Travelling-wave ion mobility time-of-flight mass spectrometry as an alternative strategy for screening of multi-class pesticides in fruits and vegetables.

This paper reports a novel approach to screening multi-class pesticides by ion mobility time-of-flight mass spectrometry detection. Nitrogen was selected as mobility gas. After optimization of the different ion mobility parameters, determination of matrix effect on the drift times was conducted using different matrix extracts. The results showed that drift time values are not influenced by the matrix and also are independent of the concentration within the working range for 100 pesticides tested, making drift time a powerful additional identification tool. Based on statistics, 2% variation criteria provides a good fit for all the pesticides targeted, and could be considered as a maximum acceptable criteria associated with the drift time parameter for identification purpose. This 2% value is in agreement with already reported criteria, for instance, for GC or LC retention time in European documents. Finally, the well-known feature of mobility to separate complex mixtures was also tested to obtain purified extracted mass spectra of pesticides present in fruit extract.

Determination of caramel colorants' by-products in liquid foods by ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS).

2-Methylimidazole, 4-methylimidazole (2-MI and 4-MI), 2-acetyl-4-(1,2,3,4-tetrahydroxybutyl) imidazole (THI) and 5-hydroxymethylfurfural (5-HMF) are neo-formed compounds generated during the manufacture of caramel colours and are transferred to the processed food. These contaminants are known to have a toxicological profile that may pose health risks. Hence, to characterise THI, 2- and 4-MI and 5-HMF levels in liquid foods, an ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed and sample preparation was divided into two analytical strategies depending on the concentration range expected in the type of foods targeted. For the determination of the imidazole substitutes (THI, 2- and 4-MI), a sample enrichment and clean-up step by strong cation solid-phase extraction was developed. This method is capable of quantifying over a range of 5 ng ml⁻¹ (LOQ) to 500 ng ml⁻¹ with recoveries of 75.4-112.4% and RSDs of 1.5-15%. For determination of 5-HMF, a standard addition method was applied covering the linear range of 0.25-30 µg ml⁻¹ with RSDs from 2.8% (for intraday precision) to 9.2% (for intermediate precision). The validated analytical methods were applied to 28 liquid food samples purchased from local markets. THI was found only in the beer samples at levels up to 141.2 ng ml⁻¹. For 2-MI, non-quantifiable traces were observed for all samples, while 4-MI was observed in all samples with large concentration variations (from < LOQ to 563.9 ng ml⁻¹). 5-HMF was found at expected concentrations, except for a sherry vinegar sample (113 µg ml⁻¹), which required a high level of dilution before following the standard addition protocol.

Dietary exposure of the Belgian adult population to non-dioxin-like PCBs.

Non-dioxin-like polychlorinated biphenyls (ndl-PCBs), and some of their metabolites, might initiate neurological, neuroendocrinological, immunological and carcinogenic effects. Dietary exposure of the Belgian adult population to ndl-PCBs was investigated in this study. Foods from five food groups, collected in Belgium in 2008, were analyzed by GC-MS/MS for the six indicator PCBs (PCB 28, 52, 101, 138, 153 and 180). Results were expressed as the sum of the six congeners. A dietary exposure assessment was performed, combining ndl-PCBs levels found in food with data from the national food consumption survey of 2004. Fish and fish products were the dominating food group in terms of contamination level, with the highest levels measured in the composite sample «other fishes¼ (18.58 ng/g FW). The dietary exposure of the Belgian population (n=3083) to ndl-PCBs ranged from 5.33 ng/kg b.w./day on average to 16.10 ng/kg b.w./day at the 99th percentile, using the lower bound concentration. The mean dietary exposure mainly originates from Fish and fish products (54.3%), followed by dairy products (28.5%). As neither EFSA nor JECFA have set a Tolerable Daily Intake for ndl PCBs, uncertainty remains about how to interpret the exposure data in terms of public health.

A rapid and environmental friendly determination of the dithiocarbamate metabolites ethylenethiourea and propylenethiourea in fruit and vegetables by ultra high performance liquid chromatography tandem mass spectrometry.

Previous published methods for the analysis of ETU and PTU are time-consuming and furthermore use dichloromethane (DCM) for extraction or clean-up. This study details the development and validation of a rapid method that combines a simple extraction step with UHPLC-ESI(+)-MS/MS. This is the first application of UHPLC-MS/MS to analyse these compounds. Besides that, we replaced DCM with a more environmental-friendly solvent. The analytical performance was evaluated with the analysis of spiked celery samples at 50 µg kg(-1) (LOQ) and 300 µg kg(-1). The recoveries were between 65% and 90% for ETU and between 71% and 127% for PTU with RSDs in repeatability and reproducibility conditions below 10% for ETU. This method is rapid (a chromatographic run time of 2 min) and can easily be performed (no laborious clean-up). The presented method is environmental friendly with significant reduction in solvent consumption.

Dietary intake of hexabromocyclododecane diastereoisomers (α-, ß-, and γ-HBCD) in the Belgian adult population.

A study was performed to assess exposure of the Belgian population to HBCD diastereoisomers. Measurements of HBCD were performed by UPLC-MS/MS, on 45 composite samples from 5 major food groups: dairy (products), meat (products), eggs, fish (products) and a group of "other" products. The medium bound estimated average daily intake (EDI) of ΣHBCD in the Belgian population was 0.99 ng kg(-1)bw d(-1). The diastereoisomer contribution to the mean EDI showed a predominance of γ-HBCD at 67%, followed by α-HBCD at 25% and 8% for ß-HBCD. These results are consistent with the pattern found in the two food groups contributing the most to the EDI: meat (products) and the group of "other" products. Anyway, it has to be noted that diastereomeric distribution of HBCD can change due to bioisomerisation in biological material. Levels of HBCD diastereoisomers found in Belgian food samples of animal origin were low in comparison with those found in other EU countries and the resulting EDI was substantially below the proposed thresholds.

Fourth WHO-coordinated survey of human milk for persistent organic pollutants (POPs): Belgian results.

Persistent organic pollutants (POPs) are chemicals that accumulate in the food chain and are toxic to humans and wildlife. The fourth World Health Organization (WHO) survey on POP levels in human milk (2006-2009) aims to provide baseline and trend information on human exposure to POPs. So far Belgium participated in all three previous rounds (1988, 1992, 2001). Whereas the first three rounds focused on determination of dioxins and PCBs in pooled (mixed) samples, the fourth survey comprised the analyses of individual milk samples for nine "basic POPs" (chlorinated pesticides and indicator PCBs) and of pooled milk samples for "basic POPs", "advanced POPs" (dioxins and dioxin-like PCBs) and "optional POPs" (polybrominated diphenylethers [PBDEs], polybrominated dioxins and dibenzofurans [PBrDD/F], mixed halogenated dioxins and dibenzofurans [PXDD/F] and hexabromocyclododecane [HBCD]). For the Belgian participation human milk samples were collected during the summer of 2006 from 197 women between 18 and 30 years old distributed over all Belgian provinces. The individual samples were analyzed in a Belgian Laboratory for "basic" POPs. A pooled sample was made from 178 individual samples and analyzed by the WHO Reference Laboratory for the "basic, advanced and optional" POPs. The results indicate that most organochlorinated pesticides banned 25-30 years ago were below or around detection limits in Belgian human milk samples although DDE was still found at low levels in all samples. Over the last five years the levels of marker PCBs and PCDD/Fs in Belgian human milk decreased, respectively, by 58% and 39%. For some of the other emerging or older compounds recent international data are needed to allow comparison. This shows the importance of international studies as run by WHO.

Dioxin and dioxin-like activity in sediments of the Belgian coastal area (Southern North Sea).

Dioxin and dioxin-like activity in sediments of the North Sea, along the Belgian coast, was assessed with the bioassay CALUX (Chemically Activated LUciferase gene eXpression). Crude extracts of the samples as well as the dioxin fraction (PCDD/Fs) obtained after a thorough clean-up procedure were analyzed with the CALUX method. When analyzing the cleaned extract, a general low contamination level is observed (around 0.1 pg CALUX-TEQ/g sediment), except at the mouth of the two main rivers-the Yser and the Scheldt-where concentrations measured are about 100 times higher (10-42 pg CALUX-TEQ/g sediment). Much higher potencies are measured for the crude extracts compared to the cleaned ones. In the crude extracts, the highest dioxin-like activities were again observed at the mouth and outflow of the two rivers (600-7200 pg CALUX-TEQ/g sediment). These activities are at least two orders of magnitude higher than the ones found at the coastal and sea stations (1.3-45 pg CALUX-TEQ/g sediment). The difference in activity between cleaned and crude sediment extracts is due to the presence of dioxin-like compounds such as, for example, non-ortho and mono-ortho polychlorinated biphenyls and polybrominated dioxins, but also to PAHs. The percentage of five major PAHs in the crude samples at the river mouths, when using the average activities in those samples, varies between 25% and 50%.