You are on page 1of 25

INCOHERENT BROADBAND CAVITY ENHANCEMENT

ABSORPTION SPECTROSCOPY FOR TRACE GAS


DETECTION
Contents
Nitrate some facts
Conventional vs Cavity enhanced absorption
spectroscopy
IBBCEAS
Experiment
- Instrumental setup
- Calibration
Results from lab measurements
Conclusion

Nitrate (NO
3
-
)
Atmospheric NO
3
-
(NO
3
-
atm
) is a mixture of gas phase
nitric acid, produced by the oxidation of NO
x
, and NO
3
-

salts formed by heterogeneous reactions involving NO
y

on aerosol surfaces
NO
3
-
is not present in the sunlit atmosphere, because it is
rapidly destroyed by photolysis.
The chemistry of the night-time atmosphere
A substantial portion of nitrate found in the soil,
stream and ground water is of atmospheric
origin
The global nitrogen cycle has been altered by
human activities:
human N
2
-fixation > 2 x natural fixation (annually)
NO
3
-
is a substantial source of new N
The negative impacts of excess N and NO
3
-

input includes
shifts in biodiversity,
soil acidification and forest decline,
eutrophication of coastal waters and estuaries and
degradation of ground and surface waters

Tracing of atmospheric
nitrate deposition in a
complex semiarid
ecosystem by University
of California
CONVENTIONAL ABSORPTION SPECTROSCOPY
A laboratory technique used to determine the
structure and concentration of a sample based on the
amount and wavelengths of light that it absorbs.

It derives concentrations of absorbing species in the
atmosphere by using a form of the Beer-Bouguer-
Lambert Law.
Beer - Bouguer - Lambert Law
Transmittance, T is calculated as


where I0 initial light intensity (power P0)
I transmitted intensity (power P)
- absorption coefficient of the sample
b path length of light through the sample

Sample
High reflectivity plano-concave dielectric mirrors
(typically R > 99.95% in the wavelength of interest)

Detector
Length = b
Advantage of Cavity Enhanced
Absorption Spectroscopy
The cavity having a length of 1m approximately could create
an effective path length of 10km








This increases the sensitivity of the instrument
I
in
(1-R)
2
(1-L) (0
th
pass)
I
in
(1-R)
2
(1-L)
3
R
2
(1
st
pass)
I
in
(1-R)
2
(1-L)
2n+1
R
2n
(n
th
pass)
Types of Cavity Enhanced Absorption
Spectroscopy

1. Cavity Ring Down Spectroscopy (CRDS)
2. Integrated Cavity Output Spectroscopy (ICOS)
3. Incoherent Broadband Cavity Enhanced
Absorption Spectroscopy (IBBCEAS)

Simple, Robust
& Economic
High temporal
resolution
Portable &
Compact
Easy integration
into
spectrometers
Applicable to
fluids
Applicable over a
wide spectral range
Theoretical
application to
solids
Theory of IBBCEAS
I
in
(1-R)
2
(1-L) (0)
I
in
(1-R)
2
(1-L)
3
R
2
(1)
I
in
(1-R)
2
(1-L)
2n+1
R
2n
(n)
+
+
+
Since R<1 and L<1
For an empty resonator with L = 0, I
o
= I
in
(1-R) (1+R)
-1

Therefore,
Assuming the losses per pass to be solely due to Beer absorption,
Theory of IBBCEAS
EXPERIMENTAL SETUP
Lab Setup: Transmitter Unit
Lab Setup: Intermediate Unit
Lab Setup: Receiver Unit

Preparation of NO
3

In The Laboratory
4 HNO
3(aq)
+ Cu
(s)
Cu(NO
3
)
2(aq)
+ 2 H
2
O
(l)
+ 2 NO
2(g)
NO
2
+ O
3
NO
3
+O
2

Using ozoniser, NO
2
inside the chamber is
made to undergo the following reaction:
Calibration of Mirror Reflectivity R
Low-loss optic [L() < 0.001, Layertec]
500 550 600 650 700 750
0
2000
4000
6000
8000
10000
C
o
u
n
t
Wavelengh
LLO
I0
Transmission without optic (I0)





Transmission with optic (LLO)
Wavelength Calibration
585.249
585.103
703.137
703.241
Neon lamp lines (NIST, USA)
Measured Neon lamp lines
using AvaSpec 3648
Results: NO
3
Measurement
Intensity of cavity signal with N
2
gas
inside the cavity
Intensity of cavity signal with NO
3
gas
inside the cavity
Results: NO
3
Measurement
' and least squares fit for
Results: NO
3
Measurement
CONCLUSION
A simple IBBCEAS setup to detect trace gases like NO
3
is
designed for the In-situ measurement.
The instrument was able to detect NO
3
concentration at
ppb levels.
The calculated error was about 7% - 9%.
Further optimizations are required to improve sensitive.
When the instrument is used in humid conditions, H
2
O
absorption lines in the spectral range of interest will
increase the amount of error.
THANK
YOU

You might also like