Method validation and geochemical modelling of chromium speciation in natural waters

Abstract The study focuses on validating reference methods such as ICP-OES and ICP-MS for detecting ultra-trace levels of chromium in groundwater, where concentrations are typically very low. Additionally, it verifies a hyphenated technique, IC-ICP-MS, for determining naturally occurring Cr(VI) in t...

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Main Authors: Piotr Rusiniak, Katarzyna Wątor, Ewa Kmiecik, Vesna Ristić Vakanjac
Format: Article
Language:English
Published: Nature Portfolio 2024-12-01
Series:Scientific Reports
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Online Access:https://doi.org/10.1038/s41598-024-77425-3
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author Piotr Rusiniak
Katarzyna Wątor
Ewa Kmiecik
Vesna Ristić Vakanjac
author_facet Piotr Rusiniak
Katarzyna Wątor
Ewa Kmiecik
Vesna Ristić Vakanjac
author_sort Piotr Rusiniak
collection DOAJ
description Abstract The study focuses on validating reference methods such as ICP-OES and ICP-MS for detecting ultra-trace levels of chromium in groundwater, where concentrations are typically very low. Additionally, it verifies a hyphenated technique, IC-ICP-MS, for determining naturally occurring Cr(VI) in tested waters. The validation process involved various chromium analysis variants, including isotopes 52Cr and 53Cr in ICP-MS and IC-ICP-MS techniques, along with specific emission lines in the ICP-OES technique. Statistical data processing revealed that the achieved limits of quantification for Cr in different techniques ranged from 0.053 µg/L to 1.3 µg/L, with the associated measurement uncertainty estimated between 14% and 19% (at a coverage factor k = 2, 95%). For speciation analysis, it was possible to quantitatively determine Cr(VI) at concentrations as low as 0.12 µg/L, with the measurement uncertainty ranging between 10% and 14%. The Kruskal-Wallis test indicated that for the 14 water samples analysed, there was no statistically significant difference in the results obtained using different analytical techniques (p > 0.05). The geochemical modelling approach applied enhances the understanding of chromium speciation in water samples, verifying the accuracy of speciation analysis and identifying specific ion forms in which Cr(III) and Cr(VI) occur. In the analysed water samples, the concentration of Cr(VI) ranges between 0.13 and 35 µg/L, with the primary form identified as the oxoanion CrO4 2−. Importantly, statistical tests demonstrated no statistically significant differences between the total chromium concentration in water and the concentration of Cr(VI), indicating that the entire concentration of total chromium corresponds to Cr(VI) speciation.
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spelling doaj-art-728ad49cefb544fc8294189d2feb3f082025-08-20T02:31:46ZengNature PortfolioScientific Reports2045-23222024-12-0114111310.1038/s41598-024-77425-3Method validation and geochemical modelling of chromium speciation in natural watersPiotr Rusiniak0Katarzyna Wątor1Ewa Kmiecik2Vesna Ristić Vakanjac3AGH University of KrakowAGH University of KrakowAGH University of KrakowFaculty of Mining and Geology, University of BelgradeAbstract The study focuses on validating reference methods such as ICP-OES and ICP-MS for detecting ultra-trace levels of chromium in groundwater, where concentrations are typically very low. Additionally, it verifies a hyphenated technique, IC-ICP-MS, for determining naturally occurring Cr(VI) in tested waters. The validation process involved various chromium analysis variants, including isotopes 52Cr and 53Cr in ICP-MS and IC-ICP-MS techniques, along with specific emission lines in the ICP-OES technique. Statistical data processing revealed that the achieved limits of quantification for Cr in different techniques ranged from 0.053 µg/L to 1.3 µg/L, with the associated measurement uncertainty estimated between 14% and 19% (at a coverage factor k = 2, 95%). For speciation analysis, it was possible to quantitatively determine Cr(VI) at concentrations as low as 0.12 µg/L, with the measurement uncertainty ranging between 10% and 14%. The Kruskal-Wallis test indicated that for the 14 water samples analysed, there was no statistically significant difference in the results obtained using different analytical techniques (p > 0.05). The geochemical modelling approach applied enhances the understanding of chromium speciation in water samples, verifying the accuracy of speciation analysis and identifying specific ion forms in which Cr(III) and Cr(VI) occur. In the analysed water samples, the concentration of Cr(VI) ranges between 0.13 and 35 µg/L, with the primary form identified as the oxoanion CrO4 2−. Importantly, statistical tests demonstrated no statistically significant differences between the total chromium concentration in water and the concentration of Cr(VI), indicating that the entire concentration of total chromium corresponds to Cr(VI) speciation.https://doi.org/10.1038/s41598-024-77425-3Hexavalent chromiumIC-ICP-MSHyphenated techniquesGeochemical modellingSpeciation analysisMethod validation
spellingShingle Piotr Rusiniak
Katarzyna Wątor
Ewa Kmiecik
Vesna Ristić Vakanjac
Method validation and geochemical modelling of chromium speciation in natural waters
Scientific Reports
Hexavalent chromium
IC-ICP-MS
Hyphenated techniques
Geochemical modelling
Speciation analysis
Method validation
title Method validation and geochemical modelling of chromium speciation in natural waters
title_full Method validation and geochemical modelling of chromium speciation in natural waters
title_fullStr Method validation and geochemical modelling of chromium speciation in natural waters
title_full_unstemmed Method validation and geochemical modelling of chromium speciation in natural waters
title_short Method validation and geochemical modelling of chromium speciation in natural waters
title_sort method validation and geochemical modelling of chromium speciation in natural waters
topic Hexavalent chromium
IC-ICP-MS
Hyphenated techniques
Geochemical modelling
Speciation analysis
Method validation
url https://doi.org/10.1038/s41598-024-77425-3
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AT katarzynawator methodvalidationandgeochemicalmodellingofchromiumspeciationinnaturalwaters
AT ewakmiecik methodvalidationandgeochemicalmodellingofchromiumspeciationinnaturalwaters
AT vesnaristicvakanjac methodvalidationandgeochemicalmodellingofchromiumspeciationinnaturalwaters