A multi-technique approach for the quantification of 60 plasticizers and selected additives using GC- and LC-MS/MS and its application for beverages in the BfR MEAL study.

The development of multi-analyte methods is always challenging, especially when the target compounds derive from many different substance classes. We present an approach to analyze up to 60 additives - mainly plasticizer - including 28 phthalates and 32 further compounds such as sebacates, adipates, citrates, fatty acid amides, among others. Our multi-analyte multi-technique approach combines a single sample preparation step with one GC-MS/MS and two LC-MS/MS quantification methods. We demonstrate the applicability for beverages by a full validation in tomato juice matrix and determining the recoveries in apple juice, mulled wine, and spirits. The approach features good reproducibilities and high precisions with limits of quantification in the low µg·kg-1 food range, enabling the method to be applied for enforcement and especially for exposure investigations. In course of the BfR MEAL study, 16 pooled beverage samples were examined and - if at all - analytes were found only in very low concentrations.

Direct inlet probe ion mobility spectrometry.

Direct inlet probe (DIP) was used as an introduction and a pre-separation step for atmospheric pressure photoionization time-of-flight ion mobility spectrometry (APPI-TOF-IMS) for the first time. IMS is an analytical technique used to separate and identify ionized molecules in the gas phase and under atmospheric pressure based on their mobility. The utilization of DIP prior to IMS gives the possibility to introduce the analytes into the gas phase and provides an additional separation based on their vapor pressure. The proof-of-principle study was done on example of eight polycyclic aromatic hydrocarbons (PAHs) with the ring number from 2 to 5, namely naphthalene, fluorene, anthracene, phenanthrene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene. All these compounds are included in EPA priority pollutant list. Moreover, benzo[a]pyrene and benzo[k]fluoranthene are marked by EPA as probably carcinogen compounds and also included into SCF and EU lists. To increase the sensitivity of DIP-APPI-IMS the analysis was performed using a dopant assisted ionization method (benzene, 74mgL-1 in N2). It was found that the heating rate of the interface plays a crucial role for the whole analytical procedure. To prove the ability of this method to analyze PAHs in the mixture, the mixtures containing up to five PAHs were analyzed. The LODs for the analyzed compounds obtained with DIP-APPI-IMS were found to be in the tens- or hundreds-of-microgram-per-liter range. The obtained results are promising enough to ensure the potential of DIP as an introduction and a pre-separation step for ion mobility based methods.

Identification of terpenes and essential oils by means of static headspace gas chromatography-ion mobility spectrometry.

Static headspace gas chromatography-ion mobility spectrometry (SHS GC-IMS) is a relatively new analytical technique that has considerable potential for analysis of volatile organic compounds (VOCs). In this study, SHS GC-IMS was used for the identification of the major terpene components of various essential oils (EOs). Based on the data obtained from 25 terpene standards and 50 EOs, a database for fingerprint identification of characteristic terpenes and EOs was generated utilizing SHS GC-IMS for authenticity testing of fragrances in foods, cosmetics, and personal care products. This database contains specific normalized IMS drift times and GC retention indices for 50 terpene components of EOs. Initially, the SHS GC-IMS parameters, e.g., drift gas and carrier gas flow rates, drift tube, and column temperatures, were evaluated to determine suitable operating conditions for terpene separation and identification. Gas chromatography-mass spectrometry (GC-MS) was used as a reference method for the identification of terpenes in EOs. The fingerprint pattern based on the normalized IMS drift times and retention indices of 50 terpenes is presented for 50 EOs. The applicability of the method was proven on examples of ten commercially available food, cosmetic, and personal care product samples. The results confirm the suitability of SHS GC-IMS as a powerful analytical technique for direct identification of terpene components in solid and liquid samples without any pretreatment. Graphical abstract Fingerprint pattern identification of terpenes and essential oils using static headspace gas chromatography-ion mobility spectrometry.

Time-of-flight ion mobility spectrometry in combination with laser-induced fluorescence detection system.

A laser-induced fluorescence (LIF) was used as a complimentary detection system for time-of-flight ion mobility spectrometry (TOF-IMS). A LIF detection system is potentially faster than a conventional electrometer detector and can provide additional (to usual for IMS drift time) analytical information, namely wavelength of fluorescence maxima and fluorescence lifetime. Therefore, better discrimination ability can be expected. Additionally, the combination of IMS and LIF operates at atmospheric pressure. This allows fluorescence measurements of specified ions and ion clusters, which would not survive in a mass spectrometer. An IMS drift cell of open design with both the electrometer and LIF detectors was designed. The feasibility of IMS-LIF was demonstrated on the example of the Xanthene dye Rhodamine 6G (R6G). Electrospray was used as an ionization source. The release and desolvation of R6G ions from the electrospray with following IMS-LIF analysis were demonstrated. The effects of experimental parameters (e.g., ion gate and drift voltages, distance to ESI emitter) are demonstrated and discussed. The obtained results are promising enough to ensure the potential of LIF as a complimentary/alternative detection system for time-of-flight ion mobility spectrometry.

X-ray ionization differential ion mobility spectrometry.

X-ray was utilized as an ionization source for differential ion mobility spectrometry (DMS) for the first time. The utilization of this ionization source increases the potential of DMS system for on-site based applications. The influence of experimental parameters (e.g. accelerating voltage, filament current, and separation field) on the analysis of model compounds was investigated and discussed. It was found that both the positive and the negative reactive ion peaks [RIP(+) and RIP(-)] formed during X-ray ionization are identical with those observed with the traditional 63Ni radioactive ion source. This is especially notable for RIP(-), because the chemistry provided by other nonradioactive sources in the negative mode is more complicated or even different than that observed with a 63Ni source. Increase of either filament current or accelerating voltage resulted in increased intensity of both RIP(+) and RIP(-). However, because of the materials used for construction of X-ray adapter the maximal level of filament current and accelerating voltage used in this study were limited to 700mA and 5kV, respectively. Analytical performance was determined with two model compounds (acetone and methyl salicylate) using X-ray and directly compared to 63Ni ionization source. When X-ray was coupled to DMS, calculated LOD values were found to be within the range of 0.17-1.52ppbv/v (concentration in the carrier gas). These values are competitive with those calculated for DMS equipped with traditional 63Ni radioactive ionization source. The obtained results are promising enough to ensure the potential of X-ray as ionization source for DMS.

Fast detection of coliform bacteria by means of gas chromatography-differential mobility spectrometry.

In this study, we demonstrate that the combination of an enzymatic method (based on Colilert-18 medium) and gas chromatography-differential mobility spectrometry (GC-DMS) can reduce the time required for detection of coliform bacteria (including Escherichia coli) from 18 to 2.5 h. The presented method includes the incubation (~2.5 h) of the sample containing coliform bacteria in Colilert-18 medium. The incubation time of 2.5 h is required for the activation of the ß-galactosidase enzyme. Produced during the incubation biomarker o-nitrophenol (ONP) can be detected by means of GC-DMS within just 200 s. The detection limit for ONP was 45 ng (on-column). The method developed in this work provides significantly shorter analysis time compared with standard methods, and can be potentially adapted to the field conditions. Therefore, this method is a promising tool for an early detection of coliform bacteria (including E. coli). Graphical Abstract Fast detection of coliform bacteria by means of GC-DMS.

Low-temperature plasma ionization differential ion mobility spectrometry.

A low-temperature plasma (LTP) was used as an ionization source for differential ion mobility spectrometry (DMS) for the first time. This ionization source enhances the potential of DMS as a miniaturized system for on-site rapid monitoring. The effects of experimental parameters (e.g., discharge/carrier gas composition and flow rate, applied voltage) on the analysis of model aromatic compounds were investigated and discussed. It was found that the nature of reactant ion positive (RIP) is dependent on the discharge/carrier gas composition. The best response to the analyte was achieved when pure nitrogen was used as the discharge/carrier gas. The ability to perform analysis with zero helium consumption is especially attractive in view of the potential application of LTP-DMS for online (and on-site) monitoring. Analytical performance was determined with six environmentally relevant model compounds (benzene, toluene, ethylbenzene, p-xylene, 1,2,4-trimethylbenzene, and naphthalene) using LTP and directly compared to APPI and APCI ((63)Ni) ionization sources. When LTP was coupled to DMS, calculated LOD values were found to be in the range of 35-257 ng L(-1) (concentration in the carrier gas). These values are competitive with those calculated for two DMS equipped with traditional ionization sources (APPI, (63)Ni). The obtained results are promising enough to ensure the potential of LTP as ionization source for DMS.

Development of an electrospray-(63)Ni-differential ion mobility spectrometer for the analysis of aqueous samples.

The feasibility of an electrospray coupled with a (63)Ni-differential ion mobility spectrometer (DMS) for the analysis of water samples was proven on examples of 2-hexanone, fluoroacetamide, l-nicotine and 1-phenyl-2-thiourea water solutions. The model substances were selected in order to cover the vapor pressure range of 0.3-1467 Pa. To reduce the inline humidity, which demonstrates a strong influence on the analyte compensation voltage, two units with a desolvation region lengths of 15.5 and 7 mm were examined. The counter gas (heated to 100 °C nitrogen) with flow rates of 100 mL min(-1) and 30 mL min(-1) for short and long desolvation units, respectively, was essential for the efficient reduction of humidity. The reduction of water content in the carrier gas to 2.2-2.4 g m(-3) and to 1.8-2.0 g m(-3) for the short and long desolvation unit, respectively, was achieved at an electrospray flow rate of 1000 nL min(-1). With this adjusted experimental setup, the detection of model substances in the water solutions, in the range of 0.1-50 mg L(-1), was performed. No correlation between the vapor pressure and signal area was observed. The high stability of the inline humidity, and the correspondingly stable carrier gas flow rate, were found to be essential for an acceptable reproducibility.