Gas phase elemental mercury: A comparison of LIF detection techniques and study of the kinetics of reaction with the hydroxyl radical

D. Bauer, L. D'Ottone, P. Campuzano-Jost, Anthony J Hynes

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

We have examined the sensitivity of single and sequential two-photon laser-induced fluorescence (LIF) techniques for the detection of elemental mercury, Hg(0), in the gas phase. Single photon LIF involves excitation of the 63P1-61S0 transition at 253.7 nm, followed by observation of resonance fluorescence. Sequential two-photon techniques follow the initial 63P1-61S0 excitation with a second excitation step to either the 71S0 or 73S1 levels followed by observation of blue or red shifted fluorescence. We have examined four variants of these approaches which all exceed the sensitivity of single photon LIF. The most sensitive detection approach involves the initial 253.7 nm excitation followed by excitation of the 71S0-63P1 transition at 407.8 nm. Fluorescence is observed on the 61P1-61S0 transition at 184.9 nm. Using this approach, our limits of detection are 0.1 ng m-3 with a 10 s integration time in air. We have also examined the effects of saturation, quenching and line-width on detection sensitivity. We have used the pulsed laser photolysis-pulsed laser-induced fluorescence (PLP-PLIF) technique to study the kinetics of the reaction of elemental mercury with the hydroxyl radical under atmospheric conditions at 298 K. We see no evidence for reaction and obtain an upper limit of 1.2×10-13 cm3 molecule-1 s-1 for the rate coefficient.

Original languageEnglish (US)
Pages (from-to)247-256
Number of pages10
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume157
Issue number2-3
DOIs
StatePublished - May 5 2003

Fingerprint

hydroxyl radicals
Mercury
Hydroxyl Radical
laser induced fluorescence
Gases
Fluorescence
vapor phases
Kinetics
Lasers
kinetics
excitation
Photons
photons
pulsed lasers
Pulsed lasers
fluorescence
sensitivity
resonance fluorescence
meteorology
photolysis

Keywords

  • Elemental mercury
  • Laser-induced fluorescence
  • Pulsed laser photolysis

ASJC Scopus subject areas

  • Bioengineering
  • Physical and Theoretical Chemistry

Cite this

Gas phase elemental mercury : A comparison of LIF detection techniques and study of the kinetics of reaction with the hydroxyl radical. / Bauer, D.; D'Ottone, L.; Campuzano-Jost, P.; Hynes, Anthony J.

In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 157, No. 2-3, 05.05.2003, p. 247-256.

Research output: Contribution to journalArticle

@article{1523399e8a784725b5238380d0ef7af6,
title = "Gas phase elemental mercury: A comparison of LIF detection techniques and study of the kinetics of reaction with the hydroxyl radical",
abstract = "We have examined the sensitivity of single and sequential two-photon laser-induced fluorescence (LIF) techniques for the detection of elemental mercury, Hg(0), in the gas phase. Single photon LIF involves excitation of the 63P1-61S0 transition at 253.7 nm, followed by observation of resonance fluorescence. Sequential two-photon techniques follow the initial 63P1-61S0 excitation with a second excitation step to either the 71S0 or 73S1 levels followed by observation of blue or red shifted fluorescence. We have examined four variants of these approaches which all exceed the sensitivity of single photon LIF. The most sensitive detection approach involves the initial 253.7 nm excitation followed by excitation of the 71S0-63P1 transition at 407.8 nm. Fluorescence is observed on the 61P1-61S0 transition at 184.9 nm. Using this approach, our limits of detection are 0.1 ng m-3 with a 10 s integration time in air. We have also examined the effects of saturation, quenching and line-width on detection sensitivity. We have used the pulsed laser photolysis-pulsed laser-induced fluorescence (PLP-PLIF) technique to study the kinetics of the reaction of elemental mercury with the hydroxyl radical under atmospheric conditions at 298 K. We see no evidence for reaction and obtain an upper limit of 1.2×10-13 cm3 molecule-1 s-1 for the rate coefficient.",
keywords = "Elemental mercury, Laser-induced fluorescence, Pulsed laser photolysis",
author = "D. Bauer and L. D'Ottone and P. Campuzano-Jost and Hynes, {Anthony J}",
year = "2003",
month = "5",
day = "5",
doi = "10.1016/S1010-6030(03)00065-0",
language = "English (US)",
volume = "157",
pages = "247--256",
journal = "Journal of Photochemistry and Photobiology A: Chemistry",
issn = "1010-6030",
publisher = "Elsevier",
number = "2-3",

}

TY - JOUR

T1 - Gas phase elemental mercury

T2 - A comparison of LIF detection techniques and study of the kinetics of reaction with the hydroxyl radical

AU - Bauer, D.

AU - D'Ottone, L.

AU - Campuzano-Jost, P.

AU - Hynes, Anthony J

PY - 2003/5/5

Y1 - 2003/5/5

N2 - We have examined the sensitivity of single and sequential two-photon laser-induced fluorescence (LIF) techniques for the detection of elemental mercury, Hg(0), in the gas phase. Single photon LIF involves excitation of the 63P1-61S0 transition at 253.7 nm, followed by observation of resonance fluorescence. Sequential two-photon techniques follow the initial 63P1-61S0 excitation with a second excitation step to either the 71S0 or 73S1 levels followed by observation of blue or red shifted fluorescence. We have examined four variants of these approaches which all exceed the sensitivity of single photon LIF. The most sensitive detection approach involves the initial 253.7 nm excitation followed by excitation of the 71S0-63P1 transition at 407.8 nm. Fluorescence is observed on the 61P1-61S0 transition at 184.9 nm. Using this approach, our limits of detection are 0.1 ng m-3 with a 10 s integration time in air. We have also examined the effects of saturation, quenching and line-width on detection sensitivity. We have used the pulsed laser photolysis-pulsed laser-induced fluorescence (PLP-PLIF) technique to study the kinetics of the reaction of elemental mercury with the hydroxyl radical under atmospheric conditions at 298 K. We see no evidence for reaction and obtain an upper limit of 1.2×10-13 cm3 molecule-1 s-1 for the rate coefficient.

AB - We have examined the sensitivity of single and sequential two-photon laser-induced fluorescence (LIF) techniques for the detection of elemental mercury, Hg(0), in the gas phase. Single photon LIF involves excitation of the 63P1-61S0 transition at 253.7 nm, followed by observation of resonance fluorescence. Sequential two-photon techniques follow the initial 63P1-61S0 excitation with a second excitation step to either the 71S0 or 73S1 levels followed by observation of blue or red shifted fluorescence. We have examined four variants of these approaches which all exceed the sensitivity of single photon LIF. The most sensitive detection approach involves the initial 253.7 nm excitation followed by excitation of the 71S0-63P1 transition at 407.8 nm. Fluorescence is observed on the 61P1-61S0 transition at 184.9 nm. Using this approach, our limits of detection are 0.1 ng m-3 with a 10 s integration time in air. We have also examined the effects of saturation, quenching and line-width on detection sensitivity. We have used the pulsed laser photolysis-pulsed laser-induced fluorescence (PLP-PLIF) technique to study the kinetics of the reaction of elemental mercury with the hydroxyl radical under atmospheric conditions at 298 K. We see no evidence for reaction and obtain an upper limit of 1.2×10-13 cm3 molecule-1 s-1 for the rate coefficient.

KW - Elemental mercury

KW - Laser-induced fluorescence

KW - Pulsed laser photolysis

UR - http://www.scopus.com/inward/record.url?scp=0037420862&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037420862&partnerID=8YFLogxK

U2 - 10.1016/S1010-6030(03)00065-0

DO - 10.1016/S1010-6030(03)00065-0

M3 - Article

AN - SCOPUS:0037420862

VL - 157

SP - 247

EP - 256

JO - Journal of Photochemistry and Photobiology A: Chemistry

JF - Journal of Photochemistry and Photobiology A: Chemistry

SN - 1010-6030

IS - 2-3

ER -