超高效液相色谱-三重四极杆串联质谱法测定蜂蜜中吡咯里西啶类生物碱

建立了蜂蜜中5种吡咯里西啶类生物碱的超高效液相色谱-串联质谱测定方法.蜂蜜样品用50%甲醇超声提取,强阳离子交换固相萃取柱净化富集,超高效液相色谱-三重四极杆串联质谱MRM模式检测,外标法定量.以Waters BEH C18(100 mm×2.1 mm,1.7μm)色谱柱分离,以含0.1%甲酸的乙腈和0.1%甲酸水溶液进行梯度洗脱.倒千里光碱、千里光宁、千里光菲啉和野百合碱在0.2—100.0μg·kg-1,克氏千里光宁在1.0—200.0μg·kg-1的浓度范围内各化合物线性关系良好,相关系数r均大于0.999,定量限在0.2—0.8μg·kg-1之间.在3个加标水平下,空白基质蜂蜜中的5种生物碱的平均回收率为82.0%—110.0%之间,相对标准偏差(RSD)小于12.5%.方法准确可靠,适合于蜂蜜中吡咯里西啶类生物碱的测定.     

Simultaneous quantification of several classes of antibiotics in water,sediments, and fish muscles by liquid chromatography-tandem mass spectrometry

Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction （SPE） by passing 1000 mL of water through hydrophilic lipophilic balanced （HLB） SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE （strong anion exchange （SAX） ＋ HLB） clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer （80：20, v/v） solution, and cleaned by SPE. Liquid chromatography-tandem mass spectrometry （LC-MS/ MS） with multiple reaction monitoring （MRM） detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%-95.8%, 48.1%-105.3%, and 59.8%- 103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification （LOQ） to 713.6 ng- L1 （ofloxacin） in surface water and from less than LOQ to 344.8 μg·kg-1 （sulphamethoxazole） in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfioxacin was the highest （up to 38.5 μg·kg-1）, but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.     

Simultaneous quantification of several classes of antibiotics in water,sediments, and fish muscles by liquid chromatography–tandem mass spectrometry

Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction (SPE) by passing 1000 mL of water through hydrophilic lipophilic balanced (HLB) SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE (strong anion exchange (SAX) + HLB) clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer (80:20, v/v) solution, and cleaned by SPE. Liquid chromatography–tandem mass spectrometry (LC-MS/MS) with multiple reaction monitoring (MRM) detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%–95.8%, 48.1%–105.3%, and 59.8%–103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification (LOQ) to 713.6 ng·L^-1 (ofloxacin) in surface water and from less than LOQ to 344.8 μg·kg^-1 (sulphamethoxazole) in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfloxacin was the highest (up to 38.5 μg·kg^-1), but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.     

全自动固相萃取-超高效液相色谱串联质谱法测定地表水中18种头孢菌素

建立了超高效液相色谱串联质谱（UPLC-MS/MS） 法测定地表水中18种头孢菌素的方法。采用全自动固相萃取技术进行前处理,地表水样经HLB固相萃取小柱富集后,用10%（V/V）的甲酸溶液（溶剂为甲醇）洗脱。优选BEH Shield RP18（1.7μm,2.1mm×100mm） 色谱柱进行分离,在电喷雾正离子（ESI+）模式下电离,多反应模式（MRM）下检测,外标法定量。结果表明：18种头孢菌素在5.0～100 μg/L 范围内线性关系良好,相关系数（r）均＞0.999,方法检出限为0.5～1.8 ng/L,测定下限为2.0～7.2 ng/L。对地表水样品进行加标回收实验,18种头孢菌素的相对标准偏差（RSD）为0.5%～14.5%,加标回收率为64.3%～92.8%。该方法自动化程度高,结果稳定可靠,适用于地表水中头孢菌素的测定。     

华北地区夏季大气亚微米颗粒物的半挥发性特征

利用热扩散管TD(Thermal Denuder)与高分辨飞行时间气溶胶质谱仪(HR-ToF-AMS)联用法,于2013年6—7月对华北地区国家环境空气质量评价区域点香河的大气PM₁(亚微米颗粒物)及其组分〔OM(有机质)、SO₄2-、NO₃-、NH₄+、Cl-〕进行连续在线观测,并实现了PM₁不同化学组分半挥发性特征的模拟分析. 结果表明:在观测期间,ρ(PM₁)平均值为 (47.9±47.3) μg/m3,其中OM贡献最大,达到38.2%〔ρ(OM)占ρ(PM₁)的比例,下同〕,之后依次为SO₄2-(33.7%)、NH₄+(13.8%)、NO₃-(12.3%)、Cl-(2.0%). 在PM₁的各化学组分中,NO₃-和Cl-的MFR(质量剩余分数)值最低(约0.40),表明二者的半挥发性最高,当温度为50 ℃时,约60%的NO₃-或Cl-进入气相中;SO₄2-的半挥发性最低,在50 ℃时仍有约90%的质量剩余;而OM和NH₄+的半挥发性居中. NO₃-的半挥发性受大气PM₁污染水平的影响,50 ℃时其半挥发性随着ρ(PM₁)的增加而升高. 当温度从50 ℃升至200 ℃时,残留有机气溶胶的O/C(原子数比)从0.47增至0.60,说明半挥发性组分多为氧化态较低的有机化合物. 此外,真空动力学粒径在60~2 000 nm的颗粒物在不同粒径段表现出相近的半挥发性. 大气PM₁半挥发性的定量分析结果可为全面认识大气颗粒物的物化性质及污染机理提供数据,也有助于空气质量模型的完善.      

Effects of ambient temperature on regulated gaseous and particulate emissions from gasoline-, E10- and M15-fueled vehicles

• Emissions from two sedans were tested with gasoline, E10 and M15 at 30°C and -7°C. • As the temperature decreased, the PM, PN and BC emissions increased with all fuels. • Particulate emissions with E10 and M15 were more sensitive to the temperature. • The PN and BC generated during cold start-up dominated those over the WLTC. Ambient temperature has substantial impacts on vehicle emissions, but the impacts may differ between traditional and alcohol gasolines. The objective of this study was to investigate the effects of temperature on gaseous and particulate emissions with both traditional and alcohol gasoline. Regulated gaseous, particle mass (PM), particle number (PN) and black carbon (BC) emissions from typical passenger vehicles were separately quantified with gasoline, E10 (10% ethanol and 90% gasoline by volume) and M15 (15% methanol and 85% gasoline by volume) at both 30°C and -7°C. The particulate emissions with all fuels increased significantly with decreased temperature. The PM emissions with E10 were only 48.0%–50.7% of those with gasoline at 30°C but increased to 59.2%-79.4% at -7°C. The PM emissions with M15 were comparable to those with gasoline at 30°C, but at -7°C, the average PM emissions were higher than those with gasoline. The variation trend of PN emissions was similar to that of PM emissions with changes in the fuel and temperature. At 30°C, the BC emissions were lower with E10 and M15 than with gasoline in most cases, but E10 and M15 might emit more BC than gasoline at -7°C, especially M15. The results of the transient PN and BC emission rates show that particulate emissions were dominated mainly by those emitted during the cold-start moment. Overall, the particulate emissions with E10 and M15 were more easily affected by ambient temperature, and the advantages of E10 and M15 in controlling particulate emissions declined as the ambient temperature decreased.     

西南典型区域夏季大气含氧挥发性有机化合物来源解析

含氧挥发性有机物（OVOCs）是大气光化学过程中的重要中间产物,是臭氧的重要来源之一.利用质子转移反应飞行时间质谱仪（PTR-TOF-MS）在成都平原对OVOCs进行观测,探讨其日变化特征、光化学反应活性、臭氧生成潜势和来源.结果表明,10个VOCs［乙醛、丙酮、异戊二烯、甲基乙基酮（methyl ethyl ketone,MEK）、甲基乙烯基甲酮（methyl vinyl ketone,MVK）、甲基丙烯醛（methacrolein,MACR）、苯、甲苯、苯乙烯、C8芳香烃和C9芳香烃］总浓度（体积分数）为（10.97±4.69）×10^-9,OVOCs为（8.54±3.44）×10^-9,芳香烃为（1.53±0.93）×10^-9,生物源VOCs为（0.90±0.32）×10^-9;光化学活性和臭氧生成潜势均排名前三的物种为：异戊二烯、乙醛和C8芳香烃;3个OVOCs物种（乙醛、丙酮和MEK）主要来源于本地生物源和人为二次源,且丙酮有较强的区域背景值,说明该地区的污染受到较为显著的区域传输的影响.本研究可加深对西南地区臭氧的区域形成机制的认识,为科学管控臭氧污染提供依据.     

运城秋冬季大气细粒子化学组成特征及来源解析

为研究运城市秋冬季细颗粒物（PM_2.5）的化学组成特征和污染来源贡献,于2018年10月15日至2019年3月15日利用四通道小流量颗粒物采样器在运城市对大气PM_2.5样品进行了连续采集.主要对水溶性离子、元素碳、有机碳和金属元素等化学成分进行了分析,并结合颗粒物化学质量重构法和正定矩阵因子分解模型（PMF）深入探讨.结果表明,采样期间PM_2.5质量浓度范围为29.37~370.11 μg·m^-3,期间有101 d高于我国《环境空气质量标准》（GB 3095-2012）中的二级标准,超标率为70.63%,说明秋冬季运城市大气污染较为严重.按照空气质量指数（air quality index,AQI）将采集样品分类为清洁,轻-中度污染和重度-严重污染,水溶性离子、有机碳、元素碳和金属元素分别占总PM_2.5浓度的40%、19%、5%、7%（清洁天）,46%、18%、4%、5%（轻-中度污染）和46%、21%、4%、4%（重度-严重污染）.二次离子NO₃^-、SO₄^2-和NH₄⁺是水溶性离子主要成分,分别占总离子浓度的81%（清洁天）、87%（轻-中度污染）和87%（重度-严重污染）.采样期间OC/EC的值分别为3.78（清洁天）、4.02（轻度-中度污染）和5.37（重度-严重污染）.随着污染程度的加剧,大气中二次有机气溶胶的污染情况也越发严重.此外,随着大气污染程度的加深,Fe和Cr元素浓度逐渐下降,而其余金属元素的浓度总体呈上升趋势.化学质量重构结果表明在运城市的PM_2.5中,二次无机盐、海盐、重金属、矿物尘、建筑尘、有机物和元素碳的质量分数分别为40%、1%、1%、5%、1%、32%和5%,且随着污染的加剧,二次无机盐的占比有所升高,矿物尘的占比降低.PMF分析结果表明,二次相关源、燃煤源、交通源与生物质燃烧及二次有机物是运城市灰霾暴发的主要原因.     

软弱煤岩体巷道围岩锚固力衰减特性研究

软弱煤岩体巷道围岩存在强度低、胶结程度差、遇水弱化等特点,正常树脂锚固时出现锚固力低、衰减速度快等问题,易造成巷道围岩严重变形破坏。利用自行研发的锚固孔底单翼倒楔形扩孔装置进行孔底扩孔锚固试验,分析了软弱煤岩体不同锚固状态下锚固力与位移的变化关系。试验结果表明:正常锚固和扩孔锚固状态下脱锚点发生前锚固力与位移曲线表现一致,脱锚点发生后正常锚固状态下残余锚固力瞬间衰减到几乎为0,而扩孔锚固状态下残余锚固力衰减程度较小,并出现残余锚固力大于脱锚力的情况;扩孔锚固状态下脱锚点处扩孔锚固的最大锚固力比正常锚固状态下平均提高2.8倍。软弱煤岩体锚固段发生脱锚界面为锚固剂与孔壁的交界面,脱锚后扩孔段锚固剂对倒楔形孔壁产生挤压破坏,从而提高了软弱煤岩体残余锚固力。试验结果为解决软弱煤岩体巷道锚网支护技术难题提供重要借鉴。     

不同通风条件下柴油池火的实验研究

为了分析不同通风条件对柴油池火燃烧特性及引燃特性的影响,进行205 mm带水垫层柴油池火的引燃实验,通过对池火燃料的质量损失速率、火焰高度、温度及热辐射等的监测,分析通风环境中柴油池火的热传递规律。结果表明:当风速为0.5 m/s时,火灾进入旺盛阶段的时间提前,火焰平均温度最高;当风速为1 m/s时,风速的增加导致油池火的质量损失速率增加,位于主火源下风向的待引燃火源获得的热辐射通量增大,火灾旺盛阶段火焰的平均温度降低,火焰高度降低,下风向相邻油盘引燃的时间提前;1 m/s情况下,205 mm带水垫层柴油池火的安全间距需增加到1D以上;通风环境对池火发展及蔓延的影响是显著的,应适当加大下风向可燃物的安全间距,合理选择通风排烟风速,优化火灾应急救援策略。