RESULTS FROM PASSIVE STAND-OFF CHEMICAL VAPOUR

DETECTION AND PLUME MONITORING USING THERMAL

HYPERSPECTRAL TECHNOLOGY

Cameron Bowles, Mark Burridge, Robert Hall and Tim Bubner

Intelligence, Surveillance and Reconnaissance Division, DSTO

Edinburgh, South Australia
cameron.bowles@dsto.defence.gov.au

Abstract
The Defence Science and Technology Organisation (DSTO) has been
conducting research in both the development of hyperspectral long wave
infrared (LWIR) experimental technology and the fundamental tools and
analysis models required as part of a passive stand-off chemical vapour
detection system. This paper covers work focused on the formulation, testing
and evaluation of the models and analysis tools, as well as empirical results
from a field trial in plume stack monitoring. The field trial showed that sulphur
hexafluoride could be detected and quantified at concentrations below 1 part
per million at ranges in excess of 50 metres by a passive Fourier transform
infrared spectrometer (FTIR).

Introduction
There has been an increasing interest in the use of hyperspectral infrared
spectroscopic techniques for thermal signature measurement and passive
remote sensing. Fourier transform infrared (FTIR) spectrometry has found a
wide utility for passive remote applications including defence surveillance,
atmospheric sounding, industrial monitoring and a plethora of remote sensing
and environmental monitoring tasks. These applications are underpinned by the
ability to detect, identify and quantify materials, which is achieved by exploiting
the fundamental chemical and spectroscopic properties of materials. It is the
nature and characteristics of these materials that determines their limits of
detection, and hence the utility of this technology. Further experimental
limitations imposed on remote passive sensing are due to broader experimental
and system factors, such as atmospheric effects, sensor performance,
background radiation sources and associated temperature contrasts.

DSTO’s Intelligence, Surveillance and Reconnaissance Division (ISRD) has

invested significant time and resources in developing this capability, which has
included the development of equipment, tools and techniques for passive stand-
off detection of gases and chemical vapour. This report covers the enabling
research into modelling and analysis, the evaluation of remote gas

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quantification models and a full field trial of an industrial plume monitoring
application for detecting and quantifying chemical vapour emissions.

Modelling
The fundamental modelling equations have been taken from Flanigan’s 3-layer
model [1, 2], which breaks the radiative transfer model into a far field, a target
gas and a near field atmospheric transmission layer. A differential radiance
spectrum (δL) can be determined by taking the difference of a target spectrum
through the plume and a background spectrum (Lbkgd) that is similar in geometry
but does not include the target plume. Under the assumption that the target gas
layer is thin in comparison to the near field [3], and that the temperature
gradient of the near field (atmosphere) is linear (i.e. the measurement is from a
ground based system), the differential radiance equation for a horizontal
measurement path can be formulated via some basic rearrangements and
substitutions to be;
[ Bnear − Lbkgd ) + (Bgas − Bnear )τ near ].
δL = (1 − τ gas )( (1)

Where B represents a wavenumber dependent Planckian curve at the subscript

temperature, and τ is the wavenumber dependent transmission function of the
subscripted component. The transmission of the near field can be determined
by atmospheric modelling programs such as MODTRAN [4], whilst the
transmission function of the gas is determined by the Beer-Lambert law
(equation 2). Chemical vapours often display ‘fingerprint’ spectra in the thermal
infrared region due to unique vibrational-rotational excitations. The strength and
position of these features being quantified by the absorption coefficients (α) of
the target molecule.
τ gas = e −αlc . (2)

Theoretical differential spectra can be calculated, by using equations 1 and 2,

where the absorption coefficients are taken from laboratory determined
reference libraries, such as the Pacific National Northwest laboratories (PNNL)
library[5]. All simulated spectra have introduced noise added to simulate the
noise equivalent spectral radiance (NESR) of the FTIR spectrometer, which is a
function of the measured resolution and the number of averaged spectra
(measurement time).

Analysis Tools
With the ability to simulate differential spectra comes the possibility to determine
the minimum column density (concentration times plume depth) required for any
set of experimental conditions that will be detectable by a given FTIR
spectrometer. By rearranging Equations 1 and 2, to be a function of the
chemical vapour column density (cl), and equating the differential radiance to
the five times the NESR of the spectrometer [2] the minimum detectable
quantity (MDQ) equation becomes;

2
 ⎛ 5 * NESR ⎞
− ln⎜1 − ⎟
⎜
⎝ [
(Bnear − Lbkgd ) + (Bgas − Bnear )τ near ] ⎟
⎠,
cl = (3)
α gas
The MDQ (Equation 3) can be iteratively solved, as a function of wavenumber
(cm-1) and temperature contrast (Bnear and Bgas), enabling the creation of a MDQ
surface. The MDQ surface (Figure 1) is shown as an inverse MDQ value for
easier visualisation, as the 1/MDQ surface trends to 0 for regions with no
spectral transitions, rather then infinity for the MDQ surface.

Figure 1: The inverse MDQ surfaces for ammonia (left) and ethanol (right), for the
Bomem MR 304 spectrometer at 256 coadded spectra at 4 cm-1 resolution.
The MDQ surface provides for a ready field reference to determine the most
advantageous experimental geometry to trade off the plume depth in the field of
view (column density), and the temperature contrast between the far field
radiance and the temperature of the chemical vapour.

Quantification of the detected chemical vapour can be performed on the

measured differential radiance spectrum (δL) using a concentration extraction
program developed at DSTO. The program corrects the measured differential
radiance spectrum for temperature fluctuations that occurred between the target
and background measurements. The program then uses a linear least squares
algorithm to fit the reference spectrum (PNNL, [5]) and any contaminants also
present in the scene. A column density can then be extracted from the scaled
reference spectrum which was fitted to the temperature and contaminant
corrected differential radiance spectrum (δLTC). If the temperature contrast is
unknown (which is typically the case for field measurements) then the
concentration extraction program includes a single channel emissivity assumed
temperature extraction procedure commonly used with hyperspectral
signatures.
⎛ δLTc ⎞
− ln⎜1 − ⎟
⎜
⎝ [
(Bnear − Lbkgd ) + (Bgas − Bnear )τ near ] ⎟
⎠,
cl = (3.27)
α gas

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Testing and Evaluation
A gas cell was designed and developed to test the modelling tools over a range
of temperature contrasts and chemical vapour concentrations. This cell
comprised a 36 litre rectangular aluminium box with internally mounted heating
crucible, thermocouples, a mixing fan and was sealed on the front and rear with
LWIR transparent polypropylene windows. The remaining internal surfaces
were coated with high emissivity paint. A 12 inch blackbody was positioned
behind the gas cell allowing for easy control of the temperature contrast of the
far field radiance for testing and evaluation purposes. Precise amounts of
volatile test solvents were placed inside the heating crucible by a chemical
injection port built into the gas cell and on evaporation a known column density
was developed inside the gas cell. By varying the amount of chemical injected
and the far field blackbody the extraction concentration program (and hence
underlying models) could be tested and evaluated as a function of the
temperature contrast (Figure 3) and column density (Figure 4).
The extracted column density of Dichloromethane as a The extracted column density of Acetone as a function
function of temperature contrast of temperature contrast
600 1600
Column Density (ppm-m)
Column Density (ppm-m)

1400
500
1200
400
1000

300 800

600
200
400
100 DCLM ACET
200
Theory Theory
0 0
0.4 0.9 1.4 1.9 2.4 2.9 3.4 3.9 4.4 4.9 -0.5 0 0.5 1 1.5 2 2.5 3 3.5
Temperature Contrast (C) Temperature Contrast (C)

The extracted column density of Ammonia as a The extracted column density of Diethylether as a
function of temperature contrast function of temperature contrast
1600 900
Column Density (ppm-m)

800
Column Density (ppm-m)

1400
700
1200
600
1000
500
800
400
600
300
400 200
200 NH3 DEE
100
Theory Theory
0 0
-2.3 -1.3 -0.3 0.7 1.7 2.7 -0.2 0.3 0.8 1.3 1.8 2.3 2.8 3.3 3.8
Temperature Contrast (C) Temperature Contrast (C)

Figure 2: The extracted experimental column density as a function of temperature

contrast (points), and the theoretical value (black line). For dichloromethane (top left),
acetone (top right), ammonia (bottom left) and diethyl ether (bottom right).
The experimentally determined column densities demonstrated good agreement
to theoretically calculated values (from the ideal gas law) for a fixed column
density and varying temperature contrast (Figure 2). There is slight deviation in
the NH3 results as the sample had an optical density of 0.28, and hence is
beginning to deviate from the Beer-Lambert law. The error bars come from the
uncertainty in the temperature contrast (±0.1 °C) and NESR value for the
measurement.

The measured column densities (as a function of volume of chemical added)

(Figure 3) also demonstrate good agreement with theoretical values for low

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concentrations, however at higher concentrations the measured column
densities begin to depart from the theoretical values. This ‘roll-off’ is expected
due to self-absorption in the vapour column at higher concentrations. This
illustrates the limits of the optically thin assumption of the Beer-Lambert law
used in this analysis.
Extracted Column Density of Dichloromethane Extracted Column Density of Acetone as a
as a function of concentration function of concentration
2000 1400
1800
Column Density (ppm-m)

Column Density (ppm-m)

1200
1600
1400 1000
1200
800
1000
800 600

600 400
400
Theory 200 Theory
200
0
DCLM 0
ACET
0 100 200 300 400 500 600 0 50 100 150 200 250 300 350 400 450
Volume Added (µL) Volume Added (µL)

Extracted Column Density of Ammonia as a Extracted Column Density of Diethylether as a

function of concentration function of concentration
1200 900

800
Column Density (ppm-m)

Column Density (ppm-m)

1000
700

800 600

500
600
400
400 300

200
200 Theory Theory
100

0
NH3 0
DEE
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
Volume Added (µL) Volume Added (µL)

Figure 3: The extracted experimental column density as a function of the volume of

chemical added to the gas box (red points), and the theoretical value (black line). For
dichloromethane (top left), acetone (top right), ammonia (bottom left) and diethyl ether
(bottom right).
The good agreement between theoretical and the experimentally extracted
column densities in these controlled experiments, validated the models and
programs used, enabling the advancement to field trials of passive stand-off
plume monitoring.

Remote Passive Plume Monitoring

The Bomem MR 304 single pixel spectrometer and the Imaging Defence
Infrared Spectrometer (IDIS) were positioned 60 metres from an industrial
processing plant that was known to perform silicon etching involving gases such
as sulphur hexafluoride (SF6) that have strong spectral absorption features in
the LWIR, The azimuthal angle was approximately 10 degrees with a clear blue
sky producing the far field ‘cold-sky’ radiance. The ambient air temperature was
22.0 °C, and this was also used as the assumed plume temperature The
apparent background temperature at the SF6 feature (946 cm-1) was
approximately -3.2 °C.

The width of the exhaust stack was 40 cm, and the plume flow rate was
estimated to be 3.0 m/s based on known flow rates for similar exhaust stacks.

5
The exit of the plume stack was measured every minute for a 30 minute period
for 256 coadded spectra at 4 cm-1 resolution. The measured differential
radiance spectra were analysed with the concentration extraction program using
the values mentioned in this section, resulting in the extracted column densities
shown in Figure 4.

Extracted Concentration of SF6 from an industrial

plume stack as a function of time
0.7
Extracted column density

0.6
of SF6 (ppm-m)

0.5

0.4

0.3

0.2

0.1

0
0 5 10 15 20 25 30

Time (min)

Figure 4: The extracted column densities of SF6 with an assumed temperature contrast
of 25.2 °C, with error bars originating from the spectrometer noise level.
The extracted column densities (Figure 4) have error bars on each point
corresponding to the MDQ. The results show a 14 minute cycle time in the
industrial process, and yields information about the exhaust system with a 3
minute rise and fall time in the emitted column density from the plume stack.
With the assumed plume stack flow-rate of 3.0 m/s, and remotely measured
cross section of the plume stack (0.126 m2), the total volume of SF6 emitted
from the plume stack during this process can be calculated by integrating under
the column density curve to be approximately 348 mL. Factory records
subsequently provided an actual release rate of 28 sccm (standard cubic
centimetres per minute), resulting in a total release volume of 392 mL for the 14
minute process. This result validates the field trial, in which the total volume of
chemical vapour was able to be extracted from a passive stand-off ground
based system with no a-priori site knowledge.

Figure 5: The IDIS measured concentration cube overlaid onto the measured plume
stack as an extracted column density (ppm-m) scaled semi-transparent over-layer.

6
The IDIS system, which was designed and developed by DSTO to be a high
signal, low noise imaging FTIR spectrometer, measured the plume stack in
parallel with the Bomem MR 304. The IDIS imaged hypercube was analysed by
the concentration extraction program, the extracted concentration cube is
shown in Figure 5, as a scaled red alpha layer, overlaid on the scene. The
results again confirm detection and quantification of SF6 at column densities
less than 1 part per million.

Summary and Conclusions

Modelling tools have been developed from Flanigans 3-layer models to allow
detection and quantification of chemical vapours from a LWIR hyperspectral
differential radiance spectrum. These models and analysis tools were validated
by well controlled laboratory experiments, using a passive stand-off FTIR
spectrometer.
This work was extended to field trials that produced positive detection and
quantification of an industrial gas (SF6) from an exhaust stack. Temporal
measurements showed a 14 minute process cycle and analysis of the passive
stand-off measurements indicated a total SF6 emission of 348 mL, with column
densities at less than 1 part per million. These results were generated with no a-
priori knowledge of the site and subsequent confirmation indicated and actual
emission of 392 mL over the 14 minute process, which was within 12.6 % of the
experimentally measured value.
Modelling and other reported results indicate these detection ranges can be
significantly extended [6] with only minor degradation of the measured signal
due to the transmission losses in the atmosphere.

References
1. Flanigan, D. F. (1996) Electro-Optical Technology for Remote Chemical
Detection and Identification. Vol. 2763, Orlando, FL, USA, SPIE
2. Flanigan, D. F. (1996) Prediction of the limits of detection of hazardous vapors
by passive infrared with the use of modtran. Appl. Opt. 35 (30) 6090-6098
3. Theriault, J.-M. (2001) Passive standoff detection of chemical vapors by
differential FTIR radiometry. DREV-TR-2000-156, valcartier QUE, Defence
research establishment valcartier
4. Berk, A., et al. (1999) Optical Spectroscopic Techniques and Instrumentation
for Atmospheric and Space Research III. Vol. 3756, Proceedings of SPIE
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Recognition Workshop, 2002. Proceedings. 31st
6. Thériault, J.-M., et al. (2004) Passive Remote Monitoring of Chemical Vapors
by Differential Fourier-Transform Infrared Radiometry: Results at a Range of
1.5 km. Appl. Opt. 43 (6) 1425-1434