Experimental delineation of the “e” ⇌ I\bar 1 and “e” ⇌ C\bar 1 transformations in intermediate plagioclase feldspars

Approximately 125 hydrothermal annealing experiments have been carried out in an attempt to bracket the stability fields of different ordered structures within the plagioclase feldspar solid solution. Natural crystals were used for the experiments and were subjected to temperatures of ～650°C to ～1,000°C for times of up to 370 days at \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =600 bars, or \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) =1,200 bars. The structural states of both parent and product materials were characterised by electron diffraction, with special attention being paid to the nature of type e and type b reflections (at h+k=(2n+1), l=(2n+1) positions). Structural changes of the type C \(\bar 1\) → I \(\bar 1\) , C \(\bar 1\) → “e” structure, I \(\bar 1\) → “e” and “e” structure → I \(\bar 1\) have been followed. There are marked differences between the ordering behaviour of crystals with compositions on either side of the C \(\bar 1\) ? I \(\bar 1\) transition line. In the composition range ～ An₅₀ to ～ An₇₀ the e structure appears to have a true field of stability relative to I \(\bar 1\) ordering, and a transformation of the type I \(\bar 1\) ? e has been reversed. It is suggested that the e structure is the more stable ordered state at temperatures of ～ 800°C and below. For compositions more albite-rich than ～ An₅₀ the upper temperature limit for long range e ordering is lower than ～ 750°C, and there is no evidence for any I \(\bar 1\) ordering. The evidence for a true stability field for “e” plagioclase, which is also consistent with calorimetric data, necessitates reanalysis both of the ordering behaviour of plagioclase crystals in nature and of the equilibrium phase diagram for the albite-anorthite system. Igneous crystals with compositions of ～ An₆₅, for example, probably follow a sequence of structural states C \(\bar 1\) → I \(\bar 1\) → e during cooling. The peristerite, Bøggild and Huttenlocher miscibility gaps are clearly associated with breaks in the albite, e and I \(\bar 1\) ordering behaviour but their exact topologies will depend on the thermodynamic character of the order/disorder transformations.     

Interdiffusion of NaSi—CaAl in peristerite

The ‘average’ interdiffusion coefficient ( \(\bar D\) ) for NaSi—CaAl exchange in plagioclase for the interval from An₀ to An₂₆ was estimated from experimentally determined homogenization times for peristerite exsolution lamellae. The average spacing between adjacent (unlike) lamellae is 554±77 Å. Dry heating in air at 1,100°C for 98 days produced no change in the exsolution microstructure; thus \(\bar D\) (dry)<10^?17 cm²/s. This limit is consistent with the recently reported ‘average’ \(\bar D\) (dry) values for the Huttenlocher interval (An_70–90) at this temperature. At 1.5 GPa with about 0.2 weight percent water added the ‘average’ diffusion coefficient from 1,100°C to 900°C is given by: \(\bar D\) (wet)=18 _?15 ⁺¹⁰⁸ (cm²/s) exp (?97±5 (kcal/mol)/RT), where R is the gas constant, and T is °K. This \(\bar D\) (wet) at 1,100°C is more than three orders of magnitude greater than \(\bar D\) (dry) for Na- and Ca-rich plagioclases.     

Schiller effects and exsolution in sodium-rich plagioclases

Plagioclase feldspars with mean compositions Ab_91,3Or_4,7An_4,0 and Ab_88,7An_10,1Or_1,2 have been studied by transmission electron microscopy and electron diffraction. The substructure consists of thin lamellae of albite and oligoclase. Two types of orientations of the lamellar planes were observed. The orientation of the more common type was found to change from (08 \(\bar 1\) ) to about ( \(\bar 1\) , 21, \(\bar 2\) ) as a function of the mean potassium content. The plane of the other type was found to be near ( \(\bar 7\) 12). Only the first type of lamellae produces visible Schiller colours.     

Standing stock and estimated production rates of phytoplankton and zooplankton in Narragansett Bay,Rhode Island

Seasonal changes in phytoplankton biomass and production, total zooplankton biomass, and biomass and potential production rates of the two dominant copepods, Acartia hudsonica (formerly called Acartia clausi) and Acartia tonsa are described for several stations in Narragansett Bay, R.I. Plankton in the bay behaved as a single population with simultaneous changes occurring at the upper bay (Station 5) and the lower bay (Station 1). Phytoplankton biomass was higher in the upper bay ( \(\bar x\) =16.95 mg chl a·m^?3) than in the lower bay ( \(\bar x\) =6.37 mg chl a·m^?3) and these 0269 0101 V differences in biomass were reflected in the phytoplankton production rates. The zooplankton, which was dominated by A. hudsonica in the spring and early summer and A. tonsa during summer and fall, showed no such consistent differences between the stations. Mean A. hudsonica biomass (St 1, \(\bar x\) ;=82.7 mg dry wt·m^?3; St 5, _ \(\bar x\) ;=95.2 mg dry wt·m^?3) exceeded that of A. tonsa (St 1, \(\bar x\) ;=56.7 mg dry wt·m^?3; St 5, \(\bar x\) ;=60.0 mg dry wt·m^?3). Potential production rates of the two Acartia 0269 0101 V spp. were strongly temperature dependent. Despite the higher biomass levels of A. hudsonica, low temperatures resulted in lower potential production rates ( \(\bar x\) ; St 1=7.25 mg C·m^?3 day^?1; \(\bar x\) ; St 5=10.77mg C·m^?3 day^?1) and biomass doubling times of up to 9.6 days. Potential production rates of A. tonsa at summer temperatures were high ( \(\bar x\) ; St 1=19.0 mg C·m^?3 day^?1; \(\bar x\) ; St 5=22.9 mg C·m^?3 day^?1) and biomass doubling times were generally less than one day.     

The order-disorder transition in gallium analogue of albite,NaGaSi3O8

The order-disorder transformation in NaGaSi₃O₈ was studied at \(P_{H_2 O} \approx 100\) bar using a hydrous sodium gallium silicate gel and synthetic Ga-albites of various degrees of order as initial materials. The structural state of the gallium albites was determined by the angle separation in X-ray powder patterns of 131 and 1 \(\bar 3\) 1, and of \(\bar 2\) 04 and 060 peaks. The direction of order-disorder transformations was found to change sharply at 938 (±3)°C. This indicates a first order phase transition in NaGaSi₃O₈ as in albite, of which it is the structural analogue.     

A dynamical model for the I\bar 1 - P\bar 1 phase transition in anorthite,CaAl2Si2O8

The non-ferroic triclinic to triclinic \(I\bar 1 - P\bar 1\) phase transition in anorthite is described in terms of the spontaneous onset of an order parameter η. A triclinic to triclinic phase transition can be driven by order parameters (representations) arising from the Γ, Z, X, U, V, R, Y, and T points of symmetry of the Brillouin zone. Each point leads to a set of two inequivalent representations and thus there is a total of sixteen inequivalent order parameters. However, only the R ₁ ⁺ representation is consistent with the change from the body-centered to primitive cell (increase of primitive cell size of two) and also with the origin of the two space groups (inversion center) being at the same position. The R ₁ ⁺ order parameter of the high symmetry triclinic phase \(P\bar 1_0\) (or equivalently \(I\bar 1\) ) causes a reciprocal lattice change and, in terms of the lower symmetry reciprocal lattice, the order parameter corresponds to the b^* point. This is consistent with experimentally observed x-ray diffuse scattering. Using induced representation theory, microscopic distortions compatible with the R ₁ ⁺ order parameter are obtained. Assuming a distortion in an arbitrary direction at the general 2(i) Wyckoff position (x₀,y₀,z₀) of \(P\bar 1_0\) (the higher symmetry phase) induced representation theory demands an opposite displacement at the position (x₀, y₀, z₀), an opposite displacement at (x₀+1,y₀+1,z₀+1), and the same displacement at ( \(\bar x\) ₀+1, \(\bar y\) ₀+1, \(\bar z\) ₀+1) of \(P\bar 1_0\) . This is also consistent with experiment. The presence of the weak c-type reflections above the transition is attributed to the fluctuating lower symmetry antiphase domains related by the translation (1/2, 1/2, 1/2).     

Transmission electron microscopy of experimentally deformed chalcopyrite single crystals

Two crystals of natural chalcopyrite, CuFeS₂, experimentally deformed at 200° C have been studied by means of transmission electron microscopy (TEM). The activated glide planes are (001) and {112}. The dislocations in (001) have the Burgers vector [110] and a predominating edge character. They are split into two colinear partials b=1/2[110] and can cross split into {112}. The dislocations in {112} consist of straight segments along low index lattice lines. They are often arranged in dipoles generating trails of loops. Few dislocations with b=1/2[ \(\overline {11} \) 1] and [1 \(\bar 1\) 0] are present and dislocations with b=[0 \(\bar 2\) 1] occur in low angle subgrain boundaries. From weak beam contrasts it is presumed that most of the dislocations gliding in {112} have b=1/2〈3 \(\overline {11} \) 〉. They are dissociated into up to four partials. Microtwins and different types of stacking faults in {112} also occur. Models of the dissociation of dislocations are discussed.     

Deformation and transformation in experimentally shock-loaded quartz

Single crystals of quartz, shock-loaded along the a axis to pressures of 22 Gpa, 24 GPa, 26 GPa and 30 GPa were examined by high-voltage transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction. Asymmetric broadenings of X-ray lines indicate spatial inhomogeneity of shock effects. X-ray streaking angles in the reciprocal lattice planes h0 \(\bar h\) l, 0k \(\bar k\) l and hki0 indicate a slight tilting deformation by rotation about [00.1] in (0001). TEM reveals glass lamellae which are mostly in (01 \(\bar 1\) 2) orientation, and are correlated with optical planar elements and with surface steps seen in SEM. No dislocations are found. There are (0001) lamellar features, probably Brazil twins. The (01 \(\bar 1\) 2) glass lamellae develop directly from bands of quartz in which intense deformation has produced a fine-scale lamellar to blocky structure, possibly also originating by twinning. Relics of crystalline structure are found in almost completely vitrified lamellae. Stishovite occurs in heavily deformed parts of the 22 GPa and 24 GPa specimens, in patches of densified glass distinct from the sharply bounded lamellae. The nucleationless, pervasive transformation of lamellae to glass, with preservation of their sharp boundaries, is attributed to defect coalescence analogous to vitrification by radiation damage (metamictization). Some patchy glass may be due to melting.     

X-ray diffraction study of the orientational order/disorder transition in NaNO3: Evidence for order parameter coupling

The orientational ordering transition R \(R\bar 3m - R\bar 3c\) in NaNO₃ near 552 K has been investigated using x-ray diffraction techniques. NaNO₃ is a model system for CaCO₃ and other minerals with orientational disorder of triangular molecules in a simple NaCl-type matrix. The temperature evolution of the integrated intensities of the superlattice reflection \(\bar 1\) 23 and the fundamental reflection 110 are discussed in terms of Landau theory of two coupled order parameters. It is shown that the known phenomenological critical exponent (Poon and Salje 1988) and the anomalous thermal expansion at T > T _tr (Reeder et al. 1988) can be understood as the result of a Z point instability which mainly describes the NO ₃ ^- disorder, and a second order parameter linked with the spontaneous strain of this phase transition.     

Cation stacking faults in magnesium germanate spinel

Widely extended, cation stacking faults in experimentally deformed Mg₂GeO₄ spinel have been studied using transmission electron microscopy (TEM). The faults lie on {110} planes. The displacement vector is of the form \(\frac{1}{4}\left\langle {1\bar 10} \right\rangle \) and is normal to the fault plane. The partial dislocations which bound the stacking fault have colinear Burgers vectors of the form \(\frac{1}{4}\left\langle {1\bar 10} \right\rangle \) which are normal to the fault plane.     

Elastic constant systematics

This papers reviews elastic constant systematics. The bulk modulus of oxides and silicates is generally predictable on the basis of density and mean atomic weight. For constant mean atomic weight, \(\bar M\) , the bulk modulus is inversely proportional to the fourth power of the molar volume, regardless of whether molar volume changes due to temperature,T, pressure,P, or crystal structure. This iso- \(\bar M\) trend has the explanation that the Grüneisen parameter, (?K/?P) _T , and ?(1/αK)(?K/?T) _P , whereK is bulk modulus and α is volumetric thermal expansion, are approximately constant for most materials. For isostructural compounds, the bulk modulus is inversely proportional to the molar volume. This isostructural trend has the explanation that a certain combination of interatomic force parameters are the same for isostructural compounds. Equivalent iso- \(\bar M\) and isostructural trends are discussed for velocity versus density. Exceptions to the systematics exist.     

Transmission electron microscope study of experimentally deformed K-Feldspar single crystals

Single crystals of sanidine which were experimentally deformed so as to introduce the (010)[100] slip system were examined by transmission electron microscopy (tem). Dislocation glide is mainly manifested in the samples deformed at 700° C, with a strain rate \(\dot \varepsilon = 1 - 2 \times 10^{ - 6} s^{ - 1} \) . In addition to the expected slip system another more important one, (12 \(\bar 1\) )[101], was found. The dislocations lying in (010) present a glissile dissociation. These observations have been discussed in term of the feldspar structure. Models for glissile dissociation in (010) are proposed: [100]=1/2[100]+1/2[100] or 1/2[101]+1/2[10 \(\bar 1\) ] and [101]=1/2[101]+1/2[101].     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Transmission electron microscopy on meteoritic troilite

Phase transitions and associated domains of meteoritic troilite (FeS) have been studied by means of transmission electron microscopy (TEM). Three polymorphs have been found, two of which can be described by superstructures of the NiAs-type structure (A, C subcell). The P \(\overline 6\) 2c (√3A, 2C) polymorph, stable at room temperature, displays antiphase domains with the displacement vector 1/3< \(\overline {\text{1}}\) 10>. In situ heating experiments showed that the P \(\overline 6\) 2c polymorph changes at temperatures of 115°–150° C into an orthorhombic pseudohexagonal transitional phase with the probable space group Pmcn (A,√3A, C). It contains antiphase domains with the displacement vector 1/2 [110] and twins with a threefold twin-axis parallel c. When heated above 210° C the transitional phase transforms into the high-temperature modification with NiAs structure (P6 ₃/mmc). All observed phase transitions are reversible. The occurrence of antiphase and twin domains, respectively, agrees with the symmetry reductions involved in the subsolidus phase transitions. This is demonstrated by group-subgroup relationships among the space groups P6 ₃/mmc, Pmcn, and P \(\overline 6\) 2c.     

Coherent elastic energies of exsolution boundaries in peristerite and böggild intergrowths

Elastic energy calculations based upon the coherent model of Willaime and Brown [Acta Cryst. A30, 316–331 (1974)] have been carried out for some exsolution textures in peristerite and Böggild intergrowths. For peristerites it is demonstrated that substitution of K for Na moves the orientation of the exsolution lamellae from (08 \(\overline {\text{1}} \) ) to about ( \(\overline {\text{1}} \) , 21, \(\overline {\text{2}} \) ) in agreement with observations. An electron microscope study of exsolution textures in labradorite and andesine plagioclases has been carried out and information about small structural differences in these lamellar structures has been obtained from elastic energy calculations.     

Tracerdiffusion of the Fe-cations in olivine (Fe x Mg1−x )2SiO4 (III)

Tracerdiffusion coefficients D _Fe* (and D _Mg*) are presented for olivines of composition (Fe _x Mg_1?x )₂SiO₄ at T=1,130° C as a function of x, and oxygen activity, a _{O 2}. Since the oxygen activity dependence of D _Fe* (D _Mg*) and that of the cation vacancy concentration are almost identical, it is concluded that a vacancy diffusion mechanism is operative in the octahedrally coordinated cation sublattices. From D _Fe* and D _Mg*, the chemical diffusion coefficient \(\bar D\) can be calculated. The calculated \(\bar D\) is in agreement with \(\bar D\) -values obtained by Boltzmann-Matano analysis of interdiffusion experiments. In addition, correlation factors are evaluated from the tracerdiffusion data in order to calculate selfdiffusion coefficients.     

Transmission electron microscopic study of experimentally deformed k-feldspar single crystals

A set of sanidine single crystals were previously deformed at 700° C in a Griggs triaxial press with different crystallographic orientations of the core so as to induce dislocation glide of different slip systems respectively. Deformed crystals have been studied by transmission electron microscopy (TEM) and the activated slip systems have been characterized for two orientations. (010)[001] and (001)1/2[ \(\overline 1 \) 10] systems expected for one orientation (main stress nearly parallel to [012]) are observed, whereas the (001)[100] system expected for the other orientation (main stress nearly parallel to [101]) is never observed. In the latter specimen the deformation is rather difficult and occurs through unexpected systems characterized as (110)1/2[1 \(\overline 1 \) 2] and (1 \(\overline 1 \) 1)1/2[110]. In all the samples studied the deformation is heterogeneous, exhibiting dislocation configurations related to temperature variations.     

Deformation twinning in calcite,dolomite, and other rhombohedral carbonates

Transmission electron microscope (tem) observations of single and multiple twins in calcite and dolomite are presented, and the results are analysed by means of selected area diffraction and trace analysis. Simple twinning in rhodochrosite and kutnahorite is also analysed. It is shown that the ordered carbonates, such as dolomite, have a common twinning plane {01 \(\bar 1\) 2} and this appears to be their only mode of deformation twinning. The carbonates with higher symmetry, such as calcite, have {01 \(\bar 1\) 8} as the primary twinning plane but calcite itself has other twinning mechanisms, of which the most important is illustrated. Crossing and stopping twins are also discussed. It is shown that twinning in calcite, which occurs predominantly at low temperatures, is characterized by the generation of large numbers of glide dislocations.     

Experimental study of subsolidus phase relations and mixing properties of pyroxene and plagioclase in the system Na2O-CaO-Al2O3-SiO2

In the system Na₂O-CaO-Al₂O₃-SiO₂ (NCAS), the equilibrium compositions of pyroxene coexisting with grossular and corundum were experimentally determined at 40 different P-T conditions (1,100–1,400° C and 20.5–38 kbar). Mixing properties of the Ca-Tschermak — Jadeite pyroxene inferred from the data are (J, K): $$\begin{gathered} G_{Px}^{xs} = X_{{\text{CaTs}}} X_{{\text{Jd}}} [14,810 - 7.15T - 5,070(X_{{\text{CaTs}}} - X_{{\text{Jd}}} ) \hfill \\ {\text{ }} - 3,350(X_{{\text{CaTs}}} - X_{{\text{Jd}}} )^2 ] \hfill \\ \end{gathered} $$ The excess entropy is consistent with a complete disorder of cations in the M2 and the T site. Compositions of coexisting pyroxene and plagioclase were obtained in 11 experiments at 1,190–1,300° C/25 kbar. The data were used to infer an entropy difference between low and high anorthite at 1,200° C, corresponding to the enthalpy difference of 9.6 kJ/mol associated with the C \(\bar 1\) =I \(\bar 1\) transition in anorthite as given by Carpenter and McConnell (1984). The resulting entropy difference of 5.0 J/ mol · K places the transition at 1,647° C. Plagioclase is modeled as ideal solutions, C \(\bar 1\) and I \(\bar 1\) , with a non-first order transition between them approximated by an empirical expression (J, bar, K): $$\Delta G_T = \Delta G_{1,473} \left[ {1 - 3X_{Ab} \tfrac{{T^4 - 1,473^4 }}{{\left( {1,920 - 0.004P} \right)^4 - 1,473^4 }}} \right],$$ where $$\Delta G_{1,473} = 9,600 - 5.0T - 0.02P$$ The derived mixing properties of the pyroxene and plagioclase solutions, combined with the thermodynamic properties of other phases, were used to calculate phase relations in the NCAS system. Equilibria involving pyroxene+plagioclase +grossular+corundum and pyroxene+plagioclase +grossular+kyani te are suitable for thermobarometry. Albite is the most stable plagioclase.     

The ferric-ferrous ratio of natural silicate liquids equilibrated in air

Results of chemical analyses of glasses produced in 46 melting experiments in air at 1,350° C and 1,450° C on rocks ranging in composition from nephelinite to rhyolite have been combined with other published data to obtain an empirical equation relating in \((X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{liq}}} /X_{{\text{FeO}}}^{{\text{liq}}} )\) to T, \(\ln f_{{\text{O}}_{\text{2}} } \) and bulk composition. The whole set of experimental data range over 1,200–1,450° C and oxygen fugacities of 10^?9.00 to 10^?0.69 bars, respectively. The standard errors of temperature and \(\log _{10} f_{{\text{O}}_{\text{2}} } \) predictions from this equation are 52° C and 0.5 units, respectively, for 186 experiments.