Appl. Phys. B 91, 195201 (2008) DOI: 10.

1007/s00340-008-2958-x

Applied Physics B
Lasers and Optics

m. triki p. cermak g. m jean e d. romaniniu

Cavity-enhanced absorption spectroscopy with a red LED source for NOx trace analysis
Laboratoire de Spectrom trie Physique, CNRS UMR 5588, Universit J. Fourier de Grenoble, e e 38402 Saint Martin dHres, France

Received: 2 October 2007/Revised version: 22 January 2008 Published online: 5 March 2008 Springer-Verlag 2008

absorption spectroscopy (IBB-CEAS) based on arc lamps has been around for a few years, but only two reports exist using light-emitting diodes (LEDs). We present a setup based on a 643-nm LED which is of interest for the simultaneous detection of NO3 and NO2 . The latter is chosen for testing as it is stable and available in calibrated diluted samples. A detection limit in the ppbv range is obtained with 2-min averaging (5 109 /cm rms baseline noise level), comparable to the best performance of chemiluminescence devices used for pollution monitoring. At 1-s acquisition time, the detection limit is below 10 ppbv. Extrapolation to NO3 yields a detection limit of a few pptv for a few minutes averaging. We also test the retrieval of absolute sample absorption (and concentration) using the cavity mirror reectivity obtained with a commercial spectrophotometer, and we conclude that a calibration based on a reference sample of known concentration is preferable for accurate concentration measurements with IBB-CEAS. Finally, we present a rigorous frequency-domain derivation of cavity transmission as a function of wavelength for a broad-band spectrally smooth source, which complements the time-domain derivation by Fiedler et al. This derivation exposes an issue with multiple transverse mode excitation inherent to this technique, which may result in slightly distorted spectral proles.
PACS 07.88.+y;

ABSTRACT Incoherent broad-band cavity-enhanced

07.60.Rd; 42.60.Da

Introduction

Nitrogen oxides (NOx ) play a crucial role in atmospheric chemistry since they affect ozone removal and production as well as mixing ratios of other radicals (particularly OH). Reaction of ozone with NO2 produces the NO3 radical, which, during night time, oxidizes several organic pollutants and forms nitric acid and peroxy radicals among other products [1]. The NO2 mixing ratio in the troposphere varies from as little as tens of pptv in clean regions to ppmv levels in heavily polluted areas. Existing monitoring techniques are often slow or lack sensitivity, require frequent calibration (chemiluminescence), or lack spatial resolution (long-path differential
u Fax: +33-4-7663-5495, E-mail: daniel.romanini@ujf-grenoble.fr

optical absorption spectroscopy (DOAS)). Therefore, for the monitoring and understanding of tropospheric chemical processes, it is important to explore and develop new techniques for the sensitive measurement of NOx species with compact and robust devices capable of in situ operation with a short response time and a large dynamic range. High-sensitivity absorption techniques based on diode lasers emitting in the blue ( 410 nm), i.e. cavity ring down spectroscopy (CRDS) [2, 3] or optical-feedback cavityenhanced absorption spectroscopy (CEAS) [4], have already demonstrated sub-ppbv NO2 sensitivity even with 0.1-s measurement time. However, spectral resolution and high sensitivity come with an optical setup which is relatively complex and expensive, due to the presence of a laser diode source and its coupling scheme to the high-nesse cavity. A simpler alternative has been demonstrated by extending CEAS to broad-band incoherent (spatially and temporally) light sources such as arc lamps [5] and ppbvpptv detection limits were recently demonstrated for NO2 and NO3 , respectively, among other molecules of atmospheric interest [6]. While arc lamps provide sufcient power density over a very large spectrum, broader in fact than the typical stop band of dielectric high-reectivity mirrors, light-emitting diodes (LEDs) may provide similar performance in a smaller spectral range more closely matching the cavity mirrors stop band. In addition, LEDs are much more power efcient, stable, compact, and long lived and do not require strong cooling compared to arc lamps. Perhaps more importantly, high-power LED sources became recently available in several spectral windows from the near infrared up to the near UV, with higher efciencies achieved in the visible range. To our knowledge, only two published reports exist to date about the successful coupling of LEDs with incoherent broad-band CEAS (IBB-CEAS), by the same group [7, 8], which again focus upon NOx detection among other species of atmospheric relevance, and another work which was recently accepted [9]. In general, IBB-CEAS schemes achieve 10 to 100 times lower sensitivity than laser-based CRDS or CEAS, with a response time in the minutes rather than in the seconds time scale. In addition, reaching below 0.1-nm resolutions demands even longer acquisition times. Still, simplicity makes IBB-CEAS competitive in several applications where very fast response and/or extreme sensitivity are not essential. It should also be noted that for NO2 or NO3 detection low spec-

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tral resolution is sufcient for selective recognition of the spectral structures of these species. In particular, at atmospheric pressure NO3 absorption bands are broader than 1 nm, while NO2 has a well-developed spectral structure even at around 1-nm resolution. We present here a performance study for a IBB-CEAS setup based on a LED source centered at 643 nm when operated close to room temperature, whose emission spectrum allows measurement of NO2 and NO3 concentrations simultaneously. The NO3 spectrum features a strong and broad peak centered at 623 nm and another peak at 662 nm, while NO2 presents an absorption spectrum characterized by a randomlooking structure with about 50% peak-to-valley excursions (at 1-nm resolution). In view of the difculty in generating known NO3 concentrations, we tested the response of our system using NO2 , which is commercially available in calibrated mixtures. Even though NO2 absorption would be strongest at around 400 nm with an average absorption level about 10 times larger than at 643 nm, the noise-equivalent detection limit for our setup is still around 1 ppbv for a few minutes measurement. This appears to be quite satisfactory for a large domain of applications, in particular for monitoring urban pollution. Given the 600 times larger optical cross section for the NO3 band at 623 nm, a detection limit in the low-pptv range is expected for this important atmospheric radical. The difference in the spectra of NO2 and NO3 guarantees that their simultaneous measurement is possible using a standard linear multicomponent analysis of the absorption spectra. The fact that a much higher sensitivity is available for NO3 appears as a desirable feature in view of the much smaller concentrations which are typical of this species, even if it is to be noted that NO3 levels strongly vary from day (almost absent) to night, with respect to those of NO2 [10]. In terms of noise-equivalent absorption, we achieved 5 109 /cm for 2-min averaging, which is comparable to what was reported with different IBB-CEAS setups. In particular, using a ber-coupled LED and a 1.5-m-long cavity with R = 99.995% mirrors at around 675 nm, a cooled charge coupled device (CCD) camera, and a moderately high resolution spectrograph, the same detection limit was achieved but with 8-min averaging [7], corresponding to pptv levels of NO3 . A very similar setup optimized for NO2 with a bered LED at 455 nm and 99.975% mirrors reached down to 2 109 /cm with only 30-s averaging [8], corresponding to a 0.1-ppbv limit for NO2 . Using cavity-attenuated phaseshift spectroscopy, a variant of cavity-enhanced absorption, Kebabian et al. [11] obtained with a 440-nm LED a detection limit of 4 1010 /cm within 10-s integration time (26-cmlong cavity with R = 99.99% mirrors). It is however to be noted that this technique provides no spectral resolution in order to discriminate among different species or between a structured absorption such as from NO2 or NO3 and unstructured ones such as from aerosols. Incidentally, it is to be noted that an interesting argument about optimizing cavity injection by using a close-to-confocal cavity was presented in that work. Finally, using a xenon arc lamp and a 4.5-m-long cavity with R = 99.76% mirrors at around 660 nm, 1 pptv and 10 ppbv detection limits were obtained for NO3 and NO2 with 1-min averaging [6]. Other important parameters not given above determine overall system performance, notably the

LED power effectively coupled into the cavity, the performance of the spectrometer (especially the CCD detector), and the mirrors intrinsic losses. The main difference of our setup compared with those in previous LED-based IBB-CEAS studies is that the LED is placed directly in front of the cavity and coupling is done through a short focal length lens. In addition, we use a commercial bered spectrograph with a room-temperature CCD, and no temperature stabilization is applied to the LED or the spectrograph.
2 Theory of IBB-CEAS

Light absorption as a function of optical frequency by a sample of thickness L is described by the well-known LambertBeer law
I() = I0 () exp(()L) ,

(1)

where I0 () and I() are the incident and transmitted intensities and the absorption coefcient is () = N(), with () and N the cross section and the number density of the absorbing species in the sample, respectively. In the case of a high-nesse cavity we have to consider the optical elds entering at different times into the cavity and interfering together after 1, 2, 3, ... round trips. This interference produces uniformly spaced transmission resonances at frequencies q = qc/2nL (q is a positive integer, c the speed of light, and n the intracavity sample refraction index), which correspond to intracavity constructive interference. This comb of resonances is described by the cavity transmission function [12]
Tc () = T 2 exp(()L) , (1 Re )2 + 4Re sin2 (kL)

(2)

where we have neglected the reection phase shift on the mirrors, T() is the mirrors transmittance,
Re = R() exp(()L)

is an effective reection coefcient per pass, and k() = 2n/c is the wave number. By denition, this cavity transmission function multiplied by the input spectral power density gives the cavity output power density. Very little transmission occurs for frequencies in between resonances, where the sine function is not close to 0 and Tc drops as low as T 2 /4. As a result of destructive interference of the circulating wave, this is four times less than the simple transmission by the two cavity mirrors if they were placed in a non-resonant conguration (sufciently tilted with respect to the optical axis not to allow resonances). On the contrary, at resonance (sin(kL) = 0) transmission is large Tc,res [T/(1 R)]2, which is possible due to the build up of a large intracavity eld due to constructive interference. Transmission may then attain 100% if we neglect losses ( R + T = 1, = 0). For a broad-band source, it is possible to calculate analytically the low-resolution cavity transmission which is observed when using a spectrograph (normally unable to resolve cavity resonances, spaced by 300 MHz for our 50-cm cavity). Indeed, we can write the transmitted intensity in a small spectral interval, e.g. corresponding to a resolved spectral element of the spectrograph, as

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the integral over this interval of Tc () times the input power density. For a broad-band source this is constant over the interval and can be factorized out of the integral, which then simply becomes the average transmission over several cavity modes. This may be calculated by analytical integration over only one cavity free spectral range, where even the sample absorption coefcient may be considered constant. This yields
Tc,BB = T 2 exp(L) . 1 R2 exp(2L)

(3)

The excitation by a spatially incoherent source of a large number of transverse modes, as needed in order to achieve sufcient light throughput, does not modify substantially this result. In fact, each transverse mode has a comb of resonances associated with it whose low-resolution transmission spectrum is then the same, except possibly for a slightly different mirror reectivity (the mirror surfaces are not perfectly homogeneous; thus, different transverse modes may experience different mirror performances). Direct ring down measurements with an optical cavity show that differences in reectivity between transverse modes may amount to several %. Cavity transmission is then written as a weighted sum of transmission functions of the type Tc,BB with different values of R, which cannot be rewritten as a single function of this type with an effective (average) reectivity value, but is presumably quite close to such a function as conrmed by the agreement of (3) with experimental results. In the limit of small absorption we can expand (3) to the rst order in :
Tc,BB T2 1 + R2 1 L 1 R2 1 R2 T2 F 1 L 2(1 R) ,

consider a LED or a lamp as emitting a continuous sequence of short pulses incoherent with one another (whose duration corresponds to the very short coherence time of the source). In order to apply (3) in practice, we should note that the spectrum observed in transmission through the cavity contains the spectral prole of the LED source and the spectral response of the bered spectrograph. We could use a system of mechanical deectors in order to sample the LED spectrum before the cavity and normalize the spectrum measured in transmission, but we would still have an undetermined multiplicative factor since the two light paths will have some small difference in overall losses. This same problem also affects direct absorption measurements using a simple cell. A way around it is to measure the transmitted spectra with and without the sample lling the cavity, all other conditions being identical. In the ratio s between these spectra, all common factors cancel out (e.g. LED emission and spectrometer response proles), and we can write
s= Tc,BB () (1 R2) exp(L) = , Tc,BB (0) 1 R2 exp(2L)

(5)

which can be inverted with respect to the sample absorbance (keeping only the solution making physical sense):
() = 1 ln L R2 1 + (R2 1)2 + 4s2 R2 2sR2 .

(6)

(4) which shows that an effective path length L eff = L F/ can be dened, where F = R/(1 R) is the cavity nesse. Even in this limit, it is not possible to convert the different contributions of transverse modes to the cavity transmission into a simpler expression containing an effective reectivity parameter (or an effective transmission). This is particularly severe over a broad spectral range where mirror reectivity changes signicantly: since the reectivity prole for different transverse modes can be assumed to be the same apart from a different multiplicative factor (close to 1), the term 1 R which appears in the above expression cannot be factorized. This may produce distortion in spectral proles derived from IBB-CEAS measurements and deserves experimental investigation. Equation (4) shows that the average cavity transmission for a broad-band source will never be larger than T/2, attained when sample absorption and mirror losses are negligible with respect to T ( R = 1 T ). This is clearly much smaller than transmission through a simple absorption cell (1). Loss of incident light intensity in fact represents a fundamental limitation in BB-CEAS. According to the transmission T of the input mirror, a fraction T of the incident light is trapped in the cavity, which can then leak out of the cavity half in the forward and half in the backward direction (which accounts for the factor 1/2). The same behavior is expected for a pulse of light of duration less than the cavity round trip, and indeed we can

Apart from potential problems associated with transverse modes as discussed above, this equation is valid in general even in the presence of appreciable attenuation of the cavity transmission by sample absorption, but not for low mirror reectivity (below 10%). Indeed, (2) for the cavity transmission is valid in the high-reectivity limit. The expression previously proposed by Fiedler et al. [5] may be obtained by simply performing a rst-order Taylor expansion for small 1 R (that is, taking 1 R as a new variable for the expansion), which is the high-reectivity limit again:
() = (1 s)(1 R) . sL

(7)

In typical conditions (e.g. for the present cavity parameters) this simplied expression delivers the right absorbance with a fractional error of only about 103 for intracavity absorption up to 10% per pass; thus, it can be safely used in most practical IBB-CEAS applications. With respect to the previous derivation of (7) by Fiedler et al., we should note that the more accurate (6) is exactly equivalent to Eq. (4) in [5] obtained by a rather different approach. Fiedler et al. recognized the existence of interference in the cavity producing transmission peaks at welldened resonance frequencies even for a broad-band incoherent source, but they preferred to base their derivation in the time domain. In the limit of a pulse much shorter than the cavity round trip time, they simply considered the pulse intensity as it is transmitted and reected multiple times inside the cavity. Even though a LED is a continuous source, this result is still valid as its coherence time is shorter than the cavity round trip time, so that its emission is equivalent to a se-

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quence of uncorrelated short pulses very closely separated in time. In fact, the interference among the elds entering the cavity at different times t , t 2 , t 3 , ... (where is the cavity round trip time), which all give a contribution to the cavity output at time t , will average to zero since these elds have uncorrelated phases, which means that the intensity (the square modulus of the amplitude) of the resulting eld is equal to the sum of the intensities of the interfering elds. We nally should note that, if we correct a small mistake in its derivation (1 R is used in place of simply T for the mirror transmission), Eq. (2) in [5] is also the same as our (3).
3 Experimental results and discussion

Our setup for NO2 measurements is presented schematically in Fig. 1. The chosen LED (LXHL-MD1D, Lumileds Luxeon [13]) has a spectrum that peaks at 643 nm (see Fig. 2). It requires about 1 W of electrical power and the nominal emitted light amounts to 44 lumens (about 190 mW). This LED is mounted on a radiator with a fan to avoid overheating and allow rapid equilibration of its temperature and thus its output spectral distribution and intensity. Part of its emission (about 10 mW) is collimated by means of a f = 15 mm lens of 1-in diameter (placed at about 1 f ) and injected into a 50-cm optical cavity formed by two high-reectivity mirrors, also 1 in in diameter. The lenscavity distance is not critical and may be minimized to reduce setup size. The cavity mirrors (50-cm radius of curvature), manufactured in the same batch by Layertec (Germany), have a maximum reectivity of 99.92% at around 630 nm. They are mounted in vacuum-tight cylindrical holders with a system of adjustment screws permitting their alignment along the cavity axis by playing on the deformation of o-ring seals. These holders are glued by epoxy to the ends of a stainless steel tube (internal diameter 1 in) forming the measurement cell and equipped with two gas ttings close to each mirror, which allow a rapid and complete sample renewal. A lens of 35 mm focal length is placed closely behind the output mirror and focuses the cavity output into a multimode ber (400-m core) connected to a low-resolution spectrometer (Stellar Net, EPP2000, FWHM resolution 1.85 nm) controlled by a PC through a USB connection.

FIGURE 2

Cavity transmission spectra obtained with the diluted NO2 sample and dry nitrogen (blank). In the inset, the blank spectrum is plotted on a logarithmic scale, showing the effect of the cavity mirrors transmission prole over the LED emission

FIGURE 1

Optical layout of the LED-based CEAS setup

This optical system is mounted on a 1-m-long aluminum rail, for a total weight of less than 10 kg (including spectrometer and laptop computer). It is insensitive to shocks, vibrations, and small alignment errors, and requires low power (< 100 W) to operate. Moreover, the alignment procedure is elementary. We need only look at the reected light spots inside the cavity. Afterwards, a ne optimization by looking at the transmitted spectrum shows a low sensitivity to alignment, and thus to alignment errors and drift. These features are favorable for any robust portable eld instrument for outdoor air pollution measurements (however, more electrical power would be needed for temperature control). For this setup, CCD saturation at the peak of the LED emission is obtained for a short integration time, about 140 ms. Further numerical averaging of these single-exposure spectra allows improving the S/N signicantly. Noise decreases initially as the inverse square root of the number of averaged spectra, as would be expected for white noise; however, at 1000 averages (about 2-min acquisition time) a S/N increase of about 16 is achieved rather than 33. In order to obtain the ratio s dened before, spectra are recorded rst with a ow of dry nitrogen and then with a ow containing NO2 . For this we use a high-pressure tank certied for 8.24 0.16 ppmv NO2 in dry synthetic air (EMI-207, Air Liquide, certication guaranteed for 1 year). In order to minimize memory effects (adsorption/desorption on surfaces) and loss of NO2 on the walls in the transfer from the sample tank to the measurement cell, we use a ow of several l/min and no ltering, and we ush the cell several minutes before making measurements. A teon tube of 4-mm internal diameter and shorter than 1 m connects the NO2 reservoir to the cell. Also, with the LED beam blocked, background spectra under the same conditions are recorded, averaged, and subtracted from all cavity transmission spectra. We do not consider longer averaging since gaining another factor of three in S/N would require more than 20 min, and this is not even granted since 1/ f noise due to system drifts seems to affect our data already after 2-min averaging. Indeed, besides falling short of the inverse-square-root dependence, we frequently notice substantial deformation in the baseline

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FIGURE 3 Reectivity of cavity mirrors and corresponding effective absorption path length, which is linearly proportional to cavity nesse ( /(1 R)) and is thus sensitive to small variations of R

of otherwise at spectra obtained as the ratio s of successive 1000-times averaged acquisitions with dry nitrogen ow. Such baseline problems are typically due to small horizontal shifts of the acquired spectral proles, due to spectrograph or LED thermal drift. In Fig. 2, we show an example of cavity transmission with and without a NO2 sample. The three minor peaks observed at 543, 752, and 822 nm, best visible in the semi-logarithmic plot in the inset of the same gure, are due to sharp minima at the edges of the mirror stop band (see the mirror transmission spectrum in Fig. 3). These minima in the reectivity occur in the wings of the LED emission spectrum where substantial power density is still present. Evidently, no cavityenhancement effect is present in correspondence to these spurious peaks. In order to determine sample absorbance directly from (7) we need the cavity mirror reectivity spectrum R(). A direct measurement by CRDS is difcult as it requires a broadly tunable laser source. For high-quality mirrors possessing a moderately high reectivity as used here, surface scattering and absorption losses of the mirrors coating should be much smaller than their transmission T(). In that case, the approximation R() 1 T() is reasonable, allowing us to derive R() from a measurement of T(). We employed a PerkinElmer spectrophotometer to obtain the mirror transmission prole, giving the effective path length (proportional to the cavity nesse) plotted together in Fig. 3. It is interesting to note that the nesse is not a at function of wavelength even close to the center of the mirror stop band. Thus, the sensitivity enhancement cannot be taken as constant across IBBCEAS spectra. As we will see, by using R() with (7) this varying nesse effect is taken into account and sample absorbance may be satisfactorily recovered over a large spectral range. Nonetheless, determination of reectivity remains a critical step. As we will be led to conclude, a more reliable alternative is calibrating concentration measurements using a reference spectrum from a sample of known concentration. On the other hand, we want here to test how well can we do using the direct inversion formula from theory, which requires knowledge of R(). A transmission measurement may

introduce important errors if we consider, for example, that an absolute error of only 0.01% (104 over a 100% scale) over a transmission value of only 0.08% (at the stop-band center) propagates to give a fractional error of 12% in the absorption coefcient through the term 1 R of (7). The same relative error is found in the estimation of cavity nesse and effective path length. By comparing reectivity measurements of the same mirrors taken at several days interval with the same spectrophotometer, errors in T appear to be wavelength dependent in our spectral region of interest and vary between 5 and 30%. To this we should add systematic errors introduced by neglecting mirror loss and other passive cavity losses (e.g. by aerosols), which should lead to an underestimation of 1 R and of the absorption (), consistently with the results described below. We also tried to obtain ring down measurements at a xed wavelength by using a bered 660-nm diode laser having a multimode emission. We used direct interruption of the laser current in order to generate ring down signals, monitored with a 900-MHz band-pass avalanche photodiode. Results are not conclusive since ring down times varied widely, apparently depending on the excited transverse mode being of higher or lower order. Selection of more or less high-order modes was simply obtained by adjusting the incident beam direction. Shorter decay times (1.2 s) were found for higher-order transverse modes (still far from being affected by the mirror edges) and longer decays (1.8 s, which corresponds to R = 99.91%) for modes close to TEM0,0 . This might indicate non-uniform losses across the mirror surface. As a last step to obtain absorbance spectra, the top section of the reectivity prole is tted by a polynomial function to reduce the noise level and this polynomial is used with (7). In Fig. 4 we compare the absorbance spectrum (1000 averages) for our 8.24-ppmv NO2 sample with a spectrum calculated from a high-resolution, high-quality NO2 optical cross section [14]. The latter is convoluted with a Gaussian of 1.85 nm FWHM to account for our instrumental function, and scaled for a concentration of 5.4 ppm that gives the best match with

FIGURE 4 Comparison of an absorption spectrum obtained by IBB-CEAS (averaging 1000 spectra) with a spectrum calculated using a reference NO2 absorption cross section by Voigt et al. [14], after convolution with a 1.85-nm FWHM Gaussian simulating our spectrometer response function. This reference spectrum is scaled for a NO2 concentration of 5.4 ppmv, which optimizes the match with the observed spectrum

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our IBB-CEAS spectrum (also shifted by 0.66 nm to compensate for spectrometer calibration error). The agreement is excellent over about 80 nm, from 590 to 670 nm, but for a concentration about 35% lower than the certied value of our sample. While this may indicate degradation and adsorption of NO2 over the walls of the gas-handling system, this result is reproducible in different experimental conditions; thus, it is likely that the discrepancy is due to a bias in the determination of the mirror reectivity. In order to achieve agreement of our spectrum with that expected for 8.24 ppmv, a constant loss of about 5 104 needs to be included in the determination of R from T ( R = 1 T Loss), which seems to be somewhat larger than expected for our mirrors, but still acceptable. However, other small baseline artifacts, in the form of bias or slope, may directly affect our data, for example due to a temperature drift of the LED emission spectrum or of the bered spectrometer response function. The sensitivity of our setup is readily estimated from the noise in a baseline measurement of () obtained as the ratio s of two successive recordings with dry nitrogen in the cavity. For 1000 averages a noise level of 5 109 /cm is found in the range of 615 to 655 nm (it gradually increases when moving out of the center of the LED emission band). By considering that, for 1-ppmv concentration, NO2 spectral features of about 106 /cm are present in this range, we would estimate the detection limit to be about 5 ppbv. However, we should take into account the number of independent data points which are available for the retrieval of the NO2 spectral contribution to a measured spectrum. This retrieval would be performed by using a standard procedure consisting in the linear t of the whole observed spectral prole by the reference spectra (NO2 , NO3 , etc.) plus a few low-order polynomials (accounting for baseline slope or bias due to spectral drifts of the source and to changing contributions of aerosol or other broad-band losses). Considering our spectral resolution ( 1.85 nm FWHM), about 15 independent data points would be available for this t, yielding a statistical improve ment of 15, and an effective detection limit of around 1 ppbv (equivalent to 3 1010 molecules/cm3). A negative effect which is not included in this estimation based on the immediate recording of two cavity transmission proles is the system drift which would occur in the larger delay needed to go from recording a prole for the sample and for the dry nitrogen blank. However, sample-exchange time could be reduced to well below 1 min, and system stability could be improved with temperature control. As we already stated, our experimental setup also allows for the detection of the NO3 radical, a species possessing a much stronger absorption band than NO2 at around 623 nm, peaking to about 1.5 1017 /cm2 [15]. By considering that the NO2 cross section features an average absorbance of about 2.5 1020 cm2 in the same spectral region, an improvement of about 600 is expected for NO3 detection, and thus a detection limit approaching 2 pptv. Another somewhat stronger NO3 absorption band is available at 662 nm; however, with the present setup, it corresponds to a lower reectivity of the mirrors and it would not present an advantage with respect to the detection limit. It also corresponds to stronger water absorption bands, whose contribution to the measured spectrum should be accounted for (in return one could estimate ambient

humidity, but probably not to high accuracy). Finally, photodissociation might affect the concentration measurement especially for the higher-energy band used here; however, photodissociation at these wavelengths is reported to have low efciency at 1 bar [1], likely due to the competing collisional relaxation.
4 Conclusions and perspectives

This study of the performance of CEAS using a broad-band LED source argues in favor of this technique in terms of sensitivity, simplicity, compactness, and robustness. For a cavity of moderately high nesse ( F 4000 here) and without pushing spectral resolution (1.85 nm FWHM), very short acquisition times are possible (140 ms) with a noise-equivalent absorption level in the spectra of 107 /cm (or 5 106 per pass). Averaging up to 2 min yields 5 109 /cm, only a factor of two from what expected for white-noise statistics, but longer averaging times are expected to yield modest improvement in the absence of temperature control. By using a certied NO2 trace mixture, we could obtain a low-resolution spectrum with high S/N which displays excellent agreement with the high-resolution spectrum by Voigt et al. [14] after convolution by our instrumental function: the maximum deviation is about 4% (of the largest absorption feature) over a 80-nm range. The detection limit for this molecule is then estimated to be 1 ppbv for 2-min averaging, about 20 ppbv at the basic 7-Hz data-acquisition rate, and 8 ppbv at 1 Hz. The same setup should allow detection of NO3 in the same spectral range with a 600 times better sensitivity, according to the well-characterized absorption spectrum of this radical. The spectral resolution would be enough to allow discriminating the two species, plus eventually determining the weak spectral contributions of water vapor and oxygen. This would be useful for a correct retrieval of NOx concentrations in eld measurements, especially if sensitivity were improved with respect to the present setup. The higher sensitivity for NO3 is a convenient feature given the typical lower levels of this (more reactive) molecule. Another advantage of this wavelength range is that Rayleigh scattering is signicantly smaller than at shorter wavelengths. The main problem encountered is determining an absolute absorption scale when trying to use the model equations of cavity transmission ((7) and previous equations) for a source with a broad and smooth emission spectrum. For this we presented a rigorous derivation starting from the high-resolution cavity response function. The main potential source of errors appears to be the experimental measurement of the reectivity spectrum of the cavity mirrors, which in our case could alone account for a 35% underestimation of the measured NO2 absorption (and thus of its concentration). This implies that a calibration by injection of a reference sample is required. However, the mirror reectivity can be calculated using (7) from the measured reference spectrum and the expected reference spectrum (for the known concentration of the reference sample). Thus, the reference sample does not need to contain the same molecule as that being measured, e.g. we could use NO2 in order to calibrate the system for NO3 . NO2 actually is a good choice given that its spectral structure covers the whole visible range.

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An Allan variance study will be needed to determine more precisely at which averaging time the detection limit stops improving, and would allow us to establish the impact of successive improvements to be implemented in order to increase system stability. In particular, the day-to-day repeatability of concentration values obtained for a stable reference sample will have to be assessed, especially after mirror cleaning or cavity realignment. Since mirrors in such a setup could gradually become covered with dust, mechanical ltering of injected air should be provided, but that might be incompatible with reactive species such as NO2 or NO3 . A promising solution consists of using an open optical cavity, with ltered air used for rinsing continuously the mirrors surfaces to protect them against aerosols or other possibly aggressive agents. We tested such a system in the past with an open-cell CRDS setup of much higher nesse, and it could operate outdoors without signal loss over several days. Taking blank or reference spectra could be done by switching into the cavity a tube allowing a ow of cleaned air or of the reference sample to ll completely the intracavity volume. Given the large signal level which we readily obtained with less than 1-s detector exposure, there is space for improvement by increasing the cavity nesse. Signal loss will be partially compensated by optimizing cavity injection and sampling of its output into the spectrometer. A higher-quality CCD could also be used. In this respect, a preliminary test was carried out using a Hamamatsu bered spectrograph equipped with a back-illuminated CCD sensor. The exposure time needed for lling the CCD (13 ms) was 10 times shorter than for the StellarNet device used here, but the observed noise levels for 100 times averaged spectral proles were only a factor of two better, even though the digitization system of the Hamamatsu device has a much better vertical resolution. This would indicate that we are probably close to the shot-

noise limit for the baseline noise. Indeed, the full well capacity for the Hamamatsu CCD is 105 electrons, and the shot noise is then 0.3% around the top of the recorded spectral prole, close to the specied noise level for the StellarNet device. By increasing the cavity nesse by a factor of 10 we then expect to gain the same factor in sensitivity if mirror losses remain comparable to transmission, which is the case with high-quality mirrors. Indeed, using a better CCD would allow obtaining a saturated cavity transmission spectrum with basically the same base exposure time that we achieve in the presented lower-nesse setup.
ACKNOWLEDGEMENTS We acknowledge the French Embassy in Tunisia and French Embassy in Slovakia for nancial support of M.T. and P.C.

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