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Anal Bioanal Chem (2006) 385: 1140–1148

DOI 10.1007/s00216-006-0513-3

TECHNICAL NOTE

Russell S. Harmon . Frank C. DeLucia Jr. .


Aaron LaPointe . Raymond J. Winkel Jr. .
Andrzej W. Miziolek

LIBS for landmine detection and discrimination

Received: 31 January 2006 / Revised: 11 April 2006 / Accepted: 26 April 2006 / Published online: 25 May 2006
# Springer-Verlag 2006

Abstract The concept of utilizing laser-induced break- Keywords Broadband LIBS . Landmine detection .
down spectroscopy (LIBS) technology for landmine Laser-induced breakdown spectroscopy
detection and discrimination has been evaluated using
both laboratory LIBS and a prototype man-portable LIBS
systems. LIBS spectra were collected for a suite of Introduction
landmine casings, non-mine plastic materials, and ‘clut-
ter-type’ objects likely to be present in the soil of a conflict The detection of landmines buried in the often highly
area or a former conflict area. Landmine casings examined heterogeneous and temporally dynamic near-surface soil
included a broad selection of anti-personnel and anti-tank environment is a difficult sensor problem, and small, low-
mines from different countries of manufacture. Other metal anti-personnel land mines present a particular
materials analyzed included rocks and soil, metal objects, challenge. Not only are landmines a threat on a battlefield,
cellulose materials, and different types of plastics. Two but they remain a significant problem for civilians around
‘blind’ laboratory tests were conducted in which 100 the world in areas of current and former conflict. Some
broadband LIBS spectra were obtained for a mixed suite of 15,000–20,000 people in more than 90 countries fall
landmine casings and clutter objects and compared with a victims to landmines each year [1]. At present, landmine
previously-assembled spectral reference library. Using a detection is generally conducted in a manner not that
linear correlation approach, ‘mine/no mine’ determinations dissimilar to that employed half a century ago. For
were correctly made for more than 90% of the samples in example, in humanitarian demining operations, deminers
both tests. A similar test using a prototype man-portable utilize a hand-held metal detector for detection and a thin,
LIBS system yielded an analogous result, validating the tapered prodding device for decision making about the
concept of using LIBS for landmine detection and character of a detected buried object. Meter-wide lanes are
discrimination. searched for metal anomalies while swinging the metal
detector back and forth just above the ground surface. After
the operator has received a signal from the metal detector,
R. S. Harmon (*)
US Army Research Office, the suspected area is probed to determine whether or not it
P.O. Box 12211 Research Triangle Park, NC 27709, USA contains a buried mine. This is also the general procedure
e-mail: Russell.Harmon@us.army.mil used for military post-operational landmine clearance,
Tel.: +1-919-5494326 although a prototype handheld system that combines a
Fax: +1-919-5494310 metal detector with a ground-penetrating radar was
F. C. DeLucia Jr. . A. W. Miziolek deployed for the first time in 2003 on a limited basis by
Weapons and Materials Research Directorate, US forces in Afghanistan. New technology for buried
US Army Research Laboratory (ARL), landmine detection and identification is needed. The ideal
Aberdeen Proving Ground, MD 21005, USA landmine sensor would detect both the exterior casing and
A. LaPointe the explosive charge contained within. Many physical and
Countermine Division, CERDC Night Vision and Electronic chemical approaches to this difficult problem of landmine
and Sensors Directorate, Ft. Belvoir, detection are currently being investigated, including laser-
Alexandria, VA 22060, USA induced breakdown spectroscopy (LIBS), which has the
R. J. Winkel Jr. attractive possibility of being a single-sensor technology
Department of Physics, US Military Academy, with the potential to detect and discriminate both the casing
West Point, NY 10996, USA of a landmine and its explosive contents.
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The use of broadband LIBS – i.e., capturing the entire single laser shots versus multiple laser shots for data
LIBS spectrum from 200–980 nm – is based on the idea collection) and investigated. The approach decided upon
that every material produces a unique broadband LIBS was a single laser ‘cleaning’ shot followed by a single laser
spectrum. The approach used in this study derives from the ‘data collection’ shot, as this was considered the approach
work of Gornushkin et al. [2], who were able to distinguish most likely to be utilized under field operation of a LIBS
a set of compositionally-similar stainless steel and cast iron landmine sensor system.
samples by examining the 230- to 310-nm region of the A man-portable (MP) LIBS system is being developed
LIBS spectra, and Anzano et al. [3], who compared LIBS by ARL, in partnership with Ocean Optics, and undergoing
spectra over the 200- to 800-nm range to distinguish testing for some applications of military and security
between the six different commercial plastic types using a interest at the ARL. The current MP-LIBS prototype
rank correlation approach. In previous studies conducted at instrumentation consists of a backpack containing a
the Army Research Laboratory (ARL), it was demonstrated computer and broadband spectrometer and a hand-held
that broadband LIBS, where the full 200- to 980-nm wand containing an actively Q-switched Nd:YAG laser
spectrum of a sample was captured, could be used to (1064 nm, 30 mJ/pulse). The operator reviews collected
discriminate between different explosive and energetic spectra and interprets data through the use of a heads-up
materials and biological agent surrogates [4–6]. This display. Like other LIBS instrumentation, the system is
technical note describes how broadband LIBS might be inherently rugged, requires no sample preparation, and
used for the discrimination of landmine casings. is suitable for the analysis of many different materials
(soils, metals, biological materials, etc.). The concept for
MP-LIBS as a confirmatory sensor system for landmine
Experimental detection envisages a soil-insertable LIBS probe similar in
form to that currently used in both military and
Laboratory and man-portable LIBS systems humanitarian demining [7] that would be used to
interrogate unknown subsurface objects. One option for
The ARL laboratory benchtop broadband LIBS system the design would deliver laser light and collect the plasma
consists of a pulsed laser, mirror and focusing lens, light emission through an optical fiber in the thin hand-held
adjustable sample stage, a fiber optic for light collection, probe with a small focusing lens in the probe tip. Another
broadband spectrometer, and desktop computer. A laser option would have the light delivery and collection through
pulse of 200 mJ of a 10-ns duration from an actively a hollow probe containing a focusing lens at the probe tip.
Q-switched Surelite Nd:YAG laser (Continuum, St. Clara, A protective shutter would be used in both designs. Also,
Calif.) operated at the fundamental wavelength is focused the use of a gas flow, most likely argon, should help to keep
by a 50-mm focal length convex lens to produce a high- the optical path free of debris and enhance the LIBS
energy spark in air that generates the high-temperature spectral signature [8].
microplasma. A sample to be analyzed is placed on the
sample stage and the height adjusted so that the laser spark
occurs on the sample surface. The laser beam diameter is Background
3 mm, with a beam divergence of 1 mr, so that the laser spot
size is about 60 μm and the crater generated on the sample Plastics are synthetic, high-molecular-weight polymers
is on the order of 100 μm. A bundle of seven 600-μm- having a carbon and hydrogen backbone. The hundreds
diameter optical fibers is oriented appropriately to collect of different, chemically-complex plastics manufactured
the light emission from the plasma. A lens is placed before today can be divided into 11 chemical classes (acetals,
the fiber optic bundle so that the plasma spark is defocused acrylics, aminics, cellulosics, phenolics, polymides, polyes-
to the point that spatial effects are eliminated and the ters, polyolefins, polyurethanes, styrenes, and vinyls) on the
individual fibers collect the same light emission. The fibers basis of the resin utilized in the polymerization process
transmit the acquired light to an Ocean Optics (Dunedin, [9, 10]. Many different chemicals and compounds are added
Fla.) Model 2000 broadband spectrometer, having a at the final synthesis stages of the polymer, or in subsequent
resolution of 0.1 nm, to separate the light from different processing, to improve or alter some characteristic(s) of the
atomic, ionic, and molecular constituents of the plasma. plastic in order to obtain products with certain desirable
The seven optical fibers are connected to seven separate physical characteristics. Binders and fillers are added during
spectrometers, each of which covers one portion of the the initial synthesis, or during subsequent processing, to
200- to 980-nm spectral range. All chemical elements can decrease the volume of resin needed in the manufacturing
be detected across this spectral range. The LIBS spectra process. Reinforcements are materials used to improve the
used in this study were collected for 2 ms after a 1.5-μs strength properties of the plastic. Flow improvers and
time delay with respect to the laser spark to reduce plasma plasticizers are substances used to increase flexibility. Other
continuum intensity. The LIBS spectra collection software additives typically present in plastics include antistatics,
and the statistical LIBS library software were provided by flame retardants, lubricants to reduce friction, pigments to
Ocean Optics. provide color, and stabilizers to protect against weathering
Several different analytical approaches were considered and degradation resulting from exposure to ultraviolet light,
(e.g., pre-analysis laser shots to ‘clean’ the sample surface, oxygen, ozone, and bacteria. Plastics in routine commercial
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use today tend to be of six general types: Type I, positions and intensities, with the two spectra for the PP
polyethylene terephthalate (PETE), Type II, low-density sample taken 4 months apart being indistinguishable. The
polyethylene (LDPE), Type III, polyvinyl chloride (PVC), most similar of the six spectra are those for the Type I and
Type IV, high-density polyethylene (HDPE), Type V, Type IV plastics – PETE and LDPE, in this figure – which
polypropylene (PP), Type VI, polystyrene (PS). have different stoichiometries, as denoted by the different
Figure 1 shows single-shot, broadband LIBS spectra for C/H line intensity ratios of the spectra, but in the case of the
samples of these six common types of commercial plastic samples analyzed must lack distinctive additives. In their
(Fig. 1a) and spectra for the same Type V plastic sample, in study of commercial plastics, Anzano et al. [2] found that
this figure PP, taken 4 months apart in the ARL laboratory PETE (Type I plastic) and PP (Type V plastic), the
(Fig. 1b). Clear differences are observed in visual polymers with the greatest difference in C/H ratio, were the
inspection of the six plastic spectra in terms of line two plastics most reliable discriminated. The instances

Fig. 1 a Comparison of single-


shot, broadband LIBS spectra
for the six different types of
common commercial plastics:
I Polyethylene terephthalate
(PETE), II high-density poly-
ethylene (HDPE), III polyvinyl
chloride (PVC), IV low-density
polyethylene (LDPE), V poly-
propylene (PP), VI polystyrene
(PS). b Single-shot, broadband
LIBS spectra for a PP sample
(Type V plastic) collected in
February 2004 and again
in June 2004
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resulting in the most confusion and incorrect identifications and a subset of eight samples of seven different types of AT
in their rank correlation approach were Types II, III, and IV mines and 18 samples of seven different types of AP mines
plastic (HDPE, PVC, and LDPE, respectively), i.e., those were used in the man-portable LIBS system experiment.
plastics of similar stoichiometry. Information about the different landmines analyzed comes
from the James Madison University Mine Action Informa-
tion Center web site [11]. Because most landmines
Test samples manufactured in more recent times are plastic and because
the detection of plastic landmines is much more difficult
A total of 21 different landmines, nine anti-personnel (AP) than that of metal mines [12], the focus of this study was on
and 12 anti-tank (AT) mines from five different countries of the identification and discrimination of plastic landmine
origin were used in the two laboratory LIBS experiments, casings.

Fig. 2 Comparison of broad-


band LIBS spectra for seven
anti-personnel (AP) landmine
casings from three different
countries of manufacture
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A broad range of natural and anthropogenic materials materials included four rocks of different composition and
(‘clutter’) of the kind likely to be present within the soil of a a Fe-rich clay soil.
conflict area or former conflict area were also analyzed.
The set of plastics and rubber included the six common
types of commercial plastic, plus samples of nylon and Results and discussion
Teflon simulants used by the Army in landmine sensor
system performance testing, plastic clips from Army The plastic used in the fabrication of US landmine casings
equipment, and a rubber Army gas mask hose. The metal is PS (Type VI plastic), and this is thought to be the case for
set comprised samples of aluminum, zinc, lead, steel, brass, landmines manufactured in other countries, with the
and rusted iron. Cellulose materials consisted of a wood exception of the flexible PFM-1 ‘butterfly’ AP mine,
box, weathered wood stick, fresh wood stick, a weathered which is made of polyethylene. However, it is to be
chemically-treated wood block, and cardboard. The earth expected that the plastic manufacturing process would
differ considerably from one country – or even one

Fig. 3 Comparison of broad-


band LIBS spectra for seven
anti-tank (AT) landmine casings
from four different countries
of manufacture
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Fig. 4 Comparison of broad-
band LIBS spectra for three of
ten laser shots (nos. 3, 7, 10)
taken on the surface of a PMN-6
AP mine casing collected during
a ten-shot test with each shot
taken at a different spot on
surface of the landmine casing

processing plant – to another in terms of the additive due to the wide variety of exotic components present in the
substances used for plasticisers, fillers, binders, stabilizers, different plastic formulations, as noted above. To extend
and pigments, so we were optimistic that single-shot, the LIBS approach to the problem of landmines at an
broadband LIBS could be used to discriminate landmine operational level, the identification and discrimination
casings from other types of objects using a linear issues must be addressed, but the distinct broadband LIBS
correlation approach to match the LIBS spectrum collected spectra observed for different mine types is an encouraging
from an individual laser shot with LIBS spectra contained factor in this regard. The degree of shot-to-shot reprodu-
in a library of different materials. The idea being tested in cibility of a LIBS signal reflects variations in the coupling
our study is that the very large variety of such additive of the laser energy to the sample surface and the resultant
substances present in different plastics should provide a temperature of the plasma that is created on the sample
basis for discriminating different types of plastic landmines surface. This phenomenon depends on a large number of
by broadband LIBS, which captures the entire elemental factors, some of which are systematic and others of which
composition of a sample. This being the case, then a LIBS are determined by the specific nature of the target surface at
spectrum should provide an individualized ‘fingerprint’ of the point of analysis. Systematic factors include the
any material analyzed, and LIBS spectra of different stability of the laser pulse intensity, the laser fluence, and
materials should be distinguishable one from another by the optical angle to the beam path and the resulting position
simple statistical analysis of the complete LIBS spectra. in the detection optic’s field of view. The most important
Figure 2 presents single-shot broadband LIBS spectra for a non-systematic factor is likely to be the nature of the
variety of plastic AP and Fig. 3 for some different plastic sample surface at the sub-millimeter scale – i.e., the surface
AT landmine casings. The LIBS spectrum of one metal AT texture and roughness of the sample at the point on the
landmine casing is included for comparison. The distinct surface where the plasma is generated – because homoge-
spectral differences between the various AP and AT mine neity and roughness consistency of the sample surface
casings that are evident in the two figures illustrate clearly presented to the focused laser beam are necessary
that there is a diversity of elemental compositions for the conditions for reproducible LIBS plasmas. Figure 4
broad spectrum. For the plastic mines, this is likely to be shows the spectra for three single laser shots taken at

Fig. 5 Comparison of single- 5000


LIBS signal intensity (counts)

shot broadband LIBS spectra for


specimen #1
M14 AP mine
four different M14 AP mine
4000
casings

3000 specimen #2

2000
specimen #3
1000
specimen #4
0
200 300 400 500 600 700 800 900 1000
Wavelength
h (nm)
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different points on the surface of a cylindrical PMN-6 total of five spectra per mine. The process was repeated for
plastic AP mine during a ten-shot data collection traverse the other plastic materials. The complete library consisted of
across the top surface of the sample. The same elemental five LIBS spectra from the two mines and three plastic
peaks are present in each of the three LIBS spectra; it is samples, for a total of 25 spectra. Next, a single-shot LIBS
only absolute peak intensities that vary systematically from spectrum was acquired for each mine and plastic sample,
one spectrum to another. This observation is attributable to and these spectra were compared to the library to ascertain if
the intrinsic roughness of the plastic mine surface at the a match could be obtained. This process was repeated 100
sub-millimeter scale. which produces differences in inci- times for each sample. On the basis of the acquired single-
dence angle of the incident laser beam, light absorption, shot LIBS spectra, one type of AP mine was identified
and surface reflectance from one point to another across the correctly 99 out of 100 times and the other mine 95 out of
surface of the mine. Equivalent single-shot LIBS spectra 100 times. One laboratory plastic sample was identified
for four different M14 AP plastic mine casings are correctly in all 100 shots, another 99 out of 100 times, and
presented in Fig. 5. Again, a high degree of spectral the third correctly identified the mine 81 out of 100 times.
similarity is observed, with differences in spectral line This initial experiment was followed by a three other
intensities being attributed to variations in the degree of tests. First, a library containing single-shot LIBS spectra
laser-sample coupling and subsequent light reflection was constructed for a sample population of multiple
during the breakdown and plasma formation events. In specimens of nine AP mines and eight AT mines, three
contrast to the matched spectra shown in Fig. 5, there is a different plastics, and one metal sample using the same
distinct difference in the character of the observed spectra broadband LIBS-pulsed laser system at a slightly higher
shown in in Fig. 6 for the two components of an AT mine, laser power (50 mJ, Q-switched, 1-ms delay). Three levels
the rubber plunger and plastic casing. of discrimination were of interest in this test: a correct
‘mine’/no-mine’ determination as well as a correct ‘mine
type’ determination and ‘specimen identification’ for
Preliminary experiments samples correctly identified as mines. Items were selected
at random from the sample suite and their single-shot
Initially, two preliminary experiments were conducted to spectra were compared to those contained in the spectral
determine how effective LIBS might be at identifying library. A correct ‘mine/no-mine’ determination was
landmines of a specific type or particular country of recorded in 46 of 59 cases – a success rate of 78%. Of
manufacture. For this test, the ARL broadband LIBS system the 46 correct mine determinations, the mine type was
was used with a pulsed, Q-switched, Big Sky (Bozeman, correctly identified in 36 cases and the specific mine
Mont.) laser operating at 30 mJ and a 1-ms delay. A library specimen was identified in 24 instances. Next, the issue of
of LIBS spectra was compiled for two AP mines of different color was examined, as several types of landmine casing
country of manufacture and for three plastic samples on are beige and different shades of green. We first ran five AP
hand in the ARL spectroscopy laboratory. To build the mine cases (three beige and two olive green) against the
library, we recorded single-shot LIBS spectra from five spectral library. All samples were correctly classified as
different locations on each mine. As a first step, the position mines, the mine color was correctly identified in all five
of each mine casing was coarsely adjusted so that the spark instances, and the exact mine casing specimen was
visually occurred on the casing surface. The position was correctly identified four of the five times. In another test,
subsequently finely adjusted until a spectrum ‘rich’ in five samples of an AP mine casing (four forest green and
spectral lines and bands was obtained. One library entry was one beige) were all correctly classified as mines, all
recorded for each location on the mine casing surface for a correctly identified by type, and the correct specimen color
was correctly identified four of the five cases. In a final test,
17 single-shot spectra were acquired for six samples of
three types of AT mine casings that were not contained in
the spectral library. All samples were correctly classified as
mines, and the correct mine type was identified in 12 of the
17 cases.

Main experiment

The various preliminary experiments described above


provided the confidence to undertake a more expansive
test that was repeated at two different points in time
4 months apart. The first test was conducted with the
pulsed, Q-switched Continuum Surelight laser operated at
200 mJ and a 2-m delay. For the second test, the same laser
Fig. 6 Broadband LIBS spectra for the TMA-5 plastic AT landmine system was operated at 50 mJ and a 2-ms delay. A diverse
and its rubber plunger sample suite was utilized in both experiments that
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consisted of multiple specimens of more than twelve further refinement of this analytical approach, even better
different types of AP and AT mines from six countries of results should be attainable. The next step in this research
manufacture, plus a diverse set of natural and anthro- will be to apply advanced statistical approaches to the mine
pogenic ‘clutter’ objects. The clutter suite included discrimination.
samples of different cellulose materials, rocks, and soils,
a variety of metal items comprised of aluminum, zinc, lead,
steel, brass, and rusted iron, the six common types of MP-LIBS experiment
commercial plastic (PETE, HDPE, PVC, LDPE, PP, and
PS), a sample of plastic and rubber from current Army A prototype man-portable LIBS system was tested for
equipment, and examples of the plastic, nylon, and wood landmine casing discrimination in a manner analogous to
simulants commonly used in the detection performance that of the laboratory system. Broadband single-shot LIBS
testing of different landmine sensor technologies. spectra were acquired for 15 different types of AT and AP
For both experiments, a library of single-shot, broad- landmine casings plus eight plastic and wood mine
band LIBS spectra was constructed consisting of the simulants. A set of samples selected at random was then
different AP and AT landmine casings (37 and 34, reanalyzed, and the individual broadband LIBS spectra
respectively) and the various clutter items (33 and 51, were compared against the library. Again, a simple linear
respectively). Once the library was constructed, a single- correlation procedure achieved a ‘mine/no-mine’ classifi-
shot broadband LIBS spectrum was acquired for 100 cation success of 90%. For samples identified as landmine
samples drawn randomly from the full sample population casings, the correct identification of a specific mine type
of landmine casings and clutter items (70 and 85, was better than 95%.
respectively), taking care to ensure that multiple samples
of each different type of material (e.g., AP mine, AT mine,
mine stimulant, plastic, rock, wood, and metal) were Summary and conclusions
analyzed. Again three levels of discrimination were of
interest in the two tests: (1) an initial correct ‘mine’ or LIBS has certain important characteristics that make it a
‘no-mine’ determination and, subsequently, for each very attractive sensor technology for military uses. Such
correct ‘mine’ classification – (2) delineation of the mine attributes include that facts that LIBS: (1) is relatively
type and (3) identification of the exact specimen where the simple and straightforward, (2) requires no sample prepa-
sample population contained multiple specimens of a ration, (3) generates a real-time response, and (4) only
particular mine type (six cases in both tests). The two engages a very small amount of sample (pico/nanograms)
independent experiments yielded essentially the same in each laser shot and microplasma event, (5) has an
highly satisfactory outcome. inherent high sensitivity, and (6) responds to all forms of
For the first test, which contained 37 mines in a sample unknowns, and, therefore, is particularly suited for the
population of a total of 70 items, a correct ‘mine/no-mine’ sensing of dangerous materials. Additionally, a LIBS
determination was obtained for 93 of the 100 analyses, sensor system can be inexpensive, configured to be man-
which is a success rate of 93%. The second test, with 34 portable, and designed for both in situ point sensing and
mines in a sample population of 85, produced an equivalent remote stand-off detection. The simplicity of the technique
result, with 92 of 100 correct ‘mine/no-mine’ determina- and the technological maturity of the components have led
tions, which is a success rate of 92%. For the correct ‘mine’ to the development of a LIBS sensor with unprecedented
classifications, the type of mine was identified correctly at performance characteristics that is both rugged and robust,
the 80% level (45 of 56) in the first test and at the 78% level making the technique ideally suited for field use.
(42 of 54) in the second test. For the correct ‘mine’ Broadband LIBS results covering the spectral region
classifications, the exact mine specimen was correctly from 200–980 nm were acquired under laboratory condi-
identified at the 52% level (29 of 56) in the first test and at tions for a variety of AP and AT landmine casings, and the
the 44% level (24 of 54) in the second test. casings subsequently reliably discriminated from typical
Overall, the results from this study are highly encoura- environmental clutter objects (plastics, wood, rocks, and
ging. In a replicated experiment, more than 90% of the 100 metal) at a success rate of greater than 90% in two
samples in mixed population of landmine casing and clutter independent laboratory tests conducted 4 months apart and
materials were correctly recognized as a ‘mine’ versus again using a prototype man-portable LIBS system. This
‘non-mine’ item. For the ‘mine’ designations, the correct performance illustrates the potential that LIBS has to be
mine type was assigned at approximately the 80% level, developed into a confirmatory sensor system for landmine
and the exact mine specimen was identified in more than detection. The man-portable concept envisioned as a
50% of the cases. Most misclassifications were under- confirmatory sensor for landmine detection is a back-
standable (e.g., the designation of a wooden AT mine case pack-based system in which an eyesafe micro-laser would
as cellulose), and the correct choice was typically the be contained in the handle of a deminer’s probe, with light
second choice in the linear correlation ranking. Only in a being delivered and collected through an optical fiber in the
very small number of cases did the linear correlation tapered tip of the metal probe. In such a configuration,
classification procedure used generate an inexplicable analyses could be made readily and reliably by touching
result classification that was totally off the mark. With the buried object that one is interested in identifying with
1148

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