Quantitative laser spectroscopic measurements of complex molecules that have a broad absorption spectra require broadly tunable laser sources operating preferably in the mid-infrared molecular fingerprint region. In this paper a novel broadband mid-infrared laser source comprising of an array of single-mode distributed feedback quantum cascade lasers was used to target a broadband absorption feature of benzene (C6H6), a toxic and carcinogenic atmospheric pollutant.
The DFB-QCL array is a monolithic semiconductor device with no opto-mechanical components, which eliminates issues with mechanical vibrations. The DFB-QCLs array used in this work provides spectral coverage from 1022.5 cm-1 to 1053.3 cm-1, which is sufficient to access the absorption feature of benzene at 1038 cm-1 (9.64 μm).
A sensor prototype based on a 76 m multipass cell (AMAC-76LW, Aerodyne Research) and a dispersive DFB-QCL array beam combiner was developed and tested. The Allan deviation analysis of the retrieved benzene concentration data yields a short-term precision of 100 ppbv/Hz1/2 and a minimum detectable concentration of 12 ppbv for 200 s averaging time. The system was also tested by sampling atmospheric air as well as vapors of different chemical products that contained traces of benzene.
Hydrogen peroxide (H2O2) is a relevant molecular trace gas species, that is related to the oxidative capacity of the
atmosphere, the production of radical species such as OH, the generation of sulfate aerosol via oxidation of S(IV) to
S(VI), and the formation of acid rain. The detection of atmospheric H2O2 involves specific challenges due to its high
reactivity and low concentration (ppbv to sub-ppbv level). Traditional methods for measuring atmospheric H2O2
concentration are often based on wet-chemistry methods that require a transfer from the gas- to liquid-phase for a
subsequent determination by techniques such as fluorescence spectroscopy, which can lead to problems such as sampling
artifacts and interference by other atmospheric constituents. A quartz-enhanced photoacoustic spectroscopy-based
system for the measurement of atmospheric H2O2 with a detection limit of 75 ppb for 1-s integration time was previously
reported. In this paper, an updated H2O2 detection system based on long-optical-path-length absorption spectroscopy by
using a distributed feedback quantum cascade laser (DFB-QCL) will be described. A 7.73-μm CW-DFB-QCL and a
thermoelectrically cooled infrared detector, optimized for a wavelength of 8 μm, are employed for theH2O2 sensor
system. A commercial astigmatic Herriott multi-pass cell with an effective optical path-length of 76 m is utilized for the
reported QCL multipass absorption system. Wavelength modulation spectroscopy (WMS) with second harmonic
detection is used for enhancing the signal-to-noise-ratio. A minimum detection limit of 13.4 ppb is achieved with a 2 s
sampling time. Based on an Allan-Werle deviation analysis the minimum detection limit can be improved to 1.5 ppb
when using an averaging time of 300 s.
The development of a continuous wave (CW), thermoelectrically cooled (TEC), distributed feedback (DFB) laser diode
based spectroscopic trace-gas sensor for ultra sensitive and selective ethane (C2H6) concentration measurements is reported. The sensor platform used tunable laser diode absorption spectroscopy (TDLAS) and wavelength modulation spectroscopy (WMS) as the detection technique. TDLAS was performed with an ultra-compact 57.6 m effective optical path length innovative spherical multipass cell capable of 459 passes between two mirrors separated by 12.5 cm. For an interference free C2H6 absorption line located at 2976.8 cm-1 a 1σ minimum detection limit of 130 pptv with a 1 second lock-in amplifier time constant was achieved.
Recent advances in the development of compact sensors based on mid-infrared continuous wave (CW), thermoelectrically
cooled (TEC) and room temperature operated quantum cascade lasers (QCLs) for the detection, quantification and
monitoring of trace gas species and their applications in environmental and industrial process analysis will be reported. These
sensors employ a 2f wavelength modulation (WM) technique based on quartz enhanced photoacoustic spectroscopy
(QEPAS) that achieves detection sensitivity at the ppb and sub ppb concentration levels. The merits of QEPAS include an
ultra-compact, rugged sensing module, with wide dynamic range and immunity to environmental acoustic noise. QCLs are
convenient QEPAS excitation sources that permit the targeting of strong fundamental rotational-vibrational transitions which
are one to two orders of magnitude more intense in the mid-infrared than overtone transitions in the near infrared spectral
region.
The development and performance of a cw, TE-cooled DFB quantum cascade laser based sensor for
quantitative measurements of ammonia (NH3) and nitric oxide (NO) concentrations present in
exhaled breath will be reported. Human breath contains ~ 500 different chemical species, usually at
ultra low concentration levels, which can serve as biomarkers for the identification and monitoring
of human diseases or wellness states. By monitoring NH3 concentration levels in exhaled breath a
fast, non-invasive diagnostic method for treatment of patients with liver and kidney disorders, is
feasible. The NH3 concentration measurements were performed with a 2f wavelength modulation
quartz enhanced photoacoustic spectroscopy (QEPAS) technique, which is suitable for real time
breath measurements, due to the fast gas exchange inside a compact QEPAS gas cell. A Hamamatsu
air-cooled high heat load (HHL) packaged CW DFB-QCL is operated at 17.5°C, targeting the
optimum interference free NH3 absorption line at 967.35 cm-1 (λ~10.34 μm), with ~ 20 mW of
optical power. The sensor architecture includes a reference cell, filled with a 2000 ppmv NH3 :N2
mixture at 130 Torr, which is used for absorption line-locking. A minimum detection limit (1σ) for
the line locked NH3 sensor is ~ 6 ppbv (with a 1σ; 1 sec time resolution of the control electronics).
This NH3 sensor was installed in late 2010 and is being clinically tested at St. Luke's Hospital in
Bethlehem, PA.
KEYWORDS: NOx, Sensors, Magnetism, Signal detection, Spectroscopy, Quantum cascade lasers, Signal to noise ratio, Magnetic sensors, Molecules, Polarization
Ultra-sensitive detection of nitrogen dioxide (NO2) in the ν3 fundamental band of NO2 using Faraday Rotation
Spectroscopy (FRS) based optical sensor platform is reported. The FRS technique is well suited for selective trace gas
measurements of paramagnetic species including the prominent air pollutants such as NO or NO2. In this paper a widely
tunable external cavity quantum cascade laser (EC-QCL) is employed as an excitation source. The available EC-QCL
mode-hop free tuning range between 1600 cm-1 and 1650 cm-1 allows to access the optimum for FRS technique 441<-440
Q-branch NO2 transition at 1613.2 cm-1 with an optical power of ~135 mW. In order to improve detection sensitivity and
reduce size of the sensor platform, a custom made 22.47 cm long Herriott multipass gas cell (MPC) with a total effective
optical path of 10.1 m was implemented. For a MPC configured NO2 FRS sensor operating in line-scanning mode a
minimum detection limit of 1.6 ppbv (1σ) and 0.15 ppb (1σ) is achieved for a 1 sec and 100 sec averaging time,
respectively. Preliminary results for long term measurements of atmospheric NO2 for the FRS sensor operating at an
optimal pressure of 30 Torr and magnetic field of 200 Gaussrms were demonstrated.
The development and performance of a continuous wave (CW), thermoelectrically cooled (TEC) external cavity
quantum cascade laser (EC-QCL) based sensor for quantitative measurements of nitric oxide (NO) concentrations in
exhaled breath will be reported. Human breath contains ~ 400 different chemical species, usually at ultra low
concentration levels, which can serve as biomarkers for the identification and monitoring of human diseases or wellness
states. By monitoring exhaled NO concentration levels, a fast non-invasive diagnostic method for treatment of patients
with asthma and chronic obstructive pulmonary disease (COPD) is feasible. The NO concentration measurements are
performed with a 2f wavelength modulation based quartz enhanced photoacoustic spectroscopy (QEPAS) technique,
which is very suitable for real time breath measurements, due to the fast gas exchange inside a compact QEPAS gas cell
(<5 mm3 typical volume). In order to target the optimal interference free NO R (6.5) absorption doublet at 1900.08 cm-1(λ~5.263 μm) a Daylight Solutions Inc. widely tunable, mode-hop free 100 mW EC-QCL was used. The sensor reference
channel includes a 10 cm long reference cell, filled with a 0.5% NO in N2 at 150 Torr, which is used for line-locking
purpose. A minimum detection limit (1σ) for the EC-QCL based line locked NO sensor is ~5 ppbv with a 1 sec update
time by a custom built control QCL compatible electronics unit.
Recent advances in the development of trace gas sensors based on the use of quantum cascade lasers
(QCLs) for the sensitive, selective detection, quantification and monitoring of small molecular gas
species with resolved spectroscopic features will be described. High detection sensitivity at ppbv and
sub-ppbv concentration levels require detection sensitivity, enhancement schemes such as multipass
absorption cells, cavity enhanced absorption techniques, or quartz enhanced photo-acoustic
absorption spectroscopy (QEPAS). These three spectroscopic methods can achieve minimum detectable absorption losses in the range from 10-8 to 10-11 cm-1/√Hz. Two recent examples of real world applications of field deployable PAS and QEPAS based gas sensors will be reported, namely the monitoring of ammonia concentrations in exhaled human breath and major urban environments.
A continuous wave, thermoelectrically cooled, distributed feedback quantum cascade laser (DFB-QCL) based
sensor platform for the quantitative detection of ammonia (NH3) concentrations present in exhaled human breath is
reported. The NH3 concentration measurements are performed with a 2f wavelength modulation quartz enhanced
photoacoustic spectroscopy (QEPAS) technique, which is very well suited for real time breath analysis, due to the fast
gas exchange inside a compact QEPAS gas cell. An air-cooled DFB-QCL was designed to target the interference-free
NH3 absorption line located at 967.35 cm-1 (λ~10.34 μm). The laser is operated at 17.5 °C, emitting ~ 24 mW of optical
power at the selected wavelength. A 1σ minimum detectable concentration of ammonia for the line-locked NH3 sensor is
~ 6 ppb with 1 sec time resolution. The NH3 sensor, packaged in a 12"x14"x10" housing, is currently installed at a
medical breath research center in Bethlehem, PA and tested as an instrument for non-invasive verification of liver and
kidney disorders based on human breath samples.
Faraday Rotation Spectroscopy (FRS) is a technique for the sensitive and selective detection of paramagnetic molecules
or radicals such as NO, NO2, O2 or OH-. Moreover FRS is suitable for atmospheric measurements due to the insensitivity
to non-paramagnetic interfering molecules such as H2O and CO2. Experimental results of an FRS sensor for the NO2detection employing an external-cavity quantum cascade laser (EC-QCL) are reported. The CW EC-QCL exhibits modehop
free (MHF) tuning between 1600 cm-1 and 1650 cm-1. This allows targeting the optimum 441←440 Q-branch NO2transition at 1613.25 cm-1. A rotation of the polarization state of the initially linearly polarized laser light is observed
when an AC magnetic field is applied to the NO2 cell, placed between two nearly crossed Rochon polarizers. This
rotation of the polarization state is proportional to the NO2 concentration and can be determined by a photodetector
located after the second polarizer. For long-term continuous measurements a second branch consisting of a detector and
reference cell filled with 0.2 % NO2 in N2 is used to lock the laser to the selected NO2 transition. A minimum detection
sensitivity (1σ) of 1 parts per billion (ppbv) was obtained for a 1 sec lock-in time constant (TC).
The ν1+ν3 combination band of uranium hexafluoride (UF6) is targeted to perform analytical enrichment measurements
using laser absorption spectroscopy. A high performance widely tunable EC-QCL sources emitting radiation at 7.74 μm
(1291 cm-1) is employed as an UF6-LAS optical source to measure the unresolved rotational-vibrational spectral
structure of several tens of wavenumbers (cm-1). A preliminary spectroscopic measurement based on a direct laser
absorption spectroscopy of methane (CH4) as an appropriate UF6 analyte simulant, was demonstrated.
With the anticipated retirement of Space Shuttles in the next few years, the re-supplying of short-lifetime sensors on the
International Space Station (ISS) will be logistically more difficult. Carbon Monoxide (CO) is a well-known combustion
product and its absence in a fire and post-fire environment is a reliable indicator for mission specialists that the air
quality is at a safe to breathe level. We report on the development and performance of a prototype compact CO sensor,
based on the PHOTONS platform [1], developed for the ISS based on tunable diode laser absorption spectroscopy
(TDLAS). A CO absorption line at ~4285 cm-1 is targeted using a distributed-feedback (DFB) laser diode operating at
room temperature. A custom designed Herriott multipass cell 16cm long, with an effective path length of 3.7 m is
employed. Mechanical, optical and electronics systems are integrated into a compact package of dimensions measuring
12.4"x 3.4"x 5". Power consumption is less than 1 W, enabling prolonged battery life. A detection limit of 3 ppm is
achieved when performing 40 second long temperature scans. A recent initial test at NASA-JSC was successful. Future
improvements include the reduction of the sampling volume, scan time and an improved CO minimum detection limit.
Nitric oxide detection with Faraday rotation spectroscopy offers excellent
sensitivity and high specificity together with outstanding long term system performance. Development of a
transportable, cryogen-free, prototype field instrument based on mode-hop-free external cavity quantum
cascade laser targeting the optimum NO Q(3/2) transition at 1875.8 cm-1 is reported . The system shows a
minimum detection limit of 5.4 ppb with a 1sec. lock-in time constant. Continuous, unattended NO
monitoring with >1 hour white noise limited averaging times is reported.
Recent advances in the development of sensors based on infrared quantum cascade lasers for the detection of trace gas
species is reported. Several selected examples of applications in environmental and industrial process monitoring as well
as in medical diagnostics using quartz enhanced photoacoustic spectroscopy and laser absorption spectroscopy will be
described.
There is a necessity of development a stable and calibrated laser sources for modern WDM telecommunication systems. Additionally simultaneous oscillations of many wavelength are required for testing and diagnostic of such systems. This regime of operation is possible in Frequency Shifted Feedback Lasers (FSFL). The multiwavelength erbium doped fiber laser is presented in this paper. The acoustooptical Bragg frequency shifter (AOFS) in the laser cavity ensures stable and multi-frequency operation by preventing steady-state regime. The wavelengths forced by Fabry-Perot filter cover part of third window (1550 nm).
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