利用毒代动力学模型研究氟虫腈在夹杂带丝蚓体内的手性选择性积累过程

农药的生物积累直接影响其毒性,但是手性农药在生物体内的选择性积累过程仍不明确.本文在恒定环境水浓度的条件下,开展手性农药氟虫腈的外消旋体及其对映体在底栖无脊椎动物夹杂带丝蚓体内的生物积累实验.在96 h和72 h的吸收和消除实验过程中,测定生物体内的氟虫腈的外消旋体和对映体浓度随时间的变化情况,构建毒代动力学模型,获取吸收和消除速率常数.结果表明夹杂带丝蚓对R-氟虫腈的生物浓缩因子(1981 L·kg~(-1)脂肪)比对S-氟虫腈(1748 L·kg~(-1)脂肪)更大.R-氟虫腈和S-氟虫腈的吸收速率常数相当,分别为311±11 L·kg~(-1)脂肪·h~(-1)和313±13 L·kg~(-1)脂肪·h~(-1),而R-氟虫腈的消除速率常数小于S-氟虫腈,分别为0.157±0.006 h~(-1)和0.179±0.008 h~(-1),因此相对较慢的消除是导致R-氟虫腈在夹杂带丝蚓体内更高生物积累的主要原因.研究说明毒代动力学参数可有效阐释手性外源物质在生物体内选择性积累的差异.     

Evaluation of photolysis and hydrolysis of pyraclostrobin in aqueous solutions and its degradation products in paddy water

This study evaluated the hydrolysis and photolysis kinetics of pyraclostrobin in an aqueous solution using ultra-high-performance liquid chromatography–photodiode array detection and identified the resulting metabolites of pyraclostrobin by hydrolysis and photolysis in paddy water using high-resolution mass spectrometry coupled with liquid chromatography. The effect of solution pH, metal ions and surfactants on the hydrolysis of pyraclostrobin was explored. The hydrolysis half-lives of pyraclostrobin were 23.1–115.5?days and were stable in buffer solution at pH 5.0. The degradation rate of pyraclostrobin in an aqueous solution under sunlight was slower than that under UV photolysis reaction. The half-lives of pyraclostrobin in a buffer solution at pH 5.0, 7.0, 9.0 and in paddy water were less than 12?h under the two light irradiation types. The metabolites of the two processes were identified and compared to further understand the mechanisms underlying hydrolysis and photolysis of pyraclostrobin in natural water. The extracted ions obtained from paddy water were automatically annotated by Compound Discoverer software with manual confirmation of their fragments. Two metabolites were detected and identified in the pyraclostrobin hydrolysis, whereas three metabolites were detected and identified in the photolysis in paddy water.     

丹江湿地国家级自然保护区及其内外区域2000—2015年土地覆被变化分析

为研究2000—2015年丹江湿地国家级自然保护区及其内外生态状况变化和保护成效,基于高分1号数据生产的2m高分辨率遥感影像数据对丹江湿地国家级自然保护区2015年人类活动状况进行分析,基于30 m分辨率的4期TM遥感影像生产的土地覆被数据和基于Modis遥感影像生产的植被覆盖度数据,对淅川县、丹江湿地国家级自然保护区及其核心区的土地覆被状况、土地覆被转类指数及其土地覆被转类途径的主导程度和3个相关区域范围内的生态系统质量以及不同区域土地覆被变化的主要变化原因进行分析。结果表明,保护区核心区的格局和质量在该区域处于最优,且土地覆被变化状况也以核心区转类指数最高;丹江湿地国家级自然保护区内的主要人类活动影响为耕地,其次包括居民点、采石场、养殖场; 15年间,保护区内外土地覆被均呈现转好趋势,但是保护区内变化优于保护区外,保护区核心区优于整个保护区,且转好的主导因素均是耕地变为湿地; 15年间植被覆盖度变化较小。     

Determination of the residue dynamics and dietary risk of thiamethoxam and its metabolite clothianidin in citrus and soil by LC-MS/MS

A modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method was developed for the determination of thiamethoxam and its metabolite clothianidin in citrus (including the whole citrus, peel and pulp) and soil samples by liquid chromatography-tandem mass spectrometry. The sample was extracted with acetonitrile and purified with octadecylsilane. The detection limits of both compounds were 0.0001–0.0002?mg kg^–1, while the limit of quantification of thiamethoxam was 0.002?mg kg^–1 and the limit of quantitation of metabolites was 0.001?mg kg^–1. The recovery was 70.37%–109.76%, with inter-day relative standard deviations (RSD) (n?=?15) values ≤9.46% for the two compounds in the four matrices. The degradation curve of thiamethoxam in whole citrus and soil was plotted using the first-order kinetic model. The half-life of the whole citrus was 1.9–6.2?days, and the half-life of the soil was 3.9–4.2?days. The terminal residue of thiamethoxam (the sum of thiamethoxam and clothianidin, expressed as thiamethoxam) was found to be concentrated on the peel. The final residual amount of thiamethoxam in the edible portion (pulp) was less than 0.061?mg kg^–1. The risk quotient values were all below 1, indicating that thiamethoxam as a citrus insecticide does not pose a health risk to humans at the recommended dosage.     

分层开采工艺对地表沉降的影响研究

分层开采是厚煤开采的经典工艺,这种工艺对地表沉降的影响比较复杂。通过测试原岩物理力学参数,利用有限元软件flac3D对分层和一次采全高时地表沉降进行了数值模拟。结果表明,如果采高较小,砌体梁距煤层较近,且采完上分层后长时间停采,给顶板再生留足时间,分层开采较一次采全高对地表沉降影响要小。     

北京市废弃微型计算机主机物料系数测算研究

微型计算机作为《废弃电器电子产品回收处理管理条例》的首批目录产品,处理企业对其拆解处理将获得基金补贴。而微型计算机主机物料系数是基金补贴的重要依据之一。为了减少微型计算机主机物料系数与实际情况的偏差,北京市环保局委托中国家用电器研究院,在北京市3家处理企业中开展台式微型计算机主机进行拆解实验,对比分析了台式微型计算机电路板物料系数不同的计算方法,并提出物料系数计算方法和系数建议,为北京市废弃电器电子产品处理企业补贴审核提供依据和政策支撑。     

水中藻类对连续流动法测定总氮结果的影响

以天津市河道、水库为研究对象,在藻类增殖期采用连续流动法与碱性过硫酸钾消解法对水体中总氮进行比对监测,同时分析水中藻类分类和藻细胞密度。试验表明:虽然两种方法测定总氮的结果精密度基本相同,但二者之间的系统误差存在显著差异,连续流动法较碱性过硫酸钾消解法的测定结果低5.4%。两种方法测定总氮结果的相对偏差与水体中藻细胞密度呈正相关性,当水体中藻细胞密度﹥2.41×108L-1时,对连续流动法测定总氮的结果产生显著影响,相对偏差超过标准规范要求。     

利用卫星遥感数据估算PM2.5浓度的应用研究进展

近年来,PM_(2.5)已成为中国大气污染的首要污染物,危害人体健康。为弥补地基监测站点在空间分布上的局限性,借助卫星遥感技术估算PM_(2.5)浓度已成为研究热点。文章总结了利用卫星估算PM_(2.5)浓度的各种研究方法,探讨了不同方法的优势和不足,指出不同方法对不同应用目的的选择性差异较大。提出,应针对不同应用目的选择相应的方法,从而取得满足各方面需求的研究成果,为未来PM_(2.5)浓度估算应用工作提供参考。     

冻融循环作用下尾矿砂抗剪强度和变形特性研究

为探究冻融循环后尾矿物理力学特性的变化特征,使用高低温试验箱和应变控制式三轴剪力仪对处于不同初始条件下的尾矿砂进行不排水不固结试验,揭示了尾矿砂的抗剪强度参数、不同围压条件下的变形模量与冻融循环次数、含水率之间的关系。结果表明:相同含水率条件下,随冻融循环次数增加,尾矿砂黏聚力先减小后趋于稳定,内摩擦角先增大后减小,围压100 k Pa和200 k Pa时变形模量逐渐减小,围压300 k Pa时变形模量呈现先减小后缓慢增大的趋势;相同冻融循环次数条件下,随尾矿砂含水率增加,其黏聚力先增加后减小、内摩擦角不断减小;不同围压条件下变形模量在总体上均呈现出不断减小的变化趋势,围压200 k Pa时变形模量总的衰减量最大,100k Pa次之,300 k Pa最小。     

对称障碍物条件下瓦斯爆炸火焰与压力波耦合作用研究

为了研究对称障碍物条件下瓦斯爆炸压力波与火焰传播的耦合作用,在150 mm×150 mm×1 700 mm的有机玻璃瓦斯爆炸管道中,距离点火端不同距离安装0.5阻塞率的对称障碍物,进行8.5%甲烷体积分数的爆炸试验,采集瓦斯爆炸的超压信号并同步拍摄火焰传播图像。结果表明:火焰穿越板式对称障碍物的过程经历了火焰加速、火焰降速到火焰再加速的过程,火焰降速的时间仅为5 ms。距离点火焰源不同长度的对称障碍物在火焰加速过程中的作用存在明显差异,近点火源的障碍物作用主要为诱导湍流,远离点火源的障碍物作用主要为湍流增强。