Jointing of two tunnel shields using artificial underground freezing

Freezing was used in the jointing section of two shields (diameter 3.14 m) which ran across at right angles and at 25-m depth under the crossing of main roads for the construction of a 2.4-m diameter sewer tunnel. The object of freezing was to create a frozen barrier to prevent the inflow of water and fine sand into the area to be excavated.

Thirty-five freeze pipes (length about 7 m) were placed from one shield conically in the direction of the flank of another shield with freeze pipes attached to its inside wall. The cooling unit was placed on unoccupied land at about 60 m distant from the jointing section and the freeze pipes were connected with the cooling unit by supply and return pipelines.

The cooling unit had a cooling capacity of 79,000 kcal/h at an evaporation temperature of −27°C and a condensation temperature of +40°C. Freezing was continued for 180 days and the CaCl₂ brine temperature was −25 to −30°C. These works were accomplished without the sinking of shaft and the use of injection, in complete safety with no traffic restriction on the road surface.     

Temperature independent thermal expansivities of sodium aluminosilicate melts between 713 and 1835 K

The thermal expansivities of eight sodium aluminosilicate liquids were derived from the slope of new volume data at low temperatures (713−1072 K) combined with the high temperature (1300−1835 K) volume measurements of Stein et al. (1986) on the same liquids. Melt compositions range from 47−71 wt% SiO₂, 0−31 wt% A1203, and 17−33 wt% Na₂O; the volume of albite supercooled liquid at 1092 K was also determined. The low temperature volumes were derived from measurements of the glass density of each sample at 298 K, followed by measurements of the glass thermal expansion coefficient from 298 K to the respective glass transition interval. This technique takes advantage of the fact that the volume of a glass is equal to the volume of the corresponding liquid at the limiting fictive temperature (T′_f), and that T′_f can be approximated as the onset of the rapid rise in thermal expansion at the glass transition in a heating curve (Moynihan, 1995). No assumptions were made regarding the equivalence of enthalpy and volume relaxation through the glass transition. The propagated error on the volume of each supercooled liquid at T′_f is 0.25%. Combination of these low temperature data with the high temperature measurements of Stein et al. (1986) allowed a constant thermal expansivity of each liquid to be derived over a wide temperature interval (763−1001 degrees) with a fitted 1σ error of 0.6–4.6%; in every case, no temperature dependence to dV/dT^liq could be resolved. Calibration of a linear model equation leads to fitted values ± 1σ (units of cm³/mole) for (26.91 ± .04), (37.49 ± .12), (26.48 ± .06) at 1373 K, and (7.64 ± .08 × 10^-3 cm³/mole-K). The results indicate that neither Si02 nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT^liq is independent of temperature between 713–1835 K over a wide range of liquid composition. Calculated volumes based on this model recover both low and high temperature measurements with a standard deviation <0.25%, whereas values of dV/dT^liq can be predicted within 5.6%.     

Constraining the potential temperature of the Archaean mantle: A review of the evidence from komatiites

The maximum potential temperature of the Archaean mantle is poorly known, and is best constrained by the MgO contents of komatiitic liquids, which are directly related to eruptive temperatures. However, most Archaean komatiites are significantly altered and it is difficult to assess the composition of the erupted liquid. Relatively fresh lavas from the SASKMAR suite, Belingwe Greenstone Belt, Zimbabwe (2.7 Ga) include chills of 25.6 wt.% MgO, and olivines ranging to Fo_93.6, implying eruption at around 1520°C. A chill sample from Alexo Township, Ontario (also 2.7 Ga) is 28 wt.% MgO, and associated olivines range to Fo_94.1, implying eruption at 1560°C. However, inferences of erupted liquids containing 32–33 wt.% MgO, from lavas in the Barberton Greenstone Belt, South Africa (3.45 Ga) and from the Perseverance Complex, Western Australia (2.7 Ga) may be challenged on the grounds that they contain excess (cumulate) olivine, or were enriched in Mg during alteration or metamorphism. Re-interpretation of olivine compositions from these rocks shows that they most likely contained a maximum of 29 wt.% MgO corresponding to an eruption temperature of 1580°C. This composition is the highest liquid MgO content of an erupted lava that can be supported with any confidence. The hottest modern magma, on Gorgona Island (0.155 Ga) contained 18–20% MgO and erupted at circa 1400°C.

If 1580°C is taken as the temperature of the most magnesian known eruption, then the source mantle from which the liquids rose would have been at up to 2200°C at pressures of 18 GPa corresponding to a mantle potential temperature of 1900°C. These temperatures are in excess of the mantle temperatures predicted by secular cooling models, and thus komatiites can only be formed in hot rising convective jets in the mantle. This result requires that Archaean mantle jets may have been 300°C hotter than the Archaean ambient mantle temperature. This temperature difference is similar to the 200–300°C temperature difference between present day jets and ambient mantle temperatures. An important subsidiary result of this study is the confirmation that spinifex rocks may be cumulates and do not necessarily represent liquid compositions.     

Strain rate effect on the compressive strength of frozen sand

Cylindrical specimens of fine Ottawa sand (A.S.T.M. designation C-109), compacted at the optimum moisture content and saturated before unidirectional freezing, have been tested in uniaxial compression at a cold room temperature of —5.5°C and strain rates between 10⁻⁷ and 10⁻² s⁻¹. The results agree with an extrapolation of data obtained by Sayles and Epanchin [1], but are much higher than those obtained by both Goughnour and Andersland [2] and Perkins and Ruedrich [3] at strain rates below 10⁻⁵ s⁻¹. There is evidence that this may be due to variation in total moisture (ice) content, the conditions under which the specimens were frozen (closed system or an open system) and to the end effects at the platen—specimen interface.     

Design of tunnel support systems using ground freezing

One of the more promising techniques in soft ground tunneling through urbanized areas is the use of artificially frozen ground for temporary tunnel support. This paper describes the general design considerations involved in the ground freezing method. Various factors are discussed which influence the selection of the freezing temperature, the thickness of the frozen zones and the spacing of the freeze pipes. The time required to achieve freezing is discussed in addition to the amount and rate of frost heave caused by the freezing.

To illustrate the applicability of the freezing method, various considerations in the design of an 8-ft. diameter tunnel in upstate New York, a 75-ft. diameter tunnel in Georgia, and a 12 1/2-ft. diameter tunnel in Washington, D.C. are discussed. All three of the tunnels were to pass immediately beneath mainline railroad tracks. A laboratory testing program was implemented to determine the effects of the repetitive train loads on the zone of frozen soil around the tunnel perimeter. Stress-controlled repeated load triaxial tests were performed on both undisturbed and remolded samples frozen from temperatures of −7°C for the New York tunnel to −10°C for the Atlanta and Washington tunnels. Static testing consisted of both quick triaxial tests and creep tests on frozen samples of the various soil types.

It was found that there was little difference between the cumulative strain response from repeated load tests and static tests for the low frequencies investigated (one-quarter to one-half cycles per minute). Hyperbolic stress—strain functions were developed to simulate the stress—strain relationship for various cumulative loading times.

The stresses and strains in the frozen soil tunnel configuration were computed by the finite element method, using both linear and hyperbolic stress—strain functions. Tangent modulus values were varied to reflect the decreasing modulus with increasing loading time. The analyses indicated that zones of frozen soil of approximately 3 ft. thick were required for both the New York and Washington tunnels. However, high tensile stresses were calculated for the Atlanta tunnel, precluding the use of the freezing method.     

Gum rosin (colophony): A suitable material for thermomechanical modelling of the lithosphere

We investigate the use of a ductile material with temperature-sensitive viscosity for thermomechanical modelling of the lithosphere. First, we consider the scaling of mechanical and thermal properties. For a normal field of gravity, the balance of stresses and body forces sets the stress scale, in proportion to the linear dimensions and the densities. The equation of thermal conduction sets the time scale. The activation enthalpy for creep sets the temperature scale; but the thermal expansivity provides an additional constraint on this temperature scale.

Gum rosin appears to be a suitable material for lithospheric modelling. We have measured its flow properties, at various temperatures, in a specially designed rotary viscometer with unusually low machine friction. The rosin is almost Newtonian. Strain rate depends upon stress to the power n, where 1.0 <n < 1.14. The viscosity varies over 5 orders of magnitude, from about 10² Pa s at 80°C, to about 10⁷ Pa s at 40°C. The activation enthalphy is thus about 250 kJ/mol. Measured with a needle probe, the thermal conductivity is 0.113 ± 0.001 W m⁻¹K⁻¹; the thermal diffusivity, (6±3) ×10⁻⁷ m² s⁻¹. Calculated from X-ray profiles, the thermal expansivity is about 3 × 10⁻⁴ K⁻¹. These thermal and mechanical properties make gum rosin suitable for thermomechanical models, where linear dimensions scale down by a factor of 10⁶; time, by 10¹¹; viscosity, by 10¹⁷; and temperature change, by 10¹.     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

Cyclic triaxial tests on frozen sand

Strain-controlled cyclic triaxial tests were performed on a one-size silica (Ottawa) sand artificially frozen into 71.1-mm-diameter cylindrical samples. Ice-saturated samples with three different sand contents were tested under the following conditions: axial strains ranging from 3 × 10⁻³ to 3 X 10⁻²%, confining pressures from zero to 1.378 MPa, frequencies of 0.05–5.0 cps and temperatures from −1 to −10 °C.

Test equipment included (1) an MTS electrohydraulic closed-loop testing system which applies the load to the sample, (2) a triaxial cell completely immersed in a low-temperature coolant for temperature control, (3) a refrigeration unit for control of the coolant temperature and constant coolant circulation and (4) measuring devices including an LVDT and load cell, together with recording devices such as a digital multimeter, an oscilloscope, a strip-chart recorder and a minicomputer.

Test results indicate that the dynamic Young's modulus increases with increasing frequency, confining pressure and sand content, but decreases with increasing strain and temperature. The damping ratio decreases with increasing frequency, sand content and lower temperatures. The influence of confining pressures and axial strain on the damping ratio are less explicit for the ranges considered. The experimental results are compared with data from other sources.     

Abiogenic Fischer–Tropsch synthesis of hydrocarbons in alkaline igneous rocks; fluid inclusion, textural and isotopic evidence from the Lovozero complex, N.W. Russia

A detailed fluid inclusion study has been carried out on the hydrocarbon-bearing fluids found in the peralkaline complex, Lovozero. Petrographic, microthermometric, laser Raman and bulk gas data are presented and discussed in context with previously published data from Lovozero and similar hydrocarbon-bearing alkaline complexes in order to further understand the processes which have generated these hydrocarbons. CH₄-dominated inclusions have been identified in all Lovozero samples. They occur predominantly as secondary inclusions trapped along cleavage planes and healed fractures together with rare H₂O-dominant inclusions. They are consistently observed in close association with either arfvedsonite crystals, partially replaced by aegirine, aegirine crystals or areas of zeolitization. The majority of inclusions consist of a low-density fluid with CH₄ homogenisation temperatures between −25 and −120 °C. Those in near-surface hand specimens contain CH₄+H₂ (up to 40 mol%)±higher hydrocarbons. However, inclusions in borehole samples contain CH₄+higher hydrocarbons±H₂ indicating that, at depth, higher hydrocarbons are more likely to form. Estimated entrapment temperatures and pressures for these inclusions are 350 °C and 0.2–0.7 kbar. A population of high-density, liquid, CH₄-dominant inclusions have also been recorded, mainly in the borehole samples, homogenising between −78 and −99 °C. These consist of pure CH₄, trapped between 1.2 and 2.1 kbar and may represent an early CH₄-bearing fluid overprinted by the low-density population. The microthermometric and laser Raman data are in agreement with bulk gas data, which have recorded significant concentrations of H₂ and higher hydrocarbons up to C₆H₁₂ in these samples. These data, combined with published isotopic data for the gases CH₄, C₂H₆, H₂, He and Ar indicate that these hydrocarbons have an abiogenic, crustal origin and were generated during postmagmatic, low temperature, alteration reactions of the mineral assemblage. This would suggest that these data favour a model for formation of hydrocarbons through Fischer–Tropsch type reactions involving an early CO₂-rich fluid and H₂ derived from alteration reactions. This is in contrast to the late-magmatic model suggested for the formation of hydrocarbons in the similar peralkaline intrusion, Ilímaussaq, at temperatures between 400 and 500 °C.     

A hydrothermal investigation of the system FeO, Fe2O3, TiO2

Phase relations in the system FeO---Fe₂O₃---TiO₂, at temperatures ranging between 300°C and 700°C, have been investigated experimentally with special refference to the reaction Fe₃O₄ + TiO₂ = Fe₂O₃ + FeTiO₃. Pressure was varied between 500 and 2000 bars but its effect was negligible. Magnetite and rutile are the stable assemblage at temperatures above 550 dgC, and hematite and ilmenite are stable for lower temperatures. The equilibrium oxygen fugacity is estimated to be 10^−17.5 bars at equilibrium temperature. It is suggested that intermediate hematite-ilmenite solid solutions are inhomogeneous, consisting of ‘domains’ of hematite and ilmenite. The ‘domains’ are too small to be resolved by X-ray diffraction techniques. The top of the solvus curve in the hematite-ilmenite solution corresponds to a temperature of 660°C. Regular solution theory is not applicable to the solid solution.     

Cooling history of lunar Mg-suite gabbronorite 76255, troctolite 76535 and Stillwater pyroxenite SC-936: The record in exsolution and ordering in pyroxenes

We have determined cooling rates of orthopyroxene crystals from two Mg-suite lunar samples (gabbronorite 76255 and troctolite 76535) and one terrestrial sample (orthopyroxenite SC-936 from the Stillwater Complex), on the basis of their Fe–Mg ordering states. In addition, a cooling rate of 76255 was determined by modeling the formation of exsolution lamellae in pyroxenes. The M1–M2 site occupancies of the orthopyroxene crystals were determined by single crystal X-ray diffraction and the rate constant for the ordering reaction was used along with calibrations of the equilibrium intracrystalline fractionation of Fe and Mg as a function of temperature to calculate cooling rates. The closure temperatures (T_C) of cation ordering are 525 °C for 76255, 500 °C for 76535 and 350 °C for SC-936 corresponding to cooling rates of 4 × 10⁻² °C/year at the closure temperature for the lunar samples and 10⁻⁶ °C/year for the Stillwater sample. A cooling rate for 76255, determined by simulating the exsolution process, is 1.7 × 10⁻² °C/year at a closure temperature for exsolution of 700 °C. The Fe–Mg ordering cooling rate determined for 76535 reflects a complex thermal history superimposed on the initial plutonic provenance established for this sample [McCallum, I.S., Schwartz, J.M., 2001. Lunar Mg suite: thermobarometry and petrogenesis of parental magmas. J. Geophys. Res. 106, 27969–27983]. The preservation of a crystallization age of 4.51 Ga and a metamorphic age of 4.25 Ga for 76535 is consistent with a model in which excavation of this sample from the lower lunar crust took place while the sample was at a temperature above the closure temperatures for the Sm–Nd, U–Pb and Ar–Ar isotopic systems. Temperatures in excess of the isotopic closure temperatures (i.e., >600 °C) in the lower lunar crust were maintained by heat diffusing from concentrations of U- and Th-rich KREEP material at the base of the crust. On the other hand, 76255 formed at a much shallower depth in the lunar crust (2 km) and was well below its isotopic closure temperatures at the time of excavation, most likely during the Serenitatis basin-forming impact event. Both lunar samples were reheated during transport to the surface and deposition in hot ejecta blankets. The reheating was short lived but apparently sufficient to redistribute Fe and Mg in M sites in orthopyroxenes. For the lunar samples, the cooling rates based on Fe–Mg ordering represent final stage cooling within an ejecta blanket.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

Fluid inclusions in Scourian granulites from the Lewisian complex of NW Scotland: evidence for CO2-rich fluid in Late Archaean high-grade metamorphism

In this paper the first fluid-inclusion data are presented from Late Archaean Scourian granulites of the Lewisian complex of mainland northwest Scotland. Pure CO₂ or CO₂-dominated fluid inclusions are moderately abundant in pristine granulites. These inclusions show homogenization temperatures ranging from − 54 to + 10 °C with a very prominent histogram peak at − 16 to − 32 °C. Isochores corresponding to this main histogram peak agree with P-T estimates for granulite-facies recrystallization during the Badcallian (750–800 °C, 7–8 kbar) as well as with Inverian P-T conditions (550–600 °C, 5 kbar). The maximum densities encountered could correspond to fluids trapped during an early, higher P-T phase of the Badcallian metamorphism (900–1000 °C, 11–12 kbar). Homogenization temperatures substantially higher than the main histogram peak may represent Laxfordian reworking (≤ 500 °C, < 4 kbar). In the pristine granulites, aqueous fluid inclusions are of very subordinate importance and occur only along late secondary healed fractures. In rocks which have been retrograded to amphibolite facies from Inverian and/or Laxfordian shear zones, CO₂ inclusions are conspicuously absent; only secondary aqueous inclusions are present, presumably related to post-granulite hydration processes. These data illustrate the importance of CO₂-rich fluids for the petrogenesis of Late Archaean granulites, and demonstrate that early fluid inclusions may survive subsequent metamorphic processes as long as no new fluid is introduced into the system.     

Status report on stability of K-rich phases at mantle conditions

Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM³⁺Si₂O₆) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning ^(K)D_(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF₃ limit F content between 6 and 8 GPa. The perovskite KMgF₃ is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. ^(M4)K-substituted potassic richterite (ideally K(KCa)Mg₅Si₈O₂₂(OH,F)₂) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H₂O K-cymrite (hydrous hexasanidine–KAlSi₃O₈·nH₂O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H₂O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K_1−x−n)₂(Mg_1−nM_n³⁺)₂Si₂O₇H_2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H₂O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □₂Mg₂Si₂O₇H₂–(K□)Mg₂Si₂O₇H–K₂Mg₂Si₂O₇ (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi₃O₈, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.     

Gas pressures and redox reactions in geothermal fluids in Iceland

The gas and redox chemistry of 100–300 °C geothermal fluids in Iceland has been studied as a function of fluid temperature and fluid composition. The partial pressures of CO₂ in dilute (mCl<500 ppm) and saline (mCl>500 ppm) geothermal fluids above 200 °C are controlled by the mineral buffer clinozoisite+prehnite+calcite+quartz. Two buffers are considered to control the H₂S and H₂ partial pressures above 200 °C depending on fluid salinity, epidote+prehnite+pyrite+pyrrhotite for dilute fluids and pyrite+prehnite+quartz+magnetite+anhydrite+clinozoisite+quartz for saline fluids. Below 200 °C, the partial pressures of CO₂, H₂S and H₂ also seem to be buffered but other minerals must be involved. Zeolites are expected to replace prehnite and epidote. Redox potential calculated on the assumption of equilibrium for the H⁺/H₂ redox couple decreases in dilute geothermal fluids with increasing temperature from about −0.5 V at 100 °C to −0.8 V at 300 °C, whereas saline geothermal fluids at 250 °C display a redox potential of about −0.45 V. A systematic discrepancy between redox couples of about 0.05–0.09 V is observed in the redox potential for the dilute geothermal fluids, whereas redox potentials agree within 0.02–0.04 V for saline geothermal waters. The discrepancies in the calculated redox potential for dilute geothermal fluids are thought to be due to a general lack of equilibrium between CH₄, CO₂ and H₂ and between H₂S, SO₄ and H₂. It is, accordingly, concluded that an overall equilibrium among redox species has not been reached for dilute geothermal fluids whereas it appears to be more closely approached for the saline geothermal fluids. The latter conclusion is based on limited database and should be treated with care. Since the various redox components are not in an overall equilibrium in geothermal fluids in Iceland these fluids cannot be characterised by a unique hydrogen fugacity, oxygen fugacity or redox potential at a given temperature and pressure.     

Oxygen and carbon isotope composition of cold-water Berriedale Limestone (Lower Permian), Tasmania, Australia

The Berriedale Limestone formed at about 80°S paleolatitude and contains many glacial dropstones. It formed during a period of major Gondwana deglaciation.

The Berriedale Limestone contains mostly bryozoans, brachiopods and bivalves, with some intraclasts and rare pellets. The faunal diversity is low and the fauna are similar to the modern cold-water foramol faunal assemblage. Micrite, microspar and spar occur as equant to well developed rhombs of calcite. The coarse spar cements are bored and are ruptured by dropstones, indicating submarine origin of low-Mg calcite at water-temperatures of around 3°C. The mixing zone cementation was preceded by erosion of early formed crystals. The eroded crystals occur as inclusions in mixing zone cements.

The fauna are characterized by heavy δ¹³C and light δ¹⁸O. The whole-rock field of δ¹⁸O-δ¹³C falls at the edge of “Normal Marine Limestone” and deviates to lighter δ¹⁸O values (down to −16.7‰ PDB). Lightest δ¹⁸O values ( −22‰ PDB) of fresh-water sparry calcite cement are similar to those in the Early Permian continental tillites, suggesting that the Permian sea was diluted by isotopically light melt waters. Micrite δ¹⁸O values (−9.2 to −12.6‰ PDB) are within the range of whole-rock values. The δ¹⁸O values of calcite in shales are lighter than limestone values.

The δ¹⁸O values of the fauna give an unrealistic range of sea-water temperatures because the fauna have equilibrated with variable amounts of melt waters. However, calculated original δ¹⁸O values of the fauna indicate temperatures < 4°C. The heaviest δ¹⁸O of fauna gives cold temperatures of 9°C (with δ_w −2.8‰) and −3°C (with δ_w −6‰). The lightest values of sparry calcite cements (−22‰ PDB) indicate that the limestone reacted with cold melt waters.

The δ¹⁸O of Permian sea is estimated to be about +1.2‰ and was diluted by melt waters as light as −27‰ SMOW.     

Paleotemperatures from fluid inclusions in halite: method verification and a 100,000 year paleotemperature record, Death Valley, CA

Maximum homogenization temperatures of fluid inclusions (Th_max) in halite (laboratory-grown crystals and modern samples, Death Valley, CA) match maximum brine temperatures during halite precipitation. Maximum brine temperatures during halite precipitation in Death Valley, late April, 1993 (34.4°C) agree with Th_max (34°C) and correlate well with average maximum air temperatures in April (31.3°C) and May (37.6°C). Th_max may be used for paleoclimate interpretations based on the close relationship between saline lake temperatures and average air temperatures from modern settings. Lower homogenization temperatures, demonstrably below the temperatures at which halite grew, are interpreted to reflect collapse of some fluid inclusion walls due to the pressure difference between the inside and outside of inclusions. By only using Th_max, the problems of anomalously low homogenization temperatures due to possible collapse of fluid inclusions are avoided. Halite samples from 30 stratigraphic intervals, 90 to 0 m (100 to 0 ka), Core DV93-1, Death Valley, CA, were used to measure homogenization temperatures of fluid inclusions. Virtually all homogenization temperatures from Core DV93-1 are below the modern Th_max of 34°C (halite precipitation late April, 1993). Lacustrine halites, deposited in a perennial saline lake 35 to 10 ka, have Th_max between 19°C and 30°C, which suggests brine temperatures approximately 4°C to 15°C below modern late April values. Ephemeral saline lake halites precipitated 60 to 35 ka have Th_max between 23°C and 28°C, 6 to 11°C below modern values. The highest Th_max value in the 100 ka record (up to 35°C) is from a halite sample formed approximately 100 ka in a climate regime somewhat colder than the modern.     

Carbonic inclusions

The paper gives an overview of the phase relations in carbonic fluid inclusions with pure, binary and ternary mixtures of the system CO₂–CH₄–N₂, compositions, which are frequently found in geological materials. Phase transitions involving liquid, gas and solid phases in the temperature range between −192°C and 31°C are discussed and presented in phase diagrams (PT, TX and VX projections). These diagrams can be applied for the interpretation of microthermometry data in order to determine fluid composition and molar volume (or density).     

Water-enhanced dynamic recrystallization and solution transfer in experimentally deformed carnallite

Cylindrical samples of polycrystalline carnallite (KMgCl₃, 6H₂O) were deformed in a triaxial apparatus at 60°C, at confining pressures between 0.1 and 31 MPa and at strain rates between 10⁻⁴ and 10⁻⁸ s⁻¹. In a number of cases, small amounts of saturated carnallite brine were added. Samples without added brine deform by intracrystalline slip, mechanical twinning, cracking, and by frictional sliding on crack surfaces. Stress-strain curves of these samples are strongly dependent on confining pressure. Addition of brine has a dramatic effect on both microstructural development and mechanical properties. Grain-boundary migration is strongly enhanced. At lower strain rates, additional intracrystalline effects start to appear, together with the onset of solution transfer. Rapid compaction in samples deformed with added brine causes high fluid pressures to develop. At higher strain rates addition of brine results in a decrease of the flow stress by a factor of two. This weakening will increase even further at strain rates below about 10⁻⁹ s⁻¹, when solution transfer becomes rate controlling. It is argued that deformation of carnallite in nature is adequately described by the flow law found for samples deformed with added brine.     

Petrogenesis of tourmaline rocks associated with Fe-carbonate–graphite metapelite, metabasite and strata-bound polymetallic sulphide mineralisation, Peloritani Mountains, Sicily, Southern Italy

Tourmalinite and tourmaline-rich rocks associated with Fe-carbonate–graphite phyllite, strata-bound polymetallic sulphide deposits, metabasite and marble were studied, for information on the mechanism of tourmaline formation in the pre-Hercynian low-grade metamorphic sequence of the Mandanici Unit in the Peloritani Mountains of Sicily, southern Italy. The major and trace element compositions of the tourmaline rocks suggest the existence of a sedimentary protolith with pre-metamorphic black shale and bedded chert. Boron was interpreted to be accumulated in a restricted sedimentary basin, between platform carbonate formations, with abundant organic matter and Fe–Al–Ti-rich laterite–bauxite soil-derived clastic supply, under a continental volcano-tectonic extensional regime accompanied by a local convective hydrothermal system along faults. Petrographic, crystal–chemical and δ¹¹B isotopic data are compatible with a model of marine sediment dewatering at temperatures below 200 °C, which caused the removal of boron from clay. Metamorphism led to the development of tourmaline in an Al–Ti-rich environment, in equilibrium with other minerals such as ilmenite, albite and muscovite. The upper temperature of metamorphism (almost 375 °C), estimated on the basis of δ¹¹B, fits geothermometric results from Δ¹³C_{carbonate–graphite} on associated rocks. The estimated value of δ¹¹B in the tourmalinite protolith, − 7.5‰ , is also compatible with continental-derived Al-rich sediments.