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Abstract: A sensitive acetylene (C2 H2 ) sensing system based on a novel triple-row circular
multi-pass cell (CMPC) was demonstrated. This CMPC has an effective optical length of 21.9 m
within an extremely small volume of 100.1 mL. We utilized wavelength modulation spectroscopy
(WMS) for absorption spectroscopy detection of C2 H2 . The distance between the two minima of
the second harmonic was used to normalize the maximum value of it, which makes the time to
obtain stable output for continuous detection shorten dramatically. A fiber-coupled distributed
feedback (DFB) diode laser emitting at 1.5316 µm was employed as a light source. An Allan
deviation analysis yielded a detection sensitivity of 76.75 ppb with a normalized noise equivalent
absorption coefficient of 8.8 × 10−10 cm−1 Hz−1/2 during an average time of 340 s. With a fast
stable time, reduced size and high detection sensitivity, the proposed sensing system is suitable for
trace gas sensing in a weight-limited unmanned aerial vehicle (UAV) and an exhalation diagnosis
for smoking test.
© 2020 Optical Society of America under the terms of the OSA Open Access Publishing Agreement
1. Introduction
The formation of acetylene (C2 H2 ), a common hydrocarbon in the troposphere, is almost entirely
anthropogenic. For this reason, acetylene is often used as a marker of anthropogenic emissions
and to track contaminated air masses in atmospheric studies [1]. Due to its flammability and other
chemical properties, C2 H2 is also an important fuel and raw material in industrial applications
[2]. Recently, it has also been found that C2 H2 can be used as a marker of smoking status and
air pollution to human health [3,4]. The exhalation concentration of C2 H2 after smoking or
exposing to polluted air can reach hundreds of ppb, followed by a relatively rapid elimination
(exponential decay) in about 3 hours. Therefore, the accurate measurement of C2 H2 is of great
significance in variety applications of scientific research, industry and medical care. Typically, in
respiratory diagnosis, in addition to high sensitivity, the gas sensing system also needs to have a
small inflation volume and fast response [5,6].
Methods based on laser absorption spectroscopy are effective approaches for gas sensing
in environmental monitoring [7], industrial process control and medical diagnosis. The most
common ones of these methods are cavity ring-down spectroscopy (CRDS) [8], quartz-enhanced
photoacoustic spectroscopy [9], and tunable diode laser absorption spectroscopy (TDLAS) [10].
Among them, TDLAS is commonly used with advantages of highly sensitivity, simple structure
and low cost [11,12]. Wavelength modulation spectroscopy (WMS) technology is the most
frequently used kind of TDLAS [13]. To achieve a high detection sensitivity, TDLAS is usually
used in combination with a multi-pass cell (MPC) which can obtain a long light path in a relatively
small volume [14–17]. The most popular MPCs are Herriott cell and its improved types [16,17].
In a Herriott cell, the effective areas where laser beams are reflected on the two mirrors are
relatively small, therefore a relatively high path-to-volume ratio (PVR) can be achieved [18].
Zheng et al., implemented C2 H2 concentration detection based on WMS using a 480 mL Herriott
#388343 https://doi.org/10.1364/OE.388343
Journal © 2020 Received 16 Jan 2020; revised 13 Mar 2020; accepted 30 Mar 2020; published 3 Apr 2020
Research Article Vol. 28, No. 8 / 13 April 2020 / Optics Express 11574
cell with an effective optical length of 9.28 m [16], and the 1σ minimum detectable concentration
of 85 ppb was achieved with an average time of 250 s. The astigmatic Herriott-type cell can
achieve an improved PVR, but it requires extremely high accuracy for manufacture and adjustment
of the mirrors. Liu and co-workers demonstrated methane (CH4 ) concentration measurement
based on WMS using a 280 mL astigmatic Herriott cell with an effective optical length of 26.4 m
[17], a detection limit of 100 ppb was obtained with a lock-in time constant of 1 ms.
Circular multi-pass cell (CMPC) is another kind of MPC in which the laser beam is reflected
back and forth on a single circular mirror [19,20]. Béla et al., designed a single-row CMPC with
an optical length of 4.1 m within 40 ml volume and realized a detection of the oxygen-isotope
ratio (18 O/16 O) in 1% carbon dioxide (CO2 ) [19]. For this kind of CMPC, the input and out beams
share the same aperture on the side wall, so it is hard to further increase the effective optical length
because of interference between fore and rear optical systems. Recently, we proposed a novel
kind of CMPC which consists of two spherical circular mirrors with identical radii of curvature,
and multiple horizontal rows of spots can be generated on the inner surfaces of the mirrors during
the reflections [21,22]. In this version, the entrance and exit are separated, and the overall optical
length can be increased without degradation of PVR. Based on the parameterization design
method, a triple-row CMPC with an effective optical length of 21.9 m within 100.1 mL was
demonstrated, which has the smallest volume among the existing MPCs with similar overall
optical path lengths [22].
In this paper, we report on an acetylene sensing system with our newly developed triple-row
CMPC based on the WMS technology in TDLAS. C2 H2 detection was performed to evaluate the
performance of the sensing system. The distance between the two minima of second harmonic
was used to normalization the peak value of second harmonic at different acquired data points to
tranquilize the data fluctuation in the earliest period of air inflation. Consequently, the time to
obtain stable output for each continuous measurement is significantly shortened. This kind of
fast stable, low-cost, compact sensing system is very suitable for trace gas measurements in harsh
environments and exhalation diagnosis, et. al. By changing probe laser to other near-infrared
distributed feedback (DFB) lasers with corresponding output center wavelengths, the system can
be also used to detect other gases.
2. Sensor configuration
2.1. Design of the C2 H2 sensor
The schematic of the C2 H2 sensor system is shown in Fig. 1(a). A fiber-coupled DFB laser
(NLK1C5GAAA, NEL, Japan) emitting at 1531 nm was employed as the probe laser. Temperature
and injection current of the laser was controlled with a diode laser controller (LDTC0520,
Wavelength, USA). The temperature and injection current were first set to ensure the initial output
wavelength of the laser was exactly at the absorption peak. A 5 Hz triangular scanning signal and
a 5 kHz sine modulation signal generated by the LabVIEW controlled data acquisition (DAQ)
card (USB6341, National Instruments, USA) are applied to modulate the injection current of
probe laser.
A fiber collimator (PAF-X-7-C, Thorlabs, USA) was used to collimate the output beam from
the DFB laser. An indicated beam from a red laser (MLL-III-660L-180mW, Changchun New
Industries Optoelectronics Tech. Co., Ltd, China) emitted at 660 nm was aligned collinearly with
the collimated probe laser through a dichroic mirror (DM10-950LP, LBTEK, China) to guide the
optical alignment of the sensing system. Then the combined laser beam was focused around the
center of the CMPC by a convex lens (f = 100 mm, Thorlabs, USA), to maintain steady beam
propagation within the cell. After reflected back and forth in the triple-row CMPC, the output
laser was then collected by an identical convex lens and focused on the InGaAs amplified detector
(PDA20CS, Thorlabs, USA). The output of the detector was sent to the DAQ card and processed
by the LabVIEW based digital lock in amplifier (LIA) to extract the corresponding 2f signals.
Research Article Vol. 28, No. 8 / 13 April 2020 / Optics Express 11575
Fig. 1. (a) Schematic of the C2 H2 sensor system. (b) Photograph of the triple-row CMPC.
DFB: distributed feedback laser; FC: fiber collimator; DM: dichroic mirror; M1, M2: convex
lens; V1, V2: valves; C&T Control: Current and temperature controller for laser; DAQ: data
acquisition card.
The sampling rate of the DAQ card was set to be 200 kHz. The low-pass filter used in the digital
LIA is a 128-order Bessel infinite impulse response (IIR) digital filter with a cut-off frequency of
80 Hz.
A photograph of the triple-row CMPCT is shown in Fig. 1(b). Outline of the CMPC is a
cylinder with a height of 24.33 mm, a radius of 68 mm; the height and radius of the inflation
volume are about 12.74 mm and 50 mm, respectively. The cell consists of two spherical circular
mirrors with identical radii of curvature of 50 mm, and three horizontal rows of reflection spots
can be generated on the inner surfaces of the mirrors. Reflectivity of the internal surfaces of
the circular mirrors is higher than 98.8% in 1000 nm -1700nm by coating with metal gold and
multilayer medium films. An absorption mask coating with black oxide film was mounted
inside the CMPC to suppress interference of stray light [22], which has three rows of holes
corresponding to designated positions of reflection spots on the circular mirrors. An effective
optical path of 21.9 m was achieved with 220 multiple reflections of laser beam within a volume
of 100.1 mL.
Fig. 2. Simulated absorption spectrum of 100 ppm C2 H2 and the curve of the DFB diode
laser wavenumber as a function of injection current at 21 °C.
Research Article Vol. 28, No. 8 / 13 April 2020 / Optics Express 11576
Fig. 3. (a) The detected second harmonic signal with 60.1 ppm C2 H2 , Sp: Sampling points.
(b) and (c) are the detected S2fmax and D2f with 60.1 ppm C2 H2 . (d) and (e) are the detected
S2fmax and D2f with 49.9 ppm C2 H2 . (f) and (g) are the detected S2fmax and D2f with 40.3
ppm C2 H2 .
Table 1. Standard deviation of S2fmax and standard deviation of D2f -normalized S2fmax
Gas species Standard deviation of S2fmax (mV) Standard deviation of D2f -normalized S2fmax (mV)
60.1 ppm C2 H2 0.0486 0.0183
49.9 ppm C2 H2 0.0339 0.0136
40.3 ppm C2 H2 0.0379 0.0138
Pure CO2 0.0539 0.0223
Fig. 4. (a) Detected S2fmax values of 40.3 ppm C2 H2 (blue), 49.9 ppm C2 H2 (red) and
60.1 ppm C2 H2 (black), respectively. (b) The S2fmax signals normalized by D2f of 40.3
ppm C2 H2 (blue), 49.9 ppm C2 H2 (red) and 60.1 ppm C2 H2 (black), respectively. (c) The
detected values of S2fmax of pure CO2 . (d) The S2fmax signals normalized by D2f of pure
CO2 .
Fig. 6. (a) Time series measurements of C2 H2 for an hour. (b) Allan standard deviation
curve of C2 H2 detection based on Fig. 6(a).
Fig. 7. The detected 2f signal with a 100.6 ppm C2 H2 at pressure of 1 atm and temperature
of 291.15 K.
Research Article Vol. 28, No. 8 / 13 April 2020 / Optics Express 11580
4. Discussion
In our system, it takes a relatively long time for S2fmax to achieve stability in some cases, which
is not caused by the fluctuation of laser intensity. Through the pure CO2 detection experiment,
we also know that it has nothing to do with low gas concentration. The total pressure and
temperature also didn’t change during the experiment, so we believe that it is mainly due to the
gas movement during the detection period. As for why the interval between the two minima
of second harmonic changed similarly with the fluctuation of maximum value of the second
harmonic, it can be inferred with the mathematical expression of the detected second harmonic.
The second harmonic obtained by digital LIA can be expressed as [24]:
2 2 1/2
I0 i1 i1
S2f = [H2 + (H1 + H3 ) cos ψ1 ] + [ (H1 + H3 ) cos ψ1 ] (2)
2 2 2
∫π
SP χL
H2 = α cos 2πftdt, (3)
π
−π
where I0 is the output optical intensity of the DFB laser, i1 is the primary intensity modulation
coefficient, and Ψ 1 is the linear phase difference between the frequency modulation and the
amplitude modulation. H1 , H2 and H3 refer to the first order, second order and third order Fourier
series of the absorption coefficient of detected gas sample, S denotes the absorption line strength,
P is the total pressure of the detected gas sample, χ refers to the gas concentration, α is the
line-shape of the absorption coefficient, f means the sinusoidal modulation frequency employed
and t refers to the time. i1 in our system is very mall, so when the detected second harmonic
signal (S2f ) reaches the two minimum values, according to Eq. (2), the H2 will be very close to
zero. Thus the positions of the two minimum values of the S2f are quite approximate to the zero
points of H2 , and they have no relationship with the gas concentration and optical length. Then
the interval of the two minimum values may be used to exclude the influence of other factors
except concentration and optical length. This deduction is consistent with our experimental
phenomenon. We can also infer that the change of absorption line-shape from the time when the
gas enters the CMPC to the time when the gas is stable may be the main reason of the fluctuation
of detected 2f signal.
5. Conclusion
We demonstrated a C2 H2 sensing system with a newly developed triple-row circular multi-pass
cell based on wavelength modulation spectroscopy. The CMPC has excellent PVR which obtains
an optical length of 21.9 m within a tiny volume of 100.1 ml. The interval of the two minima of
detected second harmonic was used to normalize the 2f signal then the precise gas concentration
was obtained once the gas was passed to the CMPC and reached a pressure of 1 atm. Other
TDLAS systems with problem of too long steady time may also be improved by the same method.
Experiments were carried out to evaluate the performance of the sensing system. A SNR of
Research Article Vol. 28, No. 8 / 13 April 2020 / Optics Express 11581
56 and a limit of detection of 76.75 ppb with an averaging time of 340 s were obtained. The
normalized noise equivalent absorption coefficient of the system is 8.8 × 10−10 cm−1 Hz−1/ 2 .
The sensing system has promising potential for gas sensing applications which calls for small
size, fast response and high measurement sensitivity.
Funding
National Key Research and Development Program of China (2018YFF0109600).
Disclosures
The authors declare no conflicts of interest.
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