Chemtcal Geology, 61 (1987) 299-308

Elsewer Scmnce Pubhshers B V, Amsterdam - - Printed m The Netherlands

299

CHEMICAL ANALYSES AND DIFFUSION STUDIES OF GASES IN ANDESITIC LAVAS" ARENAL VOLCANO (COSTA RICA)*
J L Z I M M E R M A N N 1, J L C H E M I N E E 2 ~and H D E L O R M E ~4
~Centre de Recherches Pdtrograph~ques et Gdoch~m~ques, F-54501 Vandoeuvre-les-Nanc:~ C~dex (France) ~Laboratotre de Gdolog~e, ]Ecole Normale Superleure, F-75005 Parl~ Cddex (France) ~Observato~res Volcanolog~ques, I P G P , F-75230 Par~s Cedex 05 (France) 4Laborato~re de Geoch~rn~e des Isotopes Stables, F-75000 Par~ Cddex 05 (France)
(Accepted for pubhcatmn July 11, 1986 )

Abstract
Zlmmermann, J L , Chemm~e, J L and Delorme, H , 1987 Chemmal analyses and dfffusmn studms of gases m andes1tic lavas Arenal Volcano (Costa Rlca) In E E Horn and J -J Behr (Guest-Editors), Current Research on Fluid Inclusmns, ECRFI, Gottlngen, April 10-12, 1985 Chem Geol, 61 299-308 Early m 1981, the eruptive behavior of the Arenal Volcano changed - an essentially effuswe period was mterrupted by an exploswe phase Analyses by mass spectrometry of occluded gases (H~O, C02, CO, N,, H2 and CH4) m lava samples both younger and older than the exploswe event were carried out Although the fluid phases have approximately the same composition, the more recent lavas are enrmhed m gases relative to the older ones Dehydratmn takes place at temperatures ~ 50 C higher for the older lavas Distractive H20 and CO2 dfffusmn hnes and CO/( CO + CO, ) ratms (0 35 and 0 30, respectwely), for both lava types substantmte this difference Some orgamc compounds are also present m all samples albeit m small quantltms

1. I n t r o d u c t i o n Exhalated gas analysis ~s one of the principal methods to determine the composltmn of magmatin fluids These fluids correspond to the composition of the fractmn exsolved at the time of activity However, they are often contaminated with groundwater and atmospheric gases and must be collected directly at the vents In some cases, the access to the vents is difficult, or ~mpossible, due to volcanic activity Gases entrapped in volcanic rocks are also representatlve of magmatlc fluids and may reflect the P-T-fo2 conditions m a "magma chamber"
*Contr~butmn C R P G No 692

However, these gases are present m very low quantities, contrarily to samples from vent areas in eruptive periods, the lavas are always accesstble Mass spectrometry (with ~ts high senslt~vlty) is one of the most used methods to study these magmatlc volahles (Zlmermann, 1972, Barker and Sommer, 1973, Hdkmlan et al, 1973, Kllhngley and Muenow, 1974, 1975, Prme et al, 1977, Delaney et al, 1978, Muenow, 1979, Chalgneau et al, 1980, Zimmermann et al, 1981) This experimental procedure has some mconvemences, e g the complexity of the gas mixture always g~ves mass interferences Furthermore, heating may bring about dissoclatmns, re-equlhbratmns and reactmns between

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1987 Elsevmr Scmnce Pubhshers B V

300 gases, and adsorption in the mass spectrometer source on the walls of the extraction line may occur (Zlmmermann, 1972, Andrawes and Gibson, 1979) Besides, water analyses, which are of first significance for crystalhsatlon processes (Moore, 1965, Mysen, 1983), are difficult to carry out especially when these analyses are made simultaneously with other gases (3) continuous and hnear heating from 120 to 1200 C with a rate of 400 C h 1 The first method gives the composition of gases extracted at 1200C and the water and carbon choxxde contents (contribution at higher temperature is negligible) As for incremental heating, the temperature stays constant at each step until the pressure of the released gases becomes stable, the minimum duration of a step is ~ 3 h These analyses allow to evaluate the fluids' composition at each step and to draw the release histograms of the different gases Diffusion charactenstms of these gases can be determined from these histograms (Zlmmermann, 1981, ZImmermann and Odin, 1982) using Carslaw and Jaeger (1959) data With continuous and linear heating xt is possible to observe continuously the release of each gas The corresponding curves can be considered as differential thermogravxmetrlc curves

2. Experimental process
The gases were extracted from rocks by heatmg under vacuum and separated (according to their boiling temperature ) in a cooled trap with liquid nitrogen ( - 195 C) and with an alcohol and liquid nitrogen ( - 85 C) mixture The mass spectrometer used was a T h o m s o n THN205 Carbon monoxide and nitrogen which give the same mass spectra were separated by oxidation on copper oxide at 500 C, the first is converted into carbon dioxide which is trapped a t - 1 9 5 C Calibration was made with gas standards The direct measurement of water is imprecise because of adsorption It is therefore first trapped at - 85 C, and, reduced to hydrogen m a uranium furnace at 850C (Craig, 1961) This hydrogen is measured by mass spectrometry and values were calibrated against known quantities of water introduced by means of a Hamilton mlcrohter syringe through a septum, which were reduced in the same way Measurements on standard samples (whose water contents are known) are carried out under the same conditions The line is permanently heated at 80 C to prevent adsorption Repeated measurements give less than 5% relative error. Ahquots of crushed and sieved samples (1 mm) of ~ 400 mg were used After preheating of the samples at 120C under vacuum overnight to release adsorbed gases, extraction was performed by three different methods (1) heating with only one step at 1200C during 3 5 h, ( 2 ) incremental heating with successive steps of 100C from 200 to 1200C, and

3. Samples
The arenal volcano is continuously active since September 19, 1968 After a period of explosxve activity, mainly at the beginning of the eruption (Nude ardente type) and in 1975, the activity of Arenal was characterized by contmuous blocky lava flows (more than 50) This behavior changed m 1981 and the activity became more explosive Lava flows are composed of basaltic andeslte whose chemical composition is almost constant (SiO2~54.5%, A1203~196%, F e 2 0 ~ ~ 2 6 % , F e O ~ 4 4%, M g O ~ 5 3%, C a O ~ 9%, K20 ~ 0 6%, Tx02 ~ 0 6% ) (M Lenoble, 1977, m Hernandez and Tournon, 1978) The samples were taken from four lava flows June 1979, April 1980,June 1981 and two m June 1981 during a period of explosive activity X-ray diffraction ( X R D ) shows that the crystalline phase is mostly plagioclase

4. Analytical results
The molar composition of the fluid phase extracted m one 1200 C step is nearly the same

301

TABLE I Molar c o m p o s l t m n s of released fired p h a s e ( h e a t i n g at 1200 C during 3 5 h)

Sample
AR AR AR AR

H20

C02

CO

N~

H2

(%~
67 68 63 65 3 1 5 7

(%)
20 19 24 22 2 4 0 8

(%)
10 10 10 9 9 7 8 8

(%)
15 16 16 15

(%)
0 0 0 0 06 09 06 08

CH4 (%)
0 0 0 0 01 01 01 02

SO2
tr *

Orgamc compounds* , * * **

79-6 80-8 81-1 81-2

*Unquantlfled gases ( * -- few, ** = m o s t )

for the four flows (Table I) It is formed essentially of water ( ~ 64-68%) and carbon oxides (CO2~ 19-24%, CO-~ 10%), and some other gases, mostly mtrogen (N2 ~ 1 5% ) Hydrogen, methane, organic compounds and sulphur dlomde are found as traces Orgamc compounds cannot be identified (only CH4 can be measured, and C2H2, C2H4, C2H6 and C3H6 identified with our mass spectrometer, their quantitative analysis is speculative because of mass interferences m the source of the mass spectrometer, but their existence is revealed by some of their cracking products, m particular methyl radical Elemental organic analyses performed at the Centre de Pddologie Biologxque ( N a n c y ) give carbon contents from organic compounds between 0 015 and 0 05 wt % and nitrogen contents of ~ 0 004 wt % Water and carbon dioxide measurements by mass spectrometry and by chemical methods (Karl-Fischer for H20, coulometry for CO2) show few differences between the four samples (Table II) Nevertheless, there is a systematical increase of H20 and CO2 contents m the June 1981 samples for whmh the volcano activity was more explosive These analytical results are very different from the suppositions of Newhall and Nelson (1983) based on chemical analyses of major elements Incremental heating analysis allows to compare the release histograms of the principal gases Hydrogen and methane release occurs mainly between 300 and 800C, while the release of other gases (H20, C Q , CO as the most abundant) are more spread until 1200 C,

with a stronger intensity from 400 to 1000 C Continuous and linear heating curves (heatmg rate 400C h - l ) allow to compare hberatlon of each gas m the different samples whatever their gases contents are, according

Q/Qo=[(T)
whereQ = released quantity from heating start to T ( C ) , and Qo=total released quantity assumed to be close to the initial quantity m the sample For water (Fig l a ) , the curves are the same for lavas of June 1979 and April 1980, but these are moved forward by ~ 50 C for lavas of June 1981 Moreover they have two inflection points, the first near 600 C, and the second between 1050 and 1150C (range of the emitted lava flow temperatures, Clgohm et al, 1984) These indicate perhaps three sites for water adsorption, ( < 600 C), bubbles ( < 1000 C ) and solid solution m glasses ( > 1000 C ) Liberation curves of carbon dioxide are similar for the four samples (Fig l b ) and also for hydrogen (Fig lc) and methane (Fig l d ) These gases are released before l l 0 0 C However, there is an reflection point at ~ 600 C for the methane curve, which can indicate a dissociation of heavier hydrocarbons 5. D i f f u s i o n o f g a s e s If gas release is considered as diffusion, it is characterized by the Arrhenms equation D = Do exp ( - E / R T )

302

where D = dfffusmn coefficmnt ( c m 2 s--l), Do = dlffusxon constant, E = actlvatmn energy (kcal mol-~), R = u m v e r s a l gas constant, and T = absolute temperature Assuming spherical grams, incremental heating analysas allows to calculate D and E using the Carslaw and Jaeger (1959) equatmn

F= (Qo-Q)/Qo - 1 - ~ 6 ~ n -2 e x p [ - n 2 ( r c 2 D t / a 2 ) ]
-

n=l

where F= fractional loss of gas, a - - r a d m s of supposed spherical grams, and t = t a m e of heating W h e n there ~s dfffusmn, the following equataon as linear log D/a 2 : log Do/a 2 E / R T
-

=const -E/RT The slopes of the strmght lanes an log D/a z vs 1/T plots gave the actxvatmn energy for the

hberatlon of the studmd gas For water (Table III), there are two straight hnes (Fig 2) The first one corresponds to the first steps including that of 500 C, the second ranges from the 600 C step to the 1000C step with actxvatxon energins of 1 0 + 2 and 1 6 + 2 kcal mol 1, respectavely These values apply to the first two parts of the continuous dehydratmn curves and correspond to different solutmn mechamsms alluded to above, the thard cannot appear here because there Is only one step (1200C) after the one of 1000C Assummg grams wath a dtameter of 1 mm, computed daffusxon coefficmnts are between 10 a3 and 10-12 cm 2 s 1 (for 1 1 mm, 1 21-10 -13 cm 2 s -a) Moreover, these strmght hnes (Fig 3) allow us to dastmguxsh two lava famflms (1) June 1979 and April 1980 lavas, and (2) June 1981 lavas For carbon dmxlde (Table IV), the log D/a 2 vs 1/T expressxon gives only one strmght lane for each lava flow ( Fig 3) These four strmght hnes can be also grouped together m two famlhes (1) June 1979 and Apn11980, and (2) June

TABLE II Water and C02 contents (m gramme per cent) measured by different experimental processes Extractmn, analysis Ar 79-6 Ar 80-8 AR 81-1 C02 (g%) H20 (g%) C02 (g%) AR 81-2 H20 (g%)
CO 2

H20
(g%) Heating at 1200C, grams ~ 1 mm, MS Continuous heating from 120 to 1220C, grams 1 mm, MS Glass ~<0 2 mm 1200C, MS Grams ~ 1 mm, Karl-Fischer (HeO) coulometmc (C02) analyses

C02
(g%)

H20
(g%)

(g%)

0 083

0 061

0 078

0 054

0 091

0 083

0 092

0 078

0 093

0 047

0 083

0 044

0 092

0 065

0 096

0 066

0 060

0 030

0 052

0 031

0 068

0 054

0 087

0 068

0 080

0 050

0 070

0 060

0 090

0 060

0 095

0 080

Analytic methods MS, mass spectrometry, (HeO, CO:), Karl-Fischer (H20), coulometry (C02) Errors H20, 3%, C02, 2% Permds ofsamphng AR 79-6 June 1979, AR 80-8 April 1980, AR 81-1 June 1981, Ar 81-2 June 1981

303

Q/Qo
t I

Q/Qo

+.

(~)

+.

@
+

+.

H20

\'
+

CO 2

AR 79-6
+l + " ~
~ , + ~

AR 8 0 - 8 * AR 8 1 - 1 + AR 8 1 - 2 T e m p e r a t u r e C +
200 I, 400

" ;**
I I

Temperature
I I I I

200

400

600

800

1000

1200

600

800

1000

1200

Q/Qo
1

Q/Qo
t
t

+o

+o

05

*:

CH4

H2
o

/" \
+ /

+ + +~

200
I

Temperature C
800
,

Temperature C
10 k~ 200
I L I J I

400

I, !~

6OO

1000

1 2100

400

600

800

1000

1200

Fig 1 Continuous and linear heating analyses Liberation curves of (a) H20, (b) CO,, (c) H2, and (d) CH4 Heating rate of 6 6 6 CmIn ])

1981 Their actlvatmn energms are 12 and 10 kcal mol 1, respectively Their diffusion coefficmnts at 20C are not very different from those for H20 These values are comparable to those obtained on basaltic lavas from ArdoukSba, Afar (Zlmmermann et al, 1981)

6. O r i g i n o f C 0 2 , CO, C a n d o r g a n i c compounds Carbon dioxide whose content is comprised between 0 05 and 0 08 wt % is next to water the most abundant gas in these lavas As for water

304 TABLE III Diffusion characteristics of water (Carslaw and Jaeger method) Sample Ar 79-6
T F D / a ~'

AR 80-8
F D/a 2

AR 81-1
F D/a ~

AR 81-2
F D / a -~

(~C) 200 300 400 500 600 700 800 900 1,000 1,200

(%)

(10 7s ')

(%)

(10 7s-~)

(%)

(10 7s ~)

(%)
30 10 1 161 232 427 57 6 73 1 87 3 94 0 100

(10 7S
0 048 0 33 15 43 73 30 67 74 160

1)

1 4 0 014 3 5 0 088 8 3 0 22 13 6 1 1 21 0 3 4 38 2 5 6 495 18 55 7 32 696 51 100

37 0 042 76 0 36 10 9 0 88 17 1 0 98 28 2 51 45 8 20 716 28 83 8 53 93 1 100 100

38 0 10 14 9 0 39 24 6 38 31 1 63 48 5 99 63 1 44 743 71 872 98 950 160 100

F= released fractmn, D / a 2= dfffusmn coefficient, with a = radms of supposed spherical grains

t Log D/a;' 17' "~ +x I

'

H20 x u "+ AR 79-6 o AR 80 8 x AR81 1

~.\

r
2,L "~,~o 900 ~oo
10

soo
lr5

~,oo
20

200

t C IO001T

Fig 2 Dfffusmn of water (Carslaw and Jaeger method), logD/a 2 vs 1000/T log D / a 2 =log Do/a ~-E/RT

where D=dfffusmn coefflcmnt (cm 2 s-l), Do= diffusion constant, a = radms of supposed spherical grains, E = actlvatmn energy (kcal tool- 1), proportmnal to slope of the strmght hnes, R = universal gas constant, T= absolute temperature

t h e J u n e 1979 a n d April 1980 l a v a s c o n t a i n slightly less CO2 t h a n t h o s e of J u n e 1981 ( T a b l e I I ) T h e fact t h a t CO2 a p p a r e n t l y h a s a single solution m e c h a n i s m i n d i c a t e s t h a t t h e r e ~s p r o b a b l y no c o n t a m i n a t i o n e s p e c i a l l y f r o m car-

b o n a t e d e c o m p o s i t i o n ( R m t s e m a , 1979), conc o r d a n t l y c a r b o n a t e s h a v e n o t b e e n identified b y X R D at t h e d e t e c t i o n h m l t of 1 - 2 % H o w ever, t h e 5~3C value ( - 2 7%c ) of t h e f u m a r o h c CO2 r a n g e s b e t w e e n t h a t of s e d i m e n t a r y carb o n a t e s a n d m a g m a t ] c 51aC-values ( D e l o r m e et a l , 1981 ) T h e m o l a r p e r c e n t a g e of CO is a p p r o x l m a t e l y h a l f t h a t of CO2 ( T a b l e I) T h i s is p r o b ably p a r t l y the result of r e a c t i o n s b e t w e e n gases, p a r t i c u l a r l y b e t w e e n CO2, H 2 0 a n d C C a r b o n m o n o m d e c a n be f o r m e d m a m a g matin chamber m reducing environment ( C h a l g n e a u , 1975) CO is p r e s e n t in s o m e f u m a r o h c gases ( W h i t e a n d W a r m g , 1963, C h a l g n e a u a n d F u s t e r , 1972) a n d also in t h e e x h a l a t e d gas f r o m A r e n a l ( D e l o r m e , 1983) C a r b o n c a n be m t u a t e d in m l c r o c r a c k s , vesicles or glass i n c l u s i o n s as g r a p h i t e , c a r b y n e s (--C = C-- umts hnked together) and hydroc a r b o n s ( M a t h e z a n d D e l a n e y , 1981) S o m e C a t o m s c a n also be i n s e r t e d m t h e m h c a t e struct u r e a n d m glass m a t r i x ( F r e u n d et a l , 1980, 1982) Besides, r e d u c i n g r e a c t i o n s of c a r b o n dioxide b y Fe c a n also be c o n m d e r e d ( C h a m b e r h n , 1908) O n t h e o t h e r h a n d , a p a r t of t h e c a r b o n m o n o x i d e a n d h y d r o g e n c a n be p r o d u c e d b y r e a c t i o n s of o r g a m c c o m p o u n d s a n d

305 T A B L E IV Diffusion c h a r a e t e n s t m s of CO2 (Carslaw a n d Jaeger m e t h o d ) Sample

T

AR 79-6
F D/a 2

AR80-8
F D/a 2 (lO-V s -~ )

AR 81-1
F D/a 2

AR 81-2
F D/a e (10 7s

(*C)
200 300 400 500 600 700 800 900 1,000 1,200

(%)
15 41 10 3 13 0 16 2 249 294 336 540 100

(10--7 S 1)
0 016 0 12 0 34 0 97 20 20 56 96 13

(%)
34 70 11 8 24 7 31 3 383 445 552 741 100

(%)
16 10 2 22 7 33 3 53 3 658 823 932 956 100

(10 7s 1)
0 020 0 33 32 73 22 49 100 135 160

(%)
3 1 10 0 155 225 42 1 49 9 63 1 84 7 89 7 100

1)

0 036 0 31 10 40 64 13 16 27 31

0051 0 32 14 40 12 5 21 44 86 125

F = released fraction, D/a 2 = dfffusmn coeffmmnt, wath a = radms of supposed spherical grams

~Log

D/a 2

CO2 I x 4- x x + + x + + x AR 79 6 ARS08 AR 81-1 AR 81 2

l
i
~o

"

"-o

35

10

1)

21o

10~O/T

Fxg 3 Dfffusmn of C02 (Carslaw a n d Jaeger m e t h o d ) , log D/a 2 vs 1000/T Same explanation as for water (Fig 2)

carbon dioxide within the extractmn line What is the origin of orgamc compounds whose existence is proven by CH4 and cracking peaks m mass spectra 9 Thexr presence is reported m meteorites (Anders et al, 1973) and m alkahne igneous rocks (Petersflxe and S6rensen, 1970) In basalts, Muenow (1973) heating tholentlc glass from Hawan has obtained mass spectra charactenstm of crackmg of orgamc constituents, It seems probable that most of these orgamc compounds are

entrapped during nsmg and effusion of magmatxc material through hthosphere and bmsphere Thxs hypothesis is suggested by the heterogeneous distribution of organic matter m analysed grains Unless they were formed from carbon, hydrogen, nitrogen and oxygen (peroxxde groups ) reactions at the lava surface during the eruption (Freund, 1981 and oral communication, Nancy, May 1984) or during heating of samples m the laboratory In this case, thxs would explain the formation of part (probably minor quantities) of the water and carbon oxides Methane which is stable at high temperature and pressure with low oxygen fugaclty may belong to the initial gases and could be from mantle ongm ( Gold, 1982) The same process Is possible for hydrogen However m this study, it is difficult to choose between the hypotheses concerning the ongm of hydrogen (Taylor et al, 1983) and methane in volcanic rocks Isotopic geochemistry of hydrogen and carbon (Pmeau et al, 1976, Delorme et al, 1981; Javoy et al, 1982, Delorme, 1983) shows that water m the fumarohc gases collected on the dome of Arenal in 1979 and 1980 is from meteoric origin, whereas the 613C-value is slightly heavier than magmatlc values

306 temperatures is between 1 1 0 0 and 1150cC (Clgohm et al, 1984) Nevertheless the corresponding oxygen fugac~ty ~s much lower than the estimated one m the gases sampled at the surface (Delorme, 1983) The excess of CO over that which should be present for hxgher oxygen fugacltms may be attributed to reactmns m the extractmn hne This could also explain the existence of low amount of hydrocarbons

P kbar

/
r COl(CO+C02 ) /

/
~J~ /// /~//
T C
I J L

8. Conclusions
Despite of almost sxmflar composxt:on of thexr gas phases, these four lavas form two dxstmct groups (1) June 1979 and April 1980 lava flows, with quiet emxss:on ( 2 ) June 1981 lava flow and June 1981 bomb, w~th explosive activity The second group contains slightly more fluids than the first from 0 09-0 10% H20 and 0 07-0 08% CO2 to 0 08% H20 and 0 05% C02 Their continuous dehydration curves are also different, with an interval of --50:C towards the higher temperature for the first Besides their HeO and C02 diffusion Arrhenms plots log D/a 2 vs 1 / T also mdxcate two famlhes These are also confirmed by their C O / ( C O + CO)) ratios 0 35 and 0 30 for the first and second group, respectively These ratios could correspond to an equxhbrmm temperature between CO2, CO and C of 1125 ~ and 1080 C, respectively, at a pressure of 2 5 kbar The est~mahon of P - T condltmns ~s certainly quite ~mpreose as yet and far from the oxygen fugac~ty values determined m surface from sampling m the vents (Delorme, 1983)

Fig 4 Molar compos:tmn of vapor m C02-C0 system m eqmhbrmm with C, calculated from modified Reddhch-Kwong thermodynamm functaons ( Holloway, 1977)

7. C02, CO and C equilibrium

Assuming that C02, CO and C are mltmlly present, eqmhbrmm between carbon and a CO vapor could be governed by the Boudouard relation C O 2 + C ~ - 2 CO The modffmd R e d d h c h - K w o n g ( M R K ) thermodynamic functions (Holloway, 1977, Eggler et al, 1979) allow to relate temperature, pressure and molar composition of the vapor phase (Fig 4) Analyses of the fluid phase extracted m one 1200C step (Table I) give a ratm C O / ( C O + C02) of 0 35 for the June 1979 and April 1980 lavas and a ratio of 0 30 for those of June 1981 If the pressure is 2 5 kbar (8 km deep ), ratms of 0 35 and 0 30 correspond to a temperature of 1125 and 1080C, respectively With a pressure of only 1 kbar (3 km deep), temperatures are respectively of 1080 ~ and 1040C Values are close to those of the last mflectmn point on continuous dehydration curves (Fig 2a) Moreover, the range of measured extrusion

Acknowledgements
F P m e a u gave basaltic glasses with water contents analysed with high precis:on and cnt-

307

lc~zed the manuscript M Semet improved the Enghsh and discussed also the manuscript F Lhote carried out the X-ray analyses M Vernet determined the total water and J M Portal orgamc C and N We are grateful to D Dautel, M Gorau, A Legros and C Netter for typing and dlustratmns The field expenses were supported by PIRPSEV (Programme Interdlsc~phnmre de Recherche sur la Pr~wsmn et la Surveillance des ]~ruptmns Volcamques Centre Natmnal de la Recherche Scmntff~que) References
Ander~, E , Hayatsu, R and Studmr, H M, 1973 Orgamc compounds m meteorites Science, 182 781-790 Andrawes, F F and Gibson, Jr, E K , 1979 Release and analysis of gases from geological samples Am Mineral 64 453-463 Barker, C and Sommer, M A, 1973 Mass spectrometric analysis of the volatfles released by heating or crushing rocks In Analytical Methods Developed for Apphcatlon to Lunar Samples Analyses Am Soc Test Mater, ASTM STP No 539. p 56-70 Carslaw, H S and Jaeger. J C, 1959 Conductmn of Heat m Sohds Clarendon, Oxford, 2nd ed, 510 pp Chalgneau, M . 1975 Essal sur la composltmn des gaz magmatlquesprofonds Bull Volcanol ,39 (3) 1-13 Chmgneau, M and Fuster, J M , 1972 L'~ruphon du Tenegma (La Palma, Canaries) et la composltmn des laves et gaz fumerohens C R Acad Scl, Paros, S~r D, 274(22) 2948-2951 Chalgneau, M, Hgkmlan, R and Chemm~e. J L, 1980 Magmatlc gases extracted and analy~ed from ocean floor volcamcs Bull Volcanol, 43 (1) 241-253 Chamberhn, R T , 1908 The gases m rocks Carnegm Inst Washington, Publ, 106 3-80 Clgohm, C. Borgm, A and Casertano, L, 1984 Intra-crater activity, AA-Block Lava. viscosity and flow dynamics Arenal Volcano, Costa Rlca J Volcanol Geotherm Res, 20 155-176 Craig, H , 1961 Standard for reporting concentratmns of D and ~O m natural waters Scmnce, 133 1833-1834 Delaney. J R, Mueno~, D W and Graham, D, 1978 The abondance and dlstmbutmn of water, carbon and sulfur m the glassy rims of submarine pillow basalts Geochlm Cosmochlm Acta, 42 581-594 Delorme, H , 1983 Composltmn chlmlque et lsotoplque de la phase gazeuse de volcans calcoalcahns - Am~nque Centrale et Soufm~re de la Guadeloupe Thesis, Umversit) of Pans VII, Paros, 418 pp Delorme, A, Javoy, M, Chemm~e, J L and Pmeau, F , 1981 Chemical and lsotopm composltmns of volcamc gases

from island arc and continental margins Terra Cogmta, Spec Iss, p 79 (abstract) Eggler, D H , Mysen, B 0 , Hoermg, T C and Holloway, J R, 1979 The solublhty oi carbon monoxide m slhcate melts at high pressures and its effect on slhcate phase relations Earth Planet Scl Lett, 43 321-330 Freund, F , 1981 Mechanism of the water . n d carbon dioxide solublhty m oxides and slhcates and the role of 0 Contnb Mineral Petrol, 76 474-482 Freund, F , Kathrem, H , Wengeler, H . Knobel, R and Hemen, H J , 1980 Carbon m solid solution m forsterlte - A key to the untractable nature of reduced carbon m terrestrial and cosmogemc rocks Geochlm Cosmoclm Acta, 44 1319-1333 Freund, F . Knobel, R, Wengeler, H , Kathrem, H , 0berheuser, G and Schaeffer, R G, 1982 Orgamc compounds m the early atmosphere formed ablotlcally from atomic carbon Geol Rundsch, 71 (1) 1-21 Gold, T , 1982 Mantle methane - fool's gold9 Nature (London), 300 312-313 H~kmlan, R. Chalgneau, M and Chemm~e, J L. 1973 Popping rocks and lava tubes from the Mld-Atlantm Rift valley at 36= N Nature (London), 245 371-373 Hernandez, J and Tournon, J , 1978 Analyse chlmlque des verres volcamques riches en slhce ~ la m~crosonde 61ectron.que par d~tectmn d'~nergnedes R X C R Acad Scl, Pans, S~r D, 287 1087-1090 Holloway, J R, 1977 Fugacit~ and activity of molecular species m super-critical flmds In D G Fraser (Editor}, Thermodynamics m Geology D Reldel, Boston, Mass Javoy, M , Pmeau. F and All~gre, C J , 1982 Carbon dynamic cycle Nature (London). 300 171-173 Kflhngley, J S and Muenow. D W 1974 Mass spectrometric method for the determmatmn of the size dlstnbutton of CO~ mclusmns m oh~me Am Mineral, 59 863-867 Kdhngley, J S and Muenow, D W 1975 Volatlles from Hawanan submarine basalts determined by dynamic h~gh temperature mass spectrometr~ Geochlm Cosmoehlm Acta, 39 1467-1473 Mathez, E A and Delaney, J R, 1981 The nature and dlstnbutmn of carbon in submarine basalts and pendotlte nodules Earth Planet Sc~ Lett, 56 217-232 Moore, J G . 1965 Petrology of deep-sea basalts near Hawaii Am J Scl, 263 40-52 Muenow, D W , 1979 High temperature mass spectrometnc gas release studms of Hawanan volcamc glass Pele's tears Geochlm Cosmochlm Acta 37 1551-1561 Mysen, B O, 1983 The solubility mechamsms of volatfles m silicate melts and their relatmns to crystal-andes~e hqmd equlhbrm J Volcanol Geotherm Res, 18 361-385 Newhall, C G and Melson, W G , 1983 Explosive activity associated with the growth of volcanic domes J Volcanol Geotherm Res, 17 111-1~1

308 Peters:he, I A and S~rensen, H , 1970 Hydrocarbon gases and bituminous substances m rocks from the Ihmaussaq alkahne mtrusmn, South Greenland Llthos, 3 59-76 Pmeau, F , Javoy, M and Bottmga, Y, 1976 1~C/12Cratios of rocks and mclusmns m poppmg rocks m the MldAtlantm Ridge and their bearing on the problem of :sotopm composltmn of deep-seated carbon Earth Planet Sc: Lett 29 413-429 Pnce, W F , Huntingdon, A T and Barley, D K , 1977 The effect of crushing on the release of volatile components from heated obsidian Mineral Mag, 41 551-559 Reltsema, R H , 1979 Gases of mud volcanoes m the Copper River basm, Alaska Geochlm Cosmochlm Acta, 43 183-187 Taylor, B E , Emhelberger, J C and Westnch, H R , 1983 Hydrogen isotopic ev:dence of rhyohtm magma degassmg during shallow mtrusmn and eruptmn Nature (London), 306 541-545 White, D E and Warmg, G A, 1963 Data of geochemistry volcamc emanations U S Geol Surv, Prof Pap No 440K Z:mmermann, J L, 1972 L'eau et les gaz dans les prmclpales famflles de sflmates Scl Terre, Nancy, Mdm No 22,188 pp Zlmmermann, J L , 1981 La hbdratlon de l'eau, du gaz carbomque et des hydrocarbures des cordldntes - Cm~tlque des mdcamsmes - D~termmat:on des sites - Int~r~t pdtrogdndtlque Bull Mineral, 104 325-338 Zlmmermann, J L and Odm, G S, 1982 Kmetms of the release of argon and flulds from glaucomes In G S Odm (Editor), Numermal Datmg m Stratigraphy Wiley, Chmhester, pp 345-362 Zlmmermannm J L, Chemlnde, J L and Chalgneau, M , 1981 ]~tude de la phase gazeuse occluse dans les laves de 'TArdoukSba", volcan dphdm~re d'une dorsale dmerg~e (Afar) Bull Volcanol, 44(3) 527-546