响应面法优化养殖水体中炔雌醇的固相萃取条件

在单因素试验、Plackett-Burman设计试验基础上,采用Box-Behnken响应面法对养殖水体中炔雌醇(EE2)的固相萃取条件进行优化。结果表明,洗脱液体积、洗脱液组成和淋洗液体积是影响EE2固相萃取回收率的3个主要因素;EE2的最佳固相萃取条件为:水样pH值为3,进样流量为3.0 mL/min,淋洗液为体积分数为10%的甲醇水溶液,淋洗液体积7.0 mL,洗脱液为乙酸乙酯-正己烷混合溶液(体积比为9∶1),洗脱液体积12.0 mL。该条件下养殖水样中EE2固相萃取回收率为81.6%～86.7%。     

Blast wave clearing behavior for positive and negative phases

The purpose of the research was to improve prediction of response of buildings to blast waves by including the negative phase and considering clearing of both positive and negative phases. Commonly used structural design practices, which trace their origins to military design manuals, often ignore the negative phase as well as positive phase clearing. For high explosive threats, this approach is conservative in most circumstances. However, negative phase clearing had not previously been studied for blast waves, and the implications for structural response had not been evaluated. This paper presents results of modeling negative phase blast clearing behavior for a typical blast wave and discusses the differences from positive phase clearing. The implications of including positive and negative phase clearing in building blast damage analysis are also investigated through single-degree-of-freedom (SDOF) analyses.Blast waves from explosion sources like a vapor cloud explosion (VCE), pressure vessel burst or high explosive exhibit both positive and negative phases, and the relative magnitude of the positive and negative phases varies among explosion sources and the specific circumstances of each source. A fully reflected blast wave is produced if an incident blast wave were to strike an infinitely tall and wide wall in a normal orientation. Both the positive and negative phases of the blast wave are enhanced by the reflection process. However, when an incident blast wave strikes a wall of finite size in a normal orientation, rarefaction waves are created at the edges of the wall, and the rarefactions sweep down from the roof and inward from sides. The rarefaction waves result in a clearing effect for both the positive and negative phases.Clearing relieves some of the applied blast load on the reflected wall for the positive phase. However, this is not always the case for the negative phase. As shown by the results presented in this paper, clearing may either relieve or enhance the applied negative phase blast load, depending on the duration of the blast wave and the wall dimensions.The impact of negative phase clearing on structural response for generic building components was also investigated. Nonlinear SDOF methods were used to characterize response in terms of peak positive and negative displacements. It was found that the influence of the negative phase is significant and the peak structural response can occur during negative (outward) displacement.     

卷烟膨胀烟丝生产线冷端CO_2泵装置的优化改进

为解决干冰膨胀烟丝生产线冷端液体工艺泵因机械密封长期超压和气缚现象造成损坏发生CO2泄漏而导致紧急停机抢修的问题,对干冰膨胀线冷端工艺罐系统进行了优化改进。在工艺泵吸口前管路引一根气相平衡管至工艺罐顶部,当泵吸口前管路有CO2液体时,输送管路内气化的CO2气体通过气相平衡管线释放回工艺罐内,不会进入工艺泵体内。应用结果表明,工艺泵内的憋压和气缚现象消失了,机械密封受到保护。改造前机械密封平均一个季度更换一次,改造后机械密封使用5年未损毁,达到保护干冰膨胀线冷端工艺泵机械密封的目的。     

Analysis of trace dicyandiamide in stream water using solid phase extraction and liquid chromatography UV spectrometry

An improved method for trace level quantification of dicyandiamide in stream water has been developed. This method includes sample pretreatment using solid phase extraction. The extraction procedure (including loading, washing, and eluting) used a flow rate of 1.0 mL/min, and dicyandiamide was eluted with 20 mL of a methanol/acetonitrile mixture (V/V = 2:3), followed by pre-concentration using nitrogen evaporation and analysis with high performance liquid chromatography–ultraviolet spectroscopy (HPLC–UV). Sample extraction was carried out using a Waters Sep-Pak AC-2 Cartridge (with activated carbon). Separation was achieved on a ZIC^®-Hydrophilic Interaction Liquid Chromatography (ZIC-HILIC) (50 mm × 2.1 mm, 3.5 μm) chromatography column and quantification was accomplished based on UV absorbance. A reliable linear relationship was obtained for the calibration curve using standard solutions (R² > 0.999). Recoveries for dicyandiamide ranged from 84.6% to 96.8%, and the relative standard deviations (RSDs, n = 3) were below 6.1% with a detection limit of 5.0 ng/mL for stream water samples.     

HNO_3在气相及SiO_2表面的紫外光解反应

利用紫外及红外吸收光谱等分析手段对365 nm光照下HNO3在气相与SiO2表面的光解反应进行了研究.考察了HNO3浓度、光照时间、相对湿度等条件对反应的影响.结果表明:随着HNO3浓度及光照时间的增加,光解产生的NO2和NO浓度均呈指数增加;无水汽情况下,400 Pa的HNO3光解45 min后,产生NO2及NO浓度比气相光解产生的分别高约3及1.7倍.HNO3光解产生的HONO的浓度随相对湿度的增加而呈线性增加,在SiO2颗粒物表面光解产生的NO2浓度随着相对湿度的增加而减少,而NO浓度则随之增大.400 Pa的HNO3光照45 min后,SiO2表面光解产生的HONO浓度是气相光解的3倍、SiO2表面暗反应的约30倍.     

SPE-UPLC-MS/MS法测定地下水中多种农药残留

采用固相萃取超高效液相色谱串联质谱法(SPE-UPLC-MS/MS)同时测定地下水中涕灭威、克百威、2,4滴和五氯酚等4种农药残留,通过优化试验条件,使方法在10.0μg/L～200μg/L范围内线性良好,检出限为0.003μg/L～0.006μg/L.标准溶液低、中2个质量浓度水平的加标回收率为84.1％ ～98.8...     

Molecularly imprinted polymer for analysis of trace atrazine herbicide in water

A molecularly imprinted polymer (MIP) for atrazine was synthesized by non-covalent method. The binding capacity of MIP was 1.00 mg g^{? 1} polymer. The selectivity and recovery were investigated with various pesticides which are mostly, found in the environment, for both similar and different chemical structure of atrazine. The competitive recognition between atrazine and structurally similar compounds was evaluated and it was found that the system provided highest recovery and selectivity for atrazine while low recovery and selectivity were obtained for the other compounds. The highest recovery was obtained from MIP compared with non-imprinted polymer (NIP), a commercial C₁₈ and a granular activated carbon (GAC) sorbent. The method provided high recoveries ranged from 94 to 99% at two spiked levels with relative standard deviations less than 2%. The lower detection limit of the method was 80 ng L^{? 1}. This method was successfully applied for analysis of environmental water samples.     

改进测定水中氨氮分子吸收光谱法的试验研究

水中氨氮含量是反应水质状况的重要指标。文章对测定水中氨氮气相分子吸收光谱法(标准号HJ/T195-2005)进行了改进试验研究。第一,对氧化剂的配比进行了改进,使氨氮的测定范围扩展至100μg。第二,对标准HJ/T195-2005中直接使用亚硝酸钠标准溶液做标准曲线的处理方式也做了探讨。通过一系列对比实验认为,应用硫酸铵标准溶液做工作曲线更加准确合理。最后应用改进后的气相分子吸收光谱法和纳氏比色法或滴定法对多种实际废水样品进行同时测定。结果表明,改进后的气相分子吸收光谱法测定氨氮的范围更宽,灵敏度更高和准确度更好。     

植物释放挥发性有机物(BVOC)向二次有机气溶胶(SOA)转化机制研究

利用自制玻璃生态罩,研究植物挥发性有机物（BVOC）的释放机制.在紫外光诱导条件下,BVOC经历一系列的光氧化反应,最终产生了二次有机气溶胶（SOA）.运用固相微萃取（SPME）和气相色谱-质谱联用（GC-MS）技术,对目标植物（驱蚊草）释放出的BVOC进行采样分析,共检测出7种主要化合物,其中主要为单萜类、倍半萜类、醇类和酮类物质.研究发现,在紫外光的照射下,这些BVOC可以发生光氧化反应转化为SOA.利用串联差分淌度分析仪（TDMA）测定SOA的粒径分布和SOA颗粒物的吸湿性.结果表明粒径范围大致是50～320 nm,吸湿性研究发现这些SOA具有吸湿性,生长因子可以从1.05增长到1.11.     

Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium enriched from mangrove sediments

The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase microextraction (SPME) combining with gas chromatography–mass spectrometry (GC–MS) method. Seventeen metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene, methyl ester, and phthalic acid were found. The detection of various common and novel metabolites demonstrates that SPME combining with GC–MS is a quick and convenient method for identification as well as monitoring the real time changes of metabolite concentrations throughout the degradation processes. The knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.