RESUMEN
Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) have been widely used in industry and agriculture. Due to their persistence and bioaccumulation, they were globally spread in the environment and may still be found in environmental and biological media, despite the international restrictions on production and use. The main aim of our study was to develop a simple and fast method suitable for the establishment of the reference values for 15 PCB congeners and 16 OCPs in general population subgroups. A cost- and time-saving screening procedure using gas chromatography coupled with low-resolution mass spectrometry, was improved and validated before application to the analysis of real samples. The overall method was validated including uncertainty measurement. Preliminary field data were collected from 95 volunteers living in two Italian areas. HCB, p,p'-DDE, PCB 153, PCB 138 and PCB 180 were the most frequently detected compounds. Age and residence area were found to be significant variables for the most abundant compounds, while no correlation between serum concentrations and gender was observed. Our results suggest that long-banned substances, including PCBs and the pesticides HCB and DDT's breakdown product, are still detectable in the general population.
Asunto(s)
Exposición a Riesgos Ambientales/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Hidrocarburos Clorados/sangre , Plaguicidas/sangre , Bifenilos Policlorados/sangre , Espectrometría de Masa por Ionización de Electrospray/métodos , Adulto , Cromatografía Liquida , Femenino , Humanos , Masculino , Reproducibilidad de los Resultados , Estadísticas no ParamétricasRESUMEN
3,4- and 3,5-Dichloroanilines (DCAs) are common markers of some non-persistent pesticides, e.g. linuron, diuron, vinclozolin, and iprodione. The general population may be exposed to these DCAs and/or their precursors mainly through diet. Since adverse effects on human health, such as endocrine disruption, have been reported, biological monitoring is essential for exposure assessment both of occupationally exposed subjects and of the general population. A highly sensitive and selective gas chromatography/mass spectrometry (GC/MS) method has been developed for the determination of 3,4- and 3,5-DCAs in urine using 4-chloro-2-methylaniline as an internal standard. The selected ion monitoring (SIM) mode was employed for quantitation of the analytes. The sample treatment procedure is simple and fast and no derivatization is required. The overall method was validated including uncertainty measurement. The limit of detection (LOD) and the lower limit of quantitation (LLOQ) were determined to be 0.005 and 0.010 microg/L for both analytes. The method was then applied to the establishment of reference values for a population group living in a rural area of central Italy (Novafeltria, Marche). A total of 151 out of 153 samples were found to be positive for 3,5-DCA, and 81.7% were positive for 3,4-DCA. For this group, 3,4-DCA levels ranged from 0.01 to 6.19 microg/L, while 3,5-DCA urinary concentrations were between 0.02 and 6.71 microg/L.
Asunto(s)
Compuestos de Anilina/orina , Monitoreo del Ambiente/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Residuos de Plaguicidas/orina , Humanos , Italia , Valores de Referencia , Reproducibilidad de los ResultadosRESUMEN
OBJECTIVE: To examine the congener-specific concentrations and patterns of polychlorinated biphenyls in the Italian general population. DESIGN: Two population groups were selected and monitored for the determination of up to 60 congeners in human serum. A very detailed questionnaire was administered to each participant to collect information concerning demographic, lifestyle, and medical factors. Statistical analyses were performed to examine the relationships between PCB serum levels and age. SETTING: Northern and Central Italy. PARTICIPANTS: 162 subjects from Novafeltria, Central Italy and 164 subjects from Pavia, Northern Italy. MAIN OUTCOME MEASURE: Serum concentrations of both coplanar and non-coplanar PCB congeners. Relationship between PCB levels and age. RESULTS: The mean concentration of total PCBs was found to be 2.48 and 3.93 microg/l for Novafeltria and Pavia, respectively. As waited, the most abundant congeners were CB-153, CB-138, CB-180, and CB-170. Age resulted to be the most significant determinant of PCB levels. Slight differences in the congener profile were observed in the two population groups. CONCLUSIONS: As expected, a strong correlation between age and PCB levels has been observed. It is remarkable that the correlation increased with increasing chlorination in both the population groups. Associations with other variables, such as gender, food and alcohol consumption, and cigarette smoking, appeared to be inconsistent.
Asunto(s)
Enfermedades Ambientales/sangre , Enfermedades Ambientales/epidemiología , Bifenilos Policlorados/efectos adversos , Bifenilos Policlorados/sangre , Adulto , Distribución por Edad , Femenino , Humanos , Italia/epidemiología , Masculino , Vigilancia de la Población/métodos , Distribución por Sexo , Encuestas y CuestionariosRESUMEN
The main goal of this study is to establish the reference values of individual Polychlorinated biphenyl (PCB) congeners in non-occupationally exposed subjects. Since the PCB pattern in human serum is related to the living area, two different population groups from North and Central Italy, were compared. Serum concentrations of both coplanar and non-coplanar PCB congeners were measured by using gas chromatography coupled with low-resolution mass spectrometry (HRGC-LRMS). A fast and reliable method for the determination of 60 congeners had been previously validated. Its reliability was further verified by using high-resolution mass spectrometry. Thirty-one congeners out of 60 were found at detectable concentrations in at least one sample. The mean value for total PCBs was found to be 2.48 and 3.93 microg/L for the two population groups. Eight dioxin-like PCBs were detected. In accordance with the findings from the literature, the most abundant congeners were found to be 153, 138, 180, and 170. Both univariate and multivariate analysis showed that age is a significant determinant of PCB concentrations. The correlation increased with increasing chlorination. Slight differences in the PCB pattern were observed in the two population groups.
Asunto(s)
Monitoreo del Ambiente/métodos , Contaminantes Ambientales/sangre , Bifenilos Policlorados/sangre , Adulto , Factores de Edad , Femenino , Cromatografía de Gases y Espectrometría de Masas/métodos , Humanos , Italia , Masculino , Valores de ReferenciaRESUMEN
A rapid screening method, previously developed and validated for the determination of 60 PCB congeners in human serum by using high-resolution gas chromatography coupled with low-resolution mass spectrometry, was applied to the establishment of the reference values in the general population. The reliability of this method was further confirmed by analyzing ten serum samples, obtained from the same population group involved in the original study, by electron impact ionization with either low- or high-resolution mass spectrometry. Analyses in electron capture negative ionization mode were also performed for the determination of 'dioxin-like' isomers. The data were found to be in good accordance with one another, especially for the congeners of highest environmental significance. Then, 162 real serum samples were analyzed for the presence of PCBs. Comparison with the results from other studies reported in the literature showed that a similar profile was observed; the most abundant congeners were #153, #180, #138 and #170. A statistical analysis was performed to determine whether there were significant correlations between PCB concentrations and specific variables such as age, gender, and dietary habits.
Asunto(s)
Contaminantes Ambientales/sangre , Cromatografía de Gases y Espectrometría de Masas/métodos , Bifenilos Policlorados/sangre , Espectrometría de Masa por Ionización de Electrospray/métodos , Adulto , Dioxinas/sangre , Femenino , Humanos , Italia , Masculino , Persona de Mediana Edad , Valores de Referencia , Reproducibilidad de los Resultados , Espectrometría de Masa por Ionización de Electrospray/instrumentación , Encuestas y CuestionariosRESUMEN
A method was developed for the determination of rare earth elements (REEs) in urine with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICPMS). The undiluted sample was directly injected into the graphite tube and trifluoromethane (Freon-23) was used as chemical modifier in order to reduce the vaporization temperature and the memory effect of most of the lanthanides. The detection limits were in the range 1-10 ng/L with relative standard deviation of 3-5% at concentration levels of 1microg/L, and less than 10-15% at 100 ng/L. Two different procedures, external calibration and a standard additions method, were evaluated to measure the concentration levels of lanthanides in the urine samples and the second procedure was considered to be the best choice for calibration in this work. The level of REEs in urine of 50 healthy volunteers was in the range 5-20 ng/L, above the detection limit of ETV-ICPMS.