Organic-Inorganic Interaction Recorded by Polycyclic Aromatic Steranes in Continental Epithermal Ore Deposits

Continental epithermal ore deposits are commonly associated with sedimentary organic matter, oils or solid bitumen. These organics embedded in mineral deposits can convey valuable information of the ore genesis. However, the extent to which the formation of ore minerals was recorded by organic compounds remains largely unknown, as also is how metal-rich ores interfere with the molecular proxies in the temperature regime envisaged for hydrothermal activity. The molecular compositional changes of ...     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.     

Solvent–water extraction method for the evaluation of polycyclic aromatic hydrocarbons bioavailability in coal–tar-contaminated soils

A solvent–water extraction method was proposed as an assessment tool to estimate the bioavailability of polycyclic aromatic hydrocarbons in coal–tar-contaminated soils. The approach taken was to measure the percent of polycyclic aromatic hydrocarbons extracted by a solvent–water mixture and comparing the results with the percent of polycyclic aromatic hydrocarbons degraded in a soil slurry reactor. Five soil samples from three former manufactured gas plant sites and a coal–tar disposal site which were operated between 1880 and 1947, and 1945 and 1950, respectively, in Iowa, USA were used in this study. Extraction experiments were conducted using acetone–water or ethanol–water mixtures with solvent volume fractions ranging from 1.0 to 0.4 (v/v). The percent of polycyclic aromatic hydrocarbons extracted from the various soils decreased as the volume fraction of the solvent in the solvent–water mixture was reduced. An acetone–water mixture of 0.6 was found to be appropriate in correlating the percent of polycyclic aromatic hydrocarbons degraded to the percent of polycyclic aromatic hydrocarbons extracted. For the first correlation, the percent extracted and the percent biodegraded were modified by using the molecular weights and log K _ow of polycyclic aromatic hydrocarbons, respectively. For the second correlation, the equation relating the percent extracted and the percent biodegraded was modified using soil properties such as organic carbon content and percent of clay and silt. Although the experiments were conducted for a limited number of soils, the extraction method appeared to be a good starting point in estimating the bioavailability of polycyclic aromatic hydrocarbons in coal–tar-contaminated soils.     

Organic compounds in produced waters from coalbed natural gas wells in the Powder River Basin,Wyoming, USA

The organic composition of produced water samples from coalbed natural gas (CBNG) wells in the Powder River Basin, WY, sampled in 2001 and 2002 are reported as part of a larger study of the potential health and environmental effects of organic compounds derived from coal. The quality of CBNG produced waters is a potential environmental concern and disposal problem for CBNG producers, and no previous studies of organic compounds in CBNG produced water have been published. Organic compounds identified in the produced water samples included: phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, various non-aromatic compounds, and phthalates. Many of the identified organic compounds (phenols, heterocyclic compounds, PAHs) are probably coal-derived. PAHs represented the group of organic compounds most commonly observed. Concentrations of total PAHs ranged up to 23 μg/L. Concentrations of individual compounds ranged from about 18 to <0.01 μg/L. Temporal variability of organic compound concentrations was documented, as two wells with relatively high organic compound contents in produced water in 2001 had much lower concentrations in 2002.     

Biodegradation preference for isomers of alkylated naphthalenes and benzothiophenes in marine sediment contaminated with crude oil

Contamination of coastal marine sediments with polycyclic aromatic hydrocarbons is pervasive, with major sources including anthropogenic activity and natural seepage. Biodegradation serves as a major hydrocarbon sink with evaporation and dissolution responsible for the removal of low boiling range compounds and photo-oxidation acting on many multi-substituted aromatic compounds. In this work, first-order rate constants for aerobic biodegradation were quantified for naphthalene (N), benzothiophene (BT) and their alkylated congeners (1-4 carbon substituents (C1-C4)) in laboratory experiments with oil laden marine sediments from a natural seep. Rate constants were used as proxies for microbial preference, which follows the order: naphthalene > C1N > C2N > C1BT > C2BT > benzothiophene > C3BT > C3N > C4BT > C4N, with some overlap. The application of comprehensive two dimensional gas chromatography further enabled separation and quantification of multiple structural isomers for C2N-C4N and C2BT-C4BT, with 7-12 isomers resolved for each C2N-C4N and 4-7 isomers resolved for each C2BT-C4BT. A strong isomeric biodegradation preference was noted within each of these compound classes, with rate constants varying as much as a factor of 2 for structural isomers of the same compound class. Each isomer was consumed to a low, but non-zero concentration, suggesting that their residual load in sediment may be proportional to the number of structural isomers originally present, in addition to the pattern and the number of alkyl substitutions. The simultaneous first-order biodegradation rates observed for 52 aromatic hydrocarbons resolved in this study, along with reference compounds such as n-alkanes, lends support to the concept of broad scale metabolic specificity during aerobic biodegradation of petroleum.     

Overheated, Cu-bearing magmas in the Zaldívar porphyry-Cu deposit, Northern Chile. Geodynamic consequences

The Zaldívar porphyry copper deposit, Northern Chile, consists of two major intrusions, the 290 Ma Zaldívar, and the more recent Miocene (38.7 Ma) Llamo porphyry. Five types of inclusions have been identified in quartz phenocrysts from Llamo porphyry, including melt inclusions (M), and four types of fluid inclusions, called MS (multi solids), B (brines), G (vapor-rich) and W (aqueous), respectively.Melt remnants, well preserved as M-inclusions, homogenize around 1000 °C. They show a rhyolitic composition, comparable to the most evolved acidic rhyolitic end member found elsewhere in the regional magmatism and to worldwide volcanic rhyolitic glass. High silica content in some inclusions can, however, be due to partial remelting of the quartz host during the heating run. Copper content in the same inclusions ranges between 0.03 and 0.57 wt.%, with an average concentration of 0.10 wt.%, suggesting a major magmatic source for the copper (orthomagmatic model).MS inclusions, which contain a number of solids at room temperature, mostly H₂O-bearing phases (system NaCl–KCl–((Fe, Mg, Cu)Cl)–H₂O, average salinity 70 wt.% NaCl equiv.), homogenize at magmatic temperatures (around 1000 °C). They represent the first fluids to have exsolved from the magma at depth, at a pressure of about 2 kbar. Their high homogenization temperature, comparable to values measured for melt inclusions (1000 to 1050 °C), may indicate trapping of MS and M inclusions in host phenocrysts from an immiscible mixture of silicate melt and highly saline fluids expelled from the magma during the early stage of quartz crystallization.The data indicate a magmatic origin for copper, as well as extremely high melt temperatures. These features are interpreted by magmatic differentiation of mantle-derived primitive melts, corresponding to major changes in the tectonic regime of the Andean margin, which occurred in Miocene times.     

Assessment of generation temperatures of crude oils

Biological marker maturity parameters were used to estimate the minimum HC generation temperatures of crude oils from Eastern Hungary. More than 50 oils and oil shows were analysed. Molecular- and homologous-ratios of biological marker compounds (triterpanes, steranes, mono- and triaromatic steroid hydrocarbons) were used as maturation parameters. The oils have at least five maturity stages, i.e. they have been generated under different thermal conditions. The highest reservoir temperature in each group was chosen as the best estimate of the groups' temperature just below the generation temperature, i.e. reservoirs of the group might be expected to be at shallower depths (lower temperatures) than those of the generation zone due to vertical migration into pools. For each maturation level, a threshold temperature range for genesis was inferred from reservoir temperatures; they are from 130–135°C for the least mature oils to 210–215°C for the most mature oils. In the least mature oils cracking was not observed, hence carbon–carbon cracking reactions had not taken place during their genesis. The most mature oils are intensively cracked oils; they are almost condensates. Two major genetic groups (families) of oils were found in the area. Both are present in each maturation level. The effects of migration were checked, and no influence on maturation was found. A number of the oils are in overpressured reservoirs within, or just above, the zone of the present-day active oil generation, hence the present-day temperatures of the pools must have been maximum temperatures. Contrary to the traditionally accepted temperature range for petroleum generation–maturation reactions (50–150°C), there is strong evidence from this study that the onset of oil generation requires temperatures higher than 130°C and is still proceeding above 215°C.     

Petroleum geochemistry of the Potwar Basin,Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C₂₀ and C₂₁ triaromtic steroids and the presence or absence of long chain triaromatic steroids (C₂₅, C₂₆, C₂₇, and C₂₈) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl substituted triaromatic steroids are present only for short chain compounds (C₂₀–C₂₂) and the origin of these compounds may be short chain methyl steranes from unknown biological precursors.     

Postglacial temperature anomalies and glacial isostasy

The isostatic depression of an ice-free land surface, originally caused by glacial ice, ought to be converted into a change in mean annual temperature according to the usual value for the environmental lapse rate, 6.5°C/1000 m. Calculations are undertaken to show the temperature changes, relative to present values at a site, that can be expected from this effect during the retreat of a major continental ice sheet. It is concluded that when restrained rebound is taken into account temperatures relative to the present could vary from 0°C at the start of deglaciation to about +2.32°C at the final disappearance of the Laurentide Ice Sheet. The decay of the warmer-than-present temperatures towards their current values is controlled, in this model, by isostatic recovery of the land surface. Variance estimates are built into the model and suggest that the anomaly might be as small as 0.75°C or as large as 4.0°C depending on the choice of values for crucial components such as maximum ice thickness, the proportion of isostatic deformation, and the amount of restrained rebound achieved by the time a site become ice free.     

Biodegradation of polycyclic aromatic hydrocarbon by a halotolerant bacterial consortium isolated from marine environment

The biodegradability of polycyclic aromatic hydrocarbons such as naphthalene, fluorene, anthracene and phenanthrene by a halotolerant bacterial consortium isolated from marine environment was investigated. The polycyclic aromatic hydrocarbons degrading bacterial consortium was enriched from mixture saline water samples collected from Chennai (Port of Chennai, salt pan), India. The consortium potently degraded polycyclic aromatic hydrocarbons (> 95%) at 30g/L of sodium chloride concentration in 4 days. The consortium was able to degrade 39 to 45% of different polycyclic hydrocarbons at 60 g/L NaCl concentration. Due to increase in salinity, the percent degradation decreased. To enhance polycyclic aromatic hydrocarbons degradation, yeast extract was added as an additional substrate at 60g/L NaCl concentration. After the addition of yeast extract, the consortium degraded > 74 % of polycyclic aromatic hydrocarbons at 60 g/L NaCl concentration in 4 days. The consortium was also able to degrade PAHs at different concentrations (5, 10, 20, 50 and 100 ppm) with 30 g/L of NaCl concentration. The polycyclic aromatic hydrocarbons degrading halotolerant bacterial consortium consists of three bacterial strains, namely Ochrobactrum sp., Enterobacter cloacae and Stenotrophomonas maltophilia.     

Gradual and stepwise pyrolyses of insoluble organic matter from the Murchison meteorite revealing chemical structure and isotopic distribution

To study the detailed structural and isotopic heterogeneity of the insoluble organic matter (IOM) of the Murchison meteorite, we performed two types of pyrolytic experiments: gradual pyrolysis and stepwise pyrolysis. The pyrolysates from the IOM contained 5 specific organic groups: aliphatic hydrocarbons, aromatic hydrocarbons, sulfur-bearing compounds, nitrogen-bearing compounds, and oxygen-bearing compounds. The release temperatures and the compositions of these pyrolysates demonstrated that the IOM is composed of a thermally unstable part and a thermally stable part. The thermally unstable part mainly served as the linkage and substituent portion that bound the thermally stable part, which was dispersed throughout the IOM. The linkage and substituent portion consisted of aliphatic hydrocarbons from C₄ to C₈, aromatic hydrocarbons with up to 6 rings, sulfo and thiol groups (the main reservoirs of sulfur in the IOM), and carboxyl and hydroxyl groups (the main reservoirs of oxygen). However, the thermally stable part was composed of polycyclic aromatic hydrocarbons (PAHs) containing nitrogen heterocycles in the IOM. Isotopic data showed that the aliphatic and aromatic hydrocarbons in the linkage and substituent portion were rich in D and ¹³C, while the thermally stable part was deficient in D and ¹³C. The structural and isotopic features suggested that the IOM was formed by mixing sulfur- and oxygen-bearing compounds rich in D and ¹³C (e.g., polar compounds in the interstellar medium (ISM)) and nitrogen-bearing PAHs deficient in D and ¹³C (e.g., polymerized compounds in the ISM).     

Ultrasonic wave extraction and simultaneous analysis of polycyclic aromatic hydrocarbons (PAHs) and phthalic esters in soil

A method is developed for detection of polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil samples. Ultrasonic Wave Extraction under airtight circumstances is adopted to extract the analytes in soil samples with n-hexane–acetone(V:V=1:1) as extraction solvent. This method has several advantages, including high extraction efficiency, short time, convenience and simplicity. It can be used to detect polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil.     

Development of a thermal desorption method for the analysis of particle associated polycyclic aromatic hydrocarbons in ambient air

An investigation for the analysis of polycyclic aromatic hydrocarbons in airborne particulates using thermal desorption and gas chromatography-mass spectrometry is described. Samples are obtained from ambient air using fibreglass filters and the volatile material from the filter is thermally desorbed to gas chromatograph. A 30 meter capillary column is used to separate the hydrocarbons and eight polyaromatic hydrocarbons are used to test the method and recovery is >95%. The eight polycyclic aromatic hydrocarbons anthracene, phenanthrene, fluoranthrene, pyrene, benzo (a) anthracene, chrysene, benzo (a) pyrene and benzo (e) pyrene were the most abundant PAHs found in the samples of ambient air with current method at Uxbridge-London. Application of the measurement of polycyclic aromatic hydrocarbons in ambient air samples shows that the hydrocarbons trapped in the particle phase to a lesser degree at higher ambient temperature. In conclusion a method has been developed to transfer the PAHs in particle phase from a filter to GC-MS by thermal desorption. A standard mixture of PAHs, when absorbed onto the filter, did lead to strong analyte absorbent interactions by the high percent recovery of the sample.     

Composition and syngeneity of molecular fossils from the 2.78 to 2.45 billion-year-old Mount Bruce Supergroup, Pilbara Craton, Western Australia

Shales of very low metamorphic grade from the 2.78 to 2.45 billion-year-old (Ga) Mount Bruce Supergroup, Pilbara Craton, Western Australia, were analyzed for solvent extractable hydrocarbons. Samples were collected from ten drill cores and two mines in a sampling area centered in the Hamersley Basin near Wittenoom and ranging 200 km to the southeast, 100 km to the southwest and 70 km to the northwest. Almost all analyzed kerogenous sedimentary rocks yielded solvent extractable organic matter. Concentrations of total saturated hydrocarbons were commonly in the range of 1 to 20 ppm (μg/g rock) but reached maximum values of 1000 ppm. The abundance of aromatic hydrocarbons was ∼1 to 30 ppm. Analysis of the extracts by gas chromatography-mass spectrometry (GC-MS) and GC-MS metastable reaction monitoring (MRM) revealed the presence of n-alkanes, mid- and end-branched monomethylalkanes, ω-cyclohexylalkanes, acyclic isoprenoids, diamondoids, tri- to pentacyclic terpanes, steranes, aromatic steroids and polyaromatic hydrocarbons. Neither plant biomarkers nor hydrocarbon distributions indicative of Phanerozoic contamination were detected. The host kerogens of the hydrocarbons were depleted in ¹³C by 2 to 21‰ relative to n-alkanes, a pattern typical of, although more extreme than, other Precambrian samples. Acyclic isoprenoids showed carbon isotopic depletion relative to n-alkanes and concentrations of 2α-methylhopanes were relatively high, features rarely observed in the Phanerozoic but characteristic of many other Precambrian bitumens. Molecular parameters, including sterane and hopane ratios at their apparent thermal maxima, condensate-like alkane profiles, high mono- and triaromatic steroid maturity parameters, high methyladamantane and methyldiamantane indices and high methylphenanthrene maturity ratios, indicate thermal maturities in the wet-gas generation zone. Additionally, extracts from shales associated with iron ore deposits at Tom Price and Newman have unusual polyaromatic hydrocarbon patterns indicative of pyrolytic dealkylation.The saturated hydrocarbons and biomarkers in bitumens from the Fortescue and Hamersley Groups are characterized as ‘probably syngenetic with their Archean host rock’ based on their typical Precambrian molecular and isotopic composition, extreme maturities that appear consistent with the thermal history of the host sediments, the absence of biomarkers diagnostic of Phanerozoic age, the absence of younger petroleum source rocks in the basin and the wide geographic distribution of the samples. Aromatic hydrocarbons detected in shales associated with iron ore deposits at Mt Tom Price and Mt Whaleback are characterized as ‘clearly Archean’ based on their hypermature composition and covalent bonding to kerogen.     

Off-line solid-phase extraction procedure for the determination of polycyclic aromatic hydrocarbons from aqueous matrices

An off-line solid-phase extraction procedure followed by high-performance liquid chromatography with ultraviolet detection for the determination of 16 priority polycyclic aromatic hydrocarbon pollutants in aqueous matrices was described. Diverse aspects determining extraction efficiency such as packing type (disk or cartridge), elution solvents and addition of organic modifiers to the sample were evaluated. Elution with acetonitrile yields the highest recoveries. Rinsing the sample bottle with acetonitrile and combining the rinse with the sample extract avoids the adsorption of polycyclic aromatic hydrocarbons on the walls of the water containers. The use of isopropanol or methanol 10 % (V/V) was the most appropriate amount for the enrichment of 2- to 6-ring aromatic compounds only on C18 cartridge. The recoveries for all studied polycyclic aromatic hydrocarbons are ranged from 71.4 to 95.2 % for a treated water samples of 500 mL. The proposed method gives very low detection limits (subnanograms per liter) and it has been applied to drinking water, surface water and industrial effluent (oil refinery) samples with good results.     

Results of multiyear studies on the dynamics of pollution of lake Baikal by polycyclic aromatic hydrocarbons in the area waste water discharge from the Baikal Pulp and Paper Plant

New data on the concentration and spatial distribution of the benz(a)pyrene and polycyclic aromatic hydrocarbons in bottom sediments in the testing area of the Baikal Pulp and Paper Plant (BPPP) waste water discharge in 1981–1988 and 2010 are presented in this paper. The bottom sediments in this section of the lake are strongly polluted with polycyclic aromatic hydrocarbons.     

生油岩中有机质加速溶剂萃取和索氏萃取方法对比

文章报道通过与传统的索氏萃取方法的对比,对于加速溶剂萃取(ASE 200)技术用于烃源岩可溶有机质萃取的实验方法研究结果。利用东北地区的1个泥岩样品,探讨了分散度、温度、压力对加速溶剂萃取技术的影响,确定最优化的萃取条件参数:分散度为8∶3、温度110℃、萃取压力10.3 MPa。进行方法的重现性实验,萃取结果具有很好的精密度,相对标准偏差(RSD,n=10)为2.6%。回收率达到了90%以上。采用吐哈盆地的东深1井的1个油页岩样品,从抽提的有机质、饱和烃和芳香烃组分的量上对加速溶剂萃取与传统索氏萃取进行了方法比较。采用6个样品进一步对饱和烃和芳香烃中的生物标志物进行了对比,加速溶剂萃取的烷烃、萜类、甾烷、芳烃等系列化合物的相对丰度、色谱-质谱特征、有机地化参数指标结果均与经典的索氏萃取的结果相一致。实验结果表明,加速溶剂萃取技术可有效地应用于烃源岩的有机地球化学分析测试及样品前处理。     

Pyrolysis of organic compounds in the presence of ammonia. The Viking Mars lander site alteration experiment

The influence of ammonia on the pyrolysis pattern of selected organic substances sorbed on an inorganic phase was investigated. The thermal degradation products were identified by gas chromatography-mass spectrometry. The feasibility of this technique was tested on a meteoritic sample. All substances examined react with ammonia at the pyrolysis temperature of 500°C, the major products being nitriles and heterocyclic compounds in which nitrogen was incorporated. Based on these results, a model for the non-equilibrium production of organic compounds on Jupiter is discussed. The investigation was performed in connection with the Viking lander molecular analysis. The results obtained indicate that the concentrations of ammonia in the retrorocket fuel exhaust would have been probably too small to produce significant changes in the Martian soil organic compounds if any were found.     

Estimation of bioavailability of polycyclic aromatic hydrocarbons in river sediments

This study aimed to evaluate the total concentration of polycyclic aromatic hydrocarbons in sediments of Iguassu River in Southern Brazil. Alongside the concentration, the amount of such compounds bioavailable was also evaluated. This is accomplished by comparing its total amount present in sediments and the amount extracted by n-butanol. The results showed that the total concentration of polycyclic aromatic hydrocarbons presented in sediment ranged from 4.49 to 58.75???g/g. The total amount of polycyclic aromatic hydrocarbons extracted by n-butanol ranged from 1.22 to 17.07???g/g. The use of n-butanol represents the mimetic conditions that hydrocarbons, derived from oil, could be taken up by organisms. Most of the hydrocarbons extracted by n-butanol were those with lower octanol?Cwater partition constant, usually those with three and four rings. Compounds with more than four rings were extracted in lower or insignificant amounts. Even the hydrocarbons with lower molecular weight available may be degraded or eliminated by organisms, when accumulated. Estimating bioavailability of hydrocarbons represents what specific hydrocarbons could be available to be taken up by organisms.     

The shift of the α-β transition temperature of quartz associated with the thermal expansion of granite at high pressure

Measurements are presented of volume changes in granite during room-temperature compression to 100, 200 and 300 MPa confining pressure followed by temperature increase to 900°C. Comparison with thermal expansion and compressibility data for the constituent minerals allows changes in porosity to be estimated. Under confining pressure, porosity is found to decrease with heating to 200°C through expansion of the minerals into cracks which are thought to be related to the geological cooling history of the rock. Between 200°C and 840°C porosity increases as a result of differential thermal expansion of the constituent minerals, but crack opening is increasingly suppressed at higher confining pressures. Extrapolation of the results indicates that differential thermal expansion can no longer cause crack opening in dry granite at confining pressures in excess of 450 MPa. The quartz α-β transition temperature in granite is marked by a kink in the thermal expansion curve of the rock, and it is found to increase by 60°C–70°C per 100 MPa confining pressure, as opposed to the published value of 26°C per 100 MPa for single crystals of quartz. Equations are presented which allow calculation of the effects of confining pressure and temperature on the stresses and displacements in and around a spherical inclusion embedded in a matrix of different elasticity and thermal expansion. The theory, together with a simple self-consistent model for granite, accounts semiquantitatively for the observations of thermal expansion and the effect of confining pressure thereon, and for the observed α-β transition temperatures for quartz in granite.