Residual dynamics of thiacloprid in medical herbs marjoram, thyme, and camomile and in soil

Thiacloprid is a new insecticide of the chloronicotinyl family. To assess its risk after application, residual characteristics of thiacloprid in marjoram, thyme, and camomile and in soil were studied under field conditions. The active ingredient was extracted from the plant material using a mixture of acetone-water. After filtration, the extract was concentrated to the aqueous phase, diluted with water, and portioned against ethyl acetate on a matrix solid phase dispersion column. Thiacloprid was extracted from soil using a mixture of methanol-water, filtered, and re.extracted （clean up） with dichloromethane. The residues were quantified using HPLC-MS-MS. The methods were validated by recovery experiments. Thiacloprid residues in marjoram, thyme, and camomile and in soil persisted beyond 10, 14, 14, and 21 d but no residues were detected after 14, 21, 21, and 28 d, respectively. The data obtained in this study indicated that the biexponential model is more suitable than the first-order function to describe the decline of thiacloprid in fresh marjoram, fresh thyme, and dried camomile flowers with half-life （t1/2） of 1.1, 0.7, and 1.2 d, respectively. However, both the first-order function and biexponential model were found to be applicable for dissipation of thiacloprid in soil with almost the same t1/2 values of 3.5 and 3.6 d. The results indicated that thiacloprid dissipates rapidly and does not accumulate in the tested herbs and in soil.     

苯并芘对稀有鮈鲫的内分泌干扰效应研究

为评价典型有机污染物对长江三峡库区上游特有珍稀鱼类的环境风险,本实验以稀有鮈鲫为对象,研究了低剂量多环芳烃(PAHs)暴露而引起的内分泌干扰效应.将成年稀有鮈鲫暴露于不同浓度(0、0.1、0.3、1.0和3.0μg·L-1)的苯并芘(Ba P)中28 d,测定了体质系数、性激素含量、下丘脑-垂体-性腺(HPG)轴和肝脏中与繁殖相关基因的表达.结果显示:在雌鱼中,Ba P暴露后,睾酮(T)的含量显著升高,雌二醇(E2)的水平显著下降并改变了T/E2的比值;在雄鱼中,T和E2的含量都显著下降.雌雄鱼性激素的改变可能与类固醇合成相关基因(Cyp17、Cyp19a)表达量的改变有关.Ba P暴露显著抑制了雌雄鱼肝脏中卵黄蛋白原(VTG)基因的表达.以上检测到的激素或者基因表达的改变主要发生在高剂量(3.0μg·L-1)Ba P暴露下,而长江上游库区水体中多环芳烃含量较低(100 ng·L-1),因此推测,库区存在的多环芳烃不会对三峡库区上游水体中的鱼类产生内分泌干扰效应.     

食物链途径人体健康风险评估的关键内容探讨

食物是人类生存的重要保障,食品安全事关人类生命健康.食品污染始于农田耕地,还包括生产制造、包装、贮存、运输、加工等环节,每个步骤处理不当都可能发生食品安全问题.农田为食物来源的基石,是空气、水体中污染物的汇,随着城市的扩张,人类经济活动导致农田污染加剧.人类从食物中摄取污染物与经口、呼吸、皮肤的途径一样,是人体健康风险评估不可缺少的考量因素之一.我国对食品安全非常重视,2010年1月原卫生部根据《食品安全法》建立《食品安全风险监测管理规定》和《食品安全风险评估管理规定》(试行),这两份文件涵盖了从土壤到餐桌一系列的风险过程.但由于每个过程产生的原因、污染物影响机制均不同,规定离具体实际应用目标还很远.2014年环保部以保护生态环境,保障人体健康为根本,为加强污染场地环境保护监督管理,规范污染场地人体健康风险评估,发布了《污染场地风险评估技术导则》,该文建立了土壤污染造成人体健康风险评价的操作方法.然而导则考虑了经口、皮肤、呼吸及饮用地下水等9种暴露途径和评估模型,唯独缺少经食物链暴露这一重要途径的相关内容.本文以英、美两国食物链途径的场地污染风险评估为依据开展了详细探讨,深入分析了评估程序中关于土地利用方式的分类、目标人群暴露特征、污染物在食物链中传输路径、模型选取及暴露参数等内容,以期为我国制定《食物链暴露途径风险评估导则》提供一定的参考依据和指导方法.     

Seasonal and spatial occurrence and distribution of atmospheric polycyclic aromatic hydrocarbons (PAHs) in rural and urban areas of the North Chinese Plain

Passive air sampling (PAS) was employed to study the occurrence of gaseous and particle-bound PAHs in the North Chinese Plain. The averaged concentrations of gaseous and particle-bound PAHs were 485 ± 209 ng/m³ and 267 ± 161 ng/m³, respectively. The PAHs concentrations at urban sites were generally higher than those at rural ones with ratios <1.5 in spring, summer and fall, but differences between them were not significant for the wintertime and annually averaged concentrations. This urban-rural distribution pattern was related to the PAHs emission sources. PAHs spatial variation can be partially (49%) explained by emission with a simple linear regression method. Both the gaseous and particle-bound PAHs were highest in winter and lowest in summer, with winter/summer ratios of 1.8 and 8, respectively. Emission strength was the most important factor for the seasonality.     

4种中草药的超临界CO2萃取物对霉菌的抑制效果

利用气相扩散法、固相扩散法、平板法研究了荷叶、艾叶、佩兰、细辛4种中草药的超临界CO2萃取物对霉菌的抑制作用和最低抑制浓度(MIC).结果表明,4种中草药的超临界CO2萃取物对单一或混合霉菌均有较强的抑制作用,荷叶和细辛的MIC<1.56g/L,佩兰的MIC<0.63g/L,艾叶的MIC<0.2g/L.表3参11     

Estimates of synthetic fertilizer N-induced direct nitrous oxide emission from Chinese croplands during 1980-2000

There is increasing concern that agricultural intensification in China has greatly increased N₂O emissions due to rapidly increased fertilizer use. By linking a spatial database of precipitation, synthetic fertilizer N input, cropping rotation and area via GIS, a precipitation-rectified emission factor of N₂O for upland croplands and water regime-specific emission factors for irrigated rice paddies were adopted to estimate annual synthetic fertilizer N-induced direct N₂O emissions (FIE-N₂O) from Chinese croplands during 1980-2000. Annual FIE-N₂O was estimated to be 115.7 Gg N₂O-N year⁻¹ in the 1980s and 210.5 Gg N₂O-N year⁻¹ in the 1990s, with an annual increasing rate of 9.14 Gg N₂O-N year⁻¹ over the period 1980-2000. Upland croplands contributed most to the national total of FIE-N₂O, accounting for 79% in 1980 and 92% in 2000. Approximately 65% of the FIE-N₂O emitted in eastern and southern central China.     

苯并芘和邻苯二甲酸二(2-乙基己基)酯复合暴露对稀有鮈鲫的内分泌干扰效应研究

为评价典型有机污染物共存情况下对长江上游三峡库区特有珍稀鱼类的环境风险,以稀有鮈鲫(Gobiocypris rarus)为对象,研究了多环芳烃和酞酸酯的代表物苯并芘(BaP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)单独及复合暴露而引起的内分泌干扰效应。将成年稀有鮈鲫暴露于不同浓度的BaP(0.1、1μg·L~(-1))、DEHP(10、100μg·L~(-1))和BaP+DEHP((0.1+10)、(1+100)μg·L~(-1))中28 d后,测定了体质系数、性激素含量、下丘脑-垂体-性腺(HPG)轴和肝脏中与生殖相关基因的表达。结果表明:在雌鱼中,单独BaP或DEHP暴露对鱼体性激素含量、基因表达量无显著影响; BaP和DEHP复合暴露时,高浓度组睾酮(T)含量升高但雌二醇(E2)含量下降,fsh、vtg、 cyp17和17β-hsd基因表达量上调,cyp19a则下调,表现出协同毒性。因而雌鱼中性激素水平的改变可能与类固醇合成相关基因表达量的改变有关。而无论在单独暴露或是复合暴露情况下,对雄鱼体内性激素无显著影响。以上检测到的激素或基因表达量的改变主要发生在高剂量的复合暴露组中,而长江上游三峡库区水体中多环芳烃和酞酸酯含量低于暴露的最低浓度,因此推测,库区存在的多环芳烃和酞酸酯同时作用时不会对三峡库区上游水体中的鱼类产生生殖内分泌干扰效应。     

Development of enzyme-linked immunosorbent assays for plasma vitellogenin in Chinese rare minnow (Gobiocypris rarus)

Due to the wide occurrence of endocrine disrupting chemicals in the environment, it is much of importance to develop high throughput screening method for the analysis of this kind of pollutants. Using anion-exchange membrane chromatography, vitellogenin (VTG) from the plasma of 17β-estradiol (E₂) treated Chinese rare minnow was rapidly purified within 15 min. Both polyclonal antibody (PcAb) and monoclonal antibody (McAb) against rare minnow VTG (R-VTG) were prepared in rabbit and Balb/c mice, respectively. The competitive enzyme-linked immunosorbent assays (ELISA) based on either PcAb or McAb were developed to identify and quantify R-VTG in the plasma, and these two methods showed similar characteristics. The detection limits of both assays were lower than 3 ng mL⁻¹ with the working ranges covering three magnitudes. The recovery efficiencies of PcAb and McAb based ELISA were 104.2% and 102.6%, respectively; and the intra-assay and inter-assay of these two assays were 6.2% and 9.2%, 8.6% and 12.8%, respectively. These results indicated that the described competitive ELISA methods were sensitive and valuable tools for quantifying vitellogenin in rare minnow plasma. These methods were then applied to measure R-VTG concentrations in plasma of male fish exposed to a series of E₂ concentrations. When E₂ levels were less than 10 ng L⁻¹, R-VTG levels in plasma were comparable to that in solvent control, while R-VTG levels significantly increased 15-folds and 350-folds, respectively when E₂ exposure concentrations were controlled at 10 and 50 ng L⁻¹. The high sensitivity of Chinese rare minnow to E₂ was demonstrated, making it a valuable model species to study environmental estrogens.     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

“水解酸化+接触氧化”工艺在小型企业中成药废水处理中的应用

介绍了"水解酸化+接触氧化"工艺处理具有污染物浓度高、水质水量波动大等特点的某小型企业中药废水实际工程。监测数据表明该工艺处理效果稳定、可靠,出水指标达到GB 8978—1996《污水综合排放标准》医药原料药二级标准。