Challenges and trends for halogen determination by inductively coupled plasma mass spectrometry: A review.

RATIONALE: In this review, works published in the past 25 years for fluorine, chlorine, bromine, and iodine determination in several matrices by inductively coupled plasma mass spectrometry (ICP-MS) were covered. Usually, the determination of halogens has been performed by ICP-MS using a previous sample preparation step or, more recently, by direct analysis of solid or liquid samples. METHODS: Methods based on combustion, extraction, pyrohydrolysis, sample dilution in organic or aqueous medium, and wet digestion, among others, are discussed. Moreover, the recent applications of methods based on laser ablation (LA) and electrothermal vaporization (ETV) coupled to ICP-MS are discussed. RESULTS: The main challenge for methods using sample preparation has been to obtain a final solution compatible with ICP-MS, as well as to overcome problems related to analyte losses and contamination. Interferences due to the presence of dissolved organic compounds in solution, enhancement or suppression of ionization of analytes, and related matrix effects have been of concern when using ICP-MS. For the determination of halogens by ICP-MS using LA and ETV systems, some limitations related to the difficulty of calibration are pointed out, impairing the widespread use of this approach. CONCLUSIONS: A critical view is presented for further halogen determination by ICP-MS, mainly for matrices considered difficult to digest using conventional protocols.

Determination of inorganic contaminants in carbon nanotubes by plasma-based techniques: Overcoming the limitations of sample preparation.

In this work, sample preparation of carbon nanotubes (CNTs) for further determination of inorganic contaminants was investigated using a microwave-assisted wet digestion single reaction chamber system (MAWD-SRC). Analytes (Al, As, Ca, Cd, Co, Cr, Fe, La, Mg, Mo, Ni, Pb and Zn) were determined in CNTs by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS, except for Al, Ca, Fe and Mg). Method parameters were evaluated, as the mass of CNT (25-300 mg), the temperature (220-270 °C) and the time (35-75 min) of irradiation program. The accuracy was evaluated by using a certified reference material (CRM) of CNT and also by comparison of the results with those obtained using neutron activation analysis (NAA) and high resolution continuum source graphite furnace atomic absorption spectrometry with direct solid sampling (DSS-HR-CS-GF AAS). Quantitative recoveries for all elements were obtained using 275 mg of CNTs, 6 mL of 14.4 mol L-1 HNO3 and 0.5 mL of 30% H2O2 with an irradiation program of 65 min (35 min at 270 °C). No statistical difference was observed between the results obtained after the decomposition of CNTs by MAWD-SRC with those obtained by NAA and DSS-HR-CS-GF AAS. No difference was also observed for the results using the proposed method and the values for the CRM of CNT. The use of MAWD-SRC showed good performance for CNTs digestion using relatively high sample mass (up to 275 mg), contributing to low limits of quantification (LOQs) and overcoming the current limitations of sample preparation. To the best knowledge of the authors, this work reports the highest sample mass feasible to be decomposed using wet digestion for CNTs among the methods proposed in literature.

Determination of halogens and sulfur in high-purity polyimide by IC after digestion by MIC.

In this work, a method for sample preparation of high-purity polyimide was proposed for halogens and sulfur determination by ion chromatography (IC) with conductivity detection and, alternatively, by inductively coupled plasma mass spectrometry (ICP-MS). A relatively high polyimide mass (600mg) was completely digested by microwave-induced combustion (MIC) using 20bar of O2 and 50mmolL(-1) NH4OH as absorbing solution. These conditions allowed final solutions with low carbon content (<10mgL(-1)) and suitable pH for analysis by both IC and ICP-MS. The accuracy was evaluated using a certified reference material of polymer for Cl, Br and S and spike recovery experiments for all analytes. No statistical difference (t-test, 95% of confidence level) was observed between the results obtained for Cl, Br and S by IC after MIC and the certified values. In addition, spike recoveries obtained for F, Cl, Br, I and S ranged from 94% to 101%. The proposed method was suitable for polyimide decomposition for further determination of halogens and sulfur by IC and by ICP-MS (Br and I only). Taking into account the lack of methods and the difficulty of bringing this material into solution, MIC can be considered as a suitable alternative for the decomposition of polyimide for routine quality control of halogens and sulfur using IC or ICP-MS.