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    DOI 10.1007/s00340-016-6355-6 Appl. Phys. B (2016) 122:83

    Cantilever‑enhanced photoacoustic detection of hydrogen sulfide (H2S) using NIR telecom laser sources near 1.6 µm

    H. Moser1 · B. Lendl1

    Received: 27 October 2015 / Accepted: 2 February 2016 / Published online: 31 March 2016 © The Author(s) 2016. This article is published with open access at Springerlink.com

    concentrations as low as 500 pptv manifesting in the char- acteristic odor of rotten eggs can already be detected by the human olfactory sense, the total loss of olfactory sen- sation starts at 150–200 ppmv [3]. Because of the wide occurrence of H2S in industrial processes and its often negative impact on process stabilities and product quality, its concentration needs to be tightly monitored. Further- more, safety considerations and legal concentration limits also necessitate the accurate determination of H2S levels. In practice, concentrations ranging from sub-ppm levels at low pressures to several per cents at atmospheric conditions need to be monitored. Due to such diverse requirements, H2S analyzers based on different measurement technolo- gies have been developed and are in industrial use. Apart from spectroscopic techniques based on absorption meas- urements, a range of other analytical techniques such as pulsed UV fluorescence [4], sulfur chemiluminescence [5], colorimetry employing a lead acetate tape [6], flame pho- tometry as detector in gas chromatography [7] as well as electrochemical detection techniques ranging from poten- tiometric, galvanic, coulometric and amperometric detec- tion [8] is frequently employed. It is interesting to note that in the petrochemical industry the lead acetate tape method is still in frequent use. Also, gas chromatographic methods are popular as they can be used to detect several compo- nents almost simultaneously, but this technique requires preparation and extraction of the sample gas leading to a time-consuming measurement. A general drawback of non- spectroscopic techniques is the fact that they do not allow for direct measurements. This, however, also applies to H2S detection based on UV fluorescence as this technique requires sample combustion as well as detection by chemo- luminescence, where addition of reagents is required.

    Most of the spectroscopic techniques are based on the detection of the absorption spectrum of the molecules in

    Abstract Sensitive detection of hydrogen sulfide (H2S) at different pressure levels using a cantilever-enhanced photoacoustic detector in combination with a telecom NIR L-band laser source is reported. Amplitude and wave- length modulation schemes for photoacoustic signal gen- eration are compared. A detection limit (3σ) of 8 ppmv was achieved for amplitude modulation mode with a 50-s averaging time for the H2S absorption near 1.6 µm. As compared to simulated spectra, the cantilever-enhanced photoacoustic detection approach in combination with the sufficiently stable and narrow bandwidth NIR laser is able to reproduce the rotationally resolved H2S spectrum at low pressures of 300 mbar.

    1 Introduction

    Sensitive detection of hydrogen sulfide (H2S) is essential for production control and environmental monitoring pur- poses in the field of petrochemical, paper and pulp as well as biotechnological processes. The occupational exposure limit recommended by the European Agency for Safety and Health at Work (OSHA) is 7.1 mg m−3 (5 ppmv) [1]. The permissible exposure limit value for H2S, recommended by US National Institute for Occupational Safety and Health (NIOSH), is 10 ppmv, the Immediately Dangerous to Life and Health (IDLH) level is 300 ppmv and lethal concen- trations are in the range of 2000 ppmv [2]. Although H2S

    * B. Lendl [email protected]

    1 Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164 AC, 1060 Vienna, Austria

    http://crossmark.crossref.org/dialog/?doi=10.1007/s00340-016-6355-6&domain=pdf

  • H. Moser, B. Lendl

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    the infrared (IR) spectral region. Sensors based on tuneable diode laser absorption spectroscopy (TDLAS) mostly utilize near-infrared diode lasers due to their distinguished prop- erties, such as single-mode operation, good beam quality, high repetition rate, relatively narrow line width, large cur- rent tuning range, good operability, low power consumption and low investment costs [9–11]. When measuring H2S by IR spectroscopy, high sensitivities are difficult to achieve. This is due to the intrinsically weak linestrengths of the H2S ro-vibrational features within the spectral range covered by diode lasers. These are several magnitudes lower compared to other gases of industrial interest. For example, the absorb- ance of CH4 at 1.646 µm is 1.800 × 10−5 ppm−1 m−1 com- pared to the H2S absorbance of 5.573 × 10−7 ppm−1 m−1 at 1.601 µm (factor 32) [12]. A way to overcome this draw- back is to increase the interaction path length by using mul- tipass gas cells [13–16]. This generally adds to the bulkiness of the systems, and hence, a small size is hardly achieved with H2S TDLAS sensors. The path length can be reduced by using wavelength modulation or balanced detection approaches, which furthermore improve the sensitivity of TDLAS sensors [17–19]. Although the detection of H2S concentrations of several ppb has been demonstrated by employing integrated cavity output spectroscopy approach (ICOS) [20], such sensitivities are difficult to obtain in field measurements as the robustness of this kind of systems remains limited [21, 22]. Possible alternatives to bulky mul- tipass absorption or delicate sensing schemes based on cav- ity spectroscopy are photoacoustic H2S measurement strate- gies [23–26]. A fully developed and industry-tailored H2S sensor to meet the specific selectivity requirements based on photoacoustic spectroscopy employing dual-channel longitudinal-type resonator cell with capacitive microphone readout and a LOD of 0.5 ppmv is described in [23]. An interesting rather new development in this regard is the tech- nique of cantilever-enhanced photoacoustic spectroscopy (CEPAS) [27]. In this paper, we report on our results on sensitive H2S detection at different pressure levels using a cantilever-enhanced photoacoustic detector in combination with a telecom NIR L-band laser source.

    2 Spectral characteristics of H2S in the NIR region

    The 6500–6000-cm−1 near-infrared spectral region is of interest as it can be easily accessed with commercially available telecommunication laser technology. Further- more, this spectral interval corresponds to an atmospheric window with very few cross-interactions stemming from other molecules. Vibrational overtone and combination bands of H2S can be located at 6450–6150 cm

    −1 (refer to Fig. 1).

    Regarding the spectral H2S features in the 1.6-µm region (6270–6220 cm−1), extensive research and simulation was conducted by Edwards et al. [28] and extended by Lechuga- Fossat et al. [29]. In this region, accurate line positions can be addressed to the (210) (111) and (102) bands. Reso- nances between these three states can be addressed to Cori- olis interactions between the rotational levels of the (111) vibrational state and the levels of the (210) and (012) states as well as to Darling-Dennison interactions between the (210) and (012) vibrational states [29].

    In this work, the strongest absorption feature around 6245 cm−1 (1601 nm) corresponding to the 3 transition lines listed in Table 1 was chosen for selective H2S meas- urements. The rotational levels of H2S as a three-dimen- sional asymmetric top rotator with three different recipro- cal moments of inertia are labeled by the three standard quantum numbers J, Ka and Kc [30].

    The absorption spectrum in this region is shown in Fig. 1, indicating an absorbance of 5.57 × 10−7 ppm−1 m−1 [12]. A HITRAN simulated H2S absorption spectrum around 6245 cm−1 with a total pressure ranging from 1000 to 300 mbar is shown in Fig. 2a. Splitting of the H2S band into its strongest ro-vibrational transition components (111–000) can be observed at reduced pressures. Although the sensor investigation in this work was limited to certi- fied H2S in N2 mixtures, the possibility of water (H2O) and carbon dioxide (CO2) interference is investigated via simu- lation. Absorbance spectra at a total pressure of 300 mbar of 100 ppmv H2S in a standard air matrix with 100 ppmv water and 500 ppmv CO2 content and 100 ppmv H2S in a possible process air matrix of 10,000 ppmv H2O and 5000 ppmv CO2 are shown in Fig. 2b. Negligible spectral interference can be expected from H2O lines in this wave number region, whereas possible CO2 interference has to be accounted for. Taking advantage of spectral line resolution

    6500 6400 6300 6200 6100 6000 0.0

    2.0x10-7

    4.0x10-7

    6.0x10-7

    A bs

    or ba

    nc e

    (p pm

    -1 *m

    -1 )

    Wavenumber (cm-1)

    H2S 6244.75 cm-1

    1.601 µm

    1.54 1.56 1.59 1.61 1.64 1.67 Wavelength (µm)

    6250 6245 6240 0.0

    6.0x10-7

    A bs

    or ba

    nc e

    (p pm

    -1 *m

    -1 )

    Wavenumber (cm-1)

    Fig. 1 H2S absorption spectrum in the 6500–6000-cm −1 region and

    single peak at 6250–6240 cm−1 (inset) at 25 °C and 1013 mbar

  • Cantilever-enhanced photoacoustic detection of hydrogen sulfide (H2S) using NIR telecom…

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    starting at a reduced pressure of 300 mbar, a sufficient sep- aration of ~0.3 cm−1 from the int

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