Ammonia Measurement using UV

absorption
Presented By
Amal Agharkar

Differential Optical Absorption

Spectroscopy
Ammonia measurement is challenging due to

interference of the low concentration stray gases

Measurement of ammonia with sampling instruments
is not reliable as ammonia adheres to the surface of
the inlet depending upon the concentration in the inlet
stream and on the inlet wall.
Open path spectroscopy gives better alternative to
many sampling instruments as it eliminates the
necessity of inlets.
Absorption of electromagnetic waves cause
excitation in the gas molecules.
Differential absorption can be measured over an open
path to calculate the gas concentration using BeerLamberts law.

Modified Beer-Lamberts law

By measuring spectral radiation before and after the gas

absorption it is possible to find out the gas concentration using

the Beer-Lamberts law.
There will be several trace gases which absorb radiation in the
similar wavelength range. Hence it is important to know the
contribution of the trace gases in the radiation attenuation
I()= I0()exp[-L x ii()x ci ]
Where,
- wavelength;
I() - radiation intensity in the presence of absorbers;
Io() - radiation intensity without absorbers;
L - optical path length;
() - absorption cross section of absorber;
c - concentration of absorber
i Each species that absorbs over the wavelength of interest

Modified Beer-Lamberts law (cont.)

In addition to the other atmospheric species there

are other atmospheric phenomenon.

We need to take into account Rayleighs
scattering and Mie scattering.
Scattering acts as a continuum absorption from
the perspective of the instrument and hence
extinction coefficients are to be applied to the
equation.

Instrumentation of DOAS system

This method and instrument was designed in Washington

State University hence the method is also known as WSU

method.
They designed a state of the art measurement system for
open path spectroscopy.
150 W Xe high pressure arc lamp was used owing to its
advantages over deuterium lamp in terms of stable, low
modulation UV output.
The spectrograph was a homebuilt double crossed
Czerny-Turner with a focal length of 37.5 cm on each side.
It was designed to minimize scattered light and aberrations
in the focal planes of the parabolic mirror.

The DOAS Instrument

Working of the instrument

The lamp is positioned at the side of the optical path of the

primary mirror and a folding mirror is used to direct the

light beam onto the primary mirror optical axis.
The lamp only illuminates an annulus of about 6 cm on the
outer edge of the mirror due to another folding mirror used
to image the light onto the spectrograph entrance slit
blocking most of the light from the lamp.
The outer annulus of light is directed out over the
measurement path to four 12.7 cm retroreflectors.
The light from the retroreflectors illuminates the inner
annulus of the primary mirror by translating the light from
the outer annulus.
The light is then intercepted by the folding flat and directed
into the spectrograph.

Schematic

Instrument Specifications
The spectrograph has a spectral coverage of about 42 nm
The spectral resolution is 1 nm
The detector is a homebuilt Reticon silicon photodiode

array with 1024 pixels with each pixel 25 m wide and 2.5
mm high.
The detector has an analog to digital convertor which
produces a data number (DN) for 1000 detected electrons
The leakage noise of the detector is 0.004 DN s1 pixel1
The largest variation in instrument precision is caused by
illumination changes on the optics caused by thermals in
the atmosphere

DOAS method
Advantages
In-situ measurement
Wavelength selectivity
Simultaneous measurement of variable species
Self-calibration, reading depends only on the absolute cross

section of the gas

Disadvantages
Spatially averaged measurement. Measurement cant be

taken at a point
Not all species can be measured
Not as sensitive as other methods.

OMA 300
Works on the Beer-Lamberts principle

It is an integrated monitor which is able to

measure about 100 compounds.

It measures intensity of the UV radiation entering
the sample and exiting the sample.

OMA 300 Schematic

Components of OMA 300

Nova II spectrophotometer:
Solid state build with excellent
wavelength stability
CMOS analog circuitry reduces
noise and power consumption
1024-element diode array with
~1nm resolution
Strong light throughput in low
UV region
Very low stray light due to
design without mirrors or filters
Ethernet interface for remote
access

Components of OMA 300

Human Machine Interface:
The HMI controlling the
spectrophotometer and
communication provides a
simple, touch-screen visual
interface.
HMI offers the user several
display choices (e.g. standard
numeric display, trendgraph, bar
graph).
From this interface, the user can
quickly adjust settings like how
frequently the Auto Zero is
performed, the unit of
concentration for each

Components of OMA 300

Flow Cell:
The sample (gas or liquid) from
the process stream continuously
cycles through the flow cell via
1/4 Swagelok tube fittings.
The standard flow cell is rated
up to 3,000 psi / 150 C and
made from stainless steel 316L
for corrosion-proof durability.
The path length of the flow cell
is specified by company
engineers to optimize the
measurement for the expected
concentration ranges of the
analytes.

Components of OMA 300

Fiber Optic Cables:
Fiber optic cables are used for
transmission of UV light through
the flow cell.

OMA 300
Advantages
Continuously measures ammonia concentration

with wide dynamic range

Totally solid state build with no moving parts
modern design for low maintenance
Additional software benches available for more
analytes
Disadvantages
Chances of settling of ammonia on the inlet walls of

the instrument affecting the readings.