Martin
Zühlke
*,
Leonard
Genin
,
Daniel
Riebe
and
Toralf
Beitz
University of Potsdam, Physical Chemistry, Karl-Liebknecht-Str. 24-25, 14476 Potsdam, Germany
First published on 18th January 2024
Careful quality control of complex matrices such as fuels and food is necessary due to the prevalence of counterfeit and pirated goods in global trade. The addition of taggants (indicator substances) to products or their packaging helps to ensure traceability. In order to prevent the mixing of different liquid products, such as different taxed fuels, invisible labelling (marker) can be used to detect illegal activities. This study investigates the qualitative and quantitative analysis of markers in complex fuel matrices using Resonance-Enhanced Multiphoton Ionisation (REMPI) Ion Mobility Spectrometry (IMS). The potential of REMPI as a selective ionisation technique for the detection of markers is highlighted, particularly with respect to minimizing matrix background and the possibility of detection without chromatographic pre-separation. Finding a suitable marker–wavelength combination that provides a suitable marker-to-matrix ratio allows selective ionization of markers while minimising matrix background. Matrix analysis shows that higher excitation wavelengths result in reduced matrix signals, with the low intensities observed at 355 nm for diesel and petrol matrices. Several candidate markers are evaluated based on the criteria of intense signal at 355 nm and non-leachability for the low tax labelling. The analytical performance of selected markers is evaluated, with a focus on the charge transfer reaction (CTR) between markers and matrix components. Our findings demonstrate the potential of REMPI-IMS for marker analysis in fuels without the need for chromatographic pre-separation, providing a promising approach for detecting illegal or fraudulent activities in the supply chain.
Blending of different taxed fuels is a prominent example of tax avoidance worldwide. Mixing untaxed fuels (e.g. from crude oil theft, fuel piracy and illegal trade) with low or high taxed fuels can increase profits enormously. While the regular tax on petrol or diesel is paid by the customer, the full tax has not been previously paid and therefore represents an additional profit for the distributor. As a result, oil producing and processing countries as well as the petrol industry add unique chemical signatures or a concentrate of an indicator solution to a fuel (known as tagging) in order to help track its distribution and identify any illegal or fraudulent activity in the supply chain.7–9 Different taggants can be used to label the fuel at various points including refineries, terminals, or blending facilities. The requirements for potential taggants are high: inert, non-leachable, inexpensive, easy to detect, safe to use and without an effect on the product's properties. To detect diluted or contaminated products, the marker must also be quantifiable in the complex matrix and tolerant of matrix changes.10 Tagging substances can be distinguished between covert (invisible markers) and overt (visible dyes).10 Commonly used qualitative and quantitative laboratory analyses are based on a pre-separation step, usually performed by high performance liquid chromatography (HPLC) coupled to ultraviolet-visible (UV-VIS) absorption11 or fluorescence spectroscopy as well as gas chromatography (GC) coupled to mass spectrometry (MS).12 Outside the laboratory, labeled fuel samples can be injected directly into portable spectrophoto-/spectrofluorometers or Raman spectrometers.13 Overall, there's little literature available on marker substances as it's always a struggle between governments or companies and counterfeiters, who also counterfeit the marker substances.14 Thus, implementing a completely new and even mobile analysis technique, which analyses qualitatively and potentially quantitatively, could significantly improve the situation for the manufacturers.
Ion mobility (IM) spectrometry is a robust, inexpensive, and mobile analytical technique that separates ions based on their mobility (shape and size of the ions). At atmospheric pressure ions move through an electric field gradient inside a tube of a defined length to a detector and collide with inert gas molecules in the tube. Due to their different cross sections (depending on shape and size) the ions are detected at different drift times which are related to their ion mobility.15 However, the resolving power (Rp) of most commercially available IM spectrometers is low, with Rp < 60.16 Thus, ionization sources based on chemical ionization at atmospheric pressure (APCI) or single photon ionization (SPI) would not allow detection of the marker alongside the broad matrix signal in the presence of a complex matrix like fuel.17 Therefore, chromatographic pre-separation in the gas phase is used to detect markers with these ionisation techniques, requiring longer analysis times and extensive instrumentation.18,19
Resonance-Enhanced Multiphoton Ionization (REMPI), on the other hand, allows selective ionization of markers and minimizes the matrix background at optimal laser parameters.20 REMPI is an ionization technique that consists of two steps. First, m photons are simultaneously absorbed by an atom or small molecule in the sample which excites the molecule into a higher (e.g. first) electronic state. Second, n photons are absorbed by molecule in the first electronic state and create a free electron or electron–ion pair. The simplest form of this m + n REMPI is 1 + 1 REMPI where photons of the same wavelength are absorbed in the first and second step.21 If the energy of the photon and the first electronic state is close to half the energy of the ionisation potential (resonance condition), the REMPI process is more efficient and therefore selective. Hence, a good marker–wavelength combination is necessary for a substantial marker-to-matrix ratio.22
REMPI was first implemented for spectroscopic purposes, but soon became increasingly used as an ionisation technique for polyatomic compounds in MS.23–25 Until now, it has been used for process and quality control of polycyclic aromatic hydrocarbons (PAHs) and polymers, often in conjunction with GC.20,26,27 PAH studies performed with tuneable lasers were done at laser wavelengths below 300 nm, although 1 + 1 REMPI with amine compounds would allow higher wavelengths.28,29 Almost exclusively, REMPI-MS studies have been limited to the intense UV-pulses between 193 nm and 350 nm.30
REMPI-IM spectrometry has been used so far mainly for fundamental studies, e.g. photofragmentation, charge transfer reaction monitoring, trace detection and aromatics sensing.31–36 In this study, we present qualitative and quantitative analysis of markers in fuels (petrol/diesel) using REMPI-IM spectrometry without chromatographic pre-separation. Fuel as a complex matrix with many PAHs required the use of laser wavelengths above 300 nm, or even 350 nm to obtain easily interpretable marker signals. Therefore, the marker candidates need to be studied intensively in order to select the best wavelength–marker combination. The candidates were evaluated for analytical performance (reproducibility and accuracy) with a focus on the charge transfer reaction (CTR) to or from matrix components.
Samples were prepared in small vials by pipetting dilutions from a marker stock solution prepared in hexane. The samples were injected with a syringe (Hamilton, 10 μl, Model 701 N, 26 s gauge, Bonaduz, Switzerland) into the injector of the self-made thermal desorber (TD, TC-13.006, PAS Technology, Magdala, Germany) or into the injector of the commercial GC (HP 5890 SII, Hewlett Packard, now: Agilent Technologies Inc., Santa Clara, USA). The GC was used with a short (approx. 40 cm) inactivated and uncoated silica capillary, so that both TD and GC were used only for rapid evaporation of the liquid sample. At the end of the transfer capillary a special ionization region was reached where the gaseous sample was ionized via REMPI with a Nd:YAG pumped optical parametric oscillator (OPO) laser (NT342A-SH, Ekspla, Vilnius, Lithuania). These specific ionization regions for the MS (LTQ XL, Thermo Fisher Scientific, Waltham, MA, USA) and for the IMS (self-made37, University of Potsdam) have been described previously.37,38 In the IMS the ions were detected on a Faraday plate coupled to an amplifier (NT3-ES, Physimetron, Berlin, Germany) and an oscilloscope (Handyscope, HS3, TiePie engineering, Sneek, Netherlands). Nitrogen (5.0, Praxair, Danbury, USA) was used as carrier and drift gas.
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Fig. 2 IM (red) & MS-spectra (black) with different ionization methods: (a) APCI; (b) laser ionization at 266 nm and (c) at 355 nm; (d) diesel and petrol MS-spectra and laser pulse energy in dependence of wavelength, all spectra were made with diesel socar (M1) in hexane (1![]() ![]() |
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Fig. 3 Overview of the chemical core structures of the marker candidates with nitrogen (N) for high tax labelling or without N for non-leachable low tax labelling. |
The results from the previous experiments on matrices indicated that the marker should have an intense signal at excitation wavelengths above 300 nm. The large number of UV-VIS spectra in online databases may provide a clue to this selection criterion, but they are not always related to REMPI spectra.29 Contradictory requirements in the chemical structure made the selection of suitable markers even more difficult. Larger contiguous aromatic or multiple-bond systems (π-system) result in lower ionization potentials (IPs), so less energy is required for the laser ionization and higher laser wavelengths are suitable.39 In addition, smaller IPs result in fewer electron transfer reactions (ETRs) from the marker to the matrix.40 However, for the resonance condition of REMPI, the energy difference between the half-ionization potential (1/2 IP) and the excited state (S1) must be as small as possible. According to the literature,39 the energy difference increases for aromatic systems with more than two rings. For the high tax marker candidates containing N, 1 + 1 REMPI signals above 300 nm could be found for the combination of amine and 2–3 aromatic rings. Amine-alkylation does not affect the position of 1 + 1 REMPI wavelength.41 To overcome these challenges, approximately 40 candidates for low and high tax marking were tested, focusing on molecules with different ring sizes containing pure C–H π-systems, as well as those with heteroatoms to facilitate ionization (best marker see ESI Fig. S2†).
One of the best marker candidates was N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPPD), which showed an intense M+-peak at 266 nm (Fig. 4a) with medium petrol matrix peaks at the standard REMPI wavelength of 266 nm. Firstly, the M+ peak indicates that photo-ionization is predominantly occurring. If proton transfer reactions (PTR) from matrix to marker would be the preferred way to ionize the marker the (M + 1)+-peak would be the dominant one. Secondly, at 266 nm it is possible to find a time after injection when the marker signal intensity of 1 μM marker is clearly separated from the complex matrix background for a matrix sample diluted in hexane. In any case, the matrix intensity would be increased if neat petrol were used. Therefore, an excitation wavelength above 266 nm was searched with the best marker-to-matrix-ratio. The bar graph (Fig. 4b) shows that the intensities of the TMPPD marker and the petrol matrix decrease with increasing wavelength. Even so, the marker-to-matrix-ratio increases from around two at 266 nm to a plateau of seven between 337 nm and 355 nm. Similar results were found for the marked diesel matrix. But the separation of marker and matrix peak was easier due to delayed matrix evaporation. Due to the greater flexibility offered by the Nd:YAG pump laser used, 355 nm was chosen as the preferred laser wavelength with a pulse energy of 2 mJ (see ESI Fig. S3†).
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Fig. 4 (a) MS-spectrum of marked petrol at 266 nm and (b) normalized intensity of marker or matrix over excited wavelength, both spectra: 1 μm marker TMPPD in 1![]() ![]() |
At this wavelength several potential candidates with heteroatoms and pure C–H were found for labeling high and low taxed fuels (Fig. 5). For all candidates, a successful photo-ionization was verified by the M+-peak in MS reference measurements (*-peak in the MS-spectra). In the IM spectrometer each of the selected candidates shows almost similar signal intensities in hexane and in the diesel matrix. Thus, for the diesel matrix no influence was found through the matrix. From the concentration required to achieve significant marker intensity, evidently nitrogen is an important component for ionization; higher concentrations are required for oxygen–C–H or for pure C–H marker candidates.
Firstly, calibration curves of TMPPD were measured. Broad linearity and excellent limits of detection (LODs) were found in both setups (MS and IMS, Fig. 6a and b). Thus, the low detection level of marker and the wide dynamic range allow the use of low concentrations of marker and the detection of the marker in different fuel blends. The LOD from the MS setup to the IMS deteriorates by a factor of 20. However, the matrix was diluted 1:
100 in the MS study, while neat fuel samples were used in the IMS. For the diluted matrices in MS and IMS very low matrix dependence was found (IMS data not shown here). The influence of the matrices increases for the neat matrix samples in IMS measurements. Strong memory effects prevented the marker from being compared in pure matrix in MS as well. In particular, a higher concentration of rapidly evaporating components in the petrol matrix shows a greater influence on the marker intensity due to simultaneous ionization with the marker and therefore a higher possibility for CTRs.
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Fig. 6 Calibration curve of TMPPD, (a) in MS with diluted matrix samples (1![]() ![]() |
Evaluating the accuracy of the TMPPD in the IMS setup within a single matrix is essential to ensure the reliability and reproducibility of future results. To identify commercially relevant blends such as a dilution of high tax fuel, a labelled fuel is tested with only a 5% dilution of another fuel. Therefore, a comparison of a 95% labelled fuel with a 100% labelled fuel must show a significant difference in the marker intensity within one matrix, as shown in the graph in Fig. 7a. The applicability of the TMPPD marker in different fuels was verified by checking its signal intensity in 22 different matrices (7 diesel, 15 petrol). With an average intensity of 36.7 ± 1.1 the signal is nealy constant over all matrices. A deviation of 3% was observed between matrices and equally 3% within a matrix. So, there is a good applicability in different diesel and petrol matrices with small inaccuracies. The reason for these inaccuracies is delayed marker evaporation due to matrix effects or charge transfer reactions (CTRs).
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Fig. 7 High tax marker candidate TMPPD (a) 95% vs. 100% of TMPPD in hexane diluted diesel matrix (1![]() ![]() |
One potential other additive or component with fitting IP and PA was anthracene (7.44 eV, 877.3 kJ mol−1).43 At high concentrations, anthracene is ionized at the excitation wavelength of 355 nm but is clearly distinguishable from the marker used, TMNDA, in the LIMS spectrum (Fig. 8a). In consequence the intensities of both substances can be analyzed separately. A concentration of 100 μM TMNDA gave an intensity of 0.42 (dotted horizontal line Fig. 8b). While increasing the anthracene concentration between 0.05 and 1 mM the intensity of the TMNDA signal is increasing even though the concentration of TMNDA is constant (light blue graph, Fig. 8b). The intensity of the anthracene peak instead is minimized in the presence of TMNDA compared to the neat anthracene measurements (dark blue vs. turquoise graph in Fig. 8b). This shows clearly a CTR from anthracene to TMNDA. But a significant influence on the signal intensity of TMNDA was only found above anthracene concentrations of 100 μM. In petrol the concentration is around 10 μM.44 Thus, the anthracene reaction must be just one part of the occurring CTRs.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3ay01994b |
This journal is © The Royal Society of Chemistry 2024 |