Stable carbon isotope analysis of polyphosphonate complexing agents by anion chromatography coupled to isotope ratio mass spectrometry: method development and application

Martin, Philipp R.; Buchner, Daniel; Jochmann, Maik A.; Haderlein, Stefan B.

doi:10.1007/s00216-019-02251-w

Cited by 11 publications

(6 citation statements)

References 39 publications

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“…Stable carbon isotope ratios in the residual ATMP fraction were analyzed by means of LC-IRMS, as described elsewhere. 24 Separation of ATMP from its transformation products was conducted on the UltiMate3000 HPLC-system as described earlier, except for a reduced flow rate of 500 μL min −1 . Analysis of carbon isotope ratios was conducted on a Delta V Plus IRMS, which was hyphenated to the HPLC via a LC Isolink interface (both Thermo Fisher Scientific, Bremen, Germany).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…Stable carbon isotope ratios in the residual ATMP fraction were analyzed by means of LC-IRMS, as described elsewhere . Separation of ATMP from its transformation products was conducted on the UltiMate3000 HPLC-system as described earlier, except for a reduced flow rate of 500 μL min –1 .…”

Section: Methodsmentioning

confidence: 99%

“…Besides kinetic studies, compound specific stable isotope analysis (CSIA) of light elements (e.g., 13 C/ 12 C) is a powerful approach to characterize transformation mechanisms of organic pollutants (for an extensive review on CSIA we refer to Elsner, 2010) . Carbon CSIA for polar and thus highly water-soluble compounds, can be achieved by coupling liquid chromatography to isotope ratio mass spectrometry (LC-IRMS), as recently demonstrated for three widely used polyphosphonate chelating agents including ATMP. − CSIA allows the determination of kinetic isotope effects associated with transformation reactions, that is, the difference in reaction rate constants for molecules (isotopologues) possessing either a light or heavy stable isotope of a certain element at the reactive site (for carbon: KIE C = 12 k / 13 k ) . As heavy isotopologues progressively accumulate in the remaining substrate the KIE leads to a gradual shift of the isotopic composition in the substrate over the course of its transformation.…”

Section: Introductionmentioning

confidence: 99%

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Two Pathways Compete in the Mn(II)-Catalyzed Oxidation of Aminotrismethylene Phosphonate (ATMP)

Martin

Buchner

Jochmann

et al. 2022

Environ. Sci. Technol.

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Mn(II)-catalyzed oxidation by molecular oxygen is considered a relevant process for the environmental fate of aminopolyphosphonate chelating agents such as aminotrismethylene phosphonate (ATMP). However, the potential roles of Mn(III)ATMP-species in the underlying transformation mechanisms are not fully understood. We combined kinetic studies, compound-specific stable carbon isotope analysis, and equilibrium speciation modeling to shed light on the significance of such Mn− ATMP species for the overall ATMP oxidation by molecular oxygen. The fraction of ATMP complexed with Mn(II) inversely correlated with both (i) the Mn(II)-normalized transformation rate constants of ATMP and (ii) the observed carbon isotope enrichment factors (ε c -values). These findings provide evidence for two parallel ATMP transformation pathways exhibiting distinctly different reaction kinetics and carbon isotope fractionation: (i) oxidation of ATMP present in Mn(III)ATMP complexes (ε c ≈ −10 ‰) and (ii) oxidation of free ATMP by such Mn(III)ATMP species (ε c ≈ −1 ‰) in a catalytic cycle. The higher reaction rate of the latter pathway implies that aminopolyphosphonates can be trapped in catalytic Mn-complexes before being transformed and suggests that Mn(III)ATMP might be a potent oxidant also for other reducible solutes in aqueous environments.

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Section: ■ Materials and Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Two Pathways Compete in the Mn(II)-Catalyzed Oxidation of Aminotrismethylene Phosphonate (ATMP)

Martin

Buchner

Jochmann

et al. 2022

Environ. Sci. Technol.

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“…Compound-Specific Stable Carbon Isotope Analysis of IDMP. Stable carbon isotope ratios of IDMP were analyzed using liquid chromatography coupled to isotope ratio mass spectrometry (LC-IRMS), similar to Martin et al 9 The limit of precise isotope analysis was determined to be 50 μM IDMP (Figure S5).…”

Section: (See the Si)mentioning

confidence: 99%

“…APPs appear to be poorly biodegradable but nevertheless are subject to significant elimination during wastewater treatment by sorption to sewage sludge. ,, Several abiotic transformation processes such as oxidation by H 2 O 2 (i), ozonation (ii), photolysis (UV) (iii), oxidation by Mn 2+ /O 2 (iv), or MnOOH (v) − are described for APPs leading to (potentially) persistent and (eco-) toxicologically problematic transformation products (TPs) including phosphate (all), aminomethylphosphonate (AMPA) (i, ii, iii), and iminodi(methylene phosphonate) (IDMP) (iii, v). − Please see Figure for molecular structures of three aminophosphonates.…”

Section: Introductionmentioning

confidence: 99%

Transformation of Iminodi(methylene phosphonate) on Manganese Dioxides – Passivation of the Mineral Surface by (Formed) Mn²⁺

Röhnelt,

Martin,

Buchner

et al. 2023

Environ. Sci. Technol.

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Aminopolyphosphonates (APPs) are strong chelating agents with growing use in industrial and household applications. In this study, we investigated the oxidation of the bisphosphonate iminodi(methylene phosphonate) (IDMP) – a major transformation product (TP) of numerous commercially used APPs and a potential precursor for aminomethylphosphonate (AMPA) – on manganese dioxide (MnO2). Transformation batch experiments at pH 6 revealed AMPA and phosphate as main TPs, with a phosphorus mass balance of 80 to 92% throughout all experiments. Our results suggest initial cleavage of the C–P bond and formation of the stable intermediate N-formyl-AMPA. Next, C–N bond cleavage leads to the formation of AMPA, which exhibits lower reactivity than IDMP. Reaction rates together with IDMP and Mn2+ sorption data indicate formation of IDMP-Mn2+ surface bridging complexes with progressing MnO2 reduction, leading to the passivation of the mineral surface regarding IDMP oxidation. Compound-specific stable carbon isotope analysis of IDMP in both sorbed and aqueous fractions further supported this hypothesis. Depending on the extent of Mn2+ surface concentration, the isotope data indicated either sorption of IDMP to the mineral surface or electron transfer from IDMP to MnIV to be the rate-limiting step of the overall reaction. Our study sheds further light on the complex surface processes during MnO2 redox reactions and reveals abiotic oxidative transformation of APPs by MnO2 as a potential process contributing to widespread elevated AMPA concentrations in the environment.

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Current trends and challenges in the analysis of marine environmental contaminants by isotope ratio mass spectrometry

Kuznetsova

2023

Anal Bioanal Chem

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Stable carbon isotope analysis of polyphosphonate complexing agents by anion chromatography coupled to isotope ratio mass spectrometry: method development and application

Cited by 11 publications

References 39 publications

Two Pathways Compete in the Mn(II)-Catalyzed Oxidation of Aminotrismethylene Phosphonate (ATMP)

Two Pathways Compete in the Mn(II)-Catalyzed Oxidation of Aminotrismethylene Phosphonate (ATMP)

Transformation of Iminodi(methylene phosphonate) on Manganese Dioxides – Passivation of the Mineral Surface by (Formed) Mn²⁺

Current trends and challenges in the analysis of marine environmental contaminants by isotope ratio mass spectrometry

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Stable carbon isotope analysis of polyphosphonate complexing agents by anion chromatography coupled to isotope ratio mass spectrometry: method development and application

Cited by 11 publications

References 39 publications

Two Pathways Compete in the Mn(II)-Catalyzed Oxidation of Aminotrismethylene Phosphonate (ATMP)

Two Pathways Compete in the Mn(II)-Catalyzed Oxidation of Aminotrismethylene Phosphonate (ATMP)

Transformation of Iminodi(methylene phosphonate) on Manganese Dioxides – Passivation of the Mineral Surface by (Formed) Mn2+

Current trends and challenges in the analysis of marine environmental contaminants by isotope ratio mass spectrometry

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Transformation of Iminodi(methylene phosphonate) on Manganese Dioxides – Passivation of the Mineral Surface by (Formed) Mn²⁺