Highly sensitive determination of polybrominated diphenyl ethers in surface water by GC coupled to high-resolution MS according to the EU Water Directive 2008/105/EC

Abstract

The analysis of brominated flame retardants, such as polybrominated diphenyl ethers (PBDEs), has received increased interest because of their toxicity and ubiquity. According to European Union Directive 2008/105/EC, the development of highly sensitive and selective methods capable of determining PBDEs at low concentration levels (<0.5 ng/L) is necessary. In this work, an SPE method was developed for the analysis of the six PBDEs (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154) specified by the aforementioned directive in surface waters. The analyses were performed by GC coupled to magnetic sector high-resolution MS. The conditions were also optimized to detect the target compounds in water samples at concentrations below the environmental quality standards established by European legislation. The validated method provided adequate linearity (determination coefficient, R(2) ≥ 0.9960), recovery (101-120%, except for BDE-47 at 5 ng/L, 127%), and precision values (RSD < 20%) at two fortification levels (0.2 and 5 ng/L). The method showed LODs and LOQs ranging from 0.02 to 0.05 and from 0.05 to 0.1 ng/L, respectively. The method was applied in surface water samples, allowing the determination of these compounds at the limits established by current legislation.

Optimizing GC-ICP-MS for ultra-trace quantification of PBDEs in natural water samples using species-specific isotope dilution

“…The LOQs obtained by LLE-GC-ICP-IDMS are at the same level or lower than those obtained by SPE-GC-EI-HRMS, especially for the higher brominated congeners, which usually show lower signals when using an EI source. 11 Conversely, the ICP is a hard ionization source which generates only elemental ions and the expected instrumental response should be proportional to the amount of target atoms reaching the plasma and independent of the molecular structure of the analyte. This means that higher brominated congeners, which contain a higher amount of bromine atoms, should provide a higher instrumental response in ICP-MS leading to lower ILODs.…”

“…9 The overall low concentrations of the target analytes in water, derived from their high lipophilicity, together with the challenging requirements dened by the WFD for methods that are applicable to the determination of priority pollutants, requires the development of suitable methodologies combining sensitive detection approaches with accurate and precise analytical techniques in terms of sample preparation, calibration and quantication. 10,11 Besides the mentioned techniques, typically used for the analysis of PBDEs, as well as some other semivolatile halogenated organic pollutants e.g. PCBs, hyphenated approaches based on Inductively Coupled Plasma Mass Spectrometry (ICP-MS), commonly considered only suitable for the determination of heavy metals, have recently gained a lot of interest also as sensitive detection methods for some heteroatoms such as phosphorus, sulphur, chlorine, bromine or iodine.…”

Enrichment and determination of polybrominated diphenyl ethers in environmental water samples by magnetic solid‐phase extraction with core–shell magnetic carbon microspheres before gas chromatography with mass spectrometry

“…Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants, which are found in building materials, electronics, furnishings, and textiles , ensuring our safety but also causing great damage to the environment and human health . In recent years, increasing levels of PBDEs have been detected in the global environment as well as in human tissue and other biota .…”

Determination of Aroclor 1260 in soil samples by gas chromatography with mass spectrometry and solid-phase microextraction

“…GC coupled with an electron capture detector or MS detector are the most widely accepted and reliable techniques for the quantification of PCBs because of their high sensitivity, good selectivity, and reproducibility . Traditional chemical analyses are usually very time‐consuming and expensive due to the requirement of extensive extraction and cleanup procedures that are coupled to lengthy high‐resolution gas chromatographic programs . For soil samples, the US Environmental Protection Agency (EPA) recommends a variety of different extraction methods, including Soxhlet extraction, automated Soxhlet extraction, pressurized fluid extraction, microwave extraction, ultrasonic extraction, and supercritical fluid extraction .…”