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Human milk is the healthiest option for newborns, although, under specific circumstances, infant formula is a precious alternative for feeding the baby. Except for the nutritional content, infant formulas and baby food must be pollutant-free. Thus, their composition is controlled by continuous monitoring and regulated by establishing upper limits and guideline values for safe exposure. Legislation differs worldwide, although there are standard policies and strategies for protecting vulnerable infants. This work presents current regulations and directives for restricting endocrine-disrupting chemicals and persistent organic pollutants in infant formulas. Risk assessment studies, which are limited, are necessary to depict exposure variations and assess the health risks for infants from dietary exposure to pollutants.
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The extensive use of antibiotics in livestock farming poses increased concerns for human health as residues of these substances are present in edible tissues. The aim of this study was the determination of the levels of four groups of antibiotics (sulfonamides-SAs, tetracyclines-TCs, streptomycines-STr and quinolones-QNLs) in meat samples (muscles, livers and kidneys from beef, chicken and pork) and the estimation of the dietary exposure to antibiotics from meat consumption and the potential hazard for human health. Fifty-four samples of raw meat were randomly collected in 2018 from the Cretan market, Greece and analyzed both with an enzyme-linked immunosorbent assay (ELISA) and liquid chromatography-mass spectrometry (LC-MS). According to the results derived from the ELISA method, only 2% of the meat samples were free from antibiotics, 2% were detected with 4 antibiotics and the great majority of the samples (87%) were detected with 2 to 3 antibiotics. SAs presented the highest detection frequencies for all samples whereas TCs were not detected in any bovine sample. The highest median concentration was detected for STr in bovine muscles (182.10 µg/kg) followed by QNLs (93.36 µg/kg) in pork kidneys whereas the chicken samples had higher burdens of QNLs compared to the other meat samples. LC-MS analysis showed that oxytetracycline (OTC) was the most common antibiotic in all samples. The highest median concentration of all antibiotics was detected for doxycycline (DOX) (181.73 µg/kg in pork kidney) followed by OTC in bovine liver (74.46 µg/kg). Risk characterization was applied for each of the two methods; The hazard quotients (HQ) did not exceed 0.059 for the ELISA method and 0.113 for the LC-MS method for any group of antibiotics, whereas the total hazard indexes (HI) were 0.078 and 0.021, respectively. The results showed the presence of different groups of antibiotics in meat from the Cretan market and that the health risk to antibiotics is low. A risk assessment analysis conducted for meat consumption and corrected for the aggregated exposure revealed no risk for the consumers.
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Pesticides are widely used in agriculture and their proven high toxicity makes the need of monitoring their presence in food imperative. A multi residue method is applied in apples samples (81) collected from the Greek market for the monitoring of 40 analytes. Pesticides levels were evaluated by gas and liquid chromatography-mass spectrometry using a QuEChERs protocol. Risk for consumers was assessed by a newly developed methodology, employing the source related Hazard Quotient (HQs) and the adversity specific Hazard Index (HIA). The 84% of the apple's samples were positive for at least one pesticide, 21% for one pesticide, 55.6% for two to four pesticide residues and 7.4% for more than 4 pesticide residues. The most frequently detected compound was carbendazim (45.7%) followed by chlorpyrifos (44.4.0%). The mean detected concentration levels varied from 0.169 ppm (fluopyram) to 0.005 ppm (triazophos). 19 of the 40 investigated pesticides were not detected in any apple sample. For all individual pesticides, the source related Hazard Quotient (HQs) was <1 indicating no risk. HIA, resulting from the sum of all HQs was found HIA < 1 in nine out of ten toxicity groups, except to the neurotoxicity group, which presented HIA 2.258, indicating moderate risk.
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Contaminación de Alimentos/análisis , Fungicidas Industriales/análisis , Insecticidas/análisis , Malus/química , Residuos de Plaguicidas/análisis , Cromatografía Liquida/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Grecia , Medición de Riesgo , Espectrometría de Masas en Tándem/métodosRESUMEN
Levels of dialkylphosphate (DAP) metabolites were measured in hair and urine of children that lived close to intensively farmed areas of Almeria (Southeast Spain). The levels were used as proxies for exposure of these children to organophosphate pesticides (OPs). Determinants of exposure to DAPs were also examined. Urine and hair samples were collected from 222 children aged 3-11â¯years and information on lifestyle and dietary habits was collected from questionnaires administered to mothers. Urinary DAPs were analyzed by ultra-high performance liquid-chromatography coupled to triple-quadrupole tandem mass-spectrometry (UHPLC-QqQ-MS/MS) and hair DAPs by gas-chromatography coupled to mass spectrometry (GC-MS). Detection rates ranged from 21.8% for diethylphosphate (DEP) and diethylthiophosphate (DETP) to 35.9% for dimethylphosphate (DMP) in urine; and from 42.3% for DETP to 92.8% for DMP in hair. Diethyldithiophosphate (DEDTP) was detected in 0.5% of urine samples (one child), and in 26.6% of children's hair samples. A lack of correlation was observed for individual DAP metabolites and ΣDAPs between urine and hair samples, except for DEDTP. Urinary DAP levels of our child population were lower than those reported for children from other countries, including NHANES 1999-2000 data. The main determinants of hair DAP levels were age, sex, vegetable intake, parental exposure to pesticides at work, time spent playing indoors, monthly income and father's education level. Conversely, none of the predictors studied was significantly associated with urinary DAPs except age. Overall, hair has advantages over urine as it is easier to collect, handle and store, and allows for assessment of cumulative exposure to OPs, thus providing a greater insight for human biomonitoring.
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Agricultura , Monitoreo Biológico , Cabello/química , Organofosfatos/análisis , Niño , Preescolar , Cromatografía Líquida de Alta Presión , Femenino , Cromatografía de Gases y Espectrometría de Masas , Humanos , Insecticidas/análisis , Masculino , Organofosfatos/orina , Compuestos Organofosforados/análisis , Compuestos Organofosforados/orina , Plaguicidas/análisis , España , Espectrometría de Masas en TándemRESUMEN
BACKGROUND: The aim of the present study was to identify the composition and reported chemical health hazards of the most common electronic cigarette liquids (e-liquids) in nine European Union (EU) Member States (MS) prior to adoption of the Tobacco Product Directive (TPD). MATERIALS AND METHODS: Within the Horizon2020, EUREST-PLUS study, 122 of the most commonly sold e-liquids in 9 EU MS were randomly selected and purchased. A quantitative and qualitative chemical analysis was performed using a previously validated based gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry method. The most commonly detected compounds were then divided according to the Danger Globally Harmonized System of Classification and Labelling of Chemicals (GHS) and Warning GHS codes. RESULTS: Within our qualitative analysis, 171 different compounds were detected. Discrepancies in measured versus reported nicotine concentration were identified. Forty-one (85.4%) of the most commonly detected compounds were registered with Warning GHS codes, 11 with Danger GHS codes and 9 with both codes. Of the total number of the detected compounds, 293 were attributable to fruits flavor, followed by tobacco flavor (204), nonalcoholic drinks (n = 64), desserts-sweets (n = 50), menthol - mint (n = 42) and alcohol (n = 39). Menthol which is classified as a strong irritant to skin and eye was the most frequently detected compound. CONCLUSION: A large plethora of compounds with varying warning codes was identified in e-cigarette samples. The systematic monitoring and chemical evaluation of e-liquids are warranted, so as to ensure consumer protection.
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Sistemas Electrónicos de Liberación de Nicotina , Aromatizantes/análisis , Nicotina/análisis , Cromatografía Liquida , Europa (Continente) , Cromatografía de Gases y Espectrometría de MasasRESUMEN
Bisphenol A (BPA) is one of the most common industrial chemicals and known to exert endocrine disruption activity. The aim of this study was the quantification of BPA in food stuffs on the Greek market. The applied liquid chromatography-mass spectrometry method was validated for linearity, limit of quantification, accuracy, precision and recovery. About 41.7% of the canned solid phase samples, 25.0% of the canned liquid phase samples and 43.8% of the soft drinks were positive. Mean BPA concentrations (range) were 33.4 ± 4.4 ng/g (4.90 ± 0.64-66.0 ± 8.6 ng/g) in canned solid phase, 2.70 ± 0.08 ng/ml (1.90 ± 0.06-3.50 ± 0.11 ng/ml) in canned liquid phase and 2.30 ± 0.18 ng/ml (0.40 ± 0.03-10.2 ± 0.8 ng/ml) in soft drinks. The results of this study are comparable with those reported in the literature according to which higher concentrations of BPA were detected in the solid fraction of canned food compared to their liquid fraction.
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Compuestos de Bencidrilo/análisis , Bebidas Gaseosas/análisis , Disruptores Endocrinos/análisis , Alimentos en Conserva/análisis , Fenoles/análisis , Cromatografía Liquida/métodos , Análisis de los Alimentos/métodos , Contaminación de Alimentos/análisis , Grecia , Espectrometría de Masas/métodos , Reproducibilidad de los Resultados , Sensibilidad y EspecificidadRESUMEN
In this study, we focused on the validation of a method for the simultaneous detection and quantification of cannabinoids, cocaine and opiates in hair as well as on the distribution of the drugs deposition in hair collected from different anatomical body sites. The proposed analytical procedure was validated for various parameters such as selectivity, linearity, limit of quantification, precision, accuracy, matrix effect and recovery. Four hundred and eighty-one samples were collected during 2010-2015 from 231 drug abusers. A 6-h ultrasonic-assisted methanolic extraction was applied for the isolation of the drugs. The analysis was performed in an liquid chromatography-mass spectrometry system for the opiates and cocaine and in a gas chromatography-mass spectrometry system for the cannabinoids. Cocaine was the most frequent detected drug (68.8-80.5%) followed by cannabinoids (47.6-63.3%) and opiates (34.7-46.7%) depending on the body site that the samples were collected. The mean concentrations of Δ9-tetrahydrocannabinol (THC) were 0.63 ± 2.11 for head, 0.54 ± 1.03 for pubic, 0.34 ± 0.51 for axillary and 0.18 ± 0.18 ng/mg for chest hair samples. The values of cocaine were 6.52 ± 15.98, 4.64 ± 10.77, 6.96 ± 38.21 and 3.94 ± 6.35 ng/mg, while the values of 6-monoacetylmorphine (MAM) were 3.33 ± 5.89, 3.06 ± 9.33, 1.37 ± 1.37 and 16.4 ± 1.77 ng/mg for head, pubic, axillary and chest samples, respectively. Differences between the detected concentrations of cocaine and opiates between the hair samples of different anatomical sites, as well as the ratio of drug metabolites to the parent compounds were observed in some cases. Statistically significant differences in the mean detected levels were noticed for morphine and heroin between head and pubic hair and also for cocaine and benzoylecgonine, between head and axillary hair samples. Moreover, the ratio of MAM to morphine and THC to cannabinol seems to correlate statistically with the total opiate or cannabinoid detected concentrations. The above differences could be attributed to several parameters associated with the structure, morphology, growth rate and other characteristics of the collected hair.
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Toxicología Forense/métodos , Cabello/química , Drogas Ilícitas/análisis , Detección de Abuso de Sustancias/métodos , Analgésicos Opioides/análisis , Cannabinoides/análisis , Cromatografía Liquida , Cocaína/análisis , Toxicología Forense/instrumentación , Cromatografía de Gases y Espectrometría de Masas , Cabello/crecimiento & desarrollo , Humanos , Drogas Ilícitas/farmacocinética , Límite de Detección , Reproducibilidad de los Resultados , Sensibilidad y Especificidad , Detección de Abuso de Sustancias/instrumentación , Distribución TisularRESUMEN
The present in-vivo study focuses on the genotoxic effect of the neonicotinoid pesticide imidacloprid (IMI) in rabbits. The purpose of the study was to establish a possible relationship between exposure to the pesticide (dose and duration) and genotoxicity. Furthermore, an analytical method for the simultaneous determination of IMI and its major metabolite 6-chloronicotinic acid (6-ClNA) in blood was developed and validated. The isolation of the two analytes from blood was performed by liquid-liquid extraction with dichloromethane. Analysis was performed by Liquid Chromatography - Atmospheric Pressure Chemical Ionization - Mass Spectrometry (LC-APCI-MS). The method was applied on the determination of IMI and 6-ClNA in serum samples obtained from rabbits fed with the insecticide at two low doses. Furthermore, parameters of genotoxicity and cytotoxicity were evaluated by measuring binucleated cells with micronuclei (BNMN), micronuclei (MN) and the Cytokinesis Block Proliferation Index (CBPI), in lymphocytes of exposed rabbits. The results revealed a genotoxic effect of IMI for both exposed groups. There were statistically significant differences in the frequencies of BNMN and MN between control and exposed groups but there was no dose-dependence, neither time-dependence of the genotoxic effect for the administered doses. This is the first time that long term exposure to IMI in rabbits was studied for the determination of its genotoxic effect. The genotoxic effect of IMI as it is depicted by the current study is in accordance with previous studies.
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Daño del ADN , Imidazoles/toxicidad , Insecticidas/toxicidad , Mutágenos/toxicidad , Nitrocompuestos/toxicidad , Animales , Cromatografía Liquida , Citocinesis , Imidazoles/sangre , Insecticidas/sangre , Insecticidas/metabolismo , Extracción Líquido-Líquido , Linfocitos/efectos de los fármacos , Masculino , Espectrometría de Masas , Micronúcleos con Defecto Cromosómico , Mutágenos/metabolismo , Neonicotinoides , Ácidos Nicotínicos , Nitrocompuestos/sangre , ConejosRESUMEN
Abuse of anabolic androgenic steroids is linked to a variety of cardiovascular complications. The aim of our study was to investigate the possible cardiovascular effects of nandrolone decanoate on young rabbits using echocardiography, histology and monitoring of telomerase activity, oxidative stress and biochemical markers. Fourteen rabbits were divided into three administration groups and the control group. Doses of 4mg/kg and 10mg/kg of nandrolone decanoate, given intramuscularly and subcutaneously, two days per week for six months were applied. A 4-months wash-out period followed. Focal fibrosis and inflammatory infiltrations of cardiac tissue were observed in the high dose groups. Thiobarbituric acid-reactive species (TBARS) levels were significantly increased in the high dose groups, while catalase activity decreased. Myocardial Performance Index (MPI) is the main echocardiographic index primarily affected by nandrolone administration in rabbits. Despite the preserved systolic performance, histological lesions observed associated with distorted MPI values, point to diastolic impairment of the thickened myocardium due to nandrolone treatment. Oxidative stress accumulates and telomerase activity in cardiac tissue rises. Subcutaneous administration seems to be more deleterious to the cardiovascular system, as oxidative stress, telomerase activity and biochemical markers do not appear to return into normal values in the wash-out period.
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Anabolizantes/toxicidad , Cardiopatías/inducido químicamente , Nandrolona/análogos & derivados , Animales , Antioxidantes/metabolismo , Biomarcadores/análisis , Cardiotoxicidad , Catalasa/metabolismo , Fibrosis Endomiocárdica/inducido químicamente , Fibrosis Endomiocárdica/patología , Cardiopatías/diagnóstico por imagen , Cardiopatías/patología , Inyecciones Intramusculares , Inyecciones Subcutáneas , Masculino , Miocardio/patología , Nandrolona/toxicidad , Nandrolona Decanoato , Estrés Oxidativo/efectos de los fármacos , Conejos , Telomerasa/metabolismo , Sustancias Reactivas al Ácido Tiobarbitúrico/metabolismo , UltrasonografíaRESUMEN
The electronic cigarette (e-cig) is an invention of the past few years and its popularity is rapidly growing all over the world. A rapid multicomponent analytical protocol for the analysis of the replacement liquids (e-liquids) of e-cig was developed using gas (GC) and liquid chromatography (LC)-mass spectrometry (MS). GC-MS-based methods were developed for the determination of the main humectants and polycyclic aromatic hydrocarbons (PAHs). For the determination and quantification of nicotine (NIC) and nitrosamines, appropriate LC-MS-based methods were developed. The approbated methods were applied for the analysis of 263 e-liquid samples obtained from the Greek market. The instruments response was linear; the limits of quantification ranged from 0.003 µg/mL for three PAHs to 1.187 µg/mL for glycerol. The precision was <16% for all analytes, while the mean accuracy ranged from 99.1% for NIC to 106.6% for the flavor 2,5-dimethylpyrazine. The measured concentrations of NIC were correlated with the theoretical concentrations as reported by the manufacturers. An analog relation between the concentration of the glycerol and of propylene glycol was noticed. The frequency of detection of flavors ranged from 30.4% for the methyl cyclopentenolone to 5.3% for 3.4-dimethoxybenzaldehyde. Nitrosamines and PAHs were not detected in any sample. Because a similar analytical protocol was not available from the existing literature so far, our study offers the advantage of complete analytical methods for rapid and simultaneous multicomponent identification.
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Cromatografía Liquida/métodos , Sistemas Electrónicos de Liberación de Nicotina/normas , Cromatografía de Gases y Espectrometría de Masas/métodos , Monoterpenos Acíclicos , Glicoles de Etileno/análisis , Glicerol/análisis , Límite de Detección , Monoterpenos/análisis , Nicotina/análisis , Nitrosaminas/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Propilenglicol/análisis , Control de Calidad , Reproducibilidad de los ResultadosRESUMEN
OBJECTIVE: Bisphenol A (BPA) is considered as an endocrine-disruptor in which humans are exposed daily mainly by food-contact products, toys, recycled paper and drinking containers. In this study, we validated a method for the isolation and the detection of BPA in human head hair samples and estimated the burden of BPA in hair of Greek population. METHODS: Hair samples were collected from 69 volunteers. The isolation of the BPA was performed by solidliquid extraction with methanol and its determination by a liquid chromatographymass spectrometry technique. RESULTS: The limits of quantification (LOQ = 9.7 pg mg(−1)), the accuracy (92.6%), the precision (inter 15.3%, intra 13.0%), the ion suppression (<8.1%) and the recovery (88.3%) of the method were found satisfactory. Differences in the detection rates of the positive samples as well in detected levels of BPA between rural and urban population were observed. The 41.2% of the samples collected from urban population were positive whereas the positive samples from rural population were 14.8% (p = 0.025). The mean concentration of the positive samples for the urban population was 64.1 pg mg(−1) (17.7192.8 pg mg(−1)), for the rural population 40.3 pg mg(−1) (13.172.8 pg mg(−1)) and for the children 37.9 pg mg(−1) (13.172.8 pg mg(−1)). Significant statistical differences (p = 0.021) were observed though between urban and rural population only when negative samples were replaced with LOD/2 values. CONCLUSION: The proposed method was successfully applied for the determination of BPA in hair for the estimation of the population burden to BPA.
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Compuestos de Bencidrilo/análisis , Disruptores Endocrinos/análisis , Monitoreo del Ambiente/métodos , Cabello/química , Fenoles/análisis , Adolescente , Adulto , Factores de Edad , Niño , Cromatografía Liquida , Monitoreo del Ambiente/instrumentación , Grecia , Humanos , Límite de Detección , Espectrometría de Masas , Población Rural , Extracción en Fase Sólida , Población Urbana , Adulto JovenRESUMEN
PURPOSE: The aim of this study was to evaluate the exposure of rural residents (control group) and occupational exposed population group of sprayers to organophosphorus pesticides (OPs) by measuring their non-specific dialkylphosphate metabolites (DAPs) in hair and in urine samples. All subjects (n=120) were residents of the municipality of Ierapetra, an area of intensive cultivation in Crete, Greece. METHODS: The determined OPs metabolites were DMP, DEP, DETP and DEDTP. Two different approaches were used for the analysis of the collected samples; solid-liquid extraction with sonication for hair and liquid-liquid extraction for urine. Gas chromatography-mass spectrometry (GC-MS) analysis was performed after derivatization of the isolated analytes. RESULTS AND DISCUSSION: The detection rates of DMP, DEP and DETP for both control and sprayers groups were high in both matrices, ranging from 91% to 100%. DEDTP was detected only in 9% of sprayers hair samples, while its detection rates in urine samples ranged from 83% to 90% for both population groups. Data analysis revealed significantly higher sumDAPs levels in urine of sprayers than in the urine of control group (p<0.001) and this is justified since sampling occurred during spraying periods. SumDAPs levels in hair samples of the sprayers were also significantly higher than in the hair of control group (p<0.001), confirming the long-term exposure to OPs. SumDAPs found levels in urine and hair samples of subjects were significantly correlated (Spearman׳s rho=0.728, p<0.001). Our study confirmed the elevated levels of DAPs in hair and urine samples in occupationally exposed group of sprayers in comparison to control group, even detected levels were similar in logarithmic scale.
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Monitoreo del Ambiente , Cabello/química , Fosfatos/análisis , Población Rural , Cromatografía de Gases y Espectrometría de Masas , Grecia , Humanos , Límite de Detección , Fosfatos/orina , Espectrometría de Masa por Ionización de ElectrosprayRESUMEN
Cypermethrin (CPMN) is a synthetic pyrethroid used as an insecticide in large-scale commercial agricultural applications as well as for domestic purposes. In the present study a gas chromatography-mass spectrometry (GC-MS) based method was developed and validated for the quantitation of CPMN metabolites, 3-phenoxybenzoic acid (3-PBA) and cis- and trans- 3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropane (cis- and trans- Cl2 CA). The developed method was applied for the monitoring of CPMN metabolites in hair of laboratory animals (rabbits) intentionally exposed per os to CPMN at 40 (low dose) and 80 (high dose) mg/kg weight/day for 16 weeks. The analytical method comprises three main steps: isolation of analytes from hair, analytes derivatization, and subsequent instrumental analysis by GC-MS. The limits of detection ensured by the method are 4.0, 3.9 and 1.0 pg/mg hair for cis-Cl2 CA, trans-Cl2 CA and 3-PBA, respectively. The instrument responce is linear (r(2) > 0.99) in the investigated concentrations range from 25 to 1000 pg/mg. With and between-run precision as well as accuracy were estimated and found satisfactory. Analytes were efficiently isolated by solid-liquid extraction from hair with recoveries greater than 84.8% for cis-Cl2 CA, 87.2% for trans-Cl2 CA and 96.4% for 3-PBA. Rabbit's hair showed increasing levels for all metabolites (metabolites accumulation in a time and dose dependent manner) over time and in a dose-dependent manner. The developed experimental procedure could be used for biomonitoring of population exposure to CPMN.
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Exposición a Riesgos Ambientales/análisis , Monitoreo del Ambiente/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Cabello/química , Plaguicidas/análisis , Piretrinas/análisis , Animales , Relación Dosis-Respuesta a Droga , Límite de Detección , Masculino , Plaguicidas/metabolismo , Plaguicidas/farmacocinética , Piretrinas/metabolismo , Piretrinas/farmacocinética , ConejosRESUMEN
In the current study, buprenorphine (BUP) and its major metabolite, nor-buprenorphine (NBUP), were determined in hair samples from former heroin users following Suboxone® treatment. Hair samples from 36 subjects were analyzed. The drugs of interest were isolated from hair by solid-liquid extraction with methanol and were determined by liquid chromatography-mass spectrometry, using an electrospray ionization interface. The analytical parameters of the method (such as linearity, limits of quantification, recovery, accuracy, and precision) were determined. The inter-quartile range of BUP levels was from 11.4 to 37.4 pg/mg (mean value 56.6 pg/mg) for the proximal hair segment, from 5.8 to 43.3 pg/mg for the middle hair segment (mean value 25.3 pg/mg), while a range from 4.3 to 33.9 pg/mg (mean value 105.2 pg/mg) for the distant to the root hair segment was determined. For NBUP the corresponding inter-quartile range was from 27.0 to 147.6 for the proximal segment (mean value 95.4 pg/mg), from 21.5 to 164.7 pg/mg for the middle segment (mean value 102.0 pg/mg) and from 20.4 to 103.6 pg/mg for the distant segment (mean value 156.8 pg/mg). The mean BUP/NBUP concentration ratio was 0.5. The daily dose of Suboxone® correlated significantly with BUP and NBUP levels in hair (p = 0.001 and p = 0.023) as well as with the BUP/NBUP ratio (p = 0.010). No significant correlation was found between the levels of BUP and NBUP and the duration of Suboxone® administration. The developed and validated method was successfully used for the determination of BUP and NBUP in hair samples collected from former heroin users under Suboxone® treatment.
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Buprenorfina/análogos & derivados , Buprenorfina/análisis , Cabello/química , Dependencia de Heroína/tratamiento farmacológico , Dependencia de Heroína/metabolismo , Naloxona/farmacocinética , Antagonistas de Narcóticos/farmacocinética , Buprenorfina/administración & dosificación , Buprenorfina/farmacocinética , Buprenorfina/uso terapéutico , Combinación Buprenorfina y Naloxona , Cromatografía Liquida , Femenino , Humanos , Masculino , Espectrometría de Masas , Naloxona/administración & dosificación , Naloxona/uso terapéutico , Antagonistas de Narcóticos/administración & dosificación , Antagonistas de Narcóticos/uso terapéuticoRESUMEN
The purpose of this study was to develop a rapid and cost efficient hair extraction method, using the headspace solid phase microextraction (HSSPME) technique for the simultaneous determination and biomonitoring of 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane) (DDT) and its isomers/metabolites and polychlorinated biphenyls (PCBs) in hair samples. A total of 72 head hair samples were collected from children living in urban and rural regions of the island of Crete. Two hundred milligrams of hair were digested under alkaline conditions and thermostated for 30 min at 90°C while a 65 µm PDMS/DVB fibre was exposed into the headspace of the vial. Analytical parameters of the method (time of incubation, agitation speed, recovery, precision, accuracy, carry over, matrix effect, linearity, and selectivity) were examined. Recoveries of the DDTs in the spiked hair samples were calculated from 42.3% for opDDD to 87.1% for opDDE, while recoveries for PCB congeners were from 52.6% for PCB138 to 96.6 % for PCB28. The method was applied for the analysis of authentic hair samples. Significant differences (p=0.001) of the burden to total DDTs (sumDDTs) as well as of the frequencies of detection of positive samples (p=0.020) were observed between the examined regions. Moreover, significant differences in the detected concentrations of PCB congeners were observed for PCB52 (p<0.001) and PCB28 (p=0.017) as well for their prevalence between urban and rural regions. Application of HSSPME for the biomonitoring of DDTs and PCBs biomarkers in hair was tested and successfully applied to the analysis of spiked and authentic hair samples. HSSPME was found to be substantially simpler and faster procedure than previous reported sample treatment procedures.
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DDT/análisis , Monitoreo del Ambiente/métodos , Cabello/química , Bifenilos Policlorados/análisis , Microextracción en Fase Sólida/métodos , Niño , Preescolar , DDT/análogos & derivados , Exposición a Riesgos Ambientales/análisis , Femenino , Cromatografía de Gases y Espectrometría de Masas/métodos , Grecia , Humanos , Masculino , Población Rural , Factores de Tiempo , Población UrbanaRESUMEN
Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LCAPCIMS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6- CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population. The developed analytical method comprises two main steps of analytes isolation from specimen (solid liquid extraction with methanol for hair, liquidliquid extraction with methanol for urine) and subsequent instrumental analysis by LCAPCIMS. The developed method was applied for the monitoring of IMI and 6-ClNA in hair and urine of laboratory animals (rabbits) intentionally fed with insecticide at low or high doses (40 and 80 mg kg(-1) weight d(-1) respectively) for 24 weeks. The analytes were detected in the regularly acquired hair and urine specimens and their found levels were proportional to the feeding dose and time of exposure with the exception of slight decline of IMI levels in high dose fed rabbits after 24 weeks of feeding. This decline can be explained by the induction of IMI metabolizing enzymes by the substrate. After testing on animal models the method was applied for pilot biomonitoring of Crete urban (n = 26) and rural (n = 32) population. Rural but not urban population is exposed to IMI with 21 positive samples (65.6%) and found median concentration 0.03 ng mg(-1). Maximum concentration detected was 27 ng mg(-1)
Asunto(s)
Monitoreo del Ambiente/métodos , Imidazoles/metabolismo , Insecticidas/metabolismo , Nitrocompuestos/metabolismo , Adolescente , Adulto , Animales , Cromatografía Liquida , Exposición a Riesgos Ambientales/análisis , Femenino , Grecia , Cabello/metabolismo , Humanos , Imidazoles/orina , Insecticidas/orina , Extracción Líquido-Líquido , Masculino , Espectrometría de Masas , Persona de Mediana Edad , Neonicotinoides , Ácidos Nicotínicos/metabolismo , Nitrocompuestos/orina , Conejos , Adulto JovenRESUMEN
Organophosphorus pesticides (OPs) are a group of chemicals with significant health interest, due to their wide spectrum of action and their excessive use both indoors (household) and outdoors (occupationally). The non-specific metabolites of OPs, dialkylphosphates (DAPs), are the most commonly used indicators for the assessment of cumulative OP exposure in humans. This review presents studies on human biomonitoring of OPs in the general population and in occupationally exposed humans. Furthermore, cases of OP intoxication determined by the measurement of DAP metabolites in various biological samples are included. In many studies, urine samples from both the general population and exposed populations have been analyzed mainly in Europe and America, while other matrices such as amniotic fluid, meconium, hair and blood have been less studied. A variety of analytical techniques were used for the determination of DAPs in these matrices. In studies measuring DAPs in urine samples, the detected concentrations ranged from 18 to 830ppb for the general population, while the corresponding values for exposed populations ranged from 29 to 1370ppb. Studies on amniotic fluid indicated DAP levels of 0.3-2.8ppb. Studies on meconium samples showed a concentration range of 0.5-16,000ppb. DAP levels in hair samples ranged from 40 to 165ppb for the general population and from 181.7 to 812.9ppb for the exposed population. Each matrix provides specific information on OP exposure, namely acute, long-term, chronic or prenatal. Meconium and hair can indicate cumulative exposure, while amniotic fluid is an indicator of fetal exposure to xenobiotics. Thus, various biological samples provide a more comprehensive view of OP exposure. In general, dimethylphosphate (DMP) and diethylphosphate (DEP) levels were higher in mainly urine samples, than other methyl and ethyl phosphates. In addition, results in the existing literature are sufficient to demonstrate the difference in levels of DAPs in general and occupationally exposed populations, mainly in urine and hair samples. However, more studies are needed to measure DAP levels in matrices such as amniotic fluid, meconium and hair to add to the literature and confirm existing data.