Simultaneous Determination of Chlorinated and Brominated Acetic Acids in Various Environmental Water Matrixes by High-Performance Liquid Chromatography–Inductively Coupled Plasma Tandem Mass Spectrometry without Sample Preparation

Abstract

The halogenated acetic acids (HAAs) are generally considered as environmental contaminants and are suspected to pose a major public health concern. The inductively coupled plasma mass spectrometry (ICPMS) has been improved by coupling with the tandem mass spectrometry technology (ICPMS/MS), enabling ultratrace determination of heteroatoms. There have been few reports about the determination of chlorine-containing analytes by high-performance liquid chromatography (HPLC)–ICPMS/MS but none about utilizing this technique for the speciation analysis of organic halogenated compounds in environmental matrixes. We report a rapid method for the simultaneous determination of up to nine chlorinated and brominated acetic acids by HPLC–ICPMS/MS in Austrian surface, ground, and tap water. The chromatographic separation of the main five regulated haloacetic acids (so-called HAA5: chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, and dibromoacetic acid) could be achieved in <6 min with limits of detection of 1.4–1.6 μg Cl L –1 and 0.8–1.5 μg Br L –1 for the chlorinated and brominated acetic acids, respectively. The method was validated through recovery experiments at four concentration levels (10–500 μg L –1 ) as well as by analyzing the U.S. Environmental Protection Agency (EPA) 552.2 CRM (certified reference material) in pure water and in three different water matrixes (tap, river, and groundwater), and thereby validated for repeatability (RSD% 1–10%), accuracy (±1.0–15%), and linearity ( r 2 = 0.9996–0.9999). The method fulfills the regulatory concentration limits by the EPA for HAA5 [maximum contaminant level (MCL) 60 μg L –1 ] and the limits currently being reviewed by the European Union for HAA9 (80 μg L –1 ) and demonstrates the advantages of HPLC–ICPMS/MS for the analysis of environmental water samples for halogen-tagged contaminants.

High-Resolution Elemental Mass Spectrometry Using LC-ICP-Nanospray-Orbitrap for Simultaneous and Species-Independent Quantitation of Fluorinated and Chlorinated Compounds

“…Currently, liquid chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS) is the method of choice for elemental speciation because of broad applicability of LC and robust elemental detection by ICP–MS for most elements. Moreover, analyte coverage has recently expanded by enhanced detection of Cl, Br, I, S, and P. − However, simultaneous detection of F and Cl has remained a significant challenge using this technique, while the need for such a capability has steadily risen. In particular, F and Cl appear in a sizable fraction of xenobiotics including pharmaceuticals , and environmental contaminants, making elemental speciation a desirable technology for quantitative nontargeted studies in these areas.…”

“…However, such instruments are not readily available for many users, while the current ICP-TOF instruments are generally limited to resolving powers <4000 . In contrast, more accessible ICP-QqQ-MS instruments have been utilized to resolve some of the isobaric interferences via ion–molecule reactions such as mass shifting Cl + to ClH 2 + . ,,, …”

“…Elemental speciation tracks analytes using their constituent atoms, 1 offering several attributes complementary to molecular detection: (1) compounds containing a targeted element are detected without regard for the compounds' structures. (2) The elemental selectivity and matrix tolerance improve detection for compounds of interest in the presence of concomitant molecules within a complex sample. (3) The elemental detection can be leveraged to quantify compounds without compound-specific standards.…”

“…9 In contrast, more accessible ICP-QqQ-MS instruments have been utilized to resolve some of the isobaric interferences via ion−molecule reactions such as mass shifting Cl + to ClH 2 + . 2,4,10,11 In regard to the fundamental ionization limitations in ICP− MS, F detection has been a long-standing challenge. The latest efforts for F analysis using ICP−MS have explored in-plasma formation of BaF + , 12−14 but with limited success in improving analytical performance because of difficulties in robust polyatomic ion formation inside a high-temperature ICP.…”

Semantic Annotation of Experimental Methods in Analytical Chemistry

“… Graph representations of the linear experimental sections in van Faassen et al, 28 Lajin and Goessler, 29 and Kocurek et al 30 (left), ”parallel” experiments in McAvan et al, 31 Pérez-Diez et al, 32 and Yan et al 17 (middle), and more complex methods in Venzac et al, 33 Flint et al, 34 and Lebede et al 35 (right). The graphs were rendered and the nodes colored as in Figure 1 .…”