Multi-residue determination of 130 multiclass pesticides in fruits and vegetables by gas chromatography coupled to triple quadrupole tandem mass spectrometry.

A multi-residue method has been developed and validated for the simultaneous quantification and confirmation of around 130 multiclass pesticides in orange, nectarine and spinach samples by GC-MS/MS with a triple quadrupole analyzer. Compounds have been selected from different chemical families including insecticides, herbicides, fungicides and acaricides. Three isotopically labeled standards have been used as surrogates in order to improve accurate quantitation. Samples were extracted by using accelerated solvent extraction (ASE) with ethyl acetate. In the case of spinach, an additional clean-up step by gel permeation chromatography was applied. Determination was performed by GC-MS/MS in electron ionization mode acquiring two MS/MS transitions for each analyte. The intensity ratio between quantitation transition (Q) and identification transition (q) was used as confirmatory parameter (Q/q ratio). Accuracy and precision were evaluated by means of recovery experiments in orange, nectarine, and spinach samples spiked at two concentration levels (0.01 and 0.05 mg/kg). Recoveries were, in most cases, between 70% and 120% and RSD were below 20%. The limits of quantification objective for which the method was satisfactorily validated in the three samples matrices were for most pesticides 0.01 mg/kg. Matrix effects over the GC-MS/MS determination were tested by comparison of reference standards in pure solvent with matrix-matched standards of each matrix. Data obtained showed enhancement of signal for the majority of analytes in the three matrices investigated. Consequently, in order to reduce the systematic error due to this effect, quantification was performed using matrix-matched standard calibration curves. The matrix effect study was extended to other food matrices such as raisin, paprika, cabbage, pear, rice, legume, and gherkin, showing in all cases a similar signal enhancement effect.

Surveillance of dioxins and polychlorinated biphenyls (PCBs) in food commercialized in Barcelona, Spain.

This study explored the potential use of seven congeners of polychlorinated biphenyls (PCBs-7) as indicator compounds for the presence of dioxins and PCBs in food samples, as part of the routine surveillance programme of a public health agency. Samples of 24 foodstuffs with high fat content were collected (ten fresh fish, six dairy products, five meat and three eggs). Duplicate analyses were performed. A research laboratory tested samples for seven polychlorinated dibenzo-p-dioxin (PCDDs), ten dibenzofurans (PCDFs) and twelve dioxin-like PCBs, with limits of detection in the range of ng kg(-1) (ppt). The public health services official control laboratory tested samples for PCBs-7, with a limit of quantification of 5 µg kg(-1) (ppb). The research laboratory detected the presence of dioxins and dioxin-like PCBs in all samples; fish samples had the highest levels (0.04-10.3 pg WHO-TEQ g(-1)). The public health service official control laboratory detected PCBs-7 only in five samples, which were all fish. Comparing the results in the two laboratories there seems to be an association between the detection of PCB-7 and the presence of higher levels of PCDD/Fs and dioxin-like PCBs. The use of PCB-7 as an indicator compound may be a practical surveillance strategy for those foodstuffs with higher concentrations of dioxin-like congeners.

Italy and Austria before and after study: second-hand smoke exposure in hospitality premises before and after 2 years from the introduction of the Italian smoking ban.

UNLABELLED: The aim of this paper was to compare nicotine concentration in 28 hospitality premises (HPs) in Florence and Belluno, Italy, where a smoking ban was introduced in 2005, and in 19 HPs in Vienna, Austria, where no anti-smoking law entered into force up to now. Airborne nicotine concentrations were measured in the same HPs in winter 2002 or 2004 (pre-ban measurements) and winter 2007 (post-ban measurements). In Florence and Belluno, medians decreased significantly (P < 0.001) from 8.86 [interquartile range (IQR): 2.41-45.07)] before the ban to 0.01 microg/m3 (IQR: 0.01-0.41) afterwards. In Austria (no smoking ban) the medians collected in winters 2004 and 2007 were, respectively, 11.00 (IQR: 2.53-30.38) and 15.76 microg/m3 (IQR: 2.22-31.93), with no significant differences. Measurements collected in winter 2007 in 28 HPs located in Naples, Turin, Milan (0.01 microg/m3; IQR: 0.01-0.16) confirmed post-ban results in Florence and Belluno. The medians of nicotine concentrations in Italy and Austria before the Italian ban translates, using the risk model of Repace and Lowery, into a lifetime excess lung cancer mortality risk for hospitality workers of 11.81 and 14.67 per 10,000, respectively. Lifetime excess lung cancer mortality risks for bar and disco-pub workers were 10-20 times higher than that calculated for restaurant workers, both in Italy and Austria. In winter 2007, it dropped to 0.01 per 10,000 in Italy, whereas in Austria it remained at the same levels. The drop of second-hand smoke exposure indicates a substantial improvement in air quality in Italian HPs even after 2 years from the ban. PRACTICAL IMPLICATIONS: The nation-wide smoking ban introduced in Italy on January 10, 2005, resulted in a drop in second-hand smoke exposure in hospitality premises, whereas in Austria, where there is no similar nation-wide smoking ban, the exposure to second-hand smoke in hospitality premises remains high. Given that second-hand smoke is considered a group 1 carcinogen according to the International Agency for Research on Cancer classification, the World Health Organization Framework Convention on Tobacco Control strongly recommends the implementation of nation-wide smoke-free policies in order to improve the indoor air quality of hospitality premises and workplaces. Results from our study strongly supports this recommendation.

Chlorinated organic pesticides in marketed food: Barcelona, 2001-06.

This paper reports concentration levels of 22 chlorinated organic compounds (both primary compounds and metabolites) in food marketed in the city of Barcelona (Catalonia, Spain) in 2001-06. Samples included meat products, fish and seafood, eggs, milk and dairy, vegetal oils, cereal products and derivates, vegetables, fresh fruits, dry fruits, spices, formula and baby food, tea and wine. Levels of chlorinated organic compounds were determined by gas chromatography with selective detectors: electron capture (ECD), flame photometric (FPD) and confirmation with mass-spectrometry. Chlorinated organic pesticides were detected in 7 of the 1,484 samples analyzed in the 2001-06 period (0.5%): 1 dairy product, 1 fruit, 1 olive oil and 4 vegetables. Specific pesticides detected are lindane and endosulfan alpha, beta or sulphate. A decrease in both the proportion of samples with detectable residues and in the variety of chlorinated pesticides found is visible when comparing these results with those of the previous 1989-2000 period. These results suggest the gradual disappearance of regulated chlorinated organic pesticides as a consequence of the growing worldwide implementation of current regulatory agreements.

Polycyclic aromatic hydrocarbons in food samples collected in Barcelona, Spain.

This study reports on the concentrations of eight polycyclic aromatic hydrocarbons (PAHs) in food samples collected in the city of Barcelona (Catalonia, Spain) from 2003 to 2004. Food samples included meat products, fish (fresh and smoked), other seafood (cephalopods, crustaceans, and bivalves), vegetable oil, and tea. Concentrations of benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[g,h,i]perylene, benzo[alpha]pyrene, benzo[e]pyrene, dibenz[a,h]anthracene, and indeno[1,2,3-c,d]pyrene were determined by reversed-phase high-performance liquid chromatography with fluorescence detection. PAHs were detected in most tea samples (94%), which had the highest concentration of total PAHs (mean concentration of 59 microg/kg). Other food groups with a high presence of PAHs were bivalves (present in 34% of the samples; mean value of 2.7 microg/kg) and meat products (present in 13% of the samples; mean value of 1.7 microg/kg). The PAHs detected most frequently were benzo[e]pyrene and benzo[b]fluoranthene. No sample had levels above current regulation standards. Nevertheless, the frequent presence of PAHs in bivalves, tea samples, and meat products, together with the fact that dietary sources are the main exposure to these carcinogenic compounds, suggests the need for some monitoring scheme to follow up on these trends.

Environmental tobacco smoke exposure in public places of European cities.

BACKGROUND: Exposure to environmental tobacco smoke (ETS) has important public health implications. The results of the first European multi-centre study that measured ETS exposure in a range of public places (transport, educational settings, and leisure facilities such as bars and restaurants) are presented. METHOD: Nicotine vapour phase was measured using ETS passive samplers containing a filter treated with sodium bisulfate. RESULTS: Bars and discos are the places with the highest concentrations of nicotine from ETS, median ranging from 19 to 122 microg/m(3). Restaurants had the next highest values. Concentrations of nicotine generally range from 0.1-5 microg/m(3) in airports, and from 0.5-10 microg/m(3) in train stations. Nicotine was also found in schools and universities, yet schools tended to have the lowest concentrations compared to all the other public places sampled. In hospitals levels were generally below 5 microg/m(3). CONCLUSIONS: Although there is some variability between cities, this study shows that tobacco smoke is present in most of the studied public places. The study also showed that in areas where smoking is prohibited, concentrations of nicotine are lower than in areas where smoking is allowed but they are not zero. The results of this study indicate that policies should be implemented that would effectively reduce levels of tobacco smoke in public areas.