DEPARTMENT OF THE INTERIOR

FRANKLIN K. LANE, Secretary

UNITED STATES GEOLOGICAL SURVEY

GEORGE OTIS SMITH, Director

Bulletin 693

THE EVAPORATION AND CONCENTRATION OF

WATERS ASSOCIATED WITH PETROLEUM

AND NATURAL GAS

BY

R. VAN A. MILLS

AND

ROGER C. WELLS

WASHINGTON

GOVERNMENT FEINTING OFFICE 

1919

CONTENTS.

Page.

Introduction. .......................................... .\ ................. 5

Results of the investigation. .^ .......................................... 5

Acknowledgments. ........................ f ................'.......... 7

Field work. .................:........................................ 8

Location of quadrangles studied ....................................... 9

Geology of the Appalachian oil and gas fields ............................... 9

Geologic reports relative to the areas studied ............................. ' 9

Areal geology. ......................................................... 11

Stratigraphy and structure ............................................ 11

Lithology and mineralogy of the sediments. ............................ 12

Kinds of rock. ................................................ '. ... 12

Results of petrographic examination of rock specimens. .............. 14

Results of chemical examination of rock specimens. .................. 16

Results of physical examination of rock specimens .................. 20

Characteristics of the oil and gas in the Appalachian fields. ................... 22

Occurrence and distribution of water in the strata. .......................... 22

Present distribution of water in the oil and gas bearing rocks .............. 22

Water-bearing sands. ............................................. 22

Dry sands. ............ ^ .......................:................... 23

Mode of occurrence of petroleum, natural gas, and water in the water-bearing

sands. .............................................................. 25

Oil, gas, and water mixtures. .......................................... 25

Evidence of the occurrence of oil, gas, and water mixtures. .............. 26

. Temperature and pressure. ............................................. 27

Characteristics of the Appalachian oil and gas field waters. ................... 29

Deep-seated brines and their comparison with sea water.*. ................ 29

Analyses of Appalachianv oil and gas field waters. .............. A ........ 33

Shallow well waters. .................................. .^ .............. 40

0

Changes in oil and gas field waters as deduced from field observations and

chemical analyses. .................................................. 44

Mineral deposition during the extraction of oil and gas. ................... 44

Changes in the deep-seated waters during the extraction of oil and gas. ... 50

Method of study. .................................................. 50

Comparison of waters from the same well ..........................'. 51

Comparisons of waters from the same geologic horizons in neighboring 

fields. ....................................... ;. .................. 55

Evidence that similar differences in the waters have been brought about

during geologic time ............................................ 57

Comparison of waters from different geologic horizons. ................ ° 57

Evidence of the natural escape of gases. ................... '. ........ 60

Relations between the geologic history of certain reservoir rocks and 

their included waters. ........................................... 63

Hypotheses concerning the origin of the oil and gas field waters. .............. 64

Hypotheses previously suggested. . ..................................... 64

Present hypothesis. .................................................... 67

3
4 CONTENTS.

. Page.

History of the oil and gas field waters ...................................... 68

Inclusion and migration of waters of sedimentation...................... j" 68

Changes in the waters of sedimentation.................................. 70

Deep-seated waters as agents of cementation............................ 76

 Retention of waters associated with gas and oil ..................'......... 76

Evaporation of water at depth. .............................................. 77

Variables involved..................................................... 77

Limiting moisture content of natural gas. ................................ d79

Effect of the increase of temperature with increasing depth .............. 83

Effects due to changes of pressure...................................... 84

Solubility of natural gas in oil and water. .... ^.......................... 86

Origin of the gases as related to the evaporation of the associated waters... 87

Related phenomena and deductions of practical value....................... 89

'Association of rock salt with deposits of. natural gas and petroleum........ 89

Origin of salt domes.........;..'........................................ 90

Amount of gas available for evaporation................................. 94

Accumulations of gas and oil associated with salt domes.................. 94

Induced segregation of oil and gas...................................... 95

Clogging of oil and gas sands............................................ 98

Prospecting for oil and gas............................................... 98

Determining the source of infiltrating waters............................ 99

Need for further investigation...............................:......... 100

Index........................................... '. .^..................... 101

ILLUSTRATIONS.

PLATE I. Generalized sections showing the oil and gas sands and the accompanying beds from which water and rock samples were collected. 

H. Salt crusts formed during the production of natural gas...........

. III. Incruste.d sandstone from oil wel]s near Evans City, Butler 

County, Pa............................. ..'...............'......

12

48

50

IV. Sulphate crusts from oil wells in Butler County, Pa................ 52

FIGURE 1. Index map showing location of the Summerfield and Woodsfield 

quadrangles, Ohio, the Zelienople and Butler quadrangles, Pa., 

and the names and positions of other quadrangles for which structural maps have been prepared............................... 9

 2. Sketch map showing the areal geology of the Appalachian coal basin. 11

3. Structure contour map of the Appalachian coal basin, showing contours on the Big Injun sand....................... 1............ 11

4. Curve showing the rates .of production of oil and water from well No. 

1, Schroeder heirs' farm, Miltonsburg, Malaga Township", Monroe 

County, Ohio, when water samples were collected from that well.. 51 

. 5. Temperature-vapor pressure curve for pure water.................. 81
THE EVAPORATION AND CONCENTRATION OF WATERS

ASSOCIATED WITH PETROLEUM AND

NATURAL GAS,

By E, VAN A. MILLS and R. C. WELLS.

INTRODUCTION.

BESTTLTS OF THE INVESTIGATION.

The association of saline waters/ with petroleum and natural gas 

has been widely observed, but the origin or mode of formation orf 

these waters has remained a perplexing problem. It has been commonly assumed that the dissolved salts were derived through the 

leaching of the sediments by percolating ground waters, or that the 

deep-seated brines are essentially fossil ocean waters which were included and buried in the marine sediments at the time of deposition. 

In the light of the present investigation these relatively simple concepts give way to the conclusion that the brines are the result of a 

complex and long-continued evolution in which waters of sedimentation together with ground waters from other sources have undergone 

deep-seated evaporation and concentration accompanied by noteworthy chemical changes.

Our interpretation of the mode of formation of many oil and gas 

field brines is partly the outcome of a study of changes in the brines 

incident to the extraction of gas and oil from their reservoir rocks. 

It appears that the waters undergo deep-seated concentration, 

brought about by their evaporation into moving and expanding gas. 

During this concentration there is a definite order of change in the 

relative proportions of the dissolved. constituents in the waters. 

Carbon dioxide and other gases are lost from solution. Calcium, 

magnesium, and iron separate from solution as carbonates, and under 

favorable conditions sodium and minor proportions of calcium and

1 The term water is frequently used throughout this paper to mean a dilute aqueous 

solution or weak brine.

 5
6 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

magnesium separate as chlorides a process illustrated in the salting 

up-of gas wells. A further separation of the dissolved constituents, 

more particularly of calcium, magnesium, iron, sodium, barium, 

strontium, carbonate, and silica, is brought about when waters from 

different beds and having different properties of reaction become 

mixed. Lastly, the ratio of calcium to chlorine in the waters increases and the ratio of sodium to chlorine decreases with the concentration.

It is a logical step to pass from the facts just recorded to a theory 

of the formation of the brines. The brines, as they occur in their 

' reservoir rocks, prior to the extraction of gas and oil from these 

rocks by man, vary greatly in their degree of concentration, and 

it may be stated as a rule that the concentration of the dissolved 

constituents of the waters increases with depth, and that the differences between the .concentrated and relatively dilute waters are of 

the same sort as those brought about during the artificial extraction 

of gas and oil. There are, however, noteworthy exceptions to this 

rule; waters that appear to have remained deeply buried under thick 

covers of relatively impermeable beds since their inclusion in the 

sediments seem to be less concentrated than those occurring in more 

shallow beds directly beneath and above certain unconformities.

We are led to conclude that the changes in the waters incident to 

the extraction of gas and oil are largely of the same order as those 

by which the brines were formed. Marine water of sedimentation 

and ground water from other sources have been included and deeply 

buried in the sediments, where, in association with gas and oil, they 

have migrated and undergone concentration, accompanied by changes 

in the nature and relative proportions of the dissolved constituents. 

Concentration is due in part to the leaching of the sediments by the 

migrating waters but mainly to the evaporation of water into gases 

that are moving and expanding through natural channels. Reactions 

between the dissolved constituents of different types of waters and 

between the dissolved constituents of the waters, and the organic 

and inorganic constituents of the sediments have been important 

factors in the formation of the brines and so also have mass action 

and reactions due to deep-seated thermal conditions.

During the deep-seated concentration of the 0 waters various constituents have separated from solution as their points of saturation 

were reached. Under favorable conditions the concentration has 

proceeded sufficiently to cause the deposition from solution of sodium 

chloride. Chemical reactions and precipitation have also been effective in bringing about these separations. Much evidence of what 

has taken place through deep-seated natural agencies is furnished
INTRODUCTION. 7

by studies of the salts interstitially included in the sediments from 

which gas and oil have not been extracted, but the most striking 

example of the deep-seated natural deposition of salt is furnished 

by the salt domes of Louisiana and Texas. We attribute the formation of these great salt masses largely to the geophysical and geochemical processes herein described; deep-seated evaporation and 

concentration of chloride waters due to the movement and expansion 

of gases through natural passages, more particularly through fault 

fissures, having been agencies of prime importance.

The salts deposited in wells during the extraction of gas and oil, 

those occurring interstitially in the sediments, and those constituting 

the Louisiana and Texas salt domes all agree closely in composition 

with hypothetical salts whose loss from solution during concentration has been predicated by us through comparisons of the analyses 

of the dilute and concentrated brines under scrutiny.

It is our purpose to describe the mode of concentration of these 

waters, the changes they have undergone, and som'e of the relations 

that the changes bear to the occurrence and production, of petroleum 

and natural gas. Though samples of the waters under investigation 

were collected only in the Appalachian fields, the conclusions are 

widely applicable. . : . 

As shown in the concluding chapter, many of-the principles herein 

set forth are capable of practical application, and it is intended that 

this bulletin shall be of economic value to oil and gas operators as 

well as of scientific interest. We shall feel repaid for our studies if 

we make apparent the need for further detailed field and laboratory 

investigations of the chemical and physical interactions between 

petroleum and natural gas, on the one hand, and the associated waters 

and reservoir rocks, on the other.

ACKNOWLEDGMENTS.

We are indebted to our colleagues D. Dale Condit and G. B. Kichardson for cooperation and assistance during the field investigations 

relative to this paper, and to M. I. Goldman for petrographic studies 

of rock specimens. E. S. Larsen and W. T. Schaller have also made 

brief petrographic examinations- of some of the rock and mineral 

specimens collected. A. F. Melcher made the porosity tests and S. C. 

Dinsmore many of the water analyses herein published. The hearty 

cooperation of numerous oil and gas companies and individual operators is also gratefully acknowledged. To Herman Stabler and 

Chase Palmer we are especially indebted for assistance during the 

chemical investigation of materials collected in the field and for helpful criticism and advice during the preparation of the manuscript.
8 WATEES ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

FIELD WORK.

The field investigations upon which this paper is based were made 

by R. Van A. Mills, D. Dale Condit, Frank Reeves, and G. B. Richardson during the summers of 1914, 1915, and 1916. The oil and 

gas resources of the Woodsfield and Summerfield quadrangles, in 

southeastern Ohio, were studied by Messrs. Condit, Mills, and Reeves 

for four months during the summer of 1914. Subsequently the field 

work in these .areas was continued by Mr. Mills during April and 

May, 1915, and June, 1916. Messrs. Richardson and Mills also 

studied the oil and gas resources of the Butler and Zelienople quadrangles, in western Pennsylvania, during the summer of 1915.

In the course of these economic investigations particular attention 

was paid to the distribution and mode of occurrence of the water 

associated with petroleum and natural gas, with a view to studying 

some of the physical and chemical relations between the hydrocarbons, the reservoir rocks, and the associated waters. As material 

for use in studying the possible changes that the waters have undergone, both before and after the extraction of oil and gas commenced, 

samples of oil, gas, oil and gas .bearing rocks, and the waters associated with the oil and gas were collected for laboratory study:

The oil samples were collected fresh as* the oil emerged from the 

wells and were placed in glass bottles for shipment. The gas samples 

were collected in large glass containers by the displacement of air and 

also by the displacement of water. °

In collecting water samples from deep wells it is difficult to obtain 

a truly representative sample from a particular bed. Water from 

one sandstone is likely to enter another through poorly plugged,

abandoned wells, or through and around faulty casings. The effort was therefore made to collect samples from, tightly cased wells 

and in newly drilled fields, where water from shallow sources had 

not leaked into the deeper sands through abandoned wells. The' 

samples were collected directly as the waters came from the wells 

and were therefore not affected by standing in tanks. So far as possible, the samples of water were collected where collateral data regarding the depth, thickness, texture, and structure of the productive 

sands, the geology of the region, and the history of production were 

available.

The rock samples were collected when they were freshly removed 

from the wells, except where otherwise noted. Lump samples and 

loose sand blasted from the deep beds when the wells were shot were 

collected in preference to the finely pulverized fragments contained 

in drill sludge.
GEOLOGY OF APPALACHIAN FIELDS. 9 

LOCATION OF QUADRANGLES STUDIED.

The location of the four quadrangles studied is shown on the index 

map (fig. 1). The Woodsfield and Summerfield quadrangles, which 

include parts of Belmont, Monroe, Noble, and Guernsey counties, in southeastern Ohio, are from 25 to 45 miles southwest, of 

Wheeling, W. Va., and from 25 to 40 miles north of Marietta, Ohio. 

The Butler and Zelienople quadrangles, including parts of Butler, 

Lawrence, and Beaver., counties, in western Pennsylvania, are from 

20 to 40 miles north of Pittsburgh, Pa., and about 80 miles northeast 

of the Woodsfield and Summerfield quadrangles.

Z5 60 76 100 Miles

FIGURE 1. Index map showing location of the Summerfield and Woodsfield quadrangles, 

Ohio (Nos. 1 and 2, heavily shaded), the Zelienople and Butler quadrangles, Pa.. 

(Nos. 25 and 26, heavily shaded), and the name's and positions of other quadrangles for which structural maps have been prepared (light shading). 3, Flushing ; 4, Cadiz ; 5, Steubenville ; 6, Claysville ; 7, Burgettstown ; 8, Carnegie ; 9, Beaver; 

10, Sewickley; 11, Amity; 12, Rogersville; 13, Waynesburg; 14, Wooster; 15, Foxburg ; 16, Clarion; 17, Kittanning; 18, Rural Valley ; 19, Elders Ridge; 20, Latrobe; 

21, Brownsville, 22,' Connellsville; 23, Masontown ; 24, Uniontown.

GEOLOGY OF .THE APPALACHIAN OIL AND GAS

FIELDS.

GEOLOGIC REPORTS RELATIVE TO THE AREAS STUDIED.

Two brief geologic reports on the Woodsfield and Summerfield 

quadrangles x have been published by the United States Geological

1 Condit, . D. D., Structure of the Berea oil sand in the. Summerfleld quadrangle, 

Guernsey, Noble, and Monroe counties, Ohio : U. S. Geol. Survey Bull. 621, pp. 217-231, 

1916 (Bull. 621-N) ; Structure of the Berea oil sand in the Woodsfleld quadrangle, 

Belmont, Monroe, Noble, and Guernsey counties, Ohio: Idem, pp. 233-249, 1915 (Boll. 

621-0),
10 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

Survey, and a more detailed report on the oil and gas resources of 

the same areas is now under preparation. ' Geologic reports on the 

Butler and Zelienople quadrangles are also being prepared for publication by the Survey. In addition to these, the Survey has published the following bulletins concerning oil and gas fields in Ohio, 

West Virginia, and Pennsylvania:

198. The Berea grit oil sand in the Cadiz quadrangle, Ohio, by W. T. Griswold.

1902. 43 pp., 1 pi. 

279. Economic geology of the Kittahnihg and Rural Valley quadrangles, Pa.,

by Charles Butts. 1906.' 198 pp., 11 pis. . ' 

286. Economic geology of the Beaver quadrangle. Pa. (southern Beaver and

northwestern Allegheny counties), by L. H. Woolsey. 1906. 132 pp.,

8 pis. 

300. Economic geology of the Amity quadrangle, eastern Washington County,

: Pa., by F. G. Clapp. 1907. 145 pp., 8 pis. 

304. Oil and gas fields of Green County, Pa., by R^ W. Stone and F. 'G. Clapp.

1907. 110 pp., 3 pis. 

318. Geology of oil and gas. fields in Steubenville, Burgettstown, and Claysville quadrangles, Ohio, W. Va., and Pa., by W. T. Griswold and M. J.

Munn. 1907. 196 pp., 13 pis. ' 

346. Structure of the Berea oil sand in the Flushing quadrangle, Harrisoh,

Belmout, and Guernsey counties, Ohio, by W. T. Griswold. 1908. 30 pp., 

: 2 pis. 

349. Economic geology of the Kenova quadrangle, Ky., Ohio., and W. Va., by

W. C. Phalen. 1908. 158 pp., 6 pis. 

454. Coal, Oil, and gas of the Foxburg quadrangle, Pa., by E. W. Shaw and M. J.

Munn. 1911. 85 pp., 10 pis. 

456. Oil and gas fields of the Carnegie quadrangle, Pa., by M. J. Munn. 19i3v99 pp., 5 pis. 

541-A. Oil and gas in the northern part of the Cadiz quadrangle, Ohio, by D. D.

Condit. 1913. 9 pp., 1 pi. 

621-H. Anticlines in the Clinton sand near Wooster, Wayne County, Ohio, by

C. A. Bonine. 1915. 12 pp., 1 pi.

661-A. The Cleveland gas field, Cuyahoga County, Ohio, with a study of rock 

pressure, by G. S. Rogers. 1917. 68 pp., 2 pis.

The following geologic folios contain descriptions of oil and gas 

fields in Ohio, West Virginia, and Pennsylvania:

69. Huntington, W. Va.-Ohio, by M. R. Campbell. 1900.

72. Charleston, W. Va., by M. R. Campbell. 1901.

82. Masontown-Uniontown, Pa., by M. R. Campbell. 1902. 

115. Kittanning, Pa., by Charles Butts <ancl Frank Leverett. 1904. 

121. Waynesburg, Pa., by R. W. Stone. 1905. 

146. Rogersville, Pa., by F. G. Clapp. 1907.

176. Sewickley, Pa., by M. J. Munn. 1911.

177. Burgettstown-Carnegie, Pa., by E. W. Shaw and M. J. Munn. 1911.

178. Foxburg-Clarion, Pa., by E. W. Shaw, E. F. Lines, and M. J. Munn. 1911.

180. Claysville, Pa., by M. J. Munn. 1912.

184. Kenova, Ky.-W. Va.-Ohio, by W: C. Phalen. 1912.
GEOLOGY OF APPALACHIAN FIELDS. 11

AREAL GEOLOGY.

The Appalachian oil and gas fields are in the great geosyncline 

generally known as the Appalachian coal basin, which lies between 

the Cincinnati anticline on the west 

and the Appalachian uplift on the 

east. Over most of 

the area, as shown 

by figure 2, the 

rocks exposed at 

the surface are of 

Pennsylvanian age. 

but Permian beds 

cover the center of 

the basin and both 

Mississippian and 

Devonian beds 

crop out around 

the edges.

FIGUUE 2. Sketch map showing the areal geology of the Appalachian coal basin. 11, Permian ; 12, Pennsylvanian ; 13, 

Mississippian ; 14, Devonian ; 15, Silurian ; 16, Ordoviclan.

NE"W YORK

STRATIGRAPHY 

AND STRUCTURE.

In the fields under discussion petroleum and natural gas occur associated with saline 

waters in relatively 

porous, open - textured " pay sands " 

in marine deposits 

and in continental 

deposits laid down 

at or near sea level. 

The sediments in 

southeastern Ohio 

are estimated to 

have a total thickness of more than 

9,000 feet. Some 

of the productive 

oil and gas bearing 

strata, such as those of the Catskill (?) formation in western Pennsylvania and those in the overlying coal measures, are probably not

100 Miles

FIGURE 3. Structure contour map of the Appalachian coal 

basin, showing contours on the Big Injun sand. (After 

Beeves.)
12 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

of marine origin, but were deposited sufficiently close to the sea to 

become interbedded with marine deposits. Under such conditions 

the nonmarine sediments have probably become more or less permeated by marine waters of sedimentation, as will be explained in the 

following text.

The regional structure and general position of the great Appalachian geosyncline are shown by figure 3. In the four quadrangles 

studied during the preparation of this bulletin (see fig. 1) the strata 

dip gently to the south and southeast, toward the trough of the' 

geosyncline. The dips average approximately 50 feet to the mile, 

though there are numerous minor folds in which they are more pronounced. In the Woodsfield and Sunlmerfield quadrangles, in southeastern Ohio, where a very large number of well records were procured, there is much evidence that the strata of Mississippian age 

had been distorted by small, relatively sharp folds prior to the deposition of the overlying Pennsylvanian sediments. Detailed studies 

in these two quadrangles have therefore rendered the unconformity 

between the beds of Mississippian and Pennsylvanian age especially 

evident. A generalized section of the formations in eastern Ohio is 

given on the following page.

The stratigraphic position of the reservoir rocks from which 

samples of water and of oil and gas bearing rocks were collected is 

shown in Plate I. It will be observed that these beds range in age 

from late Devonian to early Pennsylvanian. The oil and gas sands 

are for the most part lenticular, many of the productive beds at the 

same stratigraphic horizons being isolated from one another by relatively impermeable shales, tightly cemented sandstones, or gradations between the two.

For detailed descriptions and structure contour maps of the oil 

and "gas sands in southeastern Ohio and western Pennsylvania, the 

reader is referred to the publications listed on page 10.
U. S. GEOLOGICAL SURVEY BULLETIN 093 PLATE I

A

1 

Z

i

r

z

Z 

Ul 

0.

<

u. 

a.

10- to 

w 

w

i

1 

z

0

Ul

a

Monon|ahela x 

'formation

Conemau|h , 

formation ,~

Allegheny j 

'.formation ^

 .Pottsvil.le" 

 formation

Maxville 

limestone

Lo|an J

formation 

....

'

Black Hand 

formation .

Cuyaho§a 

formation '

Sunbu 

6erea sa

100

aoo

300 

400

500 

600-

700 1

800- 

900-

f 

1,000-

.

r

1,100- 

...1,200- 

1,300- 

1,400-

ry shale

ndstone 

1,600-

1,700- 

1,800- 

1,900- 

3,000-

a.iooa,zoo2;300-

 

 

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1

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 ^ -*^«^ 

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__ __ .

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.'Me!|i Creek or Mapletbwn cbai

xPittsbur|hcoal 

Upper Pittsburgh limestone niembei*

Ames("Crinoidal") limestone member

First CowRun sand 

Cambridge limestone member

Buell Run sand

Mahonin^ sandstone membsr, 

Upper Freeport coal 

Peeker sand

Lower Freeport coali

Coal 

Macksburg 500 -foot sand

Second Cow Run sand

Maxton sand

-Bi| lime JjnconVoE!!^- 

Keener sand

"|-Bi§ Injun sand

Welsh' sand

Berea sand

^\^o-~ 

 >- "^5^/v

^*»^

'"'x^

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 zj_-7r:'.

gsig= ^

ftfKSXgtfiSSffi

 tmw\ ^aaa^aatyrairyi

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pr^Fggrr'g

- =

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 -,.-.- ' ' :-_ ;

=-.;L; -. . :

=rr-r: -TT r-=

E====~=^==

========

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-rTT.-rrr^; : .:rr.

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 : : /: : : : : : : : :

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-^=~=r==i==r=i

1 7 :.. - i . r-r-r

%v^v^^

 - I,., -^z

....... ...-.

Ames("Crinoidal")

Saltsbur| sandstone 

member 

Bakerstown coal.

Brush Creek coal

Mahonin| sandstone 

member

Upper Freeport coal 

.Upper Freeport Is.member 

^Butler sandstone .m.em ben

\Lower Freeport Is. member 

\Freeport3s.rnember 

. Upper Kittanningcoal 

MiqdleKittanningcoal

Lower Kittannin§ coalKittanninfe ss. member 

Vanport Is. member 

Clarion coal 

 Clarion ss. member 

Xraifovillecoal

Homewood sandstone 

member 

Mercer coals

Connoquenes3in| sandStone member

Bi§lnjun or 

Mountain sand

Cuyaho^a formation 

Butler |as sand

VHundred-footsand

Sandy shale 

Thirty -foot S3nd

Snee sand

Bowlder sand 

Third or Gordon sand

Fourth, sand

Fifth sand 

Sixth sand

Conemau§n' Allegheny formation

Catski!l(?)formation Potts'ville Pocono grup 

GENERALIZED SECTIONS SHOWING THE OIL AND GAS SANDS AND THE ACCOMPANYING BEDS IN THE AREAS 

FROM WHICH WATER AND ROCK SAMPLES WERE COLLECTED.

A, Woodsfield and Sumnierfield quadrangles, southeastern Ohio; Ji, Western Pennsylvania in region of Butler and Zelienople quadrangles.
GEOLOGY OF APPALACHIAN FIELDS. 

Generalised section of formations in eastern Ohio.a

13

System.

Carboniferous.

|.§

<O o>

fc, w

I 

s

fl

£ "?>

o>

fc.

(Mississippian series.)

Group or 

formation.

"Washington formation.

Monongahela formation.

Conemaugh formation.

Allegheny formation.

Pottsville formation. '

Maxville limestone.

Logan formation.

Black Hand formation.

Cuyahoga formation.

Sunbury shale.

Berea sandstone.

Thickness 

(feet).

400

255-275

460-475

250-265

155-170

0-100

25-100

75-175

350-450 ?

25-40

0-40

 - Character.

Nonpersistent sandstone members 

with shale and clay of general 

reddish-brown color. A few 

thin beds of coal and limestone 

in lower portion.

Limestone, shale, and a little sandstone. . Contains the Pittsburgh, Pomeroy, Meigs Creek, 

Uniontown, ana Waynesburg 

coal beds, all of more or less value 

in the Woodsfleld quadrangle.

Irregular members grading into 

shales, commonly of reddishbrown or variegated colors. 

Upper and lower Pittsburgh 

limestone members near top; 

Ames and Cambridge limestone 

members a little below middle. 

Mahoning sandstone member at 

the base, locally productive of 

oil.

Sandstone, shale, and important 

clay and coal beds, including the 

Lower Kittanning, Middle Kittanning, and Lower and Upper 

Freeport.

Consists largely of sandstone and 

conglomerate, which rest with 

uneven contact on the eroded 

surface of the Mississippian 

beds. The sandstone is gen-' 

erally divided into several parts 

by beds of clay shale, and coals 

are also locally present.

Dark-gray and bluish to light-gray 

- limestone with interbedded 

shale and fine-grained sandstone.

Consists of sandstone, the 'Keener 

sand, interbeddod with shale; a 

valuable source of oil and gas.

Coarse sandstone interbedded 

with and grading laterally into 

sandy shale.

Mostly sandy shale in lower part, 

with a few beds of shaly sandstone.

Dark carbonaceous shale.

Berea sand, consisting of coarse to 

fine grained gray to white sandstone. Lenticular in the 

Woodsfield and Summerfield 

quadrangles.

Driller's description.'

Includes First Cow 

Run, Buell Run, and 

Mahoning sands.

Includes P e e k e r, 

Macksburg 500-foot, 

and Second Cow 

Run oil sands named 

in descending order.

Includes Maxton sand.

Big lime; includes Big 

lime sand.

Includes Keener oil 

sand.

Probably includes Big 

Injun and Squaw oil 

sands.

Includes Welsh oil 

sand.

Black shale.

Berea oil and gas sand.

a The part of this section below the Berea sandstone is taken from a paper by G; S. Rogers (The Cleveland gas field, Cuyahoga County, Ohio: U. S. Geol. Survey Bull. 661, p. 5, 1917).
14 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS. 

Generalized section of formations in eastern Ohio Continued.

- System.

Devonian or 

Carboniferous.

Devonian.

Unconformity 

Silurian.

Ordovician.

Group or 

formation.

Bedford shale;

.Ohio shale group.

Cleveland 

shale.

Chagrin shale.

Huron shale.

Olentangy? shale.

Delaware limestone.

Columbus lime- 

 stone.

Monroe formation.

Salina formation.

Niagara limestone.

"Clinton" formation.

"Medina" shale.

Shale and lime- 

' stone of Cincinnatian age.

Trenton (?) limestone. 

Thickness 

(feet).

20-40?

50-120

850-1,200

80

500-700

400-600

400-600

150-250

300-400

750-1,250

(?) .

Character.

Mottled gray, reddish, and brown- 

. ish shale.

Massive hard black bituminous, 

with a few bluish layers in lower 

portion.

Soft bluish-gray clay shale, with 

some concretionary layers.

Black and bluish shale in upper 

and lower portions, with a band 

of gray shale near middle .

Gray calcareous shale.

Blue and gray limestone, becoming dolomitic in lower part. 

Contains a 30 to 50 foot bed of 

white quartz sandstone, 350 to 

450 feet below top.

Shale, dolomite, anhydrite or 

gypsum, and rock salt. 

Dolomite and limestone. '

Crystalline limestone of various 

light colors; calcareous shale and 

thin-bedded limestone, with 

sandstone layer in lower part.

Red clay sljale, with thin layers of . 

, sandstone.

Dark shale, with thin layers . of 

limestone, especially in upper 

part.

Limestone.

Driller's description.

Ohio shale, 1,100-3,000 

feet, usually treated 

as a unit in southern 

Ohio.

Big lime; includes 

Newburg sand and 

some "stray" sands 

in lower 300 feet, 

490-1,825 feet.

Includes Little lime, 

75-150 feet.

Clinton sand, 0-60 feet.

25-75 feet.

Medina red rock.

Slate and shells.

Trenton lime.

LITHOLOGY AND MINERALOGY OF THE SEDIMENTS. 

KINDS OF ROCK.

The reservoir rocks are principally porous dolomitic limestones and 

quartzitic and calcareous sandstones interbedded with relatively impermeable shales, tightly cemented sandstones, and gradations be-
GEOLOGY OF APPALACHIAN FIELDS. 15

tween these rocks. Fragments of the oil and gas bearing rocks 

were collected when they were cleaned from wells in the different 

fields and have been examined both petrographically and chemically.

RESULTS OF PETROGRAPHIC EXAMINATION OF ROCK SPECIMENS.

For the petrographic study of the rock specimens we are indebted 

to M. I. Goldman, who reports as follows:

The results of the petrographic study, presented herewith, are only tentative,'as more detailed microscopic observations and more extensive study of the 

relation of the history and distribution of wells to the observed petrographic 

features are necessary to establish the conclusions.

The primary object of the investigation was to find any characteristics of 

the rocks that might bear on the distribution of oil in them. As the work 

progressed it appeared that, in addition, light might be thrown on some of 

the early stages of inetarnorphism and their relation to geologic conditions. It 

was found impracticable to make determinations of pore space, because, by 

the tearing out of soft minerals and in other ways, holes are produced in grinding the thin sections. As methods for the determination of the primary or 

syngenetic features of sedimentary rocks from their thin sections are still 

rather undeveloped and inadequate, no attempt was made to determine those 

features beyond recognizing that quartz, feldspar, mica, and clay substance 

were the principal constituents of the rocks examined. Otherwise the investigation was limited to the study of secondary or epigenetic minerals..

The following minerals were recognized:

Quartz as a secondary growth around the original grains and in continuous 

crystallographic orientation with them was found in almost all the sandstones 

that were not too argillaceous. The approach to quartzite was in general greatest in the deepest beds, though this relation was highly variable.

Kaolinite, known as a common mineral in sandstones, was found in fine 

crystalline aggregates filling the pore spaces.

Calcite and other carbonates seemed to be particularly abundant in productive sandstones in older fields in which wells 'were very numerous, thus 

indicating a relation to recent ground-water circulation resulting from drilling.

SiilpMdes (pyrite or marcasite) were scarce in oil and gas bearing rocks 

from the Woodsfield and Suinmerfield quadrangles and occurred mainly in the 

clays associated with carbonaceous matter, a common syngenetic relation. It 

is significant, however, as illustrating the mineralogic and chemical individuality of different fields, that in some regions outside of these areas in Ohio and 

Pennsylvania the sulphides are common in large aggregations in sandstones.

Chert and opal- growths were scarce and difficult to recognize and received 

no special attention.

Micas are probably the most significant of the secondary minerals. They 

are of various species and types, from almost colorless to yellowish green and 

from brilliantly polarizing to almost isotropic. Their differentiation from 

syngenetic micas is difficult, being based mainly on habit and distribution. 

They are the minerals that most require further study, but so far as can be 

stated at present their development in the pay sands seems to be, like that 

of the carbonates, related to circulation of water resulting from the opening of 

wells. However, as is shown in the subsequent discussion by Messrs. Mills and 

Wells, the chemical changes that resulted in the formation of these secondary 

micas; like those that produced the carbonates and other epigenetic minerals, 

probably also took place during the slow natural circulation that preceded
16 WATEES ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

drilling. In regard to changes in composition of the waters associated with 

oil and gas it is significant that some of the secondary micas are evidently 

chlorites and that magnesium would therefore have been used in forming them.

There were some indications that the development of secondary quartz and 

sulphides might also be related to the circulation of water resulting from the 

removal of oil and gas.

An interesting feature is the apparent granulation and recementing by silica 

of some of the grains of quartz in a few of the samples. This may be the 

beginning of the. mechanical part of metamorphism, but the possibility has 

also, been suggested that it is clue to crushing resulting from blows of the drill 

in sinking the well, with subsequent cementing. A choice between these two 

interpretations could be made only on the-basis of a study of the distribution 

of the samples showing this feature. The assumption of metamorphism due 

to pressure resulting from the weight of overlying beds is favored by the 

two facts that the phenomenon is apparently rare and that, so far as may be 

concluded from this preliminary study, it occurs mainly in samples from 

greater depths, especially in one from a depth of 2,230 feet.

No determinations of possible water-soluble minerals in the sections could be 

made, as these .would be removed in grinding.

It may be noticed that all the factors considered above are related to the 

occurrence and circulation of underground waters in the rocks. The underground waters in turn, as shown elsewhere in this paper, have important bearings on the occurrence of oil and gas.

A dark-brown stain, believed to be due to oil, is found in connection with 

carbonaceous matter in some of the clays, a relation well recognized in the 

oil shales of the western United States.1 No other direct relation between the 

oil and gas associated with the rocks and their microscopic features was established. The porosity would of course be "one of the most important properties 

to consider if the conditions under which thin sections are produced permitted 

its determination under the microscope.

As regards metamorphism in general, it is suggested that at least during 

the earliest stages an important factor may be the presence of open fissures or 

passages of exceptional porosity which would facilitate the flow of water 

through the rocks.

RESULTS OF CHEMICAL.EXAMINATION OF ROCK SPECIMENS.

In order to supplement the microscopic examination of the rock 

specimens obtained from the oil and gas wells, a number of chemical 

determinatiqns were made, together with a few fairly complete 

analyses. The proportions of the water-soluble constituents were 

first determined by extracting 2-gram portions of the powdered 

samples with about 100 cubic centimeters of water at ordinary temperature, filtering, evaporating the filtrates to dryness at 110° C., 

and weighing the residues. In Table 1 the results are stated as 

percentages of the rocks " soluble in water." The composition of the 

water-soluble material was not ascertained in the first determinations, but it is believed to have* been largely sodium chloride, as indicated in Tables 3 and 15. The proportion of water-soluble materials

1 See the studies of the late C. A. Davis.
GEOLOGY OF APPALACHIAN FIELDS.

ranged from 0.25 to 0.84 per cent. Next the leached portions of the 

samples were extracted with 1/10 hydrochloric acid in order to gain 

an insight into the nature of the acid-soluble constituents. The results are stated as percentages of the rock " soluble in HC1." After 

this treatment the residue was extracted with 5 per cent solution of 

sodium carbonate to determine the amount of soluble silica present.

TABLE 1. Chemical determinations on rock specimens from oil and gas wells. 

[Percentages of samples by weight. Determinations by R. C. Wells.]

Soluble in watem . ....................................

Soluble in 1/10 HC1: 

SiO, ..............................................

Fes03b.. .......................................... A1A-- ..-..--.-.-..--..-. ........................

CaO. ..............................................

MgO............................... ...............

P,0...............................................

COj. ..............................................

Soluble in 5 per cent solution of Na2C03 : 

SiO2 .. .............................................

1

0.05

.29

.95

.33

.12

.08

.02

Trace.

.15

2

0.17

.97

4.75

1.47

.37

.56

.10

2.14

.63

3

0.35

.12

2.35

.32

2.72

.73

.03

4.23

.14

4

0.84

.10

1.13

.14

1.35

.37

.01

1.80

.18

5

0.57

.04

.11

.03

.08

.02

.07

6

0.10

.08

.68

09

1Q

.09

.17

a Mainly chlorides. 6 All Fe as Fe2 03 .

1. Keener sand, of late Mississippian age; depth 1,451 to 1,469 feet; Jerusalem, Sunsbury Township. 

Mpnroe County, Ohio. Fragments of sandstone had been shot and cleaned from an old oil well and had 

lain exposed to the weather for severalmonths before being collected.

2. Shale underlying Third sand, of probable late Devonian age; depth, l,450±feet; Evans City, Butler 

County, Pa. Fragments of shale drilled from a new well and collected at once.

3. Berea sand, of early Mississippian age; Armstrongs Mills, Washington township, Belmont County, 

Ohio. Fragments of sandstone cleaned from a gas and oil well 10 years old. The sample was collected as 

soon as it was removed from the well.

4. Berea sand, of early Mississippian age; depth, 1,900± feet; Woodsfleld, Center Township, Monroe 

County, Ohio. Fragments of sandstone cleaned from a gas and oil well 10 years old. The sample was 

collected as soon as it was removed from the well.

5. Big lime sand (sandy phase of Maxvillelimestone), of late Mississippian age; depth, l,400±feet; Ozark. 

Sunsbury Township, Monroe County, Ohio. Fragments of sandstone snot and cleaned from a new oil well 

in an old field. The sample was collected as soon as it was removed from the well.

6. Third sand, of probaole late Devonian age; depth 1,430 to 1.460 feet; Evans City, Forward Township, 

Butler County. Pa. Fragments of sandstone shot and cleaned from a new oil well in a new field. The 

sample was collected as soon as it was cleaned from the well.

In Table 2 are presented the results of the more complete analyses.

TABLE 2. Analysis of rock specimens from oil and gas wells. 

[R..C. Wells, analyst.]

SiO2 ..... ............................................................

Fe8 0a (all Fe as Fe2O») .............................................

A12 08 ............................ ...................................

CaO. ...............................................................

MgO.......................................................... ......

P,06 .......................... ......................................

C02 .. ...............................................................

TI09 ................................................................

1

93.82

1.75

.73

.19

.25

.02

Trace.

.12

2.31

99.19

2

62.17

7.54

16.84

.44

1.46

.10

2.14

.87

3.95

95.51

3

85.90

2.82

1.68

2.96

..84

.03

4.23

.12

1.35

99.93

1. Keener sand, of late Mississippian age; depth, 1,451 to 1,469 feet; Jerusalem, Sunsbury Township. 

Monroe County. Ohio. Fragments of sandstone had been shot and cleaned from an old oil well and had 

lain exposed to the weather for severalmonths before being collected.

2. Shale underlying Third sand, of probable late Devonian age; depth, 1,450± feet; Evans City, Butler 

County, Pa. Fragments of shale drilled from a new well and collected at once.

3. Berea sand, of early Mississippian age; Armstrongs Mills. Washington Township, Belmont County. 

Ohio. Fragments of sandstone cleaned from a gas and oil well 10 years old. The sample was collected 

as soon as it was removed from the well.

91818° 19 2
18 WATERS ASSOCIATED WITH PETROLEUM AiSTD 3STATURAL GAS.

The chemical tests were made partly to ascertain the character of 

the cementing material. That generally found in sandy sediments 

includes silica and hydrous silicates of iron, aluminum, calcium, and 

magnesium, the composition depending somewhat on the foreign 

substances in the sand. As a matter of fact, pure siliceous sandstones 

are the exception. When, as in the rocks examined, clay, mud, and 

carbonates are also present the list of possible cements is greatly increased and includes the carbonates of iron, magnesium, and calcium 

and various phosphates and sulphates.

Tables 1 and 2 show that the proportion of carbonates in the sands 

examined is not large; in fact, carbonates are absent in the Bib lime 

sand, and only traces are found in the specimens of the Keener and 

Third sands. Much of the iron found in the shale below the Third 

sand and in the Berea sand from Woodsfield and practically all of 

that in the Berea sand.from Armstrongs Mills is present as ferrous 

carbonate, although reported as ferric oxide; the determination of 

ferrous iron is unreliable in the presence of organic matter. Magnesium was found in all but one of the sands, and some calcium in 

all. Sands 2, 3, and 4 effervesce with acid, but the other three sands 

show no appreciable effervescence. Sample 4, collected from an old 

well yielding oil and gas from the Berea sand, is salty to the taste 

and shows the largest proportion of material soluble in water. None 

of the specimens shows a marked amount of silica soluble in acid "or 

in sodium carbonate after treatment with acid, except the shale below the Third sand. This rock may contain a magnesium silicate 

which is decomposed by acid. The magnesium content .of all the 

specimens appears to be low, though it must be remarked that the 

relatively insoluble magnesium silicates would not be dissolved under 

the conditions of these experiments. Dolomite is present only in 

small amounts, but specimens of the deeply buried limestones that 

have been previously reported as dolomitic could not be procured for 

examination.

Small proportions of water-soluble salts, more particularly sodium 

chloride, were found in all the rock samples in which these constituents were sought. Some uncertainty as to the mode of occurrence 

of the salts is introduced by the small proportions contained in the 

rocks examined. The salts are present in smaller proportions than 

would be found in a sandstone having a total porosity of 15 per cent 

if it were saturated with an average Appalachian oil field brine and 

then dried. It may therefore be suggested that the salts in the specimens examined have been deposited merely by the drying of small 

amounts of brine contained in the rocks when the specimens were 

collected. This suggestion would be reasonable if the rocks had been 

saturated with water when they were collected from the wells, but 

some of them, were partty saturated with oil and came from rela-
GEOLOGY OF APPALACHIAN FIELDS. 19

tively water-dry strata. The occurrence in a sedimentary rock, now 

relatively dry of water, of 0.5 per cent of water-soluble matter, of 

which. 82.7 per cent is made up of chlorides, suggests that salts of 

this type were deposited in the rock as a result of deep-seated 

evaporation.

As will be explained later, the brines associated with oil and gas 

in the Appalachian fields have probably undergone concentration, 

and the salt that occurs in densely cemented barren rock may have 

been included in other minerals deposited chemically from the waters 

before they reached their present stage of concentration. In other 

words, water concentration and cementation have probably been more 

or less concomitant processes, and the soluble salts, especially sodium' 

chloride, may have been mechanically included in the cements. It is 

significant that chlorides, especially sodium chloride, occur in the 

densely cemented sediments and in secondary deposits of calcite and 

barite collected from oil wells. The possibility that the included 

sodium chloride was formed concomitantly with calcium carbonate 

by the mixing and concentration of waters of different types is discussed in the succeeding text. As related to the concentration problem, which is also developed in succeeding pages, it seems important 

that sodium chloride constitutes 86.5 to 100 per cent of the chlorides 

present in the samples examined, whereas the salts obtained by the 

complete evaporation of the brines contain about 20 per cent of calcium chloride and 5 per cent of magnesium chloride.

TABLE 3. Water-soluble material, chlorides, and sodium chloride in deeply

buried sediments.

[S. C. Dinsmore, analyst.]

2.......................................................

3.......................................................

4.......................................................

6.......................................................

Percentage 

of watersoluble 

material in 

the rocks.

0.131

.245

.332

.139

.509

.092

Percentage 

ofchlorides 

in the 

rocks.

0.029

.157

.173

.098

.421

.043

Percentage 

of NaCl in 

the rocks.

0.029

.150

.165

.096

.364

.043

Percentage 

of NaCl 

in the 

chlorides.

100.0

95.5

 95. 4

98.0

86.5

100.0

1. Densely cemented siliceous shale underlying Third sand; depth 1,450± feet; Evans City, Butler 

County, Pa. The shale appeared to be relatively dry of salt water and oil.

2. Hundred-foot sand; depth 1,060± feet; Evans City, Butler County, Pa. The sample was cleaned from 

the productive horizon in a new oil well in an old field. The well yielded both oil and salt water.

3. Berea sand; Armstrongs Mills, Belmont County, Ohio. Cleaned from an old oil well.

4. Third sand; depth 1;422 feet; near Evans City, Butler County, Pa. The sample was cleaned from a 

new oil well. The sand yielded oil but was reported to be relatively free from salt water.

5. Big lime sand; depth 1,400± feet; half a mile west of Ozark Village, Sunsbury Township, Monroe 

County. Ohio. The sample was cleaned from a new oil well in an old field where the Big lime sand is reported to be relatively dry of salt water.

6. Hundred-foot sand; Jefferson Township, Butler County, Pa. Cleaned from a new well in which 

gas, oil, and water were practically absent.
20 WATERS ASSOCIATED WITH PETROLEUM AISTD NATURAL GAS.

The analyses on which Table 3 is based were made in the following 

manner :

A 50-gram portion of the finely pulverized sample was leached 

with 300 cubic centimeters of distilled water at 45° C. for 17 hours, 

with frequent stirring. The resultant solution was then filtered into 

a graduated 500 cubic centimeter flask and the leached sample washed 

with distilled water until the filtrate attained a volume of 500 cubic 

centimeters. Aliquot portions, representing 10 grams of the sample, 

were taken for determinations of total water-soluble material, Ca, 

Mg, Na, K, S'04 , and Cl. The material that was soluble in water 

was determined by evaporating to dryness and heating at 110° C. 

for one hour, cooling the residue in a desiccator, and weighing. Other 

analytical determinations were made in the usual manner.

RESULTS OF PHYSICAL EXAMINATION OF ROCK SPECIMENS.

In order to study further the character of these rocks, physical 

tests were made on lump specimens to determine the percentage of 

total pore space in which oil, gas, and water might occur or in which 

mineral matter might be deposited. For this work we are indebted 

to A. F. Melcher, of the United States Geological Survey. The total 

proportions of pore space in the fragments tested are shown in Table 

4 to range from 4 or 5 up to 18 or 19 per cent of the rock volume. 

Notwithstanding the care exercised in collecting the specimens, 

some of the lumps of rock that are thought to be pay sand, which 

were obtained after productive oil and gas wells had been shot, may 

represent hard, relatively dense layers of the sandstone and not the 

porous, open-textured pay sands from which the oil and gas are derived. Apparently no consistent relation exists between the porosity 

of the sands and the size and shape of the component grains1. The 

variations in porosity are due largely to the irregularity with which 

the sediments have been cemented both before and during the extraction of oil and gas.

In addition to the porosities shown in Table 4 Richardson* reports 

that some lump samples of the Hundred-foot sand collected in Butler County, Pa., have total porosities as low as 4.5 to 7.3 per cent. 

It seems probable that the total pore space in the relatively open-textured parts of the Hundred-foot sand may be at least 15 to 18 per 

cent or more of the rock volume, though we have no positive data 

on this subject.

1 Richardson, G. B., Note on Appalachian oil field brines: Econ. Geology, vol. 12, 

pp. 39-41, 1917.
TABLE 4. Total pore space in oil and gas bearing sands and associated rocks, wit

Total weight of sample,

Total weight sieved, 

grams. . ...................

Diameter (millimeters) :

1.651-0.833........ do....

0.833-0.417. ...... .do....

0.417-0.295.. :..... do....

0.295-0.208........ do....

0.208-0.147........ do....

0.147-0.104........ do....

0.104-0.074..... ...do.... 

0.074-0.000........ do.-..

1

/53. 2390 

\31. 9740

fll. 2

\10.8 

7.955

48.0

36.8

4.9 

10.3

100.0

2.647

2

J10. 7327

},0

5.400

8.3

50.6

26.1

3.7 

11.3

100.0

2.675

3

17. 7060

12.7

6. 435

13.1

63.3

8.6 

15.0

100.0

2.659

4

40'. 8190

12.7

13. 125

2.4

29.4

53.3

10.1

1.7 

3.2

100.1

2.646

5

'41. 1200

13.1

10. 925

20.4

56.4

14.7

2.5

1.6

1.1

.7 

.9

100. 0

2.654

6

8.9700

fl.3

8.940

0.6

31.8

45.2

in 3

5.0

3.6

1.7

.4 

1.2

99.8

2.651

7

16. 2382

4.7

' 7.635

38.2

9.6 

16.2

100.0

2.665

8

14. 0895

9.7

6.450

37.6

26.0 

36.4

100.0

2.727

9'

5.7653

11.0

3.625

0.8

.8

16.6

18.3

13.8

11.2

11.0

12.0 

15.4

99.9

2.705

41.48

17.7

6.94

1.9

41.1

47.2

3 4

2.7

1.7

1.0

.5 

.6

100.1

2.65

a The rock specimens upon which these tests were made were collected by D.' Dale 

in southeastern Ohio. The physical determinations were made by A. F. Melcher.

1: Berea sand; depth 2,050± feet; Woodsfield, Center Township, Monroe County, 

Ohio. Fragment from a productive oil well;

2. Berea sand; depth 1,807-1,829 feet; Woodsfield, Center Township, Monroe County, 

Ohio. Hard, densely cemented fragment from a Berea gas well.

3. Berea sand; depth 1,440± feet; sec. 26, Buffalo Township, Noble County, 01119. 

Hard, densely cemented fragment from a nonproductive well. \

4. Keener sand; depth 1,539-1,570 feet; Woodsfield. Center Township, Monroe County, 

Ohio. From the bed which yielded gas, oil, and salt water.

5. Big Injun sand; depth 1,460-1.470± feet; Lewisville, Summit Township, Monroe 

County, Ohio. From the bed which yielded gas, oil, and salt water. The initial daily 

yield from the well was 80 barrels of oil.

6. Keener sand; depth 1,220-1,259 feet; Coats Station, Center Township, Monroe 

County. Ohio. Fragment of sandstone from the bed from which oil and salt water were 

pumped.

7. Berea sand; depth 1,535± feet; Chaseville, Seneca Township, Noble County, Ohio. 

Hard, densely cemented fragment from a nonproductive well.

8. Hard, bluish-gray shale overlying the Keener sand; depth 1,445± feet; Jerusalem, 

Sunsbury Township, Monroe County, Ohio.

9. Light bluish-gray shale underlying the Keener sand; depth 1,475± feet; Miltonsburg, Malaga Township, Monroe County, Ohio.

Condit and R. Va

10. Keener san

County, Ohio. L

production of oil 

barrels. .

11. Berea sand; 

ty, Ohio. Fragm

lected yielded bot

12. Berea sand; 

Fragment from pr

oil and gas with p

13. Gas sand; d

Fragment from a 

14. Big Injun sa

County, Ohio. F

15. Berea sand; 

ty, Ohio. Fragm

lected yielded oil 

16. Berea sand; 

tive bed. 
22 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

CHARACTERISTICS OF THE OIL AND GAS IN THE 

APPALACHIAN FIELDS.

N

The chemical examination by the Bureau of Mines of crude petroleum and natural gas collected during our field studies and the 

many other available analyses of the oils and gases from the areas 

studied x indicate that the oils are composed essentially of members 

of the paraffin series and contain no asphalt. It is evident from their 

generally low specific gravity, ranging from 0.6837 to 0.8482, and 

also from their fractional distillation, especially between 150° and 

300° C., that the oils, with but few possible exceptions, contain no 

considerable proportions of the aromatic series. The sulphur content 

of the oils is also insignificant.

Analyses of natural gas from the Appalachian fields, reported in 

percentages by volume, moisture free, show that the gas consists essentially of the paraffin hydrocarbons methane and ethane. The 

usual methane content ranges from 66.0 to 98.0 per cent and that of 

ethane from less than 1 to more than 29 per cent. The carbon dioxide 

content ranges from less than 0.1 to more than 5 per cent; and 

that of nitrogen from less than 0.5 to more than 5 per cent. The 

oxygen content is generally less than 0.5 per cent. The proportions 

of hydrogen sulphide and other minor constituents are practically 

negligible.

It is unfortunate that little or no attention has been paid to the 

accurate determination of the moisture content of natural gas as it 

is drawn from the reservoir rocks and that inadequate study has been 

given to the physical and chemical relations existing between petroleum and natural gas on the one hand and their associated waters 

and reservoir rocks on the other.

OCCURRENCE AND DISTRIBUTION OF WATER IN THE

STRATA.

PRESENT DISTRIBUTION OF WATER IN THE OIL AND GAS 

BEARING ROCKS.

WATER-BEARING SANDS.

In the Appalachian fields the oil sands of both the Pennsylvania!! 

and Mississippian series are generally water bearing throughout, 

though some of the beds are locally termed dry because they do not 

yield perceptible flows of water into open wells. Thus in the Woodsfield and Summerfield quadrangles, in southeastern Ohio, the Big 

lime sand, a lenticular sandstone in the Maxville limestone, of late

1 Day, D. T. ( The production of petroleum in 1913 : U. S. Geol. Survey Mineral Resources, 1913, pt. 2, pp. 1126-1284, 1914.
DISTRIBUTION OF WATER IF THE STRATA. 23

Mississippian age, is locally termed dry, though in places within 

these quadrangles, it is characteristically water bearing. The Keener 

and Big Injun sands in southeastern Ohio are characteristically water 

bearing, though they too fail to yield appreciable flows of water in 

certain oil and gas fields and in some barren areas. In general 

wherever in western Pennsylvania paying quantities of oil are 

found in the Hundred-foot sand, of probable early Mississippian 

age, that sand contains abundant water.

DRY SANDS.

Some of the oil and gas bearing sands are relatively free from 

water that is, they fail to yield perceptible flows of water into 

open wells and are consequently termed dry sands. In some of the 

beds of the Devonian system or of probable Devonian age, more 

particularly those of the Catskill (?) formation in western Pennsylvania, the apparent absence of water is the rule rather than the exception. Here again, however, the distribution of water is irregular, 

parts of the so-called dry sands evidently being saturated with water.

We believe that in strata penetrated by the drill the existence of a 

sand actually "dry of water is doubtful. The occurrence of small 

amounts of water in a sand may be overlooked because the water 

evaporates into gas entering wells, or because the proportion of 

water accompanying oil may be too small to be observed. Water is 

generally found at the bottoms of inclosed or covered field tanks 

that receive oil from so-called dry sands. Such sands are only relatively dry of water. The failure of a bed to yield a perceptible flow 

of gas, oil, or water into a well does not necessarily signify the absence of any of these fluids. In beds such as shales and tight sands 

the rock interstices may be too fine to emit noticeable amounts of the 

fluids, or the fluid movements into a well may be so slow as to require 

several days or even weeks to make the presence of gas, oil, or water 

noticeable. The fact that water introduced into a well is absorbed by 

a sand indicates merely the comparative dryness of that sand but in 

no way signifies the absence of water.

Several explanations have been offered to account for the so-called 

dry sands. In a recent contribution Reeves x concludes that the " non 

water-bearing " sandstones of what has been called the Catskill formation in southwestern Pennsylvania and West Virginia were dried 

out while exposed to the air under the semiarid conditions which he 

supposes to have existed during the Catskill time. He further postulates the exclusion of water from these beds during later submero

gence, owing to the presence of interstitially included air.

1 Reeves, Frank, The absence of water In certain sandstones of the Appalachian oil 

fields: Bcon. Geology, vol. 12, pp. 354-378, 1917.
24 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

The abundance of epigenetic minerals with which the so-called 

dry sands are cemented and which were evidently deposited from 

circulating water suggests to us the long-continued presence of more 

water than the so-called dry sands now contain. What therefore 

seems to be a more plausible explanation for the comparative dryness 

of certain beds is that the displacement of water in these beds by 

compacting and cementation or by the incursion of petroleum and 

natural gas l has been relatively complete, or that the sands may have 

been partly dried out by the evaporative processes herein described. 

In regard to this last suggestion, it is a significant fact that the water 

content of the strata decreases and that the-degree of concentration 

of the dissolved constituents of the waters increases with increasing 

depth.

An argument used by Reeves, that red beds are proof of the former 

existence of an arid climate, is somewhat weakened by the fact that 

red ferric oxide may be formed from hydrated ferric oxide by the 

dehydrating action of salt solutions, just as anhydrite is similarly 

formed from gypsum. Daubree 2 states that he carried out this 

dehydration experimentally in a saturated solution of sodium chloride 

at only 150° C. According to him, filie de Beaumont 3 seems to 

have been the first to point out the causal relation between salt formations and the variegated red tint of certain clays, sandstones, and 

even of salt itself. . '

In showing that water does not always disappear at depth, Reeves 4 

calls attention to the occurrence of salt water in the Lower Devonian rocks near Charleston, W. Va., and McDonald, Pa. In a deep 

well at McDonald, salt water was encountered at a depth of 6,260 

feet, presumably in the Oriskany sandstone, and rose 4,000 feet in 

the well. During the preparation of this bulletin we have collected 

and examined waters from the Upper Devonian series in Butler 

County, Pa., where the beds in many places are termed dry.

Broadly speaking, we believe that within the Appalachian basin all 

the sands reached by the drill are water bearing and that there is no 

regional level" of water saturation above which a deeply buried oil 

and gas bearing rock is dry. The so-called water surfaces, the upper 

limits of water saturation, and the so-called non water-bearing portions of the oil and gas. bearing sands are only local in their 

occurrence.

1 Johnson, R. H., The r61e and fate of the connate water in oil and gas sands: Am. 

Inst. Min. Eng. Trans., vol. 51, pp. 587-592, 1916.

2 Etudes et experiences synthe"tiques sur le metamorphisme: Annales des mines, 5th 

ser., vol. 16, p. 411, 1859; Smithsonian Inst. Ann. Kept., 1861, p. 270.

3 DaubreVs reference is " Explication de la carte ge"ologique de France, vol. 2, p. 94."

4 Reeves, Frank, The absence of water in certain sandstones of the Appalachian oil 

fields : Econ. Geology, vol. 12, pp. 354-378, 1917.
OCCURRENCE OF OIL, GAS, AND WATER IN THE SANDS. 25

The irregular distribution and arrangement of the gas, oil, and 

water contents .of the productive sands are due, no doubt, to a complex succession of events in which rock movements, the displacement 

of water by oil and gas, compacting and cementation of the sediments, conditions of structure, texture, and lenticularity of the beds, 

the evaporation of water into moving and expanding gases, and, 

finally, the movements of the fluids incident to gas and oil extraction by man have afforded important modifying conditions.

Surface waters are constantly percolating into the shallow rocks, 

so that near the surface and near the outcrops of the reservoir rocks 

the saline waters undergo dilution by incursions of water from shallower sources. The distribution of typical Appalachian oil-field 

brines, having only chloride salinity, is therefore limited to those beds 

in which the excessive influx of surface water has been prevented.

MODE OF OCCURRENCE OF PETROLEUM, NATURAL 

GAS, AND WATER IN THE WATER-BEARING SANDS.

OIL, GAS, AND WATER MIXTURES.

In order to explain more clearly the changes that the waters associated with petroleum and natural gas, undergo during the extraction of these substances from their reservoir rocks, it is necessary to 

consider the mode of occurrence. A fact that seems to have been 

generally overlooked is that in most of the water-saturated pay sands 

in the Appalachian fields the natural segregation of gas and oil 

above water is very incomplete, so that gas, oil, and water occur intimately mixed in the interstices of the pay sands. Munn1 has described this mode of occurrence of petroleum in the Sewickley quadrangle, in Pennsylvania, where portions of the Hundred-foot sand 

were inferred by him to be completely saturated with mixtures of 

oil and water. Field observations supplemented by inquiries among 

operators in the Butler and Zelienople quadrangles, in western Pennsylvania, have led to the conclusion that similar mixtures occur in 

the Hundred-foot sand throughout these two quadrangles. A more 

thorough investigation in the Woodsfield and Summerfield quadrangles, in southeastern Ohio, affords convincing evidence that this 

is a common mode of occurrence of both gas and oil in the watersaturated sands in these areas. This mode of occurrence of mixtures 

of gas, oil, and water involves a very indefinite demarcation between 

water and overlying mixtures rich in the hydrocarbons, the so-called 

oil-water surfacoe being extremely irregular gradations from mixtures containing large proportions of oil and gas to mixtures less rich 

in these substances or to water containing too little gas and oil to

1 Munn, M. J., Geology of the oil and gas fields In the Sewickley quadrangle, Pa.: 

Pennsylvania Top. and Geol. Survey Comm. Kept. 1, p. 85, 1910.
26 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

warrant production. Where the top of a typical water-bearing pay 

sand is relatively high, owing to folding or to the lenticular character 

of the sand, gas and oil are frequently found more completely segregated above the water than in the adjacent portions of the same sand 

where the mixtures are less rich in gas and oil.

Another important fact, brought forth by these detailed studies, 

is that the so-called oil-water surfaces, the irregular and indefinite 

contacts between oil and water, appear from well logs to be inclined 

in the same direction as the tops of the pay sands, though less steeply. 

Such inclined oil-water surfaces in Oklahoma have been described 

by Beal.1

EVIDENCE OF THE OCCURRENCE OF OIL, GAS, AND WATER

MIXTURES. '

Evidence bearing upon the conditions above set forth has been 

procured by inquiries among oil and gas men, together with detailed 

observations in the different fields that we have studied. Gas, oil, 

and water are generally produced simultaneously from wells drilled 

either to the tops of water-saturated pay sands or only a few feet 

into them. Many of these wells continue to produce mixtures of oil 

and water together with gas for periods of 10 to 30 years. Some of 

them flow at first several hundreds or thousands of barrels of mixed 

oil and water a clay. Those that originally yield large quantities of 

oil with practically no water generally yield both water and oil as 

the initial rates of flow diminish. These phenomena are due partly 

to the .differential flow of oil and water through the sands, but it is 

not probable that great volumes of oil, gas, and water would be 

yielded together from the top of a pay sand just tapped if the segregation of the gas and oil above the water were at all complete.

In several fields it has been possible to compare the yields from 

individual wells that were first drilled to the tops of the pay sands 

and were subsequently drilled deeper into the same pays. For example, a well near Miltonsburg, Malaga Township, Monroe County, 

Ohio, was first drilled 3 feet into the Keener sand in November, 

1915, and had an initial daily rate of production of 9 barrels of oil 

with 12 barrels of salt water. After having been pumped for three 

months the well was yielding only 3£ barrels of oil a day, though 

the daily production of water remained at about 12 barrels. In 

April, 1916, the daily rate of oil production had declined still further, though the water production remained about the same. The 

well was then drilled 6 feet deeper into the pay sand and yielded 

7 barrels of oil a day, with about 18 barrels of salt water. If at this 

place the segregation of oil above the water had been nearly com1 Beal, C. H., Geologic structure in the Cushing oil and gas field, Okla., and its relation to the oil, gas, and water: U. S. Geol. Survey Bull. 658, 1917.
TEMPERATURE AND PRESSURE. 27

plete, the increase in depth of the well would probably have brought 

about a relatively large increase in the amount of water produced 

and a correspondingly small increase in the amount of oil. On the 

contrary, however, the production of oil was increased 100 per cent 

by drilling the well deeper, whereas the production of water was increased only 50 per cent. The oil and water must have been rather 

intimately mixed, a large proportion of the oil occurring below the 

water that was being produced before the well was deepened.

The example cited is typical of a large number of such occurrences 

reported during our field studies. It must be noted, however, that 

drilling wells deeper in water-saturated sands is dangerous, because 

of the large amounts of water that may be encountered under the 

rich oil and water mixtures in the same or underlying pay sands. 

Many valuable wells have been spoiled in this way.

TEMPERATURE AND PRESSURE.

The temperatures at which oil, gas, and water occur in their reservoir rocks were not measured during our field investigations but are 

shown by the deep-well temperature measurements of Hallock,1 

Johnston,2 and Van Orstrancl 3 to range from 18° or 19° C. at a depth 

of 1,000 feet to about 33° to 36° C. at a depth of 3,000 feet. To what 

extent the rocks together with their included waters and hydrocarbons have cooled subsequent to periods of regional deformation or 

subsequent to periods of deepest burial is of course uncertain, but it 

is reasonable to assume that the waters under scrutiny have been subjected to much higher temperatures than those just quoted. Such a 

supposition is strengthened by the occurrence of highly heated saline 

waters in the oil fields of Louisiana and Texas. 

o Data relative to initial gas pressures encountered in various reservoir rocks were furnished by operators. These pressures range from 

only a few pounds to the square inch in the shallow sands to several 

hundred pounds in the deeper beds. In the Woodsfield and Summerfield quadrangles the initial gas pressures may be summarized as 

follows: Big lime sand, 400-to 440 pounds to the square inch; Keener 

sand, 470 to 480 pounds; Big Injun sand, 500 pounds; Berea sand, 

565 to 735 pounds. In the Butler and Zelienople quadrangles the 

following initial gas pressures in the deeper sands are reported: 

Hundred-foot sand, 750 to 810 pounds to the square inch; Third sand, 

750 to 820 pounds; Fourth sand, 810 to 930 pounds, and Fifth sand, 

860 to 875 pounds.

1 Hallock, William, Subterranean temperatures at Wheeling, W. Va., and Pittsburgh, 

Pa. : School of Mines Quart., vol. 18, pp. 148-153, 1897.

2 Johnston, John, Note on the temperature in the deep boring at Pindlay, Ohio: 

Am. Jour. Sci., 4th ser., vol. 36, pp. 131-133, 1913.

8 Van Orstrand, C. B., unpublished manuscript, U. S. Geological Survey.
28 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

The following table contains some data from the literature and 

from our unpublished notes on gas pressures:

TABLE 5. Initial gas pressures at different depths in several gas fields.

Name of bed.

Do....................

Do....................

Do...................

Do...................

Do...................

Do...................

Do...................

Do...................

Do...................

Do...................

(?)..... ..................

(?).......................

(1)..... ..................

(?).... ...................

Locality.

Wayne Township, Belmont County, Ohio.

laga Township, Monroe 

County, Ohio. 

Wayne Township, Belmont County, Onio. 

Woodsfield, Ohio ..........

.....do. . ..................

.....do....................

roe County, Ohio. 

ler County, Pa. 

Butler, Pa................

.....do....................

.....do....................

.....do....................

.....do....................

.....do....................

Knox County, Ohio.

Newberg, Ohio. . ..........

Cleveland, Ohio. . .........

West Virginia. ............

.....do....................

.....do.................:..

Depth 

(feet).

1,295

1,310

1,412

1,465

1,515

1.468

2,090

1,698

2,060

1,400

1,700

1,452

1,800

1,568

1.950

2,700

/ 2, 500

\ 2, 900 

3,000

950

650

4,500

4,090

2,989

947

1,370

1 650

l'800

Initial 

gas 

pressure 

(pounds 

per 

square 

inch).

280

365

400

440

475

500

710

565

735

380

780

785

600

870

225

870

810

800

1,100 

425

400-450

328

37

1,800

1,420

490

540

650

600

310

Average 

increase of 

pressure 

per 

100 feet 

(pounds 

persquare 

inch).

22

28

28

30

31

34

34

33

36

32

56

46

41

48

14

45

30

132-3814 '

42-47

50

0.82

44

47

52 .

39

39

33

41

Authority.

Data furnished by 

various oil and 

gas companies.

Do.

Do.

Do.

Do.

Do.

. Do.

Do.

Do.

Do.

Do.

Do.

Do.

Do.

Do.

Do.

Do.

I. C. White.d

Do.

Do!

Do.?

Lewis.ft

a Rogers, G. S., The Cleveland gas field, Cuyahoga County, Ohio: U. S. Geol. Survey Bull. 661, p. 37. 

1917.

& Van Horn, F. R., Reservoir gas and oil hi the vicinity of Cleveland, Ohio: Am. Inst. Min. Eng. Trans.. 

vol. 56, p. 839,1917.

c Orton, Edward, The Trenton limestone as a source of petroleum and natural gas in Ohio and Indiana: 

U. S. Geol. Survey Eighth Ann. Rept., p. 645, 1889.

d Personal communication.

«Stebinger, Eugene, Possibilities of oil and gas in north-central Montana: U. S. Geol. Survey Bull. 641, 

p. 73.1916.

/ Knapp, I. N., discussion of paper by R. W. Johnson, The rdle and fate of connate water in oil and gas 

sands: Am. Inst. Min. Eng. Trans., vol. 51. p. 593.1915.

g Knapp, I. N., discussion of paper by W. H. Kobbe, The recovery of petroleum from unconsolidated 

sands: Idem, vol. 56. p. 825,1917.

ft McMurray, W. F., and Lewis, J. 0., Underground wastes in oil and gas fields and methods of prevention: Bur. Mines Tech. Paper 130, p. 13,1916.
CHARACTERISTICS OF THE WATERS. 29

Dr. I. C. White 1 reports gas pressures in West Virginia ranging 

from 600 pounds to the square inch in the Big Injun sand to as much 

as 1,800 pounds in a sand 4,090 feet deep. Rogers 2 reported gas 

pressures of 800 to 1,100 pounds to the square inch in the so-called 

Clinton sand near Cleveland, Ohio.

Table 5 shows that in several localities there is a rough proportion 

between initial gas pressure and depth, especially in the deeper sands. 

It is well recognized that gases forming from organic matter develop 

pressure when confined. To what extent these gas pressures or " rock 

pressures " are due to this or other causes is problematic, but whatever 

the source or origin of the gases and the causes of the pressure, the 

table suggests that there have been adjustments of pressure according 

to depth. It seems probable that hydrostatic pressure, weight of 

superincumbent strata, rock movements, deep-seated thermal conditions, the long-continued formation of natural gases, and the resistance to fluid movements through the strata all enter into the 

causes for "rock pressure." In other words, "rock pressures" are 

not necessarily " fossil pressures" but represent a summation of 

effects from remote time up to the present.

CHARACTERISTICS OF THE APPALACHIAN OIL AND 

GAS FIELD WATERS.

DEEP-SEATED BRINES AND THEIR COMPARISON WITH SEA

WATER.

As the result of our studies we have concluded that the deepseated Appalachian oil and gas field brines are, in part, the derivatives of former ocean water. Certain fundamental differences in 

composition, however, exist between ocean water and the waters 

under consideration. These differences have been noted in the 

literature 3 and are strikingly shown by Table 6. In the part of the 

table on page 30 analyses of the dissolved solids are expressed as percentages of the several constituents. The proportions of total dissolved solids in the different waters are also shown here, in terms of 

grams per kilogram or grains per liter. On page 31 are shown ratios 

of some of the constituents to chlorine. As the chlorine content of 

the dissolved solids in the waters under comparison is more uniform

1 Personal communication.

3 Rogers, G. S., The Cleveland gas field, Cuyahoga County, Ohio : TJ. S. Geol. Survey 

Bull. 661, p. 37, 1917.

3 Hunt, T. S., Chemical and geological essays, pp. 11-12, Boston, 1875. Palmer, 

Chase, The geochemical interpretation of water analyses: U. S. Geol. Survey Bull. 479, 

Table 2, opposite p. 14, 1911. Washburne, C. W.f Chlorides in oil-field waters: Am. 

Inst. Min. Eng. Trans, vol. 48, pp. 687-693, 1914.
30 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

than that of the other constituents or of the total dissolved solids 

themselves, the ratios of the different constituents to chlorine are 

used as a basis for comparison. The ratios are first stated in terms 

of the actual percentages of the dissolved solids. In the lower part 

of the table these ratios are expressed in terms of the chemical 

reacting values of the constituents. The principle of reacting values 

has been applied in the interpretation and comparison of water 

analyses by several American investigators, among whom may be 

mentioned Stabler,1 Palmer,2 Spencer,3 Emmons and Harrington,4 

Van Winkle,5 Waring,6 Clapp,7 Siebenthal,8 and Eogers.9

TABLE 6. Comparison bet/ween ocean water and Appalachian oil and gas field

brines.

(Al,Fe)a03 . .................

Fe".........................

Al...........................

Ca...........................

Sr...........................

Ra

Mg. .........................

Na. .........................

K.. .........................

co3 .... .....................

ucot.. .....................

SO^.... ....................

CU. .........................

Br,I... .....................

Total dissolved solids, 

grams per kilogram. .

Ocean water.

1

1.20

3.71 

30.54 

1.11 

.05 

.31

7.68 

55.21 

.19

100.00 

/33. 01- 

\ 37.37

2

1.18

3.59 

31.08 

.71 

.18

7.72 

54.39 

1.15

100.00 

| 37.66

Bitterns 

derived from 

concentration of 

ocean water.

3

0.26

3.72 

32.06

.78

5.78 

56.18 

1.22

100.00 

275. 46

4

10.05 

20.39 

2.25

14.64 

49.99 

2.68

100.00 

337. 12

Appalachian oil and gas field waters.

Pennsylvania.

5

0.01

.03

.08

8.57 

.16 

None. 

1.46 

27.34 

.20 

None.

.02 

61.97 

.16

100.00 

122. 16

6

0.06

9.56 

1.31 

Trace. 

.94 

24150 

1.97 

None.

.02 

61.38 

.26

100.00 

263. 64

7

Trace. 

0.05

8.40 

Trace. 

Trace. 

1.47 

27.59 

.10 

None. 

None. 

.10 

62.29

100.00 

131. 89

Ohio.

8

0.06

.01 

.10 

. 8.19

1.30 

27.82 

.49 

None. 

.03 

None. 

62.00

100.00 

6 141.13

9

-v 0.41

0.10

.70 

5.18 

./.......

1.63 

29.88 

.96 

None. 

.70 

. None. 

.60.44

100.00 

6 53. 06

0 Total iron. 6 Grams per liter.

1 Stabler, Herman, Industrial water analyses and their interpretation by the engineer : Eng. News, vol. 60, p. 355, 1908.

" Palmer, Chase, The gee-chemical interpretation of water analyses: U. S. Geol. 

Survey Bull. 479, pp. 12-14, 1911; Mineralogy of waters from artesian wells at Charleston, S. C. : U. S. Geol. Survey Prof. Paper 90, pp. 92-93, 1914.

3 Spencer, A. C., Chalcocite enrichment: Econ. Geology, vol. 8, p. 646, 1913.

4 Emmons, W. H., and I-Iarrington, G. L., A comparison of waters of mines and hot 

springs: Econ. Geology, vol. 8, p. 661, 1913.

5 Van Winkle, Walton, Quality of the surface waters of Washington: U. S. Geol. 

Survey Water-Supply Paper 339, pp. 34-35, 1914; Quality of the surface waters of 

Oregon : U. S. Geol. Survey Water-Supply Paper 363, pp. 37-38, 1914.

"Waring, G. A., Springs of California: U. S. Geol. Survey Water-Supply Paper 338, 

pp. 22-23, 1914.

7 Clapp, C. H., Sharp Point hot spring, Vancouver Island, British Columbia : Canada 

Geol. Survey Summary Kept, for 1913, pp. 80-83, 1914.

8 Siebenthal, C. E., Origin of the zinc and lead deposits of the Joplin region, Missouri, Kansas, and Oklahoma: U. S. Geol. Survey Bull. 606, 1915.

8 Eogers, G, S., The interpretation of water analyses by the geologist: Econ. Geology, 

vol. 12, pp. 56-88, 1917 ; Chemical relations of the oil-field waters in San Joaquin Valley, 

Cal.: U. S. Geol. Survey Bull. 653, 1917.
CHARACTERISTICS OF THE WATERS. 31

TABLE 6. Comparison between ocean u'«4er and Appalachian oil, etc. Contcl.

Ratios of the percentages of certain constituents to that of chlorine.

- .

Ca.. :...-....................

MR..........................

SOi.........................

Ocean water.

1

0.553 

.022 

 .067 

.139

2

0.571 

.022 

.066 

.142

Bitterns 

derived from 

concentration of 

ocean water.

3

0. 571 

.005 

.066 

.103

4

0.408 

.000 

.201 

.292

Appalachian oil and gas field waters.

Pennsylvania.

5

0.441 

.138 

.024 

.0003

6

0.399 

.156 

.015 

.0003

7

0.443 

.135 

.024 

.002

Ohio.

8

0.449 

.132 

.021 

.000

9

0.494 

.080 

.027 

.000

Ratios of the reacting values ° of certain constituents to that of chlorine.

[Per thousand of chlorine.]

Na. .........................

Ca.................. .........

Mg... .......................

S0«.. .......................

852.5

38.4

196.6

102.7

880.2

38.4

192.5

104.9

880.2

8.19

193.0

76.0

628.9

586.2

216.1

679.8

244.9

68.8

.2

615.1

275.7

44.7

.2

682.9

238.7

68.8

1.19

692. 1 

233.8

61.1

.0

761.5

151.7

78.6

.0

a The moaning of the term "reacting value" is explained by Herman Stabler (Some stream waters of 

the western United States: U. S. Geol. Survey Water-Supply Paper 274. p. 167,1911) as follows: "If the 

number of parts per million (or per thousand or per hundred) of each radicle found by analysis be multiplied by its reaction coefficient (reciprocal of combining weight), a number will be obtained which may 

be called the 'reacting value' for that analysis."

1. Mean of 77 analyses of ocean water from many localities, collected by the Challenger expedition. 

W. Dittmar. analyst. Challenger Eept., Physics and chemistry, vol. 1, p. 203, 1884. Total dissolved 

solids, 3.301 to 3.737 per cent. Analysis revised to show bicarbonates by R. C. Wells, U. S. Geol. Survey 

Professional Paper 120-A, p. 15,1918.

2. Analysis of Mediterranean ocean water. Specific gravity of water, 1.0258. J. Usiglio, analyst. 

Annales chim. phys., 3d ser., vol. 27, pp. 92-172,1849. Analysis reduced to ionic form and to percentages 

of total solids by F. W. Clarke, Data of geochemistry, 3d ed., U. S. Geol. Survey Bull. 616, p. 219. 1916.

3. Analysis of Mediterranean ocean water concentrated from density of 1.0258 to density of 1.21. Reference same as that for 2. '

4. Analysis of Mediterranean ocean water concentrated from density of 1.0258 to density of 1.264. 

Reference same as that for 2.

5. Analysis of brine from Hundred-foot sand, probably of early Mississippian age; depth, 1,170 feet±. 

Sample collected from an old oil well, August 15,1915, on McGrath farm, Center Township, Butler County, 

Pa. Specific gravity of water, 1.0876. R. C. Wells, analyst. The amount of sample available for analysis 

was insufficient for a direct determination of the total carbon dioxide, if present.

6. Analysis of brine from sandstone of early Devonian age, depth 6,260± to 6,300 feet. From gas well 

8 miles southwest of Imperial, Washington County, Pa. Specific gravity of water. 1.211. George Steiger. 

analyst. Quoted by F. W. Clarke (Water analyses from the laboratory of the United States Geological 

Survey: U. S. Geol. Survey Water-supply Paper 364. p. 9,1914).

7. Analysis of brine from Hundred-foot sand, probably of early Mississippian age, depth 1,359 feet. 

Sample collected by G. B. Richardson from old oil well on farm of Charles HofFman, 5 miles northeast of 

Butler, Pa. W. B. Hicks and R. K. Bailey, analysts. Quoted by G. B. Richardson (Note on the diffusion of sodium chloride in Appalachian oil-field waters: Washington Acad. Sci. Jour., vol. 7, pp. 73-75. 

1917).

analyst.

9. Analysis'of brino from Berea sand, of early Mississippian age, depth 1,748 to 1,760 feet. Sample 

collected by R. Van A. Mills, April 28,1915, from a gas well 14 months old, on the Gulic farm. 1 mile west 

of Summerfield, Marion Township, Noble County, Ohio. S. C. Dinsmore, analyst.

It will be observed, by referring to Table 6 and to the analyses 

quoted on pages 33-39, that the concentration of the Appalachian oil 

and gas field brines ranges from slightly less to several times greater 

than that of ocean water. The ratios of sodium to chlorine, magnesium to chlorine, and sulphate to chlorine are all smaller in the oil 

and gas field waters than in ocean water, sulphate being comparatively absent in the oil and gas field waters. In contrast to this,
32 WATEKS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

the ratios of calcium to chlorine in the oil and gas field waters are 

much greater than in ocean water.

By comparing the analyses of bitterns derived from the evaporation of ocean water (3 and 4 in Table 6) with the analyses of oil and 

gas field waters shown in the same table, it will be observed that the 

differences between these types of brine become more striking as the 

evaporation of the ocean water progresses. This is due to the order 

of deposition of the dissolved constituents from ocean water during 

concentration. Calcium is deposited as carbonate and sulphate, but 

magnesium is retained longer in solution, the proportion of this constituent being consequently increased as calcium is eliminated. 

After the elimination of calcium, the proportion of sulphate remaining in solution increases, as is shown by analysis 4, Table 6. The 

sodium content of some bitterns derived from ocean water may be 

comparable with the sodium content of oil and gas field brines, but 

the other differences are none the less pronounced. These items make 

it apparent that the oil and gas field brines under consideration have 

not originated merely from the concentration of water such as now 

constitutes the ocean.

By applying Palmer's system of classification,1 the reader will see 

(Table 7) that the properties of reaction of all the oil and gas field 

waters whose analyses are shown in Table 6 lie approximately between those of normal ocean water and the concentrated ocean water 

represented by analysis 4. The properties expressed under 9, Table 7, 

approach most nearly those of normal ocean water, and the properties expressed under 6, Table 7, approach most nearly those of the 

concentrated ocean water (4). Although, as expressed by Palmer's 

classification, the properties of reaction of the waters under comparison have striking similarities, it must be noted, as shown in the preceding discussion, that the saltness of normal and concentrated ocean 

waters is due partly to sulphate, whereas the saltness of oil and gas 

field waters is due almost entirely to chloride. It should also be 

noted that the proportion of magnesium in the constituents of normal and concentrated ocean water is greater and the proportion of 

calcium is less than in the constituents of the oil and gas field brines. 

Water with the properties expressed under 9, Table 7, and the composition expressed under 9, Table 6, might be derived from normal 

ocean water by concentration if practically all the sulphate and part 

of the magnesium and sodium were removed and a certain amount of 

calcium added. In the succeeding pages we show some of the probabilities regarding these changes.

1 Palmer, Chase, The geochemlcal interpretation of water analyses: U. S. Geol. 

Survey Bull. 479, 1911.
CHARACTERISTICS OF THE WATERS. 33

TABLE 7. Properties of reaction of ocean water and of Appalachian oil and 

gas field waters, expressed in percentages.0

Properties of reaction.

Primary salinity. ............

Ocean water.

1

78.8 

20.8 

.4

100.0

2

79.4 

20.2 

.4

100.0

Bitterns derived from the 

concentration 

of ocean water.

3

81.6 

18.4 

.0

100.0

4

53.2 

46.8 

.0

100.0

Appalachian oil and gas field waters.

Pennsylvania.

5

69.2 

30.8 

.0

100.0

6

66.5 

33.5 

.0

100.0

7

69.0 

31.0 

.0

100.0

Ohio.

8

70.4 

29.6 

.0

100.0

9

'77.2 

22.2 

.6

100.0

i The waters whoso properties of reaction are shown in this table are the same as those shown in Table 6.

ANALYSES OF APPALACHIAN OIL AND GAS FIELD WATERS.

TABLE 8. Analyses of waters from the Hundred-foot sand.

Grams per liter.-

SiOs.. .................................

Fe...... ...............:...............

Al.....................................

Ca.....................................

Sr.....................................

Mg........ ............................

Na....................................

K. ....................................

HC08 -. ................. ..............

804....................................

Cl.......... ...........................

Br............ .........................

1

6.07

12:21

2.14

40.10

.14

None.

.14

90.54

145.34 

dl. 102

2

0.24

.01

.49

10.29

1.85

33.76

.26

.02

.12

78.78

125.82

3

0.18

0.04

.26

10.85

1.71

31.46

2.67

.03

.22

77.39

124.81

4

0.15

.02

.12

7.25

1.35

27.59

.16

.03

None.

59.61

96.28

5

0.11

6.12

7.48

1.35

27.37

Present.

.02

None.

58.52

94.97

6

0.78

.02

.57

13.59

'1.46

41.74

2.13

.07

None.

96.56

156.92

7

0.01

a. 11

6.04

11.40

c.21

1.95

36.30

.26

None.

Trace.

82.35

.22

132.85 

1.088

Reacting values, in milligram equivalents per liter.'

Fe.... .................................

Ca.. ...................................

Mg. ...................................

Na....................................

K. ....................................

Sr. ....................... ............

Total basic radicles ..............

HC08 . ................................

S04 . ..................................

Cl....................... ..............

Br.................... .................

Total acid radicles. ..............

2.5

610.5

176.1

1,743.4

3.6

2,536.1

2.9

2,553.4

2,556.3

0.5

513.7

152.3

1.468.0

6.0

2, 140. 5

.4

2.6

2,222.0

2,225.0

1.2

541.7

140.7

1.368.0

68.0

2,119.6

.5

4.5

2,182.0

2,187.0

362.0

111.0

1, 200. 0

4.1

1,677.1

1,681.0

1,681.0

374.0

111.0

1,190.0

1,675.0

1, 650. 0

1, 650. 0

1.0

679.0

120.0

1,815.0

54.0

2, 660. 0

1.0

2,723.0

2,724.0

0.4

569.1

160.4.

1,578.0

6.7

4 9

2,319.5

Trace.

3.0

2,326.0

o Ferrous iron.

c Barium absent.

A Calculated from content of salts. . « It is believed that these terms will be clear without elaborate explanation. A solution containing a 

milligjam equivalent per liter would be "thousandth normal" in the terms of analytical chemistry, a 

milligram equivalent of any element or radicle being as many milligrams of the element or radicle as are 

equivalent in capacity for chemical reaction to 1.008 milligrams of hydrogen or 8.000 milligra.ni!? of oxygen.

91818°--19 3
34 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS. 

TABLE 8. Analyses of waters from the Hundred-foot sand Continued.

Reacting' values, in per cent.

Sr. ....................................

Ca...... ...............................

Mg. ...................................

Na. ...................................

K. ....................................

S04 - ..................................

Cl. ....................................

Br.............................. .......

1 1

12.0

3.4

34.5

.1

.1

49.9

100.0

. 2

11.6

3.4

34.9

.1

50.0

100.0

3

12.4

3.2

32.8

1.6

.1

49.9

100.0

4

10.8

3.3

35.8

.1

50.0

100:0

5

11.3

3.4

35.3

50.0

100.0

6

12.4

2.2

34.4

1.0

50.0

100.0

7

0.1

12.2

3.5

34.1

.1

49.9

.1

100. 0

Approximate percentages of principal salts.

Cad,... ...............................

MgGl3 .... .............................

NaCl. .................................

KC1.. .................................

23.2

5.8

70.8

.2

100.0

22.5

5.7

71..5

.3

100.0

23.9

5.3

66.7

4.1

100.0

21.0

5.5

73.2

.3

100.0

22.6

5.6

71.8

100.0

25.0

3.8

68.6

2.6

100.0

24.1

5.7

69.9

.3

100.0

1. Brine from Hundred-foot sand; depth .1,359 feet; well No. 2, Charles Hoffman farm, 

Oakland Township, Butler County, Pa. Sample collected in October, 1915. Na and K 

determined by W. B. Hicks; the rest of the determinations by R. K. Bailey, Econ. 

Geology, vol. 12, p. 39, 1917.

2. Brine from Hundred-foot ,sand ; depth 1,018 to 1,035 feet; well No. 1, Harlan Book 

farm, Muddy Creek, Clay Township,, Butler County, Pa. ' This is a new oil well which 

had Just been completed when the sample was collected in October, 1915. Well drilled 

by Parker & Edwards Co. S. C. Dinsmore, analyst.

3. Brine from Hundred-foot sand; well No. 2, Mary B. Heist farm, Center and 

Butler townships, Butler County, Pa. Sample collected in September, 1915. S. C. 

Dinsmore, analyst.

4.'Brine from Hundred-foot sand; depth 1,361 to 1,387 feet; well No. 3, W. H. 

Cooper farm, Penn Township, Butler County, Pa. This was an oil well drilled about 

one year prior to the collecting of the sample. S. C. Dinsmore', analyst.

5. Same water as No. 4. Chast Palmer, analyst. 

6. Brine from Hundred-foot sand, well on the Charles Kaiser farm, eastern part of 

Summit Township, Butler County, Pa. Sample collected in September, 1915. S. C. 

Dinsmore, analyst.

7. Brine from Hundred-foot sand; depth 1,170±feet; old McCarrier & Waid well on 

McGrath farm, Pine tract, Center Township, Butler County, Pa. Sample collected in 

August, 1915. Sample was clear when collected, but reddish-yellow precipitate formed 

on standing 24 hours. R. C, Wells, analyst.

TABLE 9. Analyses of waters from various sands.

Grams per liter. ,

J

Si02 . ................

Fe...'.. ..............

Al.. .................

Ca. ..................

Sr.... ................

Mg...................

Na.. .................

K. ...................

HC03 . ...............

Cl.... ................

Br.. .................

Total..........

8

Present.

0.89

.32

9.81

.16

17.28

28.46

9

0.019

.007

.060

.030

2.640

.102

4.200

7.123

 10

1.87

.02

7.58

1 62

30.45

.09

64.93

106. 56

11

0.080

.011

.050

.010

.299

.055

.261

.435

1.201

12

0.05

6.05

2.89

c.07

.80

19.50

91

.26

38.54

.16

62.55

1.044

13

0.09

.02

.15

11.56

1.83

39.27

.70

.03

87.50

141. 15

d 1. 102

14

0.02

o.08

5.58

(U

23.85

.25

.32

50.33

.15

81.65

1.056

15

0.08

.01

.56

11.36

1 63

38.32

.51

84.71

137. 21

» Ferrous iron. Barium absent. d Calculated from salt content.
CHARACTERISTICS OF THE WATERS. 35

TABLE 9. Analyses of waters from various sands Continued. 

Reacting values, in milligram equivalents per liter.

Fe... ................

Ca. ..................

Mg...................

Na....... ............

K... .................

Sr.... ................

Total basic 

radicles ......

HC03 . ...............

SO*..................

Cl............. .......

Br. ..................

Total acid

r

8

22.3

25.V9

426M

474.6

o2.5

487.3

489. 8

9

3.0

2.5

114.8

120.3

118.5

118.5

10

1.0

378.0

133.0

1,324.0

1,836.0

1,831.0

1.831.0

11

2.5

.8

13.0

1.4

17.7

4.3

12.3

16.6

12

None.

144.3

65.8

847.8

5.9

1.6

1,067.4

4.3

1,087.0

2.0

1,093.3

13

0.6

577.9

150.6

1,707.0

17.8

2,453.9

1.0

2,468.0

2,469.0

14

3.0

278.6

84.8

1,037.0

6.4

.9

1,410.7

5.3

1,419.0

1 9

1, 426. 2

W^ 

15

0.5

507.8

134.0

1,666.0

13.0

2,381.3

1.0

2,389.0

2,390.0

Reacting values, in per cent.

Fe... ................

Ca..... ..............

^.... ...............

Na... ................

E....................

HCOj. ....... ........

Cl....................

'Br..:,.... ...........

2.3

2.6

45.1

.2

49.8

100.0

1.2

1.1

47.7

50.0

100.0

10.3

3.6

36.1

50.0

100.0

7.5

2.4

35.9

4.2

12.9'

37.1

100.0

6.6

3.1

40.0

.3

.2

49.7

.1

100.0

11.8

3.0

34.8

.4

50.0

100.0

0.1

9.8 3.'0

36.9

.2

.2

49.8"

100.0

11.9

2.8

35.0 '.3

iai n

100.0

Approximate percentages of principal salts.

Cads.... .............

MgCls .. ..............

Nad... ..............

KC1..................

4.4

4

O

} 91.3

100.0

2.4

1.8

95.8

100.0

. 12.3

6.6

81.1

100.0

U K

4.0

f 69.9

\ 11.6

100.0

12.7

5.0

81.6

100.0

22.7

5.1

71.3

.9

100.0

18.9

4.9

75.6

.6

100.0

23.0

4.7

71.6

.7

100.0

/ a Includes HS.

8. Brine from Five Hundred-foot sand ; depth 420 feet; well No. 7, Vorhies farm, 

Center Township, Noble County, Ohio. Sample collected in December, 1915. The well 

from which the sample was collected is one of a group of several shallow-sand- wells 

that yielded small amounts of oil for a few years. In March, 1917, the well was not 

being pumped.- The sample was clear when collected, but a rusty yellow precipitate 

formed during the first 24 hours after the water was collected. On standing a few 

weeks this yellowish precipitate was replaced by a black precipitate of ferrous sulphide. 

It is not known whether the iron was originally present or was contributed by the Iron 

piping in the well, but it is evident that a soluble sulphide was present and that it reacted with the iron upon standing. Chase Palmer, analyst.

9. Brine from Cow Run sand ; depth 900 feet; well of American Oil Development Co. 

on Cave Run, Pleasants County, W. Va. Production of water 2 barrels daily. S. C. 

Diusmore, analyst. Reeves, Frank, Econ, Geology, vol. 12, p. 374, 1917.

10. Brine from Salt sand; depth 1,600 feet; S. E. Elliot well No. 12, South Penn Oil 

Co., Bell Run, Lafayette district, Wirt County, W. Va. Production of water 25 barrels 

daily. S. C. Dinsmore, analyst. Reeves, Frank, op. cit., p. 374.

11. Artesian water from shallow-sand well on Neigh farm, Summit Township, Butler 

Comity, Pa. Water comes from depth of about 350 feet. S. C. Dinsmore, analyst.-

W12. Brine from Maxton sand; depth 905 feet; well No. 1, David Bintz farm, see. 33, 

Malaga Township. Mouroe County, Ohio, near Monroefleld. Well drilled in August, 

1912; sample-collected in-November, 1916. Very dark green to black oil, containing 

brownish-yellow specks collected with the water. Rust-colored precipitate at bottoiii 

of, bottle after standing 48 hours. R. C. Wells, analyst.

»/13. Brine from Big lime sand; depth 1,431 to 1,444 feet; well No. 5, F. Mellotte 

farm, northeast corner of Malaga Township, Monroe County, Ohio. Sample collected 

April 24, 1915. S. C. Dinsmore, analyst. -

</14. Brine from Big lime sand; depth 1,339 to 1,349 feet; well No. 1, Egger Bros.' 

farm, sec. 10, Malaga Township, Monroe County, Ohio, near Miltonsburg. Well completed in January, 1916; sample collected in September, 1916. Gas well, initial openflow production 1,500,000 cubic feet a day; initial gas pressure 360 pounds to the 

square inch. Production of water li barrels a week. Black deposit on inside of bottle 

in air space just above water, also dirty-gray flocculent precipitate floating at top of 

water and a somewhat lighter-colored gray flocculent precipitate at bottom of bottle. 

N6 oil was present. R. C. Wells, analyst.

» 15. Brine from Keener sand ; depth 1,451 to 1,469 feet; well No. 2, J. R. Scott farm, 

near Jerusalem, Sunsbury Township, Monroe County, Ohio. Sample collected April 24, 

1915. S. C. Dinsmore, analyst.
36 WATEES ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

TABLE 10. Analyses of waters from the Keener sand.

Si02 . ..........................

Fe..... .........................

Al

Ca..... .........................

Sr........... ...................

Mg...... .......................

Na.. ...... .....................

K......... .....................

HC03 . .........................

S0<.... ........................

Cl..............................

Br............ ..................

 -W 

16

0.08 .01-

.35

5.68

1.04

22.84

.60

.08

48.46

79.15

*

0.14

.02

.62

12.98

i.69

43.40

2.47

.04

97.96

159. 32

- v

18

8.02

1.42

28.76

.03

62.48

100.71

 7

19

0.05

o.Ol

6.05

2.98

c.08

.82

19.85

.23

.17

38.89

.11

63.24 

1.043

1"i 

0.06

6.08

11.20

1.82

38.64

.04

83.88

135.72

2*

0 04

8.34

1.48

29.74

.03

64.10

103.73

22

0.02

()4

10.84

2.99

41.53

.03

.01

91.70

147. 16

Reacting values,, in milligram equivalents per liter.

Fe..............................

Ca....................... .......

Mg.............................

Na..............................

K...................... .........

Sr............. .................

HCO.. .........................

SO*...... .......................

Cl......... .....................

Br..... .........................

Total acid radicles ........

0.4

283.9

85.5

993.0

15.0

1,377.8

1.0

1,367.0

1.3C8.0

0.6

648.0

139.5

1.887.0

63.0

2, 738. 1

.6

2,763.0

2.763.6

. 400.3

116.9

1,250.0

1,767.2

.6

1,762.6

1.762.6

148.8

67.5

863.1

5.9

1.9

1,087.2

2.8

1,097.0

1.4

1.101.2

559.2

149.7

1,680.0

2,388.9

.7

2,306.0

2.366.7

416. 0

122.0

1,293.0

1,831.0

Trace.

1,808.0

1.808.0

1.0

541.0

240.0

1,806.0

2,594.0

2, 586. 0

2.586.0

Reacting1 values, in per cent,

Sr. .............................

Ca. .............................

Mg...... .......................

Na....................... ......

K..............................

HCOa............ ..............

Cl..............................

10.4

3.1

36.0

.5

50.0

100.0

11.7

2.5

34.7

1.1

50.0

100.0

11.3

3.3

35.4

50.0

100.0

0.1

6.7

3.1

39.8

.3

.1

49.9.

100.0

11.8

3.2

35.0

50.0

100.0

11.5

3.4

.35.1

50.6

100.0

10.5

4.7

34.8

50.0

100.0

Approximate percentages of principal salts.

CaClj.... :'......................

MgCl2 ..... ......................

NaCl..... ......................

KC1. ....... .... .. . ....

20.2

5.2

73.2

1.4

100.0

22.6

4.1

70.3

3.0

100.0

22.0

5.6

72.4

100.0

13.2

5.1

81.0

.7

100.0

23.0

5.3

71.7

100. 0

22.5

5.6

n o

100.0

20.5

8.0

71.5

100.0

a Ferrous iron. Barium absent.

16. Brine from Keener sand; depth 1,465 to 1,471 feet; well No. 1, Schroeder heirs' farnij IJ miles south, 

of Miltonsburg, Malaga Township, Monroe County, Ohio. Rate of production from this new well, 150 

barrels of oil a day, with large amounts of gas and small amounts of brine when the sample was collected, 

April 24,1915. The well was the first in the field and was drilled in March, 1915. -S.C. Dinsmore, analyst. 

^ 17. Brine from Keener sand; depth 870 to 880 feet; well No. 2, Mancel Secrest farm, IJ mile's southeast 

of Chaseville, Seneca Township, Noble County, Ohio. Sample collected May 1, 1915. S. C. Dinsmore, 

Analyst. \

^ 18. Brine from Keener sand; well No. 1 (gas well), A. Clause farm, NE. J sec. 10, Malaga Township, 

Monroe County. Ohio, near Miltonsburg. Well completed February 18, 1916; sample collected in September, 1916. Chase Palmer, analyst.

J 19. Brine from Keener sand; depth 1,302 feet; well No. 4 (oil well), C. J. Clause farm, sec. 27, Malaga 

Township, Monroe County, Ohio, near Monroefield. Well drilled in July, 1913; sample collected November 7,1916. Dull amber-colored oil was collected with the water. The water was clear when collected, but a reddish rusty precipitate settled at the bottom of the bottle within 24 hours. R. C. Wells, 

analyst.

;, " 20. Brine from Keener sand; depth 1,451 to 1,469 feet; well No. 2, J. R. Scott farm, NE. J sec. 23, Suns-

^ bury' Township. Monroe County, Ohio, half a mile southeast from Jerusalem village. Old oil and gas,

well, drilled in 1904. The well is reported to have flowed and sprayed oil at the rate of 350 barrels a day

with very little water at first. In June, 1916, it was yielding daily 2 barrels of oil together with 5

barrels of water. Sample collected in August, 1916. Chase Palmer, analyst.

- 21. Brine from the same well as that described under No. 16 but collected in September, 1916. Chase 

Palmer, analyst. v

 " 22. Brine from Keener sand; depth 1,700 feet; American Oil Co.'s well on J. T. Craw farm, Cave Run, 

Pleasants County W. Va. S. C. Dinsmore, analyst. Reeves, Frank, Econ. Geology, vol. 12, p. 374,1917,
CHARACTERISTICS OF THE WATERS. 37

TABLE 11. Analyses of waters from the Big Injun sand.

Grams per liter.

SiO

Ve*........ ....................................................

Al..... ........................................................

Ca.. ......... ...................................................

Mg.............................................................

Na.. ...........................................................

K........................ .....................................

HCO3 .. .....................................:.....-............ so<.. ..........................................................

CL. ............................................................

 y

23

0.70

.02

.60

12.22

2.89

45.88

.35

.02

102. 14

164. 82

24

0.21

.03

11.94 i si

O/.D/

ft4

84.35

136. 05

25

0 19

.02

10.24

1.63

33.47

.01

74.38

119.94

26

0.13

04

17.12

2 96

53.69

121.63

195:63

Reacting values, in milligram equivalents per liter.

Je................-..........-... ...........................

Ca..... ........................................................

\^.... .........................................................

Na.. ...........................................................

K. ....... ......................................................

HC03 . ........ ...........................................!.....

so<.. ..........................................................

Cl... ...... .....................................................

0.6 

610.1 

236.6 

1,995.0 6 o

2,851.3

.3

None. 

2,181.0

2,881.3

1.0 

596.0 

149.0 

1,710.0

2,453.0

None. 

2,379.0

2,379.0

1.0 

511.0 

134.0 

1,455.0

2,101.0

None. 

2,097.0

2,097.0

1.0 

855.0 

244.0 

2,334.0

3,434.0

None. 

3,430.0

3,430.0

Reacting values, in per cent.

Ca.. ............................................................

Mg.............................................................

K. .............................................................

Cl.................. .....:......................................

10.6 

4.1 

35.1 

.2

50.0

100.0

12.5 

3.1 

34.4

50.0

100.0

12.2 

3.2 

34.6

50.0

100.0

12.4 

3.6 

34.0

60.0

100.0

Approximate percentages of principal salts.

MgCU............................ ...............................

NaCl... ........................................................

KC1............................................................

20.8 

6.9 

71.9 

.4

100.0

24.4 

5.2 

70.4

100.0

23.7 

5.3 

71.0

100.0

24.6 

5.9 

69.5

100.0

23. Brine from Big Injun sand; depth 1,200 feet; well No. 1, Henry H. Moore farm, near Summerfield, 

Marion Township, Noble County, Ohio. Sample collected Ajpril 27,1915. S. C. Dinsmore. analyst.

24. Brine from Big Injun sand; depth 1.425 feet; Carter Oil Co.'s well No. 2, on Russell heirs' farm, near 

Paden City, Wetzel County, W. Va. Production of water 5 barrels daily. S. C. Dinsmore, analyst. 

Reeves, Frank, Econ. Geology, vol. 12. p. 374,1917.

0/25. Brine from Big Injun sand; deptn 1,355 feet; E. A. Bradley well No. 2, Fiel farm, Jackson Township, 

Monroe County, Ohio. Production of water 3 barrels daily. S. C. Dinsmore, analyst. Reeves, Frank, 

op. cit., p. 374.

26. Brine from Big Injun sand; depth 2,000 feet; South Penn Oil Co.'s well No. 1, Isaiah Baker farm, 

Muddy Creek, Tyler County, W. Va. Production of water 20 barrels daily. S. C. Dinsmore, analyst. 

Reeves, Frank, op. cit., p. 374.
38 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS. 

TABLE 12. Analyses of icaters from tlie Berea, sand.

Grams per liter.

X

SiO.................................... :........ '.....

Fe............................. ......................

Al........ ............................... ;.............

Ca.. .................................................

Mg.... ........................................:......

Na.... ........ .......................................

K.. ...-................./..............................

HC03 .. ..............................................

SO4 .. ................................................ ci.............................. :....................

27

0.090

.006

.022

.220

.070

.475

.055

.146

1.045

2.129

28

0.22

.06

.37

2.75

.86

15.85

.51

.37

32.07

53.06

29,

0.14

.01

.50

2.79

1.01

19.49

.50

.05

38.69

63.18

30

0.08

9.24

2.06

32.66

.02

72.60

116.66 

1.08

W '

31

7 34

1.16

25.82

.06

55.46

98.84 

1.06

Reacting values, in milligram equivalents per liter.

Fe.. ....... ..........................................

Ca.. .................................................

Mg.. ................................................

Na.. ................................................. K............J... ......... ........ '.................;...

HC03 .. !.............................................

S04.. ....... ......................................... ci............................................... ...

0.2

11.0

5.7.

21.3

1.4

39.6

2.4

None.

29.5

31.9

2.0

137.3

71.0

689.1

13.0

912.4

6.1

None.

904.4

910.5

0.3

139.3

83.0

847.4

13.0

1.083.0

.8

None.

1,091.0

1,091.8

461.3

169.6

1, 420. 0

2, 050. 9

.4

2, 047. 0

2,047.4

366.5

95.5

1,123.0

1,585.0

.9

1,564.0

1,564.9

Reacting values, in per cent.

Fe.. .................................................

Ca. ..................................................

Mg.. ................................................

Na.l. .................................................

K. ....................................................

HCOj.. ..............................................

Cl...................................................

0.3

17.3

8.9

21.3

2.2

3.8

46.2

100.0

0.1

7.5

3.9

37.8

.7

.3

49.7

100.0

6.4

3.8

39.2

.6

"\n n

100.0

11.3

4.1

34.6

<tf\ ft

100.0

11.7

3.1

35.2

50.0

100.0

Approximate percentages of principal salts.

CaCl2 . ...............................................

MgClj...............................................

NaCl... .............................................

KC1.................................................

34.8

15.5

43.4

6.3

100.0

14..6

6.5

77.1

1.8

100.0

12.3

6.3

79.9

1.5

100.0

21.8

6.9

| 71.3

'

100.0

23.1

5.1

71.8

100.0

* 27. Brine from Berea sand; depth 2,141 to 2,162 feet; well No. 4 (old oil well), Taylor heirs' farm, 2 miles 

east of Woodsfleld, Center Township, Monroe County. Ohio. Sample collected April 26, 1915, from a 

separating tank at the well; had probably undergone dilution after being brought to the surface. S. C. 

.JDinsmore, analyst.

v 28. Brine from Berea sand; depth, 1,748 to 1,760 feet; well No. 2 (gas well), Gulic farm, 1 mile west of 

Summerfield, Marion Township, Noble County, Ohio. Sample collected April 28,1915. S. C. Dinsmore, 

analyst.

* 29. Brine from Berea sand; depth 1,570 to 1,592 feet; well No. 2, S. L. Murphy farm, near Chaseville, 

Seneca Township. Noble County, Ohio. Sample collected April 30,1915. S. C. Dinsmore, analyst. 

,30. Brine from Berea sand; depth 1,727 to 1,740 feet; well No. 1 (old oil well). J. A. Adams farm, half a 

mile west of Barnesville, Warren Township, Belmont County, Ohio. The well was yielding 48 barrels of 

oil and 8 barrels of salt water a month when visited in June, 1916; the initial yield of oil from the well about 

20 years prior to this was about 180 barrels of oil a month. Both oil and gas were produced in this field 

Sample collected July 24,1916. Chase Palmer, analyst.

 * 31. Brine from Berea sand; depth 2.141 to 2,162 foot; well No. 4 (old oil well), Taylor heirs' farm, 2 miles

 east of Woodsfleld. Center Township, Monroe County, Ohio. The well had been yielding oil and salt water 

since 1905. Sample collected July 25,1916' sample'27, collected from same well a year previously. Chase 

Palmer, analyst. H *
CHARACTERISTICS OF THE WATERS. 39

TABLE 13. Analyses of waters from various sands

Grams per liter.

SiOj.. ................................

Fe......................... ...........

Al....... .............................

Ca...... ..............................

Sr....................................

Mg............................:......

Na.... ...............................

K......... ...........................

HC03 . ...............................

so4 ..................................

Cl.. ...................................

Br.-.. .................................

Specific cravit v. ......................

32

0.01

.07

io. ie

1.48

31.65

.05

.37

70.70

114.49

33

"0.14

6.02

13.79

C'.ll

2.22

37.93

.73

.04

.18

88.82

.19

144. 17 

1.099

 34

0.05

.04

7.91

1.47

28.60

.35

.03

.01

62.65

101. 18

35

0.12

.05

.83

15.82

1.87

40.80

.95

.03

.13

97.61

158. 21

36

0.05

6.08

15.36

2.04

40.58

.76

.02

Trace.

95.80

154.69

37

0.03

.09

10.28

1.54

32.84

.03

.04

73.15

118.00

38

0.19

30.50

<*4.30

3.00

78.20

6.25

.06

196. 00

.85

319.35 

1.211

39

2.58

1.05

.44

5.01

.49

«.41

 None.

13.80

1.11

24.89 

1.160

Reacting values, in milligram equivalents per liter.

Fe...... ..............................

Ca. ..................................

Mg....... .....I......................

Na. ..................................

K..................... ...............

Sr....................................

HC03 -. ..............................

S04 .................................

Cl...... ..............................

Br..... .........................:....

2.0

507.0

122.0

1,376.0

9 nn? n

1,998.0

1,998.0

0.5

688.3

182.8

1,649.0

IS 7

2.5

2,541.8

.7

3.7

2,505.0

2.4

2,511.8

1.0

395.0

121.0

1,243.0

o n

1,769.0

1, 767. 0

1, 767. 0

790.5

154.0

1,774.0

24.4

2, 742. 9

2.3

2,752.0

2,754.3

766.8

167.9

1,764.0

19.5

2, 718. 2

2, 702. 0

2, 702. 0

3.0

513.0

127.0

1,428.0

2,071.0

2,063.0

2,063.0

7.0

1.523.0

2-17.0

3,400.0

160.0

98.0

5, 435. 0

1.0

5, 527. 0

10.0

5,538.0

129.0

35.6

217.8

19 1

24.0

418.9

389.2

13.9

403.1

Reacting values, in per cent.

Approximate percentages of principal salts.

Sr....................................

Ca...... ..............................

Mg.. ............ .'....................

Na. ..................................

K... .................................

Cl....................................

Br.. ..................................

12.7

3.0

34.3

50.0

100. 0

13.8

32.2

.4

50.0

100.0

11,2

3.4

35.2

.2

50.0

100.0

14.4

2.8

32.4

.4

50.0

100.0

14.2

3.1

32.3

.4

50.0

100.0

12.5

3.1

34.4

50.0

100.0

0.9

13.8

2.2

31.6

1.5

49.9

.1

100.0

3.0

16.0

4.4

25.1

1.5

43.3

1.7

100.0

CaClj.. ...............................

MgClj................................

NaCl.................................

KC1..................................

24.7

5.1

} 70.^

100.0

26.6

6.1

/ 66.3

\ 1.0

100.0

21.8

5.7

71.8

. . .7

100.0

27.8 -4.6

66.4

1.2

100.0

27.6

5.2

66.2

1.0

100.0

24.3

5.2

70.5

100.0

28.4

3.7

64.2

3.7

100.0

32.3

7.7

55.8

4.2

100.0

Ferrous iron. Barium absent. d Trace of Ba. e Trace of CO3 .

32. Brine from Second sand; depth 948 to 964 feet; well No. 19, A. B. Kelly farm. Tionesta Township, 

Forest County, Pa. Production of water was originally 5 barrels daily but had declined to 3 barrels daily 

when thesample was collected. S. C. Dinsmore, analyst. Reeves. Frank. Econ. Geology, vol. 12. p. 374, 1917.

33. Brine from Third or Fourth (?) sand; depth 1,842 to 1,870 feet; well No. 2 (oil well), Cyrus Step farm, 

Perm Township, Butler County,' Pa. The initial production of oil from this well, about 20 years ago, is 

reported to have been 100 barrels of oil daily, with very little water. In August, 1915, when the^sample 

was collected, the well was yielding three-fourths of a barrel of oil and 10 barrels of salt water a day. The 

usual yellowish precipitate formed at the bottom of the bottle upon standing. R. C.- Wells, analyst.

34. Brine from Fourth sand; depth 1,623 to 1,654 feet; South Penn Oil Go's, well No. 1 on D. C. Rankin 

farm, Fairview Township, Butler County, Pa. Production of water 1J barrels daily. S. C. Dinsmore, 

analyst. Reeves, Frank, op. cit.. p. 374.

35. Brine from Bowlder sand, depth 1,701 to 1,720± feet; well No. 1 (new oil well), Mrs. Henry Welsh 

farm, Penn Township, Butler County, Pa. Sample collected in September, 1915. S. C. Dinsmore, analyst.

36. Duplicate of sample 35. Chase Palmer, analyst.

37. Brine from Fifth sand; depth 2,200 feet; well No. 1 of South Penn Oil Co., on Maggie McDonald farm, 

McDonald, Allegheny County, Pa. Production of water 1 or 2 barrels daily. S. C. Dinsmore, analyst. 

Reeves, Frank, op. cit., p. 374.

38. Brine from Peoples Natural Gas Go's, well, 8 miles southwest of Imperial, Washington County, Pa. 

Depth of well when sample was collected 6,300 feet. 'Geologic horizon believed to be that of Oriskany 

sandstone. The water rose 4,000 feet in the well. This water is remarkable for its very high content of 

strontium. George Steiger. analyst. U. S. Geol. Survey Water-Supply Paper 364, p. 9, 1914.

39. Water from a deep well on Slaughters Creek, near Coalburg, W. Va. The water is said to occur at a 

depth of 5,590 feet in a stratum of fine black sand whose geologic horizon is not reported. The water rose 

in the well about 3,000 feet. Sample collected in July, 1912, by William Seymour Edwards Oil Co., Charlestonand Kanawha, W. Va. Chase Palmer, analyst. U. S. Geol. Survey Water-Supply Paper364, p. 11, 1914.
40 WATEES ASSOCIATED WITH PETROLEUM AND NATURAL GAS. 

SHALLOW WELL WATERS.

The 15 analyses shown in Table 14 are selected from the files of 

the water-resources branch of the United States Geological Survey 

and represent waters from shallow wells in or near the areas studied 

during the preparation of this bulletin. Though all the analyses 

except No. 15 were made to show the quality of the water for use in 

boilers and are incomplete, they nevertheless afford a good idea of 

the character of the waters from the shallow rocks.

Ground waters of meteoric origin, such as are obtained from shallow wells, when percolating through soils and rocks near the surface 

take into solution various mineral constituents, so that the nature 

and proportions of the dissolved constituents depend largely on the 

kinds of rock with which the waters have been in contact. Calcium, 

magnesium, and carbonate are characteristic of waters in limestone 

areas. Sulphate is generally a derivative of surface oxidation. 

Sodium, whose reacting value exceeds the combined reacting values 

of chlorine and sulphate in the waters represented by analyses 2, 8, 

9j and 15, has doubtless been derived from rocks rich in sodiumbearing minerals. Chlorine is present in all the waters analyzed 

and has been acquired either through the leaching of soluble chlorides from the shallow rocks or by the mixing of normal ground 

waters with chloride waters such as constitute the deep-seated brines.

The proportion of chlorine varies too much to warrant its use as 

a basis for extended comparison, but by comparing the analyses 

given in Table 14 with those given in Tables 8 to 13 a few broad differences between the shallow and. deep waters are apparent. The 

proportions of total dissolved solids in the shallow waters are extremely diverse but are always smaller than in the deep-seated waters. 

All but one of the shallow waters contain a relatively large proportion of sulphate, and the reacting value of this constituent exceeds 

that of chlorine in each of the waters represented by analyses 1, 2, 3,4, 

11, 12, 13, and 14. The proportions of sulphate in the deep-seated 

brines are practically negligible. The shallow waters are characterized by a large proportion of carbonate, whereas that constituent is 

present in relatively small amount in the deep-seated waters. In all the 

shallow waters except the one represented by analysis 2 calcium exceeds magnesium. This relation also holds in the deep-seated waters, 

but the proportions of calcium and magnesium in the dissolved solids 

of the shallow waters are larger than in the deep-seated waters. In 

each of the shallow waters except those represented by analyses 3, 5, 

6, and 10, the reacting value of sodium is either equal to or greater 

than that of chlorine. In the deep-seated brinss the reacting values 

of sodium are less than, those of chlorine.
CHARACTERISTICS OF THE WATERS. 41

A wide range of properties of reaction of the different shallow 

waters is shown in the lower part of Table 14. Primary salinity 

predominates in waters 5, 8, 10, and 15. The secondary chloride 

salinity of waters 3, 5, 6, and 10 indicates that .these approach most 

nearly the deep-seated oil-field brines. Primary alkalinity is the predominating property of reaction in waters 2 and 9, and secondary 

alkalinity is the principal property of reaction in the waters represented by analyses 1, 3, 4, 7, 11, 12, 13, and 14. Though primary 

salinity predominates in the waters represented under analyses 8 and 

15, the total properties of reaction of these two waters are also made 

up partly of primary alkalinity. Primary alkalimt}^ in the deep-' 

seated brines of the Appalachian fields is exceptional.

The large proportions of total dissolved solids, the relatively large 

proportions of chlorine with respect to sodium, and the comparatively small proportions of sulphate, due possibly to precipitation or 

reduction in the waters represented by analyses 5 and 15, lead to 

the conclusion that these waters are mixtures of waters from shallow 

and deep sources. Waters such as these, which are intermediate 

between normal ground waters and deep-seated brines, deserve further study than we have been able to give them. We have found it 

difficult to procure representative samples of such waters, which are 

unsatisfactory for industrial uses and are also generally excluded 

from deep wells by casings. It is probable, however, that studies 

of the waters accompanying oil in the shallow-sand territories of 

the Appalachian fields and of the waters immediately above and 

below the shallow oil sands would show, in places near the outcrops, 

evidences of the incursion of ground waters. The gradations from 

normal ground waters to characteristic deep-seated brines must 

depend partly on the extent to which the deeper waters have received 

accessions of shallow ground waters. In the succeeding pages we 

show some of the reactions that are involved when shallow ground 

waters of one type leak into oil wells and mix with deep-seated 

waters of a different type. We believe that similar changes have 

occurred in past geologic time, and this belief is strengthened by the 

fact that the reactions that would be produced by mixing and concentrating certain deep and shallow waters would bring about much 

the same difference that we observe between deep and shallow brines.
42 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

1R,

\

«

2

S

AS

ia

rH

O 

rH

0>

00

-

CO

10

. *

CO

CM

OO O O JO

ss § § is

COCO CO OS t^^H

IO CN »O 00 O ^ 

0>rH COrH

CO t- CO OiCM CO

torn ,0

CM O5 IN Cft COOO

O O' rH rH o' CM* 55 CM oi~

I CO O O r-O

rH 10 CM' co ^' oo

rH 10

OS CO ^ t-^ rH CO

OOO 00 00 COCM

CO CM CO

rH CO

CR.O I- (NCO-OIO' CO rH 1^. CO' CO*

COCN IO rH CM T

ooio T)< oca co 

oo' co' o 10 CM' gj

rHIO O rH COrH

^ 1 8*8

IOO f- rHOO

00 t- O COCOIN

UJrH ll IN 10

CM CO * O ^* CO 

CM ^ *" 3cMCO

O CM OS

rH CM CO COrH CO 

rH rH CO

: ::::::

jjj jj^g

o o'

CO

^

CO 

CO

co

CO

o 

c2

0

s

en 

1

co

o

iO

o CM'

CM

CM

gCO

rH

CO 

CO

co

§

CO

co

oo co'

CO

uents.

i constit

t

 3

og o

M

«

Percent

iO OS OS CM iO

CO CO CM

iO CO IN CR COCM

O* CM'' rH rH CO 1-^ ?5 . co

O IO '^f CO ^1* rH

OCO CM CO 

CM rH CO

 * 00 CM ^ 00 «< 

oo' **<' " ' co CM

rH rH CO

CO CO CN CO 10' 00 

rH CO

 >rt>- oo oo coo 

o co 06 co co *^r

rH rH CO CM

O IO IO O> O rH

fH " CO ^' rH CO* 

CM CO

CMr- co coco CM

CO 00 f*- rH OS

. CM <N CO

»O ^* O OS CM.O 

eo CM' co os' i-^ rr

IN *" CO CD o' Os'

 >» co; CN N oo oo

CR.CO 1-i rH CO' 

CM IO rH

o> co os r- co co

IO Tl< CM rH COOO 

rH .CO

OrH OS OOO

TCCM . CO

lH '"1 CM '~t ~*<°

££ % SSS

IOCM 00 00 IOOO

^ Jsioj '_;o^

o

8

o

8

o

8

0

8

o

8

o

8:

o

8

0

§'

o

8 .

8 o "

o

8

o

8

o

o o

s

8

S

cen per 

to

0)

' 1 '

M 

rH CO CO rH O*

t^ CM' o' t-: ej <N

^f CO O rH

CO.CO rH rH CO CO

oioo' CM' CM'IO'CM'

CO ^

 CM rH t>. ' CO 00 CO

00-H OS O 

CO.H CO

CO rH rH CO

oo * .00 i~ co o

CMCM "" »

CO CM CM . CM CM CO

O 00 CM iO OS CO .

CM' rH \6 ic ' n

if} OS O CXD Cft CO

10 ' CM ;C CN

rr CM CM

10 OS 0 CO CM <N 

CO CO OS Cft'.io' »O\

IO CO OS O * CO 

00 O O Os' CO 1<

t 1 rH CN CO

O t^ CO 00 iO t^

TT oo r- IN co

IO t» CX3 OOO CM

S3 - 9

IOCO IN CMOOO

 *' 05 co' oo CM' oi

CO rH<N

OS ^ t^ CO rH CO 

IN 10 V rH^^J

t^ CO O CM CO CM

CM rH rH CM

J«i-: Uo"3

0

I

0

81-1

o

8

o

o 

o

o

o'

o

o

8

o

 8

o

8

.0

8

.0

s

O

8

o

8

o

8

o

8

o

o
Properties of reaction, in per cent.

28. 1

13.5

58.4

100.0

10.8

72.6

16.6

100.0

12.4

29.6

. 58.0

100.0

9.6.

4.0

86.4

100.0

54.6

32.0

13.4

100.0

41.8

16.4

41.8

100.0

39.2

10.5

50.3

100.0

1. "Water from Pittsburgh & Lake Erie Railroad Co.'s well at Pittsburgh, Pa. 

Analysis furnished by Kennicott Water Softening Co.

2. Water from Noulet well, Butler, Butler County, Pa. Analysis furnished by Baltimore & Ohio Railroad Co.

3. Water from Raney well, New Castle Junction, Lawrence County, Pa. Analysis 

furnished by Baltimore & Ohio Railroad Co.

4. Water from a well 57 feet deep on Brown's farm, Venice, Washington County, Pa. 

Analysis furnished by Kennicott Water Softening Co.

5. Water from Leader Refining Co.'s well, Taylorstown, Washington County, Pa. 

Analysis furnished by Kennicott Water Softening Co.

6. Water from a shallow well at Milton, Cabell County, W. Va. Analysis furnished 

by Kennicott Water Softening Co.

7. Water from a shallow well at Eureka, Pleasant County, W. Va. Analysis furnished by Baltimore & Ohio Railroad Co.

8. Water from a driven well 100 feet deep at Smithneld, Wetzel County, W. Va. 

Analysis furnished by Baltimore & Ohio Railroad Co.

9. Water from 

furnished by Balt

10. Water from 

ysis furnished by 

11. Water from 

Analysis furnishe

^12. Water from 

furnished by Balt

/13. Water from 

furnished by Balt

 14. Water from 

by Baltimore & O

v 15. Water from 

ship, Butler Coun

pletely in Table 9 
44 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

CHANGES IN OIL AND GAS FIELD WATERS AS 

DEDUCED FROM FIELD OBSERVATIONS AND CHEMICAL ANALYSES.

MINERAL DEPOSITION DURING THE EXTRACTION OF OIL AND

GAS.

The field observations and preliminary deductions upon which the 

studies outlined in this paper are largely based are here given in considerable detail.

The so-called salting up or clogging of gas wells oy deposits of 

sodium chloride, a matter with which most petroleum geologists who 

have worked in the Appalachian fields are familiar, is a common 

cause of trouble to gas-well operators. Another cause of trouble that 

has not been generally recognized is the clogging of the productive 

sandstones themselves by the deposition of inorganic mineral matter 

in the rock interstices. During the field investigations in southeastern Ohio and western Pennsylvania preparatory for this report 

it was noted that tubings were pulled from oil and gas wells because newly deposited inorganic crusts had so caked the productive 

sands and the tubings of the wells as to interfere seriously with production. Pieces of sandstone that were shot and cleaned from old 

wells were crusted and impregnated with similar newly deposited 

materials.

Many instances of the " salting up " of gas wells were reported 

that could not be investigated, so that information on this subject 

has been partly obtained from operators. We are indebted to Mr. 

M. E. Lytle, of the Ohio Fuel Supply Co., for the following account 

of the deposition of salt in a gas well in Harrison Township, Knox 

County, Ohio. The well was drilled to the so-called Clinton sand, 

in which gas was encountered at a depth of about 2,700 feet. The 

sand was apparently dry of water, was 34 feet thick, and, under 

conditions of open flow, yielded gas at the rate of 6,800,000 cubic feet 

in 24 hours. The closed "rock pressure" was 810 pounds to the 

square inch. Tubing and pipe-line connections were put in at once, 

but, except for being blown off and tested with a pressure gage once 

a month, the well was not operated. Four months later gas from the 

well was turned into the pipe line, but within a day or so investigation proved that the well was " dead." Further investigation showed 

that the inside of the tubing was dry and free from obstructions 

clear to the bottom of the well. When the tubing was pulled out, 

salt water, which was said to have been previously excluded, leaked 

in from a shallow sand above the packer and partly filled the well. 

While this water was being bailed out, lumps of salt were found, and 

within 12 hours approximately 4,000 pounds of salt was "cleaned from 

the well. Then some gas commenced flowing. Being satisfied that 

the Clinton sand was salted up, the operators lowered 40 quarts of
CHANGES IN OIL AND GAS FIELD WATEKS. 45

nitroglycerin and exploded it at the productive horizon. This started 

gas flowing at the rate of 7,000,000 cubic feet in 24 liQurs and also 

ejected more salt. The well has been in constant use for 11 years 

and, though never clogged again, has continued to eject lumps of salt 

with the gas.

Under the conditions described it seems difficult to explain how 

great masses of salt could accumulate in the rocks at the bottom of 

the well or between the tubing and casing unless, during the time the 

well was not used, salt water leaked in from the Clinton or overlying 

sands and was exposed to the evaporative effects of expanding gas. 

This gas must have leaked, either to the surface or possibly from 

the Clinton sand into overlying beds in which lower gas pressures 

prevailed. Such movements of gas would cause the evaporation of 

relatively small quantities of salt water that might leak into the well.

Concerning a- somewhat similar deposition of salt in a Clinton 

sand gas well Mr. Lytle wrote:

In another well drilled by us, from which we used gas and which was watered 

with fresh water twice a week and allowed to stand three days out of six with 

water in it, the salt gradually formed in the tubing until it had very nearly 

filled 60 feet of 3-inch tubing and 300 feet of 2-inch. We were obliged to pull 

the packer and shoot this well. We have not had the tubing salt up since. 

This well has been producing for about 7 years.

Another striking example of the salting up of gas wells is reported 

by a field employee of the Ohio Fuel Supply Co. to have taken 

place in the Stumptown gas field, Wayne Township, Belmont County, 

Ohio. During the years 1905 to 1910 much natural gas was produced 

at this place from a sandy phase of the Maxville limestone (Big lime 

sand of Ohio, of late Mississippian age) at a depth of 1,250 feet. 

One of the wells here is reported to have yielded gas at the rate of 

5,000,000 cubic feet a day when flowing openly, the initial rock pressure being approximately 440 pounds to the square inch. No salt 

water could be detected in the wells, but the operators observed that 

crusts of crystalline salt formed about the tubings at the productive 

horizon, so as to choke the wells and retard the flow of gas. Attempts 

were made to dissolve these salt incrustations by introducing fresh 

water into some of the wells and then pumping it out, but the pump 

valves at the bottoms of the wells became so rapidly clogged by salt 

as to interfere with this procedure. The fresh water that was introduced into the wells rapidly disappeared, and sometimes when the 

wells were allowed to " blow off " to remove the water and dissolved 

salt that could not be pumped out, fine particles of dry salt were 

ejected from the wells. It seems probable that the water with its 

dissolved salt was included in the gas as a spray and was evaporated 

into the relatively great volumes of expanding gas before reaching 

the top of the well, leaving only the particles of dry salt. In some 

of the fields where salting up of gas wells was reported the salt was
46 WATERS ASSOCIATED WITH PETROLEUM AND' NATURAL GAS.

successfully removed by introducing water into the wells and subsequently pumping off or blowing off the water with the dissolved salt.

At Barnesville, Warren Township, Belmont County, Ohio, Berea 

gas wells are also reported to have become salted up, and at one place 

near the Barnesville field crystalline salt, an analysis of which is 

given in Table 15, was collected from a gas line pressure regulator 4 to 7 miles from the wells that furnished the gas. Salt was 

deposited here in so large amounts that it became necessary to remove 

the accumulations once "a year. It appears from this that particles 

of salt water were carried several miles in the form of a fine spray 

suspended in gas moving rapidly under'pressure. On further expansion of the gas more complete evaporation ojf the water took place 

and crystalline salt was deposited. The interior of the regulator was 

sometimes observed to be wet. About 15,000,000 cubic feet of gas a 

month passed through this apparatus, in which the gas line pressure 

was reduced from 100 to 20 pounds to the square inch. Three-inch 

pipe lines were in use. Small amounts of salt water were pumped 

and blown off from the Berea gas wells at Barnesville, and water 

traps were used to remove water from the gas before it went into the 

pipe lines.

Salting up of gas wells at Cleveland, Ohio, is reported by G. S. 

Rogers,1 who collected pieces of crystalline salts that formed in wells 

at the horizon of the so-called Clinton sand. This sand yields gas 

in the Cleveland field, but salt water, if present, can not be observed 

because of its evaporation into the gas. Rogers attributes the deposition of salt to the evaporation of salt water into expanding gas 

and thinks the water may leak to the Clinton sand from the higher 

lime sand (of early Devonian age; see stratigraphic table, p. 14)', 

which is known to be water bearing.

We are indebted to Dr. I. C. White for an account of the deposition of salt in a gas well near Warfield, Ky. The well burned for 

about 20 years, during which the gas was not utilized. During that 

period the well occasionally became choked by salt, but when the gas 

pressure increased sufficiently the salt was blown from the well and 

the flow of gas began again as usual.

At Woodsfield, Center Township, Monroe County, Ohio, fragments 

of salt-incrusted Berea sandstone were collected as soon as they 

were bailed from an old oil well. On examination these specimens 

were found to contain 0.59 per cent by weight of salts soluble in 

water, of which 89.5 per cent by weight was sodium chloride. The 

well had been yielding oil together with a little gas and salt water 

for ten years prior to the collection of the incrusted fragments.

In this bulletin it is possible to cite only a few of the many examples of the deposition of salt in gas and oil wells. In addition to 

the examples above cited, we. have received reports of similar

1 Rogers, G. S., The Cleveland gas field, Cuyahoga County, Ohio : U. S. Geol. Survey 

Bull. 661, pp. 19-20, 21, 31, 1917.
CHANGES IN. OIL AND GAS FIELD WATERS. 47

phenomena in Butler, Lawrence, Beaver, Armstrong, and McKean 

counties, Pa., and Belmont, Monroe, Noble, Guernsey, Knox, Wayne, 

and Licking counties, Ohio. A few isolated cases in West Virginia 

have also been reported. The short time available has not permitted 

a more extensive investigation of the subject.

The salting up of gas wells is attributed largely to the evaporative effects of expanding gas, but under certain conditions chilling 

of deep-seated brines entering the wells is another cause of the 

deposition of salt. Where great volumes of highly compressed gas 

are allowed to escape through an open well or into low-pressure gas 

lines, the temperature of salt water accompanying the gas is probably lowered sufficiently to cause the deposition of salt.

Apparently the phenomenon is common in both oil and gas fields, 

though frequently it is not observed because of the very small 

amounts of salt deposited. In the Appalachian fields the salt content of specimens of the productive sands collected from oil wells 

is usually less than 1 per cent by weight, as is shown in Tables 1 

and 3. The proportions of salt in specimens of pay sand from gas 

wells would doubtless be much greater. Analyses of some of the 

water-soluble salts collected during the studies relative to this paper 

are shown in Table 15.

TABLE 15. Analyses of water-soluble salt crusts collected 'from oil and pas wells.

Percentages by weight.

Na.............. .........................................................

Ca........................................................................ Mg ...... ................................................................

01... .....................................................................

804.......................................................................

COs......................................................................

1

38.70

0.15

Trace.

59.80

.18

.38

99.21

2

35. 2

3.4

.3

RA O

100.0

3

38.82

.09

.04

59.92

.16

.32

99.35

Conventional combinations calculated from the above figures, expressed as percentages by

weight.

NaCl.....................................................................

CaCU .....................................................................

MgCf......................................... ............................

FeS04 - ...................................................................

CaSOi.................................................................... c&cot............................ ........................................

98.37

.20

.26

.38

99.21

89.5

7.6

1.3

1.6

100.0

98.64

.14

.11

.14

.32

99.35

1. Salt crust, 98.83 per cent soluble in water, from a Clinton sand gas well, Cleveland, Ohio. Collected 

by G. S. Rogers. E. C. Wells, analyst.

2. Water-soluble portion of Berea sand from an oil well 10 years old, Woodsfleld, Center Township, 

Monroe County, Ohio, representing 0.59 per cent of the sand. B. C. Wells, analyst.

3. Silt crust, 99.03 per cent soluble in water, collected from a gas-pressure regulator between 4 and 7 

miles from the Berea wells that yielded gas together with water from wnich the salt was deposited, Barnesville, Belmont'County, Ohio. R. C. Wells, analyst.

A few examples of the deposition of inorganic substances other 

than soluble chlorides may be of interest. In Forward Township,
48 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

Butler County, Pa., fragments of a crust consisting of barium sulphate, with strontium and calcium sulphates, ferric oxide, and 

soluble chlorides, as shown by analysis 3, Table 16, were collected 

from an old oil well. The well had been yielding oil and salt water 

for about 15 years and had become badly fouled by mineral incrustations, when it was shot and cleaned. Angular fragments of the 

crust, 2 inches wide and half an inch thick, containing included 

globules of gelatinous hydrocarbons, were then collected. The crusts 

were formed at the horizon of the productive bed (Third sand, 

depth 1,470 feet).

A deposit of barium sulphate and calcium carbonate in an oil 

well was also observed in Butler Township, Butler County, Pa., 

Avhere the bottom portion of the tubing of a well was found to be 

so incrusted with these substances as to close most of the intake 

perforations completely, practically stopping production from the 

well. Only the bottom length of the tubing, the part which was immersed in salt water and oil, was incrusted. The well yielded oil and' 

salt water from the Hundred-foot sand at a depth of 1,380 feet. In 

this well the deposition of calcite upon the tubing had been followed 

by that of barium sulphate, which had, in turn, been followed by 

further deposition of calcite. The resultant banded nature of the 

crust is shown by Plate IV (p. 52). It is interesting to note that the 

crusts were so deposited upon surfaces wet with oil and water as to exclude both oil and water from the intake perforations. The well 

was double-cased halfway through the Hundred-foot sand, and the 

operators claimed that afterward practically no water leaked in 

from beds above the Hundred-foot sand.

The coarsely crystalline texture of the barium, sulphate crusts indicates slow deposition, but the cause^for this deposition in oil 

wells are uncertain. Among the possible causes 'may be mentioned 

the mixing, in the wells of dilute solutions of. soluble barium salts 

with solutions containing soluble sulphates. It seems probable that 

notwithstanding the agitation of the solutions at the productive 

horizons in the oil wells the precipitation of barium sulphate must 

have been slow, because of the very dilute solutions of sulphates and 

soluble barium salts involved. Siebenthal 1 has quoted Carles's work 2 

to show that some barium may remain in solution in the presence of 

some sulphate in bicarbonate waters. It may be that in these oil-field 

waters, particularly where bicarbonate waters leak into the wells 

from rocks near the surface, the breaking down of bicarbonates, due 

to the loss of carbon dioxide from solution, together with other gases, 

facilitates the slow deposition of barium sulphate. This mode of

1 Siebenthal, C. E., Origin of the zinc and lead deposits of the Joplin region, Missouri, Kansas, and Oklahoma: U. S. Geol. Survey Bull. 606, pp. 55-56, 1915.

s Carles, M. P., Presence de la baryte dans les eaux mine'rales sulphate'es: Annales 

chim. anal., vol. 7, pp. 91-93, 1902.
U. S. GEOLOGICAL SUHVEY BULLETIN 693 PLATE II

A. FRAGMENT OF SALT CRUST FROM A CLINTON SAND GAS WELL, CLEVELAND,

OHIO.

Collected by G. S. Rogers. The composition of the crust is shown by analysis 1, Table 15.

B. FRAGMENT OF SALT CRUST AT BARNESVILLE, OHIO.

Collected for the authors by a field employee of the Ohio Fuel Supply Co. The salt was deposited 

in a gas-line pressure regulator situated between 4 and 7 miles from the Berea wells supplying 

the gas. The composition of the crust is shown by analysis 3, Table 15.

SALT CRUSTS FORMED DURING THE PRODUCTION OF 

NATURAL GAS.

Photographs three times natural size.
CHANGES IN OIL AND GAS FIELD WATEES. 49

slow deposition is suggested by the uniform thickness and coarsely 

crystalline texture of the crusts and also by the admixture of barium 

sulphate with calcium carbonate, which would be precipitated as a 

carbonate on the loss of carbon dioxide from bicarbonate solutions.

Calcium carbonate, magnesium carbonate, and ferrous carbonate 

are deposited on tubings, on the walls of the wells, and in the interstices of productive sands. The carbonate deposits are most commonly found in the bottoms of old oil wells, though some carbonates 

are believed to be deposited in the interstices of the sands at considerable distances from the producing wells. This inference has been 

suggested by the petrographic and chemical examination of a large 

number of mineral crusts and specimens of oil and gas bearing sandstones collected from both old and new wells. Analyses of a few of 

these carbonate deposits are given in Table 16. The photographs 

reproduced in Plates II. III. and IV illustrate the mode of occurrence of the crusts.

TABLE 16. Analyses of mineral crusts collected from oil wells.

Percentages by weight.

FeO.. ......................................... ......

Fe2O8 .. ..............................................

BaO. ................................................

CaO. ................................................

SrO... ..............................................

MgO......... ........................................

COj.. ................................................

so,.... ..............................................

Si02 ..... ............................................

1

0.10

.53

.27

53.37

.16

.60

42.98

98.01

2

0.11

.69

.20

53.08

.46

.49

c43. 17

98.20

3

0.34

.11

b 61. 07

.81

1.61

Trace.

34.29

98.23

4

0.47

.32

3.63

1.44

.18

1.32

.17

91.69

.97

100. 19

5

0.60

56.71

4.41

.12

2.33

31.85

 2.12

98.14

Revised analyses.

Fe203 . .....:.......... ...............................

MgC08 . .............................................

FeCO8 .. . ............................................

BaS04 . ..............................................

SrSO4 . ..............................................

CaS04 . ..............................................

CaO .................................................

MgO.................................................

S&i... ................. .............................

0.10

.27

95.27

.23

1.33

.86

el. 99

100. 05

0.11

.20

94.90

.65

1.08

1.11

<1.80

99.85

0.34

.11

Trnnn

92.95

2.86

1.97

«1.77

100. 00

0.47

3.63

2.30

.20

.52

.29

d.03

d.09

91.69

.97

100. 19

0.60

 5.00

.25

88.26

3.91

2.12

98.14

o Essentially sodium chloride.

& Calculated for SOa. Presence proved by qualitative tests.

c Calculated to satisfy bases.

d Probably present as silicate. 

' By difference.

1. Crust cleaned from tubing of an old well yielding oil and salt water from the Hundred-foot sand, 

Summit Township, Butler County, Pa. The depth at which the crust formed is not known. The sample 

was collected from the derrick floor after the tubings had been cleaned. R. C. Wells, analyst.

2. Crust cleaned from tubing of an old oil well yielding oil and salt water from the Hundred-foot sand, 

Summit Township. Butler County, Pa., about a quarter of a mile from well where sample 1 was collected. 

The sample was collected from derrick floor after well tubings had been cleaned. R. C. Wells, analyst.

3. Crust cleaned from the bottom of a well that had been yieldingoil and salt water from the Third sand 

for about 15 years, 1 mile northeast of Water Station, Forward Township, Butler County, Pa. R. C. 

Wells, analyst.

4. Incrusted fragments of sandstone cleaned from the bottom of an old well that had been idle for about 

15 to 18 years, Evans City. Butler County, Pa. The well had formerly yielded oil and salt water from the 

Hundred-foot sand. R. C. Wells, analyst.

5. Crust (see B, PI. IV) collected from the bottom part of the tubing of an old well yielding oil, gas, and 

salt, water from the Hundred-foot sand, Butler Township, Butler County, Pa. S. C. Dinsmore, analyst.

91818° 19 4
50 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

The deposition of carbonates seems to be caused partly by the 

leaking into the wells and mixing of carbonate waters from shallow 

rocks with the deep-seated brines. When such waters are mixed and 

subsequently undergo concentration, any sodium carbonate in the 

shallow water will react with the calcium chloride of the deeper 

water to form calcium carbonate, sodium chloride, carbon dioxide, 

and water, according to the reaction

2 NaHCO3 +CaCl2 =CaCO3 +2 NaCl+C(X+H2O

In this connection it is important to note the presence of sodium 

chloride in the carbonate crusts from old oil and gas wells, and also 

the fact that calcium carbonate crusts in such wells are particularly 

abundant in Butler County, Pa., where some of the waters of the 

shallow rocks contain sodium in excess of the strong acid radicles 

and therefore have primary alkalinity. The decrease in the solubility 

of calcium carbonate in the presence of increasing proportions of 

calcium chloride is also a probable factor in the formation of these 

deposits, especially where waters that have dissolved calcium carbonate become mixed with the deep-seated waters. Another cause 

for the deposition of carbonates is the previously mentioned breaking 

down of soluble bicarbonates due merely to the liberation of carbon 

dioxide, together with other gases, from solution in water. In all 

these processes the concentration of the waters due to the removal of 

water vapor in the escaping natural gases is believed to play an 

important part.

CHANGES IN THE DEEP-SEATED WATERS DURING THE EXTRACTION OF OIL AND GAS.

METHOD OF STUDY.

The partial removal of some of the dissolved constituents from 

the waters necessarily results in changes in the proportions of the 

remaining constituents. In order to understand these changes as fully 

as possible and to correlate the evidence furnished by the deposition 

of mineral matter just described, we compared analyses of water collected at different periods of production from the initial well in a 

new oil and gas field. Similar comparisons were also made between 

waters from the same geologic horizon in old and new fields and 

between waters from different horizons in the same or neighboring 

fields. These comparisons have resulted in the discovery of certain 

general relations between the changes, in the waters during the extraction of oil and gas by man and the natural changes that have taken 

place during the lapse of geologic time.
U. S. GEOLOGICAL SURVEY BULLETIN 693 PLATE III

I INCRUSTED SANDSTONE, IMPREGNATED BY CARBONATES, FROM OLD OIL WELLS 

NEAR EVANS CITY, BUTLER COUNTY, PA.

A, Collected by R. Van A. Mills, Hundred-foot sand, depth 1,060 feet. K, Collected by a field employee 

of the South Perm Oil Co., Hundred-foot sand, depth 1,050 feet. C, Transverse section of -B.showiug 

iiiterstitially deposited carbonates as white patches. All photographs three times natural size.
CHANGES IN OIL AND GAS FIELD WATERS. 51

COMPARISON OF WATERS FROM THE SAME WELL.

Analyses of water from the Keener sand, Miltonsburg, Monroe 

County, Ohio, collected from the same well at different periods of 

production are shown in Table 17, and some of the conditions of 

production are indicated in figure 4. It is evident that the proportion of total dissolved solids in the waters collected from the same

BARRELS 

2700-

2600

2000

400-

MJr tyr.

S

\

o. :I_prc ?£

7 atoms

X

vlidsi

.Vafft

Toted

7&

trokr.

Totel

perU0*l otcms

Ol

J(K-A

i*ra/7s

cZ/25

Jan. Rd. Jlk Apr May Jrae July 

1316

ver littr

m.(tilt\

Cl.

Water

FIGURE 4. Curve showing the rates of production of oil and water from well No. 1, 

Schroeder heirs' farm, Miltonsburg, Malaga Township, Monroe County, Ohio, when 

water samples were collected from that well.

well increased as production continued. Moreover, the analyses indicate changes in the relative proportions of the different constituents, 

the ratio of calcium to chlorine being greater and the ratio of sodium 

to chlorine being smaller in the more concentrated water. Of the 

changes involved that in concentration is the most pronounced. We 

believe that such a change would be noted in waters from practically 

all initial wells in new fields where infiltrating waters are excluded
52 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

and there is a noteworthy escape of gas. This belief is based partly on 

our numerous comparisons of waters from the same sands in new 

and old fields where gas was being extracted.

TABLE 17. Analyses of brine collected at different periods of production from 

Keener sand in well No. 1, Schroeder heirs' farm, Miltonsburg, OMo.

[Depth of sand 1,465 to 1,471 feet. This was the initial well in a new oil and gas field. Analyses in grams

per liter.]

Si02 . ............................................................................

Fe. .............................................................................

Al..... ..........................................................................

Ca. .............................................................................

Mg.. ............................................................................

Na..................................... .........................................

K.. .............................................................................

C03 .- ...........................................................................

HC03 .. .........................................................................

SO<... ..........................................................................

Cl.. .............................................................................

Ca-Cl.... .......................................................................

Na-=-Cl. ....... ..................................................................

1

0.08

.01

.36

5.08

1.04

22.84

.60

.08

48.46

79.15

.117

.471

2

0 04

8 34

1.48

} 29.74

None

03

None

fwi in

103. 73

.130

464

1. Collected April 24, 1915, when the well was 1 month old. S. C. Dinsmore, analyst. Gas, oil, and 

water were flowing from the well. The approximate rate of production at that time is shown by figure 4.

2. Collected when the well was 18 montns old. Chase Palmer, analyst. The gas pressure had declined 

and the well had ceased to flow. The rate of production of oil had declined and tne rate of production 

of water had increased, as shown by figure '4.

Several explanations may be offered to account for the changes 

noted. It is believed that the evaporation of water into the escaping 

gas is the principal cause for the change in concentration. Another 

possible explanation is that the more concentrated water comes from 

a part of the sand- where the water has undergone advanced concentration either prior to drilling or in an older oil and gas field. 

The suggestion that the changes in concentration are related to the 

extraction of gas is strengthened by the fact that water from certain 

deep wells where oil and gas are practically absent has shown for 

many years no significant change in character or concentration. 1

No single explanation for the changes other than that of concentration can be advanced without reservation. It will be understood, 

for instance, that the changes in the relative proportions of the dissolved constituents may be accounted for by the leakage into the wells 

of carbonate waters having primary alkalinity. The reaction that 

is involved when such waters are mixed with the deep-seated brines 

and subsequently concentrated has been briefly described on page 

50. Relatively little sodium chloride is lost from the solution, but 

both calcium and magnesium are deposited as carbonates. This pre1 Bownocker, J. A., Salt deposits and the salt industry in Ohio: Ohio Geol. Survey, 

4th ser., Bull. 8, p. 27, 1906.

Stephenson, L. W., and Palmer, Chase, A deep well at Charleston, S. C., with a 

report on the mineralogy of the water: U. S. Geol. Survey Prof. Paper 90, p. 90, 1914.
U. S. GEOLOGICAL SURVEY BULLETIN 093 PLATE IV

A. FRAGMENTS OF A SULPHATE CRUST.

dark mass (a) is a soft waxy hydrocarbon that is included in the crust. The composition of the 

deposit is shown by analysis 3, Table 16. Photograph three times natural size.

B. FRAGMENT OF A MIXED SULPHATE AND CARBONATE CRUST FROM THE 

BOTTOM PART OF THE TURING OF AN OLD WELL YIELDING OIL, GAS, AND SALT 

WATER FROM THE HUNDRED-FOOT SAND, BUTLER TOWNSHIP,

Collected by R. Van A. Mills. Petrographic examination has shown that the specimen consists essentially of barite and calcite in alternate layers. Small amounts of sodium chloride are also present. 

The calcite and barite crystals are slightly interlocked in comblike structure.

SULPHATE CRUSTS FROM OIL WELLS IN BUTLER COUNTY, PA.
CHANGES IN OIL AND GAS FIELD WATERS. 53

cipitation tends to bring about differences in the sodium-chlorine and 

calcium-chlorine ratios, such as have been noted. Furthermore the 

extensive occurrence in the sands of secondary carbonates containing 

small proportions of sodium chloride indicates changes of this type.

The deposition "of sodium chloride, with possibly very minor 

amounts of calcium and magnesium chlorides, during the concentration of the water would also cause such changes in the relative proportions of the dissolved constituents as are actually noted. The occurrence of deposits of sodium chloride in gas wells and in the interstices of the productive rocks indicates this mode of change in many 

fields.

To ascertain, approximately, the dissolved constituents that may 

be lost frOm the brines during concentration so as to cause the differences shown in Table 17, we have made further comparisons of 

the analyses in that table, and the results are set forth in Table 18. 

Here the analyses are simplified by rejecting the minor constituents 

and by slightly altering the values for sodium until an exact balance 

between the bases and chlorine is obtained so that the dissolved constituents can be expressed as chlorides. The analyses are given 

under 1 and 2 respectively. The values in column la are obtained 

by multiplying those in column 1 by an arbitrary factor (1.482), 

which is equivalent to making a hypothetical concentration of the 

more dilute water to 67.48 per cent of its original volume. This 

hypothetical concentration has been selected in order that the calcium 

content of water la and water 2 should be approximately the same. 

Calcium chloride, being more soluble than sodium chloride, would 

not be expected to deposit with sodium chloride at first; nevertheless 

small amounts of calcium and magnesium chloride seem to accompany the sodium chloride actually found in the oil and gas bearing 

rocks, so that the hypothetical concentration has been carried to a 

point to yield a slight excess of calcium chloride. No error is thus 

introduced, inasmuch as the results more nearly agree with conditions 

actually noted. Moreover, if the hypothetical concentration of the 

dilute water should be varied slightly in either direction, the hypothetical salt dep^a/t would still approximate the salt deposits found 

in the reservoir rocks, sodium chloride being the predominating constituent.

It will be seen from Table 18 that the difference in the salt contents of the waters under comparison is expressed essentially as one 

of sodium chloride. It will also be noted that the composition of 

the salts hypothetically removed from the dilute water during its 

concentration agrees closely with the composition of natural salt deposits and with that of salt crusts collected from wells. The com-
54 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS."

p arisen therefore furnishes further evidence that the change in the 

waters may be due to the loss of sodium chloride during the concentration of the water accompanying the extraction of oil and gas.

TABLE 18. Analyses illustrating the probable loss of sodium chloride from solution during the concentration of a Keener brine issuing from the initial well 

, in a new field near Miltonsburg, Ohio.

[The figures given under 1 and 2 in this table have been, recalculated from analyses 1

and 2, Table 17.]

CaClj............ ..........................

MgCl2 ......................................

NaCl......................................

KC1. ......................................

1

Grams per 

liter. 

15.76

4.08

57.39

1.14

78.37

la

Grams per 

liter. 

23.36

6.04

> 86.78

116. 18

2-

Grams per 

liter. 

23.13

5.81

74. 16

103. 10

Grams 

(la-2). 

0.23 .'23

12.62

13.08

3

Per cent. 

1.76

1.76

96.48

100. 00

1. Simplified analysis of water collected when the well was one month old. Gas, oil, and water were

flowing from the well. The approximate rates of oil and water production are shown by figure 4 (p. 51).

la. Same water as 1, hypotnetically concentrated to 67.48 per cent of its original volume (factor 1.482).

2. Simplified analysis of water collected when the well was 18 months old. During the interval between 

the collecting of samples 1 and 2 large amounts of gas and oil had been produced from this and neighboring 

wells. The changes in the rates of production of oil and water from the well are shown by figure 4.

3. Approximately the weights and relative proportions of the salts whose removal from i.482 liters of 

water 1 together with evaporation would yield 1 liter of water 2.

From another point of view, however, it is well to note that the 

differences between the dissolved solids in the waters under comparison can be expressed merely as the differences between columns 1 and 

2 in Table 18. One liter of the more concentrated water whose dissolved constituents are represented in column 2 may be considered 

as having formed through the introduction into an equal volume of 

the more dilute water of 7.37 grams of calcium chloride, 1.73 grams 

of magnesium chloride, and 15.63 grams of sodium and potassium 

chlorides. This implies an accession to the formerly dilute water of 

salts consisting of 29.80 per cent of calcium chloride, 7 per cent of 

magnesium chloride, and 63.20 per cent of sodium and potassium 

chlorides. These salts are too soluble to have remained undissolved 

in water such as first issued from the well and were therefore not 

acquired by simple leaching during the extraction of oiland gas. It 

is possible, however, that waters containing relatively large proportions of calcium chloride may have gained access to the well from 

various sources as the extraction of oil and gas proceeded. As water 

is drawn from a sandstone reservoir more or less water doubtless 

percolates into the sand from the surrpunding rocks. Water from 

shales and other argillaceous strata might contain a relatively large 

proportion of calcium derived through the exchange of sodium in the 

brines for calcium in the reactive minerals of the shales. The
CHANGES IN OIL AND GAS FIELD WATERS. 55

nature of the reactions involved is discussed on page 75. The entrance of such waters into the sands, with or without concentration, 

may thus account for the changes in the waters noted during the extraction of oil and gas. The comparison of the waters can thus 

be made on the basis of changes of either type. We retain the comparison in terms of the loss of sodium, because it is sufficient for the 

purpose in view and because it also expresses the changes that occur 

when the waters are concentrated to the point of deposition of 

sodium chloride.

COMPARISONS OF WATERS TROM THE SAME GEOLOGIC HORIZONS IN 

NEIGHBORING FIELDS.

From numerous detailed comparisons between the dissolved constituents of waters collected from the same sands in neighboring 

fields Tables 19 and 20 have been compiled to illustrate the evidence 

thus obtained. In general, the more concentrated waters occur in the 

older fields. Also, with but few exceptions, the ratio of calcium to 

chlorine is greater and the ratio of sodium to chlorine is smaller in 

the more concentrated waters. Furthermore, it is shown that almost 

invariably the concentration of the more dilute water, together with 

the removal of dissolved constituents consisting essentially of sodium 

chloride, would yield the more concentrated water. Again, the salts 

whose removal from solution can thus be postulated agree in composition closely with the salts from wells and with natural deposits 

of chloride salts. The differences between the more dilute and more 

concentrated waters in the same sand are of practically a uniform 

type, no matter whether the waters are drawn from a single well at 

different stages in its operation or from neighboring fields where the 

conditions of production have been widely different.
56 WATEKS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

TABLE 19. Comparison of analyses of two waters from the Big lime sand showing the constituents whose removal from the more dilute water, together with 

evaporation, would yield the more concentrated water.

[Samples collected from different fields 4J miles apart in the northern part of Monroe County, Ohio.]

Fe...................................................

Ca...................................................

Mg.. ...............................................

Na. .................................................

K...................................................

HCOa.. ...... ........................................

Cl....... ............................................

Ca-Cl ..............................................

Na-r-Cl ..............................................

1

Grams 

per liter. 

0.02

.08

5. .58

1.04

23.86

.25

.32

50.40

81.55 

0.111

.473

la

Grams 

-per liter. 

0.04

.17

12.00

2.24

51.30

.54

.69

108. 36

175. 34

2

Grams 

per liter. 

0.09

.02

11.56

1.83

39.27

.69

.03

87. 50

140. 99 

0.132

.449

Grams 

(la-2). 

-0.05

.15

.44

.41

12.03

- .15

.66

20.86

34.35

J

Per cent.

0.43

1.27

1 19

34.82

1 91

60.38

100. 00

Weights and proportions of compounds whose removal from 2.150 liters of water 1, together 

with evaporation, would yield 1 liter of water 2.

[Recalculated from No. 3, above.]

cot .. ...........................................................................

H2 0a.. ..........................................................................

FeC03 ..... .....................................................................

CaC03 .- .........................................................................

CaCl2 .. ..........................................................................

MgCls...................................... .....................................

NaCl.. ..........................................................................

KC1. ............................................................................

CaS04 . . .........................................................................

Crams.

0.24

.10

.31

.20

1.00

1.01

 31.09

34.55

Per cent.

0.70

.29

.91

.58

2.90

4.66

89.96

100. 00

a This represents only the water from bicarbonates, a very small amount in comparison with the water 

lost by evaporation.

1. Brine collected September 15. 1916, from Big lime sand; depth 1,339 to 1,349 feet; new gas well in a 

new oil and gas field near Miltonsburg, Malaga Township, Monroe County, Ohio. Specific gravity of the 

water 1.0559. R. C. Wells, analyst.

la. Same water as No. 1, hypothetically concentrated to 46.51 per cent of its original volume (factor 

2.150).

2. Brine collected April 24,1915, from Big lime sand; depth 1,431 to 1?444 feet; from an old oil and eas 

field in the northeastern part of Malaga Township, Monroe County, Ohio, near Jerusalem village. S.'C. 

Dinsmore, analyst.

3. Approximately the weights and relative proportions of the constituents whose removal from 2.150 

liters of water 1, together with evaporation, would yield 1 liter of water 2.

TABLE 20. Comparison of analyses of two ivaters from the Keener sand showing the constituents whose removal from the more dilute water, together loith 

evaporation, would yield the more concentrated water.

[Samples collected from different fields 7J miles apart in the northern part of Monroe County, Ohio.]

Si 0 2 ...........-........................- .......:....

Fe.. .................................................

Ca...................................................

Qr

Mg. .................................................

Na..................................................

K.. .................................................

HCO3 ...............................................

Cl..................................... ..............

Ca:Cl... ............................................

Nan-Cl... ............................................

1

Grams 

per liter. 

0.05

.01

2.98

.08

.83

19.84

.23

.17

38.92

63.11 

.076

.510

la

Grams 

per liter. 

0.20

.14

11.62

.31

3.24

77.38

.90

.66

151. 79

246. 14

2

Grams 

per liter. 

0.08

11.36

1.63

38.32

.51

.03

84.71

136. 64 

.134

.452

Grama 

(la-2). 

0.12

.04

.26

.31

1.61

39.06

.39

.63

67.08

109. 50

i

Per cent. 

0.11

.04

.24

.28

1.47

35.67

.36

.57

61.26

100. 00
CHANGES IN OIL AND GAS FIELD WATERS.

TABLE 20. Comparison of analyses of two waters, etc. Continued.

57

Weights and proportions of compounds whose removal from 3.900 liters of water 1, together 

with evaporation, would yield 1 liter of water 2. 

[Recalculated from No. 3, p. 56.)

Si02 ............................................................................

CO 2................................................... .........................

FeCOg..........................................................................

CaCOg.. .........................................................................

CaCl2 .. ........ ..................................................................

MgCli.. .........................................................................

NaCl. ...........................................................................

KC1. ............................................................................

Grams.

0.12

.23

.09

.08

.42

.47

6.29

101. 05

.75

109. 50

Per cent.

0.11

.21

OS

.07

.38

.42

5.75

92.30

.68

100.00

a This represents only the water from bicarbonates, a very small amount in comparison with the water 

lost by evaporation.

1. Brine from Keener sand; depth, 1.302feet: sample collected November 7,1916, from a new oil well in 

a new field near Monroefield, Malaga Township, Monroe County, Ohio. Very little gas was produced in 

this field. Specific gravity of the water 1.0437. R. C. Wells, analyst.

la. Same water as No. 1, hypothetically concentrated to 25.64 per cent of its original volume (factor 

3.900). 

2. Brine from Keener sand; depth, 1,451 to 1,469 feet; sample collected April 24,1915, from an old oil and 

gas well in an old oil and gas field near Jerusalem Village, Sunsbury Township, Monroe County, Ohio. 

S. C. Dinsmore, analyst.

3. -Approximately the weights and relative proportions of the constituents whose removal from 3.900 

liters of water 1, together with evaporation, would yield 1 liter of water 2.

EVIDENCE THAT SIMILAR DIFFERENCES IN THE WATERS HAVE 

BEEN BROUGHT ABOUT DURING GEOLOGIC TIME.

COMPARISON OF WATERS FROM DIFFERENT GEOLOGIC HORIZONS.

In the foregoing text we have presented evidence that changes in 

the waters under scrutiny occur during the extraction of oil and gas 

from the reservoir rocks. The changes are indicated by differences 

in concentration, differences in the relative proportions of the dissolved constituents, the apparent loss of certain constituents from 

solution, and the possible accession of other constituents. It appears, 

however, that such changes are not only closely related to the 

extraction of oil and gas but have also occurred from natural causes 

during geologic time.

As evidence bearing on this subject we submit in Tables 21, 22, 

and 23 comparisons of waters collected from beds at different 

geologic horizons in the same-and neighboring fields. The waters 

under comparison in each table have been subjected to the effects of 

oil and gas production for approximately equal periods of time, the 

conditions of production being nearly the same, but nevertheless the 

waters show marked differences in concentration as well as in the 

proportions of their dissolved constituents. These differences are 

practically the same as those which appear to be brought about 

under the various conditions of oil and gas extraction by man. We 

are therefore led to ascribe them to the same causes. The more
58 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

concentrated solutions have probably been concentrated, owing to 

evaporation into expanding gas which has removed more water than 

has been lost from the dilute solutions. We shall next attempt, 

therefore, to examine the evidence of the natural escape of gas that 

might afford conditions for concentration and changes in the waters 

similar to those brought about during the extraction of oil and gas.

TABLE 21. Comparison of analyses of two gas-field waters from different geologic horizons, showing the constituents whose removal from the more dilute 

water, together toith evaporation, ivould yield the more concentrated water.

Si02 ....... .. ... . ................................

Fe.. ................................ :................

Ca...................................................

Mg..................................................

Na..................................................

K.... ...............................................

HCC3 . .............................................. ci... . ................................:..............

Can-Cl. ..............................................

Na-s-Cl. ............I................................

1

Grams 

per liter. 

0.22

.06

2.75

.86

15.85

.51

.37

32.07

52.69 

0.086

.494

la

Grams 

pel- liter. 

0.99

.27

12.35

3.86

71.17

2.29

1.66

143. 99

236. 60

2

Grams 

per liter, 

0.70

.02

12.22

2.88

45.88

.35

.02

102. 14

164.21 

0.120

.449

Grams 

(la-2). 

0.29

.25

.13

.98

25.29

1.94

1.64

41.35

72.37

3

Per cent. 

0.40

.35

.18

.35

34.95

2.68

2.27

57.82

100.00

Weights and proportions of compounds whose removal from 4.490 liters of water 1, together 

with evaporation, would yield 1 liter of water 2.

[Recalculated from No. 3, above.]

SiO2 ... .........................................................................

COz........................................................... ..................

H3 0o... ........................................................................

FeCOa.......................................... ................................

CaCOs. .........................................................................

MgCOs.. ........................................................................

MgClj.. .........................................................................

NaCl.......................................................... ..................

KC1... ..........................................................................

Grams.

0.29

.59

.24

.52

.33

.48

3.30

62.92

3.70

72.37

Per cent.

0.39

.80

.33

.71

.45

.66

4.56

86.98

5.12

100. 00

o This represents only the water from bicarbonates, a very small amount in comparison with the water 

lost by evaporation.

1. Brine from Berea sand; depth 1,748 to 1,760 feet; sample collected April 2S, 1915, from a gas well 1£ 

years old situated in an old gas field at Summerfield, Marion To .vnship, Noble County, Ohio. S. C. Dinsmore, analyst.

la. Same water as No. 1 hypothetically concentrated to 22.37 per cent of its original volume (factor 4.490).

2. Brine from Big Injun sand; depth 1,200 feet; sample collected April 27,1915, irom a new gas well in an 

old gas field at Summerfield, Marion Township, Noble County, Ohio, 2J miles Irom well in which sample 

1 was obtained. S. C. Dinsmore, analyst.

3. Represents approx'-nately the weights and relative proportions of the different constituents whose 

removal from 4.490 liters of water 1, together with evaporation, v,-ould yield 1 liter of water 2.
CHANGES IN OIL AND GAS FIELD WATEKS. 59

TABLE 22. Comparison of analyses of two oil and gas field waters from- different geologic horizons, showing the constituents lohose removal from- the more 

dilute water, together with evaporation, would yield the more concentrated 

voater.

SiOjj.. ...............................................

Fe.................... ...............................

Al. ..................................................

Ca.. .................................................

Mg. .................................................

Na. .................................................

K..... ..............................................

C03 .................................... .............

HCOs...-. ..........................................

S04................................................. ci. ..................................................

Ca-^Cl.... ...........................................

Na.Cl.. .............................................

1

Grams 

per liter. 

0.14

.01

.50

2.79

1.01

19.49

.50

.05

38.69

63.18 

0.072

.503

la

Grams 

per liter. 

0.06

.05

2.35

13.11

4.75

91.60

2.35

.24

181. 84

296.95

2

Grams 

per liter. 

0.14

.02

.62

12 98

1.69

43.40

2.47

.04

97.96

159.32 

0. 133

.443

Grams 

(la-2). 

0.52

.03

1.73

.13

3.06

48.20

.12

.20

83.88

137.63

3

Per cent. 

0.38

.02

1.26

09

2.22

34.99

IE

60.89

. 100.00

Weights and proportion of compounds whose removal from 4.700 liters of water 1, together 

with evaporation, would yield 1 liter of water 2.

[Recalculated from No. 3 above.] 

SiOj....................... .....................................................

C0a . ............................................................................

H.lOa. ............ ..............................................................

$oG33 .. ..................... ...................................................

CaClj.................................... .......................................

MgClj................................. ..........................................

NaCl ...........................................................................

Grams.

0.52

.07

.03

Aft

.10

.28

12.00

124.69

137.75

Per cent.

0.38

n<;

O9

04

no

.21

8.72

cn f\n

100.00

a This represents only the water from iJicarbonates, a very small amount in comparison with the water 

lost by evaporation.

1. Brine April 30,1915, from Berea sand; depth 1,570 to 1,592 feet; from an old oil and gas well in an old 

oil and gas field, Chaseville, Seneca Township, Noble County, Ohio. S. C. Dinsmore, analyst.

la. Same water as No. 1, hypothetically concentrated to 21.28 per cent of its original volume (factor 

4.700).

2. Brine from Keener sand; depth 870 to 880 feet; sample collected May 1, 1915, from an old oil and gas 

well in an old oil and gas field, Chaseville, Seneca Township, Noble County, Ohio, 1 mile from well in which 

sample 1 was obtained. S. C. Dinsmore, analyst.

3. Approximately the weights and relative proportions of the different constituents whose renoval 

from 4.700 liters of water 1 would yield 1 liter of water 2.
60 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

TABLE 23. Comparison of analyses of two oil and, gas field waters from different geologic horizons, showing the constituents whose removal from the 

more dilute water, together with evaporation, would yield the more concentrated toater.

Si02 . . ...............................................

Fe.... ...............................................

Al.................................... . .. ........

Ca...................................................

Mg.... ..............................................

Na....... ...........................................

K..... ..............................................

HC03 ..... ..........................................

S04 ................ :.................................

Cl.... ...............................................

Ca-t-Cl... ...........................................

Na-s-Cl... ...... ......................................

1

Grams 

per liter. 

0.24

.01

.49

10.29

1.85

33.76

.26

.0219*

78.78

125. 82 

0.131

.429

la

Grams 

-per liter. 

0.37

.01

.76

15.94

2.87

52.30

.40

.03

19

122. 04

194. 91

2

Grams 

per liter. 

0.12

.05

.83

15.82

1.87

40.79

.95 .03'

 13

97.61

158. 20 

0.162

.418

3

Grams 

(la-2). 

0.25 -.04

-.07

.12

1.00

11.51 -.55

nfi

24.43

36.71

Per cent. 

0.67

.32

2.68

30.80

.16

65.37

100.00

Weights and proportions of compounds whose removal from 1.549 liters of water 1, together 

with evaporation, would yield 1 liter of water 2.

[Recalculated from No. 3 above.] 

SiO2 ............................................................................

CaCh. ..........................................................................

MgCl2 .. .........................................................................

NaCl............................. ...............................................

Grams.

0.25

.26

3.92

32.86

.08

37.37

Per cent.

0.67

.70

10.48

87.94

.21

100. 00

1. Brine from Hundred-foot sand; depth 1,018 to 1,6^5 ; sample collected in September, 

1915, from a new oil well in a new oil and gas field where production had not yet begun, 

Harlan Book farm, on Muddy Creek in Clay Township, Butler County, Pa., S. C. Dinsmore, analyst.

la. Same water as No. 1, hypothetically concentrated to 64.55 per cent of its original 

volume (factor 1.549).

2. Brine from Bowlder sand ; depth 1,701 to 1,720 feet; sample collected in September, 1915, from a new oil well in a new field where production had just begun, Welsh 

farm, Penn Township, Butler County, Pa., 12| miles from field in which sample 1 was 

obtained. S. C. Dinsmore, analyst.

3. Approximately the weights and relative proportions of the constituents whose removal from 1.549 liters of water 1, together with e\7 aporation, would yield 1 liter of 

water 2.

EVIDENCE OF THE NATURAL ESCAPE, OF GASES.

Examples of gases escaping from their reservoir rocks under such 

conditions as would probably bring about the concentration of associated waters are found to-day in many parts of the world, and it is 

doubtful if there are any important oil and gas regions where surface evidences of the escape of gases are absent. The common association of gas with oil and the almost invariable evidence of the natural 

escape of oil from the known deposits substantiate this statement.

At numerous places in the Appalachian fields gas escapes in shallow-water wells and in springs, such, for instance, as have given rise
CHANGES IN OIL AND GAS FIELD WATERS. 61

to the name Burning Springs, in Wirt County, W. Va. The gas 

springs in Wirt and Kanawha counties, W. Va., have been described 

in the county reports of the West Virginia State Geological Survey. 

Similar occurrences in western New York have been repeatedly described. Concerning the natural escape of gas near Fredonia, Chautauqua County, N. Y., Ortoh 1 says: " From some of these pints gas 

constantly escapes. The currents are much weaker, however, at the 

present time than they were in earlier days. When water occupies 

the openings formed by the joints, the gas appears in bubbles, forcing 

its way through the water. Such springs were known by the early 

French explorers of the country as " fontaines qui bouillent." Escaping gas is also reported in Jefferson 2 and Allegany 3 counties, N. Y. 

Campbell 4 reports the escape of natural gas from rock crevices near 

Richlands, Tazewell County, Va. Munn 5 reports gas seepages near 

Memphis, Tenn. Gas springs are reported in New Brunswick and 

Alberta, Canada, by Clapp and others.6 Wegemann 7 reports a gas 

seepage in Palo Pinto County, Tex. "A bubbling spring of salt 

water," where gas is evidently escaping, has also been observed in 

the central Australian desert by Gregory.8

Probably the most striking examples of the natural escape of the 

hydrocarbon gases are afforded by the so-called mud volcanoes, which 

emit enormous Volumes of combustible gas, together with concentrated brines, mud, and sand. ' Thompson 9 describes mud volcano 

phenomena in Russia, Borneo, Sumatra, Burma, Colombia, and Trinidad. He describes violent eruptions of gas, which becomes ignited, 

in the Poota and Bingadi districts, near Baku, Russia, and he also 

states that " on the ridge of hills fringing the Poota Valley near Baku 

there is an area of about an acre where the escaping gas is rarely if 

ever extinguished." "In the Yenangyat district of Burma a somewhat similar phenomenon is observed at Yenang Daung." The same 

writer describes many other outbursts of gas, some of them occurring under subterranean conditions.

1 Orton, Edward, Petroleum and natural gas in New York: New York State Mus. 

Bull., vol. 6, No. 30, p. 495, 1899.

a ldem, p. 457.

8 Haworth, Erasmus, Report on oil and gas: Kansas Univ. Geol. Survey, vol. 9, 

p. 11, 1908.

4 Campbell, M. R., personal communication.

B Munn, M. J., Explorations for natural gas and oil at Memphis, Tenn.: Resources 

of Tennessee, vol. 2, No. 2, pp. 48-50, 1912.

8 Clapp, F. G., Petroleum and natural gas resources of Canada, vol. 2, pp. 52-53, 

294-295, 1915.

7 Wegemann, C. H., A reconnaissance in Palo Pinto County, Tex., with special reference to oil and gas: U. S. Geol. Survey Bull. 621, p. 53, 1916.

8 Gregory, H. E., Lovely Australia, the unique continent: Nat. Geog. Mag., vol. 30, 

p. 556, 1916.

 Thompson, A. B., Oil-field development, pp. 176-184, New York and London, 1916.
62 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

Relative to the salt industry of the East Indies, Harris 1 says:

On the Island of Java salt is also made from brine springs, which flow from 

Miocene beds and usually contain iodine and bromide salts, as well as sodium 

chloride. Many of these brines contain petroleum and gas. The most striking 

are those of Grobogan, northeast of the city of Samarang, in north-central 

Java. According to Karsten, the brines, which are associated with mud' volcanoes, are in a limestone formation that forms a circular plain half a mile in 

extent. The brine springs occur in large numbers and boil from fissures in the 

rocks. The water is strongly saline and gives very good salt on evaporation. 

In the center of the limestone region is a remarkable volcanic phenomenon. 

On approaching this from a distance one sees a dense cloud of steam that at 

intervals of several seconds rises and then, disappears. This is accompanied 

by a roar like distant thunder. Near by one perceives a hemispherical mass 

about 16 feet in diameter, composed of black mud saturated with salt water. 

This mass is regularly raised to a height of 30 feet by an underground force 

and then explodes with a deafening roar, and globular masses of the black mud 

are thrown in every direction. After an interval of two to four seconds the 

mass of mud is again raised and again torn to pieces by an explosion. For 

many years the natives have obtained salt by evaporating the brines ejected 

by these mud volcanoes. The salt water is led away in ditches to the outskirts 

of the region and is then evaporated. Some 200 metric tons are made annually.

In considering the subject further Harris adds that " small mud 

volcanoes with pools of salt water are also found on Ceram, one of 

the Spice Islands."

The escape of gases, especially methane, from unconsolidated carbonaceous sediments is so common as to require no particular comment.

Shaw 2 has described emanations of gases from the unconsolidated 

sediments at the mouths of Mississippi Elver. Knapp 3 describes 

gas seeps in Terrebonne Parish, La., and also quotes from the New 

Orleans Times-Democrat of November 26, 1911, an account of a gas 

eruption in the sea off Erin Point, Trinidad, on November 11, 1911. 

After describing the eruption, the account says: " The next day it 

was found that an island of 2^ acres had been formed. A landing 

party found the place still warm and by laying down boards were 

able to examine two cones, 12 to 15 feet high, from which gas was 

escaping. The air was saturated with the odor of sulphur and oil." 

In the same contribution Knapp quotes a report that gas is continually forcing up cones of pitch and mud in the pitch lakes region 

of Trinidad.

The occurrence of native bitumens filling fissures is in some localities a surface indication of the presence of oil and gas deposits in

1 Harris, G. D., Rock salt, its origin, geological occurrences, and economic importance 

In the State of Louisiana: Louisiana Geol. Survey Bull. 7, pp. 198-199, 1908.

2 Shaw, E. W., The mud lumps at the mouths of the Mississippi: U. S. Geol. Survey 

Prof. Paper 85, pp. 11-27, .1913.

3 Knapp, I. N., discussion of paper by Roswell H. Johnson, The r61e and fate of the 

connate water in oil and gas sands : Am. Inst. Min. Eng. Trans., vol. 51, pp. 593-597, 

1915.
CHANGES IN OIL AND GAS FIELD WATERS. 63

\ deeper reservoir rocks. In other fields fissures filled by calcite with 

i scattered inclusions of waxy hydrocarbons are considered an indica-

*' tion of oil or gas. The solubility of certain waxy hydrocarbons in

! gases under high pressure and the relative insolubility of these

^ hydrocarbons in the same gases under lower pressures, as well as the

ff> fact that much gas is evolved during the mining of native bitumens,

^ suggest that vein deposits of these substances may owe their origin

largely to the influence of gases that escaped through fissures.

Thompson 1 states that masses of bitumen are often ejected with

violence from the working faces of bitumen mines by gas which has

ft collected under pressure in the minerals.

^ Twenty years ago I. C. White 2 called attention to the association

, of deep-seated deposits of petroleum and natural gas with a fissure

i deposit of grahamite in Ritchie County, W. Va., and attributed the

" !| formation of the grahamite in part to the escape or exudation of

: petroleum accompanied by its oxidation. He furthermore cited the

y occurrence of coaly bituminous material, believed to be some of the

( hydrocarbon minerals originating from petroleum, at depths of

\ more than 1,600 feet as evidence that outflows of petroleum occurred

in the Cairo region of West Virginia " at the close of the lower

Carboniferous epoch." It seems probable that natural gas would

have accompanied such outflows of petroleum.

Subsurface movements of gas unaccompanied by surface emanations, though probably common at the present time, can not be de- 

,7 tected. Furthermore, as most of the natural gas seeps that have been 

^ described in the literature were detected by ebullitions of gas through

** surface waters, it is obvious that numerous seeps where the gas passes

* '* directly into the air have-never been detected.

RELATIONS BETWEEN THE) GEOLOGIC HISTORY OF CERTAIN RESERVOIR 

£\ ROCKS AND THEIR INCLUDED WATERS.

_ ; In the Woodsfield and Summerfield quadrangles, in southeastern 

J Ohio, the occurrence of relatively dilute waters in the deeply buried 

^ Berea sand, which is overlain several hundred feet higher by the Big 

lime, Keener, and Big Injun sands, containing more concentrated 

A waters (see Tables 21 and 22), is interesting because it suggests a 

relation between the geologic history of these reservoir rocks and the 

concentration of their included waters, namely, that the more concentrated brines are now found in the strata where geologic conditions were at one time favorable for the escape of gas and the con- 

; sequent evaporation of water.

_ * * Thompson, A. B., Oil-field development, p. 197, New York and London, 1916. 

2 Origin of grahamite: Geol. Soc. America Bull., vol. 10, pp. 277-284, 1898.

'
64 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

The Berea sand in the Woodsfield and Summerfield quadrangles 

is lenticular and is interbedded in thick deposits of shale. It 

overlies the unconformity at the base of the Mississippian series and 

is overlain by several hundred feet of relatively impermeable shale. 

In other words, the lenses of Berea sand from which water samples 

were collected and studied for this bulletin have remained deeply 

buried since the overlying shales were deposited.

The Big lime, Keener, and Big Injun sands, on the other hand, 

closely underlie the old erosion surface that marks the unconformity 

between the strata of Mississippian and Pennsylvanian age, and 

in parts of the two quadrangles the Big lime sand has evidently been 

removed by the pre-Pennsylvanian erosion. Where these formerly 

shallow rocks were not eroded they were covered only by a relatively 

thin series of limestone, shale, and sandstone that would have permitted the escape of at least a part of their gaseous content. We 

therefore infer that the brines in the Big lime, Keener, and Big 

Injun sands were concentrated largely by the evaporative effect of 

escaping gases during pre-Pennsylvanian erosion. The evaporation 

may have been assisted by arid climatic conditions. During these 

changes the waters in the lenses of Berea sand would have remained 

less subject to evaporation because the sand was protected by a thick 

cover of relatively impermeable shales.

So far we have found nothing to contradict the conclusion set 

forth above, it being improbable that this lenticular part of the 

Berea sand would constitute a channel for the deep migration of 

water entering the bed at its outcrop.

HYPOTHESES CONCERNING THE 6RIGIN OF THE OIL 

AND GAS FIELD WATERS.

HYPOTHESES PREVIOUSLY SUGGESTED.

Before fully stating our hypothesis relative to the formation, of 

the deep-seated oil and gas field brines we will discuss some of the 

suggestions offered by other investigators. As long ago as 1875 

Hunt 1 concluded that certain deep-seated chloride waters from Ontario, which are characterized by their large content of calcium and 

magnesium chlorides, are long-buried bitterns derived from the 

evaporation of ancient sea water which was considerably richer in 

calcium chloride than the sea water of the present day. He supposed that part of the sodium in this water had been deposited as 

sodium chloride and that the sulphate had been removed as gypsum. 

This hypothesis involves widespread arid conditions and an ancient 

sea containing a high proportion of calcium chloride. Arid condi1 Hunt, T. S., Chemical and geological essays, p. 117, Boston, 1875.
HYPOTHESES CONCERNING ORIGIN OF WATERS. 65

tions exist in certain parts of the world at the present time and may 

have occurred during past geologic periods that would have left the 

bitterns somewhere near their present positions.

Though the character of the ancient sea has been a subject of 

much discussion, it remains extremely hypothetical. Hunt's hypothesis regarding the excessive calcium chloride content of early ocean 

water has been supported by Lane 1 in several contributions. Daly,2 

on the other hand, postulates a limeless ocean of pre-Cambrian time, 

and in a later contribution 8 he outlines the probable changes in 

the salinity of the ocean.

We believe that the abundance of marine fossils in sediments that 

are either oil and gas bearing themselves or are interbedded with 

productive sands proves that conditions in the early seas where such 

sediments were deposited were suited to marine life that could not 

have existed in brines such as are now derived from oil and gas 

bearing sands. The changes by which the brines have been formed 

are therefore inferred by us to have taken place since the inclusion 

of the waters in sedimentary deposits.

In order to explain the abundance of calcium chloride in certain oilfield waters, Washburne 4 offers the hypothesis that ancient sea water, 

after being entrapped in the sediments, has been deprived of its 

sodium chloride by precipitation due to concentration of the water 

by the drying influence of ascending rock gases, such as nitrogen, 

carbon dioxide, and methane, but he drops this hypothesis, with mere 

mention, in favor of the hypothesis that such waters have received 

calcium and magnesium as well as sodium chlorides in emanations 

from deep-seated basic magmas. The part played by gases in the 

concentration of the brines, is the principal subject of the present 

contribution, but the assumption that deep-seated basic rocks have 

been the source of the calcium and magnesium chlorides seems, on 

consideration, to have but little evidence in its favor. There is no 

reason to assume that the oil and gas bearing strata are underlain by 

basic igneous rocks, and the data from deep drilling in the Appalachian fields furnish no substantiating evidence. Even were the presence of the basic "igneous rocks proved, it would be difficult to conceive how magmatic emanations entering the deeper sediments dur1 Lane, A. C., The chemical evolution of the ocean : Jour. Geology, vol. 14, pp. 221-225, 

1906; Mine waters and their field assay: Geol. Soc. America Bull., vol. 19, pp. 501-512, 

1908; Connate waters of the Atlantic coast [abstract] : Science, new ser., vol. 32, 

p. 190, 1910.

1 Daly, R. A., The limeless ocean of pre-Cambrlan time: Am. Jour. Scl., 4th ser., vol. 

23, pp. 93-115, 1907.

8 Daly, R. A., Some chemical conditions In the pre-Cambrlan ocean: Cong. g6ol. 

Internat., lle sess., Stockholm, 1910, Compt. rend., pp. 503-509, 1912.

* Washburne, C. W., Chlorides In oll-fleld waters: Am. Inst. Mln. Eng. Trans., vol. 48, 

pp. 687-693, 1914.

91818° 19 5
66 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

ing early or recent geologic time could have so extensively permeated 

the thousands of feet of overlying sediments.

In a well at Findlay, Ohio,1 pre-Cambrian granite or granite 

gneiss was found at a depth of 2,770 feet. This granite rock is overlain by sediments, principally quartzites, calcareous sandstones, and 

dolomitic limestones, with interbedded clays and shales, which contain oil, gas, and salt water. A natural bittern, called Blue Lick 

water,2 that occurs in beds of St. Peter (Lower Ordovician) age, was 

here found 780 feet above the granitic rocks and apparently in no 

way related to " basic magmas " as postulated by Washburne.

To substantiate his hypothesis, Washburne states that, in general, 

the total salinity of these oil-field waters increases with depth. 

There are, however, numerous exceptions to this rule. In the Woodsfield and Summerfield quadrangles, Ohio, brines from lenticular 

portions of the Berea grit are less saline than waters occurring in 

the Maxton, Big lime, Keener, and Big Injun sands, several hundred feet higher in the geologic section. The lenses of Berea sand, 

from which the relatively dilute waters are derived, are overlain and 

underlain by several hundred feet of shale. Other examples of deepseated chloride waters at higher horizons than comparatively fresh 

water are cited in the literature.3

Eichardson 4 has recently called attention to the improbability 

that the deep-seated brines in the Appalachian oil and gas fields 

are connate waters and suggests that they may have been formed by 

the prolonged leaching of great masses of sedimentary beds by percolating ground waters and by the diffusion of sodium chloride dissolved from deeply buried salt beds. The retention of the waters 

in the sediments is attributed largely .to the troughlike structure 

of the Appalachian geosyncline.

Under certain conditions these factors have been influential, but 

they do not in themselves adequately explain the formation of the 

brines. Ground waters of meteoric origin must have leached the

sediments to some extent, and where salt beds have been in contact ~ with water-bearing strata salt has undoubtedly been transferred by 

diffusion. It is improbable, however, that salt beds have occurred

1 Condit, D. D., Deep wells at Findlay, Ohio: Am. Jour. Sci., 4th ger., vol. 36, 

p. 123, 1913.

2 Condit, D. D., op. cit. Orton, Edward, Ohio Geol. Survey Kept., vol. 6, p. 298, 1888.

8 Sanford, Samuel, Saline artesian waters of the Atlantic Coastal Plain: U. S. Geol. 

Survey Water-Supply Paper 258, pp. 75-86, 1911.

Stephenson, L. W., and Palmer, Chase, A deep well at Charleston, S. C. : U. S. Geol. 

Survey Prof. Paper 90, pp. 69-94, 1915.

Rogers, G. S., Chemical relations of oil-field waters in San Joaquin Valley, Cal. : 

U. S. Geol. Survey Bull. 653, p. 21, 1917.

Lane, A. C., discussion of "Chlorides in oil-field waters," by C W. Washburne: 

Am. Inst. Min. Eng. Trans., vol. 48, p. 693, 1914.

* Eichardson, G. B., Note on Appalachian oil-field brines: Econ. Geology, vol. 12, 

pp. 37-41, 1917; Note on the diffusion of sodium chloride in Appalachian oil-field waters: 

Washington Acad. Sci. Jour., vol. 7, pp. 73-75, 1917.
HYPOTHESES CONCERNING ORIGIN" OF WATERS. 67

in proximity to all the sands of the Appalachian oil and gas fields 

in which concentrated waters are now found, and the distances 

through which the diffusion of salt has been effective can only be 

conjectured. Some additional factors to account for the concentration of the waters seem necessary. It must also be noted that 

the salts derived through the complete evaporation of brines occurring in very deep strata, those relatively near the salt beds in the 

Appalachian fields, generally contain smaller proportions of sodium 

chloride than the salts from brines occurring in shallow sands that 

are separated from salt be4s by thousands of feet of comparatively 

impermeable shale. This makes it desirable to explain more fully 

the causes for the differences in the relative proportions of the dissolved constituents in the oil and gas field waters.

PRESENT HYPOTHESIS.

The deep-seated brines of the Appalachian oil and gas fields, as 

viewed by us, are only in part the derivatives of waters of sedimentation which were included when the sediments were deposited. The 

chlorine in the brines has been derived directly or indirectly from 

the waters of sedimentation, but practically all the other noteworthy 

constituents have been derived, at least in part, from other sources.

Extensive migration and the partial expulsion of the originally 

included waters have been caused by the consolidating processes to 

which the sediments have been subjected, more especially by compacting due to the increasing weight of subsequently deposited material. Cementation, heat, rock movements, and the incursion of petroleum and natural gas have also taken part in causing the migration and expulsion of the interstitial, waters.

During periods of erosion ground waters of meteoric origin have 

from time to time entered the sedimentary rocks and have been retained and buried together with the waters of sedimentation or their 

derivatives. The final retention of the waters has been due to deep 

burial under relatively impermeable covers, to the sealing of the rock 

interstices, and to the basin-like structure of the Appalachian 

geosyncline.

Profound changes in the waters subsequent to their inclusion in 

the sediments have resulted from the mere solution of certain rock 

constituents such as chlorides, sulphates, carbonates, and silicates, 

from organo-chemical processes such as the reduction of sulphates 

during the decomposition of organic matter; from chemical reactions 

brought about through the mixing of waters having different proper-' 

ties of reaction, which is illustrated on pages 50 and 75; from reactions due to heat, as described on page 72; and from reactions 

between the dissolved constituents of the waters and the constituents
68 WATEKS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

of the rocks with which the waters have been in contact, as described ^ 

on page 74.

The waters have also undergone deep-seated concentration. This 

concentration, which we believe to have been an important factor in 

many of the changes that the waters have undergone, was assisted rf . 

in some places by heat and very generally by moving or expanding 

gases, which have carried off water as vapor. The concentration 

thus brought about has been accompanied by the. loss from the waters ( 

of certain dissolved constituents, such as carbon dioxide, together 

with other gases, carbonates of iron, calcium, and magnesium, small 

amounts of sulphates of barium, strontium, and calcium, and also .+ 

small amounts of silica as quartz or combined with other minor constituents. Under favorable conditions the concentration has proceeded to the extent of causing the separation of sodium chloride ^ 

with minor proportions of calcium, magnesium, and potassium 

chlorides.

In the succeeding pages these deep-seated processes, which have, no * 

doubt, been closely .related and which have acted together, so that 

their combined effects are now to be observed in the oil and gas field 4," 

brines, are considered in detail. ^

HISTORY OF THE OIL AND GAS FIELD WATERS.

INCLUSION AND MIGRATION OP WATERS OF SEDIMENTATION.

4-

During periods of sedimentation vast quantities of sea water are 

included interstitially in marine sediments. 1 The water content 2 of J~ 

muds such as those recently deposited along sea coasts range from 40 

or 50 per cent to as much as 90 per cent by volume. In freshly deposited, unconsolidated sands the water content may vary from 15 

or 20 per cent to more than 30 per cent of the volume. King 3 has ~ 

shown that the interstitially included waters of sedimentation, or 

"connate "waters," 4 as they have been called by some investigators, >..- 

have probably undergone extensive upward migration toward the 

regions of least pressure during the consolidation and induration of 

the sediments. The processes of compacting under increasingly 

great pressure, rearrangement of the mineral constituents of the sedi- <? 

ments, and cementation due to the deposition of dissolved mineral

F. H., Principles and conditions of the movements of ground water: U. S. 

Geol. Survey Nineteenth Ann. Kept, pt. 2, p. 77, 1898.

z King, F. H., idem. Shaw, E. W., discussion of paper by R. W. Johnson, The rQle 

and fate of the connate water in oil and gas sands : Am. Inst. Min. Bug. Trans., vol. 51, 

p. 597, 1915.

3 King, F. H., op. cit, pp. 59-294.

* The Century Dictionary defines the word " connate " as follows : " Inborn, 1mplanted at or existing from birth." The word was first used to designate interstitially 

included waters of sedimentation by A. C. Lane (Mine waters and their field assay : 

Geol. Soc. America Bull., vol. 19, pp. 501-512, 1908).
. HISTORY OF THE OIL AND GAS FIELD WATERS. 69

matter from interstitial waters were, no doubt, contributive causes 

of this expulsion of water. It also seems probable that thermal 

migration, due in part to the expansion of interstitial gases,1 and 

migration resulting from pressure accompanying rock movement 2 

may have been factors worthy of consideration. 

Relative to the migration of waters of sedimentation, King 1 says:

In the case of extensive beds of clay deposits which have given rise to shales 

and rocks of that type, it is not improbable that the extremely large original 

pore space of 40 to' 50 per cent in these sediments has been reduced to its present small proportions 8 through, compression; but be this as it may, there must 

even then have been a ground-water movement measured by the actual reduction of pore space which has taken place, for the water of sedimentation must 

of necessity have been expelled before the reduction of volume could have 

occurred*

He also says: 4

The final or nearly complete consolidation of 50,000 square miles of sediment 

1,000 feet deep, having a pore space of 33 per cent, filled with water, involves 

the actual transfer to a different region of the equivalent of a sheet of water 

50,000 square miles in area and 300 feet deep, when there is still left within the 

mass a pore space of 3 per cent filled with water.

There can be little doubt, therefore, that very great volumes of 

water of deposition have passed through or along relatively porous 

beds of sand, and that under favorable conditions water originally 

included in deeper sediments has been retained and is now. found in 

sandstone reservoirs. If this is true, it follows that waters in oil 

and gas bearing strata can not be " connate " in the strict sense of 

the word.

Lane 5 has called attention to the original differences between 

waters of sedimentation. Some were probably fresh water, others 

may have been brackish or even highly concentrated waters from 

inclosed basins, but the greatest sources of these waters were seas, 

which were probably less saline than those of present time-6 During 

their migration through the sediments the waters of sedimentation 

of different types must have undergone more or less mixing, both 

with waters of sedimentation of other types and with various ground 

waters of meteoric origin. The oil and gas field waters are believed 

to be largely the derivatives of these mixtures.

» King, F. H., op. cit, p. 84.

a Daly, M. B., The diastrophic theory : Am. Ingt. Min. Eng. Trans., vol. 52, pp. 1137-1151, 

1916. 

8 The average total porosity of shales may be considered about 13 per cent

4 King, F. H., op. cit, p. 83.

5 Lane, A. C., Mine waters and their field assay: Geol. Soc. America Bull., vol. 19, 

pp. 501-512, 1908.

* Daly, R. A., Some chemical conditions in the pre-Cambrian ocean: Cong. g6ol. 

internat, lle sess., Stockholm, 1910, Compt. rend., pp. 503-509, 1912.
70 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

CHANGES IN THE WATERS OF SEDIMENTATION. * 

The chemical changes that waters of sedimentation undergo soon < J 

after they are included in the sediments on the ocean floor .have been 

investigated by Murray and Irvine,1 who show that sea water associated with the deposits at the sea bottom is often of a different '' 

chemical composition from the normal sea water overlying the deposit, and especially so in the deposits known as blue muds. The 

mud waters were collected from coastal as well as 'pelagic deposits * 

and are shown by a series of analyses to contain only about 50 per 

cent as much sulphate as the normal ocean water. This difference is 

attributed to the reducing effects accompanying the process of decqm- £N 

position of organic matter. The reduction of the sulphate is accompanied by the formation of carbonate, the proportion of carbonate 

in the mud waters being thereby .increased. At the same time an V 

unstable sulphide of iron is deposited in the muds, imparting to them 

their characteristically blue color. It has been proved that the 

reduction of the sulphates and the contemporary formation of car- 1" 

bonate and sulphide are due not merely to the presence of decomposing organic matter but to the action of microorganisms.2 Rogers 3 * 

has recently contributed a detailed discussion of the reduction of ** 

sulphates in oil-field waters and cites evidence that the sulphates are 

reduced directly by contact with the constituents of petroleum and 

natural gas, as well as by bacterial action.

Ammonia and hydrogen sulphide formed from decomposing ^ 

organic matter have been repeatedly detected in deep ocean water 

and bottom muds, and the proportion of ammonium salts in the mud ± 

waters exceeds that in normal ocean water. It has been suggested 

that ammonium carbonate, reacting with interstitially included calcium and magnesium salts, precipitates calcium carbonate and some r 

magnesium carbonate.4 This precipitation may be increased, experi- >. 

mentally, by boiling the solution. Relative to the changes in mud 

waters, Daly discusses.the results obtained by Murray and Irvine 5 ^ 

as follows: \

'*? 

In the mud water calcium sulphate is absent, magnesium sulphate is deficient Jf

when compared with average sea water, calcium carbonate is increased, and

1 Murray, John, and Irvine, Robert, On the chemical changes in the composition of *v 

sea-water: Roy. Soc. Edinburgh Trans., vol. 37, pp. 481-507, 1895.

2 Meyer, Lother, Chemische Untersuchung der Thermen zu Landeck in der Grafschaft > 

Glatz : Jour, prakt. Chemie, Band 91, pp. 5-6, 1864. Plauchud, E., Recherches sur la '"* 

formation des eaux sulfureuses naturelles : Compt. Rend., vol. 84, p. 235, 1877; Sur la , 

reduction des sulfates par les sulfuraires, et sur la formation des sulfures me'talliques, "^ 

naturels: Idem, vol. 95, p. 1363, 18-82. Etard, A., and Oliver, L., De la reduction des 

sulfates par les e"tres vivants: Idem, vol. 95, p. 846, 1882.

3 Rogers, G. S., Chemical relations of -the oil-field waters in San Joaquin Valley, Cal. : 

U. S. Geol. Survey Bull. 653, 1917. . X

4 Daly, R. A., The limeless ofcean of pre-Cambrian time : Am. Jour. Sci., 4th ser., vol. 23, 

pp. 93-115, 1907. ' . r 

, 'Murray, John, and Irvine, Robert, op. cit. *-
HISTORY OF THE OIL AND GAS FIELD WATERS. 71

magnesium carbonate and ammonium sulphate are both present. The high 

chlorides show that the carbonates are not in excess because of fresh-water 

inflow. The ratio of magnesium carbonate to calcium carbonate is 1: 3. When 

the clear water filtered from the mud was boiled for a short time, a crystalline 

precipitate was thrown down, consisting of 73.3 per cent calcium carbonate and 

26.7 per cent magnesium carbonate. The formation of both carbonates is 

ascribed by Murray and Irvine to the reaction of ammonium carbonate chiefly 

on the sulphates, a conclusion which can not be doubted, especially in view 

of the presence of ammonium sulphate in the mud water. The alkaline carbonate was, of course, derived from decaying animal matter contained in the 

muds.

The slight increase in' the proportion of chlorine, due to its retention while certain other constituents are lost from solution, is another 

step toward the formation of the brines.

To what extent the chemical changes continue during the deeper 

burial of the mud waters can only be conjectured, though it seems 

certain that the waters associated with buried organic matter must 

have been changed during the formation of natural gas0 and petroleum. We would therefore accept Rogers's conclusions that sulphates were practically removed from the waters during the earlier 

part of the period when they were buried or during their long 

association with organic matter. As ammonia and carbon dioxide 

are not found in any noteworthy concentration in the Appalachian 

oil-field waters, it seems logical to assume that those compounds 

have either escaped with other gases or entered into more stable 

combinations.

Another striking characteristic remaining to be explained is the 

calcium and magnesium content of these deep-seated waters. Possibly the common occurrence of dolomitic limestones in oil and gas 

bearing strata may throw some light on this problem. It seems probable that some, of the magnesium in dolomite may have been contributed directly to the sediments by the same organisms that secreted 

calcium carbonate. 1 In addition to this, magnesium in solution may 

have been exchanged in part with the calcium in solid calcium carbonate, thus forming dolomite. Experimental evidence for and 

against this possibility is presented by Clarke. 2

An essential requirement for the formation of dolomite by the 

last-mentioned reaction appears to be an appreciable elevation of 

temperature. But if a moderate elevation of temperature is postulated there is the simple possibility that during thermal concentration the solutions undergo hydrolysis and magnesium is precipitated 

as hydroxide, basic carbonate, or carbonate, as indicated by the

1 Clarke, F. W., and Wheeler, W. C., The Inorganic constituents of marine invertebrates : U. S. Geol. Survey Prof. Paper 102, 1917.

2 Clarke, F. W., The data of geochemistry, 3d ed.: U. S. Geol. Survey Bull. 616, 

pp. 559-570, 1916.
72 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

studies of Davis 1 and Fisher.2 The reactions, which for simplicity 

may be regarded as those accompanying the hydrolysis of a solution 

of magnesium carbonate or of magnesium chloride 

MgC03+H2 0=Mg(OH) 2+C02 

MgCl2+2H2 0=Mg(OH) 2 -f-2HCl

would be followed by the evolution of carbon dioxide, according to 

the first equation cited or from the reaction of the hydrochloric acid 

with carbonates. ,

If, for instance, a reaction according to-the second equation should 

take place in the presence of calcium carbonate, calcium chloride, 

carbon dioxide, and water would be formed., A striking example of 

this was observed during the field studies relative to this bulletin. 

The water jackets of the gas engines used for pumping oil and water 

from the wells become badly caked with calcium carbonate crusts 

when- shallow well waters are used for cooling the engines. To 

remove these crusts oil-well brines are passed through the water 

jackets. When subjected to the heat of the engines the magnesium 

chloride in solution in the brines hydrolyzes according to the second 

equation and the calcium carbonate crusts are removed as calcium 

chloride, carbon dioxide, and water according to the reaction

CaCO3+2HCl=CaCl2+CO2+H2O

The fact that these changes take place when the oil-field brines are 

subjected to moderate heat gives direct evidence bearing on the possible loss of magnesium and accession of calcium in the waters. It 

must also be observed that the introduction of calcium chloride into 

the deep-seated waters would affect the solubility of sodium chloride 

in the same solutions and thus influence the changes that have been 

noted. In the absence of recorded quantitative data on this subject 

we have determined the solubility of sodium chloride at 25° C. in the 

presence of different amounts of calcium chloride, with the results 

stated in Table 24. The solutions were agitated in a thermostat for 

a period of over two hours for each determination. The specific 

gravity was determined by weighing 5 or 10 cubic centimeter portions run out from a pipette after filling the pipette by suction 

through a small asbestos cap which served as a filter.

1 Davis, W. A., Studies of basic carbonates: Soc.'Chem. Ind. Jour., vol. 25, p. 788, 1906.

2 Fisher, Ferd, Dingler's Polyt. Jour., vol. 212, p. 208.
HISTOEY OP THE OIL AND GAS FIELD WATERS. 73

TABLE 24. Solubility of sodium chloride in water containing calcium chloride

at 25° C.

Specific 

gravity of 

solution.

1.202

1.207

1.210

1.209

1.216

1.220

1.225

1.233

1.241

1.257

1.276

CaCl2 in

solution 

(per cent 

by weight).

0.000

1.103

2.160

3.220

5.451

7.598

9.500

11.48

17.77

21.00

24.58

NaClin

solution 

(percent 

by weight).

26.43

25.30

24.32 -

23.37

20.43

19.17

17.55

15.9.1

10.54

8.05

 5.63

It will be observed from this table that the solubility of sodium 

chloride is greatly diminished by the presence of calcium chloride. 

This accords with the fact that the concentrated oil and gas field 

waters containing the greatest proportions of calcium chloride also 

contain the smallest proportions of sodium chloride. 

. Evidence in regard to the precipitation of magnesium from heated 

sea water is given by Itowan,1 who presents a series of analyses of 

boiler crusts formed from sea water. These crusts contain from 1.8 

to 40 per cent of magnesium oxide. The crusts containing the most 

magnesium and least calcium were deposited at relatively low temperature and pressure. Those containing the most calcium and the 

least magnesium were deposited at relatively high pressure and temperature. Magnesium was probably precipitated as hydroxide and 

calcium as calcium sulphate.

It is also very probable that magnesium has been lost from the 

waters to form magnesium silicates. Hunt 2 has proved that magnesium chloride reacts with calcium silicates to form magnesium 

silicates and calcium chloride. That this or a similar reaction may 

have caused the removal of magnesium and the introduction of calcium into the waters is made to appear more probable by the fact 

that secondary magnesium silicates (chlorites) are disseminated 

through some of the oil and gas bearing rocks.

In discussing the interaction between certain silicates and the dissolved constituents of saline waters Sullivan 3 refers to the early 

investigations of Lemberg, as follows:

In 1870 Lemberg began the publication of his work on the transformation of 

silicates by salt solutions. His experiments, whose number runs into the hundreds, constitute a mine of important observations in the chemistry, of minerals

1 Rowan, F. J., The practical physics of the steam boiler, p. 613 (appendix 3), New 

York, D. Van Nostrand & Co., 1903.

 Hunt, T. S., Chemical and geological essays, p. 122, 1878.

3 Sullivan, E. C., The interaction between minerals and water solutions, with special 

reference to geologic phenomena: U. 0S. Geol. Survey Bull. 312, p. 20, 1907.
74 WATEES ASSOCIATED WITH PETEOLEUM AND NATUEAL GAS.

and of geologic processes. The silicates used were, in the main, those related 

to the zeolites, but others were included. The solutions were chiefly of salts 

of the alkalies and alkaline earths, but embraced also such bases as iron, 

aluminum, silver, and thallium. The outcome of the experiments was usually 

either (1) exchange of bases in equivalent quantity between silicate and solution; (2) addition of base to the silicate, especially from alkaline solution; 

(3) addition of entire salt; or (4) addition or subtraction of water. Frequently, if not usually, transformation to a different mineral species, often crystalline in form, ensued. Most of the work was done at temperatures ranging 

between 100° and 200° C., although some of it was performed at ordinary room 

temperature. The first papers 1 contain studies of the action of magnesium 

salt solutions on such silicates as apophyllite, gehlenite, vesuvianite, datolite, 

and wollastonite; practically equivalent substitution of magnesium for calcium 

and potassium took place. The work with wollastonite was conducted at room 

temperature and also at 100° C., with the following results:

Action of magnesium sulphate on wollastonite.

.Wollastonite after contact with MgSOd solution:

Twenty-five days at 100° C. .................................................

CaO.

44.1

27.4

1.0

MgO.

11.5

32.0

The action is the same in the cold as at 100° an approximately equivalent 

exchange of calcium for magnesium.

Palmer 2 has called our attention to the long-established use of 

sodium silicate as a precipitant of magnesium from hard waters con- t 

taining both magnesium and calcium and suggests that similar 

reactions may have occurred in nature. Artificial zeolites (complex * 

alkali aluminosilicates), under the name permutite, have recently y 

come into use in water softening. Hard water filtering through a 

bed of this material deposits its calcium and magnesium and takes 

up an equivalent amount of sodium. The permutite is regenerated -"V 

by passing through it a strong solution of sodium chloride, the mag- t_ nesium and calcium in the bed being thereby carried out as magne- '"* 

sium chloride and calcium chloride, and the sodium -zeolite is re- ^ 

newed. The reaction is reversible, going in one direction or the 

other in accordance with the concentration of calcium and magnesium or of sodium in the solution. ^

The type reaction between the constituents of a hard water and > 

an alkali aluminosilicate may be expressed as * <

Na2Al2Si2O8+Ca (HCO3 ) 2=CaAl2Si2O8+2NaHCO3 

in which K may be substituted for Na; SO4 , 2C1, -or 2NO3 for

 V 

1 Deutsch. geol. Gesell. Zeitschr., vol. 22, pp. 335, 803, 1870; vol. 24, p. 187, 1872.

2 Palmer, Chase, personal communication. r^-

H
HISTORY OF THE OIL AND GAS FIELD WATERS. 75

2(HC03 ); and Mg, Ba, or Sr for Ca. The type reaction when the 

process is reversed may be expressed as

CaAl2Si2O8+2NaCl=Na2Al2Si2 08+CaCl2

in which Mg, Ba, or Sr may be substituted for Ca, and K for Na, as 

in the preceding reaction.

It appears probable that the hydrated alkali aluminosilicates which 

occur as disseminated constituents in shales and sandstones or in beds 

such as the bentonite deposits of the western United States, and which 

originated through the decomposition of igneous and metamorphic 

rocks, have caused changes in these deeply buried waters similar to 

those just described. For instance, it is possible that hard waters containing calcium and magnesium, reacting with certain hydrated alkali 

aluminosilicates in the reservoir rocks, or with the constituents of primary alkaline waters such as are represented in Table 14 (pp. 42^t3), 

have deposited calcium and magnesium. The subsequent incursion 

of concentrated sodium chloride waters would then convert the calcium and magnesium into chlorides, the reaction being accompanied 

by an equivalent loss of sodium from solution. It is significant that 

there is a wide range of glassy rocks and minerals and their derivatives which, when hydrated, will react to remove magnesium and 

calcium from hard waters and which will give up the calcium and 

magnesium thus removed if treated with a concentrated solution of 

sodium chloride. Many of these minerals and their hydrated decomposition products have been recognized during studies of deep-sea 

deposits collected by the Challenger expedition.1 Feldspars and 

micas are common constituents of some of the oil and gas bearing 

rocks, and the fact that more of the alkali-bearing silicates are not 

recognized in the sedimentary rocks of the Appalachian oil and gas 

fields may be due to the more or. less complete alteration of these 

minerals to yield calcium and magnesium bearing silicates or other 

secondary minerals. More detailed studies of the Appalachian oil 

and gas field sediments and of the bentonite deposits and their associated waters in the western United States will doubtless throw light 

on this subject.

Another reaction between the saline waters and certain minerals in 

the sediments is described by Sullivan,2 who has discussed at some 

length the removal of potassium from saline waters through the selective action of hydrated aluminosilicates such as those that occur in 

muds and shales. The affinity of potassium for these silicates is 

greater than that of sodium, and hence they retain potassium in preference to sodium.

The concentration of the interstitially included waters by the removal of water vapor in escaping gases and to a less extent by the

1 Challenger Rept., Deep-sea deposits, p. 321, 1891. 

3 Sullivan, B. C., op. cit., p. 22.
76 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

hydration of minerals probably began soon after the waters were 

buried, and, in conjunction with chemical reaction, it has resulted in 

the loss of several constituents, among which may be mentioned calcium carbonate, calcium sulphate, and possibly some magnesium sulphate, where sulphates were present. Under favorable conditions 

the concentration was also followed by the deposition of sodium 

chloride with calcium and magnesium chlorides as impurities. The 

repeated deposition and re-solution of the salts, accompanied by the 

more ready deposition of sodium chloride and the retention or more 

ready re-solution of calcium and magnesium chlorides might also, 

have influenced the composition of the waters.

It is evident that there is a wide range of possibilities whereby the 

acquisition or loss of the various constituents in oil and gas field 

waters can be explained.

DEEP-SEATED WATERS AS AGENTS OF CEMENTATION.

Waters having primary alkalinity that is, waters whose alkalinity 

is in part such as is due to the hydrolysis of sodium and potassium 

carbonates have been recognized by Palmer* as characteristic silica 

carriers, but when waters possessing primary alkalinity react with 

solutions possessing secondary salinity that is, salinity such as is due 

to calcium and magnesium chlorides or sulphates their capacity to 

carry silica may be diminished so that quartz and other silicates will 

be deposited. Calcite, which is a common cementing material in sedimentary rocks, may also result from the mixing of solutions having 

different properties of reaction, as just described, or it may be deposited from deep-seated waters through the loss of carbon dioxide from 

solution, as explained on page 48. There can be no doubt that during the complex changes that have- affected the reservoir rocks included waters having different properties of reaction have mingled 

and reacted with one another in such a manner as to deposit certain of 

their dissolved constituents, thus cementing the sediments.

The deposition of quartz, calcite, and other cementing material is 

no doubt facilitated by the concentration of the mixtures. Such a 

process of cementation, through the agency of deep-seated waters, 

we believe to have been an important factor in the retention of gas, 

oil, and water through vast periods of geologic time. The sediments 

themselves, more especially the colloidal matter of muds, have furnished an ample source of silica and alumina for cementation.

RETENTION OF WATERS ASSOCIATED WITH GAS AND OIL.

As the result of consolidating processes which probably began in 

the sediments soon after deposition 2 and which were accompanied by

1 Palmer, Chase, The geochemical interpretation of water analyses : U. S. Geol. Survey 

Bull." 479, p. 22, 1911.

2 Leith, C. K., and Mead, W. J., Metamorphic geology, p. 191, New York, 1915.
EVAPORATION OF WATER AT DEPTH. 77

partial expulsion and rearrangement of interstitially included 

fluids, there have been gradual changes from conditions of hydraulic 

migration to those approaching capillary equilibrium. The resistance to movements of water through increasingly fine water-filled 

interstices, due to friction, adhesion, viscosity, and capillary phenomena, has gradually become so great as to prevent the escape of 

deeply buried water, oil, and compressed gases whose expansive 

power is commonly referred to as "rock pressure." Deep-seated 

conditions approaching equilibrium have then prevailed through vast 

periods of time but have-been interrupted by readjustments due to 

rock movements and to variations in depth produced bythe deposition 

or erosion of sediments. Both fissuring accompanying rock movements and erosion have in places permitted the escape or movement 

of gas, oil, and water until the rock passages again became sealed. 

The same conditions under which gas, oil, and water have been 

retained under great pressure have, of course, assisted in preventing 

the entrance of water from neighboring regions.

EVAPORATION OF WATER AT DEPTH.

VARIABLES INVOLVED.

In considering the evaporation of water at depth it may be well 

to discuss briefly some of the principles that govern evaporation both 

from the surface of the earth and from the deep-seated rocks. 

Various factors that assist evaporation at the earth's surface, such 

as heat, wind, and dryness of the atmosphere, are well known, and 

analogous factors may be supposed to have influenced evaporation 

beneath the surface. But underground conditions differ from surface conditions in several particulars. For example, the temperature may be higher than that at the surface, the pressure may be and 

generally is considerably higher than atmospheric pressure, and the 

movement of gases is in general immensely restricted compared to 

movements of the atmosphere. The possible range in temperature 

and pressure is much greater than the normal range at the surface. 

It may be stated, however, that no conclusions in the present discussion depend for their validity on the existence of temperature greater 

than 200° C. or pressure greater than 200 atmospheres.

The choice of the variables that may be said to govern evaporation 

depends somewhat on whether one has in mind merely the process of 

evaporation or the rate and amount of evaporation at some particular 

place. The movement of gas may aid in transferring water vapor 

from one region to another, just as a dry wind assists evaporation 

from the earth's surface, a certain volume of gas being no sooner 

saturated than it is replaced by a fresh volume of unsaturated gas. 

Furthermore, gases may take up moisture, if water is present, not
78 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

only at the time of formation of the gases, but subsequently, during 

expansion, as the expansion of a gas affords unsaturated space into 

which, water will pass as vapor until the space is saturated. But in 

the examples just mentioned an unsaturated condition of the gas is 

o tacitly assumed. The more common phenomenon below the surface 

will be that of an equilibrium between water vapor and aqueous 

solutions, and the essential variables governing evaporation will then 

be those affecting this equilibrium in one way or another. These 

variables are temperature, pressure, and salt content of the solution.

The discussion of evaporation may be made more precise by the 

use of the term " vapor pressure," which may be described as follows: 

If at a definite temperature a liquid is admitted into a vacuum, some 

of the liquid will evaporate and the vapor so formed will attain a 

definite pressure. This definite pressure is called the vapor pressure 

of the liquid at the given temperature, and when once it is attained 

the space is said to be saturated with the vapor. For every liquid 

there is a definite relation between temperature and the vapor pressure of the liquid. The relation between the vapor pressure of pure 

water and the corresponding temperature is shown by the vapor 

pressure curve in figure 5 (p. 81). The vapor pressure-of aqueous 

solutions decreases with increasing proportions of dissolved salts, but 

both for pure water and for solutions the vapor pressure increases 

. with rising temperature. It follows, therefore, that a moderate rise 

of temperature would largely offset the influence of dissolved salts.

Although vapor pressures may be measured by starting with a 

vacuum, as illustrated above, the amount of vapor in a given space 

and the corresponding partial pressure of the vapor formed from a 

liquid will be practically the same, "according to Dalton's law, 

whether or not another gas is present, provided only that the other 

gas is one which does not react chemically with the vapor. The concentration of water vapor in a given volume of saturated gas may 

therefore be considered as known if the temperature and .salt content of the solution involved are known. In a water-saturated sand 

gas pressure may be considered merely as one of the variables determining the volume of the gaseous space. '

Certain physical conditions are obviously required to render the 

effects of evaporation at depth permanent, and the principal requirement is the exclusion of surface waters.' Furthermore, in order to 

account for noteworthy effects produced by deep-seated evaporation 

it is necessary to postulate either long-continued evaporation at 

moderate temperature due to the formation and escape of relatively 

large quantities of gas in association with small quantities of water, 

or else, possibly, more extensive evaporation in conjunction with 

the escape of less gas at a higher temperature.
EVAPORATION OF WATER AT DEPTH. 79

LIMITING MOISTURE CONTENT OF NATURAL GAS. 

In our preliminary consideration of this problem we assumed that 

among the gases that are chemically inert with respect to water, 

natural gas would be no exception in permitting the evaporation of 

water. Subsequently the suggestion was made by one of our colleagues that water might not evaporate into natural gas containing 

the vapors of various oils as it does into air. However, we find a 

statement in the literature that Pittsburgh natural gas carries 0.7 

per cent by volume of moisture, although the temperature is not 

stated.1 To remove any possible doubt on the matter, very careful 

determinations were made of the amount of moisture that the illuminating gas used in Washington, D. C., is able to take up under ordinary conditions, with results entirely confirmatory of our anticipations. The gas used had the following composition by volume: 

Composition of illuminating gas used in Washington, D. C.

Carbon dioxide __________ 3.3 Hydrogen__________^___ 33. 5

Oxygen . 6 

Benzol_______________ . 6 

Toluol ________________ .2 

Xylol, etc_____________ .4 

Ethylene_______________ 10.0 

Carbon monoxide ________ 28.7

Methane _J_____________ 15. 0

Ethane _______________ 1. 2

Nitrogen_______________ 3. 5

97.9

A considerable volume of gas Avas passed into a large bottle over 

water, the bottle serving as a reservoir. For each determination a 

portion of the gas was passed from the bottle, first through a satur-

** ator to saturate tKe gas with moisture at a definite temperature, arid 

then through weighed calcium chloride tubes to retain the moisture. 

The calcium chloride tubes were weighed again, and the increased

** moisture content was determined. The volume of gas used was calculated from the volume of water flowing out^of an aspirator. The 

water in the aspirator had first been saturated with gas in order to 

i"1 prevent any interchange of gas between the water and the gas drawn 

t in. The calcium chloride' tubes were protected from a backward

*> diffusion of moisture by a small additional calcium chloride tube.

;> The pressure of gas in the aspirator and reservoir was kept equal to 

that of the atmosphere by regulating the flow of water or entrance 

of fresh gas. All temperatures were maintained as constant as pos3- sible, and the temperature of the saturator was measured by a thermometer giving a reading which was known to be correct within 

i» 0.02°-C. on the hydrogen scale. The saturator consisted of a large

^ ,U-tube containing strips of moist filter paper and enough water to 

seal the passage, the whole being immersed in a vessel of water which 

was maintained at a constant temperature. The calcium chloride 

tubes containing the moisture that had been removed by the gas 

were weighed with a counterpoise. The theoretical weights of water

x^ were calculated by equation (1) on page 81.

x x Burrell, G. A., and Robertson, I. W., The compressibility of natural, gas at high 

^ temperatures: Bur. Mines Tech. Paper 131, p. 5, 1916.
80 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

The amounts of moisture found in the volumes of saturated gas 

used, together with the theoretical amounts that should be found, according to the gas laws, are shown in the following table. The results of some preliminary determinations are omitted because the 

temperature of saturation was not measured with sufficient accuracy 

to make them significant.

TABLE 25. Determination of moisture in saturated illummating gas at

Washington, D. C.

No.

1. ..............................................................

2...............................................................

3...............................................................

Volume 

of gas 

used.

Cc. 

2,001 

1,990 

1,986

Temperature of 

saturator.

"C. 

22.29 20.93' 

20.85

Weight of 

water 

found.

Gram. 

0.0402 

.0365 

.0356

Weight of 

water calculated.

Gram. 

0.0395 

.0363 

.0361

From the results in Table 25 it is evident that the vapors of oily 

substances do not affect the evaporation of water into spaces occupied 

by natural gases. That a layer of oil on the surface of water might 

retard evaporation is admitted. But in the earth either' there is 

abundant time for water to become distributed between the liquid 

and gaseous phases by diffusion under static conditions, or else gas, 

oil, and water occur so irregularly mixed as to bring them into new 

and frequent association during movement, as shown more fully on 

pages 25 and 95.

The weight of moisture in a given volume of saturated gas in contact with pure water depends, first of all, on the temperature, according to the well-known temperature-vapor pressure curve of water 

shown in figure 5. The vapor pressures for a number of temperatures, taken from the Smithsonian physical tables for 1916, are given

in Table 26. »

TABLE 26. Vapor pressure of water at different temperatures on hydrogen scale.

Temperature.

°C.

0

5

10

15

20

25

30

40

50

60

70

Pressure.

Millimeters.

4.58

6.54

9.21

12.79

17154

23.76

31.83

55.34

92.54

149.5

233.8

Temperature.

°C.

80

90

100

110

120

130

140

150

160

170

180

Pressure.

Millimeters.

355.5

526

760

1.074

1,489

2,026

2,709

3,569

4,633

5,937

7,514

Temperature.

C.'

190

200

220

240

260

280

300

320

340

360

370

Pressure.

Millimeters.

9,404

11,647

17, 376

25,064

35,127

48, Oil

64,290

84, 480

109,300

139, 480

157,200

All quantitative deductions in this bulletin concerning the transportation of moisture by gases are based primarily on Table 26, which 

gives the vapor pressure when the gas is in contact with pure water. 

In dealing with a solution of salt instead of with pure water, it is 

necessary to apply a correction for the decrease of vapor pressure 

due to the dissolved substance. The vapor pressures of water from a
EVAPORATION OF WATER AT DEPTH. 81

great many kinds of solutions are known, so that almost any solution can be dealt with if required.1 The relative lowering of the

vapor pressure, -±-, where p is the vapor pressure of water and Ap

is the lowering of vapor pressure due to the presence of a dissolved 

substance, is roughly independent of the temperature a fact which 

simplifies the correction considerably. For instance, an 8 per cent 

solution of calcium chloride has a vapor pressure about 5 per cent 

lower than that of pure water, and a brine saturated with ordinary

) 75,000

150,000

8u 125,000

fc

o

2 100.000

wE75,000

.50,000

25,000

D°. 100° ' 200° 300° 

TEMPERATURE, DEGREES CEWTIQRADg

FIGUKH 5. Temperature-vapor pressure curve of pure water.

400°

salt has a vapor pressure about 25 per cent less than that of pure 

water.

The amount of moisture in a given volume of saturated gas at a 

given temperature is computed from the vapor pressure at that temperature by the gas laws as follows:

w=_Mpv

RT (1)

where w is the weight of the gas under consideration, in this case water 

vapor; M its molecular weight, equal to 18 for water; p the partialpressure of the particular gas, here the* vapor pressure of 'water, 

measured in millimeters of mercury; v the volume, in cubic centimeters, of the total space in which the gas is contained; R the gas 

constant equal to 62,360; and T the absolute temperature.

1 See any collection of physico-chemical tables, such as the Smithsonlan physical tables 

or those of Landolt-Bornstein-Meyerhoffer.

91818° 19 6
82 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

In Table 27 will be found the weights of moisture for a number of 

temperatures computed by equation (1) and expressed in grams per 

cubic meter and in pounds per 1,000 cubic feet of gas. The pressures are stated in order to show the conditions necessary for the 

maintenance of the liquid phase. If the pressure at any given temperature were not equal to or greater than that stated in the table the 

water would completely evaporate and the weight of moisture would 

be smaller'than that given in the table.

Without doubt there is considerable uncertainty in the weights 

calculated for the highest temperatures on account of deviations 

from the gas laws at the high pressures considered. Steam tables 

cover a part of the field and show slightly higher weights of steam 

at the higher temperatures and pressures. It is to be expected that 

as the density of a gas increases owing,' for instance, to compression the molecules will be brought so much more closely together 

that they will exert an attraction for one another and cause deviations from the gas laws. The solubility of water vapor in compressed 

gases is therefore probably greater than that calculated in the tables, 

but experimental data on this point are lacking. For these reasons 

the calculated figures are retained only as first approximations. It 

can be seen from the tables that a given volume of gas can transport 

surprisingly large quantities of moisture at the higher temperatures.

TABLE 27. Weights of water in saturated gas.

Temperature

0

10

20

25

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

190

200

220

240

260

280

300

320

340

360

370

(atmospheres).

0.006

.012

.023

.031

.042

.073

.122

.197

.308

.468

.692

1.00

1.41

1.96

2.67

3.56

4..70

6.10

7.81

9.89

,,12.37

15.32

22.86

32.97

46.22

63.17

84.59

111. 10

143.80

183.50

206. 80

Weight of water.

Grams per 

cubic meter.

4.84

9.39

17.27

23.01

30.32

51.02

82.69

129.5

196.7

290.6

418.1

510.7

809.9

1,093

1,451

1,893

2,435

3,088

3,866

4,788

5,861

7,107

10,170

14,090

19,020

25,060

32, 370

41,110

51, 450

63,600

70, 550

Pounds per 

 1,000 cubic 

feet.

0.302

.586

1.078

1.436

1.893

3.185

5.163

8.085

12.28

18.14

26.10

31.88

50.57

68.24

90,60

118.1

152.0

192.8

241.3

298.9

365.9 .

443.7

635.0

. 879. 7

1,187

1.564

2,021

2,566

3,212

3,971

4,405
EVAPORATION OF WATER AT DEPTH. 83

1 EFFECT OF THE INCREASE OF TEMPERATURE WITH INCREAS- 

~> ING DEPTH.

"* A.S the temperature of the earth increases about 1° C. for every 100 

feet of depth from the surface, it is evident that at depths of about 

10,000 feet aqueous solutions would attain a temperature at which 

they would boil if under atmospheric pressure. But as the pressures 

prevailing underground tend to be greater than atmospheric pressure,

"" the boiling points are likewise higher, so that it becomes somewhat 

problematic whether under ordinary conditions aqueous solutions 

would ever boil merely on account of the increase of temperature

^ with increasing depth. If free egress for the vapor were blocked 

the conversion of much water into vapor would be prevented by the 

high pressure that would be produced. In fact, the pressure caused 

simply by the weight of a continuous column of water from any 

point in the earth to the surface would be great enough to prevent 

ebullition caused merely by the increase of temperature with, depth.

_ In deep unproductive wells filled with water, therefore, or in fissures 

and channels filled with water where the evolution of gas is not

^ violent enough to displace the water, the boiling points would not 

be attained uncler the existing pressures.

As a matter of fact, however, a continuous column of water is not to 

be expected under the geologic conditions that prevail in most oil and 

gas fields. Strata such as the shales in which the more or less lenticular bodies of productive sandstone are interbedded are relatively im-

.? permeable, the water-filled rock interstices being sufficiently fine to 

modify the cumulative pressure effect of water in overlying beds.

* Moreover, the rock pores in some beds are filled with gas and oil,

** which would interfere with a so-called continuous water column. 

We see no reason to suppose, therefore, that pressures exactly equal 

to the hydrostatic pressures of corresponding water columns would be

-?'" exerted upon gases at all depths down to the zone of rock flowage, 

^ although, as pointed out on page 28, the so-called rock pressure in

* % many wells is roughly proportional to the depth. Observations in 

J>- different oil and gas fields indicate that in relatively shallow rocks 

the gas pressure may be greater or less than would be caused merely 

by the hydrostatic head of a column of water reaching the surface.

It appears that at depths greater than about 10,000 feet the ebullition of aqueous solutions would be possible only under very favorable 

conditions, but if it occurred it would result in a great concentration of the solutions. Under the conditions that generally exist, however, there would be merely a high concentration of water in the,y 

vapor phase, and the removal of this water would await an escape of 

gas, which at the temperatures under consideration would result in a 

considerable transfer of moisture, leaving either salt or more concentrated solutions behind.
84 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

Dismissing the possibility of ebullition as being too slight to be of 

any great importance to the subject in hand, we feel certain that 

wherever there is a gas in the earth in contact with a liquid the concentration of vapor in the gas will be greater the greater the depth, 

owing to the increase of temperature with increasing depth.

EFFECTS DT7E TO CHANGES OF PRESSURE.

When a gas that is not saturated with water vapor is made to move 

through water or across a surface of water, it is evident that fresh 

volumes of gas are continually coming into contact with the water. 

No sooner does a certain part of the gas become saturated or partly 

saturated with water vapor than it is replaced by another lot of 

unsaturated gas, and in this way evaporation is hastened. At any 

given temperature the amount of water vapor required to saturate a 

certain volume of gas that is, the amount of water vapor that can 

be evaporated into the fixed volume of gas is the same whether the 

gas is blown through or across the water or whether the water and 

gas are at .rest. The presence of the gas does not influence the total 

capacity of a given space to hold moisture but may afford the unsaturated space into which evaporation takes place. For instance, 

when a gas expands under a decrease of pressure, at a constant 

temperature, its capacity for taking up. moisture is increased because 

the unsaturated space occupied by the gas in increased. An expanding gas must transport increasing amounts of moisture as long as its 

expansion continues at a constant temperature in the presence of 

water.

As already stated, we have no data as to how strictly the propertionality between volume and water content holds for very highly 

compressed gases, but proportionality can certainly be assumed over 

a wide range of pressures from low pressures up. Evaporation of 

water caused by an expanding gas can therefore be offered as an explanation of the concentration of the brines even when the original 

compressed gas is saturated with moisture, as the capacity of the 

gas for moisture is created entirely by the expansion.

If the simple proportionality just mentioned is assumed, a tenfold 

expansion of methane, for example, would create a tenfold space for 

moisture. In this way it may be calculated that a cubic meter of 

gas confined at a pressure of 100 atmospheres would be able to evaporate 5,049 grams of water by the time it had expanded to atmospheric pressure, if the expansion were gradual and in contact with 

pure water at 40° C. In contact with a saturated sodium chloride 

brine the loss by evaporation would amount to about 3,800 grams of 

water, which would cause the precipitation of about 1,400 grams of 

salt. The effects with other salts and other temperatures would 

differ, as has been previously stated.
EVAPORATION OF WATER AT DEPTH. 85

i The preceding figures apply to a temperature of 40° C. At other 

^ temperatures the results would be different. They would be different, 

' * also, if the expansion took place in such a manner as to involve a 

considerable fall in temperature. As a given volume of watersaturated gas passing under constant pressure frqm a warmer to a 

colder zone would deposit water, it is evident that pressure and temperature must be considered conjointly. It is not difficult, however,

 "" to calculate by the gas laws what volume a gas would attain under 

any given temperature and pressure if its volume at any other temperature and pressure is known. The initial and final water content 

of the gas can therefore be obtained from Table 27, and the difference between these quantities will represent the weight of water 

that the gas would gain or lose, as the case may be.' The principal 

difficulties are met in attempting to postulate conditions at consid-^ 

' erable depths in the earth. A horizontal flow of gas, very gradually 

expanding in the presence of water, would certainly cause evaporation, for no effective change in temperature would be involved. For a 

« vertical flow consideration must be given to the earth temperature 

gradient, and it is possible, as already stated, that under certain

"* conditions a decrease in temperature might overcome the evaporative

> effect of gas expansion. From the slope of the vapor-pressed curve 

it is evident that temperature is more likely to become the major 

variable at the higher temperatures.

Adiabatic expansion cools a gas, and when this effect is localized 

y the cooling may be very considerable. For the purposes of our investigation, however, any condensation of moisture due to this cause 

y in gas conduits may be considered an after effect. There may possibly be regional cooling in the earth as a result of such expansion, 

but the chances seem to us to lie rather in the other direction, which 

means that ascending gases will contribute heat to the inclosing rocks.

^» However that may be, the volume and heat capacity of the strata are 

so great with reference to the probable quantities of gas involved

K that it seems logical to suppose that only small geologic temperature

^. effects could be permanently produced in this way. We have therefore restricted our discussion to the temperature changes due to a 

normal earth gradient.

j- The belief that great amounts of the natural gases undoubtedly exist 

in the earth dissolved in water and oil is warranted by the known 

solubilities of gases in both water and oil and by the commonly ob-

 s, served escape of gases from these liquids during periods of production in oil and gas fields. An increase in pressure tends to increase 

the solubility of a gas in a liquid, and it follows that any decrease in

f pressure facilitates the concomitant liberation and expansion of a 

gas so dissolved. Gases such as propane (below 97° C.) and some

 4 other hydrocarbons, as well as hydrogen sulphide (below 100° C.),
86 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

may occur at considerable depth as fluids liquefied J>y pressure. These 

fluids will of course vaporize and expand on release of the pressure, 

thus furnishing space into which water may also vaporize.

SOLUBILITY OF NATURAL GAS IN OIL AND WATER.

Knowledge of the solubility of the hydrocarbons in oil under various conditions is meager. It is stated x that 1 volume of certain 

California oils absorbs 0.15 volume of the natural gas used in Pittsburgh, Pa., and that 1 volume of claroline oil dissolves 0.31 volume 

of pure methane and 1.96 volumes of pure ethane at atmospheric 

pressure. At higher pressure the amounts dissolved would be greater. 

These figures suggest that propane and higher hydrocarbons would 

be much more soluble than ethane. Nitrogen and oxygen are far 

more soluble in petroleum than in water, and ethylene is soluble to 

the extent of 0.14 volume in 1 volume of petroleum.2 Other data on 

the solubility of certain hydrocarbons are given by McDaniel.3

The following table is quoted from Rogers: 4

Solubility of certain gaseous hydrocarbons in water. '

[At 20° C. and 760 millimeters pressure, except propane, which is at 17.8° C. and 753

millimeters pressure.]

Name. : 

Methane.... . ................................:..................

Ethane. . .......................................................

Butane .........................................................

Ethylene .......................................................

Propylene. . ....................................................

Formula.

CH4.......

C2H8 ......

C3H8 ......

CVffio......

C2H<......

C8Ha......

Volumes 

soluble 

in 100 

volumes 

of water.

3.31

4.72

6.50

0

12.2

22.1

Authority.

Winkler.o

Do.

a Winkler, L. W., Die Loslichkeit der Gasse in Wasser: Deutsche chem. Gesell. Ber., Band 34, pp. 1417- 

1421.1901.

6 Lebeau, Paul, Sur quelqnes proprie'te's physiques du propane: Compt. Rend., vol. 140, pp. 1454-1456, 

1905.

c Frankland, Edward, Ueber die Isolirung der organischen Radicals: Annalen der Chemie, Band 71, 

p. 171,1849. (Frankland states that butane is insoluble in water, but it is desirable that this early work 

be checked with the more refined methods now in use.)

^ Winkler. L. W., unpublished data cited by Landolt-BQrnstein, Physikalisch-chemische Tabellen, 

p. 604,1905. '.

«Von Than, Carl, Der Absorptionscoefflcient des Propylengases: Annalen der Chemie, Band 123, p. 187, 

1862.

In general, as the density of a gas is increased, owing to compression, for instance, the molecules are brought so much more closely 

together that they begin to show some of the properties of liquids. It 

has been shown, for example, that methane at a pressure of 300

1 Burrell, G. A., Seibert, F. M., and Oberfell, G. G., The condensation of gasoline from 

natural gas: Bur. Mines Bull. 88, pp. 29-34, 1915.

2 Gniewosz, St., and Walflsz, A., Ueber die Absorption von Gasen durch Petroleum: 

Zeitschr. physikal. Chemie, vol. 1, p. 70, 1887.

8 McDaniel, A. S., The absorption of hydrocarbon gases by nonaqueous liquids : Jour. 

Phys. Chemistry, vol. 15, pp. 587-610, 1911.

* Rogers, G. S., Chemical relations of the oil-field waters in San Joaquin Valley, Cal.: 

U. S. Geol. Survey Bull. 653, p. 106, 1917.
EVAPOBATION OF WATEB AT DEPTH. 87

) atmospheres acquires an appreciable solvent action on paraffine, 

which is deposited in brilliant spangles when the gas is allowed to

^ expand to ordinary pressure.1 Compressed ethylene is a still more 

active solvent of the higher hydrocarbons. So far as we can judge 

from the experimental evidence available, therefore, the behavior of 

water and of hydrocarbons toward gases shows a marked contrast. 

The expansion of a gas would tend to increase the evaporation of 

water, if present, but to cause the deposition of such higher hydrocarbons as might exist in the compressed gas.

ORIGIN OF THE GASES AS RELATED TO THE EVAPORATION OF 

THE ASSOCIATED WATERS.

I.

' To attempt to discuss in this bulletin the numerous theories rela-

 » tive to the origin of natural gas would be unwise. It is sufficient to

state that, if classified according to their origin, two general types

of deep-seated gases must be considered those from deep-seated inT organic sources and those evidently formed from organic remains

through the agency of microorganisms, heat, or chemical changes due

* to other causes. There is so little evidence to substantiate the hy- 

"> pothesis that the natural gases associated with petroleum are of inorganic origin that we give the subject only brief consideration. If 

inorganic gases entered the sediments the evaporative effects may 

have been similar, in some respects, to those of the organic gases. 

~ There is, however, some uncertainty as to the amount of moisture 

that would have been introduced into the sediments with gas of in- 

".^ organic origin. The chemical effects upon oil and gas field waters 

_ that might accompany the incursion of such gases have been considered, by Washburne.2 

The gases of the second type, those formed in sediments through

-,. . the agency of heat or chemical changes due to other causes, constitute

a series of hydrocarbon gases whose principal constituents are

"^. methane and ethane, together with small amounts of hydrogen, hyj drogen sulphide, carbon dioxide, and nitrogen. The formation and

escape of enormous volumes of these natural gases in the presence of

interstitially included waters would doubtless cause the evaporation0

Y and concentration of the waters from the very beginning of their

' burial. In discussing the probable changes in waters of sedimentaJr.A tion we have shown the possibilities for evaporation of this sort to

 4^ occur. No doubt such evaporation has been a factor in bringing 

about the concentration of the waters under scrutiny.

\ Villard, P., Dissolution des Hquides et des solides dans les gaz : Jour, physique, 3d ser., 

^ " vol. 5, p. 453, 1896.

a Washburne, C. W., Chlorides in oil-field waters: Am. Inst. Min. Eng. Trans., vol. 48, 

__ pp. 687-693, 1914.

*j.

-IX-
88 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

It is a familiar fact that in carbonaceous matter both the capacity i 

to emit gases and the percentage of water present show a continuous 

decrease in the series from peat to anthracite. Porter and Ovitz 1 vhave shown that upon being allowed to stand at atmospheric pressure and ordinary temperature for five months after mining, a sample 

of bituminous coal yielded a volume of methane equal to one and " 

three-fourths times the volume of the coal itself. Had the sample 

been subjected-to heat or had it stood indefinitely a much greater 

volume of gas would probably have been emitted. Concerning the ^ 

primary decomposition of coal by heat Taylor and Porter 2 say:

A high-grade bituminous coal of the gas-making type decomposes by heat 

primarily into paraffine hydrocarbons and a completely altered nonvolatile residue, with small quantities of water, CO2, and CO. The three latter products < 

are the first produced, although in small quantity; from some other types of v 

bituminous coal they are produced in greater relative quantities than from the y 

gas-coal type. Complex and varied secondary reactions induced by superheating 

the hydrocarbons, water vapor, and C03 are of great importance in industrial 

high-temperature carbonization.

The products of low-temperature carbonization from coal of the Pittsburgh 

type on an industrial scale at about 800° to 900° F. (427° to 482° C.) will consist of a rich gas amounting to 0.6 to 0.7 cubic foot per pound of coal, and a <* 

large yield of oil or tar, comprising 10. to 12 per cent of the coal. This tar consists chiefly of paraffin hydrocarbons, is very low or possibly entirely devoid of 

benzene and naphthalene derivatives, and practically devoid of free carbon. 

The gas will contain 6 to 7 per cent of unsaturated hydrocarbons and 20 to 25 

'per cent of ethane and its higher homologues and consequently will have a high 

calorific and illuminating value. The tar may be either redistilled or subject to 

cracking processes so as to produce light oils gasoline substitutes whose yield ^V 

will be greater than and probably at least double that obtained by high-temperature carbonization. >

The gas formed in such processes would of course take up moisture 

if water were present, Taking rough averages of various determinations, we have the following percentages of moisture in carbonaceous 

matter: Peat, 25 per cent; lignite, 20 per cent; bituminous coal, 8 per V 

cent; anthracite, 1.6 per cent; and finally a graphitoid rock is recorded with only 1 per cent of moisture. The conclusion seems inevitable that gases escaped during the changes that converted peat 

into anthracite and that the escaping gases assisted in carrying off 

the water as water vapor. It also seems evident that gases have escaped and that water has been removed during the metamorphism. of ' 

organic matter such as occurs in the carbonaceous shales frequently

associated with oil and gas deposits.

 , _ <^

1 Porter, H C., and Ovitz, F. K., The escape of gas from coal: Bur. Mines Tech. 

Paper 2, 1911.

2 Taylor, G. B., and Porter, H. C., The primary volatile products of the carbonization 

of coal: Mines Tech. Paper 140, pp. 50-51, 1916. j
WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS. 89

i BELATED PHENOMENA AND DEDUCTIONS OF PRAC- 

' TICAL VALUE.

V

ASSOCIATION OF BOCK SALT WITH DEPOSITS OF NATURAL GAS 

^ AND PETROLEUM.

It is a matter of common knowledge that masses of rock salt are in 

many places associated with deposits of petroleum and natural gas. 

' Striking examples are furnished by the salt domes of Louisiana and 

Texas, and somewhat similar occurrences of salt are reported in 

j southern Vera Cruz, Mexico; in Algeria; in Hanover, Germany; and 

at Maros-Ujvas, Transylvania. Harris 1 gives a comprehensive summary of the rock-salt deposits in different parts of the world, showing 

. that many of the salt masses in foreign countries resemble those of 

the Louisiana and Texas salt domes, both as to their general aspects 

> and as to their probable mode of origin. Thompson 2 suggests that 

some of the structural features in Egypt, in the Hanoverian fields of 

, Germany, and in the Ural-Caspian area may be due to salt-dome 

1 phenomena. He adds that it is not improbable that some of the 

structural features of the Rumanian and Galician oil fields are also 

associated with crystalline growths of salt that now form the " cores " 

"^ of some of the oil fields.

Although these associations have puzzled many investigators, the 

facts that have been brought out in the present paper concerning the 

evaporative action of gases seem to establish the theory that natural

-& gases under certain favorable conditions are able to concentrate 

natural waters, even to the point of depositing water-soluble salts. 

^ It is interesting in this connection to recall that Bunsen proved that 

g^ the rock salt of Wielieczka contains marsh gas.8 It is also interesting to note that in September, 1664, the first recorded explosion of 

fire damp occurred in the Hallstatt salt mine.4 Marsh gas and hyj> drogen sulphide are both present in the salt masses of northern Germany and Galicia, and there are numerous records of inflammable 

^ gases in salt mines. Knapp 5 has recently described the exudation

-^ of both gas and oil under high pressure from the salt masses at 

Belle Isle, La. It would, however, be rash to deny that the salt beds

now found near deposits of petroleum and natural gas in some parts

 

1 Harris, G. D., Rock salt, its origin, geological occurrences, and economic importance

in the State of Louisiana: Louisiana Geol. Survey Bull. 7, 1908; Oil and gas in

^ Louisiana, with a brief summary of their occurrences in adjacent States : U. S. Geol.

Survey Bull. 429, 1910.

~>. a Thompson, A. B., Oil-field development, pp. 241-245, New York and London, 1910. 

8 Annales chimie et phys., 3d ser., vol. 38, p. 269, 1853.

* Harris, G. D., Rock salt, its origin, geological occurrences, and economic importance 

in the State of Louisiana; Louisiana Geol. Survey Bull. 7, p. 173, 1908. 

v B Knapp, I. N., discussion of paper by A. F. Lucas (A review of the exploration at Bello

-7 Isle, La.) : Am. Inst. Min. Eng. Bull. 133, p. 88, January, 1918.
90 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

*

of the world owe their development as well as their preservation to t 

solar evaporation and to arid climatic conditions. We therefore dif- u 

ferentiate between the two types of salt deposits and confine this irdiscussion to those formed through deep-seated agencies.

It is obvious that the evaporative effects due to moving gases will 

depend somewhat on the distribution of water. Ee'latively small 

amounts of water subjected to evaporation into escaping gases would 

be more readily concentrated so as to deposit salt than would exces- *~ 

sive amounts of water. For instance, where the conditions are such 

as to permit the continued influx of surface waters, as in certain L 

shallow strata of the Appalachian fields, the brines do not attain, 

or at least do not retain, the same degree of concentration as those 

in the deeper strata. If, on the other hand, small quantities of salt 

water trickling, into a fissure should come into contact with unsaturated gases rising from some deeper source, the salt water would be ? 

evaporated and salt deposited in the fissure if the solution were sufficiently concentrated. The extreme concentration of some of the 

brines ejected from mud volcanoes has already been mentioned as X 

being due partly to the removal of^ water by escaping gases.

It is not necessary that the gases escape to the surface in order to '* 

cause evaporation, for in deep-seated strata, under certain conditions, v 

especially where the beds have undergone fissuring, gas may flow 

from one bed where the pressure is high to another bed where a 

lower pressure prevails. The evaporative effects of the migrating 

gas would, under these conditions, be none the less important. The ^ 

deposition of constituents other than chlorides, such as carbonates 

or sulphates, if they are present, might be caused by evaporation, , " 

so as to produce the unusual relations sometimes observed in salt 

domes. It also seems probable that where the salt masses are associated with deposits of calcium sulphate and calcium carbonate, geochemical processes yielding sodium chloride, together with the other 

compounds, have been brought about through the mixing of solu- "^ 

tions that have different properties of reaction or through reactions ^Jf 

between the constituents of certain solutions and those of the con- J± 

taining rocks.

ORIGIN OF SALT DOMES.

It is our belief that salt domes, such as are found in Louisiana ^ 

and Texas and seem to be closely related to the occurrence of ^ 

natural gas and petroleum, have been formed in part by these ^ 

geochemical processes accompanied by the evaporation of saline 

waters through the agency of escaping gases. Many of the domes 

occur along faults, and some of the salt masses are situated at the ^

intersections of fault planes. It is also significant that emanations /-

.£.-
RELATED PHENOMENA AND DEDUCTIONS OF VALUE. 91

of the gaseous hydrocarbons are commonly associated with the .salt 

domes.

The extensive literature dealing with the origin of salt deposits 

has been summarized by Hahn.1 Harris 2 reviews in detail several of 

the theories that have been advanced to explain the origin of the salt 

domes in the Gulf region of the United States.

As early as 1901 Hill 3 wrote: " These uplifts are most probably due 

to isostatic movements rather than to accumulations of gas." The 

next year, however, he ventured the opinion that the domes were 

caused* by the uplifting force of water or oil rising under enormous 

hydrostatic pressure.4 In 1904 Hager 5 proposed the " volcanic 

plug " hypothesis, an important element of which is the view that 

the cause of the domes goes back to faulting and igneous activity 

in the deeper rocks, including the intrusion of laccoliths. Certain 

features of Hager's hypothesis seem to fit the later phases of the dome 

building so well that the following quotation is made from his article, 

though we do not consider igneous activity essential to the phenomena 

under discussion:

By contact with the molten intrusives vast quantities of gas were generated 

from the reduction of metallic sulphides and the distillation of lignites and 

organic substances. These gases, accompanied by steam under tremendous 

pressure, forced their way to the surface through the unconsolidated sands and 

clays of the overlying Tertiary material, perhaps giving rise to mud volcanoes, 

such as occur in many of the world's great oil fields of the present day. Heated 

waters from great depths found vent along the same channels, carrying in 

solution carbonates of lime and magnesium,, gypsum, and salt. By ebullition and 

evaporation these solutions became concentrated until, saturation resulting, 

precipitation commenced, forming the necklike masses of salt, gypsum, and 

dolomite now encountered. With the cooling of the intrusive masses and the 

choking of the vents the process practically ceased. A period of subsidence 

followed, during which the coastal Quaternary beds, which at present cap the 

mounds, were laid down, followed by a secondary movement along the old lines 

of weakness, resulting in the present elevation of the mounds above the surrounding prairie.

Fenneman 6 discusses the domes and says:

Both the abnormal temperatures and the abnormal salinity suggest upward 

movements of ground waters. Further study may perhaps show that ground 

waters have been concerned in making the salt and gypsum of the mounds, as 

well as the crystalline limestone. * * * It may even appear that the pressure 

exerted during the growth or alteration of these bodies was sufficient to raise 

the mounds.

- 1 Hahn, F. F., The form of salt deposits; Econ. Geology, vol. 7, pp. 120-125, 1912. 

2 Harris, G. D., Rock salt, its origin, geological occurrences, and economic importance 

in the State of Louisiana : Louisiana Geol. Survey Bull. 7, p. 59, 1908. 

8 Hill, R. T., The coast prairie of Texas: Science, vol. 14, p. 326, 1901.

* Hill, R. T., The Beaumont oil field, with notes on other oil fields of the Texas region.: 

Franklin Inst. Jour., vol. 154, pp. 273-281, 1902.

B Hager, Lee, The mounds of the southern oil fields: Eng. and Min. Jour., vol. 78, 

pp. 137-139, 180-182, 1904. It appears that the idea of a volcanic neck or plug was 

In the minds of A. F. Lucas and others some time before this.

8 Fenneman, N. M., Oil fields of the Texas-Louisiana Gulf Coastal Plain: U. S. Geol. 

Survey Bull. 282, p. 121, 1906.
92 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

Harris,1 in the publication already cited, goes on to inquire: " How 

can rising columns of water be made to precipitate their salt, even 

though saturated, and, second, what is the force that lifts up a certain 

hundred or thousand feet of superficial strata in limited areas, almost 

never 2 miles across? " In brief, he answers: " Precipitation is due to 

decrease in temperature; and, second, the requisite uplifting force 

is amply accounted for by the power of growing crystals."

Against the explanation in the last sentence, it may be noted that 

the solubility of gypsum, which frequently accompanies salt in many 

of the .domes, increases with falling temperature. Moreover, two 

conditions must be assumed in this explanation of the domes, namely, 

that certain waters have been concentrated to the point of saturation and that the growth of new crystals takes place between 

rigid solids and not in free brine. Although it "is true that the 

solubility of salt decreases with falling temperature, the change is 

small. The amount of salt that will precipitate from a cubic meter 

of saturated brine on cooling from 60° to 20° C. is about 11 kilograms. This salt will occupy a volume of about 5 liters. The brine, 

however, on cooling from 60° to 20° C. contracts to the extent of 

about 18 liters, so that if the brine were held stationary, instead of 

moving and being continuously replenished, there would be a decided 

net contraction instead of an expansion. Evidently no expansive force 

could be exerted by the cooling brine. The-force sufficient to open up 

or to maintain channels for continued circulation would have to be 

exerted entirely by the solid crystals of salt. The deposition of the 

11 kilograms of salt, cited in the illustration, would leave 883 kilograms of water saturated with 317 kilograms of salt as a brine takingno part in the process, so that the amount of brine necessary to form 

a dome by deposition due to cooling would be very large. Although 

the disposition of this relatively large amount of brine can be explained by saying that it merely escaped at the surface, the theory of 

evaporation by natural gas could not only account for an initial concentration of the waters but also for the deposition of almost 30 

times as much salt as could be deposited by the simple cooling of 

a saturated brine. In other words, the quantities of salt water required for the formation of the domes by deposition due to evaporation are much less than those required by the theory of deposition 

due to cooling.

On the hypothesis of a cooling brine, then, we calculate that a 

cubic meter of saturated brine would deposit 11 kilograms of salt on 

cooling from 60° to 20° C., whereas the same amount of salt could be 

deposited from such brine, through evaporation, by the escape of 

790 cubic meters of gas at 40° C., 307 cubic meters at 60° C., or 74 

cubic meters at 100° C. If the gas expands a hundredfold at the

i Harris, G. D., op. cit., p. 76.
RELATED PHENOMENA AND DEDUCTIONS OF VALUE. 93

r

temperatures mentioned, the volumes of compressed gas required 

would be only about a hundredth of those mentioned. In short, the 

volumes of compressed gas would have to be from 24 to 260 times

<, greater than a given volume of brine to leave salt as the final product 

under reasonably favorable conditions. The volumes of gas required 

are 145 and 1,550 times the volume of salt formed at 100° C., and 40° 

C., respectively. Looked at in another way, 1 cubic meter of brine 

could deposit 11 kilograms of salt by cooling or 330 kilograms by

/ evaporation.

A factor which, so far as we know, has not been mentioned as a 

cause for the deposition of the salt forming the domes is the change

J in the solubility of the salt with a change of pressure. The solubility of salt at 24.05° C. increases from 35.90 parts per 100 parts of 

water under a pressure of 1 atmosphere, to 3T.36 parts under a pressure of 1,500 atmospheres.1 Although this change is small, it may be 

effective where saturated solutions move upward from regions of

^ very great pressure. It is comparable with the small change in solubility with change of temperature, which is the basis of Harris's

'^, theory, and the two factors influencing the solubility may act concomitantty.

Several European geologists have recently revived the old and 

long-neglected view that salt-dome structure is due to the flow of salt 

made plastic by pressure. 2 Lachmann 3 calls attention to the variety 

of deformations found in the German salt deposits and shows that the

^ structural features range from» those that are entirely conformable 

to the strata in which the salt deposits are found to those of domes

^ which show practically no relation to the adjoining strata, having 

"> apparently been formed by the flowage of salt. Arrhenius 4 has discussed some of the physical and chemical problems involved in the 

formation of the German salt deposits and applies the principles of 

Jt isostasy to explain the salt column in Drake's Saline, La. Before 

,-. this explanation can be accepted, experiments upon the plastic flow 

of salt, with special reference to the effect of temperature and 

"* pressure, the action of water, and the possibility of flow by fracturing 

and granulation, followed by recementation and recrystallization are 

needed. Inasmuch as Arrhenius assumes that solutions have acted

r : 

1 Smithsonian physical tables, p. 143, 1916.

*TV 2 Grupe, 0., Zechsteinformation und ihr Salzlager im Untergrunde des hannoverschen

^ Eichsfelds: Zeitschr. prakt. Geologic, vol. 17, p. 185, 1909. Harbort, E., Geologie der

j*_ nordhannoverschen Salzhorste: Deutsch. geol. Gesell. Monatst>er., 1910, p. 326, Lach-

^ mann, Richard, Salinare Spalteneruption. gegen Eksemtheorie: Idem, p. 597, Stille, H.,

Aufsteigen des Salzgebirges: Zeitschr. prakt. Geologie, vol. 19, p. 91, 1911.

3 Lachmann, Richard, Der Salzauftrieb, Halle, 1911. Separate from Kali, vol. 4. 

Nos. 8, 9, 22, 23, and 24, 1910. Studien ueher den .Bau von Salzmassen: Idem, vol. 6, 

3 pp. 342-353, 366-375, 397-401, 418-431, 1913.

* Arrhenius, Svante, Zur Physik der Salzlagerstiitten : Meddelanden k. v. Nobelinstitut,

-s vol. 2, No. 20, 25 pp., 1912.
94 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

to some extent as a lubricant for the movement of the salt and also 

that many of the unusual structural forms found in the German 

potash salts are due to rearrangements brought about by water given 

off from hydrated minerals at depth, we feel that, even if the preceding views are accepted, the evaporation of solutions by gases is worthy 

of consideration.

Conditions of comparative weakness that might permit the plastic 

flow of salt under great pressure would also permit the movement 

and probably the escape of solutions and gases,^especially where the 

movements of salt were accompanied by faulting and fracturing of 

the overlying strata. Probably no one of the theories we have cited 

will suffice to explain all the unusual phenomena of salt domes, but 

it is evident that in conjunction with any of the processes mentioned 

the evaporation of water into moving and expanding gas must be 

regarded as important. ~~

AMOUNT OF GAS AVAILABLE FOE EVAPORATION.

Having shown that under reasonable conditions about 145 to 1,550 

volumes of gas under a pressure of 100 atmospheres would be required 

to cause, through expansion and evaporation, the deposition of 1 

volume of salt from a saturated solution, we must now consider 

whether the supply of gas is adequate to be considered a factor in 

the formation of salt domes in this way. It is difficult to decide the 

question positively, because little is known of the conditions involved, 

such as the thickness and character pf the sediments in which gases 

might form and the dimensions and volumes of the salt masses. Even 

the origin of the gases is not known with certainty. Until the results 

of detailed studies, including deep boring, in the salt-dome region of 

Louisiana and Texas become available, calculations as to the quantity 

of gas available can have little value. Enormous volumes of gas 

are continuing to escape in the Gulf region, and we feel that although 

the amount of gas that has escaped is perhaps not sufficient to account 

for the complete development of the domes by this theory alone it 

is adequate to show that the theory sets forth at least one of the 

important factors in the development.

ACCUMULATIONS OF GAS AND OIL ASSOCIATED WITH SALT

DOMES.

In considering the escape of compressed natural gas we find that 

two facts are at once apparent. First, where deposits of natural gas 

occur only part of the available gas has escaped; second, under the 

conditions that permitted the escape of compressed gases part of 

the associated oil and wafer must also have escaped or migrated 

through the strata toward the regions of least pressure. These move-
RELATED PHENOMENA AND DEDUCTIONS OF VALUE. 95

ments may have influenced the accumulation of gas and oil by facilitating the segregation of the hydrocarbons above the water and by 

"^ causing the migration of gas and oil to favorable rock entrapments 

or reservoirs. It is not improbable that the accumulations of natural 

gas and petroleum associated with the salt domes have been formed 

partly in this way. Evidence that this principle is widely applicable 

to gas and oil deposits is furnished by the relatively complete segre7 gation of gas and oil above water in the sharply folded, more or less 

t 7 fissured anticlines of certain fields and the relatively incomplete 

segregation that has taken place in the gentle folds of the Appalachian fields.

Among the factors that have retarded the escape of gas, oil, and 

water the sealing of the rock passages by the deposition of mineral 

matter has been of prime importance. A common surface indication of petroleum and natural gas in some localities is the occurrence 

of fissures sealed by calcite or even by certain solidified hydrocarbons

themselves. 

w Where salt masses similar to those in Louisiana and Texas are unaccompanied by gas and oil, it may be assumed, if the salt masses

* are held to have originated in part through the evaporative action 

^ of natural gases, that the escape of the gases has been relatively complete. As bituminous matter :and carbonaceous shales are associated 

with many of the European salt masses, where but little gas or oil is 

^ now present, this view seems perfectly reasonable.

INDUCED SEGREGATION OF OIL AND GAS.

<4? During the more or less extensive movements through water-saturated sands, which occur incidentally to the extraction of oil and gas 

and which facilitate evaporation and concentration, oil and gas tend 

to segregate above the water in the higher portions of the pay sands.

 * This process we have termed induced segregation.1 The movements

 * by which the segregation is facilitated are caused by the expansion 

of gas under pressure, either assisted or retarded by hydrostatic 

pressure, the tendency being to replace the materials extracted 

through the wells.

It has not been possible to measure the extent of the movements

* in the sands, but by studying the porosity and thickness of the sands 

and by calculating the volumes of rock necessary to contain the vast 

quantities of oil and water that have been produced in some of the

 ^ fields, it is possible to approximate roughly the extent of migration. 

In Monroe County, Ohio, there is evidence that production from oil

wells is accompanied by movements of water, oil, and gas through

,' '._______________________________

1 Mills, R. V. A., and Wells, R. C., The evaporation of water at depth, by natural gases 

(abstract) : Washington Acad. Sci. Jour., vol. 7, pp. 309-310, 1917.
96 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

the Keener sand for distances ranging from half a mile to 1^ miles. 

Such migrations, we believe, must involve considerable segregation 

of gas and oil above the water. (r"

The principles of induced segregation are worthy of consideration > 

in the practical recovery of oil and gas. It is partly due to this segregation that certain wells which penetrate the higher parts of a watersaturated pay sand yield oil and gas more persistently than wells 

which penetrate lower parts of the same sand. In sands which are *" 

only partly filled with water or in which the water level is lowered 

during production induced migration and segregation will still occur, 

but the oil will not necessarily be found in the higher portions of 

the pay sands. A particular part of a pay sand may become so enriched by induced migration and segregation as to increase the rate 

of oil production from a certain well or group of wells, whereas t1. 

rate of production from neighboring wells will continually decrease funtil the wells are abandoned. The abandonment of wells yielding 

large amounts of water with relatively little oil may have a detrimental effect upon neighboring wells by decreasing the movements 

that bring about induced segregation, or by permitting the so-called 

" drowning out" of the productive wells by water. Many wells that '* 

have been abandoned because of their excessive yields of water might ^ 

have .been successfully operated had the geologic conditions and rearrangements of fluids been understood. Where the supply of deepseated water is very large, the continued pumping of poorly productive wells that tap relatively high portions of pay sands should >r 

bring about increased oil production through induced migration and 

segregation unless the textural conditions in the sand are unfavorable. 

On the other hand, where the water level is lowered by pumping, 

wells penetrating relatively low portions of the pay sand may be benefited. Numerous examples justifying these statements have been 

noted during the field investigations for this paper. * 

Near Miltonsburg, Monroe County, Ohio, a Keener well had an 

initial daily yield of 1£ barrels of oil, with 150 barrels of water. J 

By persistently pumping the well for one month the rate of oil . ^ 

production was slightly increased. At the end of 16 months the 

daily production was 5 barrels of oil, with 80 barrels of water. During the same period the rate of oil production from a neighboring ^ 

well increased from 4 to 7 barrels of oil a day, while the rate of water 

production decreased from 100 to 25 barrels a day. Within dis- ,w 

tances of 500 to 2,000 feet wells drilled a few months previously 

and apparently yielding oil and water from the same pay sand 

were gradually producing less oil and more water. It appears that 

the increased production from two of the wells was due to deep-
KELATED PHENOMENA AND DEDUCTIONS OF VALUE. 97

seated increments and rearrangements of the fluids, induced segregation being facilitated by conditions of structure, lenticularity, or 

texture of the productive sand.

In sec. 13, Center Township, Monroe County, Ohio, two Keener 

oil wells have yielded more than 80,000 barrels of oil and 250,000 

to 300,000 barrels of salt water, the total volume of which (oil 

and water combined) appears to be enough to fill the productive 

sand completely throughout an area of at least 1 square mile. Nevertheless these two wells are surrounded by 11 so-called dry holes 

and two poorly productive oil wells at distances of only a few hundred to a few thousand feet. The two best wells tap a relatively 

high part of the pay sand, the top of which is 6 to 9 feet higher than 

in the surrounding wells, and have been operated steadily since 1906. 

^iki the poorly productive and nonproductive wells larger quantities 

of salt water with relatively little oil were encountered in lower 

portions of the same pay sand. The water together with oil seems, 

unquestionably, to have migrated to the productive wells during 

their operation.

A somewhat similar instance of induced migration and segregation was noted near Jerusalem Village, in Sunsbury Township, 

Monroe County, Ohio, where a small group of Keener oil wells has 

yielded approximately 120,000 barrels of oil together with 400,000 

or 500,000; barrels of salt water. Of these amounts a single well on 

the J. R. Scott farm has yielded approximately 80,000 barrels of 

oil and 150,000 barrels of salt water. The top of the pay sand 

in this very productive well is 15 feet higher than in the surrounding wells. Furthermore this well was drilled in 1904 and has 

yielded oil and water steadily, whereas most of the other wells within 

distances of a few hundred to a few thousand feet have been abandoned because of the excessive yields of water with comparatively 

little oil.

Detailed; field investigations by Munn 1 suggest that induced migration and segregation may be important factors in the recovery of 

oil from the Hundred-foot and other water-bearing sands in the 

Sewickley quadrangle. The significance of hydraulic movements 

in oil and gas accumulation was emphasized by Munn 2 in 1909, and 

what we have said regarding induced migration, segregation, and 

accumulation of gas and oil can be regarded as an outgrowth from 

his work.

1 Munn, M. J., Geology of the oil and gas fields In Sewickley quadrangle: Pennsylvania Top. and Geol. Survey Comrn. Rept. 1, 1910.

2 Munn, M. J., The anticlinal and "hydraulic theories of oil and gas accumulation: 

Econ. Geology, vol. 4, pp. 509-529, 1909.

91818° 19 7
98 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

GLQGGrsrG 0F OIL AND GAS SANDS.

Another process that has an influence on the -extraction of oil and 

gas and is closely related to this investigation is the deposition of 

mineral matter in the interstices of a pay sand after extraction has 

begun. The clogging of the interstices may seal a pay sand sufficiently to retard or stop production from a well or group of wells 

long before the gas and oil are exhausted. Fart -of the trouble 

attributed to the paraffining of oil "wells is no 'doubt due to the clogging of the £ands by the deposition of mineral salts. As tlie result 

of chemical changes, such as those "which 'are expressed by the type 

reaction set forth on page 50 and which are brought about through ^ 

the mixing and concentration of certain waters having different 

properties of reaction, carbonates and sulphates are commonly depos- £ 

ited, not only in the wells and in the interstices of the productive 

sands immediately around the wells but also in portions of the sands 

that are remote from the wells. In this way many oil fields where 

the sands have been flooded by injuirous waters have been ruined; v 

A new well drilled in an old field where much oil and gas remain 

unextracted may be nonproductive owing to such clogging of the ^ 

sands.

Waters that on being concentrated deposit carbonates or that react 

with the deep-seated brines to form carbon-ate .or sulphate should be 

carefully excluded from all productive sands. If such waters have 

entered the productive sands or if it is impossible to exclude them 

from wells it may be feasible to use chemical reagents to prevent the \ 

deposition of mineral matter in the wells and the sand interstices 

or to remove such material which has previously been deposited. A ' 

detailed discussion of the practical methods of preventing or remov- fr 

ing these mineral deposits would be inappropriate in this bulletin, 

though the subject is wortliy of further investigation.

PROSPECTING FOB OIL AND GAS. ^

In prospecting for oil and gas in a region known to be petrolif- ^" 

erous the mere presence or absence of water in a deep-seated sand is 

frequently an important consideration. Thus, in prospecting the 

Hundred-foot sand for oil in western Pennsylvania, the operators 

 welcome the presence of water in the sand, because as a rule in that ^ >, 

region wells yielding mixtures of oil and water last longer and are 

more profitable. " >v:'~"

From the analyses of Appalachian oil and gas field waters that are ^ 

available, it appears that sulphates are characteristically lacking in 

the waters associated with the oil and gas, but that they are present 

in considerable proportions in the waters from shallow, nonpetrolifer- v 

ous rocks overlying oil and gas bearing deposits. Sulphates also 

occur in noteworthy amounts in waters from the deep-seated non-
RELATED PHENOMENA AND DEDUCTIONS OF VALUE. 99

petroliferous rocks in many places outside of oil and gas fields. 

Rogers 1 has described the application of these facts to the search 

for oil and gas in California, where for a number of years the 

absence of sulphates from deep-seated waters has been considered one 

indication of the proximity of oil or gas. The same principle may be 

applicable in the Appalachian as well as other fields, although the 

presence of barium and strontium in certain deep-seated brines may 

afford an explanation for the absence of sulphates in these waters.

The concentrated chloride waters associated with oil and gas in 

the Appalachian fields, besides lacking sulphates, also generally lack 

carbonate but contain noteworthy proportions of calcium. The calcium, together with sodium and magnesium, is deposited as chloride 

on complete evaporation. How generally this distinction holds true 

in waters outside of the Appalachian fields can be determined only 

by further study, but in prospecting for oil and gas in any field it 

should be advantageous to determine the characteristics of the waters 

associated with oil and gas in the nearest productive territory as compared with the waters in. nonproductive strata. *

In proved territory the presence or absence of newly deposited carbonates in the interstices of a pay sand suggests whether or not that 

part of the sand has been influenced by former production. If, for 

instance, oil, gas, and water have been drawn from that part of the 

sand, carbonates have probably been deposited in consequence of the 

liberation of carbon dioxide, together with other gases, from the 

water. Also if the sand has been flooded by waters leaking in from 

abandoned or poorly plugged wells the fact may be recognized through 

the presence of newly deposited carbonates in the interstices of the pay 

sand, through the low concentration of the constituents in the water, 

or through the high proportion of sulphate and carbonate in those 

constituents.

DETERMINING THE SOURCE OF INFILTRATING WATERS.

Some of the detrimental effects produced when waters of certain 

types leak into wells and flood oil and gas sands have been sufficiently 

described to emphasize the importance of excluding injurious waters 

from the wells. To do this most effectively the source of an infiltrating water that is causing damage to a well, a group of wells, or the 

productive sands themselves should be determined and appropriate 

efforts made to stop the leaks. Studies of the waters occurring in 

the different strata in any particular field and of the probable reactions and precipitation that might ensue when such waters are 

mixed, concentrated, or diluted to form new solutions should throw 

valuable light upon this subject, if supplemented by studies of freshly

1 Rogers, G. S., Chemical relations of the oil-field waters in San Joaquin Valley, Cal.: 

U. S. Geol. Survey Bull. 653, 1917.
100 WATERS ASSOCIATED WITH PETROLEUM AND NATURAL GAS.

formed mineral deposits and solutions collected from wells actually 

affected by infiltrating waters.

It is evident, for instance, that the injurious sulphate deposits *" 

which have interfered with the production of oil from certain old 

wells in Butler County, Pa., are due to the infiltration of sulphatebearing waters from the shallow nonpetroliferous beds, the sulphate 

having reacted with soluble barium ancl strontium salts of the deepseated brines in the wells where the leaks occurred. Carbonates are r 

similarly deposited in some of these old wells in consequence of the ^~ 

infiltration from shallow beds of primary alkaline waters which react 

with the deep-seated brines as explained on page 50. The shallow ^ 

waters causing these deposits have not been properly excluded from r 

the wells in which the deposits are formed.

NEED FOB, FTTHTHEB INVESTIGATION.

In concluding this paper we would emphasize the need for further 

investigation o| the relations between the occurrence and produc- fc 

tion of petroleum and natural gas and the chemistry of the associated waters. Preliminary studies give proof of the value of such + 

work, and there can be no doubt that future analytical and experi- fmental studies will furnish additional criteria to be applied.

Where oil and gas are being drawn from water-bearing strata, 

careful consideration should be given to the mode of occurrence of -, 

the gas, oil, and water; the movements and rearrangements they ' 

undergo incident to extraction, especially with relation to structure, 

texture, and lenticularity of the sands; the physical and chemical 

changes that the waters undergo; the effects of these changes on the 

reservoir rocks and well casings and tubings; the effects thai infiltrating waters of certain types have on the reservoir rocks and wells 

owing to concentration and to chemical reaction and precipitation; 

and the methods of remedying these effects and their causes. ^

The prevention of the formation of inorganic deposits in oil and / 

gas sands and in wells, together with the removal of such deposits 

through the use of chemical reagents, constitutes in itself an important field for study. The application of knowledge of the chemistry of oil-field waters in the exclusion of infiltrating waters from . wells or in the sealing and plugging of wells is also important. If * 

well tubings and productive sands become clogged by inorganic de- v 

posits from oil-field waters, it may be feasible to utilize knowledge 

of the processes involved to exclude injurious waters from wells. The 

waters themselves may be made to furnish cementing material. 

Further consideration of these and other technologic phases of the 

study of oil and gas field waters is outside the province of this paper ^~ 

out presents an inviting field for investigation.
INDEX.

Page.

Acknowledgments for aid __- 7

Allegany County, N. Y., escape of

gas in _ _____ 61

Aluminosilieates, alkali, precipitation 

of calcium and magnesium by 74-75

Analyses of Appalachian oil and gas

field waters_______ 33-39 

salt crusts from oil and gas

wells___________ 47

Bacteria, reduction of sulphates' by- 70 

Baku, Russia, mud volcanoes near__ 61 

Barium sulphate, deposition of, in oil

wells ___________ 47-49

Barnesville, Ohio, " salting up " of

gas wfills at ___ 46 

Benson sand, gas pressures in ___ 28 

Berea sand, analyses of brines froin_ 38 

comparison of brines from, with 

brines from Big Injun 

and Keener sands___ 57-59 

dilute waters in____________ 63-64

gas pressures in _ 27, 28 

pore space and sizes of grains

in_____________ 21 

Big Injun sand, analyses of brines

from- ____________ 37

comparison of brine from, with

brine from Berea sand_ 57-58 

concentration of brine by escape

of gas fr,om_______ 63-64 

gas pressures in _ 27,28,29 

pore space and sizes of grains in_ 21 

Big Lime sand, analyses of brines

from__ ___ 35 

comparison of waters from__ 56 

concentration of brine by escape

of gas from_______ 63-64 

gas pressures in_ ___ 27, 28 

Bitumen, gas associated with _ _ 62-63 

Boiling points, raising of, by underground pressures- ____ 83

Bowlder sand, analyses of brine

from____ 39 

Butler, Pa., gas sand, gas pressureB

in _____________ 28 

Butler quadrangle, Pa., location of_ 9 

Butler Township, Pa., crust formed

in oil well at_____ 48,100

Calcite, occurrence of. __ 15 

Calcium chloride, effect of, on the 

solubility of sodium 

chloride _________ 72-73 

Canada, escape of gas in ___ 61

Page.

Carbonates, deposition of, in oil

wells________ 48-50,100 

indications from, in prospecting. 99

Cementation, deep-seated waters as

agents of_________ 76

Center Township, Monroe County, 

Ohio, wells in, migra-. 

tion of oil to______ 97

Chlorine, ratio of other constituents 

to, in ocean and in oil,. 

field watersi _______ 31

Cleveland, Ohio, " salting up " of gas

wells at_________ 46

" Clinton " sand, gas pressures in_ 28, 29

Clogging of oil and gas sands, retarding of production by_ 44-50, 

98-100

Coal, emission of gas from._____ 88

Coalburg, W. Va., well near, analysis of water from __ 39

Comparison of waters from different

geplogic horizons___ 57-60 

from the same sand in neighboring fields________ 55-57

Concentration of saline waters___ 6

Condit, D. Dale, work of_________ 8

Connate waters, inclusion and migration of _______- 68-69

Constituents of deep-seated waters, 

changes in, during geologic time _ , 57-64 

changes in, during recent time 50-57

Cow Run sand, analysis of brine

from ________ 35

Crusts, deposition of ___ 6-7 

from oil and gas wells, plates

showing ______ 48, 50, 52 

mineral, deposition of, in oil and

gas wells _______ 47-50 

from oil and gas wells, analyses of _ _ JO 

salt, from oil and gas wells, analyses of _ __ 47

Crystallization of salt, force exerted

by _____________ 92-93

Daly, R. A., cited_____ __ 70-71 

on the saline content of the preCambrian ocean _ _ 65 

Deposits, mineral, formation of, in 

oil and gas wells_ _

44-50, 98-100

Dinsmore, S. C., analyses by.__ 7,19 

Dolomite, genesis of, in oil and

gas sands __ 71-76

101
102 INDEX.

Page.

Engines, removing crusts from 72 

Evaporation of water at depth, conditions affecting____ 77-88 

by gas ______ 45

Fenneman, N. M., cited_ 91 

Field work, record of________ 8 

Fifth sand, Allegheny County, Pa.,

analysis of brine from_ 39 

Five Hundred Foot sand, analysis of

 brine from_ ____ 35 

Flow of salt, formation of salt

domes attributed to__ 93-94 

Forward Township, Pa., crust

formed in oil well at 47-48 

Fourth sand, Butler County, Pa.,

analysis of brine from_ 39 

Fredonia, N. Y., escape of gas

near ______ _ 61

Gas, artificial, used at Washington,

D. C., composition of 79 

artificial, used at Washington, 

D. C., moisture absorbed by 79-80 

natural, characteristics of 22 

escape of _________ 60-63 

mixtures of, with water__ 25-27 

pressures of _________ 27-29 

causes of __ ______ 29 

origin of, in relation to the

evaporation of water- 87-88 

saturated, weights of water 

in, at given temperatures ___________ 81-82 

solubility of, in oil and

water __________ 86-87 

Gas fields, Appalachian, areal

geology of 11 

Appalachian, published reports

on ____________ 9-10 

stratigraphy and structure

of ____________ 11-14 

Genesis of deep-seated brines 29 

Goldman, M. L, work of_____ 7,15-16 

Grahamite, escape of gas associated

with __________ 63

Hager, Lee, cited___________ 91 

Harris, G. D., cited________ 62, 91, 92 

Harrison Township, Knox County, 

Ohio, salting up of gas 

well in _________ 44-45 

History of the oil and gas field

waters ___ _ __ 68-77 

Hundred-foot sand, analyses of

waters from _________ 33-34

comparison of brine from, with 

brine from Bowlder 

sand 60 

gas pressures in _ 27, 28 

porosity of _____________ 20 

Hunt, T. S., on the origin of deepseated chloride waters- 64-65

Page.

Infiltration of injurious waters, determination and stoppage of ________ 99-100

Investigation, subjects suggested for- 100

Java, brine springs on________ 62 

Jefferson County, N. Y., escape of

gas in________._ 61 

Jerusalem Village, Ohio, well near,

migration of oil to__ 97

Kanawha County, W. Va., gas springs

in _____________ 61 

Kaolinite, occurrence of________ l."5 

Keener sand, analyses of brin^H

from___________ 35-36 

comparison of waters from__ 51-50,

66-57 

concentration of brine by escape

of gas from ____ 63-64 

gas pressures in_________ 27, 28 

pore space and sizes of grains

in _____________ 21 

King, F. H., cited_____________ 69

Lane, A. C., on the origin of deepseated chloride waters- 65 

Larsen, E. S., work of_________ 7 

Lytle, M. E., acknowledgment to__ 44 

cited_________________ 45

Magnesium, removal of, from waters

of sedimentation ___ 70-76 

Magnesium carbonate and chloride,

hydrolysis of ______ 72

Maxton sand, analysis'of brine from_ 35 

Melcher, A. P., work of________ 7, 20 

Memphis, Tenn., escape of gas near_ 61 

Mica, occurrence of__________ 15-16

Microorganisms, reduction of sulphates 4>y _______ 70 

Migration of connate waters, causes

and results of_____ 68-69 

of oil and gas, facilitation of, by

pumping ________ 95-97 

Miltonsburg, Ohio, well near, comparison of waters from_ 51-55 

well near, oil yield of, increased

by deepening _____ 26 27

wells near, oil yield of, increased by pumping__ 96-97 

Mississippi River, escape of gases at

mouth of________ 62 

Mixtures of oil, gas, and water, evidence of __1 _______ 26-27

Mud volcanoes, occurrences of____ 61 

Muds, blue, changes in water included in________ 70-71 

Munn, M. J., study of oil and gas accumulation by _____ 97

Occurrence of water with oil and

gas _____________ 25-29

Ocean water, comparison of, with oil

and gas' field brines__ 29-33
INDEX. 103

"S

Ohio, eastern, generalized section of

formations in__-- 13 14 

Oil, characteristics of_________ 22 

mixtures of, with, water__ ___ '25-27 

Oil fields, Appalachian, areal geology of 11 

Appalachian, published reports

on_______ 9-10 

stratigraphy and structure

of ____________- 11-14 

Organic matter, decomposing, reduction of sulphates by 70 

Origin of oil-field waters, hypotheses

concerning _____ 5-7, 64-68

Palmer, Chase, acknowledgment to_ 7 

Palo Pinto County, Tex., escape of

gas in ______ _ 61 

People's Natural Gas Co.'s well,

Washington County,

Pa., analysis of brine

from____________ 39 

Permutite, use of, in softening

water____ 74-75 

Petroleum. See Oil. 

Porter, H. C., Taylor, G. B., and,

cited_________.:_ 88 

Potassium, removal of, from saline

waters . 75 

Pressure, changes of, evaporation of

moisture affected by 84-86

of gas in reservoir rocks ___ 27-29

causes of 29

Prospecting, indications that aid - 98-99

Quartz, secondary, occurrence of 15

Red color in rocks, cause of- 24 

Ree.ves, Frank, work of__ 8 

Reports, geologic, on Appalachian

oil and gas fields___ 9-10 

Results of the investigation __ 5-7 

Retention of waters in oil and gas

sands ________ 76-77 

Richardson, G. B., on the genesis of

deep-seated waters 66 67 

work of_____________ - 8 

Richlands, Va., escape of gas near 61 

Rocks, generalized sections of, from 

which samples were 

collected_________ 12 

reservoir, chemical composition

of_____________ 16-20 

deep-lying, water in____ 24 

kinds of____________ 14-15 

mineral composition of___ 15-16 

pore space and sizes of

grains in_____ 20-21 

temperatures of _______ 27 

See also Sands, oil and gas.

Salinity, primary and .secondary, of 

ocean and oil field 

waters ___________ 33

Page. 

Salt, deposition of, from cooling

brine-___________ 92-93 

deposition of, from solutions 

evaporated by moving 

gases 89-95 

solubility of, in presence of

calcium chloride __ 72-73 

increased by pressure___ 93 

'Salt domes, accumulations of gas and

oil associated with__ 94-95 

amount of gas available for

evaporation under __ 94 

origin of ________________ 90-94

Salt sand, analysis of brine from._ 35 

gas pressures in_________ 28 

" Salting up'" .of gas wells, causes of_ 45, 47 

Instances of ____________ 44-47 

Salts, crusts of, formed in oil and 

gas wells, plates showing ________!__ 48, 50, 52 

Samples, collection of________ 8

Sands, oil and gas, dilute brines in 63-64 

oil and gas, generalized sections

showing- _ 12 

water in ___________ 22-25 

Schaller, W. T., work of_______ 7 

Schroeder heirs' farm, well No. 1 on, 

constituents of waters 

from____________ 51-53 

Second sand, Forest County, Pa.,

analysis of brine frbm_ 39 

Sedimentation, waters of, changes in_ 70-76 

waters of, inclusion and migra

tion of _________ 68-69 

Segregation, induced, of oil and gas,

practical results of_ 95-97 

Solubility of salt, decreased by calcium chloride_____ 72-73 

increased by pressure . 93 

Stabler, Herman, acknowledgment to_ 7 

Stumptown gas field, Belmont 

County, Ohio, " salting 

up " of gas wells in___ 

Sullivan, E. C., cited_____________

Sulphates, damage from infiltration

of____________ 100 

indications from, in prospecting ____________ 98-99 

reduction of, in sea muds,___ 70-71 

Sulphides, occurrence of ______ 15 

Summerfield quadrangle, Ohio, location of__________ 9 

Summit Township, Butler County, 

Pa., analysis of artesian water from 35

Taylor, G. B., and Porter, H. C.,

cited___________ 88

Temperatures of oil, gas, and water_ 27 

subterranean, effect of, on the 

concentration of vapor 

in gas ________ 83-84

Terrebonne Parish, La., escapes of

gas in _ ________ 62
104 INDEX.

Page. 

Third sand, Butler County, Pa.,

analysis of brine from. 39 

" Trenton " limestone, gas pressures

in ____________ 28 

Trinidad, escapes of gas on__,__ 62

Vapor pressure, decrease of, by contact with solutions__ 80-81 

definition of____________ 78 

of water at different temperatures ___________ 80

Warfleld, Ky., " salting up " of gas

well at_________ 46

Washburne, C. W., on the source of 

chlorides in oil-field 

waters__________ 65-66

Washington, D. C., artificial gas at,

composition of _ 79

Page. Washington, D. C., artificial gas at,

moisture absorbed by 79-80 

Wells, B. C., analyses by_______ 17 

Wells, clogging of, by deposits of

salts______ 44-50,98-100 

deepened, yield of oil and water

from___________ 26-27 

shallow, composition and reacting values of water 

from___________ 41-43 

White, I. C., acknowledgment to__ 46 

Wirt County, W. Va., gas springs in_ 61 

Woodsfield, Ohio, salt crust in well

at____________ 46 

WoodsfielcJ quadrangle, Ohio, location of__________ 9

Zelienople quadrangle, Pa., location

of ___________ 9

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