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.     

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.     

Analysis of metabolic changes in Trichoderma asperellum TJ01 at different fermentation time-points by LC-QQQ-MS

Trichoderma spp. are among the most widely recognized biocontrol fungi used to inhibit pathogens and promote plant growth. These functions are related to primary and secondary metabolites. This study investigated the different metabolites in Trichoderma asperellum TJ01 cultured for 24 and 72?h using liquid chromatography with triple-quadrupole mass spectrometry. Compared to the 24?h culture of T. asperellum TJ01, the 72?h culture with amino acid metabolism tended to decrease while sugar and lipid metabolisms tended to increase. Furthermore, the 72?h culture had a higher proportion of upregulated flavonoids, in combination with a higher proportion of downregulated alkaloids, and equal proportions of upregulated and downregulated polyphenols and hormones. This study also identified a few valuable medicinal substances such as trigonelline and 5-hydroxytryptophan in T. asperellum TJ01 fermentation cultures.     

近十年鄱阳湖区极端干旱事件频发现象成因初析

近10 a来鄱阳湖区极端干旱事件频发，引起国内外媒体舆论的广泛关注。针对这一情况，运用流域降水、地表蒸散和出湖径流等数据，从流域水量收支平衡的角度，较为系统地分析了导致鄱阳湖区极端干旱事件频发的原因。结果表明，近10 a来鄱阳湖水文干旱起始日期提前，枯水期拉长。虽然干旱持续时间的长短呈现2~3 a的波动，但在总体上呈现逐渐加长的趋势。从流域水分收支的角度来看，近10 a来以水分亏缺为主，流域降水亏缺是基本的致旱因素，流域蒸散量增加则起到一定的增强作用，而出湖径流所起的作用比较复杂，在多数情况下其致旱的影响程度弱于流域降水作用。长江顶托作用强弱变化可以调节流域的水分收支平衡，强化或者减轻湖泊的干旱程度。2003、2004、2007、2008和2009年发生的极端干旱事件主要由流域水分收入项的大幅度减少所造成的，而长江水情变化在多数情况下加剧了流域水分收支的不平衡。这些研究结果明晰了鄱阳湖流域气象干旱与湖泊水文干旱之间的关系以及长江水情变化所扮演的重要角色，为应对未来的干旱变化和制定合理的抗旱防旱对策与措施提供了科学的依据     

层次分析-熵值定权法在城市水环境承载力评价中的应用

从广义水环境承载力定义出发，建立水环境承载力评价指标体系;采用层次分析－熵值定权法和向量模法对武汉市水环境承载力进行评价，该定权方法采用层次分析法确定权重，同时又引入熵值法对权重进行修正，在一定程度上减少了主观影响。该方法使评价指标的赋权达到主观与客观统一，对水环境承载力的量化更加准确与合理。该方法构造简单，便于实现计算机编程，所以应用较为简单、方便。以武汉市为例，综合考虑资源环境以及社会经济发展，建立了一套指标体系，利用向量模法对指标进行量化，结果表明武汉市2006~2010年水环境承载力逐年增大，由0129 3增长到02411，表明近些年武汉市水资源、环境与社会经济的发展协调性较好。从3个准则层中可以看出，资源与环境对武汉市水环境承载力的影响较大；社会子系统承载力评价值逐年上升，且上升趋势较快；随着经济的加速发展，经济子系统承载力评价值呈逐年下降态势     

钛基IrO2-SnO2电极在烟气海水脱硫恢复系统中的应用

采用浸渍-热分解法制备了含IrOx-TiO2中间层的IrO2-SnO2电极,得到的电极具有较高的析氯电催化活性和较强的稳定性,并通过电化学氧化法对Na2SO3海水脱硫模拟液进行处理,考察了电流密度、温度、pH值和电解时间等电解工艺参数对Na2SO3去除率和化学需氧量COD的影响。结果表明,在电流密度为200 mA/cm^2,pH值为3.5,电解440 mg/L的Na2SO3海水脱硫模拟液,15 min时Na2SO3去除率可达96.5%,COD去除率可达82.6%。     

热带海洋大气环境下X70管线钢的缝隙腐蚀行为研究

目的研究X70管线钢在热带海洋大气实海环境下的缝隙腐蚀行为。方法在距离湛江东海岛海岸50m和200 m处分别搭建楔型缝隙模型,安装大气环境Cl-收集装置和自动气象监测站。结果距离海岸越近,风速越大,大气中Cl-沉降速率也越大,X70管线钢缝隙腐蚀越严重。X70管线钢在距离海岸50 m处发生缝隙腐蚀的最大缝宽约为0.96 mm,200 m处最大缝宽约为3.75 mm,50 m处缝隙腐蚀更严重。结论缝隙腐蚀区域形成了氧浓差电池,同时随着缝隙液中Cl-向缝隙内迁移,发生闭塞区电池自催化过程,在二者共同作用下,缝隙腐蚀区域较非缝隙腐蚀区域腐蚀更严重。     

Occurrence and distribution of polycyclic aromatic carbons in sludges from wastewater treatment plants in Guangdong, China

In this study, the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) were investigated in six sludge samples collected from Guangdong Province, China. Concentrations of PAHs varying from 2,534.1 to 6,926.6 μg kg^???1 (dry sludge) were observed in three municipal wastewater treatment plants with phenanthrene (Phe), fluoranthene, and pyrene being the main compounds. In addition, 682.6 μg kg^???1 PAHs were detected in one sludge sample from a food processing plant, with fluorene, Phe, and chrysene being the main components. No PAHs were detected in sludge samples obtained from two cosmetic plants. The levels and distributional characteristics of PAHs, polychlorinated biphenyls (PCBs), and polycyclic musks (PMs) from the samples were also compared. The results of this comparison indicated that petrochemical refineries and road traffic played important roles in the PAH loads in sludge, while PMs primarily originated from domestic wastewater and industrial wastewater from cosmetic plants. Finally, the presence of 98.8 μg kg^???1 PCBs in sludge suggested diffusional emission sources from electrical components containing PCBs.     

长三角地区城市居民出行交通碳排放特征与影响机理

随着能源问题及全球变化关注，城市居民出行交通碳排放研究已成为多学科关注焦点。选择南京、宁波和常州作为长三角典型城市，基于典型居住小区问卷调查获取第一手的城市居民出行基础数据，估算与分析城市居民出行碳排放特征及影响机理。结果表明：长三角2010年城市居民人均出行交通碳排放约1 1219 kg CO2/人，日常通勤和远距离出行碳排放量之比为75[DK]∶25；城市居民日常通勤交通碳排放的主要影响因子为交通方式、出行距离、家庭年收入、年龄和性别；远距离出行交通碳排放的主要影响因子为出行距离、交通方式和家庭年收入。建议采用差别化的行政干预和经济杠杆有效调控家庭小汽车保有量增长速度，鼓励小排量汽车和清洁能源汽车消费，兼顾汽车产业发展、家庭小汽车刚性需求与节能减排需求之间的博弈平衡；优化城市功能格局，大力发展公共交通网络；加强节能减排与低碳意识宣传，鼓励与引导公共交通出行     

煤矿火灾爆炸外因火源来源及预防方法研究

对我国1950～2009年煤矿特别重大火灾、爆炸事故进行统计分析,找到引起事故的火源分布规律。结果表明,88.1%的事故由外因火源引起;引起事故的外因火源来源按发生频率大小主要有：违章放炮、仪器设备失爆、摩擦撞击、带电作业、电缆短路、拆卸设备、电缆接头漏电、明火明电、吸烟;其中,68%的外因火源来源于工人的违章行为,32%的外因火源来源于电气设备原因。在对近年外因点火源特征分析的基础上,笔者针对工人违章行为及电气设备原因提出预防措施：完善安全结构工资;逐步建立工人违章联锁制度,又称＂安全伙伴＂;对一线工人普及电气安全知识,并将可能存在明显电气安全隐患的部分分配给普通工人负责。