Noise-immune cavity-enhanced analytical atomic spectrometry — NICE-AAS — A technique for detection of elements down to zeptogram amounts

Ove Axner, Patrick Ehlers, Thomas Hausmaninger, Isak Silander, Weiguang Ma

Research output: Contribution to journalArticleScientificpeer-review

6 Citations (Scopus)

Abstract

Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is a powerful technique for detection of molecular compounds in gas phase that is based on a combination of two important concepts: frequency modulation spectroscopy (FMS) for reduction of noise, and cavity enhancement, for prolongation of the interaction length between the light and the sample. Due to its unique properties, it has demonstrated unparalleled detection sensitivity when it comes to detection of molecular constituents in the gas phase. However, despite these, it has so far not been used for detection of atoms, i.e. for elemental analysis. The present work presents an assessment of the expected performance of Doppler-broadened (Db) NICE-OHMS for analytical atomic spectrometry, then referred to as noise-immune cavity-enhanced analytical atomic spectrometry (NICE-AAS). After a description of the basic principles of Db-NICE-OHMS, the modulation and detection conditions for optimum performance are identified. Based on a previous demonstrated detection sensitivity of Db-NICE-OHMS of 5 × 10− 12 cm− 1 Hz− 1∕2 (corresponding to a single-pass absorbance of 7 × 10− 11 over 10 s), the expected limits of detection (LODs) of Hg and Na by NICE-AAS are estimated. Hg is assumed to be detected in gas phase directly while Na is considered to be atomized in a graphite furnace (GF) prior to detection. It is shown that in the absence of spectral interferences, contaminated sample compartments, and optical saturation, it should be feasible to detect Hg down to 10 zg/cm3 (10 fg/m3 or 10− 5 ng/m3), which corresponds to 25 atoms/cm3, and Na down to 0.5 zg (zg = zeptogram = 10− 21 g), representing 50 zg/mL (parts-per-sextillion, pps, 1:1021) in liquid solution (assuming a sample of 10 μL) or solely 15 atoms injected into the GF, respectively. These LODs are several orders of magnitude lower (better) than any previous laser-based absorption technique previously demonstrated under atmospheric pressure conditions. It is prophesied that NICE-AAS could provide such high detection sensitivity that the instrumentation should not, by itself, be the limiting factor of an assessment of elemental abundance; the accuracy of an assessment would then instead be limited by concomitant species, e.g. originating from the handling procedures of the sample or the environment.
Original languageEnglish
Pages (from-to)211-235
JournalSpectrochimica Acta, Part B: Atomic Spectroscopy
Volume100
DOIs
Publication statusPublished - Oct 2014
MoE publication typeA1 Journal article-refereed

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Molecular spectroscopy
Spectrometry
cavities
Graphite
Gases
molecular spectroscopy
Atoms
spectroscopy
Furnaces
Frequency modulation
Atmospheric pressure
vapor phases
Modulation
Spectroscopy
furnaces
graphite
Lasers
Liquids
atoms
prolongation

Cite this

@article{1b9fe446de934109a8a9f6396f2f96e2,
title = "Noise-immune cavity-enhanced analytical atomic spectrometry — NICE-AAS — A technique for detection of elements down to zeptogram amounts",
abstract = "Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is a powerful technique for detection of molecular compounds in gas phase that is based on a combination of two important concepts: frequency modulation spectroscopy (FMS) for reduction of noise, and cavity enhancement, for prolongation of the interaction length between the light and the sample. Due to its unique properties, it has demonstrated unparalleled detection sensitivity when it comes to detection of molecular constituents in the gas phase. However, despite these, it has so far not been used for detection of atoms, i.e. for elemental analysis. The present work presents an assessment of the expected performance of Doppler-broadened (Db) NICE-OHMS for analytical atomic spectrometry, then referred to as noise-immune cavity-enhanced analytical atomic spectrometry (NICE-AAS). After a description of the basic principles of Db-NICE-OHMS, the modulation and detection conditions for optimum performance are identified. Based on a previous demonstrated detection sensitivity of Db-NICE-OHMS of 5 × 10− 12 cm− 1 Hz− 1∕2 (corresponding to a single-pass absorbance of 7 × 10− 11 over 10 s), the expected limits of detection (LODs) of Hg and Na by NICE-AAS are estimated. Hg is assumed to be detected in gas phase directly while Na is considered to be atomized in a graphite furnace (GF) prior to detection. It is shown that in the absence of spectral interferences, contaminated sample compartments, and optical saturation, it should be feasible to detect Hg down to 10 zg/cm3 (10 fg/m3 or 10− 5 ng/m3), which corresponds to 25 atoms/cm3, and Na down to 0.5 zg (zg = zeptogram = 10− 21 g), representing 50 zg/mL (parts-per-sextillion, pps, 1:1021) in liquid solution (assuming a sample of 10 μL) or solely 15 atoms injected into the GF, respectively. These LODs are several orders of magnitude lower (better) than any previous laser-based absorption technique previously demonstrated under atmospheric pressure conditions. It is prophesied that NICE-AAS could provide such high detection sensitivity that the instrumentation should not, by itself, be the limiting factor of an assessment of elemental abundance; the accuracy of an assessment would then instead be limited by concomitant species, e.g. originating from the handling procedures of the sample or the environment.",
author = "Ove Axner and Patrick Ehlers and Thomas Hausmaninger and Isak Silander and Weiguang Ma",
year = "2014",
month = "10",
doi = "10.1016/j.sab.2014.08.016",
language = "English",
volume = "100",
pages = "211--235",
journal = "Spectrochimica Acta, Part B: Atomic Spectroscopy",
issn = "0584-8547",
publisher = "Elsevier",

}

Noise-immune cavity-enhanced analytical atomic spectrometry — NICE-AAS — A technique for detection of elements down to zeptogram amounts. / Axner, Ove; Ehlers, Patrick; Hausmaninger, Thomas; Silander, Isak; Ma, Weiguang.

In: Spectrochimica Acta, Part B: Atomic Spectroscopy, Vol. 100, 10.2014, p. 211-235.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Noise-immune cavity-enhanced analytical atomic spectrometry — NICE-AAS — A technique for detection of elements down to zeptogram amounts

AU - Axner, Ove

AU - Ehlers, Patrick

AU - Hausmaninger, Thomas

AU - Silander, Isak

AU - Ma, Weiguang

PY - 2014/10

Y1 - 2014/10

N2 - Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is a powerful technique for detection of molecular compounds in gas phase that is based on a combination of two important concepts: frequency modulation spectroscopy (FMS) for reduction of noise, and cavity enhancement, for prolongation of the interaction length between the light and the sample. Due to its unique properties, it has demonstrated unparalleled detection sensitivity when it comes to detection of molecular constituents in the gas phase. However, despite these, it has so far not been used for detection of atoms, i.e. for elemental analysis. The present work presents an assessment of the expected performance of Doppler-broadened (Db) NICE-OHMS for analytical atomic spectrometry, then referred to as noise-immune cavity-enhanced analytical atomic spectrometry (NICE-AAS). After a description of the basic principles of Db-NICE-OHMS, the modulation and detection conditions for optimum performance are identified. Based on a previous demonstrated detection sensitivity of Db-NICE-OHMS of 5 × 10− 12 cm− 1 Hz− 1∕2 (corresponding to a single-pass absorbance of 7 × 10− 11 over 10 s), the expected limits of detection (LODs) of Hg and Na by NICE-AAS are estimated. Hg is assumed to be detected in gas phase directly while Na is considered to be atomized in a graphite furnace (GF) prior to detection. It is shown that in the absence of spectral interferences, contaminated sample compartments, and optical saturation, it should be feasible to detect Hg down to 10 zg/cm3 (10 fg/m3 or 10− 5 ng/m3), which corresponds to 25 atoms/cm3, and Na down to 0.5 zg (zg = zeptogram = 10− 21 g), representing 50 zg/mL (parts-per-sextillion, pps, 1:1021) in liquid solution (assuming a sample of 10 μL) or solely 15 atoms injected into the GF, respectively. These LODs are several orders of magnitude lower (better) than any previous laser-based absorption technique previously demonstrated under atmospheric pressure conditions. It is prophesied that NICE-AAS could provide such high detection sensitivity that the instrumentation should not, by itself, be the limiting factor of an assessment of elemental abundance; the accuracy of an assessment would then instead be limited by concomitant species, e.g. originating from the handling procedures of the sample or the environment.

AB - Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is a powerful technique for detection of molecular compounds in gas phase that is based on a combination of two important concepts: frequency modulation spectroscopy (FMS) for reduction of noise, and cavity enhancement, for prolongation of the interaction length between the light and the sample. Due to its unique properties, it has demonstrated unparalleled detection sensitivity when it comes to detection of molecular constituents in the gas phase. However, despite these, it has so far not been used for detection of atoms, i.e. for elemental analysis. The present work presents an assessment of the expected performance of Doppler-broadened (Db) NICE-OHMS for analytical atomic spectrometry, then referred to as noise-immune cavity-enhanced analytical atomic spectrometry (NICE-AAS). After a description of the basic principles of Db-NICE-OHMS, the modulation and detection conditions for optimum performance are identified. Based on a previous demonstrated detection sensitivity of Db-NICE-OHMS of 5 × 10− 12 cm− 1 Hz− 1∕2 (corresponding to a single-pass absorbance of 7 × 10− 11 over 10 s), the expected limits of detection (LODs) of Hg and Na by NICE-AAS are estimated. Hg is assumed to be detected in gas phase directly while Na is considered to be atomized in a graphite furnace (GF) prior to detection. It is shown that in the absence of spectral interferences, contaminated sample compartments, and optical saturation, it should be feasible to detect Hg down to 10 zg/cm3 (10 fg/m3 or 10− 5 ng/m3), which corresponds to 25 atoms/cm3, and Na down to 0.5 zg (zg = zeptogram = 10− 21 g), representing 50 zg/mL (parts-per-sextillion, pps, 1:1021) in liquid solution (assuming a sample of 10 μL) or solely 15 atoms injected into the GF, respectively. These LODs are several orders of magnitude lower (better) than any previous laser-based absorption technique previously demonstrated under atmospheric pressure conditions. It is prophesied that NICE-AAS could provide such high detection sensitivity that the instrumentation should not, by itself, be the limiting factor of an assessment of elemental abundance; the accuracy of an assessment would then instead be limited by concomitant species, e.g. originating from the handling procedures of the sample or the environment.

U2 - 10.1016/j.sab.2014.08.016

DO - 10.1016/j.sab.2014.08.016

M3 - Article

VL - 100

SP - 211

EP - 235

JO - Spectrochimica Acta, Part B: Atomic Spectroscopy

JF - Spectrochimica Acta, Part B: Atomic Spectroscopy

SN - 0584-8547

ER -