Fluid Inclusions in Sedimentary and Diagenetic Systems

Lithos 55 Ž2001.
159–193
www.elsevier.nlrlocaterlithos
Fluid inclusions in sedimentary and diagenetic systems

Robert H. Goldstein )
UniÕersity of Kansas, Department of Geology, 120 Lindley Hall, Lawrence, KS, 66045, USA
Received 29 April 1999; accepted 3 April 2000
Abstract
Some of the major problems in sedimentary geology can be solved by using fluid inclusions in sedimentary and
diagenetic minerals. Important fluids in the sedimentary realm include atmospheric gases, fresh water of meteoric origin,
lake water, seawater, mixed water, evaporated water, formation waters deep in basins, oil, and natural gas. Preserving a
record of the distribution and composition of these fluids from the past should contribute significantly to studies of
paleoclimate and global-change research, is essential for improving understanding of diagenetic systems, and provides useful
information in petroleum geology. Applications of fluid inclusions to sedimentary systems are not without their complexi-
ties. Some fluid inclusions exposed to natural conditions of increasing temperature may be altered by thermal reequilibration,
which results in stretching, or leakage and refilling, of some fluid inclusions. Similarly, overheating in the laboratory can
also cause reequilibration of fluid inclusions, so fluid inclusions from the sedimentary realm must be handled carefully and
protected from overheating. Natural overheating of fluid inclusions must be evaluated through analysis of the most finely
discriminated events of fluid inclusion entrapment, fluid inclusion assemblages ŽFIA.. Consistency in homogenization
temperatures within a fluid inclusion assemblage, consisting of variably sized and shaped inclusions, is the hallmark of a
data set that has not been altered through thermal reequilibration. In contrast, fluid inclusion assemblages yielding variable
data may have been altered through thermal reequilibration. If a fluid inclusion assemblage has not been altered by thermal
reequilibration, its fluid inclusions may be useful as geothermometers for low- and high-temperature systems, or useful as
geobarometers applicable throughout the sedimentary realm. If a fluid inclusion assemblage has been altered partially by
thermal reequilibration, techniques for distinguishing between altered and unaltered fluid inclusions may be applied.
In studies of global change, fluid inclusions can be used as sensitive indicators of paleotemperature of surface
environments. Fluid inclusions also preserve microsamples of ancient seawater and atmosphere, the analysis of which could
figure prominently into discussions of past changes in chemistry of the atmosphere and oceans. In petroleum geology, fluid
inclusions have proven to be useful indicators of migration pathways of hydrocarbons; they can delineate the evolution of
the chemistry of hydrocarbons; and they remain important in understanding the thermal history of basins and relating fluid
migration events to evolution of reservoir systems. In studies of diagenesis, fluid inclusions can be the most definitive
record. Most diagenetic systems are closely linked to temperature and salinity of the fluid. Thus, fluid inclusions are
sensitive indicators of diagenetic environments. q 2001 Elsevier Science B.V. All rights reserved.
Keywords: Fluid inclusions; Global change; Diagenesis; Paleoclimate; Petroleum geology
)
Tel.: q1-785-864-2738; fax: q1-785-864-5276.
E-mail address: [email protected] ŽR.H. Goldstein..
0024-4937r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 4 - 4 9 3 7 Ž 0 0 . 0 0 0 4 4 - X
160 R.H. Goldsteinr Lithos 55 (2001) 159–193
1. Introduction soil surfaces as rain water, fresh lake and groundwa-

ter, and groundwater and lake water, ultimately of
In keeping with the focus of this volume, this meteoric derivation, compositionally modified
paper will concentrate on major recent advances in through rock–water interaction and evaporation.
fluid inclusions from sedimentary systems, and will Clearly, identifying fluids that have been derived
lay the groundwork for some future research direc- from meteoric precipitation is important in recon-
tions. It is not designed to be a complete literature structing paleoclimate; alteration through rock–water
review nor is it designed to summarize the systemat- interaction and evaporation also figures prominently
ics of working with fluid inclusions in detail. To get in understanding paleoclimate. For oil and gas explo-
more complete and practical coverage of the subject, ration and stratigraphy, stratigraphic surfaces of me-
see the book by Goldstein and Reynolds Ž1994. and teoric influx typically are depositional sequence
summaries by Roedder Ž1984. and Touret Ž1994.. In boundaries. Meteoric waters also are diagenetically
this paper, I do intend to focus on the problems that reactive and are important in the distribution and
can be solved with fluid inclusions from sedimentary heterogeneity of carbonate reservoir rocks. Finally,
systems, what particular focus we must have to deal meteoric waters altered through surface reactions
with fluid inclusions in these systems, what some of such as evaporation and weathering, and subsurface
the newest advances are, and what particular benefits processes such as rock–water interaction are those
such studies may produce. that make up most lake waters. Determining the
The subject of fluid inclusions in sedimentary composition of such ancient lake waters figures
systems must include all of those systems forming at prominently in reconstruction of paleoclimate history
Earth’s surface and those that extend more deeply through reconstructing water budgets of the past and
below the surface until conditions leave the diage- determining the paleo-drainage basin configuration.
netic realm and enter the metamorphic realm, let us Seawater is another fluid that is common near the
say temperatures below about 2008C. This would surface of the Earth. Today, this fluid is relatively
include evaporites formed from evaporation of saline uniform in composition and maintains a salinity near
surface and ground water, physical and chemical 35 ppt, but in the past, the total salinity may have
reactions in the subaerial realm, and physical and varied, isotopic compositions varied, and ratios of
chemical reactions in the subsurface, where a multi- major, minor and trace ions may have been different
tude of fluids exist including oil, gas, and aqueous than what they are today. The chemistry of seawater
fluids of various origin. Although normally one might may have changed so significantly through time, that
consider that glacial ice would be included in this even the major carbonate mineral precipitating from
realm, the abundant studies of fluid inclusions of air it has changed through time ŽSandberg, 1983. giving
trapped in glacial ice will not be discussed here. rise to ancient seas dominated by aragoniterhigh-Mg
calcite precipitation and seas dominated by calcite
precipitation. This variation in seawater chemistry is
further supported by secular variation in the compo-
2. Fluids of the sedimentary realm sition of evaporite minerals, with seawater of one
age giving rise to Mg-rich bitterns and seawater of
In dealing with fluid inclusions in sedimentary another age giving rise to K-rich bitterns ŽHardie,
systems, one should consider various fluids ŽFig. 1a.. 1996.. Understanding secular variations in the com-
At the surface of course is the mixture of gases in position of seawater is important as a paleoclimate
the atmosphere, a fluid with a poor geologic record indicator, for understanding the evolution of organ-
ŽBerner, 1990. the past composition of which is isms ŽStanley and Hardie, 1998., and is also impor-
incredibly important in developing a model for cli- tant for understanding the paleoecology of ancient
mate change into the future. environments, tectonic controls on global cycling of
Freshwater of meteoric origin is another important chemical constituents in nature, and the diagenetic
fluid associated with the sedimentary realm, and effect of seawater composition on carbonate sedi-
includes freshwater precipitating on sediment and ments.
R.H. Goldsteinr Lithos 55 (2001) 159–193 161
Fig. 1. Schematic representation of environments in sedimentary systems with characteristics of fluids applicable to fluid inclusion work Ža.
and diagenetic processes important for each environment Žb..
Seawater that has been modified through evapora- seawater is supersaturated with respect to aragonite
tion or meteoric dilution of seawater falls in to and calcite down to water depths on the order of
another class of fluids important in sedimentary sys- 500–1000 m in the Pacific and 2000 m in the
tems. Brackish waters, created by dilution of seawa- Atlantic. At higher latitudes, seawater is less likely
ter with meteoric water, are important diagenetic to be supersaturated with respect to carbonate miner-
fluids, which may be responsible for dissolution of als. Common diagenetic phases known to precipitate
carbonate minerals and precipitation of calcite and from seawater include fine-grained Žmicritic. ce-
dolomitization ŽLand, 1973; Goldstein and Reynolds, ments of Mg-calcite or aragonite compositions and
1994.. Seawater that has been modified through coarser Mg-calcite and aragonite cements with a
evaporation is a diagenetically reactive fluid that variety of morphologies ŽJames and Choquette,
may be important in precipitating calcite, dolomite 1990a.. Low-Mg calcite and dolomite are also known
and evaporite minerals ŽGoldstein et al., 1998.. from these systems ŽMajor and Wilbur, 1991;
As one moves more deeply into the sedimentary Vahrenkamp and Swart, 1994.. When seawater is
section, a wide variety of subsurface fluids may be mixed with freshwater of meteoric origin, there is
encountered, along with the temperature and pressure some evidence for dissolution of carbonate minerals
increase normally encountered along any thermo- as well as evidence for precipitation of low-Mg
baric gradient. Aqueous fluids ultimately may have calcite in some settings and replacement of carbonate
been derived from meteoric and marine fluids, but minerals with dolomite ŽLand, 1973; Goldstein and
typically, these have been altered so extensively Reynolds, 1994; Frank and Lohmann, 1995.. Where
through processes of evaporation at the surface, seawater evaporates, a variety of evaporite minerals
evaporite dissolution or other types of rock–water may precipitate, as well as dolomite, low-Mg calcite,
interaction that they have achieved compositions sig- and possible unstable carbonates like Mg calcite and
nificantly different from their parent fluids. These aragonite ŽGoldstein et al., 1998.. In areas where the
basinal fluids typically are very salty, may achieve carbonate sediments are exposed subaerially, mete-
concentrations well above those of marine fluids, and oric waters may percolate downward through the
contain ion ratios that reflect their evolution. Many sediment in the area above the water table, encourag-
of these fluids are quite important for precipitation of ing dissolution of unstable carbonate minerals and
diagenetic minerals such as feldspars, quartz, anhy- precipitation of calcite ŽJames and Choquette, 1990b..
drite, calcite, and dolomite. In addition to aqueous At and below the water table, meteoric fluids may
systems, the subsurface may contain petroleum and mix with other meteoric fluids of differing CO 2
various compositions of natural gas derived from content, encouraging dissolution of carbonate miner-
organic matter. als. Dissolution of unstable carbonate minerals and
outgassing of CO 2 encourages precipitation of cal-
cite in this setting. In all of the above settings minor
3. Diagenetic importance silicate diagenesis is also possible and is greatly
dependent on the composition of the pore fluids and
In addition to this simple list of fluids in nature their modification by chemical components provided
there is an incredibly significant economic incentive through interaction with the sediment. With deeper
for understanding fluid history and diagenesis. Dia- burial in basins and with increasing age of carbonate
genetic reactions are some of the most important in sediments, the originally metastable minerals of orig-
controlling porosity and permeability in aquifers and inal carbonate sediments give way to more stable
in oil and gas reservoirs ŽFig. 1b.. The diagenesis of mineralogies. As one goes deeper into the sedimen-
sedimentary rocks, and carbonates in particular, can tary section into a burial setting, or as warm fluids
be closely linked to origin of the fluid responsible from deeper in a basin are injected toward the sur-
for diagenetic alteration. face, many diagenetic reactions are driven by change
Diagenesis can even be linked to surface environ- in temperature. Among these are dissolution of min-
ment. Most sediments are deposited from marine erals as well as precipitation of feldspars, quartz and
fluids at Earth-surface temperatures. In the tropics, carbonates. So, given a sequence of diagenetic phases
in any ancient rock, determining the diagenetic envi- contain brownish solids that do not dissolve upon
ronment of its precipitation boils down to being able heating. Some of these solids may have been trapped
to determine two or three basic characteristics of the as solids in the inclusions, but undoubtedly some
fluid that precipitated it: the salinity, the temperature, have precipitated from the original fluid after its
and the pressure. These three parameters are those entrapment, providing strong evidence for changes in
most easily determined from fluid inclusions, so, the chemical makeup of those inclusion fluids after
given preservation of the right suite of fluid inclu- entrapment. At this time, it us unknown to what
sions, the analysis of fluid inclusions in diagenetic degree oil fluid inclusions are altered by post entrap-
minerals is probably the most unambiguous method ment chemical alteration. In addition, aqueous fluids
for determining diagenetic histories. in sedimentary basins typically have some amount of
dissolved organic compound ŽCollins, 1975;
Carothers and Kharaka, 1978; Hanor, 1980.. These
4. How representative are fluid inclusions? organics may break down after entrapment, causing
an irreversible chemical change to an aqueous sys-
tem. The degree to which this is a problem is as yet
4.1. Mechanisms for alteration of fluid inclusions unknown, however, consistent observations of fluid
inclusion homogenization temperatures yielding val-
One of the many processes that could alter fluid ues less than entrapment temperature, and the low
inclusions from their originally entrapped character organic content of many diagenetic fluids argue
is diffusion of inclusion components through the host against this as a ubiquitous problem.
mineral. In the diagenetic realm, it is probable that It stands to reason that intense deformation would
solutes and water do not diffuse to a significant breach fluid inclusions and cause them to be refilled
degree. Although H 2 is uncommon in most sedimen- with a new fluid ŽGoldstein, 1986.. In samples in
tary systems, hydrogen is the component that is most which such deformation has occurred, it is best to
likely to diffuse through minerals ŽHall et al., 1989; avoid working with the fluid inclusions unless the
Morgan et al., 1993.. It is not well known the degree inclusionist is interested in conditions of deforma-
to which this is a problem in sedimentary systems; it tion. Deformed samples typically are easily identi-
would be prudent to assume that hydrogen can dif- fied through petrographic means, with carbonates
fuse, potentially altering deuterium isotopic composi- typically showing abundant deformation twins
tions and other compositions of fluid inclusions. and other minerals showing undulose extinction,
Otherwise, it appears that diffusion is not a major through-going healed fractures, or other evidence of
concern in the sedimentary realm. deformation.
Inclusion fluids could alter if they react irre- It is now well known that many minerals may
versibly with their mineral host after their initial recrystallize in the diagenetic realm. Most carbonate
entrapment. Such compositional changes most likely minerals have shown both petrographic and diage-
are significant only if fluid inclusions form in a netic evidence of recrystallization or neomorphism,
metastable diagenetic mineral, such as high-Mg cal- and recrystallization of feldspars is well known in
cite. However, the degree to which trace element diagenetic systems. Any apparently primary fluid
systems reequilibrate compositionally with their min- inclusions in such systems contain fluids present
eral hosts is currently unknown. This is an area of during recrystallization of the mineral phase, and do
investigation that will require intensive research in not contain the fluids of initial precipitation ŽGold-
the future as technologies advance to allow for rou- stein, 1986.. Undoubtedly, the most powerful tool in
tine analysis of composition of inclusion fluids. recognizing recrystallization in diagenetic minerals is
One might also wonder if there were irreversible careful petrographic study in which compositional
chemical changes in inclusion fluids. In the sedimen- variation is observed to cut across concentric or
tary realm, the most important concern would be in sector growth zoning observed in cathodolumines-
organic fluids, which are inherently metastable. It is cence, etching, UV-epifluorescence. back-scattered
well known that many petroleum fluid inclusions electron imaging, or compositional staining. Such
simple textural relationships are the foundation on present during entrapment. Further, a typical aqueous
which most diagenetic studies are built. fluid inclusion that was trapped as a single homoge-
neous aqueous liquid in the high-temperature diage-
netic environment, is typically only able to nucleate
4.2. Heterogeneous entrapment a vapor bubble occupying no more than 15% of the
volume of a fluid inclusion ŽGoldstein, 1993.. If a
It is well known that for the density and composi- single aqueous inclusion contains more than 15 vol.%
tion of a fluid inclusion to be representative of bubble and if, among all of the inclusions genetically
conditions of entrapment, the inclusion must have related to a single event of fluid inclusion entrap-
been trapped as a single homogeneous fluid. For ment, there is more than 15 vol.% vapor, heteroge-
many diagenetic and sedimentary systems, this is the neous entrapment of a gas and liquid phase is likely.
case; there is only a single homogeneous fluid in the So, the careful fluid inclusionist working in sedimen-
system and that is all that is trapped in fluid inclu- tary systems must constantly be aware of the possi-
sions. Contrary to popular belief, it is not true that all bility of heterogeneous entrapment. Finding evidence
sedimentary fluids are saturated with respect to for it provides important constraints on the fluid
methane; commonly, aqueous fluids are undersatu- system and avoids the possibility of misinterpreting
rated with respect to methane and there is only a fluid inclusion data by incorrectly assuming that
single homogeneous aqueous phase. fluid inclusions were entrapped as a single homoge-
However, in nature there are many settings where neous phase.
immiscibility is possible, leading to entrapment of
multiple phases during an event of fluid inclusion
entrapment, heterogeneous entrapment. In the vadose 4.3. Necking down after a phase change
zone, the near-surface setting above the water table,
both water and air exist in pores ŽGoldstein, 1986.. It is now well known that fluid inclusions may
Below the water table, there are settings in which change their shape over time through the process
immiscible bubbles of methane and other gases may known as necking down. Typically, change in shape
exist. Deeper in the sedimentary pile, a separate gas involves a tendency for inclusions to evolve from
phase or liquid petroleum phase may exist in the irregular shapes to more globular or negative crystal
presence of an aqueous liquid phase. Finally, it is shapes to attain the state of lowest surface free
possible to entrap solid mineral particles, organic energy ŽRoedder, 1984.. In any mineral, the change
matter or even bacteria along with an aqueous phase in shape of an inclusion may even cause an origi-
during fluid inclusion entrapment. nally larger inclusion to pinch off into multiple
For each of these settings, it is clear that heteroge- smaller inclusions. Given necking down of a two-
neous entrapment of more than one phase is possible. phase fluid inclusion, a necked inclusion that hap-
In systems of heterogeneous entrapment, the bulk pened to trap a bubble would have a density much
density of fluid inclusions is different from that of lower than the original inclusion fluid, and a necked
the original system so homogenization temperatures inclusion that only trapped liquid would have a
typically are meaningless. Systems of heterogeneous density much higher than the original inclusion fluid.
entrapment Žor necking down after a phase change, This process, can severely alter fluid inclusion densi-
e.g. Fig. 3. may be recognized by variability of ties to the point of making homogenization tempera-
phase ratios among all of the inclusions genetically ture data meaningless.
related to a single event of fluid inclusion entrap- In sedimentary systems, one might wonder the
ment. If phase ratios are consistent among all of the degree to which necking down of inclusions, in the
inclusions genetically related to a single event of presence of more than one fluid phase, might be
fluid inclusion entrapment, then it is likely that only important. It can be incredibly important! The pro-
a single homogeneous fluid was entrapped, and that cess of necking down is known to take place most
those fluid inclusions have the potential to preserve rapidly at higher temperatures ŽBodnar et al., 1985;
the density and composition of the original fluid Brantley, 1992.. To evaluate the importance of neck-
ing down for sedimentary systems, let us first exam-

ine a natural aqueous fluid inclusion system, trapped
at low temperature or at high temperature, and then
subsequently heated. In this system, the fluid inclu-
sions remain in the one phase field during heating
ŽFig. 2., and any necking down during that heating,
preserves the original density in all inclusions. The
fluid inclusions may remain representative of fluid
density of the original diagenetic system. However,
during cooling of fluid inclusions trapped at high
temperatures, only a minute temperature drop is
necessary before a fluid inclusion’s isochoric path
intersects the vapor–liquid line ŽFig. 3.. This means
that during much of the cooling history of a high-
temperature fluid inclusion, a bubble may be present.
Fig. 3. P – T phase diagram for pure water with an isochore for

pure water and the liquid–vapor field boundary shown. If a fluid
inclusion were entrapped at point A, and were then cooled during
uplift to point B, a vapor bubble would be stable at this tempera-
ture but would not nucleate until further cooling toward point C.
After the bubble has nucleated and the inclusion has cooled to
point C, the inclusion may neck down to form several fluid
inclusions, only one of which contains the vapor bubble. With
further cooling toward point D, bubbles may nucleate in the
remaining all-liquid inclusions. As the inclusions are cooled to
surface temperature Žpoint D., more necking down may occur and
the bubble may be split between two inclusions. At, point D, none
of the necked down inclusions have the same density as the
original inclusion trapped at A. Also, none of these inclusions will
homogenize at point B, they will either homogenize at lower or
higher temperatures because they necked down after a phase
change occurred in the fluid inclusion Žafter Goldstein and
Reynolds, 1994..
Fig. 2. P – T phase diagram for pure water with an isochore for

pure water and the liquid–vapor field boundary. If a fluid inclu-
As a fluid inclusion necks down to form multiple
sion were trapped at 758C ŽA. and were then heated during burial inclusions, the bubble will preferentially separate
to 1308C Žpoint B., the inclusion would remain in the liquid field. into one new inclusion or another, creating fluid
If it were to neck down at point B and then were to neck down inclusions of highly variable density that differ from
again during cooling to 1008C Žpoint C., new inclusions would be the density of the original fluid inclusions.
formed that were of the same density as the original single
inclusion. With further cooling to 688C Žpoint D. a vapor bubble
Inclusionists must learn to recognize evidence for
can nucleate but generally does not nucleate unless there is further necking down after a phase change to be able to
cooling. Once the inclusions have reached room temperature evaluate the validity of density data gathered from
Žpoint E. all have nucleated bubbles. Each inclusion now has the homogenizing fluid inclusions. Many fluid inclusion-
same ratio of vapor–liquid and homogenizes at point D. This is ists mistakenly observe two fluid inclusions that
the temperature of homogenization that the single original fluid
inclusion would have produced. Necking down has had no effect
appear to be almost connected, two inclusions with a
on homogenization temperature Žafter Goldstein and Reynolds, neck joining them, and use this as the only evidence
1994.. that would be indicative of necking down. Whereas
it is true that many of these fabrics have been trapped at higher temperature and would have a
generated through necking down, these are probably bubble stable at room temperature if one could nu-
the oddballs, the ones that were caught in the act of cleate. In natural systems that have not been heated
necking down without progressing to its logical neg- artificially, it appears that there are many controls on
ative crystal or globular conclusion. Observe almost whether bubbles nucleate in high-temperature fluid
any planar array of secondary inclusions, with nega- inclusions. Size appears to be important. The small-
tive crystal shape, to see that necking down com- est inclusions are less likely to nucleate a bubble.
monly completes its journey toward regular shapes. Temperature of entrapment is also important; the
With this in mind, it would be a good idea to use lower the density Žhigher the temperature of entrap-
something other than shape to identify evidence for ment. then the more likely it is that a fluid inclusion
necking down after a phase change. Remember that a will nucleate a bubble. Composition appears to be
typical aqueous fluid inclusion that was trapped as a important as well, but this control appears to be quite
single homogeneous aqueous liquid in the high tem- complex. It is now well known that it is possible to
perature diagenetic environment, is typically only nucleate bubbles Žthrough super cooling. in fluid
able to nucleate a vapor bubble occupying no more inclusions trapped close to room temperature ŽRo-
than 15% of the volume of a fluid inclusion. If a berts and Spencer, 1995; Newell and Goldstein, 1999;
single aqueous inclusion contains a bubble occupy- Benison and Goldstein, 1999., and many have ob-
ing more than 15% of the volume of the inclusion, served that for tiny fluid inclusions, even fluid inclu-
then necking down after a phase change or heteroge- sions with densities that should yield homogeniza-
neous entrapment are both possibilities. If, among all tion temperatures as high as 1008C, bubbles have not
of the inclusions, genetically related to a single event nucleated. However, in large numbers of fluid inclu-
of fluid inclusion entrapment, there is more than 15 sion studies, especially ones with mixed densities,
vol.% vapor, then heterogeneous entrapment of a gas there appears to be a common lower cutoff of ho-
and liquid phase is likely. Furthermore, after necking mogenization temperatures from about 408C to 608C.
down of a high-temperature fluid inclusion after a This suggests that a common nucleation boundary
phase change, gas-rich and liquid-rich inclusions are for bubbles forming in fluid inclusions is at densities
commonly paired petrographically. Look for this that would yield homogenization temperatures of
pairing as an indication of necking down after a around 508C. Thus, in the absence of necking down
phase change. If you find evidence for necking down after a phase change, the presence of all liquid fluid
after a phase change, do not trust homogenization inclusions, that are in the same size range as two-
temperatures or observations of phase ratios. The phase inclusions, suggests that the all-liquid fluid
density of the original fluid inclusion has been al- inclusions were trapped at a temperature below about
tered! 508C.
4.4. Nucleation metastability 4.5. Thermal reequilibration
It is well known that some fluid inclusions at Perhaps the greatest concern for fluid inclusion
room temperature do not contain the equilibrium preservation in diagenetic minerals is their reequili-
assemblage of phases because of problems with nu- bration from internal overpressure, induced by natu-
cleation. This includes the nucleation of solid phases ral heating or heating during sample preparation. If a
Ždaughter minerals. but more importantly, involves fluid inclusion was trapped as a single liquid phase,
problems with nucleation of a bubble in a liquid-filled and then was buried through a lithostatic or hydro-
fluid inclusion. In sedimentary systems, it is com- static thermobaric gradient ŽFig. 4., it is clear that
mon to find fluid inclusions that exist at room tem- the fluid inclusion would be internally overpressured
perature as a single liquid aqueous phase. Some of relative to ambient conditions. It is now well known
these were trapped at or below room temperature and that many fluid inclusions respond to this internal
therefore should not have a bubble, but others were overpressure through decrepitation or stretching to
with the mechanism of stretching, is known as ther-

mal reequilibration.
Because many fluid inclusions in the sedimentary
realm experience conditions of increasing tempera-
ture after initial entrapment, it is important to evalu-
ate the degree to which fluid inclusions are altered
by thermal reequilibration. It is now well known that
some minerals are better containers for confining
internal overpressure than others. One of the controls
on thermal reequilibration is tensile strength of the
mineral, which is, in part, related to its hardness
ŽTurgarinov and Vernadsky, 1970., and affected by
cleavage. If one were to ask if there is any mineral
medium that can be trusted as strong enough to resist
any thermal reequilibration of fluid inclusions, one
would have to say that none exist ŽGoldstein and
Fig. 4. P – T aqueous phase diagram for pure H 2 O with hydro-
static thermobaric gradient of 288Cr100 bars and lithostatic ther-
mobaric gradient of 288Cr226 bars superimposed. If a fluid
inclusion were trapped at surface conditions Žpoint A. and were
then subjected to further heating during burial to point B, the fluid
inclusion’s internal pressure would rise significantly above the
surrounding hydrostatic pressure and lithostatic pressure at that
temperature Žafter Goldstein and Reynolds, 1994..
relieve the high internal pressures ŽBodnar and

Bethke, 1984; Goldstein, 1986; Comings and Cer-
conne, 1986; Burruss, 1987a; Mclimans, 1987;
Prezbindowski and Tapp, 1991.. If a fluid inclusion
responds through permanent plastic deformation, its
volume is increased to decrease the internal over-
pressure, producing a lower density that would yield
a new, higher homogenization temperature ŽFig. 5..
Although the fluid density changes as a result of
stretching, the composition remains identical to its
original composition. Fig. 5. P – T phase diagram for water illustrating stretching of an
Alternatively, if a fluid inclusion were to decrepi- all-liquid fluid inclusion during heating beyond temperature of
tate to relieve its high internal pressure, the inclusion entrapment. If the fluid inclusion were trapped at point A Ž758C.
could open itself to ambient pore fluid. If this were and were then heated further during burial, the inclusion’s internal
to occur, the contents of the fluid inclusion would pressure would follow an isochore toward point B, and its internal
pressure would increase greatly compared to the surrounding
leak and equilibrate with the fluid in the pore space hydrostatic pressure. If the inclusion were to stretch from this
ŽFig. 6.. Eventually, the inclusion’s conduit to the internal overpressure, its volume would increase and density and
surface could heal and the original fluid inclusion pressure would decrease. This event is represented by a drop to
cavity would be present in its original position, but point C, and places the inclusion on the new isochore. Cooling of
the fluid inclusion would now yield a higher homog- the inclusion would result in P – T conditions within the inclusion
intersecting the vapor–liquid curve at about 1008C; the inclusion
enization temperature and contain a fluid different now has the density that would produce Th measurements of
from what it originally contained ŽGoldstein, 1986.. 1008C. If the inclusion had never stretched, it would have yielded
This mechanism, of leakage and refilling, together a Th at 658C Žafter Goldstein and Reynolds, 1994..
exists a good possibility for fluid inclusions in halite

to remain unaltered even though they have been
heated to some degree ŽLowenstein and Spencer,
1990; Casas et al., 1992; Benison and Goldstein,
1999.. Moreover, cleavable minerals like calcite and
fluorite have received the same bad press, but there
is still strong evidence that reequilibration is not total
in these mineral matrices and that it is quite possible
for them to produce good data. So, no matter what
the mineral, we as fluid inclusionists should consider
that fluid inclusions in any mineral could have been
altered by thermal reequilibration, but that thermal
reequilibration has not necessarily affected every
fluid inclusion in the mineral. The most important
thing we can do as fluid inclusionists in the sedimen-
tary realm is to evaluate the degree to which fluid
inclusions have been altered by thermal reequilibra-
Fig. 6. P – T phase diagram for pure H 2 O with hydrostatic
thermobaric gradient of 288Cr100 bars and lithostatic thermobaric tion, and to develop methods for separating altered
gradient of 288Cr226 bars superimposed. If a fluid inclusion were fluid inclusion data from unaltered fluid inclusion
trapped as liquid at the surface ŽA. and were then heated during data.
burial, the fluid inclusion’s internal pressure would rise along an It is clear that there are several controls on whether
isochore toward point B. At point B, the inclusion is internally
a particular fluid inclusion will reequilibrate or not.
overpressured relative to the surrounding hydrostatic thermobaric
gradient. If the inclusion were to decrepitate from internal over- Of course, the strength of the mineral is one control,
pressure, it would immediately equilibrate with the conditions in but also the density and occurrence of dislocations,
the surrounding pore fluid and jump down to point C on the and the orientation of cleavage directions in the
hydrostatic thermobaric gradient Žif the example were for litho- crystal relative to the position of the inclusion. The
static, this would be possible too.. Because the inclusion has
point is that each fluid inclusion in a particular
decrepitated it can refill with whatever pore fluids happen to be
present at the time of opening of the inclusion. Rehealing of the mineral will behave differently during overheating. It
inclusion followed by cooling would result in inclusion P – T appears that size is quite important ŽLacazette, 1990;
conditions following a new isochore Ždifferent density and possi- Fig. 7. the larger the inclusion, the more likely it is
bly different composition. that intersects the vapor–liquid curve at to thermally reequilibrate due to internal overpres-
a higher temperature Žpoint D.. This thermal reequilibration causes
sure. Some tiny inclusions appear to be quite resis-
an increase in homogenization temperature of fluid inclusions and
may result in their refilling with new fluids Žafter Goldstein and tant to thermal reequilibration, even in a relatively
Reynolds, 1994.. weak mineral like calcite, but size is not the only
significant variable. Over a given size range in the
same mineral, with the same degree of internal over-
Reynolds, 1994.. Because the internal overpressures pressure, some fluid inclusions appear resistant to
developed in an overheated fluid inclusion is so thermal reequilibration and others do not ŽFig. 7.. In
great, it is best to assume that at least some thermal theory, the effect of shape and orientation of shape in
reequilibration is possible, even in relatively hard the crystal should dominate this variation. It is well
minerals like quartz. Likewise, if one were to ask if known that spherical shapes are highly resistant to
there is a particular mineral in which any degree of deformation from internal overpressure and that more
overheating will allow for total thermal reequilibra- irregular shapes with sharp angles have stress raisers
tion of fluid inclusions, one would also have to say that encourage deformation, especially if the stress
no such mineral has yet been demonstrated. Much raiser is oriented along a zone of weakness in the
discussion of the relative weakness of the mineral crystal. For this reason, given the variable sizes,
halite has found its way into the literature ŽRoedder shapes, and orientations of fluid inclusions trapped in
and Belkin, 1979., but it appears that there still the same conditions, the weakest fluid inclusions will
neous phase at the same time, under the exact same

conditions. One would expect that these fluid inclu-
sions would each yield the same homogenization
temperatures and that they would each yield the
same compositional data. However, if these variably
sized and shaped fluid inclusions were then subject
to natural overheating, one would expect that some
of the fluid inclusions would thermally reequilibrate
with a tiny amount of overheating, and that others
might not reequilibrate at all. During overheating,
some inclusions might even reequilibrate multiple
Fig. 7. Differential pressure Žinternal inclusion pressure — exter- times and each fluid inclusion would likely reequili-
nal pressure. in MPa Žbarsr10. required for decrepitation of fluid brate from a different amount of internal overpres-
inclusions of various shapes and sizes in calcite and quartz. Base sure, essentially at a different temperature. Given
of each shaded area is the differential pressure at which the this type of behavior, one would expect that after
weakest shape modeled should decrepitate. Top of each shaded
area is the differential pressure at which the strongest modeled
thermal reequilibration, an originally consistent group
shape should decrepitate. Dashed lines within each shaded area of inclusions would now yield highly inconsistent
define the differential pressure at which decrepitation should homogenization temperatures and may even yield
occur for shapes of intermediate strength. No inclusions should inconsistent compositional data. Such variability in
decrepitate at conditions below each shaded area. All inclusions homogenization temperature and composition, in a
should decrepitate above each shaded field. Curves are defined
using shape factors in Lacazette Ž1990. and illustrate the relation-
group of fluid inclusions all originally trapped under
ship between size and differential pressure of decrepitation for the same conditions, is our best indication of thermal
inclusions of a given shape within each mineral. Notice the reequilibration.
important controls of both size and shape on whether a fluid The only way to evaluate problems with thermal
inclusion decrepitates. See Lacazette Ž1990. for more details. reequilibration is to identify those inclusions trapped
After Lacazette Ž1990..
at the same time and evaluate if they provide vari-
able or consistent data. For that reason and because it
reequilibrate with the lowest internal overpressures provides the most detailed information about fluid
and the strongest fluid inclusions may never reequili- history, the Afluid inclusion assemblageB approach is
brate. Because of that variable response to internal the preferred method to be applied to sedimentary
overpressure, thermal reequilibration alters assem- rocks and other rocks containing fluid inclusions. A
blages of fluid inclusions that were originally consis- fluid inclusion assemblage ŽFIA. is Athe most finely
tent in composition and density; they become fluid discriminated, petrographically associated, group of
inclusions that are more variable in density and inclusionsB ŽGoldstein and Reynolds, 1994.. For ex-
perhaps variable in composition. The altered assem- ample, an FIA could be composed of all of the
blage of inclusions may contain resistant inclusions inclusions trapped along a single healed fracture, or
that essentially remain unaltered, preserving the orig- all of the inclusions trapped in the most finely
inal density and composition of the original inclu- discriminated growth zone in a single crystal. In
sions, and may contain fluid inclusions that have other words, the FIA approach is one in which the
been reequilibrated at many points on the pressure– inclusionist is forced to identify a single event of
temperature–composition path experienced during fluid inclusion entrapment, resolved to as close to an
heating of the fluid inclusions. instant of geologic time as will the petrographic
relationships allow. If the fluid inclusions in a single
FIA yield variable microthermometric data, which
5. The fluid inclusion assemblage approach does not result from necking down after a phase
change or heterogeneous entrapment, then either the
Consider a group of fluid inclusions of various fluid inclusions were trapped over an originally wide
sizes and shapes, each trapped as a single homoge- range of conditions, unresolvable as a single event of
entrapment by the petrography, or the inclusions subjected to porosity and permeability analysis typi-
were originally entrapped under the same conditions cally have been heated as well and must be avoided.
and were later partially altered by thermal reequili- When sampling core, it is especially important to
bration. Given such variable data, the safest interpre- show that they have not been subjected to whole-core
tation to make is that the inclusionist does not know analysis for porosity and permeability, because such
the degree to which the data are good or are bad. heating is not always immediately obvious from
Such variable FIAs normally cannot be used to make casual observation of a core sample.
interpretations about original conditions of entrap- During preparation, it is important to get the best
ment of fluid inclusions. Based on empirical observa- optics possible so samples typically are doubly pol-
tions of many systems, a good cutoff to define as ished. However, all mounting must be done with
consistent data in an FIA is if more than 90% of the room-temperature techniques to avoid any heating of
fluid inclusions in the FIA are within 10–158C. If in the samples. Furthermore, cutoff of samples must be
this consistent FIA, inclusions are of variable sizes done so as to avoid fracturing and heating, so most
and shapes, every measurement may be meaningful. labs use low-speed cutoff saws that avoid damage to
If on the other hand, the data from an FIA were more the sample. Finally, all preparation must be done so
widespread, it would appear that fluid inclusions as to avoid damage; that means that one must be
might have been altered by thermal reequilibration. quite gentle in preparing the samples, never exerting
One of the great weaknesses in many fluid inclusion too much pressure and never allowing samples to
studies is that the FIA approach is not followed, and heat due to friction.
because of that, detailed information is lost, and it is Once doubly polished thick sections have been
impossible to evaluate the validity of the data. prepared, they must be protected from damage. Any
staining of minerals, which typically involves etch-
ing of minerals with an acid, must be avoided, as the
6. Fluid inclusion petrography etching typically destroys all of the fluid inclusions
in the sample. Heating under an electron beam in a
The most important part of most fluid inclusion SEM or in a cathodoluminescence stage must also be
studies in sedimentary rocks is the petrographic anal- avoided, because of the heating that is generated.
ysis of samples. The first step is typically at large Also, during microthermometric work, every effort
scale Žcore or outcrop., gathering samples for finer must be made to preserve the fluid inclusions. For
work to achieve the crosscutting and stratigraphic example, that means that heating of aqueous inclu-
relationships. Then samples must be prepared to sions, to measure homogenization temperature, must
prevent alteration of the fluid inclusions. be done before freezing, because freezing of low-
temperature fluid inclusions typically results in dis-
6.1. Sample handling appearance of the bubble. These inclusions com-
monly leak or stretch from the freezing process and
Because of problems with thermal reequilibration are no longer useful for measurement of homoge-
and metastability of fluid inclusions that have been nization temperature. When samples are heated, it is
heated in the laboratory, all fluid inclusion studies important that they not be heated beyond their ho-
must avoid samples that have been heated in ways mogenization temperature before their homogeniza-
other than normal geologic heating. This means that tion temperatures are first measured. If inclusions
old thin sections and their rock chips, which have have been overheated in the lab, then it is possible
been heated for mounting, are not appropriate for a that they have been thermally reequilibrated to a
fluid inclusion study. Outcrop samples that have higher homogenization temperature.
been heated by fires are also inappropriate. Well
cuttings that have been gathered from the drilling of 6.2. Origin of fluid inclusions
oil and gas wells also should be avoided for the most
part, because the history of heating during their The most important part of a typical fluid inclu-
drying is unknown. Core and plugs that have been sion study in sedimentary rocks is petrographic anal-
ysis of samples to determine if the fluid inclusions overgrowth could be fractured away from the detrital
present will answer the scientific question posed. grain, leading to reequilibration of fluid inclusions.
Some samples may be dominated by primary fluid Primary fluid inclusions can also be recognized in
inclusions, whereas secondary, pseudosecondary, or overgrowths from their orientation relative to growth
fluid inclusions of indeterminate origin may domi- direction and confinement to growth zones ŽFig. 8D..
nate others. In many samples, the fluid inclusions of Diagenetic overgrowths on detrital feldspars are also
indeterminate origin dominate. The careful fluid in- well known. Primary fluid inclusions in such over-
clusionist in sedimentary systems must always be growths are most commonly recognized by their
able to admit that the origin of certain fluid inclu- orientation relative to growth direction ŽFig. 8F..
sions is unknown. Halite is a very common mineral of the sedimentary
realm. Halite that has grown into open water typi-
cally has abundant primary fluid inclusions that de-
6.3. Primary fluid inclusions fine cloudy and less cloudy growth zones ŽFig. 8G..
Coarse gypsum crystals also commonly contain pri-
One of the areas in which fluid inclusionists in mary fluid inclusions that are recognized by their
sedimentary rocks seem to run into trouble is the distribution along growth zones and their orientation
identification of primary fluid inclusions. Primary in growth direction ŽFig. 8F..
fluid inclusions are identified by petrographic crite-
ria. Essentially, there is only one valid criterion for
identification of primary fluid inclusions, and that is 6.4. Fluid inclusions primary to recrystallization
the identification of a petrographic relationship to
growth of the crystal. For example, in calcite, it is One of the most important discoveries of recent
common to identify primary fluid inclusions by their years has been the observation that fluid inclusions
occurrence in alternating inclusion-rich and inclu- can be trapped during recrystallization of diagenetic
sion-poor bands ŽFig. 8A.. Another criterion that minerals. Recrystallization, in the sense we are using
applies to calcite is the preferential orientation or it here, commonly involves a compositional change
shape of fluid inclusions in growth direction ŽFig. from a somewhat unstable to a more stable mineral
8A.. For dolomite, similar criteria apply; fluid inclu- phase through a process of dissolution and reprecipi-
sion occurrence might define growth zonation ŽFig. tation, mediated by a fluid phase. Commonly, one
8B. or inclusions might be oriented in growth direc- compositional growth zone in a crystal is unstable
tion. For anhydrite, which is a common coarse pre- relative to other compositional growth zones. Be-
cipitate in diagenetic systems, similar growth band- cause of this, recrystallization commonly attacks in-
ing may be defined by fluid inclusions ŽFig. 8C. or dividual growth zones within other stable growth
elongate fluid inclusions may be confined to internal, zones, trapping fluid inclusions that appear as if they
growth-defined cores of the crystals. Diagenetic were trapped during initial growth of the crystal.
quartz commonly may occur as coarse crystals Such internal recrystallization is well known in dia-
Žmegaquartz. in which primary fluid inclusions typi- genetic dolomite and calcite ŽFolk, 1965; Wojcik et
cally are defined by alternating inclusion rich and al., 1994; Luczaj and Goldstein, 2000.. In dolomite,
inclusion poor growth bands, cloudy, inclusion-rich finding rhombohedra with cloudy, inclusion-rich
cores defined by growth boundaries, fluid inclusions cores is quite common ŽFig. 9A.. For most of these,
oriented in the direction of growth, or fluid inclu- it is almost impossible to use standard transmitted
sions trapped along twins. In sandstones, diagenetic light microscopy to determine if inclusions were
quartz is found most commonly as syntaxial over- trapped during initial growth or during recrystalliza-
growths on detrital grains. In these overgrowths, tion. In baroque Žsaddle. dolomite especially, a radi-
primary fluid inclusions are found distributed most ating Žfir-tree-like. pattern is defined by the distribu-
commonly along the contact between the detrital tion of fluid inclusions ŽFig. 9B.. Such a pattern may
grain and the overgrowth ŽFig. 8D.. It is well known result from the recrystallization of an internal growth
that such contacts are zones of weakness where the zone, which caused entrapment of fluid inclusions.
Fig. 8. Sketches of distribution of primary fluid inclusions in various minerals of the sedimentary realm Žmodified from Goldstein and
Reynolds, 1994.. ŽA. Calcite; ŽB. Dolomite; ŽC. Anhydrite; ŽD. Quartz overgrowth; ŽE. Feldspar overgrowth; ŽF. Chevron halite; ŽG.
Gypsum Žmodified from Lowenstein, written communication..
In calcite, it is common for one growth zone to be form the core of the crystal. For most of these
inclusion rich ŽFig. 9C and D.. This growth zone occurrences of calcite, it may be difficult to use
may be single or one of many growth bands, or may standard transmitted light microscopy to determine if
Fig. 9. Sketches of distribution of primary fluid inclusions, some of which might result from recrystallization of internal parts of crystals
Žmodified from Goldstein and Reynolds, 1994.. ŽA. Dolomite with cloudy cores; ŽB. Baroque dolomite with internal Afir-treeB arrangement
of fluid inclusions; ŽC. Early calcite growth zone in syntaxial overgrowth on echinoderm fragment; ŽD. Cloudy core in calcite crystal; ŽE.
Partially recrystallized detrital feldspar containing fluid inclusions in recrystallized parts of grain.
inclusions were trapped during initial growth or dur- Therefore, fluid inclusionists concerned with most
ing recrystallization. Finally, it is common for detri- diagenetic minerals must evaluate the possibility of
tal feldspars to recrystallize during diagenesis. Such entrapment of primary fluid inclusions during recrys-
recrystallization may result in inclusion-rich patches tallization by evaluating the distribution of composi-
that are primary to the recrystallization of the grain tional domains in the crystal of interest. Methods
ŽFig. 9E.. useful in petrographically identifying compositional
Fluid inclusionists who work in the sedimentary variation in cements include cathodoluminescence
realm must use petrographic methods to determine if microscopy ŽBarker and Kopp, 1991; Van den
fluid inclusions were trapped during initial growth of Kerkhoff and Hein, 2001; Munz, 2001., back scat-
cement or during some later stage of recrystalliza- tered electron imaging ŽWojcik et al., 1994., UV
tion. Not doing so defeats the purpose of putting epifluorescence ŽBurruss, 1991., staining ŽDickson,
fluid inclusion entrapment into the context of a 1965. and mild etching of polished specimens ŽFolk,
careful paragenetic framework. The most helpful 1980..
approach for identifying fluid inclusion entrapment
during recrystallization is careful study of petro-
graphic relationships that are visible only by looking 6.5. Petrographic model for diagenetic systems
at compositional variation in the mineral chemistry.
The compositional variation in a mineral that has not Once fluid inclusion assemblages have been iso-
recrystallized will be reflected in either concentric or lated, petrographic work alone can lead to significant
sector growth zoning ŽFig. 10A.. For minerals that interpretations about the environment of entrapment
have recrystallized, the primary compositional zon- and the post-entrapment history of fluid inclusions
ing will be cross cut by compositional areas reprecip- ŽGoldstein, 1993.. The first part of this approach
itated during recrystallization ŽFig. 10B and C.. requires isolation of FIAs, for it only can apply to
Fig. 10. Photomicrographs illustrating various types of distribution of compositional areas in carbonate minerals. ŽA. Cathodoluminescence
photomicrograph illustrating concentric growth zoning in calcite Žwidth is 300 mm.; ŽB. Transmitted light photomicrograph of calcite
stained with alizarin red S and Potassium ferricyanide, illustrating alternating concentric growth zones in outer parts of crystals and
recrystallized patches in crystal interiors Žsee interior of crystal on left. Width is 0.88 mm; ŽB. Back scattered electron image of baroque
dolomiterankerite with radiating areas of recrystallization and fluid inclusion entrapment. Dark irregular core Žfilled arrow. is corroded and
partially replaced by late bright phase Ž4. in radiating pattern. Intermediate brightness ankerite Ž2A. dominates. Numbers are as those in
Wojcik et al. Ž1997.. Width is 260 mm. Modified from Wojcik et al. Ž1997..
fluid inclusions that were initially entrapped under After necking down after a phase change has been
the same set of conditions. Furthermore, the reaction ruled out, the petrographer must then evaluate the
to reequilibration is most easily evaluated if fluid consistency of the liquid-to-vapor ratios for two-
inclusions are of variable size and shape, so the phase fluid inclusions in the FIA. If vapor-to-liquid
inclusions of the FIA must be of variable size and ratios are highly variable, then entrapment in a het-
shape for interpretations to be made. erogeneous system is indicated. If vapor-to-liquid
Once an FIA has been isolated, it must be shown ratios are somewhat consistent, then entrapment at
that the liquid phase of inclusions is aqueous and not high temperature or near complete thermal reequili-
hydrocarbon in composition. This is accomplished bration is indicated. If vapor-to-liquid ratios are so
by studying samples using UV epifluorescence mi- consistent that each fluid inclusion would yield the
croscopy. If inclusions fluoresce, then they are com- same homogenization temperature, then fluid inclu-
posed of oil and this petrographic model does not sions were trapped at high temperature and have not
apply, but if they lack fluorescence, then they are been altered by thermal reequilibration.
most likely to be aqueous in composition. The pressure can be determined in the gas phase
The next step is to examine the variability of of fluid inclusions through crushing the sample in an
liquid-to-vapor ratios among fluid inclusions of the immersion medium ŽRoedder, 1970.. If bubbles col-
FIA. If all-liquid fluid inclusions are observed, then lapse upon crushing, then the fluid inclusion was
the petrographic means discussed earlier must be either originally entrapped or reequilibrated at high
used to rule out their origin from necking down after temperature. If the bubble expands significantly, then
a phase change. If they have not formed from neck- inclusions were trapped or reequilibrated signifi-
ing down after a phase change, then it must be cantly below the surface. If the bubble remains the
shown that they are not significantly metastable, by same size, the inclusions were trapped near the
showing that they are in the same size range as surface at one-atmosphere pressure.
two-phase inclusions Žnot just the small inclusions., The combination of these various tests are useful
and by showing that bubbles cannot be nucleated by in identifying diagenetic environments of fluid inclu-
cooling in a kitchen freezer for high salinity inclusion entrapment and post-entrapment alteration. This
sions, or in a refrigerator for low-salinity inclusions. model ŽFig. 11. is not inclusive of all diagenetic
If this can be shown, the liquid-filled fluid inclusions systems but is useful in identifying formation in the
represent entrapment at low temperature, less than low-temperature phreatic zone, the low temperature
about 508C. vadose zone, and the high-temperature, burial envi-
Fig. 11. ŽA. Schematic illustration of room-temperature distribution of vapor-to-liquid ratios within a fluid inclusion assemblage of
vadose-zone origin. Conclusions refer to interpretations that can be made about diagenetic environment given the additional observations
associated with each conclusion presented. Sample sizes and shapes are only diagrammatic. Assume that fluid inclusions within each
assemblage are of various sizes and shapes. A – Assemblage before any thermal reequilibration. B – Assemblage after moderate thermal
reequilibration. C – Assemblage after significant thermal reequilibration. Žafter Goldstein and Reynolds, 1994.. ŽB. Schematic illustration of
room-temperature distribution of vapor-to-liquid ratios within a fluid inclusion assemblage of low-temperature phreatic origin. Conclusions
refer to interpretations that can be made about diagenetic environment given the additional observations associated with each conclusion
presented. Sample sizes and shapes are only diagrammatic. Assume that fluid inclusions within each assemblage are of various sizes and
shapes. A – Assemblage before any thermal reequilibration. B – Assemblage after moderate thermal reequilibration. C – Assemblage after
significant thermal reequilibration. Žafter Goldstein and Reynolds, 1994.. ŽC. Schematic illustration of room-temperature distribution of
vapor-to-liquid ratios within a fluid inclusion assemblage of high-temperature origin. Conclusions refer to interpretations that can be made
about diagenetic environment given the additional observations associated with each conclusion presented. Sample sizes and shapes are only
diagrammatic. Assume that fluid inclusions within each assemblage are of various sizes and shapes. A – Assemblage before any thermal
reequilibration. B – Assemblage after thermal reequilibration. Žafter Goldstein and Reynolds, 1994..
ronment. Furthermore, it can be use to identify later 7.2. Methane

alteration through thermal reequilibration.
Relatively pure methane is common near the sur-
face where it results from biogenic degradation of
7. Types of fluids in inclusions organic matter Žfermentation or CO 2 reduction., and
deeper in the subsurface where it results from ther-
mogenic cracking of kerogen. In sedimentary sys-
Most fluids in the diagenetic realm are incredibly tems, a single methane phase exists, above the
complex in composition. One of the best examples of y82.18C critical point ŽFig. 13.. At room tempera-
this is seawater, a highly concentrated fluid Žabout ture, methane fluid inclusions commonly are identi-
3.5 wt.%. that has major amounts of, Naq, Mg 2q, fied by their dark and single-phase appearance. Upon
Ca2q, Kq, Sr 2q, Cly, SO42y, HCOy y y
3 , Br , F , and B cooling, these inclusions are easy to identify because
and minor amounts of many other elements. In addi- they commonly separate into distinct gas and liquid
tion, composition of organic and inorganic gases and phases below the critical point and melt at the triple
hydrocarbon liquids are also quite complex. Working point for methane at y182.58C. At room tempera-
with phase equilibria and microthermometry requires ture, crushing studies show that these inclusions exist
that the fluid inclusionist either carefully characterize at high pressures.
the composition of the fluid or make some assump-
tions as to what a good model might be for the
composition of the fluid. Some of the most common 7.3. H2 O–NaCl
model Žsimple. compositions and examples of the
phase equilibria that would apply to their interpreta- Aqueous solutions dominated by NaCl are com-
tion are summarized in the following section. Al- mon in many natural systems of the sedimentary
though it is well known that there is much more realm. In fact, this system is so common and such a
complexity than what is represented by these simple good approximation for even more complex salt
models, these models should at least provide a start- solutions, that when the composition is not well
ing point for interpreting fluid inclusion phase be- known, inclusionists commonly interpret their fluid
havior. inclusion salinities as if they were from the H 2 O–
NaCl system, calculating salinities in wt.% NaCl
equivalent. With corrections for salinity, these fluids
7.1. Freshwater behave similarly to the pure water system in that
natural, non-hydrothermal pore fluids exist at a pres-
Relatively pure H 2 O is common in sedimentary sure well above the boiling curve ŽFig. 12.. Nucle-
systems, especially near the surface and in shallow ation of a bubble only occurs after inclusion fluids
parts of basins. In sedimentary systems that have not have been trapped or reequilibrated at higher temper-
been subject to hydrothermal activity, freshwater ature and then cooled. Fluid inclusions from this
exists in the one-phase field, at a pressure above the model system are typically easily identified. The
vapor–liquid field boundary or boiling curve ŽFig. presence at room temperature of halite daughter min-
12.. It is not until these fluids are trapped or reequili- erals is the most obvious indication. Low-tempera-
brated in fluid inclusions at high temperature, and ture microthermometric phase behavior is even more
then cooled, that they reach the two-phase field useful. Look for eutectic melting behavior between
boundary. The fresh-water system is best identified the metastable eutectic at y288C and the stable
by its behavior during microthermometric cooling of eutectic at y21.28C. During warming of frozen fluid
fluid inclusions. The melting temperature of ice for inclusions, the identity of the last phase to melt and
these fluid inclusions is 08C. At room temperature, the temperature of its melting Žin the presence of a
fluid inclusions with this composition will have an bubble. are useful for evaluating the salinity of the
aqueous liquid phase and may or may not have a solution ŽFig. 14.. Inclusionists should determine if
bubble or a gas phase. the last phase to melt is ice, hydrohalite, or halite,
divalent cations ŽDavis et al., 1990.. The equilibrium

eutectic for this system is at y528C, so definite
eutectic melting at this temperature would be a posi-
tive indication that this system applies. Determining
ion ratio and salinity using microthermometric obser-
vations requires observation of the eutectic, an inter-
mediate melting event and a final melting event. In
practice, making these observations with confidence
is difficult.
7.5. Seawater
Seawater is one of the most important fluids in

the sedimentary realm. There are many diagenetic
systems that can clearly be tied to the marine sedi-
ment–water interface. Such ties are cross-cutting and
Fig. 12. P – T projection of the H 2 O system for diagenetic P – T stratigraphic relationships that either exclude the
conditions. Labeled contours are lines of constant density in possibility of fluids other than those derived from
grcm3. The shaded area shows P – T conditions that can be found seawater, or that directly link diagenesis to a marine
in the diagenetic realm Žmodified from Goldstein and Reynolds,
process such as deposition of marine internal sedi-
1994..
ment or submarine erosion. Typically, such prior
geologic knowledge, that the seawater system is the
one to apply, is the only evidence used to apply the
and evaluate the temperature of that melting to deter-
seawater model to fluid inclusions. With corrections
mine salinity.
for salinity and salt composition, seawater-derived
fluids behave similarly to the pure-water system in
7.4. H2 O–NaCl–CaCl 2
that natural, non-hydrothermal pore fluids exist at a
pressure well above the boiling curve ŽFig. 12..
Aqueous solutions dominated by NaCl and CaCl 2
Nucleation of a bubble only occurs after inclusion
are well known deep in sedimentary basins where
fluids have been trapped or reequilibrated at higher
brines have undergone significant rock–water inter-
temperature and then cooled. Typically, the salinity
action. Although brine composition deep in basins
of seawater must be determined by the temperature
can be quite complex and may have many more
of final melting of ice ŽFig. 15..
components, this class of brines serves as a good
model for the composition of many sedimentary
brines. With corrections for salinity and salt compo- 7.6. H2 O–NaCl–CH4
sition, these fluids behave similarly to the pure-water
system in that natural, non-hydrothermal pore fluids Saltwater solutions containing dissolved methane
exist at a pressure well above a boiling curve ŽFig. are important particularly in the subsurface of sedi-
12.. Nucleation of a bubble only occurs after inclu- mentary basins. In general, solubility of methane into
sion fluids have been trapped or reequilibrated at brine is relatively low, so it is common for methane
higher temperature and then cooled. The applicabil- to reach saturation with respect to aqueous solutions.
ity of this system, to your inclusions is best identi- With increasing depth in a basin Žhigher temperature
fied by microthermometric cooling of fluid inclu- and pressure. methane’s solubility increases ŽFig.
sions. After such inclusions have been frozen, they 16.. Increase in salinity decreases the solubility of
typically yield eutectic melting temperatures near methane, so understanding this system requires care-
508C. Eutectic melting temperatures below about ful characterization of the composition of fluid inclu-
408C are consistent with the presence of abundant sions ŽFig. 16.. Solubility curves plotted in P–T
Fig. 13. Ža. P–T plot of the CH 4 system. Labeled contours are lines of constant density in grcm3 . The light shaded area shows the P–T
conditions found in the diagenetic realm; for comparison, the darker shaded area shows the P–T regime present in nearshore Gulf basin
sediments Žfrom Hanor, 1980.. The area outlined by the rectangle is enlarged in Žb.. Critical point is at y82.18C, 46.3 bars; triple point is at
y182.58C Žmodified from Mullis, 1979..
space are essentially the same as bubble-point curves, room temperature., an end-member water-rich fluid
the curves defining immiscibility in the range of Žappears as liquid with a small bubble., and as
geologic interest. Entrapment of fluid inclusions from mixtures of the two. Phase equilibria of the
an immiscible system of methane and saltwater is methane-rich end member would approximate that of
likely to lead to entrapment of an end-member pure methane ŽFig. 13.. If the aqueous-rich end
methane-rich fluid Žappears as one phase and dark at member of an immiscible system were entrapped, or
Fig. 14. ŽA. T–X plot for the lower temperature, lower salinity portions of the system H 2 O–NaCl. Each point on this diagram is at
equilibrium vapor pressure. Produced from Crawford Ž1981., Roedder Ž1984. and Hall et al. Ž1988..
an aqueous fluid inclusion from a system undersatu- the methane system above. In addition, some inclu-
rated with respect to methane were entrapped, the sions may form clathrates upon cooling, and upon
phase equilibria of a fluid inclusion would follow a crushing water-rich inclusions at room temperature,
predictable path ŽFig. 17.. Evidence that is useful in bubbles in water-rich inclusions would be found to
identifying the presence of the H 2 O–NaCl compo- be under pressure. Application of the specific phase
nents are similar to the criteria discussed above for equilibria for each fluid inclusion requires relatively
the H 2 O–NaCl system. Identifying the presence of thorough characterization of methane content and
methane uses criteria similar to those developed for salinity.
7.7. Petroleum
Petroleum in fluid inclusions is best identified by

its tendency to fluoresce when excited with ultravio-
let light. Some petroleum fluid inclusions do not
fluoresce brightly enough to be detected with stan-
dard microscopic methods; these include some con-
densates Žgas-rich inclusions with a thin rim of oil.
and some oil inclusions that have lost their volatiles.
Although most oil inclusions are colorless in trans-
mitted light, some may be identified by yellowish or
Fig. 15. Seawater freezing point depression constructed from data
brownish color. Other fluid inclusions with oil can
of Lyman and Fleming Ž1940.. Note that data do not extend above be identified by particularly odd low-temperature
a salinity of 55 ppt. Žafter Goldstein and Reynolds, 1994.. microthermometric behavior that is inconsistent with
Fig. 16. Intersections of isoplethic planes for H 2 O-rich fluid with various amounts Žppm. of CH 4 with the H 2 O–CH 4 immiscibility surface
projected onto a single P–T diagram. Ža. H 2 O–CH 4 fluids containing no NaCl. Žb. H 2 O–CH 4 fluids containing 15 wt.% NaCl. Modified
from Hanor Ž1980..
other fluids. Phase behavior of oil fluid inclusions petroleum fluid inclusions with quite different com-
can be quite difficult to model because petroleum positions, one would expect markedly differing phase
compositions are so complex ŽMunz, 2001.. Given behavior ŽFig. 18.. This means that careful character-
Fig. 17. P–T phase diagram for H 2 O–CH 4 system with 3200 ppm CH 4 . Sketches of inclusions to right of plot schematically show
proportions of the phases in an inclusion at several P–T conditions ŽA, B, C, D.. Thermobaric gradient is 328Cr100 bars. Modified from
Hanor Ž1980..
Fig. 18. P–T phase diagram showing immiscibility curves and isochores of four AgenericB petroleum fluids without H 2 O, derived from
commercially available software ŽEQUI-PHASE: D.B. Robinson Research, Edmonton, Alberta, Canada. modified from Burruss Ž1992..
Mol% of components modeled are presented in the upper right. Within the envelopes two petroleum fluids would coexist; outside the curves
only a single petroleum fluid would exist. The thermobaric gradient shown is 258Cr100 bars. As pointed out by Burruss Ž1992., with
decreasing mol% CH 4 and with increasing mol% of the high molecular weight components ŽC7 and higher., the curves shift to higher
positions, and the slopes of the isochores increase Žthe fluid becomes less compressible..
ization of compositions should be needed to accu- bubble point or vapor–liquid phase boundary is
rately characterize the phase equilibria of fluid inclu- known, and so that the isochoric path is known.
sions in this system. Never apply a pressure correction unless the compo-
sition of the fluid inclusion is known well enough to
determine the fluid inclusion’s path in P–T space.
8. Geothermometry from fluid inclusions For gas-poor aqueous inclusions, the correction is
typically large and is applied by making an assump-
Procedures for interpreting the degree to which tion about the pressure of entrapment or thermobaric
aqueous fluid inclusion assemblages preserve origi- gradient along which the fluid inclusion was en-
nal homogenization temperatures can be complex. trapped ŽFig. 24.. For gas-rich aqueous inclusions, a
Flow charts of procedures and logic are helpful in large pressure correction is typically not needed be-
evaluating the observations from each FIA ŽFigs. cause homogenization takes place at high pressure,
19–23.. close to the conditions of entrapment ŽFig. 25..
8.1. FIA with consistent homogenization tempera- 8.2. FIA with highly Õariable homogenization tem-
tures peratures
The FIAs that are best for interpreting tempera- If within an FIA, phase ratios among fluid inclu-
ture of entrapment consist of variably sized and sions Žand homogenization temperatures. are highly
shaped aqueous inclusions in which 90% of the variable, most homogenization temperatures are
homogenization temperatures are within 10–158C meaningless because the variability likely resulted
ŽFig. 20.. These simple observations rule out prob- from necking down after a phase change or heteroge-
lems with thermal reequilibration, and thus, each neous entrapment from an immiscible system ŽFigs.
homogenization temperature measured, in such an 22 and 23.. If necking down after a phase change
FIA, is a record of the minimum entrapment temper- can be ruled out, the explanation remaining is immis-
ature of the fluid inclusion. The degree to which cibility. With immiscible entrapment of aqueous liq-
these homogenization temperatures underestimate uid and gas inclusions at high temperature, the liq-
true entrapment temperature depends on the amount uid-rich aqueous end members could give consistent
of gas dissolved in aqueous inclusions, the composi- homogenization temperatures Žif they have not been
tional control on the isochoric slope, and the pressure reequilibrated.. Those homogenization temperatures
of entrapment. Ultimately these factors control the are equal to the entrapment temperatures and do not
Apressure correctionB that corrects homogenization need to be corrected for pressure. In the case of
temperature to true entrapment temperature. evidence for oilrwater immiscibility, if the end
To correct homogenization temperature to entrap- member oil-rich fluid inclusions and the end-member
ment temperature, the composition of fluid inclu- aqueous-rich fluid inclusions yield the same homog-
sions must be constrained so that the position of the enization temperatures, then the system was gas
saturated and the homogenization temperatures are
equal to entrapment temperature. Finally, if in an
FIA, all-liquid inclusions are present and do not
result from significant metastability or necking down
after a phase change, then entrapment temperature
was less than about 508C ŽFig. 22..
8.3. FIA with slightly Õariable homogenization tem-

peratures
Fig. 19. Flow chart illustrating procedures for interpreting a fluid
inclusion assemblage consisting of all-liquid fluid inclusions Žafter On the other hand, many FIAs produce only
Goldstein and Reynolds, 1994.. slightly variable homogenization temperatures ŽFigs.
Fig. 20. Flow chart illustrating the procedure for interpreting a fluid inclusion assemblage with apparently consistent or moderately
consistent phase ratios. Inclusions are of various shapes and sizes Žafter Goldstein and Reynolds, 1994..
20 and 21.. Again, if all-liquid inclusions are present ods must be applied to evaluate the degree to which
and do not result from significant metastability or the original fluid inclusions are preserved or have
necking down after a phase change, then the entrap- reequilibrated.
ment temperature was less than about 508C ŽFig. 21.. It is well known now that two mechanisms of
In systems lacking all-liquid inclusions, other meth- thermal reequilibration are important, stretching, and
Fig. 21. Flow chart illustrating procedure for interpreting fluid inclusion assemblage with moderately consistent phase ratios together with
all-liquid fluid inclusions. Inclusions are of various shapes and sizes Žafter Goldstein and Reynolds, 1994..
leakage and refilling. It is also well known that in others would leak and refill, producing FIAs with
many sedimentary basins, there is a positive correla- inclusions that lie along convergent trends. The point
tion between depth Žtemperature. and salinity of pore of convergence would indicate the homogenization
fluids ŽHanor, 1984.. Given a history of thermal temperature and salinity prior to reequilibration of
reequilibration of fluid inclusions, one would predict the fluid inclusions ŽFig. 26.. The point of conver-
that some fluid inclusions would stretch and that gence is a minimum entrapment temperature for the
Fig. 22. Flow chart illustrating procedure for interpreting a fluid inclusion assemblage consisting of all-liquid fluid inclusions together with
inclusions of highly variable phase ratio. Inclusions are of various shapes and sizes Žafter Goldstein and Reynolds, 1994..
FIA before reequilibration and can be used for appli- outward indicates a decrease in temperature through
cation of a pressure correction to interpret tempera- time ŽFig. 27..
ture of entrapment. Finally, the tendency for fluid inclusions to
For some FIAs, temporal resolution is too low to reequilibrate from overheating, yields a statistical
sample an instant in time. For these, further analysis probability for partial reequilibration of fluid inclu-
of the petrographic distribution of homogenization sions in weak minerals at peak temperature. If one
temperatures within the FIA are helpful in evaluating were to measure homogenization temperatures of all
data. Given a thick growth zone containing primary inclusions in a sample of calcite, it is likely that its
fluid inclusions, one might compare the homogeniza- uppermost mode, or its highest FIA, would closely
tion temperatures from the inner part of the zone to approach, but not quite reach the maximum tempera-
those of the outer part of the zone. Consistent in- ture experienced ŽBarker and Goldstein, 1990.. Thus,
creases in homogenization temperatures outward in- in a soft mineral like calcite, the highest-temperature
dicate an increase in temperature through time. A FIA, or highest mode in all the homogenization
consistent decrease in homogenization temperature temperature data would have a statistical probability
Fig. 23. Flow chart illustrating procedure for interpreting a fluid inclusion assemblage with highly variable phase ratios and without
all-liquid fluid inclusions. Inclusions are of various shapes and sizes Žafter Goldstein and Reynolds, 1994..
of yielding a close approach to the maximum tem- tion and burial history information that can be gleaned
perature the rock has experienced ŽFig. 28.. This from fluid inclusions.
value could have nothing to do with the original
conditions of entrapment of the fluid inclusions, but 9.1. Minimum pressure of entrapment
yield data on thermal history important in reconstruc-
tion of thermal, tectonic and stratigraphic history. Minimum pressure of fluid inclusion entrapment
can be attained simply through crushing of samples
with fluid inclusions, under an immersion medium,
9. Geobarometry from fluid inclusions and using Boyle’s Law to calculate pressure before
crushing. This pressure, at room temperature, greatly
Fluid inclusions are one of the only geobarome- underestimates the true entrapment pressure.
ters available for the sedimentary realm. Because Alternatively, if the composition of the fluid in-
pressure can be translated to burial depth or water clusion and its homogenization temperature has been
depth, there is a variety of environmental informa- determined, the pressure at the point of homogeniza-
9.3. Entrapment pressure with eÕidence for immisci-

bility
In many of the low-temperature systems preserv-

ing all-liquid fluid inclusions, gas-rich fluid inclu-
sions are also preserved. These gas-rich inclusions
contain immiscible gases that were trapped as sepa-
rate phases. Because temperature of entrapment is
similar to lab temperature, crushing the samples to
determine the pressure in gas-rich inclusions is a
direct measure of the pressure of entrapment. Such
analyses have been applied successfully to identify
the vadose zone ŽGoldstein, 1990., depth and timing
of near-surface diagenesis ŽNewell and Goldstein,
1999. and should be useful in reconstructing water
depth in basins with evaporites, and with other sub-
aqueous precipitates ŽGoldstein and Reynolds, 1994.
Fig. 24. Phase diagram for pure water with one of the isochores For some systems that existed at high tempera-
for pure water and the liquid–vapor field boundary. If a fluid ture, there is abundant evidence for immiscibility in
inclusion were to homogenize at 1508C, and were composed of which a gas phase had separated from an aqueous
pure water, the inclusion must have been entrapped along the phase. For these systems, petrographic evidence must
isochore drawn. If one were to apply a pressure correction based
be used to support the occurrence of immiscibility.
on a present day thermobaric gradient of 208Cr100 bars, one
would interpret entrapment temperature to be 2038C. Then, the gas-rich fluid inclusion end member must
be found, its composition determined, and its ho-
mogenization temperature measured. These data de-
tion can be determined This pressure will greatly fine an isochore along which the inclusions were
underestimate the pressure of entrapment in gas-poor
aqueous inclusions, but may approach the pressure of
entrapment in aqueous inclusions trapped with sig-
nificant dissolved gas.
9.2. Entrapment pressure with consistent homoge-

nization temperatures
Given FIAs consisting of fluid inclusions with

variable sizes and shapes, and yielding consistent
homogenization temperatures, the pressure of entrap-
ment can be determined. To determine pressure of
entrapment, one must first determine the composition
and homogenization temperature of the fluid inclu-
sions. This defines an isochoric path along which the
fluid inclusions had been entrapped. Similar to what
was done above to determine temperature of entrap- Fig. 25. Phase diagram illustrating bubble point curve for 2000
ment ŽFigs. 24 and 25., an assumption must be made ppm methane in 15 wt.% NaCl solution. Isochore drawn is for
about the thermobaric gradient at the time of entrap- homogenization temperature at about 928C. The isochore that
projects from the 2000 ppm bubble point curve is for an interpre-
ment, or the temperature at the time of entrapment. tation of 2000 ppm methane present in the inclusion. Prior knowl-
The points at which these assumptions intersect the edge of pressure of entrapment of 850 bars is used to interpret the
isochore defines the pressure of entrapment. temperature of entrapment of 968C.
Fig. 26. Bivariate plots of Th and Tm ice from moderately variable FIAs may yield convergent trends that converge on the conditions of
initial FIA entrapment, and define leakage and refilling trends that reflect the conditions experienced during thermal reequilibration of
inclusions during progressive burial heating. ŽA. Mechanism of reequilibration for each inclusion does not change. ŽB. Mechanism of
reequilibration for each inclusion varies Žafter Goldstein and Reynolds, 1994..
entrapped. Then, the aqueous-rich end member must system, its homogenization temperature is equal to
be found. Since it was entrapped from an immiscible the entrapment temperature. The point of intersection
of the entrapment temperature and the isochore for
the gas-rich end member inclusion defines the pres-
sure of entrapment ŽFig. 29.. Alternatively, if the
composition of the aqueous-rich end member can be
determined, then a bubble point curve can be con-
Fig. 28. Scatter plot of aqueous Th data from calcite Žmeans or

Fig. 27. Schematic illustration of fluid inclusion Th data dis- upper mode. versus the present peak temperature. Dashed line of
tributed throughout a single thick growth zone. ŽA. Increase in Th 1:1 correlation is for reference. The early cements are noted for
outward indicates increase in temperature through time. ŽB. De- comparison with later cements and cements of unclear origin.
crease in Th outward indicates trend of decreasing temperature Notice how T h data closely approach present peak temperature
through time Žafter Goldstein and Reynolds, 1994.. Žafter Barker and Goldstein, 1990..
is in understanding the past, and fluid inclusions will

figure prominently into this type of research. One of
the important questions about the past deals with
change in atmosphere–ocean chemistry through time.
Fluid inclusions of seawater in marine carbonate
minerals are unique samples that may provide us
with a record of past change in composition of the
seawater–atmosphere system ŽJohnson and Gold-
stein, 1993.. Fluid inclusions in marine evaporites
provide a similar, though less directly preserved,
record of past change in the composition of the
seawater–atmosphere system ŽTim Lowenstein, per-
sonal communication..
Fig. 29. Given methane–water immiscibility, the unique pressure Further, it is possible that the composition of
and temperature of fluid inclusion entrapment can be determined. earth’s atmosphere can be analyzed directly by ex-
If the aqueous end member homogenizes at 2008C, then the tracting fluid inclusions. One example is the preser-
temperature of trapping is 2008C. If the methane phase of the vation of air bubbles in amber ŽBerner and Landis,
methane-rich end member homogenizes to liquid at y86.48C
Žignoring the invisible water., then the inclusions were entrapped
1988., but there are problems with preservation of
along the .225 methane isochore. The pressure at which this original compositions in this matrix. A better possi-
isochore intersects the entrapment temperature is the trapping bility exists in cumulate halite crystals, which formed
pressure for the fluid inclusions Žafter Goldstein and Reynolds, as floating rafts at the water–air interface. These
1994.. crystals are well known to contain fluid inclusions of
trapped air providing an opportunity for analysis of
ancient atmosphere chemistry ŽLowenstein et al.,
1994.. Speleothems are also well known to contain
structed for the system. The pressure on that bubble inclusions of trapped air ŽGoldstein, 1986., but typi-
point curve at the temperature of homogenization is cally the air in caves deviates from that of the open
the pressure of entrapment. atmosphere, so any quantitative work on the compo-
Finally, given immiscibility of two phases, such sition of ancient air in speleothems will have to
as an oil phase and an aqueous phase at high temper- reconstruct open atmosphere composition from cave
ature, careful characterization of the composition of atmosphere composition.
each fluid might allow for characterization of the Fluid inclusions from non-marine settings also
PVT properties of each. If true homogenization tem- provide direct and indirect records of paleoclimate.
perature were measured for each, then it might be In lake systems, it is well known that fluid composi-
possible to construct P–T paths along which each tion is related to relative aridity, essentially the water
was entrapped Žisochores.. The point of intersection budget. Fluid inclusions in lacustrine evaporites pro-
of these could indicate the temperature and pressure vide exceptional records of overall salinity and com-
of entrapment. It is important to remember that position, useful in reconstructing the relative aridity
application of this approach would be quite difficult, of climate ŽLowenstein et al., 1994, Wenbo et al.,
requiring thorough characterization of the composi- 1995.. Benison et al. Ž1998. used laser Raman spec-
tion of the fluid inclusions. troscopy to evaluate pH of fluid inclusions in lacus-
trine halites, which also has implications for resi-
dence time of fluids in ancient lakes. Other work on
10. Fluid inclusions and global change fluid inclusions in speleothems has produced isotopic
data on meteoric fluids, useful in reconstructing pale-
One of the most important areas of inquiry facing oclimate signals ŽHarmon et al., 1979.. Further, fluid
us all is future change in Earth’s surface environ- inclusions in evaporites and lake tufas could also
ment. One of the only ways of predicting the future provide useful data on depth of lake waters which
could be useful in understanding relative aridity of attempts have been made to interpret the PVT rela-
the climate during entrapment. tionships of oil in fluid inclusions to better evaluate
Finally, fluid inclusion data from near-surface temperature and pressure of entrapment. This work
systems are very useful in providing paleo-atmo- determines the volume of gas and liquid in fluid
sphere temperature. A good example of this is in inclusions to supplement modeling of the PVT rela-
halite from shallow lake systems. Fluid inclusions tionships ŽMacLeod et al., 1996.. Although this ap-
are supercooled to generate bubbles, and bubbles are pears to be useful information that may help in the
heated to homogenization ŽRoberts and Spencer, interpretation of oil-filled fluid inclusions, an analy-
1995.. In shallow water systems, no pressure correc- sis of the errors involved in the volume determina-
tions are needed so homogenization temperatures are tions and assumptions about composition would be a
the same as entrapment temperatures. Fluid inclu- useful addition. All in all, fluid inclusion technolo-
sions of this sort provide useful climate data for the gies figure prominently in the petroleum industry
Holocene and Pleistocene ŽLowenstein and Brown, and will continue to do so as analytical technologies
1998. as well as for very ancient systems ŽBenison develop further.
and Goldstein, 1999.. It is possible that similar ho-
mogenization temperature data could be gained from
speleothem calcite and other coarse mineral phases 12. Fluid inclusions and diagenetic systems
that precipitate near Earth’s surface.
Most diagenetic studies rely on a combination of
petrography and on isotopic and trace element analy-
11. Oil exploration and development sis of diagenetic minerals. Of these techniques, the
petrography typically provides the most unequivocal
In recent years, fluid inclusion work has become a constraints on diagenetic history. Stable isotopic and
very important tool in oil exploration and develop- trace element techniques, however, typically provide
ment. Not only have fluid inclusions figured promi- ambiguous results because of the many uncon-
nently in understanding the diagenetic controls on strained variables that affect the composition of min-
porosity evolution and thermal history, but fluid eral phases. Most diagenetic systems are defined by
inclusion work has been important in evaluating the the temperature, pressure and salinity of the fluids
history and pathways of hydrocarbon migration. active in them. For that reason, fluid inclusions are
Petroleum fluoresces with UV epi-illumination, and one of the best techniques for constraining the diage-
its color of fluorescence is tied to maturity and API netic history of sedimentary rocks. Fluid inclusions
gravity ŽLumb, 1978; McLimans, 1987; Tsui, 1990. have been successfully Žand unambiguously. applied
providing an important record of composition of to all diagenetic systems ŽGoldstein and Reynolds,
petroleum fluid inclusions. Furthermore, careful pet- 1994.. Such systems include low-temperature and
rographic analysis of fluid inclusions within the con- high-temperature ones that have never been heated
text of diagenetic history has also proven useful. and buried, but also include many low temperature
Individual events of petroleum migration commonly and high temperature systems that have been buried
can be recognized by cement superpositional or and heated beyond their conditions of entrapment.
crosscutting relationships. Detailed study of these Where present, fluid inclusions, coupled with petrog-
relationships, together with homogenization tempera- raphy, are probably the best techniques for tackling
ture measurements, is quite useful in understanding problems in diagenesis.
reservoir systematics ŽPottorf et al., 1997; Brennan
and Goldstein, 1998.. Furthermore, the extraction
and analysis of hydrocarbon fluid inclusions pro- 13. Conclusions
vides useful information for determining hydrocar-
bon migration history and for evaluating the compo- The future looks bright for fluid inclusion studies
sition of hydrocarbons ŽBurruss, 1987b, Karlsen et in sedimentary rocks. The last fifteen years has seen
al., 1993; Hall, 1996; Smith, 1997.. In recent years, a revolution in the way fluid inclusion studies have
been done in sedimentary rocks, a revolution brought Pasteris, J.D., 1998. Extremely acid Permian lakes and ground
about by the discovery that some of the fluid inclu- waters in North America. Nature 392, 911–914.
Berner, R.A., 1990. Atmospheric carbon dioxide levels over
sions in sedimentary rocks reequilibrate from natural Phanerozoic time. Science 249, 1382–1386.
overheating. This discovery led to the development Berner, R.A., Landis, G.P., 1988. Gas bubbles in fossil amber as
of a new approach, the fluid inclusion assemblage possible indicators of the major gas composition of ancient air.
approach. With this, the future looks encouraging. Science 239, 1406–1409.
There are many applications in sedimentary rocks Brantley, S.L., 1992. The effect of fluid chemistry on quartz
microcrack lifetimes. Earth Planet. Sci. Lett. 113, 145–156.
tailor-made for studies of fluid inclusions. Among Bodnar, R.J., Bethke, P.M., 1984. Systematics of stretching of
those are diagenetic studies, studies of petroleum fluid inclusions; fluorite and sphalerite at 1 atmosphere confin-
systems, temperature and pressure studies to focus ing pressure. Econ. Geol. 79, 141–161.
on tectonic, stratigraphic, and economic systems, and Bodnar, R.J., Reynolds, T.J., Kuehn, C.A., 1985. Fluid-inclusion
applications to paleoclimate and chemistry of the systematics in epithermal systems. In: Berger, B., Bethke, R.
ŽEds.., Geology and Geochemistry of Epithermal Systems:
ancient oceans and atmosphere. With the large num- wSociety of Economic Geologistsx, Reviews in Economic Geol-
ber of applications available, it is likely that new ogy 2, pp. 73–97.
uses for fluid inclusions in sedimentary rocks will Brennan, S.T., Goldstein, R.H., 1998. Fluid and thermal history of
continue to evolve. That is not to say that there will an exhumed petroleum reservoir. PACROFI program and ab-
be no new problems discovered. We, as fluid inclu- stracts, Las Vegas Žunpaginated..
Burruss, R.C., 1987a. Paleotemperatures from fluid inclusions:
sionists, need to remain forever vigilant in evaluating Advances in theory and technique. In: Naeser, N.D., McCul-
the quality of our data and our interpretations, con- loh, T.H. ŽEds.., Thermal History of Sedimentary Basins,
tinuing to question our findings so that fluid inclu- Methods and Case Histories 41 American Association of
sion studies in sedimentary systems advance. Petroleum Geologists Special Publication, Tulsa, pp. 121–131.
Burruss, R.C., 1987b. Crushing-cell, capillary column gas chro-
matography of petroleum fluid inclusions: Method and appli-
cation to petroleum source rocks, reservoirs, and low tempera-
Acknowledgements
ture hydrothermal ores. American Current Research on Fluid
Inclusions, Socorro, NM, Abstracts Žunpaginated..
Part of this paper represents a distillation of mate- Burruss, R.C., 1991. Practical aspects of fluorescence microscopy
rials developed jointly by R.H. Goldstein and T.J. of petroleum fluid inclusions. In: Barker, C.E., Kopp, O.C.
Reynolds. The collaboration of T.J. Reynolds was ŽEds.., Luminescence Microscopy and Spectroscopy 25 Soci-
essential for their development. This manuscript ben- ety of Economic Paleontologists and Mineralogists Short
efited significantly from reviews by Tom Andersen Course, Tulsa, pp. 1–7.
Burruss, R.C., 1992. Phase behavior in petroleum–water Žbrine.
and an anonymous reviewer. Partial support for de- systems applied to fluid inclusion studies. PACROFI IV,
velopment of the techniques discussed herein was Pan-American Conference on Research on Fluid Inclusions,
provided by the University of Kansas general re- Lake Arrowhead Abstracts, pp. 116-118.
search fund and NSF grants EAR-87-21229 and Carothers, W.W., Kharaka, Y.K., 1978. Aliphatic acid anions in
EAR-92-18463. This research benefited significantly oil field waters — implications for origin of natural gas. Am.
Assoc. Petrol. Geol. Bull. 62, 2441–2453.
from discussions with my colleagues and a large Casas, E., Lowenstein, T.K., Spencer, R.J., Pengxi, Z., 1992.
number of University of Kansas graduate students. Carnallite mineralization in the nonmarine, Qaidam basin,
China: evidence for the early diagenetic origin of potash
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Fluid Inclusions in Sedimentary and Diagenetic Systems

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Lithos 55 Ž2001.

Fluid inclusions in sedimentary and diagenetic systems

Keywords: Fluid inclusions; Global change; Diagenesis; Paleoclimate; Petroleum geology

1. Introduction soil surfaces as rain water, fresh lake and groundwa-

ing down for sedimentary systems, let us first exam-

Fig. 3. P – T phase diagram for pure water with an isochore for

Fig. 2. P – T phase diagram for pure water with an isochore for

4.4. Nucleation metastability 4.5. Thermal reequilibration

with the mechanism of stretching, is known as ther-

relieve the high internal pressures ŽBodnar and

exists a good possibility for fluid inclusions in halite

neous phase at the same time, under the exact same

ronment. Furthermore, it can be use to identify later 7.2. Methane

divalent cations ŽDavis et al., 1990.. The equilibrium

Seawater is one of the most important fluids in

Petroleum in fluid inclusions is best identified by

8.3. FIA with slightly Õariable homogenization tem-

9.3. Entrapment pressure with eÕidence for immisci-

In many of the low-temperature systems preserv-

9.2. Entrapment pressure with consistent homoge-

Given FIAs consisting of fluid inclusions with

Fig. 28. Scatter plot of aqueous Th data from calcite Žmeans or

is in understanding the past, and fluid inclusions will

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