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.     

Foliar response of an Ailanthus altissima clone in two sites with different levels of ozone-pollution

Potted plants of Ailanthus altissima, produced by root suckers coming from a single symptomatic mother tree, were placed in two sites in the vicinity of Florence (central Italy), with different levels of ozone pollution. These plants were kept in well watered conditions during the period May-September 1999. In the high pollution site (Settignano-SET) the level of ozone exposure (AOT40) reached at the end of the season a value of 31 ppm h, whereas in the "low pollution" site (Cascine-CAS) the exposure to ozone was 11 ppm h. A. altissima showed foliar symptoms in early July at SET and in the second half of July at CAS when exposure values reached 5 ppm h at both sites. However, at the end of August the conditions of the plantlets were rather similar in both sites. Microscopic and ultrastructural analysis were performed at the first onset of symptoms at SET (the CAS leaflets were asymptomatic). Observing the upper leaf surface where the brown stipples were visible, it was found that the cells of the palisade mesophyll displayed loss of chlorophyll and the organelles in the cytoplasm were damaged. Swelling of thylacoids was observed in the CAS leaflets, thus indicating the possible onset of a pre-visual damage. The injured cells were separated from the healthy ones by a layer of callose. We conclude that the sensitivity to ozone of A. altissima leaves is related to its leaf structure, with low leaf density and large intercellular spaces. Cell walls, as well as acting as mechanical barriers against the spread of ozone within the cell, also provide important detoxifying processes.     

Phytoremediation potential of the novel atrazine tolerant Lolium multiflorum and studies on the mechanisms involved

Atrazine impact on human health and the environment have been extensively studied. Phytoremediation emerged as a low cost, environmental friendly biotechnological solution for atrazine pollution in soil and water. In vitro atrazine tolerance assays were performed and Lolium multiflorum was found as a novel tolerant species, able to germinate and grow in the presence of 1 mg kg⁻¹ of the herbicide. L. multiflorum presented 20% higher atrazine removal capacity than the natural attenuation, with high initial degradation rate in microcosms. The mechanisms involved in atrazine tolerance such as mutation in psbA gene, enzymatic detoxification via P₄₅₀ or chemical hydrolysis through benzoxazinones were evaluated. It was demonstrated that atrazine tolerance is conferred by enhanced enzymatic detoxification via P₄₅₀. Due to its atrazine degradation capacity in soil and its agronomical properties, L. multiflorum is a candidate for designing phytoremediation strategies for atrazine contaminated agricultural soils, especially those involving run-off avoiding.     

Spiking solvent, humidity and their impact on 2,4-D and 2,4-DCP extractability from high humic matter content soils

The 2,4-dichlorophenoxyacetic acid (2,4-D) is a hormone-like herbicide widely used in agriculture. Although its half life in soil is approximately two weeks, the thousands of tons introduced in the environment every year represent a risk for human health and the environment. Considering the toxic properties of this compound and its degradation products, it is important to assess and monitor the 2,4-D residues in agricultural soils. Furthermore, experiments of phyto/bioremediation are carried out to find economic and environmental friendly tools to restore the polluted soils. Accordingly, it is essential to accurately measure the amount of 2,4-D and its metabolites in soils. There is evidence that 2,4-D extraction from soil samples seriously depends on the physical and chemical properties of the soil, especially in those soils with high content of humic acids. The aim of this work was to assess the variables that influence the recovery and subsequent analysis of 2,4-D and its main metabolite (2,4-dichlorophenol) from those soils samples. The results showed that the recovery efficiency depends on the solvent and method used for the extraction, the amount and kind of solvent used for dissolving the herbicide and the soil water content at the moment of spiking. An optimized protocol for the extraction and quantification of 2,4-D and its main metabolite from soil samples is presented.     

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.     

Kinematic planning of slew manoeuvres after actuator failure for low-cost satellites

A kinematic scheme is presented which allows for planning attitude manoeuvres of satellites after actuator failure. The scheme relies on the identification of admissible rotation axes around which the control system can deliver torque components in spite of the failure. Two techniques discussed in the literature, based on a single rotation that either minimizes the angular displacement from a given target attitude or aims a sensor exactly along a prescribed direction, are compared with a new technique based on a two-step approach, which allows for achieving any prescribed attitude by means of a sequence of two feasible rotations. Dynamic simulation is used for analysing potential capabilities and limits of the considered kinematic approaches to manoeuvre planning of under-actuated satellites.     

Dissipation of 2,4-D in soils of the Humid Pampa region, Argentina: a microcosm study

Phenoxy herbicides like 2,4-dichlorophenoxyacetic acid (2,4-D) are widely used in agricultural practices. Although its half life in soil is 7-14d, the herbicide itself and its first metabolite 2,4-dichlorophenol (2,4-DCP) could remain in the soil for longer periods, as a consequence of its intensive use. Microcosms assays were conducted to study the influence of indigenous microflora and plants (alfalfa) on the dissipation of 2,4-D from soils of the Humid Pampa region, Argentina, with previous history of phenoxy herbicides application. Results showed that 2,4-D was rapidly degraded, and the permanence of 2,4-DCP in soil depended on the presence of plants and soil microorganisms. Regarding soil microbial community, the presence of 2,4-D degrading bacteria was detected even in basal conditions in this soil, possibly due to the adaptation of the microflora to the herbicide. There was an increment of two orders of magnitude in herbicide degraders after 15d from 2,4-D addition, both in planted and unplanted microcosms. Total heterotrophic bacteria numbers were about 1x10(8) CFUg(-1) dry soil and no significant differences were found between different treatments. Overall, the information provided by this work indicates that the soil under study has an important intrinsic degradation capacity, given by a microbial community adapted to the presence of phenoxy herbicides.