Chapter 24

Properties of Produced Waters

A. Gene Collins,*

U S. DOE Bartlesville Energy Technology Center**

Introduction and History

Early U.S. settlements commonly
were located close to
salt licks that supplied salt to the population.
Often these

percent saturation and percent porosity

plotted vs. depth to construct a graphic

salt

the oil and water saturation.

The soluble mineral salts
that were extracted from the core led Torrey to suspect

springs

were

contaminated

many of the early efforts

with

to acquire

petroleum.

and

salt by digging

wells

were rewarded by finding unwanted increased amounts

of oil and gas associated with the saline waters. In the

that water

Appalachian
Mts.. many saline
along the crests of anticlines.

ty, PA, that encountered higher than average oil saturation in the lower part of the Bradford sand. This high oil

water

springs

occurred

In 1855 it was found that distillation

of petroleum produced a light oil that was similar to coal oil and better
than

whale

spurred

oil

as an

illuminant.

the search for saline

This

waters

knowledge

that contained

Using the methods of the salt producers,

Col.
Drake drilled a well on Oil Creek, near Titusville.
1859, He struck
well produced

oil.

Edward
PA. in

oil at a depth of 70 ft, and this first oil

Shortly

was indigenous

of this core were

representation
of

thereafter

The early oil producers did not realize the significance

of the oil and saline waters occurring together. In fact, it

sand.

near Custer Ci-

saturation
resulted from the action of an unsuspected
flood. the existence of which was not known when the
location

for the test well

had been selected.

part of the sand was not cored.

Toward

The upper

the end of the

cutting of the first core with a cable tool core barrel. oil
began to come into the hole so fast that it was not
necessary

to add water for the cutting

tion of the sand. Therefore,

about 3.5 B/D.

to the oil-productive

a test well was drilled

sand was cut with

oil

of the second sec-

the lower 3 ft of the Bradford

in a hole

free from

water.

Two

water

samples from this section were preserved in sealed containers for saturation
tests, and both of them, when

in oil reservoirs was generally recognized. 4 Torrey was

convinced
as early as 1928 that dispersed interstitial
water existed in oil reservoirs, but his belief was rejected

analyzed,
had a water content of about 2O%PV. This
well made about IO BOPD and no water after being shot
with nitroglycerine.
Thus, the evidence developed by the

by his colleagues

because

core analysis

did

any

was not until

not

1938 that the existence

produce

most of the producing

water

rences of mixtures
of
recognized by Griswold
that there was a definite

of interstitial

upon

completion.

wells
Occur-

oil and gas with water were

and Munn,6
but they believed
separation of the oil and water,

and that oil, gas, and water mixtures

did not occur in the

sand before a well tapped the reservoir.

It was not until
1928 that the first commercial
laboratory for the analysis of rock cores was established,

and the productivity

test after completion

provided a satisfactory
indication of the existence of immobile water, indigenous to the Bradford sand oil reservoir, which was held in its pore system and could not be
produced
Fettke

by conventional

pumping

methods.

was the first to report the presence of water in

an oil-producing
sand. However,
he thought that it might
have been introduced by the drilling process.

and the first core tested was from the Bradford

third sand

Munn*
recognized
might be the primary

(from

PA).

tion of oil and gas. However,

this theory

perimental

Mills

Now

the Bradford

with the Natl

field.

Ins1 of Petroleum

The author of the or!gmal

W2fk,<

chapter

McKcan
and Energy

County.
Research

Eartlesv~lle

on this topic I the 1962 edlllon

The
OK

was J Wade

that moving
underground
water
cause of migration and accumula-

data to back it until

had little

conducted

ex-

several

laboratory
experiments
on the effect of moving
water
and gas on water/oil/gas/sand
and water/oil/sand
systems. Mills concluded that the up-dip migration of

24-2

PETROLEUM ENGINEERING

oil and gas under the propulsive

force of their buoyancy

in water, as well as the migration

of oil, either up or
down dip, caused by hydraulic
currents, are among the
primary factors influencing
both the accumulation
and
the recovery of oil and gas. This theory was seriously
questioned
and
contemporaries.

completely

Rich I assumed
buoyancy,

rejected

that hydraulic

are effective

by

many

currents,

of

his

rather than

in causing accumulation

of oil or

water, the well can be plugged

intrusive water from a shallow

in some fields, and it is necessary to separate the oil from

the water. Most of the oil can be removed by settling.
Often, however,
an oil-in-water
emulsion forms, which
is very difficult
and various
separation.

ment of water but rather that the oil was an integral

In the early
ground, where

of the rock

fluids

along with them whether

and that it could

the movement

con-

be carried

was very slow or

about

displacing

oil during

production

to break.

In such cases, the oil is heated

surface-active

chemicals

are added to induce

days, the water was dumped

on the
it seeped below the land surface. Until

1930, the oilfield

drainage,

relatively
rapid.
The effect of water

back. However,
it often is
sand gaining access to the

well from a leaky casing or faulty completion

and this
can be repaired.
Enormous quantities of water are produced with the oil

acits retention. He did not believe that the hydraulic

cumulation
and flushing of oil required a rapid movestituent

HANDBOOK

frequently

tion.
After
1930,
evaporate the water

waters

killing

were disposed

into local

fish and even surface vegeta-

it became
common
practice
to
in earthen pits or inject it into the

was not recognized in the early days of the petroleum in

dustty in Pennsylvania.
Laws were passed, however, to
prevent operators from injecting water into the oil reser-

producing
sand or another deep aquifer.
The primary
concern in such disposal practice is to remove all oil and

voir sands through unplugged

wells. In spite of these
laws, some operators at Bradford
secretly opened the

basic sediment from the waters before pumping them into injection wells to prevent clogging of the pore spaces

well casing opposite shallow groundwater

sands to start a
watertlood
in the oil
sands.
Effect
of artificial
watertloods
were noted in the Bradford
field in 1907,

in the formation
receiving
the waste water. Chemical
compatibility
of waste water and host aquifer water also
must be ensured.

and became evident

about 5 years later in the nearby oil

calculations
of the
fields of New York. Volumetric
oil-reservoir
volume
that were made for engineering
studies of these waterflood
operations
proved that in-

terstitial

water

Garrison
concerning

was generally

and Schilthuis
the distribution

present

in the oil

sands.

gave detailed
information
of water and oil in porous

Waters

produced

with

petroleum

portance.

In years

past,

these waters

are growing
were

in im-

considered

waste and had to be disposed of in some manner. Injection of these waters into the petroleum
reservoir rock
serves three purposes: it produces additional
petroleum
(secondary
recovery),
it utilizes a potential
pollutant.
and in some areas it controls land subsidence.

of

The volume of water produced with petroleum in the

U.S. is large. In 1981 domestic oil production
was about

water saturation to formation

permeability.
The word connate
was first used by Lane and Gor-

8.6~ IO B/D and the amount of water produced with

the oil ranges from 4 to 5 times the oil production.

don

Therefore,
4.5, would

rocks,

and of the origin

water

with

and occurrence

information

concerning

to mean interstitial

of connate

the relationship

water that was deposited

with

the sediments.
The processes of rock compaction
mineral
diagenesis
result in the expulsion
of

and
large

amounts of water from sediments and movement out of

the deposit through
the more permeable
rocks. It is
therefore

highly

unlikely

that the water now in any pore

is the same as that which

was there when the particles

that surround it were deposited. White redefined connate water as fossil

water because it has been out of
contact with the atmosphere for an appreciable
gcnlogic
time period.
Thus. connate water

part of a
is distin-

water, which has entered the

2cruished from meteoric
rocks in geologically
recent times, and from juvenile
water.

which

has come from deep in the earths crust and

has never been in contact with the atmosphere.

Meanwhile.
petroleum
engineers and geologists had
learned that waters associated with petroleum could be
identified with regard to the reservoir in which they occurred by a knowledge of their chemical characteristics.
Commonlv,
the waters from different
strata differ considerably In their dissolved chemical constituents.
making the identification
easy.

Howjcvcr.

of a water from a particular

in some

dissolved constituents
not ditfcr significantly,
waters

is difficult

The amount

areas

stratutn

the concentrations

in waters from different

and the identification

of

strata do
of such

or impossible.

of water

produced

with

the oil often

in-

creases as the amount of oil produced decreases. lfthis is

edge water. nothing can be done about it. If it is botton-

the water production,

assuming
be about 38.7~ IO BID.

a factor

of

Secondary and tertiary oil recovery processes that use

water injection usually result in the production
of even
more water along with the oil. To inject these waters into
reservoir
moved

rocks,

suspended

solids

from the waters to prevent

formations.

Water

injection

and oil
plugging

systems

must

be re-

of the porous

require

xepardtors,

filters, and, in some areas, deoxygenating

and bacteria
control equipment
with chemical and physical methods
to minimize
corrosion
and plugging
in the injection
system.
In waterflooding
volume of produced

most petroleum
reservoirs,
water is not sufficient to rccovcr

the
the

additional
petroleum efficiently.
Therefore,
supplemental water must be added to the petroleum reservoir. The
use of waters from the other sources requires that the
blending
of produced
water with supplemental
water
must yield a chemically
stable mixture so that plugging
solids will not be formed.
For example,
a produced
water containing
considerable
calcium
should not be
mixed with a water containing
considerable
carbonate
because calcium

carbonate

may precipitate

and prevent

injection of the tloodwater.

The design and successful
operation of a secondary or tertiary recovery operation
requires a thorough knowledge of the composition
of the
waters

used.

Chemical
analyses of waters produced
with oil
useful in oil production
problems. such as identifying

are
the

24.3

PROPERTIES OF PRODUCED WATERS

source

of

saltwater

Intrusive

disposal

water,

projects.

planning

watcrfood

and treating

and

to prevent

corro-

tained.

A test that

ilows

water

will

assurance of an uncontaminated

give

sample.

even

higher

If only one DST

in primary,
secondary,
and tertiary
rcquircs a
Electrical
well-lo g interpretation
of the dissolved
solids concentration
and

water sample is taken for analysis. it should bc taken just

above the tool. since this is the last water to enter the tool

composltton
of the interstitial
water. Such information
also is useful in correlation
of stratigraphic
units and of

Analyses of water obtained from a DST of Smackovcr

limestone water in Rains County.
TX. show how errors

the aquifers within

these
movcmcnt
of xubsurfacc

can be caused

sion

problems

recovery.
knowlc$Fc

understand
other

the processes

minerals

without

units. and in studies of the

waters.
It is impossible
to
that accumulate

insight

into

petroleum

the nature

or

of these

and is least likely

Analyses

by

improper

of top, middle.

a SO-ft fluid recovery

depth in the drillpipe.
contaminated

waters.

to show contamination.

sampling

and bottom

of

DST

water.

samples taken from

show an increase in salinity with

indicating that the first water wa\

by mud filtrate.

I) Thus.

ple was the most representative

the bottom

sam-

of Smackovcr

water.

applicable

for obtain-

Sampling
The composition

of subsurface

water commonly

changes

with depth and also laterally

in the same
Changes may be brought about by the intrusion

aquifer.
of other

Sample Procedure
No single procedure

is universally

sari--

ing a sample of oilfield water. For cxamplc. inthrmation

may
bc desired
concerning
the dissolved
gas or
hydrocarbons
in the water or the reduced species present.

pie of a given subsurface body of water. Any one sample

is a very small part of the total mass. which may vary

such as ferrous or manganous

compounds.
Sampling
procedures applicable to the desired infomlation
must be

MJidely

used.
Some of the special

waters.

and

aquifer.

It is thus difficult

in

by

discharge

from

composition.

sites should

it

to the

generally
Also.

the

as gases come out of

solutions
approach

be selected,

fit into a comprehensive

productive
geologic basin.

is

many samples.

may change with time

and
supersaturated

saturation.
The sampling

recharge

a representative

Therefore.

necessary to obtain and analyze

samples
solution

and

to obtain

network

if possible,

to

cover

an

to
oil-

information

and sample

cases, with appropriate procedures

proper sampling.
follow.

or references

location
cited for

Sample Containing Dissolved Gas. Knowlcdgc

tain
dissolved
exploration.
OZ

hydrocarbon

gases

is

of ccrused

in

There is a tendency for some oilfield waters to become

more diluted as the oil reservoir is produced. Such dilu-

Sampling at the Flowline. Another

method

tion may result from the movement

a sample

gases is to place a

of dilute

water from

adjacent compacting
clay beds into the petroleum rescrvoir as pressure declines with the continued removal of
oil and brine.
The composition
tion

within

of oilfield

the geologic

water varies with the posi-

structure

from

which

it is ob-

tained. In some cases the salinity will increase upstructure to a maximum at the point of oil/water
contact.
Few of the samples
arc truly

collected

representative

by drillstem

formation-water

test (DST)

samples.

sampling

for analysis
device

of dissolved

in a flowline.

of obtaining

Fig. 24. I illustrates

such

a device. The device is connected to the flowline.

and
water is allowed to flow into and through the container.
which

is held

volumes

above

the

flowlinc.

of water have flowed

on the sample container

removed.
If any bubbles
sample

is discarded

until

through.

10 or

more

The lower

valve

is closed and the container

are present in the sample, the

and a new one is obtained.

During

drilling.
the pressure in the wellbore
is intentionally
maintained
higher than that in the formations.
Filtrate

Sampling at the Wellhead. It is common practice in the

from

sampling

the drilling

and this filtrate

The most truly

mud

seeps into the permeable

is the first liquid

representative

strata.

to enter the test tool.

formation-water

sample

usually is obtained after the oil well has produced for a

period of time and all extraneous fluids adjacent to the
wellhore

have

mediately
taminated

been

flushed

out.

Samples

taken

im-

after the well is completed

may be conwith drilling
fluids and/or with well complc-

tion fluids.

such as filtrate

from

cement,

tracing

fluids,

oil industry

material

before

system.

the container

tainer.

(ASTM),
(NACE).

and the Natl.

Assn. of

I8

if properly

made,

can provide

is taken.

After

flushing

the
of the

is sealed.

Fig.

24.2 illustrates

a sample at the wellhead.

a method

An extension

of

of this

method is to place the sample container in a larger container. insert the tube to the bottom of the sample conallow

the brine to overflow

both containers.

and

withdraw
the tube and cap the sample under the fluid.
At pumping wellheads the brine will surge out in heads
and be mixed with oil. In such situations a larger con-

Drillstem Test
The DST,

a sample

container,
and several volumes of fluid are displaced
bcforc the tube is removed slowly from the container and

Testing

Engineers

water from a

A plastic or rubber tube

the end of the tube is placed in the bottom

obtalnmg

and Materials

a sample of formation

at the wellhead.

can be used to transfer the sample from the sample valve

into the container (usually plastic). The source and sample container should be flushed to remove any foreign

and acids. which contain many different chemicals.

Sampling methods are discussed in publications
of the
American
Petroleum
Inst. (API), American
Sot. for
Corrosion

to obtain
valve

a reliable

for-

mation water sample. it is best to sample the water after

each stand of pipe is removed.
Normally,
the total
dissolved solids (TDS) content will increase downward
and become constant when pure formation
water is ob-

tainer equipped

with a valve

a surge tank or an oil-water

at the bottom

can be used as

separator or both. To use this

device, place the sample tube in the bottom of the large

container, open the wcllhead valve, rinse the large container

with

the well

fluid,

allow

the large

container

to

PETROLEUM ENGINEERING

24-4

This filtering

system is simple

sists of a SO-mL disposable

Valve

and an inline-disk-filter
size 47-mm diameter,
option

74

of a prefilter

HANDBOOK

and economical.

syringe,

It con-

two check

valves.

holder. The filter holder takes

0.45pm
pore size filters, with the
and depth prefilter.

After the oilfield

brine is separated from the oil, the
brine is drawn from the separator into the syringe. With

Sample
container

the syringe,
I-+

tion bottle.

it is forced

through

the filter

into the collec-

The check valves allow the syringe

to be used

as a pump for filling

the collection
bottle. If the filter
becomes clogged,
it can be replaced in a few minutes.
About 2 minutes are required to collect 250 mL of sample. Usually two samples are taken, with the one being
acidified
to pH 3 or less with concentrated
HCI or
HN03.
The system can be cleaned easily or flushed with
brine to prevent

contamination.

Sample for Stable-Isotope

have been used in several
the origin

of oilfield

pH, Eh (redox potential),

CO,, and CO2 in oilfield
brine

Stable isotopes
studies to determine

brines. 22-24

Sample for Determining

Species. A mobile analyzer

oilfield

Analysis.

research

samples

Unstable

Properties

was designed

Oz, resistivity,
S=, HCOT,
water at the wellhead.
When

are collected

in the

field

transported
to the laboratory
for analysis, many
unstable
constituents
change
in concentration.
amount

of

change

sample storage,
the constituents

sampler.

depends

on the sampling

at the wellhead

Sample Containers.

Containers

polyethylene,
other plastics,
hard
and borosilicate
glass. Glass will
fill,

and withdraw

a sample through

the valve

tom of the large container. This method

tain samples that are relatively
oil-free.

will

at the botserve to ob-

Field Filtered Sample. In some studies it is necessary to

obtain a field filtered

sample. The filtering

in Fig. 24.3 was designed

various

and has proved

system shown
successful

for

applications.

Fig. 24.2-Example
of the method used for obtaining a sample
at the wellhead.

and
of the
The

method,

ambient conditions,
and the amounts of
in the original
sample. Therefore
an

analysis of the brine

tain reliable data.
Fig. 24-l-Flowline

or

to measure

is necessary

to ob-

that are used include

rubber,
adsorb

metal cans,
various ions

such as iron and manganese, and may contribute

boron
or silica to the aqueous sample. Plastic and hard rubber
containers are not suitable if the sample is to be analyzed
to determine
its organic content. A metal container is
used by some laboratories if the sample is to be analyzed
for dissolved hydrocarbons
such as benzene.
The type of container selected depends on the planned
use of the analytical data. Probably the more satisfactory
container,

if the sample

Fig. 24.3-Example

is to be stored

for some time

of field filtering equipment.

24-5

PROPERTIES OF PRODUCED WATERS

TABLE 24.1-DESCRIPTION

NEEDED FOR EACH OILFIELD WATER SAMPLE

Sample Number
Farm or lease ~
Townshlp
of Section
State
County
Operators address (main office)
Sample obtained by
Address
Sample obtained from (lead line, separatory flow tank, etc.)

Field
Well No. ~

in the
Range
Operator
Date
Representing

Completion date of well

Name of productive zone from which sample is produced
Shale
Lime
Sand
Other
Names of formations
Name of productive
well passes through
formation
Bottom of formation
Depths: Top of formation
Top of producing zone
Bottom of producing zone
Present depth
Top of depth drilled
Bottomhole pressure and date of pressure
Bottomhole temperature
Are any chemicals added to treat well
Date of last workover
If yes, what?
Initial
Present
Well production
Casing service record,
Oil, BID
Water, B/D
Gas, cu ft/D
Method of production (primary, secondary, or tertiary)
Remarks: (such as casing leaks, communication or other pay in same well, lease or field)

before

analysis.

is the

polyethylene

bottle.

Not

all

TABLE 24.2-GEOCHEMICAL

polyethylenes
are satisfactory
because some contain
relatively
high amounts of metal contributed
by catalysts
in their

manufacture.

the plastic

The approximate

can bc determined

metal content

by a qualitative

spectrographic
technique.
If the sample is transported
during freezing temperatures,
the plastic container is less
likely to break than is glass.

Tabulation of Sample Description. Information

such as
for each sample of

that in Table 24.1 should be obtained

oilfield

water.

Water
PH
Eh
Speciilc resistwty

methods

X
0
X

Boron

::

Bromide

0
X

::
X

;
X

::
X
0

Calcium

for analyzing

oilfield

dioxide

Chlonde

waters are im-

Hydrogen

sulfide

::

methods of oilfield
water analysis during the past 20
years. They are the API and ASTM.
The API published
Recommended
Practice
45 for Analysis
of Oilfield

Oxygen
Potassium

0
0

Waters.
The ASTMs
Committee
D-19 standardizes methods
of analyzing
oilficld
brines. Methods
standardized
by

Silica

rigorous

Total dissolved solids

round-robin
ASTM

testing
committee

found in Ref. 17.

Table 24.2 illustrates

by several

laboratories

balloting

the analyses

procedures

for various

and
are

proper-

ties or constituents
of oilfield water. Methods to determine most of these properties
or constltucnts
can bc
16, 17, and 25 through

30.

Chemical Properties of Oilfield Waters

waters

Water

Barium
Bicarbonate

Magnesium
Manganese

Oilfield

Disposal

0
X

0
X

in Refs.

Water

Bacteria

Carbon

proving with respect to precision, accuracy, and speed.

There have been at least two groups trying to standardize

found

Water

Speciitc gravity

Iodine
IlOll

subsequent

Injection Generation

Carbonate

Analysis Methods for Oilfield Waters

Analytical

Steam
Produced

of

emission

WATER ANALYSES*

are analyzed

for

various

chemical

and

physical properties. Most oilfield waters contain a variety of dissolved

inorganic
and organic
compounds.

Residual hydrocarbons
Sodium
Strontium

Sulfate
Suspended

X
0
0
X

solIds

X = usually
requesm
O=somellmes requested

X
::
0

PETROLEUM ENGINEERING

24-6

TABLE 24.3-CHARACTERISTICS

Number of
Analyses*

OF SOME WATERS PRODUCED FROM APPALACHIAN

FIELDS

Constituents (mg/L)

Subsurface
Depth
(fl)

Formation

System

HANDBOOK

Ca

Mg

Na

KentuckyZ3,24
4

Devonian-Silurian

Corniferous

Mississippian

McClosky

5
Ohi0

400 to 1,506

1,520
12,160
1,700
3,400
370
830

670
3,350
990
2,180
130
320

9,520
44,740
15,700
33,600
1,860
15,500

120
1,290
ND*
ND
ND
ND

1,390
9,230
11,000
44,000
32,300
51,200
25,900
29,600
4,600
11,900

650
2,900
2,700
6,600
5,180
10,200
4.100
1O;OOO
1,500
3,000

10,500
33,600
39,500
58,600
36,000
60,700
21.600
861400
25,000
43,900

150
1,510
0
2,890
1,950
2,330
270
2,370
120
220

40
32,400
7,000
82,000
420
16,900

30
1,940
70
2,020
40
2,530

1,600
39,500
3,600
16,000
300
39,200

30
1,730
630
8,920
100
15,300
400
20,600
2,500
33,600

300
3,910
200
2,250
40
2,740
340
2,650
480
3,800

50
52,200
6,300
38,100
3,800
35,100
2,500
50,900
34,000
98,300

1,390 to 2,618

Jett

939 to 1,534

35.36

Mississippian

Blue Lick

1,843 to 3,263

Ordovician

Sub Trenton

3,820 to 5,815

Mississrppian

Second Water
Big Lime
First Water
Big Lime
Berea

2,175 to 3,270

10

Upper Devonian

12

Mississippian

5,175 to 5,300
401 to 1,592

Pennsylvania3 38
IO
7
12

Devonian

Bradford

DevonoMississippian
Devontan

Venango

Bradford III

West Virginia39

However.
few

of

29

Mtssisstppian

Big lnjun

1,390 to 3,215

Mississippian

Squaw

1,908 to 2,019

21

Mississippian

Maxton

1,287 to 3,259

44

Pennsylvanian

Salt Sand

43

Devonian

Oriskany

oil producers
the

macro

usually

properties.

are interested
This

450 to 1,960
3,036 to 8,089

in only

is understandable

IO
750
290
340
30
660
3,6::
200
6,900

basin, a large area not generally otherwise identifiable.

This division has been made arbitrarily
for convenience

because oil producers wish to spend the least amount of

money possible. Therefore,
they will look at only the

and because of the lack of a uniform system and is not intended as a precedent for any system of classification.

properties

The

that are necessary

for rcinjection
to recover
oilfield waters.

Composition

to evaluate

any treatment

more oil or to dispose

of the

,
,,
ot otltteld

dilute waters to heavy

states

or provinces

available

are

of analytical

from

listed

under each area.

The reader is referred

of Oilfield Waters

The composition

were

which

reliable

alphabetically

to the original

data for more complete

indicated

Several

thousand

oilfield

Appalachian Area. The Appalachian

files.
of pro

in the U.S.
cially

in which

area was the first

was produced commer-

petroleum

and is one of the best known

and studied geologic

features
of North
America.
Table
24.3
characteristics
of some waters
produced

The tabulated
data on water analyses
lihted alphabetically
in order of general
areas of the U.S.. Canada. and Venezuela.

palachian

subdivisions
An

sources

information.

duced waters. and much of the text was taken from the
1962 edition of this book.

the smaller

tables

waters varies from relatively

brines.

water analyses are available

on computerized
Tables 24.3 through 24. I4 show characteristics

or gcosynclines.

analyses

in the

of basins.
exception

following
arc
oil-productive
rather than by

geologic

to this

provinces.

is the

Illinois

and associated

more than 50 strata in systems

Permian.

the
Ap-

fields. F--~,

Petroleum

although

gives
from

Most

water

are produced

from

from the Cambrian

to the

of the productive

some limestones

strata are sandstones,

are productive.

Many

of the

PROPERTIESOF

PRODUCED WATERS

24-7

TABLE24.3-CHARACTERISTICSOF

SOMEWATERSPRODUCEDFROMAPPALACHIANFIELDS

Constituents
Ba

Sr

HCO,

sandstones

are nonuniform

Ohio.

19,600
93,900
31,700
61,000
14,000
26.000

Trace
10
ND
ND
ND
ND

120
820
ND
ND
ND
ND

1.022
1.120
1.036
1.070
1.020
1.039

31,600
158,330
51,060
103,730
16,530
46,100

Trace
315
0
900
0
1,240
Trace
Trace
0
1,800

110
380
20
510
60
140
30
230
20
20

30
380
150
490
30
100
210
550
0
60

18,200
77,600
113,500
189,400
113,000
216,300
114,200
193.100
52,700
93,400

0
IO
10
30
ND
ND
ND
ND
ND
ND

0
570
150
600
580
1,900
1,230
2,100
320
520

1.025
1.089
1.150
1.224
1.151
1.240
1.125
1.211
1.063
1.115

31,030
125,180
167,030
304,020
189,100
344,110
167,540
324,350
84,260
154,820

30
560
0
0
0
40

30
1,080
260
1,270
0
1.080

1,100
83,200
30,900
75,300
490
97.600

2,790
158,680
41,830
176,590
1,260
157,350

IO
70
0
40
10
1,680
10
1,330
Trace
270

5
320
0
10
20
530
5
400
10
900

70
121,000
11,330
81,130
5.830
89,900
2,500
125.000
44,300
170,000

10
830
0
70
5
220
2::
Trace
1.570

and discontinuous.

Pennsylvania.

although

and West Virginia.

The

concentrations
ofdissolved
salts in waters produced
petroleum
range from a few hundred
to more

Gth
than

300,000 IllgiL.

California. In different
duced

from

Cretaceous
principal

many

of massive thickness.
evident.
In general.
petroleum

fields of California.
oil is proreservoirs,
ranging
in age from

to Pleistocene.
productive

from

rocks.

Sandstones
Many

reservoirs

of some water

Trace
20
2
10
Trace
10
Trace
10
2
30

Trace
1,750
80
700
Trace
500
5
780
40
2,500

1.001
1.149
1.010
1.101
1.007
1.115
1.004
1.159
1.059
1.219

475
191,580
18,832
132,110
9,825
148,090
5,810
206,430
51,552
318,630

U.S. Gulf Coast. For many years since the Spindletop

dome was discovered
in 1901, copious quantities of oil
have been produced
mations

from

on the flanks,

Tertiary

and Quaternary

in the caprock,

for-

and in structures

abovle the capmck of massive salt domes. usually considered intrusive in nature. During recent years. offshore
drilling

has focused

attention

on drilling

oft the coasts of

Louisiana and Texas. Some waters produced from gulf

coast fields are quite fresh; others have concentrations
of
dissolved
salts as high
as 170.000
nngit,
(Table
24.5). 4L44

arc

is by no means as

concentrated as that from reservoirs in many other areas.

especially
the midcontincnt.
Table
24.4
gives
the
characteristics
fields, JO.41

and sands are the

of the formations

and much folding and faulting are

mineralized
water produced
with

California

TDS
O-ML)

10
690
910
3,320
50
3.200

the Big In.jun and Berea sands have been traced across
wide areas. The oil-producing
states included in the Appalachian area from which analyses were available arc
Kentucky,

Br

628:
60
230
120
250

Trace
300
0
540
IO
1,500
10
870
20
760

Cl

SO,

Specific
Gravity
60/600

0
630
ND
ND
ND
ND

(mg/L)

(continued)

produced

from

California

Illinois Basin. The Illinois

halves
linois
from

by the LaSallc
and southwestern

Indiana.

principally

Oil

from

is produced

here
and

Mississippian
sandstones and. to a smaller extent.
limestones.
TDS in the produced
waters range

from
from

I.000

fields,

roughly into
much of II-

Pennsylvanian

about

many

basin. divided
anticline.
comprises

to more than 160,000

mg/L

(Table

24.6).j5

PETROLEUM ENGINEERING

24-a

TABLE 24.4-CHARACTERISTICS

OF SOME WATERS PRODUCED FROM CALIFORNIA

System

Formation

17

Tertiary

Coalinga

1,104 to 1,916

10

Tertiary

Midway

1,495 to 3,250

Tertiary

Sunset

2,270 to 3,550

Tertiary

Kern River

Tertiary

Lost Hills

26

Tertiary

Maricopa

18

Tertiary

Zone A

TDS
Ca

Mg
10
340
IO
690
20
570

40
3,290
910
13,250
3,650
11,650

50
480
0
360
0
90

20
10
200
220
200
2,900
10
80

20
10
140
230
10
1,300
3
140

1,550
50
4,770
7,640
1,300
15,015
2,050
7,090

3900
150
460
0
510
0
340

7:
0
0
4
1,020
1,700
3,900

For purposes

associated

oil productive
of all oil-productive

of this section,

Cl

so,

FwU

90
2,520
1,010
23,550
4,360
21,420
10
60
7,740
11,950
1,170
27,100
1,300
9,560

190
7.260
10
1,380
5
40
0
20
20
630
2
110
90

580
14,640
2,140
42,120
8,145
39,320
80
2,130
13,020
21,120
2,686
47,995
5,064
21,200

value fornumber of analysesndlcated '+I'

Area. The midcontinent

areas in the U.S.

--z390
20
2,890
60
1,280

400 to 3,000
-

geographically

Na

HCO,
180
360
180
360
50
4,270

'Upper ligurein each column IS m~n~murn value and lower figureIS maximum

area is the largest

FIELDS

Constituents (mg/L)

Subsurface
Depth
(fi)

Number of
Analyses

Midcontinent

HANDBOOK

mian,

it is con-

waters

also are produced

Pennsylvanian,

duced waters from

and

Rocky

from

Jurassic,

Per-

rocks.

Pro-

Mississippian

Mt.

fields have comparatively

sidered to include Arkansas,

Kansas. northern
Louisiana, Missouri,
Nebraska, Oklahoma.
and all of Texas
except the gulf coast fields.

low concentrations
of dissolved
salts and often
characterized
by comparatively
high concentrations

are
of

bicarbonate.

the

Oil and associated brines are produced

from many
sandstones and limestones, as well as from other types of

characteristics
of some waters produced from Rocky Mt.
fields of Colorado,
Montana,
and Wyoming. 55m5y

formations,

in geologic

systems

ranging

from

of

concentration

of

dissolved

salts,

from

little

more than 1,000 to more than 350.000

mg/L.
Tables
24.7 through 24.9 present the characteristics
of some
produced waters from the midcontinent
Oklahoma,
and Texas.36-

Rocky Mt. Area. Petroleum

fields of Kansas,

rocks of the Cretaceous

is produced

system,

in Colorado,

although

TABLE 24.5-CHARACTERISTICS

of

Analyses'
42

Terilary

oil-productive
areas in Canada
are the lower Ontario Peninsula,
where oil is produced
from rocks ranging from Ordovician
to Devonian
age,

and

the

western

Fno
Norm

oil and

Alberta,

Sas-

salts, others are quite concentrated.

Tables 24.12 and
24. I3 present the characteristics
of some waters from
Canadian fields in Alberta,
Manitoba,
and Saskatchewan, hObh5

Constituents
Ca

u9
2,579 to 11 400

Coastal
Creek

40610

Oligocene

Goose

Upper

Humble

775 to

Oligocene

Damon Mound

250to

Pliocene-Miocene

Barber HIII Dome

(mg/L)

Mg

1 100

50

1.305 to 3.296

Na

HCO,
30

Powell-Mexla

so,

Cl

990

110

10

2.240
40.600
60

230

30

1.330

770

160

3,800

70

120

18,200

400

3.180
69.100

20
2.130
6.300

TDS
(m9L)
5 700
116900

353
4 500
10,860

210

33.700

54480

3.600

Trace

61.000

1.750

6.100
105000

171.300

6.700

270

40.800

principally

Depth

Eocene

provinces,

katchewan,
and the Northwest
Territories.
Reservoir
rocks in western Canada range in age from Devonian to

1,000
5

give

OF SOME WATERS PRODUCED FROM GULF COAST FIELDS (TEXAS)

FormatIon
or field

System

24.11

Canada. The principal

Subsurface
Number

and

Cretaceous. Although
many of the waters produced with
petroleum
have quite low concentrations
of dissolved

Montana. New Mexico,

Utah, and Wyoming
from many
fields in the Rocky Mt. area. The principal production
is
from

24.10

the Cam-

brian through the Upper Crctaceous.

Waters produced
with petroleum
from midcontinent
fields have a wide
range

Tables

3.010

340

70

30

550

4.460

30

12.730

240

16
230
10
210

11 300
63400
110
610
6.700
21 600

10.470
18.900
109.990

570
1.710
11.490
36400

24-9

PROPERTIES OF PRODUCED WATERS

TABLE 24.6-CHARACTERISTICS

OF SOME WATERS PRODUCED FROM ILLINOIS FIELDS

Constituents (mg/L)

Subsurface
Number

Formatton

of

12

57

M~ss~ss~pp~an

17
134

Trenton

Mwssipplan

figure

in each

Venezuela.

column

The

Venezuela
limestones.

1.200

640

22.660

30

2.970

1.020

32.220

390

1.125

960

IO

240

2,596

6.020

1.730

42.810

IS minimum

value

principal

productive

concentrations

510

3.970

10

10

25 800

47.900

1.660

83 200
82 400

50

40

340

20

3.840
30

7.500

1.830

41.830

960

1.350

IS ma~~rnum

value

formations

in

of dissolved

1.900

3.460

47.660

for number

of analyses

Indicated

oilfield

waters

determine

their

dissolved

major

constituents

analyze

tification.
log evaluation,
tal impact, geochemical

oilfield

inorganic

usually

waters

to

constituents.

are sodium,

magnesium,
chloride,
bicarbonate,
analytical
data are used in studies

calcium,

and

calcium,

and sulfate.
such as water

water treatment, environmenexploration,

and recovery
of

and anions

The major anion

The

major

TABLE 24.7-CHARACTERISTICS

Most

oilfield

in most

Kansas

C~fy Lansmg

1.228 lo 3.409

Ordovlclan

WllCOX

3.500

123

Ordowaan

Arbuckle

2.750

lo 3 770

76

Ordoviaan

VIOla

2091

lo 4 14,

27

Pennsylvania

Bartlesvllle

20

Mississippian

Mississippian

1010

to 4 679

Basal

Conglomerate

3320

to 3469

Chat

2697f0

Pennsylvaman

24

PWlSlWllX

12

SllUrlan

10

Basal

9
12

Upper

fqure

to 3 800

625 to 3 200

3 365

HlO

2 390 to 2 893

Gorham

33ooto

Pennsylanlan

PrUe

1 032 to 2.400

Cambraan

Reagan

3175f03609

Pennsylvanian

I each

column

IS mlnimum

value and lower

hgure

3 854

IO

waters

mg/L

of

silicon,

ca
2 040
16 DO0
790
14400
700
19 BOO
620
11 000
420
12 100
560
12 900
1 000
8 480
3.120
13480
230
5 220
920
3 960
2.310
11 300
1 390
5 250

IS maximum

waters

can range from

is chloride.
less than

The

10,000

waters contain

blq

N.3

Ba

840
3 950
5.560
68500
240
10.900
230
3.110
1EO
3,480
220
2.660
360
2.000
640
1.950
90
1.460
280
1.030
720
2.610
310
1.370

16940
77.000
10800
142,500
6 820
34 450
5240
52000
7550
69.800
9 150
59300
11 600
47.000
24400
66,500
3610
36600
6 560
17100
14300
68 700
9 300
43000

4
70
0
0
0
0
0
0
0
10
0
20
0
0
0
0
0
3
0
10
0
10
0
0

value for number

bromide

and iodide.

The

of these anions range from less than 50 to

Constituents

Depth
tft)

Formamn

oilfield

lead, manganese,

in most oilfield

for bromide

OF SOME WATERS PRODUCED FROM MID-CONTINENT

Subsurface

System

of

to more than 200,000

mg/L.
There are exceptions
to
some Venezuelan
oilfield
waters contain
this-e.g.,
more bicarbonate than chloride.

in oilfield

cations

iron,

concentration

more than 6.000 mg/L

of some constituents.

Some

excess

Anions
chloride

cations

barium.

zinc, 26.70.71

tion

Pennsylvanian

and magnesium.

and from less than I .OOO mg/L

me/L
for
calcium
and/or

in

ammonium,

concentrations

87

167.940

The
iden-

26

of various

and

concentrations

waters can cause solubility,

acidity,
and redox (Eh)
potential changes as well as the precipitation
and adsotp-

Number01
Analyses

25 600

14000
95 400

of these ions can range from less than

lithium,

contain
aluminum,

Cations
The presence

are sodium,

680
135870

10.000 mg/L for sodium,

to more
than
30,000

strontium,
often

minerals.

2.990

31 140
143.940

200

30

1.470

The concentrations

salts

20

8.740

910

16.430

i 28 590

Other cations that often are present in oilfield waters in

concentrations
greater than 10 mg/L
are potassium,

companies

valuable

76 000

1,660

to 3.519

62 930

700

0
980

magnesium.

Petroleum
major

93 920

840

Inorganic Constituents

The

62.830

56 700

6.600

are Tertiary
sandstones
and Cretaceous
In general. the various waters produced with

petroleum
have low
(Table 24. 14).66m69

20
1.050

(mglL)

38 300

1.045

1.104

and lower llgure

0
1 620

2.960
672 to 4,000

St Geneweve

Cl

so,

HCO_,

1.994

Cypress

Ordowclan

Na

MC!

2 437
Tar Springs

M~ss~ss~pp~an

TDS
Ca

(N

Wallersbura

Misswloolan

18

Upper

of field

System

Analyses

Depth

HCO,

of analyses

5
450
20
530
50
640
IO
650
10
520
30
670
0
180
30
130
70
480
160
840
20
330
80
410

FIELDS (KANSAS)
Speclflc

(nq/L)

so,
0
2 160
80
300
0
2 700
20
1180
1
750
0
3540
0
700
0
2.200
100
1,230
40
3.010
0
50
30
2,570

Ind~caled

and from less than IO

%+

Cl

Br

34.100
158.800
10,870
142600
12.300
79200
330
112.700
12.600
141 200
14.400
122000
20.700
58,300
42,700
137700
5,300
68.400
11.300
36,000
28.000
138.900
14,700
76,900

2.
15
Trace
3
0
Trace
0
10
2
10
1
60
0
Trace
2
3
0
2
0
0
0
0
NO
ND

-~ 30
400
80
x50Trace
60
5
90
20
200
2
3
200
400
10
420
10
70
5
10
0
0
ND
ND

Gravely
(60160~)
1040
1 159
1015
1140
,014
1 091
1012
1116
1016
1 141
,017
1140
1023
1 105
1 088
1143
1007
1075
1019
,045
1033
1 139
,021
1088

TDS
(mg,L)
53.959
256.830
28.120
369.180
20.180
145.060
6,455
160.740
20.782
224.870
24.363
201.153
33.850
116.660
70,902
222,383
9.410
113.460
19.265
58,940
45.350
221.900
26.810
126.930

PETROLEUM

24-10

TABLE 24.8-CHARACTERISTICS

OF SOME WATERS PRODUCED FROM MID-CONTINENT

Subsurlace

Number

System
PennsylvanEln

75

Formaflon
Bartlesvllle

ut1
4.489 to 5,524

94

Ordovlclan

WllCOX

3,436 to 7.233

25

Pennsyfvanlan

Layton

1,240 10 4.800

28

Ordovua"

Atbuckle

542 to 6.094

-~Ca

Mg

Ba ~--~
HCO,

Na

1.900
19000
6.800

910
2.740
1.400

18500
5.300
18900
2.200

3300
1,800
4.300

730
0

300
20

I390
0

144.000
91.300

1 175
1 103

39.010
251 460
147.820

80.230
31.300
79.000
14,000

130
0
380
0

160
10
80
0

720
0
510
0

163.000
34,900
160.000

1170
1075
1179

266.010
73.310
263.170

33,000
127.000
65,000

50,100
214.140
105 701

900
2,700

4,600
11.900

1.400
4.300

63.800
34.600
51.500

110
1
20

850
0

1.880
0

310

1.130
0

113.500

1.034
1 147
1073
1 130

81.600

1.091

200

115.000
84.200
157.000
55,400
156,000

I 129
1095
1 173

132,016
189,120
136.212
254440

1.066
1 173

90,690
250,640

29.800
121.000

1.039
1 134

50.900
140.000

1059
1.159

49.730
204.320
82.100
233.042

64,100
139.000
90,000
117,000

1075
1157
1.103
1.131

8,200
142,000
101.000
149,000

1012
1155
1115
1 164

4,400
122,000
86.300

1005
1137
1 110
1 158
1022

40
130

142.000
18.600
63,600
132,800

370
15
260

156.200
99,300
149.000

40
760
0

45,500
108.000

12

Pennsylvanian

Burgess

1,800 to 2,490

5,900

2.000

42.500

15

22

M~ss~ss~pp~an

Mississippi

1,837 lo 4.872

13.300
6400

2.600
2000

Mlssisslpplan

Mlsener

3.927 10 5.977

29,500
76.000

0
10

120
10
80
30
110

I7

Pennsylvaman

Pennsylvanian

1.258 to 6.025

10

Ordowan

Slmpso"

1.213 lo 6.495

2,500
1.100
3.200
600
3.100
1.200
3,000

200
2
30

18

22,400
4.600
18.400
1 700
15.800
5.600
17,600

57.700
43,600
72.000

17,600
61.300
24.400
71,900

10
280
0
2

0
110

22

Pennsylvania"

Skinner

1,030 to 4.567

22

Pennsylvama

Booth

1.876 to 2 300

6.200
18.700
6600
12700

1.500
3.200
1,500
2.500

22

Siluro-Devontan

Hunton

3.197 lo 5,021

300
28.900
9.700
19.600

80
4,300
1.700
2.600

31,700
67,400
42,500
56,500
4.000

0
IO
0
240
0

IO
130
5
140
15

75.900
42,800
71.700

170
5
220

660
3
170
40
940
50

27

Pennsylvania

Red Fork

2.403 to 4.650

12

Ordowclan

VIola

3.458 to 5.004

200
16000

60
2,400

2900
62,000

0
10

20

Pennsyfvan,an

Prue

2.267 to 3.587

8.500

1.300

11,700
740
7.300
14.000

3.100
230
2,900
2.200

43,400
72,900
10800
27,900

5
20
0
50

17.400
10,900
20.000
5.500
13.900
700

3.100
1,800
3.500

15

Pennsylvanian

Tonkawa

2 417 to 3,254

24

Pennsylvanian

Burbank

790 to 5.000

15

Pennsylvanian

Dutcher

1.882 to 3.218

14

Ordowuan

Bromide

2.173 to 7,569

22.400

TABLE 24.9-CHARACTERISTICS

Number of
Analyses
North-Central
33
El
7
13

System

Formation

24 100

18.800
1.48070 5430

982 to 3.163

23800

76400
43200
69,000
32.000
54700
11 500

900
2.000
400
3.500

5
2
40
0
10
10

80500

20
90

120
20
380
0
50
20
133
50
130

450

24
430
60
1.920
0
2,750
0
440
30
450
0
680
0
7.010
0
370
0
980
30
480
2

920

19,500
167,000

OF SOME WATERS PRODUCED FROM MID-CONTINENT

Subsurface
Depth
(ft)

1031

TDS
(mg/L)

12,100

Cromwell

Healdion

Grady
(60/600)

Cl

83.800
48.300

Pennsylvanian

Pennsylvanian

Speclflc
_~

SO,

I9

13

HANDBOOK

FIELDS (OKLAHOMA)

Constituents (mg/L)

Depth

of

Analyses

ENGINEERING

Constituents
Ca

Mg

Na

_
Cl

so4

1 109
1 163

103,540
228.890
141.050
189.760
11.995
258.948
155.208
243.660
7.600
204.330
139.885
230,320
30.392
102,170
172.930
253,525

1073
1 122
1024

155,235
241.930
86.900
179,500
32,110

1 183

275,270

FIELDS (TEXAS)

(mg/L)

HCO,

1076
1 160
1 171

182,660

Specific
Grawty
(60~160~)

TDS
(m9Q

Texas 50-52
20

530

460

ND

10,700

2.450

48.200

61;

690

97,900

ND

1,884 !O 2,081

14,400

2,440

58,300

300

122,200

ND

197,640

2.860
2,030

66,800

520

139,800

ND

226.680

2.540 to 2,668

16.700
10.200

52,500

630

106,000

ND

171,360

13,800

2,440

61,000

10

740

119,000

ND

196,990

3.100

370

32.100

130

250

57.500

ND

93,450

7,900

600

62,900

410

370

112,500

ND

184.680

Upper Pennsylvanian
Upper Pennsylvaman
Upper

Pennsylvanian

Upper Cretaceous

Dyson
Landreth
Woodbine

3.844 to 4.446

1,017
160,550

North and West Texas5354

21
35
47
56
50
42

Pennsylvanian
Pennsylvanian
Cambro-Ordovcian

Pennsylvanian
Permian
Permian

Cisco
Canyon
Ellenberger
Straw

700 IO 1.950
2.200 IO 7.000
3,800 to 8.370
1,700 to 6,900

San Andres
Big Lime

500

160

6.030

IO

10.000

1.015

16,700

23,100

3,000

60,400

180

400

134,000

1.157

221,080

1044

2.200

640

15,700

10

40

31,400

14.000

2,300

57,100

650

4,840

109,500

1 145

50,010
188,390

1.700

350

12,000

20

25,300

1.035

39,374

22.300

2,850

55.700

1,840

2.140

130,500

1 173

214,330

1.105

112,414

1212

262,320

3,200

810

25,500

82,900

21.300

3,500

74,300

710

710

161,800

740

310

4.400

210

350

19.800

7,900

67.000

1.840

4,900

19,000

1.033

25,010

140,500

1 154

241,940

ND
ND

356.600

250

200

210

160

890

9.800

3,700

122,500

8,600

212,000

1,710

PROPERTIES

OF

PRODUCED

WATERS

24-11

TABLE 24.10-CHARACTERISTICS

OF SOME WATERS PRODUCED FROM ROCKY MOUNTAIN FIELDS

(COLORADO AND MONTANA)
Constrtuents (mg/L)

Subsurface
Number

Depth

of
System

Analyses

(ft)

TDS

Ca

NC3

Mg

co3

HCO3

Cl

so,

ml/L)

Colorado5ss6
7

Dakota

Cretaceous

2.819 to 5.830

1,180
Frontrer

Cretaceous

Eocene

6
4

2,230 to 5.283

Wasatch
Morrtson

Jurasw
Jurassrc

1,230 IO 3.464

3,020 to 4.395
4,564 lo 6,263

Sundance

310

210

40

40

560

13,000

160

3,600

890

22,100

41,220

820

340

820

1,980

190

70

8,200

240

4.900

90

12.800

26.490

30

40

1,800

120

20

2,000

3.990

900

410

10,600

150

2,000

870

18,900

33,830

1,400

540

160

260

2.360

80

30

3,600

120

3,350

980

5,000

13,160

1,070

200

260

1,530

380

80

5,250

3,030

1,040

8,060

17.840

3.900

Montana5s-s7

Upper

10
11

Cretaceous

Lower

Cretaceous

Upper

55

Jurasw

25

Colorado

Kootenar
HIS

Quadrant

Pennsylvanian

22

Montana

Jurassic

Upper

MIssIssippian

Tensleep

Lower

Missrssippian

Madison

TABLE 24.11-CHARACTERISTICS

140

10

4,050

100

70

220

2,000

1,850

5,530

9,770

710

260

280

1,250

130

120

6,200

1,400

8,800

16,900

260

500

90

60

4.670

4,900

24
35
45
50
14
22

5
60
20
50

790
16.010

1.110

1,670

370

3,150

80

3,140

4,040

820

2.890

11,060

60

trace

30

150

1,310

10

1.560

1,390

400

5.540

440

8,470

700

20

220

trace

10

250

500

430

2,330

4,830

2,110

2,790

12,990

OF SOME WATERS PRODUCED FROM ROCKY MT. FIELDS (WYOMING)

Constttuents (mg/L)

Depth
System
Cretaceous
Cretaceous
Cretaceous
Cretaceous
Jurassrc
Jurasstc

Formatron

900 to 1,300

Shannon
Frontier

1,000 to 3.080

First Wall Creek

Second
Cleverly
Dakota

(4

Wall Creek
1,400 to 1.500
4,050 to 4.505

TDS
Ca

Jurasstc
Jurassrc
Jurassic
Permian
Pennsylvaman

19

Mississippian

20

Triassic

Dakota

4,353 to 8.500

Greybull

Sundance

Embar
Tensleep

Madtson

Mmnelusa

Na

Mg
10

10

CO,

410

250

330

trace

trace

550

130

20,000

220

5,560

HCO,

trace

Cl

so,

280

1,900

3,710

trace

1,270

trace

1,050

7,800

240

230

@WLl

20

7,670

730
19.650

70

1,890

27,900

57.340

trace

trace

200

trace

1,000

trace

220

1,420

30

100

5,320

320

5.460

60

5,940

17.230

trace

trace

1,740

trace

890

trace

1,170

3,800

40

10

7,000

590

880

6,600

22.070

trace

trace

1,040

trace

110

20

6,210

300

trace

trace

180

160

13,000

230
24

10
6.000

90
680

of

Analvses

0
290

trace

Subsurface
Number

250

trace

6.950
110

150

1,300

2,290

110

7,590

16,630

230

20

20

450

6,900

980

19,200

40,750

trace

1.000

trace

110

1,740

380

3.680

60

1,930

11.730

280

trace

trace

630

60

60

5.560

irace

trace

180

480

60

40

760

40

trace

430

60

980

820

90

2.420

520

410

40

140

1.110

400

60

6,800

330

6.850

5,880

7,700

28,020

140

30

140

210

190

10

620

630

220

5,170

1.690

5,790

3,930

17,430

40

10

30

10

98

720

250

790

10

1,000

2,500

1,080

6,350

20

trace

20

trace

20

50

114

870

180

580

20

1,080

1,940

1,070

5.740

250

50

630

190

1,930

250

3,300

450

60

1,670

550

3,870

610

7,210

PETROLEUM

24-12

TABLE 24.12-CHARACTERISTICS
Number of
AllalySeS

OF SOME WATERS PRODUCED FROM CANADIAN

Subsurface
Depth
ml

Formalton

System

ENGINEERING

Constltenls
Ca

Mg

10
50
70
620
5
1.250
-

215 10 1,890
1.670 10 2 072
2 706 10 2,744

Na

10
10
20
230
60
190
-

CO,

660
3.000
6400
19.000
1 030
9.100

SO,

320
790
580
640
180
1250

Cl

5
600
20
40
0
2500

200
4.500
6.400
29.200
670
11.000

980
67 340
240
2.000
550
1 400

1.570 to 3 323
to 2 942

3.000

lo 3 422

850
44.900
4.900
81.400
21.300
72.800

0
40
0
30
0
80

100
2.140
110
360
80
780

1 000
4,600
900
4.900
3900
4.300

870 to 2 060
1,322 lo 2 553
2516fO4604
1.698 to 3 717

more

to

than 1,400 mg/L

tration

is important

oilfield

brine

for iodide. 26 Bromide

in determining

and is an important

constituent.

Bicarbonate

many

waters.

from

oilfield

and

Their

borate,

carbonate,

100 mg/L

sulfate

fluoride,
Boron

can affect electric

an

can

hydroxide,

in

compressibility

This is expressed

organic

acid

27

System

log deflections.

26

Cretaceous

Blafrmore

This

Ca

(W
998 to 3,713

Shaunavon

3,205 to 3.413

Gravelbourg

3.290 to 4.175

sechon.

Mg

3,700 to 5,785

12

Devonian

Ntsku

4,682 to 6,927

Devonian

Duperow

2,253 to 4,024

11

MissIssippIan

Mississippian

4,487 to 5,665

Mississippian

Lodgepole

2.305 to 4,470

T,

_.

_.

(la)

except

for the pH and Eh, was writlen

by Howard

Na

CO,

870

20,300

FIELDS, PROVINCE OF SASKATCHEWAN

HCO,

Spectffc
Gravrty
SO,

190
80

B Bradley

1,300

Cl
-

(60/600)

TDS
(ma/L)

2.800

1 000

6,190

38,900
890

1.048
1.007

67,250
12.250

8,800

190

230

t2,400

300

3,100

t 3,800

1.014

31.580

470

220

11,700

140

270

14,500

1 022

27.300

620

370

t2.900

350

2,100

20,100

1.026

36.440

100

130

760

60

280

1.001

73.700

440

3,200

155,000

1 093

1,000

200

Trace

640

1 002

2.770

73,000

2,350

2,500

142,800

1 186

242.600

170
900

170

100

7.100

3,100

740

190

14,100

7.150

680

1.330
242.540

940

100

2,200

700

t ,002

4,790

17.700

860

5,000

31,100

1.040

64,560

trace

4,300

120

340

5,700

1.004

10.460

5,600

1,600

71,000

110

850

3,900

123,800

1 150

206,860

730

90

1,400

480

3,400

580

1.004

6,680

2.800

610

27,000

600

3,900

45,700

1 061

80,610

trace

trace

1,100

70

2,100

1.002

3,270

190

100

9,300

2,600

790

12,700

1.014

25,680

40

190

4,800

1.012

5,030

1,100

1,200

69,100

1,580

2,400

111.000

1.160

185,380

trace

trace

4,300

290

2,800

1.002

7,390

8,100

160

10,900

1,320

3,600

15,400

1.029

39,480

of analyses

mdlcafed

trace

Lower
Cretaceous

2,395 to 3,026

Viking

Devonian

Devonian

3,356 to 6,605

Jurassic

Jurassfc shale

3,105 to 4,325

Upper

as

3,500
2,100

9,000

11

at pressures

av

trace ~ trace 2,200x----

1,850

Mfssron Canyon

water

Constituents (mg/L)

2,300

25

formation

mathematically

OF SOME WATERS PRODUCED FROM CANADIAN

Formatron

3.940
150 380
14.150
248.990
62 930
203 880
3 150
25 680
1 840
25 780
16.120
290.070
26 760
264,300

v ( ap >

Depth

Analyses

of

(',,. = --

in excess of

of

1010
,089
1016
1157
1031
1136
1 004
1 033
1 002
1 025
1 025
1180
1 026
1176

arsenate,

Subsurface
Number

~
~
-

1 205
9,030
13.510
64.160
2.145
25.700
-

above the bubblepoint

is defined as the change in water
volume per unit water volume per psi change in pressure.

range

concentrations

TABLE 24.13-CHARACTERISTICS

The

per liter.

waters include

850
94,900
7.000
149.600
34 900
120 700
740
31 200
530
8.800
7.900
173.500
14.300
154 900

ND
ND
1010
1 060
1 006
1 032
~
-

Compressibility

marker

are present

milligrams

in oilfield

salts, and phosphates.

geochemical

of

ND
ND
10
620
ND
ND
10
460
20
220
90
110
200
1.500

Physical Properties of Oilfield Waters*

concen-

origin

concentrations

none to several thousand

Other anions found

the

Specllic
GLWy
TDS
~60/60l
(mg/L)

Br

ND
NO
10
40
ND
ND
0
20
2
20
3
10
2
20

2.200

FIELDS

(mJ/L,

HCO,

0
80
0
60
0
410

HANDBOOK

ftgure

tn each

column

IS mmmum

value

and lower

figure

is maxmum

value far number

65

PROPERTIES

OF

PRODUCED

WATERS

24-l 3

TABLE 24.14-CHARACTERISTICS
Number

OF SOME WATERS PRODUCED FROM VENEZUELAN

Constituents (mg/L)

of

Analyses

Formation

System
Tertiary

or Fteld

Ca
-170

Zeta (Quiriquire)

Mg

330
7

Eta (Quiriquire)

Tertiary

Cabtmas

Tertiary

field,

La Rosa
7

FIELDS

CO,

HCO,

TDS
Cl

SO,

(mglL)

100

~ 1,750

3,050

1,910

7,190

270

5.150

5.400

10

5,420

16,260

70

50

2:040

3;050

710

6,900

400

300

12,360

7.410

30

11 ,170

36,500

60

60

1,740

2,010

1,780

5,643

10

60

2,000

120

5,260

90

5,260

40

60

4,610

6,250

3,700

14,657

30

20

1,800

100

3,570

690

6.210

50

20

4,700

1,900

30

6,250

12,955

30

20

6,000

80

1,230

8,550

15.911

30

50

2,660

1,130

3,450

7,320

30

40

3,000

1,130

1,260

5,460

150

50

9,000

2,440

9,000

20,640

formation

Lagunillas field,

Cretaceous

Na

lceota formatlon
Bachaquero

Tertiary

Pueblo
8

Mene

Tertiary

field,
Viejo main

Grande

Pauji and
7

Punta
8

Gorda

La Paz

Cretaceous

sands

and deeper

sands

formation

S. El Mene

Cretaceous

field.

field,

Guasare
10

field,
Mason-Trujillo range

La Conception

Tertiary

sandstone

field,

El Salto formation
11

Oficma

Tertiary

and W. Guard

ftelds

OF,

sand

50

20

1,260

2,330

140

640

4,424

AB,

sand

40

30

1,360

2,780

60

560

4,830

40

30

3,080

1,100

130

4,230

8,520

40

60

4,000

1,430

5,500

11,030

140

70

7,900

3,500

150

10,500

22,260

70

70

8,400

2,050

10

12,090

22,690

L, sand

160

100

7,300

4,420

trace

9,260

21,240

M sand

110

30

7,700

2,100

20

10,900

20,860

P sand

140

80

7,800

970

11,600

20,590

S sand

330

80

8,600

1,700

100

13,050

23,860

U sand

940

180

11,800

1,100

19,800

33,820

D,

sand

Du and Eu sands
F, sand
H sand

Upper

tlgure

I each

column

1s minimum

value

and lower figure

IS maximum

value

or
1

v*--v,

T,=-

,
v ( PI--P2

. . . .. . .. .... . .

>

. . . . . . . (lb)

for number

ot analyses

mdlcated

solution on compressibility
of water with NaCl concentrations up to 200 g/cm3 is essentially negligible.
Osifs
results show no effect at gas/water ratios (GWRs) of 13
scf/bbl,

at GWRs

certainly

no

more

of 35 scf/bbl
than

a 5%

pressibility
of brine.
Laboratory
measurements

01

c,.=

Bw2 -B,I
B,.(p,
-p2),

...

...

...

resulted

probably

74 of water

in linear plots of the reciprocal

ty vs. pressure.

no effect,

increase

in

the

but
com-

compressibility
of compressibili-

The plots of l/c,

vs. p have a slope of
linear in salinity
and temperature.

m r , and intercepts
where
CkV = water compressibility
and temperature,

at the given

pressure

bbl/bbl-psi,

within the
-cw = average water compressibility
given pressure and temperature interval,
bbl/bbl-psi,
V = water

volume

temperature,
V = average
vals,

water

at the given

pressure

and

bbl,
volume

at conditions

B,,, and
B4 = water FVF p I and ~2, bbl/bbl, and
B,. = average water FVF corresponding
to V,
bbhbbl.
In an oil reservoir, water compressibility
also depends
on the salinity.
In contrast to the literature,
laboratory
measurements
by Osif 74 show that the effect of gas in

(2)

cw = water compressibility,
p = pressure, psi,
g/L

T = temperature,
ml

psi,

no gas in

where

p and T inter-

1 and 2 with p r >pz,

tested containing

l/c~,=m~p+m~C+m~T+m4,

C = salinity,
within

bbl,

PI and
p2 = pressure

Data points for the systems

solution resulted in Eq. 2.

psi - ,

of solution,
F,

= 7.033,

m2 = 541.5,
lfl3 = -531,

and

m4 = 403.3 X 103.
Eq. 2 was fit for pressures
psi, salinities

between

of 0 to 200 g NaClIL,

1,000

and 20,000

and temperatures

from 200 to 270F. Compressibilities

were independent
of dissolved gas.
Where conditions
overlap,
the agreement
with the
results reported by both Dorsey 75 and Dotson and Standing 76 is very good. Results from the Rowe and Chou

PETROLEUM

24-14

Fig. 24.4-Specific
psia.

gravity of salt solutrons at 60F and 14.7

equation agree well up to 5.000 psi (their upper pressure

limit)
but result in larger deviations
with increasing
pressure.

In almost

pressibilities

all cases, the Rowe and Chou com-

most

of formation water is a function of pressure,

and dissolved constituents.
It is determined

accurately

in the laboratory
on a representative
water densample of formation water. I7 The formation
sity is defined as the mass of the formation water per unit
volume

of the formation
density
in metric

water. For engineering

purunits (g/cm)
is considered

posts,
equal to specific
ing
calculations

gravity.
Therefore,
for most engineerdensity
and specific
gravity
are

interchangeable.

When laboratory data are not available,

the density of
fomration
water at reservoir conditions can be estimated
(usually to within & 10%) from correlations
(Figs. 24.4
through

24.6).

The only field data necessary are the den-

sity at standard

conditions,

which

the salt content

by use of Fig. 24.4.

can be obtained
The salt content

be estimated

from

NaCl

the

solutions

formation

at

HANDBOOK

14.7

resistivity

psia

vs.

(obtained

from electric log measurements) by use of Fig. 49.3 (see

Chap. 49). The density of formation
water at reservoir
conditions

are less than that of Eq. 2.

Density
The density
temperature.

Fig. 24.5-Density
of
temperature.

ENGINEERING

can be calculated

in four steps.

I. Using the temperature

and density
pressure, obtain the equivalent
weight
from Fig. 24.5.
2. Assuming
mains constant.

at atmospheric
percent NaCl

the equivalent
weight percent NaCl reextrapolate
the weight percent to reser-

voir temperature

and read the new density.

3. Knowing

the density

at atmospheric

pressure

and

reservoir temperature,
use Fig. 24.6 to find the increase
in specific gravity (density) when compressed to reservoir pressure.
blepoint,

Note that for oil reservoirs

the

saturated-with-gas

below

curves

the bub-

should

be

used; for water considered to have no solution gas, the

no-gas-in-solution
curves
should
be used. These
curves were computed
from data given by Ashby and
Hawkins.
4. The density

of formation

water (g/cm)

from

conditions

is the sum of the values read frotn

can

and 24.6.

They

can be added directly

at reservoir
Figs. 24.5

since the metric

PROPERTIES OF PRODUCED WATERS

units are referred

to the common

24-15

density

base of water (1

g/cm3).
The metric units can be changed to customary
units (1 bmicu ft) by multiplying
by 62.37.
Also the specific gravity
of formation
water can be
estimated if the dissolved solids are known. The equation is
y,*>=1+c,~xo.695x10-6,
where

Csd

is

the

. . . . I..

concentration

(mgfL).
For precise but very detailed

of

.(3)

dissolved

calculations,

solids

the reader is

referred to a recent paper by Rogers and Pitzer. 79 They

tabulated a large number of values of compressibility,
expansivity
and
specific
volume
vs.
molality ,
temperature,

and pressure.

A semiempirical

equation

of

the same type found to be effective in describing thermal

properties
of NaCl (0.1 to 5 molality)
was used to
reproduce the volumetric
data from 0 to 300C and I to
1,000 bars.

Formation Volume Factor (FVF)

The water FVF, II,., is defined as the volume at reservoir conditions
occupied by 1 STB of formation
water
plus its dissolved

gas. It represents

the change in volume

of the formation water as it moves from reservoir conditions to surface conditions.

Three effects are involved:
the liberation of gas from water as pressure is reduced,
the expansion
shrinkage

of water

of water

The water FVF

as pressure

as temperature

is reduced.

and the

is reduced.

also depends on pressure.

Fig. 24.7 is

Fig. 24.6--Specific

gravity increase with pressure--salt

a typical plot of water FVF as a function of pressure. As

the pressure is decreased to the bubblepoint,
ph. the FVF
increases as the liquid expands. At pressures below the
bubblepoint.
gas is liberated, but in most cases the FVF
still

will

increase

resulting

from

because

the shrinkage

gas liberation

of the water

is insufficient

to counter-

balance the expansion of the liquid. This is the effect

the small solubility
of natural gas in water.

of

The most accurate method of obtaining

the FVF is
from laboratory data. It also can be calculated from density correlations
accounted

if the effects

for properly.

of solution

The following

gas have been

equation

to estimate
B,,. if solution
gas is included
laboratory measurement or correlation
of P,.~:

H,,=L,..
VW

is used
in

. .

the

(4)

P r

where

V,. = volume

occupied

conditions

(weight

dissolved

in water

at reservoir

conditions

V,,. = volume
= density
= density

conditions,

pb
PRESSURE, PSI A

or standard

cu ft,

cu ft,
conditions,

ft, and

of water at reservoir

lbmicu

at

of gas

by a unit mass of water at

of water at standard

lbmicu
prc.

is negligible),

occupied

standard
p,(.

by a unit mass of water

reservoir

conditions,

ft.

The density correlations

and the methods
P,,~ and prc. were described previously.

of estimating

Fig. 24.7-Typical

plot of water FVF vs. pressure

water

PETROLEUM

24-16

The FVF of water can be less than one if the increase

in volume

resulting

from

dissolved

gas is not

great

enough to overcome the decrease in volume caused by

increased pressure. The value of FVF is seldom higher
than I .06.

tent on the viscosity of water. They may be used when

the primary contaminant
is sodium chloride.
Some engineers assume that reservoir brine viscosity
is equal to that of distilled

The resistivity

and reservoir
the viscosity

of formation

water

is a measure

by the water to an electrical

can be measured

directly

or calculated.

of the

current.

It

The direct-

pressure (a valid

The pH

R ,, $, is expressed in units of Q-m. The resistivity

The

of for-

separates a liquid and a gas or a liquid and a solid, the attractive force at the boundary usually is called surface
however.
the attractive
force at the interface
tension;
between

two liquids

tant factor

is called

in enhanced

47.

Chemical
CSSCS
and

IFT.

recovery

IFT

is an impor-

processes

(see Chap.

Flooding,
describing
Low-1FT
Phase
Behavior
and
IFT

Miccllar/Polymer
Surface tension

Flooding section).
is measured in the laboratory

Procin the
by a ten-

siometer.
by the drop method,
or by other methods.
Descriptions of these methods arc found in most physical
chemistry

pressure.

of formation

temperature.

generally

viscosity.

water,

p,, , is a function

and dissolved

solids.

of

In gcncral,

usually

is controlled

by the

pH measurement should be made in the field if a closeto-natural-conditions

value is desired. The pH of the
is not used for water

identification

but it does indicate

corrosion tendencies
dicate the presence

or correlation

possible

scale-forming

or

of a water. The pH also may inof drilling-mud

filtrate
or well-

trcatmcnt chemicals.
The pH of concentrated

brines usually

is less than 7.0.

and the pH will rise during laboratory storage. indicating

that the pH of the water in the reservoir probably is appreciably

lower than many published

the carbonate

ion to sodium

values.

chloride

Addition

solutions

will

of
raise

the pH.
If calcium
is present,
calcium
carbonate
precipitates.
The reason the pH of most oilficld
waters
rises during storage in the laboratory
is because of the
fomlation
of carbonate ions as a result of bicarbonate

results

There

is

in a negligible
little

effect

information

on

on hater
the

actual

hydrocarbons.
* In water the presence of the gas actually
causes the water molecules to interact with each other
more strongly,
thus increasing the rigidity
of the water. However.
this effect is very
not been

measured

to date.

literature

there

an

is

enormous

amount

evidence to support this concept.

For the best estimation of the viscosity
reader is referred
equations

and viscosity
small and has

In the physical

32 parameters

indirect

of water.

to a paper by Kestin (11(11.

involve

chemistry
of

the

Their cor-

for calculating

the numerical effect of pressure, temperature.

and conccntration of aqueous NaCl solutions on the dynamic and
of water.
Twenty-eight
tables
kinematic
viscosity
from

the

correlating

equations

cover

The redox potential

may

be referred

reduction

numerical cffcct of dissolved gas on water viscosity.

Gas in solution behaves entirely differently
from gas in

temperature
range from 20 to 150C. a pressure range
from 0. I to 35 mPa. and a concentration
range from 0 to
6 molal.

waters

decomposition.

brine viscosity
increases with increasing
prcsaure, inand decreasing
tempcraturc.

creasing
salinity.
Dissolved gas in the fomlation
water at reservoir condi-

gcncratcd

ranges usually

The Redox Potential (Eh)

The viscosity

relating

for the pressure

texts.

Viscosity

tions

premise

pH of oilfield

purposes.

Surface tension is a measure of the attractive force acting

at a boundary between two phases. If the phase boundary

pressure

COfibicarbonate
system. Because the solubility
of CO?
is directly proportional
to temperature and prcssurc, the

water

Surface (Interfacial) Tension (IFT)

water at atmospheric

temperature.
In this case it is assumed that
of brine is essentially
independent
of

encountered).

measurement
method
is essentially
the electrical
resistance through a 1-m cross-sectional
area of I m7
of formation
water,
The fomlation
water resistivity,
mation water is used in electric log interpretation
and for
such
use
the
value
is
adjusted
to
formation
temperature. i (See Chap. 49 for more information).

HANDBOOK

Figs. 24.X through 24. IO may be used to approximate

water viscosity
for engineering
purposes. These figures
show the effects of pressure, temperature,
and NaCl con-

Resistivity
resistance offered

ENGINEERING

often is abbreviated
to as oxidation

potential,

Eh,

and also

potential.

or pE. It is expressed

oxidation-

in volts.

and at

equilibrium
it is related to the proportions
of oxidized
and reduced
species present.
Standard
equations
of
chemical

thermodynamics

Knowledge

of how compounds
other

minerals

solubility

express

of the redox

the relationships.

potential

is useful

such as uranium.

are transported

of some elements

iron.

in aqueous
and compounds

in studies
sulfur.

and

systems.

The

depends

on

the redox potential and the pH of their environment.

Some water associated with petroleum
is interstitial
(connate)
proved

water,

in various

and has a negative

field

studies.

Eh: this has been

Knowledge

of the Eh is

useful in determining
how to treat a water before it is
rein.jected into a subsurface formation.
For example. the
Eh of the water will be oxidizing
if the water is open to
the atmosphere,

but if it is kept in a closed system

in an

oil-production
operation
the Eh should not change appreciably
as it is brought to the surface and then reinjetted. In such a situation. the Eh value is useful in determining
deposit

how much iron

in the wellbore.

Organisms

that consume

the Eh. In buried

attract

organic

will

scdimcnts,

constituents,

stay

oxygen

in solution

and not

cause a lowering

of

it is the aerobic bacteria that

which

remove

the free oxy-

gen from the interstitial

water. Sediments laid down in a
shoreline environment
will differ in degree of oxidation

24-17

PROPERTIES OF PRODUCED WATERS

I191111

PRESSURE,
Fig. 24.8-Effect

compared
ment.

with

10,000

1000

PSILI

of pressure on the viscosity of water

those laid down

For example,

in a deepwater

environ-

the Eh of the shoreline

sediments

may range from -50 to 0 mV, but the Eh of deepwater

sediments may range from - 150 to - 100 mV.
The aerobic
ly consumed;

bacteria

die when the free oxygen

the anaerobic

bacteria

attack

the sulfate

ion, which is the second most important

anion in the
seawater.
During
this attack.
the sulfate reduces to
sulfite

and then to sulfide;

H 2 S is liberated,

the Eh drops

to -600

and CaCO 3 precipitates

are

quantities
of dissolved
gases are contained
in
brines. Most of these gases are hydrocarbons;

with

other gases such as CO2 , N?.

present.

decreases

.F

Fig. 24.9-Viscosity
of sodium chloride solutions as a function
of temperature and concentration at 14.7 psia.

brines primarily

because the analytical

ficult and very time-consuming.

Knowledge
of the dissolved organic

Dissolved Gases

however,

mV,

as the pH rises

above 8.5.

Large
oilfield

TEMPERATURE

is total-

The

with

solubility

increased

of

water

the

and HzS
gases

salinity,

often

generally

and increases

Hundreds of drillstem
samples of brine from waterbearing subsurface formations in the U.S. gulf coast area
were analyzed

to determine

their

amounts

and kinds

are dif-

constituents

is im-

portant because these

origin and/or migration

constituents
are related to the
of an oil accumulation,
as well

as to the disintegration

or degradation

tion.

The

concentrations

of

organic

of an accumulaconstituents

in

oilfield brines vary widely. In general, the more alkaline

the water, the more likely that it will contain higher concentrations

pressure.

problems

organic
acids:

of

matter
however,

organic

constituents.

consists

of anions

other compounds

The

bulk

of

the

and salts of organic

also are present.

of

of the dissolved
hydrocarbons.
2o The chief constituent
gases usually was methane, with measurable amounts of
ethane, propane, and butane. The concentration
of the
dissolved hydrocarbons
generally
increased with depth
in a given formation
and also increased basinward with
regional and local variations.
In close proximity
to some
the
waters
were
enriched
in dissolved
oiltields,
hydrocarbons,
and up to I4 scf dissolved gasibbl water
was observed in some locations. A more detailed
sion of this topic is given in Chap. 22.

discus-

; 0.611

im
0 0.5.
,o

Organic Constituents
In addition
of organic
form
these

occur

to the simple
constituents
in oilfield

organic

titatively.
sent that

brines.

constituents

However,
have not

hydrocarbons,

in colloidal,

In recent

have

a large number

ionic,
been

and molecular
years,

some of

measured

TEMPERATURE,

quan-

many organic constituents

are prebeen determined
in some oilfield

Fig. 24.10-Effect

of temperature on viscosity of water.

PETROLEUM

24-18

Knowledge
of the concentrations
and other components
in oilfield
ploration.

The solubilities

of benzcnc. toluene,
brines is used in ex-

of some of these compounds

in water
elevated

at ambient conditions
tern eraturex
and
determined. x3. f:

matter.

of these and other

oilfield
brines is

It has been shown

experimentally

that

the solubilities
of some organic compounds
found in
crude oil increase with temperature
and pressure if
pressure is maintained
on the system. The increased
solubilitiea

become

significant

solubilities

decrease

with

above

150C.
The
water
salinity.

increasing

Waters associated with paraffinic

oils are likely to contain fatty acids. while those associated with asphaltic oils
more likely

contain

naphthenic

reasons

why

quantitative

recovery

is

Interpretation of Chemical Analyses

Oilfield

waters

include

all

Such

waters

have

oilfields.

characteristics.
About
70% of the
associated with waters
dissolved

solids.

waters

or brines

certain

distinct

world
petroleum
containing
more

A water containing

found

in

chemical

reserves are
than 100 g/L

dissolved

solids in

excess of 100 g/L can be classified as a brine. Waters

associated with the other 30% of petroleum reserves contain less than 100 g/L dissolved solids. Some of these
waters

are

fresher

waters

almost

fresh.

usually

However,

is attributed

the

in the Rocky

presence

to invasion

petroleum accumulated
in the reservoir
Examples of some of the low-salinity
found

of

after the
can be

fields

such as

Enos Creek, South Sunshine. and Cottonwood

Creek.
The Douleb oil field in Tunisia is another example.
of dissolved

solids found

waters depends on several factors.

are the composition

at the same time as the enclosing

rocks) or
cyigcrwric (originated
by subsequent
infiltration
into

Connate Water. The term

produced.

or

connate
implies born.
together-connascent.
There-

originated

fore. connate
terstitial

water probably

water

should bc considered

of syngenetic

origin.

Connate

an in-

water

of

this definition
is fossil water that has been out of contact
with the atmosphere for at least a large part of a geologic
period.

The

those born
restriction.

implication
with

that

connate

the enclosing

waters

are only

rocks is an undesirable

of the water

Diagenetic Water. Diagenetic

in oilfield

Some of these factors

in the depositional

en-

waters are those that have

changed chemically
and physically,
before. during,
after sediment consolidation.
Some of the reactions
occur in or to diagenetic waters include
change,
replacement
(dolomitization).
permeation,
and membrane filtration.

and
that

bacterial. ion exinfiltration

by

Formation Water. Formation

water. as defined here, is

in the rocks and is present in

water that occurs naturally

them immediately

before

drilling.

Juvenile Water. Water

derived

from

that is in primary
magma
magma is juvenile
water.

primary

Condensate

Water.

Water

associated

or

with

gas

sometimes is carried as vapor to the surface of the well

where
it condenses
and
precipitates
because
of
temperature
and pressure changes. More of this water
occurs

trap.
waters

Mt. areas in Wyoming

The composition

waters are .snl,yc,,trric'

Interstitial

(formed

acids.

Quantitative
recovery
of organic
constituents
from
oilfield
brines is difficult.
Temperature
and pressure
changes.
bacterial
actions.
adsorption.
and the high
inorganic/organic-constituents
ratio
in most oilfield
brines are some
difficult.

water is the water con

pores or spaces between the minute

in the small

rocks).

However.
the actual concentrations
organic
constituents
in subsurface
another

HANDBOOK

Interstitial Water. Interstitial

mined

grains or units of rock.

and in saline waters at

pressures
have
been

ENGINEERING

in the winter

and in colder

climates

and only

in

gas-producing
wells. This water is easy to recognize
because it contains a relatively
small amount of dissolved

solids,

mostly

derived

from

reactions

with

chemicals in or on the well casing or tubing.

Water analyses may be used to identify
the water
source. In the oil field one of the prime uses of these
analyses

is to determine

in an oil well

the source of extraneous

so that casing

water

can be set and cemented

to

vironment
of the sedimentary
rock, subsequent changes
by rock/water
interaction during sediment compaction.

prevent

changes

In some wells a leak may develop in the casing or cement, and water analyses are used to identify the water-

by rock/water

tion (if migration

interaction

occurs),

during

and changes

water

migra-

by mixing

with

other waters, including

infiltrating
younger waters such
as meteoric
waters. The following
are definitions
of
some types of water.

volved

in atmospheric

of meteoric

circulation:

groundwater

is slight

furthermore,
when

was
the

compared

inage
with

so that remedial

merit.

Seawater.

varies

Graphic Plots

of

seawater

somewhat,
but in general
will
have a composition
relative to the following
(in mg/L):
chloride--19.375,

Graphic

bromide-67,

graphical

- 10,760,
tium-8.

sulfate-2,712.
magnesium-

potassium-387.

1,294, calcium-4

sodium

13, and stron-

can be taken.

of systems have been developed.

than a

composition

action

Comparisons
of water-analysis
data are tedious and
time-consuming;
therefore.
graphical methods are commonly used for positive,
rapid identification.
A number

the age of the enclosing

rocks and is not more
small part of a geologic period.
I
The

the oil or gas horizons.

bearing horizon so that the leaking area can be repaired.

With the current emphasis on water pollution prevention.
it is very important
to locate the source of a polluting
brine

Types of Water
Meteoric Water. This is water that recently

such water from flooding

lustrate

plots of the reacting

the relative

amount

presentation

a water and classification

have been developed.

all of which

values

have some

can be made to il-

of each radical

present.

The

is an aid to rapid identification

of

as to its type.

Several methods

PROPERTIES

OF PRODUCED

Tickell Diagram. The Tickell

using

a six-axis

reaction

values

percentage
equivalent
dividing

are calculated
masses (EPMs)
of a given

and multiplying
plots

percentage

However,

with

on the axes. The

sion and
sediments

regression
of oceans and seas, even these
probably were subjected to marine waters by

by summing
the
of all the ions.

infiltration.
In any

event.

diagram

of

ion by the sum of the total

reaction
values,

water identification

X5 Percentage

by 100.

total

reaction

was developed

or star diagram.

of the ions are plotted

values
proton

the EPM

EPMs,
The

system

24-19

WATERS

values,

rather

are often

more

because the percentage

take into account

the actual

than

of

useful

in

values do not

ion concentrations.

differing only in concentrations

cannot be distinguished.

of dissolved

Water

time and tectonic

the

events

petroleum,

plus transgres-

which

formed

organic matter deposited with the sediments,

from what usually is called the source rock

from

migrated
into more

porous and permeable

sedimentary
rock.
Petroleum
(i.e., oil and gas) is less dense than water; therefore,
it
tends to float to the top of a water body regardless of
whether the water is on the sutiace or in the subsurface.
Therefore,
water associated with petroleum
in a subsurface reservoir is called an oilfield
water.
By this

constituents

definition,

any water associated

with a petroleum

deposit

Reistle Diagram. Reistle devised a method of plotting

is an oilfield

water analyses by using the ion concentrations.

* The
data are plotted on a vertical diagram. with the cations
plotted above the central zero line and the anions below.

The question of the origin of oilfield brines is difficult

to answer in a general manner. The water involved
and
the constituents dissolved in the water to form the brine

This type of diagram

can involve

often

is useful

in making

regional

correlations
or studying lateral variations in the water of
a single formation
because several analyses can be plotted on a large sheet of paper.

water.

divergent

histories.

Subsurface

water is there

either because it originally

was there or because it infiltrated
to the subsurface from the surface. If it was
there originally,
it would be endogenetic,
whereas if it

the reaction values of the

ions on a system of rectangular coordinates. 87 The cat-

infiltrated
from the surface and/or penetrated with sediment accumulations,
it would be exogenetic.
Obviously
these two types of waters could meet and

ions are plotted

mix in the subsurface

Stiff Diagram. Stiff plotted

vertical

to the left and the anions to the right of a

zero line.

The endpoints

then are connected

straight lines to form a closed diagram,

a butterfly
diagram. To emphasize
may be a key to interpretation,
by changing

by

sometimes called
a constituent that

the scales may be varied

the denominator

of the ion fraction.

usually

and thus the mixture

water of two separate origins.

product

of several variables.

dissolved

These variables

ions, salts, gases, and organic

tions between these dissolved

teraction
of the brine with

Many investigators
of comparing oilfield

petroleum,

ple. and nontechnical

construct

personnel

can be easily

trained

to

the diagrams.

Methods.

diagrams

Several

other

water

have been developed,

fresh waters,

identification

primarily

and they are not discussed

for use with

here. The Stiff

and Piper diagrams, 87~88 were ada ted to automatic

*B
and Morgan
processing
by Morgan
et al.
McNellis.
plot

* The Piper diagram

to depict

diagram

the water

shows the chemical

terms of cations

uses a multiple

analysis.

and this

composition

and anions.88

Angino

data
and

trilinear

quaternary

of the water in

plied the automated

Stiff and Piper diagrams
oilfield brines and obtained good results.

include

matter,

(I)

(2) reac-

constituents,
and (3) inthe surrounding
rocks,

etc. There are a number

of pertinent

reactions

hydration,

mineral

formation

and/or

dissolution,

ion diffusion,
gravitational
segregation
of ions,
membrane filtration,
or other osmotic effects.
It is rather

difficult

to rank the factors

more important for general consideration.

of the more important
factors probably

and

that might

be

However.
two
are the original

composition
of the water and interaction
of that water
with the rocks. If one assumes that the original water was
a marine

water and that the associated

ap-

quently

sedimentary

to some

original
portant

and Morgan

multi-

that could cause the composition

of a subsurface oilfield
brine to change in composition,
including leaching of the
rocks, ion exchange
between water and rock, redox,
mineral

Other

contain

could

ply if more than one exogenetic

water were involved.
The chemical composition
of an oilfield brine is an end

in multiples of 10. However,

when a group of waters is
being considered,
all must be plotted on the same scale.
believe that this is the best method
water analyses. The method is sim-

would

The problem

composition
factor.

rocks)

were

sediments
marine,

(subsethen

the

of the marine water could be an im-

However,
even the salinity in the various oceans and
seas is not constant.
For example.
the salinity of the

Occurrence, Origin, and Evolution of

Oilfield Waters

mg/L,

The sedimentary
rocks that now consist of stratified
deposits originally
were laid down as sediments
in
and streams.
Naturally.
these
oceans,
seas. lakes.

to 70,000 mg/L in the Red Sea. about 18,000 to 22,000

mg/L in the Black Sea, and only about I .OOO mg/L in the
Baltic Sea. Some land-locked
waters. such as the Dead

sediments

Sea. Great Salt Lake, etc., contain waters that are nearly
saturated with dissolved solids.
Studies of formation
waters in the western Canada

were filled

with

water.

This water is still pres-

ent in the stratified sediments and millions

would be considered truly connate water.
Many

large

associated

sedimentary

waters in the major oceans ranges from 33,000

strata

of years later

originally

with oceans and seas. The original

was marine
in such
therefore.

were

associated
sediments.

water.
Sediments laid down by lakes and streams would not
contain a marine water during their initial deposition.

about 40,000

sedimentary

basin

mg/L

indicate
marine

in the Mediterranean

that 85%

deposited

under

deposited
freshwater

under
brackish-water
conditions. y2 These

that 80%

of all the sedimentary

to 38,000
Sea, up

of the strata were

conditions,

while

15%

were

and possibly
under
investigators
estimated
strata

in Alberta

were

24-20

PETROLEUM

deposited

under marine

conditions.

This led to the con-

bromide

in

the

ENGINEERING

Smackover

brines

is

HANDBOOK

3,100

clusion that one could assume with negligible error that

all sedimentary
strata originally
contained seawater.

Therefore.
the average degree of concentration
brines compared to seawater is 3,100+65
=48.

Further, the study

important volumetric

ing that seawater

imate composition

indicated that evaporites

form an
part of several of the stratigraphic

is concentrated
50-fold,
the approxof a brine can be calculated. 26

units. Some of the stratigraphic

units possibly contain
bitterns subsequent to halite precipitation
but preceding

Shale Compaction

and Membrane Filtration

precipitation

Some

investigators

believe

found

in oilfield

average

of

potassium

formation

salts.

They

water salinity

calculated

of about 46,000

an
mg/L

mg/L.
of these
Assum-

waters

that

the salinity

are the result

of

variations
filtration

of

TDS. which indicated a net gain of dissolved salts. Of

the major and some minor components,
all showed a net

water

gain with the exception

periments
indicated
that
semipermeable
membranes.
nature should cause a water
of the shale membrane and

natural
shales can act as
ys.y6 This system working in
to be more saline on one side
almost fresh or less saline on

the other side. This follows

because the shale membrane

Factor
analyses.
major

of Mg and SOa.

analysis
was used in interpretation
of the
and the following
factors were considered to be

controls:

dilution

by

composition

freshwater

of the original

recharge,

seawater,

membrane

filtration,

solution of halite.
sulfate. formation

dolomitization,
bacterial reduction of
of chlorite. cation exchange on clays,
and
solubility
matter,
from
organic

contribution

first

through
was

shale.

The membrane

suggested

by

De

filtration

Sitter.

theory

Laboratory

ex-

should filter out the dissolved ions on the upflow side.

causing the water on the downflow
side to contain few or
no dissolved ions.

relationships.
It was concluded
that (I) the formation
waters of
western Canada are ancient seawaters in which the
deuterium concentration
was changed because of mixing
with

infiltrating

fresh

water,

(2)

oxygen-18

was

ex-

changed with carbonates in the rocks, and (3) dissolved

salts are in equilibrium
with the rock matrix subsequent
to their redistribution
by membrane filtration and/or dilution by freshwater recharge. Equilibrium
was attained by
such processes as dissolution
formation.

cation

exchange

from clays and organic

The majority

of evaporates,
on clays.

matter,

new mineral

desorption

and mineral

of the published

most investigators

solubilities.

research studies seem to

agree that all these controls and/or reactions

in establishing
the composition
of oilfield
ther.

of ions

agree with

are involved
brines. Fur-

the assumption

that

marine water usually is a part of the original

material
from
which
formation
waters
evolve.
Opinions,
however,
are not unanimous
with respect to how they
evolved.
The major disagreements
are related to the
membrane

filtration

ccntrating
evaporation.
It

the

is possible

oilfield

brines

theory

and to other

dissolved

solids

to reconstruct

modes of con-

such

as

the evolution

in sedimentary

seawater
of

some

basins if one reasons that

they are genetically

related to evaporites.
For example.
geochemical
and geological
studies of some very concentrated brines indicate that in deep quiescent bodies of
water. strong bitterns can persist for long periods of time
under a layer of near-normal
seawater. As a result, carbonates can precipitate from the less saline water and fall
through the bittern at the bottom, and. as compaction
proceeds.

the pore spaces

remain

filled

with

Some fossil brines once trapped have not moved

or very fast.

bitterns.
very far

Quantities of Produced Water

An

analysis

was made

water produced
their percent

of the approximate

amount

of total

U.S.

crude oil production

are:
Alabama,
0.3%;
Alaska,
19.9%;
I I .7%; Colorado,
I .O%; Florida,
I .4%;
13.4%;
0.2%;

of

with crude oil in I4 states. The states and

Montana,
1.0%; Mississippi,
New
Mexico,
2.3%;
North

in 1981

California,
Louisiana.

1.2%; Nebraska,
Dakota,
1.4%;

Texas, 31.2%; Utah, 0.8%: and Wyoming,

4.2%.
Fig. 24.1 I indicates the crude oil and water production
from wells in the 14 states. The figure indicates production

of about

4.3

bbl

water/bbl

oil.

Fig.

24.12

is a

similar graph for 13 states excluding

Alaska. This figure
indicates production
of about 5.2 bbl wateribbl
oil. Further. it can be shown
as cumulative

that oil wells produce

oil production

the older the well,

increases.

the higher

more water

In other words,

the WOR.

Recovery of Minerals From Brines

Extraction

of minerals

considered

in production

tion and development

from

oilfield

planning

brines

should

costs, (2) to prevent

environmental

damage from brine, (3) to produce potable water.

to conserve all valuable minerals and energy.
Precipitation

be

(I) to recoup explora-

is the most common

separation

and (4)
process

used in separating
minerals
from any type of brine.
Minerals recovered from brines in the U.S. include compounds of iodine, bromine.
chlorine,
sodium. lithium.
potassium, magnesium,
and calcium.
Evaporation
of a saline water or brine

will

cause the

precipitation
of calcium
carbonate.
calcium
sulfate,
sodium
chloride,
magnesium
potassium
sulfate,
chloride,

and finally

magnesium

chloride.

These are the

A geochemical
model can be built to represent
origin and evolution
of this type of brine by using

the
the

major chemicals in most brines, and this is the sequence

order in which these compounds
will precipitate.
Mere

relatively
simple
operations
evaporation.
(2) precipitation,

(I)
(4)

a brine;

mineral
leaching.

fomlation

and processes
of
(3) sulfate reduction,

and diagenesis.

and (7) expulsion

evaporites during compaction.

Experimental
work indicated
bromide

in

seawater

seawater

evaporates.

(5) ion exchange.

of

interstitial
that about

precipitates
The

average

with

fluids

(6)
from

14% of the
the

halite

concentration

as
of

preclpltation

will

therefore,

not produce

a very pure chemical

other chemical

or physical

from

processes

arc used.
For example. iodine, which is in the foml of iodide in
a brine. is recovered by these steps: (I) the iodide is oxidized to iodine,

(2) the iodine

is stripped

(3) the iodine then is reduced back

iodide is oxidized
again to iodine,

from the brine,

to iodide, (4) the

(5) the iodine is

PROPERTIES

OF PRODUCED

WATERS

24-21

13 Stclcs

(ercludlng

Aiasio)

30000

29000

27000

2700C

2
6
6
2

g
o

2600C

26000

z
I

25000

ZSOOC

7000

BOO<

H---L,Crude

,/

700(

6000

--4

76

77

78

73

6OOt
1975

5000
I!

80

77

76

Fig. 24.1 I-Crude

oil and water produced ( x 1,000 B/D) from
wells in 14 states including Alaska.

crystallized
purified

and filtered,

70

80

79

YEAR

YEAR

and (6) the iodine

crystals

are

oil and water produced ( x 1,000 B/D) from

wells in 13 states excluding Alaska.

Fig. 24.1 P-Crude

recover
study

further.

minerals

from

of the current

brines

should

and potential

make

economics.

an in-depth
Some of

Bromine is recovered by a similar though, of course,

different process. It is present in a brine as bromide. The
U.S. Bureau ofMines Yearbook9 contains information

the factors that must be determined

are (1) concentmtions of valuable minerals in a brine, (2) amount of brine
available,
(3) costs of gathering the brine, (4) costs of

on general

recovering
the minerals from the brine, (5) present
potential market demand for the recovered minerals,

recovery

technology,

domestic

production,

consumption
and uses, prices, stocks, etc., of minerals
recovered
from brines as well as minerals recovered
from

other sources.

The first plant in the U.S.

solely

to produce

iodine

1977 near Woodward,

million lbm iodineiyr
demand.

Some

in more than 40 years built

from

brine

went on stream

in

OK. It has a design capacity of 2

or about 30% of the annual U.S.

smaller-scale

operations

to

recover

iodine started in 1982 near Kingfisher,

OK.
Several plants recover bromine and other constituents
from
from

brine near El Dorado, AR.

the Smackover
formation.

The brine

is produced

Magnesium
and other chemicals are recovered from
lake brines, well brines, and seawater in plants located
near Ogden, UT; Ludington,
MI: Freeport,
TX; and
Port St. Joe, FL.
Clayton

Valley,

Lithium

is recovered

from

brine

near

NV. 98

Economic Evaluation
It is true

that

therefore,

any

market
company

demand

fluctuates

considering

with

supply;

an enterprise

to

(6) costs of delivering

the minerals

and
and

to the market. 26

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