A Non-Targeted High-Resolution Mass Spectrometry Study for Extra Virgin Olive Oil Adulteration with Soft Refined Oils: Preliminary Findings from Two Different Laboratories

This work presents a non-targeted high-resolution mass spectrometry inter-laboratory study for the detection of new chemical markers responsible of soft refined oils addition to extra virgin olive oils. Refined oils (soft deodorized and soft deacidified) were prepared on a laboratory scale starting from low-quality olive oils and analyzed together with a set of pure extra virgin olive oil (EVOO) samples and with mixtures of adulterated and pure EVOO at different percentages. The same analytical workflow was applied in two different laboratories equipped with two types of instrumentation (Q-Orbitrap and Q-TOF); a group of discriminant molecules was selected, and a tentative identification of compounds was also proposed. In summary, 12 molecules were identified as markers of this specific adulteration, and seven of them were selected as discriminative in both the laboratories, with a similar trend throughout the samples (i.e., propylene glycol 1 stearate). The results obtained in the two laboratories are comparable, concretely demonstrating the inter-laboratory repeatability of non-targeted studies. As a confirmation, the same markers were detected also in "in-house"mixtures and in suspect commercial deodorized mixtures, reinforcing the robustness of the results obtained and proving that, thanks to these molecules, mixtures containing at least 40% of adulterated oils can be detected

Metabolic fingerprinting strategy: Investigation of markers for the detection of extra virgin olive oil adulteration with soft-deodorized olive oils

As extra virgin olive oil (EVOO) is a high value commodity, it might be subject of various fraudulent practices. This study is focused on a challenging authentication issue, addition of lower grade, soft-deodorized olive oil to EVOO. In the first step, sample sets of authentic EVOOs, soft-deodorized oils and their admixtures were extracted by aqueous methanol; obtained polar fractions were then analysed by ultra-high performance liquid chromatography coupled to hybrid quadrupole time-of-flight high-resolution tandem mass spectrometry (UHPLC-QTOF-HRMS/MS). Subsequent chemometric evaluation of metabolic fingerprints enabled suggestion of several ions that might be characteristic for deodorized oils; most of tentatively identified compounds were oxidized fatty acid derivatives. In the second phase, the ‘marker' ions were employed for target analysis by ultra-high performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UHPLC-QqQ-MS/MS) what enabled achieving lower the detection limits. Two compounds were selected as the best markers for detection of soft-deodorized olive oil addition, tentatively identified as methyl ester of hydroxy octadecenoic acid and ester derivative of oleic acid

Analysis of chlormequat residue in milk by UPLC-MS/MS

Chlormequat is a plant growth regulator generally used to promote lateral branching and flowering of ornamental plants. It is also frequently used to improve yields for different types of cereals in Europe. These cereals are often processed into animal feed. Consequently chlormequat residues could potentially be found in matrices of animal origin. The MRL in milk were fixed at 0.05 mg/kg in annex I part B of the regulation 396/2005. Milk is a very complex matrix composed of different proteins and fat. Therefore, intensive clean-up is needed before injection to prevent interference or clogging during LC analysis. For the extraction, 4ml of water is added to 1g of milk just after the addition of chlormequat D4 as internal standard. The cleanup strategy selected was the use of dichloromethane andacetic acid to eliminate fat and precipitate protein, respectively. This step was followed by a solid phase extraction (SPE) of the aqueous phase on a Weak Cation Exchange cartridge. The chlormequat was eluted by using ammonium acetate, before injection on an UPLC-MS/MS system (Waters premier). Due to his ionic characteristic, no retention is observed on classical C18 column. The reverse phase polymethacrylate Shodex RSpak DE413 (150 × 4.6 mm) recommended in the CEN method prEN15054 has been selected. Isocratic condition (water/acetonitrile/ methanol/acetic acid - 71.25+17.5+7.5+3.75 V+V+V+V 50 mM ammonium acetate are used at a flow of 0.4 ml/min. The observed a retention time is 4.0 min. The analytical method has a limit of quantification of 0.025 mg/kg (limit of detection of 0.0125 mg/kg) and was validated following SANCO/12495/2011 criteria at the LOQ and at a higher level (10 times LOQ - 0.25 mg/kg). Results show a recovery of approximately 100% (between 100.6 and 103.0) with a repeatability and in-house reproducibility below 10%. These very good validation data are correlated to the robustness of the method and to the use of an isotopic surrogate.</p

Effect of household and industrial processing on levels of some pesticide residues in carrots

Pesticides are widely used in conventional agriculture to obtain a better yield for crops. They can cause toxic effects (headaches, cancer, reproductive harm and endocrine disruption). The main exposure to pesticides for humans is via food (especially by fruit and vegetables). Processing food can affect the level of pesticide residues and in some special case, more toxic by-products can be formed during processing. Different studies have been related to measure concentrations of pesticide residues after home or industrial processing. However, many processing factors (residues level in processed commodity/residue level in raw commodity) remain unknown and are necessary to estimate the level of pesticide exposure at the point of consumption after processing. To reach this objective, the combination carrots/pesticides (boscalid, chlorpyrifos, difenoconazole, dimethoate, linuron and tebuconazole) was chosen in collaboration with the Belgian Federal Agency for Safety of the Food Chain based on the number of non compliant samples, frequency and concentration level observed and on the toxicity of the pesticides. Treated carrots were grown in Belgium by Redebel sa. The amount of the pesticide residues observed in the raw material varied due to the different treatments, application times, weather conditions, the physico-chemical properties of each pesticide. Food processing (washing, peeling, blanching, microwave cooking, pasteurization and sterilization) was carried out on industrial pilot scale. Pesticides and the degradation products formed during processing were analyzed with GC–MS/MS and UHPLC–MS/MS. The washing step allowed decreasing the concentration of residues for all pesticides up to ~90%. The second process, peeling, results in a reduction comparable to washing. The blanching step, combining heat with a large quantity of water, enhanced the elimination of residues. Even residual concentrations were below 5 ppb, it was observed that microwave cooking did not reduce the level of residues while in-pack sterilization decreased most of the pesticide residues still present except difenoconazole. To conclude, most of the processing factors could be explained in terms of water solubility, the log-octanol-water-partitioning coefficients, the systemic properties of the pesticides studied and the agricultural practices.</p

Field performance of the Chemcatcher passive sampler for monitoring hydrophobic organic pollutants in surface water

Six field trials were carried out to assess the performance of the Chemcatcher passive sampler alongside spot sampling for monitoring priority hydrophobic organic pollutants (polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides) in a wide range of conditions in surface water. The trials were performed in three European rivers: Elbe (Czech Republic), Alna (Norway) and Meuse (Netherlands), in two seasons (April-June 2004, and September-October 2004). Samplers spiked with performance reference compounds (PRCs) were deployed for either 14 or 28 days. Ten spot samples of water were collected over the course of the trial and filtered through a 0.7 mu m glass fibre filter. Concentrations of pollutants measured using the Chemcatcher were compared with the average concentrations found in spot samples. This study describes the operational performance of Chemcatcher for measuring hydrophobic (log K-OW 3.7-6.8) chemicals in surface water. Site specific Chemcatcher sampling rates up to 0.5 L d(-1) were found using the PRC approach that reduced the uncertainty in estimates of sampling kinetics where temperature, local flow conditions and biofouling potential varied between sites and seasons, and with time during sampler exposure. The limits of quantification of sampled analytes ranged from one to tens ng L-1. Highest sensitivity was achieved for compounds with a favourable combination of low instrument quantification limits and high sampling rates including dieldrin, hexachlorobenzene, lindane, pentachlorobenzene, and PAHs with less than five aromatic rings. The direct comparison of time weighted average (TWA) concentrations (mostly close to method limits of detection) obtained using passive and spot sampling was possible for lindane, hexachlorobenzene, and PAHs <4 rings. Implications of using the Chemcatcher in regulatory monitoring programmes such as the European Union Water Framework Directive are discussed

European food safety research : an explorative study with funding experts' consultation

The European research area exhibits considerable opacity and fragmentation in food safety research funding and organizational structures, impeding the exploitation of existing research potential across European countries. Given that food safety is inherently linked to the societal challenges of our time, identifying and removing existing barriers to research funding in this area is crucial. Towards investigating this matter, interviews were conducted with funding bodies from six European countries to assess key issues related to research funding in general and food safety in particular. Funding experts were then invited to a workshop to jointly discuss the challenges identified and explore strategies to address them. Evaluation of the food safety research funding situation in selected European countries revealed both convergences and significant differences among national funding bodies. Engaging with funding experts provided invaluable insights into the issues encountered with research funding, such as inadequate call management staff or insufficient research funds, culminating in a set of recommendations for action to remedy the situation

Origin authentication of distillers’ dried grains and solubles (DDGS) – Application and comparison of different analytical strategies

In the context of products from certain regions or countries being banned because of an identified or non-identified hazard, proof of geographical origin is essential with regard to feed and food safety issues. Usually, the product labeling of an affected feed lot shows origin and the paper documentation shows traceability. Incorrect product labeling is common in embargo situations, however, and alternative analytical strategies for controlling feed authenticity are therefore needed. In this study, distillers’ dried grains and solubles (DDGS) were chosen as the product on which to base a comparison of analytical strategies aimed at identifying the most appropriate one. Various analytical techniques were investigated for their ability to authenticate DDGS, including spectroscopic and spectrometric techniques combined with multivariate data analysis, as well as proven techniques for authenticating food, such as DNA analysis and stable isotope ratio analysis. An external validation procedure (called the System Challenge) was used to analyze sample sets blind (i.e., none of the study laboratories knew the origin of the samples until the coordinator received the results) and to compare analytical techniques. All the techniques were adapted so as to be applicable to the DDGS matrix. They produced positive results in determining the botanical origin of DDGS (corn vs. wheat) and several of them were able to determine the geographical origin of the DDGS in the sample set. The maintenance and extension of the databanks generated in this study through the analysis of new authentic samples from a single location is essential in order to monitor developments and processing that could affect authentication.JRC.D.5-Standards for Food Bioscienc

Origin authentication of distillers' dried grains and solubles (DDGS) - Application and comparison of different analytical strategies

In the context of products from certain regions or countries being banned because of an identified or non-identified hazard, proof of geographical origin is essential with regard to feed and food safety issues. Usually, the product labeling of an affected feed lot shows origin, and the paper documentation shows traceability. Incorrect product labeling is common in embargo situations, however, and alternative analytical strategies for controlling feed authenticity are therefore needed. In this study, distillers' dried grains and solubles (DDGS) were chosen as the product on which to base a comparison of analytical strategies aimed at identifying the most appropriate one. Various analytical techniques were investigated for their ability to authenticate DDGS, including spectroscopic and spectrometric techniques combined with multivariate data analysis, as well as proven techniques for authenticating food, such as DNA analysis and stable isotope ratio analysis. An external validation procedure (called the system challenge) was used to analyze sample sets blind and to compare analytical techniques. All the techniques were adapted so as to be applicable to the DDGS matrix. They produced positive results in determining the botanical origin of DDGS (corn vs. wheat), and several of them were able to determine the geographical origin of the DDGS in the sample set. The maintenance and extension of the databanks generated in this study through the analysis of new authentic samples from a single location are essential in order to monitor developments and processing that could affect authentication