The inclusion record of fluid evolution,crack healing and trapping from a heterogeneous system during rapid cooling of pegmatitic veins (Dronning Maud Land; Antarctica)

Granitoid (pegmatite and aplite) veins in metamorphic rocks and intrusive syenites of central Dronning Maud Land, Antarctica, are flanked by conspicuous light‐coloured alteration halos, which represent the damage zone of fracture propagation. The damage zone is characterized by a high density of sealed or healed microcracks, about 1 order of magnitude above background. Fluid inclusions along healed microcracks in quartz of both pegmatite and alteration halos are inspected by optical and scanning electron microscopy, and their composition is analysed by microthermometry and quadrupole mass spectrometry. The similar inclusion record in the granitoid vein and in the damaged host rock indicates the derivation of the fluids from the hydrous melt phase. The aqueous inclusions bear abundant daughter crystals, mainly silicates, and may represent a hydrous melt. The volatile composition is variable in the system H₂O–CO₂, with mostly subordinate amounts of N₂. Phase separation with partitioning of CO₂ into the fluid phase coexisting with the hydrous melt, and possibly immiscibility in the subsolidus range, govern fluid evolution during cooling. The variable CO₂/N₂ ratio suggests mixing with fluids from an external source in the host rock and vigorous circulation at an early stage of high transient permeability. Experiments have shown that healing of microcracks at high temperatures is a matter of hours to weeks, hence similar in time scale to the cooling of the cm‐ to dm‐thick granitoid veins. In this case, rapid cooling and concomitant crack healing in a system undergoing phase separation causes a broad compositional variability of the inclusions due to necking down, and the underpressure developing in closed compartments precludes a meaningful thermobarometric interpretation.     

A fluid inclusion record of magmatic/hydrothermal pulses in acid Salar Ignorado gypsum,northern Chile

Salar Ignorado is a shallow acid saline lake hosted by a small intervolcanic basin high in the Andes Mountains of northern Chile. Modern surface waters have 3.3–4.1 pH, 0.5–3% total dissolved solids (TDS) and are actively precipitating gypsum crystals. The gypsum crystals trap the acid saline water as fluid inclusions, providing a record of recent surface water characteristics. Salar Ignorado gypsum contains three distinct types of primary fluid inclusions, which result from growth of the gypsum from surface waters. Petrography and microthermometry were performed on 27 gypsum crystals from Salar Ignorado to gain an understanding of recent water chemistry of the salar. One 18.3‐cm‐long gypsum crystal, hosting primary fluid inclusions along 28 successive growth bands, was the focus for fluid inclusion studies and allowed a record of high‐resolution chemical trends. This crystal showed a change in parent fluids during growth, from low salinity, to high salinity, back to low salinity. At the bottom of the crystal, the lowest six fluid inclusion assemblages have salinities of 1.7–5.1 eq. wt. % NaCl. The next nine fluid inclusion assemblages have significantly higher salinity (18.6–27.4 eq. wt. % NaCl) inclusions. The twelve fluid inclusion assemblages near the top of the crystal have low salinity (0.9–8.3 eq. wt. % NaCl) like those at the bottom of the crystal. The high‐salinity fluid inclusions in the middle of this gypsum crystal are interpreted to have formed during a pulse of magmatic/hydrothermal fluids to the surface, perhaps during local active volcanism. Secondary evidence of a magmatic influence on surface waters includes hydrogen sulfide and high molecular weight solid hydrocarbons within some fluid inclusions. This study is among the first detailed fluid inclusion studies of gypsum and suggests that fluid inclusions in gypsum can be paleo‐hydrogeologic proxies.     

Mineralogy and fluid inclusion gas chemistry of production well mineral scale deposits at the Dixie Valley geothermal field,USA

At the Dixie Valley geothermal field, Nevada, USA, fluid boiling triggered the precipitation of carbonate scale minerals in concentric bands around tubing inserted into production well 28–33. When the tubing was removed, this mineral scale was sampled at 44 depth intervals between the wellhead and 1227 m depth. These samples provide a unique opportunity to evaluate the effects of fluid boiling on the scale mineralogy and geochemistry of the vapor and liquid phase. In this study, the mineralogy of the scale deposits and the composition of the fluid inclusion gases trapped in the mineral scales were analyzed. The scale consists mainly of calcite from 670–1112 m depth and aragonite from 1125 to 1227 m depth, with traces of quartz and Mg‐smectite. Mineral textures, including hopper growth, twinning, and fibrous growth in the aragonite and banded deposits of fine grained calcite crystals, are the result of progressive boiling. The fluid inclusion noncondensable gas was dominated by CO₂. However, significant variations in He relative to N₂ and Ar provide evidence that the geothermal reservoir consists of mixed source deeply circulating reservoir water and shallow, air saturated meteoric water. Gas analyses for many inclusions also showed higher CH₄ and H₂ relative to CO₂ than measured in gas sampled from this well, other production wells, and fumaroles. These inclusions are interpreted to have trapped CH₄‐ and H₂‐enriched gas resulting from early stages of boiling.     

Chemical evolution of metamorphic fluids in the Central Alps,Switzerland: insight from LA‐ICPMS analysis of fluid inclusions

The chemical evolution of fluids in Alpine fissure veins (open cavities with large free‐standing crystals) has been studied by combination of fluid inclusion petrography, microthermometry, LA‐ICPMS microanalysis, and thermodynamic modeling. The quartz vein systems cover a metamorphic cross section through the Central Alps (Switzerland), ranging from subgreenschist‐ to amphibolite‐facies conditions. Fluid compositions change from aqueous inclusions in subgreenschist‐ and greenschist‐facies rocks to aqueous–carbonic inclusions in amphibolite‐facies rocks. The fluid composition is constant for each vein, across several fluid inclusion generations that record the growth history of the quartz crystals. Chemical solute geothermometry, fluid inclusion isochores, and constraints from fluid–mineral equilibria modeling were used to reconstruct the pressure–temperature conditions of the Alpine fissure veins and to compare them with the metamorphic path of their host rocks. The data demonstrate that fluids in the Aar massif were trapped close to the metamorphic peak whereas the fluids in the Penninic nappes record early cooling, consistent with retrograde alteration. The good agreement between the fluid–mineral equilibria modeling and observed fluid compositions and host‐rock mineralogy suggests that the fluid inclusions were entrapped under rock‐buffered conditions. The molar Cl/Br ratios of the fluid inclusions are below the seawater value and would require unrealistically high degrees of evaporation and subsequent dilution if they were derived from seawater. The halogen data may thus be better explained by interaction between metamorphic fluids and organic matter or graphite in metasedimentary rocks. The volatile content (CO₂, sulfur) in the fluid inclusions increases systematically as function of the metamorphic grade, suggesting that the fluids have been produced by prograde devolatilization reactions. Only the fluids in the highest grade rocks were partly modified by retrograde fluid–rock interactions, and all major element compositions reflect equilibration with the local host rocks during the earliest stages of postmetamorphic uplift.     

Rapid Na, Cu exchange between synthetic fluid inclusions and external aqueous solutions: evidence from LA-ICP-MS analysis

Three sets of equilibration experiments (Set 1 to Set 3) were performed in cold-seal pressure vessels to investigate the compositional modification of quartz-hosted fluid inclusions after entrapment. Each set of experiment consisted of two stages. In a pre-run, fluid inclusions containing 5–10 wt% NaCl and selected trace elements were synthesized at 700°C/140–200 MPa. These samples were then loaded into new capsules together with Cu-bearing solutions and some mineral buffers, and re-equilibrated at 600–800°C and 70–140 MPa for 6–8 days. LA-ICP-MS analysis of individual fluid inclusions reveals that in re-equilibration experiments in which the outer fluid was composed of KCl (±FeCl₂) up to 83% of the original Na content of pre-existing fluid inclusions were lost, and up to 5660 ppm Cu were gained. Other elements with larger ionic radii (i.e. K, Fe, Ba, Sr) were not exchanged, demonstrating that the inclusions remained physically intact and that Na and Cu were transported through quartz by diffusion. The observed Na loss from pre-existing fluid inclusions correlates positively with Cu gain, with about 1 Cu atom being gained per 10 Na atoms lost. Thus, Na and Cu (plus probably H) were exchanged by interdiffusion. Remarkably, this processes resulted in up to 10 times higher Cu concentrations in re-equilibrated inclusions than were present in the outer fluid, i.e. Cu diffused 'uphill'. Large variations of Cu concentrations relative to the concentration of other elements are common also in natural fluid inclusion assemblages. However, no evidence for a correlation between Cu content and Na content was found so far, suggesting that Cu diffusion in natural samples may be dominated by processes other than Na–Cu interdiffusion.     

Magmatic fluids immiscible with silicate melts: examples from inclusions in phenocrysts and glasses, and implications for magma evolution and metal transport

The first occurrence of immiscibility in magmas appears to be most important in the magmatic–hydrothermal transition, and thus studies of magmatic immiscibility should be primarily directed towards recognition of coexisting silicate melt and essentially non-silicate liquids and fluids (aqueous, carbonic and sulphide). However, immiscible phase separation during decompression, cooling and crystallization of magmas is an inherently fugitive phenomenon. The only remaining evidence of this process and the closest approximation of natural immiscible magmatic liquids and vapours can be provided by melt and fluid inclusions trapped in silicate glasses and magmatic phenocrysts. Such inclusions are often used as a natural experimental laboratory to model the process of exsolution and the compositions of volatile-rich phases from a wide range of terrestrial magmas. In this paper several examples from recent research on melt and fluid inclusions are used to demonstrate the significance of naturally occurring immiscibility in understanding some large-scale magma chamber processes, such as degassing and partitioning of metals.     

Composition and evolution of fluids during skarn development in the Monte Capanne thermal aureole,Elba Island,central Italy

We describe the chemistry of the fluids circulating during skarn formation by focusing on fluids trapped in calcsilicate minerals of the inner thermal aureole of the Late Miocene Monte Capanne intrusion of western Elba Island (central Italy). Primary, CH₄‐dominant, C‐O‐H‐S‐salt fluid inclusions formed during prograde growth of the main skarn‐forming mineral phases: grossular/andradite and vesuvianite. The variable phase ratios attest to heterogeneous entrapment of fluid, with co‐entrapment of an immiscible hydrocarbon–brine mixture. Chemical elements driving skarn metasomatism such as Na, K, Ca, S and Cl, Fe and Mn were dominantly partitioned into the circulating fluid phase. The high salinity (apparent salinity between 58 and 70 wt% NaCl eq.) and the C‐component of the fluids are interpreted as evidence for a composite origin of the skarn‐forming fluids that involves both fluids derived from the crystallizing intrusion and contributions from metamorphic devolatilization. Oxidation of a Fe‐rich brine in an environment dominated by fluctuation in pressure from lithostatic to hydrostatic conditions (maintained by active crack‐sealing) contributed to skarn development. Fluid infiltration conformed to a geothermal gradient of about 100°C km^?1, embracing the transition from high‐temperature contact metamorphism and fluid‐assisted skarn formation (at ca 600°C) to a barren hydrothermal stage (at ca 200°C).     

Petroleum type determination through homogenization temperature and vapour volume fraction measurements in fluid inclusions

Physical parameters of petroleum‐bearing fluid inclusions such as bulk density (ρ), molar volume (V_m), vapour volume fraction (?_vap) and homogenization temperature (T_h) are essential information to model petroleum composition (x) in inclusions and to reconstruct palaeotemperature and palaeopressure of trapping. For the main petroleum types contained in a fluid inclusion, we can follow how ?_vap and T_h are simultaneously influenced by a change of bulk density in a ?_vap versus T_h projection. We have correlated T_h and ?_vap for different petroleum compositions for a large range of bulk density values. However, postentrapment events under new pressure (P) and temperature (T) conditions can greatly modify the initial fingerprints of physical conditions and chemical composition of fluid inclusions. Re‐equilibration is frequent, especially in the case of fragile minerals. Stretching and leakage phenomenon have been simulated using the Petroleum Inclusion Thermodynamics (pit ) software, from virtual petroleum inclusions with known hydrocarbon composition. The aim of these simulations is to understand how ?_vap and T_h evolve with these re‐equilibration phenomena, with respect to the oil composition. Results of stretching simulations show a characteristic increase of T_h and ?_vap along correlation curves, with the curve shape dependent on petroleum composition. Leakage simulations show an increase of T_h and a smaller increase or even a decrease in ?_vap. Consequently, the better preserved inclusions in a given population can be presumed to be those that have the lowest T_h. Applications of T_h and ?_vap measurements of natural inclusions in calcite and in quartz showed that the fragility of the host mineral is a key factor allowing the recording of post‐entrapment events. Inclusions that have stretched or leaked are identified and the best preserved inclusions selected for evaluation of P–T–x trapping conditions. Moreover, petroleum types trapped in inclusions can be identified from ?_vap and T_h measurements without compositional modelling.     

Fluid inclusion and isotopic constraints on the origin of ore‐forming fluid of the Jinman–Liancheng vein Cu deposit in the Lanping Basin,western Yunnan,China

Extensive quartz–carbonate–Cu sulfide veins occur in clastic rocks and are spatially related to Paleocene granites in the western border of the Lanping Basin, western Yunnan, China. Abundant aqueous‐carbonic fluid inclusions occur in these veins but their origin is debated. In the Jinman–Liancheng deposit, individual primary inclusion groups contain either exclusively liquid‐rich inclusions (Gl), or coexisting liquid‐rich and vapor‐rich inclusions (Glv). Microthermometry and estimate of CO₂ content indicate that type Gl inclusions either have homogenization temperatures (Th) 238–263°C and contain c. 3.9–5.5 mole % CO₂, or have Th 178–222°C and contain c. 1.6–3.2 mole % CO₂. Type Glv inclusions are thought to represent samples of fluid unmixing that occurred at 183–218°C. At that time, the liquid phase in the unmixing fluid may contain c. 2.0–3.3 mole % CO₂. As such, the correlation of CO₂ content with Th for type Gl inclusions is thought to be caused by fluid unmixing with decreasing temperature and subsequent CO₂ escape. δ¹⁸O and δD values of the parent water mainly fall in the field below that of primary magmatic water, indicative of fluid derivation from degassed (in open system) magmatic water, with no contributions from basinal or meteoric water. Initial Sr isotopic compositions of hydrothermal carbonates suggest that the fluid was magmatic, probably derived from the Paleogene granites. δ¹³C_PDB values (?4‰ to ?7‰) of the hydrothermal carbonates and δ³⁴S_V‐CDT values of sulfides (mainly ?11‰ to +5‰) indicate that the carbon and sulfur can be derived from (degassed) magma and/or nonmagmatic sources. The CO₂‐rich and magmatic‐water‐derived fluid at Jinman–Liancheng differs from the CO₂‐poor and basinally derived fluid in sediment‐hosted stratiform Cu (SSC) deposits, which suggests that there are no genetic linkages between the vein Cu and SSC deposits in the Lanping Basin.     

In situ decarboxylation of acetic and formic acids in aqueous inclusions as a possible way to produce excess CH4

Accurate reconstruction of diagenetic P‐T conditions in petroleum reservoirs from fluid inclusion data relies on valid measurements of methane concentration in aqueous inclusions. Techniques have been developed (Raman spectrometry) to provide sufficiently accurate data, assuming measured methane concentration has not been modified after aqueous inclusion entrapment. This study investigates the likelihood that organic acids derived from petroleum fluids and dissolved in formation water might suffer decarboxylation upon postentrapment heating within the fluid inclusion chamber, thereby generating excess CH₄ in the inclusions. Four different experiments were conducted in fused silica capillary capsules (FSCCs), mimicking fluid inclusions. The capsules were loaded with acetic (CH₃COOH) or formic (HCOOH) acid solution and were heated to 250°C for short durations (<72 h) in closed‐system conditions, with or without applying a fixed P_H2. Reaction products were characterized by Raman and FT‐IR spectrometry. Results indicate that decarboxylation reactions did take place, at variable degrees of progress, and that measurable excess CH₄ was produced in one experiment using acetic acid. This suggests that methane may be produced from dissolved organic acids in natural aqueous inclusions in specific situations, possibly inducing errors in the thermodynamic interpretation.     

Fluid dynamics and fluid‐structural relationships in the Red Lake mine trend,Red Lake greenstone belt,Ontario, Canada

The Red Lake mine trend, a deformation zone in the Archean Red Lake greenstone belt that hosts the world‐class Campbell‐Red Lake gold deposit, is characterized by abundant foliation‐parallel iron‐carbonate ± quartz veins with banded colloform‐crustiform structures and cockade breccias overprinted by silicification and gold mineralization. There is an apparent incompatibility between the cavity‐fill structures of the veins and breccias (typically developed at shallow crustal depths) and the upper greenschist to lower amphibole facies metamorphic conditions recorded in the host rocks (indicating relatively deep environments). This, together with the development of veins along the foliation plane, represents an enigmatic problem that may be related to the interplay between fluid dynamics and stress field. We approach this problem through systematic study of fluid inclusion planes (FIPs) in the vein minerals, including the orientations of the FIPs and the pressure–temperature conditions inferred from fluid inclusion microthermometry. We find that fluid inclusions in the main stage vein minerals (pregold mineralization ankerite and quartz and syn‐ore quartz) are predominantly carbonic without a visible aqueous phase, whereas many inclusions in the postore stage contain an aqueous phase. Most FIPs are subvertical, and many are subparallel to the foliation. High fluid pressure coupled with the high wetting angles of the water‐poor, carbonic fluids may have been responsible for the abundance of brittle deformation features. The development of subvertical FIPs is interpreted to indicate episodic switching of the maximum principal compressive stress (σ₁) from subhorizontal (perpendicular to the foliation) to subvertical (parallel to the foliation) orientation. The subvertical σ₁ is favorable for the formation of foliation‐parallel veins, as fractures are preferentially opened along the foliation in such a stress regime, the origin of which may be linked to the fluid source.     

ICE-WEDGE CRACKS, WESTERN ARCTIC COAST

Ice-wedge ice is one of the most abundant types of nearly pure ground ice to be found along the western Arctic coast and, indeed, in many other permafrost areas of the world. Ice wedges grow because thermal contraction cracks open in winter and become infilled with water in spring to form incremental ice veinlets. Long-term winter observations along the western Arctic coast have provided details of crack opening and closing, propagation, and cracking frequency. Ice-wedge cracking is sensitive to climatic factors, particularly the winter snowfall. Therefore, long-term monitoring of ice-wedge cracks should be of interest in the study of climatic change and the interpretation of the size-age relations of ice wedges.     

Recognising burnt vein quartz artefacts in archaeological assemblages

The primary aims of this study were to determine how vein quartz behaves in an open wood fire and to suggest how burnt quartz may reliably be distinguished from unburnt quartz. Experimental burning was conducted on 10–50 mm pieces of knapped quartz collected from outcrops and beach cobbles near a later Mesolithic and Neolithic quartz scatter at Belderrig, north County Mayo, Ireland. Burning resulted in considerable fragmentation, with the majority of post-burning fragments <10 mm in size. Compared to experiments with flint, few quartz pieces were expelled from the hearth during burning, probably due to lower water content. Burning reduced the lustre and transparency of quartz and oxidized any iron-bearing rock impurities to a red-brown or pink colour, but these changes could only be diagnostic of burning where unburnt quartz of the same type is available for comparison. Burning did not affect the texture of the quartz, though quartz grain boundaries became more visible in some samples. Under the microscope, all >5 μm fluid inclusions in quartz lost their fluid contents, often with the development of fluid escape structures, and this is likely to be a reliable discriminant between burnt and unburnt vein quartz generally, even in the absence of unburnt material for comparison. Burning also creates microfractures, but this feature does not provide a diagnostic test of burning as there is considerable overlap between burnt and unburnt samples in microfracture density.     

Palaeo‐formation water evolution in the Latrobe aquifer,Gippsland Basin,south‐eastern Australia continental shelf

Offshore fresh or brackish groundwater has been observed around the globe and represents an interesting but unusual freshwater reserve. Formation waters in sedimentary basins evolve at geological time through fluid–rock interactions and water movements in aquifers. However, the mechanism and timing of freshwater displacing and mixing with pre‐existing formation water offshore under the seafloor has not been investigated in many cases. The growing need for developing freshwater resources in deeper parts of sedimentary basins that have not been economic or technically feasible in the past, may potentially lead to an increasing conflict with petroleum production or injection of carbon dioxide. For being able to assess and mitigate possible impacts of fluid production or injection on groundwater flow and quality, a better understanding of the natural history of the interaction between fresh meteoric water and deep basin formation water is necessary. A low‐salinity wedge of meteoric origin with less than 5000 ppm currently extends to about 20 km offshore in the confined Latrobe aquifer in the Gippsland Basin (Australia). The Latrobe aquifer is a freshwater resource in the onshore, hosts major petroleum reservoirs and has been considered for carbon dioxide storage in the offshore parts of the basin. The objective of this study is to constrain the evolution of formation water in the Latrobe aquifer by investigating the water naturally trapped in fluid inclusions during burial. The measured palaeo‐salinities from onshore and offshore rock samples have a minimum of about 12 500 ppm (NaCl equivalent) and a maximum of about 50 000 ppm. Most of the salinities are in the 32 000–35 000 ppm range. There is no evidence for freshwater in fluid inclusions and the variation in palaeo‐salinity across the basin is consistent with the palaeogeography of deposition of the sedimentary rocks. The current low‐salinity water wedge must have started to form recently after most of the diagenetic processes that led to the trapping of water in fluid inclusions happened. The minimum homogenisation temperatures (T_h) recorded are consistent with current formation temperature. However, they are generally higher than present day suggesting that hotter temperatures were attained in the past. The T_h and salinity data together suggest that the fluid inclusions record the diagenetic modification of connate water to higher salinities over a time period that was accompanied by an increase in temperature, consistent with a westward palaeo‐fluid flow from the deeper part of the basin through the aquifer. Subsequent pore‐water evolution from palaeo‐ to current day conditions is consistent with an influx of fresher and cooler meteoric water into the Latrobe Group. The meteoric recharge originates from the area of the Baragwanath anticline in the onshore part of the basin where the Latrobe Group subcrops at high elevations.     

Package FLUIDS. Part 3: correlations between equations of state, thermodynamics and fluid inclusions

The computer package FLUIDS ( Bakker 2003 ) has been revised to calculate fluid properties in pores and inclusions. The programs are provided with a Graphical User Interface (GUI) and are adapted to new operating systems, including MacOS, Windows and Linux. The van der Waals equation of state has been added to the group Loners and is used to illustrate a large variety of calculation procedures for many thermodynamic parameters and properties. The mathematical transformations can be applied to any equation of state with the form p ( V , T , n ), i.e. the pressure of a multi-component fluid is expressed as a function of volume, temperature and amount of substance. The fluid properties that are usually observed in microthermometric analyses of fluid inclusions, such as phase separation, phase coexistence and stability, can be predicted with these equations of state by using its spinodal and critical point calculations, in addition to fugacity calculations of liquid and vapour phases. The computer program LonerW can be freely downloaded from the website: http://fluids.unileoben.ac.at/Computer.html .     

Red calcite: an indicator of paleo‐karst systems associated with bauxitic unconformities

A unique red calcite generation, which fills fractures/cavities, is hosted by Mesozoic carbonates in the Transdanubian Range, Hungary. Solid inclusions are located along growth zones of calcite. Hematite, the most abundant solid inclusion, gives the red colour of it. Outcrop‐scale geometry, mineralogical features and detrital mineral assemblage (hematite, gibbsite, goethite, kaolinite, smectite, illite, Cr‐spinel, monazite, xenotime, zircon, apatite and Ti‐oxide) of calcite precipitates suggest strong correlation between the calcite and nearby karst bauxite deposits. Fluid inclusion petrography and microthermometry (T < 50°C; salinity from 0 to 0.17 NaCl eq. w%) of primary fluid inclusions, and the stable isotope trend of the calcite, following the meteoric water line, clearly indicate vadose and phreatic meteoric origin in a near‐surface karst system. The late Cretaceous to mid‐Eocene unconformity‐related cavity‐filling deposits occur close to the surface; indicating that the most recent Quaternary exhumation re‐exposed those surfaces that existed at the time of calcite mineralization. Thus, red calcite precipitates are interpreted as being speleothems, vestiges of the subterranean part of the pre‐Middle Eocene karst. The infiltrated, fine bauxite particles enclosed by the calcite are the witnesses of the once areally extensive pre‐Middle Eocene bauxitic blanket that became partially eroded by the time of the deposition of the cover beds. Red calcite when found in core samples may provide good evidence on bauxite formation associated with the overlying unconformity, even if it was later removed by erosion. Therefore, presence or absence of red calcite may be used as distinguishing criteria between karst episodes with or without bauxite formation.     

Freezing and melting behaviors of H2O‐NaCl‐CaCl2 solutions in fused silica capillaries and glass‐sandwiched films: implications for fluid inclusion studies

Fluid inclusions of the H₂O‐NaCl‐CaCl₂ system are notorious for their metastable behavior during cooling and heating processes, which can render microthermometric measurement impossible or difficult and interpretation of the results ambiguous. This study addresses these problems through detailed microscopic examination of synthetic solutions during cooling and warming runs, development of methods to enhance nucleation of hydrates, and comparison of microthermometric results with different degrees of metastability with values predicted for stable conditions. Synthetic H₂O‐NaCl‐CaCl₂ solutions with different NaCl/(NaCl + CaCl₂) ratios were prepared and loaded in fused silica capillaries and glass‐sandwiched films for microthermometric studies; pure solutions were used with the capillaries to simulate fluid inclusions, whereas alumina powder was added in the solutions to facilitate ice and hydrate crystallization in the sandwiched samples. The phase changes observed and the microthermometric data obtained in this study have led to the following conclusions that have important implications for fluid inclusion studies: (i) most H₂O‐NaCl‐CaCl₂ inclusions that appear to be completely frozen in the first cooling run to ?185°C actually contain large amounts of residual solution, as also reported in some previous studies; (ii) inability of H₂O‐NaCl‐CaCl₂ inclusions to freeze completely may be related to their composition (low NaCl/(NaCl + CaCl₂) ratios) and lack of solid particles; (iii) crystallization of hydrates, which is important for cryogenic Raman spectroscopic studies of fluid inclusion composition, can be greatly enhanced by finding an optimum combination of cooling and warming rates and temperatures; and (iv) even if an inclusion is not completely frozen, the melting temperatures of hydrohalite and ice are still valid for estimating the fluid composition.     

The mechanism of fluid infiltration in peridotites at Almklovdalen, western Norway

A major Alpine‐type peridotite located at Almklovdalen in the Western Gneiss Region of Norway was infiltrated by aqueous fluids at several stages during late Caledonian uplift and retrogressive metamorphism. Following peak metamorphic conditions in the garnet–peridotite stability field, the peridotite experienced pervasive fluid infiltration and retrogression in the chlorite–peridotite stability field. Subsequently, the peridotite was infiltrated locally by nonreactive fluids along fracture networks forming pipe‐like structures, typically on the order of 10 m wide. Fluid migration away from the fractures into the initially impermeable peridotite matrix was facilitated by pervasive dilation of grain boundaries and the formation of intragranular hydrofractures. Microstructural observations of serpentine occupying the originally fluid‐filled inclusion space indicate that the pervasively infiltrating fluid was characterized by a high dihedral angle (θ > 60°) and ‘curled up’ into discontinuous channels and fluid inclusion arrays following the infiltration event. Re‐equilibration of the fluid phase topology took place by growth and dissolution processes driven by the excess surface energy represented by the ‘forcefully’ introduced external fluid. Pervasive fluid introduction into the peridotite reduced local effective stresses, increased the effective grain boundary diffusion rates and caused extensive recrystallization and some grain coarsening of the infiltrated volumes. Grain boundary migration associated with this recrystallization swept off abundant intragranular fluid inclusions in the original chlorite peridotite, leading to a significant colour change of the rock. This colour change defines a relatively sharp front typically located 1–20 cm away from the fractures where the nonreactive fluids originally entered the peridotite. Our observations demonstrate how crustal rocks may be pervasively infiltrated by fluids with high dihedral angles (θ > 60°) and emphasize the coupling between hydrofracturing and textural equilibration of the grain boundary networks and the fluid phase topology.     

Fluid effect on hydraulic fracture propagation behavior: a comparison between water and supercritical CO2‐like fluid

The initiation of hydraulic fractures during fluid injection in deep formations can be either engineered or induced unintentionally. Upon injection of CO₂, the pore fluids in deep formations can be changed from oil/saline water to CO₂ or CO₂ dominated. The type of fluid is important not only because the fluid must fracture the rock, but also because rocks saturated with different pore fluids behave differently. We investigated the influence of fluid properties on fracture propagation behavior by using the cohesive zone model in conjunction with a poroelasticity model. Simulation results indicate that the pore pressure fields are very different for different pore fluids even when the initial field conditions and injection schemes (rate and time) are kept the same. Low viscosity fluids with properties of supercritical CO₂ will create relatively thin and much shorter fractures in comparison with fluids exhibiting properties of water under similar injection schemes. Two significant times are recognized during fracture propagation: the time at which a crack ceases opening and the later time point at which a crack ceases propagating. These times are very different for different fluids. Both fluid compressibility and viscosity influence fracture propagation, with viscosity being the more important property. Viscosity can greatly affect hydraulic conductivity and the leak‐off coefficient. This analysis assumes the in‐situ pore fluid and injected fluid are the same and the pore space is 100% saturated by that fluid at the beginning of the simulation.     

MICROSTRUCTURAL CHARACTERIZATION OF EARLY WESTERN GREEK INCUSE COINS*

In this research, we studied the compositional, crystallographic and microstructural properties of a series of incuse silver didrachmae stemming from the Achaean colonies of Metapontum and Caulonia. In this paper, we address the following points: (i) the metal sources, (ii) the fabrication process and (iii) degradation phenomena, such as incrustation and embrittlement. In this investigation, we employed energy‐dispersive X‐ray fluorescence spectroscopy, X‐ray diffractometry, and scanning electron and optical microscopies. The patina is mainly composed of chlorargirite. The coins consist of a silver‐rich alloy containing ～ 1% of Au and Cu. Metallographic and local compositional analyses revealed a complex scenario of inclusions. In one instance, unalloyed copper grains, two‐phase copper/bismuth globuli and high‐bismuth filaments were observed. In other cases, globular Cu ₂ S (chalcocite) inclusions were noticed. The presence of SiO ₂ and iron oxide inclusions is ubiquitous in these samples. Distorted twin lines and strain lines can be detected, denoting work‐hardening of recrystallized flans. Grain polygonalization can occasionally be noticed, hinting at secondary recrystallization processes. The irregularly shaped iron oxide particles often act as crack initiation sites. Fracture facets are generally intergranular. On some areas, intergranular decohesion is also observed. Open cracks sometimes contain AgCl. The strain lines that can be noticed on the fracture surfaces indicate work‐hardening and residual microstructural deformation. Information regarding inclusions and the presence of significant amounts of gold can be tentatively used to address provenancing and fabrication issues.