Enhancing Essential Oil Extraction from Lavandin Grosso Flowers via Plasma Treatment.

This study explores the impact of plasma treatment on Lavandin Grosso flowers and its influence on the extraction of essential oils (EOs) via hydrodistillation. Short plasma treatment times enhance the yield of EO extraction from 3.19% in untreated samples to 3.44%, corresponding to 1 min of plasma treatment, while longer treatment times (10 min) show diminishing returns to 3.07% of yield extraction. Chemical characterization (GC/MS and ATR-FTIR) indicates that plasma treatments do not significantly alter the chemical composition of the extracted EOs, preserving their aromatic qualities. Investigations into plasma-surface interactions reveal changes at the nanometer level, with XPS confirming alterations in the surface chemistry of Lavandin Grosso flowers by reducing surface carbon and increasing oxygen content, ultimately resulting in an increased presence of hydrophilic groups. The presence of hydrophilic groups enhances the interaction between the surface membrane of the glandular trichomes on Lavandin Grosso flowers and water vapor, consequently increasing the extraction of EOs. Furthermore, microscopic SEM examinations demonstrate that plasma treatments do not affect the morphology of glandular trichomes, emphasizing that surface modifications primarily occur at the nanoscale. This study underscores the potential of plasma technology as a tool to enhance EO yields from botanical sources while maintaining their chemical integrity.

Meeting the European Commission performance criteria for the use of triple quadrupole GC-MS/MS as a confirmatory method for PCDD/Fs and dl-PCBs in food and feed samples.

Until recently, European Union (EU) legislation required the use of high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC-HRMS) based on magnetic sector analyzers as a standard approach for confirmatory analysis of dioxins (PCDDs) and furans (PCDFs) in feed and food. However, recent technological advances in MS instruments enabled other alternative analytical techniques to meet the same analytical criteria as those requested for HRGC-HRMS. In this sense, triple quadrupoles (GC-MS/MS) can be a realistic alternative for the analysis of dioxins. In this work, the performance of GC-MS/MS technology was evaluated against the criteria demanded by the EU for confirmatory analysis of dioxins and PCBs in food and feed. Thus, the study comprises a number of parameters including chromatographic separation, limit of quantification, linearity, repeatability, and ion ratio precision. Analyses of solvent standards as well as sample extracts (inter-calibration extracts and certified reference materials) were also considered within the scope of this study. Additionally, direct comparisons of the results obtained by GC-MS/MS with those from GC-HRMS were made. The results of this work suggested that GC-MS/MS was highly sensitive and selective for confirmatory analysis of PCDD/Fs and related compounds in food and feed samples and meets all the criteria requested by the European Commission.

Potential of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry for screening and quantification of hexabromocyclododecane.

A fast method for the screening and quantification of hexabromocyclododecane (sum of all isomers) by gas chromatography using a triple quadrupole mass spectrometer with atmospheric pressure chemical ionization (GC-APCI-QqQ) is proposed. This novel procedure makes use of the soft atmospheric pressure chemical ionization source, which results in less fragmentation of the analyte than by conventional electron impact (EI) and chemical ionization (CI) sources, favoring the formation of the [M - Br](+) ion and, thus, enhancing sensitivity and selectivity. Detection was based on the consecutive loses of HBr from the [M - Br](+) ion to form the specific [M - H5Br6](+) and [M - H4Br5](+) ions, which were selected as quantitation (Q) and qualification (q) transitions, respectively. Parameters affecting ionization and MS/MS detection were studied. Method performance was also evaluated; calibration curves were found linear from 1 pg/µL to 100 pg/µL for the total HBCD concentration; instrumental detection limit was estimated to be 0.10 pg/µL; repeatability and reproducibility, expressed as relative standard deviation, were better than 7% in both cases. The application to different real samples [polyurethane foam disks (PUFs), food, and marine samples] pointed out a rapid way to identify and allow quantification of this compound together with a number of polybrominated diphenyl ethers (BDE congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two other novel brominated flame retardants [i.e., decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)] because of their presence in the same fraction when performing the usual sample treatment.

Triple quadrupole tandem mass spectrometry: A real alternative to high resolution magnetic sector instrument for the analysis of polychlorinated dibenzo-p-dioxins, furans and dioxin-like polychlorinated biphenyls.

This paper reports on the optimisation, characterisation, validation and applicability of gas chromatography coupled to triple quadrupole mass spectrometry in its tandem operation mode (GC-QqQ(MS/MS) for the quantification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs, dioxins) and dioxin-like polychlorinated biphenyls (DL-PCBs) in environmental and food matrices. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for the analysis of this type of compounds and samples. Good repeatability for areas (RSD = 1-10%, for PCDD/Fs and DL-PCBs) and for ion transition ratios (RSD = 0.3-10%, for PCDD/Fs, and 0.2-15%, for DL-PCBs) and low instrumental limits of detection, 0.07-0.75 pg µL(-1) (for dioxins) and 0.05-0.63 pg µL(-1) (for DL-PCBs), were obtained. A comparative study of the congener specific determination using both GC-QqQ(MS/MS) and gas chromatography-high resolution mass spectrometry (GC-HRMS) was also performed by analysing several fortified samples and certified reference materials (CRMs) with low (feed and foodstuffs), median (sewage sludge) and high (fly ash) toxic equivalency (TEQ) concentration levels, i.e. 0.60, 1.83, 72.9 and 3609 pg WHO-TEQ(PCDD/Fs) g(-1). The agreement between the results obtained for the total TEQs (dioxins) on GC-QqQ(MS/MS) and GC-HRMS in all the investigated samples were within the range of ±4%, and that of DL-PCBs at concentration levels of 0.84 pg WHO-TEQs (DL-PCBs) g(-1), in the case of feedstuffs, was 0.11%. Both instrumental methods have similar and comparable linearity, precision and accuracy. The GC-QqQ(MS/MS) sensitivity, lower than that of GC-HRMS, is good enough (iLODs in the down to low pg levels) to detect the normal concentrations of these compounds in food and environmental samples. These results make GC-QqQ(MS/MS) suitable for the quantitative analysis of dioxins and DL-PCBs and a real alternative tool to the reference sector HRMS instruments.

Atmospheric-pressure chemical ionization tandem mass spectrometry (APGC/MS/MS) an alternative to high-resolution mass spectrometry (HRGC/HRMS) for the determination of dioxins.

The use of a new atmospheric-pressure chemical ionization source for gas chromatography (APGC) coupled with a tandem quadrupole mass spectrometry (MS/MS) system, as an alternative to high-resolution mass spectrometry (HRMS), for the determination of PCDDs/PCDFs is described. The potential of using atmospheric-pressure chemical ionization (APCI) coupled to a tandem quadrupole analyzer has been validated for the identification and quantification of dioxins and furans in different complex matrices. The main advantage of using the APCI source is the soft ionization at atmospheric pressure, which results in very limited fragmentation. APCI mass spectra are dominated by the molecular ion cluster, in contrast with the high energy ionization process under electron ionization (EI). The use of the molecular ion as the precursor ion in MS/MS enhances selectivity and, consequently, sensitivity by increasing the signal-to-noise ratios (S/N). For standard solutions of 2,3,7,8-TCDD, injections of 10 fg in the splitless mode on 30- or 60-m-length, 0.25 mm inner diameter (id), and 25 µm film thickness low-polarity capillary columns (DB5MS type), signal-to-noise (S/N) ratios of >10:1 were routinely obtained. Linearity was achieved in the region (correlation coefficient of r(2) > 0.998) for calibration curves ranging from 100 fg/µL to 1000 pg/µL. The results from a wide variety of complex samples, including certified and standard reference materials and samples from several QA/QC studies, which were previously analyzed by EI HRGC/HRMS, were compared with the results from the APGC/MS/MS system. Results between instruments showed good agreement both in individual congeners and toxic equivalence factors (TEQs). The data show that the use of APGC in combination with MS/MS for the analysis of dioxins has the same potential, in terms of sensitivity and selectivity, as the traditional HRMS instrumentation used for this analysis. However, the APCI/MS/MS system, as a benchtop system, is much easier to use.

Comprehensive study on dioxin contents in binder and anti-caking agent feed additives.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in some additives widely employed as binder and anti-caking agents in feedstuffs, such as kaolin, bentonite, zeolite, etc. with an special attention on sepiolite samples. Owing to their physico-chemical properties, the little information of these materials reported in the literature, the variability of PCDDs/PCDFs found in a preliminary evaluation and the absence of reference materials highlighted further research needed. Therefore, an extensive study on the analytical procedures based on the classical methods was performed with sepiolite samples. The study includes evaluation of reproducibility and repeatibility. To this end, a series of intra-day and nine inter-day analysis were made. The methodolgy was also assessed against the sample size and series of 12.5, 25, 37.5 and 50 g were analyzed. In all cases, the results confirmed good correlation with the parameters evaluated.

Study on PCDDs/PCDFs and co-PCBs content in food samples from Catalonia (Spain).

The results of a surveillance programme on polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (co-PCBs) determination in 70 foodstuffs samples produced all over the four provinces of Catalonia is presented. The study included the analyses of raw milk, pure virgin olive oil, butter, chicken. pork and mussel samples collected between November 1999 and January 2000. Milk, virgin oil, pork or butter presented a variable dioxin and co-PCBs content, even though the limits proposed in the draft of the EC Regulation for its commercialization in the European countries were not reached. The levels of PCDDs/PCDFs and co-PCBs determined in chicken samples varied between 0.36-3.59 pg I-TEQ/g fat chicken (0.4--3.8 WHO-TEQ/g fat). Just one case presented remarkable content of dioxins (about 30 pg I-TEQ/g fat) with a complex congener-specific profile which indicates the presence of an external contamination. On the other hand, a congener-specific profile dominated by 2,3,7,8-TCDF and OCDD was observed in mussel samples from Catalonia. This fact was also observed in mussel samples from other sites in Spain.