The surface composition of two samples from the highly shocked, glass-coated lunar basalt (12054) and from four glass-coated fragments from the 1-2 mm (14161) fines were examined by X-ray photoemission spectroscopy to determine whether the agglutination process itself is responsible for the difference between their surface and bulk compositions. Auger electron spectroscopy of glass balls from the 15425 and 74001 fines were analyzed to understand the nature, extent, and behavior of volatile phases associated with lunar volcanism. Initial results indicate that (1) volatiles, in the outer few atomic layers sampled, vary considerably from ball to ball; (2) variability over the surface of individual balls is smaller; (3) the dominant volatiles on the balls are S and Zn; and (4) other volatiles commonly observed are P, Cl, and K

Cirlin, E. H.

Grant, R. W.

Housley, R. M.

English

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https://ntrs.nasa.gov/search.jsp?R=19790009612 2020-03-22T01:25:45+00:00Z
;h;iSA-CR-160102) LUNAR SAMPLE ANALYSIS
	 N79-17783
annual Report, 1 Feb. - 31 Dec. 1978
(F07.krell International Science Center) 6 p
HC AU2/MF A01
	 CSCL 03B	 Unclas
G3/91 13517
SC507.40AR
	
January 31, 1979
LUNAR SAMPLE ANALYSIS
ANNUAL REPORT NO. 7
For Period
February 1, 1978 thru December 31, 1978
General Order No. 507
Contract No. NAS9-11539
Prepared for
s	 National Aeronautics and Space Administration
Lyndon B. Johnson Space Center
Science and Applications Directorate
Houston, Tz,-xas, 77058
FEIi J y%^ ,
RECEIVED,
NASA STi FAGIUM
ACCESS CEPS.
R. M. Housley
Principal Investigator
This work was sponsored by the National Aeronautics and Space
Administration. Reproduction in whole or in part is permitted
for any purpose of the United States Government.
Q
Rockwell International
Science Center
by
Ec
ei
iOb Rockwell InternationalScience Center
10	 SC507.40AR
X-RAY PHOTOEMISS:ON STUDIES OF THE SURFACE COMPOSITION OF LUNAR IMPACT GLASS
SAMPLES INCLUDING 12054: R. M. Housley and R. W. Grant, Rockwell
International Science Center, Thousand Oaks, California 91360.
It has been known for some time now that the surfaces of lunar
regolith samples are significantly enriched in heavy isotopes of 0, Si, C, N,
and S with respect to their parent materials. Several mechanisms including
hydrogen stripping, micrometeorite vaporization, solar wind sputtering, and
preferential sticking of vaporized or sputtered atoms have been suggested to
account for the isotopic enrichments. These mechanisms would also lead to
characteristic elemental fractionation patterns.
The surface compositions of regolith fines samples do indeed differ
from their bulk compositions (1,2), but not in a way which fits with quali-
tative expectations for any of the above mechanisms. This led to the
suggestion (1,2) that the surface compositions of impact produced glasses
in the regolith might differ from their bulk com positions when they are
formed.	 The main cause of the difference between surface and bulk
compositions of lunar fines might be the agglutination process itself.
To test this hypothesis we have used x-ray photoemission spectro-
scopy (XPS) to measure the surface compositions of four glass coated fragments
from the 1-2 mm 14161 fines.
We have also studied two samples from the unique lunar rock 12054.
This is a highly shocked basalt whose top surface was almost completel y coated
with glass. Its orientation on the lunar surface when collected was well
documented and it appear q to have s pent its entire surface residence,
estimated to be 1-3 x 10 5 years, in this orientation (3).
Our sample 12454,68 from the upper surface is heavily microcratered
and partly covered with accreta. Sample 12054,69 from a reentrant crack
which apparently did not look directly out to space, shows no craters or
accreta visible at 4Ox with a binocular microscope.
It was anticipated that com parison of data on these 12054 samples
would also provide direct evidence on chemical fractionation produced by
solar wind sputtering or vapor deposition.
Surface compositions for both groups of samples obtained from XPS
data in the 0-200 eV binding energy range by a procedure previously described
(2) are given in Table 1. For comparison, the bulk composition obtained by
Janke et al. (4) on the =1 mm size fraction of the same Apollo 14 fines
sample, and the average com position of the 12054 glass as obtained by Schaal
and Hdrz from 25 microprobe analyses are also given. In the Fe row, R
indicates that the Fe is moderately reduced, com parable to the state observed
in bulk fines samples.	 RJR indicates weakly reduced Fe and NR indicates no
reduction. The surface compositions have been renormalized to 100 percent
excluding the volatiles Na, Cl, S, P, and K.
Looking at data on the 12054,69 crack surface we see a strong Fe
enrichment and moderate Mg and Ca depletions. There is also a strong surface
enrichment in the volatiles Na, Cl, ?, S, and K, and no Fe reduction.
On the 12054 too surface we see a very similar pattern for the
nonvolatile elements with Fe enrichment and !^g and Ca depletion. The volatile
elements, however, were present at much lower levels, which were not quanti-
tatively determined. Reduction of Fe was pronounced, but somewhat less than
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that observed in mature fines samples. The only clearly evident effects of
the surface exposure are the reduction of Fe ana the strong depletion in
volatile elements.
Turning now to the 14161 samples, the one showing no reduced Fe
has significant surface P. All four show surface depletions in Al and Mg
while Fe and Si are variable. No evidence for exposure induced changes in
major element chemistry is apparent.
Although far from conclusive, these results lend support to the
hypothesis that impact inauced glass formation itself makes a major contri-
bution to the observed differences between surface and bulk composition in
lunar fines samples (1,2). The depletion in surface volatiles associated
with Fe reduction suggests that at least a modest amount of sputtering
accompanies solar wind implantation.
The absence of evidence for major element changes associated with
vapor deposition or solar wind sputtering leaves unresolved the dominant
mechanism responsible for producing the heavy isoto pe enrichments observed
in lunar fines. However, if solar wind sputtering is important, the surface
enrichments in S and K and depletions in Ca (2) produced by impact glass
generation can contribute to understanding why S and K are much more highly
fractionated than Ca (6).
REFERENCES: (1) Nefedov, V. I., Urusov, V. S. and Zhavoronkov, N. M. (1972)
poklady Akademii Nauk SSSR 207, p. 698-701.
(2) Housley, R. M. and Grant, R. W. (1977) Proc. Lunar Sci. Conf.
8th, p. 3885-3899.
(3) Hartung, J. B., Horz, F., Morrison, 0. A., Schaeffer, 0. A.,
Schonfeld, E. and Zook, H. A. (1978) Lunar Science IX,
P. 165-a67.
(4) Wanke. H. et al. (1972) Proc. lunar Sci. Conf. 3rd, p. 1251-
1268.
(5) Schaal, R. B. and Horz, F. (1977) Proc. Lunar Sci. Conf. 8th,
P. 1697-1729.
(6) Russel, W. A., Papanastassiou, D. A., Tombrello, T. A. and
Eastein. S. (1977) Proc. Lunar -ci. Conf. 3th, p.37/91-
3805.
M
X-RAY PHOIOOEMISSI(tii STUDIES
2
*	 Janke et al. (4)
** Schaal and Horz (5)
TABLE 1.
14161	 14161
1	 2
Surface compositions of lunar glass
expressed in atomic percent.
14161	 14161	 I	 14163
	
12054,68
3	 4	 Bulk*	 Top
samples
12054,69
Crack
Si 17.78 20.05 18.65 18.54 18.01 15.40 16.27
Az 6.18 6.88 6.66 6.45 7.96 4.41 3.14
Mg 3.65 3.44 3.66 4.16 5.15 3.26 3.43
Fe 7.22 3.10 5.17 4.43 3.25 13.97 14.06
R R 'WR NR R NR
Ca 4.35 4.87 4.34 4.89 4.08 3.23 3.10
Ti 0.38 - 0.36 0.44 0.41 i 0.62 0.72
0 60.43 61.75 61.17 61.10 61.14 59.11 59.28
Na 1.8
Cl ` 0.2
S 0.9
P 0.7 I
0K I f i 1.5
I^
t
12054
But k**
16.96
4.39
5.39
6.42
4.81
1.39
50.25
0.17
X-RAY PHOTOEMISSION STUDIES
Housley, R. M., et al.
01% Rockwell InternationalScience Center
SC507.40AR
3
e01% Rockwell International
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SC507.40AR
SCANNING AUGER MICROPROBE AND ATOMIC ABSORPTION
STUDIES OF LUNAR VOLCANIC VOLATILES:
E. H. Cirlin and R. M. Housley, Rockwell Internation Science Center
Thousand Oaks, California 91360
We report new experimental results obtained as part of our continuing
effort to understand the nature, extent, and behavior of volatile phases
associated with lunar volcanism. Such understanding of the behavior of
volatile phases is necessary for the proper description of lunar volcanism
and for the interpretation of volatile trace metal depletion in lunar basalts
or enrichment in lunar fines.
We are making a new series of Auger studies of glass balls from the
15425 and 74001 fines using a recently acquired PHI model 590 scanning Auger
microprobe (SAM). The electron beam in this instrument can be focused down
to a diameter of 1000 A and can be scanned to obtain an image similar to-that
obtained with a scanning electron microscope (SEM). Selected spectra
obtained from balls in the three well identified volcanic categories (1) are
shown in Fig. 1.
Initial results indicate that: 1) Volatiles, in the outer few atomic
layers sampled by Auger spectroscopy, vary considerably from ball to ball, in
each class, ranging from nearly unobservable low values to values giving
spectra similar to those shown in Fig. 1. 2) Variability over the surface
of individual balls is smaller, as long as chipped areas are avoided.
3) The dominant volatiles on balls in all three classes are S and Zn.
4) Other volatiles commonly observed are P, Cl, and K.
Although direct comparison of Auger data with SEM x-ray fluorescence
data on the same spots has not yet been done, it appears from the general
level of x-ray intensities reported by 'utler and Meyer (2) that 5 to 10 times
more S and Zn must exist in a diffuse zone <O.5 µm thick than is seen in the
outer few atomic layers.
Thermal release profiles of Zn and Cd obtained from individual
particles and bulk samp'.es of 74001 black glass, by flameless atomic
absorption techniques (3), indicate that the major fractions of these
elements reside on the surfaces of grains. This agrees with results obtained
for Zn by Wasson et al. (4) using leaching experiments.
These results all support the picture of volatile transport during
lunar volcanism previously outlined by Butler and Meyer (2). At the time
of eruption or during the very early high temperature portion of their
existence volatiles are very effectively outgassed from lunar pyroclastic
glasses. Later volatiles begin to recondense on the glass balls while they
are still hot enough for significant diffusion to take place. Finally, up to
about a monolayer of volatiles condense after they have cooled to the point
where diffusion is negligible.
REFERENCES: (1) P. Butler, Jr. (1978) Lunar Science IX, p. 143-145.
(2) P. Butler, Jr. and C. Meyer, Jr. (1976) Proc. Lunar Sci. Conf. 7th,
p. 1561-1581. (3) E. H. Cirlin and R. M. Housley (1977) Proc. Lunar Sci. Conf.
8th, p. 3931-3940. (4) J. T. Wasson, W. V. Boynton, G. W. Kallemeyn, L. L.
Sundberg, and C. H. 'dai (1976) Proc. Lunar Sci. Conf. 7th, p. 1583-1595.
4
-M
Oilk Rockwell International
SCANNING AUGER MICROPRUBE STUDIES
	
Science Center
5C507.40AR
Cirlin E.H. and Housley K.M.
:ns
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;4001.:05
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r	 !RCWN i^,Ass
SI
I
I
I
:CC	 :^ao
Fig. 1. Auger soectra of glass balls from the three
recognic_d lunar volcanic oyroclastic er:,ups.
'tote the volatile coatings 4ith 5 and Cn p re-
dominant and R, C1, and K sometimes important.


Lunar sample analysis

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