Atmos. Meas. Tech.

, 4, 1227–1240, 2011
www.atmos-meas-tech.net/4/1227/2011/ Atmospheric
doi:10.5194/amt-4-1227-2011 Measurement
© Author(s) 2011. CC Attribution 3.0 License. Techniques

Diode laser-based cavity ring-down instrument for NO3, N2O5, NO,

NO2 and O3 from aircraft
N. L. Wagner1,2 , W. P. Dubé1,2 , R. A. Washenfelder1,2 , C. J. Young1,2 , I. B. Pollack1,2 , T. B. Ryerson1 , and S. S. Brown1
1 NOAA Earth System Research Laboratory, R/CSD7, 325 Broadway, Boulder, CO 80305, USA
2 Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USA
Received: 9 February 2011 – Published in Atmos. Meas. Tech. Discuss.: 3 March 2011
Revised: 31 May 2011 – Accepted: 14 June 2011 – Published: 28 June 2011

Abstract. This article presents a diode laser-based, cavity analytical standard, provides a complete and accurate pic-
ring-down spectrometer for simultaneous in situ measure- ture of nighttime nitrogen oxide chemistry. The instrument
ments of four nitrogen oxide species, NO3 , N2 O5 , NO, NO2 , performance is demonstrated using data acquired during a re-
as well as O3 , designed for deployment on aircraft. The in- cent field campaign in California.
strument measures NO3 and NO2 by optical extinction at
662 nm and 405 nm, respectively; N2 O5 is measured by ther-
mal conversion to NO3 , while NO and O3 are measured by 1 Introduction
chemical conversion to NO2 . The instrument has several ad-
vantages over previous instruments developed by our group The nitrate radical, NO3 and its reservoir species, dinitrogen
for measurement of NO2 , NO3 and N2 O5 alone, based on pentoxide (N2 O5 ) are important trace gases in the nocturnal
a pulsed Nd:YAG and dye laser. First, the use of continu- atmosphere (Wayne et al., 1991). NO3 is formed by reaction
ous wave diode lasers reduces the requirements for power of ozone with NO2 (Reaction R1), and reacts with NO2 to
and weight and eliminates hazardous materials. Second, de- reversibly form N2 O5 (Reaction R2).
tection of NO2 at 405 nm is more sensitive than our previ-
ously reported 532 nm instrument, and does not have a mea- O3 + NO2 → NO3 + O2 (R1)
surable interference from O3 . Third, the instrument includes
chemical conversion of NO and O3 to NO2 to provide mea- NO3 + NO2  N2 O5 (R2)
surements of total NOx (= NO + NO2 ) and Ox (= NO2 + O3 )
on two separate channels; mixing ratios of NO and O3 are These species are typically present at very modest levels dur-
determined by subtraction of NO2 . Finally, all five species ing daytime (less than 1 pptv) because NO3 undergoes rapid
are calibrated against a single standard based on 254 nm O3 photolysis and reaction with NO, which is present during the
absorption to provide high accuracy. Disadvantages include day and in close proximity to large NOx emission sources
an increased sensitivity to water vapor on the 662 nm NO3 during the night.
and N2 O5 channels and a modest reduction in sensitivity for
NO3 + hυ → NO2 + O
these species compared to the pulsed laser instrument. The (R3)
→ NO + O2
in-flight detection limit for both NO3 and N2 O5 is 3 pptv
(2 σ , 1 s) and for NO, NO2 and O3 is 140, 90, and 120 pptv NO3 + NO → 2 NO2 (R4)
(2 σ , 1 s) respectively. Demonstrated performance of the in-
strument in a laboratory/ground based environment is better The nitrate radical is a strong oxidant and is consumed
by approximately a factor of 2–3. The NO and NO2 mea- by reactions with biogenic VOCs and sulfur compounds,
surements are less precise than research-grade chemilumi- and some classes of highly reactive anthropogenic VOCs
nescence instruments. However, the combination of these (Atkinson, 1991). N2 O5 undergoes heterogeneous uptake
five species in a single instrument, calibrated to a single to aerosol. Its hydrolysis leads either to non-photochemical
conversion of NOx to soluble nitrate via production of HNO3
(Jones and Seinfeld, 1983), or to activation of photola-
Correspondence to: S. S. Brown bile halogens through formation of nitryl chloride, ClNO2
([email protected]) (Finlayson-Pitts et al., 1989; Thornton et al., 2010). Thus,

Published by Copernicus Publications on behalf of the European Geosciences Union.

1228 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3

NO3 and N2 O5 are intermediates in a number of impor- and N2 O5 (Dubé et al., 2006). This is advantageous in terms
tant atmospheric chemical transformations, and understand- of size, weight, power consumption, and elimination of toxic
ing their atmospheric concentrations is an important topic of dyes. The main disadvantage to this approach is its increased
current research. sensitivity to water vapor. Implications of the water vapor
Much of the prior database for understanding these pro- sensitivity for aircraft measurements are described further
cesses was based on measurements of NO3 by differential below. A second diode laser centered near 405 nm is used
optical absorption spectroscopy (DOAS) over a long, open for detection of NO2 by CRDS and of NO and O3 by chemi-
path or by passive techniques using natural light sources cal conversion to NO2 . The NO2 channel provides not only a
(Platt et al., 1980; Solomon et al., 1989; Plane and Nien, direct measurement of this compound, but also a method for
1992). Such measurements have been extremely useful in calibrating the NO3 and N2 O5 measurements via the conver-
developing an understanding of the factors that govern night- sion of these compounds to NO2 in excess NO as described
time chemistry. In situ instruments add to this database by by Fuchs et al. (2009). The NO2 measurement is itself cal-
enabling measurements from mobile platforms, such as air- ibrated against a standard based on ultraviolet absorption of
craft and ships (e.g., Brown et al., 2007a), and from tall tow- ozone at 254 nm as described by Washenfelder et al. (2011),
ers (e.g., Brown et al., 2007b). The in situ measurements providing a common analytical standard for all five species
are valuable for characterizing the strong vertical gradients measured by this instrument.
characteristic of the nocturnal boundary layer or for measure- The combination of these five trace gases provides a com-
ments within the residual daytime boundary layer. plete picture of the nighttime chemistry shown in Reac-
Cavity ring-down spectroscopy (CRDS) is a sensitive tech- tions (R1)–(R4). Measurements of NO2 and O3 provide
nique for in situ measurement of atmospheric trace gases the source for NO3 formation. Direct measurement of NO3
(Brown, 2003). In situ measurement of NO3 was first devel- and N2 O5 allow for understanding of their chemistry in the
oped approximately a decade ago and was based on CRDS nighttime atmosphere. Measurement of NO characterizes the
with either a pulsed dye laser (Brown et al., 2002) or ex- most important nighttime sink for NO3 in near source regions
tended cavity diode laser (King et al., 2000). Thermal con- (e.g., low altitude over urban areas). This paper describes the
version of N2 O5 to NO3 in a second channel enabled direct design and operation of this instrument, and its deployment
measurement of the sum of the two compounds and mea- on aircraft.
surement of N2 O5 itself by difference. This development
ultimately led to the deployment of a CRDS instrument for
NO3 and N2 O5 on aircraft (Dubé et al., 2006). Although the 2 Instrument description
pulsed laser system used in this instrument had a relatively
small footprint, such laser systems are in general somewhat CRDS is commonly used for sensitive detection of trace
cumbersome for field instruments because of their require- gases and has been described in several reviews (Busch and
ments for power and weight (30 kg and 0.5 kW). In addition, Busch, 1999; Brown, 2003; Atkinson, 2003). CRDS is a di-
the use of toxic dyes and solvents requires hazardous ma- rect absorption spectroscopy in which the optical path length
terials that are not ideal for field environments, especially is enhanced by a high finesse cavity formed by a set of two
aircraft. highly reflective mirrors. A laser is directed into the cavity,
The aircraft instrument described above also incorporated the optical intensity builds in the cavity, and then the laser
measurements of NO2 by pulsed laser CRDS at 532 nm by is turned off quickly compared with the decay of optical in-
taking advantage of the Nd:YAG laser second harmonic that tensity in the cavity. The exponential decay of light intensity
was used to pump the dye laser (Osthoff et al., 2006). These from the cavity is monitored by measuring the light transmit-
NO2 measurements required active subtraction of an interfer- ted through the back mirror. When an absorber is present, the
ence from ozone, but were otherwise accurate (Fuchs et al., exponential decay time constant is reduced, providing an ab-
2010). These CRDS NO2 measurements have recently been solute measurement of optical extinction, as given in Eq. (1).
further developed using a diode laser with a center wave- Rl 1

1

length near 405 nm (Fuchs et al., 2009). Because there is no σ [A] = α = − (1)
c τ τ0
significant interference from ozone at this wavelength, this
approach is capable of simultaneous detection of NO via its Here, σ is the absorption cross-section corresponding to the
conversion to NO2 in excess ozone. We have also recently absorber, averaged under the spectrum of the laser, [A] is
demonstrated the analogous conversion of O3 to NO2 in ex- the concentration of the absorber, α is the optical extinction
cess NO (Washenfelder et al., 2011). coefficient (units of inverse length), c is the speed of light, τ
In this paper, we describe a single CRDS instrument based and τ0 are the exponential decay constants with and without
on diode lasers that measures NO3 , N2 O5 , NO, NO2 , and the absorber in the cavity and Rl is the ratio of the total length
O3 . Unlike the previous instruments from our group, this in- of the cavity to the length over which the absorber is present.
strument uses a diode laser near the maximum in the NO3 The instrument described here consists of two largely in-
absorption spectrum at 662 nm for the measurement of NO3 dependent parts that share a common set of electronics, data

Atmos. Meas. Tech., 4, 1227–1240, 2011 www.atmos-meas-tech.net/4/1227/2011/

850
N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3 1229

851
Fig. 1. Instrument schematic. The upper part framed in red shows the NO3 and N2 O5 measurement. The lower part framed in blue shows
the NO, NO2 and O3 measurement. BS denotes a beamsplitter. A photo of the optical bench instrument is shown on the right.
852 Figure 1. Instrument schematic. The upper part framed in red shows the NO3 and N2O5
853 measurement. The
acquisition, frame and lower
optical partsystem.
mounting framed Theinfirst
blue similar
showsto the NO,
our 405 nm NO and O3scheme
NO22detection measurement.
(Fuchs et al.,
part is the measurement of NO3 and N2 O5 using a 662 nm 2009). Since the nominal 0.5 nm width of the diode laser
854 BS
diodedenotes a beamsplitter.
laser. The second A photo
is the measurement of NO2 ,of
NO,the
and optical bench
spectrum instrument
overlaps is longitudinal
more than 2000 shown onmodes
theofright.
the
O3 using an additional 405 nm diode laser. The two parts of 93 cm cavities, it couples passively without active control of
855 the instrument have separate inlets that are only connected the laser spectrum or cavity modes. On-axis coupling also
together during automated calibrations, as described further allows for a more compact (i.e., smaller diameter) sample
below. A schematic of the instrument is shown in Fig. 1 with cell, decreasing sample residence time and simplifying the
NO3 /N2 O5 measurement framed in red and the NO/NO2 /O3 optical alignment. Second, this instrument incorporates an
measurement framed in blue. A photo of the instrument is automated calibration for NO3 and N2 O5 against the NO2
shown in the right panel of Fig. 1. channels.
Light is provided by a continuous wave (cw) diode laser
2.1 NO3 and N2 O5 measurement (Power Technology Inc., Fabry-Perot diode model IQµ se-
ries), with an output power of approximately 100 mW. The
Previous NO3 and N2 O5 instruments from our group were laser can be temperature tuned over a range of 15–33 ◦ C,
based on cavity ring-down spectroscopy using a pulsed dye corresponding to center wavelengths 659.1–662.7 nm, al-
laser and a Nd:YAG laser to pump the dye laser. Diode lasers, though individual laser diodes typically vary in tuning range.
which are available at wavelengths near the 662 nm absorp- Upon request, the manufacturer selected a diode with tun-
tion maximum of the nitrate radical, are a suitable alternative ing range that includes the nitrate radical’s absorption peak
that are smaller, lighter, lower in power consumption and do near 662 nm. The laser spectrum is typically composed of
not require hazardous material. Like pulsed dye lasers, com- between 2–4 modes of the laser cavity. Each mode is sepa-
mercially available Fabry-Perot diode lasers are spectrally rated by ∼0.4 nm and has a width of ∼0.3 nm. The intensity
broad enough to couple passively to the mode structure of the in each mode is determined by the temperature of the laser
optical cavity (Fuchs et al., 2009). They are also spectrally diode. Certain temperatures give output spectra that are dom-
narrow enough to provide a specific measurement for the ni- inated by 1, or at most 2, of these 0.3 nm modes. A compact
trate radical. Ayers et al. (2005) and Schuster et al. (2009) spectrometer (Ocean Optics USB4000) is used to monitor
have already demonstrated the use of similar diode lasers for the laser spectrum. The diode temperature is set to maximize
detection of NO3 and N2 O5 . The instrument described here the spectral overlap with the nitrate radical’s absorption. The
is similar to these instruments aside from two distinct differ- laser operates in cw mode and is modulated on and off by a
ences. First, our instrument uses an on-axis rather than an 0–5 volt square wave input. The rise and fall time of the in-
off-axis alignment to couple the laser to the optical cavity, tensity is less than 30 ns, which is rapid on the time scale of

www.atmos-meas-tech.net/4/1227/2011/ Atmos. Meas. Tech., 4, 1227–1240, 2011

 856
1230 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3

the intensity decay from the optical cavity. The laser is op-
tically isolated from the cavities in this on-axis alignment in
order to prevent potentially damaging back reflections from
entering the laser. The isolators consist of a single linear
polarizer that is placed in front of the laser, and three sepa-
rate quarter waveplates; one placed directly in front of each
cavity. This design ensures that the polarization through the
beamsplitters remains linear, so that the polarization sensi-
tivity of the beamsplitters does not degrade the performance
of the isolators.
The cavities consist of two 25 mm diameter, 1 m radius of
curvature high-reflectivity dielectric mirrors. The mirrors are
separated by 93 cm and mounted to an optical breadboard in
a custom bellows mount that allows optical alignment and
a flexible seal to the sample volume, from which the mir-
857
rors themselves are isolated. The cleanliness of the mirrors
is maintained by a small purge flow, 25 sccm, of ultrapure air Fig. 2. Upper panel: ring-down trace from one of the 662 nm cav-
(zero air) over each mirror to separate the mirror surface858
from Figure 2.with
ities, along Upper panel:
the fit to Ring-down
the ring-down trace
trace. The lowerfrom
panel one of th
the sample flow. Light transmitted through the back mirror shows the fit residual as a percentage of the fit.
859
of the each cavity is collected by an optical fiber and detected fit to the ring-down trace. The lower panel shows the f
on a photomultiplier tube (PMT) (Hamamatsu HC120-05M).
A colored glass filter (Schott RG665) is used immediately 860 fit.
of 400 µs at 500 hPa pressure. All of the performance char-
before the PMT to reject stray light. acteristics described in this paper have been achieved with
The ring-down traces are digitalized using 14-bit oscil-
861 the lower reflectivity mirrors, which give a larger intensity
loscope card (National Instruments PCI-6132) at a rate of throughput and allow a higher repetition rate. Instrument per-
2.5 × 106 samples s−1 . A digital output of the oscilloscope formance with the higher reflectivity mirrors is not substan-
card is used to modulate the laser intensity normally at tially different. For the lower reflectivity mirrors, the laser is
500 Hz, but this can be adjusted to increase the number of modulated at 500 Hz, and 0.2 s is needed to acquire 100 ring-
ring-down traces acquired or duration of each ring-down down traces; thus the overall signal acquisition rate should be
trace. The ring-down traces are transferred to a computer 5 Hz. However, due to overhead from transferring ring-down
over the PCI bus and co-added in lots of 100. The number traces to the computer memory, fitting the ring-down traces,
of ring-down traces in each lot can be adjusted to correspond and auxiliary measurements, the actual data acquisition rate
with the laser modulation frequency and the desired measure- of the measurement is currently limited to 3 Hz.
ment frequency. The co-added ring-down traces are then fit The sampling and inlet configuration for NO3 and N2 O5
to a single exponential decay. The ring-down traces are fit us- is equivalent to that described by Fuchs et al. (2008) and is
ing the techniques described by Everest and Atkinson (2008). described only briefly here. Because NO3 and N2 O5 are re-
Usually, the digital Fourier transform method is used; how- active gases, the inlet is constructed from Teflon tubing and
ever the linear, LRS, and Levenberg-Marquardt methods are fittings. The shortest possible residence time is needed in or-
also available. When using the linear fitting method, the laser der to minimize wall losses for NO3 , which has been shown
is turned off after every lot of 100 ring-down traces to mea- previously to have a first order loss with respect to reactions
sure the zero level of the PMTs. During ambient sampling, on Teflon inlet walls of approximately 0.2 s−1 (Dubé et al.,
only the fit parameters are saved and ring-down traces are 2006).
discarded after fitting. The inlet consists of several parts and is shown in Fig. 1.
The upper panel of Fig. 2 shows a co-added ring-down The first is a short length of 0.4 cm inner diameter tubing
trace acquired while sampling laboratory air at a cell pres- to bring ambient air from outside into the aircraft or instru-
sure of 504.6 hPa. The 1/e time constant for this ring-down ment enclosure. Following this there are addition points for
trace is 217.98 ± 0.05 µs where the error is the covariance NO used to determine the instrument zero, zero air used to
of the fit parameter. The time constant is determined by overflow the inlet, and NO3 /N2 O5 additions for calibration.
the combination of Rayleigh scattering losses, mirror re- Next, a short length of 1.6 mm inner diameter tubing is used
flectivity, and cavity alignment. The mirror reflectivity is as a flow restriction to drop the pressure to approximately
99.999 %, or 10 ppm transmission. The lower panel in Fig. 2 half of ambient. A Teflon membrane (Pall Corp. R2PJ047,
shows the fit residual as a percentage of the ring-down trace. 2 µm pore size, 25 µm thickness) is used in an automatic fil-
Higher reflectivity mirrors (Advanced Thin Films, Inc.) with ter changer describe by Dubé, et al. (2006) to remove aerosol
R = 99.9995 % (5 ppm transmission) have also been used in from the sample flow. After the filter, the flow is split and
this instrument and give a ring-down time constant in excess delivered to each of the two sample cells by 0.64 cm inner

Atmos. Meas. Tech., 4, 1227–1240, 2011 www.atmos-meas-tech.net/4/1227/2011/

29
N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3 1231

diameter tubing. A 78 cm length of 0.79 cm inner diameter 2.2 NO, NO2 , and O3 measurement
tubing along the axis of each cavity creates the sample cell.
Flows are set using flow controllers positioned downstream Measurement of NO2 is integral to the NO3 and N2 O5 cali-
of the sample cells. One cell remains at ambient tempera- brations and measurements of inlet transmission. Measure-
ture to measure the concentration of NO3 . The sample gas in ment of NO2 using a 405 nm diode laser improves its sensi-
the other channel is heated to convert N2 O5 to NO3 in order tivity compared to our previously described, 532 nm instru-
to detect the sum of NO3 and N2 O5 . For this channel the ment (Osthoff et al., 2006; Fuchs et al., 2010), since the NO2
gas flow is heated in three stages that are designed to rapidly cross-section is approximately 4 × larger at 405 nm. Further-
bring the gas to a temperature sufficient to thermally disso- more, the interference from ozone is essentially eliminated,
ciate N2 O5 and then to hold it at a temperature where the since its absorption cross-section is approximately 4 × 104
equilibrium in Reaction (R1) is shifted mainly toward NO3 . times smaller than that of NO2 at 405 nm. Both NO and O3
For example, the conversion of N2 O5 to NO3 based on its can be measured by the same instrument via conversion to
equilibrium constant is greater than 98 % for ambient NO2 NO2 ; conversion of NO to NO2 in excess ozone has been de-
levels less than 10 ppbv at 75 ◦ C. The first section is 0.64 cm scribed previously by Fuchs et al. (2009), while conversion
inner diameter tubing, 40 cm long and held at 130 ◦ C. The of O3 to NO2 in excess NO has been described by Washen-
second is 25 cm long and held at 80 ◦ C to reduce thermal felder et al. (2011).
gradients and minimize flow noise in the sample cell which A second diode laser centered at 405 nm (Power Tech-
is held at 75 ◦ C. nology Inc., Fabry-Perot diode model IQµ series) provides
A third 662 nm channel is used to continuously monitor the light source for the CRDS detection of NO2 . Unlike the
the optical extinction from species other than NO3 , such as 662 nm diode laser, this diode laser is not actively tempera-
NO2 , O3 and water vapor. It consists of an optical cavity ture tuned and is held at a constant 20 ◦ C. We have found the
and sample cell downstream of the NO3 sample cell. NO is center wavelength to be stable over the lifetime of the laser
continuously added to this sample cell in the same manner as by repeated checks against a calibrated grating spectrome-
the instrument zeroing described below. ter. The laser output power of 80 mW is divided into three
The total flow through the inlet is controlled at a con- equal parts using a 33 % beamsplitter and a 50 % beamsplit-
stant volumetric flow rate that is adjusted for conditions of ter. The three cavities are constructed in the same manner as
a particular measurement campaign. Typical flows for re- the 662 nm cavities, except that a bandpass filter centered at
cent aircraft measurements described below were 15 and 405 nm is used in front of the photomultiplier to reject stray
9 LPM (liters per minute) for the NO3 and NO3 + N2 O5 sam- light. The layout is shown schematically in Fig. 1.
ple cells, respectively. As in our previously described in- The data acquisition for the 405 nm channels is done in
strument, the zero for the NO3 measurement is determined the same way as for the 662 nm channels using a second os-
by adding a small amount of NO to the inlet. In an ex- cilloscope card to modulate the laser and acquire the ring-
cess of NO, NO3 is rapidly converted via Reaction (R4) down down traces. The 405 nm mirrors have a reflectivity
(k = 2.6 × 10−11 cm3 molecule−1 at 298 K) into NO2 , which of 99.9965 % (35 ppmv transmission) and give typical back-
has an absorption cross-section that is approximately 4 × 104 ground time constants of 40 µs at a pressure of 840 hPa. Be-
times smaller than that of NO3 at 662 nm. This zero method cause the time constants on the 405 nm cavities are shorter
does not influence optical extinction due to ambient lev- than the 662 nm cavities, the laser is modulated at four times
els of O3 , NO2 or H2 O and is therefore highly specific for the frequency, or 2 kHz. Ring-down traces are acquired in
NO3 . A small flow of a 100 ppmv NO in N2 mixture is lots of 400 and co-added to achieve the same overall data ac-
added to the inlet flow to produce an NO concentration of quisition rate (3 Hz) as the 662 nm side of the instrument. It
∼1012 molecules cm−3 , designed to give >99.9 % conver- is not required that both the 662 nm channels and the 405 nm
sion of NO3 to NO2 before the flow enters the axis of the NO3 channels acquire the ring-down traces in lots corresponding
measurement cell. The zero of the instrument is typically 5 s to equal acquisition time but doing so maximizes the total
in duration and is measured at arbitrary intervals depending number of ring-down traces collected.
on requirements. During aircraft ascent and descent, when The NO, NO2 and O3 sample cells have a separate in-
changes in pressure lead to rapid changes in background time let from the NO3 /N2 O5 measurement, and the inlet is sim-
constant due to Rayleigh scattering, the zero interval can be pler because the 405 nm cavities are operated at ambient
as short as once per minute. On level flight legs or for ground pressure and the measured species are less reactive. The
based measurements, a zero interval of 3–5 min is normally inlet and sample cells are constructed with Teflon tubing
sufficient to track any changes in τ0 due to cavity alignment and fittings. Ambient air is drawn in through a length of
or variable background absorbers. 0.4 cm inner diameter tubing to a 1 µm pore size Teflon filter
(Pall Corp. R2PL047) in a commercial, PFA Teflon mount
(Savillex). The smaller pore-size filter ensures rejection of
smaller size aerosol to which the 405 nm channels may in
principle be more sensitive. Loss of NO, NO2 and O3 on

www.atmos-meas-tech.net/4/1227/2011/ Atmos. Meas. Tech., 4, 1227–1240, 2011

1232 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3

these filters is negligible. There is no evidence for a signal they might occur without large, excess O3 , are effectively re-
due to aerosol extinction on the downstream side of these versed by reaction of NO3 with the excess NO (Reaction R4).
filters during sampling of ambient air. Following the filter, The excess NO added to this channel does contain an un-
the flow is split into three equal parts and delivered to the avoidable contamination of NO2 , which can produce a large
sample cells. Before entering each sample cell, there is a re- background signal. An FeSO4 converter on the outlet of the
actor consisting of a 33 cm length of 0.95 cm inner diameter standard cylinder reduces this NO2 contamination consider-
tubing. The flow rate through each channel is controlled at ably to a background level of 0.5–2 ppbv within the sample
2.7 LPM (volumetric) to maintain a residence time of 0.6 s cell (Washenfelder et al., 2011).
(plug flow) within each reactor while sampling from vari- Maintaining a constant conversion efficiency of O3 and
able external pressures from the aircraft. On the first channel NO to NO2 is a potential challenge for sampling from an
which is used for the NO2 measurement, the purpose of the aircraft platform since the ambient pressure (and hence the
reactor is only to match the residence time of all three chan- reactant concentration and reactor residence time) is variable
nels, so that NO2 may be accurately subtracted from NOx or with aircraft altitude. Flows on all three 405 nm channels are
Ox , as described below. controlled at constant volumetric rates, rather than constant
The second channel measures total NOx via conversion mass flow rates, to maintain constant residence time and re-
of NO to NO2 in excess O3 . A 12 sccm flow of 0.3 % actant number density in each reactor. Addition of a constant,
ozone is added at the beginning of the reactor via a three mass flow of the excess reactant with a well-defined mix-
way valve that allows switching of this ozone addition to a ing ratio to the variable, volumetric flow produces a constant
vent line. The ozone is generated by passing a flow of pure number density in each reactor as the aircraft ascends and
oxygen over a mercury-argon lamp (UVP 90-0004-01). The descends. For example, the number density of NO in the Ox
resulting ozone concentration in the sample cell is approxi- sample cell is the product of mixing ratio of the NO standard
mately 4 × 1014 (∼16 ppmv at 1 atmosphere and 298 K) and cylinder (MR), the total number density in the sample cell
(Nd ) and the ratio of the volumetric flows (FNOvol and F vol ) as
is measured periodically from the change in optical extinc- cell
tion at 405 nm (∼6 × 10−9 cm−1 ) upon switching the ozone shown in Eq. (2). Here, P is the pressure in the sample cell,
flow into and out of the sample cell. This measurement P0 is the standard pressure, k is Boltzmann’s constant, T is
the sample cell temperature, and FNO STD is the volumetric flow
is checked less frequently using a commercial ozone mon-
itoring instrument. The background extinction due to this of the reactant at standard pressure and temperature which
added ozone changes the ring-down time constant by ap- is directly proportional to the mass flow and independent of
proximately 0.25 µs from its nominal value of 40 µs at at- pressure.
mospheric pressure (1013 hPa). The presence of this large vol
excess ozone converts NO quantitatively to NO2 via Reac- FNO
[NO] = MR × Nd × vol
(2)
tion (R5). Fcell

O3 + NO → NO2 + O2 (R5) P F STD (P0 /P )

= MR × × NO vol
kT Fcell
k298 = 1.9 × 10−14 cm−3 molecule−1 s−1
Because the flow through the sample cell is maintained at a
Conversion of NO to NO2 under these reactor conditions is constant volumetric rate, the only pressure dependences in
greater than 99 %. A small correction of 1–2 % is required Eq. (2) are the number density and the reactant volumetric
to account for the further oxidation of NO2 to higher oxides flow, and they cancel each other. The result is a reactant
of nitrogen, NO3 and N2 O5 , via Reactions (R1) and (R2) number density that is independent of pressure. Thus, the
(Fuchs et al., 2009). The measured NOx concentration is also conversion efficiencies outlined above do not vary with air-
corrected for the small dilution (∼0.5 %) due to the addition craft altitude.
of the O3 /O2 flow. The current scheme for acquiring a zero time constant for
The third channel measures total odd oxygen, Ox = the 405 nm channels is identical to that used previously with
NO2 + O3 , via the analogous conversion of O3 to NO2 in our 532 nm CRDS NO2 instrument, namely to slightly over-
excess NO. A small flow of NO from a standard mixture flow the inlet with zero air. The overflow is added through
of NO in N2 (Scott-Marin) is added at the beginning of a concentric piece of Teflon tubing with an inner diameter
the reactor to produce an excess concentration of NO iden- slightly larger than the outer diameter of the inlet tubing and
tical to the excess O3 concentration in the NOx channel which extends slightly (2–4 cm) beyond the inlet tubing. Ad-
(i.e. 4 × 1014 molecules cm−3 ). The excess NO quantita- dition through this concentric inlet minimizes the pressure
tively (greater than 99 %) converts O3 in the ambient sam- difference between the zero and signal measurements, which
ple flow to NO2 via Reaction (R5). There is no need for can be significant (1 hPa or greater) if the zero air overflow
an additional correction for further oxidation of NO2 on this is added through a simple tee fitting. Such pressure differ-
channel since Reactions (R1)–(R2), to the small extent that ences between the zero and sample measurement change the

Atmos. Meas. Tech., 4, 1227–1240, 2011 www.atmos-meas-tech.net/4/1227/2011/

 862
N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3 1233

Rayleigh scattering background, which must be corrected for

after the measurement. An additional correction is needed to
account for the difference in humidity between ambient air
and the dry zero air used to overflow the inlet. The differ-
ence in the Rayleigh scattering cross-section of water vapor
and air was measured at 405 nm by Fuchs et al. (2009) to
be 5 × 10−27 cm2 , leading to a maximum correction equiv-
alent to 0.15 ppbv NO2 at 80 % RH (22 ◦ C) . Actual water
vapor corrections are typically smaller, however. The poten-
tial for an NO2 impurity in the zero air limits the applicabil-
ity of this zero scheme for sampling in remote environments,
where ambient NOx may be comparable to the NOx impurity
in commercial zero air. Chemiluminescence measurements
863
at our laboratory have found the zero air (Scott-Marin Ultra-
zero) to have less than 10 pptv of NOx . Zero measurements
occurred every 3 min during ambient sampling and lasted 864 Fig. 3. 3
Figure Pressure dependence
. Pressure of the effective
dependence NO2 cross-section
of the effective at
NO2 cross-section a
15 s to allow for the zero air to completely fill the sample 405 nm. The pressure-dependent cross-section is parameterized by
865 pressure-dependent cross-section
2nd order polynomial and is parameterized
used for calculating by 2nd order poly
NO2 concentration
cell.
during aircraft sampling at variable altitudes and cell pressures. The
The optical extinction due to excess O3 on the NOx chan-866 calculating NO2 concentration
pressure dependence may be due to during aircraft
the variation sampling
in the NO crossat variable a
2
nel, and the NO2 impurity in the added NO on the Ox chan- section itself, or to pressure dependence
dependence inmay
Rl from Eq. (1). Here,
867 pressures. The pressure be due to the variation in t
nel, are not affected by the addition of zero air to the inlet. the cross section is fit to a pressure dependence assuming constant
Thus, no correction is required for these small, background868 itself, or tothough
Rl of 1.15, pressure dependence
this choice in Rl from Eq (1). Here, the cross
is arbitrary.
optical extinctions.
869 pressure dependence assuming constant Rl of 1.15, though this choi
such that it delivers standard additions of NO2 independent
3 Calibrations from the CRDS instrument itself. The calibrator is also field
portable and can be used for routine calibration on a daily
Although cavity ring-down spectroscopy is, in principle, an basis. Typical calibration curves use a series of NO2 mix-
absolute method, calibrations are required if either the inlet ing ratios between 0–200 ppbv, with the effective NO2 cross-
transmission efficiency for a particular trace gas is not unity, section determined as the slope of a plot of measured optical
or if the effective absorption cross-section can vary as a func- extinction against NO2 concentration. The effective cross-
tion of sampling conditions (i.e., temperature, pressure, laser section is the NO2 cross-section integrated under the laser
spectrum). The former is the case for NO3 and N2 O5 , which spectrum and divided by Rl , which is ratio of the cavity
are reactive trace gases whose transmission through the inlet length to the length over which the absorber is present.
system may vary. The latter is potentially the case for NO2 The cell pressure in the 405 nm channels varies signifi-
(and by extension, NO and O3 in this instrument) since its cantly with altitude, typically between 500–900 hPa over the
absorption cross-section varies with pressure, temperature, altitude range of the NOAA WP-3 aircraft and is typically
and laser spectrum. We have recently developed calibration 80–100 hPa below ambient pressure. Therefore, any pressure
standards for NO3 and N2 O5 based on their conversion to dependence in the effective cross-section for NO2 , or in the
NO2 (Fuchs et al., 2008) and for NO2 based on conversion of ratio of the cross section to Rl in Eq. (1), will directly affect
standard additions of O3 , as described above (Washenfelder the measurement from aircraft. Literature spectra for NO2
et al., 2011). The following sections outline these calibration do indeed show a pressure dependence (e.g. Vandaele et al.,
schemes and their implementation in the current version of 1998), but only for spectral features too fine to be resolved
this aircraft instrument. by the laser system in the CRDS instrument. Nevertheless,
the ratio of the effective NO2 absorption cross-section to Rl ,
3.1 NO2 calibration i.e., σ /Rl , shows a distinct pressure dependence, as shown in
Fig. 3. The value of σ /Rl decreases by approximately 6 %
The 405 nm laser diodes provided by the manufacturer vary between 1000–500 hPa. The calibration curve in Fig. 3 is
in center wavelength; hence, the effective cross-section for the result of multiple determinations in the field30 on differ-
each laser must be calibrated by standard NO2 additions. ent days, which were reproducible at any given pressure to
Standard concentrations of O3 are generated and measured within ±2 %. For the purpose of calculating the NO2 con-
using a commercial ozone monitor, then quantitatively con- centration, the cross-section is parameterized by a 2nd order
verted to NO2 , which is measured on the CRDS instrument, polynomial. The measured pressure dependence of the ef-
as described above. The calibrator contains its own NO fective cross-section may be due to a variation of the actual
cylinder and flow controllers for conversion of O3 to NO2 cross-section or a pressure dependence of Rl . Regardless of

www.atmos-meas-tech.net/4/1227/2011/ Atmos. Meas. Tech., 4, 1227–1240, 2011

1234 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3

Fig. 4. The right panel shows the NO3 (blue) and water vapor (red) absorption spectrum around 662 nm. A typical laser spectrum is also
shown. The left panel shows the measured water sensitivity along with predicted sensitivity neglecting the non-exponential terms. The
measured sensitivity is fit to a 2nd order polynomial and used to correct the field data.

the source of the pressure dependence, the effective cross- HITRAN database (Rothman et al., 2009) is shown in red
section is still valid for determination of the NO2 concentra- on Fig. 4 along with the nitrate radical absorption spectrum
tion. (blue) and typical diode laser spectrum (gray). Our previous,
pulsed dye laser instrument had a narrow bandwidth which
3.2 NO3 cross-section and water vapor sensitivity effectively resolved this water vapor spectrum, and could be
tuned off resonance with the discrete water vapor lines while
The cross-section for NO3 is determined using the absorp- still being tuned effectively to the maximum in the NO3
tion spectrum measured by Yokelson et al. (1994) shown in absorption spectrum. The output of the diode laser, by con-
Fig. 4 and temperature-dependence determined by Osthoff trast, unavoidably overlaps multiple water vapor lines, mak-
et al. (2007). Although the absorption spectrum peaks at ing the instrument much more sensitive to this interference.
2.17 × 10−17 cm2 for 298 K, the effective cross-section in Furthermore, because the water vapor absorption spectrum
this instrument is a convolution of the measured cross-section consists of several peaks under the laser bandwidth, the vari-
and the laser spectrum and is therefore smaller than the peak ation in absorption cross-section can lead to non-exponential
absorption. Using a typical laser spectrum shown Fig. 4, the ring-down traces.
effective cross-section was 2.03 × 10−17 cm2 , a reduction of The measured sensitivity to water vapor is shown in Fig. 4
7 %. One drawback of 662 nm diode laser used in this in- (right panel). The extinction is not linear with respect to wa-
strument is that the intensity in different modes, and thus ter concentration because the ring-down transients become
its spectral output, is not stable on the time scale of hours. slightly non-exponential at higher optical extinctions because
Based on several measured laser spectra, this instability leads of the mismatch between the discrete, water vapor lines and
to a variation of 1.5 % in the effective NO3 cross-section. the broadband laser source (Zalicki and Zare, 1995). How-
The cross-sections measured by Yokelson et al. (1994) and ever, the data can be corrected by using the fitted polyno-
Osthoff et al. (2007) are accurate to ±4 %. In this instru- mial as an effective concentration-dependent cross-section as
ment the variability of spectrum increases the inaccuracy of shown in Eq. (3).
the effective cross-section to ±6 %. The laser spectrum is
f ([H2 O]) c −1
 
1
currently measured infrequently (e.g., once per flight) using τcorrected = + (3)
a small grating spectrometer (Ocean Optics, USB4000) but τ Rl
will be incorporated into routine data acquisition in the fu- τcorrected is the exponential decay time constant that would be
ture. The NO3 cross-section is temperature dependent, as measured in the absence of water vapor. τ is the measured
described previously, such that the effective cross-section for exponential decay constant. f ([H2 O]) is the fitted polyno-
the heated channel is 1.68 × 10−17 cm2 molecule−1 at 348 K. mial sensitivity and requires an independent measurement of
Water vapor has an absorption in the 662 nm region of the the water vapor mixing ratio. The linear term in the poly-
spectrum. The potential for water vapor interference with nomial fit corresponds to the water vapor cross-section when
NO3 measurements is well known from broadband optical averaged over the laser spectrum and agrees well with the
measurements of NO3 (e.g. Langridge et al., 2008; Solomon value calculated using the water vapor cross-section obtained
et al., 1989). The water vapor spectrum at 20 ◦ C from the from the HITRAN database, 2.05 × 10−26 cm2 . This linear

Atmos. Meas. Tech., 4, 1227–1240, 2011 www.atmos-meas-tech.net/4/1227/2011/

879 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3 1235

880
Fig. 5. Example calibration sequences for (A) N2 O5 and (B) NO3 . For the N2 O5 calibration, the N2 O5 source is added directly to the inlet,
while for the NO3 calibration it first passes through a heater881
to convertFigure 5. toExample
it primarily calibration
NO3 . The sequence sequences
of the calibration, for (A)
indicated by theN2O5 and
numbers across the top, includes (1) zero measurement; (2) addition of N2 O5 /NO3 source; (3) titration of the NO3 /N2 O5 source with excess
NO to convert it to 2 × NO2 ; (4) N2 O5 /NO3 source switched 882 off, NOcalibration, the N2ONO
titration on to determine 5 source is the
2 content of added
addeddirectly
NO; and (5) toNOthe inlet, w
titration turned off. The calibration is given by Eq. (4) and is effectively the ratio of 2 1 (N2 O5 )/1NO2 (or 2 1NO3 /1NO2 ) marked in the
figure, where 1NO2 is corrected for the small additional NO883 firstNO
2 in the added passes through
source given by theadifference
heater between
to convert
Eqs. (4)itand
primarily
(5) in the to NO3.
sequence above. For the data shown in the figure, the N2 O5 transmission is 99 %. The NO3 calibrations factors are shown for the ambient
channel – NO3 , (A) – and the heated channel – NO3 (B), and 884are 87 %calibration, indicated by the numbers across the top, include
and 85 %, respectively.

885 addition of N2O5 / NO3 source; 3) titration of the NO3 / N2O

absorption is insensitive to the presence of added NO, and 3.3 NO3 and N2 O5 inlet transmission
880 will therefore only interfere with the measurement of 886NO3 convert it to 2 × NO2; 4) N2O5 / NO3 source switched off, N
and N2 O5 if the water vapor mixing ratio changes rapidly Wall loss of NO3 on the Teflon surfaces of the inlet and
881 Figure 5. Example calibration sequences for (A) N2O25 content
on the time scale of the instrument zero frequency. 887Such NO and (B)of
measurement NO
cellstheis. added
3 the FormosttheNO; N2Oand 5)source
significant
5
NO titration
of uncer- turned of
variations can, in principle, be corrected by the reference tainty for CRDS measurement of NO3 and N2 O5 (Dubé et
882 calibration, the N2though
channel (see above), O5 source is added
in practice
888to the
directly
the active correc-
Eq. (4)
inlet,
al.,
and
while
2006).
is effectively
for the NOof3the
Characterization
ratio of 2∆(N O5)/∆NO2 (or 2∆
the NO3 and Nit2 O5 2transmis-
calibration
tion described here proved as useful as a reference889 chan- sion efficiency ∆has
NObeen described byfor Fuchs
theetsmall
al. (2008).
883 first passes
nel. For through
ground a heater to convert
based measurements, it primarilyfigure,
simple interpolation to
TheNO where
3. Theprovides
following sequence2 is corrected
a shortofdescription
the additional NO
of the method and
884
between zeros would normally be sufficient. However,
calibration, indicated by the numbers across 890 for given
the top, by thethat
the changes
includes 1)difference
are specificbetween
zero measurement; (4)
to the current
2)and (5) in
instrument the sequence
design.
aircraft sampling, which may rapidly traverse regions of The calibration scheme for NO3 is based on its chemical con-
885 higher or lower
addition of Nabsolute 891 theversion
humidity (e.g., on vertical profiles), figure, the2 N
to NO 2Oexcess
with 5 transmission
NO by Reactionis 99%.(R4), The NO3 calibrat
the same
2O5 / NO3 source; 3) titration of the NO3 / N2O5 source with excess NO to
the interferences must be actively corrected via Eq. (3). A as used for zeroing the 662 nm channels. The resulting NO2
886 worst-caseit change
convert to 2 × inNO relative humidity of 0 to 100892 %, or ambient channel
has negligible inlet(NOloss 3andA)can andbethe heatedbychannel
measured CRDS at(NO3 B),
2; 4) N2O5 / NO3 source switched off, NO titration on to determine
3.5 × 1017 cm−3 (2.9 % mixing ratio at 20 ◦ C and 505 hPa 405 nm to provide a standard for the 662 nm NO3 measure-
893 respectively.
887 NO 2 content
in the of the
sample cells),
−9 −1
added
would resultNO;
in anand 5) NO
additional titration turned
extinction ment. N off.
2 O5 The calibration
transmission is given
efficiency can be bymeasured simi-
of 7 × 10 cm , or the equivalent of 30 pptv of NO3 /N 894 O
2 5 . larly by chemical and thermal conversion of N2 O5 to NO2 .
888 Eq. (4) and
In practice, weis effectively
have never observedthe variations
ratio of in2∆background
(N2O5)/∆NODuring2 (or 2 ∆ NO /
transmission
3 ∆ NO ) marked
efficiency
2 in
measurementthe the inlet is over-
extinction that are this extreme; however active correction re- flowed with zero air to avoid interference from ambient O3
889 figure, where ∆NO2 is corrected for the small additional
mains a necessity. and NO. NO2 in the added NO source
When the water vapor concentration is approximately con- Each measurement of NO3 transmission efficiency has five
890 given by thethe
stant between difference
zero and the between (4) and (5) in
signal measurement, the sequence
there above. For the data shown in
steps shown in Fig. 5. First, the zero of the instrument is mea-
is an additional, small error due to fitting the slightly non-
891 the figure, the N2O5 transmission is 99%. The NO3 sured as discussed
calibrations above.are
factors Second,
shown the for
NO3the source is added
exponential ring-down transients in the presence of water va- to the tip of the NO3 /N2 O5 inlet and the mixing ratio NO3 is
892 por as though
ambient they were
channel (NO single exponentials to retrieve con-
3 A) and the heated channel (NO measured
3 B), and in 662
arenm87% channels. The amount of NO2 32
and 85%, coming
centrations of NO3 or N2 O5 . This effect produces a measure- from the source directly is measured in the NO2 channel. As
893 respectively.
ment error of less than 0.2 % for either compound. described above, for ambient sampling, the inlet for the NO2 ,
Although much smaller, both NO2 and NO3 have some NOx and Ox channels is separate from the NO3 and N2 O5 in-
894 variation in the cross-section under the laser spectrum like let; however, during the transmission measurements the NO2
water vapor. We have not observed non-exponential ring- channel must be connected to the NO3 /N2 O5 inlet. This con-
downs from either NO2 or NO3 . For NO2 the exponential nection is made via the three-way valve shown in Fig. 1,
character of the ring-down trace is further confirmed by the which switches the instrument between sampling and cali-
linear extinction as a function of the NO2 concentration dur- bration mode. Unlike the previously described pulsed laser
ing calibrations. instrument, in which the NO3 and NO2 measurements were

www.atmos-meas-tech.net/4/1227/2011/ 32 Atmos. Meas. Tech., 4, 1227–1240, 2011

1236 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3

in series, they are in parallel in this instrument, such that the NO3 and NO are added to the inlet separately, during
measurements of NO3 or N2 O5 occur simultaneously with steps 2 and 4 respectively.
that of NO2 . The third step of the transmission efficiency To relate ambient concentrations with those measured in
measurement is to add NO3 and NO simultaneously to the the sample cells, three separate transmission efficiencies are
NO3 /N2 O5 inlet. The reaction of NO3 and NO quantitatively required: (1) the transmission of N2 O5 through the heated
converts NO3 into NO2 producing two molecules of NO2 for inlet, Te (N2 O5 ), which is the combination of the transmis-
each molecule of NO3 added to the inlet. During this step sion efficiency for N2 O5 itself, the conversion efficiency to
the NO2 channel measures NO2 from three sources: NO2 NO3 , and the transmission of NO3 through the heated inlet;
coming directly from the N2 O5 calibration source, NO2 pro- (2) the transmission of NO3 through the ambient channel,
duced by the reaction of NO3 and NO, and the NO2 impurity Teambient (NO3 ); and (3) the transmission of NO3 through the
present in the NO addition. The fourth step is to shut off the heated channel, Teheated (NO3 ) (Dubé et al., 2006; Fuchs et
NO3 /N2 O5 addition from the calibration source, but leave the al., 2008). For the NO3 channel only the inlet transmission
NO flow present to measure the NO2 impurity present in this of NO3 is needed to determine the ambient NO3 concentra-
NO. The fourth step accounts for this contamination. The tion, Eq. (5). However, because N2 O5 is converted to NO3
fifth step is a second zero measurement, with no addition of in the inlet and consequently lost to the walls, the inlet trans-
either NO or NO3 /N2 O5 . mission of both NO3 and N2 O5 is needed to calculate the
The N2 O5 transmission efficiency can be measured by a ambient N2 O5 concentration, Eq. (6).
similar five step procedure with the addition of N2 O5 to the
[NO3 ]cell
inlet instead of NO3 ; however, during the third step a heater [NO3 ]amb = (5)
is used to convert the N2 O5 into NO3 which is then converted Teambient (NO3 )
to NO2 by reaction with NO. This heater is along the connec-
([NO3 ] + [N2 O5 ])cell − Teheated (NO3 ) [NO3 ]amb
tion between the NO3 /N2 O5 inlet and the NO2 sample cell [N2 O5 ]amb = (6)
Te (N2 O5 )
and is followed by a short section of nylon tubing which acts
as an NO3 scrubber, as described in Fuchs et al. (2008). In [NO3 ]amb and [N2 O5 ]amb are the ambient concentration of
this configuration, the scrubber serves to remove NO3 from NO3 and N2 O5 . [NO3 ]cell and ([NO3 ] + [N2 O5 ])cell are the
the flow produced by thermal decomposition of N2 O5 when concentrations measured in the sample cells.
the NO addition is off during step 2, so that the NO2 chan- Figure 5 illustrates the scheme for an example calibration.
nel measures only the NO2 arising from thermal dissociation Panel a shows the N2 O5 transmission measurement, while
of N2 O5 and not any optical extinction from NO3 . It also panel b shows the NO3 transmission measurements in both
prevents recombination of NO3 with NO2 in the NO2 sam- the ambient and heated measurement cells, which is done
ple cell. (Both the heater and scrubber are necessary for the simultaneously by addition of NO3 to both channels. In field
NO3 transmission measurement as well, because our source calibrations during CalNex showed no dependence of NO3
can not produce pure NO3 . It is unavoidably contaminated transmission efficiency on NO3 mixing ratio over the range
with N2 O5 .) During addition of NO, all NO3 produced in the 0.3–4.3 ppbv, although calibrations on any given day were
heater between the inlet and the NO2 sample cell is converted normally performed at a single concentration.
to 2 × NO2 , which is not affected by the scrubber.
Calibration samples of N2 O5 or NO3 are generated by
passing a small flow of zero air over a sample of solid N2 O5 4 Detection limits, accuracy, and sample data
stored in a trap at −78 ◦ C (dry ice). The source produces
N2 O5 with less than 2 % NO3 or, if switched through an ad- Figure 6 shows a representative measurement of the NO3 and
ditional heater mounted in the calibration box, greater than N2 O5 instrument baseline precision in our laboratory while
90 % NO3 . sampling zero air. The Allan variance plot gives a detection
The transmission efficiency can be calculated using the limit under ∼1 pptv (2 σ ) in 1 s for both species. For NO3 ,
measurements taken during each of the five steps. Equa- this sensitivity is comparable to, but slightly worse than that
tion (4) then gives the expression for the transmission effi- reported by Dubé et al. (2006) (e.g., 0.5 pptv, 1 s, 2 σ ) using
ciency as the ratio between measured NO3 during step 2 in the Nd:YAG/dye laser instrument. For N2 O5 , the sensitiv-
the 662 nm channel and 1/2 the NO2 generated from the con- ity is slightly improved over the pulsed laser version (e.g.,
version in Reaction (R4). 2 pptv, 1 s, 2 σ ), although the improvement derives more
from reduction in the optical noise associated with the fast
2 × [NO3 ] flow in the heated channel than with any change in the op-
Te = (4) tical system itself. The reduction in precision compared to
[NO2 ]source+NO − [NO2 ]source − [NO2 ]NO
the previously reported, pulsed laser instrument is due to a
Here, [NO2 ]source+NO is the NO2 concentration when both combination of factors, including reduced performance from
the NO3 and NO are added to the inlet during step 3, and the composite optical bench and cavity ring-down mirrors
[NO2 ]source and [NO2 ]NO are the NO2 concentrations when experience during the CalNex field intensive, and is not due

Atmos. Meas. Tech., 4, 1227–1240, 2011 www.atmos-meas-tech.net/4/1227/2011/

 Allan
0.1
8
6

N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3 1 10 100 1237
895 Figure 6 Integration time (s)

Elapsed Time (s) Elapsed time (s)

0 500 1000 1500 2000 0 500 1000 1500 2000
4 4

N2O5 (pptv)
NO3 (pptv)

A B
2 2
0 0
-2 -2
-4 -4
1.6 pptv in 0.34 sec
1.4 pptv in 0.34 sec
1 1
Allan Dev. 2σ (pptv)

0.82 pptv in 1 sec 0.99 pptv in 1 sec

Allan Dev. 2σ (pptv)

8 8
6 6

4 4

2 2

0.1 0.1
8 8
6 6

1 10 100 1 10 100
Integration time (s) Integration time (s)
896
Elapsed
Fig. 6. Allan variance plots for time (upper)
the NO (s) and N2 O5 (lower) measurements when sampling synthetic zero air. Both channels have a
3 897 Figure 6. Allan variance plots for the NO3 (upper) and N2O5 (lower) m
2 σ precision
0 better500
than 1 pptv1000
in 1 s. 1500 2000
4 898 sampling synthetic zero air. Both channels have a 2σ precision better
N2O5 (pptv)

B
2
0
solely-2 to the introduction of diode lasers. Due to environ- contributing to the accuracy are uncertainty in the cross-
mental-4 effects (e.g. vibrations on the aircraft) and variations section, Rl , inlet loss and filter aging. Because the filter aging
1.6 pptv in 0.34 sec
in the ambient air (e.g. temperature gradients), the precision can only decrease the measured mixing ratios, it only con-
of the18instrument is 0.99
reduced
pptv inwhile
1 sec sampling ambient air in tributes to the upper limit of the accuracy. The same factors
Allan Dev. 2σ (pptv)

flight. 6The in-flight detection limits are determined from day- contribute to the accuracy of the NO3 measurement (−9 %,
4
time measurements during CalNex when the ambient mixing +12 %, 1 σ ). However, the inlet loss of NO3 is more uncer-
ratios of2 both NO3 and N2 O5 were below the laboratory de- tain leading to a decreased accuracy compared with N2 O5 .
tection
0.1
limits and were 3 pptv (2 σ ) in 1 s for both NO 3 and For measurements of NO, NO2 and O3 , the accuracy
N2 O5 .86 is dominated by uncertainty of the effective cross-section
The laboratory 1
detection limits
10
for the NO100 2 and O3 mea- which is directly related to the ±2 % accuracy of the UV
surements have been reported in a separate publications ozone monitor used to measure the cross-section as describe
896 Integration time (s)
(Washenfelder et al., 2011) and are 46 pptv and 56 pptv (1 s, in section 3.1. There is additional uncertainty (±1 %) in the
2 σ ) respectively. Our previously reported, ground based dilution associated with the NO addition required 33 to convert
897 Figure 6. Allan variance plots for the NO 3 (upper) and N2O5 (lower) measurements when
NOx instrument (Fuchs et al., 2009) exhibits a better pre- the O to NO . The total accuracy for each of three measure-
3 2
898 cision of 22 pptv (2 σ , 1 s). In-flight baseline precision can ments is ±3
sampling synthetic zero air. Both channels have a 2σ precision better than 1 pptv in 1 s. % (1 σ ).
be determined during zero measurements, which are 10–15 s This aircraft instrument was deployed during the CalNex
in duration. For NO, NO2 , and O3 the in-flight detection lim- campaign in California on the NOAA WP-3 aircraft and took
its were 140 pptv, 90 pptv, and 120 pptv, respectively. These measurements on 25 research flights. An example of the per-
detection limits are the average precision of 140 zero mea- formance and utility of this instrument is shown in Fig. 7,
surements from an 8 h flight on 3 June 2010. During some which shows data from a flight in the Los Angeles basin on
time periods, the aircraft measurements of NO, NO2 and O3 3 June 2010. The flight track is shown on the left panel
also suffer from an optical instability in flight that leads to of the figure. This flight includes a series of vertical pro-
drifts on the order of 0.1–0.3 ppbv in flight. The longer-term files over the ocean and the urban area of the Los Angeles
baseline instability is most likely related to the mechanical basin. The flight began in late evening and landed 2 hours
stability of the optical cavity alignments on these channels. after sunrise. The second panel shows the measured NO3
Investigation into the source of this instability and potential and N2 O5 concentrations during the flight along with alti-
solutions is ongoing, although it could be addressed by sim- tude. The yellow background indicates the solar elevation
ply increasing the frequency of zero measurements from the angle and time of sunrise. The mixing ratios of NO3 and
current 5 min interval. We anticipate improvements, 33 primar- N2 O5 vary strongly with altitude, consistent with the previ-
ily in the data acquisition software, to improve the precision ous measurements of vertical stratification within the night-
of the NOx and O3 channels on the aircraft instrument. time atmosphere (Brown et al., 2007a).
The accuracy of the NO3 and N2 O5 measurements were The NO, NO2 and O3 data for the same flight are shown in
described in detail by Fuchs et al. (2008), are unchanged the left panels of Fig. 8. Very little NO was encountered dur-
by modifications described here. The N2 O5 accuracy ing darkness on this flight since the majority of the sampled
ranges from −8 % to +11 % (1 σ ). The major uncertainties air masses were distant from direct NOx emission sources.

www.atmos-meas-tech.net/4/1227/2011/ Atmos. Meas. Tech., 4, 1227–1240, 2011

 1238 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3

Fig. 7. Sample NO3 and N2 O5 data from the flight on 3 June 2010. The left panel shows the flight track in the Los Angeles basin. The right
panel shows the NO3 (blue) and N2 O5 (red) mixing ratios measured during the flight along with the aircraft altitude in gray. The yellow
background indicates the time of sunrise.
905

measurable levels of NO, which peaked near 30 ppbv during

landing at Ontario airport.
The standard P-3 instrument for measurement of ambi-
ent NO, NO2 and O3 is a custom-built, high-precision, re-
search grade chemiluminescence (CL) instrument (Ryerson
et al., 1999, 2000, 2003). The NO2 channel of the CL instru-
ment has recently undergone substantial improvement to the
photolysis system for conversion of NO2 to NO and mod-
ifications of inlet and sample flow path for improved time
response of all channels (Pollack et al., 2011). The right
three panels of Fig. 8 show the scatter plots comparing NO,
NO2 , and O3 measurements from the 405 nm CRDS instru-
ment with those from the CL instrument at 1 s time resolu-
tion. The instruments agree to within 3 % for NO, 5 % for
NO2 , and 1 % for O3 measurements, which is within the
summed accuracy of both instruments for each species. Cor-
relation among all measurements was excellent, with R 2 val-
ues ≥0.99. Much of the scatter in the correlation plots is
the result of synchronization between the instruments when
transecting NOx plumes with sharp edges. Although CRDS
is lower in precision than the CL instrument and is subject
to some baseline instability as described above, the compar-
906 isons in Fig. 8 demonstrate that it is accurate, at least at larger
Fig. 8. The left panels show sample NO (upper panels), NO2 (mid- NOx and O3 values.
907 Figure 8. The
dle panels) andleft panelspanels)
O3 (lower show sample NO from
mixing ratio (upper
bothpanels), NO2 (middle
the CRDS panels) and O3
One common diagnostic used to understand the nighttime
instrument in red and the chemiluminescence (CL) measurements
908 (lower panels) mixing ratio from both the CRDS instrument in red reactivity and the of NO3 and N2 O5 is their steady state atmospheric
in blue for the 3 June flight. The right panels show the correlations
909 chemiluminescence
of the two measurements(CL)for
measurements in bluewas
each species. There fora the June
small
rd lifetime
3 flight.
pop- The (Platt et al., 1984). The steady state lifetime of a
right panels
ulation of points on this flight for which there was a deviation on species can be determined from its rate of production and
910 show the correlations of the two measurements for each species. There was a small defined in Eqs. (7) and (8) for NO3 and
its concentration,
the NO2 measurement, likely related to the zero measurement on
911 one or the other
population instruments.
of points Thesefor
on this flight deviations were was
which there not observed N2the
a deviation on O5 (Brown
NO2 et al., 2003).
on other CalNex flights. [NO3 ]
912 measurement, likely related to the zero measurement on one or the τother instruments.
SS (NO3 ) = ≈ kNO3 + kN2 O5 Keq [NO2 ]

−1
(7)
k1 [O3 ] [NO2 ]
913 These deviations were not observed on other CalNex flights.  −1
[N2 O5 ] kNO3
Several NO2 plumes were encountered throughout the night, τSS (N2 O5 ) = ≈ kN2 O5 + (8)
k1 [O3 ] [NO2 ] Keq [NO2 ]
many of which showed distinct anticorrelations with O3 due
to titration and subsequent nighttime chemistry within these Here τSS (NO3 ) and τSS (N2 O5 ) are the steady state lifetimes
plumes. After sunrise, the NOx containing plumes showed and k1 is the rate constant for Reaction (R1). When the steady

Atmos. Meas. Tech., 4, 1227–1240, 2011 www.atmos-meas-tech.net/4/1227/2011/

914 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3 1239

References

Atkinson, D. B.: Solving chemical problems of environmental

importance using cavity ring-down spectroscopy, Analyst, 128,
117–125, doi:10.1039/b206699h, 2003.
Atkinson, R.: Kinetics and mechanisms of the gas-phase reactions
of the NO3 radical with organic-compounds, J. Phys. Chem. Ref.
Data, 20, 459–507, 1991.
Ayers, J. D., Apodaca, L., Simpson, W. R., and Baer, D. S.: Off-
axis cavity ring-down spectroscopy: Application to atmospheric
nitrate radical detection, Appl. Optics, 44, 7239–7242, 2005.
Brown, S. S.: Absorption spectroscopy in high-finesse cavi-
ties for atmospheric studies, Chem. Rev., 103, 5219–5238,
doi:10.1021/cr020645c, 2003.
Brown, S. S., Stark, H., Ciciora, S. J., McLaughlin, R. J., and Rav-
915 ishankara, A. R.: Simultaneous in situ detection of atmospheric
NO3 and N2 O5 via cavity ring-down spectroscopy, Rev. Sci. In-
Fig. 9. The lifetimes of NO3 (blue) and N2 O5 (red) for the 3 June strum., 73, 3291–3301, rd doi:10.1063/1.1499214, 2002.
916 Figure
flight. The9lifetimes
. Thewerelifetimes ofusing
calculated NOconcentrations
3 (blue) and N2O5 (red)
measured forS.the
Brown, S., June
Stark, 3H., flight. The A. R.: Applicabil-
and Ravishankara,
by a single instrument. ity of the steady state approximation to the interpretation of at-
917 lifetimes were calculated using concentrations measured by aobservations
mospheric single instrument.
of NO3 and N2 O5 , J. Geophys. Res.-
Atmos., 108, 5219–5238, doi:10.1029/2003jd003407, 2003.
state approximation is valid the lifetimes can be used to deter- Brown, S. S., Dubé, W. P., Osthoff, H. D., Stutz, J., Ryerson, T. B.,
mine the pseudo first-order loss rate of NO3 and N2 O5 , kNO3 Wollny, A. G., Brock, C. A., Warneke, C., de Gouw, J. A., At-
and kN2 O5 . Keq is the equilibrium constant for Reaction (R2). las, E., Neuman, J. A., Holloway, J. S., Lerner, B. M., Williams,
In past field campaigns, this analysis would require data from E. J., Kuster, W. C., Goldan, P. D., Angevine, W. M., Trainer,
M., Fehsenfeld, F. C., and Ravishankara, A. R.: Vertical profiles
at least two separate instruments. Figure 8 demonstrates the
in NO3 and N2 O5 measured from an aircraft: Results from the
advantage of the combined measurements of nighttime ni- NOAA P-3 and surface platforms during NEAQS 2004, J. Geo-
trogen oxides (NO2 , NO3 and N2 O5 ) and O3 into a single phys. Res., 112, D22304, doi:10.1029/2007JD008883, 2007a.
instrument. Figure 9 shows the steady state lifetimes for the Brown, S. S., Dubé, W. P., Osthoff, H. D., Wolfe, D. E., Angevine,
flight of 30 May. The lifetimes of NO3 range from 0–1.5 h W. M., and Ravishankara, A. R.: High resolution vertical distri-
and lifetimes up to 3 h are observed for N2 O5 . Thus, the butions of NO3 and N2 O5 through the nocturnal boundary layer,
combination of NO2 , O3 with NO3 and N2 O5 , all tied to a Atmos. Chem. Phys., 7, 139–149, doi:10.5194/acp-7-139-2007,
single analytical standard, provides a complete and accurate 2007b.
representation of nighttime nitrogen oxide chemistry. Busch, K. W. and Busch, M. A.: Cavity-ringdown spectroscopy,
American Chemical Society, Washington, DC, 1999.
Dubé, W. P., Brown, S. S., Osthoff, H. D., Nunley, M. R., Ciciora,
5 Conclusions S. J., Paris, M. W., McLaughlin, R. J., and Ravishankara, A.
R.: Aircraft instrument for simultaneous, in situ measurement of
The article has described an aircraft instrument for atmo- NO3 and N2 O5 via pulsed cavity ring-down spectroscopy, Rev.
spheric measurements of NO3 , N2 O5 , NO, NO2 , and O3 Sci. Instrum., 77, 034101, doi:10.1063/1.2176058, 2006.
by cavity ring-down spectroscopy. NO3 and NO2 are mea- Everest, M. A. and Atkinson, D. B.: Discrete sums for the rapid
sured directly using a diode lasers with center wavelengths determination of exponential decay constants, Rev. Sci. Instrum.,
79, 023108, doi:10.1063/1.2839918, 2008.
of 662 nm and 405 nm. N2 O5 is thermally converted to NO3
Finlayson-Pitts, B. J., Ezell, M. J., and Pitts, J. N.: Formation
for measurement and NO and O3 are chemically converted
of chemically active chlorine compounds by reactions of atmo-
to NO2 and measured. Each channel is regularly calibrated spheric NaCl particles with gaseous N2 O5 and ClONO2 , Nature,
in the field by a scheme linking the cross-sections of each 337, 241–244, 1989.
measured species to the O3 cross-section at 254 nm. The Fuchs, H., Dubé, W. P., Ciciora, S. J., and Brown, S. S.: Determina-
inlet transmission of NO3 and N2 O5 is also measured reg- tion of inlet transmission and conversion efficiencies for in situ
ularly in the field. The performance of the instrument was measurements of the nocturnal nitrogen oxides, NO3 , N2 O5 and
demonstrated during its first deployment on the NOAA P-3 NO2 , via pulsed cavity ring-down spectroscopy, Anal. Chem.,
in California during a 2010 field intensive. 80, 6010–6017, doi:10.1021/ac8007253, 2008.
Fuchs, H., Dubé, W. P., Lerner, B. M., Wagner, N. L., Williams, E.
Acknowledgements. This work was funded in part by NOAA’s J., and Brown, S. S.: A sensitive and versatile detector for atmo-
Atmospheric Chemistry and Climate Program. spheric NO2 and NOx based on blue diode laser cavity ring-down
spectroscopy, Environ. Sci. Technol., 43, 7831–7836, 2009.
Edited by: W. R. Simpson

www.atmos-meas-tech.net/4/1227/2011/ Atmos. Meas. Tech., 4, 1227–1240, 2011

36
1240 N. L. Wagner et al.: Diode laser-based cavity ring-down instrument for NO3 , N2 O5 , NO, NO2 and O3

Fuchs, H., Ball, S. M., Bohn, B., Brauers, T., Cohen, R. C., Dorn, Ryerson, T. B., Huey, L. G., Knapp, K., Neuman, J. A., Parrish, D.
H.-P., Dubé, W. P., Fry, J. L., Häseler, R., Heitmann, U., Jones, D., Sueper, D. T., and Fehsenfeld, F. C.: Design and initial char-
R. L., Kleffmann, J., Mentel, T. F., Müsgen, P., Rohrer, F., acterization of an inlet for gas-phase NOy measurements from
Rollins, A. W., Ruth, A. A., Kiendler-Scharr, A., Schlosser, E., aircraft, J. Geophys. Res.-Atmos., 104, 5483–5492, 1999.
Shillings, A. J. L., Tillmann, R., Varma, R. M., Venables, D. Ryerson, T. B., Williams, E. J., and Fehsenfeld, F. C.: An efficient
S., Villena Tapia, G., Wahner, A., Wegener, R., Wooldridge, P. photolysis system for fast-response NO2 measurements, J. Geo-
J., and Brown, S. S.: Intercomparison of measurements of NO2 phys. Res.-Atmos., 105, 26447–26461, 2000.
concentrations in the atmosphere simulation chamber SAPHIR Ryerson, T. B., Trainer, M., Angevine, W. M., Brock, C. A., Dissly,
during the NO3Comp campaign, Atmos. Meas. Tech., 3, 21–37, R. W., Fehsenfeld, F. C., Frost, G. J., Goldan, P. D., Holloway,
doi:10.5194/amt-3-21-2010, 2010. J. S., Hubler, G., Jakoubek, R. O., Kuster, W. C., Neuman, J.
Jones, C. L. and Seinfeld, J. H.: The oxidation of NO2 to nitrate – A., Nicks Jr., D. K., Parrish, D. D., Roberts, J. M., Sueper, D.
day and night, Atmos. Environ., 17, 2370–2373, 1983. T., Atlas, E. L., Donnelly, S. G., Flocke, F., Fried, A., Pot-
King, M. D., Dick, E. M., and Simpson, W. R.: A new method for ter, W. T., Schauffler, S., Stroud, V., Weinheimer, A. J., Wert,
the atmospheric detection of the nitrate radical (NO3 ), Atmos. B. P., Wiedinmyer, C., Alvarez, R. J., Banta, R. M., Darby, L.
Environ., 34, 685–688, 2000. S., and Senff, C. J.: Effect of petrochemical industrial emis-
Langridge, J. M., Ball, S. M., Shillings, A. J., and Jones, R. L.: A sions of reactive alkenes and NOx on tropospheric ozone for-
broadband absorption spectrometer using light emitting diodes mation in Houston, Texas, J. Geophys. Res., 108, ACH8-1-24,
for ultrasensitive, in situ trace gas detection, Rev. Sci. Instrum., doi:10.1029/2002jd003070, 2003.
79, 123110, doi:10.1063/1.3046282, 2008. Schuster, G., Labazan, I., and Crowley, J. N.: A cavity ring
Osthoff, H. D., Brown, S. S., Ryerson, T. B., Fortin, T. J., Lerner, down/cavity enhanced absorption device for measurement of
B. M., Williams, E. J., Pettersson, A., Baynard, T., Dube, W. P., ambient NO3 and N2 O5 , Atmos. Meas. Tech., 2, 1–13,
Ciciora, S. J., and Ravishankara, A. R.: Measurement of atmo- doi:10.5194/amt-2-1-2009, 2009.
spheric NO2 by pulsed cavity ring-down spectroscopy, J. Geo- Solomon, S., Miller, H. L., Smith, J. P., Sanders, R. W., Mount, G.
phys. Res., 111, D12305, doi:10.1029/2005JD006942, 2006. H., Schmeltekopf, A. L., and Noxon, J. F.: Atmospheric NO3 1.
Osthoff, H. D., Pilling, M. J., Ravishankara, A. R., and Measurement technique and the annual cycle, 40◦ N, J. Geophys.
Brown, S. S.: Temperature dependence of the NO3 absorp- Res., 94, 11041–11048, 1989.
tion cross section above 298 K and determination of the equi- Thornton, J. A., Kercher, J. P., Riedel, T. P., Wagner, N. L., Cozic,
librium constant for NO3 + NO2 − N2 O5 at atmospherically rel- J., Holloway, J. S., Dube, W. P., Wolfe, G. M., Quinn, P. K., Mid-
evant conditions, Phys. Chem. Chem. Phys., 9, 5785–5793, dlebrook, A. M., Alexander, B., and Brown, S. S.: A large atomic
doi:10.1039/b709193a, 2007. chlorine source inferred from mid-continental reactive nitro-
Plane, J. M. C. and Nien, C. F.: Differential optical-absorption gen chemistry, Nature, 464, 271–274, doi:10.1038/nature08905,
spectrometer for measuring atmospheric trace gases, Rev. Sci. 2010.
Instrum., 63, 1867–1876, 1992. Vandaele, A. C., Hermans, C., Simon, P. C., Carleer, M., Colin,
Platt, U., Perner, D., Winer, A. M., Harris, G. W., and Pitts, J. R., Fally, S., Merienne, M. F., Jenouvrier, A., and Co-
N.: Detection of NO3 in the polluted troposphere by differen- quart, B.: Measurements of the NO2 absorption cross-section
tial optical-absorption, Geophys. Res. Lett., 7, 89–92, 1980. from 42 000 cm−1 to 10 000 cm−1 (238–1000 nm) at 220 K and
Platt, U. F., Winer, A. M., Bierman, H. W., Atkinson, R., and Pitts 294 K, J. Quant. Spectrosc. Ra., 59, 171–184, 1998.
Jr., J. N.: Measurement of nitrate radical concentrations in conti- Washenfelder, R. A., Dubé, W. P., Wagner, N. L., and Brown,
nental air, Environ. Sci. Technol., 18, 365–369, 1984. S. S.: Measurement of atmospheric ozone by cavity ring-
Pollack, I. B., Lerner, B. M., and Ryerson, T. B.: Evaluation of ul- down spectroscopy, Environ. Sci. Technol., 45, 2938–2944,
traviolet light-emitting diodes for detection of atmospheric NO2 doi:10.1021/es103340u, 2011.
by photolysis - chemiluminescence, J. Atmos. Chem., 65(2–3), Wayne, R. P., Barnes, I., Biggs, P., Burrows, J. P., Canosa-Mas,
111–125, doi:10.1007/s10874-011-9184-3, 2011. C. E., Hjorth, J., LeBras, G., Moortgat, G. K., Perner, D., Poulet,
Rothman, L. S., Gordon, I. E., Barbe, A., Benner, D. C., Bernath, G., Restelli, G., and Sidebottom, H.: The nitrate radical: Physics,
P. E., Birk, M., Boudon, V., Brown, L. R., Campargue, A., chemistry, and the atmosphere, Atmos. Environ. A-Gen., 25, 1–
Champion, J. P., Chance, K., Coudert, L. H., Dana, V., Devi, 203, 1991.
V. M., Fally, S., Flaud, J. M., Gamache, R. R., Goldman, Yokelson, R. J., Burkholder, J. B., Fox, R. W., Talukdar, R. K.,
A., Jacquemart, D., Kleiner, I., Lacome, N., Lafferty, W. J., and Ravishankara, A. R.: Temperature-dependence of the NO3
Mandin, J. Y., Massie, S. T., Mikhailenko, S. N., Miller, C. absorption-spectrum, J. Phys. Chem., 98, 13144–13150, 1994.
E., Moazzen-Ahmadi, N., Naumenko, O. V., Nikitin, A. V., Or- Zalicki, P. and Zare, R. N.: Cavity ring-down spectroscopy for
phal, J., Perevalov, V. I., Perrin, A., Predoi-Cross, A., Rins- quantitative absorption-measurements, J. Chem. Phys., 102,
land, C. P., Rotger, M., Simeckova, M., Smith, M. A. H., 2708–2717, 1995.
Sung, K., Tashkun, S. A., Tennyson, J., Toth, R. A., Vandaele,
A. C., and Vander Auwera, J.: The HITRAN 2008 molecular
spectroscopic database, J. Quant. Spectrosc. Ra., 110, 533–572,
doi:10.1016/j.jqsrt.2009.02.013, 2009.

Atmos. Meas. Tech., 4, 1227–1240, 2011 www.atmos-meas-tech.net/4/1227/2011/