Fluorine-selective post-plasma chemical ionization for enhanced elemental detection of fluorochemicals

Tanen, Jordan L.; White, Samuel; Ha, Duong Thi; Jorabchi, Kaveh

doi:10.1039/d2ja00430e

Cited by 5 publications

(4 citation statements)

References 21 publications

(63 reference statements)

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“…Ideally, new ionization chemistries should be developed to address these areas in a fundamental fashion. For example, we have recently demonstrated that Sc(NO 3 ) 2 (H 2 O) n + acts as a more selective reagent ion for HF detection . As a result, the HF detection dependence on plasma chemistry is reduced, and tolerance for matrix effects from Cl is improved.…”

Section: Discussionmentioning

confidence: 99%

“…Interface. An improved design of the post-plasma chemical ionization interface 25 was utilized for better control of plasma sampling. This design was fitted to the entrance of a Q Exactive Orbitrap-MS as illustrated in Figure 1.…”

Section: Chemical Ionizationmentioning

confidence: 99%

“…For example, we have recently demonstrated that Sc(NO 3 ) 2 (H 2 O) n + acts as a more selective reagent ion for HF detection. 25 As a result, the HF detection dependence on plasma chemistry is reduced, and tolerance for matrix effects from Cl is improved. Similar selective chemistries for detection of other nonmetals are needed and are under development in our group to enhance multielement methods for robust and facile quantitation of compounds without standards.…”

Section: ■ Conclusionmentioning

confidence: 99%

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Multielement Detection of Nonmetals by Barium-Based Post-ICP Chemical Ionization Coupled to Orbitrap-MS

Hahm,

Redeker,

Jorabchi

2024

J. Am. Soc. Mass Spectrom.

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Prevalence of F, Cl, S, P, Br, and I in pharmaceuticals and environmental contaminants has promoted standard-free quantitation using analyte-independent heteroatom responses in inductively coupled plasma (ICP)-MS. However, inplasma ionization challenges and element-dependent isobaric interference removal methods have hampered the multielement nonmetal detection in ICP-MS. Here, we examine an alternative approach to enhance multielement detection capabilities. Analytes are introduced into an ICP leading to post-plasma formation of HF, HCl, H 3 PO 3 , H 2 SO 4 , HBr, and HI, which are then chemically ionized to BaF + , BaCl + , BaH 2 PO 3 + , BaHSO 4 + , BaBr + , and BaI + via reactions with barium-containing ions supplied by a nanospray. Subsequent ion detection by high-resolution MS provides an element-independent approach for resolving isobaric interferences. We show that elemental response factors using these ions are linear within 2 orders of magnitude and independent of analytes' chemical structures. Using a single set of operating parameters, detection limits <1 ng/mL are obtained for Cl, Br, I, and P, while those for F and S are 1.8 and 6.2 ng/mL, respectively, offering improved multielement quantitation of nonmetals. Further, insights into ionization mechanisms indicate that the reactivities of reagent ions follow the order BaNO 2. Notably, the least reactive ions are generated directly by nanospray, suggesting that modification of these ions via interaction with plasma afterglow is critical for achieving good sensitivities. Moreover, our experiments indicate that the element-specific plasma products follow the order HF < H 2 SO 4 ∼ HCl < H 3 PO 3 ∼ HBr ∼ HI for their propensity to react with reagent ions. These insights provide guidelines to manage matrix effects and offer pathways to further improve the technique.

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Section: Discussionmentioning

confidence: 99%

Section: Chemical Ionizationmentioning

confidence: 99%

Section: ■ Conclusionmentioning

confidence: 99%

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Multielement Detection of Nonmetals by Barium-Based Post-ICP Chemical Ionization Coupled to Orbitrap-MS

Hahm,

Redeker,

Jorabchi

2024

J. Am. Soc. Mass Spectrom.

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“…The problem of inefficient ionisation of F in the Ar ICP-MS was addressed by Tanen et al 58 who developed a post-ICP chemical ionisation method to form BaF + ions. They achieved this using an interface composed of two chambers.…”

Section: Instrumentation Fundamentals and Chemometricsmentioning

confidence: 99%

Atomic spectrometry update: review of advances in atomic spectrometry and related techniques

Evans,

Pisonero,

Smith

et al. 2024

J. Anal. At. Spectrom.

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Notizen aus der Chemie

Delaittre¹,

Dierkes²,

Heine³

et al. 2023

Nachr Chem

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Fluorine-selective post-plasma chemical ionization for enhanced elemental detection of fluorochemicals

Abstract: Elemental analysis of fluorochemicals has received a renewed attention in recent years stemming from increased use of fluorinated compounds. However, fundamental drawbacks of in-plasma ionization have hindered ICPMS applications in...

Cited by 5 publications

References 21 publications

Multielement Detection of Nonmetals by Barium-Based Post-ICP Chemical Ionization Coupled to Orbitrap-MS

Multielement Detection of Nonmetals by Barium-Based Post-ICP Chemical Ionization Coupled to Orbitrap-MS

Atomic spectrometry update: review of advances in atomic spectrometry and related techniques

Notizen aus der Chemie

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