Fluid Inclusions in Minerals:

Fig.1

300

Fig.2

Fig.3

As was discussed earlier, majority of mineral deposits in the crust owe their origin to the activity of a hot aqueous fluid in the crust. Firstly, these fluids are of diverse sources such as a crystallizing felsic pluton, a pile of sediments or sediments+volcanics undergoing metamorphism, fluids present in the pore spaces of sediments in basins, fluids exsolved from deeper interior (mantle) sources and the meteoric water percolating in the subsurface. Secondly, these fluids, by virtue of their temperature (often pressure) and

dissolved electrolytes, acquire tremendous solubility of metals which they transport (from rocks with which they interact at higher temperature conditions) and deposit at different locales where appropriate physicochemical conditions are encountered. Thirdly, these fluids operate at diverse geological domains (deeper crust, ocean floor, folded, faulted, sheared zones in the crust etc). The physicochemical conditions of formation of minerals from such fluids can be retrieved with the help of fluid inclusions in the minerals, which precipitate from these fluids. The figure above is a sketch to explain the entrapment process of fluid inclusions in minerals. Imagine that the crystal drawn in three dimension grew from a fluid starting as a seed crystal. Because of growth irregularity and/or faster growth rate, the crystal was leaving tiny cavities that were getting filled up by the fluid from which the crystal was growing. Because there is no definite order of formation of these cavities, they are distributed randomly as shown in the first figure.

Fig. 4

The second figure in addition shows an inclined plane (imagine a fracture plane) that served as a conduit for circulation of fluid could be immediately after the formation of the crystal or much later. This later fluid also interacted with the host crystal and healed the fracture by depositing the same material of the host crystal and in the process of healing, left cavities filled up by the secondary fluid, much the same way as primary fluid is trapped. The third figure shows a section of the crystal cut perpendicular to the vertical axis and a thickness of 300 micron. Here we see the inclined healed fracture plane as a linear zone containing the tiny inclusions arranged in a linear trail. We also see the primary inclusions, some in focus and others out of focus. In nature, crystals do not grow alone and also do not grow with perfect crystal faces as shown in the first figure. The actual case is shown in Fig.4 as you see a mineral aggregate (say quartz) in thin (thicker here) section. Discrete grains are shown containing fluid inclusions as part of three

dimensional network and in addition, there is a linear array of smaller inclusions that cut across many grains. Clearly, the linear array of inclusions on a healed crack were trapped later than the precipitation of the quartz aggregate since the fracture traverses through all grains. The inclusions as part of three dimensional array, formed during the primary growth of the host mineral are the primary inclusions and the ones present on healed cracks traversing through many grains are secondary inclusions. It is the primary inclusions which are useful for characterizing the parent fluid from which the mineral precipitated. Secondary inclusions could be of more than one generation and also are useful for understanding the full spectrum of fluid activity. We shall consider the primary inclusions only. Based on bulk composition fluid inclusions can be categorized as either aqueous (water-rich liquid with variable concentration of dissolved solids), mixed aqueous+gas (most commonly CO2 with variable content of CH4, C2H6 and on special cases N2 and Ar) and gas-rich inclusions.

Aqueous biphase inclusion

Aqueous Vapor Aqueous Liquid

(L+V)

Aqueous polyphase (L+V+S) inclusion

Daughter Crystal Aqueous Vapor Aqueous Liquid Carbonic Liquid

Aqueous carbonic inclusion

Carbonic Vapor Aqueous Liquid Carbonic Liquid

(Laq+Lcarb+Vcarb)

Pure carbonic inclusion (L+V) the carbonic liquid need not be pure
Carbonic Vapor

The above four figures are representative of the various types of fluid inclusions that occur in minerals precipitating from fluids in a wide variety of environments. It may be noted that the polyphase inclusions can have more than one daughter phases indicating the very high content of dissolved solids. Study of fluid inclusions is based on the following basic assumptions: 1) The entrapment process is homogeneous and the heterogeneous state in which we see them in room temperature condition is a result of post-entrapment phase change. It may be noted that the fluid might on special circumstances might have been heterogeneous (coexistence of liquid+vapor or two immiscible liquids) but the cavity individually traps either of the phases. 2) Once entrapped, the fluid behaves as a closed system i.e. nothing is added or lost from the cavity. Therefore, once trapped, the fluid evolves on a constant density / constant composition path in the pressure-temperature space. This constant density path has a constant slope in the P-T space (straight line) and the path is called an isochore. The following diagram helps to understand the entrapment process of a water-rich liquid in its one-phase liquid field. The unary water system is shown with the vapor and liquid fields and the liquid-vapor equilibrium curve (the boiling curve). An inclusion trapped at pressure-temperature conditions referred to as P1T1 evolves down the isochore until it intersects the boiling curve at P2T2 at which a vapor phase nucleates. Subsequent decrease of pressure and temperature makes the inclusion follow the boiling curve with increase in the volume of the vapor phase till P3T3 (room temperature and pressure at which we observe them). Entrapment of inclusions containing daughter crystals can also be visualized in the same way. The only difference is that the parent fluid in that case has to be concentrated brine that would precipitate a halite daughter crystal on decrease in temperature and would follow the liquidus in the NaCl-H2O system (also a straight line segment) till it intersects the boiling curve. Similarly, inclusions containing two liquids can also be visualized as entrapped in the one-phase homogeneous condition.

P1T1

Pressure

L
P2T2 P3T3

Cp

V
Th Tt

Temperature

Temperature Estimate from Fluid Inclusions: We shall consider the aqueous biphase situation only. In the diagram P3T3 precisely corresponds to the room temperature and vapor pressure (at room temperature). If we heat the inclusion, it will follow the boiling curve (with increasing vapor pressure) with gradual decrease in the volume of the vapor bubble up to P2T2 at which, the vapor bubble will disappear. In other words, the inclusion becomes homogeneous and the point can be designated as the temperature of homogenization (Th). The inclusion follows the straight line path (isochore) on further heating and the slope of the isochore depends on the density of the inclusion fluid which is the same as the density calculated at Th and is denoted as Th. We do not have any idea where the inclusion was trapped and in absence of any independent estimate of pressure or temperature can only approximate the temperature of the ore fluid from Th. Since we measure Th in a large number of such inclusions present in many samples of the ore in a deposit, we get a range in Th and have a crude estimate of the temperature of the ore fluid. On instances where we have an independent estimate of pressure, we draw the isochore of the inclusion and get a point on the isochore on the basis of pressure estimate. From this, we can get the temperature of trapping. As depicted in the figure, suppose we could estimate P1 and get T1 by dropping a perpendicular on the temperature axis and call it as temperature of trapping (Tt). We can correct our temperature now. The difference Tt-Th is called pressure correction to the temperature of homogenization. If we can do it to all the inclusions studied, we can get the range in the actual temperature of the ore fluid. On many instances we do not get any independent estimate of temperature or pressure and have to be happy with what we get from our homogenization experiment.

While heating experiments are conducted to constrain the thermal characteristic of the ore fluid, freezing experiments are conducted to make a crude and gross estimate of the salinity (total dissolved solids).

Halite + liq
0.1

Liquid 0 Ice +Liquid -20.8 E (ice + hydrohalite) Hydrohalite+liq

H2O

23.3

26.3

NaCl

The above is a T-X phase diagram of the H2O-NaCl system at low temperatures where the depression in freezing point of water is depicted on either side of the eutectic point (E) from 0 C which is the freezing point of pure water. If an inclusion is at room temperature (represented by the star in the diagram) is cooled it follows the arrow without undergoing any change until it reaches the cotectic curve where ice forms. Further decrease in temperature makes it moves along the cotectic with growth of ice and the residual liquid getting richer w.r.t. NaCl until it reaches E where both ice and hydrhalite (NaCl.2H2O) form and the inclusion is totally frozen. The reverse is also true if the inclusion is at any lower temperature and is totally frozen and is slowly warmed, on reaching point E, NaCl2.H2O melts giving ice+liquid and on further waring, moves up the cotectic till the ice crystal melts. This temperature is noted as the depression in freezing point and can be easily translated to wt% NaCl with an equation fitted to the cotectic curve. Freezing behavior of inclusions containing NaCl between 23.3 and 26.3 wt% also behaves in an analogous manner with the only difference that the solid to melt finally is NaCl.2H2O. Inclusions containing more than 26.3 wt% NaCl (room temperature solubility limit) will usually have a NaCl daughter crystal and such inclusions are not subjected to freezing. Once we know the salinity in wt% NaCl, we homogenize the inclusion by heating and calculate the density at temperature of homogenization and plot the isochore if we have a formulation on pressure as a linear function of temperature at that density (which have been formulated empirically from large database on volumetric

properties of salt-water systems). It may be noted that although natural fluids contain lot many other species than NaCl, we approximate the salinity in terms of NaCl and express as wt% NaCl equivalent (the observed depression in freezing point is a cumulative effect of all salts present and is same if the entire salt is NaCl). This works well if chloride is the dominant anion but would be quite erroneous if other anionic species are present. Inclusions are first cooled and then heated to note the homogenization temperature. Such data on salinity and temperature on individual inclusions (called as paired data) are plotted to decipher the dominant process that operated during the evolution of the fluid.

Critical curve
6 7

T e m p er at ur e

Halite saturation

Salinity (wt % NaCl) eq.)

The above diagram shows some frequently observed trends when paired salinity-Th data are plotted from many ore deposits. Trend 2 is particularly interesting (near isothermal increase in salinity of the fluid) and indicates boiling of the fluid. Since boiling brings about quite a bit of change in chemistry (change in pH because of partitioning of volatiles into the vapor) of the ore fluid that favors precipitation, this trend is quite important. However, it may be noted that this trend must be supported by occurrence of liquid-rich and vapor-rich inclusions which must occur together and homogenize at the same temperature in different modes (refer to your class note). Trends such as 1-5 are generally observed when fluids of identical temperature but contrasting salinity mix (one may be basinal and the other may be meteoric). Trends like 4-7 are observed when fluids of very high temperature and salinity (mostly magmatic) is mixed with low-temperature and low

saline fluid (meteoric). These two trends are quite common. Trend 3-6 would indicate simple cooling of the parent fluid and is rather uncommon. Use of Stable Isotopes of Oxygen and Hydrogen in Study of Hydrothermal Deposits. Hydrothermal fluids can be of diverse origin such as magmatic, metamorphic, meteoric, connate and juvenile; the last being quite rare. Often groundwater and sea water are also important mineralizaers which are ultimately derived from meteoric water but have modified chemistry because of the complicated processes operating in the sea and underground. One of the major objectives of study of hydrothermal deposits is to trace out the origin of the fluid on almost instances there is interplay of fluids of more than one source. Stable isotopes (you must know the difference between stable and radiogenic isotopes) of oxygen, hydrogen, sulfur and carbon provide important signatures of the origin of the fluid. We shall see only stable isotopes of oxygen and hydrogen for our purpose. Because stable isotopes of light elements have significant mass difference, they do fractionate in nature between reservoirs or during process of interaction. For example if the isotopes of oxygen (16O and 18O) are considered, there is a mass difference of about 16%. In case of hydrogen it is 100%! Put in a simple terms, heavier isotopes are preferably partitioned into molecules with stronger bonds and the vice versa. For example, when clouds precipitate in form of rain, the water is enriched with respect to the heavier isotope and when water evaporates (say from the surface of the ocean) the vapor is depleted with respect to the heavy isotope. Without going much into the theoretical details, we can visualize that the energy of molecules in a vapor/liquid/solid is by virtue of the interactions among electrons plus translational, rotational and vibrational components of the atoms. Molecules with different isotopes of the same element in equivalent positions have different energies because of the difference in the vibrational component. Energy of a molecule at 0 K has a certain finite value called the zero point energy which is greater than the minimum of h. The vibrational frequency of atoms is inversely proportional to the square root of mass, implying higher vibrational frequency for lighter isotopes and in turn weaker bond which is easily broken. Molecules with lighter isotopes are more reactive. The reverse is the process for heavier isotopes. Isotopic fractionation: The enrichment or depletion with respect to the heavier isotope is denoted by ; for example if we consider the two isotopes of oxygen 18O and 16O (abundance of 99.63 and 0.1995 % respectively) 18O is represented by a formula as

And is expressed as per mil (/oo). The standard is a material whose ratio of the two isotopes are known (analyzed at many laboratories and internationally accepted). The parameter may have +ve (enrichment w.r.t heavy isotope) or ve (depleted w.r.t. the heavy isotope) values which is an important indication of the reservoir from where the fluid came and the process of fractionation it underwent. There are standards for other isotopes as well (such isotopes of carbon and sulfur). We shall consider the isotopes of oxygen and hydrogen only for now and see their importance in tracing the ancestry of the fluid.

The diagram below is a plot of the D versus 18O where the fields of some important types of water are plotted.
0 SMOW -40 metamorphic

-80 Most geothermal systems -120 magmatic

-160 -20 -10 0 10 20

The meteoric water line is on the basis of values of rain water precipitating all over the globe. The line can be approximated by a straight line equation as D = 8 18O + 10. some of the trends are significant. The range of magmatic water is restricted because of the narrow temperature range of 700 1100 C of magmatic melts in the crust. The fluid exchanges the isotope with a hot magma and thus is more enriched with the heavier isotope. There is an overlap between the magmatic and metamorphic water since there is overlap in the P-T regime of magmatism and metamorphism. Most geothermal waters plot on linear arrays as shown, parallel to the X-axis since water only exchanges oxygen isotopes with the rocks. In contrast, connate water have linear arrays with variation in both since both hydrogen (present as hydroxyl sites in hydrous minerals such as clays in sediments) and oxygenisotopes are exchanged. Thus, isotopic ratios of oxygen and hydrogen, if could be measured in the parent fluid that gave rise to mineralization, the ancestry could be ascertained. The ratio of oxygen and hydrogen isotopes could be measured in the fluid extracted from fluid inclusions, from hydrothermal alteration minerals or from the host minerals. The stable isotope (of O and H) data can be used in conjunction with fluid inclusion data to constrain fluid source as has been demonstrated from the diagram. The other important piece of information that can be drawn from stable isotope ratios is the temperature. This is based on the fact that fractionation of isotopes of light elements is a function of temperature. This temperature dependence is applicable to mineral-mineral and mineral-fluid pairs. For example we can write these reactions for the equilibrium fractionation of isotopes of oxygen: Si16O18O + H216O = Si16O16O + H218O fractionation with quartz) (one oxygen site is involved in the

Si16O18O + Fe316O4 = Si16O16O + Fe316O318O4 (fractionation between quartz and magnetite) The fractionation in these cases is represented by a parameter

The parameter is related to the equilibrium constant of these reactions by a relation

One needs to determine the A-B i.e. the difference in the value of the two minerals or the mineral and fluid in equilibrium and have to have a relationship between temperature and 100 ln . This relationship is determined from experiments and empirical fits. For example the relationship for magnetite and quartz is

And is applicable in the range of 250 to 500 deg C. There are calibrations available in the literature for many such pairs of minerals and mineral-water pairs. Now suppose a fluid inclusion work has been done on a sample of quartz in equilibrium with magnetite. If the O-isotopic ratio of quartz and magnetite are determined, it can be translated to temperature which will be the trapping temperature assuming negligible fractionation between quartz and magnetite after their formation. If temperature is known, pressure can be determined from the isochore of the inclusions. The reverse can also be meaningfully applied to understand the source of fluid. If we approximate the temperature of the ore fluid from homogenization experiments, and have measured the isotopic ratio of the host mineral (say quartz), we can calculate the isotopic ratio of fluid at that temperature and can know the source. In this case, we need not go for measuring the isotopic ratio of the extracted fluid.