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Home ›› About Speciation ›› Speciation News

Phosphorus Speciation Analysis Using Ion Chromatography Coupled with ICP-MS to Investigate Transformations on Reactive Surfaces

(07.09.2025)

A collaborative team of researchers from the United States and Ireland has developed a robust analytical method for phosphorus (P) speciation. By coupling ion chromatography (IC) with inductively coupled plasma mass spectrometry (ICP-MS), they achieved highly sensitive detection and quantification of diverse phosphorus compounds, enabling detailed studies of transformation pathways on reactive surfaces.

Background:
Phosphorus (P) is a vital yet often limiting element in terrestrial and aquatic ecosystems. It occurs in numerous chemical forms, broadly classified as:

Inorganic P – phosphates (HxPO4(3–x)–), reduced oxyanions (e.g., phosphine, hypophosphite, phosphite), condensed phosphates (pyro-, meta-, polyphosphates).
Organic P – such as phospholipids and nucleotides.

These compounds span wide concentration ranges across environmental compartments, complicating analysis—particularly when molecular structures are unknown. Transformations among P species strongly influence their bioavailability, plant uptake, microbial toxicity, and treatability.

Understanding the reactivity of organic and inorganic P is critical for developing mitigation and recovery strategies. For example, converting non-reactive P to phosphate enables removal from wastewater, reducing eutrophication risks, while recovered P can be valorized as struvite or biosolids for agricultural use. Alongside biological transformations mediated by microbes, plants, or animals, abiotic, surface-catalyzed hydrolysis has emerged as a promising pathway. Notably, binuclear lanthanide complexes such as cerium oxide (CeO₂) are highly effective dephosphorylating agents.

The Study:

To investigate phosphorus transformations on reactive surfaces, the research team established an advanced IC-ICP-MS method. The technique provides:

High sensitivity across both inorganic and organic species.
Compatibility with complex environmental matrices.
Direct quantification without extensive sample pretreatment or prior knowledge of P structures.

Chromatographic Separation:
Eight P compounds were separated using a high-performance liquid chromatography (HPLC) system (NexSAR 200, PerkinElmer) equipped with an anion exchange column (IonPac AS17-C, 4 × 250 mm) and guard column (IonPac AG17-C, 4 × 50 mm, ThermoFisher). Separations were conducted at 25 °C with eluents:

A: ultrapure water (pH 7.0)
B: 100 mM NaOH in ultrapure water (pH 13.5).

Coupling with ICP-MS

The IC column effluent was directed via PEEK capillary into the nebulizer of an ICP-MS system (NexION 1000, PerkinElmer) fitted with a cyclonic spray chamber thermostated at 2 °C. Instrument calibration and plasma optimization were performed daily. To minimize spectral interferences on ^31P⁺ (e.g., ^14N^16O^1H⁺, ^15N^16O⁺, ^12C^18O^1H⁺), helium kinetic energy discrimination (KED) mode was applied.

Environmental and Hydrolysis Experiments

Environmental water samples (lake, tap, wastewater) were analyzed for total P following microwave digestion and ICP-MS quantification. Hydrolysis experiments with CeO₂ suspensions were conducted in foil-wrapped flasks under agitation (200 rpm). Samples were collected at multiple time points (0 to 72 h), centrifuged (10,000 rpm, 10 min), filtered (0.22 μm), and analyzed by IC-ICP-MS within two hours.

Key Findings

Environmental matrices:

Anaerobic digestate supernatant contained ~99% phosphate.
Pony Lake fulvic acid revealed two distinct organic P peaks differing in size/polarity.

Transformation pathways:

IC-ICP-MS effectively tracked hydrolysis products from both inorganic and organic precursors on reactive CeO₂ surfaces.
Triphosphate and adenosine triphosphate (ATP) underwent rapid dephosphorylation.
Hydrolysis occurred stepwise, with the loss of single phosphate groups rather than larger moieties.

Conclusion

The developed IC-ICP-MS method provides a powerful platform for phosphorus speciation across diverse matrices. It enables simultaneous detection of inorganic and organic compounds with minimal sample preparation, offering new insights into transformation mechanisms on reactive surfaces such as CeO₂. This approach holds promise for advancing P cycling research, environmental monitoring, and the design of recovery strategies.

The original study:

Tingyu Li, Austin Henke, Baile Wu, Zhe Zhao, Alireza Farsad, Michael Serpa, Pierre Herckes, Paul Westerhoff, Phosphorus Speciation Using Ion Chromatography Coupled with ICP-MS Elucidates Transformations of Phosphorus Compounds on Reactive Surfaces, Water Res., 288 (2025) 124554. DOI: 10.1016/j.watres.2025.124554

Used techniques and instrumentation:

PerkinElmer NexSar 200 HPLC System

PerkinElmer NexION 1000 ICP-MS System

Related studies (newest first):

M. Athmer, A.M. Röhnelt, T.J. Maas, S.B. Haderlein, U. Karst, Comprehensive IC-ICP-MS analysis of polyphosphonates and their transformation products, J. Chromatogr. A, 1748 (2025) 465843. DOI: 10.1016/j.chroma.2025.465843.

A.S. Baidya, E.E. Stüeken, On-line chloride removal from ion chromatography for trace-level analyses of phosphite and other anions by coupled ion chromatography–inductively coupled plasma mass spectrometry, Rapid Commun. Mass Spectrom., 38/1 (2024) e9665. DOI: 10.1002/rcm.9665

J.J. Carroll, C. Sprigg, G. Chilvers, I. Delso, M. Barker, F. Cox, D. Johnson, C.A. Brearley, LC-ICP-MS analysis of inositol phosphate isomers in soil offers improved sensitivity and fine-scale mapping of inositol phosphate distribution, Methods Ecol. Evol., 15/3 (2024) 530-543. DOI: 10.1111/2041-210X.14292

Y.Q. Jia, S.H. Sun, S. Wang, X. Yan, J.S. Qian, B.C. Pan, Phosphorus in water: A review on the speciation analysis and species specific removal strategies, Crit. Rev. Environ. Sci. Technol., 53/4 (2023) 435-456. DOI: 10.1080/10643389.2022.2068362

S. Otto, B. May, R. Schweiggert, Comparison of ion chromatography conductivity detection (IC-CD) and ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) for the determination of phosphonic acid in grapevine plant parts, wine, and soil, J. Agric. Food Chem., 70/33 (2022) 10349-10358. DOI: 10.1021/acs.jafc.2c02782

C. Vosse, G.M. Thyssen, M. Sperling, U. Karst, H. Hayen, Complementary approach for analysis of phospholipids by liquid chromatography hyphenated to elemental and molecular mass spectrometry, Anal. Sci. Adv., 1/1 (2020) 46-55. DOI: 10.1002/ansa.20190009

X.Y. Zhu, J. Ma, Recent advances in the determination of phosphate in environmental water samples: Insights from practical perspectives, TrAC Trends Anal. Chem., 127 (2020), 115908. DOI: 10.1016/j.trac.2020.115908

D. Armbruster, U. Müller, O. Happel, Characterization of phosphonate-based antiscalants used in drinking water treatment plants by anion-exchange chromatography coupled to electrospray ionization time-of-flight mass spectrometry and inductively coupled plasma mass spectrometry, J. Chromatogr. A, 1601 (2019) 189-204. DOI: 10.1016/j.chroma.2019.05.014

B. Lajin, W. Goessler, Direct speciation analysis of organophosphorus environmental pollutants in water by HPLC-ICPMS/MS, Talanta, 196 (2019) 357-361. DOI: 10.1016/j.talanta.2018.12.075

A.K. Venkatesan, W.H. Gan, H. Ashani, P. Herckes, P.K. Westerhoff, Size exclusion chromatography with online ICP-MS enables molecular weight fractionation of dissolved phosphorus species in water samples, Water Res., 133 (2018) 264-271. DOI: 10.1016/j.watres.2018.01.048

D.B. Chu, K. Klavins, G. Koellensperger, S. Hann, Speciation analysis of sugar phosphates via anion exchange chromatography combined with inductively coupled plasma dynamic reaction cell mass spectrometry – optimization for the analysis of yeast cell extracts, J. Anal. At. Spectrom., 29/5 (2014) 915-925. DOI: 10.1039/C4JA00043A

A. Rugova, M. Puschenreiter, J. Santner, L. Fischer, S. Neubauer, G. Koellensperger, S. Hann, Speciation analysis of orthophosphate and myo-inositol hexakisphosphate in soil- and plant-related samples by high-performance ion chromatography combined with inductively coupled plasma mass spectrometry, J. Sep. Sci., 37/14 (2014) 1711-1719. DOI: 10.1002/jssc.201400026

C.K. Schmidt, B. Raue, H.J. Brauch, F. Sacher, Trace-level analysis of phosphonates in environmental waters by ion chromatography and inductively coupled plasma mass spectrometry, Int. J. Environ. Anal. Chem., 94/4 (2014) 385-398. DOI: 10.1080/03067319.2013.831410

O.J. Lechtenfeld, B.P. Koch, W. Geibert, K.-U. Ludwichowski, G. Kattner, Inorganics in organics: Quantification of organic phosphorus and sulfur and trace element speciation in natural organic matter using HPLC-ICPMS, Anal. Chem., 83/23 (2011) 8968-8974. DOI: 10.1021/ac201765a

Z.L. Chen, W.X. He, M. Beer, M. Megharaj, R. Naidu, Speciation of glyphosate, phosphate and aminomethylphosphonic acid in soil extracts by ion chromatography with inductively coupled plasma mass spectrometry with an octopole reaction system, Talanta, 78/3 (2009) 852-856. DOI: 10.1016/j.talanta.2008.12.052

M. Popp , S. Hann, A. Mentler, M. Fuerhacker, G. Stingeder, G. Koellensperger, Determination of glyphosate and AMPA in surface and waste water using high-performance ion chromatography coupled to inductively coupled plasma dynamic reaction cell mass spectrometry (HPIC–ICP–DRC–MS). Anal. Bioanal. Chem., 391/2 (2008) 695-9. DOI: 10.1007/s00216-008-2037-5

Z.X. Guo, Q.T. Cai, Z.Q. Yang, Ion chromatography/inductively coupled plasma mass spectrometry for simultaneous determination of glyphosate, glufosinate, fosamine and ethephon at nanogram levels in water, Rapid Commun. Mass Spectrom., 21/10 (2007) 1606-1612. DOI: 10.1002/rcm.3003

Z.X. Guo, Q.T. Cai, Z.G. Yang, Determination of glyphosate and phosphate in water by ion chromatography—inductively coupled plasma mass spectrometry detection, J. Chromatogr. A, 1100/2 (2005) 160-167. DOI: 10.1016/j.chroma.2005.09.034

B.B.M. Sadi, A.P. Vonderheide, J.A. Caruso, Analysis of phosphorus herbicides by ion-pairing reversed-phase liquid chromatography coupled to inductively coupled plasma mass spectrometry with octapole reaction cell, J. Chromatogr. A, 1050/1 (2004) 95-101. DOI: 10.1016/j.chroma.2004.04.083