Lecture slides from Prof.

Bob Bodnar
(Virginia Tech, Dept. of
Geological Sciences)

RJB - FLUIDS IN THE EARTH

 Fluids in the Earth
The dominant agent of
physical, chemical and
biological evolution on
Earth is H2O.

It is water that makes

the Earth unique amongst
the other bodies in the
Solar system.
We all live on this water
planet which we have
mistakenly chosen to
call Earth.
RJB - FLUIDS IN THE EARTH Anonymous
 Fluids in the Earth

RJB - FLUIDS IN THE EARTH

 Fluids in the Earth

RJB - FLUIDS IN THE EARTH

The Hydrologic Cycle

The conventional hydrologic

cycle describes the near-surface
water reservoirs and the movement
of water between these reservoirs.
The oceans contain the largest
proportion of water in the near-
surface environment, and water
from all reservoirs is eventually
cycled through the atmosphere.

Atmosphere
Biosphere
Surface Water = exosphere
Groundwater
Oceans
Glaciers & Polar Ice
Spreading centers and subduction zones are the location
for cycling of water through the geosphere, and magmas
and minerals serve as the hosts for water storage and
transport in the geosphere
Most (all?) ore deposits exist only because
of the important role played by water in
concentrating and depositing ore metals

Roll Front U deposits

GW, CC
 Most (all?) ore deposits exist only because
of the important role played by water in
concentrating and depositing ore metals

MVT deposits Epithermal Ag-Au deposits

GW, CC SW, GW, CC
Most (all?) ore deposits exist only because
of the important role played by water in
concentrating and depositing ore metals

Porphyry Cu-Mo-Au deposits

CC, UM, SW, GW, ATM
Most (all?) ore deposits exist only because
of the important role played by water in
concentrating and depositing ore metals

Oceans, UM

Massive Sulfide deposits

 Fluids in the Earth

RJB - FLUIDS IN THE EARTH

 Fluids in the Earth

RJB - FLUIDS IN THE EARTH

 Geochemical Tracers
Sources of waters often can
be inferred based on the fluid
composition and trace
components. D/H and 18O/16O
ratios are the most direct
means of inferring the source
of the water. Other
characteristics, such as
salinity, Cl/Br, 3He/4He, S, C &
Pb isotopes tell us something
about the source(s) of those
components, which may or
not be the same as the source
of the water.

RJB - FLUIDS IN THE EARTH

 Inc
r
Inc eas
r ing
Inc eas
re ing latit
u
as
ing elev de

RJB - FLUIDS IN THE EARTH

dis atio
tan n
ce
fro
m
oc
ea
n
O & H Isotopes
 S Isotopes
By themselves, sulfur isotopes usually do not provide unequivocal information
concerning the source of sulfur because the isotopic compositions of sulfur in
the various terrestrial reservoirs overlap, and the isotopic composition can be
modified by various biological and inorganic reactions. In the porphyry copper
deposits, the consistent 34S ≈0‰ is consistent with a magmatic source of S.

RJB - FLUIDS IN THE EARTH From Ohmoto & Rye, GHOD2 (1979)
 C Isotopes
Carbon isotopes in the various terrestrial
reservoirs overlap, and common
reservoirs do not have a unique isotopic
signature. 13C in deposits clearly
associated with magmatic hydrothermal
activity overlap values from deposits that
have no association with magmas.

RJB - FLUIDS IN THE EARTH From Ohmoto & Rye, GHOD2 (1979)
 Cl/Br Systematics

Cl/Br systematics can provide

evidence for the involvement of
seawater, and changes that
seawater-derived fluids might
have undergone as a result of
evaporation or mixing.

RJB - FLUIDS IN THE EARTH

 Cl/Br Systematics
Cl/Br analyses of fluid
inclusions in the Irish
Pb/Zn deposits suggest
that the ore fluids were
seawater that
evaporated to halite
saturation, with some
involvement of meteoric
fluids.

RJB - FLUIDS IN THE EARTH

 Rare Gases (He)
Ra = 3He/4He (atm) = 1.4 x 10-6 3
He is derived from
the mantle,
whereas 4He is
produced by the
radioactive decay
of U, Th and K
(mostly on the
continental crust).
A high 3He/4He
ratio implies an
input from the
mantle.

RJB - FLUIDS IN THE EARTH

 Rare Gases (He)
Analysis of geothermal
fluids from various
geothermal systems in the
western U.S. indicates
input of variable amounts
of deep fluids. Systems
associated with plate
boundaries (Geysers,
Lassen) show a higher
mantle input than systems
distant from plate
boundaries and hosted in
continental environments
(Nevada and Utah
systems).

RJB - FLUIDS IN THE EARTH

 Gas Chemistry
Analysis of fluid inclusion gases
may help to constrain the origin
of fluids in hydrothermal
systems. At the Geysers
system in California, fluid
Early
inclusions in early veins
indicate trapping of magmatic
gas, whereas later fluids
Late
indicate the influx of surface
waters into the system.

From Moore et al., Chem. Geol. 173 (2001)

RJB - FLUIDS IN THE EARTH

 Gas Chemistry

Early

Analysis of fluid inclusions

in different stages of the
paragenesis at the La Guitarra
epithermal deposit (Mexico) indicate
mixing of magmatic and meteoric
waters during the entire paragenesis, with a
larger proportion of magmatic fluids during the
latest silver sulfosalt stage
Late
RJB - FLUIDS IN THE EARTH From Camprubi et al., Chem. Geol. 231 (2006)
An Introduction to Fluid Inclusions
 What are Fluid Inclusions?
When a mineral forms in the presence of a fluid phase,
some of the fluid may be trapped as defects in the growing
crystal to produce fluid inclusions. Fluid inclusions are
also produced when mineral precipitation occurs in the
process of healing fractures in existing minerals.

The fluid phase may be liquid or vapor, and may include

aqueous solutions, volatiles such as CO2, CH4, N2, etc.,
liquid hydrocarbons, or silicate, carbonate or sulfide melts.

When observed at ambient conditions in the laboratory,

most fluid inclusions contain more than one phase.
Classification of Fluid Inclusions
Fluid inclusions are classified based on (1) when they
were trapped relative to mineral growth, and
(2) room temperature phase properties.

Temporal classification constrains the timing of inclusion

trapping relative to mineralization and structural events.

Room temperature phase relations provide information

on the compositions of the inclusions and constrain the
types of analyses that will be used to study the inclusions
and the order in which various analyses will be done.
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
22°C
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
22°C
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
-90°C
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor) Room Temperature
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum Th

Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Homogenization by critical behavior
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
V(CO2)
Halite-bearing L(CO2)

CO2-bearing L(H2O)

Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
V(CO2)
Two-Phase (liquid + vapor)
Liquid-rich L(CO2)
Vapor-rich
L(CO2)
Halite-bearing
CO2-bearing L(H2O)
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor) V(CO2)
L(H2O)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
L(CO2)
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
H
Multi-phase S
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
 Classification of Fluid Inclusions Based
on Room Temperature Phase Relations
Single Phase
Two-Phase (liquid + vapor)
Liquid-rich
Vapor-rich
Halite-bearing
CO2-bearing
Multi-phase
Petroleum
Melt inclusions
Temporal Classification of Fluid Inclusions
Temporal Classification of Fluid Inclusions

Primary
Temporal Classification of Fluid Inclusions

Primary
Inclusions
in quartz
(Goldstein,
2003)
Temporal Classification of Fluid Inclusions
Secondary
Temporal Classification of Fluid Inclusions

Pseudo-
secondary
(Goldstein, 2003)
In a fluid inclusion study, which inclusions
(primary, secondary, pseudosecondary)
should we measure?

It depends!
Which inclusions (primary, secondary,
pseudosecondary) one measures depends
on the question or geologic problem that
is being addressed.
While it is important to identify the temporal classification of
fluid inclusions, it is more important to recognize temporally-
associated groups of inclusions, and how the inclusions
are related to the process being investigated.

6a Petrographically
4c 6b associated fluid
4a inclusions are referred
to as fluid inclusion
5 assemblages. An FIA
3
represents the finest
1 (smallest) temporal
2 resolution possible
to constrain inclusion
4b 6c
trapping.

(From Goldstein, 2003)

 Roedder’s Rules
Obtaining valid information concerning the original
trapping conditions for fluid inclusions is based on
three assumptions, referred to as “Roedder’s Rules”.

1. The inclusion traps a single, homogeneous phase.

2. Nothing is added to, or removed from, the inclusion

following trapping.

3. The inclusion volume remains constant following

trapping, i.e., represents an isochoric system.
How do we test “Roedder’s Rules”?
1. Can you identify a Fluid Inclusion Assemblage?

2. Using petrography, do all the inclusions in the FIA

“appear” to have the same number of phases and in
the same proportions (or is there a bimodal distribution)?

3. Do all inclusions in the FIA show similar behavior

during microthermometry?

4. If the answer to all questions above is “YES”, the

fluid inclusions probably obey Roedder’s Rules.
Trapping of multiple phases, leakage, and changes
in inclusion volume after trapping all lead to variations
in phase relations and/or microthermometric behavior.
Fluid Inclusion Literature
The Bible of fluid inclusion research

While the Reviews in Mineralogy

book was published more than
20 years ago, it is still one of the
most useful sources of information
for the beginning and experienced
inclusionist.
Fluid Inclusion Literature
Modern inclusionists will
recognize that most of the
information contained in
this book is either incorrect
or a gross over-simplification
of the truth. However, it
represents an important
historical summary of the
state-of-the-art in fluid
inclusion research in the
1930s to 1950s and is
highly recommended for
any serious student of
fluid inclusions.
Fluid Inclusion Literature
This book grew out of
a very successful short
course taught by the
authors over a period of
several years. Contains
much useful practical
information on fluid
inclusions.
Fluid Inclusion Literature
Don’t be fooled by the
title of this book. Yes, it
does focus on fluid inclusions
in diagenetic environments.
But, the description of the
practical and applied aspects
of fluid inclusion research
remains the clearest, most
detailed and correct
summary published to date.
The description is applicable
to studies of fluid inclusions
in any environment.
Fluid Inclusion Literature

Papers from the

ECROFI and
PACROFI meetings
are generally
published as
special issues of
international
journals.
Fluid Inclusion Literature
For over 3 decades
starting in 1968 the
Fluid Inclusion Research
(FIR) volumes represented
the most complete
compilation of fluid
inclusion-related papers
available. The FIR volumes
became less useful when
instant access to journals
became available through
the internet in the 1990s.
Publication ceased in 1998.
Fluid Inclusion Literature

Fluid Inclusions: Analysis

and Interpretation is the
result of a fluid inclusion
short course held in 2003.
Contains chapters written
by experienced researchers
and summarizes current
knowledge in the field.
Fluid Inclusion Literature

Melt Inclusions in plutonic

rocks is the product of a
melt inclusion short course
held in 2006. Contains
chapters written by
experienced researchers
and summarizes current
knowledge in the field.
H2O
H2O
H2O
H2O
H2O
 Immiscibility in one-component system
At room temperature, what is
the liquid to vapor ratio of
H2O fluid inclusions trapped
on the boiling curve at about
310°C?
The inclusion that traps the
liquid phase will contain 70
volume % liquid and 30
volume % vapor at room
temperature.
What about the inclusion that
traps the vapor phase?
Modified from Fisher, 1976
Köln 2007
H2O-NaCl
H2O-NaCl
H2O-NaCl
H2O-NaCl
H2O-NaCl
H2O-CO2-NaCl
 Limits of immiscibility for H2O-CO2-NaCl
Addition of NaCl and CO2 to
H2O causes the critical point
and region of immiscibility to
migrate to higher
temperatures and higher
pressures.
As a result, fluid immiscibility
in “real” geofluids containing
significant amounts of both
salts and gases is possible
over a wide range of PT
conditions encountered in
the crust.

From Schmidt & Bodnar, 2000

Köln 2007
 Limits of immiscibility for H2O-CO2-NaCl
Microthermometric data
obtained from fluid
inclusions containing NaCl
and CO2 are often
interpreted in a manner
analogous to that used for
two-component systems.
This approach has led to
many incorrect
interpretations of the PT
conditions of trapping of
multi-component fluid
inclusions.
Modified from Hendel & Hollister, 1981
What are the compositions
of the coexisting phases in
the (H2O-6 wt% NaCl) - CO2
system indicated on the TX
diagram?
Köln 2007
 Limits of immiscibility for H2O-CO2-NaCl
Bodnar, unpublished
If the bulk composition of the fluid is given by
the white dot, at these same PT conditions,
what are the compositions of the coexisting
phases?
Köln 2007
Ternary diagram showing
the limits of the two-fluid-
phase field (blue) at a fixed
P&T for the system H2O -
NaCl - CO2. Referring to the
TX diagram on the previous
slide, point “C” represents
the bulk composition of the
system, and points “A” and
“B” represent the locations
along the (H2O-6 wt% NaCl)
- CO2 pseudobinary where
the path enters (“A”) and
leaves (“B”) the two-phase
field. At this P&T, for a bulk
composition “C” at 200°C
and 1 kb, the compositions
of the coexisting phases are
given by “D” and “E”.?
 Seminar 2: Transport and precipitation of
magma/fluids in mineral systems

Step 1: Select Mineral System (MS) and read up on key features.

Step 2: What are the characteristic physico-chemical features of the

magma/fluid?

Step 3: Develop a table that summarizes the P-T-X-fO2-fs2-pH-Eh (physico-

chemical characteristics) of the magma/fluids.

Step 4: Show key diagrams that support the physico-chemical

conditions of the magmas/fluids.

Step 5: How is the magma/fluid moved from the source to the

depositional site?

Step 6: Develop diagrams that summarize the magma/fluid dynamics

(e.g., Sibson fault-valve model).
 Seminar 2: Transport and precipitation of
magma/fluids in mineral systems

Step 7: How are the metals (major) precipitated from the magma/fluids.

Step 8: Provide key diagrams (solubility) that show what chemical

reactions are necessary to precipitate the sulfides/oxides in question.

Step 9: Place the chemical reactions into a geological model. What are the
geological processes that cause the chemical reaction to proceed in the
first place.

Step 10: Develop a 20 minutes Power Point presentation (10 minutes

each student), maximum 25 slides)