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