SINGLE DEVICE FOR MONITORING OF ALL GREENHOUSE GASES & POLLUTANTS,

COMPARISON WITH OTHER METHODS

Monitoring of air pollution and greenhouse gases (GHG) is one of the most important task s
for limiting global warming and protecting human health. Ambient air (outdoor) pollution
can shorten lives and has a strong impact on the daily lives, causing various respiratory
diseases [1].
Various networks of air quality and pollution
monitoring stations were built worldwide.
Such stations include instrumentation for
measurement of concentrations of GHG and
air pollutants in surrounding air. The GHG
monitoring includes measurements of CO 2 ,
CH 4 , O 3 , N 2 O and H 2 O. The air pollution
monitoring includes: NO 2 , NO, SO 2 , CO and
NH 3 . Typical air quality monitoring modules
consists of several gas analyzers targeted for Figure 1. Air pollution and GHG emission in urban areas
specific types of GHG or air pollutants. Each of
these instruments is usually based on a different measurement principle. Such approach
makes air quality monitoring stations bulky, stational, difficult to operate and requires
specially trained personal. To address these issues MIRO Analytical AG developed a new gas
analyzer based on direct laser absorption spectroscopy that allows simultaneous
measurements of all GHG and air pollutants (up to 10 gases) within a single device.
In this document we present the results of s imultaneous measurements with MIRO 10 gas
analyzer and corresponding reference methods used for GHG and air pollution monitoring.

Typical air monitoring systems MIRO MGA 10 – GP gas analyzer

> 5 different instruments for different gases Single instrument for up to 10 gases,
one measurement principle for all gases

Cross sensitivities No cross sensitivities

Bulky: not mobile Compact: mobile applications
External servers needed Autonomous online monitoring
Weight: 200 kg Weight: 20 kg
© 2021 MIRO Analytical AG 1
COMPARISON CAMPAIN: PARALLEL MEASURMENTS WITH MIRO MGA 8 – GP AND
REFERENCE METHODS FOR GHG AND AIR POLLUTION MEASURMENTS

During the period between May 2018 till June 2018 the MIRO MGA 8 – GP analyzer (without
CH 4 and SO 2 ) was installed together with reference instruments for monitoring in parallel:
CO, NO, NO 2 , O 3 , NH 3 , H 2 O, CO 2 , N 2 O. The table below shows the overview of the main
reference methods used in the parallel measurements with MIRO MGA 8 – GP analyzer.

The MGA – NO 2 instrument is installed at the NABEL monitoring station and it was tested in
parallel measurements with CLD device (see details in the use case: here).

Gases Description of the reference method Main limitations

NO and Chemiluminescence detection (CLD) – estimation of Cross sensitivity

NO 2 NO2 concentration based on measurement of the light Low conversion factor
intensity produced by reaction of NO with O3 giving an (10-70%, can be increased
excited state of NO2 plus oxygen (O2) [2]. up to 90% with photolytic
converter)

O3 Ultraviolet (UV) absorption spectroscopy – measure Low precision and

of light absorption in the UV region, while passing sensitivity
through sample cell [3].
CO Non-dispersive infrared (IR) spectroscopy – IR beam Need a reference gas
passes through sampling chamber and each gas Slow measurements
component absorbs some particular frequency. In
parallel a reference gas, typically nitrogen, is used in
another chamber. By measuring the amount of
absorbed IR light at particular frequency, the
concentration of the gas component is determined [4].
NH 3 , Cavity ring-down spectroscopy (CRDS) – in this Slow measurements
H 2 O, technique, single-frequency laser is coupled in cavity Amount of gases that
CO 2 , that consists out of two (sometimes three) mirrors,
can be analyzed is
N2 O then the cavity is filled with circulating laser light.
When the photodetector reaches a threshold level the limited by availability
laser is switched off, and the laser light keeps running of the mid/near IR
between the mirrors, and due to nonideal reflectivity lasers used
decays in time. This decay is called “ring down”. When High price of the
sample gas is filled inside the cavity it is absorbing the
instruments due to
laser light. Then by comparing two states with and
high cost of reflective
without sample gas the concentration of specific
molecules in the gas can be identified by comparing mirrors, lasers and
the corresponding ring down times. The condition photodetectors
when the sample is in absorbing/non-absorbing state
can be achieved by tuning the laser in and out of
resonance with the molecular absorption line [5].

© 2021 MIRO Analytical AG 2

MIRO Analytical’s multicomponent gas analyzer (MGA) is based on the direct IR laser
absorption spectroscopy and allows direct selective measurements of 10 gases
simultaneously.

LASER ABSORPTION SPECTROSCOPY

Laser absorption spectroscopy (LAS) is a modern technique that is broadly used for real -
time sensing of trace gases. This method involves a tunable narrow-linewidth laser (usually
in the Infrared region) that is tuned through some wavelength range and the light
absorption in the sample gas is measured as a function of that wavelength. The schematic
illustration of the working principle of LAS is presented in Figure 2.

Figure 2. Schematic illustration of laser absorption spectroscopy method

The concentration of corresponding gas component is determined by application of the

Beer-Lambert’s law that provides the relation between absorbance and concentration of an
absorbing species:

𝐼(𝜈) = 𝐼0 (𝜈) exp −𝛼 (𝜈)𝐿

Where 𝐼 (𝜈) and 𝐼0 (𝜈) is the transmitted and the incident light intensity correspondently at
the frequency 𝜈 . The 𝛼(𝜈) = 𝜎(𝜈)𝑁0 𝐶 is the absorption coefficient of the sample with
concentration 𝐶. The Loschmidt constant 𝑁0 is the number density (molecules per unit
volume), which is a function of temperature 𝑇 and pressure 𝑃, and 𝜎 (𝜈) is the absorption
cross section of the absorbing species.
When light of the mid-IR laser source is passing through a gas sample cell containing
measured gas, an absorption feature can be detected if the frequency of the light source
corresponds to the frequency of a rotational-vibrational (ro-vibrational) transition. Then
using the known conditions such as gas temperature 𝑇, optical path length 𝐿, pressure 𝑃

© 2021 MIRO Analytical AG 3

and absorption cross section 𝜎 (𝜈), the concentration of gas can be determined by applying
analytical fitting of the absorption using parameters fr om the HITRAN database [6].
Implementation of different lasers that can be tuned in the specific frequency regions allows
to cover different combinations
of trace gases.

INSRUMENT’S SPECIFICATION

The table below contains the

precisions of MIRO 8 gases
analyzer (MGA 8 – GP) and the
corresponding instruments
used for the reference
measurements.

The precisions for different

8
gases of MGA – GP are
determined by Allan-Werle
variance that allows to estimate Figure 3. Example of Allan-Werle deviation curves for CO and N2O
stability of the device due to gases that shows precision of 5 ppt and 7 ppt correspondently
noise processes and drifts in
the system [7].

Precision of reference MIRO instrument precision

Reference
Gas measurement
measurement 1s 100-200s
@5s or longer
CO Non-dispersive IR
7 ppb 0.4 ppb 0.07 ppb
spectroscopy
NO Chemiluminescence
0.2 ppb 0.8 ppb 0.08 ppb
detection (CLD)
NO 2 Chemiluminescence
0.2 ppb 0.25 ppb 0.007 ppb
detection (CLD)
O3 UV absorption
1 ppb 0.7 ppb 0.15 ppb
spectroscopy
NH 3 Cavity ring-down
0.03 ppb 0.1 ppb 0.015 ppb
spectroscopy (CRDS)
H2 O Cavity ring-down
80 ppm 40 ppm 6 ppm
spectroscopy (CRDS)
CO2 Cavity ring-down
70 ppb 800 ppb 80 ppb
spectroscopy (CRDS)
N2 O Cavity ring-down
0.02 ppb 0.5 ppb 0.01 ppb
spectroscopy (CRDS)

© 2021 MIRO Analytical AG 4

RESULTS OF PARALLEL MEASUREMENTS WITH MIRO MGA 8 – GP INSTUMENT AND
REFERNCE METHODS

During the period between 17.05.2018 till 05.06.2018 measurements with MIRO MGA10 GP
analyzer were running in parallel with reference instruments in the same environmental
conditions. Reference instruments that were used for the parallel measurements:

CO Non-dispersive IR detector

NO and NO 2 CLD ambient NOx monitor

O3 UV absorption photometric analyzer

CO 2 (H 2 O, CO) CRDS analyzer

NH 3 CRDS analyzer

N2O CRDS N 2 O analyzer

The results of the parallel measurements of various gases concentrations are presented in
Figure 3. The gap in the MIRO MGA 8 - GP measurement data was due to the absence of the
instrument at 24.05.2018, because it was taken for a conference presentation.

Figure 4. Results of the parallel measurements with MIRO MGA 8 – GP analyzer and reference devices

To compare the performances of the MGA 8 – GP and reference instruments we built

correlation functions between concentrations measured with two methods for the 2 weeks

© 2021 MIRO Analytical AG 5

measurement period. The results of the correlation functions are presented in the Figure
5.

Figure 5. Correlation functions between concentrations measured with MGA8 – GP analyzer and corresponding
concentrations measured with reference methods

© 2021 MIRO Analytical AG 6

CONCLUSION & OUTLOOK

The results of parallel measurements with MGA 8 – GP analyzer together with the reference
instruments show a good correlation between concentration values for the trace -gases:
CO, NO and NO 2 , O 3 , NH 3 , H 2 O, CO 2 , N 2 O. In comparison with the reference instruments
the MGA 8 – GP analyzer allows:

- to achieve higher precision

- to exclude cross sensitivities for all gases
- to reduce maintenance costs
- to perform fast measurements (speed up to 10 Hz) with a compact and mobile
device (weight 20 kg)
- to reduce power consumption of the GHG and pollution monitoring systems ( up to
10 gases in one compact device)

REFERENCES

1. Ambient air pollution: A global assessment of exposure and burden of disease, report
of WHO (World Health Organization) 2016, link
2. M. Steinbacher et al., Nitrogen oxide measurements at rural sites in Switzerland: Bias
of conventional measurement techniques, Journal of Geophysical Research, 112,
D11307, 2007.
3. P. F. Levelt et al., Science Objectives of the Ozone Monitoring Instrument , IEEE
Transactions on geoscience and remote sensing, 44, 5, 1199-1206, 2006.
4. T. -V. Dinh et al., A review on non-dispersive infrared gas sensors: Improvement of
sensor detection limit and interference correction, Sensors and Actuators B: Chemical,
231, 529-538, 2016
5. H. Fuchs et al., A Sensitive and Versatile Detector for Atmospheric NO2 and NOX Based
on Blue Diode Laser Cavity Ring-Down Spectroscopy, Environ. Sci. Technology, 43, 7831
– 7836, 2009
6. [Link]
7. P. Werle et al., The limits of signal averaging in atmospheric trace -gas monitoring by
tunable diode-laser absorption spectroscopy (TDLAS), Applied Physics B, 57, 131–139,
1993.

© 2021 MIRO Analytical AG 7

RELATED PRODUCT MGA 10 – GP

CONTACTS

MIRO Analytical AG
Widenholzstrasse 1
8304 Wallisellen
[Link]
Switzerland
Email: support@[Link]
Tel: +41 44 830 91 53

© 2021 MIRO Analytical AG 8