水环境中26种类固醇激素的分析方法研究

建立了固相萃取-超高效液相-串联质谱法同时测定水环境中26种类固醇激素的分析方法。明确了取样体积为500 m L,Cleanert PEP为富集柱,乙酸乙酯为洗脱剂,甲醇为溶剂进行提取操作。选择了正离子模式,以0. 1%甲酸/甲醇-水为流动相,负离子模式以0. 1%氨水/乙腈-水为流动相,试样经AcquityTMUPLC BEH C18色谱柱分离后,选用质谱检测模式进行定性、定量分析。通过方法验证,26种类固醇激素的方法检出限为0. 3～1. 5 ng/L,测定下限为1. 2～6. 0 ng/L,代表性样品测定结果的相对标准偏差为2. 6%～13. 7%(n=6),加标回收率为71. 2%～121%。该方法操作便捷,灵敏度高,精密度和准确度良好,可适用于水环境中多种痕量、超痕量类固醇激素的定性定量分析。     

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.     

加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

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。     

农地整治权属调整中农户认知对行为响应的作用机制--基于改进TPB及多群组SEM

农地整治权属调整是实现农业规模化和现代化的重要手段,而农户有效参与是推动权属调整的内在动力,研究农地整治权属调整中农户认知对其行为响应的作用机制,有助于高效引导农户参与权属调整,并为制定农地整治权属调整的政策提供科学依据。基于改进计划行为理论和湖北省11个县(市、区)1044份农户抽样调查数据,采用多群组结构方程模型探究了农地整治权属调整中不同类型农户认知对其行为响应的作用机制。结果表明:农地整治权属调整中农户行为逻辑符合改进计划行为理论,农户的行为态度、主观规范、知觉行为控制交互影响行为意愿,进而转换为行为响应,政府支持在行为意愿和行为响应之间起到部分中介作用。总体上,农户行为响应是"自发性""诱发性"和"约束性"三重行动逻辑的结合,且"自发性"占主导地位。多群组结构方程估计结果表明,纯农型与兼业Ⅰ型农户的行为响应受到"自发性""诱发性"和"约束性"三重影响,兼业Ⅱ型农户受到"自发性"和"诱发性"双重影响,非农型农户仅受到"诱发性"单一影响。因此,为引导农户积极参与农地整治权属调整,应该分别针对各类农户相应地提高其参与的"自发性"和"诱发性",降低"约束性",充分发挥农村社会经济组织的作用,将四种不同类型农户的利益需求统筹考虑,降低权属调整过程中利益协调难度。     

河湖水环境问题及管理和治理模式

本文首先介绍了我国当前的河湖水环境现状,分析了我国水资源存在的一系列问题,主要问题包括水体污染和富营养化;河湖面积严重萎缩,河湖水的功能逐渐退化;难以降解的有机污染物污染量加大。有针对性地提出了改善我国河湖水环境的管理以及治理模式,进一步落实了保护河湖水环境工作,加强水资源周围生态环境的文明建设,实现河湖水环境的可持续发展。     

An LC-MS/MS method for creatine and creatinine analysis in paraquat-intoxicated patients

Abstract

A sudden increase in serum creatinine after paraquat intoxication has been reported in several clinical studies. However, this dramatic change of creatinine may be possibly due to an interconversion of creatine-creatinine in relation to paraquat toxicity. In order to investigate the creatine-creatinine relationship, a liquid chromatography tandem mass spectrometry in combination with electrospray ionization was developed and validated for simultaneous determination of creatine and creatinine in the serum. The chromatographic separation was achieved on a Gemini® C₆-Phenyl column with a gradient elution consisting of 0.1% formic acid in ultrapure water and methanol as the mobile phase. The method yielded suitable levels of specificity and selectivity, and calibration curves of creatine and creatinine in serum were linear over the concentration range of 0.5–200?µg mL^?1. The limit of quantification of both compounds was 0.5?µg mL^?1, and the method was accurate within the recovery range of 96.23–102.75%, indicating the robustness of the method. The method was successfully applied to toxicological samples from paraquat-intoxicated patients, and the concentrations of creatine and creatinine were quantified. High creatine concentrations in serum samples were observed which may lead to high serum creatinine despite normal kidney function as creatine is converted to creatinine in proportion to its concentration.     

矿井热宽温度环境人体热健康分区热调节模型*

为评价矿井热环境中工人职业健康安全状况，提出矿井热宽温度环境人体热健康状态的基本特征与生理要求，分析热宽温度环境人体分区热调节规律与热健康状态的对应关系。基于生物控制论的观点，提出热宽温度范围内不同热应力作用下人体分区热调节机制，建立人体分区热调节模型。结果表明:模型能实现对环境热应力作用下人体物理热平衡状态与生理状态的参数化描述，揭示多因素作用下人体热健康状态的热应力边界与变化规律。分区热调节模型提供了人体热健康状态定量模拟平台，通过参数调整可使模型适应研究需求，模型为井下热环境工人职业健康安全状况分析与评价提供了可参考的思路与方法。     

Hierarchical pre-positioning of emergency resources for a chemical industrial parks concentrated area

Accidents in chemical industrial parks always cause fateful damage which can be reduced greatly by providing emergency resources sufficiently and timely. One effective way to enhance the emergency response capacity and agility is by pre-positioning of emergency resources for the potential accidents. The Yangtze River Delta of China is a large region where a large number of chemical industrial parks are concentrated. According to the distributing characteristics of demand points in this region, a mathematical model of hierarchical pre-positioning of emergency resources is proposed to ensure that accidents in all chemical industrial parks in this region can be responded timely and effectively. Considering accident domino effect and minimizing the total cost, the model gives optimal decisions of pre-positioning emergency resources, including the location and inventory of depots. The innovative hierarchical pre-positioning method greatly reduces the total cost in the premise of sufficient preparation for supplying emergency resources. Finally, in a visual graph of the Yangtze River Delta, the model is applied and the result shows its applicability.     

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.