JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 91, NO.

B12, PAGES 12,327-12,338,NOVEMBER 10, 1986

Advances in Soil Gas Geochemical Exploration for Natural Resources'

Some Current Examples and Practices
J. HOWARD MCCARTHY, JR., AND G. MICHAEL REIMER
U.S. GeologicalSurvey, Denver, Colorado

Field studieshave demonstrated that gas anomalies are found over buried mineral deposits.Abnormally high concentrationsof sulfur gasesand carbon dioxide and abnormally low concentrations of
oxygenare commonly found over sulfideore deposits.Helium anomaliesare commonly associatedwith
uranium depositsand geothermal areas. Helium and hydrocarbon gas anomalies have been detectedover
oil and gas deposits.Gasesare sampledby extracting them from the pore spaceof soil, by degassingsoil
or rock, or by adsorbing them on artificial collectors.The two most widely used techniquesfor gas
analysisare gas chromatographyand mass spectrometry.The detection of gas anomaliesat or near the
surfacemay be an effectivemethod to locate buried mineral deposits.

INTRODUCTION

tion of gases,current practices and techniquesused in gas

geochemistry,and examplesof the use of gasesin exploration

Further, we searchfor the veins by observingthe hoar-frosts,

which whiten all herbage except that growing over the veins,
becausethe veins emit a warm and dry exhalation which hinders
the freezing of the moisture...

are described.
GENERATION

OF GAS ANOMALIES

Gas anomalies are generated by both primary (hypogene)

and secondary (supergene)processes.Examples of primary
processesare outgassingfrom the mantle and deep crust, magIt is generally acceptedthat new depositsof metals, oil and matic differentiation leading to active venting of volatiles
gas, and other resourcesmust continually be found to ensure through volcanoesor seafloorspreadingcenters,and emplacefuture economic and social progress.Despite this need, the ment of hydrothermal ore deposits.Secondaryprocessesgenrate of discoveryof new mineral depositsand oil and gas fields erate gas anomalies through the interaction of the hydrohas declined in the last few years, largely becausemost of the sphere,biosphere,and atmospherewith crustal rocks and mindeposits that are exposed at the surface have already been eral deposits.Examples include the generation of sulfur gases
found. Most of the ore depositsmined in the past and being and carbon dioxide during oxidation of sulfide ore bodies and
mined today were discoveredbecausethey cropped out at the hydrocarbon gasesfrom natural gas and petroleum deposits.
surface.Similarly, many oil and gas deposits were discovered Helium and radon are generatedby radioactive decay and are
by oil or gas seepsat the surface[Mclver, 1984]. Increasingly, transportedand accumulatedby supergeneand hypogeneprogeologistsrealize that our search for new deposits must now cesses.
"De Re Metallica"--Georgius Agricola, 1556

concentrate

on those concealed

beneath

the surface and that

prospectingfor them will require new exploration techniques. Primary Gases

One such technique is to measure gasesthat emanate from
Primary gasesare emitted from the mantle and deep crust
buried mineral depositsand escapeto the surface.
through volcanoes,spreadingcenters,and deep-seatedfaults
There are two reasonsfor the increasinginterest in the use (Figure 1). One of the earliest studies of volcanic emanations
of gasesfor geochemicalexploration: (1) In addition to anwas conducted by Zies [1938] in the Valley of Ten Thousand
cient observationsnoting the occurrenceof gasesaround ore
Smokes in Alaska. He found that fumarole gasescontained
deposits [Agricola, 1556], recent field and laboratory studies about 99.5% water; other componentshe identifiedwere CO2,
indicate that gasesoccur at or near the surfaceabove virtually
GO, 02, CH4, H2S, H2, N2, Ar, HC1, and HF. Zies proposed
all mineral deposits,either as primary componentsor as reac- that these gasesaccumulated as late-stage differentiates of a
tion products [Lovell et al., 1979; Lovell and Hale, 1983; deep-seatedrhyolitic magma. Many of the same gases were
Hinkle and Kantor, 1978; Hale and Moon, 1982; McCarthy,
found at Kilauea volcano in Hawaii [Shepherd, 1938; Green1972; Tanner, 1964, 1978; Taylor et al., 1982; Jones and land et al., 1985], as well as SO2, S2,and SO3. In addition, F,
Drozd, 1983; Mclver, 1984; Philp and Crisp, 1982]. (2) The C1, Br, and I have been reported in gasesfrom volcanoesin
development of new and sensitiveanalytical instruments, such Japan [Shitiura et al., 1964]. Organic halides have been reas the gas chromatograph and the mass spectrometer, has ported in gasesfrom Mauna Loa and Kilauea in Hawaii and
enabled us to measure both high and extremely low con- from Mount St. Helens in the United States [Howard et al.,
centrations of gasesfound in nature. Studies on the diffusion
1980]. Evidence for deep outgassingis found in differencesin
and transport of gaseshave been carried out by a number of the composition of gasesand their isotopic makeup. Dymond
scientists[Tanner, 1964, 1978; Stahl et al., 1981; Leythaeuser and Hogan [1973] measured the noble gases in midocean
et al., 1982, 1983; Kvenvoldenand Claypool, 1980; Kristiansson ridge basalts and found that the abundance patterns of the
and Malmquist, 1980; Roberts, 1981; Reimer and Orton, 1976; noble gases resembled those of the sun rather than those of
Reimer et al., 1979]. In this paper the generation and migrathe earth's atmosphere. They concluded that the basalts con-

tained primordial noble gases.Similarly,3He is enrichedin

This paper is not subject to U.S. copyright. Published in 1986 by
the American GeophysicalUnion.

tectonicsettingswhere mantle-derivedmaterial is being injected into the crust. Lupron and Craig [1975, 1981] and Craig et

Paper number 5B5883.

al. [1975] found 3He enrichmentat submarinevolcanicvents

12,327

12,328

MCCARTHY AND REIMER:SOIL GASESIN GEOCHEMICALEXPLORATION

H20,CO 2,cO,N 2,He

CH4,SO2,F,GI,Br,I

He3,H2S,H2,cO
Ne,Ar,Kr,Xe

He3,H2
%

Centers

PRIMARY

thermal maturation or "cracking" [Waples, 1981]. The required temperatures (80-200C) are attained when the
organic material is deeply buried by sediments.Petroleum,
formed by the samecatagenicprocess,also containsgases.
Secondary gasesare also produced by inorganic reactions.
For example, CO2 results from the reaction of acid groundwaters with calcareousminerals. Acid groundwatersare found
around oxidizing sulfide bodies, and not only is CO2 formed
in such settings,but 02 is consumed[Lot)ell et al., 1979, 1983;
Lovell and Hale, 1983; Hale and Moon, 1982] Sulfur gas
speciesare also produced [Hinkle and Kantor, 1978; Hinkle,
1984; Hinkle and Dilbert, 1984; Kesler, 1984]. COS and CS2
are the most abundant sulfur gasesdetected,but H2S and SO2
have also been found (Figure 2).
Hydrogen gas is often detectedin field studies.Severalinvestigatorshave proposedthat a natural electrochemicalpotential existsaround an oxidizing sulfidebody producing hydrogen ions [Bolviken and Lotn, 1975; Govett, 1976; Govett
and Chork, 1977]. McGee et al. [1984] and Sato et al. [1984]

\-antle Volcanoes
rust

Spreading

carbongasesare producedfrom complexorganicmatterby

Deep

GAS

Faults

EXHALATIONS

Fig. 1. Some gasesthat have bccn identified in primary gaseous

and vapor emanations.

along the East Pacific Rise. Craig and Lupton [1976] measured Ne, He, and H isotope ratios in oceanic basalts and
concludedthat thesegaseswere probably mantle derived.
Some emanations of CO2 appear to be mantle derived
based on carbon isotope measurements.CO2 gas collected

from phreaticmaarsin Alaskawerefoundto havea 63C

value of -6.36%0, suggestinga deep source [Barnes and

detectedH 2 in areasof seismicand geothermalactivity and

suggestedthat it is generatedby the reaction of ferrousiron
mineralswith water. If H 2 is available, volatile hydridessuch
as AsH3 and SbH3 may be formed. The widespread oc-

currence of As and Sb minerals in epithermal gold deposits

suggeststhat these volatile compounds may be detected over
Carbon monoxide is also found in volcanic emanations at
suchdeposits.
Kilauea, Hawaii [Shepherd,1938], at Erta 'Ale, Ethiopia [Gi7Mercury vapor has also been successfullyused as a geo7enbach
and LeGuern,1976], and at Nyiragongolava lake in
chemical indicator of buried ore deposits [Rose et al., 1979].
Africa [Gerlach, 1980a]. Wherever CO is detectedin gases
Mercury is commonlyenrichedin ore minerals[Jonassonand
from fumarolesand volcanoes,reducing conditionsare indiBoyle, 1972], particularly sulfides,and is volatile; henceit may
cated by low partial pressuresof 02 and by the presenceof
be a usefulpathfinder for such ores [McCarthy, 1972].
other reducedgases,suchas H2, H2S, and CH,, and a deepHelium is found in high concentrations associated with
seatedsourceis suggested.
various types of energyresources,including uranium deposits,
Methane and other light hydrocarbonsfound in volcanic
oil and gas deposits,and hot water geothermal occurrences.
gases and tholeiitic basalts from the Mid-Atlantic Ridge
Helium is continuouslyproduced in the earth's crust from the
[Pineau et al., 1976] and the East Pacific Rise [Welhan and
alpha particles that are emitted by the natural radioactive
Craig7,1979] are enrichedin 3C, suggesting
a thermogenic
decay of uranium and thorium. Where uranium-containing
and probably deep source.Gold [1979] has proposedthat
minerals are concentrated in a deposit, higher helium consomemethane is primordial.
centrationsin the vicinity may be an indicator of the deposit.
Sulfur gasesdetectedin volcanicemanationsare SO2 (the
Oil and gas are naturally found in sometypes of reservoirsor
most abundant and most often reported), H2S, 82, and COS.
traps, and helium is trapped along with other gasesand has
Isotope measurements
by $akai et al. [1982] of SO2 from
been used as a geochemicalindicator for both oil and gas
Kilauea volcano indicated a deep-seated source. Similarly,
[Potorskiand Quirt, 1981; Roberts, 1981].
McCoy, 1979].

sulfurisotopestudiesby Arnoldand $heppard[1981] of sulfide

minerals from the East Pacific Rise indicate that the sulfides

"... are only compatiblewith a dominantlymagmaticsource."

All the halogenshave been found in volcanicgases[Gerlach, 1980b; Shi7iuraet al., 1964; White and Warin7,1963]
and in fluid inclusions[Roedder,1972] with C1 being the most
abundant in both. Evidence that halogen complexesmay be
important in the transport of metals in hydrothermalsolutions [Krauskopf,1979], coupledwith their volatility, suggests
that they may serveas explorationguidesif they are released
during weathering.
Primary gasesdetectedat the surfacemay only indicate
mantleoutgassing,
commonlyalongdeep-seated
faults;if mineral depositsoccuralong thesefaults,the primary gasesmay
be usefulin exploration.

Migration of Gases

Two processeswhereby gases migrate are diffusion and

masstransport. Diffusion takes place in any medium, and the
rate is determined by the character of the medium, the size
and molecular weight of the diffusing species,and the temperature of the gas. Although diffusion is the probable mechanism for slow transport of gasesover short distances,particu-

CO2,H2S,SO 2,CS 2

COS

I I.,..? I I i,O2 Consumed

Sulf

SecondaryGases

Secondarygasesare those generatedby the interaction of

rocks and ores with the hydrosphere, atmosphere, or biosphere. Examples of major secondary gas production are
found in the large natural gas fields of the world. Hydro-

SECONDARY

Fig. 2.

GAS

EXHALATIONS

Somegasesproduced(or consumed)
aroundoxidizingsulfide bodies.

MCCARTHY AND REIMER' SOIL GASESIN GEOCHEMICALEXPLORATION

larly below the water table [Rose et al., 1979], masstransport

is the only mechanismthat can account for rapid migration
over considerabledistances.Gasesdissolvedin a fluid (gas or
liquid) can move through interconnectingspacesin rock or
soil. Faults or fracturesprovide channelwaysfor mass transport of fluid and contained gases. Fault zones have been
mapped by measuring gasesemanating from them [Kasimov

12,329

:.:

.........
-.

.:.-.'?'"

':':::'!11
':.:..
-

:::::::-.

:.

.....

...:::,,..
........
.............

"-:. ,--i

et al., 1978].

Helium is a very light, diffusivegas and can move through

the overlyingrock fasterthan heaviergases.Becauseof these
characteristics
and its inertness,it hasbeensuccessfuly
usedin
exploration for energy resources.Hot geothermalwaters frequently contain high concentrationsof helium, becausethey
are formedat depthwherethe partial pressureof He is greater
and helium is more soluble in hot water than in cold water. As

these waters convectivelycirculate and cool, the gas is re-

..-d;';;?.",
'.......

-:.-...--

%?.::::
........

:::
..........
----:;4
-,...;:
....

;/:..:.
' '

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

,'"'..:::;;;';::::
'................
':'";:;;:;:;%:::;,::,.-,
r.:-.-..:
...............
.,'::'":
..............
:::
............

, ,-..:..........
.......

leased.

The detectionof rapid changesin the concentrationof gases

and vapors at the surfaceor in drill holes is compelling evidence for mass transport. McCarthy et al. [1970] measured
mercury vapor at the ground surface over a mercury deposit
in the western

United

States and found

a 20-fold

increase

burden could account for these results.

Tanner [1959] measured radon in drill holes that intersected a uranium ore deposit in the southwestern United States.
an inverse

relation

between

radon

in the drill

hole

and barometric pressureon a daily basis, and concluded that

changesin barometric pressureexerted a pumping action that
caused an increase or decrease of Rn in the drill hole. He also

stated that "Experimental evidenceand theoretical treatment

of the migration of radon have led to the conclusion that
diffusion is not the mechanism whereby large amounts of
radon migrated from uraniferous rock into drill holes"
[Tanner, 1959]. He observed that the ore and enclosing rock
had appreciablepermeability and porosity and that, under the
influence of changing barometric pressure, air would move
along paths of greatest permeability and carry the radon with
it.

NOON

I00*f

[ .

(.nO
<I'r

NOON

/TEMPERATURE

?? %/

>_

MEECUE
13::

--)

.....

,,,

5 ......

k.N_/ o

--BAROMETRIC
PRESSURE

,,

..................... "'''-.......
..........................
,;..';'*":"';:;;::-:. ............
:;:--'-%:%-.:--
...................
_ .
;:'""'::':2:("J:'.;:;
:'
-;.
:.................
..:.-:;::::::;
::'";; ":';
..... ;.::b:-----.
......

in

Hg within 4 hours (Figure 3). The highest concentration of

mercury coincided with the maximum rate of fall of barometric pressure.These investigatorsconcludedthat changesin
barometric pressure exerted a pumping action, much like a
piston, that resultedin rapid releaseof Hg vapor to the atmosphere. Only mass transport of Hg through permeable over-

He found

4
........

24.0

, ,,

Fig. 3. Hourly variation of mercury in soil gas, temperature, and

barometric pressure, Silver Cloud mine near Battle Mountain,
Nevada [from McCarthy et al., 1970].

Fig. 4. Soilgassamplingprobewith air-tightfittingon top.

In a more recent study of measurements of Rn-222 in soil

gas over a uranium deposit, Tanner [1978] concludes,"Where
a uranium deposit lies more than a few meters below the
water table, the diffusion processis not adequate to result in
significant soil gas anomalies from migrating Rn-222; a
[mass] transport mechanism is required."
Although gas transport by diffusion has been demonstrated
at depth, particularly for hydrocarbons [Leythaeuser et al.,
1982, 1983], we think that many of the soil gas anomalies
observed

at or near the surface are the result of mass trans-

port. However, Tanner [1978] concludes that both diffusion

and mechanical transport play a role in migration of Rn.
SAMPLING

Gases are sampledby (1) extracting the gasesfrom the pore

spaceof soil, commonly at a depth of 0.5 to 1 m, (2) degassing
soil or rock by heating, or (3) placing artificial collectors beneath the surfaceof the soil to adsorb gasesover a period of
time. The most direct method is to samplegas in the soil pore
space.This can be accomplishedby augering to the desired
depth, placing a hollow tube in the hole, and sealingit off with
a packer [Arias et al., 1982]. After equilibration, a measured
volume of soil gas is pumped out for analysis. Another
method is to drive a hollow steel probe into the soil and
withdraw a small volume of pore spacegas [Lovell and Hale,
1983]. We useda sampleprobe developedfor He samplingby
the U.S. Geological Survey [Reirner and Bowles,1979] for the
soil gas studies reported here (Figure 4). The probe is driven
into the ground to a depth of 0.75 m by a sliding hammer on
the shaft of the probe. An air-tight fitting is placed over the

top of the probe,and 5 cm3 of soilgasis withdrawnthrougha

septum into a hypodermicsyringefor analysis.An advantage
of the probe is that a tight seal is usually attained, which
prevents dilution of the sample with surface air. Becausethe
concentration of gases in soil pore space is commonly low
(parts per million or parts per billion), measurementrequires
sensitiveanalytical methods.

12,330

MCCARTHYAND REIMER.'SOILGASESIN GEOCHEMICAL

EXPLORATION

Another means of sampling gasesis to degas rock or soil trometer. Recent analytical advancesallow us to measure the
samples,usuallyby heatingin closedcontainers.The desorbed trace concentrationsof gasesthat emanate from mineral degasesin the head space of the container are then analyzed. posits;for example,concentrationsof H2S and COS over sulSoilsare good natural collectorsof gas becauseclay and fide depositsare in the parts per billion range [Hinkle and

organicconstituentsof soils stronglyadsorbgases[Hinkle,

Kantor, 1978; Hinkle and Dilbert, 1984].

The average concentration of helium in the atmosphereis

5.240 ppm [Gluckauf, 1946; Oliver et al., 1984], and variations
rising from below the surface.The collectorsare placed in of lessthan 1% of this value have been found to be significant
invertedcupsunder the surfaceof the soil and left for several as indicators of energy resources[Roberts et al., 1975; G. E.
days or weeksbeforethay are retrievedand the gas is ana- Goldak, unpublished report, 1974]. Laboratory-based mass
lyzed.Hinkle and Kantor [1978] usedartificialzeolitesas gas spectrometricanalyseshave the sensitivityto detect suchsmall
variations, but are expensiveand time consumingto perform.
collectors. R. W. Klusman and K. J. Voorhees [Bisque, 1983]
have developedanother type of gas collector: a thin wire However, small, portable massspectrometersof the type typicoated with activated charcoal is buried in a cup 6-12 in cally used for leak detection in vacuum systems,and specifibelow the surface. After 1-2 weeks the collector is taken to the
cally designedto detect helium, have been found to provide
laboratoryfor analysisby massspectrometry.An older, simi- adequate sensitivity to analyze low, energy-related conlar samplingtechnique,the track-etchtechniqueusedto mea- centrations [Reimer, 1976; Dyck and Pelchat, 1977; G. E.
sure radon, has been successfullyapplied to exploration for Goldak, unpublished report, 1974]. Systems based on the
uranium and thorium [Gingrich,1984]. In all the gas-sampling small mass spectrometerhave been designedto operate in the
techniquesthat use collectors,the gasesare adsorbedover a field, analyzing a sample within several minutes, with a sensiperiodof time,thuslargelyeliminatingdiurnalvariationsthat tivity of 20 ppb helium.
The gas analyzer used in many of the studiesreported here
can strongly influence direct gas sampling. Higher concentrationsof gasesare commonly found when degassing is a quadrupole massspectrometerinterfaced with a programrock, soil, or artificial collectorsthan are found in soil pore mable calculator (Figure 5). In a quadrupole mass specspace;thuslesssensitive
analyticalmethodsmightbe usedfor trometer, ionized gas moleculesare acceleratedalong the axis
between four cylindrical rods. A combined electrostatic and
the desorbed gas.
Samplingof gasesfrom aircrafthas shownenrichmentof radiofrequency field imposed by the rods allows only those
SO2in air oversulfidedeposits[RouseandStevens,
1971] and ions with a specificmass-to-chargeratio to pass through. By
of Hg in air overmercuryand porphyry-copper
deposits[Mc- varying the voltages on the rods at a constant rate, ions of
Carthyet al., 1969].Theseexperimentalsurveysare suggestive various massesare sequentially scanned and measured. The
but provideno adequatebasisfor assessing
theeffectiveness
of analyzer can detect atomic or molecular speciesranging in
mass from 2 to 300 atomic mass units (amu); however, the
airborne sampling.
Norman [1983] analyzedgasesin fluid inclusionsfrom 10 range usedin this study was for gasspeciesfrom 2 to 100 amu.
Ag-Au epithermaldepositsand found that the principalin- This range is scannedin about 40 s.
1984; Hinkle and Dilbert, 1984].
Artificial collectors have also been used to collect gases

clusiongaseswere nitratedhydrocarbons,H2S, N2, and CO2.

Gases found in inclusions from gold-rich areas contained
> 1% H2S and were rich in CnHnNn,while epithermaldepositsin volcanicrockswith no Au, Ag, or sulfideminerals
contained no organics or H2S.
Gases found in fluid inclusions from a Mississippi Valley-

........--

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

....-..-:
.....
..,.
',.,
....

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

['3

.....

type depositin New Mexico includedCO2, C-C6 hydrocarbons,and N 2 [Norman et al., 1985]. Inclusionsrelatedto
sulfide mineralization were rich in H2S.

Hedenquistand Henley [1985] comparedfluid inclusionsin

active geothermalsystemswith inclusionsin base and preciousmetal ore deposits.They concludedthat "epithermalore
depositsform from hydrothermalsystemsanalogousto those
we see active today," and further that, "in any systemwhere
eithersalinityor gascontentis high, a baseor preciousmetal
ore depositmay be formed."
The three above-mentioned

studies contribute to an under-

standingof ore-formingprocesses
and fluidsand at leastimply
that gasesfoundin fluid inclusionsmay be usefulin explora-

': ..

'.'

'.

tion. Inclusionswith high gas contentsare more likely to be

associatedwith ore, and measurementof specificgases,suchas

H2S and CO2, and hydrocarbons

can indicatefavorableareas
[Norman, 1983].
ANALYSIS

The gas chromatograph is the most commonly used instrument for gas analysis.In the past few years, remarkable advancesin instrumentation and gas separation have made possible extremely sensitive and rapid gas analysis. Another instrument commonly used for gas analysis is a mass spec-

Fig. 5. Truck-mounted gas analyzer (quadrupole mass mass spectromete0 and programmable calculator. The quadrupole mass spectrometer is manuhctured by UTI Corporation of Sunnyvale, California; a model 100 C is interfaced with a Tectronic 31 calculator. The
complete assembly as hbdcated and installed in a field vehicle by
Pernicka Corporation of Fort Collins, Colorado. (Use of brand
names and manuhcturers' nameshere is for descriptivepurposesonly
and doesnot imply endorsementby the U.S. Geological Survey.)

MCCARTHYANDREIMER:SOILGASES
IN GEOCHEMICAL
EXPLORATION

The gas analyzer is mounted in a four-wheel drive vehicle,

and power is provided for the instrument by a 160-amp alter-

12,331

SOUTH

NORTH

4.0

nator, two 12-V batteries, and a dc-ac converter. About 1100

W of power is neededwhen the instrument is operating. Constant power is provided by running the vehicleengineat about

2.0

1200 rpm.

The limit of detection of the mass spectrometeris about 15

ppm for CH4, 0.01% for CO2, and < 1% for 02. Calibration
curves were prepared for CO2 and CH4 using varied concentrations of standard gases.A calibration curve was prepared for 02 by successivedilutions of air with N 2. Instrument responseis linear, and the reproducibility is + 5%. Ionization energy is 70 V. A permanent record of relative concentration is printed out on paper tape besideeach mass unit.
It takes about 7 min at each site to collect and analyze the soil
gassample.
Lovell and Hale [1983] used separate instruments to analyze soil air for CO2 and 02. These instrumentsare portable
and provide gas analysesin the field. Lovell and Hale demonstrated that these two gasesare good indicators of oxidizing
sulfide bodies' hence for detection of this type of deposit the
measurement of other gases is unnecessary.However, other
gasessuch as COS and H2S are also useful guides to sulfide
deposits [Hinkle and Kantor, 1978' Hinkle, 1984' Hinkle and
Dilbert, 1984], and volatile hydrocarbon gases are detected
above oil and gas deposits [Jones and Drozd, 1983]. Thus a
gas analysisfacility that is capable of analyzing many gasesat
once (suchas a massspectrometer)is advantageous.
FIELD

STUDIES

The use of soil gasesin geochemicalexploration is indicated

when searchingfor buried mineral deposits,particularly when
the suspecteddepositsare coveredby exotic overburdensuch
as glacial till, alluvial sediments,or desert sand. Sampling of
surface soils in these types of transported overburden (and
analysisfor ore-relatedtrace elements)may not reflect underlyingdeposits.In the examplecited below, a soil sampling
survey and analysis of the soils for several metals did not
reveal the depositin bedrock (H. Alminas, unpublisheddata,
1984]. However, soil gasescan reflectsuchdeposits.
An example showing the use of soil gasesover a massive
sulfide deposit in glaciated terrain is illustrated in Figures 6
and 7. The massivesulfide depositis near the town of Crandon in northern Wisconsin [May and Schmidt, 1982-l, in an
area where severalepisodesof glaciation have left as much as
65 m of glacial drift coveringthe bedrock.The depositoccurs
in metamorphicrocks,is a near-verticaltabular body, striking

G
I

Z14

B
i

!
i

Fig. 6. CO 2 and 0 2 in soil gas along traverseG-G' over the

Crandon massivesulfidedeposit,Wisconsin.Tick marks on horizontal axis show samplesites;samplinginterval is 15 m (50 ft), exceptfor
a 53-m (175-ft) gap in the middle, where no sampleswere collected.
Data points on the curvescorrespondwith sample sites(tick marks).
Total traverse length is about 360 m (1200 ft). Shaded blocks in
Figure 6a showlocation of ore, and the solid dot indicatesan isolated
lens of sulfide minerals.

N85W, and consists of a stratabound massive sulfide zone

and an underlying stringer zone at the suboutcrop contact

with the overlyingglacial deposits.We sampledsoil gas along
severaltraversesnormal to the strike of the elongate deposit
and well beyond the subcroparea of the deposit.Figure 6a is
a plot of percent CO2 in soil gas on one of these traverses
(G-G'). Sample intervals were 15 m (50 ft) except for a 53-m
gap in the center, where no samples were obtained. Total
length of the traverseis about 360 m (1200 ft). The high CO2
anomaly occurs over and to the north of the deposit. The
highest CO2 concentrationis 4% by volume compared with
0.035% in air. The 02 concentrationalong the same traverse
is shown in Figure 6b. In general,where the CO2 is anomalously high, the 02 is anomalouslylow. The lowest 02 concentration in the soil gas is only slightly more than half of its
concentration in air. The oxidation of sulfide minerals by
groundwater forms sulfuric acid, which attacks calcareous and

other minerals (e.g., CaCO3) and thereby releasesCO2. We

believe that both these anomalies

are a result of active oxida-

tion of sulfideminerals where CO2 is being produced and 02

is being consumed.
Carbon dioxide is also produced by decay of organic matter
in the soil, but measurement of gasesin similar soils away
from the sulfide deposit shows a background level averaging
less than 0.2% CO2. Because the surface environments are
similar, there is no evidenceto suggestthat biological production of CO2 would be any differentin soils whether over
the depositor beyondit. The fact that the CO2 concentrations
in soil gas over the depositare an order of magnitudehigher
than background argues against biological processesas the
mechanism producing the CO2 anomalies.
Another traversethat crossesthe deposit showssimilar patterns for CO2 and 02. A plot of CO2 in soil gas along this

12,332

MCCARTHY
ANDREIMER.'
SOILGASES
IN GEOCHEMICAL
EXPLORATION
SOUTH

traverse (D-D') is shown in Figure 7a. The sample interval is

15 m (50 ft) except for the last five sites, which are separated
by 30-m (100-ft) intervals. The total length of the traverse is
about 450 m (1500 ft). High CO2 anomalies occur over the ore
deposit and over an area to the north where no drill data are
available. A plot of 02 along the same traverse is shown in
Figure 7b. The low 02 anomalies coincide with high CO2
anomalies.One matched pair of low 02, high CO2 anomalies
occursover the ore deposit,and another is over someisolated

NORTH

1.0

sulfidelenses.Figures7a and 7b also illustratethe reproducibility of soil gas measurementson different days. The reproducibility is reasonablygood; although the absolute concentrations of gasesare not the same, the pattern is. Other
investigatorshave found similar antithetical CO2 and 02 pat-

ternsin soil gasesovermineraldeposits[Lovellet al., 1980,

1983; Lovell and Hale, 1983; Glebovskayaand Glebovskii,
1960].

Soil gas surveysat this and other depositshave revealed

volatile hydrocarbon gases;those that have been recognized
are methane, ethane, propane, and butane (and evidencefor
others exists). Other investigators [Carter and Cazalet, 1984]
have found hydrocarbon gases in rocks and used them as
pathfindersin mineral exploration.Figure 7c showsplots for
methane (CH4) along the same traverse shown in Figures 7a
and 7b. Although the background-to-anomalyratio is only
about 1:2, one of the anomalies occurs over the ore deposit
and another is to the north, coincidingwith the CO2 and 02
anomalies.The relationshipof hydrocarbon gasesand mineral
depositswill be discussedfurther.
Plots for CO2 in soil gas are shown in Figure 8 along a
traversecrossingover three roll-front uranium depositsin the
Powder River Basin, Wyoming. The sample interval was 75 m
(250 ft), and the length of the traverse is 1.6 km (1 mi). High

.I

.O5

ee

CO2 anomaliesoccur over the depositsand extend to the

north. The sandstonesthat host the depositsdip gently to the
north, and groundwater flow is also to the north. The groundwater may have been responsiblefor the northerly displacement of the CO2 soil gas anomalies. The traverse was run

1.6

SOUTH

NORTH

200
.'-',,''
. IO0t

Fig. 7. CO2, 02, and CH in soil gas along traverseD-D' over the
Crandon massivesulfidedeposit,Wisconsin.Tick marks on horizon-

tal axis showsamplesites;samplingintervalis 15 m (50 ft) exceptat

the far right, where it is 30 m (100 ft). Data points on the curves
correspondwith sample sites (tick marks). Total traverselength is
about 450 m (1500 ft). Shadedblocksin Figure 7a showlocation of
ore, and solid dots indicate isolated lenses of sulfide minerals. Solid

Fig. 8. CO 2 in soil gas along a traversecrossingthree roll-front

uranium depositsin the Powder River Basin,Wyoming.Tick marks
on horizontal axis show samplesites;samplinginterval is 75 m (250
ft), and total traverselengthis 1.6 km (1 mi). Solid dots showlocation
of depositsalong the traverse,and numbersin parentheses
indicate
depth to depositsin feet. Solid line showsresultsof samplingfrom
south to north in the morning; dashedline reflectssamplingfrom

and dashed lines representsampling and analysison two separate

north to south in the afternoon. The consistent offset between the two

days.

measurements
is due to an analyticalflaw (seetext).

MCCARTHY AND REIMER'SOIL GASESIN GEOCHEMICAL

EXPLORATION
10407'30"

4337 ' 30"

10352'30"

10400'

JPs

12,333

EXPLANATION
to Early Cretaceous age

.i"
'lSedimentary
rcks
f
Quaterna

..'

JPs

InyanKaraGroup
of Early
age

Cretaceous

j--

Sedimentary
rocksof Jurassic
to
Permian age

Contact
Fault

u-Upthrown side

d-Downthrown
side
Dashed where projected
// Isogram
showing
dissolvedhelium

z/% content
interval of
is ground
lx10 -b.water.Contour
cm He/cm H?O

DEWEY

3.54

TERRACE

(In vicinity of LongMountain

structuralZone,conto_u
interval

!s25x10-6
cm
3 He/cm H20)
lsogram dashed where infered

Uranium deposit -Includes some

undeveloped
prospects
Location of sample and dissolved

lm.
08 heliumcontent

10345',

43o30 '

4330'

JPs

QKs

I
Cheyenne

QKs

x 6

4322 '30"

QKs

13

Approximate

Mean

Declination

1974

QKs

KM

4315'
103o45 '

Fig. 9.

Dissolvedheliumdistributionin groundwaterof the Inyan Kara Group of the southernBlackHills.

toward the north in the morning (solid line) and toward the
south in the afternoon (dashedline). The nearly perfect offset
of the plots from each other led us to suspecta flaw in the
analytical procedure. We discoveredthat we had a "memory
effect" from the previous sample; some of the gas from the
previoussampleremainedin the inlet systemof the gas analyzer and contributed to the next measurement.We have since
corrected this sourceof error by thoroughly flushing the inlet
systemwith air between each sample.
RADON

Helium

and radon

of the radioactive

monly used in explorationfor uranium. Helium is formed

from the alpha particlesemitted during the decaysequences.
Both helium and radon have been used to explore for oil,

naturalgas,and geothermal
energyand havebeenusedin
experimentsto predict volcaniceruptionsand earthquakeactivity.

Informative
reviewsand casehistories
of radonusehave
beenpublishedfairly recently,as the techniquegainedrenewed interest from the energy-relatedresearchof the 1970's

AND HELIUM

are members

itself radioactive. Radon-222, with a half-life of 3.8 days is

derived from the U-238 series and is the isotope most com-

[Tanner,1978;Rubin,1978;Soonawala
and Telford,1980;
disinte-

gration seriesof uranium and thorium. They are inert gaseous

molecules' radon is the immediate progeny of radium, and is

Kraner et al., 1964]. The use of helium in exploration is a

recentdevelopment,and casehistoriesare few but informative
[Reimer et al., 1970; Dyck, 1976; Butt and Gole, 1984].

12,334

MCCARTHY AND REIMER' SOIL GASESIN GEOCHEMICALEXPLORATION

10352' 30"

10400'

43
37'30"
10407
'30"

...-

Inyan
Kara
Group
of Early

Cretaceous age

...

JPs

EXPLANATION

Sedimentary
rocks
of Quaternary
to Early Cretaceous age

Sedimentary
rocks
of Jurassic
to
Permian age
Contact
Fault u-Upthrown side

d
"

d-Downthrown
side
Dashed where projected

Line showing dissolved radon

content of ground water. Dashed

DEWEY

where inferred
Hachures indicate

TERRACE

value

closed

low

Contour interval = 10,50p

curies/liter H20
X

Uranium deposit -Includes

some

undeveloped
prospects
Location of sample and dissolved

1%8 Radon
content
4330 '
...

10345,,
43o30 ,

QKs

I
cheterme

QKs

4322' 30"

13

Approximate

Mean

Declination

1974

QKs
5

KM

QKs

4315'1
104 00'

4315,
10345'
,

Fig. 10. Dissolvedradon distributionin groundwaterof the Inyan Kara group of the southernBlack Hills.

The migrationand measurement

of heliumand radonhave mationon the flowrateandmixingof waterfromtherecharge
been the subject of much debate. The magnitude of external areas.

effectssuchas hydrologycontrollingplacementand meteorologycontrollingconcentrationgradientsis quitevariable.Also,

structuresuchas fractures,joints, and faultsplay a major part
in determiningthe localconcentrationof radon.
Althoughmany studiesdiscussthe useof helium and radon
separately, greater interpretative capabilities are achieved
when combinedwith other techniques.An exampleof the con-

Formationscroppingout o,ermostof the studyareaare,in

ascendingorder, the Skull Creek Shaleand Mowry Shaleof
Early Cretaceousage and the Belle Fourche Shale of Late
Cretaceousage.The formationsrangein thicknessfrom 45 to
75, 40 to 53, and 56 to 130 m, respectively.The Inyan Kara
Group, which containsthe uranium depositsof the Edgemont
district,lies immediatelybelow the Skull Creek Shale(Figure

juctive use of Rn and He is provided by the following field

study.Radon and helium analyseswereperformedon groundwater samplescollectedin the EdgemontUranium District in
the Black Hills of Wyoming and South Dakota [Bowleset al.,
1980]. Previous studies had yielded information on the
groundwater chemistry, and tritium data provided infor-

9).
Within the buried sedimeltarysection,the PahasapaLimestone of Mississippianage and the Minnelusa Formation of
Permianand Pennsylvanianagehave a significantbut indirect
role in the formation of the uranium deposits[Bowlesand
Braddock, 1963; Bowles, 1968]. Breccia pipes that bottom

MCCARTHY
ANDREIMER:
SOILGASES
IN GEOCHEMICAL
EXPLORATION

12,335

within the upper anhydritic part of the Minnelusa Formation

are major conduits for artesian recharge of the Inyan Kara
Group at the margin of the Black Hills.
Uranium deposits in the Edgemont Uranium District are
presentboth above and below the water table (Figure 9). Deposits lie above the water table at the outcrop of the Inyan
Kara Group on the hogbackeast of the study area.
Drilling has reportedly encountered economic deposits of
reduced uranium lying below the water table within the study
area southeastof Dewey (Figure 9).
Uranium is introduced into the Inyan Kara Group rocks
with the artesian recharge of calcium-magnesium sulfate
water, but during the middle to late Tertiary, significant
amounts of uranium probably were also introduced by downward percolating meteoroic waters that leached overlying tuffaceous sandstones and mudstones of Oligocene age. As
groundwater migrates downdip within the Inyan Kara, it is
modified by ion exchange and sulfate reduction to either a
sodium sulfate or a sodium bicarbonate type water, and redox
potentials decrease correspondingly. Reduction of sulfate in
the groundwater has been a major factor in creating a favorable environment for the precipitation of uranium. The depletion of dissolveduranium from the reducing groundwater has
prevented the detection of uranium depositsby an analysis of
uranium in solution.However, helium and radon generatedby
uranium depositscan be readily detected in reducing ground-

generation must lie updip toward the area of artesian recharge.

In summary, the dissolvedhelium detection techniquemay
be more difficult to apply to uranium exploration in areas of
very rapid groundwater flow, because insufficient time exists

waters.

for

Water sampleswere collected,and the gas in the headspace

was analyzed for radon and helium. Dissolved helium in the
groundwater samplesfrom the Inyan Kara ranges from 0.22

solved helium as the groundwater pases through a uranium

deposit.
However, the analysis of dissolved radon and helium in
groundwater complements other hydrochemical exploration
techniques used in the search for uranium. Anomalous concentrations of helium in reducing groundwaters in the study
area provided an exploration target, whereasanalysesof dissolved uranium during earlier investigationsyielded no indication of a uranium deposit.

x 10-6 to >130 x 10-6 cm3 He/cm3 H20. Low concentrationsof dissolvedhelium (<1 x 10-6 cm3 He/cm3
H20 ) commonly are presentnear the Inyan Kara outcrop and
less frequently occur within the structural zones (Figure 9).
Helium concentrationsgenerally increasedowndip to as much

as 2 x 10-6 cm3 He/cm3 H20. However, within the Long

Mountain

structural

zone the dissolved

helium

solvedheliumdetectedin the area(> 130 x 10-6 cm3 He/cm3

H20 ) occurredin the Long Mountain structural zone.
Dissolved radon in the groundwater from the Inyan Kara
Group ranges from 1 to 167 pCi/L (Figure 10). The general
distribution pattern for dissolvedradon (Figure 10) is the opposite of that for dissolvedhelium. For the most part, dissolved radon decreasesdowndip, ranging from as much as 53
pCi/L near the Inyan Kara outcrop to as little at 1 pCi/L west
of the CheyenneRiver. The largestconcentrationsof dissolved
radon (167 and 151 pCi/L)occur in the Dewey structural
zone.

Helium generatedin rocks of pre-Cretaceousage is apparently introducedinto the Inyan Kara Group within the artesian water from the Minnelusa Formation. Control samplesof
ascendingMinnelusa waters collected outside the study area
yielded dissolved helium and dissolved radon in con-

centrationsranging from 0.09 x 10-6 to 200 x 10-6 cm3

He/cm3 H20 and from 16 to 23 pCi/L, respectively.
The highhelium

was

found

in

the

water

within the mineralizedrock; that is, this time spanis not long
enough for the generation and accumulation of anomalous
concentrations of dissolved helium before the groundwater
flows out of the mineralized ground. Farther downdip within
and near the Long Mountain structural zone, anomalous con-

centrationsof dissolvedhelium (130 x 10-6 and 85 x 10-6

cm3 He/cm3 H20 ) providea favorablegeochemical

targetfor
uranium exploration. The absenceof high dissolvedradon in
the anomalous helium samplesindicatesthat the postulated
uranium depositsare not penetratedby the wells that yield the
anomalous concentrations of helium, but the site of helium

the accumulation

of anomalous

concentrations

of dis-

concentration

is mostly 1 order of magnitude higher than the concentrations

presentat comparabledistancesfrom the Inyan Kara outcrop
elsewherein the study area. The largest concentrationof dis-

est dissolved

Inyan Kara outcrop, and then the groundwater flows extremely rapidly downdip toward the confluence of the
Cheyenne River and Beaver Creek, where much of the water
apparently leaks upward and discharges into the surface
drainage. The westward flow rate was calculated from the
tritium data to be as much as 1 mi/yr. (14.4 m/d) [Gott et al.,
1974]. Low dissolvedhelium concentrationsin the groundwater extend far downdip within the area outlined by the
tongue of tritiated water. It is concluded that the high flow
rate allows the groundwater only a very short residencetime

from

Evans

HYDROCARBONS

ASSOCIATED WITH

MINERAL

DEPOSITS

As shown in Figure 7c, methane was found in soil gas over

the Crandon massive sulfide deposit. We have also found
methane and other light hydrocarbons in soil gas over
porphyry copper deposits, disseminated gold deposits, and
other types of deposits.Methane is the most abundant hydrocarbon

in all these cases. Its occurrence

can be accounted

for

by bacteriogenic production under anoxic conditions, as in

bogs or swamps.Enhalt 1-1974]has estimated that 80% of the
methane in the atmosphereis of recent biologic origin based

on measurementof 'C. However, the higher hydrocarbons

(C2 +) are not ordinarily produced by bacteria. At least some
of the light hydrocarbonsfound around mineral depositsmay
be produced by catagenesis,the same processwhereby oil and
gas are produced from kerogen. It is generally agreed [Hunt,
1979] that oil and gas are produced by thermal maturation of
complex organic matter (kerogen). The temperatures required
are about 80 to 200C; petroleum geologists refer to this
temperature range as the "oil window" [Waples, 1981]; that
is, the optimum temperature range for the production of oil.
At higher temperaturesthe oil degrades,and methane gas is
the dominant product. In many cases,the temperatures attained by hydrothermal systemsemplacing mineral deposits
are more than sufficient to "crack" organic matter in surrounding rocks, producing methane and other light hydro-

Plunge, where 4.0% helium has been detectedin the free gases.
A high rate of groundwaterflow in the Burdock area apparently is responsible for the absence of anomalous concentrations of dissolved helium, which would be expected carbons.
downflow from a uranium deposit reported to be of commerAn example that illustrates this concept is found in the
cial size and grade. A strong artesian recharge occursnear the work of Simoneitet al. [1979] in the Guaymas basin, Gulf of

12,336

MCCARTHY AND REIMER: SOIL GASESIN GEOCHEMICALEXPLORATION

California. Core samplesof organic-rich sedimentswere found

to have a strong petroliferousodor and when analyzed were
found to contain high concentrationsof gasoline-rangehydrocarbons(C2-C8). These investigatorsconcludedthat the high
geothermal gradient in the basin resulted in thermal maturation of organicmatter in the sediment.At another nearby site,
gasoline-rangehydrocarbons were formed by thermal stress
from sills and/or dikes that intruded the sediments[Simoneit
et al., 1979]. Rashid and McAlary [1977] also reported that
organic matter in Cretaceous sediments on the Scotian Shelf
thermally matured as a result of heat from a shallow salt
dome, producinggaseoushydrocarbons.
OIL AND GAS EXPLORATION

Measurement of hydrocarbon gases is increasinglybeing

used in the search for oil and natural gas fields. Two recent
reviewsillustrate the useof gasesin explorationfor oil and gas
and give casehistories [Jones and Drozd, 1983; Horvitz, 1985].
Developmentof sensitivegas chromatographswith flame ionization detectors that rapidly measure hydrocarbons in the
parts per billion range has made geochemicalexploration surveys for oil and gas routine [Mclver, 1984; Philp and Crisp,
1982]. By measuring gas compositions and ratios of light
hydrocarbons--methane, ethane, propane, and butane--one
can predict whether oil or gas is more likely to be discovered
in the subsurface[Jonesand Drozd, 1983]. The higher paraffin
homologs that are thermogenically produced are associated
with petroleum reservoirs,whereas a predominance of methane may indicate a natural gas reservoir.
Methane alone can be misleading,as it is produced by bacteria in the near-surfaceenvironment. However, ratios of C
/C2 + C3 can be used to distinguish thermogenic from bacteriogenic gas. Carbon isotopes are also used to elucidate the

origin of gases,as biogenicmethaneis highlydeplectedin 3C.

The origin of a gas can be establishdby plotting the ratio

C1/C2 -[-C3 againstx3C[Waples,1981].

In addition to representingseepageof hydrocarbon gases
from buried reservoirs,light hydrocarbonsmay form zoning
patterns around and over petroleum and mineral deposits
[Herbert, 1984]. When light hydrocarbons diffuse from a
source, the lightest (methane) will diffuse farther and more
rapidly than the higher homologs and will form haloes. Thus
careful measurementof these hydrocarbonsmay indicate the
direction of the source.(These haloes can be comparedwith
trace element zoning patterns found around mineral deposits
[Rose et al., 1979].) Hydrocarbon gasesextractedfrom rocks
have been found to correlate with mineral depositsin Ireland
[Carter and Cazalet, 1984]. These investigatorsfound that the
ratio of methane to heavier hydrocarbons is unusually high
around mineral deposits and that methane haloes extend for
many kilometers.
DISCUSSION AND CONCLUSIONS

Gases measured

at or near the surface can delineate

buried

mineral deposits,even through thick overburden.Sulfur gases,

CO2, and O2 can indicate oxidizing sulfidedeposits.Hydrocarbon gasesand helium have been successfullyused in the
search for petroleum and natural gas. Radon and helium gas
anomalies have led to the discoveryof uranium and thorium
deposits. Laboratory studies are revealing which gases are
given off by mineralsin simulatedweatheringconditions.Both
field and laboratory studies are increasingour knowledge of
gaseousemanations and our confidencein their use for exploration. Gasescan indicate buried depositswhere other geochemical samplingmedia fail, and this is particularly true for

those depositscovered by exotic overburden.As with any exploration technique, analysisof gaseswill be most usefulwhen
used in conjunction with other tecnhiques. For example,
where geophysical methods indicate a buried electrical conductor that may or may not be a mineral deposit, gas
measurementsmay resolvethe question.
The use of soil gasesin exploration, however, is not without
pitfalls. As Peachey et al. [1985, p. 201] points out, "...although orebodies could sometimes be detected clearly, in
someinstancesthe data were more equivocaland in othersthe
techniques failed." These investigators found that gases are
occludedin wet ground or in areas of impeded drainage. Ball
et al. [1985, p. 181] concludedfrom their studiesthat "soil gas
methods are least successfulfor deeply buried orebodies or
where the concentationof sulphideminerals in the deposit is
similar

to that in the host rock."

Gas measurementsseem to pose greater problems in wet

environments.Some indicator gasesthat are highly solublein
water (H2S, SO2, CO2) dissolve to form nonvolatile ionic or
molecularspecies.And as Roseet al. [1979, p. 499] note, only
a small fraction of these gases"would be likely to escapein
the vapor phase from an environment containing abundant
water." Despite this, CO2 anomalies in soil gas have been
found over a massivesulfidedepositin wet terrain [McCarthy
et al., 1986].
Meteorological variations affect the migration and concentration of soil gases, particularly in the near surface.
Reimer [1979] found that the concentration of helium in soil
gaswas affectedby wind speed,precipitation, and atmospheric
pumping, but at sampling depths below 1 m, theseeffectswere
minimal. The concentration of mercury vapor measuredat the
ground surfacewas found to changemarkedly throughout the
day as a result of changesin barometric pressure [McCarthy
et al., 1970]. McCarthy et al. [1986] also concluded that
meteorological changeshave little effect when soil gas is sampled at depths of 0.5 m or greater.
Gaseshave applicationsother than helping to locateenergy
resources.Gas distribution is frequently controlled by geologic
structure such as faults or joints. Variations in the gas flux
from deep faults may prove to be reliable precursorsfor the
prediction of earthquakes or volcanic eruptions [Reimer,
1981; Friedman and Reimer, 1986].
Increasingly sensitive and rapid analytical instruments
allow us to measuremany hitherto untestedgasesthat may be
significantin geochemicalexploration for many different types
of mineral deposits. We believe that gas geochemistrywill
contribute to the discovery of mineral deposits in the vast
covered

areas of the earth.

REFERENCES

Agricola,G., De Re Metallica, Froben, Basel,1556.(Translatedfrom

Latin by H. C. Hooverand L. H. Hoover,Dover, New York, 1950).
Arias, J., J. Lovell, and M. Hale, Developmentand applicationof
vapour geochemistrytechniquesto minerals exploration in overburdencoveredareasof northernChile,Rev. Geol.Chile,16, 23-80,
1982.

Arnold, M., and S. M. F. Sheppard,East Pacific Rise at latitude

21N: Isotopic compositionand origin of the hydrothermalsulphur, Earth Planet. Sci. Lett., 56, 148-156, 1981.

Ball, T. K., R. A. Nicholson,and D. Peachey,Gas geochemistry

as an
aid to detection of buried mineral deposits, Trans. Inst. Min.
Metall. Sect. B, 94, 181-188, 1985.

Barnes,I., and G. A. McCoy,Possiblerole of mantle-derived

CO2 in
causingtwo "phreatic"explosionsin Alaska, Geology,7, 434-435,
1979.

Bisque,R. E., New geochemicaltechniqueusedin the Denver Basin,

West. Oil Rep., 40, 23-26, 1983.
Bolviken, B., and O. Logn, An electrochemicalmodel for element

MCCARTHY
ANDREIMER:
SOILGASES
IN GEOCHEMICAL
EXPLORATION

12,337

distribution around sulphide bodies, in GeochemicalExploration

1974, edited by I. L. Elliott and W. K. Fletcher, pp. 631-648, Else-

Herbert, S., Irish ideas improve mineral reconnaissance,Min. Mag.,

vier, New York, 1975.

Hinkle, M. E., Volatile constituentsof soils and soil gasesover the

sulfide depositsat Johnson Camp, Arizona, U.S.A., paper presented
at the 1984 International Chemical Congress of Pacific Basin Societies, Honolulu, Hawaii, Dec. 16-21, 1984.

Bowles, C. G., Theory of uranium deposition from artesian water in

the Edgemont District, southern Black Hills, Black Hills Area,
South Dakota, Montana, Wyoming, Guideb. Wyo. Geol. Assoc.
Annu. Field Conf.,20, 125-130, 1968.
Bowles, C. G., and W. A. Braddock, Solution breccias of the Minnelusa Formation in the Black Hills, South Dakota and Wyoming,
Short Papers in Geology and Hydrology, U.S. Geol. Surv. Prof.
Pap. 475-C, C91-C95, 1963.
Bowles, C. G., G. M. Reimer, J. M. Been, and D. G. Murrey, Helium
investigationsin the Edgemont uranium district, southern Black
Hills, South Dakota and Wyoming, U.S. Geol. Surv. Open File Rep.
80-1077, 27 pp., 1980.
Butt, C. R. M., and M. J. Gole, Helium determination in mineral
exploration, Rep. NERDDP/EG/84/271, 351 pp., Dep. of Resourc.
and Energy, Canberra, Australia, 1984.
Carter, J. S., and P. C. D. Cazalet, Hydrocarbon gases in rocks as
pathfinders for mineral exploration, Prospectingin Areas of Glaciated Terrain 1984, Trans. Inst. Min. Metall. Sect. B, 93, 11-20,
1984.

Craig, H., and J. E. Lupton, Primordial neon, helium, and hydrogen

in oceanic basalts, Earth Planet. Sci. Lett., 31, 369-385, 1976.

Craig,H., W. B. Clarke,and M. A. Beg,Excess3He in deepwater on

the East Pacific Rise, Earth Planet. Sci. Lett., 26, 125-132, 1975.

Dyck, W., The use of helium in mineral exploration, J. Geochem.

Explor., 5, 3-20, 1976.
Dyck, W., and J. C. Pelchat, A semi-portablehelium analysisfacility,
Report of Activities, Part C, Geol. Surv. Can. Pap. 77-1C, 85-87,
1977.

Dymond, J., and L. Hogan, Noble gas abundancepatterns in deepsea basalts--Primordial gasesfrom the mantle, Earth Planet. Sci.
Lett., 20, 131-139, 1973.
Enhalt, D. H., The atmospheric cycle of methane, Tellus, 26, 58-70,
1974.

Friedman, I., and G. M. Reimer, Helium at Kilauea, U.S. Geol. Surv.

Prof. Pap. 1350, in press,1986.
Gerlach, T. M., Chemical characteristicsof the volcanic gases from

Nyiragongo lava lake and the generation of CH,-rich fluid inclusions in alkaline rocks, J. Volcanol. Geotherm. Res., 8, 177-189,
1980a.

Gerlach, T. M., Evaluation of volcanic gas analysesfrom Kilauea

Volcano, J. Volcanol. Geotherm.Res., 7, 295-317, 1980b.

Giggenbach, W. F., and F. LeGuern, The chemistry of magmatic

gases from Erta'Ale, Ethiopia, Geochim. Cosmochim. Acta, 40,
25-30, 1976.

150, 50-54, 1984.

Hinkle, M. E., and G. A. Dilbert, Gases and trace elements in soils at

the North Silver Bell deposit, Pima County, Arizona, J. Geochem.

Explor., 20, 323-336, 1984.

Hinkle, M. E., and J. A. Kantor, Collectionand analysisof soil gases

emanatingfrom buried sulfidemineralization,JohnsonCamp area,
CochiseCounty, Arizona, J. Geochem.Explor., 9, 209-216, 1978.
Horvitz, L., Geochemical exploration for petroleum, Science, 229,
821-827, 1985.

Howard, B., A. Mesereau, and P. Mariani, Analysis of gas samples

from Mount St. Helens, Am. Lab., 117-118, 1980.
Hunt, J. M., Petroleum Geochemistryand Geology,W. H. Freeman,
San Francisco, Calif., 1979.

Jonasson,I. R., and R. W. Boyle, Geochemistry of mercury and origins of natural contamination of the environment, Can. Min.
Metall. Bull., 65, 32-39, 1972.
Jones,V. T., and R. J. Drozd, Predictionsof oil or gas potential by
near-surfacegeochemistry,Bull. Am. Assoc.Pet. Geol., 67, 932-952,
1983.

Kasimov, N. S., M. I. Kovin, Y. V. Proskuryakov, and N. A.

Shmel'kova,Geochemistryof the soilsof fault zones(exemplifiedby
Kazakhstan), Soy. Soil Sci., 11, 397-406, 1978.
Kesler, S. E., Soil and fluid inclusiongas analysisin mineral exploration, paper presentedat the 1984 International Chemical Congress
of Pacific Basin Societies,Honolulu, Hawaii, Dec. 16-21, 1984.
Kraner, H. W., G. L. Schroeder, R. D. Evans, Measurements of the

effects of atmosphericvariables on Radon-222 flux and soil gas

concentrations,in The Natural RadiationEnvironment,edited by J.
A. S. Adams and W. M. Lowder, p. 191, University of Chicago
Press,Chicago,Ill., 1964.
Krauskopf, K. B., Introduction to Geochemistry,McGraw Hill, New
York, 1979.

Kristiansson,K., and L. Malmquist, A new model mechanismfor the

transportation of radon through the ground, paper presented at
50th Annual International Meeting, Soc.of Explor. Geophys.,Houston, Tex., Nov. 16-20, 1980.

Kvenvolden, K. A., and G. E. Claypool, Origin of gasoline-range

hydrocarbonsand their migration by solution in carbon dioxide in
Norton Basin, Alaska, Bull. Am. Assoc.Pet. Geol.,64(7), 1078-1086,
1980.

Leythaeuser, D., R. G. Schaefer, and A. Yuk!er, Role of diffusion in

primary migration of hydrocarbons, Bull. Am. Assoc.Pet. Geol., 66,

Gingrich, J. E., Radon as a geochemicalexploration tool, J. Geochem.

408-429, 1982.
Explor., 21, 19-39, 1984.
Leythaeuser, D., R. G. Schaefer,and H. Pooch, Diffusion of light
Glebovskaya, V. S., and S.S. Glebovskii, The possibility of applihydrocarbons in subsurfacesedimentary rocks, Bull. Am. Assoc.
cation of gas surveys in prospecting for sulfide deposits, Transl.
Pet. Geol., 67, 889-895, 1983.
603, Geol. Surv. of Can., Ottawa, 1960.
Lovell, J. S, and M. Hale, Application of soil-air carbon dioxide and
Gluckauf, E., A microanalysisof the helium and neon contents of air,
oxygen measurements to mineral exploration, Trans. Inst. Min.
Proc. R. Soc. London, 185, 89-98, 1946.
Metall. Sect. B, 92, 28-32, 1983.
Gold, T., Terrestrial sourcesof carbon and earthquake outgassing,J.
Lovell, J. S., M. Hale, and J. S. Webb, Soil air disequilibriaas a guide
Pet. Geol., (3), 3-19, 1979.
to concealedmineralization at Keel, Eire, Prospectingin Areas of
Gott, G. B., D. E. Wollcott, and C. G. Bowles, Stratigraphy of the
Glaciated Terrain 1979, Trans. Inst. Min. Metall. Sect. B, 45-50,
Inyan Kara Group and localization of uranium deposits,southern
1979.
Black Hills, South Dakota and Wyoming, U.S. Geol. Surv. Prof.
Lovell, J. S., M. Hale, and J. S. Webb, Vapour geochemistryin minPap. 763, 1974.
eral exploration, Min. Mag., 143, 229-239, 1980.
Govett, G. J. S., Detection of deeply buried and blind sulfide deposits Lovell, J. S., M. Hale, and J. S. Webb, Soil air carbon dioxide and
by measurement
of H and conductivityof closelyspacedsurface
oxygen measurementsas a guide to concealed mineralization in
soil samples,J. Geochem.Explor., 6(3), 359-382, 1976.
semi-arid and arid regions,J. Geochem.Explor., 19, 305-317, 1983.

Govett, G. J. S., and C. Y. Chork, Detectionof deeplyburiedsulphide Lupton, J. E., and H. Craig, ExcessHe3 in oceanicbasalts--Evidence
depositsby measurementof organiccarbon,hydrogenion, and
for terrestrial primordial helium, Earth Planet. Sci. Lett., 26, 133conductancein surfacesoils, Prospectingin Areas of Glaciated
139, 1975.
Terrain 1977, Trans. Inst. Min. Metall., 49-55, 1977.
Greenland, L. P., W. I. Rose, and J. B. Stokes, An estimate of gas
emissionsamd magmatic gas content from Kilauea volcano, Geochim. Cosmochim.Acta, 49, 125-129, 1985.
Hale, M., and C. J. Moon, Geochemical expressionsat surface of
mineralization concealedbeneath glacial till at Keel, Eire, in Prospectingin Areas of GlaciatedTerrain 1982, edited by P. H. Davenport, pp. 228-239, Canadian Institute of Mining and Metallurgy,
Montreal, 1982.

Hedenquist, J. W., and R. W. Henley, The importance of CO2 on

freezing point measurementsof fluid inclusions: Evidence from
active geothermalsystemsand implicationsfor epithermal ore deposition, Econ. Geol., 80, 1379-1406, 1985.

Lupton, J. E., and H. Craig, A major helium-3 source at 15Son the

East Pacific Rise, Science,214, 13-18, 1981.

May, E. R., and P. G. Schmidt, The discovery,geology, and mineralogy of the Crandon Precambrian massivesulfide deposit, Wisconsin, Precambrian Sulfide Deposits, H. S. Robinson Mem. Vol., Spec.
Pap. Geol. Assoc.Can., 25, 446-480, 1982.
McCarthy, J. H., Jr., Mercury vapor and other volatile componentsin
the air as guides to ore deposits,J. Geochem.Explor., 1, 143-162,
1972.

McCarthy, J. H., Jr., W. W. Vaughn, R. E. Learned, and J. L.

Meuschke, Mercury in soil gas and air--A potential tool in mineral
exploration, U.S. Geol. Surv. Circ. 609, 1-16, 1969.
McCarthy, J. H., Jr., J. L. Meuschke, W. H. Ficklin, and R. E.

12,338

MCCARTHY AND REIMER:SOIL GASESIN GEOCHEMICAL

EXPLORATION

Learned, Mercury in the atmosphere,Mercury in the Environment,

U.S. Geol. Surv. Profi Pap., 713, 37-39, 1970.
McCarthy, J. H., Jr., R. N. Lambe, and J. A. Dietrich, A casestudy of
soil gasesas an exploration guide in glaciated terrain--Crandon
massivesulfidedeposit,Wisconsin,Econ. Geol.,81, 408-420, 1986.
McGee, K. A., A. J. Sutton, and M. Sato, Observationsof hydrogen
gas eventsprior to volcanic seismicity,paper presentedat the 1984
International Chemical Congressof Pacific Basin Societies,Honolulu, Hawaii, Dec. 16-21, 1984.
McIver, R. D., Near-surface hydrocarbon surveysin oil and gas exploration, Oil Gas d., 82, 115-117, 1984.
Norman, D. I., Gases in epithermal Ag-Au ore fluids (abstract), GSA
Abstr. Programs,15, 654, 1983.
Norman, D. I., T. Wupoa, B. R. Putnam III, and R. W. Smith, Mississippi Valley-type deposit, New Mexico: Insight from composition
of gasesin fluid inclusions,Can. Mineral., 23, 353-368, 1985.
Oliver, B. M., J. G. Bradley, and H. Farrar IV, Helium concentration
in the earth's lower atmosphere, Geochim. Cosmochim.Acta, 48,

Roberts, A. A., I. Friedman, T. J. Donovan, and E. H. Denton,

Helium survey,A possibletechniquefor locating geothermal reservoirs, Geophys.Res. Lett., 2, 209-210, 1975.
Roedder, E., Composition of fluid inclusions, U.S. Geol. Surv. Profi
Pap. 440-rid, 1972.
Rose, A. W., H. E. Hawkes, and J. S. Webb, Geochemistryin Mineral
Exploration, 657 pp., Academic, New York, 1979.
Rouse, G. E., and D. N. Stevens, The use of sulfur dioxide gas geochemistry in the detection of sulfide deposits(abstract), Min. Eng.,
22, 65, 1971.
Rubin, R. M., Literature survey on radon distributions in soil and air,
Rep. GJBX-110-80, 63 pp., U.S. Dep. of Energy, Grand Junction,
Colo., 1978.
Sakai, H., T. J. Casadevall, and J. G. Moore, Chemistry and isotope
ratios of sulfur in basalts and volcanic gasesat Kilauea Volcano,
Hawaii, Geochim.Cosmochim.Acta, 46, 729-738, 1982.
Sato, M., K. A. McGee, and A. J. Sutton, Anomalous hydrogen emissionsalong seismogenicfaults in California, paper presentedat The
1759-1768, 1984.
1984 International Chemical Congress of Pacific Basin Societies,
Peachey, D., R. A. Nicholson, and T. K. Ball, Discussion on use of
Honolulu, Hawaii, Dec. 16-21, 1984.
carbon dioxide and oxygenin soil gasesto detect hidden orebodies, Shepherd, E. S., The gasesin rocks and some related problems, Am. d.
Trans. Inst. Min. Metall. Sect. B, 94, 201-203, 1985.
Sci., 35-A, 311-351, 1938.
Philp, R. P., and P. T. Crisp, Surfacegeochemicalmethodsused for
Shigiura, T., Y. Mizutani, and S. Dana, Fluorine, chlorine, bromine,
oil and gas prospecting--A review, d. Geochem.Explor., 17, 1-34,
and iodine in volcanic gases,d. Earth Sci. Nagoya Univ., 11(2),
1982.
272-278, 1964.
Pineau, F., M. Javoy,and Y. Bottinga,C3/C2 ratios of rocksand Simoneit, B. R., M. A. Mazurek, S. Brenner, P. T. Crisp, and I. R.
Kaplan, Organic geochemistryof recent sedimentsfrom Guaymas
inclusions in popping rocks of the mid-Atlantic ridge and their
Basin,Gulf of California, Deep Sea Res.,26A, 879-891, 1979.
bearing on the problem of isotopic compositionof deep-seated
Soonawala, N.M., and W. M. Telford, Movement of radon in overcarbon, Earth Planet. Sci. Lett., 29, 413-421, 1976.
burden, Geophysics,45, 1297, 1980.
Pogorski,L. A., and G. S. Quirt, Helium emanometryin exploringfor
Stahl, W., E. Faber, B. D. Carey, and D. L. Kirksey, Near-surface
hydrocarbons,1, in UnconventionalMethods in Explorationfor Peevidence of migration of natural gas from deep reservoirs and
troleum and Natural Gas, edited by B. M. Gottleib, pp. 124-135,
SMU Press, Dallas, Tex., 1981.
sourcerocks, Bull. Am. Assoc.Pet. Geol.,65(9), 1543-1550, 1981.
Rashid, M. A., and J. D. McAlary, Early maturation of organic Tanner, A. B., Meteorological influence on radon concentration in
matter and genesis of hydrocarbons as a result of heat from a
drill holes, Min. Eng., 11, 706-708, 1959.
shallow piercement salt dome, d. Geochem.Explor., 8, 549-570,
Tanner, A. B, Radon migration in the ground: A review, in The
1977.
Natural Radiation Environment, edited by J. A. S. Adams and W.
M. Lowder, pp. 161-190, University of Chicago Press,Chicago,II1.,
Reimer, G. M., Design and assemblyof a portable helium detector for
1964.
evaluation as a uranium exploration instrument, U.S. Geol. Surv.
Tanner, A. B., Radon migration in the ground: A supplementary
Open File Rep. 76-398, 18, 1976.
review, U.S Geol. Surv. Open File Rep. 78-1050, 1978.
Reimer, G. M., The use of soil gas helium concentrationsfor earthTaylor, C. H., S. E. Kesler, and P. L. Cloke, Sulfur gasesproduced by
quake prediction: Studiesof factors causingdiurnal variation, U.S.
the decompositionof sulfide minerals: Application to geochemical
Geol. Surv. OpenFile Rep. 79-1623, 68, 1979.
exploration, d. Geochem.Explor., 17, 165-186, 1982.
Reimer, G. M., Helium soil-gasvariations associatedwith recent cenfor Exploration Geologists,Burgess
tral California earthquakes: Precursor or coincidence?,Geophys. Waples, D., Organic Geochemistry
Publishers,Minneapolis, Minn., 1981.
Res. Lett., 8, 433-435, 1981.
Welhan, J. A., and H. Craig, Methane and hydrogen in East Pacific
Reimer, G. M., and C. G. Bowles, Soil gas helium concentrationsin
Rise hydrothermal fluids, Geophys.Res. Lett., 6(11), 829-831, 1979.
the vicinity of a uranium deposit,Red Desert, Wyoming, U.S. Geol.
White, D. E., and G. A. Waring, Volcanic emanations, U.S. Geol.
Surv. Open File Rep. 79-975, 1979.
Surv. Prof. Pap. 440-K, 1963.
Reimer, G. M., and J. K. Otton, Helium in soil gas and well water in
Zies, E.G., The concentration of the less familiar elements through
the vicinity of a uranium deposit, Weld County, Colorado, U.S.
igneousand related activity, Am. d. Sci., 35A, 385-404, 1938.
Geol. Surv. Open File Rep. 76-699, 1976.
Reimer, G. M., E. H. Denton, I. Friedman, and J. K. Otton, Recent
J. H. McCarthy, Jr., and G. M. Reimer, U.S. Geological Survey,
developmentsin uranium exploration using the U.S. Geological
Box 25046, MX/912, Denver Federal Center, Denver, CO 80225.
Survey's mobile helium detector, d. Geochem.Explor., 11, 1-12,
1979.

Roberts, A. A., Helium emanometryin exploring for hydrocarbons,2,

in UnconventionalMethods in Explorationfor Petroleumand Natural Gas, edited by B. M. Gottleib, pp. 136-149, SMU Press,Dallas,
Tex., 1981.

(ReceivedNovember 27, 1985;

revised May 12, 1986;
acceptedMay 28, 1986.)