土壤和西瓜中五氯硝基苯的残留检测与消解动态研究

为了解五氯硝基苯在土壤和西瓜中的消解动态及残留状况,研究了土壤和西瓜中五氯硝基苯的气相色谱检测方法,并在山东济南和浙江杭州进行了土壤和西瓜中五氯硝基苯残留状况和消解动态规律研究的田间试验.结果表明,在0.01～0.5 mg/kg的添加水平内,土壤和西瓜中五氯硝基苯的平均添加回收率为83.41%～93.17%,变异系数为3.37%～9.74%;土壤和西瓜中五氯硝基苯的最小检出量均为1.2×10-12 g,其中西瓜中五氯硝基苯的最低检出质量比为0.001 mg/kg,土壤中为0.005 mg/kg.田间残留试验表明,五氯硝基苯在土壤和西瓜中的残留消解动态规律符合一级动力学反应模型,在土壤、全瓜和瓜瓤中的消解半衰期分别为4.13～6.08 d、4.28～4.92 d和3.67～4.10 d.按推荐剂量和1.5倍推荐剂量在西瓜上各喷施质量分数为40%的多菌灵·五氯硝基苯可湿性粉剂1～2次,2次施药间隔为7 d,距最后1次施药7 d时,五氯硝基苯在瓜瓤中的最高残留量为0.005 8 mg/kg,低于规定的果菜类蔬菜中五氯硝基苯的最大残留限量标准0.1 mg/kg.     

畜禽粪便和污水中金霉素及其代谢物的液质联用( LC-MS/MS)检测方法研究

建立了畜禽粪便和污水中金霉素(CTC)及其两种代谢物——差向金霉素(ECTC)和异金霉素(ICTC)的LC - MS/MS检测方法.粪便样品经Na2EDTA - Mcllvaine缓冲液(pH=4)分别提取3次,离心,收集上清液,过Waters的Oasis HLB固相萃取小柱净化、浓缩.用6mL0.01 mol·L-1草酸甲醇溶液洗脱,收集洗脱液,40℃水浴氮气吹至近干,甲醇定容至1 mL,过0.22μm滤膜,用LC- MS/MS测定.污水取100 mL经滤纸和0.65 μm纤维膜过滤后,加1 mL 5% Na2EDTA溶液,调节pH值至7.0,然后过预先用5 mL甲醇和10 mL Na2EDTrA- Mcllvaine缓冲液(pH=4)活化过的Waters Oasis HLB固相萃取小柱,净化、浓缩,后用6 mL0.01 mol·L-1草酸甲醇溶液洗脱,收集洗脱液,40℃水浴氮气吹至近干,甲醇定容至1 mL,过0.22 μm滤膜,上机测定.该方法在10～1 000μg·L-1之间呈线性相关,金霉素、差向金霉素和异金霉素的平均回收率分别为79.64% ～ 97.23%、75.34% ～ 98.37%和73.67% ～ 95.08%,日间偏差在1.78% ～6.18%,日内偏差在1.07%～6.28%.粪便样品和污水样品中的检测限分别为20μg·kg-1和10μg·L-1,符合作为检测方法的要求.     

百菌清在马铃薯中的最终残留及土壤中消解动态研究

为评价百菌清在马铃薯上的使用安全性及土壤中的消解动态残留,建立了百菌清在马铃薯及土壤中的残留分析方法,2016—2017年在湖南长沙和河北石家庄两地进行了720 g/L百菌清悬浮剂在马铃薯上的施用,分析了其有效成分百菌清在马铃薯上的消解动态和最终残留。马铃薯、土壤样品用体积比为1∶1的丙酮-乙腈的混合液振荡提取,提取液经盐析、浓缩后用乙腈定容,气相色谱法检测。结果表明,在添加水平为0. 02 mg/kg、0. 20 mg/kg和2. 00 mg/kg时,马铃薯中百菌清残留量检测方法的添加回收率为81. 1%～110. 5%,相对标准偏差(RSD)为4. 4%～11. 9%;土壤中百菌清残留量检测方法的添加回收率为82. 4%～111. 6%,RSD为6. 3%～10. 9%。百菌清在马铃薯上以高剂量(3 240. 0 g/hm~2)、低剂量(2 160. 0 g/hm~2) 2个剂量分别施药3次和4次,最后一次施药后7 d、14 d、21 d的马铃薯的最大残留量均值分别为0. 084 mg/kg、0. 026 mg/kg、0. 020 mg/kg。百菌清在土壤中的残留消解动态规律符合一级动力学反应模型,其消解半衰期为3. 63～8. 35 d,在土壤环境中较易降解。     

不同环境介质中异丙隆残留的前处理方法研究

利用高效液相色谱法(HPLC)测定水、土壤和植物中除草剂异丙隆的残留量.采用LC-18固相萃取小柱分离、净化和富集水中异丙隆残留;利用丙酮/水(体积比为3:1)振荡提取土壤中的异丙隆残留,并通过硅胶柱层析净化、分离;以乙酸乙酯为提取剂,采用超声波提取植物样品中的异丙隆残留,并用Florisil固相萃取小柱净化、分离.利用HPLC-UVD(Ultraviolet Detector,紫外检测器)定性、定量测定水、土壤和植物样品中异丙隆残留量.结果表明,异丙隆HPLC的线性检测范围为0.1～16 mg/L,决定系数\%R2\%=0.999 9,最低检测浓度为0.012 mg/L.水的加标回收率为90.7%～91.1%,相对标准偏差为3.0%～12.0%;土壤的加标回收率为88.4%～97.4%,相对标准偏差为6.9%～9.8%;植物的加标回收率为94.4%～99.9%,相对标准偏差为4.6%～9.0%.研究为异丙隆残留的检测提供了一种有效方法.     

蜂蜜中氯霉素残留的检测及净化方法研究

建立了反相高效液相色谱-离子阱质谱法检测蜂蜜中氯霉素残留的方法.前处理采用改良的QuEChERS方法进行快速提取和净化.采用初级次级胺进行固相分散净化,可有效吸附蜂蜜中的糖类及有机色素等杂质.提取物在流动相甲醇:水(0.2%乙酸胺)=45:55(体积比)中,用整体色谱柱进行快速分离和质谱检测.并对MS检测中2种离子化方式(电喷雾ESI及大气压化学APCI)、各种离子化方式下正负离子模式及离子检测方法(总离子检测TIC和选择性离子监测MRM)进行了综合比较,最终确定采用电喷雾电离法(ESI)负离子模式、多反应离子监测(MRM)对氯霉素进行定性定量分析.在0.2～200μg/kgg添加浓度下,添加回收率水平在78%～93%间,变异系数在3.9%以下.该方法的检出限为0.1μg/kg,在0.1～100 μg/L浓度范围内,线性方程为y=58.753x 34867,相关系数R2=0.999 5.     

水稻、土壤和田水中氟啶脲残留检测与消解动态研究

为了解氟啶脲在水稻、土壤和田水中的消解动态及其残留状况,建立了氟啶脲在水稻、土壤和田水中的液相色谱检测方法,并在天津、浙江杭州和广西南宁开展了两年氟啶脲在水稻和土壤中消解动态规律和残留状况田间试验.结果表明,采用乙腈提取水稻稻米、稻壳和茎叶样品,丙酮提取土壤和田水样品,液相色谱仪带紫外检测器测定,外标法定量,在0.03～1 mg·kg-1添加水平范围内,水稻、土壤和田水中氟啶脲的平均添加回收率为84.94%～98.73%,变异系数为2.84%～9.44%;水稻、土壤和田水中氟啶脲的最小检出量为5.6×10-11 g,最低检出质量比为:茎叶0.01 mg·kg-1,稻壳0.01 mg·kg-1,稻米和土壤0.005 mg·kg-1,田水0.003 mg·kg-1.田间试验表明,氟啶脲在水稻、土壤和田水中残留消解动态规律符合方程Ct=C0e-kt;氟啶脲·三唑磷31%乳油在水稻茎叶、土壤和田水中的消解半衰期分别为6.27～7.83 d、5.28～7.36 d和6.01～7.06 d.最终残留试验结果表明,在水稻上手动喷雾施药氟啶脲·三唑磷31%乳油,按推荐剂量325.5 ga.i.·hm-2和1.5倍推荐剂量488.25 ga.i.·hm-2施药,兑水喷雾处理1～2次,两次施药间隔为7 d,距最后一次施药采收间隔期为35 d时,氟啶脲在水稻稻米和土壤中的残留量分别为ND～0.028 0 mg·kg-1和ND～0.014 8 mg·kg-1.参照日本"肯定列表制度"规定氟啶脲在稻米中的最大允许残留限量MRL值为0.05 mg·kg-1,按照1.5倍推荐剂量在水稻上施药1～2次,其有效成分之一氟啶脲在水稻稻米中残留是安全的.     

微电解-催化氧化-吸附法处理二硝基苯废水

二硝基苯生产废水具有硝基苯类化合物浓度高,盐量高,难降解等特点.CODCr的平均质量浓度为10 g/L,含盐量达30 g/L.采用微电解-催化氧化-吸附法对该废水进行处理.结果表明:经微电解处理后硝基苯类物质的去除率可达90%以上,铁碳还原后的废水再经催化氧化和活性炭吸附后,废水的CODCr去除率达到96%,硝基苯类物质、色度的去除率接近100%,出水可达到<污水综合排放标准>(GB8978-1996)规定的三级排放标准,是一种效果良好的二硝基苯类废水的处理方法.     

Tenax富集-毛细管气相色谱法同时测定环境空气中12种氯苯类化合物

建立了毛细管气相色谱法同时分离快速测定环境空气中12种氯苯类有机污染物的方法.采集10 L空气样品,用Tenax吸附管富集氯苯类化合物,石油醚淋洗解析,DB-23毛细管柱分离,电子捕获检测器检测.空气中氯苯类化合物的最低检测浓度分别为:氯苯20 μg/m3,二氯苯0.5～0.8 μg/m3,三氯苯0.08～0.1 μg/m3,四氯苯0.03～0.05 μg/m3,五氯苯、六氯苯0.01 μg/m3.在空白试验中,回收率为90.7%～100.6%,相对标准偏差低于7.16%(n=5).结果表明,该测定方法简便、快速、准确、重现性好,适合环境空气中12种氯苯类化合物的痕量测定.     

10%丁醚脲微乳剂在甘蓝和土壤中的残留及消解动态研究

建立了丁醚脲在甘蓝及土壤中残留量的高效液相色谱检测方法,并采用田间试验方法对丁醚脲在甘蓝及土壤中的残留消解动态进行研究,开展了最终残留试验.结果表明,在0.05～5.0 mg/kg添加水平范围内,丁醚脲在甘蓝和土壤中的平均添加回收率为82.5%～100.9%,相对标准偏差为4.5%～7.5%.残留消解动态研究表明,丁醚脲在甘蓝和土壤中的降解符合方程式Ct=C0e-kt;10%丁醚脲微乳剂在甘蓝和土壤中的半衰期分别为2.87～2.99 d和3.37～3.57 d.最终残留试验研究表明,在施用有效成分约为0.02～0.04 g/m2,施药1～2次,每次施药间隔期为7 d的情况下,北京市试验地内,10%丁醚脲微乳剂在甘蓝中的残留量为ND～0.18 mg/kg,土壤中的残留量为0.09～0.37 mg/kg;湖南冷水江市试验地内,10%丁醚脲微乳剂在甘蓝中的残留量为ND～0.24 mg/kg;土壤中的残留量为0.11～0.46mg/kg.对照日本的最大残留限量标准,产品符合我国及日本规定的质量安全要求.     

雾化-UV/O_3氧化硝基苯的实验研究

为了寻求一种经济有效的处理硝基苯废水的方法.通过雾化头把废水打成雾状,同时,在装置中通入O3引入紫外光,在装置中进行雾化-氧化.实验表明,整个体系中,液滴粒径、硝基苯浓度、pH值、反应时问等因素对硝基苯去除率影响最大,雾化-UV/O3氧化硝基苯法能够有效去除硝基苯.实验得到的最佳反应条件为:液滴粒径控制在50/μm.硝基苯质量浓度为50me/L,pH值为8.臭氧反应时间30min.采用雾化-UV/O3氧化硝基苯废水,取得了很好的去除效果,硝基苯去除率达到94.34%,二级雾化降解效率达到98.25%.     

硫酸储罐爆炸事故分析及预防

介绍了山东省某化工有限公司苯胺厂的工人在废硫酸罐顶部焊接管线时发生的一起废硫酸罐爆炸事故。通过对事故发生经过及现场情况的调查分析,找出了导致事故发生的原因,由于废硫酸罐耐酸瓷瓦破损,废硫酸渗漏与罐体接触反应产生的氢气,与由苯-稀硫酸萃取分离器串入废硫酸罐的苯或硝基苯蒸气及罐内空气混合形成爆炸性混合物,遇到因违章操作产生的明火、高温发生爆炸。通过对这次事故的详细描述、分析,在吸取事故教训的基础上,提出了相应的预防措施,为预防类似事故的发生提供参考。     

Permeability of Organic Solvents Through Two-Layer Safety Gloves Determined by a Gravimetric Method

Organic solvents are harmful to humans, and many of them are recognized as carcinogens. Therefore, it is necessary to protect hands from contact with them. Most methods for testing solvent resistance of gloves use gas chromatography. However, these methods are expensive and so complex that they present application problems for most glove producers and users. A simple gravimetric method to test solvent resistance o f gloves was developed. It was tested by measuring the permeability of organic solvents such as white spirit, acetone, isopropyl alcohol, benzene, p-xylene, and trichloroethylene through gloves made of natural rubber, polyvinyl chloride, neoprene, perbunan, polyvinyl alcohol, and two-layer gloves made of natural rubber and neoprene. This method proved to be a simple, economical, and reliable way to examine glove permeability.     

急倾斜矿体空场法开采的矿柱回收与卸压开采效果数值分析

矿柱回采方法不恰当,将致使大量矿柱残留采场而无法经济、安全地回收。为了解决上述问题,避免或消除深部开采产生的地压灾害,提出了间隔矿柱抽采法回采间柱,"V"型松动爆破并上盘底板松动爆破隔断开采,采用FLAC3D数值模拟了矿柱回采及深部卸压开采的应力变化过程,将数值模拟结果与实际开挖进行了对比,并在此基础上评价了矿柱回收及卸压开采的效果。结果表明:间隔抽采矿柱后,1 010 m中段第一分层顶柱及其以下保留的矿柱不会发生冒落,但上盘局部千枚岩会因长期拉伸疲劳破坏而垮塌,为了避免采空区顶板长期暴露、垮落而造成出矿贫化,必须加快出矿;"V"型松动爆破并上盘底板松动爆破隔断开采,降低了910 m中段开采的应力集中程度,基本消除了910 m中段开采时发生岩爆的应力条件;回收过矿柱的相邻采空区的分隔间柱,其回采宽度不应超过1/2;相邻两采空区都间隔抽采间柱并卸压开采后,960 m中段基本实现了垮塌的千枚岩或残留矿柱充填采空区,从而消除了采空区隐患。     

Evaluation of Eremurus spectabilis for production of bio-oils with supercritical solvents

Eremurus spectabilis samples were liquefied in organic solvents (methanol, ethanol and acetone) with (sodium hydroxide and ferric chloride) and without catalyst in a cylindrical reactor at temperatures of 270, 290 and 310 °C under supercritical conditions. The effects of liquefaction parameters such as temperature, catalyst and solvent on product yields were investigated. The liquid products were extracted with diethyl ether and benzene using an extraction procedure. The product yields in supercritical methanol, ethanol and acetone were found to as 41.6%, 53.8% and 64.3% in the non-catalytic runs at 310 °C, respectively. The highest conversion was obtained in supercritical acetone in the presence of ferric chloride (10%) at same temperature in the catalytic runs. The produced liquids in acetone were analyzed and characterized by elemental, Fourier transform infrared spectroscopy (FT-IR), gas chromatography–mass spectrometry (GC–MS). The liquid products (bio-oils) obtained with acetone contained various types of components including aromatics, nitrogenated and oxygenated compounds. As the bio-oils obtained exhibit high heat values, E. spectabilis is presented as a potential feedstock candidate for production of bio-fuels or valuable chemicals.     

Recovery of methyl orange and Congo red from aqueous solutions using tri-octyl amine (TOA) in benzene as carrier

The recovery of anionic azo dyes namely Congo red (CR), methyl orange (MO) from acidic aqueous solutions using tri-octyl amine (TOA) as an extractant has been investigated. The percentage of extraction of MO and CR increases with an increasing TOA concentration. The anionic dyes were extracted from aqueous solution at pH 2.0 ± 0.1. The extracted dye has been back extracted into aqueous solutions using sodium hydroxide, sodium carbonate and sodium bicarbonate. The organic phase obtained after the stripping of dyes was washed with dilute sodium hydroxide solution to neutralize any sulphuric acid trapped or adhered to the solvent and then with distilled water. This solvent was reused in succeeding extraction of dyes. The influencing parameters were; the effect of diluents, effect of extractant concentration, effect of pH, effect of interference study, effect of equilibrium time, various stripping reagents and stripping phase ratio. The characterization studies such as UV and IR spectra of extracted and stripped MO and CR was also studied.     

Fuel recovery from waste oily sludge using solvent extraction

Solvent extraction was used to recover oil from waste sludge generated from the storage of crude petroleum. Different solvent-to-sludge mass ratios were used for two solvents, methyl ethyl ketone (MEK) and LPG condensate (LPGC). Several parameters were compared, such as oil recovery as a percent of the original sludge mass, and reduction in carbon residue, ash content, and asphaltene content. A 4:1 solvent-to-sludge ratio was found to be optimum for both solvents. The MEK extraction recovered 39% by mass of the sludge as recovered oil. The LPGC recovered 32%. The amount of asphaltenes in the fuel oil was related to the concentration of fuel oil in the solvent phase during the extraction, suggesting that asphaltenes are extracted mainly by the fuel oil components, not the solvent. The physical properties and metal content of the recovered oil were measured. The recovered oil was distilled to provide diesel fuel. This diesel fuel contained high levels of sulfur and carbon residue, as well as a high diesel index, indicating the fuel requires further treatment prior to use as a fuel.     

Sample Preparation Followed by High Performance Liquid Chromatographic (HPLC) Analysis for Monitoring Muconic Acid as a Biomarker of Occupational Exposure to Benzene

Factors affecting solid phase extraction (SPE) of trans,trans-muconic acid (ttMA), as a benzene biomarker, including sample pH, sample concentration, sample volume, sample flow rate, washing solvent, elution solvent, and type of sorbent were evaluated. Extracted samples were determined by HPLC-UV(highperformance liquid chromatography-ultraviolet). The analytical column was C18, UV wave length was 259 nm, and the mobile phase was H2O/methanol/acetic acid run at flow rate of 1 ml/min. A strong anion exchange silica cartridge was found successful in simplifying SPE. There was a significant difference between recoveries of ttMA when different factors were used (p < .001). An optimum recovery was obtained when sample pH was adjusted at 7. There was no significant difference when different sample concentrations were used (p > .05). The optimized method was then validated with 3 different pools of samples showing good reproducibility over 6 consecutive days and 6 within-day experiments.     

Sample preparation followed by high performance liquid chromatographic (HPLC) analysis for monitoring muconic acid as a biomarker of occupational exposure to benzene.

Factors affecting solid phase extraction (SPE) of trans,trans-muconic acid (ttMA), as a benzene biomarker, including sample pH, sample concentration, sample volume, sample flow rate, washing solvent, elution solvent, and type of sorbent were evaluated. Extracted samples were determined by HPLC-UV (high performance liquid chromatography-ultraviolet). The analytical column was C18, UV wave length was 259 nm, and the mobile phase was H(2)O/methanol/acetic acid run at flow rate of 1 ml/min. A strong anion exchange silica cartridge was found successful in simplifying SPE. There was a significant difference between recoveries of ttMA when different factors were used (p < .001). An optimum recovery was obtained when sample pH was adjusted at 7. There was no significant difference when different sample concentrations were used (p > .05). The optimized method was then validated with 3 different pools of samples showing good reproducibility over 6 consecutive days and 6 within-day experiments.     

固相萃取-气相色谱-FPD法检测生活饮用水中的氧乐果、甲拌磷和二嗪磷残留量

研究建立固相萃取-气相色谱-FPD法检测生活饮用水中的氧乐果、甲拌磷和二嗪磷残留量的分析方法。将采集的生活饮用水过滤后上自动固相萃取仪,选择HLB固相萃取柱净化、富集,丙酮洗脱,洗脱液氮吹至近干,丙酮定容至1.0 mL,上气相色谱-FPD仪检测,外标法定量。实验结果表明,本方法具有快速、准确、高效等特点,可以用于生活饮用水中的氧乐果、甲拌磷和二嗪磷等有机磷类杀虫剂残留量的检测。     

混凝土高温爆裂性能影响因素及预防措施综述

对混凝土高温爆裂成因进行总结,综述高温下混凝土内部蒸汽压力的测试手段、降低混凝土内部蒸汽压力方法、提高混凝土在高温中的抗高温爆裂性能的方法,以及总结了升温速率对混凝土高温爆裂的影响,并提出了几种预防混凝土高温爆裂的措施,为混凝土高温爆裂研究提供依据。