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Atmospheric ozone concentration measurement by UV light-emitting diode

radiation absorption

Article  in  Bulletin of the Lebedev Physics Institute · February 2013

DOI: 10.3103/S106833561302005X

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ISSN 1068-3356, Bulletin of the Lebedev Physics Institute, 2013, Vol. 40, No. 2, pp. 50–53. 
c Allerton Press, Inc., 2013.
Original Russian Text 
c I.V. Nikolaev, V.N. Ochkin, F.Yu. Khadzhiiskii, S.N. Tskhai, V.F. Chirkin, 2013, published in Kratkie Soobshcheniya po Fizike, 2013, Vol. 40,
No. 2, pp. 36–41.

Atmospheric Ozone Concentration Measurement

by UV Light-Emitting Diode Radiation Absorption
I. V. Nikolaev, V. N. Ochkin, F. Yu. Khadzhiiskii, S. N. Tskhai∗ , and V. F. Chirkin
Lebedev Physical Institute, Russian Academy of Sciences,
Leninskii pr. 53, Moscow, 119991 Russia
∗
E-mail: tskhai@lebedev.ru
Received May 15, 2012

Abstract—The concentration of ozone produced in the atmosphere under mercury lamp light is
measured using an UV light-emitting diode by the absorption spectrum in the range of 260–
270 nm. The absorbance and ozone concentration measurement sensitivity is k = 8 · 10−7 cm−1
and ∼3 ppbv, respectively.

DOI: 10.3103/S106833561302005X

Keywords: UV light-emitting diode, ozone, absorption spectroscopy.

Introduction. A large number of papers are devoted to the study and measurements of the atmo-
spheric ozone concentration, which is caused by its unique properties. On the one hand, atmospheric
ozone absorbs solar ultraviolet radiation harmful for living cells; its applications in chemical technolo-
gies, biology and medicine, agriculture, and so forth are very wide. At the same time, ozone is a very toxic
substance capable of killing living organisms. In the Russian Federation, this substance is attributed to
the first (highest) danger class of harmful materials. Its maximum allowable concentration is 0.1 mg/m3
or 50 ppbv [1].
Currently, a number of methods for measuring the ozone concentration, based on chemilumi-
nescence, UV radiation absorption, and electrochemical methods are developed. Chemiluminescence
methods have high sensitivity and operating speed; however, the use of solid phosphors requires
frequent calibration; in the case of gaseous phosphors, continuous gas pumping should be provided.
Electrochemical methods provide high sensitivity, but have low selectivity.
The most commonly used method for measuring ozone by UV absorption is mostly implemented
using a low-pressure mercury lamp in which ∼80% of emission intensity can correspond to the line of
253.7 nm coinciding with the Hartley absorption band maximum [1]. This principle is used in a number
of devices characterized by high sensitivity and operating speed. In [2], a compact personal device
with a sensitivity of 1.5 ppbv, based on a standard device (2BTechnologies, model 202) modification,
is described.
Other UV sources are also used. In [3], ozone measurements were performed by the optoacoustic
method using absorption of the fourth harmonic of the Nd:YAG laser, λ = 266 nm. The sensitivity was
0.1 ppbv for 20-s acquisition.
The use of a narrow-band UV source is associated with errors caused by absorption of other
molecules (I2 [4], ClO [5], SO2 [6], and a number of organic compounds). In this case, additional devices
are required to separate pure ozone, e.g., using chemical methods.
The ozone molecule can be selected by the absorption spectrum using a broadband or tunable light
source. To improve the sensitivity of absorption measurements, a high-Q cavity is successfully used
as a multiple-pass cell, which allows a significant increase in the optical path length. In such systems,
measurements with diode lasers demonstrate high sensitivity. In [7], ozone content was measured by
diode laser (404 nm) radiation attenuation in a cavity with mirrors with a reflectance of 0.999965. The
concentration of NO2 molecules resulted from the chemical reaction of O3 and NO was measured. The
ozone measurement accuracy was 26 pptv.

50
 ATMOSPHERIC OZONE CONCENTRATION MEASUREMENT 51

Fig. 1. Schematic of the experimental setup.

Broadband light sources, such as Xe lamps and light-emitting diodes, are also actively used. In
[8], using a 75-W Xe lamp and an external cavity with mirror reflectances of 99.8%, absorption cross
sections of gases, including ozone, were measured in the range of 335–375 nm.
Light-emitting diodes are very promising for developing light and compact devices with low energy
consumption. The number of studies using light-emitting diodes in the gas analysis steadily increases
in the last decade (see [9, 10]). Ranking below the systems with diode lasers in the spectral radiation
density, schemes with light-emitting diodes demonstrate sensitivities [11] comparable to the best laser
results [12]. At the same time, light-emitting diodes exhibit novel capabilities associated with spectral
range extension to the UV region still inaccessible for diode lasers.
However, in practice, ozone concentration measurements using light-emitting diodes is still re-
stricted to the visible and near-UV region. In [13], NO2 and O3 measurements were performed using
diodes emitting in the regions of 442, 525, and 850 nm by changes in the chromatographic plate
transmittance at these wavelengths; the ozone determination sensitivity was 0.42 ppbv. In [14], ozone
absorption cross sections were measured using three light-emitting diodes (365, 405, and 455 nm) with
external high-Q cavities with an accuracy of 2% in the range of 350–470 nm, where the absorption
cross section does not exceed 10−22 cm2 . In [2], it is mentioned that a light-emitting diode was used
to measure ozone concentrations as a source emitting in the region of 255 nm; however, according to
the estimates of the authors, the noise in this case was hundred times higher than in experiments with a
mercury lamp.
In the present study, ozone concentration was measured by the radiation absorption spectrum of
a light-emitting diode in the region of 265 nm close to the absorption cross section maximum of the
Hartley band. A simple single-pass optical cell was used without recourse to chemical procedures.
Experimental setup. The schematic of the experimental setup is shown in Fig. 1. A UVTOP 265
light-emitting diode with an emission maximum at a wavelength of 267 nm was used as a source.
Radiation passed through a stainless steel cell 50 cm long closed by quartz windows on both sides.
At the cell output, radiation was focused into a light guide connected to a SOLARTTISL40-2-1024
USB spectrometer with an incorporated CCD sensor which sent the data to a computer. The spectral
resolution was Δλ = 1.4 nm.
Ozone was produced in air under UV radiation of a high-pressure PRK-2 mercury lamp. Using a fan,
air with an increased ozone concentration was pumped through the cell. To determine the light-emitting
diode intensity without absorption (baseline), the cell was filled with pure nitrogen in which the radiation
loss for Rayleigh scattering is almost identical to the loss in air.

BULLETIN OF THE LEBEDEV PHYSICS INSTITUTE Vol. 40 No. 2 2013

52 NIKOLAEV et al.

Fig. 2. (a) Air absorption spectrum and (b) ozone absorption cross section [15].

Fig. 3. Square root of the Allan variance of the measured absorbance. The dashed curve corresponds to the behavior of
normal noise.

Results. Figure 2 shows the absorption spectrum in air with ozone generated by irradiation with the
mercury lamp. There is also shown the ozone absorption cross section [15, 16].
At the light-emitting diode wavelength of 267 nm, the absorption cross section is s ≈ 9 · 10−18 cm2
[15], the measured absorbance is k = 5.2 · 10−6 cm−1 at the measurement time of ∼10 s. Accordingly,
the ozone concentration is N = k/s = 6 · 1011 cm−3 = 21 ppbv.

BULLETIN OF THE LEBEDEV PHYSICS INSTITUTE Vol. 40 No. 2 2013

 ATMOSPHERIC OZONE CONCENTRATION MEASUREMENT 53

The measurement sensitivity was estimated by the Allan method [17]. Figure 3 shows the curve of
the square root of the Allan variance of the absorbance. We can see that the optimum averaging time is
∼1.5 min; in this case, the absorbance measurement sensitivity is k = 8 · 10−7 cm−1 , which corresponds
to the ozone concentration measurement sensitivity of ∼3 ppbv.
Conclusion. Using an UV light-emitting diode (260–270 nm), the absorption spectrum of ozone
produced in the atmosphere upon exposure to radiation of a high-pressure continuous mercury lamp
was measured. The good correlation of the measured absorbances with the data on absorption cross
sections indicates high selectivies of О3 detection. In this simplest scheme, the absorbance and ozone
concentration measurement sensitivity were k = 8 · 10−7 cm−1 and ∼3 ppbv, respectively; the latter
value is significantly lower than the maximum permissible concentration.

ACKNOWLEDGMENTS
This study was supported by the Russian Foundation for Basic Research, projects nos. 10-02-
01111-a and 11-08-01127-a, and the program “Fundamental Optical Spectroscopy and its Applica-
tions” of the Department of Physical Sciences of the Russian Academy of Sciences.

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