南京市主要饮用水源水中有机污染物的遗传毒性研究

运用鼠伤寒沙门氏菌 /哺乳动物微粒体酶系 ( Ames)试验 ( DNA)、SOS/Umu试验 (基因 )和蚕豆根尖微核试验(染色体 )对不同季节 (枯、丰、平 )南京市主要水厂的水源水中有机污染物的遗传毒性进行了研究。以 XAD-2树脂为吸附剂 ,丙酮 -甲醇的混合液为洗脱液 ,浓缩水样中有机物 ,并对部分阳性水样进行了有机组分的定性分析 ( GC/MS法 )及其污染源调查。结果发现 ,不同季节水样均有不同程度的遗传毒性检出 ,其中以上元门水厂水质最劣 ;同时通过 GC/MS法分析 ,发现阳性水样中存在有美国 EPA所列的多种优先污染物以及其它黑名单上所属的有毒有害物质 ,应当引起足够的重视     

Uptake and bioavailability of persistent organic pollutants by plants grown in contaminated soil

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of endosulfan compounds from slurry spiked soil (10, 20 and 40 microg g(-1)) was consistent (92.9 +/- 4.4% for n= 9). However, ageing of endosulfan compounds on the slurry spiked soil resulted in lower recoveries (average losses were 12.5% after 14 days ageing of slurry spiked soil). The uptake of POP's was assessed by measuring the amount of endosulfan compounds in roots and leaves from lettuce plants after 10, 20 and 33 days. In addition, control plants grown in uncontaminated soil were monitored and analysed. It was found that endosulfan compounds were present in the roots of all lettuce plants irrespective of soil spike level or age of plant. In the 33 day lettuce plants where the soil was spiked at the highest level (50 microg g(-1)) endosulfan compounds were determined in the leaves. The root to leaf ratio was found to be 3.1 for alpha-endosulfan, 46.0 for beta-endosulfan, and 24.3 for endosulfan sulfate. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of endosulfan compounds. No detectable endosulfan compounds were determined in the gastric extracts while small quantities (range 0.06-0.12 microg g(-1)) were found in the intestinal extraction. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection.     

Tenax-TA extraction as predictor for free available content of polycyclic aromatic hydrocarbons (PAHs) in composted sewage sludges

The usability of the solid phase extraction method with Tenax-TA adsorbent for the forecasting of polycyclic aromatic hydrocarbon losses during sewage sludges composting has been evaluated in the present study. Four municipal sewage sludges were composted for 76 days. The PAH content in the sludges ranged from 3674 to 11 236 microg kg(-1). After composting, a significant reduction of PAH content was observed. The range of the PAH sum loss ranged from 29.3 to 48.6%. The share of fraction extracted by Tenax-TA in the sludges at the onset of the composting ranged from 28.1 to 54.0% in relation to the PAH sum, and from 0.31 to 100% for individual PAHs. After 76 days of composting, the presence of Tenax-TA extracted PAHs was still observed in the sludges. A significant reduction of this fraction was noted in the case of three sewage sludges. PAH's Tenax-TA fraction in the case of one sewage sludge did not undergo any changes during composting. A satisfactory prediction of PAH losses by the Tenax-TA method was rarely observed. The best reflection of the PAH losses was observed in the case of fluoranthene, anthracene and indeno[1,2,3-cd]pyrene.     

Comparison of SFE with Soxhlet in the analyses of PCDD/PCDFs and PCBs in sediment

The efficiency of supercritical fluid extraction (SFE) for the isolation of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) from sediments was investigated by comparing SFE with Soxhlet. Five sediments obtained from an international interlaboratory study were used as a test material. SFE was performed with an automatic system where extracted analytes were collected by solid-phase trapping using carbon mixed with Celite as an adsorbent. For the first time, SFE of the most toxic PCBs, coplanar PCBs, was studied with real sediment samples. The majority of PCBs investigated, a total of 38 congeners from tri- to decachlorinated, were quantitatively extracted from sediment by SFE with pure CO2 at pressure 400 atm and temperature 100 degrees C. Under these conditions a successful extraction was obtained also for PCDD/PCDFs except for hepta- and octachlorinated congeners. Copper powder added to the sediment efficiently prevented the transfer of sulfur from the sample during SFE. The TEQs of both PCDD/PCDFs and PCBs obtained by SFE corresponded well with those obtained by the Soxhlet-based method. The reproducibility of SFE was high for both groups.     

Antimony speciation in terrestrial plants. Comparative studies on extraction methods

A suitable method for the extraction of antimony species from plant materials prior to IC-HG-AFS analysis is presented. The extraction efficiency with different extraction systems using various aqueous and aqueous/solvent mixtures was initially evaluated by analysing the Virginia Tobacco Leaves Certified Reference Material. The concentration of antimony extracted was compared with the total antimony content in the plant material measured by HG-AFS after focused microwave-acidic digestion using HNO3 and H2O2. The proposed extraction procedures were applied to antimony speciation in several plants from a natural terrestrial environment impacted by mining activities. End-over-end agitation (4 h) followed by sonication (1 h) extraction using 0.1 mol l(-1) citric acid was found to provide the best extraction efficiency while also giving reliable speciation information. Both inorganic and methylantimony species were found in the extractable portion of some terrestrial plants.     

加速溶剂萃取-固相萃取净化-高效液相色谱法测定玉米作物中多环芳烃含量

建立了加速溶剂萃取-固相萃取净化-高效液相色谱测定玉米作物中15种多环芳烃的方法,优化了试验条件.方法线性关系良好,15种多环芳烃的检出限在0.003 8～0.079μg/kg之间,空白加标试验的相对标准偏差在3.9%～11.7%之间,基质加标回收率在69.3%～115.3%之间.实际样品的测定结果表明,该方法分离效果...     

基于ZIF-L的微固相萃取技术测定地表水中痕量典型多环芳烃

制备类沸石咪唑酯骨架ZIF-L材料,将其用作微固相萃取吸附剂,处理水中萘、苊、苊烯、芴、菲、蒽、荧蒽、芘等8种痕量典型多环芳烃,再用HPLC测定。试验表明,ZIF-L对上述多环芳烃的萃取效率明显高于商品化萃取材料C 18和多壁碳纳米管。方法在0.100μg/L^200μg/L范围内线性良好,方法检出限为0.02μg/L^0.03μg/L,标准溶液5次测定结果的RSD为4.7%~9.5%,实际水样加标回收率为84.5%~115%。将该方法用于北太湖5个点位水样的测定,测定值为未检出~3.40μg/L。     

Investigation of arsenic speciation on drinking water treatment media utilizing automated sequential continuous flow extraction with IC-ICP-MS detection

Three treatment media, used for the removal of arsenic from drinking water, were sequentially extracted using 10 mM MgCl2(pH 8), 10 mM NaH2PO4(pH 7) followed by 10 mM (NH4)2C2O4(pH 3). The media were extracted using an on-line automated continuous extraction system which allowed the arsenic in each of the extraction fluids to be speciated on-line using IC-ICP-MS. The 10 mM MgCl2 preferentially extracted As(III) from each of the media. The percentage of the arsenic extracted by the MgCl2, relative to a HNO3/H2O2 digestion of the media, ranged from 0.1-2.3% for the three solids. The next sequential extraction fluid, 10 mM NaH2PO4, extracted some of the residual As(III) remaining on each of the media but the predominant species extracted was As(V). The 10 mM NaH2PO4 extracted 15.3 to 42.8% of the total arsenic relative to a total digested concentration for each of the media. The As(III) and As(V) stability studies conducted in these two extraction fluids indicated that conversion between As(III) and As(V) was not significant for the short extraction fluid sample contact time associated with the on-line continuous flow extraction cell. Finally, the 10 mM (NH4)2C2O4 extraction fluid was utilized in an off-line analysis mode because the Fe and As concentrations extracted from the media were not compatible with direct ICP-MS detection. The (NH4)2C2O4 extracted 2.9-29% As(III) for all three media and caused an oxidation of As(III) to As(V) during the extraction period for one of the three media. The sum of the arsenic from each of the three extraction fluids represented 92%, 44% and 53% of the available total arsenic for the three media, respectively. The speciation results for each media were obtained by adding all the speciation results from all three extraction fluids together and the resulting distribution of As(III)/As(V) compared well with the speciation results obtained via XANES.     

固相萃取-GC/MS法测定水中16种有机氯农药

采用HLB固相萃取柱富集水样,乙酸乙酯溶剂洗脱,加入氘代菲作为内标,利用气相色谱/质谱联用法选择离子模式测定水中16种有机氯农药,优化了固相萃取条件。16种有机氯农药在5.00μg/L~250μg/L范围内线性良好,按1 L水样计算,方法最低检出限为1.4 ng/L~19.4 ng/L,相对标准偏差为3.5%~20.0%,平均加标回收率为44.7%~119%。     

Salmonella mutagenicity analysis of water samples from Çamaltı saltern

Mutagenicity analysis of water samples from Camalti Saltern, Turkey were investigated by applying Salmonella mutagenicity test. Plate incorporation assay was applied in the absence of metabolic activation. XAD 4 and XAD 16 columns were used for the fractionation of the water samples. The results obtained were negative in both TA 98 and TA 100. Although the number of revertants of XAD 16 extract in station B were higher than the revertants in the other stations for TA 98 strain when compared to the solvent control. However this was not significant to be considered as mutagenic. The results were discussed for the future analysis.     

Characterization of 14C-naphthol uptake in excised root segments of clover (Trifolium pratense L.) and fescue (Festuca arundinaceae Screb.)

An isolated root uptake test (IRUT) was used to characterize the bioaccumulation of ¹⁴C-naphthol in excised root segments obtained from 6-month-old hydroponically grown plants: two varieties of fescue (Festuca arundinaceae Schreb.) and one variety of clover (Trifolium pratense L.). Naphthol uptake rates were directly related to naphthol concentration in the range 0.01 to 0.2 uM. The incubation time required for equilibrium to be reached between naphthol in root tissue and in solution was between 9 and 12 h. Tests using metabolic inhibitors, KCN, NaN₃, and DNP, indicated that naphthol uptake may be the result of both passive and active mechanisms. Q₁₀ values for naphthol uptake ranged from 1.05 to 1.16.     

Solid phase extractive preconcentration of silver from aqueous samples

N,N-dibutyl-N1-benzoylthiourea (DBBT) impregnated onto a polymeric matrix, Amberlite XAD-16 was prepared. The separation and enrichment of Ag(I) from solution was investigated. Effective extraction conditions were optimized in column methods prior to determination by atomic absorption spectrometry. The optimum pH range for quantitative adsorption is 2-5. Quantitative recovery of Ag was achieved by stripping with 1 mol L(-1) thiourea in 1 mol L(-1) HCl. The sorption capacity of resin is 0.115 mmol Ag+ g(-1) resin. The relative standard deviation and detection limit was 3.1% for 1 microg Ag+ mL(-1) solution and 0.11 microg L(-1), respectively. The method was used for the determination of silver in geological water samples.     

Remediation aspect of microbial changes of plant rhizosphere in mercury contaminated soil

Phytoremediation, an approach that uses plants to remediate contaminated soil through degradation, stabilization or accumulation, may provide an efficient solution to some mercury contamination problems. This paper presents growth chamber experiments that tested the ability of plant species to stabilize mercury in soil. Several indigenous herbaceous species and Salix viminalis were grown in soil collected from a mercury-contaminated site in southern Poland. The uptake and distribution of mercury by these plants were investigated, and the growth and vitality of the plants through a part of one vegetative cycle were assessed. The highest concentrations of mercury were found at the roots, but translocation to the aerial part also occurred. Most of the plant species tested displayed good growth on mercury contaminated soil and sustained a rich microbial population in the rhizosphere. The microbial populations of root-free soil and rhizosphere soil from all species were also examined. An inverse correlation between the number of sulfur amino acid decomposing bacteria and root mercury content was observed. These results indicate the potential for using some species of plants to treat mercury contaminated soil through stabilization rather than extraction. The present investigation proposes a practical cost-effective temporary solution for phytostabilization of soil with moderate mercury contamination as well as the basis for plant selection.     

Simultaneous determination of insecticide fipronil and its metabolites in maize and soil by gas chromatography with electron capture detection

An integrated method for the simultaneous determination of insecticide fipronil and its three metabolites, desulfinyl, sulfide, and sulfone, in maize grain, maize stem, and soil was developed. This three-step method uses liquid–solid extraction with ultrasound or mechanical grinding, followed by liquid–liquid partitioning and florisil solid-phase extraction (SPE) for cleanup. The quantification was conducted by gas chromatography–electron capture detection in triplicate for each sample. The method was validated with five replicates at three fortification concentrations, 0.002, 0.01, and 0.1 mg kg^?1, in each matrix and gave mean recoveries from 83 to 106 % with relative standard deviation ≤8.9 %. The limits of quantification (LOQ) were 0.002 mg kg^?1 for the compounds in all matrixes. In the field study in Beijing and Shandong 2012, fipronil-coated maize seeds were planted and the proposed method was applied for checking the possible existence of four compounds in maize and soil samples, but none of them contained residues higher than the LOQs in both application rates. Moreover, the dissipation of fipronil in soil fits first-order kinetics with half-lives 9.90 and 10.34 days in Beijing and Shandong, respectively. Combined with an adequate sample treatment, this technique offers good sensitivity and selectivity in the three complex matrixes. The results could provide guidance for the further research on pesticide distribution and safe use of fipronil as seed coat in cereals.     

快速溶剂萃取-气相色谱/串联质谱法测定农作物中的有机氯农药

建立快速溶剂萃取,固相萃取柱净化,气相色谱/串联四极杆质谱检测分析农作物中23种有机氯农药残留的方法。以油菜为样品,加标浓度为5、10、25、50μg/kg时,平均回收率在72%~101%之间,相对标准偏差3%~14%(n=5)。8种农作物(莴笋、黄瓜、蒜苗、辣椒、油菜、茄子、玉米和水稻)加标浓度为25μg/kg时的平均回收率在71%~113%之间,相对标准偏差3%~16%(n=5)。方法检出限0.75~1.76μg/kg之间。     

区域土壤中氯苯类化合物测定及分布研究

以区域内16个土壤样品为研究对象,采用超声波萃取法对样品中的氯苯类污染物进行提取,并用气相色谱仪分类和测定,以保留时间定性,外标法定量。结果表明,利用超声波提取土壤中氯苯类是可行的,并能够进行分类检出;预处理中提取的最佳、合理的溶剂为正己烷;实验还得出了11种氯苯类化合物在18min内全部流出的最佳色谱条件。检测数据显示区域土壤内主要氯苯类污染物为二氯苯、四氯苯和六氯苯。     

Comparison of arsenic uptake ability of barnyard grass and rice species for arsenic phytoremediation

In this research, the relative performance in arsenic (As) remediation was evaluated among some barnyard grass and rice species under hydroponic conditions. To this end, four barnyard grass varieties and two rice species were selected and tested for their remediation potential of arsenic. The plants were grown for 2 weeks in As-rich solutions up to 10 mg As L^?1 to measure their tolerance to As and their uptake capabilities. Among the varieties of plants tested in all treatment types, BR-29 rice absorbed the highest amount of As in the root, while Nipponbare translocated the maximum amount of As in the shoot. Himetainubie barnyard grass produced the highest biomass, irrespective of the quantity of As in the solution. In all As-treated solutions, the maximum uptake of As was found in BR-29 followed by Choto shama and Himetainubie. In contrast, while the bioaccumulation factor was found to be the highest in Nipponbare followed by BR-29 and Himetainubie. The results suggest that both Choto shama and Himetainubie barnyard grass varieties should exhibit a great potential for As removal, while BR-29 and Nipponbare rice species are the best option for arsenic phytoremediation.     

Simultaneous derivatization and extraction of nitrophenols in soil and rain samples using modified hollow-fiber liquid-phase microextraction followed by gas chromatography–mass spectrometry

A simple and sensitive method based on a modified hollow-fiber liquid-phase microextraction followed by gas chromatography–mass spectrometry has been successfully developed for the extraction and simultaneous derivatization of some nitrophenols (NPs) in soil and rain samples. Microwave-assisted solvent extraction was used for the extraction of NPs from the soil, while the rain sample was directly applied to the previously mentioned method. Briefly, in this method, the analytes were extracted from aqueous samples into a thin layer of organic solvent (dodecane?+?10 % tri-n-octylphosphine oxide) sustained in the pores of a porous hollow fiber. Then, they were back-extracted using a small volume of organic acceptor solution (25 μl; 10 mg/L N-methyl-N-(trimethylsilyl)trifluoroacetamide, as derivatization reagent, in acetonitrile) that was located inside the lumen of the hollow fiber. Under the optimized extraction conditions, enrichment factors of 255 to 280 and limits of detection of 0.1 to 0.2 μg/L (S/N?=?3) with dynamic linear ranges of 1–100 μg/L were obtained for the analytes. The accuracy of the approach was tested by the relative recovery experiments on spiked samples, with results ranging from 93 to 113 %. The method was shown to be rapid, cost-effective, and potentially interesting for screening purposes.     

Investigation of trace elements in agricultural soils by BCR sequential extraction method and its transfer to wheat plants

In this study, soil samples were collected from Edirne, Turkey in both summer and winter seasons and subjected to the modified Community Bureau of Reference (BCR) sequential extraction procedure in order to investigate the chemical partitioning of metals in soils and to predict heavy metals uptake by wheat grains which grown at the same soils. The samples were subjected to a three stage extraction procedure proposed by the BCR. The three phases that were separated out in the following order: (1) carbonate, exchangeable, (2) Fe?CMn oxides, and (3) organic matter. Metal concentrations of soil fractions and grain samples were determined by inductively coupled plasma atomic emission spectroscopy. The wheat samples were prepared to analysis using microwave acid digestion procedure. The pseudo-total concentrations of metals were determined after aqua regia digestion. The analytical accuracy of the method was evaluated by using the Standard Reference Materials (BCR 142R Light Sandy Soil, NIST 2711 Montana Soil, and NIST 2704 Buffalo River Sediment). The sum of the metal contents obtained from the modified BCR sequential extraction procedure and pseudo-total metal contents for soil samples were used to calculate recovery values. In order to evaluate the bioavailability of metals, the relationships between the wheat-metal and soil-extractable metal concentrations were compared.     

土壤和河流沉积物中六六六和滴滴涕残留的测定

采用密闭微波提取、超声波提取、索氏提取对土壤和河流沉积物进行前处理,提取液经弗罗里硅土柱净化或浓硫酸净化.通过回收率实验和精密度实验对三种提取方法和两种净化方法进行比较,建立了微波提取土壤和河流沉积物中六六六和滴滴涕,浓硫酸净化,气相色谱一质谱测定的分析方法,方法回收率在84%～110%之间,精密度(RSD)在2.8%～9.9%之间.采用该方法对阜阳市废弃农药厂周围的土壤和河流沉积物中六六六和滴滴涕进行了监测.