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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.
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
Mirror
Laser
Spectrograph
Lens
Vacuum
Gauge Laser
Q-Switch
Detector Laser
Flashlamp
Sample
Chamber
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
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
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)
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
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)
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)
40000
intensity at 7 torr to the lower pressure intensity was 2.2
189.04 As(I)
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)
139.65 Cl(I)
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)
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
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
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.
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