Application of chemiluminescence to monitoring of trace atmospheric species

Thesis/Dissertation · Sun Jan 01 04:00:00 EST 1989

OSTI ID:6811779

Burkhardt, M R

This dissertation concerns the development of analytical instrumentation based on gas phase chemiluminescence for the monitoring of nitric acid, methyl nitrate, peroxyacetyl nitrate, and total acidity. Nitric acid was converted to NO and NO{sub 2} by a 400 C glass beads converter and the resulting NO{sub 2} was monitored by a luminol-based detector. A CrO{sub 3} converter was used to convert the NO generated in the system to NO{sub 2} to lower the detection limit of the instrument. The detection limit of the configuration was 0.30 ppb of nitric acid. Peroxyacetyl nitrate (PAN) and NO{sub 2} were separated and detected with a novel gas chromatographic system which did not require compressed gas cylinder. Air that has been scrubbed by passing it over FeSO{sub 4} was used as the carrier gas which eliminates the need for any compressed gas cylinders. The detection limits for the instrument (PAN-GC) were 0.12 ppb for PAN and 0.20 ppb for NO{sub 2}. Methyl nitrate was separated from PAN and NO{sub 2} using a modified version of the PAN-GC. A 200 C quartz converter inserted between the end of the column and the detector in the PAN-GC, converts methyl nitrate and PAN into NO{sub 2} for detection by the luminol-based detector. The detection limits are 0.30 ppb for PAN, 0.30 ppb for methyl nitrate, and 0.20 ppb for NO{sub 2} The development of a total acidity detector based on the reaction of O and F atoms with hydrazoic acid (HN{sub 3}) was also carried out. Several methods for converting atmospheric acidity to HN{sub 3} were tested. These included packed bed, coated filters, and denuder methods. The system was calibrated with nitric acid and hydrochloric acid and the characterization of the response to various organic acids was investigated. The detection limits for nitric acid and for hydrochloric acid were 0.51 ppb and 0.63 ppb, respectively.

• Research Organization: Denver Univ., CO (USA)
• OSTI ID: 6811779
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
540120* -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (1990-)
AIR POLLUTION
AIR POLLUTION MONITORING
AIR POLLUTION MONITORS
ATMOSPHERIC CHEMISTRY
CALIBRATION
CHEMILUMINESCENCE
CHEMISTRY
CHROMATOGRAPHY
ECOLOGICAL CONCENTRATION
ESTERS
GAS CHROMATOGRAPHY
HYDROGEN COMPOUNDS
INORGANIC ACIDS
LUMINESCENCE
MEASURING INSTRUMENTS
MONITORS
NITRATES
NITRIC ACID
NITRIC ACID ESTERS
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PEROXYACETYL NITRATE
POLLUTION
SEPARATION PROCESSES
TRACE AMOUNTS