Fluorescence Assay by Gas Expansion

This is a ground-based laser-induced fluorescence instrument for detection of OH, HO2, and
RO2 radicals. FAGE involves low-pressure laser-induced fluorescence spectroscopy. It is a
highly selective and sensitive technique, ideal for the measurement of OH in the atmosphere.
Laser-induced fluorescence (LIF) is a spectroscopic method in which an atom or molecule
is excited to a higher energy level by the absorption of laser light followed by spontaneous
emission of light. It was first reported by Zare and coworkers in 1968. LIF is used for studying
structure of molecules, detection of selective species and flow visualization and measurements.

Importance of HO in Troposphere
An atmosphere is a layer of gases surrounding a planet or other material body, that is held in
place by the gravity of that body. The troposphere is the lowest region of the atmosphere
extending from the Earth’s surface to the tropopause at 10– 18 km.
There is an important radical in the atmosphere ''the hydroxyl radical(OH)''. OH, is called
natural detergent, as it removes many of the gases that are causing pollution. Like methane
and carbon dioxide.

 It is the primary daytime oxidizing species responsible for the removal of CO, CH4 (and
higher hydrocarbons), H2, NO2, H2S, (CH3)2S, NH3, the hydrochlorofluorocarbons
(HCFCs) and hydrofluorocarbons (HFCs).
 The concentration of OH defines the oxidizing capacity of the atmosphere and hence
the ability to control levels of species that contribute to global warming, acid rain, and
photochemical smog. Intermediate peroxy radicals, of which HO2 is the simplest, are
generated during the oxidation of trace gases and a fast-photochemical cycle (see
diagram below) links these radicals with OH.
 OH, is highly reactive, with the balance between production and destruction rates
giving an atmospheric lifetime under clean conditions of ~1 s (less under polluted
conditions), and consequently tropospheric concentrations are extremely low. Daytime
maxima are in the range of (1-10) x 106 molecule cm-3 (0.04 - 0.4 pptv).
 HO2 has a longer lifetime of ~100 s with a typical daytime maximum concentration of
~108 molecule cm-3 (~4 pptV).
The short atmospheric lifetimes of OH and HO2 mean that their concentrations are determined
by local chemical conditions, such as solar flux and levels of NOx, rather than transport, making
them ideal candidates with which to test our understanding of atmospheric chemistry through
measurements and zero-dimensional modelling.

The Sources, Interconversions and Sinks for HOx (and ROx) in The
Troposphere
The hydroxyl radical, OH, is the atmosphere’s most important oxidizer and cleansing agent. A
close chemical relative, the hydroperoxyl radical, HO2, is a major source of tropospheric
ozone. It reacts with NO to form NO2, which is then photolyzed, creating O3.
 i. The main known urban HOx sources are the photolysis of ozone, formaldehyde
(HCHO), and HONO. Ozone photolysis produces an excited oxygen atom, which reacts
with water forming two OH radicals per photolyzed O3 molecule. One channel in the
photolysis of formaldehyde leads to formation of two HO2 radicals. HONO can build
up during nighttime and is easily photolyzed, potentially leading to significantly
enhanced OH levels in the early morning.
ii. Other possible HOx sources have been discovered recently. In polluted air, O3 can
react with alkenes to produce a significant amount of OH. Because this source requires
no photolysis, these reactions produce OH, and thus HO2, both day and night. At
present, photolytic HOx sources are thought to be far more significant than
nonphotolytic HOx sources.

Fig 1; The sources, interconversions and sinks for HOx (and ROx) in the troposphere.

iii. OH, and HO2 undergo propagation reactions that lead to rapid interconversion between
these radicals. OH, reacts with CO or O3 producing HO2, and the oxidation of
hydrocarbons by OH leads to formation of peroxy radicals, RO2, and HO2. In the
presence of NO, RO2 is converted to HO2, which reacts with NO or O3 to form OH.
Hydrocarbon oxidation frequently leads also to the formation of HCHO, increasing this
source of HOx.
iv. The main sink for HOx in the polluted boundary layer is the reaction of OH with NO2
forming nitric acid, HNO3. In cleaner air, the reactions HO2 + HO2, HO2 + RO2, and
HO2 + OH are most important. Other sinks, such as deposition, heterogeneous
chemistry in cloud drops and on aerosols, and formation of other chemicals such as per
nitric acid are usually considered to be minor.
 v. At high NO and NO2, HO2 should decrease almost quadratically as NO increases
because NO reacts with HO2 to cycle HO2 to OH and OH reacts with NO2, which is
usually in photo stationary state with NO, to form HNO3, thus terminating the cycle.

NO2 + hv (λ< 420 nm) NO + O (3 P)

Fig 2; HOx radical cycle

Oxidation of Methane
Methane is one of the greenhouse gases. It is 25 times more potent than CO2, as it absorbs more
IR than CO2.OH is very important as it clean methane from troposphere. The oxidation of
methane is illustrative of the major role of the hydroxyl radical in that the atmospheric
concentration of CH4 is in the main controlled by reaction with OH. Ozone is also produced
within the troposphere by oxidation of CO and hydrocarbons (principally CH4) in the presence
of NOx. One of the earliest estimates of the global source of ozone in the troposphere was done
by scaling the emission inventories of CH4 and CO.
The day time tropospheric chemistry is driven by OH and the night time by NO3.

Types of FAGE
There are two types of FAGE based on the method of application of instrument. That are;

1. Ground-Based FAGE
2. Air-Craft FAGE

The aircraft FAGE instrument, designed to make measurements of OH and HO2radicals in

the free troposphere. The Ground based instrument consists of a container.

Fig 5; Ground-Based FAGE

Fig 6; Air-Craft FAGE

Physical Specifications
Foot print: 5.9 m (L) x 2.35 m (W) x 2.35 m (H)

Weight: 10 Tones
Power: 10 kwatts (at 400 V, 32 amps)
Operation temperature: -10 min°C to +40 max°C
Site Requirements
o 3 phase power is required to operate the instrument.

o Adequate access and hard-standing for container lorry for drop-off and pick-up.

o Solid, reasonably level ground for positioning the container.

o Minimal shading.
 The FAGE Technique
OH, is present in the troposphere at extremely low concentrations, typically on the order
of 1 × 106 molecule cm−3, and has a very short lifetime. Detection of this radical is
therefore a great experimental challenge. The FAGE (Fluorescence Assay by Gas
Expansion) technique is utilized for the task. FAGE involves low-pressure laser-induced
fluorescence spectroscopy. It is a highly selective and sensitive technique, ideal for the
measurement of OH in the atmosphere.

 Ambient air is drawn into a detection

cell at low pressure (~1 Torr) through a
pinhole nozzle (~1 mm diameter).
 A laser beam tuned to 308 nm is passed
perpendicularly across the gas beam,
causing on-resonance fluorescence of
the OH radicals.
 The expansion of the sampled gas into
the low-pressure cell reduces collisional
quenching of the excited OH radical,
extending the fluorescence lifetime
sufficiently to enable temporal
discrimination between the laser pulse
and OH fluorescence. Fig 3; Ground Base FAGE
 The fluorescence is filtered and
focused onto a photomultiplier tube and
analyzed by photon counting.
 The resultant signal is converted into
an OH concentration by calibration.
The FAGE technique can also be used
to make HO2 measurements by means
of chemical conversion to OH with NO,
followed by LIF detection.
 Current detection limits are 6 ×
105 molecule cm−3 for OH and 1 ×
106 molecule cm−3 for HO2. Data is
taken with 30 second integration time.

Fig 4; Fluorescence Scheme

 Modelling Studies

Numerical models based on kinetic and mechanistic data derived from laboratory studies
can be used to aid our understanding of the composition of the atmosphere, and can be used
to simulate concentrations of short-lived free radical species such as OH and HO2. Field
measurements of these species therefore provide an ideal test for atmospheric models, and
a combination of field measurements and modelling studies can be used to examine our
understanding of the atmosphere. Modelling studies provide valuable insight to
atmospheric chemistry on local, regional and global scales, and can be used to inform
policy decisions regarding pollution, public health and climate change.By doing such work
we hope to provide a link back to laboratory studies to identify areas in which current
recommendations for the kinetics and mechanisms used in atmospheric models may require
improvement.

i. Master Chemical Mechanism (MCM)

ii. DSMACC
iii. GEOS-Chem

OH Reactivity Measurement
OH, reactivity measurements are made using a laser-induced pump and probe technique.
Ambient air is drawn through a flow-tube and a beam of 266 nm light, pulsed along the flow-
tube, photolysis ambient ozone (or lab generated ozone if ambient levels are low) generating
O(1D) which reacts with ambient H2O (v) present to form OH:
O3 + hv → O(1D) + O2
O(1D) + H2O → 2OH
The [OH] generated in the flow tube is kept sufficiently low that pseudo-first-order conditions
are maintained, thus the absolute OH concentration does not need to be known. The OH
undergoes an exponential decay, monitored by a FAGE cell coupled to the end of the flow-
tube:
[OH]t=[OH]0 exp (− (k’ + k’ wall) t)
where k’ represents the reactive decay rate, the inverse of the chemical lifetime, τOH, given by:
k’=Σki [X]i
where [X]i represents the concentration of an atmospheric trace gas and ki the rate coefficient
for its reaction with OH at the temperature of the flow-tube, and k’wall is the non-reactive
loss of OH mainly due to wall losses or diffusion out of the 266-nm beam.
Service and Calibration
The instrument is calibrated at regular intervals (twice weekly) during deployment. Known
concentrations of OH and HO2 are generated in a turbulent flow reactor by flowing
humidified air past a Hg penray lamp which photolysis H2O at 185 nm to form OH (and
HO2 in the presence of O2):

H2O + 185 nm → OH + H
H + O2 → HO2
With knowledge of the H2O(v) concentration (measured using a calibrated GE dew point
hygrometer), the absorption cross section of H2O at 185 nm, flow velocities and lamp flux the
concentration of the radicals can be accurately calculated.
The lamp flux is determined before and after each deployment using N2O actinometry: Briefly,
a known concentration of N2O is flowed through the turbulent flow reactor, N2O is photolyzed
to NO by the Hg lamp and detected using a trace level NOx analyzer which has been calibrated
using a certified NO standard.
Health and Safety
 Eye Safety; This instrument contains a class 4 laser system. Only laser-trained
individuals should have access to the container when the instrument is in operation.
There are no beams external to container / Roof-top box. All beams within container
are enclosed and delivered by optic fibers. Laser goggles worn for all alignments.
Door sign indicating lasers on; restricted access.
 Manual handling; Two people are required for set-up and pack-up of the instrument
and good lifting practices should be employed. No access is permitted on the roof of
the container before safety barriers have been erected by trained individuals. A side-
lift is fitted to the container and is used for moving items on and off the roof. Safety
hats required when walking close to the container and on the
roof. Wires/tubing should be kept away from pathways, held over head height in the
container. Walkways kept free of clutter and access to exit kept clear.
 Electric safety
Single point insulation fitted. Waterproof container, armored cable, RCD protection.
All equipment electrical safety tested.
 Chemical hazards; Toxic gases are used during the operation of the instrument (CO,
NO): Cylinders are secured and the container is kept well ventilated. Vacuum lines
are leak tested and gas usage is monitored. Gases should be locked away when
unattended and a CO alarm is housed in the container.
Example
The Average Diurnal Cycle of Ozone and Total Peroxide in Clean Oceanic Air As
Measured At Cape Grim During January 1992

The test of the chemistry and theory developed to date must lie in the measurement of radical
chemistry in the field under a range of atmospheric conditions. An elegant piece of
experimental evidence for the photochemical destruction of ozone and the role of radicals in
in-situ photochemistry comes from studies in the remote marine boundary layer over the
southern ocean at Cape Grim, Tasmania (41uS).
The marine boundary layer is particularly suitable for making photochemical measurements
owing to its stable and chemically simple nature.
  During the sunlit hours an ozone loss of about 1.6 ppbv occurs between mid-morning
and late afternoon. This loss of ozone is followed by an overnight replenishment to a
similar starting point.
 In contrast, the peroxide concentration decreases overnight from 900 pptv to 600 pptv
and then increases from 600 pptv to 900 pptv between mid morning and late afternoon.
 It is worth noting that the magnitude of this anti-correlation of ozone and peroxide is
dependent on season.
 That is, in summer when photochemistry is at a maximum, the ozone concentration is
at its lowest value.
 By contrast, during winter when photochemistry is at a minimum, boundary layer ozone
values approach lower free tropospheric values.
Pathway O3 removal O3 addition

Photochemistry Deposition Photochemistryb Entrainment

Jan.–Feb. (Summer) 1.19 0.18 0.56 2.1
Aug.–Sep. (Winter) 0.61 0.35 0.29 0.1
Jan.–Feb. (Summer) 87% 13% 21% 79%
Aug.–Sep. (Winter) 64% 36% 74% 26%

Table;Calculated average ozone removal and addition rates according to pathway ppbv day21 (upper part)
and fractional contributions to overall production or destruction pathways (lower part) on a seasonal basis
from measurements made in the marine boundary layer at Cape Grim, Tasmania

That was a little about FAGE and tropospheric chemistry…

 References
https://hal.archives-ouvertes.fr/hal-00923973/file/Supplementary_material.pdf
http://web.gps.caltech.edu/classes/ge148c/Monks2005_CSR.pdf
http://people.atmos.ucla.edu/jochen/publications/2003JD003551.pdf
https://en.wikipedia.org/wiki/Hydroxyl_radical#Importance_in_Earth.27s_atmosp
here
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3864279/
file:///C:/Users/ZA%20Chohan/Downloads/1314968110_pnas.201314968SI.pdf
https://www.ncas.ac.uk/index.php/en/279-amf-main-category/amf-fage/1329-
fluorescence-assay-by-gas-expansion-fage
http://www.rsc.org/images/environmental-brief-no-3-2014_tcm18-237724.pdf
www.chem.leeds.ac.uk/fage