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.     

Formaldehyde determination in seawater. Preliminary application to coastal samples at Terra Nova Bay (Antarctica)

A sensitive spectrofluorimetric-FIA (flow injection analysis) method for formaldehyde (HCHO) determination was improved with the aim of analysing seawater samples.The fluorescence emission versus HCHO concentration shows a linear pattern from sub microg L(-1) to about 1000 microg L(-1). The reproducibility at 15 ppb level is about 2%. Interferences from other aldehydes were checked; only glyoxal shows a significative interference, but only when its concentration is about 6000 times higher than that of formaldehyde. Superficial (microlayer, just sub-pack or sea-ice free sea surface) and deep (along the water column, sub-pack or in sea-ice free areas) seawater samples were collected near the coast at Terra Nova Bay (Ross Sea, Antarctica) during the 1998/1999 and 2001/2002 Italian Antarctic Expedition. We report here the preliminary results of the spectrofluorimetric-FIA determination of the HCHO content. The mean seawater superficial formaldehyde concentration was 15 microg L(-1); the concentration along the water column ranged between 4.5 to over 40 microg L(-1)(20 microg L(-1) mean concentration), usually with a maximum value for the 30 m depth, corresponding to a fluorescence maximum. The sampling was repeated 7 times in the austral summer in order to evaluate seasonal changes in the formaldehyde concentration/seawater depth profiles. The results show changes in the formaldehyde concentration at different depths.     

An evaluation of the PM2.5 trace elemental composition in the Venice Lagoon area and an analysis of the possible sources

Global emissions reported by many authors have shown as natural and anthropic sources can contribute to the principal aerosol classes, but values change according the local scenario. The Venice Lagoon is exposed to different anthropic source emissions like vehicular traffic, industrial thermoelectric power plant, petrochemical plant, incinerator plant, domestic heating, ship traffic, glass factories and airport. Samplings of PM_2.5 were daily performed between March and November 2007 in Sacca San Biagio island (Venice), and values of PM_2.5 concentration and element concentration were obtained. Monthly average concentrations (μg m^?3) during this period show higher values during the spring and the autumn. A good relationship between data obtained and concentration values from environmental local agencies is evidenced, both for PM_2.5 from urban area (Venezia Mestre), and for PM₁₀ sampled in the same area, as well as the influence of some meteorological parameters on PM_2.5 concentration sampled. Trace elements samples were measured by an Inductively Coupled Plasma-Quadrupole Mass Spectrometry (ICP-QMS), and values (ng m^?3 and μg g^?1) for elements regulated by European directives (As, Cd, Ni, Pb), as well as, other elements (Na, Al, K, Ti, V, Mn, Fe, Co, Zn, Se, Ag) are also reported. Data analysis by mean of Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF) pointed out four principal groups of elements like Mn–Fe–K, As–Se–Cd, V–Co, and Pb that could be assigned to specific sources of the Venetian wetland basin.     

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.     

Trace elements in size-segregated urban aerosol in relation to the anthropogenic emission sources and the resuspension

Size segregated particulate samples of atmospheric aerosols in urban site of continental part of Balkans were collected during 6 months in 2008. Six stages impactor in the size ranges: Dp?≤?0.49 μm, 0.49?2?≈?30 %) followed by traffic (PC2, σ²?≈?20 %) that are together contributing around 50 % of elements in the investigated urban aerosol. The EF model shows that major origin of Cd, K, V, Ni, Cu, Pb, Zn, and As in the fine mode is from the anthropogenic sources while increase of their contents in the coarse particles indicates their deposition from the atmosphere and soil contamination. This approach is useful for the assessment of the local resuspension influence on element’s contents in the aerosol and also for the evaluation of the historical pollution of soil caused by deposition of metals from the atmosphere.     

Enrichment of organic pollutants in the sea surface microlayer (SML) at Terra Nova Bay, Antarctica: influence of SML on superficial snow composition

Concentrations of dissolved and particle-associated n-alkanes, phthalates and polycyclic aromatic hydrocarbons (PAHs) were measured in sea surface microlayer (SML) and sub-surface water (SSL) samples collected in the coastal area of Terra Nova Bay, Antarctica, during the Austral spring 1998/1999. SML concentrations of the selected organic compounds were higher than SSL values and the enrichment factors were greater in the particulate phase than in the dissolved phase. During the same campaign, "fresh" snow samples, collected at different altitudes (from sea level up to 2670 m) near the coast on Mt Melbourne, immediately after a snowy event, were analysed in order to provide more information on air/sea exchange processes. The same classes of organic compounds found in sea water were also present in "fresh" snow samples. The surfactant fluorescent organic matter (SFOM), adsorbed on the microdrop aerosol surface, could be considered the main constituent of the enrichment and the carrier at higher altitudes of organic compounds. In fact, hydrocarbons (n-alkanes and PAHs), which are not surfactants like phthalates, could interact with SFOM and follow the same fate.     

Comparison of PM10 concentrations and metal content in three different sites of the Venice Lagoon: An analysis of possible aerosol sources

The Venice Lagoon is exposed to atmospheric pollutants from industrial activities, thermoelectric power plants, petrochemical plants, incinerator, domestic heating, ship traffic, glass factories and vehicular emissions on the mainland. In 2005, construction began on the mobile dams (MOSE), one dam for each channel connecting the lagoon to the Adriatic Sea as a barrier against high tide. These construction works could represent an additional source of pollutants. PM₁₀ samples were taken on random days between 2007 and 2010 at three different sites: Punta Sabbioni, Chioggia and Malamocco, located near the respective dam construction worksites. Chemical analyses of V, Cr, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl and Pb in PM₁₀ samples were performed by Inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) and results were used to identify the main aerosol sources. The correlation of measured data with meteorology, and source apportionment, failed to highlight a contribution specifically associated to the emissions of the MOSE construction works. The comparison of the measurements at the three sites showed a substantial homogeneity of metal concentrations in the area. Source apportionment with principal component analysis (PCA) and positive matrix factorization (PMF) showed that a four principal factors model could describe the sources of metals in PM₁₀. Three of them were assigned to specific sources in the area and one was characterised as a source of mixed origin (anthropogenic and crustal). A specific anthropogenic source of PM₁₀ rich in Ni and Cr, active at the Chioggia site, was also identified.