Managing argon interference during measurements of 18O/16O ratios in O2 by continuous-flow isotope ratio mass spectrometry
Monitoring changes in stable oxygen isotope ratios in molecular oxygen allows for studying many fundamental processes in bio(geo)chemistry and environmental sciences. While the measurement of 18 O/ 16 O ratios of O 2 in gaseous samples can be carried out conveniently and from extracting moderately s...
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| Veröffentlicht in: | Analytical and bioanalytical chemistry 2022-08, Vol.414 (20), p.6177-6186 |
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| creator | Bopp, Charlotte E. Bolotin, Jakov Pati, Sarah G. Hofstetter, Thomas B. |
| description | Monitoring changes in stable oxygen isotope ratios in molecular oxygen allows for studying many fundamental processes in bio(geo)chemistry and environmental sciences. While the measurement of
18
O/
16
O ratios of
O
2
in gaseous samples can be carried out conveniently and from extracting moderately small aqueous samples for analyses by continuous-flow isotope ratio mass spectrometry (CF-IRMS), oxygen isotope signatures,
δ
18
O, could be overestimated by more than 6
‱
because of interferences from argon in air. Here, we systematically evaluated the extent of such Ar interferences on
18
O/
16
O ratios of
O
2
for measurements by gas chromatography/IRMS and GasBench/IRMS and propose simple instrumental modifications for improved Ar and
O
2
separation as well as post-measurement correction procedures for obtaining accurate
δ
18
O. We subsequently evaluated the consequences of Ar interferences for the quantification of O isotope fractionation in terms of isotope enrichment factors,
ϵ
O
, and
18
O kinetic isotope effects (
18
O KIEs) in samples where
O
2
is consumed and Ar:
O
2
ratios increase steadily and substantially over the course of a reaction. We show that the extent of O isotope fractionation is overestimated only slightly and that this effect is typically smaller than uncertainties originating from the precision of
δ
18
O measurements and experimental variability. Ar interferences can become more relevant and bias
ϵ
O
values by more than
2
‱
in aqueous samples where fractional
O
2
conversion exceeds 90%. Practically, however, such samples would typically contain less than 25
μ
M of
O
2
at ambient temperature, an amount that is close to the method detection limit of
18
O/
16
O ratio measurement by CF-IRMS.
Graphical abstract |
| doi_str_mv | 10.1007/s00216-022-04184-3 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_9314310</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2691049945</sourcerecordid><originalsourceid>FETCH-LOGICAL-c381t-8b1f2c80c6c5ba8c14a63ce98a2295306747ca3a114f426834ce60c81f58339d3</originalsourceid><addsrcrecordid>eNp9kc2LFDEQxRtR3A_9BzwFvHjp3aoknUlfBFn8gpW56DlkMtVjlu6kTdLK-NebsZcVPXiqgvq9Rz1e07xAuEKAzXUG4Kha4LwFiVq24lFzjgp1y1UHjx92yc-ai5zvALDTqJ42Z6LTEiWq8-bnJxvswYcDs-kQA_OhUBooUXDE9ks6XSayeUk0USiZxYGh3l6j2rJki4-5StiWs92RuRiKD0tccjuM8QfzOZY408qxyebM8kyupDhRScdnzZPBjpme38_L5su7t59vPrS32_cfb97ctk5oLK3e4cCdBqdct7PaobRKOOq15bzvBKiN3DgrLKIcJFdaSEcKnMah00L0e3HZvF5952U30d7VGMmOZk5-suloovXm70vwX80hfje9QCkQqsGre4MUvy2Ui5l8djSONlANa7jqEWTfy66iL_9B7-KSQo13oiT0PYCsFF8pl2LOiYaHZxDMqVqzVmtqteZ3tUZUkVhFeT61QumP9X9UvwAioqZH</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2694099004</pqid></control><display><type>article</type><title>Managing argon interference during measurements of 18O/16O ratios in O2 by continuous-flow isotope ratio mass spectrometry</title><source>SpringerLink Journals (MCLS)</source><creator>Bopp, Charlotte E. ; Bolotin, Jakov ; Pati, Sarah G. ; Hofstetter, Thomas B.</creator><creatorcontrib>Bopp, Charlotte E. ; Bolotin, Jakov ; Pati, Sarah G. ; Hofstetter, Thomas B.</creatorcontrib><description>Monitoring changes in stable oxygen isotope ratios in molecular oxygen allows for studying many fundamental processes in bio(geo)chemistry and environmental sciences. While the measurement of
18
O/
16
O ratios of
O
2
in gaseous samples can be carried out conveniently and from extracting moderately small aqueous samples for analyses by continuous-flow isotope ratio mass spectrometry (CF-IRMS), oxygen isotope signatures,
δ
18
O, could be overestimated by more than 6
‱
because of interferences from argon in air. Here, we systematically evaluated the extent of such Ar interferences on
18
O/
16
O ratios of
O
2
for measurements by gas chromatography/IRMS and GasBench/IRMS and propose simple instrumental modifications for improved Ar and
O
2
separation as well as post-measurement correction procedures for obtaining accurate
δ
18
O. We subsequently evaluated the consequences of Ar interferences for the quantification of O isotope fractionation in terms of isotope enrichment factors,
ϵ
O
, and
18
O kinetic isotope effects (
18
O KIEs) in samples where
O
2
is consumed and Ar:
O
2
ratios increase steadily and substantially over the course of a reaction. We show that the extent of O isotope fractionation is overestimated only slightly and that this effect is typically smaller than uncertainties originating from the precision of
δ
18
O measurements and experimental variability. Ar interferences can become more relevant and bias
ϵ
O
values by more than
2
‱
in aqueous samples where fractional
O
2
conversion exceeds 90%. Practically, however, such samples would typically contain less than 25
μ
M of
O
2
at ambient temperature, an amount that is close to the method detection limit of
18
O/
16
O ratio measurement by CF-IRMS.
Graphical abstract</description><identifier>ISSN: 1618-2642</identifier><identifier>EISSN: 1618-2650</identifier><identifier>DOI: 10.1007/s00216-022-04184-3</identifier><identifier>PMID: 35841416</identifier><language>eng</language><publisher>Berlin/Heidelberg: Springer Berlin Heidelberg</publisher><subject>Ambient temperature ; Analytical Chemistry ; Argon ; Biochemistry ; Characterization and Evaluation of Materials ; Chemistry ; Chemistry and Materials Science ; Continuous flow ; Environmental science ; Evaluation ; Food Science ; Fractionation ; Gas chromatography ; Isotope fractionation ; Isotope ratios ; Isotopes ; Isotopic enrichment ; Laboratory Medicine ; Mass spectrometry ; Mass spectroscopy ; Monitoring/Environmental Analysis ; Oxygen ; Oxygen isotopes ; Research Paper ; Scientific imaging ; Spectroscopy</subject><ispartof>Analytical and bioanalytical chemistry, 2022-08, Vol.414 (20), p.6177-6186</ispartof><rights>The Author(s) 2022</rights><rights>The Author(s) 2022. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c381t-8b1f2c80c6c5ba8c14a63ce98a2295306747ca3a114f426834ce60c81f58339d3</citedby><cites>FETCH-LOGICAL-c381t-8b1f2c80c6c5ba8c14a63ce98a2295306747ca3a114f426834ce60c81f58339d3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1007/s00216-022-04184-3$$EPDF$$P50$$Gspringer$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1007/s00216-022-04184-3$$EHTML$$P50$$Gspringer$$Hfree_for_read</linktohtml><link.rule.ids>230,314,776,780,881,27901,27902,41464,42533,51294</link.rule.ids></links><search><creatorcontrib>Bopp, Charlotte E.</creatorcontrib><creatorcontrib>Bolotin, Jakov</creatorcontrib><creatorcontrib>Pati, Sarah G.</creatorcontrib><creatorcontrib>Hofstetter, Thomas B.</creatorcontrib><title>Managing argon interference during measurements of 18O/16O ratios in O2 by continuous-flow isotope ratio mass spectrometry</title><title>Analytical and bioanalytical chemistry</title><addtitle>Anal Bioanal Chem</addtitle><description>Monitoring changes in stable oxygen isotope ratios in molecular oxygen allows for studying many fundamental processes in bio(geo)chemistry and environmental sciences. While the measurement of
18
O/
16
O ratios of
O
2
in gaseous samples can be carried out conveniently and from extracting moderately small aqueous samples for analyses by continuous-flow isotope ratio mass spectrometry (CF-IRMS), oxygen isotope signatures,
δ
18
O, could be overestimated by more than 6
‱
because of interferences from argon in air. Here, we systematically evaluated the extent of such Ar interferences on
18
O/
16
O ratios of
O
2
for measurements by gas chromatography/IRMS and GasBench/IRMS and propose simple instrumental modifications for improved Ar and
O
2
separation as well as post-measurement correction procedures for obtaining accurate
δ
18
O. We subsequently evaluated the consequences of Ar interferences for the quantification of O isotope fractionation in terms of isotope enrichment factors,
ϵ
O
, and
18
O kinetic isotope effects (
18
O KIEs) in samples where
O
2
is consumed and Ar:
O
2
ratios increase steadily and substantially over the course of a reaction. We show that the extent of O isotope fractionation is overestimated only slightly and that this effect is typically smaller than uncertainties originating from the precision of
δ
18
O measurements and experimental variability. Ar interferences can become more relevant and bias
ϵ
O
values by more than
2
‱
in aqueous samples where fractional
O
2
conversion exceeds 90%. Practically, however, such samples would typically contain less than 25
μ
M of
O
2
at ambient temperature, an amount that is close to the method detection limit of
18
O/
16
O ratio measurement by CF-IRMS.
Graphical abstract</description><subject>Ambient temperature</subject><subject>Analytical Chemistry</subject><subject>Argon</subject><subject>Biochemistry</subject><subject>Characterization and Evaluation of Materials</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Continuous flow</subject><subject>Environmental science</subject><subject>Evaluation</subject><subject>Food Science</subject><subject>Fractionation</subject><subject>Gas chromatography</subject><subject>Isotope fractionation</subject><subject>Isotope ratios</subject><subject>Isotopes</subject><subject>Isotopic enrichment</subject><subject>Laboratory Medicine</subject><subject>Mass spectrometry</subject><subject>Mass spectroscopy</subject><subject>Monitoring/Environmental Analysis</subject><subject>Oxygen</subject><subject>Oxygen isotopes</subject><subject>Research Paper</subject><subject>Scientific imaging</subject><subject>Spectroscopy</subject><issn>1618-2642</issn><issn>1618-2650</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><sourceid>C6C</sourceid><sourceid>BENPR</sourceid><recordid>eNp9kc2LFDEQxRtR3A_9BzwFvHjp3aoknUlfBFn8gpW56DlkMtVjlu6kTdLK-NebsZcVPXiqgvq9Rz1e07xAuEKAzXUG4Kha4LwFiVq24lFzjgp1y1UHjx92yc-ai5zvALDTqJ42Z6LTEiWq8-bnJxvswYcDs-kQA_OhUBooUXDE9ks6XSayeUk0USiZxYGh3l6j2rJki4-5StiWs92RuRiKD0tccjuM8QfzOZY408qxyebM8kyupDhRScdnzZPBjpme38_L5su7t59vPrS32_cfb97ctk5oLK3e4cCdBqdct7PaobRKOOq15bzvBKiN3DgrLKIcJFdaSEcKnMah00L0e3HZvF5952U30d7VGMmOZk5-suloovXm70vwX80hfje9QCkQqsGre4MUvy2Ui5l8djSONlANa7jqEWTfy66iL_9B7-KSQo13oiT0PYCsFF8pl2LOiYaHZxDMqVqzVmtqteZ3tUZUkVhFeT61QumP9X9UvwAioqZH</recordid><startdate>20220801</startdate><enddate>20220801</enddate><creator>Bopp, Charlotte E.</creator><creator>Bolotin, Jakov</creator><creator>Pati, Sarah G.</creator><creator>Hofstetter, Thomas 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argon interference during measurements of 18O/16O ratios in O2 by continuous-flow isotope ratio mass spectrometry</title><author>Bopp, Charlotte E. ; Bolotin, Jakov ; Pati, Sarah G. ; Hofstetter, Thomas B.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c381t-8b1f2c80c6c5ba8c14a63ce98a2295306747ca3a114f426834ce60c81f58339d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Ambient temperature</topic><topic>Analytical Chemistry</topic><topic>Argon</topic><topic>Biochemistry</topic><topic>Characterization and Evaluation of Materials</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Continuous flow</topic><topic>Environmental science</topic><topic>Evaluation</topic><topic>Food Science</topic><topic>Fractionation</topic><topic>Gas chromatography</topic><topic>Isotope fractionation</topic><topic>Isotope ratios</topic><topic>Isotopes</topic><topic>Isotopic enrichment</topic><topic>Laboratory Medicine</topic><topic>Mass spectrometry</topic><topic>Mass spectroscopy</topic><topic>Monitoring/Environmental Analysis</topic><topic>Oxygen</topic><topic>Oxygen isotopes</topic><topic>Research Paper</topic><topic>Scientific imaging</topic><topic>Spectroscopy</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Bopp, Charlotte E.</creatorcontrib><creatorcontrib>Bolotin, Jakov</creatorcontrib><creatorcontrib>Pati, Sarah G.</creatorcontrib><creatorcontrib>Hofstetter, Thomas B.</creatorcontrib><collection>SpringerOpen</collection><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>Aluminium Industry Abstracts</collection><collection>Biotechnology Research Abstracts</collection><collection>Ceramic Abstracts</collection><collection>Computer and Information Systems Abstracts</collection><collection>Corrosion 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Science Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Analytical and bioanalytical chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Bopp, Charlotte E.</au><au>Bolotin, Jakov</au><au>Pati, Sarah G.</au><au>Hofstetter, Thomas B.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Managing argon interference during measurements of 18O/16O ratios in O2 by continuous-flow isotope ratio mass spectrometry</atitle><jtitle>Analytical and bioanalytical chemistry</jtitle><stitle>Anal Bioanal Chem</stitle><date>2022-08-01</date><risdate>2022</risdate><volume>414</volume><issue>20</issue><spage>6177</spage><epage>6186</epage><pages>6177-6186</pages><issn>1618-2642</issn><eissn>1618-2650</eissn><abstract>Monitoring changes in stable oxygen isotope ratios in molecular oxygen allows for studying many fundamental processes in bio(geo)chemistry and environmental sciences. While the measurement of
18
O/
16
O ratios of
O
2
in gaseous samples can be carried out conveniently and from extracting moderately small aqueous samples for analyses by continuous-flow isotope ratio mass spectrometry (CF-IRMS), oxygen isotope signatures,
δ
18
O, could be overestimated by more than 6
‱
because of interferences from argon in air. Here, we systematically evaluated the extent of such Ar interferences on
18
O/
16
O ratios of
O
2
for measurements by gas chromatography/IRMS and GasBench/IRMS and propose simple instrumental modifications for improved Ar and
O
2
separation as well as post-measurement correction procedures for obtaining accurate
δ
18
O. We subsequently evaluated the consequences of Ar interferences for the quantification of O isotope fractionation in terms of isotope enrichment factors,
ϵ
O
, and
18
O kinetic isotope effects (
18
O KIEs) in samples where
O
2
is consumed and Ar:
O
2
ratios increase steadily and substantially over the course of a reaction. We show that the extent of O isotope fractionation is overestimated only slightly and that this effect is typically smaller than uncertainties originating from the precision of
δ
18
O measurements and experimental variability. Ar interferences can become more relevant and bias
ϵ
O
values by more than
2
‱
in aqueous samples where fractional
O
2
conversion exceeds 90%. Practically, however, such samples would typically contain less than 25
μ
M of
O
2
at ambient temperature, an amount that is close to the method detection limit of
18
O/
16
O ratio measurement by CF-IRMS.
Graphical abstract</abstract><cop>Berlin/Heidelberg</cop><pub>Springer Berlin Heidelberg</pub><pmid>35841416</pmid><doi>10.1007/s00216-022-04184-3</doi><tpages>10</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1618-2642 |
| ispartof | Analytical and bioanalytical chemistry, 2022-08, Vol.414 (20), p.6177-6186 |
| issn | 1618-2642 1618-2650 |
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| source | SpringerLink Journals (MCLS) |
| subjects | Ambient temperature Analytical Chemistry Argon Biochemistry Characterization and Evaluation of Materials Chemistry Chemistry and Materials Science Continuous flow Environmental science Evaluation Food Science Fractionation Gas chromatography Isotope fractionation Isotope ratios Isotopes Isotopic enrichment Laboratory Medicine Mass spectrometry Mass spectroscopy Monitoring/Environmental Analysis Oxygen Oxygen isotopes Research Paper Scientific imaging Spectroscopy |
| title | Managing argon interference during measurements of 18O/16O ratios in O2 by continuous-flow isotope ratio mass spectrometry |
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