An Acid Fumarolic Gas 

From Kilauea Iki 

Hawaii 

By K. J. MURATA 

THE 1959-60 ERUPTION OF KILAUEA VOLCANO, HA WAil 

GEOLOGICAL SURVEY PROFESSIONAL PAPER 537-C 

A study of a highly acid Jumarolic 

gas and of its chemical effect on 

basaltic pumice 

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1966 
UNITED STATES DEPARTMENT OF THE INTERIOR 

STEW ART L. UDALL, Secretary 

· GEOLOGICAL SURVEY 

William T. Pecora, Director 

For sale by the Superintendent of Documents, U.S. Government Printing Office 

·Washington, D.C. 20402- Price 15 cents (paper cover) 
1.. 

CONTENTS 

Abstra~t------------------------------------------- Introduction ______________________________________ _ 

Acknowledgments _____________________________ :... ____ _ 

Location of fumarole and method of collecting the sample_ 

Composition of the condensate ___ ----- ______________ _ 

Page 

C1 

1 

1 

1 

2 

Acid alteration of the pumice ________________________ _ 

Selenium content of the sulfur _______________________ _ Summary _________________________________________ _ 

References ________________ --_---------·_----- ____ - __ 

TABLES 

Page 

C4 

5 

5 

6 

Page 

TABLE 1. Chemical analysis of a steam condensate from the pumice cone of Kilauea Iki___ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ C2 

2. Composition of steam condensates, volcanic gases, volatiles extracted from lavas, and sea water________________ 3· 

3. Analyses of altered and original pumice from Kilauea Iki_ ________________________________________________ :_ 4 

4. Selenium content of native sulfur from Kilauea VolcanO--------------------------------------------------- 5 

III 

7~9-f\~7-A!'i 
·THE- ·1959-60 ERUPTION OF KILAUEA VOLCANO, HAWAII 

AN 'ACID Ft1MAROLIC GAS FROM KILAUEA IKI, HAWAII' 

ABSTRACT 

A condensate of fumarolic gases, collected·from the degassing 

pumice-cinder cone of Kilauea Iki during the 1959 eruption, 

proved to be essen.tially 2N HOI: The acid gases were observed 

to decompose surficial pumice thoroughly, leaving opaline pseudomorphs of pumice fragments and forming subsurface nodular 

deposits of mixed chlorides of aluminum, iron, magriesium, and 

other elements leached out of the pumice. Native sulfur deposited around the fumaroles contained almost 3 percent selenium. 

INTRODUCTION 

The purpose of this paper is to record the composition of a single sample of a fumarolic gas collected on 

the pumice-cinder cone of Kilauea Iki, formed during 

the 1959 summit eruption of Kiiauea Volcano, and to 

describe the chemical alteration of basaltic pumice by 

this gas. When condensed,. the water-rich gas formed 

a solution that was essentially 2N HOI. Only a few 

of the high-temperature Kilauea gas. samples analyzed 

by Shepherd ( 1921, 1938) were rich in chlorine, most 

of them containing more sulfur compounds, such as Sz, 

SOz, and S03 , than chlorine. The emphasis placed in 

recent decades on gases from the solfatara at Sulphur 

Bank on I{ilauea (Macdonald, 1944; Payne and Mau, 

1946; Naughton and Terada, 1954) has also tended to 

draw attention away from chlorine toward carbon di~ 

oxide, hydrogen sulfide, and other components that predominate in low-temperature exhalations. 

That the composition of fumarolic gases is temperature dependent has been known for a long time from the 

investigations of Deville and Leblanc ( 18;>8) , ,Ail en 

and Zies ( 1923) , N emoto and others ( 1957}, Ellis 

(1957), and Naboko ·(19[)9), among others. ·Thus, a 

single sample represents only a brief interval in the 

history of a cooling chemical system th~t changes GOntinuously. The nature o.f the sample _from Kilauea Iki 

indicates thq,t it represents'an early high-temperature 

exhalation. · 

AC~NOWLEDGMENTS. 

Many of the writer's colleagues have contributed information, samples, and analyses for this study. The 

789-687~65----2 

COIJ.tributions are aclmowledged individually at appropriate places in the text. R. T. Okamura helped greatly 

with the collection of the samples. .W. U. Ault, D. H. 

Richte'r, and D. E. White provided helpful advice and 

data throughout the course of the investigation. 

LOCATION OF FUMAROLE AND METHOD OF 

COLLECTING THE SAMPLE 

The gas sample was collected on the large cone of 

pumice, cinder, and spatter that formed downwind 

from the lava fountain at Kilauea Iki. Hot pyroclastics, many incandescent and some still fluid, were 

heaped continuously for a week on the bluff above the 

vent during the first phase of the eruption. The resultant cone was first explored on November 23, 1959, 

2 days after the end of the first eruptive phase, and 

samples of the gas and altered pumice were collected 

on the summit of the cone at that time.· Further additions of pyroclastic debris to the cone were made intermittently dur.ing 16 spasmodic eruptions that occurred 

subsequently .over a ·period of a month. 

The cone is a "rootless" structure perched on the rinn 

of Kilauea Ild pit crater and has no direct connection 

'to an underground supply of magma or magmatic gas. 

Owing to the low heat conductivity of the outermost 

cooled blanket of pumice and cinder, the interior part 

remained hot after the eruption, with only negligible 

cooling in the 2 days between the end of activity a.nd 

sampling. It is supposed that magmatic gases dissolved 

in basaltic glass were expelled through devitrification 

and crystallization of the glass as the cone cooled slowly. 

Acid vapors were being exhaled at the summit along 

minor faults that formed as a result of slumping and 

sliding of the cone into the pit crater. The fault lines 

were delineated on the surface by conspicuous yellow 

deposits of native sulfur and decomposed pumice. ·The 

localization of gas emission along faults may have been 

due to the presence within the cone of relatively impermeable layers of spatter material which were 

fractured locally by the faults. 

Cl 
C2 THE 1959-60 ERUPTION OF KILAUEA VOLCANO, HAWAII 

TABLE 1~-Chemical analysis of a steam condensate from the pumice cone of Kilauea I ki 

[Analysts: S. M. Roger and H. C. Whitehead] 

Constituent Parts per million Equi~il~!s per 

Cations 

Fortunately for our purpose, there was very little 

rain during the first eruptive phase of IGlauea Iki. 

During this period only about an inch fell, and for 2 

days prior to the date of gas collection, less than 0.1 inch 

(W. U. Ault, written commun., 1961). It is therefore 

believed that the fumarolic gas was almost entirely of 

magmatic origin and had a 1ninimum of contamin·ation 

b t y me · t H · · · t d d H (totalacidity) ------------------ . eonc wa er. owever, some a1r was 1n ro uce Na ___________ . _________________ _ 1, 910 1,894.84 

4.9 . 21 

owing to the generally porous nature of the pumice- K------------------------------

cinder cone (Ault, 1960). The separate question of pos- ~H~-~~===================-===== 

1.1 . 03 

.o . 0 

0 0 

sible contamination of the magma by sea water. deep· · .. As,.-.,.-._.:. __________________ ------

within the volcano is considered later. , . TotaL--------------------I---.----I-----

.o . 0 

The gas sample was collected as a steam condensate. 

A spot marked by· copious evolution of steam was first 

selected, and the temperature of the gas was determined 

· by W. U. Ault to be 328° Cat a depth of 1112 feet beneath the surface.· A hole about 2 feet deep and 1 foot 

]n diameter was then dug, and a large inverted glass 

funnel provided with a long glass stem was buried in 

the hole. The stem of the funnel was connected to an 

inclined length of .Pyrex glass tubing 8 feet long, which 

served as an air condenser. A 500-n1l (milliliter) 

Ehrlenmeyer Pyrex flask immersed in a bucket of water 

served as the receiver, and the gas was led to it by pumping on an outlet in the stopper of the flask with a suction 

pump, manually operated. Periodic addition of solid 

·carbon dioxide kept tlie water in the bucket reasonably · 

cool, and condensation of steam was almost complete. 

After several hours of .pumping, about 450 ml of condensate was obtained. 

A solution of cadmium nitrate left exposed in a beaker 

within the steaming area of the collection site for 2 

hours gave·no indication of the presence of hydrogen 

sulfide. The strong choking odor of sulfur dioxide ·must 

have a:ffected.(mr sense of smell because we did not recognize the presen9e of hydrochloric acid in the issuing 

vapors. Some elemental sulfur condensed with water 

in the air condense:r; ~ : Part of the sulfur was drawn into 

the receiver·, but that remainirig in the a!r condenser 

was not recovered. . .. 

COMPOSITION OF THE CONDENSATE 

The chemical analysis of the steam condensate, made 

by S. M. Rogers. and H. C. Whitehead, is presented in 

table 1. The condensate is virtually 1.9N HCL . The 

content of sulfate is a measure of the total quantity of 

both sulfurous· and sulfuric acid in the fumarolic vapor. 

Although the elemental sulfur that deposited in the air 

condenser was not recovered, there is no doubt that 

chloride. -w:as more abundant than sulfur and its 

compounds.· 

Anions 

Cl ___________ :._ ·---------------

Br-------------------------·- _ F 

1---------------------~-------·- _____________________________ _ 

804----------------·----------- B _____________________________ _ 

Si02 S ---------------------------- (elemental) ___________________ _ Se (elemental) __________________ _ 

TotaL----------------~---

1,926.0 1,895.08 

68,600 1,934.52 

246 3.08 

4.5 .04 

20 1. 05 

430 . 8. 95 

3.2 ---------·--- . 0 ------------ 400+ ------------ 12+ ------------ 1----------1---------

69,715. 7+ 1,947.64 

Density at 20°C ___________________ grams per milliliter __ l.031 

A small part of the sample was neutralized with 

sodium hydroxide, and the resulting salt was analyzed 

spectrographically by Joseph Ha:ffty in order to detect 

constituents other than those reported in table 1. A 

blank sample prepared by neutralizing reagent-grade 

hydrochloric acid with the same sodium hydroxide was 

analyzed at the same time. The salt prepared from ~he 

· fumarolic condensate was found to contain no element 

at a significantly higher concentration than the blank. 

Although an extens~ve discussion of the Kilauea Iki 

condensate does npt seem warranted, comparison~ .with 

a . few previously described volcanic gases and gases 

extracted from Kilauea· basalts will serve to place the 

nature of the condensate in a proper light. The .comparisons are made in table 2 in which th~ elemental 

compositions are expressed as gram atoms per 1,000 

grams of water. A natural fumarolic condensate very 

similar to the sampl!3 from Kilauea Iki has been described from the andesitic volcano Ebeko in the Kuriles 

(Ivanov, 1957). Its. composition is given in column 2 

of table 2. Another somewhat similar material is a 

cond~nsate obtained during the 1950-51 eruption of the 

basaltic volcano. Oshima in Japan (Iwasaki, 1951). 

It proved to be a strong solution of ferric ch.loride in 

1.4N HCl and contained no sulfate. A part of the ferric 

chloride of this material may have been derived from 

the iron pipe that was used in it~ c~llection. 
AN ACID 1fUMAROLIC 9AS FROM KILAUEA IIO C3 

TABLE 2.-Composition of steam condensates, volcanic gases, volatiles extracted from lavas, and sea water 

[Gram atoms per l,doo grams water] 

Steam condensates Kilauea gases Volatiles in Kilauea lavas Sea water 

2 3 4 '5 6 7 8 9 10 

Element 

F---------~-------------- 6. 86 20. 90 

01-----~-----------------

0. 0011 ' 

2. 0140 

·0. 0039. 

1. 8508 6. 03 1. 53 0. 81 

15 

5 1. 65 1. 71 

19. 49 

1. 08 

0. 000068 

. 5544 Br ______________________ _ . 0032 . 0006 . 00083 

8 

~------------------~----- _______________________ _ 

0---------~-------------

. '00004 

. 0177+ 

Present 

.. 00031 

. 000003 .. 0107 

Present 

Present 

5. 30 

4. 28 

6. 04 

' 4. 73 

3. 34 - ----- - - 4.53 4 

2. 33 

8. 07 

1. 46 2. 86 

4. 66 . 1. 76 

. 0000004 

. 0286 

B . 0024 ______________________ _ 

Atomic ratio F: OL _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ · . 0055 . 00211 

. 0003 

3 4. 15 12. 22 18. 05 

. 00043 

.. 0000123 

Br:OL___________________ . 0016 . 00150 

S: OL____________________ . 0088+ 

B:OL___________________ . 000015 . 0058 . 879 3. 95 4. 12 ______ _._ 1. 41 . 85 2. 65 . 0516 

1. Kilauea Iki, condensate recalculated from table 1. 

2. Ebeko Volcano, upper crater, natural condensate, Paramushir Island, the Kuriles; 

B.S. Krapivina, analyst (Ivanov, 1957}. 3. J aggar's sample 2, gas from Halemaumau lava lake, Mar. 1, 1918 (Shepherd, 1938). 4. Jaggar's sample 3, gas from Halemaumau lava lake, Mar. 2,1918 (Shepherd, 1938). 

5. Jaggar's sample 4, gas from Halemaumau lava lake, Mar. 2, 1918 (Shepherd, 1938). 0. Kilauea Iki eruption, average content of volatiles in lavas of the first phase, calculated from conventional rock analyses (K. J. Murata and D. H. Richter, 

unpub. data) and water determinations (I: I. Friedman, unpub. data). 

Columns 3-5 of table 2 represent chlorine-rich gas 

samples collected from the molten lava of the Halemaumau lava lake by T. A. J aggar in March, 1918. Shepherd's work ( 1938) indicated that Kilauea gases usually 

contained only a tenth to a hundredth as much chlorine 

as do these samples. But the three samples show that 

magmatic gases with chlorine content comparable to 

that of the IGlauea Iki condensate have been found 

previously on l{ilauea. Likewise some samples of volatiles extracted from Kilauea lavas by heating under·. 

vacuum (Shepherd, 1938) were as rich in chlorine ( cols. 

7-9, table 2). Even the conventional chemical analyses 

of IGlauea Iki lavas suggest the possibility of gases 

containing molal concentrations of chlorine or hydrochloric acid (col. 6, table 2). Thus, a condensate like 

the 1.9N HCl of J{ilauea Iki would not be entirely'unexpected and ·would represent pristine exhalation from 

IGlauea·magma. 

The concentrations of fluorine and total sulfur in 

Kihiuea gases and lava volatiles are about equal to or 

greater than that of chlorine. Shepherd ( 1938) did not 

determine fluorine in most of his gas samples from the 

lava lake of Halemaumau, but in one sample he found 

the F: Cl atomic ratio to be 4.62 and the S: Cl ratio, 

1.03 (Day and Shepherd, 1913), in harmony with proportions indicated by the lava volatiles ( cols. 6-9, table 

. 2). The condensate from Kilauea Iki is thus deficient 

in fluorine and sulfur relative to chlorine when compared to the high-temperature gases of Kilauea. Like 

all previously analyzed gases from Kilauea, the Kilauea 

Iki' gas also contained appreciable amounts. of C02 as 

. 00078 

7. Gas extracted from lava dipped out of Halemaumau lava lake in 1919 (Shepherd, 1938). . . 8. Gas extracted from pahoehoe lava of the 1923 Kilauea eruption (Shepherd, 1938). 9. Gas extracted from lava collected from Halemaumau lava lake in 1917 (Shepherd, 1938). . 10. Average sea water (Rankama and Bahama, 1950). 

a "fixed" component (Ault, 1960), which would not 

appear in the analysis o:£ the acid condensate. 

On the basis of the chlorine content, the condensate 

is 3.6 times more concentrated than normal sea water 

(col. 10, table 2). Although the derivation o:£ hyQ.rochloric acid by contamination o:£ the magma with sea 

water at depth is ~onceivable, this difference in concentration and the discrepancies in the ratios o:£ fluorine, 

sulfur, and boron to chlorine in the two materials (even 

after making allowances for possible metasomatic reactions o:£ the fumarolic gas) seem to argue against sea 

water as the major source of the acid. 

The ratio o:£ bromine to chlorine in the condensate is 

very close to that in sea water, but White (1957, 1960) 

called. attention to the fairly prevalent constancy o:£ this 

ratio in nature, which renders ito:£ uncertain diagnostic 

value. · Fumarolic vapors of the dacitic volcano ShowaShinzan also contained bromine and chlorine in a ratio 

close to that of sea water (Nemoto and others, 1957, 

p. 115-133). On the other hand, ·Br:Cl ratios substantially higher and lower than that of ~ea water have 

been reported for solfataric gases of the andesitic 

volcano Sheveluch (Basharina, 1956). 

The presence of hydrochloric acid in gases exhaled 

by many volcanoes far removed :from the sea or saline 

deposits has led to the general belief that hydrochloric 

acid is a common primary constituent of Inagmas. The 

Hawaiian Islands, however, are immersed in and impregnated with sea water, and the possibility of entry o:£ 

sea water into magn1a conduits·is ever·present. A brief 

episode of such an entry at shallow depths was observed 
C4 THE 1 9 5 9-;6 0. ERUPTION OF KILAUEA. VOLCANO:,- HAw AI! 

during the 1960 fhirik eruption of I\:ilauea at Kapoho: 

Sea salts not only could yield hydrochloric acid through 

hydrolysis but also could add soda to the magn1a, thereby possibly helping to form hyperalkalic magmas. The 

possibility of. a marine contribution to magmas thus remains one of the outstanding questions in Hawaiian 

volcanism. 

If we assume that the gas initially released from the· 

hot pumice wjthin the l(ilau-ea Iki cone had the usual · 

composition of high-temperature magmatic gases of 

l(ilaueu,, the relative paucity of fluorine and sulfur jn 

the fumarolic condensate suggests that these elements 

were removed through interaction· with the pumice as 

the gas migrated to the surface. An extensive fluorineand sulfur-metasomatism of the interior pumice may 

have been in process (N aboko, 1957; Lovering, 1957). 

Observations at the surface revealed an intense decomposition of the pumice by hydrochloric and, to a les~r 

extent, sulfuric and hydrofluoric acids. 

ACID ALTERATION OF THE PUMICE 

Along the gas-emitting faults on the pumice hill, the 

uppermost few inches of the pumice was thoroughly decomposed to siliceous. pseudomorphs of pumice fragments. The highly porous pseudomorphs had absorbed 

much ferric chloride and consequently had a deep orange 

color in sharp contrast to the black of the unaltered 

or slightly altered pumice. Below this surficial layer, 

the black pumice fragments did not appear to be much 

affected, although the fumarolic gas was streaming all 

around and through them. At· many points, the subsurface fragments Yvere cemented into hard irregular 

nodules, as much as· 6 inches long, by crystallization of 

various salts (mostly chlorides) l'eached out of the surface layer. No nodules were found at a depth greater 

than about a foot below the surface. It must be remembered that these observations pertain: only to a very early 

stage in the -degassing of the hot interior pumice and 

alteration of the surface pumice. Later observations by 

Ault (1960) indicated increasing contamination of the 

fumarolic gas by air. 

The localization of the zone of intense alteration to 

the uppermost· few inches of pun1ice ~as very striking 

and was attributed at first solely to the formation of 

sulfuric acid in the surface layer through air oxidation 

of sulfur dioxide. Later, when the preponderance of 

hydrochloric acid in the fumarolic vapor and of chlorides in the crystallized salts were realized, it became apparent that access· of air may also have been promoted 

the action of hydrochloric acid on the pmnice. The 

_oxidat~on of its ferrous iron to ferric iron probably reifdered the glassy pumice more susceptible to.· attack· by 

hydrochloric acid. Also, the acid solution that formed 

in the surface layer of pumice through condensation of 

the vapor may have been a moFe potent agent for decomposing the pumice than the original vapor (Naboko, 

1959). 

A sa1nple of the pseudomorphic surficial material was 

washed with IN HCl and with water to remove the 

. occluded ferric chloride; it was then air dried and 

assayed by rapid-analysis 1nethods (Shapiro and Brannock, 1956). Th~ analysis is given-in table 3:· 

. TABLE 3.-A?wlyses of altered and original pumice from Kilauea 

Iki 

[Analyst of altered pumice: Rapid analysis group, Washington; analyst of unaltered 

pumice, sample S-9: D. F. Powers (K. J. Murata and D. H. Richter, unpub. data)] · 

Altered Pumice 

Recalculated 

Composition to a~~~rous 

SiOz __________________ ..:__ 79.2 95; 2 

AbOa--------------------- 1.0 1.2 

Fe20a-- ------------------ 1 • 46 1. 55 

FeO ____________________ ..:._ ---------- ---------- MgO_____________________ . 17 . 20 

CaO_ -------------------- . 14 . 17 N a20 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . 06 . 07 

K20--------------------- .04 .05 H20 (total) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 17. 0 _________ _ 

Ti02------ --------- __ ____ 2. 0 2. 4 

P205--------------------- . 14 . 17 

MnO___________________ _ .01 .01 

C02-- ______________________________________ _ Cl __________________________________________ _ 

F ____________________ ..:. ___ --------------------

SubtotaL _________ ·--- 100 100 

Less 0 __________ - - - - - _ - - - - - - - - - - - - - - - - - - -

TotaL __________ _ 100 100 

1 Total iron as Fe20a~ 

Fresh pumice 

48.41 

11.62 

1. 36 

10.29 

13.34 

9.77 

1. 94 

. 47 

. 04 

2.30 

. 23 

. 17 

. 01 

. 02 

. 03 

100.00 . 01 

99.99 

The composition shown in colun1n 1 of t~ble 3 corresponds to that of hydrous silica with minor amounts of 

the other common ·constituents of basalt.. According 

to B. J. Skinner, the X-ray diffraction pattern of this 

sample shows a single diffuse maxilnum typical of amorphous silica. On an anhydrous basis (col. 2, . table 3) 

the 1naterial is 95 percent silica. Hydrochloric and 

sulfuric acids had Q.ecomposed the surficial pumice 

thoroughly and left behind only siliceous pseudomorphs 

of the pumice fragments. 

Nodules of the ·previously mentioned· cemented pumice 

were first exmnined qualitatively in the chemical laboratory of the Hawaiian Volcano Observatory. The crystallized salts that constituted the yellow cement· were 

readily soluble in water, and the resulting solution gave 

strong .test for 01-, Fe+2, Fe+3, Ca+2, Mg+2, 'Al+3, and Na+. 

Tests· :for sulfate and fluoride indicated only a moderate 

.amount, and negative 'tests were obtained for ammonium 

ion and for elemental sulfur. 
AN ACID FUMAROLIC GAS FROM KILAUEA IKI C5 

A representative saniple of the nodules was sent to 

the Denver laboratory of the U.S. Geological-8urvey 

for mineralogical study~ Because of an accident in 

transit the originally hard cementing substance decomposed into a pasty mass through hydration and oxida..: 

tion. F. A. Hildebrand found niost of ·it by X-ray 

in 1913 from the.lava lake of Halemaumau. Tl~e seleni-

· ferous sulfur of Kilauea Iki constitutes an excellent 

·example of a trace magmatic constituent becoming sepa-

:rated and cm1centrated through the process of vapor 

'transport. 

examination to be amorphous. Only a small amourit of , TABLE 4.-Selenium content of native sulfur from Kilauea V olea no 

. halite and anatase could be identified in the X-ray dif- sam-. 

fraction patterns. The general instability of the ce- ple 

Source Reference Selenium 

(percent) 

n1enting substance was also manifested in the gradual --l------------:---l--------l---

decomposition of the samples that were retained in cov- 1 Steam conde~sate, Kilauea J. W. Budinsky 2. 9 · Iki cone. Collected Nov. and Irving ered jars in Hawaii .. Aithough the crystalline phases · 23, 1959, by K. J. Murata May, anaconstituting the cement remain mostly unidentified, and R. T: Okamura. lysts. . 2 Altered pumice, Kilauea Iki _____ do _________ 1. 1 

there is no doubt that they were chlorides (and some cone. · Collected Nov. 23, 

sulfates and fluorides) of the major elements of basalt. l~:~~~~c!d. ~i~u~~rb~~l- They represented acid-soluble constituents of the sur- disulfide. 

ficial pumice, and. the siliceo. us I)Seu'ctomorphs of pumice 3 "Blowhole" cinder cone, 1955 Lakin (1961); 

W. A. Bowles, 

Jr., analyst. 

.16 · flank eruption. Collected 

fragments, the acid-insolubleresidue. ·January 1957 by T. S. 

SELENIUM CONTENT OF THE SULFUR 

The elemental sulfur present as a sediment in .the 

sample of steam condensate was filtered off and analyzed : 

qualitatively by means of an X-ray fluorescence spectrometer. Because D. E. vVhite and R. A. Gulb1~m~dsen 

obtained strong indications of selenium in this sulfur, 

it and another sample, collected from the pumice cone 

of l{ilauea Iki, were analyzed for selenium by J. ,V. 

Budinsky and Irving May, with the results shown for 

samples 1 and 2 in table 4. All previous determinations 

of selenium in sulfur from IGlauea volcano are included ' 

in table 4. The IGlauea Iki ·sulfur is remarkably rich 

in selenium and is only exceeded by sample 8 collected 

in 1840 by J. D. Dana, while a n1ember of the Wilkes ' 

expedition. 

Sulfur that was depositing in 1957 in and around the 

vents of the 1955 flank eruption of IGlauea contained 

about a tenth of a percent of selenium (samples 3-5, 

table 4). Sample 6 from the low-temperature solfatara 

of Sulphur Bank had only 4 ppm (parts per million) of 

selenium. The data of table 4 suggest that the concentration of selenium is highest in high-temperature exhalations and becomes progressively less in cooler vapors 

of fumaroles and solfataras. 

The amount of selenium present in the primitive . 

magma of IG1auea is not known but is probably only a 

few parts per million or less. Kilauea lavas studied by 

Davidson and Powers (1959) uniformly contained less 

than 2 ppm of the element. An idea of the order of 

magnitude of concentration of selenium in the magmatic gas of IGlauea is gained from the fact that Byers 

and others (1936) found 0.005 milligram selenium in 

600 cubic centimeter of a sample that had been collected 

4 

5 

6 

7 

8 

Lovering. 

New pit crater, Kalapana 

road, 1955 flank eruption. 

Collected January 1957 by 

T. S. Lovering. 

Spatter cone on roadcut 

northeast of Kalapana, 

1955 flank eruption. Collected January 1957 by 

T. S. Lovering. 

Sulphur Bank solfatara at the 

summit. Collected January 1957 by T. S~ Lovering. 

Great· Solfatara on the southwest· rift near Halemau- mau. Collected in 1921 by 

T. A. Jaggar before the 

great overflow of Mar. 7, 

1921. 

Sulfur-impregnated lava, 

from unspecified locality on the volcano. Collected in 

1840 by J. D. Dana. 

_____ do ________ _ 

- _·_- _dq ______ ----

_____ do _______ ·_ 

Byers and 

others· (1936). 

. 16 

. 09 

. 0004 

. 22 

Brown (1916) ___ 5.18 

SUMMARY 

The lone sample of acid gas from the pun1ice hill 

of IGlauea Iki raises more geochemical questions than 

it answers. But it does call attention to· the possibility 

of hydrochloric acid ·being a more common constituent 

of IGlauea gases than wa$ hitherto realized. The attack 

of basaltic. pumice by hydrochloric acid produces ch1oeides of ferrous iron, magnesium, calcium, and other 

major elements of basalt. In future studies, the need 

for special precautions to prevent the decompositionof 

these salts through hydration and oxidation is indicated. 

The selenium in the sulfur associated with the gas 

recalls other minor elements, such as copper (Murata, 

1960), that are exhaled during eruptions of basaltic volcanoes, and thereby emphasizes the importance of volcanic contributions to the oceans (Wedepohl, 1960). 
C6 THE 1959-60 ERUPTION OF KILAUEA VOLCANO, HAWAII 

REFERENCES 

Allen, E. T., and Zies, E. G., 1923, A chemical study of the 

fumaroles of the Katmai region: Natl. Geog. Soc., Contributed Tech·. Papers, Katmai ser., no. 2, p. 75-155. 

Ault, W. U., 1960, Geochemical research during the 1959-60 

activity of Kilauea volcano: Geochem. Soc., Geochem. News, 

no. 25, p. 1-5. 

Basharina, L. A., 1956, Fumaroles of the volcano Sheveluch during September-December 1953: Akad. Nauk. SSSR., Biul. 

Vulkan. Ctantsii, no. 24, p. 21-27; additional data in Naboko 

( 1959) p. 194. 

Brown, G. V., 1916, Composition of the selensulphur from 

Hawaii: Am. Jour. Sci., ser. 4, v. 42, p. 132-134. 

Byers, H. G., Williams, K. T., and Lakin, H. W., 1936, Selenium 

in Hawaii and its probable source in the United States: 

Jour. Indus. and Eng. Chemistry, v. 28, no. 7, p. 821-823 .. 

Davidson, D. F., and Powers, H. A., 1959, Selenium content of 

some volcanic rocks from Western United States and 

Hawaiian Islands: U.S. Geol. Survey Bull. 1084-C, p. 60-81. 

Day, A. L., and Shepherd, E. S., 1913, Water and volcanic activity: Geol. Soc. America Bull., v. 24, p. 573-606. 

Deville, C. S., and Leblanc, F. 1858, Memoir on the chemical 

composition of gases exhaled during volcanic activity in 

southern Italy: Annales chim. phys., ser. 3, v. 52, p. 5-63. 

Ellis, A. J., 1957, Chemical equilibrium in. magmatic gases: Am. 

Jour.Sci.,v.255,no.6,p.416-431. 

Ivanov, V. V., 1957, The present hydrothermal activity of the 

volcano Ebe~o on the Isle of Paraml.tshir: Geochemistry 

[~eokhiniiya], no.1, p. 77-92 [Engli~h ed.]. 

Iwasaki, Iwaji, 1951, Geochemical investigations of volcanic 

Oshima, Izu; translation no. 427 by Engineer Intelligence 

Div., Office of the Engineer, Headquarters U.S. Army Pacific 

Far East Command, April 1959: Jour.· Geography Tokyo, 

v. 60, no. 3 (681), p.140-143. 

Lakin, H. W., 1961, Geochemistry of selenium in relation to agriculture, in Selenium in agriculture: U.S. Dept. Agriculture, 

Agr. Handb. 200, p. 3-12. 

Lovering, T. S., 1957, Halogen-acid alteration of ash at Fumarole 

No. 1, Valley of Ten Thousand Smokes, Alaska: Geol. Soc. 

America Bull., v. 68, no. 12, pt. 1, p. 1585-1603. · 

Macdonald, G. A., 1944, Solfataric alteration of rocks at Kilauea 

volcano: Am. Jour. Sci., v. 242, no. 9, p. 496-505. 

Murata, K. J., 1960, Occurrence of CuCl emission in ·volcanic 

flames: Am. Jour. Sci., v. 258, no. 10, p. 769-772. 

Naboko, S. I., 1957, A case of gaseous fluorine metasomatism at 

an active volcano: Geochemistry- [ Geokhimiya], no. 5, p. 

452-455 [English ed.]. 

--- 1959, Volcanic exhalations and the products of their 

reactions: Akad. Nauk SSSR, Lab. Vulkanologii, Trudy, 

v.16, p.1-301. 

Naughton, J. J., and Terada, Kazuji, 1954, Effect of eruption of 

Hawaiian volcanoes on the composition and carbon isotope 

content of associated volcanic and fumarolic gases: Sci., 

v. 120, p. 580-581. 

0 

N emoto, Tadahiro, Hay aka wa, Masami, Takahashi, Kiyoshi, and 

Oana, Shinya, 1957, Report on the geological, geophysical, 

and geochemical st1!dies of Usu volcano (Showa-Shinzan): 

Geol. Survey Japan Rept. 170, 149 p. [in Japanese]. 

Payne, J. H., and Mau, K. T., 1946, A study of the chemical 

alteration of basalt in the Kilauea region of Hawaii: Jour. 

. Geology, v. 54, no. 6, p. 345-358. 

Rankama, KalervQ, and Sahama, Th. G., ·1950, Geochemistry : 

Chicago, Univ. Chicago Press, 912 p. 

Shapiro, Leonard, and Brannock, W. "\V., 1956, Rapid analysis 

of silicate rocks: U.S. Geol. Survey Bull. 1036-C, p. 19-56. 

Shepherd, E. s:, 1921, Kilauea gases, 1919: Hawaiian Volcano 

Observatory Bull., v. 9, p. 1-6. 

-.-- 1938, The gases in rocks and some related problems: 

Am. Jour. Sci., ser. 5, 35-A, p. 311-351. 

Wedepohl, K. H., 1960, Trace-analytical investigations of deepsea clays from the Atlantic : Geochim. et Cosmochim. Acta, 

v. 18, p. 200-231. 

White, D. E., 1957, Thermal waters of volcanic origin: Geol. Soc. 

America Bull., v. 68, no. 12, pt. 1, p. 1637-1657. 

--- 1960, Summary of chemical characteristics of some 

waters of deep origin, in Short papers in the geological 

sciences: U.S. Geol. Survey Prof. Paper 400-B, p. B452-

B454.