Advanced separation of mineral oil aromatic hydrocarbons by number of aromatic rings using donor-acceptor-complex chromatography to extend on-line coupled liquid chromatography-gas chromatography.

An automated implementation for a subfractionation of mineral oil aromatic hydrocarbons (MOAH) into a mono-/di-aromatic fraction (MDAF) and a tri-/poly-aromatic fraction (TPAF) is presented, which is highly demanded by the European Food Safety Authority (EFSA) respecting the genotoxic and carcinogenic potential of MOAH. For this, donor-acceptor-complex chromatography (DACC) was used as a selective stationary phase to extend the conventional instrumental setup for the analysis of mineral oil hydrocarbons via on-line coupled liquid chromatography-gas chromatography-flame ionization detection (LC-GC-FID). A set of six new internal standards was introduced for the verification of the MOAH fractionation and a quantification of MDAF and TPAF, respectively. The automated DACC approach was applied to representative petrochemical references as well as to food samples, such as rice and infant formula, generally showing well conformity with results obtained by state-of-the-art analysis using two-dimensional GC (GCxGC). Relative deviations of DACC/LC-GC-FID compared to GCxGC-FID methods regarding the ≥ 3 ring MOAH content ranged between -50 and +6 % (median: -2 %, all samples, only values above limit of quantification). However, crucial deviations mainly result from "border-crossing" substances, e.g., dibenzothiophenes or partially hydrogenated MOAH. These substances can cause overestimations of ≥ 3 ring MOAH fraction during GCxGC analysis due to co-elution, which is mostly avoided using the DACC approach. Furthermore, the DACC approach can help to minimize underestimations of toxicologically relevant ≥ 3 ring MOAH caused by an unavoidable loss of MOAH during epoxidation, since natural olefins, such as terpenes, predominantly elute in MDAF, which was exemplarily shown for an olive oil and a terpene reference. The presented approach can be implemented easily in existing LC-GC-FID setup for an automated and advanced screening of MOAH to lower the need for elaborate GCxGC analysis also in routine environments.

Assessing the half-life and degradation kinetics of aliphatic and aromatic hydrocarbons by bacteria isolated from crude oil contaminated soil.

Pollution from the oil industries and refineries has worsened various environmental compartments. In this study, indigenous oil degrading bacteria were isolated from crude oil obtained from an Oil and Natural Gas Corporation (ONGC) asset in Ankleshwar, Gujarat, India. Based on 16S rRNA phylogeny, they were identified as Pseudomonas boreopolis IITR108, Microbacterium schleiferi IITR109, Pseudomonas aeruginosa IITR110, and Bacillus velezensis IITR111. The strain IITR108, IITR109, IITR110, and IITR111 showed 80-89% and 71-78% degradation of aliphatic (C8-C40) and aromatic (4-5 ring) hydrocarbons respectively in 45 d when supplemented with 3% (v/v) waste crude oil. When compared to individual bacteria, the consortium degrades 93.2% of aliphatic hydrocarbons and 85.5% of polyaromatic hydrocarbons. It was observed that the total aliphatic and aromatic content of crude oil 394,470 µg/mL and 47,050 µg/mL was reduced up to 9617.75 µg/mL and 4586 µg/mL respectively in 45 d when consortium was employed. The rate kinetics analysis revealed that the biodegradation isotherm followed first order kinetics, with a linear correlation between concentration (hydrocarbons) and time intervals. The half-life of aliphatic (C8-C40) and aromatic hydrocarbons ranged from 200 to 453 h and 459-714 h respectively. All the bacteria efficiently produced catabolic enzymes such as alkane monooxygenase, alcohol dehydrogenase, and lipase during the degradation of crude oil. These findings indicated that the bacterial consortium can be a better candidate for bioremediation and reclamation of aliphatic and aromatics hydrocarbon contaminated sites.

Investigation of the effect of refining on the presence of targeted mineral oil aromatic hydrocarbons in coconut oil.

The goal of this work was to investigate the impact of refining on coconut oil particularly on the most toxicologically relevant fraction of the mineral oil aromatic hydrocarbon (MOAH) contamination, namely the fraction composed by the three to seven aromatic rings. A fully integrated platform consisting of a liquid chromatography (LC), a comprehensive multidimensional gas chromatography (GC) (LC-GC × GC) and flame ionization detector (FID) was used to obtained a more detailed characterization of the MOAH sub-classes distribution. The revised EN pr 16995:2017-08 official method was used for preparing the samples, both with and without the auxiliary epoxidation step. Crude coconut oil was spiked with different MOAH standards, namely naphthalenes, alkylated naphthalenes, benzo(a)pyrene, and its alkylated homologues. Refining was modelled by deodorization at 230 °C, stripping with 10 kg/h of steam under 1 mbar vacuum for 3 h. Complete removal of the naphthalenes and reduction of more than 98.8% of the benzo(a)pyrenes was observed. Epoxidation had a significant impact on the MOAH fraction with more than three rings, but with a high dependency on the sample matrix, being significantly less evident in the refined samples than in the crude ones.

A study on the impact of harvesting operations on the mineral oil contamination of olive oils.

During the 2020-21 olive oil campaign, the contribution of harvesting operations to mineral oil saturated (MOSH) and aromatic hydrocarbon (MOAH) contamination was studied. Oils extracted from hand-picked olives (15 different olive groves) generally had background MOSH (<2.7 mg/kg), and no quantifiable MOAH. In 40% of the cases, an important contamination increase was observed after harvesting operations. Except for one sample (325.8 and 111.0 mg/kg of MOSH and MOAH, respectively), other samples reached 4.3-33.7 mg/kg of MOSH and 1.1-11.3 mg/kg of MOAH. Accidental leaks of lubricants and/or contact with lubricated mechanical parts, were identified as important sources of contamination. Chromatographic traces obtained by on-line high-performance liquid chromatography (HPLC)-gas chromatography (GC)-flame ionization detection (FID) allowed for source identification. A comprehensive two-dimensional gas chromatographic platform (GC × GC) with parallel FID/MS detection was implemented for confirmation and to attempt the characterization of the contaminations. Good harvesting practices are suggested to minimize contamination risks.

[Characterization of VOCs Emissions from Caged Broiler House in Winter].

Volatile organic compound (VOCs) emissions from poultry and livestock facilities affect the surrounding environmental quality and human health. However, VOCs emissions from broiler houses have been less characterized, and studies of related dominant odorants, carcinogenic risk, and ozone formation potential are still lacking. To fill this research gap, VOCs pollutants emitted from a broiler house were investigated in this study. The VOCs emission characteristics of the broiler house during three different periods of broiler growth (early, middle, and later) were analyzed using gas chromatography-mass spectrometry. The results showed that 77 types of VOCs were detected, including 16 types of halogenated hydrocarbons, 21 types of alkanes, 5 types of olefins, 12 types of aromatic hydrocarbons, 15 types of oxygenated volatile organic compounds (OVOCs), and 8 types of sulfides. During the entire 42-day growth period, the concentrations of halogenated hydrocarbons, alkanes, olefin, aromatic hydrocarbons, and OVOCs in the broiler house showed few changes. However, with the growth of broilers, the intake of sulfur-containing amino acids and the fecal emission coefficient increased, resulting in the gradual conversion of the VOCs to sulfide. Therefore, emissions of sulfur-containing VOCs increased in the early and middle growth periods. Moreover, the increase in ventilation in the house during the later growth period resulted in a decrease in the sulfur-containing VOCs concentrations. The dominant odorants in the broiler house were naphthalene, ethyl acetate, acetaldehyde, carbon disulfide, dimethyl disulfide, methanethiol, methanethiol, and thiophene. Methanethiol had the highest odorous values, ranging from 2172.4 to 19090.9. Meanwhile, there were acceptable levels of carcinogenic risk in the early and middle growth periods, with a lifetime cancer risk (LCR) of 7.7×10-6 and 4.5×10-6, respectively. The average ozone formation potential (OFP) was (1458.9±787.4) µg·m-3. The results of this study can provide a scientific basis for the monitoring of malodorous substances and formulation of emission reduction strategies in broiler production.

Automated workflow utilizing saponification and improved epoxidation for the sensitive determination of mineral oil saturated and aromatic hydrocarbons in edible oils and fats.

Refined edible oils and fats are known to contain olefins resisting the typical epoxidation used for the sample preparation of mineral oil saturated and aromatic hydrocarbons (MOSH and MOAH). These olefins can be misinterpreted as MOAH and are therefore an important reason for inconsistent results between laboratories. Collaborative trials confirm this assumption for low MOAH contents near the quantitation limits regularly. In the scope of this work, a new epoxidation approach was developed. Persistent olefins in refined oils could be successfully epoxidized with performic acid. The reaction kinetics was investigated using model substances for biogenic olefins and MOAH. It was rationalized why certain olefins resist epoxidation and which MOAH can potentially get lost. A prominent peak cluster in the MOAH fraction of refined palm oils could be identified by means of GC-MS and explained why it cannot be epoxidized. Based upon this, an automated and streamlined workflow for sample preparation and analysis was composed tackling major problems identified in previously published methods. Optimized and miniaturized saponification, extraction, epoxidation, and enrichment paired with online LC-GC-FID led to a robust method that was tested and validated for edible oils and fats (RSDR < 7% for MOSH and MOAH at values of 14.9 and 2.1 mg/kg, respectively). Due to increased sample amount and minimized blank values, quantitation limits below 1 mg/kg for MOSH and MOAH were achieved. The trueness of the method was verified by analyzing collaborative trial samples.

Development of an analytical method for the determination of mineral oil aromatic hydrocarbons (MOAH) from printing inks in food packaging.

An analysis method was developed to detect chemical markers of mineral oil aromatic hydrocarbons (MOAH) from offset printing inks in food packaging materials. 16 aromatic hydrocarbons were used as target analytes and different solid phase extraction procedures (SPE) and gas chromatography coupled to mass spectrometry (GC-MS) were tested. The concentration range studied was 0.1-7.5 µg g-1 with R2 higher than 0.9963, intraday RSD values below 5 %, RSD values between days lower than 12 %, recoveries higher than 80 %, LOD and LOQ lower than 0.09 µg g-1. Ten of the target analytes were identified in offset printing inks at concentrations between 2.28 and 8.59 µg g-1. Nine of them were also identified in the food packages examined in concentrations ranging from 0.10 to 0.33 µg g-1. These compounds were: methylnaphthalene, 2-methylnaphthalene, biphenyl, 2,6-dimethylnaphthalene, acenaphthene, 3,3',5,5'-tetramethylbiphenyl, 4,6-dimethyldibenzothiophene, 1-methylpyrene, benzo(b)naphtha(1,2-d)thiophene and 9,9'-dimethylfluorene. Mineral oil in food packaging was previously analysed by GC with flame ionization detection (FID).

Comparison of PAC and MOAH for understanding the carcinogenic and developmental toxicity potential of mineral oils.

The carcinogenicity and developmental toxicity of unrefined mineral oil is related to its 3-7 ring polycyclic aromatic compounds (PAC) content. Therefore, refining operations focus on the targeted removal PAC from mineral oil that may contain aromatics of low toxicological concern. There are thus, two types of aromatic substances in mineral oil: hazardous and non-hazardous. The first type consists of 3-7 ring PAC which may be naked (unsubstituted) or lowly alkylated. The second type or non-hazardous consists of 1-7 ring aromatics with high degree of alkylation or lack of bay or fjord regions. Although these are toxicologically different, they may both elute in the same fraction when using chromatography. To understand how these two aromatic types are related we have assessed the entire mineral oil refinement process by measuring total mineral oil aromatic hydrocarbons (MOAH) content by chromatography next to regulatory hazard tests which focus on 3-7 ring PAC. MOAH content is positively correlated to its molecular weight resulting in aromatic content bias for high viscosity substances. Hazard to 3-7 ring PAC is best controlled by the validated IP346 or modified Ames test. We explain the concept of high vs low alkylation by shortly reviewing new data on alkylated PAC.

Anaerobic degradation of benzene and other aromatic hydrocarbons in a tar-derived plume: Nitrate versus iron reducing conditions.

The anaerobic degradation of aromatic hydrocarbons in a plume originating from a Pintsch gas tar-DNAPL zone was investigated using molecular, isotopic- and microbial analyses. Benzene concentrations diminished at the relatively small meter scale dimensions of the nitrate reducing plume fringe. The ratio of benzene to toluene, ethylbenzene, xylenes and naphthalene (BTEXN) in the fringe zone compared to the plume zone, indicated relatively more loss of benzene in the fringe zone than TEXN. This was substantiated by changes in relative concentrations of BTEXN, and multi-element compound specific isotope analysis for δ2H and δ13C. This was supported by the presence of (abcA) genes, indicating the presumed benzene carboxylase enzyme in the nitrate-reducing plume fringe. Biodegradation of most hydrocarbon contaminants at iron reducing conditions in the plume core, appears to be quantitatively of greater significance due to the large volume of the plume core, rather than relatively faster biodegradation under nitrate reducing conditions at the smaller volume of the plume fringe. Contaminant concentration reductions by biodegradation processes were shown to vary distinctively between the source, plume (both iron-reducing) and fringe (nitrate-reducing) zones of the plume. High anaerobic microbial activity was detected in the plume zone as well as in the dense non aqueous phase liquid (DNAPL) containing source zone. Biodegradation of most, if not all, other water-soluble Pintsch gas tar aromatic hydrocarbon contaminants occur at the relatively large dimensions of the anoxic plume core. The highest diversity and concentrations of metabolites were detected in the iron-reducing plume core, where the sum of parent compounds of aromatic hydrocarbons was greater than 10 mg/L. The relatively high concentrations of metabolites suggest a hot spot for anaerobic degradation in the core of the plume downgradient but relatively close to the DNAPL containing source zone.

Solar-activated zinc oxide photocatalytic treatment of real oil sands process water: Effect of treatment parameters on naphthenic acids, polyaromatic hydrocarbons and acute toxicity removal.

Oil sands process water (OSPW) is an industrial process effluent that contains organic compounds such as naphthenic acids (NAs) and polyaromatic hydrocarbons (PAHs), as well as large quantities of inorganic compounds in its mixture. OSPW requires effective treatment for successful reclamation and water reuse. This study investigated the impact of solar-activated zinc oxide (ZnO) photocatalysis on the degradation and removal of NAs and PAHs in OSPW, as well as the elimination of its acute toxicity. With catalyst particles suspended in the effluent (at 1 g/L) under simulated solar radiation of steady irradiance of ~278 W/m2, more than 99% removal of NAs was achieved after 4 h of treatment, while nearly all PAHs were simultaneously oxidized within the same reaction time. The photocatalytic treatment appeared to selectively convert classical NAs faster than oxidized NAs. Additionally, NAs with higher double-bond equivalents (DBEs) and higher carbon numbers seemed more susceptible to photocatalytic destruction than others. An overall pseudo first-order rate constant of 1.14 × 10-2 min-1, and a fluence-based rate constant of 6.81 × 10-1 m2/MJ were recorded in apparently hydroxyl radicals (OH) and superoxide (O2-) radicals mediated NAs degradation mechanisms. Assessment of the toxicity levels in raw and treated OSPW samples by using Microtox® bioassay indicated that the photocatalytic treatment resulted in ~50% reduction in acute toxicity. Furthermore, we showed that by monitoring the expression levels of key proinflammatory genes using qPCR that treated OSPW significantly reduced the ability of raw OSPW to activate the inflammatory response of immune cells. This indicates that at acute sub-lethal exposure doses, photocatalytic treatment also reduces immunotoxicity. Overall, our results suggest that the ZnO-based photocatalytic degradation of these NAs and PAHs in OSPW could be a significant treatment process aimed at detoxifying OSPW.

Optimization and validation of microwave assisted saponification (MAS) followed by epoxidation for high-sensitivity determination of mineral oil aromatic hydrocarbons (MOAH) in extra virgin olive oil.

A rapid and solvent-saving method, based on microwave-assisted saponification (MAS) followed by epoxidation and on-line liquid chromatography (LC) - gas chromatography (GC) - flame ionization detection (FID), was optimized and validated for high-sensitivity MOAH determination in extra virgin olive oils. Quantitative recoveries and good repeatability were obtained even at concentrations of added mineral oils close to the LOQ (0.5 mg/kg for the total hump, 0.2 mg/kg for each single C-fraction). The validated method, also applied for MOSH determination (C-fraction LOQ: 0.5 mg/kg), was used to analyse 18 extra virgin olive oils from the Italian market or oil mills, and 10 additional samples extracted in the laboratory (with an Abencor apparatus) from hand-picked olives. The former resulted contaminated with variable amounts of MOSH and MOAH (on average 19.0 mg/kg and 2.5 mg/kg, respectively), while the latter showed no detectable MOAH, and low and rather constant MOSH (generally below 2.0 mg/kg).

Mineral oil saturated and aromatic hydrocarbons quantification: Mono- and two-dimensional approaches.

The determination of the level of mineral oil contamination in foods is a well-known problem. This class of contaminants is generally divided into mineral oil saturated and aromatic hydrocarbons with different toxicological relevance and analytical challenges. Among the many challenges, data interpretation and integration represent an important source of uncertainty in the results provided by different laboratories leading to a variation evaluated on the order of 20%. The use of multidimensional comprehensive gas chromatography (GC × GC) has been proposed to support the data interpretation but the integration and the reliability of the results using this methodology has never been systematically evaluated. The aim of this work was to assess the integration and quantification performance of a two-dimensional (2D) software. The data were generated using a novel, completely automated platform, namely LC-GC × GC coupled to dual detectors, i.e., time-of-flight mass spectrometer (MS) and flame ionization detector (FID). From a systematic study of the failures of the two-dimensional quantification approach a novel solution was proposed for simplifying and automating the entire process. The novel algorithm was tested on ad hoc created samples (i.e. a paraffin mixture added of n-alkanes) and real-world samples proving the agreement of the results obtained by LC-GC × GC and the traditional mono-dimensional approach. Moreover, the benefits of using an entirely integrated platform were emphasized, particularly regarding the identity confirmation capability of the MS data, which can be easily translated into the 2D FID quantification feature.

A portable gas chromatograph for real-time monitoring of aromatic volatile organic compounds in air samples.

We describe the design and performance evaluation of a portable gas chromatograph suitable for the analysis of volatile organic and odorous compounds at trace levels. The system comprises a carbon nanotube sponge preconcentrator, an electronic pressure control (EPC) unit, a temperature-programmable column module, and a fast-response photoionization detector. A built-in tablet computer controls instrumental parameters and chromatogram display functions. The compact GC with dimensions of 35 cm (l) × 26 cm (w) × 15 cm (h) is self-contained, weighing less than 5 kg without a battery pack, and uses no auxiliary compressed gases. Our design has three main advantages over conventional portable GCs: recharging configuration of ambient air as the carrier gas using a miniature diaphragm pump, precise control of column flow by the built-in canister and EPC system, and rapid thermal desorption of the preconcentrator facilitated by intrinsic resistivity of the carbon nanotube sponge. A 30 m, 0.28 mm I.D. capillary column operated at a head pressure of 14 psi provided a peak capacity of 55 for a 10 min isothermal analysis. The temperature-programmability feature could decrease the analysis time of less than 5 min for vapor mixture of benzene, toluene, ethylbenzene, and o-xylene. More than a 100-fold increase in sensitivity by preconcentrating a sample adsorption volume of 90 mL resulted in improved detection limits of 0.13 (benzene), 0.20 (toluene), 0.23 (ethylbenzene), and 0.28 (o-xylene) ppb (v/v). Our instrument displayed good stability and reproducibility of retention times (< 0.14% RSD) and intensities (< 4.5% RSD) for continuous measurements using the preconcentrator over 10 h. Thus, continuous and on-site determinations of trace volatile organic compounds in air samples with this instrument appear feasible.

Exposure to organic solvents and hepatotoxicity.

The purpose of this study was to identify the long-term effect of chemical exposure on the liver. Laboratory tests included alanine aminotransferase (ALT) dosage and oxidative stress tests, such as thiobarbituric acid reactive substances in plasma and superoxide dismutase (SOD) and glutathione S-transferase analysis in erythrocytes. The cross-sectional study comprised 70 workers, 30 of them exposed to organic solvents and 40 not exposed. All those exposed presented at least 5 years of exposure to solvents. Hepatitis B and C, known hepatic disease, comorbidities, use of alcohol, illicit drugs or hepatotoxic medications, smoking, body mass index >30, female sex and age (<18 or >65) were excluded from the sample. Results indicated that elevated ALT was more frequent in the exposed group compared to controls: 33% vs. 10.5%, with a statistical significance (p < 0.05). Thiobarbituric acid reactive substances were significantly elevated (p < 0.01) in the exposed group in comparison to controls. Antioxidant enzymes were more elevated in the exposed group compared to controls: SOD 7.29 (4.30-8.91) USOD/mg of protein vs. 3.48 (2.98-5.28) USOD/mg of protein and GST 2.57 µmol/min/mg of protein (1.80-4.78) vs. 1.81 µmol/min/mg of protein (1.45- 2.30) µM/min/mg of protein. The results suggest an association between exposure to organic solvents and hepatotoxicity.

Epoxidation for the analysis of the mineral oil aromatic hydrocarbons in food. An update.

On-line coupled high performance liquid chromatography-gas chromatography-flame ionization detection (HPLC-GC-FID) used for determining mineral oil aromatic hydrocarbons (MOAH) in foods, particularly in certain oils and fats, may be disturbed by interfering olefins present as natural food components or resulting from raffination of the oils and fats. While some interference can be coped with by disregarding their peaks, others overload GC to the extent of obscuring the MOAH or form humps which need to be distinguished from the hump formed by the MOAH. In the latter cases, it is necessary to remove these interferences prior to HPLC-GC analysis. So far, epoxidation of the olefins to increase their retention time beyond that of the MOAH in HPLC is the best method available, though imperfect by causing some loss of MOAH and sometimes incomplete removal of the interference. Two methods are re-evaluated; preference is given to a slightly modified version of that proposed by Nestola and Schmidt. The performances are comparable: the losses of MOAH are similar and with both methods not all interfering olefins may be removed from refined edible oils. However, the Nestola/Schmidt method has practical advantages, the main ones being that no cooling is necessary and no solvent needs to be evaporated, which facilitates automation. Potential residual interferences must be recognized and subtracted, which can be by the characteristics of the hump they form in HPLC-GC-FID, by GCxGC-FID or by GCxGC-MS using characteristic mass fragments.

Optimization of a solid-phase microextraction technique for chloro­ and nitro- substituted aromatic compounds using design of experiments.

A rapid and sensitive direct immersion solid-phase microextraction (SPME) technique for the analysis of seven chloro (Cl-) and nitro (NO2-) substituted anilines, toluenes, and nitrobenzenes from small volume (1.5 mL) aqueous samples was optimized for gas chromatography using Design of Experiments (DoE). Screening of the SPME factors was performed by a fractional factorial DoE, and the optimization of influential factors was achieved with a central composite multi-response surface DoE. Extraction time, pre-SPME agitation speed, extraction temperature, and desorption temperature were identified as significant factors and their values were set using a desirability function that maximized the extraction of the seven target analytes. Extraction time and agitation speed showed significant interactions for most analytes (α = 0.05). The relative standard deviations (RSDs) for within-day and between-day analyses were below 8%, suggesting that the method was repeatable and reproducible. The obtained limits of detection were in the low µg/L range (1-10) using a Flame Ionization Detector, far below what is needed for industrial contaminated sites (usually >1 mg/L). The optimized SPME method increased the analyte concentration up to 2-3 orders of magnitude compared with direct GC injection. The optimized SPME method was applied to two groundwater samples from a contaminated site in which the concentrations of three of the target analytes were ranged from 0.06 to 9.42 mg/L with RSDs <11%. When the concentrations of the target analytes in the sample matrix were higher than 0.5 mg/L, a competition for the SPME extraction sites was observed where analytes with higher affinity for the fiber material replaced the analytes with lower affinity. As a result, dilution of highly contaminated samples is recommended. This study provided for the first time an analytical method for the quantification of frequently co-occurring contaminants from the chloro­ and nitro- substituted aniline, toluene, and nitrobenzene families.

Toxic compounds in a cutlery microenterprise: A case study.

BACKGROUND: The aim of this study was to characterize solid particulate aerosol derived from a cutlery microenterprise and to investigate substances associated with activities performed within the work environment. OBJECTIVE: Suspended particulate matter (SPM) was collected at different locations in the cutlery workshop and near machines used by workers, using passive sampling devices fitted with polytetrafluoroethylene filters, onto which total particulate material was deposited. The substances present in the SPM were analyzed using gas chromatography-mass spectrometry (GC-MS). RESULTS: Identification of the substances was performed using the National Institute of Standards (NIST) library and automated mass spectral deconvolution and identification system. (AMDIS) software, considering at least 70% probability. The concentration of total dust, obtained using a gravimetric method, was approximately 1 mg.m-3. CONCLUSION: The toxic substances found in the SPM included halogenated hydrocarbons (containing chlorine, fluorine, and iodine) and aromatic hydrocarbons. The toxic substances included naphthalene, which is classified as carcinogenic.

Supercritical fluid chromatography as a rapid single-step method for the determination of mineral oil saturated and aromatic hydrocarbons in purified mineral oils for food and cosmetics applications.

Mineral oil hydrocarbons are used in the consumer goods sector for the elaboration of a wide range of foods and cosmetics. Traditional methods for determining their levels and composition are time consuming and laborious, besides requiring complex instrumentation. Here a simple and fast method was developed that uses columns packed with silver-modified silica in supercritical fluid chromatography with flame ionization and UV detection (SFC-FID/UV) for the determination of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in purified mineral oil samples. The method requires no sample preparation apart from dilution. Direct quantification of MOSH and MOAH was possible for samples with MOSH/MOAH ratios around one. For other samples deconvolution of the MOSH and MOAH humps in the FID chromatogram using the UV signal was needed since baseline separation of the two fractions could not be obtained. Validation of the method performance showed an excellent linearity (R2 > 0.9995) in the range of concentrations tested (2.5-100 mgmL-1) and a better repeatability than the standard methods (<5%). MOAH detection limits were better than 0.36% MOAH, which makes the method sufficiently sensitive for analysis of all but the highest purity mineral oils. The proposed SFC-FID/UV method was suitable for the analysis of mineral oils with viscosities and molecular weights below approximately 56 mm2s-1 and 450 gmol-1. The quantitative results of the new method were not statistically significantly different from those obtained with the standard SPE-GC-FID method where the new method has the advantages of a better repeatability, simpler operation and a significantly shortened analysis time. This new method could potentially also be used for the analysis of mineral oil contaminations in consumer products such as foods. However, in this case additional sample clean-up and preconcentration steps are needed for reducing matrix interferences from e.g. triglycerides and olefins and for improving the detection limits.

Dietary exposure of the Belgian population to mineral oil.

Recently, presence of mineral oil in numerous foods has been detected. The analysis of mineral oil in food is convoluted since it comprises MOSH (saturated hydrocarbons) and variable amounts of mainly alkylated MOAH (aromatic hydrocarbons). Both fractions have a different toxicological profile and therefore they need to be assessed separately. For Belgium, occurrence data are available comprising concentrations of 217 food samples. These data were used, in combination with the 2014/15 Belgian Food Consumption Survey data, in a lower bound scenario to evaluate the dietary exposure of the Belgian population. Exposure to mineral oil was much lower compared to the results previously reported by EFSA and RIVM. The main contributors in Belgium were similar to previous studies (i.e. cereal products and oils), but an important additional contribution of non-alcoholic drinks was identified due to the presence of mineral oil in coffee. However, the concentration of mineral oil was determined from the dry product by applying a dilution factor with transfer rate of 100%, and not in the prepared coffee.This study gives an account of the dietary exposure of the Belgian population to mineral oil for the first time and reports the associated uncertainties.

Comprehensive off-line silver phase liquid chromatography × gas chromatography with flame ionization and vacuum ultraviolet detection for the detailed characterization of mineral oil aromatic hydrocarbons.

Highly purified mineral oils used for the elaboration of pharmaceutical, food and cosmetic products can contain residual mineral oil aromatic hydrocarbons (MOAH). Quantification of the MOAH level as well as detailed characterization of the aromatic species present is important for safety evaluations and for optimization of the purification process. Two comprehensive off-line silver phase liquid chromatography × gas chromatography (AgLC × GC) methods, one with flame ionization detection (FID) and another with vacuum ultraviolet detection (VUV), were developed for MOAH analysis. The methods showed a better resolution between the MOSH and MOAH groups compared to the traditional online LC-GC methods due to the different retention mechanisms employed in the two dimensions, albeit that the gain was less than seen e.g. in edible oil analysis. An important advantage of the new comprehensive AgLC × GC methods is that the use of markers to determine the MOSH/MOAH cut-point is no longer needed, because all the eluent coming from the LC separation is transferred as narrow fractions to the GC. Due to the use of silver based stationary phases in the first separation dimension, a group-type separation of the mineral oil according to the degree of aromaticity (aliphatics, mono-aromatics and poly-aromatics) was obtained. Moreover, thanks to the use of VUV detection, the new method also delivered additional structural information on the different groups of compounds present.