SPINEL, KALSILITE, CLINOPYROXENE AND OLIVINE by

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TABLE OF CONTENTS LIST OF FIGURES ………………………………………………………………….…..8 ABSTRACT.......................................................................................................................9 INTRODUCTION............................................................................................................11 Explanation of the Problem and Its Context..................................................................11 Literature Review..........................................................................................................11 Explanation of Dissertation Format..............................................................................12 PRESENT STUDY ..........................................................................................................12 Analytical Complications due to Common Defects found in Minerals .......................13 Applications of Crystal Chemistry to Geological Problems .......................................15 Case Study: San Carlos Project …………………………………………...................18 I. Objective …………………………………………………………………….......18 II. Geological background …………………………………………………….......20 III. Studied samples: rock classification and petrography .……………………......23 IV. Pressure estimates for SC samples and crystal chemistry of clinopyroxene ....25 V. Closest-packing of oxygen atoms in spinel, cpx and olivine as a function of T, P and X ………………………………………………………………………26 FIGURES ……………………………………………………………………...…….…30 REFERENCES …………………………………………………………………...……..37 APPENDIX A: INVESTIGATION OF SYNTHETIC MG1.3V1.7O4 SPINEL WITH MGO INCLUSIONS: CASE STUDY OF A SPINEL WITH AN APPARENTLY OCCUPIED INTERSTITIAL SITE …...................................................………………..41 APPENDIX B: AN APPARENT SYMMETRY P6322 SPACE GROUP AND MEROHEDRAL TWINNING: STRUCTURAL INVESTIGATION OF KALSILITE AT CRYOGENIC TEMPERATURES ..…………………………………………….….73 APPENDIX C: SINGLE-CRYSTAL X-RAY DIFFRACTION STUDIES ON SPINELS FROM THE SAN CARLOS VOLCANIC FIELD, ARIZONA: SPINEL AS GEOTHERMOMETER ...…………………………………………………………104 6
TABLE OF CONTENTS – Continued APPENDIX D: CRYSTAL CHEMISTRY OF CLINOPYROXENE IN THE TWO TYPES OF MANTLE XENOLITHS FROM SAN CARLOS VOLCANIC FIELD, AZ .…………………………………………………………………………….145 APPENDIX E: INVESTIGATION OF DISTORTIONS FROM ITS IDEAL CLOSEST-PACKING IN OLIVINE AS A FUNCTION OF TEMPERATURE, PRESSURE AND COMPOSITION …………………………………….………….... 192 7
Page 1 and 2: CRYSTAL CHEMICAL AND STRUCTURAL ANA
Page 3 and 4: STATEMENT BY AUTHOR This dissertati
Page 5: DEDICATION This dissertation is ded
Page 9 and 10: ABSTRACT Natural and synthetic comm
Page 11 and 12: Explanation of the Problem and its
Page 13 and 14: (APPENDIX C), clinopyroxene (APPEND
Page 15 and 16: etween observed structure and the m
Page 17 and 18: close to 1.0 for Fa24 at room tempe
Page 19 and 20: crystallization can provide useful
Page 21 and 22: limit of ~ 25 kbars in the equilibr
Page 23 and 24: isotopes (Zartman and Tera 1973). F
Page 25 and 26: crystals are present (up to 1 cm) (
Page 27 and 28: Downs (2001). I examined packing di
Page 29 and 30: the substitution of Co for Mg resul
Page 31 and 32: Figure 2. Two melting indicators, A
Page 33 and 34: Fig. 3 cont. (b) (c) (d) 33
Page 35 and 36: Fig. 3 cont. (h) (i) 35
Page 37 and 38: REFERENCES Aoki, K. (1975) Origin o
Page 39 and 40: Princivalle, F., Della Giusta, A.,
Page 41 and 42: APPENDIX A: INVESTIGATION OF SYNTHE
Page 43 and 44: (XEDS) suggested that the Mg-rich i
Page 45 and 46: The presence of a small amount of c
Page 47 and 48: However, the inclusions were too sm
Page 49 and 50: Turner (1968). The refined paramete
Page 51 and 52: is occupied, the nearest octahedral
Page 53 and 54: the observed tetrahedral bond dista
Page 55 and 56: length because of its low abundance
Page 57 and 58:
Devanathan, R., Yu, N., Sickafus, K
Page 59 and 60:
Nowell, M.M. and Wright, S.I. (2004
Page 61 and 62:
Figure 1. BSE images of (a) the sel
Page 63 and 64:
Figure 2. XEDS maps and statistics.
Page 65 and 66:
Figure 3. EBSD patterns of (a) spin
Page 67 and 68:
Figure 5. Two possible structural i
Page 69 and 70:
Table 1. Chemical composition of Mg
Page 71 and 72:
Table 3. Comparison of refinement r
Page 73 and 74:
APPENDIX B: AN APPARENT SYMMETRY P6
Page 75 and 76:
Additionally, the same crystal from
Page 77 and 78:
displacive transformation between P
Page 79 and 80:
1955) and later in most kalsilite (
Page 81 and 82:
temperatures on a Bruker X8 APEX si
Page 83 and 84:
oxygen, O1, and assigning O1 off th
Page 85 and 86:
layers was on the 3-fold axis. This
Page 87 and 88:
ecame more perpendicular to the c a
Page 89 and 90:
Downs, R.T. (2000) Analysis of harm
Page 91 and 92:
Figure 1. Unit-cell volume changes
Page 93 and 94:
c-c o 0.06 0.04 0.02 0.00 -0.02 -0.
Page 95 and 96:
Table 1. Chemical composition (wt%)
Page 97 and 98:
Table 3. Summary of crystal data an
Page 99 and 100:
Table 4. Refinement results at room
Page 101 and 102:
Table 4. cont. ====================
Page 103 and 104:
Table 4. cont. ====================
Page 105 and 106:
Single-crystal X-ray diffraction of
Page 107 and 108:
to the host basalt but rather they
Page 109 and 110:
O and T-O bond distances (u = 0.262
Page 111 and 112:
temperature of TQ onto the equilibr
Page 113 and 114:
higher value of Rw, but it insures
Page 115 and 116:
would rigidly constrain the optimiz
Page 117 and 118:
these three figures. In addition to
Page 119 and 120:
Closure temperatures, Tc, for our s
Page 121 and 122:
Bond distances, T-O vs. M-O, are pl
Page 123 and 124:
Finger, L.W. and Prince, E. (1975)
Page 125 and 126:
diffraction study of MgAl2O4 at tem
Page 127 and 128:
Figure 1. Chemistry of spinels from
Page 129 and 130:
129
Page 131 and 132:
131
Page 133 and 134:
Figure 4. Closure temperatures vers
Page 135 and 136:
Figure 6. Bond distances, M-O vs. T
Page 137 and 138:
Table 2. Structural refinement resu
Page 139 and 140:
Table 2. cont. Sample SC 1 SC 11 SC
Page 141 and 142:
Table 4. Cation distribution, inver
Page 143 and 144:
Table 4. cont. Sample Occ T Occ M F
Page 145 and 146:
APPENDIX D: CRYSTAL CHEMISTRY OF CL
Page 147 and 148:
effect on Ucp in case of clinopyrox
Page 149 and 150:
Pyroxene is an important mineralogi
Page 151 and 152:
and M polyhedra (VT and VM, respect
Page 153 and 154:
Ganguly 2003). Liermann and Ganguly
Page 155 and 156:
crystal chemistry of those samples.
Page 157 and 158:
Experimental Crystals were selected
Page 159 and 160:
of both xenoliths types. The absenc
Page 161 and 162:
temperature and pressure for the sa
Page 163 and 164:
elationships among geometrical para
Page 165 and 166:
We examined the datasets to find th
Page 167 and 168:
Figure 6 shows a correlation betwee
Page 169 and 170:
References Basu, A.R. and MacGregor
Page 171 and 172:
Galer, S.J.G. and O’Nions, R.K. (
Page 173 and 174:
Princivalle, F., Salviulo, G., Fabr
Page 175 and 176:
Witt-Eickschen, G. and Seck, H.A. (
Page 177 and 178:
Figure 2. Estimated pressure and te
Page 179 and 180:
(b) 179
Page 181 and 182:
(b) 181
Page 183 and 184:
Figure 6. Correlation between Ucp (
Page 185 and 186:
Table 1. Chemical composition of th
Page 187 and 188:
Table 2. cont. SC19 SC1 SC11 a (Å)
Page 189 and 190:
Table 3. cont. SC19 SC1 SC11 M1 y 0
Page 191 and 192:
Table 5. Pressure and temperature e
Page 193 and 194:
Investigation of distortions from i
Page 195 and 196:
ideal geometry. For olivine, while
Page 197 and 198:
and shown to have a widely ranging
Page 199 and 200:
this viewpoint gave meaningful resu
Page 201 and 202:
201 After the X-ray data collection
Page 203 and 204:
Discussion (1) Relationship between
Page 205 and 206:
NiMgSiO4 (Henderson et al. 2001), F
Page 207 and 208:
increases. As Thompson and Downs (2
Page 209 and 210:
correlated with the average radii o
Page 211 and 212:
211 We have shown in Uchida et al.
Page 213 and 214:
Belokoneva, E.L., Ivanov, Y.A., Sim
Page 215 and 216:
Kimata, M. and Nishida, N. (1987) T
Page 217 and 218:
Smyth, J.R. (1975) High-temperature
Page 219 and 220:
Figure 2. x coordinate vs. y coordi
Page 221 and 222:
Figure 4. Ucp (Å 2 ) as a function
Page 223 and 224:
Ucp 0.075 0.070 0.065 (b) Ucp = 0.0
Page 225 and 226:
Figure 7. Changes in lengths of O-O
Page 227 and 228:
Table 1. Chemical composition of th
Page 229 and 230:
Table 2. cont. SC19 SC1-2 SC11-4 SC
Page 231 and 232:
Table 3.cont. SC8 SC2 SC19 SC1-2 SC
Page 233:
Table 4. Ucp of selected silicate a
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SPINEL, KALSILITE, CLINOPYROXENE AND OLIVINE by

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