TitaniQ: a titanium-in-quartz geothermometer

Titanium is one of many trace elements to substitute for silicon in the mineral quartz. Here, we describe the temperature dependence of that substitution, in the form of a new geothermometer. To calibrate the “TitaniQ” thermometer, we synthesized quartz in the presence of rutile and either aqueous fluid or hydrous silicate melt, at temperatures ranging from 600 to 1,000°C, at 1.0 GPa. The Ti contents of quartz (in ppm by weight) from 13 experiments increase exponentially with reciprocal T as described by:

Garnet-clinopyroxene geothermometer

A garnet-clinopyroxene geothermometer based on the available experimental data on compositions of coexisting phases in the system MgO-FeO-MnO-Al₂O₃-Na₂O-SiO₂ is as follows: $$T({\text{}}K) = \frac{{8288 + 0.0276 P {\text{(bar)}} + Q1 - Q2}}{{1.987 \ln K_{\text{D}} + 2.4083}}$$ where P is pressure, and Q1, Q2, and K _D are given by the following equations $$Q1 = 2,710{\text{(}}X_{{\text{Fe}}} - X_{{\text{Mg}}} {\text{)}} + 3,150{\text{ }}X_{{\text{Ca}}} + 2,600{\text{ }}X_{{\text{Mn}}} $$ (mole fractions in garnet) $$\begin{gathered}Q2 = - 6,594[X_{{\text{Fe}}} {\text{(}}X_{{\text{Fe}}} - 2X_{{\text{Mg}}} {\text{)]}} \hfill \\{\text{ }} - 12762{\text{ [}}X_{{\text{Fe}}} - X_{{\text{Mg}}} (1 - X_{{\text{Fe}}} {\text{)]}} \hfill \\{\text{ }} - 11,281[X_{{\text{Ca}}} (1 - X_{{\text{Al}}} ) - 2X_{{\text{Mg}}} 2X_{{\text{Ca}}} ] \hfill \\{\text{ + 6137[}}X_{{\text{Ca}}} (2X_{{\text{Mg}}} + X_{{\text{Al}}} )] \hfill \\{\text{ + 35,791[}}X_{{\text{Al}}} (1 - 2X_{{\text{Mg}}} )] \hfill \\{\text{ + 25,409[(}}X_{{\text{Ca}}} )^2 ] - 55,137[X_{{\text{Ca}}} (X_{{\text{Mg}}} - X_{{\text{Fe}}} )] \hfill \\{\text{ }} - 11,338[X_{{\text{Al}}} (X_{{\text{Fe}}} - X_{{\text{Mg}}} )] \hfill \\\end{gathered} $$ [mole fractions in clinopyroxene Mg = MgSiO₃, Fe = FeSiO₃, Ca = CaSiO₃, Al = (Al₂O₃-Na₂O)] K _D = (Fe/Mg) in garnet/(Fe/Mg) in clinopyroxene. Mn and Cr in clinopyroxene, when present in small concentrations are added to Fe and Al respectively. Fe is total Fe²⁺+Fe³⁺.     

Aluminum in quartz as a geothermometer

Quartz forming in aluminum-saturated environments has a trace aluminum content which varies linearly and directly with its temperature of crystallization. The aluminum content varies at a rate of approximately 1 ppm Al per 3.6° C change in temperature. Use of this geothermometer gives temperatures which are consistent with those expected by geologic reasoning or through the use of other geothermometers.     

An olivine-clinopyroxene geothermometer

The iron-magnesium exchange reaction between olivine and calcium-rich clinopyroxene is formulated as a geothermometer. It is shown that the clinopyroxene M1 site must be nonideal and it is expressed as a regular solution. The appropriate mixing parameters are calculated from a set of groundmass olivine-clinopyroxene pairs from lavas for which there are groundmass iron-titanium oxide temperatures. The pressure dependence of the geothermometer is calculated from abailable experimental work, and is approximately 5°C per kilobar. Layered gabbros from the Kap Edvard Holm Complex, East Greenland, show no significant variation of temperature with structural height in the intrusion, while those of Skaergaard give temperatures which do not have a consistent variation with height. Continued equilibration during post-crystallisation cooling is a possibility in slowly cooled intrusions. Inclusions in diamond give a pressure-temperature line consistent with formation at 1300°C at 55 kb, 1400°C 72 kb and 1500°C 90 kb. Ultrabasic xenoliths in Basutoland kimberlites have similar pressure-temperature lines. Lavas, including alkali basalts, basanites, andesites and rhyolites give temperatures from 1025°C to 890° C.     

Calcic amphibole equilibria and a new amphibole-plagioclase geothermometer

There is currently a dearth of reliable thermobarometers for many hornblende and plagioclase-bearing rocks such as granitoids and amphibolites. A semi-empirical thermodynamic evaluation of the available experimental data on amphibole+plagioclase assemblages leads to a new thermometer based on the Al^iv content of amphibole coexisting with plagioclase in silica saturated rocks. The principal exchange vector in amphiboles as a function of temperature in both the natural and experimental studies is \(\left( {Na\square _{ - 1} } \right)^A \left( {AlSi_{ - 1} } \right)^{T1}\) . We have analysed the data using 3 different amphibole activity models to calibrate the thermometer reactions 1. $$1. Edenite + 4 Quartz = Tremolite + Albite$$ 2. $$2. Pargasite + 4 Quartz = Hornblende + Albite.$$ The equilibrium relation for both (1) and (2) leads to the proposed new thermometer $$T = \frac{{0.677P - 48.98 + Y}}{{ - 0.0429 - 0.008314 ln K}} and K = \left( {\frac{{Si - 4}}{{8 - Si}}} \right)X_{Ab}^{Plag} ,$$ where Si is the number of atoms per formula unit in amphiboles, with P in kbar and T in K; the term Y represents plagioclase non-ideality, RTlnγ_ab, from Darken's Quadratic formalism (DQF) with Y=0 for X _ab>0.5 and Y=-8.06+25.5(1-X _ab)² for X _ab<0.5. The best fits to the data were obtained by assuming complete coupling between Al on the T1 site and Na in the A site of amphibole, and the standard deviation of residuals in the fit is ±38°C. The thermometer is robust to ferric iron recalculation procedures from electron probe data and should yield temperatures of equilibration for hornblende-plagioclase assemblages with uncertainties of around ±75° C for rocks equilibrated at temperatures in the range 500°–1100° C. The thermometer should only be used in this temperature range and for assemblages with plagioclase less calcic than An₉₂ and with amphiboles containing less than 7.8 Si atoms pfu. Good results have been attained on natural examples from greenschist to granulite facies metamorphic rocks as well as from a variety of mafic to acid intrusive and extrusive igneous rocks. Our analysis shows that the pressure dependence is poorly constrained and the equilibria are not suitable for barometry.     

Ni in chrome pyrope garnets: a new geothermometer

Proton microprobe analyses of the minerals in garnet-peridotite xenoliths from kimberlites show that the partitioning of Ni between chrome pyrope garnet and olivine is strongly temperature(T)-dependent. The range of Ni contents in olivines is small relative to that in the analyzed garnets; a geothermometer therefore can be derived, based only on the Ni content of garnet. This allows estimation of T for single Cr-pyrope grains, such as the inclusions in diamonds, if these can be assumed to have equilibrated with olivine.     

A nepheline-alkali feldspar geothermometer

A nepheline-alkali feldspar geothermometer has been developed which is based on the thermodynamics of an Na—K exchange reaction between nepheline and alkali feldspar. The activities are formulated in terms of site occupancies, and the regular solution model is used to represent non-ideal mixing of the cations on each site. The distribution of Na and K on the alkali sites in nepheline is calculated from published nepheline-brine ion-exchange data. The standard Gibbs energy of the geothermometer reaction is calculated from experimental data on coexisting nephelines and alkali feldspars (Hamilton and MacKenzie, 1960, 1965). The geothermometer is applied to nepheline syenites from the Precambrian Igdlerfigssalik intrusion, S.W. Greenland, and gives temperatures which suggest that nepheline and alkali feldspar continue to equilibrate with cooling after they crystallise from the magma.     

A precise olivine-augite Mg-Fe-exchange geothermometer

 Olivine and augite that were experimentally equilibrated in the temperature interval 1175–1080°C at 1 bar in natural basaltic and andesitic bulk compositions are used to calibrate an Mg-Fe²⁺ cation-exchange geothermometer. Within its temperature interval of experimental calibration, and over a broad range in olivine Mg/Fe ratio, the geothermometer has a standard error of ±6°C. In compositionally simpler synthetic systems, the same calibration retrieves appropriate experimental temperatures up to at least 1250°C. In application to intermediate and felsic volcanic rocks erupted at ∼1080 –800°C (below the range of experimental calibration), calculated olivine-augite temperatures are in good agreement with Fe-Ti oxide thermometry in the same samples. These results encourage confidence in the olivine-augite geothermometer over at least the 800–1250°C interval at low pressures. Sparse experimental data up to 1250°C at higher pressures for olivine + augite in the assemblage olivine + plagioclase + augite ± pigeonite or orthopyroxene suggest that the low-pressure calibration recovers experimental temperatures without systematic bias to pressures of 10 kbar. Examples illustrate applications to determining igneous equilibration temperatures in holocrystalline extrusive and intrusive rocks, and to estimating intratelluric H₂O content dissolved in magmas. Received: 24 February 1995 / Accepted: 1 March 1996     

Regression diagnostics and robust regression in geothermometer/geobarometer calibration: the garnet-clinopyroxene geothermometer revisited

Abstract The calibration of geothermometers and geobarometers should involve not only the determination of the parameters in the equation used, but also the uncertainties on, and the correlations between, these parameters. This necessitates the use of a technique such as least squares. Given the poor performance of least squares in the presence of outliers in the data, techniques for identifying outliers for exclusion—regression diagnostics, and techniques for handling data which include outliers—robust regression and jackknifing, are essential. These techniques are summarized and their importance is emphasized, and they are applied to the calibration of the garnet-clinopyroxene Fe-Mg exchange geothermometer.
The experimental data of Raheim & Green (1974) and Ellis & Green (1979) are explored using regression diagnostics to discover outliers in the data. After exclusion of the two influential outliers found, a new geothermometer equation for garnet-clinopyroxene Fe-Mg exchange is derived using robust regression and based on all the data: thus, T (K) = 2790 + 10 P + 3140x_ca,g/1.735 + In K _D where T is in Kelvin and P is in kbar. This equation, as might be hoped, is essentially identical to that of Ellis & Green (1979). Equations for calculating the uncertainty in a calculated temperature, contributed by uncertainties in the calibration, are also derived.     

The garnet-clinopyroxene Fe-Mg geothermometer — a reinterpretation of existing experimental data

Experimental data on the partitioning of Fe²⁺ and Mg between garnet and clinopyroxene (Råheim and Green 1974; Mori and Green 1978; Ellis and Green 1979) have been used to construct a new expression for the garnet-clinopyroxene geothermometer, including a curvilinear relationship between In Kd and X _Ca(ga): T(°C)=((-6173(X_Ca)²+6731 X _Ca+1879 +10 P(kb))/(lnKd+1.393))–273Application of this geothermometer to a suite of samples of eclogites and associated omphacite-garnet-bearing gneisses from the uppermost allochthon within the North Norwegian Caledonides shows that the calculated temperatures do not vary with rather great variations in the mg number of the garnet (0.17–0.54) and Na content of the clinopyroxene (0.11–0.44). Temperatures below 900° C calculated using the present equation are somewhat lower than those obtained by the method of Powell (1985), the difference being larger for lower temperatures and lower values of X _Ca.     

The use of coexisting calcite-ankerite solid solutions as a geothermometer

Limited solid solution of Mg and Fe²⁺ occurs in calcite coexisting with dolomiteankerite. This substitution is strongly temperature-dependent. Experimentally determined calcite compositions co-existing with a dolomite phase are available in the binary system CaCO₃-MgCO₃ between 500° C and 900° C (Harker and Tuttle, 1955). This information is extrapolated to lower temperatures and is combined with three synthetic calcite-ankerite pairs determined at 400° C, 450° C and 500° C (Rosenberg, 1967).The compositions of six naturally occurring calcites coexisting with ankerites from Sofala, N.S.W. are not accurately known, but X-ray determined compositional limits assuming firstly Mg substitution then Fe substitution yield maximum and minimum values for both possibilities. These limits are plotted on the ternary CaCO₃-MgCO₃-FeCO₃ together with the experimentally derived solvus isotherms. Assuming equilibration at constant temperature, actual compositions of these natural calcites plot along the 415° C isotherm.     

The fractionation of nickel between olivine and augite as a geothermometer

The coexisting olivine, clinopyroxene and glass of five samples collected from the Makaopuhi lava lake in Hawaii, at temperatures ranging from 1050 to 1160°C were analysed for nickel with an electron probe microanalyser. The results strongly suggest that the distribution of nickel between these three phase pairs well obeys the thermodynamic partition law, and that under favourable conditions, the distribution coefficients permit the estimation of the crystallisation temperature within an accuracy of 10–20°C.It is concluded that the application of the Makaopuhi data to plutonic and to other volcanic rocks should be carried out with caution because the effect of pressure and the changing composition of the phases upon the numerical values of the distribution coefficients is not known quantitatively.     

A re-evaluation of the olivine-spinel geothermometer

The Irvine olivine-spinel geothermometer, as formulated by Jackson (1969), appears to yield magmatic temperatures when applied to plutonic rocks such as the Stillwater Complex but Evans and Wright (1972) have demonstrated that it gives temperatures in excess of 2,000 ° C when applied to volcanic assemblages. A re-evaluation of the geothermometer has shown that more realistic temperatures can be obtained for volcanic rocks by using a different free energy value of FeCr₂O₄ in the formulation. The revised geothermometer gives temperatures in the range 1,100–1,300 ° C for samples from Kilauea and 500–800 ° C for basic plutonic rocks from layered intrusions, indicating that Mg and Fe²⁺ have re-equilibrated at subsolidus temperatures in these intrusions as suggested by Irvine (1965). This theory was tested by heating uncrushed natural samples from layered intrusions to magmatic temperatures for periods ranging from two days to four weeks. The result was a marked increase in the Mg/Fe²⁺ ratio in the spinels and a decrease in the Mg/Fe²⁺ ratio in the olivines, confirming that considerable subsolidus re-equilibration had taken place in the unheated samples.     

Raman spectra of carbonaceous material in metasediments: a new geothermometer

Metasedimentary rocks generally contain carbonaceous material (CM) deriving from the evolution of organic matter originally present in the host sedimentary rock. During metamorphic processes, this organic matter is progressively transformed into graphite s.s. and the degree of organisation of CM is known as a reliable indicator of metamorphic grade. In this study, the degree of organisation of CM was systematically characterised by Raman microspectroscopy across several Mesozoic and Cenozoic reference metamorphic belts. This degree of organisation, including within‐sample heterogeneity, was quantified by the relative area of the defect band (R2 ratio). The results from the Schistes Lustrés (Western Alps) and Sanbagawa (Japan) cross‐sections show that (1) even through simple visual inspection, changes in the CM Raman spectrum appear sensitive to variations of metamorphic grade, (2) there is an excellent agreement between the R2 values calculated for the two sections when considering samples with an equivalent metamorphic grade, and (3) the evolution of the R2 ratio with metamorphic grade is controlled by temperature (T). Along the Tinos cross‐section (Greece), which is characterised by a strong gradient of greenschist facies overprint on eclogite facies rocks, the R2 ratio is nearly constant. Consequently, the degree of organisation of CM is not affected by the retrogression and records peak metamorphic conditions. More generally, analysis of 54 samples representative of high‐temperature, low‐pressure to high‐pressure, low‐temperature metamorphic gradients shows that there is a linear correlation between the R2 ratio and the peak temperature [T(°C) = ?445 R2 + 641], whatever the metamorphic gradient and, probably, the organic precursor. The Raman spectrum of CM can therefore be used as a geothermometer of the maximum temperature conditions reached during regional metamorphism. Temperature can be estimated to ± 50 °C in the range 330–650 °C. A few technical indications are given for optimal application.     

Evaluation of deep temperatures of hydrothermal systems by a new gas geothermometer

The chemical composition of gas mixtures emerging in thermal areas can be used to evaluate the deep thermal temperatures. Chemical analyses of the gas compositions for 34 thermal systems were considered and an empirical relationship developed between the relative concentrations of H₂S, H₂, CH₄ and CO₂ and the reservoir temperature. The evaluated temperatures can be expressed by: $\text{t°C =}\text{24775}\text{α + β + 36.05}\text{?273}$ where $\text{α = 2 log}\text{CH}{}_4\text{CO}{}_2\text{?log}\text{H}{}_2\text{CO}{}_2\text{?3 log}\text{H}{}_2\text{S}\text{CO}{}_2$ (concentrations in % by volume) and β = 7 logP_co2     

Towards a more complete record of magmatism and exhumation in continental arcs,using detrital fission-track thermochrometry

The NE Asian margin was the locus of an Andean-style subduction zone during most of the Mesozoic and Cenozoic. The Ukelayat flysch is a 10 to 15 km thick section of marine turbidites that were deposited in a 500 km long forearc basin along the outboard edge of this convergent margin. It was structurally overridden during the early Tertiary by an obducted island arc, the Olytorsky terrane. We present new fission-track (FT) grain ages from unreset detrital zircons. These data provide precise information about depositional age of the Ukelayat and the temporal evolution of the Asian margin continental arc, which provided much of the sediment for the Ukalayat. Because all sandstones contain a large fraction of first-cycle volcanic zircons (euhedral, colorless), we infer that the youngest component of the FT grain age distribution, designated P1, closely approximates the time of deposition. Twenty-seven samples have yielded P1 ages ranging from ~44 to 88 Ma, which indicates continuous magmatic activity in the arc from the Late Cretaceous to Middle Eocene. A second component (P2) records progressive exhumation of the basement to the Okhotsk-Chukotka arc. The difference between P1 and P2 ages indicates steady exhumation at ~200–400 m/Myr from ~90 to 44 Ma. This finding implies the removal of 9 to 18 km of rock in the most deeply exhumed parts of the source region. A change in exhumation rates at ~70 Ma may coincide with an eastward shift in the locus of volcanism from the Okhotsk-Chukotka arc to the younger Western Kamchatka-Koryak arc.     

Towards a pro-community-based water resource management system in Northwest Cameroon: practical evidence and lessons of best practices

This paper examines community-based water supply management (CBWSM) in three rural districts of Northwest Cameroon as well as a review of the literature focusing on some successful community-based natural resource management initiatives in sub-Saharan Africa. Using empirical and secondary data collected through participatory research methods, it is argued that CBWSM has failed to achieve sustainable water supplies in Northwest Cameroon. Findings revealed that centralized control, the prevalence of poverty, passive involvement of public, private and grassroots community has continued to thwart water supplies within these districts. It is important to note that in any natural resource management system, power becomes a crucial factor as it determines who has and does not have access to common-pool resources. This paper argues that argues that strong traditional leadership, resolute devolution, and active participation of rural communities will facilitate and invigorate a platform for capturing the views of diverse user groups and this can bring about a people-centered and community-driven development process. Some aspects of best practice arising from successful case studies in Cameroon can contribute significantly to promoting the development of effective CBWSM in other rural communities with similar characteristics in and out of Cameroon. This will be possible only if rural groups are involved and engaged in the management of their resources while integrating some aspects of best practice.