环境中的药物——LC-MS/MS分析地表水和地下水

成百上千的活性物质正被用于人药和兽药处方中.由于药物的广泛应用,它们的残留物可通过多种途径进入环境.虽然主要通过尿和粪便的排泄,但是药品生产中的排放也应被考虑.当抗生素用于水产业,就会产生更直接的影响.污水处理设备不能完全除去药物,因此药物会出现在地表和地下水样品中.近年来,人们对环境中药物的兴趣正在增加,需要建立一种快速、灵敏、有选择性的方法来分析水样.     

Serum levels of PCDDs, PCDFs and PCBs in non-occupationally exposed population groups living near two incineration plants in Tuscany, Italy

A pilot study was carried out in Tuscany, Italy, to provide preliminary information on the concentrations of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), and selected non-dioxin-like PCBs (NDL-PCBs) in groups of subjects living in the vicinity of two incineration plants. Seventy-four volunteers were enrolled from areas identified as under a potential impact from incinerator emissions and from not exposed areas. No significant differences were observed between subjects living in the two types of areas. Total concentrations of PCDDs, PCDFs, and DL-PCBs resulted to be in the range 23-30 pg WHO-TEQ g(-1), lipid base, for subjects in the 27-54 year age groups, while concentrations increased to 40-44 pgTEQ g(-1) for the two 55-67 year age groups. The levels of PCDDs and PCDFs were in good agreement with those observed for unexposed population groups in Italy, while the contribution to total TEQ from DL-PCBs was appreciably higher than those currently observed in the general population in Italy and other countries. As to NDL-PCBs, serum levels of the six "indicator" congeners were in the range 240-300 ng g(-1), lipid base, for subjects in the 27-54 year age groups. A raise in NDL-PCB body burden (430-470 ng g(-1), lipid base) was observed for the two 55+ year age groups, in agreement with the expected age-dependent increase. The findings from this study do not show an incremental exposure to PCDDs and PCDFs in the samples from subjects living around the two incineration plants, whereas PCB congener profiles in all samples suggest a possible impact on the area of interest of industrial activities from near industrial settlements.     

Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from Italian women living in Rome and Venice

The levels of selected polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were measured in human milk samples from the areas of Venice and Rome, primarily in order to characterize the current levels of infant exposure to PCBs and PBDEs due to breast feeding in Italy. Sixteen non-dioxin-like PCBs, including the traditional indicator congeners, and 11 PBDEs, comprising the relevant PBDE-47, PBDE-99, and PBDE-153, were determined. Congeners were selected for analysis according to their relative abundance in human tissues, toxicological relevance, and diffusion in the environment. Dietary habits of the milk donors were recorded by questionnaires; mothers of the Venice area were classified into three groups according to their consumption of local fish, molluscs, and other fishery products. Sigma(16)(PCBs) and Sigma(11)(PBDEs) (ng g(-1) fat) for the areas of Venice and Rome were respectively, 250-390 and 240, and 1.6-2.8 and 4.1. An increase of fish and fishery product consumption could not be associated with an increase of PCB and PBDE levels in milk.     

Chemometric data analysis application to Sparus aurata samples from two offshore farming plants along the Apulian (Italy) coastline

The levels of polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), non-dioxin-like polychlorobiphenyls (NDL-PCBs), and polybromodiphenyl ethers (PBDEs) in fish collected from two marine offshore farming plants were determined. Each sample was constituted by specimens of the same size collected at the same time in four different seasons along the farming year. The feeds given were of industrial origin and the plants were positioned in two different sites respectively exposed to different environmental characteristics. A chemometric approach was applied to interpret the subtle differences observed in fish body burdens across the three chemical groups taken into consideration. The approach consisted in a stepwise multivariate process including a hierarchical cluster analysis (CA) and a linear discriminant analysis (DA). The two main clusters determined by CA were subjected to the canonical DA, backward and forward selection procedures to select the best discriminative functions. A clear temporal and spatial discrimination was found among the samples. Across the three chemical groups, the monthly separation seemed to depend on the growth process and the main exposure was due to the feed. In addition, the two plants differed significantly from the environmental point of view and the most important discriminating group of chemicals were the NDL-PCBs. The approach resulted really effective in discriminating the subtle differences and in individuating suggestions to improve the quality of culturing conditions.     

Increased levels of polychlorobiphenyls in Italian women with endometriosis

Endometriosis has been hypothesised to be linked to persistent and toxic organochlorinated chemicals. Dioxins and dioxin-like compounds have in particular been associated with the disease, mainly on the basis of experimental studies. Data in women are conflicting. A case-control study on 80 Italian nulliparous women of reproductive age was carried out to assess whether there is a correlation between the presence of endometriosis and blood levels of polychlorobiphenyls (PCBs), a family of ubiquitary environmental pollutants which comprises congeners with dioxin-like activity. Higher levels of PCBs were found in women with endometriosis. A mean cumulative value of 410 ng g(-1), lipid base, was found in cases versus the value of 250 ng g(-1) observed in the control group (odds ratio for upper tertile 4.0, CI 95% 1.3-13; p = 0.0003). PCB increase involved both dioxin-like (PCBs 105, 118, 156, and 167) and non-dioxin-like congeners (PCBs 101, 138, 153, 170, 180).     

Cross-sectional biomonitoring study of pesticide exposures in Queensland,Australia, using pooled urine samples

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography–tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a “U-shaped” trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.     

High concern chemicals in top layer sediments of the northern Adriatic seabed as markers of old waste dumpings

The results are presented of a survey planned to assess the presence of high concern chemicals in sediments collected in a northern sector of the Adriatic sea neighboring the Venice lagoon. For the assessment, persistent marker chemicals were selected from the families of polycyclic aromatic hydrocarbons, polychlorobiphenyls, polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), and chlorinated pesticides. Based on the chemical-specific concentrations and PCDD+PCDF profiles determined in the sediments analyzed, dumping zones appear to have existed approximately 5-6km away from lagoon shoreline. Contamination levels exceed the quality criteria established by the pertinent Italian national regulation at many sampling sites, eventually reflecting ("fingerprinting") industrial activities once performed in the industrial settlement of Porto Marghera within the Venice lagoon. In coastal samples, concentration levels appear to be lower than those determined at offshore sampling sites.