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Spectrochimica Acta Part B 60 (2005) 237 – 248

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Use of the vacuum ultraviolet spectral region for laser-induced breakdown


spectroscopy-based Martian geology and exploration
Leon Radziemskia,*, David A. Cremersb, Katharine Benellib, Cynthia Khoob, Ronny D. Harrisc
a
Research Corporation, 4703 E. Camp Lowell, Suite 201, Tucson, AZ 85712, United States
b
Group C-ADI, MS J565, Los Alamos National Laboratory, Los Alamos, NM 87545, USA
c
Group EES-2, MS J495, Los Alamos National Laboratory, Los Alamos, NM 87545, USA

Received 3 November 2004; accepted 15 December 2004


Available online 30 January 2005

Abstract

Several elements important to planetary geology (e.g. Br, C, Cl, P, S) and the human exploration of Mars (e.g. toxic elements such as As)
have strong emission lines in the purge and vacuum ultraviolet (VUV) spectral region (100–200 nm). This spectral region has not been
extensively studied for space applications using geological samples. We studied emissions from the laser-induced breakdown spectroscopy
(LIBS) plasma in this region using a sample chamber filled with 7 torr (930 Pa) of CO2 to simulate the Martian atmosphere. Pressures down
to 0.02 torr were also used to evaluate the effect of the residual CO2 on the spectra and to begin investigating the use of VUV-LIBS for airless
bodies such as asteroids and the Moon. Spectra were recorded using a 0.3-m vacuum spectrometer with an intensified CCD (ICCD) camera.
The effects of time delay and laser energy on LIBS detection at reduced pressure were examined. The effect of ambient CO2 on the detection
of C in soil was also evaluated. Lines useful for the spectrochemical analysis of As, Br, C, Cl, P, and S were determined and calibration
curves were prepared for these elements. Although LIBS is being developed for stand-off analysis at many meters distance, the experiments
reported here were aimed at in-situ (close-up) analysis.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Laser-induced breakdown spectroscopy; LIBS; Mars; Geological analysis

1. Introduction Science Laboratory (MSL) rover planned for 2009. These


are: assess landing site geology; investigate planetary
Currently, laser-induced breakdown spectroscopy (LIBS) processes relevant to past habitability, including the role
is being developed for future use on missions to the surface of water; assess the biological potential of target environ-
of Mars because of its stand-off analysis capability [1–5] ments; and determine the presence of materials toxic to
and other advantages compared to elemental analysis plants and humans.
methods (e.g. APXS [6] and X-ray fluorescence [7]) used Monitoring in the vacuum ultraviolet (VUV) may allow
on prior Mars surface probes. These advantages include detection of certain elements important to these objectives
rapid analysis (b1 minute) and the ability to remove dust (e.g. As, Br, C, Cl, P, S) that are more difficult to detect
layers and ablate through weathered rock surfaces. LIBS has using wavelengths N200 nm. Reasons for this include (1)
been used under simulated Mars atmospheric conditions to stronger emission lines for these elements (e.g. S, P) in the
obtain useful analytical data on elements found in minerals, VUV region and (2) fewer spectral interferences compared
rocks, and soil between 200 and 900 nm. LIBS capabilities to the UV and visible regions, in which the density of
fit into four of the five mission objectives of the Mars emission lines is greater. Also, by using the VUV instead of
the IR spectral region to monitor certain elements, instru-
ment design may be simplified through reduction of the
* Corresponding author. Tel.: +1 520 571 1111; fax: +1 520 571 1119. required spectral coverage, as the majority of element lines
E-mail address: ljr@rescorp.org (L. Radziemski). of interest lie in the UV and blue spectral regions.
0584-8547/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2004.12.007
238 L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248

LIBS experiments using the VUV region have been plasma emission. Low pressures are also of interest to LIBS
reported previously. In 1992, Aguilera et al. initiated LIBS analysis of the Moon and other airless bodies such as
investigations in the VUV by describing the application to asteroids [23].
the analysis of steels [8]. Other studies of steel by Sturm et
al. [9], Khater et al. [10], and Hemmerlin et al. [11]
followed. In 2002 Khater et al. reported on laboratory 2. Experimental
analysis of steels over the wavelengths of 40–160 nm using
a 820 mJ/pulse Nd:YAG laser [12]. A detection limit for C 2.1. Apparatus
in steel of just over 1 ppm using the C(III) 97.7 nm line was
determined. Laboratory microanalysis of steel was per- A schematic of the apparatus used here is shown in Fig. 1.
formed using spectral features down to 150 nm [13]. Spectral dispersion was provided by a McPherson Model
Detection limits for S, C, and P were in the ppm range. 218 0.3-m vacuum spectrometer with a 5.08 cm wide
Kaski et al. [14] described results for sulfide mineral grating having 2400 grooves per mm. The theoretical
identification using LIBS, with spectra taken in the near resolving power was 120,000, producing a resolution of
VUV (175–210 nm) in a N2 purged atmosphere. The same 0.0013 nm at 150 nm. The detector was an Andor
group reported measuring Cl/C and Br/C ratios in pure intensified CCD (ICCD) camera (DH534-18F-05) with
organic solids [15]. Nitrogen and Ar were used to purge the VUV optics (MgF2 window) and 10241024 pixels (13
spectrograph and sample chamber and spectra down to 135 microns square). Each spectrum spanned 14 nm, corre-
nm were recorded. A comparison of Br detection in the near sponding to 0.014 nm per pixel, and a reciprocal linear
IR and VUV regions has been reported recently [16]. The dispersion of about 1 nm per mm. Since the pixel width in
limit of detection for the Br line at 130.99 nm was found to wavelength was 10 the theoretical resolution, it was the
be significantly lower than that obtained using near IR lines. limiting factor in resolution, except when the entrance slit
Our goal here is to investigate the VUV detection of some width exceeded 13 microns (usually the case). The ICCD
elements important to Mars exploration. These elements are was controlled by Andor MCD software. Intensifier gate
As, Br, C, Cl, P, and S. The biogenic elements C, S, and P delays varied from 0 to 1.5 As and unless stated otherwise,
(along with N, H, and O) are of obvious importance. gate widths were typically 20 As long. A delay generator
Phosphorus has been discussed as a key element in the (SRS DG 535) was used to set the detector gate width and
search for extinct life on Mars: areas showing anomalously delay relative to the laser pulse. The sensitivity of the
high concentrations of this element in deposits at or near the detection system decreased significantly for wavelengths
Martian surface may harbor remains of past organisms [17]. below about 110 nm.
Chlorine and sulfur are of interest because these are enriched A few experiments were conducted to determine
in Martian soils and models have been proposed to account detection limits using UV and visible lines as described in
for this which include aerosols produced by volcanic activity Section 3.6 below. For these, the detection system was a 0.5-
[18,19] and the hydrothermal alteration of rocks [20,21]. m spectrograph (Chromex 500IS) and an ICCD detector
High concentrations of SO3 (e.g. 30%) and Cl, indicative of (Oriel Instaspec V). This system was more sensitive to the
past water, have been found recently by the Mars Explora- longer wavelengths than the vacuum spectrometer and
tion Rovers (MER) in the area of Meridiani Planum [22]. In detector used for VUV measurements.
addition, the high concentrations of Cl and S suggest a soil Laser pulses of 7 ns duration, having a Gaussian-like
component that may contain high levels of toxic elements spatial profile, were generated using a Q-switched Nd:YAG
such as As, Pb, and Cd. Determining toxic elements is of laser operating at 1064 nm. The 8-mm diameter laser pulses
interest to manned Mars exploration because fine dusts were focused vertically downward onto the samples by a 20-
containing these species may be deposited on spacesuits and cm focal length glass lens (25 mm diameter) with the
other equipment and then carried through airlocks into plasma formed about 2 cm from the spectrometer entrance
spacecraft. In the Apollo moon landings, for example, the slit. The laser pulse repetition rate was 5 or 10 Hz. Pulse
ubiquity of lunar dust in the Lunar Excursion Module after energies of 40 mJ were used to simulate the energy
extravehicular activities was readily apparent even on these achievable by a compact LIBS module currently under
short duration missions. The longer surface residence times development for a future rover mission. A sealed acrylic
and flight duration of a Mars mission would greatly increase chamber mounted over the spectrograph entrance slit
the exposure of personnel to toxic materials making their housed the samples. The chamber was evacuated using an
detection more critical. oil-free pump (Tribodyne by Danielson) and then backfilled
Here we surveyed these elements and studied the spectral with CO2 gas to the desired pressure. The spectrometer and
output of the plasma in the VUV region from 100 to 200 nm chamber were pumped from the chamber side to avoid
using a sample chamber filled with 7 torr (930 Pa) of CO2 to ablated debris accumulating on the slit because of gas flow
simulate the Martian atmosphere. Additional experiments through the slit as happened in preliminary experiments.
were done at pressures down to 0.02 torr to determine the Pressures used were 7 torr of CO2 (930 Pa), and lower
effects of the CO2 atmosphere and these lower pressures on pressures of 0.26 and 0.020 torr of residual CO2 or air. The
L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248 239

From CO2 Tank

Mirror

Laser
Spectrograph

Lens

Vacuum
Gauge Laser
Q-Switch
Detector Laser
Flashlamp

Sample
Chamber

Gate Pulse Pulse


Generator

Laser Pulse SAMPLE


HOLDER To Vacuum
To Computer Plasma
Light to
Slit

Fig. 1. Apparatus used to analyze samples at Mars atmospheric pressure (7 torr) and pressures down to 0.02 torr. Up to eight samples were mounted on the
rotatable sample stage.

lower pressures were useful in determining the effects of 2.5%; K2SO4: 2.5%) at fixed concentrations but contain
CO2 absorption on the spectra. As discussed below, even at minor and trace elements with known concentrations in the
0.020 torr there is still observable absorption in some range 1–1000 ppm. For a few samples, a surrogate matrix was
spectral regions. devised by mixing sea sand (SiO2) with the clay bentonite
The chamber contained a rotatable stage, upon which up (e.g. SiO2: 49.9–55.19%; TiO2: 0.96–1.52%; Al2O3: 15.51–
to eight samples were positioned for sequential analysis 19.6%; Fe2O3: 6.50–10.20%; MgO: 1.34–2.72%; CaO:
without opening the chamber. The samples were tilted (458) 0.11–5.57%; Na2O: 0.43–3.65%; K2O: 0.61–2.06%). All
toward the slit (Fig. 1) so the groove ablated into the powdered samples (3–4 g) were pressed into pellets (32 mm
samples would not block light from the base of the plasma diam.  4 mm thick) prior to analysis.
from reaching the spectrometer slit. Note that a lens was not
used to focus the plasma light onto the entrance slit. 2.3. Atmospheres
Although light collection in his configuration would be less
than that achieved with lens imaging of the plasma light The major constituents of the Martian atmosphere [24]
onto the entrance slit, this geometry was chosen for its are CO2 (95.32%) and N2 (2.7%). Minor constituents (in
simplicity and as a configuration that may be deployed in an ppm) are Ar (1.6), O2 (0.13), CO (0.08), H2O (210), NO
actual compact in-situ LIBS analyzer. (100), Ne (2.5), HDO (0.85), Kr (0.03), and Xe (0.08). We

2.2. Samples
Table 1
Sample parameters of interest for calibration and detection limit
The type of samples used here depended on the experiments
measurement. For survey spectra, used to identify element
Element Concentration Matrix Source
emission lines, samples containing elements of interest at range (wt.%)
high concentrations were used. These included Al metal, except as noted
graphite, NaCl, NaCl in soil, KBr, KBr in soil, Los As 0–1000 ppm Los Alamos soil AAS solution
Alamos soil, elemental S in soil and phosphate samples. Br 0.99–24.9 Los Alamos soil KBr powder
Samples containing the elements of interest at known C 0.49–4.4 Colorado soil Naturally occurring,
concentrations were used to prepare calibration curves. majority carbonate
Cl 4.6–25.1 KCl, bentonite KCl powder
These samples are summarized in Table 1. Synthetic silicate
and sea sand
powders (Brammer Standard Company, GBW077xx series) P 0.04–0.43 Phosphate, Naturally occurring
were also used to map out strong VUV emission lines of Miracle GrowR
major elements normally found in geological samples. These S 0.51–20.1 Sea sand and Elemental sulfur
samples have major elements (SiO2: 72%; Al2O3: 15%; bentonite
S 0.51–25 Los Alamos soil Elemental sulfur
Fe2O3: 4%; CaMg(CO3)2 (pure dolomite): 4%; Na2SO4:
240 L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248

approximated the Mars atmosphere by using CO2 at 7 torr, 7 torr


slightly above the midrange of seasonal pressure variations
measured at the Viking landing sites [25]. Although the
ablation and excitation characteristics of the laser plasma
change significantly with pressure [26–29], the minor gases
are expected to have a negligible effect on plasma properties
and hence the analytical results.
Carbon dioxide [30], molecular oxygen [31], and water
vapor [32] have significant absorption bands below 200 nm.
In our case, CO2 was the major absorber. As described
below, we compare the CO2 absorption spectrum (based on
Ref. [30]) in the 115–205 nm region along with the
spectrum of a synthetic silicate powder (GBW07710),
showing the wavelengths of significant absorption. 0.00012 torr
The lowest pressure conveniently obtained in our
apparatus was 0.02 torr. That was not sufficiently low to
totally eliminate absorption in the 130–160 nm regime
from residual gases. The light path from the spark through
the spectrograph to the face of the detector was 115 cm
long. For both O2 and CO2, at the lowest pressures
achieved here, the absorption coefficients are high enough
to produce strong absorption in the region between 130
and 160 nm. The most notable effect of this was the
absence, at 0.26 torr of CO2, of the strong neutral Cl
resonance lines at 137.9 and 138.9 nm (while 133.5 nm
and 134.7 nm were observed).

Fig. 2. Images of the laser plasma formed on basalt rock in ambient CO2
pressures of 7 and 0.00012 torr. The width of each image is about 4 cm.
3. Results and discussion

3.1. Plasma appearance


3.2. Survey spectra
As noted above, plasma characteristics are strongly
dependent on ambient pressure. The appearance of the Survey spectra were taken from 100 to 200 nm in 10 nm
plasma at 7 and 0.00012 torr are shown in Fig. 2. These increments that overlapped by about 2 nm at each edge.
photos were obtained using the image mode of an ICCD These spectra were taken both in 0.02 Torr and at 7 Torr of
camera system (Princeton Instruments ICCD 576/RB with CO2, and with delays that enhanced different spectral
ST-135 controller) with a delay of 2 As and an 80 As gate features. Each spectrum was the sum of 50 shots. Samples
width. A different chamber and pumping arrangement was included As in soil, an As-containing mineral, and soil
used from that shown in Fig. 1 to record these images. At 7 spiked with KBr, KCl, and elemental S. The goal was to
torr, the plasma appears as a large luminous ball due to determine the strong emission lines of each element in the
significant expansion of the plasma at pressures below VUV region over the range of sensitivity of our detection
atmospheric pressure. As the pressure is decreased further, system. As an example, in Fig. 3 we show the spectrum of a
however, the visible volume of the luminous ball decreases synthetic silicate powder (GBW07710) from 115 to 205 nm
because of fewer collisions of species in the plasma with the taken in a pressure of 0.02 torr of air. The delay time was
surrounding atmosphere. In this case, the ablated material 100 ns and gate width was 20 As. The emissions in this
expands away from the surface into the low pressure region spectrum due to major elements will be similar to those seen
above the surface. This results in decreased excitation of from many other geological samples and can therefore serve
ablated species as described below in Section 3.5. At as a guide to possible interferences with minor and trace
0.00012 torr, only a small surface plasma is observed due to analyte emissions in this spectral region. The major features
the lack of a significant confining atmosphere. Species are observed belong to neutral or ionized atomic Al, C, H, N, O,
readily ejected at high velocity away from the laser–target S, and Si. We have included an overlay of the CO2
interaction zone on the surface. This small plasma, however, absorption spectrum [30] to indicate where it will have the
still provides useful, although reduced, analytical capabil- most influence. Since some of the CO2 features are fairly
ities compared to the plasma formed at higher pressures sharp, the effect of this gas will depend on the details of
[33]. overlap of those features with spectral lines of interest. Lines
L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248 241

Absorption coefficient (cm-1)


30 CO2

20

10

0
115 125 135 145 155 165 175

130.5 O(I)
130.2 O(I)

167.0 Al(II)
149.3 N(I)

185.5 Al(III)
Signal

180.7 S(I)

190.1 Si(I)
193.1 C(I)
174.3 N(I) 172.2 Al(II)
174.5 N(I) 176.4 Al(II)
165.7 C(I)

186.3 Al(III)
156.1 C(I)

198.4 Si(I)
121.5 H Lα

182.0 S(I)
120.0 N(I)

125 135 145 155 165 175 185 195

Wavelength (nm)

Fig. 3. Spectrum of synthetic silicate (GBW 07710) from 100 to 200 nm with major features identified. Relative absorption of CO2 is also shown. Emission
lines from major elements are labeled.

between 130 and 160 nm, however, will not be useful for Fig. 5(b) shows the LIBS spectrum obtained from
analytical purposes in a Mars atmosphere. pressed KCl. This spectrum was obtained with the sample
Spectra of selected analytes are shown in Figs. 4–6. in CO2 at a pressure of 0.26 torr. Even at this low pressure,
Arsenic lines recorded from 1000 ppm As in soil and the there is strong absorption of the strong Cl(I) lines at 136.34,
mineral cobaltite [(Co, Fe)AsS] are shown in Fig. 4. The 137.95, 138.97, 138.99, and 139.65 nm with the latter four
neutral As lines at 189.04, 193.76, and 197.26 nm appear lines not observed at all due to absorption by residual CO2
weakly on the spectra in comparison with the doubly [Al(II), even though, according to wavelength tables [34], these
Si(II), Ca(II)] and triply ionized species [Al(III)] of other lines are stronger than the Cl(I) line observed at 134.72 nm.
elements present in soil at high concentrations. As shown Fig. 6 shows (a) P lines from a phosphate sample (4.9%
here, these As lines, although weak, will probably be P) and (b) S lines from soil spiked with elemental S at high
interference free for other geologic materials making them (25%) and low (0.51%) concentrations. The pressure was 7
useful analyte lines. torr CO2. Other lines due to S were observed (e.g. Fig. 4)
Fig. 5(a) shows the LIBS spectrum of KBr in soil (1000 but these were not as strong as the three S lines shown here.
ppm Br) obtained at 0.25 torr CO2. In the region from 150 to
165 nm there are a number of Br lines, which are strong 3.3. Line intensity as a function of pressure
emitters [34]. All of these were observed. The Br(I) line at
153.17 nm, identified as being on the edge of the 153.35 In a LIBS measurement in an ambient atmosphere, the
Si(II) line, was verified by comparing the spectrum of pure observed intensity of an emission line depends on several
KBr with KBr in soil. Of the six Br(I) lines in this region, pressure related processes. First, the mass of ablated material
those at 154.07, 157.48, 157.64, 158.23, and 163.34 nm will and the excitation properties of the laser plasma are pressure
be useful as analytical lines. dependent [1]. Second, if the atmospheric gas between the
242 L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248

80000
(a) 1000 ppm As/soil indicative of water. On earth, typical concentrations of C
in soil are a few weight percent. A LIBS detection limit for

193.09 C(I)
60000 C in soil of about 300 ppm has been determined using the
186.23 Al(II) 247.8 nm C(I) line [35]. Other lines, such as 193.0 and
Signal

165.7 nm should be more sensitive, useful to monitor C at

199.56 Fe(III)
40000

197.26 As(I)
lower levels. Because the Mars atmosphere is about 7 torr

193.76 As(I)

198.75 Fe(III)
CO2, however, determining the concentration of C in the
189.04 As(I)
190.13 Si(I)

20000 target may be complicated. As the pressure is reduced, the


amount of C in the CO2 gas above the sample decreases and
this will act to decrease the C(I) signal.
0
To evaluate this effect, the relative changes in the strong
186 191 196
80000
C(I) line at 165.7 nm and the Al(II) line at 167.0 nm at
(b) pressures of 7 and 0.28 torr of CO2 (delay time was 500 ns)
185.47 Al(III)

185.07 Si(I) Cobaltite


185.80 Al(II)
180.73 S(I)

184.75 Si(I)
(Co, Fe)AsS were monitored. Five replicate spectra of 50 shots averaged
60000 each were taken at both pressures. The sample was soil with
181.69 Si(II)
182.03 S(I)

1.94% C. For C(I) at 165.7 nm, the ratio of the peak


186.23 Al(II)
184.01 Ca(II)
Signal

40000
intensity at 7 torr to the lower pressure intensity was 2.2
189.04 As(I)

with a standard deviation of about 20%. For Al(II) 167.0


190.03 S(I)
182.62 S(I)

nm, the same ratio was 0.86 with a standard deviation of


20000 about 15%. Therefore, the Al(II) signal increased slightly
whereas the C(I) signal decreased by over half as the
0
pressure was reduced, indicating the large effect of
179 184 189
Wavelength (nm) 40000

163.34 Br(I)
(a) KBr in soil

160.85 Fe(II)
161.19 Al(III)
157.64 Br(I) 158.23 Br(I)
157.48 Br(I)
Fig. 4. Spectra of (a) As in soil and (b) cobaltite mineral. Pressure was 0.27

162.99 Si(I)
153.17 Br(I)

156.14 C(I)
torr CO2.

160.58 Al(III)
153.35 Si(II)
154.07 Br(I)
Signal

plasma and the detector absorbs at the wavelength(s) of the 20000 154.82 C(IV)
152.67 Si(II)

emitting species, the transmitted light intensity will also


change with pressure (CO2, Fig. 3). In addition, if the gas (e.g.
CO2) contains the element of interest in the target (e.g. C in
soil), a signal can arise from plasma excitation of the gas
which adds to the signal from the target. 0
150 155 160 165
Fig. 3 shows the broad absorption of CO2 in the region
115–175 nm. There are several strong emission lines in this
15000
region due to elements of interest. Signals from two such (b) KCl
elements (Cl(I) at 134.72 nm and Br(I) at 154.07 nm) are
134.72 Cl(I)
133.57 Cl(I)

shown in Fig. 7 as a function of CO2 pressure. For these


measurements, the lowest achievable pressure was about
0.26 torr. These results, demonstrate, however, that as the 10000
CO2 pressure is reduced below about 1 torr, the transmitted
131.97 N(I)
Signal

emission intensity increases significantly. It should be kept


in mind, however, that changes in plasma excitation and
138.97/138.99 Cl(I)
135.17 Cl(I)

mass of ablated material due to pressure are convoluted in


5000
136.34 Cl(I)

these data. However, the data show that as the pressure is


137.95 Cl(I)

139.65 Cl(I)

reduced from 2 to 0.26 torr, a factor of 8, the intensity of the


recorded emissions increases by about a factor of 10,
suggesting the main effect in this pressure regime account-
ing for a change in line intensity is absorption by the 0
ambient CO2 gas. 132 137 142 147
Wavelength (nm)
3.4. Effect of CO2 atmosphere on the carbon emission signal
Fig. 5. Spectra of (a) Br in soil as KBr and (b) KCl powder in 0.26 torr of
CO2. The arrows on the Cl lines (which indicate the peaks of these lines),
Carbon, when measured with other elements, is of according to published tables of line intensities [34], will lie off the
interest because it is found in carbonates, which are intensity scale in the absence of CO2 absorption.
L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248 243

30000
4.9% P in phosphate presence of CO2 results in a loss of sensitivity of the
(a)

174.74 Si(I)
calibration curve. The ratio of the slopes of the linear curve
20000 fits is 2.1. For soil with 0.73% C content, a change in CO2

178.29 P(I)
178.77 P(I)
pressure from 0.26 to 7 torr produces an increase in the
Signal

181.45 Ca(II)
180.73 Ca(II)
176.64 Al(I)
177.50 P(I)
193.1 nm C(I) line intensity by a factor of 2.5. Similar
10000 results were obtained by monitoring the C(I) line at 247.8
nm at 0.26 and 7 torr CO2 where the difference in
0
calibration curve slopes was 2.0. These results show that
172 174 176 178 180 182 ambient CO2 would not be an impediment to monitoring C
80000
in geological samples on Mars although careful calibration
(b) S in soil will be required.
180.73 S(I)
182.03 S(I)

60000
182.62 S(I)

3.5. Intensity as a function of delay time and laser energy


25% S
Signal

40000
0.51% S It is well known in LIBS spectroscopy that the more
20000 highly ionized species in the spark typically decay more
quickly than neutrals and those of lower ionization. Also, as
0 pressure is reduced, higher ionization stages of certain
175 180 185 190 species become observable. For example, here we observed
Wavelength (nm) Al(III) and P(IV). To investigate this phenomenon, spectra
were recorded from 178 to 186 nm at different time delays
Fig. 6. Spectra of (a) P in a phosphate sample (4.9% P) and (b) S in soil at
and two pressures. The detector gate width was 100 ns.
high (25%) and low (0.51%) concentrations. Pressure was 7 torr CO2.
Using a phosphate sample, lines of P(I), Ca(II), Al(III)
and P(IV) were observed. Fig. 9 shows the decay curves for
these lines at 7 torr (9a) and at 0.25 torr (9b). Table 2 lists
atmospheric CO2 on the C signal in this pressure regime.
the 1/e decay times for several of these lines at the two
Note that these lines lie on the edge of CO2 absorption
pressures. The accuracy is estimated to be F50%. At each
(Fig. 3) and so should not be strongly affected by the change
pressure there is a monotonic decrease in decay time with
in pressure. In any event, decreased absorption through
increasing ion stage as expected. In addition, at 7 torr, the
decreased pressure will tend to increase the C(I) signal at
delay time at which the peak emission intensity of a species
165.7 nm slightly but a large signal decrease was observed.
occurs increases in the order P(IV): Ca(II) and Al(III): P(I).
A second evaluation of the effect of CO2 on the detection
Here the P(I) lines at 178.77 and 185.92 nm (average of two
of C in soil is shown in Fig. 8 in the form of calibration
lines separated by 0.05 nm) have maximum intensity at
curves obtained at 0.26 and 7 torr CO2. The 193.1 nm C(I)
delays of 600 and 800 ns, respectively. In contrast, at the
line was monitored so there was no effect due to absorption
lowest pressure, the maximum emission intensities of the
of this wavelength by CO2 gas. As the data show, the
(II) and (III) species occur at zero delay whereas the
intensities of the P(I) lines at 178.77 and 185.92 nm
maximize at about 200 and 500 ns, respectively. Also, the
1.2
decay times decrease, in general, with reduced pressure
Cl (I) 134.72 nm
Br (I) 154.07 nm
16000
0.8
Norm. signals

7 torr CO2
12000
Signal

0.4
8000

0.26 torr CO2


4000

0
0 2 4 6
0
CO2 pressure (torr) 0 1 2 3 4 5
C (%)
Fig. 7. Normalized intensities of the Br(I) line at 154.07 nm and Cl(I) at
134.72 nm as a function of CO2 pressure. Samples were soil with KBr and Fig. 8. Carbon calibration curves for C (193.1 nm) in soil at 0.26 and 7 torr
KCl added. CO2.
244 L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248

Fig. 9. Temporal decay of selected emission lines at (a) Mars pressure of 7 torr CO2 and (b) 0.25 torr. Details of the temporal dependence of P(I) and P(IV) at
the two pressures are shown on the expanded center plots. The scales in both figures are the same to allow for easy comparison. P(I) at 185.94 nm is the average
of this line with P(I) at 185.89 nm.

because of fewer collisions at the lower pressures to re- maximize at the longest delay times and therefore would be
excite the atoms. It is interesting to note that the greatest more sensitive to changes in the collision rate in the plasma,
difference in decay times between the two pressures occurs which because of the rapidly expanding plasma at 0.25 torr,
for the neutral species P(I). The intensities of these species would be far fewer than at the higher pressure of 7 torr.
Qualitatively, the differences described above for the
decay characteristics of species at the two pressures agree
Table 2 with the plasma images of Fig. 2. At 7 torr a relatively large
Decay times (1/e) for spectral lines around 180 nm
luminous ball is observed on the surface in which ablated
Element and 1/e time (ns) 1/e time (ns) species are repetitively excited many times during the
wavelength (nm) @ 0.025 torr air @ 7 torr CO2
plasma lifetime. This explains the maximum intensity
P(I) 178.77 1280 3510
occurring for all species at delay times greater than zero at
P(I) 185.92 1030 5495
Ca(II) 184.00 540 520 7 torr pressure. At the reduced pressure of 0.25 torr, the
Al(III) 185.47 120 143 plasma volume shrinks significantly and there are far fewer
Al(III) 186.28 160 245 collisions for excitation (factor of 28 based on pressure
P(IV) 188.85 46 73 alone). In addition, ablated material can more easily leave
L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248 245

60000
the sample surface and expand into the surrounding low
pressure region.
Laser pulse energy is important because it determines the 40000
mass of ablated material and the size of the plasma. Both

Signal
factors will affect the observed line intensities. Fig. 10
20000
shows the intensities of P(I), Ca(II) and Al(III) from a
phosphate sample for laser energies in the range 17 to 60
mJ/pulse. The value of 17 mJ was the minimum energy at 0
which reproducible plasmas were formed on the sample. For 0 10 20 30
S (%)
these measurements, the time delay was 500 ns to prevent
saturation of the detection system at the highest energy of 60 3000

mJ. The pressure was 0.25 torr. Note that the P(I) and Ca(II)
lines were observed at all energies and these intensities 2000
increased linearly with increased energy. Because of the low

Signal
pressure and 500 ns delay, P(IV), seen from the same
1000
sample in the data of Fig. 9a, was not observed here at any
energy. From Fig. 9a (7 torr), P(IV) has decayed completely
by 300 ns at 40 mJ and P(IV) was not observed at all in 0
Fig. 9b (0.25 torr). Also, because of the 500 ns delay, Al(III) 0 250 500 750 1000
was not observed at energies b40 mJ since from Fig. 9b, As (%)
Al(III) had decayed completely by 500 ns after plasma 8000
formation using a 40 mJ pulse. At energies N40 mJ however,
Al(II) lines appear, and increase in intensity with increased 6000
energy.
Signal

These results demonstrate a significant difference 4000


between LIBS at atmospheric pressure and LIBS at the
lower pressures in terms of pulse energy. Specifically, by 2000
increasing the laser energy at low pressure, the emission line
density can be increased through the appearance of higher 0
0 10 20 30
ionization stages. Generally, at atmospheric pressure, Cl (%)
increased pulse energy produces more intense emissions
from already existing lines, rather than leading to more Fig. 11. Calibration curves for S (180.73 nm), As (189.04 nm), and Cl
highly ionized species. (133.57 nm) in soil. Laser pulse energy was 40 mJ.

3.6. Calibration curves and detection limits


40000
P(I) 178.77 From the spectral surveys described above, lines were
selected for use in calibration curves and in the determi-
Ca(II) 184.00
nation of detection limits for elements important to Martian
Al(III) 185.47 geology. Some of the better linear calibration curves
30000
P(I) 185.94 obtained here are shown in Fig. 11 for S (180.73 nm), As
(189.04 nm), and Cl (133.57 nm). Table 1 contains relevant
Al(III) 186.28
information about the concentrations and matrix for each
Signal

20000 sample. The results of the measurements and relevant


conditions are listed in Table 3. The pulse energy was 40
mJF10%. These results are compared in a few cases with
values obtained from non-VUV lines on similar samples and
10000 similar ambient atmospheres.
The expression used for the detection limit was C L=3s/m
where s is the average standard deviation of the analyte
signal determined from the three lowest analyte concen-
0
0 20 40 60 80
trations, and m is the linear slope of the calibration curve
from the same three concentrations. The percent relative
Laser Energy (mJ/pulse) standard deviation (%RSD) is the average of the individual
Fig. 10. Intensities of P(I), Ca(II), and Al(III) as a function of laser pulse values for the lowest three concentration samples in the
energy. Time delay was 500 ns and the pressure was 0.25 torr. group.
246 L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248

Table 3 significantly greater (e.g. 43% vs. 7–11%) accounting in


Detection limits for selected elements of interest to Mars exploration part for our greater detection limit. The greater RSD values,
Element Line (nm) CO2 press. Delay (ns) CL %RSD i.e. poorer precision, could be due to visible changes in the
(torr) (20 As gate) (%)a
surface of the pressed powder sample by repetitive ablation.
As 189.0 7 200 0.044 26 The results obtained here along with recent data from the
Br 154.1 0.25 100 5.9 43
MERs show that VUV-LIBS would be a useful diagnostic
Br 163.3 0.25 100 5.6 53
C 247.8 7 500 0.24 7.6 [22] in view of its simplicity and ability to ablate through
C 193.1 7 500 0.32 6.3 surface layers. For example, analysis of the rock bGuadalupeQ
C 165.7 7 0 0.51 23 located in the Meridiani Planum site on Mars showed, after
Cl 133.6 0.25 500 7.5 27 grinding of the rock surface by the RAT (rock abrasion tool),
P 178.3 7 1500 0.028 16
that sulfate salt levels reached 30% by weight with the
S 180.7 7 0 1.03 9
S 182.6 7 500 1.77 30 relative abundance of SO3/Cl on the order of 24 [36]. Based
S 545.4 7 500 0.11 10 on the detection limits obtained here, the presence of S would
Laser energy was 40 mJ. be readily detectable whereas Cl may be detectable but
a
Here C L=3s/m where s is the average of the standard deviations of the quantification would be difficult with a detection limit here of
analyte signals determined from the three samples of lowest analyte 7.5%. The Cl concentration in bGuadalupeQ is on the order of
concentration, and m is the linear slope of the calibration curve. The units 1.2%. The presence of sulfates at other Meridiani Planum
are weight percent unless otherwise noted.
sites investigated such as soil at the Opportunity landing site
(approx. 6%) and in the rock McKittrick (approx. 12.5% pre-
The value in using the VUV spectral region for the RAT, 25% after RAT grinding) could also be detected based
detection of some of the elements of interest for Mars on the results obtained here.
exploration has been well-established. Detection limits b10 Again from recent MER data, detection of Br on Mars
ppm were obtained for C, S, and P in steel, for example [9]. shows concentration ranges extending from about 20 to
Comparison of detection limits obtained here with literature 1000 ppm [37]. This is significantly below the detection
values show that, in general, our limits are significantly limit achieved here but the upper values are within the limit
higher for geological samples. This could be due to many of detection in argon obtained using the 130.99 nm Br(I)
factors, the most obvious being the difference in exper- line and a more complex LIBS apparatus [16]. Further work
imental apparatuses and operational parameters and because needs to be carried out to determine if suitably low detection
our measurements were carried out at reduced pressure in limits can be achieved for Br and Cl by improvements in the
CO2. Here, we attempted to duplicate the sampling LIBS system. For example, using lens or mirror collection
geometry and laser pulse energy likely to be incorporated of the plasma light would increase emission signals. Such
into a practical in-situ compact LIBS analyzer for a space changes, however, will complicate the LIBS system
probe. Even in view of these experimental differences, compared to the simple but non-optimized light collection
however, it is instructive to compare results. method used here.
Using the setup of Fig. 1, the C detection limits obtained On the other hand, the detectability of As, C, P, and S
here (Table 3) lie in the range 0.24–0.51%, depending on the demonstrated here are within useful capabilities for Mars
emission line. For 247.8 nm, the limit was the lowest, missions. In addition, the ability to ablate a rock repetitively
0.24%, which should be compared with the previous result and penetrate through surface layers while conducting a
of 0.03% obtained by one of the authors using the same line LIBS measurement offers distinct advantages compared to
but with a more conventional LIBS detection system (e.g. the use of a mechanical device such as the RAT currently
fiber optic collection of plasma light, 50 mJ/pulse, and with deployed on the MERs.
the sample in air at atmospheric pressure [35]). Our detection
limit here was a factor of ten greater. Similarly, using the S(I)
lines of 180.6 and 180.7 nm, the detection limit obtained with 4. Conclusions
the VUV setup was about an order of magnitude greater than
that obtained using the 545.4 nm line with a conventional The use of some VUV emission lines for elements of
LIBS setup (fiber optic light collection and greater pulse interest to Martian geology has been demonstrated using in-
energy) and the sample in 7 torr CO2. situ detection (e.g. focusing distance of a few cm). Elements
Previous studies of Br detection in the VUV show that examined include As, Br, C, Cl, P, and S, which are difficult
low detection limits can be obtained for this element [16]. to monitor using lines at wavelengths greater than 200 nm.
For example, using a more complex lens-based light Useful detection limits were determined and measurement
collection system suitable for process control and conduct- precision was typical of that obtained for LIBS measure-
ing the analysis in an argon atmosphere (1000 mbar), a ments at longer wavelengths. Lines were identified that did
detection limit of 0.05% for Br in thermoplasts was not show spectral interferences with major elements likely
determined. The value obtained here was 5.6% for Br in to be found in geological samples. Even at Mars atmos-
soil at 0.25 torr CO2. In addition, our RSD values were pheric pressure of 7 torr, however, there is strong CO2
L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248 247

absorption hindering the detection of emissions in the range sion spectrometry figures of merit, Spectrochim. Acta 56B (2001)
of 130–160 nm. For pressure below about 1 torr, lines in this 661 – 669.
[12] M.A. Khater, J.T. Costello, E.T. Kennedy, Optimization of the
region become more intense as this absorption decreases. emission characteristics of laser-produced steel plasmas in the vacuum
VUV lines will be useful for detection of some elements at ultraviolet: significant improvements in carbon detection limits, Appl.
Mars pressures, especially for in-situ detection. For stand- Spectrosc. 56 (2002) 970 – 983.
off analysis at many meters, however, the useful VUV [13] I. Radivojevic, C. Haisch, R. Niessner, S. Florek, H. Becker-Ross, U.
Panne, Microanalysis by laser-induced plasma spectroscopy in the
spectral range will be reduced due to CO2 absorption.
vacuum ultraviolet, Anal. Chem. 76 (2004) 1648 – 1656.
[14] S. Kaski, H. Hakkanen, J. Korppi-Tommola, Sulfide mineral
identification using laser-induced plasma spectroscopy, Miner. Eng.
Acknowledgements 16 (2003) 1239 – 1243.
[15] S. Kaski, H. Hakkanen, J. Korppi-Tommola, Determination of Cl/C
This work was funded, in part, by the NASA under- and Br/C ratios in pure organic solids using laser-induced plasma
spectroscopy in near vacuum ultraviolet, J. Anal. At. Spectrom. 19
graduate student research program and by NASA’s Mars (2004) 474 – 478.
Instrument Development Program (MIDP). Los Alamos [16] I. Radivojevic, R. Niessner, C. Haisch, S. Florek, H. Becker-Ross, U.
National Laboratory is operated by the University of Panne, Detection of bromine in thermoplasts from consumer
California for the U.S. Department of Energy. electronics by laser-induced plasma spectroscopy, Spectrochim. Acta
59B (2004) 335 – 343.
[17] G. Weckwerth, M. Schidlowski, Phosphorus as a potential guide in
the search for extinct life on Mars, Adv. Space Res. 15 (1995)
References 185 – 191.
[18] B.C. Clark, A.K. Baird, R.J. Weldon, D.M. Tsusaki, L. Schnabel, M.P.
[1] A.K. Knight, N.L. Scherbarth, D.A. Cremers, M.J. Ferris, Character- Candelaria, Chemical composition of Martian fines, J. Geophys. Res.
ization of laser-induced breakdown spectroscopy (LIBS) for applica- 87 (1982) 10059 – 10067.
tion to space exploration, Appl. Spectrosc. 54 (2000) 331 – 340. [19] A. Banin, F.X. Han, I. Kan, A. Cicelsky, Acidic volatiles and the Mars
[2] R.C. Wiens, R.E. Arvidson, D.A. Cremers, M.J. Ferris, J.D. Blacic, soil, J. Geophys. Res. 102 (1997) 13341 – 13356.
F.P. Seelos IV, Combined remote mineralogical and elemental [20] H.E. Newsom, J.J. Hagerty, Chemical components of the Martian soil:
identification from rovers: field and laboratory tests using reflectance melt degassing, hydrothermal alteration, and chondritic debris,
and laser-induced breakdown spectroscopy, J. Geophys. Res. [Planets] J. Geophys. Res., [Planets] 102 (1997) 19345 – 19355.
107 (E11) (2002). [21] H.E. Newsom, J.J. Hagerty, F. Goff, Mixed hydrothermal fluids and
[3] R. Brennetot, J.L. Lacour, E. Vors, A. Rivoallan, D. Vailhen, S. the origin of the Martian soil, J. Geophys. Res., [Planets] 104 (1999)
Maurice, Mars analysis by laser-induced breakdown spectroscopy 8717 – 8728.
(MALIS): influence of Mars atmosphere on plasma emission and [22] Data from MER rovers is posted on the website: http://www.jpl.nasa.
study of factors influencing plasma emission with the use of Doehlert gov/missions/mer/.
designs, Appl. Spectrosc. 57 (2003) 744 – 752. [23] D.L. Domingue, A.F. Cheng, Near earth asteriod rendezvous: the
[4] F. Colao, R. Fantoni, V. Lazic, A. Paolini, G.G. Ori, L. Marinangeli, science of discovery, Johns Hopkins APL Tech, Dig. 23 (2002) 6 – 17.
A. Baliva, Investigation of LIBS feasibility for in-situ planetary [24] web site: http://nssdc.gsfc.nasa.gov/planetary/factsheet/marsfact.html.
exploration: an analysis on Martian rock analogues, Planet. Space Sci. [25] R.W. Zurek, Comparative aspects of the climate of Mars: an
52 (2004) 117 – 123. introduction to the current atmosphere, in: H.H. Kieffer, B.M.
[5] B. Sallé, J.-L. Lacour, E. Vors, P. Fichet, S. Maurice, D.A. Cremers, Jakosky, C.W. Snyder, M.S. Matthews (Eds.), Mars, The University
R.C. Wiens, Laser-induced breakdown spectroscopy for Mars surface of Arizona Press, Tucson, 1992, pp. 799 – 817.
analysis: capabilities at stand-off distances and detection of chlorine [26] J.M. Vadillo, J.M. Fernandez-Romero, C. Rodriguez, J.J. Laserna,
and sulfur elements, Spectrochim. Acta, Part B: Atom. Spectrosc. 59 Depth-resolved analysis by laser-induced breakdown spectrometry at
(2004) 1413 – 1422. reduced pressure, Surf. Interface Anal. 26 (1998) 995 – 1000.
[6] B.C. Clark, A.K. Baird, H.J. Rose Jr., P. Toulmin III, R.P. Christian, [27] J.M. Vadillo, J.M. Fernandez-Romero, C. Rodriguez, J.J. Laserna,
W.C. Kelliher, A.J. Castro, C.D. Rowe, K. Keil, G.R. Huss, The Effect of plasma shielding on laser ablation rate of pure metals at
Viking X-ray fluorescence experiment: analytical methods and early reduced pressure, Surf. Interface Anal. 27 (1999) 1009 – 1015.
results, J. Geophys. Res. 82 (1977) 4577 – 4594. [28] Y. Iida, Atomic emission characteristics of laser-induced plasmas in an
[7] T. Economou, Chemical analysis of Martian soil and rocks obtained argon atmosphere at reduced pressure, Appl. Spectrosc. 43 (1989)
by the Pathfinder alpha proton X-ray spectrometer, Radiat. Phys. 229 – 234.
Chem. 61 (2001) 191 – 197. [29] M. Kuzuya, O. Mikami, Effect of argon pressure on spectral emission
[8] J.A. Aguilera, C. Aragon, J. Campos, Determination of carbon content of a plasma produced by a laser microprobe, J. Anal. At. Spectrom. 7
in steel using laser-induced breakdown spectroscopy, Appl. Spectrosc. (1992) 493 – 497.
46 (1992) 1382 – 1387. [30] E.C.Y. Inn, K. Watanabe, M. Zelikoff, Absorption coefficients of
[9] V. Sturm, L. Peter, R. Noll, Steel analysis with laser-induced gases in the vacuum ultraviolet: Part III. CO2, J. Chem. Phys. 21
breakdown spectrometry in the vacuum ultraviolet, Appl. Spectrosc. (1953) 1648 – 1650.
54 (2000) 1275 – 1278. [31] K. Watanabe, E.C.Y. Inn, M. Zelikoff, Absorption coefficients of
[10] M.A. Khater, P. van Kampen, J.T. Costello, J.-P. Mosnier, E.T. oxygen in the vacuum ultraviolet, J. Chem. Phys. 21 (1953)
Kennedy, Time-integrated laser-induced plasma spectroscopy in the 1026 – 1030.
vacuum ultraviolet for the quantitative elemental characterization of [32] K. Watanabe, M. Zelikoff, Absorption coefficients of water vapor in
steel alloys, J. Phys. D: Appl. Phys. 33 (2000) 2252 – 2262. the vacuum ultraviolet, JOSA 43 (1953) 753 – 755.
[11] M. Hemmerlin, R. Meilland, H. Falk, P. Wintjens, L. Paulard, [33] R.D. Harris, D.A. Cremers, C. Khoo, K. Benelli. Detection of
Application of vacuum ultraviolet laser-induced breakdown spec- Geological Materials at Pressures b1 micron: Application to the Moon
trometry for steel analysis—comparison with spark-optical emis- and Asteroids, to be submitted to Applied Spectroscopy.
248 L. Radziemski et al. / Spectrochimica Acta Part B 60 (2005) 237–248

[34] J. Reader, C.H. Corliss, Wavelengths and Transition Probabilities for soil carbon with laser-induced breakdown spectroscopy (LIBS),
Atoms and Atomic Ions, NSRDS-NBS 68, U.S. Government Printing Journal of Environmental Quality 30 (2001) 2002 – 2206.
Office, 1980. [36] Web site: http://www.jpl.nasa.gov/missions/mer/images.cfm?id=1132.
[35] D.A. Cremers, M.H. Ebinger, D.D. Breshears, P.J. Unkefer, S.A. [37] Web site: http://www.jpl.nasa.gov/missions/mer/images.cfm?id=632.
Kammerdiener, M.J. Ferris, K.M. Catlett, J.R. Brown, Measuring total