Origin of coronas in metagabbros of the Adirondack mts., N. Y.

Metagabbros from two widely separated areas in the Adirondacks show development of coronas. In the Southern Adirondacks, these are cored by olivine which is enclosed in a shell of orthopyroxene that is partially, or completely, rimmed by symplectites consisting of clinopyroxene and spinel. Compositions of the corona phases have been determined by electron probe and are consistent with a mechanism involving three partial reactions, thus:

1. Olivine=Orthopyroxene+(Mg, Fe)⁺⁺.
2. Plagioclase+(Mg, Fe)⁺⁺+Ca⁺⁺=Clinopyroxene+Spinel+Na⁺.
3. Plagioclase+(Mg, Fe)⁺⁺+Na⁺=Spinel+more sodic plagioclase+Ca⁺⁺.

Reaction (a) occurs in the inner shell of the corona adjacent to olivine; reaction (b) in the outer shell; and (c) in the surrounding plagioclase, giving rise to the spinel clouding which is characteristic of the plagioclase in these rocks. Alumina and silica remain relatively immobile. These reactions, when balanced, can be generalized to account for the aluminous nature of the pyroxenes and for changing plagioclase composition. Summed together, the partial reactions are equivalent to:

1. Olivine + Anorthite = Aluminous orthopyroxene + Aluminous Clinopyroxene + Spinel (Kushiro and Yoder, 1966).

In the Adirondack Highlands, coronas between olivine and plagioclase commonly have an outer shell of garnet replacing the clinopyroxene/spinel shell. The origin of the garnet can also be explained in terms of three partial reactions:

1. Orthopyroxene+Ca⁺⁺=Clinopyroxene+(Mg, Fe)⁺⁺.
2. Clinopyroxene+Spinel+Plagioclase+(Mg, Fe)⁺⁺=Garnet+Ca⁺⁺+Na⁺.
3. Plagioclase+(Mg, Fe)⁺⁺+Na⁺=Spinel + more sodic plagioclase+Ca⁺⁺.

These occur in the inner and outer corona shell and the surrounding plagioclase, respectively, and involve the products of reactions (a)-(d). Alumina and silica are again relatively immobile. Balanced, and generalized to account for aluminous pyroxenes and variable An content of plagioclase, they are equivalent to:

1. Orthopyroxene+Anorthite+Spinel=Garnet (Green and Ringwood, 1967).

Amphibole coronas about opaque oxides in rocks of both areas are the result of oxide/plagioclase reactions with addition of magnesium from coexisting olivine. Based on published experimental data, pressure and temperature at the time of corona formation were on the order of 8 kb and 800° C for the garnet bearing coronas, with somewhat lower pressures indicated for the clinopyroxene/spinel coronas.     

Kinetic rate laws as derived from order parameter theory II: Interpretation of experimental data by laplace-transformation,the relaxation spectrum,and kinetic gradient coupling between two order parameters

A unifying theory of kinetic rate laws, based on order parameter theory, is presented. The time evolution of the average order parameter is described by $$\langle Q\rangle \propto \smallint P(x)e^{^{^{^{^{^{^{ - xt} } } } } } } dx = L(P)$$ where t is the time, x is the effective inverse susceptibility, and L indicates the Laplace transformation. The probability function P(x) can be determined from experimental data by inverse Laplace transformation. Five models are presented:

1. Polynomial distributions of P(x) lead to Taylor expansions of 〈Q〉 as $$\langle Q\rangle = \frac{{\rho _1 }}{t} + \frac{{\rho _2 }}{{t^2 }} + ...$$
2. Gaussian distributions (e.g. due to defects) lead to a rate law $$\langle Q\rangle = e^{ - x_0 t} e^{^{^{^{^{\frac{1}{2}\Gamma t^2 } } } } } erfc\left( {\sqrt {\frac{\Gamma }{2}} t} \right)$$ where x ₀ is the most probable inverse time constant, Γ is the Gaussian line width and erfc is the complement error integral.
3. Maxwell distributions of P are equivalent to the rate law 〈Q〉∝e^?k√t .
4. Pseudo spin glasses possess a logarithmic rate law 〈Q〉∝lnt.
5. Power laws with P(x)=x ^a lead to a rate law: ln〈Q〉=-(α + 1) ln t.

The power spectra of Q are shown for Gaussian distributions and pseudo spin glasses. The mechanism of kinetic gradient coupling between two order parameters is evaluated.     

Ca-Fe-Mg olivines: phase relations and a solution model

Reversed phase equilibrium experiments in the system (Ca, Mg, Fe)₂SiO₄ provide four tielines at P?1 bar and 1 kbar and 800° C–1,100° C. These tielines have been used to model the solution properties of the olivine quadrilateral following the methods described by Davidson et al. (1981) for quadrilateral clinopyroxenes. The discrepancy between the calculated phase relations and the experimentally determined tielines is within the uncertainty of the experiments. The solution properties of quadrilateral olivines can be described by a non-convergent site-disorder model that allows for complete partitioning of Ca on the M2 site, highly disordered Fe-Mg cation distributions and limited miscibility between high-Ca and low-Ca olivines. The ternary data presented in this paper together with binary solution models for the joins Fo-Mo and Fa-Kst have been used to evaluate two solution parameters: $$\begin{gathered} F^0 \equiv 2(\mu _{{\rm M}o}^0 - \mu _{{\rm K}st}^0 ) + \mu _{Fa}^0 - \mu _{Fo}^0 = 12.660 (1.6) kJ, \hfill \\ \Delta G_*^0 \equiv \mu _{{\rm M}gFe}^0 + \mu _{FeMg}^0 - \mu _{Fo}^0 - \mu _{Fa}^0 = 7.030 (3.9) kJ. \hfill \\ \end{gathered} $$ . Ternary phase quilibrium data for olivines tightly constrain the value of F⁰, but not that for ΔG _* ⁰ which describes nonideality in Fe-Mg mixing. From this analysis, we infer a function for the apparent standard state energy of Kst: $$\begin{gathered} \mu _{{\rm K}st}^0 = - 102.79 \pm 0.8 - (T - 298)(0.137026) \hfill \\ + (T - 298 - T1n(T/298))(0.155519) \hfill \\ + (T - 298)^2 (2.8242E - 05)/2 \hfill \\ + (T - 298)^2 (2.9665E + 03)/(2T(298)^2 ) kJ \hfill \\ \end{gathered} $$ where T is in Kelvins and the 298 K value is relative to oxides.     

The origin of basaltic rocks in Niutoushan area— high pressure differentiation

The Niutoushan basaltic cone, consisting of subalkali (quartz-tholeiite and olivine-tholeiite) and alkali basalts, is Late Tertiary in age. Its major characteristics are generalized as follows:

1. Both early subalkali and late alkali bali basalts are formed under the same geological environment.
2. The continuity in chemical composition from subalkali to alkali and the low FeO/MgO in alkali basalts show that they are the products of cognate magmatic differentiation.
3. The change from low REE abundance and weak enrichment of LREE in subalkali to high REE abundance and strong enrichment of LREE in alkali basalts indicates obvious REE enrichment and fractionation during magmatic differentiation. Weak positive Eu anomalies in the REE patterns are indicative of their formation under low oxygen fugacity conditions.
4. According to the calculated values, 70–75% of the primary olivine tholeiitic magma had been separated as subalkaline basaltic magma, the rest residual magma became alkaline basaltic magma. This result is consistent to the field observation that the outcrop area of subalkali basalts is four times as much as that of alkali basalts.
5. The basaltic rocks of Niutoushan show an S-type distribution straddling the thermal barrier on Ol′-Ne′-Qu′ diagram and an evolution tendency for Ne to increase with increasing FeO/MgO. This is in agreement with the melting experimental data on olivine basalts at 10–20 kb.
6. Mantle-derived inclusions (spinel lherzolite) in this area occur in both alkali olivine basalts and olivine tholeiites. The latter is of extremely rare occurrence. The formation temperature and pressure of the inclusions in alkalibasalts and olivine tholeiites have been calculated. The results show that the alkaline basaltic magma was separated from the subalkaline basaltic magma at about 20 kb.

Basaltic rocks in Niutoushan were formed through the so-called “high pressure differentiation”, that is, at about 20 kb the crystallization of clinopyroxene and orthpyroxene resulted in the separation of subalkaline basaltic magma from the primary olivine tholeiitic magma, and then the residue gradually became alkaline olivine basaltic magma.     

Compositions and textures of relic forsterite in carbonaceous and unequilibrated ordinary chondrites

Several percent of the olivine in the C2, C3 and unequilibrated ordinary chondrites (UOC) can be distinguished by blue cathodoluminescence (CL) and an unusual composition for forsterite. This olivine has the following textural features:

• 1.(1) forms cores in single olivine grains;
• 2.(2) shows subhedral to euhedral boundaries against rim olivine;
• 3.(3) rarely contains inclusions;
• 4.(4) has embayments containing olivine like that of the rim;
• 5.(5) occurs within chondrules especially in UOC meteorites.

The blue olivine is always Fe-poor (0.25 < FeO < 1.0%) and shows the following average and maximum values (%): Al₂O₃ (0.25, 0.5), TiO₂ (0.05, 0.09), CaO (0.5, 0.8), Cr₂O₃ (0.15, 0.5), and MnO (0.02, 0.15); vanadium is present. Within a single olivine and within all blue olivines Al, Ca and Ti are strongly positively correlated as are Mn, Fe, and Cr in olivine surrounding the blue. The blue cores are not zoned but each element shows a marked change at the boundary of the blue with Al showing the most rapid change. These are interpreted as diffusion profiles between rim and core olivine.Textures suggest initial free growth probably from a gas and later addition of olivine by liquid crystallization to form single crystals or chondrules. The unusual olivine composition indicates high temperature growth from a refractory-rich reservoir with Al entering olivine in tetrahedral coordination. Vapor growth is suggested as the process allowing the high minor element levels. The occurrence of blue olivine in all primitive meteorites indicates that it is relic material which was widespread prior to chondrule and hence meteorite formation. Similarities in composition exist between this relic olivine and olivine of cosmic dust and Deep Sea Particles pointing to this olivine being a common component in all primitive extraterrestrial material.     

Comparison of the raman microprobe spectra of (Mg,Fe)2SiO4 and Mg2GeO4 with olivine and spinel structures

Raman microprobe (RMP) spectra were produced for each of the olivine and spinel structured phases of Mg₂GeO₄ and (Mg, Fe)₂SiO₄. The assembled data show that bands due to the tetrahedra in silicate and germanate olivines shift in a way that indicates a dominant mass effect. This correspondence is difficult to make in spinels due to differences in structural type. Differences in Fe/Mg content of olivine shift the tetrahedral vibration bands only slightly, but their linear shifts could be used to indicate the composition of the phase.     

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.     

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.

     

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 ( \(\delta S_1 ^{34} \) ).

     

Carbon Dioxide in igneous petrogenesis: I

A number of experimental CO₂ solubility data for silicate and aluminosilicate melts at a variety of P- T conditions are consistent with solution of CO₂ in the melt by polymer condensation reactions such as SiO _4(m ^4? +CO_2(v)+Si _n O _3n+1(m) ⁽²ⁿ⁺¹⁾ ?Si _n+1O _3n+4(m) ^(2n+4)? +CO _3(m ^)2? . For various metalsilicate systems the relative solubility of CO₂ should depend markedly on the relative Gibbs free change of reaction. Experimental solubility data for the systems Li₂O-SiO₂, Na₂O-SiO₂, K₂O-SiO₂, CaO-SiO₂, MgO-SiO₂ and other aluminosilicate melts are in complete accord with predictions based on Gibbs Free energies of model polycondesation reactions. A rigorous thermodynamic treatment of published P- T-wt.% CO₂ solubility data for a number of mineral and natural melts suggests that for the reaction CO_2(m) ? CO_2(v)

1. CO₂-melt mixing may be considered ideal (i.e., { \(a_{{\text{CO}}_{\text{2}} }^m = X_{{\text{CO}}_{\text{2}} }^m \) );
2. \(\bar V_{{\text{CO}}_{\text{2}} }^m \) , the partial molal volume of CO₂ in the melt, is approximately equal to 30 cm³ mole^?1 and independent of P and T;
3. Δ C _p ⁰ is approximately equal to zero in the T range 1,400° to 1,650 °C and
4. enthalpies and entropies of the dissolution reaction depend on the ratio of network modifiers to network builders in the melt. Analytic expressions which relate the CO₂ content of a melt to P, T, and \(f_{{\text{CO}}_{\text{2}} } \) for andesite, tholeiite and olivine melilite melts of the form

$$\ln X_{{\text{CO}}_{\text{2}} }^m = \ln f_{{\text{CO}}_{\text{2}} } - \frac{A}{T} - B - \frac{C}{T}(P - 1)$$ have been determined. Regression parameters are (A, B, C): andesite (3.419, 11.164, 0.408), tholeiite (14.040, 5.440,0.393), melilite (9.226, 7.860, 0.352). The solubility equations are believed to be accurate in the range 3<P<30 kbar and 1,100°<T<1,650 °C. A series of CO₂ isopleth diagrams for a wide range of T and P are drawn for andesitic, tholeiitic and alkalic melts.     

The role of water in the 1944 Vesuvius eruption

The P-T path of magma associated with the 1944 Vesuvius eruption has been outlined on the basis of probe mineralogy and the relationships between the crystallising phases. Equilibrium P-T values, obtained from the reactions:

1. CaMgSi₂O_6(liq) = CaMgSi₂O_6(cpx)
2. NaAlSi₃O_{8 (liq)} = NaAlSi₃O_{8 (plag)}
3. CaAl₂Si₂O_{8 (plag)}=CaAl₂SiO_6(cpx)+SiO_2(liq) have been established for three intracrustal crystallisation stages: I) 8.0 kbar and 1255 °C; II) 4.0 kbar and 1178 °C; III) 0.5 kbar and 1105 °C.

The H₂O content in the magma has been estimated from an experimental calibration of \(a_{^{CaMgSi_2 O_6 } }^{liq}\) as a function of \(X_{H_2 O}^{liq}\) at P _tot = 2 kbar. The estimated water contents of the magma for the three stages, I) 0.7%; II) 0.9%; III) 1.1%, are consistent with the pattern of activity of the 1944 Vesuvius eruption and with the relationship between the lavas. The shallow depth of H₂O-saturation of the magma, 0.24 kbar at 1100 °C, is consistent with the eruption sequence of lava flows followed by lava fountain activity.     

Origin of biotite-hornblende-garnet coronas between oxides and plagioclase in olivine metagabbros,Adirondack region,New York

Complex multivariant reactions involving Fe-Ti oxide minerals, plagioclase and olivine have produced coronas of biotite, hornblende and garnet between ilmenite and plagioclase in Adirondack olivine metagabbros. Both the biotite (6–10% TiO₂) and the hornblende (3–6% TiO₂) are exceptionally Titanium-rich. The garnet is nearly identical in composition to the garnet in coronas around olivine in the same rocks. The coronas form in two stages:

1. Plagioclase+Fe-Ti Oxides+Olivine+water =Hornblende+Spinel+Orthopyroxene±Biotite +more-sodic Plagioclase
2. Hornblende+Orthopyroxene±Spinel+Plagioclase =Garnet+Clinopyroxene+more-sodic Plagioclase

The Orthopyroxene and part of the clinopyroxene form adjacent to olivine. Both reactions are linked by exchange of Mg²⁺ and Fe²⁺ with the reactions forming pyroxene and garnet coronas around olivine in the same rocks. The reactions occur under granulite fades metamorphic conditions, either during isobaric cooling or with increasing pressure at high temperature.     

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.

     

The reversed alumina contents of orthopyroxene in equilibrium with spinel and forsterite in the system MgO-Al2O3-SiO2

Equilibrium alumina contents of orthopyroxene coexisting with spinel and forsterite in the system MgO-Al₂O₃-SiO₂ have been reversed at 15 different P-T conditions, in the range 1,030–1,600° C and 10–28 kbar. The present data and three reversals of Danckwerth and Newton (1978) have been modeled assuming an ideal pyroxene solid solution with components Mg₂Si₂O₆ (En) and MgAl₂SiO₆ (MgTs), to yield the following equilibrium condition (J, bar, K): $$\begin{gathered} RT{\text{ln(}}X_{{\text{MgTs}}} {\text{/}}X_{{\text{En}}} {\text{) + 29,190}} - {\text{13}}{\text{.42 }}T + 0.18{\text{ }}T + 0.18{\text{ }}T^{1.5} \hfill \\ + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP = 0,} \hfill \\ \end{gathered} $$ where $$\begin{gathered} + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP} \hfill \\ = [0.013 + 3.34 \times 10^{ - 5} (T - 298) - 6.6 \times 10^{ - 7} P]P. \hfill \\ \end{gathered} $$ The data of Perkins et al. (1981) for the equilibrium of orthopyroxene with pyrope have been similarly fitted with the result: $$\begin{gathered} - RT{\text{ln(}}X_{{\text{MgTs}}} \cdot X_{{\text{En}}} {\text{) + 5,510}} - 88.91{\text{ }}T + 19{\text{ }}T^{1.2} \hfill \\ + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP = 0,} \hfill \\ \end{gathered} $$ where $$\begin{gathered} + \int\limits_1^P {\Delta V_{T,P}^{\text{0}} dP} \hfill \\ = [ - 0.832 - 8.78{\text{ }} \times {\text{ 10}}^{ - {\text{5}}} (T - 298) + 16.6{\text{ }} \times {\text{ 10}}^{ - 7} P]{\text{ }}P. \hfill \\ \end{gathered} $$ The new parameters are in excellent agreement with measured thermochemical data and give the following properties of the Mg-Tschermak endmember: $$H_{f,970}^0 = - 4.77{\text{ kJ/mol, }}S_{298}^0 = 129.44{\text{ J/mol}} \cdot {\text{K,}}$$ and $$V_{298,1}^0 = 58.88{\text{ cm}}^{\text{3}} .$$ The assemblage orthopyroxene+spinel+olivine can be used as a geothermometer for spinel lherzolites, subject to a choice of thermodynamic mixing models for multicomponent orthopyroxene and spinel. An ideal two-site mixing model for pyroxene and Sack's (1982) expressions for spinel activities provide, with the present experimental calibration, a geothermometer which yields temperatures of 800° C to 1,350° C for various alpine peridotites and 850° C to 1,130° C for various volcanic inclusions of upper mantle origin.     

Thermodynamics of plagioclases I: Theory of the I\bar 1 - P\bar 1 phase transition in anorthite and Ca-rich plagioclases

Landau theory of the \(P\bar 1 - I\bar 1\) phase transition in Ca-rich plagioclases reveals the sensitivity of the phase transition behaviour to a) Al, Si disorder, b) structural replacement of Ca by Na, and c) inhomogeneities of lattice strains. The following effects are predicted:

1. A tricritical phase transition exists in fully ordered anorthite. Al, Si disorder and Na, Ca exchange lead to second order phase transitions.
2. The transition temperatures depend sensitively on the degree of Al, Si disorder and the chemical composition of the Ca-rich plagioclases. Increasing Na-content decreases the transition temperatures.
3. The thermal evolution of c and d reflections depends on the homogeneity of the crystal and do not necessarily reflect the temperature evolution of the macroscopic lattice strain. A simple quadratic dependence of the X-ray scattering intensity on the order parameter exists only for fully ordered, homogeneous anorthite.

The role of inhomogeneous Al, Si distributions and lattice relaxations are discussed including possible structural modulations.     

Thermodynamic calculation of peridotite phase relations in the system MgO-Al2O3-SiO2-Cr2O3, with some geological applications

The system MgO-Al₂O₃-SiO₂(MAS) comprises 88–90% of the bulk composition of an average peridotite. The MAS ternary is thus a suitable starting point for exploring peridotite phase relations in multicomponent natural systems. The basic MAS phase relations may be treated in terms of the reactions (see list of symbols etc).

1. py (in Gt)=en (in Opx)+mats (in Opx),
2. en (in Opx)+sp (in Sp)=mats (in Opx)+fo (in Ol), and
3. py (in Gt)+fo (in Ol)=en (in Opx)+sp (in Sp).

Extensive reversed phase equilibria data on these three reactions by Danckwerth and Newton (1978), Perkins et al. (1981), and Gasparik and Newton (1984) employing identical experimental methods in the same laboratory have been used by us to deduce the following internally consistent thermodynamic data applying the technique of linear programming:ΔH ₂₉₈₍₁₎ ⁰ = 2536 J, ΔS ₂₉₈₍₁₎ ⁰ =? 6.064 J/K;ΔH ₂₉₈₍₂₎ ⁰ = 29435 J, ΔS ₂₉₈₍₂₎ ⁰ = 8.323 J/K; andΔH ₂₉₈₍₃₎ ⁰ =?26899 J, ΔS ₂₉₈₍₃₎ ⁰ =?14.388 J/K.These data are also found to be consistent with results of calorimetry. Figure 2 shows the calculated phase relations based on our thermodynamic data; they are consistent with the phase equilibria experiments. Successful extension of the MAS phase relations to multicomponent peridotites pivots on the extent to which the effects of the “non-ternary” (i.e. other than MAS) components can be quantitatively handled. Particularly hazardous in this context is Cr₂O₃, although it barely makes up 0.2 to 0.5 wt% of such rocks. This is because Cr⁺³ fractionates extremely strongly into Sp. This study focuses on the peridotite phase relations in the MgO-Al₂O₃-SiO₂-Cr₂O₃ (MASCr) quaternary. Thermodynamic calculations of the MASCr phase relations have been accomplished by using ΔH ₂₉₈ ⁰ and ΔS ₂₉₈ ⁰ values for the reactions (1) through (3) indicated above, in conjunction with data on thermodynamic mixing properties of

1. binary Sp (sp-pc) crystalline solution (Oka et al. 1984),
2. ternary Opx (en-mats-mcts) crystalline solution (this study), and
3. binary Gt (py-kn) crystalline solution (this study).

The results are shown in P-T projections (Figs. 3a and b) and isobaric-isothermal sections of MASCr in a projection through the component fo onto the SiO₂-Al₂O₃-Cr₂O₃ ternary (Figs. 4a and b). The most important results of this work may be summarized as follows:

1. With increasing incorporation of Cr⁺³ into Sp and Gt, the X _mats isopleths of the reactions (1) and (2) are shifted to higher temperatures (Fig. 3a); simultaneously, the spinel-peridotite to garnet-peridotite phase transition is moved to higher pressures (Fig. 3b).
2. At identical P and T, the X _mats values of Opx coexisting in equilibrium with Ol and Sp is strongly dependent upon the X _pc value in the latter phase (Figs. 4a and b). Accurate correction for the composition of Sp is, therefore, a necessary precondition for geothermometry of the spinelperidotites.
3. The discrepant temperatures reported by Sachtleben und Seck (1981, Fig. 5) from the spinel-peridotites of the Eifel area (systematically too high temperatures as a function of X _pc in Sp) are demonstrated to be the result of ignoring the nonideality in the chromian spinels.

     

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.

     

Phase equilibria among pumpellyite,lawsonite, epidote and associated minerals in low grade metamorphic rocks

Phase relations of pumpellyite, epidote, lawsonite, CaCO₃, paragonite, actinolite, crossite and iron oxide are analysed on an Al-Ca-Fe³⁺ diagram in which all minerals are projected from quartz, albite or Jadeite, chlorite and fluid. Fe²⁺ and Mg are treated as a single component because variation in Fe²⁺/Mg has little effect on the stability of phases on the diagram. Comparison of assemblages in the Franciscan, Shuksan, Sanbagawa, New Caledonia, Southern Italian, and Otago metamorphic terranes reveals several reactions, useful for construction of a petrogenetic grid:

1. lawsonite+crossite + paragonite = epidote+chlorite + albite + quartz + H₂O
2. lawsonite + crossite = pumpellyite + epidote + chlorite + albite+ quartz + H₂O
3. crossite + pumpellyite + quartz = epidote + actinolite + albite + chlorite + H₂O
4. crossite + epidote + quartz = actinolite + hematite + albite + chlorite + H₂O
5. calcite + epidote + chlorite + quartz = pumpellyite + actinolite + H₂O + CO₂
6. pumpellyite + chlorite + quartz = epidote + actinolite + H₂O

     

Sedimentmikrobioiogie und ihre geologischen Aspekte

The influence of bacteria on recent sediments was first discussed in 1885, whenFischer andGazert were discussing the cycle of substances in the sea as well as in sediments. The influence of bacteria on the cycling of C, N, S, P in recent sediments and the open sea was soon accepted by marine geologists. Nevertheless, only very few experiments have, so far, shown more than qualitative and quantitative data collection in various restricted areas. This is due to the extensive and complicated chain of reactions on the surface of sediments and in the sediment itself. Biologists are asking for the amount of organic and inorganic matter which is reworked and released to the sea. Geologists usually emphasize the amount of substances which are sedimentated. For biologists the sediment is only part of their dominant ecosystem (the sea). While, for geologists the “sea” is only furnishing and influencing their first range system sediment. How much then, are bacteria involved in the slow process of conversion from a recent sediment to sedimentary rocks? Bacteria influence more or less strongly and to a more or less advanced degree of diagenesis:

1. The organic matter in sediments and the final form in which it is found.
2. The anions CO₃ ^2?, NO₃ ^?, OH-, SO₄ ^2?, PO₄ ^3? as well as their intermediate stages and the resulting minerals.
3. The cations H⁺, NH₄ ⁺, Ca²⁺, Fe²⁺, Fe³⁺, and a series of metals which are dissolved or precipitated by microbial activities as for example Fe, Mn, Cu, Ag, V, Co, Mo, Ni, U, Se, Zn.
4. The equilibrium of silicium. At least diatoms and radiolarians are precipitating silica, while other reactions which have been proved are not yet shown to influence marine sediments.
5. p_H-values and oxidation-reduction potentials of the sediment.
6. The composition of interstitial waters.
7. The surface activity of minerals, since bacteria are growing especially on particle surfaces.
8. The energy content and temperature of sediments.
9. The texture of fine grained sediments.
10. The fossilization of microfauna, macrofauna and trace fossils.

Sedimentology and mineralogy may also influence the bacterial activities and the composition of the microflora within sediments. Methods and problems of sediment microbiology are demonstrated by some investigations in the German Bay (North Sea) in connection with the first German Underwater Station (UWL). Ecological work proves to be difficult in various directions. The main cause of difficulties in microbiological work on sediments are the great variety of different factors influencing the environment (microbial, chemical, physical, mineralogical), the difficulty of taking representative samples, and the small amount of data which has been collected so far.     

The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4

Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe²⁺ which is a major constituent of the upper mantle. Previous calculations for Fe₂SiO₄ ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S _CFS). We have calculated free energy changes (ΔG _CFS) due to differences of crystal field splittings between Fe₂SiO₄ spinel and fayalite from: ΔG _CFS=?ΔCFSE?TΔS _CFS, as functions of P and T, for different energy splittings of t _2g orbital levels of Fe²⁺ in spinel. The results indicate that ΔG _CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe₂SiO₄, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg_1?x Fe _x )₂SiO₄ are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.