Validity of self-reported indicators to assess secondhand smoke exposure in the home.

INTRODUCTION: Questionnaires are widely used to assess secondhand smoke (SHS) exposure. However, the validity of self-reported SHS exposure indicators has been rarely assessed. We aimed to assess correlations, sensitivity, specificity, and predictive values between self-reported SHS exposure indicators and airborne nicotine concentrations. METHODS: We performed a cross-sectional study with a convenience sample of 175 homes in Barcelona and Santiago de Compostela, Spain. Airborne nicotine samples were collected from participants' homes and a self-administered questionnaire was completed on SHS exposure in the home. Spearman correlations coefficients and sensitivity, specificity and predictive values were assessed between self-reported SHS exposure indicators and nicotine concentrations in the home. RESULTS: All self-reported SHS exposure indicators correlated moderately strongly with airborne nicotine concentrations (Spearman correlations coefficient ranging from 0.58 to 0.65). Moreover, sensitivities and negative predictive values between self-reported indicators and the presence of nicotine in the home were below 66.4% while specificities and positive predictive values were over 78.4%. The "number of people usually smoking in the home" showed the best results (rs = 0.65, p < 0.001; sensitivity = 50.4%, specificity = 95.2%, PPV = 95.0, NPV = 51.3). CONCLUSIONS: The self-reported SHS indicators assessed in this study showed moderate and strong correlations, low sensitivities, and high specificities. Among them, the best results were obtained with the "number of people usually smoking in the home".

Second-hand smoke exposure in homes with children: assessment of airborne nicotine in the living room and children's bedroom.

BACKGROUND: The introduction of 'smoke-free laws' has reduced the population's exposure to second-hand smoke (SHS), although SHS is still an issue in homes and other public places. Children are vulnerable to its health effects, and their greatest exposure occurs at home. OBJECTIVES: To assess airborne nicotine concentration of the living room and children's bedroom of homes with children under 13 years of age, and to analyse factors associated with these levels. METHODS: We conducted a cross-sectional study in Barcelona in 2015-2016, selecting a convenience sample from families with at least one child under 13 years of age. The sample comprised 50 families with smokers and 50 without. We measured airborne nicotine concentrations in the living room and children's bedroom, and, using a questionnaire administered to the parents, collected information about smoking habits at home. RESULTS: Homes without smokers showed nicotine concentrations below the limit of detection (<0.02 µg/m3), while those with at least one smoker showed 0.16 µg/m3 in the living room and 0.12 µg/m3 in the bedroom. When smoking was allowed inside home, these values increased to 1.04 and 0.48 µg/m3, respectively. Moreover, nicotine concentrations in both rooms were strongly correlated (r=0.89), and higher nicotine levels were associated with the number of cigarettes smoked in the living room, smoking rules, the number of smokers living at home and tobacco smell. CONCLUSIONS: Homes with smokers present SHS in the living room and in the children's bedroom. Therefore, programmes focused on reducing children's SHS exposure are urgently needed.

Analysis of non-steroidal anti-inflammatory drugs in milk using QuEChERS and liquid chromatography coupled to mass spectrometry: triple quadrupole versus Q-Orbitrap mass analyzers.

We developed a Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method for the high throughput determination of 10 non-steroidal anti-inflammatory drugs (NSAIDs) in milk samples using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) with a triple quadrupole (QqQ) instrument and an electrospray ionization (ESI) source. The new extraction procedure is highly efficient, and we obtained absolute recoveries in the range 78.1-97.1 % for the extraction and clean-up steps. Chromatographic separation is performed in the gradient mode with a biphenyl column and acidic mobile phases consisting of water and acetonitrile containing formic acid. The chromatographic run time was about 12 min, and NSAID peaks showed a good symmetry factor. For MS/MS detection, we used multiple reaction monitoring (MRM) mode, using ESI in both positive and negative modes. Our method has been validated in compliance with the European Commission Decision 657/2002/EC, and we obtained very satisfactory results in inter-laboratory testing. Furthermore, we explored the use of a hybrid high resolution mass spectrometer, combining a quadrupole and an Orbitrap mass analyzer, for high resolution (HR) MS/MS detection of NSAIDs. We achieved lower NSAID quantification limits with Q-Orbitrap high resolution mass spectrometry (HRMS/MS) detection than those achieved with the QqQ instrument; however, its main feature is its very high selectivity, which makes HRMS/MS particularly suitable for confirmatory analysis.

Second-hand smoke exposure in indoor and outdoor areas of cafés and restaurants: Need for extending smoking regulation outdoors?

Smoke-free legislation in indoor public places has concentrated smokers in the areas outside building entrances or other outdoor areas. This study assessed the drift of second-hand smoke between outdoor and indoor areas of cafés and restaurants in Barcelona, Spain, and characterized the exposure on outdoor terraces. Using a cross-sectional design, we monitored vapor-phase nicotine in indoor areas and outside entrances simultaneously (n=47), and on some outdoor terraces (n=51). We computed the median nicotine concentration and interquartile range (IQR) to describe the data and performed multivariate analysis to describe nicotine concentration and its determinants. The overall median nicotine concentration indoors was 0.65µg/m(3) (IQR: 0.29-1.17µg/m(3)), with significant differences based on the number of smokers at the entrance (p=0.039). At outside entrances, the overall median nicotine concentration was 0.41µg/m(3) (IQR: 0.21-1.17µg/m(3)). The nicotine concentrations indoors and at the corresponding outside entrances were not significantly different, and the multivariate analysis confirmed the relationship between these variables. On terraces, the overall median nicotine concentration was 0.54µg/m(3) (IQR: 0.25-1.14µg/m(3)), but it increased to 0.60µg/m(3) when a tobacco smell was perceived, 0.72µg/m(3) on closed terraces, 1.24µg/m(3) when there were >6 smokers, and 1.24µg/m(3) when someone smoked >20min. Multivariate analysis confirmed the outdoor terrace area, the season, the type of enclosure, and the number of smokers as the most relevant variables explaining nicotine concentration (R(2)=0.396). These findings show that second-hand smoke exposure exists in indoor areas due to smokers smoking at the outside entrances. In addition, exposure may occur on outdoor terraces when smokers are present and the terrace is enclosed to some extent. Thus, the current Spanish law does not fully protect non-smokers from second-hand smoke and supports extending regulation to some outdoor areas.

Human health risks derived from dietary exposure to toxic metals in Catalonia, Spain: temporal trend.

The present study was aimed at estimating the current (2012) dietary intake of arsenic (As), cadmium (Cd), mercury (Hg), and lead (Pb) by the population of Catalonia, Spain. The temporal trends with respect to previous surveys, performed in 2000, 2005, and 2008, were also determined. For that purpose, metal concentrations were analyzed in a number of widely consumed foodstuffs. A speciation study was also conducted by experimentally determining the levels of inorganic As (InAs) and methylmercury (MeHg) in the same food items. Furthermore, the dietary intake of those metals and species was calculated both deterministically and probabilistically by considering two food consumption surveys: ENCAT and ENIDE, representative of the Catalan and Spanish populations, respectively. An important temporal decrease of the dietary intake was noted for most elements, irrespective of the age-gender population group. Considering data for a male adult, the current dietary intake of As, InAs, Cd, Hg, MeHg, and Pb was estimated in 216, 2.6, 8.7, 10, 7.3, and 8.4 µg/day, respectively, being these values lower than the respective provisional tolerable weekly intakes (PTWIs) or benchmark dose lower confidence limits (BMDLs). Moreover, new calculations by means of ENIDE survey indicated similar results to those previously obtained by ENCAT, with the exception of MeHg, whose intake exceeded the maximum recommended values for some part of the population. Although our data are similar to those frequently found in other European countries, the important intake of MeHg, which is linked to the high consumption of fish and shellfish, deserves further investigation.

A false positive case due to matrix interference in the analysis of ronidazole residues in muscle tissue using LC-MS/MS.

In contrast with the information of the inspection body concerning the use of ronidazole, several non compliant muscle samples were detected using a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method in accordance with confirmation criteria of Decision 2002/657/EC. This led to the suspicion that non compliance could be due to false positive results. In this context, a liquid chromatography-high resolution mass spectrometry (LC-HRMS) method was developed and sample extracts were re-analyzed, resolving the co eluting isobaric interfering peak, which also has an interfering product ion with the transition product (m/z 201>140).

A need for determination of arsenic species at low levels in cereal-based food and infant cereals. Validation of a method by IC-ICPMS.

The present study arose from the need to determine inorganic arsenic (iAs) at low levels in cereal-based food. Validated methods with a low limit of detection (LOD) are required to analyse these kinds of food. An analytical method for the determination of iAs, methylarsonic acid (MA) and dimethylarsinic acid (DMA) in cereal-based food and infant cereals is reported. The method was optimised and validated to achieve low LODs. Ion chromatography-inductively coupled plasma mass spectrometry (IC-ICPMS) was used for arsenic speciation. The main quality parameters were established. To expand the applicability of the method, different cereal products were analysed: bread, biscuits, breakfast cereals, wheat flour, corn snacks, pasta and infant cereals. The total and inorganic arsenic content of 29 cereal-based food samples ranged between 3.7-35.6 and 3.1-26.0 µg As kg(-1), respectively. The present method could be considered a valuable tool for assessing inorganic arsenic contents in cereal-based foods.

Targeted analysis with benchtop quadrupole-orbitrap hybrid mass spectrometer: application to determination of synthetic hormones in animal urine.

Sensitive and unequivocal determination of analytes/contaminants in complex matrices is a challenge in the field of food safety control. In this study, various acquisition modes (Full MS/AIF, Full MS+tMS/MS, Full MS/dd MS/MS and tSIM/ddMS/MS) and parameters of a quadrupole-orbitrap hybrid mass spectrometer (Q Exactive) were studied in detail. One of the main conclusions has been that, reducing the scan range for Full MS (using the quadrupole) and targeted modes give higher signal-to-noise (S/N) ratios and thereby better detection limits for analytes in matrix. The use of Q Exactive in a complex case, for the confirmatory analysis of hormones in animal urine is presented. A targeted SIM data dependent MS/MS (tSIM/ddMS/MS) acquisition method for determination of eight synthetic hormones (trenbolone, 17α ethinylestradiol, zeranol, stanozolol, dienestrol, diethylstilbestrol, hexestrol, taleranol) and a naturally occurring hormone (zearalenone) in animal urine were optimized to have sensitive precursors from targeted SIM mode and trigger MS/MS scans over the entire chromatograph peak. The method was validated according to EC/657/2002. CCα (decision limit) for the analytes ranged between 0.11 µg L(-1) and 0.69 µg L(-1) and CCß (detection capability) ranged between 0.29 µg L(-1) and 0.90 µg L(-1).

Determination of aminoglycoside residues in kidney and honey samples by hydrophilic interaction chromatography-tandem mass spectrometry.

Two methods based on liquid chromatography-tandem mass spectrometry were developed for the determination of ten aminoglycosides (streptomycin, dihydrostreptomycin, spectinomycin, apramycin, paromomycin, kanamycin A, gentamycin C1, gentamycin C2/C2a, gentamycin C1a, and neomycin B) in kidney samples from food-producing animals and in honey samples. The methods involved extraction with an aqueous solution (for the kidney samples) or sample dissolution in water (for the honey samples), solid-phase extraction with a weak cation exchange cartridge and injection of the eluate into a liquid chromatography-tandem mass spectrometry system. A zwitterionic hydrophilic interaction chromatography column was used for separation of aminoglycosides and a triple quadrupole mass analyzer was used for detection. The methods were validated according to Decision 2002/657/EC. The limits of quantitation ranged from 2 to 125 µg/kg in honey and 25 to 264 µg/kg in the kidney samples. Interday precision (RSD%) ranged from 6 to 26% in honey and 2 to 21% in kidney. Trueness, expressed as the percentage of error, ranged from 7 to 20% in honey and 1 to 11% in kidney.

The power of hyphenated chromatography/time-of-flight mass spectrometry in public health laboratories.

Laboratories devoted to the public health field have to face the analysis of a large number of organic contaminants/residues in many different types of samples. Analytical techniques applied in this field are normally focused on quantification of a limited number of analytes. At present, most of these techniques are based on gas chromatography (GC) or liquid chromatography (LC) coupled to tandem mass spectrometry (MS/MS). Using these techniques only analyte-specific information is acquired, and many other compounds that might be present in the samples would be ignored. In this paper, we explore the potential of time-of-flight (TOF) MS hyphenated to GC or LC to provide additional information, highly useful in this field. Thus, all positives reported by standard reference targeted LC-MS/MS methods were unequivocally confirmed by LC-QTOF MS. Only 61% of positives reported by targeted GC-MS/MS could be confirmed by GC-TOF MS, which was due to its lower sensitivity as nonconfirmations corresponded to analytes that were present at very low concentrations. In addition, the use of TOF MS allowed searching for additional compounds in large-scope screening methodologies. In this way, different contaminants/residues not included in either LC or GC tandem MS analyses were detected. This was the case of the insecticide thiacloprid, the plant growth regulator paclobutrazol, the fungicide prochloraz, or the UV filter benzophenone, among others. Finally, elucidation of unknowns was another of the possibilities offered by TOF MS thanks to the accurate-mass full-acquisition data available when using this technique.

Hydrophilic interaction chromatography for the analysis of aminoglycosides.

The effect of mobile-phase constituents (pH and ionic strength) and chromatographic behaviour of ten aminoglycosides (streptomycin, dihydrostreptomycin, spectinomycin, apramycin, paramomycin, kanamycin A, gentamycin C1, gentamycin C2/C2a, gentamycin C1a and neomycin) in the bare silica, amino, amide and zwitterionic phases of hydrophilic interaction chromatography (HILIC) were studied systematically. Among the stationary phases studied, the zwitterionic phase provided the best separation of aminoglycosides. The effect of pH, ionic concentration and column temperature on retention time, peak shape and sensitivity was studied using a central composite design. pH affected sensitivity of the detection of analytes but not the retention time. High ionic strength in the mobile phase was necessary to control the ionic interactions between ionised aminoglycosides and the hydrophilic phase, thereby influencing peak shape and retention time. Column temperature affected sensitivity of the detection but not the retention time. During method development, crosstalk between the MS/MS channels of the analytes was observed and resolved.

Multiresidue method for pesticide residue analysis in food of animal and plant origin based on GC or LC and MS or MS/MS.

A multiresidue method based on GC or LC and MS or MS/MS for the determination of 204 pesticides in diverse food matrixes of animal and plant origin is described. The method can include different stages of cleanup according to the chemical characteristics of each sample. Samples were extracted using accelerated solvent extraction. Those with a high fat content or that contained chlorophyll required further purification by gel permeation chromatography and/or SPE (ENVI-Carb). The methodology developed here was fully validated; the LOQs for the 204 pesticides are presented. The LOQ values lie between 0.01 to 0.02 mg/kg. However, in some cases, mainly in baby food, they were as low as 0.003 mg/kg, thereby meeting European Union requirements on maximum residue levels for pesticides, as outlined in European regulation 396/2005 and the Commission Directive 2003/13/EC. The procedure has been accredited for a wide scope of pesticides and matrixes by the Spanish Accreditation Body (ENAC) following ISO/IEC 17025:2005, as outlined in ENAC technical note NT-19.

Total and inorganic arsenic in marketed food and associated health risks for the Catalan (Spain) population.

Inorganic arsenic (iAs) is considered to be a human carcinogen. In this paper, total (As) and iAs contents of 215 food products and drinks (i.e., seafood, fruits and vegetables, meat products, oils and fats, rice and rice products, seasonings, and alcoholic drinks) marketed in Catalonia (Spain) were quantified by inductively coupled plasma-mass spectrometry. The analytical method described was used for different food products, obtaining feasible results without the need to couple LC-ICP-MS for iAs. Daily As and iAs intakes for the average adult Catalan consumer were estimated at 354 and 6.1 µg/day/person, respectively, using consumption data from the Catalan Nutrition Survey (ENCAT). The highest As content was found in seafood, contributing 96% of dietary As intake, whereas rice presented the highest iAs values, corresponding to 67% of dietary iAs intake. As cooking process may affect iAs content, boiled rice was evaluated, showing an iAs reduction (up to 86%) when using higher water volumes (30:1 water/rice ratio) than those used in previous studies. This iAs exposure was slightly below the exposure risk range stated by the European Food Safety Authority (0.3-8 µg/kg of body weight/day), although the possibility of a risk to the population with high rice consumption cannot be excluded.

Secondhand smoke exposure in hospitality venues in Europe.

BACKGROUND: Although in the last few years some European countries have implemented smoking bans in hospitality venues, the levels of secondhand smoke (SHS) in this occupational sector could still be extremely high in most countries. OBJECTIVE: The aim of this study was to assess exposure to SHS in hospitality venues in 10 European cities. METHODS: We included 167 hospitality venues (58 discotheques and pubs, 82 restaurants and cafeterias, and 27 fast-food restaurants) in this cross-sectional study. We carried out fieldwork in 10 European cities: Vienna (Austria), Paris (France), Athens (Greece), Florence and Belluno (Italy), Galway (Ireland), Barcelona (Spain), Warsaw and Lublin (Poland), and Bratislava (Slovak Republic). We measured vapor-phase nicotine as an SHS marker. RESULTS: We analyzed 504 samples and found nicotine in most samples (97.4%). We found the highest median concentrations in discos/pubs [32.99 microg/m(3); interquartile range (IQR), 8.06-66.84 microg/m(3)] and lower median concentrations in restaurants/cafeterias (2.09 microg/m(3); IQR, 0.49-6.73 microg/m(3)) and fast-food restaurants (0.31 microg/m(3); IQR, 0.11-1.30 microg/m(3)) (p < 0.05). We found differences of exposure between countries that may be related to their smoking regulations. Where we sampled smoking and nonsmoking areas, nicotine concentrations were significantly lower in nonsmoking areas. CONCLUSIONS: Hospitality venues from European cities without smoking regulations have very high levels of SHS exposure. Monitoring of SHS on a regular basis as well as a total smoking ban in hospitality sector would be needed.

Secondhand smoke in hospitals of Catalonia (Spain) before and after a comprehensive ban on smoking at the national level.

OBJECTIVE: To assess changes in secondhand smoke exposure by means of airborne nicotine concentrations in public hospitals of Catalonia (Spain) before and after a comprehensive national smoking ban. METHODS: We monitored vapor-phase nicotine concentrations in 44 public hospitals in Catalonia (Spain) before the smoking ban (September-December 2005) and one year after (September-December 2006). We installed 5-7 sampling devices per hospital for 7 days in different places (228 pairs of samples), and 198 pairs of samples were available for the final analysis. RESULTS: The median nicotine concentration declined from 0.23 microg/m(3) (interquartile range: 0.13-0.63) before the law to 0.10 microg/m(3) (interquartile range: 0.02-0.19) after the law (% decline=56.5, p<0.01). We observed significant reductions in the median nicotine concentrations in all hospital locations, although secondhand smoke exposure was still present in some places (main hospital entrance, emergency department waiting rooms, fire escapes, and cafeterias). CONCLUSIONS: Secondhand smoke in hospitals has decreased after the ban. Assessment of airborne nicotine concentrations appears to be an objective and feasible system to monitor and reinforce the compliance of smoke-free legislations in this setting.

Determination of synthetic hormones in animal urine by high-performance liquid chromatography/mass spectrometry.

A method was developed for the extraction of stanozolol, taleranol, zeranol, hexestrol, dienestrol, ethynylestradiol, diethylstilbestrol, and trenbolone from animal urine. The analytes were extracted from the matrix by enzymatic hydrolysis, solid-phase extraction, and liquid-liquid extraction. Detection and quantitation were performed on a high-performance liquid chromatography system coupled to a triple quadrupole mass spectrometer. The identification criteria met the European Union regulations. Validation of this method established a decision limit between 0.2 and 0.9 microg/L and a detection capability between 0.3 and 1.0 microg/L, depending on the analyte.

[Pesticides in the diet: adding pieces to the puzzle]. / Plaguicidas en la dieta: aportando piezas al rompecabezas.

OBJECTIVES: To improve information on exposure to pesticides through diet in Spain by reporting the results on 88 pesticide parameters in 1,109 food samples obtained between 1998 and 2003 as part of the Barcelona program for research on the health quality of foods. MATERIAL AND METHOD: The results are presented by food groups. For fruits and vegetables, the results were compared with those for the previous period. Statistical comparisons were performed using the chi2 test. RESULTS: Of the 1,109 samples, 116 were positive for pesticides (10.5%). Persistent chlorinated compounds were detected in 1.5% and other compounds were found in 14.4%. Positive results were concentrated in fruits, vegetables, spices, cereals and their derivatives. There were no positive results among vegetable oils, eggs or fish products, and almost none in dairy products and meats. Fruits contained the greatest number of pesticides but none were persistent. Vegetables contained fewer pesticides, but some of these were persistent chlorinated compounds. Comparison of the results for fruits and vegetables with those of the 1989-97 period revealed no significant trends. CONCLUSIONS: Although a considerable number of samples contained pesticides, most of these were not persistent chlorinated compounds. The number of pesticides in fruits was notable.

[Measurement of exposure to environmental tobacco smoke in education centers, health centers, transport facilities and leisure places]. / Medición de la exposición al humo ambiental de tabaco en centros de enseñanza, centros sanitarios, medios de transporte y lugares de ocio.

OBJECTIVES: To describe levels of exposure to environmental tobacco smoke (ETS) in various public places in Barcelona (Spain). MATERIAL AND METHOD: Vapor-phase nicotine was measured with passive samplers containing a sodium bisulfate treated filter with a 37 mm diameter. The places sampled were primary and secondary schools, hospitals, primary care centers, train stations, subways, universities, airports, restaurants and discotheques. RESULTS: Primary and secondary schools and health centers had the lowest levels of ETS exposure, with mean concentrations of less than 1 microg/m3. The mean values found in transport and universities were 2.16 microg/m3 in train stations, 3.30 microg/m3 in subways, 4.30 microg/m3 in airports and 4.97 microg/m3 in universities. The highest concentrations were found in restaurants and discotheques, with mean values of 12.36 microg/m3 in restaurants and 130.65 microg/m3 in discotheques. All samples taken from primary and secondary schools, airports, subways, restaurants and discotheques contained ETS. Likewise, 90% of the samples taken from train stations and 96% of those from universities contained ETS. Seventy-nine percent of the samples from hospitals and 58% of those from primary care centers contained ETS. CONCLUSIONS: The results confirm that passive smoking is an important public health problem in Spain and that greater efforts are needed to enforce smoke-free policies in public spaces and workplaces.

Plaguicidas en la dieta: aportando piezas al rompecabezas / Pesticides in the diet: adding pieces to the puzzle

Objetivos: Mejorar la informacion sobre la exposicion a plaguicidas mediante la dieta en nuestro pais con la presentación de los resultados de deteccion de 88 parametros de (..) (AU)

Objectives: To improve information on exposure to pesticides through diet in Spain by reporting the results on 88 pesticide parameters in 1,109 (AU)