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Quantification of polybrominated diphenyl ethers by means of GC-ICP-MS

(07.11.2018)


Background:
Trace and ultra-trace elemental analysis is most often based on the use of inductively coupled plasma-mass spectrometry (ICP-MS). The inductively coupled plasma (ICP) is a powerful and robust atomizer and ionization source that due to its high temperature (>6000 K) destroys molecules nearly quantitatively. On one side this is a disadvantage with respect to molecular information that is totally lost. On the other side this is releasing the elements from the compounds irrespectively of their structure allowing for compound-independent calibration (CIC). Using CIC, compounds can be quantified by using one of their elements as target analytes without having a standard for each compound. Also the ICP is relatively robust against matrix effects influencing the ion yield. This opens the possibility to quantify compounds in real samples by using one compound with the same target element as calibrant. However, since the molecular information is lost in the ICP, compounds must be separated before entering the ICP. Such can be done by hyphenating the ICP-MS with a separation module such as gas chrpmatography (GC) or high-performance liquid chromatography (HPLC).


The new sudy:
A Chinese group of researchers investigated whether CIC was applicable for the quantification of polybrominated diphenyl ethers (PBDEs) by using GC-ICP-MS.

PBDEs are organobromine compounds used as flame retardants. The family of PBDEs consists of 209 possible substances, which are called congeners (PBDE = C12H(10−x)BrxO (x = 1, 2, ..., 10 = m + n)). The number of isomers for mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and decabromodiphenyl ethers are 3, 12, 24, 42, 46, 42, 24, 12, 3 and 1, respectively.


The researchers tested the influence of the matrix, the GC  conditions and parameters of sample introduction on the response of 11 PBDEs.  The researchers found that under optimized conditions using pulsed splitless injection, the elemental response of bromine of each PBDE becomes very close to each other, alloying CIC at least for tri- to hepta-brominated compounds. The elemental response of bromine in PBDEs decreases with increasing boiling point because the analyte is not completely transferred to the ICP from the GC system.
 
When analysing real samples such as fish tissue, a pronounced matrix effect reduced the elemental response for bromium to about 68 to 98 % related to the reference standard. However this effect could be reduced to 99-106% by using an isomer for calibration.   



The original study:

Chi Zhang, Xiuqin Li, Yanling Chen, Chao Wei, Xiaomin Li, Qinghe Zhang, The compound-independent calibration of polybrominated diphenylethers isomers using gas chromatography-inductively coupled plasma mass spectrometry, J. Chromatogr. A, 1576 (2018) 120-130. DOI: 10.1016/j.chroma.2018.09.035



Used techniques and instrumentation:

Agilent 8800 Triple Quad ICP-MS



Related studies (newest first)

P. Novak, T. Zuliani, R. Milacic, J. Scancar, Development of an analytical method for the determination of polybrominated diphenyl ethers in mussels and fish by gas chromatography- inductively coupled plasma mass spectrometry, J. Chromatogr. A, 1524 (2017) 179-187. DOI: 10.1016/j.chroma.2017.09.059

C. Swart, F. Gantois, P. Petrov, J. Entwisle, H. Goenaga-Infante, M. Nousiainen,M. Bílsel, B. Binici, A. Gonzalez-Gago, D. Pröfrock, A.C. Gören, Potential reference measurement procedures for PBDE in surface water at levels required by the EU Water Frame Directive, Talanta, 152 (2016) 251–258. DOI: 10.1016/j.talanta.2016.01.066.

P. Novak, T. Zuliani, R. Milacic, J. Scancar, Development of an analytical method for the determination of polybrominated diphenyl ethers in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry, Anal. Chim. Acta, 915 (2016) 27–35. DOI: 10.1016/j.aca.2016.02.022.

A. González-Gago, D. Pröfrock, A. Prange, Optimizing GC-ICP-MS for ultra-trace quantification of PBDEs in natural water samples using species-specific isotope dilution, J. Anal. At. Spectrom., 30 (2015) 180–190. DOI: 10.1039/C4JA00112E.

P. Novak, T. Zuliani, R. Milacic, J. Scancar, Development of an analytical procedure for the determination of polybrominated diphenyl ethers in environmental water samples by GC-ICP-MS, Anal. Chim. Acta, 827 (2014) 64–73. DOI: 10.1016/j.aca.2014.04.020.

K. Kalachova, T. Cajka, C. Sandy, J. Hajslova, J. Pulkrabova, High throughput sample preparation in combination with gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-MS/MS): a smart procedure for (ultra)trace analysis of brominated flame retardants in fish, Talanta, 105 (2013) 109–116. DOI: 10.1016/j.talanta.2012.11.073.

Hiroaki Tao, Tetsuya Nakazato, Mikio Akasaka, Ramaswamy Babu Rajendran, Sofia Elouali, Plasma Gas-Switching Method for Gas Chromatography/Inductively Coupled Plasma Mass Spectrometry and Determination of Polybrominated Diphenyl Ethers with High Precision and Sensitivity, Anal. Sci., 24 (2008) 1529-1536. DOI: 10.2116/analsci.24.1529

R.F. Swarthout Jr, J.R. Kucklick, W.C. Davis, The determination of polybrominated diphenyl ether congeners by gas chromatography inductively coupled plasma mass spectrometry, J. Anal. At. Spectrom. 23 (2008) 1575-1580. DOI: 10.1039/b809173k.

Qin Xiao, Bin Hu, Jiankun Duan, Man He, and Wanqing Zu, Analysis of PBDEs in Soil, Dust, Spiked Lake Water, and Human Serum Samples by Hollow Fiber-Liquid Phase Microextraction Combined with GC-ICP-MS, J. Am. Soc. Mass Spectrom., 18/10 (2007) 1740–1748. DOI: 10.1016/j.jasms.2007.07.006

A.P. Vonderheide, M. Montes-Bayon, J.A. Caruso, Development andapplication of a method for the analysis of brominated flame retardants byfast gas chromatography with inductively coupled plasma mass spectrometric detection, J. Anal. At. Spectrom., 17 (2002) 1480–1485. DOI: 10.1039/b207521k.

Dietmar Glindemann, Gunter Ilgen, Reimer Herrmann, Thomas Gollan, Advanced GC/ICP-MS design for high-boiling analyte speciation and large volume solvent injection, J. Anal. At. Spectrom., 17/10 (2002) 1386-1389. DOI: 10.1039/b109951p

María Montes-Bayón, Manuel Gutiérrez Camblor, Jose Ignacio García Alonso, Alfredo Sanz-Medel, An alternative GC-ICP-MS interface design for trace element speciation, J. Anal. At. Spectrom., 14/9 (1999) 1317-1322. DOI: 10.1039/a901760g


EVISA News related to GC-ICP-MS for speciation analysis (newest first)


October 7, 2007: Agilent Technologies publishes Handbook of Hyphenated ICP-MS Applications
August 19, 2007: Thermo Fisher Scientific Introduces Speciation Analysis Capabilities For High Resolution ICP-MS

last time modified: November 7, 2018




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