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。     

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。     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

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。     

隧道救援站通风网络优化设计及人员疏散研究*

为确定铁路隧道救援站最佳通风结构，对烟道布置提出合理建议，采用计算流体力学（CFD）的方法，对铁路隧道救援站通风网络进行优化设计。同时，采用模拟计算的方法对救援站人员疏散进行模拟分析，确定救援横通道布置及防护门开度设置的合理性。研究结果表明:在同等通风参数工况设置下，采用多节点排烟竖井结构后各救援横通道流量分配更均匀，救援站压力平衡性更好，通风效率可提升15%；通过疏散模拟证实，在长560 m的紧急救援站范围内设置10条疏散横通道，横通道设1.7 m宽的逃生门能够满足疏散要求。     

铁路沿线可燃重气储罐最小隔离区域划分探讨*

为保护铁路线，以某化工厂距离高铁路线最近的丙烯球罐为例，提出丙烯球罐泄漏最小隔离区域划分方法以及2种保护高铁线路方案，利用重气扩散模型和定量风险评价（QRA）软件分别进行丙烯扩散模拟、爆炸模拟，并进行危险与可操作性分析（HAZOP）和保护层分析（LOPA）。结果表明:球罐发生泄漏及火灾爆炸等事故，会给附近铁路线带来严重破坏；丙烯泄漏或球罐因周围其他设备设施或可燃物质着火而温度升高时，保护措施不足；隧道的安全可靠性要高于仅设1道防爆墙，隧道长度需覆盖最小隔离区域的可及范围，在扩散区域内也需设立普通挡墙，在极度危险情况下，需要实施高铁停开等保护措施。     

Morphological characteristics of flashing jet throughout superheated liquid release

Many release problems involve two-phase releases of hazardous materials of superheated liquids with high energy into the atmosphere. Such accidents are accompanied by violent phase transition and form catastrophic flashing jets. In this work, experimental and theoretical analyses were conducted to investigate dynamic characteristics of flashing jet morphology and their dependence on pressure-decay dynamics under different storage pressures, superheats, and nozzle diameters. Flashing jet morphology and angle throughout two-phase releases were captured by a high-speed camera, and the corresponding source pressure in the superheated liquid tank was measured simultaneously. Results show that three typical phases, expansion, stabilization, and decay, are characterized throughout two-phase release based on the evolution of flashing jet morphology. The jet initially expands gradually due to the enhancement of phase transition intensity, and then keeps stable when the intensity reaches its maximum, and terminally decays rapidly due to the depletion of superheated liquid. Phase transition intensity at the nozzle exit is mainly controlled by the pressure-decay dynamics. Bubbles nucleation inception sites gradually move upstream of the nozzle during the pressure decay process increasing the phase transition intensity. The increase of storage pressure, superheat and nozzle diameter promotes the mechanical and thermodynamic effects on the jet breakup. The significant increase of mechanical and thermodynamic effects effectively accelerates droplets evaporation and further affects flashing jet morphology.     

Metabolic uncoupler, 3,3′,4′,5-tetrachlorosalicylanilide addition for sludge reduction and fouling control in a gravity-driven membrane bioreactor

• Effects of metabolic uncoupler TCS on the performances of GDMBR were evaluated. • Sludge EPS reduced and transformed into dissolved SMP when TCS was added. • Appropriate TCS increased the permeability and reduced cake layer fouling. • High dosage aggravated fouling due to compact cake layer with low bio-activity. The gravity-driven membrane bioreactor (MBR)system is promising for decentralized sewage treatment because of its low energy consumption and maintenance requirements. However, the growing sludge not only increases membrane fouling, but also augments operational complexities (sludge discharge). We added the metabolic uncoupler 3,3′,4′,5-tetrachlorosalicylanilide (TCS) to the system to deal with the mentioned issues. Based on the results, TCS addition effectively decreased sludge ATP and sludge yield (reduced by 50%). Extracellular polymeric substances (EPS; proteins and polysaccharides) decreased with the addition of TCS and were transformed into dissolved soluble microbial products (SMPs) in the bulk solution, leading to the break of sludge flocs into small fragments. Permeability was increased by more than two times, reaching 60–70 L/m²/h bar when 10–30 mg/L TCS were added, because of the reduced suspended sludge and the formation of a thin cake layer with low EPS levels. Resistance analyses confirmed that appropriate dosages of TCS primarily decreased the cake layer and hydraulically reversible resistances. Permeability decreased at high dosage (50 mg/L) due to the release of excess sludge fragments and SMP into the supernatant, with a thin but more compact fouling layer with low bioactivity developing on the membrane surface, causing higher cake layer and pore blocking resistances. Our study provides a fundamental understanding of how a metabolic uncoupler affects the sludge and bio-fouling layers at different dosages, with practical relevance for in situ sludge reduction and membrane fouling alleviation in MBR systems.     

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.     

基于3S技术对太湖底质及水质总磷的研究

应用3S技术研究了太湖底质与水质总磷(TP)的分布情况,并结合水华频次分析了其相关性。结果表明:2016—2018年,太湖底质TP年均值在433~537 mg/kg波动,水质TP年均值从0.064 mg/L上升至0.087 mg/L。从空间分布来看,底质TP、水质TP和水华频次均呈现“西高东低”的规律,太湖西部区尤其是竺山湖区是需要开展治理的重点区域。3年间,太湖西部区水质TP上升,而底质TP与入湖河流TP下降,说明内源磷污染是太湖西部区水质TP升高的主要原因,须加强科学清淤。