatures to obviate the expensive firing process was developed.

  17. Nano-network electronic conduction in iron and nickel olivine phosphates

    NASA Astrophysics Data System (ADS)

    Herle, P. Subramanya; Ellis, B.; Coombs, N.; Nazar, L. F.

    2004-03-01

    The provision of efficient electron and ion transport is a critical issue in an exciting new group of materials based on lithium metal phosphates that are important as cathodes for lithium-ion batteries. Much interest centres on olivine-type LiFePO4, the most prominent member of this family. Whereas the one-dimensional lithium-ion mobility in this framework is high, the electronically insulating phosphate groups that benefit the voltage also isolate the redox centres within the lattice. The pristine compound is a very poor conductor (? ~ 10-9 S cm-1), thus limiting its electrochemical response. One approach to overcome this is to include conductive phases, increasing its capacity to near-theoretical values. There have also been attempts to alter the inherent conductivity of the lattice by doping it with a supervalent ion. Compositions were reported to be black p-type semiconductors with conductivities of ~10-2 S cm-1 arising from minority Fe3+ hole carriers. Our results for doped (and undoped) LiMPO4 (M = Fe, Ni) show that a percolating nano-network of metal-rich phosphides are responsible for the enhanced conductivity. We believe our demonstration of non-carbonaceous-network grain-boundary conduction to be the first in these materials, and that it holds promise for other insulating phosphates.

  18. Magnetism in olivine-type LiCo(1-x)Fe(x)PO4 cathode materials: bridging theory and experiment.

    PubMed

    Singh, Vijay; Gershinsky, Yelena; Kosa, Monica; Dixit, Mudit; Zitoun, David; Major, Dan Thomas

    2015-12-14

    In the current paper, we present a non-aqueous sol-gel synthesis of olivine type LiCo1-xFexPO4 compounds (x = 0.00, 0.25, 0.50, 0.75, 1.00). The magnetic properties of the olivines are measured experimentally and calculated using first-principles theory. Specifically, the electronic and magnetic properties are studied in detail with standard density functional theory (DFT), as well as by including spin-orbit coupling (SOC), which couples the spin to the crystal structure. We find that the Co(2+) ions exhibit strong orbital moment in the pure LiCoPO4 system, which is partially quenched upon substitution of Co(2+) by Fe(2+). Interestingly, we also observe a non-negligible orbital moment on the Fe(2+) ion. We underscore that the inclusion of SOC in the calculations is essential to obtain qualitative agreement with the observed effective magnetic moments. Additionally, Wannier functions were used to understand the experimentally observed rising trend in the Nel temperature, which is directly related to the magnetic exchange interaction paths in the materials. We suggest that out of layer M-O-P-O-M magnetic interactions (J?) are present in the studied materials. The current findings shed light on important differences observed in the electrochemistry of the cathode material LiCoPO4 compared to the already mature olivine material LiFePO4. PMID:26548581

  19. A new method to synthesize olivine phosphate nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, D. H.; Kim, T. R.; Im, J. S.; Kang, J. W.; Kim, J.

    2007-12-01

    Well-crystalline LiFePO4 nanoparticles were prepared by the polyol process without post heat treatments. X-ray diffraction showed an orthorhombic phase without any discernible existence of impurities. The particles showed highly crystalline nature of rod and plate like morphologies with an average size of 300 nm. The initial discharge curve of LiFePO4 showed a capacity of 168 mAh g-1 at a 0.1 C rate in the voltage range of 2.5-4 V with good retention at high rate current densities. This amounts to a utilization efficiency of 98%, with excellent reversibility in extended cycles. LiFePO4 nano-particle showed a high capacity of 102 mAh g-1 at a high rate of 6.4 C.

  20. Studies on graphene enfolded olivine composite electrode material via polyol technique for high rate performance lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Muruganantham, Rasu; Sivakumar, Marimuthu; Subadevi, Rengapillai; Ramaprabhu, Sundara; Wu, Nae-Lih

    2015-09-01

    The graphene enfolded LiFePO4/C composite cathode material has been prepared via low temperature polyol process, followed by a simple chemical reaction method. The low viscous polyol solvent (DEG) (35.7 mPa s at 25°C) and usage of low temperature process (below 245°C) aid the graphene tightly encapsulated on the LiFePO4 surface that plays an important role, especially in the high rate performances over long cycles, efficiently preventing the separation of the graphene and LiFePO4 during the reaction processes, hence realizing the full potential of the active materials. The graphitization on LiFePO4/C remarkably increased the electronic conductivity of LiFePO4. The layered sheets of graphene wrapped on LiFePO4 particles provide void between graphene sheets and LiFePO4 surfaces, which facilitate the diffusion of Li+. This approach opens up a method to attain the theoretical capacity of LiFePO4. The material exhibits a superior electrochemical performance such as initial discharge capacities of 169.6 and 92 mAhg-1 at 0.1 and 30 C rates, respectively. It has an excellent capacity retention and diminutive capacity fading. The nanosize of LiFePO4 particle causes a shorter diffusion path, which reduces the time for Li+ migration between cathode and electrolyte. [Figure not available: see fulltext.

  1. Origin of olivine at Copernicus

    NASA Technical Reports Server (NTRS)

    Pieters, C. M.; Wilhelms, D. E.

    1985-01-01

    The central peaks of Copernicus are among the few lunar areas where near-infrared telescopic reflectance spectra indicate extensive exposures of olivine. Other parts of Copernicus crater and ejecta, which were derived from highland units in the upper parts of the target site, contain only low-Ca pyroxene as a mafic mineral. The exposure of compositionally distinct layers including the presence of extensive olivine may result from penetration to an anomalously deep layer of the crust or to the lunar mantle. It is suggested that the Procellarum basin and the younger, superposed Insularum basin have provided access to these normally deep-seated crustal or mantle materials by thinning the upper crustal material early in lunar history. The occurrences of olivine in portions of the compositionally heterogeneous Aristarchus Region, in a related geologic setting, may be due to the same sequence of early events.

  2. Origin of olivine at Copernicus

    NASA Astrophysics Data System (ADS)

    Pieters, Carle M.; Wilhelms, Don E.

    1985-02-01

    The central peaks of Copernicus are among the few lunar areas where near-infrared telescopic reflectance spectra indicate extensive exposures of olivine. Other parts of Copernicus crater and ejecta, which were derived from highland units in the upper parts Of the target site, contain only low-Ca pyroxene as a mafic mineral. The exposure of compositionally distinct layers including the presence of extensive olivine may result from penetration to an anomalously deep layer of the crust or to the lunar mantle. We suggest that the Procellarum basin and the younger, superposed Insularum basin have provided access to these normally deep-seated crustal or mantle materials by thinning the upper crustal material early in lunar history. The occurrences of olivine in portions of the compositionally heterogeneous Aristarchus Region, in a related geologic setting, may be due to the same sequence of early events.

  3. Origin of olivine at Copernicus

    NASA Astrophysics Data System (ADS)

    Pieters, C. M.; Wilhelms, D. E.

    1985-02-01

    The central peaks of Copernicus are among the few lunar areas where near-infrared telescopic reflectance spectra indicate extensive exposures of olivine. Other parts of Copernicus crater and ejecta, which were derived from highland units in the upper parts of the target site, contain only low-Ca pyroxene as a mafic mineral. The exposure of compositionally distinct layers including the presence of extensive olivine may result from penetration to an anomalously deep layer of the crust or to the lunar mantle. It is suggested that the Procellarum basin and the younger, superposed Insularum basin have provided access to these normally deep-seated crustal or mantle materials by thinning the upper crustal material early in lunar history. The occurrences of olivine in portions of the compositionally heterogeneous Aristarchus Region, in a related geologic setting, may be due to the same sequence of early events.

  4. A reduced order electrochemical and thermal model for a pouch type lithium ion polymer battery with LiNixMnyCo1-x-yO2/LiFePO4 blended cathode

    NASA Astrophysics Data System (ADS)

    Li, Xueyan; Choe, Song-Yul; Joe, Won Tae

    2015-10-01

    LiNixMnyCo1-x-yO2 (NMC) and LiFePO4 (LFP) as a cathode material have been widely employed for cells designed for high power applications. However, NMC needs further improvements in rate capability and stability that can be accomplished by blending it with LFP. Working mechanism of the blended cells is very complex and hard to understand. In addition, characteristics of the blended cells, particularly the plateau and path dependence of LFP materials, make it extremely difficult to estimate the state of charge and state of health using classical electric equivalent circuit models. Therefore, a reduced order model based on electrochemical and thermal principles is developed with objectives for real time applications and validated against experimental data collected from a large format pouch type of lithium ion polymer battery. The model for LFP is based on a shrinking core model along with moving boundary and then integrated into NMC model. Responses of the model that include SOC estimation and responses of current and voltage are compared with those of experiments at CC/CV charging and CC discharging along with different current rates and temperatures. In addition, the model is used to analyze effects of mass ratios between two materials on terminal voltage and heat generation rate.

  5. Influence of lithium vacancies on the polaronic transport in olivine phosphate structure

    NASA Astrophysics Data System (ADS)

    Murugavel, Sevi; Sharma, Monika; Shahid, Raza

    2016-01-01

    Intercalation and deintercalation of lithium ions in cathode materials are of principal to the operation of current rechargeable lithium ion batteries. The performance of lithium ion batteries highly relies on the active cathode material which includes cell potential, power/energy density, capacity, etc. An important issue in this class of material is to resolve the factors governing the electron and ion transport in olivine phosphate structure. In this class of material, there is still an open debate on the mechanism of charge transport including both polarons and lithium ions. On the one hand, this is due to the large disparity between the experimental results and the theoretical model predictions. On the other hand, this is also due to the lack of precise experimental measurement without any parasitic phases in a given cathode material. Here, we present the polaronic conduction in lithiated triphylite LiFePO4 (LFP) and delithiated heterosite FePO4 (FP) by means of broadband ac impedance spectroscopy over wide range temperatures and frequency. It is found that the LFP phase possess two orders of higher polaronic conductivity than FP phase despite having similar mobility of polarons in both phases. We show that the differences in the polaronic conductivity of two phases are due to the significant differences in concentration of polarons. It is found that the formation energy of polarons in individual phases is mainly determined by the corresponding defect state associated with it. The temperature dependent dc conductivity has been analyzed within the framework of Mott model of polaronic conduction and explored the origin of polaronic conduction mechanism in this class of material.

  6. Drastically Enhanced High-Rate Performance of Carbon-Coated LiFePO4 Nanorods Using a Green Chemical Vapor Deposition (CVD) Method for Lithium Ion Battery: A Selective Carbon Coating Process.

    PubMed

    Tian, Ruiyuan; Liu, Haiqiang; Jiang, Yi; Chen, Jiankun; Tan, Xinghua; Liu, Guangyao; Zhang, Lina; Gu, Xiaohua; Guo, Yanjun; Wang, Hanfu; Sun, Lianfeng; Chu, Weiguo

    2015-06-01

    Application of LiFePO4 (LFP) to large current power supplies is greatly hindered by its poor electrical conductivity (10(-9) S cm(-1)) and sluggish Li+ transport. Carbon coating is considered to be necessary for improving its interparticle electronic conductivity and thus electrochemical performance. Here, we proposed a novel, green, low cost and controllable CVD approach using solid glucose as carbon source which can be extended to most cathode and anode materials in need of carbon coating. Hydrothermally synthesized LFP nanorods with optimized thickness of carbon coated by this recipe are shown to have superb high-rate performance, high energy, and power densities, as well as long high-rate cycle lifetime. For 200 C (18s) charge and discharge, the discharge capacity and voltage are 89.69 mAh g(-1) and 3.030 V, respectively, and the energy and power densities are 271.80 Wh kg(-1) and 54.36 kW kg(-1), respectively. The capacity retention of 93.0%, and the energy and power density retention of 93.6% after 500 cycles at 100 C were achieved. Compared to the conventional carbon coating through direct mixing with glucose (or other organic substances) followed by annealing (DMGA), the carbon phase coated using this CVD recipe is of higher quality and better uniformity. Undoubtedly, this approach enhances significantly the electrochemical performance of high power LFP and thus broadens greatly the prospect of its applications to large current power supplies such as electric and hybrid electric vehicles. PMID:25970716

  7. Multiple origins for olivine at Copernicus crater

    NASA Astrophysics Data System (ADS)

    Dhingra, Deepak; Pieters, Carle M.; Head, James W.

    2015-06-01

    Multiple origins for olivine-bearing lithologies at Copernicus crater are recognized based on integrated analysis of data from Chandrayaan-1 Moon Mineralogy Mapper (M3), Lunar Reconnaissance Orbiter (LRO) Narrow Angle Camera (NAC) and Kaguya Terrain Camera (TC). We report the diverse morphological and spectral character of previously known olivine-bearing exposures as well as the new olivine occurrences identified in this study. Prominent albedo differences exist between olivine-bearing exposures in the central peaks and a northern wall unit (the latter being ?40% darker). The low-albedo wall unit occurs as a linear mantling deposit and is interpreted to be of impact melt origin, in contrast with the largely unmodified nature of olivine-bearing peaks. Small and localized occurrences of olivine-bearing lithology have also been identified on the impact melt-rich floor, representing a third geologic setting (apart from crater wall and peaks). Recent remote sensing missions have identified olivine-bearing exposures around lunar basins (e.g. Yamamoto et al., 2010; Pieters et al., 2011; Kramer et al., 2013) and at other craters (e.g. Sun and Li, 2014), renewing strong interest in its origin and provenance. A direct mantle exposure has commonly been suggested in this regard. Our detailed observations of the morphological and spectral diversity in the olivine-bearing exposures at Copernicus have provided critical constraints on their origin and source regions, emphasizing multiple formation mechanisms. These findings directly impact the interpretation of olivine exposures elsewhere on the Moon. Olivine can occur in diverse environments including an impact melt origin, and therefore it is unlikely for all olivine exposures to be direct mantle occurrences as has generally been suggested.

  8. The ascent of kimberlite: Insights from olivine

    NASA Astrophysics Data System (ADS)

    Brett, R. C.; Russell, J. K.; Andrews, G. D. M.; Jones, T. J.

    2015-08-01

    Olivine xenocrysts are ubiquitous in kimberlite deposits worldwide and derive from the disaggregation of mantle-derived peridotitic xenoliths. Here, we provide descriptions of textural features in xenocrystic olivine from kimberlite deposits at the Diavik Diamond Mine, Canada and at Igwisi Hills volcano, Tanzania. We establish a relative sequence of textural events recorded by olivine during magma ascent through the cratonic mantle lithosphere, including: xenolith disaggregation, decompression fracturing expressed as mineral- and fluid-inclusion-rich sealed and healed cracks, grain size and shape modification by chemical dissolution and abrasion, late-stage crystallization of overgrowths on olivine xenocrysts, and lastly, mechanical milling and rounding of the olivine cargo prior to emplacement. Ascent through the lithosphere operates as a "kimberlite factory" wherein progressive upward dyke propagation of the initial carbonatitic melt fractures the overlying mantle to entrain and disaggregate mantle xenoliths. Preferential assimilation of orthopyroxene (Opx) xenocrysts by the silica-undersaturated carbonatitic melt leads to deep-seated exsolution of CO2-rich fluid generating buoyancy and supporting rapid ascent. Concomitant dissolution of olivine produces irregular-shaped relict grains preserved as cores to most kimberlitic olivine. Multiple generations of decompression cracks in olivine provide evidence for a progression in ambient fluid compositions (e.g., from carbonatitic to silicic) during ascent. Numerical modelling predicts tensile failure of xenoliths (disaggregation) and olivine (cracks) over ascent distances of 2-7 km and 15-25 km, respectively, at velocities of 0.1 to >4 m s-1. Efficient assimilation of Opx during ascent results in a silica-enriched, olivine-saturated kimberlitic melt (i.e. SiO2 >20 wt.%) that crystallizes overgrowths on partially digested and abraded olivine xenocrysts. Olivine saturation is constrained to occur at pressures <1 GPa; an absence of decompression cracks within olivine overgrowths suggests depths <25 km. Late stage (<25 km) resurfacing and reshaping of olivine by particle-particle milling is indicative of turbulent flow conditions within a fully fluidized, gas-charged, crystal-rich magma.

  9. Experimental Study of Olivine-rich Troctolites

    NASA Astrophysics Data System (ADS)

    Mu, S.; Faul, U.

    2014-12-01

    This experimental study is designed to complement field observations of olivine-rich troctolites in ophiolites and from mid-ocean ridges. The olivine-rich troctolites are characterized by high volume proportion of olivine with interstitial plagioclase and clinopyroxene. Typically the clinopyroxene occurs in the form of few large, poikilitic grains. The primary purpose of this study is to investigate the effects of cooling process on the geometry of the interstitial phases (clinopyroxene and plagioclase). Experiments are conducted in a piston cylinder apparatus by first annealing olivine plus a basaltic melt with a composition designed to be in equilibrium with four phases at ~ 1 GPa and 1250C. Initially, we anneal the olivine-basalt aggregates at 1350 C and 0.7 GPa for one week to produce a steady state microstructure. At this temperature only olivine and minor opx are present as crystalline phases. We then cool the samples over two weeks below their solidus temperature, following different protocols. The post-run samples are sectioned, polished, and imaged at high resolution and analyzed by using a field emission SEM. Initial observations show that under certain conditions clinopyroxene nucleates distributed throughout the aggregate at many sites, forming relatively small, rounded to near euhedral grains. Under certain conditions few cpx grains nucleate and grow with a poikilitic shape, partially or fully enclosing olivine grains, as is observed in natural samples. As for partially molten aggregates quenched form the annealing temperature, the microstructure will be characterized by tracing phase boundaries on screen by using ImageJ software. The geometry of the interstitial phases will be quantified by determining the grain boundary wetness, in this case the ratio of the length of polyphase to single phase (olivine-olivine) boundaries. Compositional data will also be used to study the change in major element compositions before and after the cooling process.

  10. Olivine-dominated asteroids: Mineralogy and origin

    NASA Astrophysics Data System (ADS)

    Sanchez, Juan A.; Reddy, Vishnu; Kelley, Michael S.; Cloutis, Edward A.; Bottke, William F.; Nesvorn, David; Lucas, Michael P.; Hardersen, Paul S.; Gaffey, Michael J.; Abell, Paul A.; Corre, Lucille Le

    2014-01-01

    Olivine-dominated asteroids are a rare type of objects formed either in nebular processes or through magmatic differentiation. The analysis of meteorite samples suggest that at least 100 parent bodies in the main belt experienced partial or complete melting and differentiation before being disrupted. However, only a few olivine-dominated asteroids, representative of the mantle of disrupted differentiated bodies, are known to exist. Due to the paucity of these objects in the main belt their origin and evolution have been a matter of great debate over the years. In this work we present a detailed mineralogical analysis of twelve olivine-dominated asteroids. We have obtained near-infrared (NIR) spectra (0.7-2.4 ?m) of asteroids (246) Asporina, (289) Nenetta, (446) Aeternitas, (863) Benkoela, (4125) Lew Allen and (4490) Bamberry. Observations were conducted with the Infrared Telescope Facility (IRTF) on Mauna Kea, Hawai'i. This sample was complemented with spectra of six other olivine-dominated asteroids including (354) Eleonora, (984) Gretia, (1951) Lick, (2501) Lohja, (3819) Robinson and (5261) Eureka obtained by previous workers. Within our sample we distinguish two classes, one that we call monomineralic-olivine asteroids, which are those whose spectra only exhibit the 1 ?m feature, and another referred to as olivine-rich asteroids, whose spectra exhibit the 1 ?m feature and a weak (Band II depth 4%) 2 ?m feature. For the monomineralic-olivine asteroids the olivine chemistry was found to range from Fo49 to Fo70, consistent with the values measured for brachinites and R chondrites. In the case of the olivine-rich asteroids we determined their olivine and low-Ca pyroxene abundance using a new set of spectral calibrations derived from the analysis of R chondrites spectra. We found that the olivine abundance for these asteroids varies from 0.68 to 0.93, while the fraction of low-Ca pyroxene to total pyroxene ranges from 0.6 to 0.9. A search for dynamical connections between the olivine-dominated asteroids and asteroid families found no genetic link (of the type core-mantel-crust) between these objects.

  11. Olivine in Almahata Sitta - Curiouser and Curiouser

    NASA Technical Reports Server (NTRS)

    Zolensky, M. E.; Herrin, J.; Mikouchi, T.; Satake, W.; Kurihara, T.; Sandford, S. A.; Milam, S. N.; Hagiya, K.; Ohsumi, K.; Friedrich, J. M.; Jeniskens, P.; Shaddad, M. H.; Le, L.; Robinson, G. A.

    2010-01-01

    Almahata Sitta (hereafter Alma) is an anomalous, polymict ureilite. Anomalous features include low abundance of olivine, large compositional range of silicates, high abundance and large size of pores, crystalline pore wall linings, and overall finegrained texture. Tomography suggests the presence of foliation, which is known from other ureilites. Alma pyroxenes and their interpretation are discussed in two companion abstracts. In this abstract we discuss the composition of olivine in Alma, which is indicative of the complexity of this meteorite.

  12. An Amoeboid Olivine Aggregate in LEW 85300

    NASA Technical Reports Server (NTRS)

    Komatsu, M. D.; Yamaguchi, A.; Fagan, T. J.; Zolensky, M. E.; Shiran, N.; Mikouchi, T.

    2016-01-01

    Amoeboid Olivine aggregates (AOAs) are irregularly shaped objects commonly observed in carbonaceous chondrites. Because they are composed of fine-grained olivine and Ca-Al-rich minerals, they are sensitive indicators for nebular process and parent body alteration of their parent bodies. Recently an AOA was found in a carbonaceous clast in polymict eucrite LEW 85300. The bulk major element composition of the clast matrix in LEW 85300 suggests a relation to CM, CO and CV chondrites, whereas bulk clast trace and major element compositions do not match any carbonaceous chondrite, suggesting they have a unique origin. Here we characterize the mineralogy of AOA in LEW 85300 and discuss the origin of the carbonaceous clasts. Results and Discussion: The AOA is located in an impact melt vein. Half of the aggregate shows recrystallization textures (euhedral pyroxene and molten metal/FeS) due to impact melting, but the remaining part preserves the original texture. The AOA is composed of olivine, FeS and Mg,Al-phyllosilicate. Individual olivine grains measure 1-8 microns, with Fe-rich rims, probably due to impact heating. Olivines in the AOA are highly forsteritic (Fo95-99), indicating that the AOA escaped thermal metamorphism [4]. Although no LIME (Low-Fe, Mn-Enriched) olivine is observed, forsterite composition and the coexistence of Mg,Al-phyllosilicate suggest that the AOA is similar to those in the Bali-type oxidized CV (CVoxB) and CR chondrites. However, it should be noted that fayalitic olivine, which commonly occurs in CVoxB AOA, is not observed in this AOA. Also, the smaller grain size (<8 microns) of olivine suggests they may be related to CM or CO chondrites. Therefore, we cannot exclude the possibility that the AOA originated from a unique carbonaceous chondrite.

  13. Exsolved Ferromagnesian Olivine: Why Only in Divnoe?

    NASA Astrophysics Data System (ADS)

    Petaev, M. I.

    1995-09-01

    Recently Petaev and Brearley [1] showed that lamellar structure in olivine grains in the Divnoe meteorite was produced by the low-temperature exsolution of primary homogeneous grains. Exsolved olivine in Divnoe is in accordance with the thermodynamic model of olivine solid solution of [2], which predicts a miscibility gap in ferromagnesian olivines below ~340 degrees C within a compositional range that widens with decreasing temperature. Experiments on the coexistence of olivines having a range of compositions with aqueous solutions of (Fe,Mg)Cl2 [3] suggest that exsolution in ferromagnesian olivines could occur even at temperatures as high as ~400 - 450 degrees C. However, [1] remains the only observation of exsolution in natural olivines so far. This means either that (1) the exsolution in Divnoe olivine is unique, or (2) olivine grains in other slowly cooled coarse-grained rocks has not been studied closely enough to detect them. This work attempts to clarify the issue. Olivine grains from selected meteorites (Springwater pallasite, Lowitz mesosiderite, ALHA 84025 brachinite, Gorlovka H3-4 chondrite and Krymka L3 chondrite, and the Calcalong Creek lunar meteorite) and terrestrial rocks (San Carlos forsterite and Rockport fayalite) were studied by EPMA using the same equipment and technique as in [1]. Among meteorites, pallasites and mesosiderites are known to have slowest cooling rates at low temperatures. Olivines in the Springwater pallasite (Fa18) [4] and the Lowitz mesosiderite (Fa15-37) [5] are compositionally comparable with that of Divnoe (Fa23-29) [1], and it was expected that exsolved olivine grains would be found there. Olivines from other samples were studied for comparison. No lamellar structure was observed in BSE images of the olivine grains studied. The variations of Fa contents in olivine grains from all samples but Springwater and Lowitz meteorites display no regular pattern, and are basically within the 2sigma uncertainty range (+/-0.2 mole % Fa). As expected, olivines from the Lowitz mesosiderite and, especially, from the Springwater pallasite display somewhat larger variations, within the ranges of 20.1 - 21.0 and 15.8 -17.7 mole % Fa, respectively. The olivine in Springwater shows a surprisingly regular pattern of minima spaced at ~ 16 micrometers. For reasons that are unclear all 'minima' analyses have low totals (90.47-94.31 wt.%), whereas most other analyses have totals > 97%. However, stoichiometry of all analyses is perfect; cation totals per 4 oxygens are 3.00+/-0.01, with very minor excess of Si over Mg+Fe in the 'minima' analyses. The results obtained so far suggest that lamellar structure of olivine grains in the Divnoe meteorite is unique. While chemical variability is found in the Springwater and Lowitz olivines, there is no lamellar structure, and the magnitude of the variations is 1.5 - 2 times smaller than it is in Divnoe olivines. Since olivine compositions in Divnoe, Lowitz and Springwater are similar, the structural differences among them must be due to different thermal histories. The lack of lamellar structure in the Lowitz olivine implies that even the slowest cooling down to 250 degrees C recorded in mesosiderites [6] does not result in olivine exsolution. It is possible that Divnoe experienced secondary reheating followed by prolonged low-temperature annealing. This would also account for the lack of shock features in the Divnoe opaque minerals [7] and the difference in distributions of cosmic-ray track lengths and densities between olivine and pyroxene [8]. References: [1] Petaev M. I. and Brearley A. J. (1994) Science, 266, 1545-1547. [2] Sack R. O. and Ghiorso M. S. (1989) Contrib. Mineral. Petrol., 102, 41-68. [3] Schulien S. (1980) Contrib. Mineral. Petrol., 74, 85-91. [4] Buseck P. R. (1977) GCA, 41, 711-740. [5] Delaney J. S. et al. (1980) Proc. LPSC 11th, 1073-1087. [6] Ganguly J. et al. (1994) GCA, 58, 2711-2723. [7] Petaev M. I. et al. (1994) Meteoritics, 29, 182-199. [8] Petaev M. I. et al. (1990) LPS XXI, 950-951.

  14. Aligned Olivine in the Springwater Pallasite

    NASA Astrophysics Data System (ADS)

    Fowler-Gerace, N.; Tait, K.; Moser, D.; Barker, I.; Tian, B. Y.

    2014-12-01

    The mechanism by which olivine grains became embedded within iron-nickel alloy in pallasite meteorites continues to be a matter of scientific debate. Geochemical and textural observations have failed to fully elucidate the origin and history of the olivine crystals; however, little research attention has been devoted to their crystallographic orientations within the metal matrix. Klosterman and Buseck [1] found no crystallographic preferred orientation of olivine in nine pallasites, but the Leitz five-axis universal stage method imposed limitations on precision (estimated within ˜4◦) and sample size (only 10 crystals were measured in the Springwater pallasite, for instance). Using Electron Backscatter Diffraction, we have collected crystallographic orientation data (accurate to ±0.5◦ [2]) for 343 crystals within ˜65 cm2 sample surface from Springwater. Though no global crystallographic preferred orientation exists, very low misorientations are observed among [100] axes of olivine crystals within specific texturally-defined domains. Combined with our thorough characterization of large-scale Springwater textures, the definitively non-random spatial distribution of olivine orientations reveals the nature of the olivine's initial formation environment as well as the sequence of events subsequent to metal incorporation. [1] Klosterman and Buseck. 1973. J Geophys Res 78(32):7581-7588. [2] Oxford Instruments. 2013. http://www.ebsd.com/.

  15. Atom Probe Tomography of Olivine

    NASA Astrophysics Data System (ADS)

    Parman, S. W.; Gorman, B.; Jackson, C.; Cooper, R. F.; Jaeger, D.

    2010-12-01

    Here we present atom probe tomographic (APT) analyses of natural olivine. APT provides three-dimensional trace element and isotopic analysis with sub-nanometer spatial resolution. It has been used for many years in engineering and materials science, but has not been applied to geological materials because traditional APT can only be used on conducting (usually metal) samples. The recent development of laser assisted APT has changed this situation, and now semi-conductors and insulators can be analyzed (Marquis et al., 2009, Kelly et al 2007). Potentially, this opens APT to extensive use in geoscience as many Fe-bearing silicates are semi-conductors. In this study, we explore the capability of the new class of APT instrumentation to analyze geological materials. APT involves the controlled evaporation of small, cylindrical specimens (100's nm in diameter) within an electric field. Specimens are typically prepared using in-situ focused-ion-beam (FIB) liftout and shaping techniques. Evaporated atoms are accelerated to a detector plate that records the position of the atom with sub-nm precision. Evaporated atoms are measured using time-of-flight mass spectrometry, allowing both elemental and isotopic determination. Since the method progressively ablates into the needle, the final analytical result is a nm-scale 3-dimensional image in which the position and identity of each detected atom is known. Typical mass resolution is between 200 and 1200 (full-width at half maximum) and typical concentration detection limits are 10 ppm. The number of potential applications of APT to igneous, metamorphic and sedimentary materials is large, ranging from studies of mineral and melt inclusions, to fine scale layering in minerals, to reaction surfaces and diffusion profiles. Much recent progress in the geochemical and petrologic fields has been driven by the increasing spatial resolution of the ion probe and laser ablation ICPMS. The ability of APT to provide atom-scale mass spectrometry should continue this trend. The main limitations to atom probe analysis of geological materials are the ability to control heat flow during laser pulsing and the associated ability to control clustering during field evaporation. Both of these factors can be controlled through specimen preparation and varying the atom probe experimental factors. Olivine specimens were properly analyzed using laser pulsed APT through the use of shallow (nominally 1mm) FIB liftouts and wide shank angle specimen apices. APT settings were found to give the best mass resolution using low specimen temperatures, 0.2 nJ laser energy, and 50 kHz pulse repetition rate. Increasing any of these values increases the amount of thermal tails due to excessive heat buildup, reducing the mass spectrum resolution, and ultimately affecting the spatial resolution of the reconstruction. Marquis EA, Miller MK, Blavette D, Ringer SP, Sudbrack CK and Smith DW (2009). MRS Bulletin 34: 725-730. Thomas F. Kelly, David J. Larson, Keith Thompson, Roger L. Alvis, Joseph H. Bunton, Jesse D. Olson, Brian P. Gorman, Ann. Rev. Mat. Res. 37: 681-727.

  16. Amoeboid olivine aggregates in the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Grossman, L.; Steele, I. M.

    1976-01-01

    Greyish-brown irregularly-shaped aggregates composed predominantly of olivine make up nearly 2% of the Allende meteorite by volume. Many of the aggregates are constructed of subspherical lumps of micron-sized crystals of olivine, pyroxene, nepheline and sodalite surrounded by coarser-grained olivine. Rarely, anorthite, spinel and perovskite are also present. The olivine ranges in composition from Fo64 to Fo99. Pyroxenes range from aluminous diopside to hedenbergite to very Al-rich and Ti-Al-rich varieties. The nepheline contains 1.6-2.4% K2O and 1.6-5.2% CaO but the sodalite is significantly poorer in these elements. The spinel contains 2.1-13.4% FeO. Textural information and oxygen isotopic data suggest that the aggregates are composed of primary, solid condensates from the solar nebula. The perovskite, spinel and Ti-Al-rich pyroxenes are the remains of high-temperature condensates, but the olivine compositions and the presence of feldspathoids indicate that some of the grains continued to react with the solar nebular vapor in the temperature range 500-900 K.

  17. Shock-produced olivine glass - First observation

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.; Ahrens, T. J.; Lally, J. S.; Nord, G. L., Jr.; Christie, J. M.; Heuer, A. H.

    1977-01-01

    Transmission electron microscope (TEM) observations of an experimentally shock-deformed single crystal of natural peridot, /Mg(0.88)Fe(0.12)/2SiO4, recovered from peak pressures of about 56 billion pascals revealed the presence of amorphous zones located within crystalline regions with a high density of tangled dislocations. This is the first reported observation of olivine glass. The shocked sample exhibits a wide variation in the degree of shock deformation on a small scale, and the glass appears to be intimately associated with the highest density of dislocations. This study suggests that olivine glass may be formed as a result of shock at pressures above about 50 to 55 billion pascals and that further TEM observations of naturally shocked olivines may demonstrate the presence of glass.

  18. A search for olivine activation volume

    NASA Astrophysics Data System (ADS)

    Li, L.; Weidner, D.; Mei, S.; Raterron, P.; Chen, J.; Durham, W.

    2003-04-01

    Knowledge of the rheological properties of mantle materials is critical in modeling the dynamics of the Earth. The flow law of olivine defined at mantle pressure and temperature is especially important since the pressure dependence of rheology may affect our estimation for the strength of olivine in the Earth's interior. Conventional deformation methods in defining the flow law of olivine have to face factors of large uncertainties of differential stress measurements and/or limited confining pressure for deformation. In this study, high-temperature (up to 1473 K) deformation experiments of polycrystalline olivine (average grain size < 5 micron) at pressure up to 6.5(0.2) GPa were conducted in-situ using large-volume high-pressure apparatus (Deformation DIA) and synchrotron x-ray radiation. More than 30% strain was generated during the uniaxial compression. The sample lengths during the deformation process were monitored by x-ray radiography. The strain rate was derived with precision up to 10-6. Macroscopic differential stress was measured at constant strain rate ( 10-5 s-1) using a multi-element solid-state detector combined with a conical slit. The new data, measured at 1473 and 1273K at 6.5 and 3GPa, fits well an empirical power-law creep flow law under the condition that the activation energy is 520(20) kJ/mol and the activation volume is less than 3 cm^3/mol. Consistent with TEM observations on recovered samples, tests for grain size dependence of flow, and the empirical power law exponent, we conclude that power-law creep is the dominant flow mechanism for dry olivine at upper mantle conditions. The success of defining the flow law for olivine in this study also symbolizes a huge opening for defining the rheological flow law for other materials in the Earth's interior.

  19. Shock Effects in Olivine from Mocs Chondrite

    NASA Astrophysics Data System (ADS)

    Iancu, O. G.; Miura, Y.; Iancu, G.

    1995-09-01

    The Mocs (syn. Moci) meteorite, classified as L6 chondrite by Van Schmus and Wood [1] and recently reclassified as L5-6 by Miura et al. [2], fell on February 3, 1882, 16.00 hrs. , over a large area (15 km by 3 km) in Transylvania (Cluj District). Olivine from six fragments of the Mocs chondrite was analyzed by optical microscopy, scanning electron microscopy with energy dispersive X-ray analysis and X-ray powder diffractometry. Olivine occurs as grains in matrix or chondrules: barred olivine chondrules, composed of parallel sets of prismatic olivine crystals and devitrified glass and porphyritic olivine chondrules, which consist mainly of fine-grained olivine crystals and glassy materials of feldspsr composition. In order to determine the mineralogical and chemical effects of shock metamorphism (induced by collisions in space of the Mocs chondrite parent body), in every thin section, ten to twenty of the largest, randomly distributed olivine single crystals were examined by optical polarizing microscope with 20X- or 40X- objectives [3] and with a JEOL JSM-5400 scanning electron microscope for higher magnifications. The mineralogical effects observed are: undulatory extinction, irregular fractures, planar fractures, mosaicism and planar deformation features. These, correlated with the presence of small amounts of maskelynite (An 12-19) indicate that the maximum shock degree this meteorite experienced was S-5 [3]. The quantitative chemical analysis of 77 olivine grains in matrix from all thin sections (6), determined by a JEOL JSM-5400 scanning electron microscope with JED 2001 energy dispersive X-ray analysis at the Yamaguchi University, shows a variation in composition from Fa23 to Fa27 mole % fayalite (Avg. Fa25; PMD 2.3%), indicative of the L-group. The Fayalite content of olivine from chondrules ranges from Fa23 to Fa27 (Avg. Fa25; PMD 1.74%). According to DEER et al. [4], olivine composition can be measured also by X-ray powder diffractometry as Fa (mol per cent) = 100-(4233.91-1494.59 x d130). By using a RIGAKU computer assisted-diffractometer (radiation Cu K alpha = 1.54059) at the Yamaguchi University, the d130 value of olivine from Mocs meteorite was calculated as 2.781 A and the fayalite content as Fa23 mole % fayalite (Forsterite-ferroan as of IMA files, 1993) consistent also with the L-group. The cell parameters and density determined from the X-ray diffraction pattern are: a=4.779; b=10.297; c=6.032; V=296.857 and Dx=3.446 g/cm3. References: [1] Van Schmus W. R. and Wood J. A. (1967) GCA, 31, 747-765. [2] Miura Y. et al. (1995) Proc. NIPR Symp. Antarct. Meteorites, 8, in press. [3] Stoffler D. et al. (1991) GCA, 55, 3845-3867. [4] Deer W. A. et al. (1992) 2nd edition, 4.

  20. The origin of ferrous zoning in Allende chondrule olivines

    NASA Technical Reports Server (NTRS)

    Peck, Julia A.; Wood, John A.

    1987-01-01

    Very similar major and minor element compositions are noted in the ferrous olivine occurring in chondrules at olivine grain boundaries, along cracks in olivine grains, interleaved with enstatite, and in the inner portions of exposed olivine grain surface rims; simultaneous formation by a single process is therefore suggested. The ferrous chondrule olivine probably formed by the reaction of chondrules with very hot nebular vapors over a period of several hours, followed by the condensation of residual metal vapors onto those olivine surfaces that were in direct contact with the gas as the system cooled. The ferrous chondrule olivine that occurs interleaved with enstatite in Allende does not have a composition idendical to, and is not the precursor of, matrix olivine.

  1. Barred olivine chondrules in ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Weisberg, Michael K.

    1987-01-01

    The characteristics of 125 barred olivine chondrules identified in polished thin sections of 26 H-L-LL3-6 chondrites were studied, using an electron microprobe for determining mineral abundances and a broad-beam electron microprobe for determining bulk compositions. Compared with all chondrule types in the H-L-LL3 ordinary chondrites, the barred olivine chondrules were found to be enriched in FeO, Al2O3, Na2O, and K2O and depleted in SiO2 and MgO; they were also found to be enriched in the feldspathic component. It is concluded that the precursor components of barred olivine chondrules consisted of a mixture of an olivine-rich component, a refractory-rich component containing Al2O3, TiO2, and CaO, and a volatile-rich alkalic component. This unusual combination implies high temperatures of melting for the refractory component and low temperatures for the volatile component, supporting the hypothesis of Grossman and Wasson (1983) that the alkalies condensed on the alumina already available.

  2. Transmission electron microscopy of subsolidus oxidation and weathering of olivine

    USGS Publications Warehouse

    Banfield, J.F.; Veblen, D.R.; Jones, B.F.

    1990-01-01

    Olivine crystals in basaltic andesites which crop out in the Abert Rim, south-central Oregon have been studied by high-resolution and analytical transmission electron microscopy. The observations reveal three distinct assemblages of alteration products that seem to correspond to three episodes of olivine oxidation. The olivine crystals contain rare, dense arrays of coherently intergrown Ti-free magnetite and inclusions of a phase inferred to be amorphous silica. We interpret this first assemblage to be the product of an early subsolidus oxidation event in the lava. The second olivine alteration assemblage contains complex ordered intergrowths on (001) of forsterite-rich olivine and laihunite (distorted olivine structure with Fe3+ charge balanced by vacancies). Based on experimental results for laihunite synthesis (Kondoh et al. 1985), these intergrowths probably formed by olivine oxidation between 400 and 800??C. The third episode of alteration involves the destruction of olivine by low-temperature hydrothermal alteration and weathering. Elongate etch-pits and channels in the margins of fresh olivine crystals contain semi-oriented bands of smectite. Olivine weathers to smectite and hematite, and subsequently to arrays of oriented hematite crystals. The textures resemble those reported by Eggleton (1984) and Smith et al. (1987). We find no evidence for a metastable phase intermediate between olivine and smectite ("M" - Eggleton 1984). The presence of laihunite exerts a strong control on the geometry of olivine weathering. Single laihunite layers and laihunite-forsteritic olivine intergrowths increase the resistance of crystals to weathering. Preferential development of channels between laihunite layers occurs where growth of laihunite produced compositional variations in olivine, rather than where coherency-strain is associated with laihunite-olivine interfaces. ?? 1990 Springer-Verlag.

  3. Trace-Element Diffusion Coefficients in Olivine

    NASA Astrophysics Data System (ADS)

    Spandler, C.; O'Neill, H. S.

    2006-12-01

    We have undertaken chemical diffusion experiments at 1300C to determine both crystal/melt partition coefficients and diffusion coefficients for a wide range of trace elements in forsteritic olivine. Experiments were conducted at 1 atm under controlled fO2 for up to 25 days using synthetic melts made to a composition in equilibrium with olivine for major elements, and doped with selected trace elements. The melt was put into a 5 mm diameter cylindrical hole in gem quality San Carlos olivine crystals drilled paralell to the a axis. Diffusion profiles were obtained both for trace elements that were added to the starting material and diffuse into the olivine, and also for several trace elements present at natural abundances in the olivine that diffuse out. The profiles were measured across sections perpendicular to crystal/melt boundary at a variety of crystallographic orientations (confirmed by EBSD) by laser-ablation ICP-MS. A thin laser slit oriented parallel to the crystal/melt interface was traversed from the melt through the crystal. Element concentrations were fitted to the diffusion equation to obtain both diffusion coefficients and concentrations at the crystal/melt interface, and hence partition coefficients. Calculated diffusivities for many trace elements (Ca, REE, Y, Sc, V, Cr, Ni, Co, Mn, Na, Li, Be, Ti) are relatively fast (D = 10-16 to 10^{-13 m2/s at 1300C). The diffusion of Li in olivine (approx. D = 10^{-15} m2/s) is only slightly slower than REEs and similar to divalent cations, in good agreement with inferences from zoning profiles in natural olivine [1]. This rate is considerably slower than for plagioclase and clinopyroxene [2], a result which has important implications for interpreting Li isotopic data from mantle-derived rocks. The fastest diffusing trace element we observe is Be. Applying our diffusion and partition coefficients to the model of Qin et al. [3], we calculate that the REEs of olivine-hosted melt inclusions in the mantle will extensively re-equilibrate with external magma in weeks (heavy REEs) to a few years (light REEs). These timescales are significantly shorter than the times estimated for the production and extraction of magma from the mantle or magma residence in the lower crust, implying anomalous melt inclusions are probably not a direct result of melting of heterogeneities in the mantle. Instead, anomalous melt inclusions likely form by assimilation processes shortly before eruption [4] and so may be useful monitors of such processes. Refs: [1] Parkinson et al., Abstract, Goldschmidt Conference 2006; [2] Coogan et al., EPSL 240, 415-424 (2005); [3] Qin et al. Am. Min. 77, 565-576 (1992); [4] Danyushevsky et al., J. Petrol. 45, 2531-2553 (2004).

  4. Dislocation Microstructures in Experimentally Deformed wet Olivine

    NASA Astrophysics Data System (ADS)

    Sharp, T. G.; Jung, H.; Karato, S.

    2002-12-01

    Seismic anisotropy in the upper mantle is generally considered to be the result of lattice preferred orientations (LPOs) of olivine as a result of mantle flow. Therefore seismic anisotropy in the upper mantle can be used to probe fabrics and therefore flow directions. Jung and Karato (2001) have demonstrated that fabrics developed in experimentally deformed olivine are dependent on H2O fugacity and stress. Fabric type C, which develops at moderate experimental stresses and high H2O fugacities, has [001] subparallel to the slip direction and (100) subparallel to the shear plane. Fabric type B, which develops at high stresses and high H2O fugacities has [001] subparallel to the slip direction and (010) subparallel to the shear plane. To investigate the role of H2O in olivine fabric transitions, we are using high-resolution and conventional transmission electron microscopy (HRTEM and TEM) to characterize the dislocation microstructures and core structures in experimentally deformed samples of Fabric types B and C. Initial results for Fabric type C (sample JK11 of Jung and Karato, 2001) show a dominance of mixed-character and screw dislocations with Burgers vectors b = [001]. This Burgers vector, combined with the (100) being subparallel to the shear plane, is consistent with the (100)[001] slip system being dominant in the C-type fabric. This slip system, which is of minor importance in dry olivine, may be favored in wet samples by changes in the dislocation core structure. We are currently using HRTEM imaging to characterize the dislocation core structures in deformed samples with type C and type B fabrics.

  5. Exploring exogenic sources for the olivine on Asteroid (4) Vesta

    NASA Astrophysics Data System (ADS)

    Le Corre, Lucille; Reddy, Vishnu; Sanchez, Juan A.; Dunn, Tasha; Cloutis, Edward A.; Izawa, Matthew R. M.; Mann, Paul; Nathues, Andreas

    2015-09-01

    The detection of olivine on Vesta is interesting because it may provide critical insights into planetary differentiation early in our Solar System's history. Ground-based and Hubble Space Telescope (HST) observations of Asteroid (4) Vesta have suggested the presence of olivine on the surface. These observations were reinforced by the discovery of olivine-rich HED meteorites from Vesta in recent years. However, analysis of data from NASA's Dawn spacecraft has shown that this "olivine-bearing unit" is actually impact melt in the ejecta of Oppia crater. The lack of widespread mantle olivine, exposed during the formation of the 19 km deep Rheasilvia basin on Vesta's South Pole, further complicated this picture. Ammannito et al. (Ammannito, E. et al. [2013a]. Nature 504, 122-125) reported the discovery of local scale olivine-rich units in the form of excavated material from the mantle using the Visible and InfraRed spectrometer (VIR) on Dawn. These sites are concentrated in the walls and ejecta of craters Arruntia (10.5 km in diameter) and Bellicia (41.7 km in diameter), located in the northern hemisphere, 350-430 km from Rheasilvia basin's rim. Here we explore alternative sources for the olivine in the northern hemisphere of Vesta by reanalyzing the data from the VIR instrument using laboratory spectral measurements of meteorites. Our rationale for using the published dataset was to bypass calibration issues and ensure a consistent dataset between the two studies. Our analysis of the VIR data shows that while the interpretation of their spectra as an olivine-rich unit is correct, the nature and origin of that olivine could be more complicated. We suggest that these olivine exposures could also be explained by the delivery of olivine-rich exogenic material. This hypothesis is supported by meteoritical evidence in the form of exogenic xenoliths containing significant amount of olivine in some of the HED meteorites from Vesta. Previous laboratory work on HEDs show that potential sources of olivine on Vesta could be different types of olivine-rich meteorites, either primitive achondrites (acapulcoites, lodranites, ureilites), ordinary chondrites (H, L, LL), pallasites, or carbonaceous chondrites (e.g., CV). Based on our spectral band parameters analysis, the lack of correlation between the location of these olivine-rich terrains and possible mantle-excavating events, and supported by observations of HED meteorites, we propose that a probable source for the olivine seen in the northern hemisphere corresponds to remnants of impactors made of olivine-rich meteorites. The best curve-matching results with laboratory spectra suggest these units are HED material mixed with either ordinary chondrites, or with some olivine-dominated meteorites such as R-chondrites.

  6. Search for Olivine Spectral Signatures on the Surface of Vesta

    NASA Technical Reports Server (NTRS)

    Palomba, E.; De Sanctis, M. C.; Ammannito, E.; Capaccioni, F.; Capria, M. T.; Farina, M.; Frigeri, A.; Longobardo, A.; Tosi, F.; Zambon, F.; McSween, H. Y.; Mittlefehldt, D. W.; Russell, C. T.; Raymond, C. A.; Sunshine, J.; McCord, T. B.

    2012-01-01

    The occurrence of olivines on Vesta were first postulated from traditional petrogenetic models which suggest the formation of olivine as lower crustal cumulates. An indirect confirmation is given by their presence as a minor component in some samples of diogenite meteorites, the harzburgitic diogenites and the dunitic diogenites, and as olivine mineral clasts in howardites. Another indication for this mineral was given by interpretations of groundbased and Hubble Space Telescope observations that suggested the presence of local olivine-bearing units on the surface of Vesta. The VIR instrument onboard the DAWN mission has been mapping Vesta since July 2011. VIR acquired hyperspectral images of Vesta s surface in the wavelength range from 0.25 to 5.1 m during Approach, Survey and High Altitude Mapping (HAMO) orbits that allowed a 2/3 of the entire asteroid surface to be mapped. The VIR operative spectral interval, resolution and coverage is suitable for the detection and mapping of any olivine rich regions that may occur on the Vesta surface. The abundance of olivine in diogenites is typically lower than 10% but some samples richer in olivine are known. However, we do not expect to have extensive exposures of olivine-rich material on Vesta. Moreover, the partial overlap of olivine and pyroxene spectral signatures will make olivine difficult to detect. Different spectral parameters have been used to map olivine on extraterrestrial bodies, and here we discuss the different approaches used, and develop new ones specifically for Vesta. Our new methods are based on combinations of the spectral parameters relative to the 1 and 2 micron bands (the most prominent spectral features of Vesta surface in the visible and the infrared), such as band center locations, band depths, band areas, band area ratios. Before the direct application to the VIR data, the efficiency of each approach is evaluated by means of analysis of laboratory spectra of HED meteorites, pyroxenes, olivines and their mixtures.

  7. Shock effects in olivine and implications for Hugoniot data

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.

    1980-01-01

    New observations of shock deformation in single-crystal olivine are presented for the range in peak pressures from about 16 to 75 GPa. A nonequilibrium model is suggested for the behavior of olivine under shock which explains the densification associated with a mixed-phase region and which is consistent with all available observations, yet which bears little similarity to the equilibrium behavior of olivine at high pressure.

  8. Water and Carbon Dioxide Adsorption at Olivine Surfaces

    SciTech Connect

    Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

    2013-11-14

    Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbon dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.

  9. Diffusive Fractionation of Lithium Isotopes in Olivine

    NASA Astrophysics Data System (ADS)

    Homolova, V.; Richter, F. M.; Watson, E. B.; Chaussidon, M.

    2014-12-01

    Systematic lithium isotope variations along concentration gradients found in olivine and pyroxene grains from terrestrial, lunar and martian rocks have been attributed to diffusive isotopic fractionation [Beck et al., 2006; Tang et al., 2007]. In some cases, these isotopic excursions are so large that a single grain may display isotopic variability that spans almost the entire range of documented terrestrial values [Jeffcoate et al., 2007]. In this study, we present the results of experiments to examine diffusive isotopic fractionation of lithium in olivine. The experiments comprised crystallographically oriented slabs of San Carlos olivine juxtaposed with either spodumene powder or a lithium rich pyroxene crystal. Experiments were conducted at 1 GPa and 0.1MPa over a temperature range of 1000 to 1125?C. Oxygen fugacity in the 0.1MPa experiments was controlled using the wustite-magnetite and nickel-nickel oxide solid buffer assemblages. Lithium concentrations generally decrease smoothly away from the edges of the grains; however, experiments involving diffusion parallel to the a-axis consistently show peculiar wavy or segmented concentration profiles. Lithium diffusivity parallel to the c-axis is on the order of 1E-14m2/s at 1100?C. The diffusivity parallel to the c-axis is more than an order of magnitude faster than diffusion parallel to the b-axis and correlates positively with oxygen fugacity. The lithium isotopic composition, ?7Li = 1000 * ((?7Lisample- ?7Ligrain center)/ ?7Ligrain center), shows a decrease away from the edge of the grain to a minimum value (up to 70 lighter) and then an abrupt increase back to the initial isotopic composition of the olivine grain. This isotopic profile is similar to those found in natural grains and an experimental study on diffusive fractionation of lithium isotopes in pyroxene [Richter et al., 2014]. Results from the present study are modeled using the approach of Dohmen et al. [2010], which assumes lithium diffusion occurs on both a metal and interstitial site and that lithium is able to jump between these two sites. The best fits to the results show that diffusive isotopic fractionation may occur on both the interstitial and metal site but the degree of diffusive isotopic fractionation is always greater on the interstitial site.

  10. Discovery of Olivine in the Nili Fossae Region of Mars

    USGS Publications Warehouse

    Hoefen, T.M.; Clark, R.N.; Bandfield, J.L.; Smith, M.D.; Pearl, J.C.; Christensen, P.R.

    2003-01-01

    We have detected a 30,000-square-kilometer area rich in olivine in the Nili Fossae region of Mars. Nili Fossae has been interpreted as a complex of grabens and fractures related to the formation of the Isidis impact basin. We propose that post-impact faulting of this area has exposed subsurface layers rich in olivine. Linear mixture analysis of Thermal Emission Spectrometer spectra shows surface exposures of 30% olivine, where the composition of the olivine ranges from Fo30 to Fo70.

  11. Vaporization Studies of Olivine via Knudsen Effusion Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Costa, G. C. C.; Jacobson, N. S.

    2014-01-01

    Olivine is the major mineral in the Earth's upper mantle occurring predominantly in igneous rocks and has been identified in meteorites, asteroids, the Moon and Mars. Among many other important applications in planetary and materials sciences, the thermodynamic properties of vapor species from olivine are crucial as input parameters in computational modelling of the atmospheres of hot, rocky exoplanets (lava planets). There are several weight loss studies of olivine vaporization in the literature and one Knudsen Effusion Mass Spectrometry (KEMS) study. In this study, we examine a forsterite-rich olivine (93% forsterite and 7% fayalite, Fo93Fa7) with KEMS to further understand its vaporization and thermodynamic properties.

  12. Mineralogical Comparison of Olivine in Shergottites and A Shocked L Chondrite: Implications for Shock Histories of Brown Olivine

    NASA Technical Reports Server (NTRS)

    Takenouchi, A.; Mikouchi, T.; Yamaguchi, A.; Zolensky, M. E.

    2015-01-01

    Most Martian meteorites are heavily shocked, exhibiting numerous shock features, for example undulatory extinction of olivine and pyroxene, the presence of diaplectic glass ("maskelynite") and the formation of shock melt. Among these shock features, olivine darkening ("brown" olivine) is unique in Martian meteorites because no other meteorite group shows such a feature. Although the presence of brown olivine in shergottites was reported thirty years ago, detailed observation by TEM has not been performed until the NWA 2737 chassignite was discovered, whose olivine is darkened, being completely black in hand specimen. Fe metal nano-particles were found in NWA 2737 olivine which are considered to have been formed by olivine reduction during heavy shock. Subsequently, magnetite nano-particles were also found in other Martian meteorites and the coexistence of Fe metal and magnetite nano-particles was reported in the NWA 1950 shergottite and some Fe metal nano-particles were mantled by magnetite. Therefore, the formation process of nano-particles seems to be complex. Because "brown" olivine is unique to Martian meteorites, they have a potential to constrain their shock conditions. In order to better understand the shock history of Martian meteorites, we compared olivine in several shergottites with that in a highly-shocked L chondrite which contains ringwoodite.

  13. RELICT Olivines in Micrometeorites from Greenland and Antarctica

    NASA Astrophysics Data System (ADS)

    Beckerling, W.; Klock, W.; Bischoff, A.

    1993-07-01

    Previously, [1] studied the bulk chemistry and texture of 223 micrometeorites from Greenland (size: 100-200 micrometers): 82% spherical, 6% porous, and 12% monomineralic particles or particles with unique textures and from Antarctica (size: 50-100 micrometers): 24% spheres, 62% porous, and 14% particles with unique textures. In order to obtain information about the origin of micrometeorites we have studied minerals within these particles that escaped melting during atmospheric heating. Relict olivine grains occur in 27 spheres, 3 porous particles, and 11 particles with unique textures. Relict olivines (mostly > 5 micrometers in apparent size) can be distinguished from secondary crystallized (subsequent to atmospheric melting) olivines by their grain size, morphology, composition, and/or the presence of Fe/Ni-metal inclusions in olivine. Previously, [2] studied 26 Mg-rich olivines from Antarctic micrometeorites and [3] investigated about 70 olivines in micrometeorites from Antarctica and Greenland. Within the 41 micrometeorites containing such grains, 98 relict olivines were analyzed by electron microprobe, representing a much wider range of compositions than reported by [2]. In most micrometeorites, only one or two relict olivines occur and were large enough to be analyzed. In some particles, however the Fa-contents of several relict olivines were obtained (Fig. 1). Relict olivines with Fa-contents below 5.2 mol% Fe are abundant (Fig. 1). One forsterite within a porous particle is manganese- enriched and similar in composition to LIME olivines known from IDPs and primitive meteorites [4]. Comparing olivines from chondrites with those in micrometeorites, Fa-poor olivines occur in Type I chondrules from carbonaceous chondrites [5] and as isolated olivines in the matrix of C2, C3, and unequilibrated ordinary chondrites [2]. Between Fa(sub)5.2 and Fa(sub)~12 a gap exists in the distribution of the Fa-contents (Fig. 1). Relict olivines, however, with about 12 and 30 mol% Fa occur. These Fa- contents are similar to those of equilibrated H, L, and LL chondrites and may indicate that many particles are related to ordinary chondrites. In addition, several other micrometeorites contain olivines with Fa-contents exceeding those of olivines in ordinary chondrites. Considering chondrites as potential material of their origin, they may be related to matrix olivines in Type III carbonaceous chondrites and to olivines in Type II chondrules [5]. In six micrometeorites relict olivines with highly variable compositions were analyzed, indicating that the precursor was unequilibrated prior to thermal processing during atmospheric entry. Comparing all data, it appears that the larger-sized particles from Greenland may contain a slightly higher abundance of forsteritic relict olivines than the small particles from Antarctica. However, we cannot rule out that this observation is a result of insufficient data. References: [1] Beckerling W. et al. (1992) Meteoritics, 27, 200- 201. [2] Steele I. M. (1992) GCA, 56, 2923-2929. [3] Christophe Michel-Levy M. and Bourot-Denise M.(1992) Meteoritics, 27, 73-80. [4] Klock W. et al. (1989) Nature, 339, 126-128. [5] McSween H. Y. (1977) GCA, 41, 477-491.

  14. Olivine in an unexpected location on Vesta's surface.

    PubMed

    Ammannito, E; De Sanctis, M C; Palomba, E; Longobardo, A; Mittlefehldt, D W; McSween, H Y; Marchi, S; Capria, M T; Capaccioni, F; Frigeri, A; Pieters, C M; Ruesch, O; Tosi, F; Zambon, F; Carraro, F; Fonte, S; Hiesinger, H; Magni, G; McFadden, L A; Raymond, C A; Russell, C T; Sunshine, J M

    2013-12-01

    Olivine is a major component of the mantle of differentiated bodies, including Earth. Howardite, eucrite and diogenite (HED) meteorites represent regolith, basaltic-crust, lower-crust and possibly ultramafic-mantle samples of asteroid Vesta, which is the lone surviving, large, differentiated, basaltic rocky protoplanet in the Solar System. Only a few of these meteorites, the orthopyroxene-rich diogenites, contain olivine, typically with a concentration of less than 25 per cent by volume. Olivine was tentatively identified on Vesta, on the basis of spectral and colour data, but other observations did not confirm its presence. Here we report that olivine is indeed present locally on Vesta's surface but that, unexpectedly, it has not been found within the deep, south-pole basins, which are thought to be excavated mantle rocks. Instead, it occurs as near-surface materials in the northern hemisphere. Unlike the meteorites, the olivine-rich (more than 50 per cent by volume) material is not associated with diogenite but seems to be mixed with howardite, the most common surface material. Olivine is exposed in crater walls and in ejecta scattered diffusely over a broad area. The size of the olivine exposures and the absence of associated diogenite favour a mantle source, but the exposures are located far from the deep impact basins. The amount and distribution of observed olivine-rich material suggest a complex evolutionary history for Vesta. PMID:24196707

  15. Fast grain growth of olivine in liquid Fe-S and the formation of pallasites with rounded olivine grains

    NASA Astrophysics Data System (ADS)

    Solferino, Giulio F. D.; Golabek, Gregor J.; Nimmo, Francis; Schmidt, Max W.

    2015-08-01

    Despite their relatively simple mineralogical composition (olivine + Fe-Ni metal + FeS ± pyroxene), the origin of pallasite meteorites remains debated. It has been suggested that catastrophic mixing of olivine fragments with Fe-(Ni)-S followed by various degrees of annealing could explain pallasites bearing solely or prevalently fragmented or rounded olivines. In order to verify this hypothesis, and to quantify the grain growth rate of olivine in a liquid metal matrix, we performed a series of annealing experiments on natural olivine plus synthetic Fe-S mixtures. The best explanation for the observed olivine grain size distributions (GSD) of the experiments are dominant Ostwald ripening for small grains followed by random grain boundary migration for larger grains. Our results indicate that olivine grain growth in molten Fe-S is significantly faster than in solid, sulphur-free metal. We used the experimentally determined grain growth law to model the coarsening of olivine surrounded by Fe-S melt in a 100-600 km radius planetesimal. In this model, an impact is responsible for the mixing of olivine and Fe-(Ni)-S. Numerical models suggest that annealing at depths of up to 50 km allow for (i) average grain sizes consistent with the observed rounded olivine in pallasites, (ii) a remnant magnetisation of Fe-Ni olivine inclusions as measured in natural pallasites and (iii) for the metallographic cooling rates derived from Fe-Ni in pallasites. This conclusion is valid even if the impact occurs several millions of years after the differentiation of the target body was completed.

  16. Olivine in the Southern Isidis Basin

    NASA Technical Reports Server (NTRS)

    2007-01-01

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) took this observation of the transition region between Libya Montes and the Isidis Basin on Mars at 17:16 UTC (12:16 p.m. EST) on January 2, 2007, near 3.6 degrees north latitude, 84.1 degrees east longitude. The image was taken in 544 colors covering 0.36-3.92 micrometers, and shows features as small as 18 meters (60 feet) across. The image is about 11 kilometers (7 miles) wide at its narrowest point.

    The Isidis Basin resulted from of a gigantic impact on the surface of Mars early in the planet's history. The southern rim, where this target is located, is a region of complex geology and part of the planetary dichotomy boundary that separates the older southern highlands from the lower, younger northern plains. The image on the left was constructed from three visible wavelengths (RGB: 0.71, 0.60, 0.53 microns) and is a close approximation of how the surface would appear to the human eye. The image on the right was constructed from three infrared wavelengths (RGB: 2.49, 1.52, 1.08 microns) chosen to highlight variations in the mineralogy of the area. Of interest is that features in this image not only differ in color, but also in texture and morphology. The gray areas absorb similarly at all wavelengths used in this image, but display absorptions at other wavelengths related to the iron- and magesium-rich mineral pyroxene. The reddest areas absorb strongly at the wavelengths used for green and blue, which is attributable to another iron- and magesium-rich mineral, olivine. The brownish areas show subdued mineral absorptions and could represent some type of mixture between the other two materials. The presence of the mineral olivine is particularly interesting because olivine easily weathers to other minerals; thus, its presence indicates either the lack of weathering in this region or relatively recent exposure.

    CRISM's mission: Find the spectral fingerprints of aqueous and hydrothermal deposits and map the geology, composition and stratigraphy of surface features. The instrument will also watch the seasonal variations in Martian dust and ice aerosols, and water content in surface materials -- leading to new understanding of the climate.

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad.

  17. Chemical dispersion among Apollo 15 olivine-normative mare basalts

    NASA Technical Reports Server (NTRS)

    Ryder, Graham; Steele, Alison

    1988-01-01

    Analysis of Apollo 15 olivine-normative mare basalts for major and minor elements suggests that the hypothesis that the coarser-grained varieties (olivine microgabbros) consist of two chemical groups is incorrect. Instead, it is found that there is a single group including vesicular, coarse-grained, and fine-grained basalts. For the entire suite, the dispersion of compositions along the olivine trend is too great to be explained by short-range unmixing of an unfractionated flow. It is suggested that the general trend for the suite is olivine separation, probably through crystal settling. The textures, mineralogical characteristics, and chemical variation of the olivine-normative basalts are shown to be consistent with a sequence of thin fractionating flows, all from a common parent.

  18. Did Ordinary Chondrite Impactors Deliver Olivine to Vesta?

    NASA Astrophysics Data System (ADS)

    Le Corre, Lucille; Reddy, Vishnu; Sanchez, Juan A.; Cloutis, Edward A.; Izawa, Matthew R.; Mann, Paul

    2014-11-01

    Ground-based and Hubble Space Telescope observations of asteroid Vesta suggested the presence of olivine. However, subsequent analysis of data from NASAs Dawn mission proved that this olivine-bearing unit, identified as Oppia crater and its ejecta blanket, was composed of HED impact melt rather than olivine. The lack of widespread olivine in the 19 km deep Rheasilvia basin on the South Pole suggests that the crust-mantle boundary was not breached during the formation of the basin, and that Vestas crust is thicker than originally anticipated. Recently, local-scale olivine units have been reported in the walls and ejecta of two craters, Arruntia and Bellicia, located in the northern hemisphere of Vesta, 350-430 km from the Rheasilvia basin (Ammannito et al., 2013). These units were interpreted as exposed plutons by Clenet et al. (2014) rather than of mantle origin excavated during the formation of the Rheasilvia basin. We explored alternative sources for these olivine-rich units by reanalyzing the data published by Ammannito et al. (2013). Our mineralogical analysis gives olivine abundance between 70-80 vol.% consistent with those obtained previously (>60%). The pyroxene ferrosilite content and olivine abundance of the olivine-rich units are similar to ordinary chondrites. Meteoritic evidence suggests contamination of HEDs by several ordinary chondrite impactors including H, L and LL chondrites. This includes howardite JaH 556, which contains ~20 vol.% H chondrite material mixed with HED impact melt. Based on the non-diagnostic curve match and detailed mineralogical analysis using diagnostic spectral band parameters, we conclude that the olivine units in the northern hemisphere of Vesta could be explained by the delivery of exogenic H/L chondrite material rather than being a product of planetary differentiation.

  19. Cotectic proportions of olivine and spinel in olivine-tholeiitic basalt and evaluation of pre-eruptive processes

    USGS Publications Warehouse

    Roeder, P.; Gofton, E.; Thornber, C.

    2006-01-01

    The volume %, distribution, texture and composition of coexisting olivine, Cr-spinel and glass has been determined in quenched lava samples from Hawaii, Iceland and mid-oceanic ridges. The volume ratio of olivine to spinel varies from 60 to 2800 and samples with >0.02% spinel have a volume ratio of olivine to spinel of approximately 100. A plot of wt % MgO vs ppm Cr for natural and experimental basaltic glasses suggests that the general trend of the glasses can be explained by the crystallization of a cotectic ratio of olivine to spinel of about 100. One group of samples has an olivine to spinel ratio of approximately 100, with skeletal olivine phenocrysts and small (100 ??m) spinel crystals that show evidence of two stages of growth, and a volume ratio of olivine to spinel of 100 to well over 1000. The olivine and spinel in this group have crystallized more slowly with little physical interaction, and show evidence that they have accumulated in a magma chamber. ?? 2006 Oxford University Press.

  20. Boron, beryllium, and lithium, partitioning in olivine

    SciTech Connect

    Neroda, Elizabeth

    1996-05-01

    A one atmosphere experimental study was performed to determine the mineral/melt partition coefficients for B, Be, and Li in forsteritic olivine. Two compositions were chosen along the 1350{degrees}C isotherm, 1b (Fo{sub 17.3} Ab{sub 82.7} An{sub 0} by weight) and 8c (Fo{sub 30} Ab{sub 23.3} An{sub 47.8}, by weight) were then combined in equal amounts to form a composition was doped with 25ppm Li, B, Yb, Nb, Zr, Sr, and Hf, 50ppm Sm, and 100ppm Be, Nd, Ce, and Rb. Electron and ion microprobe analyses showed that the olivine crystals and surrounding glasses were homogeneous with respect to major and trace elements. Partition coefficients calculated from these analyses are as follows: 1b: D{sub B} = 4.41 ({+-} 2.3) E-03, D{sub Be} = 2.86 ({+-} 0.45) E-03, D{sub Li} = 1.54 ({+-} 0.21) E-01, 50/50: D{sub B} = 2.86 ({+-} 0.5) E-03, D{sub Be} = 2.07 ({+-} 0.09) E-03, D{sub Li} = 1.51 ({+-} 0.18) E-01, 8c: D{sub B} = 6.05 ({+-} 1.5) E-03, D{sub Be} = 1.81 ({+-} 0.03) E-03, D{sub Li} = 1.31 ({+-} 0.09) E-01. The results of this study will combined with similar data for other minerals as part of a larger study to understand the partitioning behavior of B, Be, and Li in melting of the upper mantle at subduction zones.

  1. Remote Compositional Analyses of Lunar Olivine-Bearing Lithologies

    NASA Astrophysics Data System (ADS)

    Isaacson, P.; Clark, R. N.; Head, J. W.; Klima, R.; Petro, N. E.; Pieters, C. M.; Staid, M.; Sunshine, J. M.; Taylor, L. A.; Thaisen, K. G.; Tompkins, S.

    2009-12-01

    The Moon Mineralogy Mapper (M3) is a guest instrument on Chandrayaan-1, Indias first mission to the Moon. M3 is an imaging spectrometer covering the wavelength range of 430 nm - 3000 nm, and was designed to map the mineralogy of the lunar surface. The high spectral resolution of M3 enables the diagnostic absorption features of lunar minerals to be identified clearly, while the high spatial resolution of M3 allows the identification and mapping of distinct lithologic units. Olivine is an important mineral with which to interpret the petrologic evolution of igneous rocks. The composition of olivine (Mg#) is used to indicate the degree of evolution of the source magma from which a sample crystallized. Visible to near-infrared reflectance spectroscopy is sensitive to the Mg# of olivine, as the diagnostic olivine absorption features shift in response to changing major element abundances (Mg and Fe) content. These changes in diagnostic absorption features can be detected by modeling the individual absorption bands with the Modified Gaussian Model (MGM). Spectra of lunar olivines differ from spectra of their terrestrial and synthetic counterparts due to the inclusions of Cr-spinel common to lunar olivines; however, analysis of lunar olivine mineral separates in terrestrial laboratories and modeling of the resulting reflectance spectra have been able to unravel the chromite effects on the olivine spectrum. Previous efforts at remote compositional analysis of lunar olivine have been limited by spectral resolution and coverage or by spatial resolution. However, the spatial and spectral resolution provided by M3 enable olivine composition to be determined remotely in a spatial context. We are in the process of identifying olivine-bearing lithologies on the lunar farside and analyzing the olivine composition with the modified MGM approach. Initial compositional analyses have been completed for a crater on the rim of the Moscoviense basin that appears to be largely dominated by olivine and relatively free from other optically active mafic phases such as pyroxene. Significant occurrences of other rocks dominated optically by olivine (e.g., troctolites) have been identified elsewhere around the basin. Olivine-dominated rocks in the lunar sample collection almost certainly formed through secondary magmatic processes following crystallization of the lunar magma ocean (the so-called Mg-suite). It is possible that similar processes produced the olivine-dominated lithologies around Moscoviense, although the scale of the intrusion required would likely be quite large. It is also possible that the Moscoviense impact event scattered locally-occurring olivine-rich rocks over the broad area observed. Preliminary compositional analysis results range from ~Fo50 to ~Fo75, broadly consistent with olivine compositions found in analyses of feldspathic lunar meteorites (likely to originate from the Feldspathic Highlands Terrane on the farside), as well as with olivines found in Apollo 16 troctolites.

  2. The pattern of Ni and Co abundances in lunar olivines

    NASA Astrophysics Data System (ADS)

    Longhi, John; Durand, Sedelia R.; Walker, David

    2010-01-01

    Near liquidus experiments on peridotite and other olivine normative compositions from 1.7 to 6 GPa confirm the applicability of exchange-based empirical models of Ni and Co partitioning between olivine and silicate liquids with compositions close to the liquidus of peridotite. Given that most estimates of lunar bulk composition are peridotitic, the partitioning models thus lend themselves to calculation of olivine compositions produced during the early stages of magma ocean crystallization. Calculation of olivine compositions produced by fractional crystallization of a model lunar magma ocean, initially 700 km deep, reveals a prominent maximum in Ni concentration versus fraction crystallized or Mg' (molar MgO/(MgO + FeO)), but a pattern of monotonically increasing Co concentration. These patterns qualitatively match the puzzling patterns of Ni and Co concentrations observed in lunar rocks in which forsteritic olivines in magnesian suite cumulates have lower Ni and Co abundances than do less magnesian olivines from low-Ti mare basalts, and olivines from the ferroan anorthosite suite (FAS) have lower Ni, but similar Co to mare basalt olivines. The Ni and Co abundances in olivines from the magnesian suite cumulates can be reconciled in terms of fractional crystallization of a deep magma ocean which initially produces a basal dunite comprised of the hottest and most magnesian olivine overlain by an olivine-orthopyroxene (harzburgite) layer that is in turn overlain by an upper zone of plagioclase-bearing cumulates. The ultramafic portion of the cumulate pile overturns sending the denser harzburgite layer, which later becomes a portion of the green glass source region, to the bottom of the cumulate pile with Ni- and Co-rich olivine. Meanwhile, the less dense, but hottest, most magnesian olivines with much lower Ni and Co abundances are transported upward to the base of the plagioclase-bearing cumulates where subsequent heat transfer leads to melting of mixtures of primary dunite, norite, and gabbronorite with KREEP (a K-REE-P enriched component widely believed to be derived from the very latest stage magma ocean liquid). These hybrid melts have Al 2O 3, Ni, and Co abundances and Mg' appropriate for parent magmas of the magnesian suite. Ni and Co abundances in the FAS are consistent with either direct crystallization from the magma ocean or crystallization of melts of primary dunite-norite mixtures without KREEP.

  3. Mineralogy of interplanetary dust particles from the 'olivine' infrared class

    NASA Technical Reports Server (NTRS)

    Christoffersen, R.; Buseck, P. R.

    1986-01-01

    Analytical electron microscopy observations establish that olivine is abundant and the predominant silicate phase in three interplanetary dust particles (IDPs) from the 'olivine' infrared spectra category. Two of the particles have microstructures resembling those of most nonhydrous chondritic IDPs, consisting of micron to submicron grains together with a matrix composed of amorphous carbonaceous material and sub-500 A grains. In addition to olivine these particles respectively contain enstatite and magnetite, and pentlandite plus Ca-rich clinopyroxene. The third IDP consists mostly of olivine and pyrrhotite with little or no matrix material. Olivine grains in this particle contain prominent solar-flare ion tracks with densities corresponding to a space-exposure age between 1000 to 100,000 years. Although the three particles have olivine-rich mineralogies in common, other aspects of their mineralogies and microstructures suggest that they experienced different formation histories. The differences between the particles indicate that the olivine infrared spectral category is a diverse collection of IDPs that probably incorporates several genetic groups.

  4. The olivine macrocryst problem: New insights from minor and trace element compositions of olivine from Lac de Gras kimberlites, Canada

    NASA Astrophysics Data System (ADS)

    Bussweiler, Yannick; Foley, Stephen F.; Prelević, Dejan; Jacob, Dorrit E.

    2015-04-01

    This study presents detailed petrographical and geochemical investigations on remarkably fresh olivines in kimberlites from the EKATI Diamond Mine™ located in the Tertiary/Cretaceous Lac de Gras kimberlite field within the Slave craton of Canada. Olivine, constituting about 42 vol.% of the analyzed samples, can be divided into two textural groups: (i) macrocrystic olivines, > 100 μm sub-rounded crystals and (ii) groundmass olivines, < 100 μm subhedral crystals. Olivines from both populations define two distinct chemical trends; a "mantle trend" with angular cores, showing low Ca (< 0.1 wt.% CaO) and high Ni (0.3-0.4 wt.% NiO) at varying Mg# (0.86-0.93), contrasts with a "melt trend" typified by thin (< 100 μm) rims with increasing Ca (up to 1.0 wt.% CaO) and decreasing Ni (down to 0.1 wt.% NiO) contents at constant Mg# (~ 0.915). These findings are in agreement with recent studies suggesting that virtually all olivine is composed of xenocrystic (i.e. mantle-related) cores with phenocrystic (i.e. melt-related) overgrowths, thereby challenging the traditional view that the origin of kimberlitic olivine can be distinguished based on size and morphology. The two main trends can be further resolved into sub-groups refining the crystallization history of olivine; the mantle trend indicates a multi-source origin that samples the layered lithosphere below the Slave craton, whereas the melt trend represents multi-stage crystallization comprising a differentiation trend starting at mantle conditions and a second trend controlled by the crystallization of additional phases (e.g. chromite) and changing magma conditions (e.g. oxidation). These trends are also seen in the concentrations of trace elements not routinely measured in olivine (e.g. Na, P, Ti, Co, Sc, Zr). Trace element mapping with LA-ICP-MS reveals the distribution of these elements within olivine grains. The trace element distribution between the two trends appears to be consistent with phenocrystic olivine overgrowths mainly originating from dissolved orthopyroxene, showing enrichment in Zr, Ga, Nb, Sc, V, P, Al, Ti, Cr, Ca and Mn in the melt trend. In a sample of magmatic kimberlite from the Leslie pipe, the amount of xenocrystic and phenocrystic olivine is estimated to be around 23 vol.% and 19 vol.%, respectively. Subtraction of this xenocrystic olivine from the Leslie bulk composition, aimed at estimating the parental kimberlite melt, results in a minor decrease of Mg# (by about 0.01) and SiO2 content (by about 3 wt.%), whereas CaO increases (by about 3 wt.%).

  5. Experimental Reproduction of Olivine rich Type-I Chondrules

    NASA Technical Reports Server (NTRS)

    Smith, Robert K.

    2005-01-01

    Ordinary chondritic meteorites are an abundant type of stony meteorite characterized by the presence of chondrules. Chondrules are small spheres consisting of silicate, metal, and sulfide minerals that experienced melting in the nebula before incorporation into chondritic meteorite parent bodies. Therefore, chondrules record a variety of processes that occurred in the early solar nebula. Two common types of unequilibrated chondrules with porphyritic textures include FeO-poor (type I) and FeO-rich (type II) each subdivided into an A (SiO2-poor) and B (SiO2-rich) series. Type IA chondrules include those with high proportions of olivine phenocrysts (>80% olivine) and type IB chondrules include those with high proportions of pyroxene phenocrysts (<20% olivine). An intermediate composition, type IAB chondrules include those chondrules in which the proportion of olivine phenocrysts is between 20-80%. We conducted high-temperature laboratory experiments (melting at 1550 C) to produce type I chondrules from average unequilibrated ordinary chondrite (UOC) material mixed with small amounts of additional olivine. The experiments were conducted by adding forsteritic rich olivine (San Carlos olivine, Fo 91) to UOC material (GRO 95544) in a 30/70 ratio, respectively. Results of these high temperature experiments suggest that we have replicated type IA chondrule textures and compositions with dynamic crystallization experiments in which a heterogeneous mixture of UOC (GRO 95544) and olivine (San Carlos olivine) were melted at 1550 C for 1 hr. and cooled at 5-1000 C/hr using graphite crucibles in evacuated silica tubes to provide a reducing environment.

  6. Detection of new olivine-rich locations on Vesta

    NASA Astrophysics Data System (ADS)

    Palomba, Ernesto; Longobardo, Andrea; De Sanctis, Maria Cristina; Zinzi, Angelo; Ammannito, Eleonora; Marchi, Simone; Tosi, Federico; Zambon, Francesca; Capria, Maria Teresa; Russell, Christopher T.; Raymond, Carol A.; Cloutis, Edward A.

    2015-09-01

    The discovery of olivine on Vesta's surface by the VIR imaging spectrometer onboard the Dawn space mission has forced us to reconsider our views of Vestan petrogenetic models. Olivines were expected to be present in the interior of Vesta: in the mantle of a vertically layered body as invoked by the magma ocean models, or at the base (or within) the mantle-crust boundary as proposed by fractionation models. Olivines have been detected by VIR-Dawn in two wide areas near Arruntia and Bellicia, regions located in the northern hemisphere. Interestingly, these olivine-rich terrains are far from the Rheasilvia and the more ancient Veneneia basins, which are expected to have excavated the crust down to reach the mantle. In this work we present our attempts to identify other undetected olivine rich areas on Vesta by using spectral parameters sensitive to olivine such as the Band Area Ratio (BAR) and other specific parameters created for the detection of olivines on Mars (forsterite, fayalite and a generic olivine index). As a preliminary step we calibrated these parameters by means of VIS-IR spectra of different HED meteorite samples: behaviors versus sample grain size and albedo were analyzed and discussed. We selected the BAR and the Forsterite Index as the best parameters that can be used on Vesta. A cross-correlation analysis has been applied in order to detect olivine signature on the VIR hyperspectral cubes. These detections have then been confirmed by an anti-correlation analysis between the BAR and one of the olivine parameters, independent of the first method applied. In agreement with the recent discovery, Arruntia and Bellicia were found to be as the most olivine-rich areas, i.e. where the parameter values are strongest. In addition we detected 6 new regions, all but one located in the Vesta north hemisphere. This result confirms again that the old petrogenetic models cannot be straightforwardly applied to Vesta and should be reshaped in the view of these new detections. An alternative and very recent option can be represented by the model according to which surface "eruption" of material from the mantle, including olivine can reach the surface of Vesta.

  7. The case for a cognate, polybaric origin for kimberlitic olivines

    NASA Astrophysics Data System (ADS)

    Moore, Andy E.

    2012-01-01

    Kimberlitic olivines typically show a continuous range in size and texture rather than two discrete populations. The cores of small euhedral olivines commonly provide the template for the final crystal shape, which in turn closely matches morphologies produced by crystallization from a moderately under-cooled magma. Cores and edges of the majority of all olivines define a continuous compositional field, which can be interpreted in terms of Raleigh crystallization. Marked chemical gradients at the olivine margins are linked to rapid physico-chemical changes to the magma associated with loss of volatiles during the late stages of emplacement. Thus, rapid crystallization of groundmass olivines would deplete the magma in Ni, but increase Ca activity. The latter would be enhanced by decreasing pressure coupled with loss of CO 2 from the carbonate-bearing kimberlite magma. For mantle olivines and the most refractory olivines in kimberlites (~ Fo 94) to be in equilibrium with bulk rock compositions matching those of Mg-rich macrocrystic and aphanitic kimberlites (Mg# ~ 88) requires a mineral-melt Mg-Fe distribution coefficient of 0.47. This is well within the experimentally determined range for this distribution coefficient in carbonate-bearing systems. In southern African post-Gondwana alkaline pipe clusters, the average bulk rock Mg# and composition of the associated most Mg-rich olivine both decrease sympathetically from the interior to the continental margin, which is also consistent with a cognate origin for the olivines. A kimberlite magma following a plausible P-T trajectory relative to the CO 2/H 2O peridotite solidus would initially experience superheating, resulting in partial resorption of early-formed olivines that crystallized on the cool conduit walls. It would become supersaturated as it crossed the carbonated peridotite "ledge", resulting in tabular and hopper growth forms typical of euhedral olivine cores. With further ascent, the magma would once again become superheated, resulting in partial resorption of these cores. Thus, apparently complex textures and internal zonation patterns of kimberlitic olivines are predicted by a plausible magma P-T trajectory.

  8. Fluorine in Olivines from Plutonic, Extrusive, and Hypabyssal Suites

    NASA Astrophysics Data System (ADS)

    Guggino, S. N.; Hervig, R. L.; Bell, D. R.

    2007-12-01

    Fluorine contents in a wide range of naturally-occurring olivine grains were determined by secondary ion mass spectrometry (SIMS) using a Cs+ primary beam, detection of negative secondary ions and an auxiliary electron gun for charge neutralization. A range of minerals and glasses containing 3 to 1300 ppm F were used to calibrate the secondary ion signal. Matrix effects appear to be small, and because fluorine has a high electron affinity, sensitivity is high (sub-ppm). Olivines from the study by Simkin and Smith (J. Geol., 1970) were analyzed for their F contents and span a range of suites that include upper mantle xenoliths and kimberlites, plutonic intrusives, ophiolites, shallow hypabyssal picrites and teschenites, and extrusive alkaline and tholeiitic basalts. Overall, the olivines in this study show a range of F concentrations from 0.5 to 32 ppm. Olivines from high- pressure environments show the highest individual and average F values, however large variations are also observed in this suite. Mantle xenoliths from this sample collection show a maximum and average F value of 14 and 4.1 ppm, respectively, and one olivine from kimberlite contains 32 ppm F. Earlier analyses from our laboratory (Hervig and Bell, 2005 Fall AGU) show a larger range in F from mantle-derived olivines. Plutonic intrusives and ophiolites, including layered intrusives and cumulates, show a range of F contents from 0.5 to 15 ppm, with an average value of 4 ppm. Olivines from the Kiglapait layered intrusion, Labrador show F content increasing with degree of fractional crystallization until the P2O5 content of the rock begins to increase. At this point, F in olivine decreases, presumably indicating partitioning of F into apatite. In the Hawaiian suites studied, F in olivine was high (8-12 ppm) in evolved andesites and lower (1-8 ppm) in more primitive basalts. Hypabyssal suites include a peridotite dike from Skye, (F < 1 ppm), a chilled olivine dolerite from Bornaskitaig (F = 2 ppm), a picrite from Igdlorsuit, Greenland (F = 4 ppm), and a teschenite from Black Jack Sill, Australia (F = 1.5 ppm). Fluorine measurements on the Simkin and Smith olivines are consistent with earlier observations that F is highest in OH-rich olivines (i.e., upper mantle xenoliths in kimberlites; Hervig & Bell, AGU Fall Mtg 2005).

  9. Olivines from Kimberlites and Diamonds: Problem of Origin

    NASA Astrophysics Data System (ADS)

    Sobolev, N. V.; Sobolev, A. V.; Tomilenko, A. A.; Kovyazin, S. V.; Kuzmin, D. V.

    2011-12-01

    Mg-rich olivine Fo [100Mg/(Mg + Fe)] 85-94 is the principal mineral of kimberlites, peridotite xenoliths and diamond inclusions. It is completely altered in common kimberlites, however, it is absolutely fresh in a huge block from Udachnaya-East kimberlite in Yakutia (Russia). Pioneering studies of this unaltered kimberlite resulted in a discovery of high role of a mantle chlorine along with very low water content (Kamenetsky et al., 2004, Geology, 32: 845-848). Two olivine populations are distinguished, which are represented by oval-rounded unzoned or partly zoned xenocrysts of olivine I (more than 1 mm) and well defined zoned phenocrysts ( 0.05-1.0 mm) of olivine II (e.g. Kamenetsky et al., 2008, J.Petrol., 49: 823-839). The cores of olivine II are compositionally similar to olivine I with Mg# 86-94, but rims of olivine II and partly preserved rims of olivine I have constant Fo values about 89-90. We report here the results of major and minor elements analyses by EPMA of more than 300 grains of olivine I and olivine II, both of cores and rims by high precision approach (Sobolev et al., 2007, Science, 316: 412-417) to minor elements including Ti, Al, Cr, Ca, Mn, Ni, Co using the high sample current and high counting time, which was found optimal to obtain limit of detection about 10 ppm. Several grains of analyzed olivines contain clinopyroxene (cpx) and pyrope (prp) inclusions confirming their high pressure origin. One large olivine I grain contains clusters of cpx ( 33 grains) and prp ( 6 grains) inclusions., having a range in Cr2O3 (1.52- 2.36 wt%) , Al2O3 (0.99-5.53 wt%) and Na2O (1.45-5.96 wt%) for cpx and Cr2O3 (3.51-4.42 wt%) and CaO (5.64-6.61 wt%) for prp, showing disequilibrium in olivine I core, containing 200 ppm Ti. This is completely different from any peridotite xenoliths, confirming the uniqueness of this assemblage. The systematic high Ti ( more than 150 ppm) of all studied cores of olivine grains containing low T (Ca# 43.3-48) cpx and prp inclusions confirm the listed differences from all olivines from peridotites and diamonds (e.g. Sobolev et al., 2009, Lithos, 112S: 701-713.). Earlier, similar Ti abundance was reported only for olivines from dunite nodules in Greenland kimberlites (e.g. Arndt et al., 2010, J. Petrol., 51: 573-602).We suggest that Ti-bearing olivine, represented more that 70% of studied samples, is a part of high pressure pyrope lherzolite assemblage, which was formed and grew during the formation and early evolution of kimberlites

  10. Olivine and Pyroxene Compositions in Fine-Grained Chondritic Materials

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael E.; Frank, D.

    2011-01-01

    Our analyses of the Wild-2 samples returned by the Stardust Mission have illuminated critical gaps in our understanding of related astromaterials. There is a very large database of olivine and low-calcium pyroxene compositions for coarse-grained components of chondrites, but a sparse database for anhydrous silicate matrix phases. In an accompanying figure, we present comparisons of Wild-2 olivine with the available chondrite matrix olivine major element data. We thus have begun a long-term project measuring minor as well as major element compositions for chondrite matrix and chondritic IDPs, and Wild 2 grains. Finally, we wish to re-investigate the changes to fine-grained olivine and low-Ca pyroxene composition with progressive thermal metamorphism. We have examined the LL3-4 chondrites which because of the Hayabusa Mission have become very interesting.

  11. Trace elements in the Allende meteorite. IV - Amoeboid olivine aggregates

    NASA Technical Reports Server (NTRS)

    Grossman, L.; Ganapathy, R.; Davis, A. M.; Methot, R. L.

    1979-01-01

    INAA data for Ca, Sc, Hf, La, Ce, Sm, Eu, Tb, Yb, Lu, Os, Ir, Ru, Na, Cl, Br, Fe, Mn, Cr, Co, Au, As, and Sb are presented for ten amoeboid aggregates from the Allende meteorite. Only one lacks olivine. Seven of the remainder, as a group, have cosmic proportions of refractory lithophile and siderophile elements and appear to have formed when coarse-grained Allende inclusion material underwent partial reaction with a low-temperature nebular gas and mixture with FeO-rich olivine. The other two have highly fractionated abundances of refractory elements relative to one another compared to Cl chondrites, including Group II REE patterns, and probably formed by the mixing of fine-grained Allende inclusion material with FeO-rich olivine. Non-refractory siderophile components are also different in composition in each type of amoeboid olivine aggregate.

  12. The Microstructure of a Micrometeorite Impact into Lunar Olivine

    NASA Astrophysics Data System (ADS)

    Noble, S. K.; Keller, L. P.; Christoffersen, R.; Rahman, Z.

    2015-11-01

    Through TEM analysis of the cross-section of a ~20 µm diameter crater into an olivine single crystal we can see first-hand the effects of a single impact, including the creation of nanophase iron in the melt.

  13. Systematics of Vanadium in Olivine from Planetary Basalts

    NASA Technical Reports Server (NTRS)

    Karner, J. M.; Papike, J. J.; Shearer, C. K.

    2002-01-01

    The systematics of vanadium in olivines from the Earth, Moon and Mars allows for the comparison of planetary basalt origin and igneous setting and process. Additional information is contained in the original extended abstract.

  14. Olivine Weathering: Abiotic Versus Biotic Processes as Possible Biosignatures

    NASA Technical Reports Server (NTRS)

    Longazo, T. G.; Wentworth, S. J.; McKay, D. S.; Southam, G.; Clemett, S. J.

    2001-01-01

    A preliminary study to determine how abiotic versus biotic processes affect the weathering of olivine crystals. Perhaps the differences between these weathering processes could be used as biosignatures. Additional information is contained in the original extended abstract.

  15. Olivine Deposits Associated with Impact Basins and Craters on Mars

    NASA Astrophysics Data System (ADS)

    Ody, A.; Poulet, F.; Langevin, Y.; Gondet, B.; Bibring, J.; Carter, J.

    2011-12-01

    An analysis of the 1?m olivine spectral signature applied to the entire and final OMEGA dataset [1] shows numerous olivine-bearing deposits in the 3 main basins of Mars (Argyre, Isidis and Hellas). These signatures are among the strongest of Mars, which suggests compositions with higher iron content and/or larger grain size and/or larger abundance than the ones of widespread olivine-bearing deposits observed on large parts of the southern highlands [1]. A spectral modeling based on a radiative transfer model [2] indicates that their compositions are still close to the forsterite one with abundance in the range of [15,40%] and grain sizes of a few hundreds of ?m. These deposits are exclusively localized on Noachian terrains. Distribution of these deposits around Argyre basin clearly takes the form of discontinuous patches of olivine-bearing rocks on the basin terrace, which strongly suggest that their formation is related to the basin formation event. Recent numerical simulations of basin formation show that impact that formed the Argyre basin could have excavated upper mantle materials and emplaced discontinuous patches of melted mantle on the basin terraces [3]. The observed olivine deposits in Argyre are thus interpreted as olivine-bearing material excavated from the upper mantle during the impact. Olivine deposits distribution around the Hellas basin is not as clear as for Argyre because of young resurfacing processes that strongly affected its region. Olivine deposits are fewer and mainly localized on the northern terrace of Hellas. Most of them are detected in crater ejecta, while a few similar to Argyre olivine discontinuous patches are also observed suggesting that a mantle origin as for Argyre is possible. Olivine has been detected by several datasets in the Nili Fossae region and in the south of Isidis basin. The spectral modeling of OMEGA spectra indicates an olivine abundance of about 40% and megacrysts of several millimeters for the region of Nili Fossae [2]. Several plausible hypotheses has been discussed to explain this unusual concentration of olivine-rich outcrops in Nili Fossae assuming three possibilities for their emplacement relative to the formation of the Isidis basin : pre-impact [4,5], contemporaneous [6], or post-impact [7]. The pretty unique settings and compositions of these deposits in comparison to the two other major basins indicate a different origin, with the post-impact one as the preferred one. Other several localized exposures with strong olivine signature are also found throughout the southern highlands and the northern plains mostly associated with craters. Olivine-bearing material is found in craters floors but also in some crater ejecta implying the presence of an olivine-rich underlying layer. Of special interest are some craters totally filled by olivine-rich lava lakes, which could have erupted through local (impact-related) fractures. [1] A. Ody et al. (2011) LPSC XXXXII.[2] F. Poulet et al. (2009), Icarus 201, 84-101.[3] Stewart S. (2010) AGU, San Francisco, abstract #P43A-08. [4] Hoefen et al. (2003) Science,302,627-630.[5] Hamilton and Christensen (2005), Geology,33,433-436.[6]J.F. Mustard et al. (2007), JGR, 112, E08S03.[7] L.L Tornabene et al. (2008), JGR, 113, E10001.

  16. Kamacite and olivine in ordinary chondrites - Intergroup and intragroup relationships

    NASA Astrophysics Data System (ADS)

    Rubin, A. E.

    1990-05-01

    Results are presented from high-precision electron microprobe analyses of olivine and kamacite in a suite of 134 ordinary chondrites (OCs). The compositional ranges of these phases are defined for each OC group (high total Fe, low total Fe, and low total Fe/low metallic Fe). Anomalous OCs that have olivine and/or kamacite compositions that lie outside the established ranges are identified. The phases in the chondritic clasts of the Netschaevo iron meteorite are characterized to determine the relationship between Netschaevo and OCs. Intragroup variations of olivine and kamacite compositions with petrologic type are examined and OCs that contain olivine and/or kamacite grains with aberrant compositions are identified as fragmental breccias. Also, a search for new metallic Fe-Ni phases with extreme compositions is conducted. As a result of these analyses, several meteorites are reclassified.

  17. Detection of new olivine-rich locations on Vesta

    NASA Astrophysics Data System (ADS)

    Palomba, E.; Longobardo, A.; De Sanctis, M.; Tosi, F.; Capria, M.; Capaccioni, F.; Ammannito, E.; Raymond, C.; Russell, C.

    2014-07-01

    The recent discovery of olivines on Vesta by the VIR imaging spectrometer onboard the Dawn space mission changed dramatically the vision about the Vestan petrogenetic models [1]. Before that, olivines were expected to be present in the Vesta interior: in the mantle of a vertically layered body as invoked by the magma ocean models [2] or at the base of (or within) the mantle-crust boundary as claimed by fractionation models [3]. Olivines were detected by VIR-Dawn in two wide areas near the Arruntia and Bellicia regions. These are located in the northern hemisphere and not in the south, where the Rheasilvia and the more ancient Veneneia huge basins should have excavated the crust down to reach the mantle. In this work, we present our attempts to retrieve other undetected olivine-rich areas on Vesta by using spectral parameters sensitive to olivine such as the Band Area Ratio (BAR) and other specific parameters created for the detection of olivines on Mars (forsterite, fayalite, and a generic olivine index [4,5]). As a preliminary step, we calibrated these parameters by means of VIS-IR spectra of different HED meteorite samples: their behaviors as a function of sample grain size and albedo were retrieved and discussed. We selected the BAR and the forsterite index as the best parameters that can be used on Vesta and applied two independent methods to detect olivine signatures on the VIR hyperspectral cubes: a cross-correlation and an anti-correlation analysis between the BAR and one of the olivine parameters. In agreement with the recent discovery, Arruntia and Bellicia were the most olivine rich areas. In addition, we detected 6 new regions, all but one located in Vesta's northern hemisphere. This result confirms again that the old petrogenetic models cannot be applied, in a straightforward way, to Vesta and should be reshaped in the view of these new detections. An alternative and very recent option can be represented by the model described in [4], in which surface ''eruption'' of material from the mantle, including olivine, can reach the surface of Vesta.

  18. Aluminum speeds up the hydrothermal alteration of olivine

    NASA Astrophysics Data System (ADS)

    Andreani, Muriel; Daniel, Isabelle; Pollet-Villard, Marion

    2014-05-01

    The reactivity of ultramafic rocks toward hydrothermal fluids controls chemical fluxes at the interface between the internal and external reservoirs of silicate planets. On Earth, hydration of ultramafic rocks is ubiquitous and operates from deep subduction zones to shallow lithospheric environments where it considerably affects the physical and chemical properties of rocks and can interact with the biosphere. This process also has key emerging societal implications, such as the production of hydrogen as a source of carbon-free energy. To date, the chemical model systems used to reproduce olivine hydrothermal alteration lead to the formation of serpentine with sluggish reaction rates. Although aluminum is common in geological environments and in hydrothermal systems in particular, its role in serpentinization or olivine dissolution has not been investigated under hydrothermal conditions. Nevertheless, abundant Al supply is expected in fluids released from dehydration of metapelites in subduction zones as well as during the hydrothermal alteration of gabbros at mid-ocean ridges. Aluminum was also abundant in primitive environments of both the Earth and Mars, stored in either Al-rich minerals like plagioclase or Al-enriched ultramafic lavas. We have investigated the role of Al on the hydrothermal alteration of olivine in a series of experiments performed in a low-pressure diamond anvil cell while following the reaction progress in situ by optical imaging and Raman spectroscopy. Experiments were run for 4.5 to 7.5 days with two olivine grains reacted in saline water (0.5 molal NaCl) at 200C and 300C, and P=200 MPa. After two days, olivine crystals were fully transformed to an aluminous serpentine, also enriched in iron. The presence of Al in the hydrothermal fluid increases the rate of olivine serpentinization by more than one order of magnitude by enhancing olivine solubility and serpentine precipitation. The mechanism responsible for this increased solubility has to be further investigated but this result motivates a re-evaluation of the natural rates of olivine serpentinization and of olivine hydrolysis in general in a wide range of settings where olivines or peridotites are intimately associated with Al-providers. Such a fast reaction rate may affect the contribution of reaction-enhanced processes at the micrometer-scale, such as reaction-driven cracking, already proposed for enhancing serpentinization or carbonation of olivine. The effect of Al on lower crust and upper mantle metasomatism is expected to be even stronger at higher pressure in subduction zones where those reactions control the rheology and physical properties of the subducting plate and mantle wedge.

  19. Dissolution of olivine in basaltic liquids: experimental observations and applications.

    USGS Publications Warehouse

    Thornber, C.R.; Huebner, J.S.

    1985-01-01

    Rates of olivine dissolution in synthetic lunar basalt 77115 and a silica-enriched 77115 composition (Sil-77115) at superliquidus temperatures have been determined. Dissolution-rate data have been applied to the problem of the thermal history of fragment-laden impact-melt rocks of the lunar highlands. Textural and chemical criteria are discussed for the recognition of olivine resorption (and growth) phenomena in igneous rocks. -J.A.Z.

  20. Thermal Emission Spectroscopy of 1 Ceres: Evidence for Olivine

    NASA Technical Reports Server (NTRS)

    Witteborn, F. C.; Roush, T. L.; Cohen, M.

    1999-01-01

    Thermal emission spectra of the largest asteroid 1 Ceres obtained from the Kuiper Airborne Observatory display features that may provide information on its surface mineralogy. A plot of the Ceres spectrum (calibrated using alpha Boo as a standard) divided by a standard thermal model (STM) is shown. Also shown is the emissivity spectrum deduced from reflectivity measurements for olivine grains <5 microns in diameter. The general shape of the Ceres and the olivine curves agree in essential details, such as the maxima from 8 to 12 microns, the minimum between 12 and 14 microns, the broad peak near 17.5 micron, and the slope beyond 22 micron. (Use of the 10 to 15-micron grain reflectivities provides a better match to the 12- to 14-micron dip. We used a value of unity for beta, the beaming factor associated with small-scale surface roughness in our STM. Adjustment of beta to a lower value raises the long-wavelength side of the Ceres spectrum, providing an even better match to the olivine curve.) The emissivity behavior roughly matches the emission coefficients which were calculated for olivine particles with a particle radius of 3 microns. Their calculations show not only the negative slope from 23 to 25 pm, but a continued decrease past 30 micron. The Ceres emissivity is thus similar to that of small olivine grains from 8 to 30 micron, but olivine's emissivity is lower from 5 to 8 pm.

  1. Deconvolution of lunar olivine reflectance spectra: Implications for remote compositional assessment

    NASA Astrophysics Data System (ADS)

    Isaacson, Peter J.; Pieters, Carl M.

    2010-11-01

    Lunar olivines typically contain inclusions of Cr-spinel (chromite) that influence their measured optical properties. These altered optical properties complicate modeled predictions of olivine composition from reflectance spectra. Approaches developed for inclusion-free terrestrial olivine spectra must be modified to be applied to chromite-bearing lunar olivine spectra. We present a revised approach for predicting the compositions of chromite-bearing lunar olivines using the Modified Gaussian Model (MGM). The results of this revised approach for chromite-bearing lunar olivines are consistent with previous results for terrestrial olivine reflectance spectra, and successfully predict the olivine's composition. These results are an important step in compositional assessment of remotely-sensed olivine spectra, and are essential to ongoing investigations of that topic. Our results are based on a limited set of available lunar olivine separates, and would be strengthened by the inclusion of additional compositions.

  2. Determining the composition of olivine on asteroidal surfaces

    NASA Technical Reports Server (NTRS)

    Sunshine, Jessica M.; Pieters, Carle M.

    1993-01-01

    Olivine was remotely identified as a major component on many S- and A-type asteroids based on qualitative analyses of broad absorption features near 1.0 micron in their telescopic reflectance spectra. Laboratory studies showed that this diagnostic olivine absorption feature is composed of three individual absorption bands resulting from electronic transitions of Fe(+2) in distorted M1 and M2 sites. Both the overall absorption feature and each of the individual absorption bands are also known to vary systematically as a function of olivine composition. Thus, it should be possible to remotely determine the composition of olivine present on the surfaces of the various olivine-rich asteroids. However, extrapolation of laboratory studies to compositional interpretation of asteroid spectra is complicated by several factors: observational noise; lower spectral resolution; compositional heterogeneities (including the presence of other phases such as pyroxenes and/or metal); and the effects of alteration processes. In order to address such complex problems, a quantitative approach to spectral analysis, the modified Gaussian model (MGM) was developed by Sunshine et al., which deconvolves spectra into their constituent absorption bands. The MGM, a refinement of the Gaussian model, more accurately adheres to the physical processes involved in electronic transition absorptions. Under the MGM, each spectrum is modeled in log reflectance and energy as a sum of absorption bands superimposed onto a baseline or continuum. Each absorption band is described by three model parameters (center, width, and strength) which can be interpreted and used to infer composition. One of the strengths of the MGM is that it allows compositional information to be extracted directly from measured spectra and is therefore complementary to other approaches to modeling asteroid spectra which require the use of meteorites and/or terrestrial samples as spectral analogs. A quantitative understanding of the properties of olivine absorptions was established by using the MGM to analyze a laboratory suite of spectra spanning a full range of olivine compositions.

  3. The origin of high hydrogen content in kimberlitic olivine: Evidence from hydroxyl zonation in olivine from kimberlites and mantle xenoliths

    NASA Astrophysics Data System (ADS)

    Hilchie, Luke; Fedortchouk, Yana; Matveev, Sergei; Kopylova, Maya G.

    2014-08-01

    Olivine macrocrysts in kimberlites are the most H-rich natural olivines known. Their xenocrystic provenance makes unclear whether H-enrichment occurred in the mantle prior to entrainment in kimberlite magma or during ascent. We present a Fourier transform infrared (FTIR) spectroscopy-based study of H zonation in kimberlite-derived olivine macrocrysts and/or olivine in xenoliths from the kimberlites Jericho (Nunavut, Canada), Beartooth (Northwest Territories, Canada), and Pipe 200 and Matsoku (Lesotho). The objective of the study was to determine whether changes in the concentration or speciation of H defects in proximity to the host kimberlite could yield insights into the origin of H-enrichment. Within the Group 1 region of the FTIR spectrum (~ 3420-3700 cm- 1), we find that olivines within xenoliths and macrocrysts show weak zonation or significant H depletions in rims. Peaks in the Group 2 region (~ 3260-3420 cm- 1) in Beartooth olivines show marked decrease in the crystal margins in comparison to Group 1 peaks. We find no preserved evidence for kimberlite-related H-enrichment in our dataset. We ascribe H depletion to diffusive H loss to infiltrating kimberlitic media. Diffusion models using coefficients previously applied to dehydrogenation of olivine and assuming a dry environment produce extremely short ascent durations incompatible with the results of other geospeedometers. This mismatch suggests that the poorly developed zonation in Jericho and Beartooth olivines indicates water-enrichment and/or faster ascent of these melts (in comparison to Pipe 200 and Matsoku), resulting in greater retention of mantle-derived H. A further significant factor in the mismatch is the differing speciation of H in most natural mantle-derived olivines in comparison to those used in diffusion experiments. We argue that the presence of presumably mantle-derived Group 2 H in olivine macrocrysts indicates rapid ascent of magma exsolving water-rich fluid, permitting preservation of these faster-diffusing defects only in particularly rapidly ascending kimberlite magmas. This interpretation explains empirical correlations between the presence of Group 2 bands, water-derived diamond resorption features, and volcaniclastic kimberlite facies.

  4. Optimization of Carbon Coatings on LiFePO4

    SciTech Connect

    Doeff, Marca M.; Wilcox, James D.; Kostecki, Robert; Lau, Grace

    2005-07-14

    The electrochemical performance of LiFePO{sub 4} in lithium cells is strongly dependent on the structure (disordered/graphene or D/G ratio) of the in situ carbon produced during synthesis from carbon-containing precursors. Addition of pyromellitic acid (PA) prior to final calcination results in lower D/G ratios, yielding a higher-rate material. Further, improvements in electrochemical performance are realized when graphitization catalysts such as ferrocene are also added during LiFePO{sub 4} preparation, although overall carbon content is still less than 2 wt.%.

  5. A Method for the Flux Growth of Intermediate Composition Olivine

    NASA Astrophysics Data System (ADS)

    Deangelis, M. T.; Anovitz, L. M.; Labotka, T. C.; Frederick, D. A.

    2009-05-01

    Though solid solution of iron and magnesium between forsterite (Mg2SiO4) and fayalite (Fe2SiO4) is possible in the olivine crystal structure, the high oxygen fugacity condition of the terrestrial mantle inhibits the widespread crystallization of intermediate (Fo40-Fo60) composition olivine. This limitation is not the same for some other inner solar system bodies (e.g. the Moon and Mars), where conditions are reducing and olivine compositions are wide ranging. Unfortunately, the amount of samples from the Moon and Mars is extremely limited; with only Apollo and Luna mission samples, lunar meteorites, and Martian meteorites available for direct mineralogic and petrologic characterization. These characterizations have provided a useful basis for many spectroscopic and modeling interpretations, but many fundamental questions remain and may only be answerable through either direct observation of rocks or by analog experimentation. The motivation for our work on growth of intermediate olivine crystals, therefore, is to create realistic starting material for use in Mars and Moon analog experiments. A variety of crystal growth methods have been previously used to synthesize olivine, including: the Czochralski-pulling (CZ) method, the floating-zone image furnace (FZ) method, and sol-gel processing techniques. Both the CZ and FZ methods have the advantage of producing large crystals, but the growth apparatus and regulation of reduced atmospheric conditions during growth can make these techniques both time and cost intensive. Sol-gel processing to produces olivine fibers is a useful chemical technique, but obtaining larger grain sizes can be difficult. An alternative method for crystal growth is through the use a flux, which can grow crystals relatively quickly and inexpensively. We have grown synthetic crystals of intermediate composition (Fo30-Fo70) olivine using a lithium borate (B5Li3O9) flux. The starting material was a mixture of magnesite (MgCO3), siderite (FeCO3), and quartz (SiO2) powder in a 1:1:1 ratio. The advantage of using siderite is that the iron is already present in the ferrous form. Upon heating and decarbonation, this mixture represents a bulk composition of Fo50 (FeMgSiO4) olivine. Flux was then added to the starting material mixture so that the final mixture was 50% starting material and 50% flux by weight. This final mix was then placed in a platinum crucible that was heated to 1100 °C in a vacuum furnace for three days. The use of a vacuum furnace ensured that conditions remained reducing during crystal growth. The result was growth of olivine crystals that are generally small (< 1 mm in length) and have euhedral crystal form. These crystals have been analyzed by electron microprobe, and are systematically zoned from core to rim with Mg-rich cores (˜Fo70) transitioning to Fe-rich rims (˜Fo30). This zoning represents an expected heterogeneity due to olivine growth from a finite reservoir of starting material. The flux growth of this intermediate composition olivine was primarily a 'proof of concept' experiment, and showed that olivine crystals can be grown using a flux under sub-solidus conditions. Additional crystal growth experiments would be useful to gauge the response of olivine to changes in temperature, duration, and composition of the flux + starting material mixture.

  6. Formation of a metastable olivine wedge in a descending slab

    SciTech Connect

    Devaux, J.P.; Schubert, G.; Anderson, C.

    1997-11-01

    We present a thermal model of a descending slab in which the transformation of olivine to spinel is controlled by pressure- and temperature-dependent reaction kinetics. Two different formulations of the kinetics are considered with the main discriminant being the temperature range over which olivine converts to spinel at pressures of about 15 GPa (about 500{degree}{endash}515{degree}C and 560{degree}{endash}650{degree}C). We use a finite element method to solve the coupled heat conduction (perpendicular and parallel to the dip of the slab) and kinetics equations, and we include the latent heat of the phase transformation. Latent heat release together with heat conduction parallel to the dip of the slab reduces significantly the length of the metastable olivine wedge and results in a very thin ({approx_lt}5km) two-phase region. We employ the thermal parameter v{tau}sin{delta} (v is the velocity of the descending slab, {tau} is the age of the slab, and {delta} is the dip of the slab to the horizontal) to interpret the results for the length of the metastable wedge. For values of the thermal parameter smaller than about 4000 and 7000 km, depending on the model of the kinetics, no metastable olivine wedge exists (the critical value of 7000 km for the thermal parameter corresponds to the kinetics model with the lowest transition temperature range). The length of the metastable olivine wedge is also found to be very sensitive to the model of the kinetics and to the effects of adiabatic heating. If the occurrence of deep earthquakes is related to the transformation of metastable olivine to spinel, then data on earthquake depth versus thermal parameter require that the onset of the reaction takes place at temperatures of about 550{degree}{endash}575{degree}C. In this case the slab thermal parameter must be larger than 10,000 km for the metastable olivine wedge to extend down to 660 km depth. But deep earthquakes occur near 660 km depth in slabs with thermal parameter as small as about 5000 km (South America, for example). Either some deep earthquakes are unrelated to olivine metastability or our knowledge of olivine-spinel reaction kinetics is incomplete.{copyright} 1997 American Geophysical Union

  7. Extraction of in situ cosmogenic 14C from olivine

    USGS Publications Warehouse

    Pigati, J.S.; Lifton, N.A.; Timothy, Jull A.J.; Quade, Jay

    2010-01-01

    Chemical pretreatment and extraction techniques have been developed previously to extract in situ cosmogenic radiocarbon (in situ 14C) from quartz and carbonate. These minerals can be found in most environments on Earth, but are usually absent from mafic terrains. To fill this gap, we conducted numerous experiments aimed at extracting in situ 14C from olivine ((Fe,Mg)2SiO4). We were able to extract a stable and reproducible in situ 14C component from olivine using stepped heating and a lithium metaborate (LiBO2) flux, following treatment with dilute HNO3 over a variety of experimental conditions. However, measured concentrations for samples from the Tabernacle Hill basalt flow (17.3 ?? 0.3 ka4) in central Utah and the McCarty's basalt flow (3.0 ?? 0.2 ka) in western New Mexico were significantly lower than expected based on exposure of olivine in our samples to cosmic rays at each site. The source of the discrepancy is not clear. We speculate that in situ 14C atoms may not have been released from Mg-rich crystal lattices (the olivine composition at both sites was ~Fo65Fa35). Alternatively, a portion of the 14C atoms released from the olivine grains may have become trapped in synthetic spinel-like minerals that were created in the olivine-flux mixture during the extraction process, or were simply retained in the mixture itself. Regardless, the magnitude of the discrepancy appears to be inversely proportional to the Fe/(Fe+Mg) ratio of the olivine separates. If we apply a simple correction factor based on the chemical composition of the separates, then corrected in situ 14C concentrations are similar to theoretical values at both sites. At this time, we do not know if this agreement is fortuitous or real. Future research should include measurement of in situ 14C concentrations in olivine from known-age basalt flows with different chemical compositions (i.e. more Fe-rich) to determine if this correction is robust for all olivine-bearing rocks. ?? 2010 by the Arizona Board of Regents on behalf of the University of Arizona.

  8. Tracing Oxygen Fugacity in Asteroids and Meteorites Through Olivine Composition

    NASA Technical Reports Server (NTRS)

    Sunshine, J. M.; Bus, S. J.; Burbine, T. H.; McCoy, T. J.

    2005-01-01

    Olivine absorptions are known to dominate telescopic spectra of several asteroids. Among the meteorite collection, three groups (excluding Martian meteorites), the pallasites, brachinites, and R group chondrites are plausible analogs to olivine-rich asteroids in that they are dominated by olivine. These meteorite groups have distinct petrologic origins. The primitive achondrite brachinites (which include both depleted and undeleted subgroups) are products of relatively minor differentiation and evolved in oxidizing environments. R chondrites are also thought to have formed in high oxygen states, but are closely related to ordinary chondrites (yet with their own distinct compositions and oxygen isotopic signatures). In contrast, pallasites, widely thought to be mantle components from much more evolved bodies, formed in more reducing environments. Petrologic indicators that are identifiable in spectral data must be used in order to infer the petrologic history of asteroids from surveys of their actual population. As discussed below, olivine composition (e.g. Fa#) can provide key constraints in exploring the origin and significance of olivine dominated asteroids.

  9. Olivine Composite Cathode Materials for Improved Lithium Ion Battery Performance

    SciTech Connect

    Ward, R.M.; Vaughey, J.T.

    2006-01-01

    Composite cathode materials in lithium ion batteries have become the subject of a great amount of research recently as cost and safety issues related to LiCoO2 and other layered structures have been discovered. Alternatives to these layered materials include materials with the spinel and olivine structures, but these present different problems, e.g. spinels have low capacities and cycle poorly at elevated temperatures, and olivines exhibit extremely low intrinsic conductivity. Previous work has shown that composite structures containing spinel and layered materials have shown improved electrochemical properties. These types of composite structures have been studied in order to evaluate their performance and safety characteristics necessary for use in lithium ion batteries in portable electronic devices, particularly hybrid-electric vehicles. In this study, we extended that work to layered-olivine and spinel-olivine composites. These materials were synthesized from precursor salts using three methods: direct reaction, ball-milling, and a coreshell synthesis method. X-ray diffraction spectra and electrochemical cycling data show that the core-shell method was the most successful in forming the desired products. The electrochemical performance of the cells containing the composite cathodes varied dramatically, but the low overpotential and reasonable capacities of the spinel-olivine composites make them a promising class for the next generation of lithium ion battery cathodes.

  10. Applicability of Henry's Law to helium solubility in olivine

    NASA Astrophysics Data System (ADS)

    Jackson, C.; Parman, S. W.; Kelley, S. P.; Cooper, R. F.

    2013-12-01

    Applicability of Henry's Law to helium solubility in olivine We have experimentally determined helium solubility in San Carlos olivine across a range of helium partial pressures (PHe) with the goal of quantifying how noble gases behave during partial melting of peridotite. Helium solubility in olivine correlates linearly with PHe between 55 and 1680 bar. This linear relationship suggests Henry's Law is applicable to helium dissolution into olivine up to 1680 bar PHe, providing a basis for extrapolation of solubility relationships determined at high PHe to natural systems. This is the first demonstration of Henry's Law for helium dissolution into olivine. Averaging all the data of the PHe series yields a Henry's coefficient of 3.8(×3.1)×10-12 mol g-1 bar-1. However, the population of Henry's coefficients shows a positive skew (skewness = 1.17), i.e. the data are skewed to higher values. This skew is reflected in the large standard deviation of the population of Henry's coefficients. Averaging the median values from each experiment yields a lower Henry's coefficient and standard deviation: 3.2(× 2.3)×10-12 mol g-1 bar-1. Combining the presently determined helium Henry's coefficient for olivine with previous determinations of helium Henry's coefficients for basaltic melts (e.g. 1) yields a partition coefficient of ~10-4. This value is similar to previous determinations obtained at higher PHe (2). The applicability of Henry's Law here suggests helium is incorporated onto relatively abundant sites within olivine that are not saturated by 1680 bar PHe or ~5×10-9 mol g-1. Large radius vacancies, i.e. oxygen vacancies, are energetically favorable sites for noble gas dissolution (3). However, oxygen vacancies are not abundant enough in San Carlos olivine to account for this solubility (e.g. 4), suggesting the 3x10-12 mol g-1 bar-1 Henry's coefficient is associated with interstitial dissolution of helium. Helium was dissolved into olivine using an externally heated pressure vessel (Brown University). The starting materials were prepared by cutting gem-quality San Carlos olivine (~Fo90) into small blocks (~4×2×1 mm) using a diamond wafering blade saw and polishing with alumina slurries and colloidal silica. Analysis was completed by laser ablation-mass spectrometry using a 193 nm excimer laser and a MAP 215-50 specifically tuned for He (Open University, UK). Laser ablation pit depth varied from 2 to 40 μm, and no correlation between pit depth and [He] is observed after accounting for variations PHe across the different experiments. This lack of correlation indicates a close approach to equilibrium was achieved over the experimental durations. Two analyses yielded spuriously high [He] (>3 std. dev. from the population mean, n = 85), and these analyses were not used to calculate Henry's coefficients. The two spuriously high analyses, in combination with the right skew of Henry's coefficients calculated from individual data points, suggests gem-quality San Carlos olivine contains volumes with anomalously high helium solubility. The nature of these volumes is currently under investigation. However, despite their presence, helium is still highly incompatible in olivine during partial melting. [1] Lux GCA 1987 [2] Heber et al. GCA 2007 [3] Shcheka & Keppler Nature 2012 [4] Walker et al. PEPI 2009

  11. Barred olivine 'chondrules' in lunar spinel troctolite 62295

    NASA Technical Reports Server (NTRS)

    Roedder, E.; Weiblen, P. W.

    1977-01-01

    Several objects have been found in sections of lunar igneous spinel troctolite 62295 that resemble certain meteoritic barred olivine chondrules. Each consists of an apparently spherical single crystal of Fo90 olivine, approximately 0.6-0.8 mm in diameter, containing a set of approximately 30-40 subparallel stringers of An95 plagioclase, whereas the stringers in ordinary meteoritic chondrules consist of glass. The olivine of the 62295 chondrules is also more magnesian, and is radially zoned, having a relatively iron-rich core and rim and an iron-poor intermediate zone. Several possible origins are proposed: impact-generated melt globules solidified in flight, spherical phenocrysts, and meteoritic chondrules, but none of these seems adequate to explain the detailed observations.

  12. Exogenic olivine on Vesta from Dawn Framing Camera color data

    NASA Astrophysics Data System (ADS)

    Nathues, Andreas; Hoffmann, Martin; Schäfer, Michael; Thangjam, Guneshwar; Le Corre, Lucille; Reddy, Vishnu; Christensen, Ulrich; Mengel, Kurt; Sierks, Holger; Vincent, Jean-Baptist; Cloutis, Edward A.; Russell, Christopher T.; Schäfer, Tanja; Gutierrez-Marques, Pablo; Hall, Ian; Ripken, Joachim; Büttner, Irene

    2015-09-01

    In this paper we present the results of a global survey of olivine-rich lithologies on (4) Vesta. We investigated Dawn Framing Camera (FC) High Altitude Mapping Orbit (HAMO) color cubes (∼60 m/pixel resolution) by using a method described in Thangjam et al. (Thangjam, G., Nathues, A., Mengel, K., Hoffmann, M., Schäfer, M., Reddy, V., Cloutis, E.A., Christensen, U., Sierks, H., Le Corre, L., Vincent, J.-B, Russell, C.T. [2014b]. Meteorit. Planet. Sci. arXiv:1408.4687 [astro-ph.EP]). In total we identified 15 impact craters exhibiting olivine-rich (>40 wt.% ol) outcrops on their inner walls, some showing olivine-rich material also in their ejecta and floors. Olivine-rich sites are concentrated in the Bellicia, Arruntia and Pomponia region on Vesta's northern hemisphere. From our multi-color and stratigraphic analysis, we conclude that most, if not all, of the olivine-rich material identified is of exogenic origin, i.e. remnants of A- or/and S-type projectiles. The olivine-rich lithologies in the north are possibly ejecta of the ∼90 km diameter Albana crater. We cannot draw a final conclusion on their relative stratigraphic succession, but it seems that the dark material (Nathues, A., Hoffmann, M., Cloutis, E.A., Schäfer, M., Reddy, V., Christensen, U., Sierks, H., Thangjam, G.S., Le Corre, L., Mengel, K., Vincent, J.-B., Russell, C.T., Prettyman, T., Schmedemann, N., Kneissl, T., Raymond, C., Gutierrez-Marques, P., Hall, I. Büttner, I. [2014b]. Icarus (239, 222--237)) and the olivine-rich lithologies are of a similar age. The origin of some potential olivine-rich sites in the Rheasilvia basin and at crater Portia are ambiguous, i.e. these are either of endogenic or exogenic origin. However, the small number and size of these sites led us to conclude that olivine-rich mantle material, containing more than 40 wt.% of olivine, is basically absent on the present surface of Vesta. In combination with recent impact models of Veneneia and Rheasilvia (Clenet, H., Jutzi, M., Barrat, J.-A., Gillet, Ph. [2014]. Lunar Planet Sci. 45, #1349; Jutzi, M., Asphaug, E., Gillet, P., Barrat, J.-A., Benz, W. [2013]. Nature 494, 207-210), which predict an excavation depth of up to 80 km, we are confident that the crust-mantle depth is significantly deeper than predicted by most evolution models (30 km; Mittlefehldt, D.W. [2014]. Asteroid 4 Vesta: A Fully Differentiated Dwarf Planet. NASA Technical Reports Server (20140004857.pdf)) or, alternatively, the olivine-content of the (upper) mantle is lower than our detection limit, which would lead to the conclusion that Vesta's parent material was already depleted in olivine compared to CI meteorites.

  13. An olivine-free mantle source of Hawaiian shield basalts.

    PubMed

    Sobolev, Alexander V; Hofmann, Albrecht W; Sobolev, Stephan V; Nikogosian, Igor K

    2005-03-31

    More than 50 per cent of the Earth's upper mantle consists of olivine and it is generally thought that mantle-derived melts are generated in equilibrium with this mineral. Here, however, we show that the unusually high nickel and silicon contents of most parental Hawaiian magmas are inconsistent with a deep olivine-bearing source, because this mineral together with pyroxene buffers both nickel and silicon at lower levels. This can be resolved if the olivine of the mantle peridotite is consumed by reaction with melts derived from recycled oceanic crust, to form a secondary pyroxenitic source. Our modelling shows that more than half of Hawaiian magmas formed during the past 1 Myr came from this source. In addition, we estimate that the proportion of recycled (oceanic) crust varies from 30 per cent near the plume centre to insignificant levels at the plume edge. These results are also consistent with volcano volumes, magma volume flux and seismological observations. PMID:15800614

  14. Reversibility of Lpo in Olivine during Deformation at High Pressure

    NASA Astrophysics Data System (ADS)

    Li, L.; Weidner, D. J.

    2014-12-01

    Olivine texture has been reported as an important contributor to the seismic anisotropy in the upper mantle. Experimental studies of deformation of olivine have also shown flow-driven lattice preferred orientation. In this study, we focus on in situ control and monitoring of LPO formation of olivine using synchrotron X-ray radiation coupled with DDIA multi-anvil deformation device. Using an energy-dispersive X-ray coupled a 10-element SSD detector; we apply a sinusoidal stress on the sample, which allows identification of growth of LPO in the specimen with relative robust signal even with small strain fields. Our data show palpable correlations among stress, strain and LPO as well as the variations among sub-grains marked by individual (hkl). This study is to demonstrate the versatile functions of X-ray for characterizing the deformation study of minerals.

  15. Iddingzitized olivine in mantle xenoliths: evidence for (really) early alteration

    NASA Astrophysics Data System (ADS)

    Low, P. C.; Schultz, L.; Stier, N.

    2011-12-01

    Iddingsite is an alteration product of olivine (or pyroxene) that contains goethite and some combination of maghemite, hematite, orthopyroxene, Mg-rich phyllosilicates, amorphous silica, and a temperature and a pressure-appropriate SiO2 polymorph and lacks the definite structure or chemical composition requisite of classification as a mineral. The process of iddingsitization is most commonly discussed as a low-temperature, near-surface phenomenon involving the oxidation and inorganic hydroxylation of olivine during weathering. High-temperature iddingsite (sometimes referred to as magmatic iddingsite) is also discussed in the literature and is generally attributed to reactions that occur at low pressure in response unusually high water content and/or high oxygen fugacity in pre-eruptive mafic magmas or during the process of extrusion and cooling or to hydrothermal metasomatism. Xenoliths from the Ponderosa flow of the Uinkaret Volcanic Field located along the Colorado River just downstream from Lava Falls in the Western Grand Canyon include spinel-bearing dunite, harzburgite, and olivine-rich lherzolite samples that exhibit geochemical characteristics that are consistent with residues of 5-17% partial melting. Olivine from xenoliths collected from this flow contain olivine that is either entirely fresh (no evidence of alteration) or olivine that has been ubiquitously partially iddingzitized with some samples containing both the green-colored fresh samples and the red-colored altered samples mere centimeters apart. Preliminary in situ FTIR mapping of water peaks in the region of 3700-3000 cm-1 indicate notable peak near 3680 cm-1 (a region of the spectrum associated with the presences of serpentine minerals) in altered samples. Iddingsite exhibits two distinct morphologies in these samples, one thicker (about 1 micrometer across) occurring mostly along fractures in the olivine grains, and the other much thinner occurring along crystallographically-oriented planes in olivine. Some of the partially altered olivine crystals exhibiting the later texture contain deformational kink bands that, given that the young eruption age of the host basalt, post-dates any crustal activity that could be responsible for such a fabric at this location, much have occurred in the lithospheric mantle. Textural evidence that the iddingzitized areas of these olivine crystals pre-date the kink banding suggests that the alteration of these olivines occurred in the mantle. Post-entrainment alteration is unlikely particularly given the close proximity of altered and unaltered samples with similar post-entrainment history and the fact that the host basalts are not particularly hydrous. The variety of alteration in xenoliths at this location suggest that the entraining flows are either sampling small regions of the mantle that contains very high gradients with regard to water content or oxygen fugacity or are sampling relatively large areas. Quantitative analysis of volatiles in altered and unaltered olivine crystals planned in order to better constrain these gradients.

  16. Thermal Emission Spectroscopy of 1 Ceres: Evidence For Olivine

    NASA Astrophysics Data System (ADS)

    Witteborn, Fred C.; Roush, Ted L.; Cohen, Martin

    2000-03-01

    Thermal emission spectra of the largest asteroid, 1 Ceres, obtained from the Kuiper Airborne Observatory display features that may provide information about its surface mineralogy. The emissivity, obtained by dividing the spectra by a standard thermal model, is compared with emissivity spectra of olivines and phyllosilicates deduced via Kirchoff's law from reflectivity measurements. The spectra provide a fairly good match to fine grained olivines (0 to 5 μm size range). The smoothness of the spectrum beyond 18 μm is an indication of particles smaller than 50 μm. While the abrupt rise in emissivity near 8 μm matches many silicates, the distinct emissivity minimum centered near 12.8 μm is consistant with iron-poor olivines, but not with phyllosilicates. It suggests the presence of opaques and does not exclude a mixture with organics and fine-grained phyllosilicates.

  17. Thermal Emission Spectroscopy of 1 Ceres: Evidence for Olivine

    NASA Astrophysics Data System (ADS)

    Witteborn, Fred. C.; Roush, Ted L.; Cohen, Martin

    1999-01-01

    Thermal emission spectra of the largest asteroid, 1 Ceres, obtained from the Kuiper Airborne Observatory display features that may provide information about its surface mineralogy. The emissivity, obtained by dividing the spectra by a standard thermal model, is compared with emissivity spectra of olivines and phyllosilicates deduced via Kirchoff's law from reflectivity measurements. The spectra provide a fairly good match to fine grained olivines (0 to 5 micrometer size range). The smoothness of the spectrum beyond 18 micrometers is an indication of particles smaller than 50 micrometers. While the abrupt rise in emissivity near 8 micrometers matches many silicates, the distinct emissivity minimum centered near 12.8 micrometers is consistant with iron-poor olivines, but not with phyllosilicates. It suggests the presence of opaques and does not exclude a mixture with organics and fine-grained phyllosilicates.

  18. The identification of crystalline olivine in cometary silicates

    NASA Astrophysics Data System (ADS)

    Campins, H.; Ryan, E. V.

    1989-06-01

    An intermediate-resolution spectrum of the 8-13 micron region in comet Halley is obtained which shows a prominent silicate emission feature with structure not observed before in other comets or in interstellar silicates. The presence of a strong 11.3 micron peak reported by Bregman and coworkers is confirmed, and evidence is found for additional structure in the band. By comparison with spectra of interplanetary dust particles and laboratory silicates, it is concluded that small crystalline olivine particles are a major component of the silicates in this comet; other silicates (e.g., amorphous or hydrated) must also be present. The identification of crystalline olivine in this part of the spectrum is supported by the observation of four peaks in 20-50 micron airborne spectra of this comet which have also been attributed to olivine.

  19. Amoeboid olivine aggregates from CH carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Krot, Alexander N.; Park, Changkun; Nagashima, Kazuhide

    2014-08-01

    Amoeboid olivine aggregates (AOAs) in CH carbonaceous chondrites are texturally and mineralogically similar to those in other carbonaceous chondrite groups. They show no evidence for alteration and thermal metamorphism in an asteroidal setting and consist of nearly pure forsterite (Fa<3; in wt%, CaO = 0.1-0.8, Cr2O3 = 0.04-0.48; MnO < 0.5), anorthite, Al-diopside (in wt%, Al2O3 = 0.7-8.1; TiO2 < 1), Fe,Ni-metal, spinel, and, occasionally, low-Ca pyroxene (Fs1Wo2-3), and calcium-aluminum-rich inclusions (CAIs). The CAIs inside AOAs are composed of hibonite, grossite, melilite (k13-44), spinel, perovskite, Al,Ti-diopside (in wt%, Al2O3 up to 19.6; TiO2 up to 13.9), and anorthite. The CH AOAs, including CAIs within AOAs, have isotopically uniform 16O-rich compositions (average ?17O = -23.4 2.3, 2SD) and on a three-isotope oxygen diagram plot along ?slope-1 line. The only exception is a low-Ca pyroxene-bearing AOA 1-103 that shows a range of ?17O values, from -24 to -13. Melilite, grossite, and hibonite in four CAIs within AOAs show no evidence for radiogenic 26Mg excess (?26Mg). In contrast, anorthite in five out of six AOAs measured has ?26Mg corresponding to the inferred initial 26Al/27Al ratio of (4.3 0.7) 10-5, (4.2 0.6) 10-5, (4.0 0.3) 10-5, (1.7 0.2) 10-5, and (3.0 2.6) 10-6. Anorthite in another AOA shows no resolvable ?26Mg excess; an upper limit on the initial 26Al/27Al ratio is 5 10-6. We infer that CH AOAs formed by gas-solid condensation and aggregation of the solar nebula condensates (forsterite and Fe,Ni-metal) mixed with the previously formed CAIs. Subsequently they experienced thermal annealing and possibly melting to a small degree in a 16O-rich gaseous reservoir during a brief epoch of CAI formation. The low-Ca pyroxene-bearing AOA 1-103 may have experienced incomplete melting and isotope exchange in an 16O-poor gaseous reservoir. The lack of resolvable ?26Mg excess in melilite, grossite, and hibonite in CAIs within AOAs reflects heterogeneous distribution of 26Al in the solar nebula during this epoch. The observed variations of the inferred initial 26Al/27Al ratios in anorthite of the mineralogically pristine and uniformly 16O-rich CH AOAs could have recorded (i) admixing of 26Al in the protoplanetary disk during the earliest stages of its evolution and/or (ii) closed-system Mg-isotope exchange between anorthite and Mg-rich minerals (spinel, forsterite, and Al-diopside) during subsequent prolonged (days-to-weeks) thermal annealing at high temperature (?1100 C) and slow cooling rates (?0.01 K h-1) that has not affected their O-isotope systematics. The proposed thermal annealing may have occurred in an impact-generated plume invoked for the origin of non-porphyritic magnesian chondrules and Fe,Ni-metal grains in CH and CB carbonaceous chondrites about 5 Myr after formation of CV CAIs.

  20. Grinding methods to enhance the reactivity of olivine

    SciTech Connect

    Summers, Cathy A.; Dahlin, David C.; Rush, Gilbert E.; O'Connor, William K.; Gerdemann, Stephen J.

    2004-01-01

    The Albany Research Center (ARC) conducted studies of mechanical activation by conventional and ultra-fine grinding techniques to enhance olivine reactivity in mineral carbonation reactions. Activated olivine is one of several solid feed materials used at ARC in reactions with carbon dioxide to form carbonate minerals. This paper compares grinding techniques via energy demand data and product characteristics, including particle size distributions, surface areas, full width at half maximum (FWHM) XRD analyses, and particle morphology by SEM analyses. Reactivity was gauged by percent conversion to carbonate in subsequent carbonation tests.

  1. Global investigation of olivine on Mars: Insights into crust and mantle compositions

    NASA Astrophysics Data System (ADS)

    Ody, A.; Poulet, F.; Bibring, J.-P.; Loizeau, D.; Carter, J.; Gondet, B.; Langevin, Y.

    2013-02-01

    present the distribution of olivine on Mars, derived from spectral parameters based on the 1 µm olivine absorption band. The olivine can be defined with respect to two spectral end-members: type 1 corresponds to olivine with low iron content and/or small grain size and/or small abundance, and type 2, which corresponds to olivine with higher iron content and/or larger grain size and/or larger abundance. The spatial and statistical analysis of the global olivine distribution points out five major geological settings where olivine is detected: (1) Early Hesperian olivine-bearing smooth crater floors and flat intercrater plains throughout the southern highlands; (2) olivine deposits around the three main basins Argyre, Hellas, and Isidis; (3) olivine in intercrater dunes, crater ejecta, or extended deposits in the northern plains; (4) olivine associated with outcrops and sand in the floor of Valles Marineris; and (5) olivine-bearing butte outcrops in the vicinity of Hellas. The geological context, the age, and the composition of the olivine detections associated with these five major geological settings are detailed. Their origin and the implication of their occurrence on the composition of the Martian mantle and crust, as well as on the evolution of Mars volcanism are discussed.

  2. Trace Element Compositions of Pallasite Olivine Grains and Pallasite Origin

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, David W.; Herrin, J. S.

    2010-01-01

    Pallasites are mixtures of metal with magnesian olivine. Most have similar metal compositions and olivine oxygen isotopic compositions; these are the main-group pallasites (PMG). The Eagle Station grouplet of pallasites (PES) have distinctive metal and olivine compositions and oxygen isotopic compositions. Pallasites are thought to have formed at the core-mantle boundary of their parent asteroids by mixing molten metal with solid olivine of either cumulatic or restitic origin. We have continued our investigation of pallasite olivines by doing in situ trace element analyses in order to further constrain their origin. We determined Al, P, Ca, Ga and first row transition element contents of olivine grains from suite of PMG and PES by LA-ICP-MS at JSC. Included in the PMG suite are some that have anomalous metal compositions (PMG-am) and atypically ferroan olivines (PMG-as). Our EMPA work has shown that there are unanticipated variations in olivine Fe/Mn, even within those PMG that have uni-form Fe/Mg. Manganese is homologous with Fe2+, and thus can be used the same way to investigate magmatic fractionation processes. It has an advantage for pallasite studies in that it is unaffected by redox exchange with the metal. PMG can be divided into three clusters on the basis of Mn/Mg; low, medium and high that can be thought of as less, typically and more fractionated in an igneous sense. The majority of PMG have medium Mn/Mg ratios. PMG-am occur in all three clusters; there does not seem to be any relationship between putative olivine igneous fractionation and metal composition. The PMG-as and one PMG-am make up the high Mn/Mg cluster; no PMG are in this cluster. The high Mn/Mg cluster ought to be the most fractionated (equivalent to the most Fe-rich in igneous suites), yet they have among the lowest contents of incompatible lithophile elements Al and Ti and the two PMG-as in this cluster also have low Ca and Sc contents. This is inconsistent with simple igneous fractionation on a single, initially homogeneous parent asteroid. For Al and Ti, the low and high Mn/Mg clusters have generally uniform contents, while the medium cluster has wide ranges. This is also true of analyses of duplicate grains from the medium cluster pallasites which can have very different Al and Ti contents. Those from the low and high clusters do not. These observations suggest that pallasite olivines are not cumulates, but rather are restites from high degrees of melting. The moderately siderophile elements P and Ga show wide ranges in the high Mn/Mg cluster, but very uniform compositions in the medium cluster, opposite the case for Al and Ti. There is no correlation of P or Ga and Fe/Mn as might be expected if redox processes controlled the contents of moderately siderophile elements in the olivines. The lack of correlation of P could reflect equilibration with phosphates, although there is no correlation of Ca with P as might be expected

  3. Chemical zonation in olivine-hosted melt inclusions

    NASA Astrophysics Data System (ADS)

    Newcombe, M. E.; Fabbrizio, A.; Zhang, Youxue; Ma, C.; Le Voyer, M.; Guan, Y.; Eiler, J. M.; Saal, A. E.; Stolper, E. M.

    2014-07-01

    Significant zonation in major, minor, trace, and volatile elements has been documented in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (e.g., MgO, FeO, Cr2O3, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H2O, and F, components with a lower concentration in the host olivine than in the melt (e.g., Al2O3, SiO2, Na2O, K2O, TiO2, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions, concurrent with diffusive propagation of the boundary layer toward the inclusion center. Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na2O, K2O) by coupling to slow diffusing components such as SiO2 and Al2O3. Concentrations of H2O and F decrease toward the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects. A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150-13,000 C h-1 from the liquidus down to ~1,000 C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1,000 C ranges from 40 s to just over 1 h. Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization. All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

  4. Influence of aluminum on the hydrothermal alteration rate of olivine

    NASA Astrophysics Data System (ADS)

    Andreani, M.; Daniel, I.; Pollet-Villard, M.

    2013-12-01

    The reactivity of ultramafic rocks under hydrothermal conditions controls chemical fluxes at the interface between the internal and external reservoirs of silicate planets. On Earth, hydration of ultramafic rocks is ubiquitous and operates from deep subduction zones to shallow lithospheric environments where it considerably affects the physical and chemical properties of rocks and can interact with the biosphere. This process also has key emerging societal implications, such as the production of hydrogen as a source of carbon-free energy. To date, the chemical model systems used to reproduce olivine hydrothermal alteration lead to the formation of serpentine with sluggish reaction rates. Although aluminum is common in geological environments and in hydrothermal systems in particular, its role in serpentinization or olivine dissolution has not been investigated under hydrothermal conditions. Nevertheless, abundant Al supply is expected in fluids released from dehydration of metapelites in subduction zones as well as during the hydrothermal alteration of gabbros at mid-ocean ridges. Aluminum was also abundant in primitive environments of both the Earth and Mars, stored in either Al-rich minerals like plagioclase or Al-enriched ultramafic lavas. We have investigated the role of Al on the hydrothermal alteration of olivine in a series of experiments performed in a low-pressure diamond anvil cell while following the reaction progress in situ by optical imaging and by confocal Raman spectroscopy. Experiments were run for 4.5 to 7.5 days with two olivine grains reacted in saline water (0.5 molal NaCl) at 200C and 300C, and P=200 MPa. After two days, olivine crystals were fully transformed to an aluminous serpentine, also enriched in iron. The very fast precipitation of serpentine may inhibit magnetite nucleation here. However, this does not rule out an H2 production since serpentines classically incorporate non negligible amount of ferric iron in their structure. The presence of Al in the hydrothermal fluid increases the rate of olivine serpentinization by more than one order of magnitude by increasing olivine solubility and enhancing serpentine precipitation. The mechanism responsible for this increased solubility has to be investigated further but this result motivates a re-evaluation of the natural rates of olivine serpentinization and of olivine hydrolysis in general in a wide range of settings where olivines or peridotites are intimately associated with Al-providers. Such a fast reaction rate may affect the contribution of reaction-enhanced processes at the micrometer-scale, such as reaction-driven cracking, already proposed for enhancing serpentinization or carbonation of olivine. The effect of Al on lower crust and upper mantle metasomatism is expected to be even stronger at higher pressure in subduction zones where those reactions control the rheology and physical properties of the subducting plate and mantle wedge. Finally, this study also provides a way to accelerate serpentinization reactions towards economically feasible time-scale and temperature for industrial H2 production and/or CO2 remediation.

  5. A Study of Olivine Alteration to Iddingsite Using Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Kuebler, K. E.; Wang, Alian; Haskin, L. A.; Jolliff, B. L.

    2003-01-01

    A crucial task of Mars surface science is to determine past environmental conditions, especially aqueous environments and their nature. Identification of mineral alteration by water is one way to do this. Recent work interprets TES spectra as indicating altered basalt on Mars. Olivine, a primary basaltic mineral, is easily altered by aqueous solutions. Alteration assemblages of olivine may be specific to deuteric, hydrothermal, surface water, or metamorphic environments. Raman spectra are produced by molecular vibrations and provide direct means for studying and identifying alteration products. Here, we present a combined study of changes in the chemical composition and Raman spectra of an olivine as it alters to iddingsite. Iddingsite is found in some SNC meteorites and is presumably present on Mars. The term 'iddingsite' has been used as a catch-all term to describe reddish alteration products of olivine, although some authors ascribe a narrower definition: an angstrom-scale intergrowth of goethite and smectite (presumably saponite) formed in an oxidizing and fluid-rich environment. Alteration conserves Fe (albeit oxidized) but requires addition of Al and H2O and removal of Mg and Si. The smectite that forms may be removed by continued alteration. Dehydration of the goethite forms hematite. Our purpose is to study the mineral assemblage, determine the structural and chemical variability of the components with respect to the degree of alteration, and to find spectral indicators of alteration that will be useful during in-situ analyses on Mars.

  6. Solar Radiation Management and Olivine Dissolution Methods in Climate Engineering

    NASA Astrophysics Data System (ADS)

    Kone, S.

    2014-12-01

    An overview of solar radiation management and olivine dissolution methods allows to discuss, comparatively, the benefits and consequences of these two geoengineering techniques. The combination of those two techniques allows to concomitantly act on the two main agents intervening in global warming: solar radiation and carbon dioxide. The earth surface temperature increases due mainly to carbon dioxide (a greenhouse gas) that keeps the solar radiation and causes the global warming. Two complementary methods to mitigate climate change are overviewed: SRM method, which uses injected aerosols, aims to reduce the amount of the inbound solar radiation in atmosphere; and olivine dissolution in water, a key chemical reaction envisaged in climate engineering , aiming to reduce the amount of the carbon dioxide in extracting it from atmosphere. The SRM method works on scenarios of solar radiation decrease and the olivine dissolution method works as a carbon dioxide sequestration method. Olivine dissolution in water impacts negatively on the pH of rivers but positively in counteracting ocean acidification and in transporting the silica in ocean, which has benefits for diatom shell formation.

  7. Near-Infrared Optical Constants of Olivine and Pyroxene

    NASA Astrophysics Data System (ADS)

    Trang, D.; Lucey, P. G.; Gillis-Davis, J.; Cahill, J. T.; Klima, R. L.; Isaacson, P.

    2012-12-01

    Producing mineral maps of planetary bodies is useful for petrological studies, future colonization, and resources. Estimating the physical and chemical properties of a surface, however, is complicated due to parameters such as, grain size and shape, mineral chemistry, space weathering, and ambient temperature. Radiative transfer modeling is one method to calculate mineral proportions and chemistry from reflectance spectra. However, radiative transfer modeling requires knowledge of the optical constants of minerals of interest. In this study, we characterized the near-infrared optical constants of two common mafic minerals, olivine and pyroxene, with a wide distribution of chemistries. Particularly, we parameterized the imaginary index of refraction, k, in the near-infrared portion of the spectrum of natural olivines as a function of foresterite content and synthetic pyroxenes as a function of wollastonite and ferrosilite content. For each k-spectrum, we modeled each absorption features and continuum using the Modified Gaussian Model (MGM) with three Gaussians and an inverse linear function respectively. We find that our fitting routine characterizes the k-spectra of olivine and pyroxene consistently. Additionally, we described each parameter of MGM and the continuum with a regression or multiple regressions as a function of mineral chemistry. Thus providing the optical parameters of olivine and pyroxene needed for radiative transfer modeling. Scatter observed between optical parameters and mineral chemistry could be the result of minor cations (e.g., Mn2+), grain size, and cation ordering. Future work will seek to characterize these effects on derived optical parameters.

  8. The search for exsolved ferromagnesian olivines: A meteoritic survey

    NASA Astrophysics Data System (ADS)

    Petaev, Michail I.

    1996-11-01

    Olivine grains from selected meteorites (the Springwater pallasite, the Lowicz mesosiderite, the ALH 84025 brachinite, the Krymka LL3 chondrite, and the Calcalong Creek lunar meteorite) and terrestrial rocks (San Carlos forsterite and Rockport fayalite) were studied by optical microscopy and high-precision electron microprobe analysis. Detailed microprobe traverses revealed regular igneous zoning in the Krymka and Calcalong Creek olivines. Traverses across the San Carlos forsterite grain are flat and display no chemical variations larger than the 2? range of counting error (0.2 mol% Fa). Traverses across olivine grains in the ALH 84025, Lowicz, and Springwater meteorites show regular patterns of periodic or wavy chemical variations well exceeding the 2? uncertainty range. However, no lamellar structure was seen in backscattered electron images. It is suggested that the periodic chemical variations may be due to spinodal decomposition of primary, more or less homogeneous grains. I conclude that the absence of earlier reports of such variations simply means that olivine grains in equilibrated meteorites have not been examined closely enough to detect them.

  9. Far-infrared continuum absorption of olivine at low temperatures

    NASA Astrophysics Data System (ADS)

    Mutschke, H.; Zeidler, S.; Chihara, H.

    2013-10-01

    The far-infrared continuum opacity of cold dust is an important quantity for the study of debris disks in planetary systems and of protoplanetary disks. Olivine is considered the most abundant crystalline dust species in such environments. We present spectroscopic absorption measurements on olivine plates of the order of a millimeter thickness at wavelengths between 60 and 400 μ m for temperatures down to 10 K. Our data reveal a strong temperature dependence of the continuum absorption coefficient, i.e. more than an order of magnitude decrease at 100 μ m for 10 K compared to room temperature. The absolute values are generally much lower than those measured with olivine powders embedded into polyethylene pellets, even if the difference between plate and powder samples is taken into account by theoretical models. In contrast to this, the room temperature data are in relatively good agreement with simulations using optical constants determined from reflection measurements. At low temperatures, the absorption coefficient of olivine was measurable with sufficient accuracy only up to 90 μ m for 10 K and up to 110 μ m for 100 K. These data reveal a drastic change in the spectral slope (from β ~ 2.0 to β > 5.0) for the continuum underlying the 69-μ m band, which is not predicted by the low-temperature optical constants determined for forsterite.

  10. Micromechanical modeling of the viscoplastic behavior of olivine

    NASA Astrophysics Data System (ADS)

    Castelnau, O.; Blackman, D. K.; Lebensohn, R. A.; Ponte CastaEda, P.

    2008-09-01

    Efforts to couple mantle flow models with rheological theories of mineral deformation typically ignore the effect of texture development on flow evolution. The fact that there are only three easy slip systems for dislocation glide in olivine crystals leads to strong mechanical interactions between the grains as the deformation proceeds, and subsequent development of large viscoplastic anisotropy in polycrystals exhibiting pronounced Lattice Preferred Orientations. Using full-field simulations for creep in dry polycrystalline olivine at high temperature and low pressure, it is shown that very large stress and strain rate intragranular heterogeneities can build up with deformation, which increase dramatically with the strength of the hard slip system (included for the purpose of enabling general deformations). Compared with earlier nonlinear extensions of the Self-Consistent mean-field theory to simulate polycrystal deformation, the "Second-Order" method is the only one capable of accurately describing the effect of intraphase stress heterogeneities on the macroscopic flow stress, as well as on the local stress- and strain rate fluctuations in the material. In particular, this approach correctly predicts that olivine polycrystals can deform with only four independent slip systems. The resistance of the fourth system (or accommodation mechanism), which is likely provided by dislocation climb or grain boundary processes as has been observed experimentally, may essentially determine the flow stress of olivine polycrystals. We further show that the "tangent" model, which had been used extensively in prior geophysical studies of the mantle, departs significantly from the full-field reference solutions.

  11. Effect of secondary phase formation on the carbonation of olivine.

    PubMed

    King, Helen E; Plmper, Oliver; Putnis, Andrew

    2010-08-15

    Large-scale olivine carbonation has been proposed as a potential method for sequestering CO(2) emissions. For in situ carbonation techniques, understanding the relationship between the formation of carbonate and other phases is important to predict the impact of possible passivating layers on the reaction. Therefore, we have conducted reactions of olivine with carbonated saline solutions in unstirred batch reactors. Altering the reaction conditions changed the Mg-carbonate morphology. We propose that this corresponded to changes in the ability of the system to precipitate hydromagnesite or magnesite. During high-temperature reactions (200 degrees C), an amorphous silica-enriched phase was precipitated that was transformed to lizardite as the reaction progressed. Hematite was also precipitated in the initial stages of these reactions but dissolved as the reaction proceeded. Comparison of the experimental observations with reaction models indicates that the reactions are governed by the interfacial fluid composition. The presence of a new Mg-silicate phase and the formation of secondary products at the olivine surface are likely to limit the extent of olivine to carbonate conversion. PMID:20704252

  12. Textural evidence bearing on the origin of isolated olivine crystals in C2 carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Richardson, S. M.; Mcsween, H. Y., Jr.

    1978-01-01

    In some cases the mechanical competence of chondrules in carbonaceous chondrites has been reduced by alteration of their mesostasis glass to friable phyllosilicate, providing a mechanism by which euhedral olivines can be separated from chondrules. Morphological features of isolate olivine grains found in carbonaceous chondrites are similar to those of olivine phenocrysts in chondrules. These observations suggest that the isolated olivine grains formed in chondrules, by crystallization from a liquid, rather than by condensation from a vapor.

  13. Olivine in kimberlites: metasomatism of the deep lithospheric mantle

    NASA Astrophysics Data System (ADS)

    Cordier, Carole; Sauzeat, Lucie; Arndt, Nicholas; Boullier, Anne-Marie

    2014-05-01

    Most kimberlites contain abundant mantle microxenoliths (nodules) and xenocrysts, mainly composed of olivine. We present here a geochemical and microstructural study of nodules from well-preserved type-I kimberlites from Kangamiut region in Greenland, the sequel of a preliminary study of Arndt et al. (2010). A striking feature of these and many other kimberlites is the wide range of olivine composition (Fo83 to Fo94) from nodule to nodule in a single kimberlite sample, contrasting with the olivine homogeneity within a single nodule (variation of less than 0.5 mol. %). We defined three chemical zones within normally zoned nodules based on Fo and Ni variations. Xenocrystic cores have high and constant Fo and Ni contents. Outer rims crystallized from the kimberlitic magma have constant Fo content (Fo88) coupled with significant decrease in Ni content (from 2500 to 500 ppm). Transition zones between cores and rims, along grain boundaries and along fluid inclusion trails have variable Fo content (Fo93 to Fo88) but roughly constant Ni content (from 3000 to 25000 ppm) and their composition mimics that defined by the nodules. Microstructural study of transition zones associated with curvilinear grain boundaries suggests these zones are produced during fluid-assisted plastic deformation. We propose that the transition zones formed during reaction of mantle peridotite with CO2-rich fluid, a process that removes the pyroxene and garnet components. The compositional variations of the transition zones monitor at the fine scale the processes that produce the chemical variability of olivine from nodule to nodule. We propose that the range of olivine composition records the position of sample relative to fluid-rich zones, grain boundaries for transition zones and larger conduits for broader scale variations registered in the nodules. This conclusion implies that metasomatic processes that produced the range of olivine composition and removed pyroxene and garnet from the initial peridotite occurred within the lithospheric mantle and not within the kimberlite magma during it ascent toward the surface. Arndt, N. T.; Guitreau, M.; Boullier, A. M.; Le Roex, A.; Tommasi, A.; Cordier, P. & Sobolev, A. V. (2010): Olivine, and the origin of kimberlite. Journal of Petrology, 51, 573-602.

  14. The effect of mineral paragenesis on Al diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Zhukova, Irina; O'Neill, Hugh; Capbell, Ian

    2014-05-01

    Al is the most abundant trivalent impurity of olivine and is particularly important because its concentration in olivine is temperature dependant, and it therefore has potential as a geothermometer (Wan, et al. 2008). Furthermore recent studies show that the incorporation of water into the olivine lattice is affected by the presents of trivalent cations such as Al3+ (Berry, et al. 2007; Hauri, et al. 2006). The Al distribution in olivines from volcanic rocks is often zoned and mantle olivines may also show an inhomogeneous distribution of Al, whereas the majority of other trace elements homogenized by diffusion (Mallmann, et al. 2009; McKibbin, et al.). However, there are no quantitative experimental data for Al diffusion in olivine, probably because the combination of low concentration rate and low diffusion rate make measurement difficult. We investigated the effect of silica activity on the diffusion rate of Al in forsterite at varying temperatures using solid-state buffer assemblages. Our study aimed to quantify the effect of major cation activities on the diffusion and concentration of Al in forsterite and also provide insights into the mechanism of Al substitution into the olivine lattice. The activities of SiO2, MgO and Al2O3 were buffered in each experiment by four different mineral associations: forsterite + periclase + spinel (fo+per+sp); forsterite + spinel + sapphirine (fo+sp+spr); forsterite + sapphirine + cordierite (fo+spr+cor); forsterite + cordierite + enstatite (fo+cor+en). Iron oxide in proportion of FeO/(FeO+MgO) = 0.1 was added to mixtures for San Carlos olivine experiments. Diffusion experiments were performed at the one-atmosphere vertical tube furnaces modified to control the fO2 by CO-CO2 gas mixing or in a box furnace in air for 10 - 28 days at temperatures from 1100 to 1500oC and logfO2 -0.7 and -5.7. The experiment with the San Carlos olivine was performed at 1300oC and at logfO2 = -5.7. In order to obtain equilibrium concentrations of the point defects we performed some experiments with pre-annealing. Diffusion profiles were measured by LA-ICP-MS in a traverse mode. The Al content of forsterite decreases with temperature dependence, increasing the potential of Al in olivine as a geothermometer. We obtain the activation energy of 379 kJ/mol for the high aSiO2 experiments, which is close within error of the value of 364 kJ/mol for the low aSiO2 experiments implying a common diffusion mechanism. The pre-exponential factor, however, increases by 5 orders of magnitude from low aSiO2 (fo+per+sp buffer) to high aSiO2 (fo+cor+en buffer). The much higher diffusivity at high aSiO2 indicates that Al diffusion occurs through octahedral cation site vacancies.

  15. The geoengineering potential of artificially enhanced silicate weathering of olivine

    NASA Astrophysics Data System (ADS)

    Khler, Peter; Hartmann, Jens; Wolf-Gladrow, Dieter A.

    2010-05-01

    Geoengineering is a proposed action to manipulate Earth's climate in order to counteract global warming from anthropogenic greenhouse gas emissions. We investigate in more detail the potential of a specific geoengineering technique, the carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification, because it influences the global climate via the carbon cycle. We here show the consequences of this technique for the chemistry of the surface ocean at rates necessary for geoengineering. We calculate that olivine dissolution has the potential to sequestrate up to one Pg C yr-1 directly, if olivine is distributed as fine powder over land areas of the humid tropics. The carbon sequestration potential is limited by the saturation concentration of silicic acid. In our calculations for the Amazon and Congo river catchments a maximum annual dissolution of 1.8 and 0.4 Pg of olivine seems possible, corresponding to the sequestration of 0.5 and 0.1 Pg C yr-1. Open water dissolution of fine grained olivine and an enhancement of the biological pump by the rising riverine input of silicic acid might increase our estimate of the carbon sequestration, but additional research is needed here. We finally calculate with a carbon cycle model the consequences of sequestration rates of 1 to 5 Pg C yr-1 for the 21st century by this technique. At maximum this technique would reduce global warming by 1 K and counteract ocean acidification by a rise in surface ocean pH by 0.1 in the year 2100.

  16. Exsolution of ferromagnesian olivine in the Divnoe meteorite

    NASA Astrophysics Data System (ADS)

    Petaev, M. I.; Brearley, A. J.

    1994-07-01

    The Divnoe meteorite is a granoblastic olivine-rich primitive achondrite whose textural and mineralogical characteristics suggest extensive recrystallization during slow cooling in the temperature range from approximately 1000 to approximately 500 C and lower. Olivine grains in this meteorite show a lamellar appearance in BSE images, caused by minor micrometer-scale chemical variations in Fe, Mg, and Mn contents between adjacent lamellae. Ten grains of lamellar olivine were studied in detail by Electron Probe Microanalysis (EPMA) and optical microscopy and two of these by Transmission Electron Microscopy (TEM). The olivine grains studied are essentially free of minor elements (Ti, Al, Cr, Ni, Ca, Na) except for Mn, and fall in the compositional range found by an earlier study. While the compositional ranges of Fe-poor and Fe-rich lamellae overlap, the differences between lamellae richest and poorest in Fe are quite similar, suggestive of their formation by an equilibrium process. Fine-scale microprobing has confirmed earlier compositional data, but has reduced lamella thicknesses to a few micrometers, which is in a good agreement with TEM observations. The structural and compositional data obtained strongly suggest that the lamellar structure in these olivine grains was produced by an exsolution process, which is in qualitative agreement with a recent thermodynamic analysis of phrase relations in the system Mg2SiO4-FeSiO2. Cracks in Fe-rich lamellae could result from expansion during the exsolution process due to the volume difference between Fe-rich and Fe-poor lamellae.

  17. Geoengineering potential of artificially enhanced silicate weathering of olivine.

    PubMed

    Khler, Peter; Hartmann, Jens; Wolf-Gladrow, Dieter A

    2010-11-23

    Geoengineering is a proposed action to manipulate Earth's climate in order to counteract global warming from anthropogenic greenhouse gas emissions. We investigate the potential of a specific geoengineering technique, carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification, because it influences the global climate via the carbon cycle. If important details of the marine chemistry are taken into consideration, a new mass ratio of CO(2) sequestration per olivine dissolution of about 1 is achieved, 20% smaller than previously assumed. We calculate that this approach has the potential to sequestrate up to 1 Pg of C per year directly, if olivine is distributed as fine powder over land areas of the humid tropics, but this rate is limited by the saturation concentration of silicic acid. In our calculations for the Amazon and Congo river catchments, a maximum annual dissolution of 1.8 and 0.4 Pg of olivine seems possible, corresponding to the sequestration of 0.5 and 0.1 Pg of C per year, but these upper limit sequestration rates come at the environmental cost of pH values in the rivers rising to 8.2. Open water dissolution of fine-grained olivine and an enhancement of the biological pump by the rising riverine input of silicic acid might increase our estimate of the carbon sequestration, but additional research is needed here. We finally calculate with a carbon cycle model the consequences of sequestration rates of 1-5 Pg of C per year for the 21st century by this technique. PMID:21059941

  18. Geoengineering potential of artificially enhanced silicate weathering of olivine

    PubMed Central

    Köhler, Peter; Hartmann, Jens; Wolf-Gladrow, Dieter A.

    2010-01-01

    Geoengineering is a proposed action to manipulate Earth’s climate in order to counteract global warming from anthropogenic greenhouse gas emissions. We investigate the potential of a specific geoengineering technique, carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification, because it influences the global climate via the carbon cycle. If important details of the marine chemistry are taken into consideration, a new mass ratio of CO2 sequestration per olivine dissolution of about 1 is achieved, 20% smaller than previously assumed. We calculate that this approach has the potential to sequestrate up to 1 Pg of C per year directly, if olivine is distributed as fine powder over land areas of the humid tropics, but this rate is limited by the saturation concentration of silicic acid. In our calculations for the Amazon and Congo river catchments, a maximum annual dissolution of 1.8 and 0.4 Pg of olivine seems possible, corresponding to the sequestration of 0.5 and 0.1 Pg of C per year, but these upper limit sequestration rates come at the environmental cost of pH values in the rivers rising to 8.2. Open water dissolution of fine-grained olivine and an enhancement of the biological pump by the rising riverine input of silicic acid might increase our estimate of the carbon sequestration, but additional research is needed here. We finally calculate with a carbon cycle model the consequences of sequestration rates of 1–5 Pg of C per year for the 21st century by this technique. PMID:21059941

  19. Diffusive over-hydration of olivine-hosted melt inclusions

    NASA Astrophysics Data System (ADS)

    Hartley, Margaret E.; Neave, David A.; Maclennan, John; Edmonds, Marie; Thordarson, Thor

    2015-09-01

    The pre-eruptive water content of magma is often estimated using crystal-hosted melt inclusions. However, olivine-hosted melt inclusions are prone to post-entrapment modification by H+ diffusion as they re-equilibrate with their external environment. This effect is well established for the case of H+ loss from olivine-hosted inclusions that have cooled slowly in degassed magma. Here we present evidence for the opposite effect: the addition of H+ into inclusions that are held in melts that are enriched in H2O with respect to the trapped melts. The compositional variability in a suite of 211 olivine-hosted inclusions from the Laki and Skuggafjll eruptions in Iceland's Eastern Volcanic Zone indicates that diffusive H+ gain governs the H2O content of incompatible trace element depleted inclusions. Individual eruptive units contain olivine-hosted inclusions with widely varying incompatible element concentrations but near-constant H2O. Furthermore, over 40% of the inclusions have H2 O /Ce > 380, significantly higher than the H2O/Ce expected in primary Icelandic melts or mid-ocean ridge basalts (150-280). The fact that the highest H2O/Ce ratios are found in the most incompatible element depleted inclusions indicates that hydration is a consequence of the concurrent mixing and crystallisation of compositionally diverse primary melts. Hydration occurs when olivines containing depleted inclusions with low H2O contents are juxtaposed against more hydrous melts during mixing. Melt inclusions from a single eruption may preserve evidence of both diffusive H+ loss and H+ gain. Trace element data are therefore vital for determining H2O contents of melt inclusions at the time of inclusion trapping and, ultimately, the H2O content of the mantle source regions.

  20. Olivine as a key to unlocking Kilauea's magmatic history

    NASA Astrophysics Data System (ADS)

    Garcia, M. O.; Norman, M. D.

    2011-12-01

    Olivine is a ubiquitous mineral in Hawaiian basalts. It is on the liquidus at pressures <0.5 GPa and has the potential to record numerous petrologic processes including the histories of parental magma composition changes, crystal fractionation, magma mixing and crustal contamination. These processes are recorded in olivine composition (major and trace elements, and isotopes) and by melt inclusions trapped within olivine. Here we focus on Kilauea's historical lavas (1820-present) to evaluate the magmatic history one of world's most active volcanoes. Kilauea has shown dramatic variations in it eruptive rate and style (from vigorous, quiescent effusion in 1820 to infrequent explosive activity in 1924 and then to its highest effusion during the last decade). Eruption rates correlate with whole-rock compositional and isotopic variations (P-G 1999). Most Kilauea lavas have normally zoned olivine in equilibrium with whole-rock compositions which belies complex magma chamber processes. Parental magma composition changed rapidly based on the heterogeneity of melt inclusion compositions in higher Mg olivine (>86 forsterite). Melt inclusions from single eruptions show wider variation in ratios of Ca/Al and Nb/Y than observed in lavas for the historical period. Thus, the mantle source is heterogeneous on a small scale and small batches of compositionally distinct melt are frequently delivered to the volcano. These magma batches undergo mixing, fractionation and after caldera collapses (e.g.1924), crustal contamination in the summit reservoir. This work demonstrates that an Ernstonian approach, using minerals to understand petrologic processes, is key to unlocking Kilauea's magmatic processes. Pietruszka, A.P. and Garcia, M.O., 1999, J. Petrol. 40, 1321-1342.

  1. Evidence for equilibrium conditions during the partitioning of nickel between olivine and komatiite liquids.

    USGS Publications Warehouse

    Budahn, J.R.

    1986-01-01

    Olivine-liquid partition coefficients for Ni(DNi), calculated from Ni vs MgO abundance variations in komatiite series basalts, compare favourably with experimentally determined values, if Ni variations in olivine-controlled basalts can be modelled with an equation that assumes equilibrium between the entire olivine crystal and its coexisting liquid.-J.A.Z.

  2. Characterization by EBSD of dislocations and disclinations in olivine: implications for the rheology of olivine-rich aggregates

    NASA Astrophysics Data System (ADS)

    Cordier, P.; Demouchy, S. A.; Beausir, B.; Taupin, V.; Fressengeas, C.

    2013-12-01

    The rheology of olivine-rich rocks remains poorly understood. Only intracrystalline deformation mechanisms involving dislocations are quite well known. In orthorhombic olivine only two slip directions, [100] and [001] can be activated. Most characterizations performed so far involve transmission electron microscopy studies at high magnifications or, at a larger scale, optical or scanning electron microscopy on decorated samples. In the latter case, no detailed characterization of the defects could be done. Orientation maps obtained from high-resolution electron backscattered diffraction allow recovering components of the lattice curvature tensor which in turn allow determination of components of the dislocation density tensor. The geometrically necessary dislocation content can thus be imaged. Recently Beausir & Fressengeas (2013) have shown that with this technique, components of the disclination density tensor could also be determined. Several examples have been provided in metallic alloys. In this study we show that olivine aggregates (both experimentally and naturally deformed) contain pervasive evidence of disclinations dipoles at grain boundaries. The implications on the plastic behavior of olivine rocks are discussed based on a numerical model of the response to an applied shear stress of a grain boundary made of disclinations. Beausir, B. & Fressengeas, C., Disclination densities from EBSD orientation mapping. International Journal of Solids and Structures 50 (1), 137-146 (2013).

  3. Lattice preferred orientations of olivine in the schistosed antigorite serpentinite

    NASA Astrophysics Data System (ADS)

    Soda, Y.; Ando, J.; Mizukami, T.; Morishita, T.

    2011-12-01

    The lattice preferred orientation (LPO) of the schistosed antigorite serpentinite is considered as causes of the seismic anisotropy observed at the subduction zones (Katayama et al., 2009; Jung, 2011) and the natural examples are reported by several researchers (Bezacier et al., 2010; Hirauchi et al., 2010; Soda and Takagi, 2010). Formation process of the antigorite LPO is unclear, especially at primary serpentinized stage. To understand the development of micro-structures of antigorite serpentinite, we made structural analyses of serpentinite schist and the former peridotite fabric. Samples were taken from lenticular serpentinite bodies (< 1km) stack in Jurassic accretionary complex, Toba area, Southwest Japan. The serpentinite consist of olivine, antigorite, meta-clinopyroxene and Cr-spinel. The foliation and lineation of serpentinite is defined by parallel alignment of elongated olivine grain and antigorite blades, which make up mylonitic textures, such as a porphyroclast system and composite planar fabric. Antigorite blades show syn-kinematic growth in pressure shadows and pull-apart of olivine porphyroclast. In the less serpentinized part, antigorite blades are crystallized along the grain boundary of olivine. We measure the LPOs of coarse olivine grains in the serpentinite schist using a u-stage. The X, Y and Z directions represent directions of lineation, normal to lineation within the foliation and normal to foliation, respectively. The LPOs of olivine show point maximum or partial girdle distribution, and these concentrated crystal axes are incongruous with X, Y and Z direction. The a[100] axes of olivine are parallel to the serpentinite foliation, and form a point maximum several degrees away from the Y direction. The b[010] axes and the c[001] axes are concentrated Z and X direction forming a partial girdle normal to Y direction, respectively. Boudier et al. (2010) have reported the topotactic relationship between olivine and antigorite. They show that the (100)ol is parallel to the (001)atg or the (010)ol is parallel to the (001)atg. And, the a[100] axes of olivine are normal to serpentinite foliation with point maximum in the thin section scale. However, in the case of this study, the simple topotactic relationship does not connect the fabric in the thin section scale of serpentinite schist. Although, more detail analysis need to discuss the formation of antigorite LPO, the other mechanisms, such as crystal plastic deformation or diffusion-precipitation, might cause rearrangement of antigorite fabric. References Bezacier, L. et al., 2010, Earth and Planetary Science Letters, 289, 198-208. Boudier, F. et al., 2010, Journal of Petrology 51, 495-512. Hirauchi et al., 2010, Earth and Planetary Science Letters, 299, 196-206. Jung, H., 2011, Earth and Planetary Science Letters, 307, 535-543. Katayama, I., et al., 2009, Nature, 461, 1114-1118. Soda, Y. and Takagi, H., 2010, Journal of Structural Geology, 32, 792-802.

  4. Olivine vitrophyres - A nonpristine high-Mg component in lunar breccia 14321

    NASA Technical Reports Server (NTRS)

    Shervais, John W.; Taylor, Lawrence A.; Lindstrom, Marilyn M.

    1988-01-01

    The presence of olivine vitrophyres in breccia 14321 is discussed, suggesting that olivine vitrophyres could account for the high-Mg component of soils and breccias in the lunar highlands. The olivine vitrophyre clasts from 14321 have high bulk MgO and the Mg/(Mg+Fe) ratio is 78 percent. The olivine vitrophyres are impact melt rocks and are rich in KREEP. The high MgO concentration is manifest by skeletal quench crystals of olivine that constitute about 30 percent of the mode.

  5. Chemical variation and zoning of olivine in lunar dunite 72415 - Near-surface accumulation

    NASA Technical Reports Server (NTRS)

    Ryder, Graham

    1992-01-01

    Electron microprobe remeasurements have been used to reevaluate the range of olivine compositions, including CaO, in lunar dunite sample 72415 and compare that range with olivines in established plutonic rocks. Olivines from ferroan anorthosite 62237 and samples from the Stillwater intrusion were analyzed; literature data for other lunar and terrestrial plutonic samples were used for comparisons. The analyses show that the lunar dunite 72415 contains a range of olivine compositions, that the olivines are zoned, and that they have CaO abundances that are consistent with shallow hypabyssal rather than deep plutonic accumulation.

  6. Olivine and Carbonate Globules in ALH84001: A Terrestrial Analog, and Implications for Water on Mars

    NASA Technical Reports Server (NTRS)

    Treiman, A. H.

    2005-01-01

    Carbonate globules in ALH84001 are associated with small olivine grains an unexpected finding because the olivines equilibrated at high T while the carbonate is chemically zoned and unequilibrated. A possible explanation comes from a terrestrial analog on Spitsbergen (Norway), where some carbonate globules grew in cavities left by aqueous dissolution of olivine. For ALH84001, the same process may have acted, with larger olivines dissolved out and smaller ones shielded inside orthopyroxene. Carbonate would have been deposited in holes where the olivine had been. Later shocks crushed remaining void space, and mobilized feldspathic glass around the carbonates.

  7. Real Time Pore Structure Evolution during Olivine Mineral Carbonation

    NASA Astrophysics Data System (ADS)

    Zhu, W.; Fusseis, F.; Lisabeth, H. P.; Xiao, X.

    2014-12-01

    Aqueous carbonation of ultramafic rocks has been proposed as a promising method for long-term, secure sequestration of carbon dioxide. While chemical kinetics data indicate that carbonation reaction in olivine is one of the fastest among the mg-bearing minerals, in practice, the factors that limit the extent and rate of carbonation in ultramafic rocks are fluid supply and flux. On the one hand, reaction products could produce passivating layer that prohibits further reactions. On the other hand, the increases in solid volume during carbonation could lead to cracking and create new fluid paths. Whether carbonation in ultramafic rocks is self-limiting or self-sustaining has been hotly debated. Experimental evidence of precipitation of reaction products during olivine carbonation was reported. To date, reaction-driven cracking has not been observed. In this paper, we present the first real-time pore structure evolution data using the x-ray synchrotron microtomography. Sodium bicarbonate (NaHCO3) solution was injected into porous olivine aggregates and in-situ pore structure change during olivine carbonation at a constant confining pressure (12 MPa) and a temperature of 200oC was captured at 30 min. interval for ~160 hours. Shortly after the experiment started, filling-in of the existing pores by precipitation of reaction products was visible. The size of the in-fills kept increasing as reactions continued. After ~48 hours, cracking around the in-fill materials became visible. After ~60 hours, these cracks started to show a clear polygonal pattern, similar to the crack patterns usually seen on the surface of drying mud. After ~72 hours, some of the cracks coalesced into large fractures that cut-through the olivine aggregates. New fractures continued to develop and at the end of the experiment, the sample was completely disintegrated by these fractures. We also conducted nanotomography experiments on a sub-volume of the reacted olivine aggregate. Orthogonal sets of incipient cracks were observed, providing clear evidence that these cracks are generated by isotropic tensile stresses. This strongly indicates that the observed cracking was caused by volume expansion during mineral carbonation. The experimental results provide a mechanism for near 100% alteration of ultramafic rocks observed in nature.

  8. Evidences and consequences of slow hydrogen diffusion in olivine

    NASA Astrophysics Data System (ADS)

    Padron-Navarta, J. A.; Hermann, J.; O'Neill, H. S.

    2014-12-01

    In the most abundant upper mantle phase, olivine, the presence of hydrogen significantly modifies the timescale of chemical diffusion, plastic deformation, electrical conductivity and the attenuation of seismic waves. Early experiments showed that hydrogen is the fastest species able to diffuse through the olivine lattice. We have found, however, experimental and natural evidence suggesting that hydrogen diffusion can also be orders of magnitude slower. In olivine there are four different hydrogen substitution mechanisms, associated with Mg vacancies, Si vacancies, trivalent cations and titanium substitution, hereafter referred to as H[Mg], H[Si], H[triv] and H[Ti] respectively. We experimentally investigated the dehydroxylation of synthetic forsterite with two contrasting hydrous defect populations: (1) dominated by H[Si], and H[Ti] with subsidiary H[Mg] and H[triv]; and (2) H[Si] exclusively. The loss rates of H[Mg] and H[triv] are in agreement with previous measurements of bulk hydrogen diffusion in forsterite, but the decrease in H[Ti] and H[Si] are ~1.5 and ~ 3 orders of magnitude slower, respectively. The activation energy and pre-exponential terms derived in these experiments are in agreement with the empirical correlation recently proposed based on the Meyer-Nedel compensation law (Jones 2014, G3, 15, 2616-2631). Natural observations attest further to slow hydrogen diffusivity in olivine dominated by H[Ti] and H[Si]. Metamorphic olivines formed after dehydration reactions in the Alpine orogeny preserve their original water contents despite long times of exhumation (2-3 Ma). Closure temperature calculations suggest that using previous fast diffusion rates, these olivines should reequilibrate down to 400C. Only slow hydrogen diffusion coefficients such as those corresponding to H[Si] are able to explain the observed preservation of water content at the peak metamorphic temperature (700-800C). These findings have implications for estimating the ascent rate of xenoliths, which are more consistent with other independent constrains, as recently noted (Hilchie et al. 2014, Lithos, 202-203, 429-441). They are also required to assess the time necessary to equilibrate experimental charges, since for the different hydrous defects this time would vary by orders of magnitudes.

  9. Performance improvement of lithium manganese phosphate by controllable morphology tailoring with acid-engaged nano engineering.

    PubMed

    Guo, Hui; Wu, Chunyang; Liao, Longhuan; Xie, Jian; Zhang, Shichao; Zhu, Peiyi; Cao, Gaoshao; Zhao, Xinbing

    2015-01-20

    Olivine-type lithium manganese phosphate (LiMnPO4) has been considered as a promising cathode for next-generation Li-ion batteries. Preparation of high-performance LiMnPO4 still remains a great challenge because of its intrinsically low Li-ion/electronic conductivity. In this work, significant performance enhancement of LiMnPO4 has been realized by a controllable acid-engaged morphology tailoring from large spindles into small plates. We find that acidity plays a critical role in altering the morphology of the LiMnPO4 crystals. We also find that size decrease and plate-like morphology are beneficial for the performance improvement of LiMnPO4. Among the plate-like samples, the one with the smallest size shows the best electrochemical performance. After carbon coating, it can deliver high discharge capacities of 104.0 mAh g(-1) at 10 C and 85.0 mAh g(-1) at 20 C. After 200 cycles at 1 C, it can still maintain a high discharge capacity of 106.4 mAh g(-1), showing attractive applications in high-power and high-energy Li-ion batteries. PMID:25559416

  10. The solubility of olivine in basaltic liquids - An ionic model

    NASA Technical Reports Server (NTRS)

    Herzberg, C. T.

    1979-01-01

    A model is presented which enables the temperature at which olivine is in equilibrium with any alkali-depleted basaltic compound to be calculated to within + or - 30 C. It is noted that the error increases substantially when applied to terrestrial basalts which contain several weight percent alkalis. In addition the model predicts and quantifies the reduced activity of SiO4(4-) monomers due to increasing SiO2 concentrations in the melt. It is shown that the coordination of alumina in melts which precipitate olivine only appears to be dominantly octahedral, while titanium acts as a polmerizing agent by interconnecting previously isolated SiO4(4-) monomers. It is concluded that the model is sufficiently sensitive to show that there are small repulsive forces between Mg(2+) and calcium ions which are in association with normative diopside in the melt.

  11. Helium diffusion in olivine based on first principles calculations

    NASA Astrophysics Data System (ADS)

    Wang, Kai; Brodholt, John; Lu, Xiancai

    2015-05-01

    As a key trace element involved in mantle evolution, the transport properties of helium in the mantle are important for understanding the thermal and chemical evolution of the Earth. However, the mobility of helium in the mantle is still unclear due to the scarcity of measured diffusion data from minerals under mantle conditions. In this study, we used first principles calculations based on density functional theory to calculate the absolute diffusion coefficients of the helium in olivine. Using the climbing images nudged elastic band method, we defined the diffusion pathways, the activation energies (Ea), and the prefactors. Our results demonstrate that the diffusion of helium has moderate anisotropy. The directionally dependent diffusion of helium in olivine can be written in Arrhenius form as follows.

  12. Grinding methods to enhance the reactivity of olivine

    SciTech Connect

    Summers, Cathy A.; Dahlin, David C.; Rush, Gilbert E.; O'Connor, William K.; Gerdemann, Stephen J.

    2005-08-01

    The Albany Research Center (ARC) conducted studies of mechanical activation by conventional and ultrafine grinding techniques to enhance olivine reactivity in mineral carbonation reactions. Activated olivine is one of several solid feed materials used at ARC in reactions with carbon dioxide to form carbonate minerals. This paper compares grinding techniques via energy demand data and product characteristics, including particle size distributions, surface areas, full-width-at-half-maximum (FWHM) XRD analyses, and particle morphology by SEM analyses. Reactivity was calculated by percent conversion to carbonate in subsequent carbonation tests. Particle size reduction has the greatest impact on reactivity, and wet grinding is more energy efficient than dry grinding. Large additional inputs of energy to increase surface area or reduce crystallinity do not result in proportional improvements in reactivity.

  13. Low-temperature plastic rheology of olivine determined by nanoindentation

    NASA Astrophysics Data System (ADS)

    Kranjc, Kelly; Rouse, Zachary; Flores, Katharine M.; Skemer, Philip

    2016-01-01

    Low-temperature plasticity is a deformation mechanism that occurs mainly at high stress and low temperatures and may be important in the shallow lithosphere, at the tips of cracks, and in laboratory experiments. Previous studies investigating the low-temperature plasticity of the mineral olivine have exhibited wide variability in their extrapolations to the athermal flow strength or Peierls stress. To better constrain the rheology of olivine, nanoindentation tests were performed on samples in the temperature range of 0-175C. The indentation properties were converted to uniaxial properties using a finite element-based method. The data were fit to a standard flow law for low-temperature plasticity, and Peierls stresses between 5.32 and 6.45 GPa were obtained. These results provide increased confidence in the extrapolation of high-pressure and high-temperature laboratory experiments to low-temperature conditions and illustrate the applicability of nanoindentation methods to the study of mineral rheology.

  14. Experimental study of Mg isotope fractionation during olivine dissolution

    NASA Astrophysics Data System (ADS)

    Qiu, L.; Wang, Z.

    2012-12-01

    The dissolution of silicate minerals plays important roles in modifying the chemical composition of the ocean and earth crust. Previous studies show secondary clay minerals produced as a by-product of dissolution are enriched in heavy Mg isotopes compared with their protolith. In this study, batch olivine dissolution experiments were conducted in an autoclave to understand the evolution of Mg isotope composition in the solution as a function of controlled experimental conditions, including initial pH of the fluid (10.02 or 2.02), temperature (50, 100, or 200oC), olivine-grain size (<30?m powder or single olivine grain of ~0.2g/each), and duration of the experiments (up to ~60 hours). At the end of experiments, solid minerals were characterized by SEM and EM, and the solution was analyzed for major and trace element, and Mg isotope compositions by Element-XR and Neptune at Yale University. The Mg/Si ratio of the solution and the SEM and EM characterization of the solid phases indicate the formation of secondary mineral-talc in experiments with alkaline solutions, is consistent with the calculated saturation index. Significant Mg isotope fractionations were also observed in these experiments, which decrease with increasing temperature (e.g., up to ~ -5.8 at 50oC vs. -0.72 at 200oC), but increase with increasing the duration of the experiments. In contrast, little fractionation was observed in experiments with acidic solutions at low temperatures, or short duration of the experiments at high temperatures. These results indicate that dissolution of olivine (even in our closed system experiments) is a surface controlled process, during which Mg isotopes fractionate insignificantly, whereas secondary minerals formed during the process are strongly enriched in heavy Mg isotopes, leaving the solutions depleted in 26Mg. The fractionation factors between solution and talc have been estimated for these experiments as well.

  15. Chemical frost weathering of olivine: Experimental study and implications

    NASA Technical Reports Server (NTRS)

    Harris, S. L.; Huguenin, R. L.

    1987-01-01

    New experimental results are reported on the frost weathering of olivine. After first weathering, a decrease in Fe sup 2(+)M(2) absorption bands were noted. This decrease is related to the protonation of O(+) in the mineral. It is contented that this reaction may result in the regolith storage of 100 to 1000 m of H(sub 2) over the history of Mars.

  16. Experimental Replication of Relict "Dusty" Olivine in Type 1B Chondrules

    NASA Technical Reports Server (NTRS)

    Lofgren, Gary E.; Le, L.

    2002-01-01

    Introduction: Relict "dusty" olivine is considered to be a remnants of previous chondrule forming events based on petrographic and chemical evidence. Dynamic crystallization experiments confirm that dusty olivine can be produced by reduction of FeO-rich olivine in Unequilibrated Ordinary Chondrite (UOC) material. The results of these experiments compliment those of who also produced dusty olivine, but from synthetic starting materials. Techniques: Dynamic crystallization experiments were conducted in which UOC material was reduced in presence of graphite. Starting material was coarsely ground GR095554 or WSG95300 that contained olivine of Fo 65-98. Approximately 75 mg. of UOC material was placed in a graphite crucible and sealed in an evacuated silica tube. The tube was suspended in a gas-mixing furnace operated at 1 log unit below the IW buffer. The experiments were as brief as 1.5 hrs up to 121 hrs. Results: Dusty olivine was produced readily in experiments melted at 1400 C for I hr. and cooled between 5 and 100 C/hr or melted at 1300-1400 C for 24 hours. Fe-rich olivine (dusty olivine precursors) that have been partially reduced were common in the experiments melted at 1400 C and cooled at 1000 C/hr or melted at 1200 C for 24 hrs. Relict olivine is absent in experiments melted at 1400 for 24 hrs, melted above 1400 C, or cooled more slowly than 10 C/hr. Relict olivine in the experiments has minimum Fo value of 83 . Thus even in the shortest experiments the most Fe-rich olivine has been altered significantly. The precursor olivine disappears in a few to many hours depending on temperature. The experiments show Fe-rich olivine in all stages of transition to the new dusty form. The olivine is reduced to form dusty olivine in a matter of a few hours at temperatures less than 1400 C and in minutes at higher temperatures. The reduction appears to proceed from the rim of the crystal inward with time. The reduction appears initially rectilinear as if controlled by crystallography, but with time Fe-metal blebs are randomly distributed throughout the olivine. In a given experiment, dusty olivine can be found in varying stages of development, but in the longest experiments, the Fe-metal blebs are dominant and they appear to be migrating out of the olivine. The composition of the dusty olivine ranges from Fo 94-99. The Cr, Mn, and Ca content of the newly formed, dusty olivine is slightly less on average that the precursor olivine, but is till with the range of type 1 olivine. Chadacrysts in the low Ca pyroxene are most common in the higher temperature, more slowly cooled experiments and range in composition from Fo 90-99. Application to chondrule formation: These experiments place time-temperature limits on the preservation of Fe-rich olivine and the production of dusty olivine during chondrule forming events. The reduction process proceeds in a few hours at temperatures above 1400 C and in 10's of hours at temperature between 1200 and 1300 C. This result further confirms th at chondrules form in a few hours to days as suggested earlier. The experiments also confirm that dusty olivine can form from typical Fe-rich olivine in UOC material during the recycling of such olivine in the chondrule forming process.

  17. Origin of plagioclase-olivine inclusions in carbonaceous chondrites

    SciTech Connect

    Sheng, Y.J.; Hutcheon, I.D.; Wasserburg, G.J. )

    1991-02-01

    Plagioclase-Olivine Inclusions (POIs) are an abundant group of chondrule-like objects with igneous textures found in carbonaceous chondrites. POIs consist of plagioclase, olivine, pyroxene, and spinel, and cover a wide range of compositions between Type C Ca-Al-rich Inclusions (CAIs) and ferromagnesian chondrules. POIs are distinguished from CAIs by the absence of melilite, lack of refractory siderophile-rich opaque assemblages, more sodic plagioclase, and abundance of olivine and aluminousenstatite. Rare accessory minerals including armalcolite, zirconolite, rutile, and sapphirine are found in several POIs. The petrographic and chemical properties of POIs indicate that they are not condensates or evaporative residues but formed by melting or partial melting of pre-existing solids. Seven of fourteen POIs contain isotopically fractionated Mg, and despite their textures these POIs are not isotopically homogeneous. A comparison of the essential characteristics of POIs and CAIs suggests that the major processes leading to formation of POIs - including condensation, dust/gas fractionation, aggregation of chemically and isotopically disparate materials, and partial melting - are common to most CAIs and chondrules. We present a scenario for the formulation of these objects and conclude that the homogeneity of the final assemblage - CAI, POI, or chondrule - is primarily a reflection of the thermal history rather than the nature of precursor materials.

  18. New measurements of activation volume in olivine under anhydrous conditions

    NASA Astrophysics Data System (ADS)

    Durham, W. B.; Mei, S.; Kohlstedt, D. L.; Wang, L.; Dixon, N. A.

    2009-01-01

    A new cell assembly for the deformation-DIA (D-DIA) shows promise for limiting the water content of samples and providing a more mechanically stable environment for deformation. The 6-mm cubic cell consists of a 6-mm diameter mullite sphere cradled in a web of unfired pyrophyllite. The pyrophyllite flows during initial compression of the D-DIA to form gaskets between the six anvils while the mullite flows to become a nearly cubic-shaped pressure medium. Measurements on olivine indicate more than one order of magnitude drop in water content to <40 ppm H/Si compared with the boron-epoxy medium. Improved mechanical stability is achieved by elimination of the thermocouple from the assembly and determination of temperature from calibration curves of furnace power vs. temperature. Three samples of polycrystalline orthopyroxene-buffer San Carlos olivine have been deformed in high-temperature creep in the new cell, at pressures of 2.7-4.9 GPa and temperatures near 1473 K. Strength is consistent with that measured in the gas-apparatus at lower pressures. Over the pressure range investigated we resolve an activation volume for creep of dry olivine of V* = 9.5 ± 7 × 10 -6 m 3/mol.

  19. Creep behavior of Fe-bearing olivine under hydrous conditions

    NASA Astrophysics Data System (ADS)

    Tasaka, Miki; Zimmerman, Mark E.; Kohlstedt, David L.

    2015-09-01

    To understand the effect of iron content on the creep behavior of olivine, (MgxFe(1 - x))2SiO4, under hydrous conditions, we have conducted tri-axial compressive creep experiments on samples of polycrystalline olivine with Mg contents of x = 0.53, 0.77, 0.90, and 1. Samples were deformed at stresses of 25 to 320 MPa, temperatures of 1050 to 1200C, a confining pressure of 300 MPa, and a water fugacity of 300 MPa using a gas-medium high-pressure apparatus. Under hydrous conditions, our results yield the following expression for strain rate as a function of iron content for 0.53 ? x ? 0.90 in the dislocation creep regime: ??=??0.90((1-x/0.1))1/2exp[2261030.9-x/RT]. In this equation, the strain rate of San Carlos olivine, ??0.90, is a function of T, ?, and fH2O. As previously shown for anhydrous conditions, an increase in iron content directly increases creep rate. In addition, an increase in iron content increases hydrogen solubility and therefore indirectly increases creep rate. This flow law allows us to extrapolate our results to a wide range of mantle conditions, not only for Earth's mantle but also for the mantle of Mars.

  20. Value enhancement of olivine process dust through air classification

    NASA Astrophysics Data System (ADS)

    Kleiv, R. A.

    2012-03-01

    As a result of the production of dry olivine sand products at A/S Olivin's production plant at Åheim in western Norway, an annual quantity of some 20000-30000 t of process dust is produced. The bulk of this material is currently being sold as a slag conditioner at a relatively low price; hence, alternative uses of the process dust are now being sought. Information regarding the chemical composition of the material as a function of particle size facilitates product modifications through exclusion or mixing of individual size fractions. This paper demonstrates how such information can be obtained from air classification experiments when these are combined with chemical analysis of the produced size fractions. The classification and subsequent analysis of the olivine process dust revealed that the finer size fractions had high loss on ignition (LOI) values and were relatively low in MgO when compared with the bulk analysis. Removal of the finer fractions resulted in a remaining coarse product of significantly higher quality. The coarse material could be used as a raw material for further processing; it could be recycled or it could constitute a new product in itself.

  1. Olivine-rich asteroids in the main asteroid belt

    NASA Astrophysics Data System (ADS)

    DeMeo, Francesca E.; Polishook, David; Carry, Benoit; Moskovitz, Nick; Burt, Brian; Binzel, Rick

    2015-11-01

    Olivine-dominated asteroids, classified as A-types with near-infrared spectral measurements are largely thought to be the mantle remnants of disrupted differentiated small bodies. These A-type asteroids hold clues to asteroid differentiation and to the collisional history of those differentiated bodies. Preliminary studies of the abundance and distribution of A-type asteroids were performed by Carvano et al. (2010) and DeMeo & Carry (2013, 2014) using the Sloan Digital Sky Survey (SDSS). To confidently identify these olivine-dominated A-type asteroids, however, near-infrared spectral measurements are needed to identify the distinct broad and deep 1-micron olivine absorption feature. Using the Sloan Digital Sky Survey Moving Object Catalog to select A-type asteroid candidates, we have performed a near-infrared spectral survey of over 70 asteroids with SpeX on the IRTF. We present the abundance and distribution of A-type asteroids throughout the main asteroid belt and compare these results with similar surveys for basalt-rich V-type asteroids (e.g. Moskovitz et al. 2008). This work is supported by NASA under grant number NNX12AL26G issued through the Planetary Astronomy Program.

  2. Dislocations in olivine: insights from numerical modeling (Invited)

    NASA Astrophysics Data System (ADS)

    Cordier, P.; Metsue, A.; Carrez, P.; Denoual, C.; Mainprice, D.

    2009-12-01

    Olivine (Mg,Fe)2SiO4 is the main constituent of the Earths upper mantle (down to 410 km deep). The rheology of, and convection in, the upper mantle are therefore controlled by the deformation mechanisms of this mineral. Numerous experimental studies have been undertaken leading to a good description of the deformation mechanisms and rheological properties of this mineral at low pressure < 1 GPa. Based on this knowledge, crystallographic preferred orientations in olivine are commonly used to infer fossil mantle flow patterns from seismic anisotropy measurements. However, recent studies have shown that [001] glide is enhanced over [100] glide when pressure increases or when trace amounts of water are dissolved in the crystals(1). These observations have a lot of implications on our understanding of the rheology of the upper mantle and call for a more detailed description of dislocation cores and dynamics. The Peierls-Nabarro (PN) model including ?-surface energies has been used to model dislocation cores in olivine. However, the standard approach, which is restricted to the description of planar cores, which cannot be universally applied in the case of olivine. The occurrence in olivine of long straight screw [001] dislocations raise the question of the origin of lattice friction. A recent study based on full atomistic calculations (using the THB1 potential) has shown that [001] screw dislocations exhibit 3D core spreading(2). This issue must be addressed to understand the [100] to [001] glide crossover and its potential sensitivity to pressure. In this study, a novel method coupling Peierls-Nabarro and element-free Galerkin methods (called PNG) is presented. This technique expands the possibilities of previously reported calculations, in particular in permitting the modeling of 3D dislocation cores. We show that, [100] dislocations may exhibit non-collinear dissociation in the (010) plane. The PNG model confirms the occurrence of 3D core spreading of [001] screw dislocations. The lattice friction is not very sensitive to confining pressure between 0 and 10 GPa. However, [001] dislocations exhibit a complex sensitivity to the applied shear stress tensor with a significant deviation from the Schmid law under pressure. (1) Jung, Mo & Green (2009) Nature Geoscience 2, 73. (2) Carrez, Walker, Metsue & Cordier (2008) Phil. Mag. 88(16), 2477.

  3. Petrogenesis and Nd-, Pb-, Sr-isotope geochemistry of the Cenozoic olivine melilitites and olivine nephelinites (ankaratrites) in Madagascar

    NASA Astrophysics Data System (ADS)

    Melluso, Leone; le Roex, Anton P.; Morra, Vincenzo

    2011-12-01

    The Cenozoic ankaratrites of the Alaotra, Takarindoha-Vatomandry and Votovorona (NE Ankaratra) volcanic fields, Madagascar, range from olivine ( monticellite) melilitites, through olivine-melilite nephelinites to olivine ( leucite) nephelinites. The rocks show significant compositional ranges in their coexisting magmatic minerals (olivine-group minerals, melilite, clinopyroxene, nepheline, leucite, Ba-phlogopite, perovskite, ilmenite, spinels, apatite), and evidence of distinct parental magmas, often in different facies of the same vent. Primitive compositions (high Mg#, Cr and Ni concentrations) are found in each volcanic district, and a few lavas contain mantle xenoliths or xenocrysts. The rocks show enrichment in the most strongly incompatible elements (e.g., Ba and Nb up to 200 times primitive mantle, La/Ybn = 24 to 40), with troughs at K and smooth, decreasing patterns towards the least incompatible elements in mantle-normalized diagrams. The Nd-Pb-Sr isotope geochemistry indicates a marked heterogeneity of the mantle sources of the various districts (e.g., 206Pb/204Pb = 18.68-18.77, 87Sr/86Sr = 0.704011-0.704207 for the Alaotra-Votovorona districts; 206Pb/204Pb = 19.04-19.14, 87Sr/86Sr = 0.703544-0.704017 for the Takarindoha-Vatomandry districts), with significant differences to other Cenozoic mafic volcanic rocks of northern Madagascar. The genesis of the Madagascan ankaratrites is related to rifting events which triggered low-degree partial melting of a garnet peridotite enriched in dolomite and incompatible-element-rich phases, in the lowermost lithosphere. Despite marked geochemical similarities, the source of the Madagascan melilitites bears no isotopic similarity to the HIMU-related sources of melilitites of eastern and southern Africa.

  4. LA-ICP-MS mapping of olivine from the Brahin and Brenham meteorites: Complex elemental distributions in the pallasite olivine precursor

    NASA Astrophysics Data System (ADS)

    McKibbin, Seann J.; O'Neill, Hugh St. C.; Mallmann, Guilherme; Halfpenny, Angela

    2013-10-01

    To investigate the early history of olivine from the Main-Group pallasites Brahin and Brenham, we have spatially mapped their trace-element distributions using laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICP-MS). Brahin olivine interiors contain ˜100-200 μm patches enriched in Cr, Al, Ti, V, Sc and Ga, separated by linear enrichments of P; these structures bear no relation to current crystal morphologies. Rather, cross-cutting relationships suggest they predate olivine-metal mixing. Brenham olivine also has internal variations for these elements. By contrast, Ni and Co concentrations in olivine from both meteorites decrease near crystal margins, as expected for freezing-in of profiles formed during diffusive re-equilibration with metal during cooling. Brenham olivine also has decreasing Al, Cr and Ti near the margin. Correlations between concentrations of Cr and Al exist for individual Brahin olivine grains, but do not hold over multiple grains, indicating a heterogeneous precursor. Al and Ti are correlated over multiple grains in Brahin, interpreted as Ti cations decorating pre-existing Al-defects. In Brenham olivine, similar geochemical trends exist, but the Cr-Al relationship probably represents both grain margin effects and pre-existing internal heterogeneity. The preservation of structure for elements which are normally fast diffusers in olivine hinges on coupled substitutions involving Al, which along with P diffuses much more slowly than most other elements under some conditions. Al concentrations in olivine are low and variable (3-33 ppm) which is inconsistent with crystallisation from a normal silicate melt; Al-in-olivine thermometers indicate that pallasite olivine was formed in a low-temperature environment. Following its delivery to the magma ocean/core-mantle boundary, Al-P systematics were not substantially modified. Assuming diffusivities for Al and P that are similar to Si (since they reside in the same crystallographic site) and temperatures of 1600-1650 K (from the melting point of the metal and the absence of orthopyroxene in pallasites) an upper limit on the residence time of pallasite olivine of ˜1 Ma can be inferred by the persistence of trace element detail over scales of 100 μm. Following the olivine-metal mixing event, homogeneous Ni and Co distributions were modified by diffusion; Cr and V were partially modified; Al and P were essentially unchanged.

  5. Annealing of deformed olivine single-crystals under 'dry' conditions

    NASA Astrophysics Data System (ADS)

    Blaha, Stephan; Katsura, Tomoo

    2013-04-01

    Knowledge of rheological properties of Earth's materials is essential to understand geological processes. Open questions are the water content and crystallographic orientation dependences of dislocation creep rate, because the dominant slip system changes with increasing water content, which suggest different dislocations have different water content dependence. This project focuses on olivine, which is the most abundant mineral of the upper mantle. It is also considered to be the weakest phase and hence should control the rheology of the upper mantle. Several slip systems were reported for olivine, which are [100](010), [001](010), [001](100) and [100](001), each of which appear under different water content and stress conditions [1]. For this purpose we started to obtain data for 'dry' conditions, providing basic knowledge to understand the effect of water. Variation in dislocation creep rate according to change in physical conditions can be estimated by dislocation recovery experiments [2]. In this technique, deformed crystals are annealed, in which the dislocation density is expected to decrease due to coalescence of two dislocations. Dislocation densities are measured before and after the annealing. Dislocation mobility, which should be directly proportional to the dislocation creep rate, is estimated based on the change in dislocation density and duration of annealing. This technique has significant advantages partly because informations of strain rate and deviatoric stress, which are difficult to measure, are unnecessary, and partly because dislocation annealing is conducted under quasi-hydrostatic conditions, which allows wide ranges of P and T conditions. The first step of the experiments is to deform a single crystal of olivine. For this purpose, we developed an assembly, which deforms a single crystal in simple-shear geometry and prevent breakage, sub-grain formation and recrystallization of the crystal. Olivine single-crystals were placed in the high-pressure assembly so that a particular slip system is activated. The assemblies were compressed to 3 GPa. The shear deformation was conducted at 1600 K. EBSD measurements indicate that the recovered crystals are single crystals and sub-grain formation did not occur in most cases. The second step is to anneal the samples under the same P-T conditions as those of the deformation experiments. Annealing experiments are also performed at ambient pressures at 1600 K. Dislocation density was measured by means of the oxidation decoration technique [3]. The samples were firstly polished and then oxidized at 1200 K for 50 min. The dislocations are preferably oxidized, so that presence of dislocation can be observed using SEM. First Results indicate that the dislocation density decreased by annealing by 1/4 with an annealing period of 10 h for dislocations with b = [001]. References [1] H. Jung and S. I. Karato. Water-induced fabric transitions in olivine. Science, 293(5534):1460-1463, 2001. [2] S. I. Karato, D. C. Rubie, and H. Yan. Dislocation recovery in olivine under deep upper mantle conditions: Implications for creep and diffusion. Journal of Geophysical Research, 98(B6):9761-9768, 1993. [3] D. L. Kohlstedt, C. Goetze, W. B. Durham, and J. V. Sande. New technique for decorating dislocations in olivine. Science, 191(4231):1045-1046, March 1976.

  6. The morphology and surface features of olivine in kimberlite lava: implications for ascent and emplacement mechanisms

    NASA Astrophysics Data System (ADS)

    Jones, T. J.; Russell, J. K.; Porritt, L. A.; Brown, R. J.

    2013-12-01

    Many kimberlite rocks contain large proportions of ellipsoidal-shaped xenocrystic olivine grains that are derived mainly from the disaggregation of peridotite. Xenocrystic olivine grains from a lava erupted from the Quaternary Igwisi Hills kimberlites, Tanzania, are compared to phenocrystic olivine, liberated from picritic lavas, and mantle olivine, liberated from a fresh peridotite xenolith, in order to examine the potential modification of olivine surface textures due to transport from the mantle to the surface within kimberlite magmas. Image analysis, SEM imagery and laser microscopy reveals significant differences in the surface features and morphologies of the three crystal populations. Xenocrystic olivine grains are characterised by rough surfaces, ellipsoidal shapes and impact pits. Mantle olivines are characterised by flaked surfaces and indented shapes consistent with growth as a crystal aggregates. Phenocrystic olivines are smooth-surfaced and exhibit flat crystal faces. We infer that the distinctive shapes and surfaces of xenocrystic olivine grains resulted from three distinct mechanical processes attending their rapid transport from their source in the mantle lithosphere: (1) penetrative flaking from micro-tensile failure induced by rapid decompression; (2) sustained abrasion and attrition arising from particle-particle collisions between grains in a turbulent, volatile-rich flow regime, and; (3) higher energy particle-particle collisions that produced impact cavities superimposed on decompression structures. The combination of these processes during the rapid ascent of kimberlite magmas is responsible for the distinctive ellipsoidal shape of olivine xenocrysts found in kimberlites worldwide.

  7. From olivine to ringwoodite: a TEM study of a complex process

    NASA Astrophysics Data System (ADS)

    Pittarello, Lidia; Ji, Gang; Yamaguchi, Akira; Schryvers, Dominique; Debaille, Vinciane; Claeys, Philippe

    2015-05-01

    The study of shock metamorphism of olivine might help to constrain impact events in the history of meteorites. Although shock features in olivine are well known, so far, there are processes that are not yet completely understood. In shock veins, olivine clasts with a complex structure, with a ringwoodite rim and a dense network of lamellae of unidentified nature in the core, have been reported in the literature. A highly shocked (S5-6), L6 meteorite, Asuka 09584, which was recently collected in Antarctica by a Belgian-Japanese joint expedition, contains this type of shocked olivine clasts and has been, therefore, selected for detailed investigations of these features by transmission electron microscopy (TEM). Petrographic, geochemical, and crystallographic studies showed that the rim of these shocked clasts consists of an aggregate of nanocrystals of ringwoodite, with lower Mg/Fe ratio than the unshocked olivine. The clast's core consists of an aggregate of iso-oriented grains of olivine and wadsleyite, with higher Mg/Fe ratio than the unshocked olivine. This aggregate is crosscut by veinlets of nanocrystals of olivine, with extremely low Mg/Fe ratio. The formation of the ringwoodite rim is likely due to solid-state, diffusion-controlled, transformation from olivine under high-temperature conditions. The aggregate of iso-oriented olivine and wadsleyite crystals is interpreted to have formed also by a solid-state process, likely by coherent intracrystalline nucleation. Following the compression, shock release is believed to have caused opening of cracks and fractures in olivine and formation of olivine melt, which has lately crystallized under postshock equilibrium pressure conditions as olivine.

  8. A New Spinel-Olivine Oxybarometer: Near-Liquidus Partitioning of V between Olivine-Melt, Spinel-Melt, and Spinel-Olivine in Martian Basalt Composition Y980459 as a Function of Oxygen Fugacity

    NASA Technical Reports Server (NTRS)

    Papike, J. J.; Le, L.; Burger, P. V.; Shearer, C. K.; Bell, A. S.; Jones, J.

    2013-01-01

    Our research on valence state partitioning began in 2005 with a review of Cr, Fe, Ti, and V partitioning among crystallographic sites in olivine, pyroxene, and spinel [1]. That paper was followed by several on QUE94201 melt composition and specifically on Cr, V, and Eu partitioning between pyroxene and melt [2-5]. This paper represents the continuation of our examination of the partitioning of multivalent V between olivine, spinel, and melt in martian olivine-phyric basalts of Y980459 composition [6, 7]. Here we introduce a new, potentially powerful oxybarometer, V partitioning between spinel and olivine, which can be used when no melt is preserved in the meteorite. The bulk composition of QUE94201 was ideal for our study of martian pyroxene-phyric basalts and specifically the partitioning between pyroxene-melt for Cr, V, and Eu. Likewise, bulk composition Y980459 is ideal for the study of martian olivine-phyric basalts and specifically for olivine-melt, spinel-melt, and spinel-olivine partitioning of V as a function of oxygen fugacity.

  9. Phosphorus zoning in olivine of Kilauea Iki lava lake, Hawaii

    NASA Astrophysics Data System (ADS)

    Fabbrizio, Alessandro; Beckett, John R.; Baker, Michael B.; Stolper, Edward M.

    2010-05-01

    Kilauea Iki lava lake was formed when the lavas of the 1959 summit eruption of Kilauea volcano ponded in Kilauea Iki pit crater, as described by [1]. The main chamber of this lake has been drilled repeatedly from 1960 to 1981 as the lake has cooled and crystallized and partial descriptions of core can be found in [2-7]. The bulk of the core consists of a gray, olivine-phyric basalt matrix [3]. Rapid diffusion of divalent cations through olivine at magmatic temperatures can delete information on early-formed zoning and thus information on early magmatic history, recorded in olivine during its growth, is often largely lost [8-11]. In the last years many studies [8-11] have shown that natural olivine, terrestrial and extraterrestrial, from several localities and rock types can preserve a complex zoning in P (sometimes associated with Cr and Al). Simple crystallization experiments conducted by [10] and [11] were able to replicate these features (i.e., sector and oscillatory zoning). Here, we describe P, Cr and Al zoning in olivine from the 1981 drilling of Kilauea Iki lava lake hole #1 (KI81-1) [6]. K? X-ray intensity maps and major and minor element quantitative analyses were obtained using the Caltech JEOL JXA-8200 electron microprobe. We acquired P, Cr, Al, Fe and Ti X-ray maps simultaneously at 15 kV and 400 nA, a beam diameter of 1 ?m, pixel spacing of 1-2 ?m, and count times of 420-1500 msec/step were used depending on the dimension of the crystal. 15 kV and 40 nA with a beam diameter of 1 ?m were used to collect quantitative analyses. P2O5 contents of the Iki olivines range from below detection limit to 0.30 wt%. Zoning in phosphorus, based on X-ray intensity maps, was observed in all olivines we examined. The P zoning patterns of the olivines display several styles. P shows oscillatory zoning comparable to that seen in terrestrial and extraterrestrial igneous olivines and in experimentally grown olivine [8-11]; high P regions, inside the crystals, outline low P chambers and P enriched zones were also observed; near the margins of the crystals is possible to find the presence of discontinuous sets of P-enriched bands that generally outline euhedral crystal forms; some crystals are characterized by P-enriched ghosts of relict crystals in their interior that are associated with probable undercooling and/or with an initial pulse of rapid crystal growth [8, 10]. Phenocrysts and microphenocrysts are frequently unzoned in major and minor divalent cations (Fe, Mg, Mn, Ca, Ni), but all are zoned in P. Variations in Cr and Al correlate spatially with P but are much fainter or absents, in some crystal the P-enriched bands are superimposed with small crystals of chromite (?1 ?m) aligned along the P zoning. Probably these chromites were formed by precipitation from the original Cr and Al bands. In no case was observed Ti zoning. [1] Richter D.H. et al. (1970) US Geol Surv Prof Pap 537-E, 73 p. [2] Richter D.H., Moore J.G. (1966) US Geol Surv Prof Pap 537-B, 26 p. [3] Helz R.T. (1980) Bull Volcanol 43-4, 675-701. [4] Helz R.T. et al. (1984) US Geol Surv Open File Rep 84-484, 72 p. [5] Hardee H.C. et al. (1981) Geophys Res Lett 8, 1211-1214. [6] Helz R.T., Wright T.L. (1983) US Geol Surv Open File Rep 83-326, 66 p. [7] Helz R.T. (1987) Geochem Soc Spec Pub 1, 241-258. [8] Beckett J.R. et al. (2008) LPSC abs. 1726. [9] Mccanta M.C. et al. (2008) LPSC abs. 1807. [10] Milmann-Barris M.S. et al. (2008) CMP 155, 739-765. [11] Mccanta M.C. et al. (2008) GCA 72-12, S1, A610.

  10. Enhanced olivine carbonation within a basalt as compared to single-phase experiments: the impact of redox and bulk composition on the dissolution kinetics of olivine

    NASA Astrophysics Data System (ADS)

    Sissmann, O.; Brunet, F.; Martinez, I.; Guyot, F. J.; Verlaguet, A.; Pinquier, Y.; Garcia, B.; Chardin, M.; Kohler, E.; Daval, D.

    2014-12-01

    Olivine (Mg,Fe)2SiO4, which is one of the major mineral constituents of mafic and ultramafic rocks, has an attractive potential for CO2 mineral sequestration, as it possesses a high content of carbonate-forming divalent cations and exhibits one of the highest dissolution rate amongst rock-forming minerals. This study reports drastic differences in carbonation yields between experiments performed on olivine-rich basalt samples and on olivine separates (a more restricted chemical system). Batch experiments were conducted in water at 150C and pCO2 = 280 bars on a Mg-rich tholeiitic basalt (9.3 wt.% MgO and 12.2 wt.% CaO), composed of olivine, Ti-magnetite, plagioclase and clinopyroxene. After 45 days of reaction, 56 wt.% of the initial MgO has reacted with CO2 to form Fe-bearing magnesite (Mg0.8Fe0.2)CO3 along with minor calcium carbonates. The substantial decrease of olivine content upon carbonation supports the idea that ferroan magnesite formation mainly follows from olivine dissolution. In contrast, in experiments performed under similar run durations and P/T conditions with a San Carlos olivine separate (47.8 wt.% MgO) of similar grain size, only 5 wt.% of the initial MgO content reacted to form Fe-bearing magnesite. The overall carbonation kinetics of the basalt is enhanced by a factor of 40. It could be accounted for by differences in chemical and textural properties of the secondary-silica layer which covers reacted olivine grains in both types of sample. A TEM inspection of mineral surfaces shows that the thin amorphous silica layer (~100 nm) is porous in the case of the basalt sample and that it contains significant amounts of iron and aluminum. Thus, we propose that the composition of the olivine environment itself can strongly influence the olivine dissolution-carbonation process. Consequently, laboratory data obtained on olivine separates might yield a conservative estimate of the true carbonation potential of olivine-bearing basaltic rocks. More generally, this study questions the approach which consists in evaluating the carbonation potential of a rock based on experiments on separate minerals. It also emphasizes the impact of fO2 and potential co-injected gases on the olivine dissolution-carbonation process.

  11. Petrogenetic linkages among Martian basalts: Implications based on trace element chemistry of olivine

    NASA Astrophysics Data System (ADS)

    Shearer, C. K.; Burger, P. V.; Papike, J. J.; Borg, L. E.; Irving, A. J.; Herd, C.

    2008-10-01

    The shergottites exhibit a range of major and trace element compositions, crystallization ages, and initial Sr, Nd, Hf, and Pb isotopic compositions. To constrain the physical mechanisms by which shergottites obtain their compositional characteristics, we examined the major and trace element record preserved in olivine in the more primitive shergottites. Based on such characteristics as the Mg#, V zoning, calculated DNi,Co, the olivine in Y-980459 are most likely phenocrysts. Many of these same characteristics indicate that the olivines in other shergottites are not in equilibrium with the adjacent melt. However, in most cases they are not xenocrystic, but additions of olivine from the same basaltic system. Elephant Moraine (EET) A79001 may be an exception with the olivine data suggesting that it is xenocrystic. In this case, the olivine crystallized from a reduced and LREEdepleted melt and was incorporated into an oxidized and enriched basalt. Vanadium and CaO in olivine appear to record the appearance of spinel and pyroxene on the liquidus of most of the shergottites. Most of the olivine shergottites represent basalts produced by melting of reduced (IW to IW + 1), depleted mantle sources. Olivine data indicate that many of the primary melts derived from this source had similar Ni, Co, and Mn. Shergottites such as Northwest Africa (NWA) 1110/1068 and perhaps Roberts Massif (RBT) 04261 that appear to be derived from more enriched sources have distinctly different olivine. In the case of NWA 1110/1068, the olivine data suggests that the enriched component was added to system prior to olivine crystallization.

  12. Olivine-Wadsleyite-Pyroxene Epitaxy: Element and Volatile Distributions at the 410km Discontinuity

    NASA Astrophysics Data System (ADS)

    Smyth, J. R.; Miyajima, N.; Huss, G. R.; Hellebrand, E.; Rubie, D. C.; Frost, D. J.

    2010-12-01

    We have synthesized hydrous peridotite-composition samples at 13GPa and 1400C with co-existing coarse grains (~100 micrometer) of olivine, wadsleyite, clinoenstatite, and melt in a multi-anvil press. The olivine grains contain fine-scale lamellae of wadsleyite and clinoenstatite that likely resulted from small temperature fluctuations during the four-hour experiment. Major-element compositions were determined by electron microprobe and H contents by secondary ion mass spectroscopy (SIMS). The olivine is about Fo93 in composition and contains about 650 ppm by weight H2O. The wadsleyite is about Fo87 in composition and contains about 1650 weight percent H2O. The clinoenstatite is about En96 in composition and about 440 ppm H2O. High resolution transmission electron microscopy of the lamellae and host show that the olivine and wadsleyite share their close-packed oxygen planes so that the wadsleyite lamellae are nearly planar and perpendicular to the [1 0 0] of olivine. The wadsleyite lamellae thus have their [1 0 1] and [1 0 -1] directions parallel to the [1 0 0] of olivine. Additionally, a second orientation relation with the [001] of olivine parallel to [100] of wadsleyite is also found as are incoherent blebs of wadsleyite in olivine. The coexisting melt phase quenched to a feathery mass of mostly wadsleyite crystals. Neither a quenched glass phase nor a nominally hydrous phase was observed. The lamellae indicate that the olivine-wadsleyite transformation can proceed effectively by coherent mechanisms that could potentially preserve lattice preferred orientation. The observed rapid coherent inversion from olivine to wadsleyite means that a metastable preservation of olivine below 410 km is unlikely under slightly hydrous conditions. The distribution of H among the nominally anhydrous phases implies that dehydration of peridotites by partial melting is inefficient so that complete dehydration of subducting slabs is unlikely. SEM-BSE image of wadsleyite (W) blebs and lamellae in olivine (O).

  13. LIME silicates in amoeboid olivine aggregates in carbonaceous chondrites: Indicator of nebular and asteroidal processes

    NASA Astrophysics Data System (ADS)

    Komatsu, Mutsumi; Fagan, Timothy J.; Mikouchi, Takashi; Petaev, Michail I.; Zolensky, Michael E.

    2015-07-01

    MnO/FeO ratios in olivine from amoeboid olivine aggregates (AOAs) reflect conditions of nebular condensation and can be used in concert with matrix textures to compare metamorphic conditions in carbonaceous chondrites. LIME (low-iron, Mn-enriched) olivine was identified in AOAs from Y-81020 (CO3.05), Kaba (CV~3.1), and in Y-86009 (CV3), Y-86751 (CV3), NWA 1152 (CR/CV3), but was not identified in AOAs from Efremovka (CV3.1-3.4) or Allende (CV>3.6). According to thermodynamic models of nebular condensation, LIME olivine is stable at lower temperatures than Mn-poor olivine and at low oxygen fugacities (dust enrichment <10 solar). Although this set of samples does not represent a single metamorphic sequence, the higher subtypes tend to have AOA olivine with lower Mn/Fe, suggesting that Mn/Fe decreases during parent body metamorphism. Y-81020 has the lowest subtype and most forsteritic AOA olivine (Fo>95) in our study, whereas Efremovka AOAs are slightly Fe-rich (Fo>92). AOA olivines from Kaba are mostly forsteritic, but rare Fe-rich olivine precipitated from an aqueous fluid. A combination of precipitation of Fe-rich olivine and diffusion of Fe into primary olivine grains resulted in iron-rich compositions (Fo97-59) in Allende AOAs. Variations from fine-grained, nonporous matrix toward higher porosity and coarser lath-like matrix olivine can be divided into six stages represented by (1) Y-81020, Efremovka, NWA 1152; (2) Y-86751 lithology B; (3) Y-86009; (4) Kaba; (5) Y-86751 lithology A; (6) Allende. These stages are inferred to represent general degree of metamorphism, although the specific roles of thermally driven grain growth and diffusion versus aqueous dissolution and precipitation remain uncertain.

  14. [Study on the FTIR spectra of OH in olivines from mengyin kimberlite].

    PubMed

    Ai, Qun; Yang, Zhi-jun; Zeng, Xiang-qing; Zheng, Yun-long; Hu, Piao-ye

    2013-09-01

    The results of FTIR spectra study of OH in olivines from Mengyin kimberlite show that there are more than 60 OH absorption peaks in the range of 3800-3000 cm(-1). We identified four major spectral features in the OH absorption bands of kimberlitic olivines. One is with nuOH in the range of 3800-3700 cm(-1), which is caused by the vapour of the room circumstance, and can not be regarded as intrinsic or non-intrinsic nuOH of the olivines. Another one is with nuOH in the range of 3710-3620 cm(-1), which belongs to three "water"-bearing minerals including serpentine, talc and Mg-bearing amphiboles, which is the non-intrinsic nuOH of the olivines. There is the possibility that H in hydrous minerals mainly entered into olivines during post-emplacement processes of the kimberlite magma. The third one is with nuOH in the range of 3620-3425 cm(-1), which originated from H occupying the Si-defect in the olivine structure, forming humite-like defects, and/or the defects that H occupies (Mg,Fe)-depletion, which is certainly attributed to the intrinsic nuOH of the olivines. In this case, H possibly entered into olivines following its immersion in the high temperature and rich fluid kimberlite magma in the mantle circumstance. The last one is with nuOH in the range of 3425-3000 cm(-1). In this area, nuOH is assigned to fluid inclusions of the olivines, and is the non-intrinsic nuOH of olivines. Fluid inclusions can enter into the olivines either during post-emplacement processes of the kimberlite magma or during the periods that olivines were formed in the mantle. PMID:24369634

  15. Deformation of olivine single crystals under lithospheric conditions

    NASA Astrophysics Data System (ADS)

    Demouchy, S.; Tommasi, A.; Cordier, P.

    2012-12-01

    The rheology of mantle rocks at lithospheric temperatures (<1000°C) remains poorly constrained, in contrast to the extensive experimental data on creep of olivine single crystals and polycrystalline aggregates at high temperature (T > 1200°C). Consequently, we have performed tri-axial compression experiments on oriented single crystals and polycrystalline aggregates of San Carlos olivine at temperatures ranging from 800° to 1090°C. The experiments were carried out at a confining pressure of 300 MPa in a high-resolution gas-medium mechanical testing apparatus at constant strain rates ranging from 7 × 10-6 s-1 to 1 × 10-4 s-1 . Compression was applied along three different crystallographic directions: [101]c, [110]c and [011]c, to activate the several slip systems. Yield differential stresses range from 88 to 1076 MPa. To constrain hardening, stick-and-slip, or strain localization behaviors, all samples were deformed at constant displacement rate for finite strains between 4 to 23 %. Hardening was observed in all experiments and the maximum differential stress often overcame the confining pressure. EBSD mapping highlights macroscale bending of the crystalline network in three crystals. TEM observations on several samples show dislocations with [100] and [001] Burgers vectors in all samples, but dislocation arrangements vary. The results from the present study permit to refining the power-law expressing the strain rate dependence on stress and temperature for olivine, allowing its application to the lithospheric mantle. Our experiments confirm that previous published high-temperature power flow laws overestimate the strength of lithospheric mantle and that the transition to low-temperature creep occurs at higher temperatures than it has previously been established.

  16. Experimental constraints of the olivine crystals compaction in cumulus layer

    NASA Astrophysics Data System (ADS)

    Forien, M.; Bagdassarov, N.; Schmidt, M. W.

    2009-12-01

    The layered intrusions are the result of magma crystallization and differentiation in a form of lateral structures, which are often observed in magmatic chambers. They are markers of processes occurring during a prolonged cooling stage (several tens of thousands years for bodies 1 km in size). There is no unique explication for the mechanism of layering during the intrusion formation. The most plausible mechanism proposed to explain the observed layering includes the coupled crystal settling and residual liquid advection. In the layers containing a large crystal fraction (> 66 vol%) and a small percentage of the residual liquid, the compaction mechanism and the decrease of cumulate layer porosity due to the diffusion adjustment of grain boundaries could effectively occur. In this study, the compaction mechanisms of crystals settling in magma chambers have been modelled with the use of a high temperature centrifuge. The suspensions of olivine crystals and a basaltic melt (33 vol% and 67 vol%, respectively) were centrifuged at the melting temperature of basalt (temperature range of 1270-1280°C). The experiments were conducted at 200-1500 g under a pressure between 0.8-1.1 GPa. During centrifugation run olivine grains are compacted because of the x-time enhanced centrifugation force which is equivalent to x-time larger volume of crystals compacting from above. After crystals have reached a maximum compaction concentration due to this accelerated piling from above, their locations and porosity in cumulates change under the influence of the solution - recrystallisation process. The concentration of crystals in a cumulate layer increases much slower than during their sedimentation. The solution-precipitation and recrystallisation process is a diffusion type mechanism of compaction and has not been addressed experimentally before. Evidences of the precipitation - recrystallisation process of olivine grains in centrifuged samples with TEM analyses are revealed. In fact, knowing that Ca is characteristic only for MORB-melt, the first feature is the presence of Ca at the interface of two adjacent Ol-grains even when the melt phase is escaped. Another evidence of the diffusion compaction is the presence of some small melt inclusions at the growing Ol-boundaries of compacting Ol-grains. Finally, the precipitation - recrystallisation process of olivine grains during the cumulus compaction stems from the observation that the new boundary between two Ol-grains is distinct and not fully crystallized as the interior of grains. This indicates some MORB melt elements (for example, enrichment in Ca) prevent to recrystallize Ol in a fully crystalline structure.

  17. Olivine-type NaCd(AsO4)

    PubMed Central

    Weil, Matthias

    2013-01-01

    The title compound, sodium cadmium orthoarsenate, adopts the olivine [Mg2(SiO4)] structure type in space group Pnma, with Na (site symmetry -1) and Cd (.m.) replacing the two Mg positions, and the AsO4 tetrahedron (.m.) the SiO4 tetrahedron. The crystal structure is made up of a nearly hexagonal closed-packed arrangement of O atoms stacked along [001]. The Na and Cd atoms occupy one half of the octahedral voids in alternate layers stacked along [100], and one eighth of the tetrahedral voids are occupied by As atoms. PMID:24454011

  18. Chromium valences in ureilite olivine and implications for ureilite petrogenesis

    NASA Astrophysics Data System (ADS)

    Goodrich, C. A.; Sutton, S. R.; Wirick, S.; Jercinovic, M. J.

    2013-12-01

    Ureilites are a group of ultramafic achondrites commonly thought to be residues of partial melting on a carbon-rich asteroid. They show a large variation in FeO content (olivine Fo values ranging from ?74 to 95) that cannot be due to igneous fractionation and suggests instead variation in oxidation state. The presence of chromite in only a few of the most ferroan (Fo 75-76) samples appears to support such a model. MicroXANES analyses were used in this study to determine the valence states of Cr (previously unknown) in olivine cores of 11 main group ureilites. The goal of this work was to use a method that is independent of Fo to determine the oxidation conditions under which ureilites formed, in order to evaluate whether the ureilite FeO-variation is correlated with oxidation state, and whether it is nebular or planetary in origin. Two of the analyzed samples, LEW 88774 (Fo 74.2) and NWA 766 (Fo 76.7) contain primary chromite; two others, LAP 03587 (Fo 74.4) and CMS 04048 (Fo 76.2) contain sub-micrometer-sized exsolutions of chromite + Ca-rich pyroxene in olivine; and one, EET 96328 (Fo 85.2) contains an unusual chromite grain of uncertain origin. No chromite has been observed in the remaining six samples (Fo 77.4-92.3). Chromium in olivine in all eleven samples was found to be dominated by the divalent species, with valences ranging from 2.10 0.02 (1?) to 2.46 0.04. The non-chromite-bearing ureilites have the most reduced Cr, with a weighted mean valence of 2.12 0.01, i.e., Cr2+/Cr3+ = 7.33. All low-Fo chromite-bearing ureilites have more oxidized Cr, with valences ranging from 2.22 0.03 to 2.46 0.04. EET 96328, whose chromite grain we interpret as a late-crystallizing phase, yielded a reduced Cr valence of 2.15 0.07, similar to the non-chromite-bearing samples. Based on the measured Cr valences, magmatic (1200-1300 C) oxygen fugacities (fO2) of the non-chromite-bearing samples were estimated to be in the range IW-1.9 to IW-2.8 (assuming basaltic melt composition), consistent with fO2 values obtained by assuming olivine-silica-iron metal (OSI) equilibrium. For the primary chromite-bearing-ureilites, the corresponding fO2 were estimated (again, assuming basaltic melt composition) to be ?IW to IW+1.0, i.e., several orders of magnitude more oxidizing than the conditions estimated for the chromite-free ureilites. In terms of Fo and Cr valence properties, ureilites appear to form two groups rather than a single Cr-valence (or fO2) vs. Fo trend. The chromite-bearing ureilites show little variation in Fo (?74-76) but significant variation in Cr valence, while the non-chromite-bearing ureilites show significant variation in Fo (?77-95) and little variation in Cr valence. These groups are unrelated to petrologic type (i.e., olivine-pigeonite, olivine-orthopyroxene, or augite-bearing). The chromite-bearing ureilites also have lower contents of Cr in olivine than most non-chromite-bearing ureilites, consistent with predictions based on Cr olivine/melt partitioning in spinel saturated vs. non-spinel-saturated systems. Under the assumption that at magmatic temperatures graphite-gas equilibria controlled fO2 at all depths on the ureilite parent body, we conclude: (1) that ureilite precursor materials having the Fo and Cr valence properties now observed in ureilites are unlikely to have been preserved during planetary processing; and (2) that the Fo and Cr valence properties now observed in ureilites are consistent with having been established by high-temperature carbon redox control over a range of depths on a plausible-sized ureilite parent body. The apparent limit on ureilite Fo values around 74-76 suggests that the precursor material(s) had bulk mg# ? that of LL chondrites.

  19. Inherited Pb isotopic records in olivine antecryst-hosted melt inclusions from Hawaiian lavas

    NASA Astrophysics Data System (ADS)

    Sakyi, Patrick Asamoah; Tanaka, Ryoji; Kobayashi, Katsura; Nakamura, Eizo

    2012-10-01

    Dislocation textures of olivine grains and Pb isotopic compositions (207Pb/206Pb and 208Pb/206Pb) of olivine-hosted melt inclusions in basaltic lavas from three Hawaiian volcanoes (Kilauea, Mauna Loa, and Koolau) were examined. More than 70% of the blocky olivine grains in the studied samples have a regular-shaped dislocation texture with their dislocation densities exceeding 106 cm-2, and can be considered as deformed olivine. The size distribution of blocky olivine grains shows that more than 99% of blocky olivines coarser than 1.2 mm are identified as deformed olivine. These deformed olivine grains are identified as antecrysts, which originally crystallized from previous stages of magmatism in the same shield, followed by plastic deformation prior to entrainment in the erupted host magmas. This study revealed that entrainment of mantle-derived crystallization products by younger batches of magma is an important part of the evolution of magnesium-rich Hawaiian magma. Lead isotopic compositions of melt inclusions hosted in the olivine antecrysts provide information of the evolutionary history of Hawaiian volcanoes which could not have been accessed if only whole rock analyses were carried out. Antecryst-hosted melt inclusions in Kilauea and Koolau lavas demonstrate that the source components in the melting region changed during shield formation. In particular, evidence of interaction of plume-derived melts and upper mantle was observed in the earliest stage of Koolau magmatism.

  20. Mantle Origin of Olivine-rich Troctolites in a Rift Environment

    NASA Astrophysics Data System (ADS)

    Faul, U.; Garapic, G.; Michibayashi, K.

    2014-12-01

    Olivine-rich troctolites from Krivaja-Konjuh massif in the Dinarides (Bosnia and Herzegovina) represent a unique natural laboratory to study melt segregation and retention in originally fertile rift-related mantle rocks. Petrographic and chemical analyses of coexisting minerals (olivine and interstitial clinopyroxene, spinel and plagioclase) show that olivine and spinel are of mantle origin, and interstitial clinopyroxene and plagioclase are products of crystallization of trapped melt. Geochemical and microstructural observations (dissolution of pyroxene) indicate that this trapped melt started off at larger depth and that it was silica undersaturated when it reached the plagioclase stability field. The original mantle olivine remained and texturally equilibrated with the melt, which is evident from the high Ni content and euhedral crystal habit in thin sections. This suggests that the melt that crystallized the interstitial phases, clinopyroxene and plagioclase, was saturated in olivine and probably similar to MORB-type melt. The interstitial phases show no sign of deformation. A mantle origin of olivine is corroborated by EBSD data that show a progressive misorientation across individual olivine grains due to previous episodes of deformation within the mantle. By contrast, grains originating from cumulate crystallization should show little internal deformation. Therefore we suggest that olivine-rich troctolites are not crystallization products, but rather products of reaction of melt with the lherzolitic mantle. The evidence of trapped melt in those rocks provides a new insight into the crust-mantle transition at slow spreading ridges and continental rifts where olivine-rich troctolites have been observed.

  1. Magmatic history and parental melt composition of olivine-phyric shergottite LAR 06319: Importance of magmatic degassing and olivine antecrysts in Martian magmatism

    NASA Astrophysics Data System (ADS)

    Balta, J. Brian; Sanborn, Matthew; McSween, Harry Y.; Wadhwa, Meenakshi

    2013-08-01

    Several olivine-phyric shergottites contain enough olivine that they could conceivably represent the products of closed-system crystallization of primary melts derived from partial melting of the Martian mantle. Larkman Nunatak (LAR) 06319 has been suggested to represent a close approach to a Martian primary liquid composition based on approximate equilibrium between its olivine and groundmass. To better understand the olivine-melt relationship and the evolution of this meteorite, we report the results of new petrographic and chemical analyses. We find that olivine megacryst cores are generally not in equilibrium with the groundmass, but rather have been homogenized by diffusion to Mg# 72. We have identified two unique grain types: an olivine glomerocryst and an olivine grain preserving a primary magmatic boundary that constrains the time scale of eruption to be on the order of hours. We also report the presence of trace oxide phases and phosphate compositions that suggest that the melt contained approximately 1.1% H2O and lost volatiles during cooling, also associated with an increase in oxygen fugacity upon degassing. We additionally report in situ rare earth element measurements of the various mineral phases in LAR 06319. Based on these reported trace element abundances, we estimate the oxygen fugacity in the LAR 06319 parent melt early in its crystallization sequence (i.e., at the time of crystallization of the low-Ca and high-Ca pyroxenes), the rare earth element composition of the parent melt, and those of melts in equilibrium with later formed phases. We suggest that LAR 06319 represents the product of closed-system crystallization within a shallow magma chamber, with additional olivine accumulated from a cumulate pile. We infer that the olivine megacrysts are antecrysts, derived from a single magma chamber, but not directly related to the host magma, and suggest that mixing of antecrysts within magma chambers may be a common process in Martian magmatic systems.

  2. Temperature-dependent Infrared Optical Constants of Olivine and Enstatite

    NASA Astrophysics Data System (ADS)

    Zeidler, S.; Mutschke, H.; Posch, Th.

    2015-01-01

    Since the Infrared Space Observatory (ISO) mission, it has become clear that dust in circumstellar disks and outflows consists partly of crystalline silicates of pyroxene and olivine type. An exact mineralogical analysis of the dust infrared emission spectra relies on laboratory spectra, which, however, have been mostly measured at room temperature so far. Given that infrared spectral features depend on the thermal excitation of the crystal's vibrational modes, laboratory spectra measured at various (low and high) temperatures, corresponding to the thermal conditions at different distances from the star, can improve the accuracy of such analyses considerably. We have measured the complex refractive index in a temperature range of 10-973 K for one mineral of each of those types of silicate, i.e., for an olivine and an enstatite of typical (terrestrial) composition. Thus, our data extend the temperature range of previous data to higher values and the compositional range to higher iron contents. We analyze the temperature dependence of oscillator frequencies and damping parameters governing the spectral characteristics of the bands and calculate absorption cross-sectional spectra that can be compared with astronomical emission spectra. We demonstrate the usefulness of our new data by comparing spectra calculated for a 100 K dust temperature with the ISO SWS spectrum of IRAS 09425-6040.

  3. TEMPERATURE-DEPENDENT INFRARED OPTICAL CONSTANTS OF OLIVINE AND ENSTATITE

    SciTech Connect

    Zeidler, S.; Mutschke, H.; Posch, Th. E-mail: harald.mutschke@uni-jena.de

    2015-01-10

    Since the Infrared Space Observatory (ISO) mission, it has become clear that dust in circumstellar disks and outflows consists partly of crystalline silicates of pyroxene and olivine type. An exact mineralogical analysis of the dust infrared emission spectra relies on laboratory spectra, which, however, have been mostly measured at room temperature so far. Given that infrared spectral features depend on the thermal excitation of the crystal's vibrational modes, laboratory spectra measured at various (low and high) temperatures, corresponding to the thermal conditions at different distances from the star, can improve the accuracy of such analyses considerably. We have measured the complex refractive index in a temperature range of 10-973 K for one mineral of each of those types of silicate, i.e., for an olivine and an enstatite of typical (terrestrial) composition. Thus, our data extend the temperature range of previous data to higher values and the compositional range to higher iron contents. We analyze the temperature dependence of oscillator frequencies and damping parameters governing the spectral characteristics of the bands and calculate absorption cross-sectional spectra that can be compared with astronomical emission spectra. We demonstrate the usefulness of our new data by comparing spectra calculated for a 100 K dust temperature with the ISO SWS spectrum of IRAS 09425-6040.

  4. Olivine-rich exposures in the South Pole-Aitken Basin

    NASA Astrophysics Data System (ADS)

    Yamamoto, Satoru; Nakamura, Ryosuke; Matsunaga, Tsuneo; Ogawa, Yoshiko; Ishihara, Yoshiaki; Morota, Tomokatsu; Hirata, Naru; Ohtake, Makiko; Hiroi, Takahiro; Yokota, Yasuhiro; Haruyama, Junichi

    2012-03-01

    The distribution and the geological context of the olivine-rich exposures in the South Pole-Aitken (SPA) Basin on the Moon were investigated based on the spectral data obtained from the Spectral Profiler (SP) and Multiband Imager (MI) onboard the Japanese lunar explorer Kaguya/SELENE. The olivine-rich exposures are found only in the peak rings or central peaks of the Schrdinger basin and Zeeman crater, which are located in the outer region of the SPA Basin and not in the center region. On a localized scale, the olivine-rich materials are exposed on landslide features on the crater walls or sloped wall of the central peaks or the peak rings. Another observational finding is the co-existence of olivine-rich and plagioclase-rich materials on a kilometer scale spanning most of the olivine-rich sites in the Schrdinger basin. Pyroxene-rich materials are found in fresh craters outside the peak rings or the central peaks with olivine-rich materials. Based on these results, the following scenario are proposed: (1) the impact to form the SPA Basin melted a large amount of the lunar upper mantle and crust, and distributed the melted materials to the outer region; (2) local differentiation of melted materials hid the olivine-rich materials in the center region of the SPA Basin; (3) later impacts that formed the Schrdinger and Zeeman craters excavated and exposed the olivine-rich materials to the surface again; and (4) space weathering and regolith gardening obscured the olivine-rich spectra at the exposure sites, but recent, small scale impacts or landslides on the sloped wall exposed fresh olivine-rich materials, allowing the identification of the olivine-rich exposures by spectral remote-sensing. This suggests that several, different scale events play an important role in forming the surface distributions of originally deep-seated materials on the Moon, as well as on other planetary bodies.

  5. Morphology and surface features of olivine in kimberlite: implications for ascent processes

    NASA Astrophysics Data System (ADS)

    Jones, T. J.; Russell, J. K.; Porritt, L. A.; Brown, R. J.

    2014-05-01

    Most kimberlite rocks contain large proportions of ellipsoidal-shaped xenocrystic olivine grains that are derived mainly from disaggregation of peridotite. Here, we describe the shapes, sizes and surfaces of olivine grains recovered from kimberlite lavas erupted from the Quaternary Igwisi Hills volcano, Tanzania. The Igwisi Hills kimberlitic olivine grains are compared to phenocrystic olivine, liberated from picritic lavas, and mantle olivine, liberated from a fresh peridotite xenolith. Image analysis, scanning electron microscopy imagery and laser microscopy reveal significant differences in the morphologies and surface features of the three crystal populations. The kimberlitic olivine grains form smooth, rounded to ellipsoidal shapes and have rough flaky micro-surfaces that are populated by impact pits. Mantle olivine grains are characterised by flaked surfaces and indented shapes consistent with growth as a crystal aggregate. Phenocrystic olivine exhibit faceted, smooth-surfaced crystal faces. We suggest that the unique shape and surface properties of the Igwisi Hills kimberlitic olivine grains are products of the transport processes attending kimberlite ascent from mantle source to surface. We infer that the unique shapes and surfaces of kimberlitic olivine grains result from three distinct mechanical processes attending their rapid transport through the thick cratonic mantle lithosphere: (1) penetrative flaking from micro-tensile failure induced by rapid decompression; (2) sustained abrasion and attrition driven by particle-particle collisions between grains within a turbulent, volatile-rich flow regime; and (3) higher-energy particle-particle collisions producing impact cavities superimposed on decompression structures. The combination of these processes during the rapid ascent of kimberlite magmas is responsible for the distinctive ellipsoidal shape of olivine xenocrysts found in kimberlites worldwide.

  6. Phosphorus as indicator of magmatic olivine residence time, morphology and growth rate

    NASA Astrophysics Data System (ADS)

    Sobolev, Alexander; Batanova, Valentina

    2015-04-01

    Phosphorus is among of slowest elements by diffusion rate in silicate melts and crystals (e.g. Spandler et al, 2007). In the same time it is moderately incompatible to compatible with olivine (Brunet & Chazot, 2001; Grant & Kohn, 2013). This makes phosphorus valuable tracer of olivine crystallization in natural conditions. Indeed, it is shown that natural magmatic olivine crystals commonly posses strong and complicated zoning in phosphorus (Milman-Barris et al, 2008; Welsch et al, 2014). In this paper we intend to review phosphorus behavior in olivine in published experimental and natural olivine studies and present large set of new EPMA data on phosphorus zoning in olivine phenocrysts from MORBs, OIBs, komatiites and kimberlites. We will show that sharp olivine zones enriched in phosphorus by a factor of 10-20 over prediction by equilibrium partition may be due to formation of P-rich boundary layer on the interface of fast growing olivine. This is proved by finding of small-size (normally 10 mkm or less) exceptionally P-rich melt inclusions in olivine, which are otherwise similar in composition to typical melt. These observations could provide potential olivine growth speedometer. We will also demonstrate, that sharp zoning in phosphorus may provide valuable information on the residence time of olivine crystals in different environments: magma chambers and conduits as well as mantle sources. This study has been founded by Russian Science Foundation grant 14-17-00491. References: Spandler, et al, 2007, Nature, v. 447, p. 303-306; Brunet & Chazot, 2001, Chemical Geology, v. 176, p. 51-72; Grant & Kohn, 2013, American Mineralogist, v. 98, p. 1860-1869; Milman-Barris et al, 2008, Contr. Min. Petrol. v. 155, p.739-765; Welsch et al, 2014, Geology, v. 42, p.867-870.

  7. Experimental modeling of the cooling history of Apollo 12 olivine basalts

    NASA Technical Reports Server (NTRS)

    Donaldson, C. H.; Usselman, T. M.; Williams, R. J.; Lofgren, G. E.

    1975-01-01

    An analog of the Apollo 12 olivine vitrophyres has been crystallized in a 1-atm gas-mixing furnace at cooling rates ranging between 1250 and 0.7 C/hr and isothermally at degrees of supercooling ranging from 10 C to 325 C. Mineral chemistry, crystal shapes, grain sizes and textures are systematically related to cooling rate and degree of supercooling. At linear cooling rates not exceeding 40 C/hr the texture is porphyritic - large olivine crystals are set in a groundmass of finer-grained pyroxene, plagioclase, and ilmenite; a later generation of olivine never crystallizes. There are three shapes of olivine crystals in the Apollo 12 olivine vitrophyres: glomerocrysts of subhedral crystals, large subequant skeletons, and highly elongate skeletons. These result from three generations of nucleation and a two-stage cooling history - a slow preeruption stage and a rapid continuously increasing posteruption stage. It seems likely that the Apollo 12 olivine basalt magmas were erupted with olivine crystals in suspension. The nucleation temperature of olivine in cooling-rate experiments is dependent on the experimental technique, and hence results of cooling experiments should be applied with caution.

  8. Systematics of Ni, Co, Cr and V in Olivine from Planetary Melt Systems: Martian Basalts

    NASA Technical Reports Server (NTRS)

    Herd, C. D. K.; Jones, J. H.; Shearer, C. K.; Papike, J. J.

    2001-01-01

    Secondary Ion Mass Spectrometry (SIMS) data for Ni, Co, Cr, and V in olivine in martian basalts is compared to data from lunar and terrestrial basalts. We use experimentally-derived and published D values to calculate as-yet unsampled, olivine-bearing, non-cumulus melt compositions. Additional information is contained in the original extended abstract.

  9. Olivine and Carbonate Globules in ALH84001: A Terrestrial Analog, and Implications for Water on Mars

    NASA Astrophysics Data System (ADS)

    Treiman, A. H.

    2005-03-01

    Low-temperature carbonate globules in ALH84001 are found near olivine grains that equilibrated at T>800 C. Terrestrial analogs from Spitsbergen (Norway) suggest an explanation of this association; the carbonate globules may have been deposited in cavities where olivine had been dissolved out.

  10. Visualizing the Magnetic Behavior of Chondrule Dusty Olivine Using Electron Holography

    NASA Astrophysics Data System (ADS)

    Shah, J.; Muxworthy, A. R.; Almeida, T. P.; Kovcs, A.; Russell, S. S.; Genge, M. J.; Dunin-Borkowski, R. E.

    2015-07-01

    We present the first off-axis electron holography study of natural dusty olivine in Bishunpur (LL3.1) to investigate its nanoscale rock magnetic properties. We find highly magnetic, multi-vortex domain structures within the dusty olivine kamacite.

  11. Dynamic Recrystallization of Olivine Aggregates During High-strain Deformation

    NASA Astrophysics Data System (ADS)

    Bystricky, M.; Kunze, K.; Burlini, L.

    2001-12-01

    We have investigated the high shear strain behaviour of polycrystalline olivine aggregates using a high-pressure, high-temperature Paterson torsion apparatus. Olivine samples hot-pressed from San Carlos powders were deformed at temperatures of 1200-1250° C, a confining pressure of 300 MPa, and an oxygen fugacity near either the Fe/FeO or the Ni/NiO buffer. The experiments were performed in the dislocation creep field, at constant twist rates corresponding to shear strain rates of 3*E-5}s{-1 to 3*E-4}s{-1, to total shear strains of up to 7. Experiments on natural dunites from Kohistan, Pakistan, are now being performed under similar conditions. In all the experiments on hot-pressed aggregates, deformation appeared to be steady-state up to shear strains of γ ~0.2. The peak stress values were consistent with previous rheological data on the dislocation creep of olivine obtained in compression experiments under dry conditions. After the initial peak stress, progressive weakening occurred with strain, leading to a total weakening of the aggregate of ~15-25% at γ >4. At high shear strains (γ =5 to 7), softening was less and less pronounced, suggesting nearly steady-state behaviour. Stepping tests performed at various shear strains yielded stress exponents of ~3.2, typical of deformation by dislocation creep. FTIR analyses of deformed samples indicate that deformation occurred under essentially dry conditions (<30 ppm H/Si). Simple shear microstructures and lattice preferred orientations were analyzed using optical microscopy and electron backscatter diffraction. At strains up to γ ~0.5, microstructural analyses show evidence for dislocation creep and recovery in the form of deformation lamellae. Highly irregular grain boundaries with multiple bulges suggest incipient recrystallization by grain boundary migration. Subgrain rotation recrystallization appears to dominate at higher strains, as evidenced by multiple subgrains and core-and-mantle structures. At strains of γ >=5, recrystallization is nearly complete, with the formation of a strong foliation sub-parallel to the shear plane. About ~5% of remaining porphyroclasts consist of ribbons with highly stretched tails and asymmetric porphyroclasts showing subgrains and deformation features. There is no microstructural evidence for any shear localization. During the deformation, the texture evolved through a transient deformation texture (γ ~0.5) with [100] axes distributed oblique to the shear direction, into a recrystallization texture (γ ~5) with sharp [100] maxima parallel to the shear direction and girdles of [010] and [001] normal to that direction, consistent with "easy slip" on the (010)[100] system.

  12. Extended planar defects and the rapid incorporation of Ti4+ into olivine

    NASA Astrophysics Data System (ADS)

    Burgess, Katherine D.; Cooper, Reid F.

    2013-10-01

    The formation of extended planar defects in minerals such as olivine is related to high point defect concentration and can be driven by large gradients in chemical potential, where the energy of the system is lowered by the ordering of defects along specific planes in the crystal. The presence of extended defects has the potential to create the (apparently) anomalous ionic diffusion in olivine as reported recently (Spandler and O'Neill in Contrib Mineral Petrol 159(6):791-818, 2010). High-resolution transmission electron microscopy and energy-filtered imaging were done using experimental samples designed to examine the impact of a TiO2 and f O2 on the potential to form such defects in ferromagnesian olivine. Doped basalt (5 wt% TiO2)-olivine reaction couple experiments were run at 1 atm and 1,310 and 1,410 °C for 50 h at various f O2, ranging from 102 below to 102 above the quartz-fayalite-magnetite buffer. Our results show that extended planar defects in olivine, parallel to {101}ol and occurring in ordered "clusters" with a prolate spheroid geometry 5-25 nm across and extending up to 150 nm into the olivine, are present near the olivine-glass interfaces in all of our experimental high-TiO2 basalt-olivine samples. Increased Ti content in the olivine is associated with the defects; ordering of Ti4+ and octahedral site vacancies leads to a two- or three-layer superstructure in the olivine. Defect nucleation and growth is driven by the large TiO2 chemical potential gradient across the phase boundary at the start of the experiments, which provides access to microstructures not otherwise present.

  13. Remote compositional analysis of lunar olivine-rich lithologies with Moon Mineralogy Mapper (M3) spectra

    NASA Astrophysics Data System (ADS)

    Isaacson, Peter J.; Pieters, Carle M.; Besse, Sebastien; Clark, Roger N.; Head, James W.; Klima, Rachel L.; Mustard, John F.; Petro, Noah E.; Staid, Matthew I.; Sunshine, Jessica M.; Taylor, Lawrence A.; Thaisen, Kevin G.; Tompkins, Stefanie

    2011-04-01

    A systematic approach for deconvolving remotely sensed lunar olivine-rich visible to near-infrared (VNIR) reflectance spectra with the Modified Gaussian Model (MGM) is evaluated with Chandrayaan-1 Moon Mineralogy Mapper (M3) spectra. Whereas earlier studies of laboratory reflectance spectra focused only on complications due to chromite inclusions in lunar olivines, we develop a systematic approach for addressing (through continuum removal) the prominent continuum slopes common to remotely sensed reflectance spectra of planetary surfaces. We have validated our continuum removal on a suite of laboratory reflectance spectra. Suites of olivine-dominated reflectance spectra from a small crater near Mare Moscoviense, the Copernicus central peak, Aristarchus, and the crater Marius in the Marius Hills were analyzed. Spectral diversity was detected in visual evaluation of the spectra and was quantified using the MGM. The MGM-derived band positions are used to estimate the olivine's composition in a relative sense. Spectra of olivines from Moscoviense exhibit diversity in their absorption features, and this diversity suggests some variation in olivine Fe/Mg content. Olivines from Copernicus are observed to be spectrally homogeneous and thus are predicted to be more compositionally homogeneous than those at Moscoviense but are of broadly similar composition to the Moscoviense olivines. Olivines from Aristarchus and Marius exhibit clear spectral differences from those at Moscoviense and Copernicus but also exhibit features that suggest contributions from other phases. If the various precautions discussed here are weighed carefully, the methods presented here can be used to make general predictions of absolute olivine composition (Fe/Mg content).

  14. Mantle-crust interactions in the oceanic lithosphere: Constraints from minor and trace elements in olivine

    NASA Astrophysics Data System (ADS)

    Sanfilippo, Alessio; Tribuzio, Riccardo; Tiepolo, Massimo

    2014-09-01

    Minor and trace element compositions of olivines are used as probes into the melt-rock reaction processes occurring at the mantle-crust transition in the oceanic lithosphere. We studied mantle and lower crustal sections from the Alpine Jurassic ophiolites, where lithospheric remnants of a fossil slow-spreading ocean are exposed. Olivines from plagioclase-harzburgites and replacive dunites (Fo = 91-89 mol%) and from olivine-rich troctolites and troctolites (Fo = 88-84 mol%) were considered. Positive correlations among the concentrations of Mn, Ni, Co, Sc and V characterize the olivines from the dunites. These chemical variations are reconciled with formation by melts produced by a mixed source consisting of a depleted peridotite and a pyroxene-rich, garnet-bearing component melted under different pressure conditions. We thereby infer that the melts extracted through these dunites channels were not fully aggregated after their formation into the asthenospheric mantle. Olivines from the olivine-rich troctolites and the troctolites are distinct by those in the dunites by lower Ni and higher concentrations of Mn and incompatible trace elements (Ti, Zr, Y and HREE). Fractional crystallization cannot reproduce the chemical variations of the olivines from the olivine-rich troctolites and the troctolites. In these rock-types, the olivines commonly show heterogeneous Ti, Zr, Y and HREE compositions, which produce variable Ti/Y and Zr/Y values. We correlate these olivine characteristics with events of reactive melt migration occurred during the formation of the primitive lower oceanic crust. We propose that the migrating melts formed at the mantle-crust transition via interaction with mantle peridotites during periods of low melt supply.

  15. Remote compositional analysis of lunar olivine-rich lithologies with Moon Mineralogy Mapper (M3) spectra

    USGS Publications Warehouse

    Isaacson, P.J.; Pieters, C.M.; Besse, S.; Clark, R.N.; Head, J.W.; Klima, R.L.; Mustard, J.F.; Petro, N.E.; Staid, M.I.; Sunshine, J.M.; Taylor, L.A.; Thaisen, K.G.; Tompkins, S.

    2011-01-01

    A systematic approach for deconvolving remotely sensed lunar olivine-rich visible to near-infrared (VNIR) reflectance spectra with the Modified Gaussian Model (MGM) is evaluated with Chandrayaan-1 Moon Mineralogy Mapper (M 3) spectra. Whereas earlier studies of laboratory reflectance spectra focused only on complications due to chromite inclusions in lunar olivines, we develop a systematic approach for addressing (through continuum removal) the prominent continuum slopes common to remotely sensed reflectance spectra of planetary surfaces. We have validated our continuum removal on a suite of laboratory reflectance spectra. Suites of olivine-dominated reflectance spectra from a small crater near Mare Moscoviense, the Copernicus central peak, Aristarchus, and the crater Marius in the Marius Hills were analyzed. Spectral diversity was detected in visual evaluation of the spectra and was quantified using the MGM. The MGM-derived band positions are used to estimate the olivine's composition in a relative sense. Spectra of olivines from Moscoviense exhibit diversity in their absorption features, and this diversity suggests some variation in olivine Fe/Mg content. Olivines from Copernicus are observed to be spectrally homogeneous and thus are predicted to be more compositionally homogeneous than those at Moscoviense but are of broadly similar composition to the Moscoviense olivines. Olivines from Aristarchus and Marius exhibit clear spectral differences from those at Moscoviense and Copernicus but also exhibit features that suggest contributions from other phases. If the various precautions discussed here are weighed carefully, the methods presented here can be used to make general predictions of absolute olivine composition (Fe/Mg content). Copyright ?? 2011 by the American Geophysical Union.

  16. In situ observation of crystallographic preferred orientation of deforming olivine at high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Ohuchi, Tomohiro; Nishihara, Yu; Seto, Yusuke; Kawazoe, Takaaki; Nishi, Masayuki; Maruyama, Genta; Hashimoto, Mika; Higo, Yuji; Funakoshi, Ken-ichi; Suzuki, Akio; Kikegawa, Takumi; Irifune, Tetsuo

    2015-06-01

    Simple-shear deformation experiments on polycrystalline olivine and olivine single-crystal were conducted at pressures of 1.3-3.8 GPa and temperatures of 1223-1573 K to understand the achievement of steady-state fabric strength and the process of dynamic recrystallization. Development of crystallographic preferred orientation (CPO) of olivine was evaluated from two-dimensional X-ray diffraction patterns, and shear strain was measured from X-ray radiographs. The steady-state fabric strength of the A-type fabric was achieved within total shear strain of γ = 2. At strains higher than γ = 1, an increase in concentration of the [0 1 0] axes mainly contributes to an increase in fabric strength. At strains higher than γ = 2, the magnitude of VSH/VSV (i.e., ratio of horizontally and vertically polarized shear wave velocities) scarcely increased in most of the runs. The VSH/VSV of peridotite (70 vol.% olivine + 30 vol.% minor phases) having the steady-state A-type olivine fabric coincides with that of recent global one-dimensional models under the assumption of horizontal flow, suggesting that the seismic anisotropy observed in the shallow upper mantle is mostly explained by the development of A-type olivine fabric. Experimental results on the deformation of single-crystal olivine showed that the CPO of olivine is influenced by the initial orientation of the starting single crystal because strain is concentrated in the recrystallized areas and the relic of the starting single crystal remains. In the upper mantle, the old CPO of olivine developed in the past may affect the olivine CPO developed in the present.

  17. Infrared spectra of olivine polymorphs - Alpha, beta phase and spinel

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.

    1980-01-01

    The infrared absorption spectra of several olivines (alpha phase) and their corresponding beta phase (modified spinel) and spinel (gamma) high-pressure polymorphs are determined. Spectra were measured for ground and pressed samples of alpha and gamma A2SiO4, where A = Fe, Ni, Co; alpha and gamma Mg2GeO4; alpha Mg2SiO4; and beta Co2SiO4. The spectra are interpreted in terms of internal, tetrahedral and octagonal, and lattice vibration modes, and the spinel results are used to predict the spectrum of gamma Mg2SiO4. Analysis of spectra obtained from samples of gamma Mg2GeO4 heated to 730 and 1000 C provides evidence that partial inversion could occur in silicate spinels at elevated temperatures and pressures.

  18. The distribution of olivine in the crater Copernicus

    NASA Technical Reports Server (NTRS)

    Lucey, Paul G.; Hawke, B. R.; Horton, Keith

    1991-01-01

    Multispectral imaging in the visible and near-IR at four wavelengths (0.73, 0.96, 1.45, and 1.99 micron) of Copernicus crater has been used to map the distribution of olivine-rich, pyroxene-poor material known previously to occur in the central peak complex. Three additional portions of the crater exhibit spectral characteristics similar to those of the central peaks, strongly suggesting the presence of material similar to that exposed in the central peaks. These areas are a scarp forming a portion of the northern rim of Copernicus, and two slump blocks in the north wall which may have been derived from the same portion of the ejecta now exposed in the rim scarp. These occurrences decrease the minimum allowable depth for this unusual material in the Copernicus target site though still represent some of the deepest material exposed by Copernicus.

  19. Additional Sr Isotopic Heterogeneity in Zagami Olivine-Rich Lithology

    NASA Technical Reports Server (NTRS)

    Misawa, K.; Niihara, T.; Shih, C.-Y; Reese, Y. D.; Nyquist, L. E.; Yoneda, S.; Yamashita, H.

    2012-01-01

    Prior isotopic analyses of Zagami have established differing initial Sr-87/Sr-86 (ISr) ratios of among Zagami lithologies, fine-grained (FG), coarse-grained (CG), and dark mottled lithologies (DML)]. The Zagami sample (KPM-NLH000057) newly allocated from the Kanagawa Prefectural Museum of Natural History contained DML and the Ol-rich lithology which included more ferroan olivines (Ol-rich: Fa(sub 97- 99) vs late-stage melt pockets: Fa(sub 90-97)]). We have combined mineralogy-petrology and Rb-Sr isotopic studies on the Kanagawa Zagami sample, which will provide additional clues to the genesis of enriched shergottites and to the evolution of Martian crust and mantle

  20. Collisional Processing of Comet Surfaces: Impact Experiments into Olivine

    NASA Technical Reports Server (NTRS)

    Lederer, S. M.; Jensen, E. A.; Cintala, M. J.; Smith, D. C.; Nakamura-Messenger, K.; Keller, L. P.; Wooden, D. H.; Fernandez, Y. R.; Zolensky, M. E.

    2011-01-01

    A new paradigm has emerged where 3.9 Ga ago, a violent reshuffling reshaped the placement of small bodies in the solar system (the Nice model). Surface properties of these objects may have been affected by collisions caused by this event, and by collisions with other small bodies since their emplacement. In addition, objects in the Kuiper Belt are believed to undergo extensive collisional processing while in the Kuiper Belt. Physical manifestations of shock effects (e.g., planar dislocations) in minerals typically found in comets will be correlated with spectral changes (e.g. reddening, loss and shift of peaks, new signatures) to allow astronomers to better understand geophysical impact processing that has occurred on small bodies. Targets will include solid and granular olivine (forsterite), impacted over a range of impact speeds with the Experimental Impact Laboratory at NASA JSC. Analyses include quantification of the dependence of the spectral changes with respect to impact speed, texture of the target, and temperature.

  1. Phyllosilicate and Olivine around a Fracture in Nili Fossae

    NASA Technical Reports Server (NTRS)

    2007-01-01

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) took this observation of part of the Nili Fossae region at the western margin of the Isidis impact basin at 3:07 (UTC) on December 12, 2006, near 21.9 degrees north latitude, 78.2 degrees east longitude. The image was taken in 544 colors covering 0.36-3.92 micrometers, and shows features as small as 18 meters (60 feet) across. The image is about 11 kilometers (7 miles) wide at its narrowest point.

    The Isidis basin resulted from a gigantic impact on the surface of Mars early in the planet's history. The image of the Isidis basin at the top left is the colored elevation data from the Mars Orbiter Laser Altimeter (MOLA) overlain on a digital image mosaic from the Viking mission. Reds represent higher elevations, and blue lower elevations. The western rim of the Isidis basin has numerous, concentric troughs (or 'fossae') which may have formed during faulting associated with the impact event. Since then, the Nili Fossae region has since been heavily eroded, and is one of the most mineralogically diverse spots on Mars.

    This CRISM image targets one of region's smaller fractures. The image is shown overlain on the Viking digital image mosaic at lower left. The lower right CRISM image was constructed from three visible wavelengths (0.71, 0.60 and 0.53 microns in the red, green and blue image planes, respectively) and is close to what the human eye would see. The blue on the right of the image is an artifact from light scattering in the atmosphere. The upper right image was constructed from three infrared channels (2.38, 1.80 and 1.15 microns in the red, green and blue image planes, respectively) to highlight the mineralogy of the area. The bright green areas are rich in 'phyllosilicates,' a category of minerals including clays. The purple material along the walls of the fracture likely contains small amounts of the iron- and magnesium-rich mineral pyroxene. The yellow-brown material contains the iron- and magnesium-rich mineral olivine. Olivine and pyroxene are minerals associated with igneous activity.

    Overlaying CRISM data with images from the High-Resolution Imaging Science Experiment (HiRISE) camera shows that the phyllosilicates are in small, eroded outcrops of rock. The olivine is most abundant in sand dunes on the surface. The use of these two instruments together reveals more about the history of the region: Olivine sands covered the area shown in the image after the interaction of water and rock formed the phyllosilicates and after the fracture formed.

    The Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad.

  2. Olivine friction at the base of oceanic seismogenic zones

    USGS Publications Warehouse

    Boettcher, M.S.; Hirth, G.; Evans, B. M.

    2007-01-01

    We investigate the strength and frictional behavior of olivine aggregates at temperatures and effective confining pressures similar to those at the base of the seismogenic zone on a typical ridge transform fault. Triaxial compression tests were conducted on dry olivine powder (grain size ???60 ??m) at effective confining pressures between 50 and 300 MPa (using Argon as a pore fluid), temperatures between 600??C and 1000??C, and axial displacement rates from 0.06 to 60 ??m/s (axial strain rates from 3 ?? 10-6 to 3 ?? 10-3 s-1). Yielding shows a negative pressure dependence, consistent with predictions for shear enhanced compaction and with the observation that samples exhibit compaction during the initial stages of the experiments. A combination of mechanical data and microstructural observations demonstrate that deformation was accommodated by frictional processes. Sample strengths were pressure-dependent and nearly independent of temperature. Localized shear zones formed in initially homogeneous aggregates early in the experiments. The frictional response to changes in loading rate is well described by rate and state constitutive laws, with a transition from velocity-weakening to velocity-strengthening at 1000??C. Microstructural observations and physical models indicate that plastic yielding of asperities at high temperatures and low axial strain rates stabilizes frictional sliding. Extrapolation of our experimental data to geologic strain rates indicates that a transition from velocity weakening to velocity strengthening occurs at approximately 600??C, consistent with the focal depths of earthquakes in the oceanic lithosphere. Copyright 2007 by the American Geophysical Union.

  3. Stereochemically constrained complex organic molecules extracted from olivine crystal matrix

    NASA Astrophysics Data System (ADS)

    Gerasimenko, I.; Freund, F. T.; Imanaka, H.; Rodgers, R.

    2011-12-01

    Paradoxically, the dense solid state of magmatic minerals is a medium, in which organic synthesis can take place. The reason is that gas-fluid components such as H2O, CO/CO2/N2 and H2S are omnipresent in terrestrial magmatic environments. Any silicate mineral that crystallizes from such magmas will incorporate small quantities of the fluid-phase components in the form of structurally incompatible low-z impurities. During cooling the solute species undergo a redox conversion, resulting in chemically reduced low-z elements. To the extent that these low-z impurities are diffusively mobile, they will exsolve to the surface and/or to major structural defects inside the crystal matrix such as dislocations. Dislocations provide a 3-D structured environment, where the low-z impurities will tend to form stereochemically constrained polyatomic Cn-H-O-N-S entities, which we call organic protomolecules. In Nature, during weathering, such protomolecules will be released into the environment in the form of complex organic molecules. In our study we crush samples under clean conditions as a way to expose Cn-H-O-N-S entities at the fracture surfaces. We conduct identical experiments with selected large olivine single crystals, mm-sized olivine from peridiotite nodules from the San Carlos Volcanic Field, Arizona, and the vesiculated basalt that had carried the nodules upward in the volcanic conduit. We Soxhlet-extract the crushed powders with water, THF and ethyl acetate. The extracts are analyzed at the FTICR-MS facility at Florida State University using ultrahigh resolution Mass Spectrometry techniques capable of determining the chemical composition of the organic molecules up to 600 amu and more. So far we have found several analog sequences of oxygen-rich aliphatic hydrocarbons, families with up to 34 carbon atoms, probably poly-carboxylic acids, and some families containing sulfur.

  4. The x ray microprobe determination of chromium oxidation state in olivine from lunar basalt and kimberlitic diamonds

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Bajt, S.; Rivers, M. L.; Smith, J. V.

    1993-01-01

    The synchrotron x-ray microprobe is being used to obtain oxidation state information on planetary materials with high spatial resolution. Initial results on chromium in olivine from various sources including laboratory experiments, lunar basalt, and kimberlitic diamonds are reported. The lunar olivine was dominated by Cr(2+) whereas the diamond inclusions had Cr(2+/Cr(3+) ratios up to about 0.3. The simpliest interpretation is that the terrestrial olivine crystallized in a more oxidizing environment than the lunar olivine.

  5. Fe 2+-Mg partitioning between olivine and basaltic melts: Applications to genesis of olivine-phyric shergottites and conditions of melting in the Martian interior

    NASA Astrophysics Data System (ADS)

    Filiberto, Justin; Dasgupta, Rajdeep

    2011-04-01

    Fe 2+-Mg partitioning between olivine and basaltic melt, expressed by the exchange coefficient, K Dol - melt Fe - Mg [=( XmeltMg/ XolivineMg)/( XmeltFe 2 + / XolivineFe 2 + )] is widely used to check if a rock composition may represent a mantle-derived magma, to demonstrate equilibrium between coexisting olivine and groundmass in mafic-ultramafic systems, both in experiments and in natural assemblages, and to constrain liquid lines of descent where olivine is the dominant fractionating phase. However, K Dol - melt Fe - Mg of 0.30, which is appropriate for understanding most terrestrial basalts petrogenesis may not apply for Martian basalts as K Dol - melt Fe - Mg is known to depend strongly on the melt compositions and Martian systems produce basalts that are distinctly richer in iron than terrestrial basalts. Here we compiled experimental data on olivine-melt equilibria of Martian and terrestrial basalt compositions to parameterize the effect of magma composition on K Dol - melt Fe - Mg and derive the K Dol - melt Fe - Mg applicable for Martian magmatic systems. We find that the equilibrium relationship between olivine and basaltic melt in Martian systems is described by K Dol - melt Fe - Mg of 0.35 0.01. Applying the newly parameterized values of K Dol - melt Fe - Mg to olivine-phyric shergottites suggest that the only known Martian meteorites where the olivine cores and the bulk composition are in equilibrium and therefore could represent magma compositions are: Yamato 980459, NWA 5789, and NWA 2990. LAR 06319, which has been suggested to represent a near magma composition, actually contains ~ 11 wt.% excess olivine. All other ol-phyric shergottites contain significant excess olivine (20-52 wt.%). Further, assuming that the basalts analyzed by the Mars Exploration Rovers at Gusev crater and the Bounce Rock in Meridiani Planum lie on olivine control lines, we have used our newly parameterized K Dol - melt Fe - Mg to estimate primary magmas in equilibrium with the model Martian mantle. Application of geothermobarometers to new primitive magma compositions suggest that basalt generation in the Martian mantle occurs at greater depths and higher temperatures than previously thought.

  6. Martian Dunite NWA 2737: Petrographic Constraints on Geological History, Shock Events, and Olivine Color

    SciTech Connect

    Treiman,A.; Dyar, M.; McCanta, M.; Noble, S.; Pieters, C.

    2007-01-01

    Meteorite Northwest Africa (NWA) 2737 is the second known chassignite, an olivine-rich igneous rock with mineral compositions and isotopic ratios that suggest it formed on Mars. NWA 2737 consists of ?85% vol. olivine (Mg, molar Mg/(Mg + Fe), of 78.3 {+-} 0.4%), which is notable because it is black in hand sample and brown in thin section. Other minerals include chromite, pyroxenes (augite, pigeonite, orthopyroxene), and diaplectic glass of alkali-feldspar composition. Aqueous alteration is minimal and appears only as slight dissolution of glass. NWA 2737 formed by accumulation of olivine and chromite from a basaltic magma; the other minerals represent magma trapped among the cumulus grains. Minerals are compositionally homogeneous, consistent with chemical equilibration in late and postigneous cooling. Two-pyroxene thermometry gives equilibration temperatures 1150 C, implying a significant time spent at the basalt solidus. Olivine-spinel-pyroxene equilibria give ?825 C (possibly the T of mesostasis crystallization) at an oxidation state of QMF-1. This oxidation state is consistent with low Fe3+ in olivine (determined by EMP, Moessbauer spectra, and synchrotron micro-XANES spectroscopy) and with {approx}10% of the iron in pyroxene being Fe3+. NWA 2737 experienced two shock events. The first shock, to stage S5-S6, affected the olivine by producing in it planar deformation features, intense mosaicism and lattice strain, and abundant droplets of iron-nickel metal, 5-15 nm in diameter. At this stage the olivine became deeply colored, i.e., strongly absorbing at visible and near-infrared (NIR) wavelengths. This shock event and its thermal pulse probably occurred at {approx}170 Ma, the Ar-Ar age of NWA 2737. The colored olivine is cut by ribbons of coarser, uncolored olivine with long axes along [100] and shorter axes on {l_brace}021{r_brace} planes: These are consistent with the easy slip law for olivine [100]{l_brace}021{r_brace}, which is activated at moderate strain rate at high temperature. Within these ribbons the olivine was coarsened and the iron metal globules coalesced to micron-sized grains. The ribbons also are mosaicized and cut by planar fractures, which bespeak a second shock event, possibly that of ejection from Mars. The deeply colored olivine in NWA 2737 is unusual and represents a new 'ground truth' type for remote sensing of Mars. Understanding the occurrence of the brown color in olivine in NWA 2737 places important constraints on interpretation of optical measurements.

  7. Oxygen isotopic composition of individual olivine grains from the Allende meteorite

    NASA Technical Reports Server (NTRS)

    Weinbruch, S.; Zinner, E. K.; El Goresy, A.; Steele, I. M.; Palme, H.

    1993-01-01

    The oxygen isotopic composition of a variety of individual olivine grains (including refractory forsterite grains, cores of isolated olivine grains, FeO-rich rims, and individual matrix olivine grains) from the Allende CV3 meteorite was investigated by ion microprobe mass spectrometry, in order to obtain information on the formation mechanism of these samples. It was found that the most primitive (i.e., refractory) olivine in Allende is far less enriched in O-16 than are spinel and pyroxene in Ca,Al-rich inclusions, suggesting that Allende olivine must have formed in an environment that is less enriched in O-16 compared to the gas from which Ca,Al-inclusions are formed. FeO-rich (26-30 wt pct) rims of isolated olivine grains are significantly higher in delta-O-17 and delta-O-18 than forsteritic cores, suggesting that these rims formed by condensation from an oxidized gas with higher delta-O-17 than delta-O-18. Matrix olivine was found to be highest in FeO and to have the lowest enrichment in O-16.

  8. Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt

    NASA Technical Reports Server (NTRS)

    Usui, T.; Shearer, C. K.; Righter, K.; Jones, J. H.

    2011-01-01

    Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.

  9. Oxygen isotopic composition of relict olivine grains in cosmic spherules: Links to chondrules from carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Rudraswami, N. G.; Prasad, M. Shyam; Nagashima, K.; Jones, R. H.

    2015-09-01

    Most olivine relict grains in cosmic spherules selected for the present study are pristine and have not been disturbed during their atmospheric entry, thereby preserving their chemical, mineralogical and isotopic compositions. In order to understand the origin of the particles, oxygen isotope compositions of relict olivine grains in twelve cosmic spherules collected from deep sea sediments of the Indian Ocean were studied using secondary ion mass spectrometry. Most of the data lie close to the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line, with ?17O ranging from -5 to 0. The data overlap oxygen isotopic compositions of chondrules from carbonaceous chondrites such as CV, CK, CR and CM, which suggests that chondrules from carbonaceous chondrites are the source of relict grains in cosmic spherules. Chemical compositions of olivine in cosmic spherules are also very similar to chondrule olivine from carbonaceous chondrites. Several olivine relict grains in three cosmic spherules are 16O-rich (?17O -21.9 to -18.7), similar to oxygen isotopic compositions observed in calcium aluminum rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), and some porphyritic chondrules from carbonaceous chondrites. These grains appear to have recorded the initial oxygen isotopic composition of the inner solar nebula. Three olivine grains from two cosmic spherules have ?18O values >+20, which could be interpreted as mixing with stratospheric oxygen during atmospheric entry.

  10. The influence of water on the Peierls stress of olivine at high pressures

    NASA Astrophysics Data System (ADS)

    Mei, S.; Suzuki, A. M.; Xu, L.; Kohlstedt, D. L.; Dixon, N. A.; Durham, W. B.

    2012-04-01

    To investigate the influence of water on the low-temperature plasticity of olivine under lithospheric conditions, we carried out a series of creep experiments on polycrystalline olivine at high pressures (~6 GPa), relatively low temperatures (873 ? T ? 1173 K), and hydrous conditions using a deformation-DIA. Samples were fabricated from fine powdered San Carlos olivine under hydrous conditions. In the experiments, a sample column composed of a sample and alumina pistons was assembled with a talc sleeve and graphite resistance heater into a 6.2-mm edge length cubic pressure medium. Experiments were carried out at the National Synchrotron Light Source at Brookhaven National Laboratory. In a run, differential stress and sample displacement were monitored in-situ using synchrotron x-ray diffraction and radiography, respectively. The low-temperature plasticity of olivine under hydrous conditions is constrained by our data with a Peierls stress of 4.2 0.3 GPa. This value is much lower than those reported the Peierls stress for olivine under anhydrous conditions (~ 6 - 15 GPa, Evans and Goetze, 1979; Raterron et al., 2004; Mei at al., 2010), indicating a significant influence of water on the low-temperature plasticity of olivine. The low-temperature flow behavior of olivine under hydrous conditions quantified in this study provides a necessary constraint for modeling the dynamic activities occurring within lithospheric mantle especially for those regions with the presence of water such as beneath a mid-ocean ridge and along a subducting slab.

  11. H Diffusion in Olivine and Pyroxene from Peridotite Xenoliths and a Hawaiian Magma Speedometer

    NASA Technical Reports Server (NTRS)

    Peslier, A. H.; Bizimis, M.

    2014-01-01

    Hydrogen is present as a trace element in olivine and pyroxene and its content distribution in the mantle results from melting and metasomatic processes. Here we examine how these H contents can be disturbed during decompression. Hydrogen was analyzed by FTIR in olivine and pyroxene of spinel peridotite xenoliths from Salt Lake Crater (SLC) nephelinites which are part of the rejuvenated volcanism at Oahu (Hawaii) [1,2]. H mobility in pyroxene resulting from spinel exsolution during mantle upwelling Most pyroxenes in SLC peridotites exhibit exsolutions, characterized by spinel inclusions. Pyroxene edges where no exsolution are present have less H then their core near the spinel. Given that H does not enter spinel [3], subsolidus requilibration may have concentrated H in the pyroxene adjacent to the spinel exsolution during mantle upwelling. H diffusion in olivine during xenolith transport by its host magma and host magma ascent rates Olivines have lower water contents at the edge and near fractures compared to at their core, while the concentrations of all other chemical elements appear homogeneous. This suggests that some of the initial water has diffused out of the olivine. Water loss from the olivine is thought to occur during host-magma ascent and xenolith transport to the surface [4-6]. Diffusion modeling matches best the data when the initial water content used is that measured at the core of the olivines, implying that mantle water contents are preserved at the core of the olivines. The 3225 cm(sup -1) OH band at times varies independantly of other OH bands, suggesting uneven H distribution in olivine defects likely acquired during mantle metasomatism just prior to eruption and unequilibrated. Diffusion times (1-48 hrs) combined with depths of peridotite equilibration or of magma start of degassing allow to calculate ascent rates for the host nephelinite of 0.1 to 27 m/s.

  12. Melt Connectivity and Its Effect on Grain Growth in Natural Olivine Aggregates: An Experimental Study

    NASA Astrophysics Data System (ADS)

    Hashim, L.; Sifre, D.; Prcigout, J.; Gards, E.; Le Trong, E.; Gaillard, F.

    2014-12-01

    To better constrain the rheology of the mantle, experimental studies on olivine grain growth have been conducted (Faul and Scott, 2006; Karato, 1989; Nichols and Mackwell, 1991) since the grain size is an important parameter under dynamic regimes (e.g. diffusion creep and grain boundary sliding). In order to better define the melt effect on the rheological response of a partially molten olivine aggregate, we have experimentally investigated the effect of melt on olivine grain growth and the connectivity of this melt phase. Experiments were performed in 3/4" piston cylinders at 500 MPa confining pressure, different temperatures (i.e. 1100C, 1250C and 1400C) and four durations (1h, 12h, 72h and 15 days). Starting material was composed of natural San Carlos olivine (5 ?molivines were previously handpicked and annealed under controlled oxygen fugacity conditions close to the FMQ buffer. After the experiments, the melt connectivity was assessed through scanning electron microscope (SEM) images in backscattered electron mode. Electron backscatter diffraction (EBSD) maps of each sample were also collected in order to determine the olivine grain sizes as a function of time and melt content. References Faul, U. H., Scott, D., 2006. Grain growth in partially molten olivine aggregates. Contributions to Mineralogy and Petrology 151 (1), 101-111. Karato, S.-I., 1989. Grain growth kinetics in olivine aggregates. Tectonophysics 168 (4), 255-273. Nichols, S. J., Mackwell, S. J., 1991. Grain growth in porous olivine aggregates. Physics and Chemistry of Minerals 18 (4), 269-278. Sifr, D., Gards, E., Massuyeau, M., Hashim, L., Hier-Majumder, S., Gaillard, F., 2014. Electrical conductivity during incipient melting in the oceanic low-velocity zone. Nature 509 (7498), 81-85.

  13. Magnetic properties of natural and synthetic olivines: high-field measurements

    NASA Astrophysics Data System (ADS)

    Ferre, E. C.; Martin-Hernandez, F.

    2004-12-01

    Olivine [(Fex, Mg1-x)2 SiO4] is an orthosilicate solid solution between fayalite [Fe2 SiO4] and forsterite [Mg2 SiO4]. Olivine is a major constituent of the Earth mantle that is abundant in oceanic and continental peridotites and mantle xenoliths. The magnetic properties of olivines have been previously investigated using gem quality natural crystals known as peridots (Zabargad) or using laboratory grown synthetic crystals. Magnetic investigations are generally performed using low magnetic field or neutron diffraction techniques. Optical microscopy and TEM imagery reveal that most olivine crystals host iron oxides formed by exsolution during cooling. Theoretically, the magnetic susceptibility of olivine should decrease linearly from fayalite to fayalite as a function of the Fe content. The magnetic behavior should range from antiferromagnetic at high Fe content, paramagnetic at intermediate Fe contents and diamagnetic at very low Fe contents. New magnetic measurements, performed on various high field instruments (vibrating sample magnetometer, torque magnetometer, cantilever magnetometer), both on natural and synthetic samples, display ferromagnetic behavior, interpreted as due to the systematic presence of titanomagnetite inclusions in olivine crystals. These results emphasize the need to conduct measurements in high field in order to isolate the intrinsic paramagnetic properties of olivines. These measurements demonstrate the orthorhombic nature of the intrinsic paramagnetic properties, but also yield new data concerning the relationship between crystallographic axes, magnetic anisotropy and other physical anisotropies: [100] = K1, [010] = K2 and [001] = K3. Preliminary results also indicate substantial variations in degree of paramagnetic anisotropy (P) and paramagnetic shape factor (T). For Fo92, P = 1.359 and T = -0.845. These intrinsic paramagnetic properties are used to model the magnetic behavior of olivine across a range of temperatures relevant to planetary exploration. They are also used to evaluate the possible effects of olivine deformation on its intrinsic properties. For example, deformation-induced striped iron zoning is anticipated to strongly modify crystal magnetic anisotropy.

  14. Cr, Mn, and Ca distributions for olivine in angritic systems: Constraints on the origins of Cr-rich and Ca-poor core olivine in angrite LEW87051

    NASA Technical Reports Server (NTRS)

    Mikouchi, T.; Mckay, G.; Le, L.

    1994-01-01

    Angrite meteorites are a type of basaltic achondrites that are noted for their very old cyrstallization ages (4.55 b.y.) and unusual chemical and mineralogical properties. In spite of great interest, only four angrites have been found. LEW87051 is the smallest one which weighs 0.6 g. It is a porphyritic rock with coarse subhedral to euhedral olivines set in a fine-grained groundmass which clearly represents a crystallized melt. The largest uncertainty about the petrogenesis of LEW87051 is the relationship between the large olivine crystals and the groundmass. Prinz et al. suggests that olivines are xenocrysts, while McKay et al. proposed a fractional cyrstallization model based on experimental studies. However, the crystals have Cr-rich and Ca-poor cores which do not match experimental olivines. Although Jurewicz and McKay tried to explaine the zoning of the rim by diffusion, some features are not explained. There also exists a definite composition boundary of Fe(2+) and MnO between the core and the rim. To clarify the origin of these olivines, we have performed experiments using LEW87051 analogs to measure the effects of oxygen fugacity on distribution coefficients of various elements in an angritic system.

  15. Trace Elements in Olivine in Italian Potassic Volcanic Rocks Distinguish Between Mantle Metasomatism by Carbonatitic and Silicate Melts

    NASA Astrophysics Data System (ADS)

    Foley, S. F.; Ammannati, E.; Jacob, D. E.; Avanzinelli, R.; Conticelli, S.

    2014-12-01

    The Italian Peninsula is the site of intense subduction-related potassic magmatism with bimodal character in terms of silica activity: Ca-poor silica-saturated lamproitic rocks and Ca-enriched silica-undersaturated leucitites. Lamproitic magmas formed in the early phases of magmatic activity and were followed by leucititic magmas. The primary magmas are generated in the sub-continental lithospheric mantle at the destructive plate margin, and both series have olivine as the first crystallizing phenocrysts. Trace elements in olivine phenocrysts are important in recognizing metasomatic effects on the mineralogy of the mantle source. Since Ni is the most compatible trace element in olivine, particularly in alkaline melts, modal changes of olivine in the source strongly affect its bulk partition coefficient, and therefore its content in primary melts and in olivine that crystallizes from them.The concentration of other compatible trace elements (e.g. Mn, Co) in olivine phenocrysts also depends on the abundance of olivine in the magma source. Ni contents in olivine of the Italian rocks show a clear bimodal distribution. Olivine from lamproitic samples has systematically higher Fo and Ni contents, whereas olivine from leucititic rocks never exceeds Fo92 and has markedly lower Ni, reaching among the lowest levels ever observed in olivine phenocrysts in primitive melts. The Mn/Fe ratio of olivine is also sensitive to changes of the modal abundance of olivine in the source, 100*Mn/Fe of olivine from lamproitic rocks never exceeds 2, while it is always >1.8 in leucititic rocks, meaning that the leucitite source regions are much richer in olivine. Lithium is generally enriched in the crust and in sediments compared to the lithospheric mantle and to mantle-derived melts,so that Li in olivine above 10 ppm is suggested to indicate recycled sediments. Li contents are up to 35 ppm in leucititic olivines and up to >50 ppm in lamproitic olivines, confirming the recycling of crustal material into the mantle wedge. Our data indicate opposite effects for metasomatism by silicate- and carbonate-rich melts, namely the removal and growth of olivine, respectively. This new line of evidence establishes olivine as a key tool to investigate the role of carbonatitic and silicate melts in the Earth's mantle.

  16. Olivines in the Kaba carbonaceous chondrite and constraints on their formation

    NASA Astrophysics Data System (ADS)

    Hua, X.; Buseck, P. R.

    1993-03-01

    Kaba is unique in containing almost pure fayalitic olivine (Fo(sub 0.1)). Its coexistence with pure forsterite up to Fo(sub 99.6) and normal (Fo(sub 92) to Fo(sub 59)) and reversely (Fo(sub 0.4) to Fo(sub 4.7)) zoned olivines suggest that the Kaba olivines are in thermodynamic disequilibrium and experienced a complicated history. The fayalite is sufficiently pure that it is unlikely that it could have been produced by fractional crystallization. A gas-solid reaction under oxidizing conditions (H2O/H2 ratio approximately 10) is probably responsible for its formation.

  17. 3D Quantitative Confocal Laser Microscopy of Ilmenite Volume Distribution in Alpe Arami Olivine

    NASA Astrophysics Data System (ADS)

    Bozhilov, K. N.

    2001-12-01

    The deep origin of the Alpe Arami garnet lherzolite massif in the Swiss Alps proposed by Dobrzhinetskaya et al. (Science, 1996) has been a focus of heated debate. One of the lines of evidence supporting an exhumation from more than 200 km depth includes the abundance, distribution, and orientation of magnesian ilmenite rods in the oldest generation of olivine. This argument has been disputed in terms of the abundance of ilmenite and consequently the maximum TiO2 content in the discussed olivine. In order to address this issue, we have directly measured the volume fraction of ilmenite of the oldest generation of olivine by applying confocal laser scanning microscopy (CLSM). CLSM is a method which allows for three-dimensional imaging and quantitative volume determination by optical sectioning of the objects. The images for 3D reconstruction and measurements were acquired from petrographic thin sections in reflected laser light with 488 nm wavelength. Measurements of more than 80 olivine grains in six thin sections of our material yielded an average volume fraction of 0.31% ilmenite in the oldest generation of olivine from Alpe Arami. This translates into 0.23 wt.% TiO2 in olivine with error in determination of ±0.097 wt.%, a value significantly different from that of 0.02 to 0.03 wt.% TiO2 determined by Hacker et al. (Science, 1997) by a broad-beam microanalysis technique. During the complex geological history of the Alpe Arami massif, several events of metamorphism are recorded which all could have caused increased mobility of the mineral components. Evidence for loss of TiO2 from olivine is the tendency for high densities of ilmenite to be restricted to cores of old grains, the complete absence of ilmenite inclusions from the younger, recrystallized, generation of olivine, and reduction in ilmenite size and abundance in more serpentinized specimens. These observations suggest that only olivine grains with the highest concentrations of ilmenite are close to the original amount of TiO2 incorporated in the olivine. Our measurements show maximum volume fraction of ilmenite of 1.21%, corresponding to 0.9±0.38 wt.% of TiO2. Even the most conservative scenario reveals concentration of TiO2 in olivine of more than 0.5 wt.%, a value comparable to that reported by Dobrzhinetskaya et al. (1996) and an order of magnitude greater than any previous measurement of TiO2 in olivine. Experiments by Dobrzhinetskaya et al. (Chem. Geol, 2000) found that such high solubility can occur, but only at P>10GPa at mantle temperatures.

  18. Fayalitic Olivine in Matrix of the Krymka LL3.1 Chondrite

    NASA Astrophysics Data System (ADS)

    Weisberg, M. K.; Zolensky, M. E.; Prinz, M.

    1995-09-01

    INTRODUCTION. Matrix persists as one of the most poorly characterized chondritic components. Its aggregational nature makes it an excellent place to search for primitive chondritic components that prevailed in the nebula during and after chondrule formation as well as components recording processes that predated and postdated accretion. In this study we focus on the occurrence and formation of the fayalitic olivine in the matrix of the Krymka LL3.1 unequilibrated ordinary chondrite. RESULTS. We limited our study to matrix areas clearly sandwiched between chondrules and did not include chondrule rims. In Krymka, matrix is coarser-grained and more Fe-rich than the rim material. Matrix is also highly variable in the size, shape and composition of its components, whereas chondrule rims appear more uniform. Krymka matrix is an aggregation of diverse mineral and lithic components. Mineral components include olivine, enstatite, diopsidic pyroxene, Ti-Al-rich Ca-pyroxene, hedenbergite, amorphous silicate material, spinel, oxides, troilite, and metal. Olivine is clearly dominant (~75% normative) and occurs in a variety of textures and compositions. Fayalitic olivine (Fa(sub)(58-94), avg.=Fa(sub)(72)) is ubiquitous throughout the matrix and occurs as (1) Isolated platelets (typically 1-3 micrometers x 3-5 micrometers, with some up to 10 micrometers in length), (2) Platelet clusters, which include randomly oriented platelets and/or intergrown platelets, (3) Platelet overgrowths which are overgrowths of parallel platelets on surfaces of larger (10-300 micrometers), more magnesian (Fa(sub)(4-34), avg.=Fa(sub)(19)) olivine fragments, (4) Euhedral-subhedral crystals (1-10 micrometers) which are often associated with and compositionally similar to platelets, and (5) Fluffy aggregates - irregularly shaped porous aggregates of submicron crystals. TEM study of the overgrowths reveals that the direction of elongation of the fayalitic platelets is along the c axis corresponding with the c direction of the larger olivine substrate. The larger, more magnesian olivine fragments are generally single crystals, but in some cases are associated with pyroxene (Fs(sub)(5-27),Wo(sub)(0.5-2)) or high-Ca pyroxene. These larger olivines are compositionally similar to chondrule olivines, whereas the fayalitic platelets are texturally and compositionally unlike olivines in chondrules. Fayalitic olivine with morphologies similar to those in Krymka matrix occur in the Chainpur LL3.4 and Ngawi LL3 matrix, but are much less common. These textures may have been characteristic of all primitive ordinary chondrite matrix, but were generally overprinted by metamorphic recrystallization. DISCUSSION: Fayalitic olivine in Krymka matrix records a process that has important implications for understanding the evolution of ordinary chondrites. It may form under oxidizing nebular conditions through solid state reactions in the presence of free silica, or vapor-solid reactions in a gas with a high silica activity [1,2]. Textural observations have been used to support a nebular origin for similar fayalitic olivine in CV3 matrix, and thermodynamic calculations indicate it could form in a nebula with a supersolar H2O/H2 ratio [3]. Vaporization experiments show that at ~10^(-6) bar and ~1650K olivine evaporates incongruently to produce a fayalitic vapor [4]. However, textural arguments favoring post-accretion formation of the fayalitic olivine in ordinary chondrite matrix and in CV3 dark inclusions have also been presented [5,6]. Thus, we consider three hypotheses for the formation of the fayalitic olivine in Krymka matrix: (1) vapor-solid reactions between a silica-rich vapor and metallic Fe degrees in the nebula, (2) vaporization of olivine-rich material to produce a fayalite vapor, followed by recondensation, or (3) parent body heating/dehydration of pre-existing phyllosilicates. Although the platy layered structure of some of the fayalitic olivine is suggestive of the layered structures of phyllosilicates and some fayalitic olivine texturally resembles saponite replacing olivine (as observed in the Kaidun CR chondrite), the platelet overgrowths on larger olivine crystals probably represent growth features and not a replacement of phyllosilicates. The platy morphology of fayalitic olivine could also indicate growth from a vapor consistent with hypotheses 1 and 2. The wide range in compositions of associated fayalitic olivine platelets suggests that they did not all form in the same environment and were not in contact under high enough temperatures to result in equilibrium; therefore, we conclude that the fayalitic olivine formed in a nebular environment. The fayalitic olivine platelets and associated fayalitic olivine in Krymka matrix may record vapor solid reactions under oxidizing nebular conditions or partial evaporation of a more Mg-rich olivine to produce a fayalite vapor, followed by recondensation. Formation through heating/dehydration of phyllosilicates is less likely. References. [1] Nagahara H. (1984) GCA, 48, 2581-2595. [2] Nagahara H. and Kushiro I. (1987) EPSL, 85, 537-547. [3] Hua X. and Buseck P. R. (1995) GCA, 59, 563-578. [4] Nagahara H. et al. (1994) GCA, 58, 1951-1963. [5] Alexander C. M. et al. (1989) EPSL, 95, 187-207. [6] Kojima T. and Tomeoka K. (1994) Meteoritics, 29, 484.

  19. Olivines in the Kaba carbonaceous chondrite and constraints on their formation

    NASA Technical Reports Server (NTRS)

    Hua, X.; Buseck, P. R.

    1993-01-01

    Kaba is unique in containing almost pure fayalitic olivine (Fo(sub 0.1)). Its coexistence with pure forsterite up to Fo(sub 99.6) and normal (Fo(sub 92) to Fo(sub 59)) and reversely (Fo(sub 0.4) to Fo(sub 4.7)) zoned olivines suggest that the Kaba olivines are in thermodynamic disequilibrium and experienced a complicated history. The fayalite is sufficiently pure that it is unlikely that it could have been produced by fractional crystallization. A gas-solid reaction under oxidizing conditions (H2O/H2 ratio approximately 10) is probably responsible for its formation.

  20. Cellular Precipitates Of Iron Oxide in Olivine in a Stratospheric Interplanetary Dust Particle

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1996-01-01

    The petrology of a massive olivine-sulphide interplanetary dust particle shows melting of Fe,Ni-sulphide plus complete loss of sulphur and subsequent quenching to a mixture of iron-oxides and Fe,Ni-metal. Oxidation of the fayalite component in olivine produced maghemite discs and cellular intergrowths with olivine and rare andradite-rich garnet. Cellular reactions require no long-range solid-state diffusion and are kinetically favourable during pyrometamorphic oxidation. Local melting of the cellular intergrowths resulted in three dimensional symplectic textures. Dynamic pyrometamorphism of this asteroidal particle occurred at approx. 1100 C during atmospheric entry flash (5-15 s) heating.

  1. An Olivine-Rich Crater in Tyrrhena Terra

    NASA Technical Reports Server (NTRS)

    2008-01-01

    This image of the ejecta of a crater in the Tyrrhena Terra region was taken by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) at 0328 UTC on February 23, 2007 (10:28 p.m. EST on February 22, 2007), near 13 degrees south latitude, 67 degrees east longitude. CRISM's image was taken in 544 colors covering 0.36-3.92 micrometers, and shows features as small as 18 meters (60 feet) across. The region covered is roughly 9 kilometers (5.6 miles) wide at its narrowest point.

    Named for a classic albedo feature, Tyrrhena Terra is an extensive, heavily-cratered part of Mars' southern highlands, some 2,300 kilometers (1,430 miles) at its broadest extent. It is located to the northeast of the Hellas basin. The region imaged by CRISM is to the north of Hellas Planitia and just east of the crater Huygens in Tyrrhena Terra's western end.

    The uppermost image in the montage above reveals the location of the CRISM image on a mosaic taken by the Mars Odyssey spacecraft's Thermal Emission Imaging System (THEMIS). The CRISM image is located inside a large, flat-floored crater measuring about 52 kilometers (32 miles) across. The image includes a small crater and its ejecta blanket, an apron of material thrown out during a crater's formation, both located inside the larger crater.

    The lower left image is an infrared false-color image that reveals the extent of the ejecta blanket. It also includes ejecta from another small crater located just east of the CRISM image.

    The lower right image shows the strengths of mineral absorptions, and reveals the composition of the ejecta and surrounding material. The ejecta surrounding the small impact crater is thickest at the crater's rim, and becomes thinner to discontinuous at the blanket's outer edge. This small crater's ejecta blanket shows an enhanced spectral signature of the mineral olivine, as does the ejecta from the small crater just out of view to the east. In contrast the surrounding material is rich in the volcanic mineral pyroxene. This relationship demonstrates the layered characteristic of rocks forming the southern highlands: olivine-rich rock was buried by pyroxene-rich materials on the larger crater's floor, probably volcanic lavas. Later, the small crater penetrated the pyroxene-rich rock, excavated the underlying olivine-bearing unit, and deposited it as ejecta.

    CRISM is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, Laurel, Md., the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad. NASA's Jet Propulsion Laboratory, a division of the California Institute of Technology in Pasadena, manages the Mars Reconnaissance Orbiter and the Mars Science Laboratory for NASA's Science Mission Directorate, Washington. Lockheed Martin Space Systems, Denver, built the orbiter.

  2. Olivine-metal mixtures: Spectral reflectance properties and application to asteroid reflectance spectra

    NASA Astrophysics Data System (ADS)

    Cloutis, Edward A.; Sanchez, Juan A.; Reddy, Vishnu; Gaffey, Michael J.; Binzel, Richard P.; Burbine, Thomas H.; Hardersen, Paul S.; Hiroi, Takahiro; Lucey, Paul G.; Sunshine, Jessica M.; Tait, Kimberly T.

    2015-05-01

    Olivine-rich asteroids appear to be common in the main asteroid belt as well as present in the near-Earth asteroid population. There are a number of meteorite classes that are dominated by olivine ± metal. To determine whether relationships exist between these asteroids and meteorites, we spectrally characterized a number of olivine + meteoritic metal powder intimate and areal mixtures, pallasite slabs, and olivine powders on a metal slab. Our goal is to understand the spectral characteristics of olivine + metal assemblages and develop spectral metrics that can be used to analyze reflectance spectra of olivine-dominated asteroids. We found that the major olivine absorption band in the 1 μm region is resolvable in intimate mixtures for metal abundances as high as ∼90 wt.%. The wavelength position of the 1 μm region olivine absorption band center is sensitive to Fa content but insensitive to other variables. However, the band minimum position moves to shorter wavelengths with increasing metal abundance due to changes in spectral slope. The full width at half maximum (FWHM) of this band and reflectance at 1.8 μm are both most sensitive to olivine Fa content, metal abundance, and grain size, and much less to the presence of nanophase iron that reddens spectra. Reflectance at 0.56 μm and the 1.8/0.56 μm reflectance ratio are sensitive to these same parameters as well as to nanophase iron-associated spectral reddening. The wavelength position of the local reflectance maximum in the 0.7 μm region moves to longer wavelengths with increasing metal abundance and is most useful for constraining metal abundance in high metal-content mixtures. Pallasite slab spectra differ in a number of respects from powdered assemblages and multiple spectral parameters can be used to discriminate them. The spectra of increasingly fine-grained olivine + metal assemblages and those involving low-Fa olivine show increasing spectral dominance by metal. Systematic application of multiple spectral metrics allows olivine + metal assemblage properties such as Fa content, olivine/metal ratio, and grain size to be quantified or constrained. Analysis of reflectance spectra of 22 presumed olivine ± metal-rich asteroids indicates that most of them possess low- to medium-Fa content olivine (Fa<∼67), with variable abundances of macroscopic metal. A number exhibit visible region absorption bands that are indicative of some fraction of coarser-grained olivine (>45 μm). Most asteroid spectra can be plausibly linked to specific olivine ± metal-bearing meteorite classes. Most of the asteroid spectra examined exhibit some degree of spectral reddening below ∼1.8 μm which is most consistent with the presence of fine-grained nanophase iron, likely produced by space weathering.

  3. Water in Olivine and its High-Pressure Polymorphs

    NASA Astrophysics Data System (ADS)

    Thomas, S. M.; Jacobsen, S. D.; Bina, C. R.; Reichart, P.; Moser, M.; Dollinger, G.; Hauri, E. H.

    2014-12-01

    Theory and high-pressure experiments imply a significant water storage capacity of nominally anhydrous minerals (NAMs), such as olivine, wadsleyite and ringwoodite, composing the Earth's upper mantle and transition zone to a depth of 660 km. The presence of water, dissolved as OH into such nominally anhydrous high-pressure silicates, notably influences phase relations, melting behavior, conductivity, elasticity, viscosity and rheology. The first direct evidence for hydration of the transition zone has recently been reported by Pearson et al. (2014) and Schmandt et al. (2014). Knowledge of absolute water contents in NAMs is essential for modeling the Earth's interior water cycle. To take advantage of IR spectroscopy as highly sensitive water quantification tool, mineral-specific absorption coefficients are required. Such calibration constants can be derived from hydrogen concentrations determined by independent techniques, such as secondary ion mass spectrometry (SIMS), Raman spectroscopy or proton-proton(pp)-scattering. Broad beam pp-scattering has been performed on double-polished mm-sized mineral platelets (Thomas et al. 2008), but until recently analysis was not feasible for smaller samples synthetized in high-pressure apparati. Here we present first results from pp-scattering microscopy studies on ?m-sized single crystals of hydrous olivine, wadsleyite and ringwoodite, which were synthesized at various pressure-temperature conditions in a multi-anvil press. The method allows us to quantify 3D distributions of atomic hydrogen in ?m dimensions. These self-calibrating measurements were carried out at the nuclear microprobe SNAKE at the Munich tandem accelerator lab using a 25 MeV proton microbeam. We provide hydrogen depth-profiles, hydrogen maps and H2O concentrations. Pp-scattering data and results from independent Raman and SIMS analyses are in good agreement. Water contents for a set of high-pressure polymorphs with varying Fe-concentrations range from 0.8 wt% to 2.5 wt% H2O. From experimental data for Fo83, Fo87, Fo90 and Fo100 compositions we calculate mineral-specific absorption coefficients for the quantification of H2O using IR-spectroscopy, compare them with previously estimated values and discuss IR calibrations for major phases of the Earth's mantle.

  4. Metastable olivine wedge beneath northeast China and its applications

    NASA Astrophysics Data System (ADS)

    Jiang, G.; Zhao, D.; Zhang, G.

    2013-12-01

    When the Pacific slab subducted into the mantle transition zone, there might exist a metastable olivine wedge (MOW) inside the slab due to the phase transition. Lots of researchers have adopted such various methods to detect the characteristics of this MOW as the forward modeling of travel times, shear wave amplitude patterns, teleseismic P wave coda, receiver function imaging, thermodynamic simulation and so on. Almost all results could be more or less affected by the source, the receiver and/or the velocity model passed through by the seismic rays. In this study, we have used 21 deep earthquakes, greater than 400 km and locating beneath northeast China, to study the velocity within the MOW. For more precisions, we have done further modifications in two ways based on our previous studies. (1) Double-difference location method is used to relocate all events with an error of 1-2 km with the data recorded by stations both at northeast China and at Japan. All relocated events locate in a zone about 30 km away from the upper boundary of Pacific slab. (2) Double residual travel times, generated by an event-pair at a common station at only Japan, are used to constrain the velocity anomaly rather than the residuals themselves. As a result, we have found that an ultra-lower velocity zone (ULVZ), averagely -7% relative to the iasp91 model, exists within the subducted Pacific slab around the deep earthquakes, which might be represented as the metastable olivine wedge. Because of the lower-velocity corresponding to the lower-density, the MOW would provide upward buoyancy forces which might prevent the slab from free subduction into the mantle transition zone. This feed-back mechanism of MOW to the slab is called ';parachute-effect', which is characterized by other researchers. In addition, the existence of the ULVZ or the MOW in the slab may supply a possible mechanism for triggering deep earthquakes, called ';phase transformation faulting', which was already proposed few decades ago but now is proved further by our result. Therefore, our study is not only instructive for realizing the dynamic process of slab subduction, but also helpful for analyzing the mechanism of deep earthquakes.

  5. Reactive flow as dominant evolution process in the lowermost oceanic crust: evidence from olivine of the Pineto ophiolite (Corsica)

    NASA Astrophysics Data System (ADS)

    Sanfilippo, Alessio; Tribuzio, Riccardo; Tiepolo, Massimo; Berno, Davide

    2015-10-01

    The Jurassic Pineto ophiolite from Corsica exposes a ~1-km-thick troctolite-olivine-gabbro sequence, interpreted to represent a lowermost sector of the gabbroic oceanic crust from a (ultra-)slow spreading system. To constrain the petrogenesis of the olivine-gabbros, minor and trace element analyses of olivine (forsterite = 84-82 mol%) were carried out. Olivine from the olivine-gabbros is depleted in incompatible trace elements (Sc, V, Ti, Y, Zr and heavy rare earth elements) with respect to olivines from associated troctolites. Depleted incompatible element compositions are also shown by olivine (forsterite = 86 mol%) from a clinopyroxene-rich troctolite. The incompatible element compositions of olivine argue against a petrogenetic process entirely driven by fractional crystallization. We propose that melts migrating through an olivine-plagioclase crystal mush chemically evolved by reaction with the existing minerals, changing in composition as it flowed upward. The melt residual from these interactions led to partial dissolution of preexisting olivine and to crystallization of clinopyroxene, generating olivine-gabbro bodies within a troctolite matrix. Reactive flow was the major evolution process active in the ~1-km crustal transect exposed at the Pineto ophiolite, producing lithological variations classically attributed to fractional crystallization processes.

  6. Structural and Electrochemical Characterization of Lithium Transition Metal Phosphates

    NASA Astrophysics Data System (ADS)

    Hashambhoy, Ayesha Maria

    The lithium ion battery has emerged as one of the most promising hybrid vehicle energy storage systems of the future. Of the potential cathode chemistries explored, lithium transition metal phosphates have generated a significant amount of interest due to their low-cost precursors, potential ease of synthesis, stability, and their environmentally friendly nature. This is in contrast to layered oxide systems such as LiCoO2, which have long been considered state of the art, but are now being reevaluated due to their structural instability at elevated temperatures, and higher cost. In particular, LiFePO4 has an operating potential comparable to those batteries available on the market (˜3.5V vs. Li/Li+), and higher theoretical specific capacity (170mAh/g vs. that of LiCoO2 which is 140mAh/g). The manganese analog to LiFePO4, LiMnPO4, exhibits a higher operating potential (˜4.1V v Li/Li+), and the same theoretical capacity, however Li-ion diffusion through this structure is much more rate limited and its theoretical capacity cannot be realized at rates suitable for commercial applications. The purpose of this work was threefold: 1) To explore the impact of Fe substitution on Mn sites in LiMnPO 4. 2) To examine the effects of alterations to the particle/electrolyte interface on rate capability. 3) To explore a novel fabrication route for LiMnPO4 using microwaves, and determine an optimal power and time combination for best performance. The coexistence of Fe and Mn on the transition metal site M, of LiMPO 4 resulted in an improved apparent Li-ion diffusivity in both Fe and Mn regimes as compared to that observed for LiFePO4 and LiMnPO 4 respectively. Calculations made from two different analysis methods, cyclic voltammetry (CV) and galvanostatic intermittent titration (GITT) drew this same conclusion. The signature characteristics observed from the CVs pertaining to single and dual phase reactions led to a delithiation model of LiFe0.5Mn0.5PO4 proposing the localization of half the Li atoms with Fe and half with Mn. Following this work, pure LiMnPO 4 was explored. LiMnPO4 was successfully fabricated using rapid, solid state microwave irradiation. Three classes of materials were prepared to study the effects of particle size, carbon coating, and electrolytic environment on rate capability. Reduction in particle size, carbon coating, and the aqueous electrolyte environment provided the most favorable conditions for performance enhancement. Based on the initial promising results of solid state microwave synthesis, further studies were conducted to optimize irradiation parameters. C-LiMnPO 4 fabricated at 200W for 5.0 minutes demonstrated the most superior rate capability. This material attained its full theoretical specific capacity, showing promise for the advancement of materials fabricated via this method.

  7. Reinvestigation of the olivine-spinel transformation in Ni2SiO4 and the incongruent melting of Ni2SiO4 olivine

    NASA Technical Reports Server (NTRS)

    Ma, C.-B.

    1974-01-01

    The olivine-spinel transformation and the melting behavior of Ni2SiO4 were investigated over the PT ranges of 20-40 kbar, 650-1200 C, and 5-13 kbar, 1600-1700 C, respectively. It was confirmed that Ni2SiO4 olivine melts incongruently at high pressures and that it is a stable phase until melting occurs. The PT slope of the incongruent melting curve is approximately 105 bars/deg. The olivine-spinel transformation curve was shown to be a reversible univariant curve, and could be expressed by the linear equation P(bars) equals 23,300 + 11.8 x T(deg C). The transformation curve determined by Akimoto et al. (1965) is nearly parallel to that of the present work, but lies at pressures about 12% lower.

  8. Trace element composition of olivine - implications for the evolution of the olivine gabbro-troctolite-hosted Voisey's Bay Ni-Cu-Co sulfide deposit, Labrador

    NASA Astrophysics Data System (ADS)

    Bulle, F.; Layne, G. D.

    2011-12-01

    The Mesoproterozoic Voisey's Bay intrusion is part of the Nain Plutonic Suite, which transects the 1.85 Ga collisional boundary between the Proterozoic Churchill Province and the Archean Nain Province in Eastern Labrador. The intrusion comprises a group of troctolitic to olivine gabbroic bodies linked by olivine gabbro dikes; together these rocks host the world-class Voisey's Bay Ni-Cu-Co sulfide deposit. Zones of massive and disseminated sulfide mineralization (Reid Brook, Discovery Hill, Mini-Ovoid and Ovoid) occur within a dike and at the entry line of this dike into a larger intrusion termed the Eastern Deeps [1, 2, 3]. At least two pulses of magma have generated the intrusion and the associated sulfide mineralization; an initial surge that achieved sulfide saturation by interacting with upper crustal rocks, and a later pulse of fresh, undepleted magma that forced the initial magma upwards and both remobilized the immiscible sulfide liquid and upgraded it in metal content [1, 2, 3]. Previous research [1, 2] has shown that the Ni content of olivine from the distinct sulfide-bearing host rocks is highly variable, and also indicative of both magma mixing and interaction of silicate magmas with sulfide. To further validate the significance of the olivine chemistry as a tracer for ore-forming petrological processes, we have determined the abundances of Cr, Mn, Co, Ni, Zn in olivines from the various mafic lithologies of the Eastern Deeps intrusion using Secondary Ion Mass Spectrometry. We present systematic variations in Mn, Co, Ni and Zn with Fo-content in olivines for both sulfide-free and sulfide-bearing zones. Olivines from mineralized and brecciated troctolitic/gabbroic zones display significantly higher Mn (up to 11,000 ppm) and Zn (up to 550 ppm) concentrations than those from nominally barren counterparts. The barren troctolite, broadly termed normal troctolite (NT), is a petrographically homogenous plagioclase and olivine cumulate. However, olivine compositional data establish the presence of "reef-like" horizons with, for instance, elevated Ni concentrations (up to 2,500 ppm), versus surrounding horizons where values of ? 1,500 ppm are predominant. These horizons correspond with deflections in the whole-rock MgO, Fe2O3 and MnO contents. If these horizons are widespread and traceable laterally within the intrusion it would imply that: (1) a "cryptic-layering" might be preserved in olivines from the otherwise homogenous NT - indicating either crystallization from an input of fresh, undepleted mafic magma, or an interaction of those olivines with a Ni-rich sulfide liquid [1, 2], (2) the high Mn and Zn concentrations, coupled with lower forsterite values, are probably a result of crystallization from a country rock-contaminated mafic magma, and therefore, might act as a mineral-based indicator for the assimilation of upper crustal material. These observations may assist in developing a signature for olivines that have been in contact with highly contaminated (and thus potentially sulfide saturated) magmas. [1] Li et al. (2000) Econ. Geol. 95, 771-799. [2] Li and Naldrett (1999) Lithos 47, 1-31. [3] Lightfoot and Naldrett (1999) GAC Vol. 13, 1-30.

  9. Fayalitic olivine in matrix of the Krymka LL3.1 chondrite: Vapor-solid growth in the solar nebula

    NASA Astrophysics Data System (ADS)

    Weisberg, Michael K.; Zolensky, Michael E.; Prinz, Martin

    1997-11-01

    Fayalitic olivine (Fa54-94) is a ubiquitous component in the matrix of Krymka (LL3.1) as well as in other highly unequilibrated chondrites (ordinary and carbonaceous). In Krymka, the fayalitic olivine has an unusual anisotropic platy morphology that occurs in at least five types of textural settings, which can be characterized as: (1) isolated platelets, (2) clusters of platelets, (3) euhedral to subhedral crystals, (4) overgrowths of platelets on forsteritic olivine, and (5) fluffy (porous) aggregates. From TEM investigation, the direction of elongation of the platy olivine overgrowths on forsteritic olivine substrates is along the c axis and in most cases it corresponds with the c axis of the substrate olivine, suggesting that the fayalitic olivine grew in this unusual morphology and is not a replacement product of preexisting material. The fayalitic olivine in the matrix of Krymka is compositionally similar to olivine with platy morphology in the matrix of some CV3 chondrites and both have similar Fe/Mn ratios, but important morphological differences indicate that their relationship needs to be explored further. Textural and compositional data indicate that the fayalitic olivine in the matrix of Krymka, as well as in some other unequilibrated ordinary chondrites, formed prior to final lithification of the meteorite and probably prior to parent body accretion. We find that formation of the fayalitic olivine by vapor-solid growth provides the best explanation to our observations and data, and is the only feasible mechanism for the formation of fayalitic olivine in the matrix of Krymka. We propose that the fayalitic olivine formed by vaporization and recondensation of olivine rich-dust, during a period of enhanced dust/gas ratio in the nebula.

  10. Excitation and relaxation of olivine after swift heavy ion impact

    NASA Astrophysics Data System (ADS)

    Gorbunov, S. A.; Medvedev, N. A.; Rymzhanov, R. A.; Terekhin, P. N.; Volkov, A. E.

    2014-05-01

    A multiscale model was developed to describe excitation and initial relaxation of an insulator after an impact of a swift heavy ion (SHI) decelerated in the electronic stopping regime. This model consists of a combination of three methods: (a) Monte Carlo simulations of the nonequilibrium kinetics of the electron subsystem of a solid at the femtosecond scale after the projectile passage. The complex dielectric function (CDF) is used to construct the cross sections for the MC model taking into account a collective response of the electron ensemble to excitation. (b) A molecular-kinetic approach describing further spatial spreading of electrons after finishing of ionization cascades up to hundred femtoseconds. And (c) molecular dynamics simulations of a reaction of the lattice on the excess energy transferred from the relaxing electron subsystem at the picosecond time scale. The dynamic structure factor (DSF) formalism is used to calculate the electron-lattice energy exchange in a general way which is valid for sub-picosecond timescales, beyond the phononic approximation of the lattice dynamics. The calculations were performed for 2 GeV Au ion in olivine, demonstrating a heating of the lattice up to 700 K in the nanometric scale picoseconds after the projectile passage.

  11. Charge Localization and Transport in Lithiated Olivine Phosphate Materials

    SciTech Connect

    Yu, Jianguo; Rosso, Kevin M.; Liu, Jun

    2011-11-10

    We report density functional theory (DFT) calculations for olivine-type LiTMPO4 and TMPO4 (TM=Mn, Fe, Co, Ni) structures, using GGA+U and the B3LYP hybrid density functional that includes nonlocal Fock exchange. TM is typically characterized in terms of the formal oxide states of 2+ or 3+, corresponding to TM with localized charge in LiTMPO4 and TMPO4 structures, respectively, in which electron transport would take place by thermally activated hopping of electrons strongly localized on the transition metal (small polarons). In this work, we assess the validity of the concept of formal TM oxidation states in these materials, and conclude that the valence depends in large part on the strength of d-p hybridization. Stable small polaron formation, i.e., mixed 2+ and 3+ valence states, appears to require that the ratio of differences in the metal and oxygen ionic charges (dQTM/dQO) of the two end member phases is larger than 2, corresponding to the mixed-valence TM system. If the ratio of dQTM/dQO is smaller than 2, excess electrons prefer delocalization and the system behaves more single-valence like with charge transport more akin to metallic conduction. The critical ratio emerging from our analysis may turn out to be relevant to other transition metal systems as well, as a criterion to discriminate single-valence or mixed-valence characteristics and hence the predominant conduction mechanism.

  12. Water in Pyroxene and Olivine from Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Peslier, A. H.

    2012-01-01

    Water in the interior of terrestrial planets can be dissolved in fluids or melts and hydrous phases, but can also be locked as protons attached to structural oxygen in lattice defects in nominally anhydrous minerals (NAM) like olivine, pyroxene, or feldspar [1-3]. Although these minerals contain only tens to hundreds of ppm H2O, this water can amount to at least one ocean in mass when added at planetary scales because of the modal dominance of NAM in the mantle and crust [4]. Moreover these trace amounts of water can have drastic effects on melting temperature, rheology, electrical and heat conductivity, and seismic wave attenuation [5]. There is presently a debate on how much water is present in the martian mantle. Secondary ionization mass spectrometry (SIMS) studies of NAM [6], amphiboles and glass in melt inclusions [7-10], and apatites [11, 12] from Martian meteorites report finding as much water as in the same phases from Earth's igneous rocks. Most martian hydrous minerals, however, generally have the relevant sites filled with Cl and F instead of H [13, 14], and experiments using Cl [15] in parent melts can reproduce Martian basalt compositions as well as those with water [16]. We are in the process of analyzing Martian meteorite minerals by Fourier transform infrared spectrometry (FTIR) in order to constrain the role of water in this planet s formation and magmatic evolution

  13. Metastable olivine provides regional constraints on hydrogen content based on transformation kinetics

    NASA Astrophysics Data System (ADS)

    Du Frane, W. L.; Sharp, T. G.; Mosenfelder, J. L.; Leinenweber, K. D.

    2009-12-01

    The existence of metastable olivine has been debated as a possible trigger of deep focus earthquakes. Of equal importance, its existence may constrain the amount of hydrogen being subducted into the Earths transition zone. Olivine transformation rates into wadsleyite and ringwoodite have been demonstrated to be dependent on hydrogen content, and determine whether metastable olivine persists into the Earths mantle transition zone as downwelling material. For nominally anhydrous olivine, in this and previous studies, transformation rates decrease over time as a rigid reaction rim is formed. If viscoelastic relaxation of the rim occurs at a relatively slow rate, strain energy resulting from the negative volume change of the reaction counteracts the chemical free energy driving force for growth. It has been proposed that hydrogen enhances olivine transformation rates through hydrolytic weakening of the growth rim, which promotes relaxation of transformation stress, but it is not clear how much hydrogen is required for this mechanism to occur. We present ringwoodite growth rate measurements for interface-controlled growth, using olivine spheres hydrated in a piston cylinder with 75 +/- 15 ppm H2O and nominally anhydrous San Carlos olivine spheres with ? 10 ppm H2O. Hydrogen contents have been determined using new FTIR and SIMS data that indicate that hydrogen partitions into the growth rim as it forms. As the rim continues to grow and the core becomes depleted, the rim will eventually exhaust itself of hydrogen and may later become rigid if there is not enough hydrogen available to weaken the growth rim throughout transformation. However, we did not see evidence of non-linear rim growth in samples with 75 ppm H2O, with up to 76% growth fraction at 1100 C. For olivine initially containing 75 ppm H2O, the ringwoodite growth rates at 18 GPa are 5.1(+/-0.4)x10-11 at 700 C, 1.8(+/- 0.6)x10-9 m/s at 900 C, 3.8(+/-1.5)x10-8 at 1100 C with activation enthalpy of 187 +/- 40 kJ/mol. These rates are similar to rates for olivine with 300 ppm D2O: 2.1x10-9 m/s at 900 C, 18 GPa with activation enthalpy of 232 kJ/mol [Diedrich, et al., 2009]. The similarity of growth rates for olivine containing a range of H2O (75-300 ppm) suggests that even a small amount of hydrogen can significantly enhance olivine growth rates as long as enough hydrogen partitions to the rim to hydrolytically weaken it, and prevent the buildup of elastic strain energy. Nominally anhydrous olivine may also transform at a similar rate if the growth rims have sufficiently high viscoelastic relaxation rates in Earth. Without the effects of elastic strain energy, growth rates of this magnitude have been demonstrated by thermo-kinetic models to be incompatible with formation of a metastable olivine wedge [Marton, et al., 2006]. Therefore if metastable olivine exists within subducting slabs, olivine must contain less than 75 ppm H2O and transformation rates must be reduced by elastic strain energy. Evidence of metastable olivine in subducting slabs would thus produce regional constraints on hydrogen content in earths transition zone.

  14. Systematic Ion Irradiation Experiments to Olivine: Comparison with Space Weathered Rims of Itokawa Regolith Particles

    NASA Astrophysics Data System (ADS)

    Matsumoto, T.; Tsuchiyama, A.; Watanabe, N.; Yasuda, K.; Miyake, A.; Nakauchi, Y.; Okada, T.; Abe, M.; Yada, T.; Uesugi, M.; Karouji, Y.; Nakato, A.; Hashiguschi, M.; Kumagai, K.

    2015-11-01

    We performed H and He ion irradiation experiments using olivine fragments, in order to reveal formation time-scales of space weathered rims and formation processes of blisters by solar wind irradiation.

  15. Optical absorption and radiative heat transport in olivine at high temperature

    NASA Technical Reports Server (NTRS)

    Shankland, T. J.; Nitsan, U.; Duba, A. G.

    1979-01-01

    Results are presented of measurements of the optical absorption spectra (300-8000 nm) of olivine as a function of temperature (300-1700 K) under conditions of controlled and known oxygen fugacity within the stability field of the samples. The absorption spectra are used to calculate the temperature-dependent radiative transfer coefficient of olivine and to numerically study the accuracy of the method. The present absorption measurements in olivine under oxidizing conditions known to be within the olivine stability field indicate that the effective radiative conductivity K(R) is lower than that obtained in previous studies under different experimental conditions. The lower value of K(R) makes it more likely that some of the earth's internal heat is removed by convection and less likely that thermal models involving conduction and radiation alone will satisfactorily explain thermal conditions in the earth's mantle.

  16. Trace Element Distribution Between Olivine and Kirschsteinite in Angra Dos Reis

    NASA Technical Reports Server (NTRS)

    Fittipaldo, M. M.; Jones, R. H.; Shearer, C. K.

    2003-01-01

    The angrites are a small and enigmatic group of basaltic achondrites that possess unique mineralogical and chemical properties. The dominant mineralogy of the seven angrite members (Angra dos Reis, LEW 86010, LEW 87051, Asuka 881371, Sahara 99555, D Orbigny, and a new Moroccan member) is fassaite, olivine, and plagioclase. Angrites display a wide range of thermal histories, with Angra dos Reis (AdoR) exhibiting a cooling history different from that of the rapidly cooled members and from LEW86010, a more slowly cooled member. AdoR could represent either a cumulate or a porphyritic igneous rock that was later altered by metamorphism. We are re-examining the thermal history of AdoR in light of the more recently described angrite members. Our emphasis is a trace element study of low-Ca olivine, which we refer to as olivine, and high-Ca olivine, which we refer to as kirschsteinite, in AdoR.

  17. Olivine-Orthopyroxene Equilibrium in Metal-rich Systems: Applications to Achondrites and Equilibrated Chondrites

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Benedix, G. K.; McCoy, T. J.

    2003-01-01

    Olivine and orthopyroxene are major minerals in every type of stony meteorite. The majority of achondritic meteorites and silicate-bearing iron meteorites have experienced high temperatures. If these temperatures persisted for an extended period of time then the iron contents of olivine and orthopyroxene should be in equilibrium. In their study of ungrouped clasts and chondritic meteorites, suggested that the equilibrium compositions of olivine and orthopyroxene should fall on a mixing line between LL chondrites and aubrites. Here we show that this is not necessarily the case and that a range of FeO contents in olivine and orthopyroxene can be in equilibrium with each other. The key parameters that determine the equilibrium Fe content in these minerals are temperature, oxygen fugacity (fO2), and silica activity (aSiO2).

  18. Amoeboid Olivine Aggregates (AOAs) in the Efremovka (CVR) Chondrite: First SIMS Trace-Element Results

    NASA Astrophysics Data System (ADS)

    Ruzicka, A.; Floss, C.; Hutson, M.

    2008-03-01

    SIMS trace-element results for six inclusions in Efremovka imply that condensation was important in the formation of AOAs and that precursor compositions or mode of origin were different for olivine in AOAs and in chondrules.

  19. Are Megacrysts in Olivine-Phyric Shergottites Xenocrysts, Phenocrysts, or Something Else?

    NASA Astrophysics Data System (ADS)

    Balta, J. B.; McSween, H. Y.

    2011-03-01

    We argue based on detailed analyses and modeling of shergottite LAR 06319 that its olivines are antecrysts, formed from a melt similar to the current groundmass and entrained from a cumulate pile prior to eruption.

  20. Optical constants of olivine particles between wavelengths of 7 and 200 microns

    SciTech Connect

    Mukai, Tadashi; Koike, Chiyoe Kyoto Pharmaceutical Univ. )

    1990-09-01

    Emission features are computed for spherical olivine particles of 0.03, 0.3, 3.0, and 30 micron radii, on the basis of laboratory determinations of the olivine particles' optical constants over the 7 to 200 micron range. It is noted that, while particles of radii smaller than 0.3 microns exhibit emission peaks at 16.3, 18.6, 23, 28, and 33.6 microns, together with a 10-micron region twin-peak structure, these readings weaken for particle radii of 3 microns or more. The appearance of the twin-peak feature in Comet P/Halley is accordingly judged to imply the presence of olivine particles smaller than 1 micron in radius; alternatively, such smaller olivines' enhancement may occur in the comet, which also exhibits a 10-micron silicate band twin-peak feature. 26 refs.

  1. Carbon in glass inclusions of Allende, Vigarano, Bali, and Kaba (CV3) olivines

    NASA Astrophysics Data System (ADS)

    Varela, Maria Eugenia; Metrich, Nicole; Bonnin-Mosbah, Michelle; Kurat, Gero

    2000-11-01

    Carbon contents and distribution have been measured in glass inclusions in olivines of CV3 carbonaceous chondrites by using the 12C(d,p) 13C nuclear reaction. All olivines from the four studied meteorites had low carbon contents (<70 ppm). Conversely, glasses of glass inclusions in the same olivines had highly variable carbon contents, all above 100 ppm. Glass inclusions in olivines from meteorites of the oxidized group (Allende, Kaba, and Bali) had carbon contents that varied from 100 to about 2000 ppm, whereas those from the reduced group member Vigarano were surprisingly poor in C (averaging 300 ppm). These relative abundances of carbon in these glasses of reduced and oxidized CV3 meteorites are in contrast to the abundances of interstellar SiC in these meteorites. This indicates that glass inclusions in olivines could have behaved, with respect to carbon, as closed systems that have escaped elemental exchange processes. The carbon content of the glasses is, therefore, likely to be primary and reflect the physico- chemical conditions during the formation of the host olivine and glass inclusions. The redox conditions prevailing during secondary processing of the olivines (e.g., metasomatic Fe-Mg exchange, Ca-Na exchange) appear not to have influenced the carbon distribution. Carbon could have been trapped initially as a refractory carbon species (e.g., carbide) by clear glass inclusions. Despite the fact that the nature of neither the primary nor that of the secondary C species was established, the commonly heterogeneous distribution of C in glass inclusions in olivines suggests entrapment of a solid C-bearing precursor.

  2. Effect of metamorphism on isolated olivine grains in CO3 chondrites

    NASA Technical Reports Server (NTRS)

    Jones, Rhian H.

    1993-01-01

    The presence of a metamorphic sequence in the CO3 chondrite group has been shown previously to result in changes in properties of chondrule silicates. However, the role of isolated olivine grains during metamorphism of these chondrites has not been addressed. Isolated olivine grains in two metamorphosed CO3 chondrites, Lance and Isna, have been investigated in this study in order to assess the compositional properties of isolated olivine grains that may be attributable to metamorphism. Compositional changes in isolated olivines with increasing petrologic subtype are very similar to changes in chondrule olivines in the same chondrites. Olivine compositions from all occurrences (chondrules, isolated grains, and matrix) converge with increasing petrologic subtype. The degree of equilibration of minor elements is qualitatively related to the diffusion rate of each element in olivine, suggesting that diffusion-controlled processes are the most important processes responsible for compositional changes within the metamorphic sequence. The data are consistent with metamorphism taking place in a closed system on the CO3 chondrite parent body. Fe-poor olivine grains in metamorphosed chondrites are characterized by an Fe-rich rim, which is the result of diffusion of Fe into the grains from Fe-rich matrix. In some instances, 'complex', Fe-rich rims have been identified, which appear to have originated as igneous overgrowths and subsequently to have been overprinted by diffusion processes during metamorphism. Processes experienced by CO3 chondrites are more similar to those experienced by the ordinary chondrites than to those encountered by other carbonaceous chondrites, such as the CV3 group.

  3. A Tale of Two Olivines: Magma Ascent in the Auckland Volcanic Field, New Zealand

    NASA Astrophysics Data System (ADS)

    Smid, E. R.; McGee, L. E.; Smith, I. E.; Lindsay, J. M.

    2013-12-01

    The Auckland Volcanic Field (AVF) is a nephelinitic to subalkali basaltic monogenetic field centered on the city of Auckland, New Zealand. Lavas are olivine-phyric, and the deposits of several volcanoes in the field contain olivine crystals with chrome spinel (Cr-spinel) inclusions. Microprobe analyses show at least two populations of olivine, categorised by their Mg# and their spinel inclusion compositions: the first has olivines that are euhedral, have compositions slightly less forsteritic than expected for whole rock Mg#, and have Cr-spinel inclusions with relatively low Cr2O3 contents of ~20%. These are interpreted as antecrysts inherited from the mantle source that yielded their host magma. The second population is characterised by olivines that are sub- to euhedral, are significantly more forsteritic than expected from their host whole rock Mg#, and have Cr-spinel inclusons with relatively high Cr2O3 contents of ~50%. These are interpreted as xenocrysts. The composition of these high Cr2O3 spinels very closely resembles the composition of spinels within olivines in dunite sampled from the Dun Mountain Ophiolite on the South Island of New Zealand. The northward extension of the Dun Mountain complex beneath the North Island is defined by the Junction Magnetic Anomaly, marking a crustal terrane boundary that underlies the Auckland Volcanic Field. These data indicate that the magmas that have risen to produce the volcanoes of the Auckland Volcanic Field have carried crystals from an underlying ultramafic crust as well as from their asthenospheric source. Euhedral olivine crystals which do not contain Cr-spinel are also present in AVF lavas and these are interpreted as true phenocrysts that crystallised directly from their host magmas. The lack of reaction textures at crystal margins suggests rapid ascent rates. A crustal origin for the xenocrysts not only has large implications for ascent rate modelling of olivines, but also for the crustal structure of the Auckland area and possible magma ascent paths under the AVF.

  4. Chemical zoning and homogenization of olivines in ordinary chondrites and implications for thermal histories of chondrules

    NASA Technical Reports Server (NTRS)

    Miyamoto, Masamichi; Mckay, David S.; Mckay, Gordon A.; Duke, Michael B.

    1986-01-01

    The extent and degree of homogenization of chemical zoning of olivines in type 3 ordinary chondrites is studied in order to obtain some constraints on cooling histories of chondrites. Based on Mg-Fe and CaO zoning, olivines in type 3 chondrites are classified into four types. A single chondrule usually contains olivines with the same type of zoning. Microporphyritic olivines show all four zoning types. Barred olivines usually show almost homogenized chemical zoning. The cooling rates or burial depths needed to homogenize the chemical zoning are calculated by solving the diffusion equation, using the zoning profiles as an initial condition. Mg-Fe zoning of olivine may be altered during initial cooling, whereas CaO zoning is hardly changed. Barred olivines may be homogenized during initial cooling because their size is relatively small. To simulated microporphyritic olivine chondrules, cooling from just below the liquidus at moderately high rates is preferable to cooling from above the liquidus at low rates. For postaccumulation metamorphism of type 3 chondrites to keep Mg-Fe zoning unaltered, the maximum metamorphic temperature must be less than about 400 C if cooling rates based on Fe-Ni data are assumed. Calculated cooling rates for both Fa and CaO homogenization are consistent with those by Fe-Ni data for type 4 chondrites. A hot ejecta blanket several tens of meters thick on the surface of a parent body is sufficient to homogenize Mg-Fe zoning if the temperature of the blanket is 600-700 C. Burial depths for petrologic types of ordinary chondrites in a parent body heated by Al-26 are broadly consistent with those previously proposed.

  5. Clast-laden nature and the origin of Luna 24 olivine-vitrophyres

    NASA Technical Reports Server (NTRS)

    Basu, A.; Mckay, D. S.; Fruland, R. M.

    1978-01-01

    The study shows that Luna 24 olivine-vitrophyric particles are actually fragments of clast-laden melt and are not from a very low titanium (VLT) mare basalt flow. Diversity of composition and clast population, and morphological similarity to ropy glasses suggest an impact melt origin. Compositionally, the olivine-vitrophyres resemble the high magnesian VLT basalts, which may have been the target and source of the impact melt.

  6. Angrite LEW87051: Are the olivines pheno's or xeno's? A continuing story

    NASA Technical Reports Server (NTRS)

    Jurewicz, A. J. G.; Mckay, G. A.

    1993-01-01

    The achondrite LEW87051 is a porphyritic basalt consisting of large subhedral to euhedral zoned olivines in a finer-grained groundmass. The texture of this groundmass looks remarkably like a quenched melt. However, although the rock is clearly igneous, its exact origins and history are under dispute. From petrographic observations, Prinz felt that the large olivines were xenocrysts and that the zoning reflected interaction with an unrelated, CAI-enriched melt. McKay et al. was able to model the olivines as phenocrysts, whose zoning was the result of a parent melt that changed in composition as material crystallized, e.g., fractional crystallization in a closed system, and calculated a parent melt composition. Jurewicz and McKay compared the calculated parent melt composition with actual partial melts from CV and CM chondrites. They showed that the calculated melt was substantially different from equilibrium melts of these chondrites; however, the LEW87051 groundmass composition was similar to some of the low temperature partial melts, although slightly enriched in AN (or depleted in OL) components. This study presents the results of an independent petrologic look at other olivines in LEW87051 and the preliminary results of a quantitative model for the major zoning in these olivines as diffusive-exchange with an olivine-saturated, low temperature angritic melt.

  7. A comparison of FeO-rich, porphyritic olivine chondrules in unequilibrated chondrites and experimental analogues

    NASA Technical Reports Server (NTRS)

    Jones, Rhian H.; Lofgren, Gary E.

    1993-01-01

    Experimentally produced analogues of porphyritic olivine (PO) chondrules in ordinary chondrites provide an important insight into chondrule formation processes. We have studied experimental samples with PO textures grown at three different cooling rates (2, 5 and 100 C/h), and samples that have been annealed at high temperatures (1000-1200 C) subsequent to cooling. These are compared with natural chondrules of similar composition and texture from the ordinary chondrites Semarkona (LL3.0) and ALH 81251 (LL3.3). Zoning properties of olivine grains indicate that the Semarkona chondrules cooled at comparable rates to the experiments. Zoning in olivine from chondrules in ALH 81251 is not consistent with cooling alone but indicates that the chondrules underwent an annealing process. Chromium loss from olivine is very rapid during annealing and calculated diffusion coefficients for Cr in olivine are very similar to those of Fe-Mg interdiffusion coefficients under the same conditions. Annealed experimental samples contain an aluminous, low-Ca pyroxene which forms by reaction of olivine and liquid. No similar reaction texture is observed in ALH 81251 chondrules, and this may be evidence that annealing of the natural samples took place at considerably lower temperatures than the experimental analogues. The study supports the model of chondrule formation in a cool nebula and metamorphism of partly equilibrated chondrites during reheating episodes on the chondrite parent bodies.

  8. Single-Crystal Elasticity of San Carlos Olivine in the Earth's Mantle

    NASA Astrophysics Data System (ADS)

    Mao, Z.; Lin, J. F.; Fan, D.; Yang, J.; Zhuravlev, K. K.; Tkachev, S. N.

    2014-12-01

    Olivine is the most abundant mineral in the Earth's upper mantle. Studies on the elasticity of olivine attracted extensive research interests in the past few decades and have provided important constraints on the composition and structure of the Earth's upper mantle. Of particular importance is the single-crystal elasticity of olivine which is essential for understanding the anisotropy structure of the upper mantle. However, previous experimental studies on the single-crystal elasticity of olivine are limited to high pressure and ambient temperature or high temperature and ambient pressure. Much of our current knowledge on the velocity and anisotropy structures of the upper mantle heavily relies on extrapolations of limited experimental results. Here, we have studied the single-crystal elasticity of San Carlos olivine, [(Mg0.9Fe0.1)2SiO4], up to 20 GPa and 900 K using Brillouin spectroscopy and X-ray diffraction in an externally-heated diamond anvil cell at GSECARS of the Advanced Photon Source, Argonne National Laboratory. The simultaneously high pressure-temperature experiments allow us to investigate the combined effect of pressure and temperature on the velocity and anisotropy of olivine. These results have been applied to model the velocity structure, Vp and Vs anisotropy, Vp/Vs ratio, and Poisson's ratio of the Earth's upper mantle. Comparing the modeling results with seismic observations allow us to have a more comprehensive understanding on the velocity and anisotropy structure of the Earth's upper mantle.

  9. Characterization and Petrologic Interpretation of Olivine-Rich Basalts at Gusev Crater, Mars

    NASA Technical Reports Server (NTRS)

    McSween, H. Y.; Wyatt, M. B.; Gellert, R.; Bell, J. F., III; Morris, R. V.; Herkenhoff, K. E.; Crumpler, L. S.; Milam, K. A.; Stockstill, K. R.; Tornabene, L. L.; Arvidson, R. E.; Bartlett, P.; Blaney, D.; Cabrol, N. A.; Christensen, P. R.; Clark, B. C.; Crisp, A.; DesMarais, D. J.; Economou, T.; Farmer, J. D.; Farrand, W.; Ghosh, A.; Golombek, M.; Gorevan, S.; Greeley, R.

    2006-01-01

    Rocks on the floor of Gusev crater are basalts of uniform composition and mineralogy. Olivine, the only mineral to have been identified or inferred from data by all instruments on the Spirit rover, is especially abundant in these rocks. These picritic basalts are similar in many respects to certain Martian meteorites (olivine-phyric shergottites). The olivine megacrysts in both have intermediate compositions, with modal abundances ranging up to 20-30%. Associated minerals in both include low-calcium and high-calcium pyroxenes, plagioclase of intermediate composition, iron-titanium-chromium oxides, and phosphate. These rocks also share minor element trends, reflected in their nickel-magnesium and chromium-magnesium ratios. Gusev basalts and shergottites appear to have formed from primitive magmas produced by melting an undepleted mantle at depth and erupted without significant fractionation. However, apparent differences between Gusev rocks and shergottites in their ages, plagioclase abundances, and volatile contents preclude direct correlation. Orbital determinations of global olivine distribution and compositions by thermal emission spectroscopy suggest that olivine-rich rocks may be widespread. Because weathering under acidic conditions preferentially attacks olivine and disguises such rocks beneath alteration rinds, picritic basalts formed from primitive magmas may even be a common component of the Martian crust formed during ancient and recent times.

  10. Geochemistry and origin of metal, olivine clasts, and matrix in the Dong Ujimqin Qi mesosiderite

    NASA Astrophysics Data System (ADS)

    Kong, Ping; Su, Wen; Li, Xianhua; Spettel, Bernhard; Palme, Herbert; Tao, Kejie

    2008-03-01

    The Dong Ujimqin Qi mesosiderite is the first recorded fall of a stony-iron meteorite in China. According to silicate textures and metal composition, this meteorite is classified as a member of subgroup IB. Instrumental neutron activation analyses (INAA) of metals show that the matrix metal has lower concentrations of Os, Ir, Re, and Pt, but higher concentrations of Ni and Au than the 7.5 cm metal nodule present in the meteorite. We attribute these compositional differences to fractional crystallization of molten metal. Studies of olivine clasts show that FeO contents are uniform in individual olivine crystals but are variable for different olivine clasts. Although concentrations of rare earth elements (REEs) change within olivine clasts, they all exhibit a vee-shaped pattern relative to CI chondrites. The relatively high concentrations of REEs in olivine and the shape of REE patterns require a liquid high in REEs and especially in light REEs. As such a liquid was absent from the region where basaltic and gabbroic clasts formed, mesosiderite olivine must have formed in a part of the differentiated asteroid that is different from the location where other mesosiderite silicate clasts formed.

  11. Characterization and petrologic interpretation of olivine-rich basalts at Gusev Crater, Mars

    USGS Publications Warehouse

    McSween, H.Y.; Wyatt, M.B.; Gellert, Ralf; Bell, J.F.; Morris, R.V.; Herkenhoff, K. E.; Crumpler, L.S.; Milam, K.A.; Stockstill, K.R.; Tornabene, L.L.; Arvidson, R. E.; Bartlett, P.; Blaney, D.; Cabrol, N.A.; Christensen, P.R.; Clark, B. C.; Crisp, J.A.; Des Marais, D.J.; Economou, T.; Farmer, J.D.; Farrand, W.; Ghosh, A.; Golombek, M.; Gorevan, S.; Greeley, R.; Hamilton, V.E.; Johnson, J. R.; Joliff, B.L.; Klingelhofer, G.; Knudson, A.T.; McLennan, S.; Ming, D.; Moersch, J.E.; Rieder, R.; Ruff, S.W.; Schrorder, C.; de Souza, P.A.; Squyres, S. W.; Wanke, H.; Wang, A.; Yen, A.; Zipfel, J.

    2006-01-01

    Rocks on the floor of Gusev crater are basalts of uniform composition and mineralogy. Olivine, the only mineral to have been identified or inferred from data by all instruments on the Spirit rover, is especially abundant in these rocks. These picritic basalts are similar in many respects to certain Martian meteorites (olivine-phyric shergottites). The olivine megacrysts in both have intermediate compositions, with modal abundances ranging up to 20-30%. Associated minerals in both include low-calcium and high-calcium pyroxenes, plagioclase of intermediate composition, iron-titanium-chromium oxides, and phosphate. These rocks also share minor element trends, reflected in their nickel-magnesium and chromium-magnesium ratios. Gusev basalts and shergottites appear to have formed from primitive magmas produced by melting an undepleted mantle at depth and erupted without significant fractionation. However, apparent differences between Gusev rocks and shergottites in their ages, plagioclase abundances, and volatile contents preclude direct correlation. Orbital determinations of global olivine distribution and compositions by thermal emission spectroscopy suggest that olivine-rich rocks may be widespread. Because weathering under acidic conditions preferentially attacks olivine and disguises such rocks beneath alteration rinds, picritic basalts formed from primitive magmas may even be a common component of the Martian crust formed during ancient and recent times. Copyright 2006 by the American Geophysical Union.

  12. Disclinations provide the missing mechanism for deforming olivine-rich rocks in the mantle.

    PubMed

    Cordier, Patrick; Demouchy, Sylvie; Beausir, Benot; Taupin, Vincent; Barou, Fabrice; Fressengeas, Claude

    2014-03-01

    Mantle flow involves large strains of polymineral aggregates. The strongly anisotropic plastic response of each individual grain in the aggregate results from the interactions between neighbouring grains and the continuity of material displacement across the grain boundaries. Orthorhombic olivine, which is the dominant mineral phase of the Earth's upper mantle, does not exhibit enough slip systems to accommodate a general deformation state by intracrystalline slip without inducing damage. Here we show that a more general description of the deformation process that includes the motion of rotational defects referred to as disclinations can solve the olivine deformation paradox. We use high-resolution electron backscattering diffraction (EBSD) maps of deformed olivine aggregates to resolve the disclinations. The disclinations are found to decorate grain boundaries in olivine samples deformed experimentally and in nature. We present a disclination-based model of a high-angle tilt boundary in olivine, which demonstrates that an applied shear induces grain-boundary migration through disclination motion. This new approach clarifies grain-boundary-mediated plasticity in polycrystalline aggregates. By providing the missing mechanism for describing plastic flow in olivine, this work will permit multiscale modelling of the rheology of the upper mantle, from the atomic scale to the scale of the flow. PMID:24572356

  13. Disclinations provide the missing mechanism for deforming olivine-rich rocks in the mantle

    NASA Astrophysics Data System (ADS)

    Cordier, Patrick; Demouchy, Sylvie; Beausir, Benot; Taupin, Vincent; Barou, Fabrice; Fressengeas, Claude

    2014-03-01

    Mantle flow involves large strains of polymineral aggregates. The strongly anisotropic plastic response of each individual grain in the aggregate results from the interactions between neighbouring grains and the continuity of material displacement across the grain boundaries. Orthorhombic olivine, which is the dominant mineral phase of the Earth's upper mantle, does not exhibit enough slip systems to accommodate a general deformation state by intracrystalline slip without inducing damage. Here we show that a more general description of the deformation process that includes the motion of rotational defects referred to as disclinations can solve the olivine deformation paradox. We use high-resolution electron backscattering diffraction (EBSD) maps of deformed olivine aggregates to resolve the disclinations. The disclinations are found to decorate grain boundaries in olivine samples deformed experimentally and in nature. We present a disclination-based model of a high-angle tilt boundary in olivine, which demonstrates that an applied shear induces grain-boundary migration through disclination motion. This new approach clarifies grain-boundary-mediated plasticity in polycrystalline aggregates. By providing the missing mechanism for describing plastic flow in olivine, this work will permit multiscale modelling of the rheology of the upper mantle, from the atomic scale to the scale of the flow.

  14. Olivine-rich rims surrounding chondrules in the Mokoia CV3 carbonaceous chondrite: Further evidence for parent-body processes

    NASA Astrophysics Data System (ADS)

    Tomeoka, Kazushige; Ohnishi, Ichiro

    2014-07-01

    Fine-grained rims surrounding chondrules and inclusions in the Mokoia CV3 carbonaceous chondrite can be divided into phyllosilicate-rich and olivine-rich types. We present a petrographic and electron microscopic study of the olivine-rich rims and their host objects (referred to as chondrules/olivine-rich rims). The olivine-rich rims consist mainly of Fe-rich olivine and very minor phyllosilicate (saponite). Their host chondrules contain minor saponite and phlogopite, which resulted from aqueous alteration of anhydrous silicates. Mineralogical and compositional characteristics of the chondrules/olivine-rich rims suggest that they experienced mild thermal metamorphic effects. The rims commonly contain veins of coarse-grained Fe-rich olivine, magnetite, and Fe-(Ni) sulfides. The chondrules show abundant evidence of alteration along their peripheries, and the alteration textures suggest a mechanism for rim formation by replacement of the chondrules. Initially, enstatite and opaque nodules preferentially reacted to form coarse, platy, Fe-rich olivine crystals, which were subsequently divided into finer grains. Forsterite was also replaced by Fe-rich olivine. As the alteration advanced, these Fe-rich olivines were disaggregated, mixed with simultaneously produced saponite, and formed rims. In contrast, the surrounding matrix shows no evidence of such alteration and metamorphism. These observations indicate that the chondrules/olivine-rich rims did not experience these secondary processes in their present setting. The results suggest that the chondrules/olivine-rich rims experienced extensive replacement reactions in an environment in which aqueous fluids existed but only in minor amounts. They have probably also undergone simultaneous and/or subsequent mild thermal metamorphism. We suggest that the chondrules/olivine-rich rims are actually clasts transported from a relatively dry region in the parent body that was different from the region where Mokoia was finally lithified.

  15. Diffusive Fractionation of Lithium Isotopes in Olivine Grain Boundaries

    NASA Astrophysics Data System (ADS)

    Homolova, V.; Watson, E. B.

    2012-12-01

    Diffusive fractionation of isotopes has been documented in silicate melts, aqueous fluids, and single crystals. In polycrystalline rocks, the meeting place of two grains, or grain boundaries, may also be a site of diffusive fractionation of isotopes. We have undertaken an experimental and modeling approach to investigate diffusive fractionation of lithium (Li) isotopes by grain boundary diffusion. The experimental procedure consists of packing a Ni metal capsule with predominantly ground San Carlos olivine and subjecting the capsule to 1100C and 1GPa for two days in a piston cylinder apparatus to create a nominally dry, 'dunite rock'. After this synthesis step, the capsule is sectioned and polished. One of the polished faces of the 'dunite rock' is then juxtaposed to a source material of spodumene and this diffusion couple is subject to the same experimental conditions as the synthesis step. Li abundances and isotopic profiles (ratios of count rates) were analyzed using LA-ICP-MS. Li concentrations linearly decrease away from the source from 550ppm to the average concentration of the starting olivine (2.5ppm). As a function of distance from the source, the 7Li/6Li ratio decreases to a minimum before increasing to the background ratio of the 'dunite rock'. The 7Li/6Li ratio minimum coincides with the lowest Li concentrations above average 'dunite rock' abundances. The initial decrease in the 7Li/6Li ratio is similar to that seen in other studies of diffusive fractionation of isotopes and is thought to be caused by the higher diffusivity (D) of the lighter isotope relative to the heavier isotope. The relationship between D and mass (m) is given by (D1/D2) =(m2/m1)^?, where ? is an empirical fractionation factor; 1 and 2 denote the lighter and heavier isotope, respectively. A fit to the Li isotopic data reveals an effective DLi of ~1.2x10^-12 m/s^2 and a ? of 0.1. Numerical modelling was utilized to elucidate the relationship between diffusive fractionation produced in the grain boundaries versus the lattices of the individual grains of the 'dunite rock'. The model assumes a linear grain boundary juxtaposed to the long side of a rectangular crystal lattice. During a simulation, the diffusant may directly enter the lattice or the grain boundary. Once in the grain boundary, the diffusant may then continue to diffuse away from the source until the end of the simulation or, alternatively, it may be incorporated into the lattice at some point during its travels down the grain boundary. The model system is similar to that considered by Whipple-LeClaire (1963) and our model results agree well with their analytical solution. Preliminary modeling results show that the distinctive minimum in the isotopic ratio is only produced when diffusive fractionation occurs in the grain boundary and not when the fractionation occurs only in the lattice. This suggests that the isotopic profile observed in the experiments may be a product of diffusive fractionation in grain boundaries. Implications of these results extend to the longevity of Li isotopic heterogeneities in the mantle, and suggest that the isotopes of other elements, which have a large relative mass difference, may also be diffusively fractionated by grain boundary diffusion.

  16. Abiotic Versus Biotic Weathering Of Olivine As Possible Biosignatures

    NASA Technical Reports Server (NTRS)

    Longazo, Teresa G.; Wentworth, Susan J.; Clemett, Simon J.; Southam, Gordon; McKay, David S.

    2001-01-01

    We are investigating the weathering of silicate minerals by both purely inorganic, and biologically mediated processes using field-emission scanning electron microscopy (FESEM) and energy dispersive x-ray spectroscopy (EDS). By resolving surface textures and chemical compositions of weathered surfaces at the sub-micron scale we hope to be able to distinguish abiotic from biotic weathering processes and so establish a new biosignature applicable to the study of astromaterials including but not limited to the Martian meteorites. Sterilized olivine grains (San Carlos, Arizona) no more than 1-2 mm in their longest dimension were optically assayed to be uniform in color and free of inclusions were selected as weathering subjects. Prior to all experiments surface morphologies and Fe/Mg ratios were determined for each grain using FE-SEM and EDS. Experiments were divided into two categories abiotic and biotic and were compared with "naturally" weathered samples. For the preliminary experiments, two trials (open and closed to the ambient laboratory environment) were performed under abiotic conditions, and three trials under biotic conditions (control, day 1 and day 2). The open system abiotic trials used sterile grains heated at 98 C and 200 C for both 24 and 48 hours in 1L double distilled de-ionized water. The closed system abiotic trials were conducted under the same conditions but in a sealed two layer steel/Teflon "bomb" apparatus. The biotic trials used sterile grains mounted in a flow-through device attached to a wellhead on the Columbia River aquifer. Several discolored, altered, grains were selected to document "natural" weathering surface textures for comparison with the experimental samples. Preliminary results indicate there are qualitative differences in weathered surface textures among all the designed experiments. The olivine grains in abiotic trials displayed etching, pitting, denticulate margins, dissolution and clay formation. The scale of the features ranged from tens to a few microns with textures that remained relatively sharp and were crystallographically controlled. These results were comparable to that observed in the "naturally" weathered comparison/reference grains. Chemical analysis by EDS indicates these textures correlated with the relative loss of Mg and Fe cations by diffusional processes. In contrast the biotic results indicated changes in the etching patterns on the scale of hundreds of nm, which are neither sharp nor crystallographically controlled (nanoetching). Organisms, organic debris and/or extracellular polymeric substances (biofilm) were often in close proximity or direct contact with the nanoetching. While there are many poorly constrained variables in natural weathering experiments to contend with, such as the time scale, the chemistry of the fluids and degree of biologic participation, some preliminary observations can be made: (1) certain distinct surface textures appear correlated with the specific processes giving rise to these textures; (2) the process of diffusing cations can produce many similar styles of surface textural changes; and (3) the main difference between abiotic and biotically produced weathering is the scale (microns versus nanometers) and the style (crystallographically versus noncrystallographically controlled) of the textural features. Further investigation into nanosize scale surface textures should attempt to quantify both textures and chemical changes of the role of microorganisms in the weathering of silicates. Additional experiments addressing nanoscale textures of shock features for comparison with the current data set.

  17. Laboratory measurements of the viscous anisotropy of olivine aggregates.

    PubMed

    Hansen, L N; Zimmerman, M E; Kohlstedt, D L

    2012-12-20

    A marked anisotropy in viscosity develops in Earth's mantle as deformation strongly aligns the crystallographic axes of the individual grains that comprise the rocks. On the basis of geodynamic simulations, processes significantly affected by viscous anisotropy include post-glacial rebound, foundering of lithosphere and melt production above subduction zones. However, an estimate of the magnitude of viscous anisotropy based on the results of deformation experiments on single crystals differs by three orders of magnitude from that obtained by grain-scale numerical models of deforming aggregates with strong crystallographic alignment. Complicating matters, recent experiments indicate that deformation of the uppermost mantle is dominated by dislocation-accommodated grain-boundary sliding, a mechanism not activated in experiments on single crystals and not included in numerical models. Here, using direct measurements of the viscous anisotropy of highly deformed polycrystalline olivine, we demonstrate a significant directional dependence of viscosity. Specifically, shear viscosities measured in high-strain torsion experiments are 15 times smaller than normal viscosities measured in subsequent tension tests performed parallel to the torsion axis. This anisotropy is approximately an order of magnitude larger than that predicted by grain-scale simulations. These results indicate that dislocation-accommodated grain-boundary sliding produces an appreciable anisotropy in rock viscosity. We propose that crystallographic alignment imparts viscous anisotropy because the rate of deformation is limited by the movement of dislocations through the interiors of the crystallographically aligned grains. The maximum degree of anisotropy is reached at geologically low shear strain (of about ten) such that deforming regions of the upper mantle will exhibit significant viscous anisotropy. PMID:23257885

  18. Calculations of Li Ion Diffusion in Olivine Phosphates

    SciTech Connect

    Dathar, Gopi Krishna Phani; Sheppard, Daniel; Stevenson, Keith J.; Henkelman, Graeme

    2011-09-13

    Kinetic pathways of Li-ion diffusion in olivine phosphates are calculated from density functional theory (DFT). Previously reported theoretical diffusion rates for Li ions and vacancies in defect-free crystalline FePO? and LiFePO? are six orders of magnitude faster than experimentally measured values. This discrepancy can be resolved by considering the different components of Li kinetics, including diffusion in the bulk, on the surface, in the presence of defects, and in varying local environments. Using DFT+U, we quantify each of these effects and determine that, while bulk diffusion is affected by strain and Li concentration, these are not significant enough to explain the slow diffusion observed in experiment. However, surface diffusion is observed to have have high barriers, which could contribute to slow kinetics in nanostructured cathodes. Anti-site defects also provide a possible explanation for slow diffusion, but only for vacancy diffusion in LiFePO?, which has a barrier of 0.71 eV, compared to 0.29 eV in defect-free channels. In FePO?, a concerted Li-ion diffusion mechanism around the anti-site defect is found to have a low barrier of 0.35 eV, allowing for facile cross-channel diffusion at room temperature. The difference between Li-ion and vacancy diffusion is understood in terms of a favorable coordination between Li ions and localized electrons on Fe centers at the transition states for Li-ion hopping in FePO?. Greater distances between vacancies and holes at the transition states for vacancy diffusion lead to higher diffusion barriers.

  19. Experimental Partitioning of Cr(3+) and Sc(3+) into Olivine: Mechanisms and Implications

    NASA Technical Reports Server (NTRS)

    Jones, John; Mackwell, S. J.

    2006-01-01

    Olivine (Mg, Fe)Si2O4 does not, by stoichiometry, accept cations such as Sc(3+) or Cr(3+). However, the partition coefficients of Sc and Cr between olivine and liquid are significant 0.2-1.0. We have measured Cr(3+) partition coefficients of near unity and have grown olivines with nearly 3 wt.% Sc2O3. Therefore, there must be a simple means of charge balancing 3+ ions in a crystal structure that was obviously not designed to receive other than 2+ ions on the olivine M sites. The simplest explanation is that two 3+ ions enter the olivine structure by displacing three 2+ ions and creating an M site vacancy. Even this explanation has difficulties. For minor elements in our experiments (1 wt.%) the odds of a minor element 3+ ion finding a second 3+ for charge balance are of the order of 100:1 against. Because of the reducing conditions of our experiments, Fe(3+) will not suffice; and Al(3+) is not in sufficient quantity in olivine for charge balance. Therefore, Cr or Sc must, in effect, charge balance itself. For true trace elements, the problem is compounded many times. For an ion at the 10 ppm level the chances of finding a second (for example) Sc ion is approx.10(exp 5):1 against. Of course, any other 3+ ion would suffice but comparisons between percent level doping experiments and trace level partitioning indicate that Henry s law is obeyed. This implies that the same substitution mechanism occurs at both the percent and tens of ppm levels. There are two simple solutions to this problem: (i) The electrical conductivity of olivine is such that charge balance need not be local. This requires substantial domains within the olivine crystal in electrical contact by migration of vacancies or electronic defects. (ii) The 3+ cation brings along its own charge-balancing ion because it existed as a dimer in the silicate liquid. Olivine is not a true insulator but is actually a p-type semiconductor. Even so, electrical communication by this means is unlikely over the tens or hundreds of unit cells that would be required for charge balance to be local. Therefore, we cautiously favor the idea that melt speciation is the means by which 3+ ions enter the olivine structure. Possibly this model might be tested by in situ XAFS measurements or by molecular dynamical calculations.

  20. Reaction rim growth on olivine in silicic melts: Implications for magma mixing

    USGS Publications Warehouse

    Coombs, M.L.; Gardner, J.E.

    2004-01-01

    Finely crystalline amphibole or pyroxene rims that form during reaction between silicic host melt and cognate olivine xenocrysts, newly introduced during magma mixing events, can provide information about the timing between mixing and volcanic eruptions. We investigated rim growth experimentally by placing forsteritic olivine in rhyolitic and rhyodacitic melts for times between 25 and 622 h at 50 and 150 MPa, H2O-saturated, at the Ni-NiO buffer. Rims of orthopyroxene microlites formed from high-silica rhyolite and rhyodacite melts at 885??C and 50 MPa, and in the rhyolite at 150 MPa and 885??C. Rims of amphibole with lesser orthopyroxene formed in the rhyolite at 150 MPa and 800??C and in the rhyodacite at 150 MPa and 885??C. Irregular, convolute olivine edges and mass balance between olivine, melt, and rim phases show that olivine partly dissolved at all conditions. Iron-rich zones at the exteriors of olivines, which increased in width parabolically with time, show that Fe-Mg interdiffusion occurring in olivines was not outpaced by olivine dissolution. Linear increases of the square of rim widths with time suggest that diffusion within the melt is the rate-controlling process for olivine dissolution and rim growth. Rims grew one-half to one order-of-magnitude faster when melt water contents were doubled, unless conditions were far above the liquidus. Rim growth rate in rhyolite increases from 0.055 ?? 0.01 ??m2/h at 885 ??C and 50 MPa to 0.64 ?? 0.13 ??m2/h at 800 ??C and 150 MPa. Melt composition has a lesser effect on rim growth rates, with growth rate increasing as melt SiO2 content decreases. Pyroxene rims on olivines in andesite erupted from Arenal volcano (Costa Rica) grew at a rate of 3.0 ?? 0.2 ??m2/h over an eleven-year period. This rate is faster than those of the experiments due to lower melt viscosity and higher temperatures, and suggests that a magma mixing event preceded the start of the eruption by days.

  1. CO2-induced small water solubility in olivine and implications for properties of the shallow mantle

    NASA Astrophysics Data System (ADS)

    Yang, Xiaozhi; Liu, Dingding; Xia, Qunke

    2014-10-01

    H2O and CO2 are important components of fluids in the mantle at ?30-150 km depth, and may affect strongly water dissolution in nominally anhydrous olivine; however, available experimental hydrogenation of olivine has been nearly exclusively carried out in coexistence with H2O (CO2-free). In this study, the effect of CO2 on water solubility in olivine has been investigated by H-annealing natural olivine under peridotite- and fluid-saturated conditions. Experiments were conducted at 1.5-5 GPa and 1100-1300 C, with oxygen fugacity controlled by Ni-NiO and with either H2O or H2O-CO2 as buffering fluid. The olivine shows no change in composition during the experiments. The infrared spectra of the hydrated olivine are characterized by prominent OH bands from ?3650 to 3000 cm in all the runs, at both high frequency (>3450 cm) and low frequency (<3450 cm), and the H2O solubility is ?120-370 ppm for the olivine in coexisting with H2O, and ?65-180 ppm for the olivine in coexisting with H2O-CO2. When CO2 is present in the buffering fluid, the H2O solubility of olivine is reduced by a factor of ?2, due to effect on the partitioning of water between minerals and coexisting fluid, and the measured H2O solubility shows independence on fluid composition (the molar ratio of CO2 to CO2 + H2O at ?0.2-0.5) given pressure, temperature and oxygen fugacity. Olivine equilibrated in the shallow mantle is probably dominated by OH groups in the wavenumber ?3650-3000 cm, and the intensity of OH bands at low frequency may be higher than or comparable to those at higher frequencies. The storage capacity of water in the shallow mantle in previous estimates may have been overestimated by a factor of at least ?4 if the observed effect of CO2 on water solubility is correct. Our results have profound influence on understanding partial melting, electrical conductivity anomalies and metasomatism in the shallow mantle.

  2. The legacy of crystal-plastic deformation in olivine: high-diffusivity pathways during serpentinization

    NASA Astrophysics Data System (ADS)

    Plmper, Oliver; King, Helen E.; Vollmer, Christian; Ramasse, Quentin; Jung, Haemyeong; Austrheim, Hkon

    2012-04-01

    Crystal-plastic olivine deformation to produce subgrain boundaries composed of edge dislocations is an inevitable consequence of asthenospheric mantle flow. Although crystal-plastic deformation and serpentinization are spatio-temporally decoupled, we identified compositional readjustments expressed on the micrometric level as a striped Fe-enriched ( bar{X}_{text{Fe}} = 0.24 0.02 (zones); 0.12 0.02 (bulk)) or Fe-depleted ( bar{X}_{text{Fe}} = 0.10 0.01 (zones); 0.13 0.01 (bulk)) zoning in partly serpentinized olivine grains from two upper mantle sections in Norway. Focused ion beam sample preparation combined with transmission electron microscopy (TEM) and aberration-corrected scanning TEM, enabling atomic-level resolved electron energy-loss spectroscopic line profiling, reveals that every zone is immediately associated with a subgrain boundary. We infer that the zonings are a result of the environmental Fe2+Mg-1 exchange potential during antigorite serpentinization of olivine and the drive toward element exchange equilibrium. This is facilitated by enhanced solid-state diffusion along subgrain boundaries in a system, which otherwise re-equilibrates via dissolution-reprecipitation. Fe enrichment or depletion is controlled by the silica activity imposed on the system by the local olivine/orthopyroxene mass ratio, temperature and the effect of magnetite stability. The Fe-Mg exchange coefficients K_{text{D}}^{{{text{Atg}}/{text{Ol}}}} between both types of zoning and antigorite display coalescence toward exchange equilibrium. With both types of zoning, Mn is enriched and Ni depleted compared with the unaffected bulk composition. Nanometer-sized, heterogeneously distributed antigorite precipitates along olivine subgrain boundaries suggest that water was able to ingress along them. Crystallographic orientation relationships gained via electron backscatter diffraction between olivine grain domains and different serpentine vein generations support the hypothesis that serpentinization was initiated along olivine subgrain boundaries.

  3. Single-Crystal Elasticity of San Carlos Olivine in the Earth's Mantle

    NASA Astrophysics Data System (ADS)

    Mao, Z.; Lin, J.; Fan, D.; Yang, J.; Zhuravlev, K. K.; Tkachev, S. N.

    2013-12-01

    Based on the pyrolitic compositional model, olivine is the most abundant mineral in the Earth's upper mantle. Experimental and theoretical studies on physical, chemical, and transport properties of olivine have attracted extensive research interests over last decades and have greatly contributed to our understanding on the structure and composition of the Earth's upper mantle. Single-crystal elasticity of olivine at relevant pressure-temperature conditions is of particular importance in constraining the composition, interpreting the observed anisotropy, and understanding the seismic tomography and heterogeneity of the region. However, single-crystal elasticity of olivine has never been investigated at simultaneous high pressure-temperature conditions of the upper mantle. Much of our current knowledge on the velocity structures of the upper-mantle minerals heavily relies on extrapolations of limited mineral physics results. In this study, we have studied single-crystal elasticity of San Carlos olivine [(Mg0.9Fe0.1)2SiO4] up to 16 GPa and 750 K using Brillouin spectroscopy and X-ray diffraction in an externally-heated diamond anvil cell. We have derived full elastic tensors of the olivine at high pressure-temperature conditions, providing crucial constraints on the combined effects of pressure and temperature on the single-crystal elasticity of olivine. These results have been applied to model the velocity structures and seismic Vp/Vs anisotropies of the Earth's upper mantle and olivne mantle wedge in the subduction are by combing with literature deformation results. Here we will present these results to address current outstanding issues in the geophysics, geochemistry, and seismology of the upper mantle.

  4. Experimental constraints on formation of hematite in olivine at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Zhang, Yanfei; Wang, Chao; Wu, Yao; Liu, Wenlong; Jin, Zhenmin

    2015-10-01

    Iron-rich oxides, such as magnetite or hematite, have been reported in olivine grains in many orogenic garnet peridotites from continental collision zones. Whether these iron-rich minerals originate from dry oxidation, dehydrogenation-oxidation or exsolution from a precursor wadsleyite phase is debatable. This paper explores high-pressure and high-temperature experiments in a hydrous harzburgite system, by taking advantage of electron backscattered diffraction (EBSD) analyses, to examine the formation of hematite in olivine. Experimental results show that hematite can be formed within olivine grains at pressures >6 GPa and temperatures in the 1073-1473 K range. EBSD analysis suggests that hematite rods (not associated with clinopyroxene) and host olivine have the following crystallographic relations: < 0001 rangle _{{Hem}} // [100]_{{Ol}} , < 10{-}10rangle _{{Hem}} //[001]_{{Ol}} , < 11{-}20rangle _{{Hem}} //[010]_{{Ol}} , which are consistent with those observed in natural garnet peridotite from the Dabie-Sulu ultra-high-pressure (UHP) metamorphic terrane. It is postulated that both hydroxide (OH-) and hydrogen (H+) ions have the potential to oxidize Fe2+ to Fe3+, followed by rapid dehydrogenation and slow Fe diffusion, thus forming hematite within the olivine grains. It is proposed that dehydrogenation-oxidation is the most likely formation mechanism of hematite inclusions within olivine, with the following two requirements: an ample amount of H2O and specific P- T conditions (>6 GPa, at 1073 K). Such conditions are consistent with those calculated in natural garnet peridotites from the Dabie-Sulu UHP metamorphic terranes. The present study also indicates that hematite (or magnetite?) inclusions in olivine contain important clues about the tectonic evolution of UHP rocks in continental crust collision zones.

  5. Temperature Dependence and Recoil-free Fraction Effects in Olivines Across the Mg-Fe Solid Solution

    NASA Technical Reports Server (NTRS)

    Sklute, E. C.; Rothstein, Y.; Dyar, M. D.; Schaefer, M. W.; Menzies, O. N.; Bland, P. A.; Berry, F. J.

    2005-01-01

    Olivine and pyroxene are the major ferromagnesian minerals in most meteorite types and in mafic igneous rocks that are dominant at the surface of the Earth. It is probable that they are the major mineralogical components at the surface of any planetary body that has undergone differentiation processes. In situ mineralogical studies of the rocks and soils on Mars suggest that olivine is a widespread mineral on that planet s surface (particularly at the Gusev site) and that it has been relatively unaffected by alteration. Thus an understanding of the characteristics of Mossbauer spectra of olivine is of great importance in interpreting MER results. However, variable temperature Mossbauer spectra of olivine, which are needed to quantify recoil-free fraction effects and to understand the temperature dependence of olivine spectra, are lacking in the literature. Thus, we present here a study of the temperature dependence and recoil-free fraction of a series of synthetic olivines.

  6. Modal mineralogy of the surface of Vesta: Evidence for ubiquitous olivine and identification of meteorite analogue

    NASA Astrophysics Data System (ADS)

    Poulet, F.; Ruesch, O.; Langevin, Y.; Hiesinger, H.

    2015-06-01

    The observations of the surface of 4 Vesta by the Visible and Infrared Mapping Spectrometer (VIR) onboard the Dawn spacecraft reveals that its composition is dominated by pyroxenes with olivine in very localized spots. To derive new constraints on the surface composition of the asteroid, we apply a scattering model to VIR reflectance spectra. The model is first calibrated by performing a non-linear deconvolution of laboratory spectra of mineral mixtures and howardite, eucrite, diogenite (HED) meteorites. Abundance estimates of minerals are accurate to within 15-25% for the analyzed samples, while the estimated particle sizes are within the intervals of actual sizes. Grain size effects complicate spectral deconvolution and estimation of modal abundances of samples (both HED and mineral mixtures) that contain olivine. The magnesium-rich olivine detection threshold is 10-20% for large grain sizes (100s ?m) and several 10s% for small grain sizes (<50 ?m). Major expected minerals (low-calcium pyroxenes, high-calcium pyroxenes, plagioclase and olivine) can provide satisfactory fits of VIR spectra with excellent residuals ?1%. Terrains with the strongest low-calcium pyroxene signatures are well representative of diogenites. The best fits of any unit are obtained by including Fo70 olivine at an abundance level of 10-20%, with an uncertainty of ?10%. Olivine is therefore likely to be ubiquitous over the whole surface of Vesta. Olivine is coarser grained (a few hundred ?m) than other minerals such as orthopyroxene and clinopyroxene (grain sizes typically smaller than 100 ?m). Both the grain size variance and the modal mineralogy are consistent with the lithologic size and mineral distributions of howardites containing olivine phenocryst-bearing melt. These howardites are the best petrologic analogues of Vesta. Such a surface assemblage could be the result of successive melting and mixing processes due to impacts. The compositional view confirms that Vesta underwent major homogenization processes, resulting in a relatively uniform modal mineralogy and explaining the lack of specific olivine enrichment in the Rheasilvia ejecta.

  7. Space Weathering in Olivine and the Mineralogy of (Some) M-Class Asteroids

    NASA Astrophysics Data System (ADS)

    Britt, Daniel; Kohout, Tomas; Schelling, Patrick; Consolmagno, Guy J.

    2014-11-01

    One aspect of space weathering of airless bodies is the production of nanophase iron (npFe0) from Fe bearing silicate minerals. The combined effects of low oxygen fugacity and solar-wind implanted H tend to result in strongly-reduced surfaces that can be chemically activated by heating due to micrometeorite impacts. The mineral kinetics of olivine makes it particularly vulnerable to reduction, decomposition, and npFe0 production. Kohout et al. has recently developed a new method of controlled npFe0 production on olivine powder grains that mimics the essential features of this weathering process and was developed to quantitatively evaluate spectral changes related to space weathering and presence of npFe0. Compared to fresh olivine the treated samples exhibit spectral characteristics of space weathering including spectral darkening, shallowing and attenuation of 1 m olivine absorption band, and reddening. The attenuation of the 1 m band significantly shrinks the band FWHM and shifts the much reduced band center to shorter wavelengths around 0.95 m. These spectral changes are related to increasing amounts of npFe0 and the disruption of the crystal structure of the parent olivine. Significantly, the darkened, reddened, and band attenuated olivine spectra are a close match to a number of M-class asteroids. What is particularly interesting is the match with the weak absorption band near 0.95 m seen in many M-class asteroids (i.e. 16 Psyche, 22 Kalliope, 55 Pandora to name a few). One of the major issues in asteroid science is the relative scarcity of olivine asteroids (the Great Dunite Shortage coined by Bell et al in Asteroids II). One possibility worth further study is that asteroidal olivine may be hidden by the relative ease with which it weathers. The surface chemical and micrometeorite environment in the asteroid belt may produce over time a spectrum for an olivine-rich surface that is remarkably similar to that of an M-class asteroid.

  8. Sulfide mineralization in magmas: Investigating the effect of re-equilibrating olivine xenocrysts

    NASA Astrophysics Data System (ADS)

    Currier, R. M.; Marsh, B. D.

    2011-12-01

    Large amounts of entrained olivine xenocrysts are common features of many mafic magmas. It is only natural that mantle derived melts mechanically destabilize and incorporate disaggregated wall rock material during ascension and transport. Bowen noticed this in 1928 and many subsequent studies at, for example, Kilauea have noted an abundance of these 'Tramp Crystals' in proportion to the eruptive flux. These olivines are distinguished by their high, nonequilibrium magnesium contents (Fo:88-92), and, due to the very fast interdiffusion rates of iron and magnesium in olivine (~10-7-10-9 mm2/s), these crystals are often rimmed in iron-rich olivine, or, if given enough time, become completely re-equilibrated with the surrounding melt. Because this exchange occurs in a finite volume of liquid, the composition of the liquid during xenocryst re-equilibration may be strongly affected and driven from its normal course of evolution. The magnitude of this change is clearly a function of the relative amount of xenocrysts and the compositional difference between liquid and crystals. Because mantle olivine is always more forsteritic than the equilibrium olivine composition of the liquid, re-equilibration of olivine increases the magnesium content and decreases the iron content of the liquid. A possible outcome is a decrease in the saturation point of sulfide. The saturation point of sulfide in magmas is sensitive to the concentration of iron. This is a fundamentally important consideration, given the fact that the PGE content of sulfides reflects the cumulative amount of magma the sulfide "sees," and higher temperature saturation greatly increases the odds of sulfide existence and longevity. Presented is a model predicting sulfide saturation with varying loads of xenocrystic olivine within a solidifying body. Even at high temperatures, reasonable fractions of xenocrysts can lower the sulfide saturation concentration over 200 ppm. The model is then compared to a world-class sulfide ore body that is loaded with olivine crystals-the Jinchuan ore body, China, and provides a reasonable, alternative explanation for sulfide formation and deposition.

  9. Impact of geoengineering with olivine dissolution on the carbon cycle and marine biology

    NASA Astrophysics Data System (ADS)

    Köhler, P.; Abrams, J.; Völker, C.; Wolf-Gladrow, D. A.; Hartmann, J.

    2012-04-01

    We investigate the potential of a specific geoengineering technique: the carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification. If details of the marine chemistry are taken into consideration, a new mass ratio of CO2 sequestration per olivine dissolution of about 1 is achieved, 20% smaller than previously assumed. We calculate that this approach has the potential to sequestrate up to 1 Pg of C per year directly, if olivine is distributed as fine powder over land areas of the humid tropics, but this rate is limited by the saturation concentration of silicic acid. These upper limit sequestration rates come at the environmental cost of pH values in the rivers rising to 8.2 in examples for the rivers Amazon and Congo (Köhler et al., 2010). The secondary effects of the input of silicic acid connected with this approach leads in an ecosystem model (ReCOM2.0 in MITgcm) to species shifts aways from the calcifying species towards diatoms, thus altering the biological carbon pumps. Open ocean dissolution of olivine would sequestrate about 1 Pg CO2 per Pg olivine from which about 8% are caused by changes in the biological pumps (increase export of organic matter, decreased export of CaCO3). The chemical impact of open ocean dissolution of olivine (the increased alkalinity input) is therefore less efficient than dissolution on land, but leads due to different chemical impacts to a higher surface ocean pH enhancement to counteract ocean acidification. We finally investigate open ocean dissolution rates of up to 10 Pg olivine per year corresponding to geoengineering rates which might be of interest in the light of expected future emission (e.g. A2 scenario with emissions rising to 30 PgC/yr in 2100 AD). Those rates would still sequestrate only less than 20% of the emission until 2100, but would require that the nowadays available shipping capacity of tankers and bulk carriers is entirely used for olivine dissolution ten times a year. Reference Köhler, P.; Hartmann, J. and Wolf-Gladrow, D. A. (2010) Geoengineering potential of artificially enhanced silicate weathering of olivine, Proceedings of the National Academy of Science 107, 20228-20233, doi: 10.1073/pnas.1000545107.

  10. Dislocation Microstructures in Deformed Olivine Displaying the C-type and B-type Fabrics

    NASA Astrophysics Data System (ADS)

    Sharp, T. G.; Jung, H.; Fitz Gerald, J.; Karato, S.

    2003-12-01

    Because seismic anisotropy in the upper mantle is commonly a result of lattice preferred orientations (LPOs) of minerals as a result of mantle flow, seismic anisotropy is used to probe fabrics and therefore flow directions in the mantle. Jung and Karato, (2001) have shown that the fabrics developed in experimentally deformed olivine are dependent on H2O fugacity and stress, suggesting that olivine fabric in the upper mantle can provide a means of probing H2O content and stress. Olivine fabrics, known as B-type and C-type, occur in olivine deformed under high H2O fugacity and high stress. In order to extrapolate these experimental deformation fabrics to the mantle, one must understand how H2O changes the mechanisms of plastic deformation in olivine. Experimentally deformed olivine samples with C-type and B-type fabrics have been examined by TEM to determine dislocation microstructures, core structures and active slip systems. In the C-type sample, we examined a relatively large olivine grain with its b axis normal to the TEM foil and the a and b axes approximately 45 from the slip direction. Tilt boundaries along (100) and (001), consisting of edge dislocations with b = [100] and b = [001], respectively, indicate that the dominant slip systems are (001)[100] and (100)[001]. HRTEM imaging of the b = [100] and b = [001] edge dislocations along [010] shows no dissociation for b = [100], whereas the b = [001] dislocations are dissociated into 1/2[-101] and 1/2 [101] partial dislocations separated by 3 nm along the (-101) plane. The C-type fabric, which occurs in wet olivine deformed at low stress, results from the domination of the (100)[001] slip system over the (010)[100] slip system that produces the A-type fabric. Based on the abundance of b = [001] edge dislocations, we infer that the presence of hydrogen in olivine reduces Peierls stresses for glide of b = [001] screw dislocations in (100). The more complicated microstructures in the B-type sample will be presented at the meeting.

  11. Atomic-scale simulation of space weathering in olivine and orthopyroxene

    NASA Astrophysics Data System (ADS)

    Quadery, Abrar H.; Pacheco, Shaun; Au, Alan; Rizzacasa, Natalie; Nichols, Joshua; Le, Timothy; Glasscock, Cameron; Schelling, Patrick K.

    2015-04-01

    Classical molecular dynamics was used to study the annealing of anion and cation Frenkel defects in olivine and orthopyroxene minerals. While it was found that for both minerals, reorganization of the Si-O bonds, often accompanied by large Si displacements, occurs to maintain the fourfold coordination of the SiO4 tetrahedra, important differences are observed in their annealing behavior. Specifically, cation defects are substantially more mobile in olivine than in orthopyroxene leading to rapid annihilation of cation Frenkel defects and formation of extended defects in olivine. By contrast, the diffusion rate of anion defects in orthopyroxene is much higher than that in olivine and also exhibits large anisotropy. Consequently, it was found that diffusion in orthopyroxene occurs without significant annihilation of anion Frenkel defects or trapping of anion interstitials or vacancies into clusters. The results obtained here are discussed in the context of space weathering of olivine and orthopyroxene. Specifically, two important observations are made which may explain previous experimental results. First, ion irradiation experiments that show reduced tolerance for radiation damage in orthopyroxene may be explained by the rapid, one-dimensional anion mobility which prevents healing of the lattice. Second, laser heating experiments which show that orthopyroxene has enhanced tolerance to reduction and the evolution of nanophase Fe inclusions could be due to the observed rapid anion diffusion in orthopyroxene, which might allow the bulk to act as a reservoir for the surface.

  12. Olivine in terminal particles of Stardust aerogel tracks and analogous grains in chondrite matrix

    NASA Astrophysics Data System (ADS)

    Frank, David R.; Zolensky, Michael E.; Le, Loan

    2014-10-01

    The dearth of both major and minor element analyses of anhydrous silicate phases in chondrite matrix has thus far hindered their comparison to the Wild 2 samples. We present 68 analyses of olivine (Fa0-97) in the coarse-grained terminal particles of Stardust aerogel tracks and a comprehensive dataset (>103 analyses) of analogous olivine grains (5-30 ?m) isolated in CI, CM, CR, CH, CO, CV3-oxidized, CV3-reduced, C3-ungrouped (Acfer 094 and Ningqiang), L/LL 3.0-4, EH3, and Kakangari chondrite matrix. These compositions reveal that Wild 2 likely accreted a diverse assortment of material that was radially transported from various carbonaceous and ordinary chondrite-forming regions. The Wild 2 olivine includes amoeboid olivine aggregates (AOAs), refractory forsterite, type I and type II chondrule fragments and/or microchondrules, and rare relict grain compositions. In addition, we have identified one terminal particle that has no known compositional analog in the meteorite record and may be a signature of low-temperature, aqueous processing in the Kuiper Belt. The generally low Cr content of FeO-rich olivine in the Stardust samples indicates that they underwent mild thermal metamorphism, akin to a petrologic grade of 3.05-3.15.

  13. Shock-Induced Transformation Exsolution Lamellae in Olivine in Black Veins of the Mbale Meteorite

    NASA Astrophysics Data System (ADS)

    Chen, M.; Wopenka, B.; El Goresy, A.

    1995-09-01

    Mbale is a shocked L6 chondrite [1]. Some shock-induced veins of 0.1 to 2 mm width intersect the meteorite. The veins consist of diaplectic plagioclase glass, unmelted silicate fragments including olivines and pyroxenes, and the shock-induced melt materials consisting of metal-troilite intergrowths, microcrystalline pyroxene and olivine, and silicate glass. Here we report the first finding of shock-induced exsolutions in olivine that appear as compositionally different lamellae which presumably formed at high pressure by inversion of olivine (alpha) to the beta+gamma polymorphs. Olivine compositions in the chondritic part of Mbale range from Fa(sub)22.5 to Fa(sub)26 (average Fa(sub)24). In contrast, the exsolved olivines in the shock-induced veins (30 to 100 mm in diameter) consist of alternating Fe-rich (Fa(sub)22-32) and Fe-poor (Fa(sub)9.9-18.5) lamellae that range in width from less than 0.5 micrometers to up to 10 micrometers. Each individual lamella actually consists of microcrystals of less than 0.5 micrometers in diameter with rather diffuse borders within the lamella. The lamellae occur in ~30 micrometer segments which were formed by faulting and displacement. Micro-Raman spectroscopy confirms that both types of exsolution lamellae currently have the olivine (alpha) structure. The partially melted veins of Mbale may have reached a post-shock peak temperature of 1473 K >= T <= 1873 K. Based on the phase diagrams of the olivine(alpha)-wadsleyite(beta)-ringwoodite(gamma) transformations in the system Mg(sub)2SiO(sub)4-Fe(sub)2SiO(sub)4 at 1473 K [2], olivine of composition ~Fa(sub)24 should exsolve at equilibrium conditionsins to beta- + gamma-phases at P >12.7 GPa, and transform to a single gamma-phase at >15 GPa. Figure 1 shows that the determined compositions of the Fe-rich and Fe-poor lamellae in Mbale match perfectly the compositions at the beta + gamma/gamma and the beta + gamma/beta phase boundaries, respectively. Since these grains depict well ordered lamellar structure displaced by several faults, the exsolution lamellae of olivine must have nucleated before faulting. TEM studies of ringwoodite in black veins in other shocked chondrites indicate that the original olivine has transformed into a mosaic of ringwoodite grains in nano-meter size range [3,4]. The observed lamellar structure in Mbale olivines is indicative of exsolution transformation from single grains before faulting of the olivines and definitely before solidification of the silicate melt to glass in the vein. We therefore consider it unlikely that the shock-induced olivine lamellae were produced via retrograde exsolution from gamma to gamma + beta. Our findings strongly suggest that the exsolutions were produced from an originally homogeneous olivine (alpha) by the following mechanism: Original homogenous olivine exsolved at P>12.7 GPa and 1473 K >=T <= 1873 K into Fe-poor beta- and Fe-rich gamma-phases possibly along [001] which is the predominant dislocation orientation in olivine during deformation [4,5]. The dislocations in olivine may have provided the nucleation sites for the beta- and gamma-phases due to their reduced activation barrier to nucleation. The grains were then faulted to several segments of 30 micrometers in diameter. A cooling rate of >= 260 K/s during the solidification of the shock-induced melt was estimated in the interval of 1223-1673 K, based on the metallic dendrite arm spacing or cell width of ~14 micrometers [6]. The cooling of the veins after the solidification of metal and silicate melts should have been much slower than 260 K/s because of the homogeneous Ni-concentration within the metallic dendrites. We interpret the survival of the lamellar structure as due to a nonlinear cooling rate: (1) very fast cooling after pressure release thus inhibiting obliteration of the lamellae by diffusion; followed by (2) slow cooling <1223 K thus leading to inversion of gamma and beta lamellae to alpha without chemical homogenization. References: [1] Jenniskens P. et al. (1994) Meteoritics , 29, 246-254. [2] Akaogi M. et al. (1989) JGR, 94, 15671-15685. [3] Madon M. and Poirier J. P. (1983) Phys. Earth Planet. Inter., 33, 31-44. [4] Price G. D. et al. (1979) Contrib. Mineral. Petrol., 71, 211-218. [5] Ashworth J. R. and Barber D. J. (1975) EPSL, 13, 43-50. [6] Scott E. R. D. (1982) GCA, 46, 813-823. Fig.1. Olivine (alpha)- wadsleyite (beta)- ringwoodite (gamma) relations in the system Mg(sub)2SiO(sub)4-Fe(sub)2SiO(sub)4 at 1473 K (after Akaogi et al. [2]). The compositions of the Fe-poor and Fe-rich lamellae of a representative olivine grain are plotted as open circles. Note that in all cases the compositions of the lamellae plot exactly at the the beta + gamma/beta and beta + gamma/gamma phase boundaries.

  14. Shock-induced fine-grained recrystallization of olivine - Evidence against subsolidus reduction of Fe/2+/

    NASA Technical Reports Server (NTRS)

    Ahrens, T. J.; Tsay, F.-D.; Live, D. H.

    1976-01-01

    Electron spin resonance (ESR) studies have been carried out on three single grains of terrestrial olivine (Fo90) shock loaded along the 010 line to peak pressures of 280, 330, and 440 kbar. The results indicate that neither metallic Fe similar to that observed in returned lunar soils nor paramagnetic Fe(3+) caused by oxidation of Fe(2+) has been produced in these shock experiments. Trace amounts of Mn (2+) have been detected in both shocked and unshocked olivine. The ESR signals of Mn(2+) show spectral features which are found to correlate with the degree of shock-induced recrystallization observed petrographically. The increasing mass fraction of recrystallized olivine correlates with increasing shock pressures. This phenomenon is modelled assuming it results from the progressive effect of the shock-induced transformation of the olivine to a yet unknown high-pressure phase and its subsequent reversion to the low-pressure olivine phase. The mass fraction of recrystallized material is predicted to be nearly linear with shock pressure.

  15. Low-temperature plasticity of olivine revisited with in situ TEM nanomechanical testing

    PubMed Central

    Idrissi, Hosni; Bollinger, Caroline; Boioli, Francesca; Schryvers, Dominique; Cordier, Patrick

    2016-01-01

    The rheology of the lithospheric mantle is fundamental to understanding how mantle convection couples with plate tectonics. However, olivine rheology at lithospheric conditions is still poorly understood because experiments are difficult in this temperature range where rocks and mineral become very brittle. We combine techniques of quantitative in situ tensile testing in a transmission electron microscope and numerical modeling of dislocation dynamics to constrain the low-temperature rheology of olivine. We find that the intrinsic ductility of olivine at low temperature is significantly lower than previously reported values, which were obtained under strain-hardened conditions. Using this method, we can anchor rheological laws determined at higher temperature and can provide a better constraint on intermediate temperatures relevant for the lithosphere. More generally, we demonstrate the possibility of characterizing the mechanical properties of specimens, which can be available in the form of submillimeter-sized particles only. PMID:26998522

  16. Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, D. W.; Rumble, D., III

    2006-01-01

    Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.

  17. Near-infrared spectral reflectance of mineral mixtures - Systematic combinations of pyroxenes, olivine, and iron oxides

    NASA Technical Reports Server (NTRS)

    Singer, R. B.

    1981-01-01

    Near-infrared spectral reflectance data are presented for systematic variations in weight percent of two component mixtures of ferromagnesium and iron oxide minerals used to study the dark materials on Mars. Olivine spectral features are greatly reduced in contrast by admixture of other phases but remain distinctive even for low olivine contents. Clinopyroxene and orthopyroxene mixtures show resolved pyroxene absorptions near 2 microns. Limonite greatly modifies pyroxene and olivine reflectance, but does not fully eliminate distinctive spectral characteristics. Using only spectral data in the 1 micron region, it is difficult to differentiate orthopyroxene and limonite in a mixture. All composite mineral absorptions were either weaker than or intermediate in strength to the end-member absorptions and have bandwidths greater than or equal to those for the end members. In general, spectral properties in an intimate mixture combine in a complex, nonadditive manner, with features demonstrating a regular but usually nonlinear variation as a function of end-member phase proportions.

  18. High pressure and temperature fabric transitions in olivine and variations in upper mantle seismic anisotropy

    NASA Astrophysics Data System (ADS)

    Ohuchi, T.; Kawazoe, T.; Nishihara, Y.; Nishiyama, N.; Irifune, T.

    2010-12-01

    Crystallographic preferred orientation (CPO) of olivine, which is developed by dislocation creep, controls the seismic anisotropy in the upper mantle. Strong seismic anisotropy observed in the oceanic lithosphere decreases monotonically with depth, and it rapidly decreases below 200 km depth (e.g., Montagner and Kennett, 1996; Montagner, 1998). The low seismic anisotropy in the deep upper mantle has been attributed to the transition from dislocation to diffusion creep (Karato, 1998) or the development of an olivine CPO with low seismic anisotropy (Courvy et al., 2004; Mainprice et al., 2005). It has recently been reported that the easiest slip system in olivine changes depending on pressure (Raterron et al., 2007; 2009), suggesting a pressure-induced transition of CPO type in olivine. However, the effect of pressure on the CPO patterns of olivine has been controversial: Simple-shear deformation experiments on olivine aggregates at 11 GPa and 1673 K using stress-relaxation techniques show that C-type fabric (developed by the (100)[001] slip system) can be developed in the deep upper mantle (Courvy et al., 2004). However, their experiments were conducted under wet conditions (289-2248 ppm H/Si of water in olivine), and some authors pointed out that the development of C-type fabric is due to the water effect (e.g., Jung et al., 2009). More recently, a series of simple-shear deformation experiments reported a pressure-induced fabric transition in olivine from A-type (developed by the (010)[100] slip system) to B-type (developed by the (010)[001] slip system) at 3 GPa under dry conditions (e.g., Jung et al., 2009), while deformation experiments on orientated single crystals of olivine showed a change of the dominant slip direction from b = [100] to [001] at higher pressures (5-7 GPa) under dry conditions (Raterron et al., 2007; 2009). Therefore, further extensive studies are needed to clarify the effects of pressure and temperature on the CPO of olivine under the upper mantle conditions. We have conducted simple-shear deformation experiments on olivine aggregates at pressures P = 2.1-7.6 GPa, temperatures T = 1493-1673 K, and shear strain rates of 1.5-7.510-5 s-1 under dry conditions using a deformation-DIA apparatus with the MA-6-6 system (Nishiyama et al., 2008). We found that the rapid decrease in seismic anisotropy is caused by the fabric transition from A-type to B-type-like fabric at 7.6 GPa. Temperature dependencies of the CPO patterns of B-type-like fabrics developed at 7.6 GPa were also observed. The fabric transition occurring at 7.6 GPa result in low seismic anisotropy at greater depths, consistent with seismological observations. Thus, the variations of CPO with pressure and temperature in olivine under dry conditions can explain the seismic anisotropy signatures observed in the upper mantle, without invoking other mechanisms.

  19. Thermal histories of CO3 chondrites - Application of olivine diffusion modelling to parent body metamorphism

    NASA Technical Reports Server (NTRS)

    Jones, Rhian H.; Rubie, David C.

    1991-01-01

    The petrologic sequence observed in the CO3 chondrite group has been suggested to be the result of thermal metamorphism on a parent body. A model developed to examine the possibility that chondrule and matrix olivines equilibrated in situ, during parent body metamorphism is presented. The model considers Fe-Mg interdiffusion between chondrule and matrix olivines. Zoning profiles comparable to those observed in chondrule olivines from partially equilibrated members of the series are reproduced successfully. Metamorphism of CO3 chondrites on a parent body is therefore a viable model for the observed equilibration. Results indicate that peak metamorphic temperatures experienced by the CO3 chondrites were around 500 C, and that the range of peak temperatures between unequilibrated and equilibrated subtypes was relatively narrow, around 100 C.

  20. Chemical zoning and diffusion of Ca, Al, Mn, and Cr in olivine of springwater pallasite

    NASA Technical Reports Server (NTRS)

    Zhou, Y.; Steele, Ian M.

    1993-01-01

    The pallasites, consisting mainly of Fe-Ni metal and olivine, are thought to represent the interior of a planetary body which slowly cooled from high temperature. Although the olivines are nearly homogeneous, ion microprobe studies revealed variations of Ca, Ti, Co, Cr, and Ni near grain edges. These variations were thought to represent diffusion in response to falling temperature of the parent body. Pallasite cooling rates have been estimated based on kamacite taenite textures but results differ by x100. In principle elemental profiles in olivine can allow estimates of cooling rate if diffusion coefficients are known; in addition, given a cooling rate, diffusion coefficients could be derived. Data are presented which show that apparent diffusion profiles can be measured for Al, Ca, Cr, and Mn which qualitatively agree with expected diffusion rates and have the potential of providing independent estimates of pallasite cooling rates.

  1. The influence of bulk composition and dynamic melting conditions on olivine chondrule textures

    NASA Technical Reports Server (NTRS)

    Connolly, Harold C., Jr.; Hewins, Roger H.

    1991-01-01

    The effects of the bulk composition and the dynamic melting conditions on the texture of olivine chondrules were investigated in a series of heating experiments. It is shown that variations in the olivine chondrule textures can be produced by varying the FeO/(FeO + MgO) ratio between the average Type IA and Type II chondrule compositions, could affect the texture of a chondrule at a constant initial melting temperature and heating time. A range of the heating times and the masses of precursor spheres caused variations in the degree of melting and in chondrule textures. Chondrule textures were distributed on a graph of initial temperatures vs. FeO/(FeO + MgO) ratios as bands parallel to the olivine disappearance curve. This graph could be used to predict chondrule textures from Fe/(FeO + MgO) ratios at specific initial melting temperatures.

  2. Low-temperature plasticity of olivine revisited with in situ TEM nanomechanical testing.

    PubMed

    Idrissi, Hosni; Bollinger, Caroline; Boioli, Francesca; Schryvers, Dominique; Cordier, Patrick

    2016-03-01

    The rheology of the lithospheric mantle is fundamental to understanding how mantle convection couples with plate tectonics. However, olivine rheology at lithospheric conditions is still poorly understood because experiments are difficult in this temperature range where rocks and mineral become very brittle. We combine techniques of quantitative in situ tensile testing in a transmission electron microscope and numerical modeling of dislocation dynamics to constrain the low-temperature rheology of olivine. We find that the intrinsic ductility of olivine at low temperature is significantly lower than previously reported values, which were obtained under strain-hardened conditions. Using this method, we can anchor rheological laws determined at higher temperature and can provide a better constraint on intermediate temperatures relevant for the lithosphere. More generally, we demonstrate the possibility of characterizing the mechanical properties of specimens, which can be available in the form of submillimeter-sized particles only. PMID:26998522

  3. Preferred Orientation Evolution of Olivine Grains as an Indicator of Change in the Deformation Mechanism

    NASA Astrophysics Data System (ADS)

    Lychagin, D. V.; Tishin, P. A.; Kulkov, A. S.; Chernyshov, A. I.; Alfyorova, E. A.

    2015-09-01

    The paper presents the results of investigations of deformed natural polycrystalline olivine. The relationship of the structure of polycrystalline olivine grains to three modal size distributions has been revealed. Grains of different size were observed to be strained at threshold temperatures of 950, 775, and 650°C. It has been demonstrated that the microstructure develops as the dislocation mechanism changes from diffusion creep to grain boundary sliding. The changes in deformation mechanisms promote the change in the preferred crystallographic orientations of olivine from type A to type D and then to type B. The relation of the transitions between different types of orientations to the conditions of deformation in the lower layers of the lithosphere at the plate boundaries is discussed.

  4. Laboratory spectra of amorphous and crystalline olivine: An application to comet Halley IR spectrum

    SciTech Connect

    Blanco, A.; Orofino, V. . Ist. di Fisica); Bussoletti, E.; Fonti, S. ); Colangeli, L. . Facolta' di Ingegneria); Stephens, J.R. )

    1990-01-01

    Among the various silicates proposed as components of cosmic dust grains, olivine is considered one of the most likely materials. In this work we present the infrared spectra of three different types of olivine grains: crystalline, amorphous, and synthetic (also amorphous). While the first and second sample derive from the same natural mineral, the third one has been prepared in laboratory according to the relative cosmic abundances of the elements. The experiment data are used to fit the emission feature observed in the comet Halley spectrum between 8 and 13 {mu}m. Satisfactory results are obtained by using synthetic olivine mixed with a small amount (5%) of crystalline grains. 4 refs., 2 figs.

  5. Peridotite and pyroxenite components in the sources of Grande Comore lavas: evidence from olivine compositions

    NASA Astrophysics Data System (ADS)

    Weiss, Y.; Class, C.; Goldstein, S. L.

    2013-12-01

    Grande Comore (Ngazidja) is the youngest Island of the Comores Archipelego in the Indian Ocean, located in the Somali Basin between Africa and Madagascar. The island formed by two volcanoes. Karthala is an active shield volcano, and La Grille is composed mainly of monogenetic cinder cones. The island represents interaction between a mantle plume and oceanic lithosphere and previous studies suggested, based on the major, trace elements and Sr-Nd-Pb-Os isotopic relationships of the lavas, that the alkali basalts of Karthala reflect mainly plume derived melts, while the basanites of La Grille are the products of interaction of plume melts with the metasomatized oceanic lithosphere. Here we report the chemical composition of olivine phenocrysts of Karthala lavas (5 samples), old Karthala (1) and La Grille (3) that were previously analyzed for their major, trace elements and Sr, Nd, Pb, Os and He isotopic compositions. Olivine phenocrysts from Karthala lavas have higher Mn and Ca, lower Al and slightly lower Ni content compared to olivines from La Grille at similar Mg#. Olivines from ';Old Karthala'are close in composition to those from La Grille and the content of Cr is similar between all three groups. The average Mn/Fe and Ca/Fe ratios of olivines of the samples positive correlate with the Sr-Pb-Os isotope ratios of the corresponding whole rocks, and Karthala has higher values than La Grille. These ratios negatively correlate with Nd-He isotope ratios, as well as with the La/Gd, Gd/Yb and Nb/K of the host lavas. The average Ni/Mg and Al/Mg ratios of the olivines correlate with the isotopic and trace element ratios of the whole rocks as well, but display trends in the opposite direction to the ones observed for Mn/Ca over Fe. Previous studies have proposed that the minor element (Ni, Mn and Ca) composition in olivine can be used to infer the proportions of peridotite vs pyroxenite and thus, the amount of recycled ocean crust in the source lithologies of magmas (Sobolev et al., 2007. The amount of recycled crust in sources of mantle-derived melts. Science, 306, 412-417). The Karthala olivines have high Mn/Fe and Ca/Fe and are similar in composition to olivines in MORB, suggesting 10-35% melt contribution from a pyroxenite source. La Grille and old Karthala olivines, on the other hand, are closer in composition to olivines from the Makapuu stage of the Koolau Island in Hawaii and represent 50-75% pyroxenite-derived melt. However, the Ni/Mg ratios in the Grande Comore lavas are relatively constant, unlike MORB, Koolau and other OIBs. Indeed the pyroxenite, which melts within the lithosphere to contribute to the La Grille and old Karthala lavas, most probably, due to metasomatic processes, differs from asthenospheric pyroxenite, which has been suggested to form by the interaction of recycled oceanic crust and peridotite in a rising plume. Thus, our data indicate that lithospheric pyroxenite formed by metasomatism of the lithospheric mantle can be distinguished from pyroxenite from mantle recycling from olivine phenocryst compositions in OIBs.

  6. Comet-like mineralogy of olivine crystals in an extrasolar proto-Kuiper belt

    NASA Astrophysics Data System (ADS)

    De Vries, B.

    2014-09-01

    Some planetary systems harbour debris disks containing planetesimals such as asteroids and comets. Collisions between such bodies produce small dust particles, the spectral features of which reveal their composition and, hence, that of their parent bodies. A measurement of the composition of olivine crystals (Mg(2-2x)Fe(2x)SiO(4)) has been done for the protoplanetary disk HD100546 and for olivine crystals in the warm inner parts of planetary systems. The latter compares well with the iron-rich olivine in asteroids (x < 0.29). In the cold outskirts of the Beta Pictoris system, an analogue to the young Solar System, olivine crystals were detected but until recently their composition remained undetermined, leaving unknown how the composition of the bulk of Solar System cometary olivine grains compares with that of extrasolar comets. We (de Vries et al. 2012, Nature) reported the first detection of the 69-micrometre-wavelength band of olivine crystals in the spectrum of Beta Pictoris (see supplemented figure). Because the disk is optically thin, we can associate the crystals with an extrasolar proto-Kuiper belt a distance of 15-45 astronomical units from the star, determine their magnesium-rich composition (x=0.01+/-0.001) and show that they make up 3.6+/-1.0 per cent of the total dust mass. These values are strikingly similar to those for the dust emitted by the most primitive comets in the Solar System, even though Beta Pictoris is more massive and more luminous and has a different planetary system architecture.

  7. Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts

    NASA Astrophysics Data System (ADS)

    Taura, Hiroshi; Yurimoto, Hisayoshi; Kurita, Kei; Sueno, Shigeho

    Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)<-->(Al, Cr) at low pressure to (Si, Mg)<-->(Al, Al) and (Mg, Mg)<-->(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution.

  8. Diffusive modification of primary zoning in olivine cores in Angrite LEW 87051. [Abstract only

    NASA Technical Reports Server (NTRS)

    Mikouchi, T.; Mckay, G.; Miyamoto, M.; Takeda, H.

    1994-01-01

    Angrite LEW 87051 consists of large olivine crystals set in a fine-grained groundmass that clearly represents a crystallized melt. A few olivines contain Ca-poor, Cr-rich cores that crystallized from a very different melt than the outer part of the crystals constituting the majority of olivine in LEW 87051. We evaluate a model in which the cores formed through fractional crystallization of one melt, then were incorporated into a different melt as xenocrysts, whereupon the original zoning patterns were modified by diffusion. Using a similar approach, we calculate zoning patterns for the cores that would result from perfect fractional crystallization, compare them with the observed zoning, and determine whether the differences could result from diffusive modification consistent with known diffusion rates for Ca, Mn, and Cr. Using distribution coefficients from the 1400 C, IW + 1 experiments, we computed CaO, Cr2O3, and MnO abundances in the hypothetical parent melt by inverting the olivine at the centers of the cores. We further assumed that the primary zoning profile for CaO is essentially unmodified, because the diffusion rate of Ca in olivine is slow. We carried out the fractional crystallization calculation until the calculated Ca content was that observed at break in zoning profiles at the outer edge of the core. We then normalized the distance of this calculated profile to the length of the observed profile in the olivine core and calculated profiles for MnO and Cr2O3. The CaO zoning profile agrees well with the observed profile. The observed MnO profile is slightly higher than the calculated profile near the edge. Diffusion calculations indicate that reversal of the general trend of primary zoning through diffusion would require that diffusion of Cr is 5-10x faster than that of Mn.

  9. Rheological contrast between olivine and garnet at high pressures under anhydrous conditions

    NASA Astrophysics Data System (ADS)

    Mei, S.; Suzuki, A. M.; Kohlstedt, D. L.; Durham, W. B.; Dixon, N. A.

    2010-12-01

    In this study, we carried out experiments investigating the rheological contrast between olivine and garnet, two major components of the mantle, at mantle temperatures and pressures. Experiments were carried out using a deformation-DIA at the National Synchrotron Light Source at Brookhaven National Laboratory. Samples were fabricated from powdered minerals; olivine was from San Carlos and garnet from the Dabie-Sulu orogenic belt in China. In the experiments, a cold-pressed cylinder of fine-grained olivine and one of garnet, each with a diameter of ~1.1 mm and a length of ~0.8 mm, were stacked together, separated by a nickel foil disk. This duplex sample was assembled with alumina pistons, a boron nitride sleeve, and graphite resistance heater into a 6.2-mm edge length cubic mullite-pyrophyllite pressure cell. Experiments were carried out at 1373 - 1573 K and pressures of 3 - 5 GPa. With the synchrotron x-ray beam, a time series of in-situ radiographs enables monitoring of the instantaneous lengths of both deforming samples at the same temperature, pressure, and load. At our experimental conditions, both samples deform with stress exponents of n ? 3 and with activation energies of Q ? 300 kJ/mol. Samples of olivine deform only a factor of ~1.5 faster than samples of garnet of similar grain size, indicating that there is no significant rheological contrast between samples of olivine and garnet under anhydrous conditions. This result, which is the first direct comparison of the rheological behavior of olivine and garnet, provides a solid basis for modeling the rheological structures of subducted lithosphere.

  10. New Insights on the Rheology of Olivine Deformed under Lithospheric Temperature Conditions

    NASA Astrophysics Data System (ADS)

    Cordier, P.; Demouchy, S. A.; Mussi, A.; Tommasi, A.

    2014-12-01

    Rheology of mantle rocks at lithospheric temperatures remains poorly constrained, since most experimental studies on creep mechanisms of olivine single crystals ((MgFe)2SiO4, Pbnm) and polycrystalline olivine aggregates were performed at high-temperatures (T >> 1200oC). In this study, we report results from deformation experiments on oriented single crystals of San Carlos olivine and polycrystalline olivine aggregate at temperatures relevant of the uppermost mantle (ranging from 800o to 1090oC) in tri-axial compression. The experiments were carried out at a confining pressure of 300 MPa in a high-resolution gas-medium mechanical testing apparatus at various constant strain rates (from 7 x 10-6 s-1 to 1 x 10-4 s-1). Mechanical tests show that mantle lithosphere is actually weaker than previously inferred from the extrapolation of high-temperature experiments. In this study, we present characterization of dislocation microstructures based on transmission electron microscopy and electron tomography. It is shown that below 1000C, dislocation activity is restricted to [001] glide with a strong predominance of {110} as glide planes. We observe recovery mechanisms which suggest that the mechanical properties observed in laboratory experiments represent an upper bound for the actual behavior of olivine under lithospheric mantle conditions. Moreover, the drastic reduction in slip system activity observed questions the ability of deforming olivine aggregates in the ductile regime at such temperatures. We show that ductility is preserved thanks to the activation of alternative deformation mechanisms in grain boundaries involving disclinations.

  11. Comet-like mineralogy of olivine crystals in an extrasolar proto-Kuiper belt.

    PubMed

    de Vries, B L; Acke, B; Blommaert, J A D L; Waelkens, C; Waters, L B F M; Vandenbussche, B; Min, M; Olofsson, G; Dominik, C; Decin, L; Barlow, M J; Brandeker, A; Di Francesco, J; Glauser, A M; Greaves, J; Harvey, P M; Holland, W S; Ivison, R J; Liseau, R; Pantin, E E; Pilbratt, G L; Royer, P; Sibthorpe, B

    2012-10-01

    Some planetary systems harbour debris disks containing planetesimals such as asteroids and comets. Collisions between such bodies produce small dust particles, the spectral features of which reveal their composition and, hence, that of their parent bodies. A measurement of the composition of olivine crystals (Mg(2-2x)Fe(2x)SiO(4)) has been done for the protoplanetary disk HD 100546 (refs 3, 4) and for olivine crystals in the warm inner parts of planetary systems. The latter compares well with the iron-rich olivine in asteroids (x ≈ 0.29). In the cold outskirts of the β Pictoris system, an analogue to the young Solar System, olivine crystals were detected but their composition remained undetermined, leaving unknown how the composition of the bulk of Solar System cometary olivine grains compares with that of extrasolar comets. Here we report the detection of the 69-micrometre-wavelength band of olivine crystals in the spectrum of β Pictoris. Because the disk is optically thin, we can associate the crystals with an extrasolar proto-Kuiper belt a distance of 15-45 astronomical units from the star (one astronomical unit is the Sun-Earth distance), determine their magnesium-rich composition (x = 0.01 ± 0.001) and show that they make up 3.6 ± 1.0 per cent of the total dust mass. These values are strikingly similar to those for the dust emitted by the most primitive comets in the Solar System, even though β Pictoris is more massive and more luminous and has a different planetary system architecture. PMID:23038467

  12. Olivine Weathering and Sulfate Formation Under Cryogenic Conditions

    NASA Astrophysics Data System (ADS)

    Niles, P. B.; Golden, D. C.; Michalski, J. R.

    2013-12-01

    High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide-spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa-like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo-concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0C in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars-like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above -40C. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial sulfur-rich volcanism, and sulfur-rich surface deposits also makes it very likely that sul-fate aerosols have also been an important component of the martian atmosphere. Thus mixtures of ice, dust, and sulfate aerosols are likely to have been common on the martian surface. Given the fact that it is not difficult to achieve surface temperatures above -40C on Mars throughout its history, it seems likely that sulfate formation on Mars is controlled by the availability of sulfate aerosols and not by the martian climate. The current polar regions of Mars and Earth provide interesting analogs. Large regions of sulfate-rich material have been detected on and around the modern north polar region of Mars. The prevalence of ice-dust mixtures in this region and the existence of sulfates within the ice cap itself are strong evidence for the origin of the sulfates from inside the ice deposits. In addition sulfates have been found in ice deposits in Greenland and Mount Fuji on Earth that have been attributed to forming within the ice deposit. These sulfates can form either through interaction with dust particles in the atmosphere or through weathering inside the ice itself.

  13. Olivine Weathering aud Sulfate Formation Under Cryogenic Conditions

    NASA Technical Reports Server (NTRS)

    Niles, Paul B.; Golden, D. C.; Michalski, J.

    2013-01-01

    High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide-spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa-like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo-concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0degC in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars-like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above -40degC. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial sulfur-rich volcanism, and sulfur-rich surface deposits also makes it very likely that sulfate aerosols have also been an important component of the martian atmosphere. Thus mixtures of ice, dust, and sulfate aerosols are likely to have been common on the martian surface. Given the fact that it is not difficult to achieve surface temperatures above -40degC on Mars throughout its history, it seems likely that sulfate formation on Mars is controlled by the availability of sulfate aerosols and not by the martian climate. The current polar regions of Mars and Earth provide interesting analogs. Large regions of sulfaterich material have been detected on and around the modern north polar region of Mars. The prevalence of ice-dust mixtures in this region and the existence of sulfates within the ice cap itself are strong evidence for the origin of the sulfates from inside the ice deposits. In addition sulfates have been found in ice deposits in Greenland and Mount Fuji on Earth that have been attributed to forming within the ice deposit. These sulfates can form either through interaction with dust particles in the atmosphere or through weathering inside the ice itself.

  14. Olivine-hosted melt inclusions as an archive of redox heterogeneity in magmatic systems

    NASA Astrophysics Data System (ADS)

    Hartley, M. E.; Shorttle, O.; Maclennan, J.; Moussallam, Y.; Edmonds, M.

    2014-12-01

    Crystal-hosted melt inclusions are able to preserve information about the geochemical diversity of melts present within magmatic systems, including information about both the oxygen fugacity (fO2) of their mantle source and the redox evolution of their carrier melt. However, the ferric iron proportions (Fe3+/?Fe) measured in olivine-hosted melt inclusions are partially controlled by post-entrapment processes, such that inclusions may no longer preserve a record of the fO2 at which they were trapped. Post-entrapment crystallisation (PEC) of olivine onto the inclusion walls during cooling sequesters Fe2+ into olivine. Olivine-hosted melt inclusions may also maintain H2O and fO2equilibrium with their external environment via coupled proton and metal vacancy diffusion through the olivine crystal lattice. In this study we present a combination of XANES, major, trace and volatile element (C, H, S, F, Cl) analyses from a suite of 100 olivine-hosted melt inclusions from the AD 1783 Laki eruption, Iceland. The inclusions are hosted in Fo86-Fo68 olivines, and have experienced up to a maximum of 7% PEC. They preserve a diverse range of melt compositions similar to that seen in global mid-ocean ridge basalts. Composition-dependent CO2-H2O solubility models have been used to determine the pressures of inclusion trapping. Many of the melt inclusions have experienced diffusive H+ re-equilibration with their external environment: trace element depleted inclusions with low initial H2O concentrations have gained H+ via diffusive exchange with a more H2O-rich carrier melt, which is a consequence of concurrent mixing and crystallisation of diverse primary melt compositions in the Laki magmatic system. This sample set therefore presents a unique opportunity to deconvolve the post-entrapment crystallisation and diffusion processes that modify Fe3+/?Fe in olivine-hosted melt inclusions, permitting the recovery of the true extent of magmatic redox variability present at the time of inclusion trapping.

  15. Dehydration breakdown of antigorite and the formation of B-type olivine CPO

    NASA Astrophysics Data System (ADS)

    Nagaya, Takayoshi; Wallis, Simon R.; Kobayashi, Hiroaki; Michibayashi, Katsuyoshi; Mizukami, Tomoyuki; Seto, Yusuke; Miyake, Akira; Matsumoto, Megumi

    2014-02-01

    Peridotite formed by contact metamorphism and dehydration breakdown of an antigorite schist from the Happo area, central Japan shows a strong olivine crystallographic preferred orientation (Ol CPO). The lack of mesoscale deformation structures associated with the intrusion and the lack of microstructural evidence for plastic deformation of neoblastic grains suggest that olivine CPO in this area did not form as a result of solid-state deformation. Instead, the good correspondence between the original antigorite orientation and the orientation of the newly formed olivine implies the CPO formed by topotactic growth of the olivine after antigorite. Ol CPO is likely to develop by a similar process in subduction zone environments where foliated serpentinite is dragged down to depths where antigorite is no longer stable. The Happo Ol CPO has a strong a-axis concentration perpendicular to the lineation and within the foliation-commonly referred to as B-type Ol CPO. Seismic fast directions parallel to the ocean trench are observed in many convergent margins and are consistent with the presence of B-type Ol CPO in the mantle wedge of these regions. Experimental work has shown that B-type CPO can form by dislocation creep under hydrous conditions at relatively high stresses. There are, however, several discrepancies between the characteristics of natural and laboratory samples with B-type Ol CPO. (1) The formation conditions (stress and temperature) of some natural examples with B-type CPO fall outside those predicted by experiments. (2) In deformation experiments, slip in the crystallographic c-axis direction is important but has not been observed in natural examples of B-type CPO. (3) Experimental work suggests the presence of H2O and either high shear stress or relatively low temperatures are essential for the formation of B-type CPO. These conditions are most likely to be achieved close to subduction boundaries, but these regions are also associated with serpentinization, which prevents strong olivine CPO patterns from forming. We show B-type Ol CPO can form as a result of static topotactic growth of olivine after high-temperature breakdown of foliated serpentinite. These results resolve the discrepancies between experimental and natural examples of B-type CPO and show the need to rethink the formation process of olivine CPO in convergent margins. Topotactic growth of olivine after antigorite can account for the inferred distribution of B-type Ol CPO in the mantle wedge more successfully than dislocation creep.

  16. Experimental shock metamorphism of mono- and polycrystalline olivine - A comparative study

    NASA Technical Reports Server (NTRS)

    Bauer, J. F.

    1979-01-01

    The paper reports on a series of controlled shock recovery experiments which have been performed on over 40 samples including monocrystalline, polycrystalline, dunite, and porous particulate olivine-bearing targets. Results of the mineralogical and petrological analyses of these samples are used to establish a general and comparative diagnosis of shock effects generated in various olivine-bearing materials. Finally, some experiments are conducted under different ambient pO2 conditions so that information on the distribution of observed impact features is derived as a function not only of peak pressure and texture of the target sample, but also of specific environmental conditions.

  17. Seismic evidence for olivine phase changes at the 410- and 660-kilometer discontinuities.

    PubMed

    Lebedev, Sergei; Chevrot, Sbastien; van der Hilst, Rob D

    2002-05-17

    The view that the seismic discontinuities bounding the mantle transition zone at 410- and 660-kilometer depths are caused by isochemical phase transformations of the olivine structure is debated. Combining converted-wave measurements in East Asia and Australia with seismic velocities from regional tomography studies, we observe a correlation of the thickness of, and wavespeed variations within, the transition zone that is consistent with olivine structural transformations. Moreover, the seismologically inferred Clapeyron slopes are in agreement with the mineralogical Clapeyron slopes of the (Mg,Fe)2SiO4 spinel and postspinel transformations. PMID:12016311

  18. Deformation of olivine-orthopyroxene aggregates: Implications for the strength of the lithosphere

    NASA Astrophysics Data System (ADS)

    Farla, R.; Cai, Z.; Karato, S.

    2011-12-01

    In order for plate tectonics to occur on Earth, the base of the oceanic lithosphere must be relatively weak ("yield stress" less than ~200 MPa). Such a weak layer is not consistent with a model where homogeneous deformation of pure olivine by dislocation creep is assumed. Previous studies on orthopyroxene (opx) showed (i) opx (with certain orientations) has much lower strength than olivine at low temperature and (ii) recrystallized grain-size of opx is smaller than that of olivine. These observations suggest that opx might play an important role in reducing the strength of an olivine + opx mixture at lithospheric conditions. To explore this idea, we have started a series of experimental studies to investigate the rheological behavior of olivine + opx mixtures. The rheology of a synthetic coarse-grained aggregate (oli: 75%, opx: 25%), was explored at high confining pressure (1.5 GPa) in the Griggs-type apparatus to avoid opx transformation to proto-enstatite. The range of temperature was 900 - 1200C and deformation experiments were (nearly) constant strain-rate. In the first stage, relatively dry San Carlos olivine powders were encapsulated in nickel and hot-pressed in the Griggs apparatus at 1300C and 1.3 GPa for 7.5 hours to promote grain growth. A nearly homogeneous grain-size of 10 - 50 ?m was obtained (to ensure dislocation creep during deformation). The hot-pressed pellet was subsequently cut into thin slices, 400 ?m thick. Each slice was sandwiched between two grooved alumina pistons and again placed in a nickel capsule. The pressure medium used in these experiments was CsCl, which reduced friction considerably (in comparison to e.g. MgO) and provided a clear indication of the 'hit point' and improved stress estimation. At 1200C CsCl was mixed with MgO to minimize persuasive melting of the salt. Results have shown that the olivine - opx aggregate began to deform above 900C at high pressure. At 1000C deformation was accompanied by the onset of dynamic recrystallisation on the boundaries of parent grains. At 1100C, the degree of recrystallization increased with deformation becoming increasingly concentrated on grain boundaries near parallel to the orientation of the strain marker. In all experiments we have performed so far, the stress continuously increased with strain, and no evidence of weakening nor shear localization was observed. However, the degree of recrystallization systematically increased with temperature, and evidence for mixing of recrystallised orthopyroxene and olivine grains was observed. At higher temperature, higher water content and/or lower strain-rates, the influence of dynamic recrystallization will be more extensive.

  19. First finding of burkeite in melt inclusions in olivine from sheared lherzolite xenoliths.

    PubMed

    Korsakov, Andrey V; Golovin, Alexander V; De Gussem, Kris; Sharygin, Igor S; Vandenabeele, Peter

    2009-08-01

    For the first time burkeite was observed as a daughter phase in the melt inclusions in olivine by Raman spectroscopy. The olivine comes from sheared lherzolite xenoliths from the Udachnaya-East kimberlite pipe (Yakutia, Russia). This anhydrous sulfate-carbonate mineral (Na(6)(CO(3))(SO(4))(2)) is generally considered to be a characteristic mineral in saline soils or in continental lacustrine evaporite deposits. Recently, however, this mineral was identified in hydrothermal fluids. Our observations indicate that burkeite can also be formed from a mantle-derived melt. PMID:19058996

  20. Ringwoodite Lamellae in Olivine from the S6 Chondrite Tenham: The Transformation Mechanism

    NASA Astrophysics Data System (ADS)

    Xie, Z.; Sharp, T. G.; Decarli, P. S.

    2006-12-01

    Ringwoodite lamellae in partially transformed olivine have been reported to occur in the shock-induced melt veins or near the melt veins in heavily shocked (S6) chondrites [1-4]. These features were interpreted to have formed by a coherent intracrystalline transformation mechanism like that observed in experimentally transformed samples by Kerschhofer et al. [5-7]. However, our SEM and TEM observations on the partially transformed olivine suggest that the transformation is incoherent and occurs along specific orientation [4], which is in agreement with the new interpretation of ringwoodite lamellae based on new SEM and SXRD observations [8]. Here we report more detailed TEM results, which are crucial to understand the transformation mechanism. Abundant ringwoodite lamellae were found in olivine grains, which occur as host-rock fragments entrained in melt veins and pockets. These partially transformed olivines are commonly intergrown with enstatite and plagioclase in multi-phase fragments. High-resolution SEM images reveal that the ringwoodite lamellae are not continuous, but rather polycrystalline ringwoodite with crystal size about 1 mm. Preliminary TEM results show that olivine are heavily deformed or occur as fine olivine grains, and ringwoodite lamellae consist of individual ringwoodite grains in the matrix of olivine fine grains. The discontinuous lamellar textures that we observe strongly suggest that the lamellae consist of many distinct ringwoodite crystallites rather than single-crystal lamella. It is possible that lamellae of polycrystalline ringwoodite in olivine could form by a mechanism analogous to the formation of planar deformation features (PDF), representing preferential transformation along specific crystallographic defect planes of the host phase. [1 Chen et al. (2004) Proceedings. of NAS 101(42), 15033-15037. [2] Ohtani et al. (2004) EPSL 227(3-4), 505- 515. [3] Beck, et al. (2005) Nature 435, 1071-1074. [4] Xie and Sharp (2006), LPSC XXXVII, 2306.pdf. [5] Kerschhofer et al. (1996) Science 274 (5284), 79-81. [6] Kerschhofer et al. (1998) Mineralogical magazine 62(5),617-638. [7] Kerschhofer et al. (2000) PEPI 121, 59-76. [8] Chen et al. (2006) Meteoritics Planet. Sci. (41), 731-737.

  1. Development of olivine Crystal Preferred Orientation in Oshima peridotite body as a remnant of oceanic lithosphere

    NASA Astrophysics Data System (ADS)

    Tasaka, M.; Toriumi, M.; Wataru, N.

    2008-12-01

    To know the mantle flow kinematics, investigation of the seismic anisotropy is common method in upper mantle. Anisotropy is linked to crystal preferred orientations (CPOs) of olivine which is most abundant and weakest mineral in upper mantle. However the quantitative investigation analyses of natural CPO data have not succeeded yet. So, we must understand how olivine CPOs develops with strain in deformation settings. The Oshima peridotite body is the lower part of the Yakuno ophiolite in SW Japan (Ishiwatari, 1985a, b). This body consists dominantly of dunite and harzburgite deformed in upper mantle. This peridotites display various microstructures such as coarse grained granoblastic texture (0.7-1.0mm), elongated porphyroclastic texture (1.0mm-) and fine grained equigranular texture (0.1mm-). We analyzed CPOs of olivine using EBSD method. The results show that CPOs of olivine was formed by (0kl)[100] or (010)[100] slip system. In order to characterize the CPOs, we first determined the fabric strength and orientation distribution density of the principal crystallographic axes (J-index and M-index; Tommasi et al., 2000 and Skemer et al., 2005). According to those studies with increasing monotonously strain, the value of J- and M-index also increases. The Oshima peridotite body shows the various fabric strength from J=2.95 to 16.26 (M=0.040 to 0.384). On this presentation, we propose a new inversion method of mantle deformation by matching the model CPO patterns with natural CPOs in the Alpine type peridotites. Furthermore, we investigated two kind of angles of olivine together with CPOs at the same time to analyze CPOs development during mantle deformation. There are; (1) Angles between slip plane of each olivine grain and sample lineation. (2) Misorientation angles between adjacent olivine grains. The different angles between the slip plane of olivine grains and the rock lineation (1) are controlled by lattice rotation due to dislocation glide (Sevillano et al., 1976). And the misorientation angles between neighboring grains (2) are governed by the local deformation kinetics involving dislocation climb process. From these two parameters (1) and (2) associated with strain, we can construct "gfabric distribution diagrams"h for deformed mantle rocks which can be compared to the J-index of the some samples. The more strain increases (=stronger fabrics), the more "gfabric distribution diagrams"h tends to concentrate. This study enables us to study together dislocation glide and recrystallization, which both contribute to CPO development.

  2. The olivine-ilmenite thermometer. [partitioning effect of temperature on iron ions and magnesium

    NASA Technical Reports Server (NTRS)

    Andersen, D. J.; Lindsley, D. H.

    1979-01-01

    It is noted that the partitioning of Fe(2+) and Mg between olivine and ilmenite is temperature-dependent and can serve as a geothermometer if the activity-composition relations are determined. The paper reports on the study of the partitioning from 700-980 C at 1 kbar and 800-900 C at 13 kbar, and develops a solution model to account for the nonideality of olivine in the binary system fosterite-fayalite and for ilmenite in the ternary system ilmenite-geikielite-hematite. A comparison with crystallization experiments shows that this thermometer may be safely extrapolated to temperatures higher than those of the exchange experiments.

  3. Short- and long-term olivine weathering in Svalbard: implications for Mars.

    PubMed

    Hausrath, E M; Treiman, A H; Vicenzi, E; Bish, D L; Blake, D; Sarrazin, P; Hoehler, T; Midtkandal, I; Steele, A; Brantley, S L

    2008-12-01

    Liquid water is essential to life as we know it on Earth; therefore, the search for water on Mars is a critical component of the search for life. Olivine, a mineral identified as present on Mars, has been proposed as an indicator of the duration and characteristics of water because it dissolves quickly, particularly under low-pH conditions. The duration of olivine persistence relative to glass under conditions of aqueous alteration reflects the pH and temperature of the reacting fluids. In this paper, we investigate the utility of 3 methodologies to detect silicate weathering in a Mars analog environment (Sverrefjell volcano, Svalbard). CheMin, a miniature X-ray diffraction instrument developed for flight on NASA's upcoming Mars Science Laboratory, was deployed on Svalbard and was successful in detecting olivine and weathering products. The persistence of olivine and glass in Svalbard rocks was also investigated via laboratory observations of weathered hand samples as well as an in situ burial experiment. Observations of hand samples are consistent with the inference that olivine persists longer than glass at near-zero temperatures in the presence of solutions at pH approximately 7-9 on Svalbard, whereas in hydrothermally altered zones, glass has persisted longer than olivine in the presence of fluids at similar pH at approximately 50 degrees C. Analysis of the surfaces of olivine and glass samples, which were buried on Sverrefjell for 1 year and then retrieved, documented only minor incipient weathering, though these results suggest the importance of biological impacts. The 3 types of observations (CheMin, laboratory observations of hand samples, burial experiments) of weathering of olivine and glass at Svalbard show promise for interpretation of weathering on Mars. Furthermore, the weathering relationships observed on Svalbard are consistent with laboratory-measured dissolution rates, which suggests that relative mineral dissolution rates in the laboratory, in concert with field observations, can be used to yield valuable information regarding the pH and temperature of reacting martian fluids. PMID:19191538

  4. Olivine Composition of the Mars Trojan 5261 Eureka: Spitzer IRS Data

    NASA Technical Reports Server (NTRS)

    Lim, L. F.; Burt, B. J.; Emery, J. P.; Mueller, M.; Rivkin, A. S.; Trilling, D.

    2011-01-01

    The largest Mars trojan, 5261 Eureka, is one of two prototype "Sa" asteroids in the Bus-Demeo taxonomy. Analysis of its visible/near-IR spectrum led to the conclusion that it might represent either an angritic analog or an olivine-rich composition such as an R chondrite. Spitzer IRS data (5-30 micrometers) have enabled us to resolve this ambiguity. The thermal-IR spectrum exhibits strong olivine reststrahlen features consistent with a composition of approximately equals Fo60-70. Laboratory spectra of R chondrites, brachinites, and chassignites are dominated by similar features.

  5. A new systematic approach using the Modified Gaussian Model: Insight for the characterization of chemical composition of olivines, pyroxenes and olivine-pyroxene mixtures

    NASA Astrophysics Data System (ADS)

    Clnet, Harold; Pinet, Patrick; Daydou, Yves; Heuripeau, Frdrick; Rosemberg, Christine; Baratoux, David; Chevrel, Serge

    2011-05-01

    An automatic procedure has been implemented on the original MGM approach ( Sunshine et al., 1990) in order to deal with an a priori unknown mafic mineralogy observed in the visible-near infrared by reflectance spectroscopy in the case of laboratory or natural rock spectra. We consider all the mixture possibilities involving orthopyroxene, clinopyroxene and olivine, and use accordingly for each configuration different numbers of Gaussians, depending on the potential complexity of the mixture. A key issue is to initialize the MGM procedure with a proper setting for the Gaussians parameters. An automatic analysis of the shape of the spectrum is first performed. The continuum is handled with a second order polynomial adjusted on the local maxima along the spectrum and Gaussians parameters initial settings are made on the basis of laboratory results available in the literature in the case of simple mixtures of mafic minerals. The returned MGM solutions are then assessed on spectroscopic grounds and either validated or discarded, on the basis of a mineralogical sorting. The results presented in this paper are a first quantitative step to characterize both modal and chemical compositions of pyroxenes and olivines. A demonstration of the methodology on specific examples of binary and ternary olivine-pyroxenes mixtures has been made, which shows that the different non-linear effects which affect the Gaussian parameters (center and strength) can be successfully handled. Of note is the fact that the band center positions associated with the different mafic minerals are not set here in the inverse problem, and thus the MGM outputs are truly informative of the chemical composition of pyroxenes and olivines. With the consideration of some limits on the detection thresholds, these results are quite promising for increasing the operational use of the Modified Gaussian Model with large hyperspectral data sets in view of establishing detailed mineralogical mappings of magmatic units.

  6. Nitrogen Isotopes in Olivine Separates from Volcanic Arcs, Hot Spots and Continental Mantle Xenoliths

    NASA Astrophysics Data System (ADS)

    Fischer, T. P.; Takahata, N.; Sano, Y.; Hilton, D. R.

    2004-12-01

    We report the first nitrogen isotopic data of olivine separates from volcanic arcs (Cerro Negro, Nicaragua; Izalco, El Salvador; Turrialba, Costa Rica; Ichinomegata, Japan). In addition, we report nitrogen isotopic data of olivine separates from ocean islands (Hawaii, Reunion, Iceland) and continental mantle xenoliths (San Carlos, Arizona). Samples were processed by crushing and analyzed using a modified noble gas mass spectrometer (VG3400). N concentrations range from 0.6 to 22 micro ccSTP/g olivine. The 15N/14N ratios (expressed in the ? 15N notation where ? 15N sample = {[(15N/14N)sample/(15N/14N)Air]-1} X 1000) of olivine separates are distinctly different from air (0.0 ) and range from lower than mean MORB (- 5 ) to values characteristic of (subducted) oceanic sediments (+ 7 ). Positive ? 15N values are found in olivines from volcanic arcs: Cerro Negro 1992 ash (+ 6.2 1.6 ), Izalco lava flow (+ 5.1 0.7 ), Ichinomengata spinel lherzolite (+ 1.1 0.5 ) with the exception of Turrialba lava (- 1.7 2.5 ). Olivines from hot spots have both positive and negative ? 15N signatures: Iceland, Theistareykir - northern rift zone (- 8 1.6 ), Hawaii, dunite from 1801 Kaupulehu flow of Hualuai volcano (+ 3.1 0.3 ) and Reunion dunite (+ 0.2 0.5 ). The San Carlos mantle xenolith has a value of - 1.5 2.5 . 40Ar/36Ar ratios of the samples as determined in this study or reported in the literature are significantly higher than air (295.5) in olivines from Ichinomegata, San Carlos, Iceland, Reunion and Hawaii. The olivines from Cerro Negro have a 40Ar/36Ar ratio of 306, close to that of air. The 3He/4He ratios of the samples are higher than the MORB value of 8.0 RA (RA is the 3He/4He of air), the exception being Cerro Negro (6.1 RA). Hawaii, Reunion and Iceland have 3He/4He of 10.3, 12.9 and 12.3 RA, respectively. ? 15N signatures of fumarole gas samples collected at Cerro Negro (+ 4.9 0.1 ), Turrialba (- 1.0 0.3 ) and localities close to Izalco (+ 4.0 0.4 ) are identical (within error) to those of the olivine separates. The results obtained in this study are significant and show that 1) N isotopes in olivine separates and volcanic/hydrothermal gas emissions both sample volatiles that are primarily derived from the magma source. 2) subduction of oceanic sediments and transfer of N through the mantle wedge controls the N isotopic composition in volcanic arcs as sampled by olivine separates and gas discharges. 3) the N isotopic signature of hot spot related volatiles is variable but the samples from Hawaii, and to a lesser extent from Reunion, support the idea that surficial N (from subducted sediments or oceanic basement) is recycled into the lower mantle. 4) N as sampled by the San Carlos mantle xenolith may record a greater extent of air contamination than the other samples. Alternatively, N data of San Carlos and the Iceland northern rift zone suggests that the N isotopic signature of the upper mantle may be more variable than previously inferred from MORB samples.

  7. Space Weathering of Olivine in Lunar Soils: A Comparison to Itokawa Regolith Samples

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Berger, E. L.

    2014-01-01

    Regolith particles from airless bodies preserve a record of the space weathering processes that occurred during their surface exposure history. These processes have major implications for interpreting remote-sensing data from airless bodies. Solar wind irradiation effects occur in the rims of exposed grains, and impact processes result in the accumulation of vapordeposited elements and other surface-adhering materials. The grains returned from the surface of Itokawa by the Hayabusa mission allow the space weathering "style" of a chondritic, asteroidal "soil" to be compared to the lunar case. Here, we present new studies of space-weathered olivine grains from lunar soils, and compare these results to olivine grains from Itokawa. Samples and Methods: We analyzed microtome thin sections of olivine grains from the 20-45 micron fractions of three lunar soils: 71061, 71501 and 10084 (immature, submature and mature, respectively). Imaging and analytical data were obtained using a JEOL 2500SE 200kV field-emission scanning-transmission electron microscope equipped with a thin-window energy-dispersive x-ray spectrometer. Similar analyses were obtained from three Hayabusa olivine grains. Results and Discussion: We observed lunar grains showing a range of solar flare track densities (from <10(exp 9) to approx.10(exp 12)/sq cm). The lunar olivines all show disordered, highly strained, nanocrystalline rims up to 150-nm thick. The disordered rim thickness is positively correlated with solar flare track density. All of the disordered rims are overlain by a Si-rich amorphous layer, ranging up to 50-nm thick, enriched in elements that are not derived from the host olivine (e.g., Ca, Al, and Ti). The outmost layer represents impact-generated vapor deposits typically observed on other lunar soil grains. The Hayabusa olivine grains show track densities <10(exp 10)/sq cm and display disordered rims 50- to 100-nm thick. The track densities are intermediate to those observed in olivines in immature and submature lunar soils and indicate surface exposures of approx. 10(exp 5) years. The outermost few nanometers of the disordered rims on Hayabusa olivines are more Si-rich and Mg- and Fe-depleted relative to the cores of the grains and likely represent a minor accumulation of impact-generated vapors or sputter deposits. Nanophase Fe metal particles are less abundant in the Hayabusa rims compared to the rims on lunar grains. Conclusions: The Hayabusa and lunar olivine grain rims have widths and microstructures consistent with formation from atomic displacement damage from solar wind ions. The space weathering features in the Hayabusa grains are similar to those observed in olivines from immature to submature lunar soils. A major difference, however, is that the Hayabusa grains appear to lack the hypervelocity impact products (melt spherules, thick vapor deposits, and abundant nanophase Fe metal particles) that are common in lunar soil grains with a similar exposure history.

  8. A valid Margules formulation for an asymmetric ternary solution - Revision of the olivine-ilmenite thermometer, with applications

    NASA Technical Reports Server (NTRS)

    Andersen, D. J.; Lindsley, D. H.

    1981-01-01

    A derivation of a valid asymmetric ternary Margules expression for the excess free energy is presented, and the olivine-ilmenite thermometer is revised accordingly. Although the effect on the thermometer is relatively small, the revision results in improved precision. Estimated temperatures of equilibration are presented for olivine and ilmenite from lunar and terrestrial rocks.

  9. Reduced chromium in olivine grains from lunar basalt 15555 - X-ray Absorption Near Edge Structure (XANES)

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Jones, K. W.; Gordon, B.; Rivers, M. L.; Bajt, S.; Smith, J. V.

    1993-01-01

    The oxidation state of Cr in 200-micron regions within individual lunar olivine and pyroxene grains from lunar basalt 15555 was inferred using X-ray Absorption Near Edge Structure (XANES). Reference materials had previously been studied by optical absorption spectroscopy and included Cr-bearing borosilicate glasses synthesized under controlled oxygen fugacity and Cr-doped olivines. The energy dependence of XANES spectral features defined by these reference materials indicated that Cr is predominantly divalent in the lunar olivine and trivalent in the pyroxene. These results, coupled with the apparent f(02)-independence of partitioning coefficients for Cr into olivine, imply that the source magma was dominated by divalent Cr at the time of olivine crystallization.

  10. In situ Ultrasonic Velocity Measurements Across the Olivine-spinel Transformation in Fe2Si04

    SciTech Connect

    Liu, Q.; Liu, W; Whitaker, M; Wang, L; Li, B

    2010-01-01

    Compressional (P) and shear (S) wave velocities across the olivine-spinel transformation in Fe{sub 2}SiO{sub 4} were investigated in situ using combined synchrotron X-ray diffraction, X-ray imaging, and ultrasonic interferometry up to 5.5 GPa along the 1173 K isotherm. The onset of the spinel to olivine transformation at 4.5 GPa and olivine to spinel transition for Fe{sub 2}SiO{sub 4} at 4.8 GPa was concurrently observed from X-ray diffraction, the amplitude of the ultrasonic signals, the calculated velocities, and the ratio of P and S wave velocities (v{sub P}/v{sub S}). No velocity softening was observed prior to the fayalite to spinel transition. The velocity contrasts across the Fe{sub 2}SiO{sub 4} spinel to fayalite phase transition are derived directly from the measured velocities, which are 13 and 12% for P and S waves, respectively, together with a density contrast of 9.4%. A comparison with literature data indicates that the changes in compressional-wave velocity and density across the olivine-spinel transformation in Fe{sub 2}SiO{sub 4} are comparable to those with different iron concentrations in the (Mg,Fe){sub 2}SiO{sub 4} solid solution, whereas the shear wave velocity contrast decreases slightly with increasing iron concentration.

  11. Mn-Cr ages of Fe-rich olivine in two Rumuruti (R) chondrites

    NASA Astrophysics Data System (ADS)

    Sugiura, N.; Miyazaki, A.

    2006-05-01

    Mn-Cr systematics in olivine of two Rumuruti (R) chondrites was investigated. Mn/52Cr ratios up to 1800 and 1300, and ?53Cr of up to 25 and 7 were observed for NWA 753 and Sahara 99531, respectively. All data points of NWA 753 show a linear correlation between ?53Cr values and Mn/52Cr ratios on the isochron diagram. The inferred initial 53Mn/55Mn ratio for NWA 753 is (1.84 0.42(2?)) 10-6. In the case of Sahara 99531, a positive correlation interpreted as an isochron for 53Mn/55Mn = 2.75 1.55 (2?) 10-6 was obtained for only one chondrule. Data from other chondrules in Sahara 99531 give an upper limit of 53Mn/55Mn = 0.49 10-6. The Mn-Cr ages of NWA 753 and a chondrule in Sahara 99531 are slightly older than that of the angrite LEW 86010 (Lugmair and Shukolyukov, 1998). Other chondrules in Sahara 99531 are at least 5 Ma younger than the LEW 86010. The Mn-Cr ages of olivine in R chondrites correspond to the time when olivine became a closed system either during slow cooling from the peak metamorphic temperature or during rapid cooling by impact excavation. In either case the olivine closure occurred earlier than the final assembly of the brecciated chondrites.

  12. Correlative Microscopy and Visible/Near-Infrared Spectral Analysis of Simulated Solar Wind Implanted Olivine

    NASA Astrophysics Data System (ADS)

    Kuhlman, K. R.; Kvit, A. V.; Baba, K.; Poplawsky, J. D.; Hiroi, T.; Isheim, D.

    2015-11-01

    Here we present the results of the first atom probe tomography (APT) and scanning transmission electron microscopy study (STEM) of San Carlos olivine (Fo90.1) exposed to simulated solar wind-based space weathering due to hydrogen (~1keV/amu).

  13. Chlorine/Bromine Ratios in Fracture-filling Aqueous Alteration Products in Nakhla Olivine

    NASA Technical Reports Server (NTRS)

    Sutton, S. R.; Rao, M. N.; Dreibus, G.; McKay, D. S.; Waenke, H.; Wentworth, S.; Newville, M.; Trainor, T.; Flynn, G. J.

    2002-01-01

    The Cl/Br ratios in fracture-filling materials in veins in Nakhla olivine was determined using x-ray microprobe (Br) and EDX (Cl) techniques. The Cl/Br ratio of 55 (standard deviation: 13) shows that the secondary altered material is pristine, extraterrestrial and akin to the Martian soil. Additional information is contained in the original extended abstract.

  14. Pyroxenes and olivines: Structural implications of shock-wave data for high pressure phases

    NASA Technical Reports Server (NTRS)

    Jeanloz, R.; Ahrens, T. J.

    1975-01-01

    The nature of the shock-induced, high-pressure phases of olivine and pyroxene rocks is examined in the light of data for the densities of a new class of perovskite-related silicate structures. Also examined are some new Hugoniot and release adiabat data for bronzite. Reexamining available shock data for magnesian pyroxenes and olivines leads to the conclusion that they define a mixed phase (or disequilibrium) region to about the 100 GPa range, related to the kinetics of phase transformation in these silicates. By recognizing this point, certain discrepancies in previous interpretations of shock data can be explained. A set of theoretical Hugonoits for pyroxene and olivine stoichiometry, perovskite-bearing assemblages was constructed based on their properties deduced from high-pressure work, showing that the shock data is compatible with transformations to perovskites in the 45-7GPa region. Finally, the shock data indicate very similar properties for olivine and pyroxene at high pressures making them both equally likely candidates for the lower mantle.

  15. Compositional Variations of Olivines and Pyroxenes in Chondritic Interplanetary Dust Particles

    NASA Astrophysics Data System (ADS)

    Zolensky, M.; Barrett, R.

    1992-07-01

    It is a fundamental goal of interplanetary dust particle (IDP) research to determine the sources and histories of these primitive extraterrestrial materials. Chondritic IDPs have been divided into anhydrous and hydrous varieties. The presumption is that hydrated IDPs experienced aqueous alteration on parent bodies (hydrous asteroids or possibly comets). We wish to discover whether the anhydrous IDPs were the initial raw materials for these reactions. We report here analyses of olivines and pyroxenes from 22 large (>15 micrometers) chondritic IDPs: 11 anhydrous and 11 hydrous. We find there exists no significant difference in the compositions of olivines from olivine vs. pyroxene dominated IDPs. The degree of heterogeneity of these olivine compositions from anhydrous IDPs (Fo44-100) is great, significantly exceeding that of the olivines from the hydrous IDPs (Fo76-100) we examined. We observe the same relationship for orthopyroxenes (En57-100 for anhydrous, En79-100 for hydrous). Interestingly, we encountered true diopsides predominantly in pyroxene-dominated hydrous IDPs. Some anhydrous IDPs also displayed restricted compositional ranges for olivines and pyroxenes. For sulfate- containing anhydrous IDPs, olivines and orthopyroxenes had the ranges Fo91-100 and En94-100; for melted (atmospherically ablated) IDPs these ranges were Fo90-100 and En91-94. Are hydrous and anhydrous IDPs genetically related? With the exception of some from the serpentine class (Bradley and Brownlee, 1991), all chondritic IDPs have nearly identical mineralogies (Zolensky and Lindstrom, 1992). The compositional ranges of olivines and pyroxenes in these materials are quite dissimilar, with those from hydrous IDPs being relatively magnesium-rich; however this could be explained by a relatively greater ease of destruction of iron-rich silicates during aqueous alteration. It is known that increasing the Fe^2+ content of olivine decreases the temperature at which serpentinization occurs (Deer et al., 1982). This is apparently due to greater dislocation densities for Fe-rich olivines, and oxidation of Fe^2+. If a similar phenomenon affects alteration of pyroxenes and olivines to smectite, then the genetic relation of hydrous to anhydrous IDPs is permitted by our results. We have already reported that the Mg-Fe compositional range exhibited by phyllosilicates in hydrated IDPs is nearly identical to that of olivines and pyroxenes in anhydrous IDPs (Zolensky and Lindstrom, 1992); this observation also permits a genetic link between these IDP types. However, it is also possible that hydrous are not genetically related to anhydrous IDPs. We note that the relatively Mg-rich compositions of olivines and orthopyroxenes in sulfate-containing IDPs can also be explained by preferential destruction of Fe-rich olivines by oxidation of Fe^2+. The ablated IDPs are merely showing the results of equilibration. Are chondritic IDPs merely small samples of the parent bodies of chondritic meteorites? Aside from differences in bulk composition and physical properties, IDPs differ from all chondritic meteorites except CIs and CMs in the compositional ranges of olivines and pyroxenes (for olivines: CV3- Fo40-60; CO3- Fo40-70; H3, L3 and LL3- Fo30-80; Scott et al., 1988; Dodd, 1981). Although a few hydrous IDPs (a subset of the serpentine class particles) are apparently related to CMs (Zolensky and Lindstrom, 1992), the majority are mineralogically dissimilar. Small carbonaceous clasts contained within certain meteorites (e.g., CR chondrites, the Bholghati howardite, LEW 85300 polymict eucrite and Kaidun carbonaceous breccia) have similar mineralogies to some IDPs (Zolensky et al., 1992), although more detailed analyses of these materials are still required. In summary, most chondritic IDPs are compositionally and mineralogically distinct from chondritic meteorites, but have apparently experienced similar conditions of origin and evolution both in the solar nebula and on parent bodies. References: Bradley and Brownlee (1991) Science 251, 549; Deer, Howie, and Zussman (1982) Rock-Forming Minerals, p. 77; Dodd (1981) Meteorites, A Petrologic-Chemical Synthesis, p. 45; Scott et al. (1988) in Meteorites and the Early Solar System, 721; Zolensky and Lindstrom (1992) Proc. Lunar and Planet. Sci. Conf. 22, 161; Zolensky et al. (1992) Lunar and Planet. Sci. XXIV, 1587.

  16. Spinel from Apollo 12 Olivine Mare Basalts: Chemical Systematics of Selected Major, Minor, and Trace Elements

    NASA Technical Reports Server (NTRS)

    Papike, J. J.; Karner, J. M.; Shearer, C. K.; Spilde, M. N.

    2002-01-01

    Spinels from Apollo 12 Olivine basalts have been studied by Electron and Ion microprobe techniques. The zoning trends of major, minor and trace elements provide new insights into the conditions under which planetary basalts form. Additional information is contained in the original extended abstract.

  17. The fate of fluid inclusions during high-temperature experimental deformation of olivine aggregates

    NASA Astrophysics Data System (ADS)

    Carter, Matthew J.; Zimmerman, Mark E.; Teyssier, Christian

    2015-05-01

    Torsion experiments on initially wet and dry olivine aggregates at equivalent deformation conditions investigated the fate of fluid inclusions (FIs) during high-temperature deformation. Wet samples were produced by adding water to San Carlos olivine powders before hot pressing; those hot pressed without water are considered dry. After hot pressing, wet and dry aggregates have comparable grain sizes, but wet aggregates have more abundant primary FIs. Talc jackets were fitted around some wet and dry samples prior to deformation to hydrate samples during deformation via talc dehydration at elevated temperature, whereas other samples were deformed without talc. At similar strain rates (~1.0 10-4 s-1), the peak shear stress for the dry sample (no talc) was 190-220 MPa, whereas all other samples reached 180 MPa; the strengths of wet ( talc) and dry (+ talc) specimens appear similar. Deformed samples reveal abundant FIs, reduced grain size, shape preferred orientation of olivine, and a pervasive low-angle fabric (C') to the shear plane defined by aligned FIs. Samples deformed with talc have FI-rich and FI-depleted domains; where FIs are abundant, the C' fabric is better developed and grain size is smaller. Electron backscatter diffraction pole figures suggest that olivine deformed in the dislocation creep regime via the (010)[100] slip system. Results of these experiments suggest that FIs are redistributed during dislocation creep, leading to the development of grain-scale, high-diffusivity pathways.

  18. Moessbauer spectra of olivine-rich achondrites - Evidence for preterrestrial redox reactions

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Martinez, S. L.

    1991-01-01

    Moessbauer spectral measurements at 4.2 K were made on several ureilites and the two shergottites found in Antarctica, as well as two ureilite falls, three SNC meteorite falls, and two finds in order to distinguish products of preterrestrial redox reactions from phases formed during oxidative weathering on the earth. The spectra indicated that several ureilites contain major proportions of metallic iron, much of which resulted from preterrestrial carbon-induced reduction of ferrous iron in the outermost 10-100 microns of olivine grains in contact with carbonaceous material in the ureilites. The cryptocrystalline nature of these Fe inclusions in olivine renders the metal extremely vulnerable to aerial oxidation, even in ureilites collected as falls. It is inferred that the nanophase ferric oxides or oxyhydroxides identified in Brachina and Lafayette were produced by terrestrial weather of olivines before the meteorites were found. The absence of goethite in two olivine-bearing Antarctic shergottites suggests that the 2 percent ferric iron determined in their Moessbauer spectra also originated from oxidation on Mars.

  19. Methodology of Space Weathering Simulation and Its Application on Olivine and Pyroxene Samples

    NASA Astrophysics Data System (ADS)

    Malina, Ondrej; Kohout, Tomas; Tucek, Jiri; Filip, Jan; Britt, Daniel; Zboril, Radek

    2015-11-01

    Here, we reported a two-step thermal treatment method [1] for the space weathering simulation and the differences in the formation of metallic iron nanoparticles (npFe0) on the surface of olivine and pyroxene samples are discussed.In general, the main goal is in controlled size of npFe0 formed on the surface of olivine and pyroxene and in quantification of the related spectral changes. The transmission electron microscopy (TEM) after double-heating method revealed two significant features. First, different sizes and concentration of npFe0 are observed, and secondly, due to more resistance of pyroxene (e.g. [2]), higher temperatures are needed to produce the same amount of npFe0 as in the olivine case. [1]Results from TEM are fully consistent with reflectance spectra, which show progressive changes as a function of the increasing npFe0 amount. The reason for the observed differences in reflectance spectra can be found in the crystal structure and local environment at each crystallographic position of both samples. It is very similar as in the case of laser heating experiments (e.g. [2]), where the surface of orthopyroxene is significantly more resistant to reduction than olivine due to mobility of oxygen and cation diffusions from the bulk to surface of the samples.References:[1] Kohout T. et al. (2014) Icarus, 237, 75-83[2] Quadery A. et al (2015) JGR-Planets 120, 1-19.

  20. Measurement of activation volume for creep of dry olivine at upper mantle pressure

    NASA Astrophysics Data System (ADS)

    Dixon, N. A.; Durham, W. B.; Suzuki, A. M.; Mei, S.; Kohlstedt, D. L.; Hustoft, J. W.

    2011-12-01

    Olivine is the most abundant and weakest phase in the upper mantle, and thus its rheological properties have a critical role in controlling convective flow in this region. A resilient obstacle to understanding the behavior of olivine in the mantle has been the difficulty of determining activation volume (V*), the influence of hydrostatic pressure on flow strength. The bulk of previous studies examining V* were conducted at low pressure (<300 MPa) and small pressure ranges in gas-medium deformation apparatuses, limiting precision and raising questions about application to relevant geological conditions. For this study, we conducted deformation experiments on dry polycrystalline olivine in the D-DIA apparatus. The development of a new hybrid soft-fired pyrophyllite/mullite sample assembly allowed for a broadened pressure range (2-9 GPa), while stress and strain were measured in-situ with synchrotron x rays. Refinement in diffraction technique has allowed stress resolution of 0.01 GPa. For the pressure range in this study, we have measured an average activation volume of about 17 cm^3/mol for dry polycrystalline San Carlos olivine. This is a substantial pressure effect, representing a pressure-induced viscosity increase of nearly 7 orders of magnitude from the base of the lithosphere to the bottom of the upper mantle.

  1. Spinels and oxygen fugacity in olivine-phyric and lherzolitic shergottites

    NASA Astrophysics Data System (ADS)

    Goodrich, C. A.; Herd, C. D. K.; Taylor, L. A.

    2003-12-01

    We examine the occurrences, textures, and compositional patterns of spinels in the olivine- phyric shergottites Sayh al Uhaymir (SaU) 005, lithology A of Elephant Moraine A79001 (EET-A), Dhofar 019, and Northwest Africa (NWA) 1110, as well as the lherzolitic shergottite Allan Hills (ALH) A77005, in order to identify spinel-olivine-pyroxene assemblages for the determination of oxygen fugacity (using the oxybarometer of Wood [1991]) at several stages of crystallization. In all of these basaltic martian rocks, chromite was the earliest phase and crystallized along a trend of strict Cr-Al variation. Spinel (chromite) crystallization was terminated by the appearance of pyroxene but resumed later with the appearance of ulvospinel. Ulvospinel formed overgrowths on early chromites (except those shielded as inclusions in olivine or pyroxene), retaining the evidence of the spinel stability gap in the form of a sharp core/rim boundary (except in ALH A77005, where subsolidus reequilibration diffused this boundary). Secondary effects seen in chromites include reaction with melt before ulvospinel overgrowth, reaction with melt inclusions, reaction with olivine hosts (in ALH A77005), and exsolution of ulvospinel or ilmenite. All chromites experienced subsolidus Fe/Mg reequilibration. Spinel-olivine-pyroxene assemblages representing the earliest stages of crystallization in each rock essentially consist of the highest-Cr#, lowest-fe# chromites not showing secondary effects plus the most magnesian olivine and equilibrium low-Ca pyroxene. Assemblages representing the onset of ulvospinel crystallization consist of the lowest-Ti ulvospinel, the most magnesian olivine in which ulvospinel occurs as inclusions, and equilibrium low-Ca pyroxene. The results show that, for early crystallization conditions, oxygen fugacity (fO2) increases from SaU 005 and Dhofar 019 (~QFM -3.8), to EET-A (QFM -2.8) and ALH A77005 (QFM -2.6), to NWA 1110 (QFM -1.7). Estimates for later conditions indicate that in SaU 005 and Dhofar 019 oxidation state did not change during crystallization. In EET-A, there was an increase in fO2 that may have been due to mixing of reduced material with a more oxidized magma. In NWA 1110, there was a dramatic increase, indicating a non-buffered system, possibly related to its high oxidation state. Differences in fO2 among shergottites are not primarily due to igneous fractionation but, rather, to derivation from (and possibly mixing of) different reservoirs.

  2. Elasticity of single-crystal olivine at high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Mao, Zhu; Fan, Dawei; Lin, Jung-Fu; Yang, Jing; Tkachev, Sergey N.; Zhuravlev, Kirill; Prakapenka, Vitali B.

    2015-09-01

    Elasticity of single-crystal San Carlos olivine has been derived from sound velocity and density measurements at simultaneous high pressure-temperature conditions up to 20 GPa and 900 K using in situ Brillouin spectroscopy and single-crystal X-ray diffraction in externally-heated diamond anvil cells. These experimental results are used to evaluate the combined effect of pressure and temperature on full elastic constants of single-crystal olivine to better understand its velocity profiles and anisotropies in the deep mantle. Analysis of the results shows that the shear moduli display strong concave behaviors as a function of pressure at a given high temperature, while the longitudinal modulus, C11, and the off-diagonal moduli, C12 and C13, exhibit greater temperature dependence at higher pressures than at relatively lower pressures. Using a finite-strain theory and thermal equation of state modeling for a pyrolitic mantle composition along an expected mantle geotherm, our results show that the magnitude of the VP and VS jumps at the 410-km depth are 6% and 6.4%, respectively, which are greater than that found in seismic observations, suggesting a mantle olivine content of 40-50 vol%, which is less than what is expected for the pyrolite model. Our modeled velocity profiles for a metastable olivine wedge in the subduction slabs along a representative cold slab geotherm are 6% and 10% lower than those of wadsleyite and ringwoodite, respectively, at corresponding depths of the normal mantle. Our modeled results also show that metastable olivine in the cold slabs could have strong VP and VS anisotropies. The maximum VP anisotropy is estimated to be 19-22% at transition zone depth, whereas the maximum VS splitting is 13-23% and increases with depth. As a result, the presence of a metastable olivine wedge at the transition zone depth would exhibit a seismic signature of low velocity and strong seismic anisotropy which are consistent with recent seismic observations for various locations of the slabs and can be used as mineral physics constraints for future seismic detections of the metastable olivine wedges in the deep mantle.

  3. Albedo and Christiansen Feature Relationships among Remotely Sensed Extreme Lunar Compositions: Olivine and Silica Rich Locations

    NASA Astrophysics Data System (ADS)

    Song, E.; Lucey, P. G.; Ohtake, M.; Greenhagen, B. T.; Glotch, T. D.

    2012-12-01

    Data from the Diviner Lunar Radiometer experiment is sensitive to the ratio of mafic minerals and plagioclase, as well as the presence of significant quantities of silicic mineral such as alkali feldspar or quartz through the position of the Christiansen Feature (CF) that is sensitive to these minerals [1]. Recently [2] reported widespread occurrences of abundant olivine, and suggested that these locations were plagioclase poor, and hence may expose portions of the lunar mantle. We have extracted CF positions from several of the locations of [2] and find that some of them have extreme CF positions indicating high olivine abundances and low plagioclase abundances. The CF is also sensitive to space weathering, where maturity moves the CF position to longer wavelengths, complicating the compositional interpretation. To mitigate this we also examine the 750nm albedo of the locations and compare these to several types of controls. Albedo is derived from a 500-m resolution mosaic of Kaguya Multiband Imager data that has been corrected for topographic shading to a uniform unit of radiance factor illuminated at 30 degrees. We find that the Apollo landing sites form a linear trend when CF is plotted against albedo, consistent with their relative iron contents and plagioclase contents. However, the olivine-rich locations often fall very significantly off this trend, with only a minority falling on the Apollo trend defined principally by pyroxene-plagioclase ratio. The locations with the most extreme CF values form a parallel trend that is consistent with olivine-plagioclase variation. Using CF values for pure minerals from [3], the most extreme values of CF correspond to an olivine content of 80%, close to the dunite composition reported by [2]. Silica rich regions from [4] also fall well off the trend, toward low CF values. This is consistent with the presence of silica-rich minerals, and the only moderate albedo of these locations (between the albedos of Apollo 14 and 16) shows these are not composed of pure but unusual feldspar, but are compositionally distinct and must contain some dark minerals. [1] Greenhagen, B. T. et al. (2010), Science, doi:10.1126/science.1192196. [2] Yamamoto, S. et al. (2010), Nat. Geosci., doi:10.1038/ngeo897. [3] Donaldson Hanna, K. et al. (2012), JGR, doi:10.1029/2011JE003862. [4] Glotch, T. D. et al. (2010), Science, doi:10.1126/science.1192148. Albedo vs CF for Apollo sites, olivine-rich locations [2] and silica-rich regions [4]. The Apollo sites form a linear trend, consistent with plagioclase-pyroxene mixtures, whereas the silica- and olivine-rich locations fall well off the trend consistent with their extreme compositions.

  4. Olivine alteration and H2 production in carbonate-rich, low temperature aqueous environments

    NASA Astrophysics Data System (ADS)

    Neubeck, Anna; Duc, Nguyen Thanh; Hellevang, Helge; Oze, Christopher; Bastviken, David; Bacsik, Zoltn; Holm, Nils G.

    2014-06-01

    Hydrous alteration of olivine is capable of producing molecular hydrogen (H2) under a wide variety of hydrothermal conditions. Although olivine hydrolysis (i.e., serpentinization) has commonly been assessed at elevated temperatures (>100 C), the nature of these reactions in relation to H2 production at lower temperatures has not been systematically evaluated, especially with regard to carbonate-rich fluids. Specifically, carbonate formation may kinetically infringe on geochemical routes related to serpentinization and H2 production at lower temperatures. Here time-dependent interactions of solid, liquid, and gaseous phases with respect to olivine hydrolysis in a carbonate-rich solution (20 mM HCO3-) at 30, 50 and 70 C for 315 days is investigated experimentally. Within the first two months, amorphous Si-rich (i.e., talc-like) and carbonate phases precipitated; however, no inhibition of olivine dissolution is observed at any temperature based on surface chemistry analyses. High-resolution surface analyses confirm that precipitates grew as spheroids or vertically to form topographic highs allowing further dissolution of the free olivine surfaces and exposing potential catalysts. Despite no magnetite (Fe3O4) being detected, H2 increased with time in experiments carried out at 70 C, indicating an alternative coupled route for Fe oxidation and H2 production. Spectrophotometry analyses show that aqueous Fe(II) is largely converted to Fe(III) potentially integrating into other phases such as serpentine and talc, thus providing a viable pathway for H2 production. No increase in H2 production was observed in experiments carried out at 30 and 50 C supporting observations that incorporation of Fe(II) into carbonates occurred faster than the intertwined processes of olivine hydrolysis and Fe(III) oxidation. Overall, carbonate formation is confirmed to be a major influence related to H2 production in low-temperature serpentinization systems. We studied low temperature aqueous alteration of olivine in carbonate and silica-rich solutions. H2 was formed linearly at 70 C, probably coupled to Fe(II) oxidation. Gas, liquid and solid phases were studied and coupled to geochemical modeling. Amorphous and microcrystalline talc-like precipitations were formed. Zn concentration in solution is increasing linearly with time and temperature.

  5. Fault Reactivation During the Olivine to Wadsleyite Transition: A Mechanism for Deep Focus Earthquakes

    NASA Astrophysics Data System (ADS)

    Dobson, D.; de Ronde, A.; Heidelbach, F.; Meredith, P.; Boon, S.

    2006-12-01

    Slip plane orientations of some deep-focus earthquakes suggest that earthquakes can be triggered by reactivation of pre-existing faults in the transition zone. In order to test this theory, we have studied the effect of the olivine-wadsleyite transition on the remobilization of pre-existing olivine faults by performing axisymmetric deformation experiments in a multi-anvil apparatus. Experiments were performed on 3 mm long, 1.5 mm wide cores of San Carlos olivine polycrystals at temperatures of 1173-1273 K and pressures of 6-14 GPa. Microseismicity (AE) related to brittle events in the sample was monitored using 8 1-5 MHz bandwidth PZT transducers that are attached to the back truncations of the tungsten carbide anvils. Cold axisymmetric compression of olivine to 6 GPa pressure results in a conical fault system that crosscuts the sample. AE hypocenters locate near faults and indicate high P-low T frictional sliding. The fault zones consist of fine-grained olivine gouge with a fractal dimension of 2.6±0.1 between 0.1-10 μm grain sizes. The gouge has a random CPO after isothermal compression from 6 to 7 GPa at 1173 K in 1 hour. AE signals from the fault zones during hot compression were indistinguishable from those observed during cold compression and near consistent with stick-slip behavior. Subsequent isothermal compression into the wadsleyite stability field shows no AE-activity. A pre-existing olivine fault zone deformed at 14 GPa and 1173-1273 K was replaced in 20 minutes by wadsleyite with a narrow grain size range (~0.8-1.0 μm). Fault zone wadsleyite has a clear CPO with a- and b-axes oriented in the direction of and perpendicular to the shear direction respectively. This suggests that wadsleyite accommodated renewed fault displacement by dislocation creep. Wadsleyite outside the fault zones does not have a CPO. Thus, under these conditions, fault zone wadsleyite appears weaker than the "wall rock" olivine, suggesting a mechanical weakening during the transition. Such a shear localization process on old faults might contribute to seismogenic slip within the Earth, where run-away processes are possible.

  6. Mineral Compositions from the Hawaii Scientific Drilling Project (HSDP): Preliminary Results Part III - Olivine

    NASA Astrophysics Data System (ADS)

    Putirka, K. D.; Smart, C. M.; Polfer, K. M.

    2004-12-01

    Olivines are the most prevalent phenocrysts in Hawaiian lavas and thus offer a more complete temporal coverage of magmatic processes compared to phenocrysts of more restricted occurrence. As in parts I and II (see accompanying abstracts) we examine olivine compositions from HSDP core samples, which provide a temporal view of the Mauna Kea magma plumbing system. In general, mineral compositions are valuable because they provide an archive of liquid compositions; the compositional record of liquids is always murky due to the facility with which liquids are blended. But minerals, such as olivine, are resistant to re-equilibration and hence provide a much more complete record of the range of liquid compositions that enter a magma plumbing system. Olivine compositions are of particular interest since the Fo content (Mg/(Mg + Fe) ratio) is highly sensitive to T. Olivines that are sampled through the HSDP core thus provide a window into temperature variations across the Hawaiian hot spot. Most olivines are not in Fe-Mg exchange equilibrium with their host whole rock samples. This results is unsurprising and has been noted in numerous studies of olivine phenocrysts at Hawaii. This lack of equilibration limits the precision with which crystallization temperatures can be extracted. But comparisons of Mg/(Mg + Fe) (Fo content) with core depth reveal interesting qualitative results. Most notable are two aspects: (a) Fo contents exhibit nearly constant maximum values throughout the 3000 m of core, near Fo = 90. (b) In contrast, minimum Fo values appear to decrease with decreasing depth. The first observation is counter to what was expected. As Mauna Kea moved over the hot spot, one might expect maximum temperatures to decrease in response to the tapping of cooler mantle material. But near constant maximum values suggest that the hottest parts of the plume are delivered to Hawaiian conduits throughout their eruptive history. In contrast, the decrease in minimum Fo values with time might indeed reflect some T variation across the plume, and is consistent with observations of plagioclase (see part II). We hypothesize that the progressive decrease of Fo contents reflects a gradual decline in eruptive recurrence intervals: as magma supply rates wane, and eruption recurrence intervals increase, the magma conduit may progressively become choked off at various depths, with the result that individual magma batches are stored at a greater range of depths for longer periods of time. But even as supply rates decline, the hottest magmas that are supplied to a conduit during the shield-building stage seem somehow to still be available to the conduit during waning periods of volcanic activity.

  7. High Melt Porosity in the Lower Oceanic Crust Inferred from Phosphorus Zoning in Olivine

    NASA Astrophysics Data System (ADS)

    Hellebrand, E.; Welsch, B. T.; Hammer, J. E.

    2013-12-01

    The canonical view that the lower oceanic crust is composed of cumulates of fractional crystallization has been intensely debated in recent years. Migrating melts, reacting with previously crystallized minerals in the crystal mush, can modify the mineralogy and phase proportions inside the lower crust, as well as the composition of erupted MORB [1]. An extreme product of reactive melt migration was discovered during IODP Legs 304/305 at Atlantis Massif (MAR 30N). In this 1.5 km deep drillhole, there are several sequences of olivine-rich troctolite with ';textbook cumulate texture', which may be associated with the contact of a gabbroic pluton into peridotite [2,3]. While there is little ambiguity about the geological relationships, the exact mechanism for the in-situ reactive transformation of mantle peridotites into lower crustal gabbroic lithologies is still poorly understood. One widespread textural feature in support of the dominant role of reactive melt migration is the occurrence of interstitial and vermicular high-Mg# cpx, which form post-compaction at very low melt porosities. The rare screens of opx-bearing mantle peridotites in this drillhole also preserve evidence for low-porosity replacement of mantle opx by gabbroic cpx [4], with minimal volume change. However, we will show that a significant and possibly the main mass of the olivine crystals in the olivine-rich troctolites do not form at low melt porosities, but instead in a melt-rich local environment. Initially, olivines crystallize as rapidly grown dendrites, which is marked by distinct enrichments of the slowly diffusing element phosphorus. Subsequent slow growth produces the main mass of the otherwise P-free olivine crystal. Our observations on natural basalt-hosted and experimentally grown olivines indicate that strong undercooling in a crystal-poor environment is required for dendrite formation. By extrapolation, this would require a crystal-poor melt lens at the top of an evolving gabbroic intrusion into overlying lithospheric mantle peridotites. Disintegration and partial dissolution of the peridotite minerals can provide the conditions for compositional (rather than thermal) undercooling and promote the rapid growth of new olivines inside the deep melt lens. [1] Lissenberg, C.J. & Dick, H.J.B. (2008) EPSL 271, 311-325. [2] Suhr, G. et al. (2008) G3, doi: 10.1029/2008GC002012. [3] Drouin, M. et al. (2009) Chem. Geol. 264, 71-88. [4] von der Handt, A. & Hellebrand, E. (2010) AGU Fall Meeting abstract.

  8. Origin of Aristarchus Olivine Deposits Based on M3, WAC, and Diviner Analyses

    NASA Astrophysics D