Elsevier

Journal of Chromatography A

Volume 1386, 20 March 2015, Pages 22-30
Journal of Chromatography A

Rapid screening and identification of multi-class substances of very high concern in textiles using liquid chromatography-hybrid linear ion trap orbitrap mass spectrometry

https://doi.org/10.1016/j.chroma.2015.01.077Get rights and content

Highlights

  • Multi-class SVHCs in textiles can be detected by HPLC-LTQ/Orbitrap.

  • The theoretical assignments of major product ions were predicted in present work.

  • MS2 confirmation can be more accurate with the theoretical m/z of predicted assignments.

Abstract

A new analytical method was established and validated for the analysis of 19 substances of very high concern (SVHCs) in textiles, including phthalic acid esters (PAEs), organotins (OTs), perfluorochemicals (PFCs) and flame retardants (FRs). After ultrasonic extraction in methanol, the textile samples were analyzed by high performance liquid chromatography-hybrid linear ion trap Orbitrap high resolution mass spectrometry (HPLC-LTQ/Orbitrap). The values of LOQ were in the range of 2–200 mg/kg. Recoveries at two levels (at the LOQ and at half the limit of regulation) ranged from 68% to 120%, and the repeatability was lower than 13%. This method was successfully applied to the screening of SVHCs in commercial textile samples and is useful for the fast screening of various SVHCs.

Introduction

Substances having potential serious and irreversible effects on human health and the environment are identified as substances of very high concern (SVHCs) [1]. SVHCs are one group of chemicals listed in the REACH, which is a European Union regulation adopted to protect humans and the environment from the risks posed by chemicals used in different areas while enhancing the competitiveness of the EU chemical industry [2]. SVHCs such as phthalic acid esters (PAEs), organotins (OTs), perfluorochemicals (PFCs) and flame retardants (FRs) are widely used in the manufacturing of textiles as plasticizers, stabilizers, stain-resistant materials and flame retardant additives, and their health effects have gained public attention. The European Chemicals Agency (ECHA) requires that the weight of an SVHC used at more than one thousand kilograms a year cannot exceed 0.1% of the total weight of the products; otherwise, the producer must abide by the notification obligation of REACH regulations. Additionally, other regulations such as OEKO-TEX® Standard 100 [3] and the Restricted Substances List (RSL) [4] define criteria for the use and limitations of SVHCs.

At present, methods used for the determination of PAEs, OTs, PFCs and FRs are mainly GC coupled with flame photometric detectors or mass spectrometric detectors [5], [6], [7] or LC-MS and LC-MS/MS [8], [9], [10], [11]. However, GC has some limitations for the analysis of SVHCs. As for OTs, GC inevitably includes a derivatization step that affects the accuracy and precision, especially for the analysis of complex biological or environmental matrices [12]. For most brominated flame retardants, the high temperature of GC may lead to their degradation [13]. LC can avoid these drawbacks. In particular, LC-MS/MS has high sensitivity and a wide linear range when operated in the selected reaction monitoring (SRM) mode. However, LC-MS/MS also has some limitations: the number of analytes is limited when operating in SRM mode. In full-scan mode, LC-MS/MS shows a low sensitivity, which limits the capabilities for screening applications. Moreover, because of “unit resolution” MS, these methods cannot be used for the analysis of untargeted compounds [14]. The Orbitrap with high resolution and high mass accuracy shows high sensitivity and selectivity, which can allow for the analysis of compounds in complex matrices with minimum or even no sample clean-up. The full-scan mode in the Orbitrap can provide data for all the compounds in a sample, which is useful for screening analysis.

To date, the Orbitrap has been used extensively in proteomics and food safety research [14], [15], [16], but few studies have been reported on the detection of SVHCs in textiles [17], [18]. Due to the difficulties in establishing a simultaneous method of analysis for multi-class compounds with different physicochemical properties, previous reports have mainly involved a single class of SVHCs. Therefore, the aim of this study is to develop a rapid and reliable screening and confirmation method for the detection of 19 SVHCs, including PAEs, OTs, PFCs and FRs, in textiles using the HPLC-LTQ/Orbitrap.

Section snippets

Materials and chemicals

Methanol, acetonitrile and dichloromethane (HPLC-grade) were purchased from Merck (Darmstadt, Germany). Formic acid (HPLC-grade) and ammonium acetate (HPLC-grade) were purchased from Sigma–Aldrich (Steinheim, Germany). Ultrapure Milli-Q water with 18.2  cm−1 was obtained using a Milli-Q® Advantage A10® system (Millipore, Milford, MA, USA). SVHC analytical standards, including dipentyl phthalate (DPP) (99.2%), diisopentyl phthalate (DIPP) (99.5%), n-pentyl-isopentyl phthalate (DniPP) (49.0%),

Results and discussion

In this work, 19 SVHCs were studied, including PAEs, OTs, PFCs and FRs. To obtain the best analytical conditions, the optimization of chromatographic separation and MS confirmation was necessary, especially for the detection of multi-class compounds that have a wide range of physicochemical properties.

Conclusion

An HPLC-LTQ/Orbitrap method for detection of multi-class SVHCs, including PAEs, OTs, PFCs and FRs, in textiles was developed and validated. The high mass resolution and full-scan mode with narrow mass extraction windows (5 ppm) can dramatically simplify the progress of pretreatment and improve method selectivity. Moreover, the use of Trace Finder and Mass Frontier software makes screening and confirmation more convenient and accurate. This method can be successfully applied to the determination

Acknowledgements

This work was supported by the General Administration of Quality Supervision, Inspection and Quarantine (AQSIQ), an industrial public service scientific research project of the Ministry of Science and Technology of the P. R. China (201310062), and the science and technology planning project of the AQSIQ of the P. R. China (2011IK037).

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