金银花中有机磷农药残留分析及其冲泡过程迁移模型研究

为确保消费者饮茶安全,建立了QuEChERS-GC-MS/MS快速测定金银花和其茶汤中6种有机磷农药(对硫磷、倍硫磷、特丁硫磷、治螟磷、丙溴磷、灭线磷)残留的检测方法。金银花和茶汤分别经乙腈和乙酸乙酯提取、盐析离心、混合净化剂(10 mg MWCNTs、15 mg PSA、150 mg无水硫酸镁)净化、0.22μm滤膜过滤后,供GC-MS/MS检测。结果表明:金银花和茶汤中,有机磷农药在1～1 000μkg和1～1 000μg/L呈现良好的线性关系,R~20.991;在4个添加水平下,回收率在67.2%～110.3%,相对标准偏差小于19%(n=6);金银花和茶汤中,有机磷农药定量限分别为1μg/kg和1μg/L。在此基础上,深入研究了金银花在冲泡过程中6种有机磷农药的迁移预测模型,表明农药迁移率(TR)与农药的正辛醇-水分配系数(Kow)关联性较大,由此获得预测模型为lg TR=-0.536 2 1g Kow+3.915 2(lg Kow3),R~2=0.914,拟合度较好;而农药迁移率与水溶解度(Ws)并未表示出关联性。该检测方法和迁移模型的建立将有利于更深层次认知农药化学污染物在金银花浸泡过程中的迁移行为,以期为制定金银花中有机磷农药最大残留限量标准提供科学依据和技术支撑。     

Distribution of POPs,pesticides and antibiotic residues in organic honeys from different production areas

Demand for honey is increasing, especially if it is organic and if its nutritional properties are linked to untreated environments in order to guarantee quality for health. Sources of contamination of honey can be divided into environmental and apicultural. Therefore, the distribution of persistent organic pollutants, pesticides and antibiotic residues from geographical areas with different contamination sources (high anthropic impact, intensive farming, husbandry and low anthropic impact) was investigated in order to confirm the potential transfer of xenobiotics into the supply chain and to give beekeepers tools for the selection of areas dedicated to organic production. The presence of polychlorinated biphenyls, polybrominated diphenyl ether and polycyclic aromatic hydrocarbons was confirmed, not only in proximity to highly urbanised centres, where the concentrations were higher, but in all environment contexts, confirming their ubiquity. No antibiotics or neonicotinoids were detected in 95 organic honeys, demonstrating the absence of apicultural treatments and consequently the good quality of honey of different areas. These results are important due to the undefined regulatory European situation on honey antibiotic limits.     

QuEChERS-高效液相色谱法测定食品中4种氨基甲酸酯类农药残留

结合QuEChERS前处理方法，建立了采用高效液相色谱法（HPLC）测定食品中4种氨基甲酸酯类农药残留的方法。以乙腈作为提取溶剂，无水硫酸镁、PSA和GCB净化，C18柱为色谱分离柱，甲醇-水为流动相，检测波长范围190～300 nm进行检测。结果表明，4种农药在6.5 min内实现了基线分离，线性相关系数（R2）≥0.999 8，检出限为2～5 μg/kg，样品加标平均回收率为82.5%～99.3%，精密度试验结果相对标准偏差（RSD）为1.64%～3.30%。该方法操作简单，灵敏度高，结果准确可靠。     

液相色谱-串联质谱法测定进出口人参、西洋参中蚜灭磷等6种农药

建立了人参、西洋参中凝胶色谱-固相萃取-液相色谱-串联质谱法测定蚜灭磷、吡虫啉、涕灭威、甲基内吸磷、甲硫威、辛硫磷6种农药的分析方法。样品经丙酮超声提取,凝胶色谱(GPC)净化后,固相萃取(SPE)净化,在HPLC/MS/MS多反应监测(MRM)模式下进行了定性和定量分析方法。在上述检测方法条件下,所测的6种农药的最低检出限为0.01 mg/kg,回收率范围为79.2%~107.3%,线性范围为0.01~0.2 mg/kg。     

Controlling Diffuse Pollution of Groundwater from Agriculture and Industry

The greatest threat of contamination to groundwater resources is posed by pollutants from diffuse sources, yet legislation in the UK has until recently been focused on point sources. The problem of widespread pollution from industrial sources is described and compared with that from agriculture. The legislative controls available under the Water Resources Act 1991 are outlined, and the approach adopted by the National Rivers Authority in its Groundwater Protection Policy is discussed with respect to the concept of groundwater vulnerability.     

Pesticides in groundwater: some observations on temporal and spatial trends

Following a monitoring programme of private shallow boreholes a total of 22 different pesticides were detected in 14 shallow boreholes in the Triassic Sherwood Sandstone aquifer of south Yorkshire, UK between January 2002 and November 2003. Of the 294 positive detections made, 34% were detected in excess of the permitted concentration value (PCV) (drinking water standard) for individual pesticides. Pesticides were detected in 11 (78%) of the boreholes, and in eight (57%) at concentrations exceeding the PCV on at least one occasion. These findings were complemented by data from deeper boreholes in which concentrations exceeding the PCV were also detected. Pesticide occurrence could be related to landuse; mecoprop and isoproturon were frequently detected at several locations reflecting the arable landuse, dicamba at a golf course, and atrazine, propazine and terbutryn near a railway. Temporal variations have emerged at individual sites and across the study area as the result of extended and frequent monitoring.     

Pesticides in rain and roof runoff waters from an urban region

The levels of organonitrogen, organochlorine and organophosphorus pesticides were monitored in rain and roof runoff waters in Gdańsk (Poland) over a period of 6 months (October 2000 – March 2001). Buildings included in the study were of different ages, and covered with a variety of roofing materials. Samples were collected during the precipitation events. Pesticides were determined by gas chromatography combined with NPD and ECD detection. Bromofos, heptachlor epoxide and o,p′-DDE were detected the most often in the samples collected. In general, pesticide concentrations were higher in roof runoff than in rainwater. The type of the roofing material had a significant effect on the pesticide levels in runoff waters. The highest analyte levels were recorded in October and November, when the temperature was the highest.     

Pollutant concentrations and fluxes in both stormwater and wastewater at the outlet of two urban watersheds in Nantes (France)

A two-year study of pollutants in both the stormwater and wastewater of urban watersheds has been conducted in Nantes (France). The present paper discusses the characteristics of pollutants transported by stormwater and wastewater collection networks in two urban watersheds. A physicochemical characterisation of the effluents was performed, along with an estimation of pollutant fluxes discharged into the Gohards River. Suspended solids (SS), trace metals, polycyclic aromatic hydrocarbons (PAHs) and pesticides were studied. SS, Zn, Cu and glyphosate were the main pollutants in stormwater and wastewater. In the watersheds examined, the pyrolitic origin of PAHs (mainly from traffic) was determined through ratios, with fluoranthene and pyrene being predominant. Despite a reduction in the use of pesticides in Nantes Metropolitan area, herbicides containing glyphosate were still detected in stormwater. It should be noted that this herbicide is widely used by homeowners, a fact that may explain its occurrence in stormwater.     

Chemical contaminants, health indicators, and reproductive biomarker responses in fish from the Colorado River and its tributaries

Common carp (Cyprinus carpio), black bass (Micropterus spp.), and channel catfish (Ictalurus punctatus) were collected from 14 sites in the Colorado River Basin (CRB) to document spatial trends in accumulative contaminants, health indicators, and reproductive biomarkers. Organochlorine residues, 2,3,7,8-tetrachlorodibenzo-p-dioxin-like activity (TCDD-EQ), and elemental contaminants were measured in composite samples of whole fish, grouped by species and gender, from each site. Selenium (Se) and mercury (Hg) concentrations in fish were elevated throughout the CRB, and pesticide concentrations were greatest in fish from agricultural areas in the Lower Colorado River and Gila River. Selenium concentrations exceeded toxicity thresholds for fish (>1.0 microg/g ww) at all CRB sites except the Gila River at Hayden, Arizona. Mercury concentrations were elevated (>0.1 microg/g ww) in fish from the Yampa River at Lay, Colorado; the Green River at Ouray National Wildlife Refuge (NWR), Utah and San Rafael, Utah; the San Juan River at Hogback Diversion, New Mexico; and the Colorado River at Gold Bar Canyon, Utah, Needles, California, and Imperial Dam, Arizona. Concentrations of p,p'-DDE were relatively high in fish from the Gila River at Arlington, Arizona (>1.0 microg/g ww) and Phoenix, Arizona (>0.5 microg/g ww). Concentrations of other formerly used pesticides including toxaphene, total chlordanes, and dieldrin were also greatest at these two sites but did not exceed toxicity thresholds. Currently used pesticides such as Dacthal, endosulfan, gamma-HCH, and methoxychlor were also greatest in fish from the Gila River downstream of Phoenix. Total polychlorinated biphenyls (PCBs; >0.11 microg/g ww) and TCDD-EQs (>5 pg/g ww) exceeded wildlife guidelines in fish from the Gila River at Phoenix. Hepatic ethoxyresorufin O-deethylase (EROD) activity was also relatively high in carp from the Gila River at Phoenix and in bass from the Green River at Ouray NWR. Fish from some sites showed evidence of contaminant exposure as indicated by fish health indicators and reproductive biomarker results. Multiple health indicators including altered body and organ weights and high health assessment index scores may be associated with elevated Se concentrations in fish from the Colorado River at Loma, Colorado and Needles. Although grossly visible external or internal lesions were found on most fish from some sites, histopathological analysis determined many of these to be inflammatory responses associated with parasites. Edema, exophthalmos, and cataracts were noted in fish from sites with elevated Se concentrations. Intersex fish were found at seven of 14 sites and included smallmouth bass (M. dolomieu), largemouth bass (M. salmoides), catfish, and carp and may indicate exposure to endocrine disrupting compounds. A high proportion of smallmouth bass from the Yampa River at Lay (70%) was intersex but the cause of this condition is unknown. Male carp, bass, and catfish with low concentrations of vitellogenin were common in the CRB. Comparatively high vitellogenin concentrations (>0.2 mg/mL) were measured in male bass from the Green River at Ouray NWR and the Colorado River at Imperial Dam and indicate exposure to estrogenic or anti-androgenic chemicals. Anomalous reproductive biomarkers including low GSI and gonadal abnormalities (calcifications, edema, and parasites) observed in fish downstream of Phoenix are likely related to the poor water-quality of the Gila River in this area.