X-ray and electron-optical investigation of synthetic high-temperature plagioclases

High-temperature plagioclases NaAlSi₃O₈(Ab)-CaAl₂Si₂O₈(An) have been prepared by dry devitrification of glasses. X-ray powder photographs were taken to follow the time-temperature dependence of indicators of structural state and to determine the lattice parameters of the plagioclases as well as their K-exchanged equivalents. Transmission electron microscopy (TEM) has been used to study the anorthite-type antiphase domain textures. The results are as follows:

1. TEM and X-ray powder data suggest to subdivide the high-temperature plagioclase series into three structural regions: (a) An0 to An30–40: monalbite/analbite to high albite-type structures, (b) An60–70 to An100: anorthite-type structures, (c) An30–40 to An60–70: transitional structures assumed to represent the early stages in the development of the structural complexities found in chemically intermediate low temperature plagioclases.
2. b-Antiphase domains typical for the anorthite-type structure could be imaged in samples ranging between An100 and An67.5, whereas c-antiphase domains have only been found in An90 and An100. The b-domains developed during isothermal crystallization, rather than cooling. The transition from the anorthite-type structure (S.G.I \(\bar 1\) ) to an intermediate C \(\bar 1\) -type structure at An60–70 appears to be a gradual one.
3. The relative contribution of various structural and chemical influences on the cell edges and angles is discussed in detail. It is shown that the nonlinear variation of γ with An content is due to incomplete Al,Si disorder in the high series.

     

The effect of Al/Si disorder on the I \bar 1-P \bar 1Co-Elastic phase transition in Ca-rich plagioclase

The influence of Al/Si disorder in the anorthite tetrahedral framework upon the I \(\bar 1\) -P \(\bar 1\) displacive transition of that framework has been investigted at high-temperature by powder X-ray diffraction. The temperature-dependence of the order parameter in a heat-treated (disordered) anorthite and a Ca-rich plagioclase has been determined from spontaneous strain measurements. Both samples show appreciable disorder, with Q _od = 0.88 in both cases. In each, the critical exponent β appears to be intermediate between values for classical tricritical (1/4) and second-order (1/2) phase transitions. This critical behaviour is consistent with a Landau potential in which the coefficient of the quartic term is positive but smaller than the coefficient of the sixth order term, corresponding to a second-order phase transition close to a tricritical point. There does not appear to be any defect strain tail near T _c and inhomogeneities in Q _od appear to be on rather a short length scale in these samples. The role of changing Q _od appears to be more important than that of changing composition (albite component). The data are interpreted using a model of a homogeneous field due to changing Q _od which renormalizes the transition temperature, T _c ^* , and the fourth order coefficient, B _eff, in the Landau expansion. The results are consistent with classical Landau behaviour, and demonstrate the care which must be taken in interpreting apparently non-classical critical exponents for phase transitions close to a tricritical point.     

Thermodynamics of plagioclase II: Temperature evolution of the spontaneous strain at the I\bar 1 \leftrightarrow P\bar 1 phase transition in anorthite

The temperature dependence of the lattice parameters of pure anorthite with high Al/Si order reveals the predicted tricritical behaviour of the \(I\bar 1 \leftrightarrow P\bar 1\) phase transition at T _c ^* =510 K. The spontaneous strain couples to the order parameter Q° as x _i∝S _xQ ⁱ Q°² with S _xQ ¹ =4.166×10^?3, S _xQ ² =0.771×10^?3, S _xQ ³ =?7.223×10^?3 for the diagonal elements. The temperature dependence of Q° is $$Q^{\text{o}} = \left( {1 - \frac{T}{{510}}} \right)^\beta ,{\text{ }}\beta = \tfrac{{\text{1}}}{{\text{4}}}$$ A strong dependence of T _c ^* , S _xQ ⁱ and β is predicted for Al/Si disordered anorthite.     

Kationenaustausch an Plagioklasen

A series of K-plagioclases have been produced metastably by ion-exchanging the plagioclases in KCl-melt. Chemical analyses and re-exchange experiments (with NaCl-melt) have proved that the K-plagioclases are truly isomorphous with plagioclases. Because of their isomorphous nature it was possible to mix them in different proportions and homogenise them, thereby producing ternary feldspars of different compositions in the system Or-Ab-An. A comparative study of the lattice constants of plagioclases, their K-equivalents and the different ternary feldspars calculated using powder data leads to the following conclusions:

1. It is possible to dertermine by X-ray methods the anorthite content of a plagioclase to an accuracy of ±1% An.
2. The influence of the ionic size of the bigger cations Na, Ca, and K and that of order/disorder are different on different lattice constants and it is possible to distinguish these two effects.
3. The b-parameter indicates a definite structural change in plagioclases at about 25–30% An.
4. It is possible to predict the average Al/Si-distributions in the four different positions T_1(o), T_1(m), T_2(o) and T_(m) of all plagioclases of all stable structural states, using the c-parameter of their K-equivalents.

     

Thermodynamics of plagioclase III: Spontaneous strain at the I\overline 1 - P\overline 1 phase transition in Ca-rich plagioclase

The lattice parameters of anorthites An₉₈Ab₂ and An₁₀₀ have been measured from 22 to 1100 K. The spontaneous strain arising from the \(I\overline 1 - P\overline 1\) displacive transition in An₉₈ follows second order Landau behaviour. The spontaneous strain (? _s) couples quadratically to the order parameter (Q ⁰) with ? _s∝Q ⁰²∝(T _c ^* ?T) and T _c ^* =530 K in An₉₈. This is in contrast to the tricritical behaviour observed in pure anorthite. These observations are consistent with a Landau model for the free energy of Ca-rich plagioclases in which Al/Si order and Na content renormalize the fourth order coefficient.     

High-temperature 29Si MAS NMR spectroscopy of anorthite (CaAl2Si2O8) and its P\bar 1-I\bar 1structural phase transition

We present ²⁹Si MAS NMR data for a well-ordered natural anorthite, obtained in situ at temperatures of from 25 to 500° C, which follow the changes in the aluminosilicate framework through the P $\bar 1$ -I $\bar 1$ structural phase transition. Pairs of peaks due to sites offset by approximately 1/2 [111] converge through the P $\bar 1$ phase and only four peaks are present above about 241° C. The variation of the peak positions with temperature and correlations based on structural data for the P $\bar 1$ and I $\bar 1$ phases allow assignment of all the MAS-NMR peaks to crystallographic sites. A Landau-type analysis gives an expression that relates the separation of pairs of con verging peaks to the local order parameter for the P $\bar 1$ -I $\bar 1$ transition, from which we determine its temperature dependence. Data for the best-constrained set of peak positions give for the order parameter critical exponent β = 0.27±0.04, consistent with previous results indicating that the P $\bar 1$ -I $\bar 1$ transition in pure anorthite is tricritical. No significant change in the ²⁹Si spin-lattice relaxation rate occurs across the P $\bar 1$ -I $\bar 1$ transition.     

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).     

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.     

Spontaneous strain below the I\bar 1 - P\bar 1 transition in anorthite at pressure

The phase transition between the and phases of anorthite has been studied at elevated pressure by single-crystal X-ray diffraction in a diamond-anvil cell. The phase transition is shown to be first-order in character for both end-member anorthite (CaAl₂Si₂O₈) and for an anorthite with a small amount of albite component (NaAlSi₃O₈) in solid solution. Reversals of the transition across the phase boundary at three other compositions show that the transition pressure (P _Tr) increases with increasing albite content. This behaviour is compared with that observed at elevated temperatures, and is analysed in terms of Landau theory.     

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.     

Microscopic dynamic and macroscopic thermodynamic character of the I\bar 1 - P\bar 1 phase transition in anorthite

The dynamic character of the phase transition in anorthite from Monte Somma has been studied by high-temperature hard mode infrared spectroscopy. The mean local order parameter, as revealed by the temperature evolution of the frequencies of absorption bands between 540 and 620 cm_-1, follows classical second-order Landau behaviour with a critical exponent β = 1.. There is no observable first-order step. Anomalous line broadening of the 582 cm_-1 band indicates that dynamic fluctuations with a relaxation time τ ≈ 10⁻¹⁰ s exist over a limited temperature interval of approximately 150 K about T_c, and decay rapidly as T becomes greater than T_c. Previous order-disorder models of the high-temperature phase are not supported by these results. The Ca-flip motions, which we link to the line broadening, stabilize the driving soft mode of the transition. These flip motion fluctuations do not give rise to departures from the classical Landau theory because of the essential co-elastic nature of the phase transition. In the light of these results the structural instability can be described as an essentially displacive transition.     

Raman spectroscopic investigation of the order parameter behaviour in hypersolvus alkali feldspar: Displacive phase transition and evidence for Na-K site ordering

Hard mode Raman spectroscopy (HMRS) on hypersolvus alkali feldspar shows a temperature dependence of the order parameter of the displacive \({{C2} \mathord{\left/ {\vphantom {{C2} {m{\text{ - }}C\bar 1}}} \right. \kern-0em} {m{\text{ - }}C\bar 1}}\) phase transition following mean-field behaviour: $$Q \sim \sqrt {T_c - T;} 300 {\text{K}} \lesssim T< T_c $$ At lower temperatures, a spontaneous saturation sets in, which is attributed to site-ordering effects of the alkali atoms even in hypersolvus anorthoclase. Fluctuational line broadening of Si-O viration bands is explained by strong lattice distortions around alkali positions and local deformation of the Al,Si,O network. The thermodynamic relevance of these distortions is discussed in relation to the possibility of an additional diffuse phase transition occurring atT _d =302 K. The experimental results of HMRS are compared with those on Al,Si ordered and disordered albite, where no fluctuation broadening occurs.     

Low temperature\lg f_{O_2 } - pH diagrams of sulfur isotope evolution in an equilibrium hydrothermal system

According to Sakai-Ohmoto's theory regarding the evolution of sulfur isotopes in hydrothermal systems, in conjunction of new data on chemical resaction equilibrium constants and equilibrium isotopic fractionation factors as well as on individual ion activity coefficients of aqueous sulfur species, the following lgfo₂.-pH diagrams are constructed:

1. mole fractions of aqueous sulfur species (X _i ),
2. stability fields of some minerals in the Fe-S-O system,
3. diagram depicting the oxidation-reduction-state ratio for aqueous sulfur species (R′)
4. isotopic compositions of sulfur compounds ( \(\delta S_1 ^{34} \) ).

     

Equilibrium thermodynamics of Al/Si ordering in anorthite

Variations in the equilibrium degree of Al/Si order in anorthite have been investigated experimentally over the temperature range 800-1535° C. Spontaneous strain measurements give the temperature dependence of the macroscopic order parameter, Q, defined with respect to the \(C\bar 1 \rightleftharpoons I\bar 1\) phase transition, while high temperature solution calorimetric data allow the relationship between Q and excess enthalpy, H, to be determined. The thermodynamic behaviour can be described by a Landau expansion in one order parameter if the transition is first order in character, with an equilibrium transition temperature, T _tr, of ～2595 K and a jump in Q from 0 to ～0.65 at T_tr. The coefficients in this Landau expansion have been allowed to vary with composition, using Q=1 at 0 K for pure anorthite as a reference point for the order parameter. Published data for H and Q at different compositions allow the calibration of the additional parameters such that the free energy due to the \(C\bar 1 \rightleftharpoons I\bar 1\) transition in anorthite-rich plagioclase feldspars may be expressed (in cal. mole^-1) as: \(\begin{gathered}G = \tfrac{1}{2} \cdot 9(T - 2283 + 2525X_{Ab} )Q^2 \\ {\text{ + }}\tfrac{1}{4}( - 26642 + 121100X_{Ab} )Q^4 \\ {\text{ + }}\tfrac{1}{6}(47395 - 98663X_{Ab} )Q^6 \\ \end{gathered}\) where X _Ab is the mole fraction of albite component. The nature of the transition changes from first order in pure anorthite through tricritical at ～An₇₈ to second order, with increasing albite content. The magnitude of the free energy of \()\) ordering reduces markedly as X _Ab increases. At ～700° C incommensurate ordering in crystals with compositions ～An₅₀–An₇₀ needs to have an associated free energy reduction of only a few hundred calories to provide a more stable structure. These results, together with a simple mixing model for the disordered ( \()\) ) solid solution, an assumed tricritical model for the incommensurate ordering and published data for ordering in albite have been used to calculate a set of possible free energy relations for the plagioclase system. The incommensurate structure should appear on the equilibrium phase diagram, but its apparent stability with respect to the assemblage albite plus anorthite at low temperatures depends on the values assigned to the mixing parameters of the $$$$ solid solution.     

Thermodynamics of sodium feldspar I: Order parameter treatment and strain induced coupling effects

The thermodynamic behaviour of Na-rich feld-spars is derived from a Landau-type free energy expression which contains two order parameters. One order parameter describes the structural distortion during the displacive phase transition between monalbite and analbite, the other the Al, Si order. The structural phase transition \(C2/m - C\bar 1\) in sodium feldspar under thermal equilibrium is due to both order parameters and is accompanied by a crossover between a thermal regime with low Al, Si order (high-albite) and a thermal regime with high Al, Si order (low-albite). The crossover is a smooth function of temperature. Simple formulae are given for the calculation of thermodynamic potentials for thermal equilibrium and for metastable phases with temperature independent Al, Si order.     

Laihunite—A new iron silicate mineral

Laihuite reported in the present paper is a new iron silicate mineral found in China with the following characteristics:

1. This mineral occurs in a metamorphic iron deposit, associated with fayalite, hypersthene, quartz, magnetitc, etc.
2. The mineral is opaque, black in colour, thickly tabular in shape with luster metallic to sub-metallic, two perfect cleavages and specific gravity of 3.92.
3. Its main chemical components are Fe and Si with Fe³⁺>Fe²⁺. The analysis gave the formula of Fe Fe _1.00 ³⁺ ·Fe _0.58 ²⁺ ·Mg _0.03 ²⁺ ·Si_0.96O₄.
4. Its DTA curve shows an exothermic peak at 713°C.
5. The mineral has its own infrared spectrum distinctive from that of other minerals.
6. This mineral is of orthorhombic system; space group:C _2h ^/5 ?P2₁/c; unit cell:α=5.813ű0.005,b=4.812ű0.005,c=10.211ű0.005,β=90.87°.
7. The Mössbauer spectrum of this mineral is given, too.

     

Geochemistry of uranium in sediments of the Bohai Gulf,China

The following conclusions can be drawn from the work reported in this paper:

1. Sixteen samples were determined for uranium by spectrophotometric method. The uranium content in the sea floor sediments of the Bohai Gulf ranges from 1.6 to 6.3 ppm, with an average of 4.3 ppm.
2. Statistical data show close relationship between U concentration and grain size. Relatively larger amount of uranium was found accumulated in mud than in sand. The bulk of uranium is assumed to be derived from terrestrial detrital minerals.
3. A positive correlation between U and Fe is recognized. Similar relation also can be seen between U and Al. The plot of U concentration vs. Fe is linear, and can be expressed by the linear regression equation:Y=?0.37+1.35X. The plot of U against Al gives an equation ofY=?2.48+1.01X.
4. The average U/C_org. ratio for these sediments is 7×10^?4, and the average ratios of U/P, U/Mn, and U/CaCO₃ are 100×10^?4, 50×10^?4 and 2×10^?4, respectively.
5. Compared with the abundances of other shelf sediments, the average concentration of U in the area under consideration is close to that of sediments on the selves of Japan and the Gulf of Mexico, and the Black Sea. Uranium concentration in the Bohai Gulf sediments is comparable to that of the continental crust, but differs from that of deep-sea clay.

     

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.     

Untersuchung von suspendiertem Material in den Hydrothermallaugen des Atlantis-II-Tiefs

Suspended matter was separated from the hydrothermal brines of the Atlantis-II Deep in the Red Sea. Contents of iron, manganese, copper, and zink collected on membrane filters were measured by X-ray-flourescence, and the main results were:

1. Metal concentrations in suspended form were lower by 10^?1 to 10^?5 compared to the dissolved concentrations of the brines.
2. Suspended copper and zink were enriched most pronounced in the deeper brine zone — markedly so in the SW-basin, values there ranged between 10 and 30μg/l, one Zn-value was as high as 60μ/l, the other basins contained mostly less than 1 to 10μg/l.
3. Iron, copper, and zink in the deeper brine zone and in few cases also in the 50°-brine were suspended in the form of sulfide compounds. This conclusion is based only on the slightly purple-, green-, and blue-colored gray hues of the material on the filters and its rapid oxidation upon contact with the air.
4. In the transition zone of the 50°/60°-brine iron hydroxides were highly concentrated with values ranging up to 1000μg Fe/l.
5. Suspended manganese is found only within the transition zone of brine to the normal sea water, where up to 200μg Mn/l in form of darkbrown manganese hydroxides were found.
6. Concurrently with the increased thermal activity since 1966 more strongly reducing conditions within the brines seemed apparent which were caused by discharge of higher amounts of Sulfides into the basins. Increased precipitation of heavy metal sulfides was found to be most pronounced in the SW-basin.

     

A new X-Ray method to determine the anorthite content and structural state of plagioclases

The possibility of converting a plagioclase into its K-equivalent (Viswanathan, 1970) has given a new simple method to determine its anorthite content. The 4 values of the reflections 201 and 400 in the powder patterns of K-plagioclases vary almost linearly with anorthite content and are practically independent of structural state. Hence either of them or both can be used for the determination of anorthite content. The structural state of acidic plagioclases can be estimated approximately by plotting the 4 values of the lines, 204 and 060, in Fig. 2. This method is particularly useful for determining the anorthite content of plagioclases in fine-grained rocks and synthetic products where other methods including electron microprobe analyser fail.