An optimized two-step derivatization method for analyzing diethylene glycol ozonation products using gas chromatography and mass spectrometry

The ozonation of hydroxyl compounds(e.g., sugars and alcohols) gives a broad range of products such as alcohols, aldehydes, ketones, and carboxylic acids. This study developed and optimized a two-step derivatization procedure for analyzing polar products of aldehydes and carboxylic acids from the ozonation of diethylene glycol(DEG) in a non-aqueous environment using gas chromatography–mass spectrometry. Experiments based on Central Composite Design with response surface methodology were carried out to evaluate the effects of derivatization variables and their interactions on the analysis. The most desirable derivatization conditions were reported, i.e., oximation was performed at room temperature overnight with the o-(2,3,4,5,6-pentafluorobenzyl) hydroxyl amine to analyte molar ratio of 6, silylation reaction temperature of 70°C, reaction duration of 70 min, and N,O-bis(trimethylsilyl)-trifluoroacetamide volume of 12.5 μL. The applicability of this optimized procedure was verified by analyzing DEG ozonation products in an ultrafine condensation particle counter simulation system.     

30CrMnSiA高强钢在工业和海洋大气环境中的腐蚀行为研究

目的为30CrMnSiA高强钢的大气腐蚀防护设计、应用范围扩展和开发新钢种提供有益的借鉴和参考。方法采用腐蚀质量损失、XRD和SEM研究了30CrMnSiA高强钢在工业和海洋大气环境暴露60个月的大气腐蚀行为。结果 30CrMnSiA高强钢在工业和海洋大气环境中腐蚀质量损失随暴露时间变化的双对数函数分别是lgΔw=2.245+0.387lg t和lgΔw=2.822+0.637lg t。纤铁矿和针铁矿是两种大气环境中形成的腐蚀锈层的主要成分,除了纤铁矿和针铁矿外,在海洋大气环境形成的锈层中还发现了四方纤铁矿。随着暴露时间的延长,在海洋大气环境中形成的锈层呈现逐渐剥落的趋势。结论 30CrMnSiA高强钢在海洋大气环境中表现出较高的腐蚀敏感性,在工业大气环境中表现出较低的腐蚀敏感性。     

自动固相萃取-气相色谱质谱法测定饮用水源地水中有机氯农药的研究

建立了自动固相萃取-气相色谱质谱仪测定饮用水源地水体中8种痕量有机氯农药的检测法.采用Supelclean ENVI-18固相萃取柱以10 mL/min流速富集500 mL水样,再依次用7.5 mL乙酸乙酯和10 mL二氯甲烷进行洗脱.8种物质在0.188 mg/L~2.04 mg/L范围内线性良好,相关系数均在0.997以上;检出限为0.011μg/L~0.034μg/L;实际水样加标回收率为82.9%~103%,相对标准偏差为0.7%~8.3%.该方法自动化程度高、检出限低、灵敏度高、结果准确,适用于饮用水源地水体中痕量有机氯农药的测定.     

典型煤化工企业硫代谢特征及其质量平衡

针对煤化工行业排放数据,不同来源数据存在较大差异,社会各界对其真实性、准确性存在诸多质疑,因而有必要从新的角度对排放统计数据进行评估.选取某典型煤化工企业,采用物料平衡方法核算了该企业硫代谢通量,探讨了其代谢特征,核算结果清晰显示了该企业硫的主要来源和去向,为减排及政策制定提供了科学依据.该企业2014年硫输入输出基本平衡,平衡项表征的统计误差在可接受范围内,误差产生原因包括原料含硫系数不稳定、固废含硫系数缺失、废气监测难度大,成分复杂等.不同来源SO_2排放量对比分析显示,排污申报数据略高于基准核算值,后评估数据偏小,而环境统计数据远大于基准值.数据的真实性与准确性有待提高;不同层次、不同部门统计方法有待完善及统一;无组织排放是重要的硫输出途径,不容忽视.     

邯郸市PM_(10)、PM_(2.5)和PM_(1.0)在线监测研究

对2015年3月—2016年2月邯郸市大气中的PM_(10)、PM_(2.5)和PM_(1.0)进行了在线监测,探讨了其质量浓度的变化特征,并分析了其质量浓度与风速、风向的关系。结果表明:邯郸市颗粒物质量浓度水平较高,β射线吸收法所监测的PM_(10_WET)、PM_(2.5_WET)和PM_(1.0_WET)年均浓度值分别为202.5,114.8,81.1μg/m~3,PM_(2.5_DRY)/PM_(10_WET)和PM_(2.5_WET)/PM_(10_WET)分别为0.58、0.70,PM_(1_DRY)/PM_(2.5_WET)和PM_(1_WET)/PM_(2.5_WET)分别为0.58、0.71,PM_(2.5)为PM_(10)中的主要组成,PM_(1.0)为PM_(2.5)中的主要组成。邯郸市PM_(10)、PM_(2.5)和PM_(1.0)质量浓度冬季最高;PM_(10)、PM_(2.5)和PM_(1.0)日变化峰值为上午09:00左右,谷值为下午16:00左右,扬沙、降雨,霾和春节不同条件下PM_(10)、PM_(2.5)和PM_(1.0)差异明显。邯郸市PM_(10)、PM_(2.5)和PM_(1.0)的浓度高值主要分布在风向0°~100°和175°~225°、风速小于1 m/s的情况下。     

Prediction of germination rates of weed species: Relationships between germination speed parameters and species traits

In fields, the timing of weed emergence flushes is mostly related to the timing and rate of seed germination, which depend on seed dormancy level, soil temperature and water potential conditions as well as soil tillage and crop sowing date. Seed germination parameters are essential in weed dynamics models to account for the effects of soil conditions on weed demography. Since these parameters are difficult to measure, our objective was to test the possibility of estimating them from easily accessible information. Seed germination parameters (germination lag-time, time to mid-germination and mid-germination rate) were measured or collected from the literature for 25 weed species with contrasted seed characteristics. Correlations were then searched for between these parameters and morphological, chemical and physiological seed traits as well as seed dormancy level. The dormancy level was positively correlated with speed of germination parameters. Earliness of germination was positively correlated with seed lipid content and the seed area to mass ratio. Germination was also earlier and faster in species with a high base temperature for germination. These relationships explained about half the observed variability in germination speed parameters but should be further tested before being used to predict the germination behaviour of weed species in the field in different seasons.     

北京灰霾天气PM10中微量元素的分布特征

采用电感耦合等离子体质谱法(ICP-MS)对北京市2008年4月和5月不同采样点采集的灰霾天PM₁₀样品中的15种微量元素进行了分析,得出了Ti、Fe、Zn、Sn、Pb为全样样品中相对含量较高元素;Ti、Mn、Ni、Cu、Zn、Pb是水溶样样品中相对含量较高元素。与晴天相比,灰霾天样品中微量元素可溶性增强,对人体危害更严重。与2002年分析数据进行对比,因2002年缺少Cr、Cd元素的测试值,全样样品中除了Co、Ni、Cu、Mo元素外,其余测试元素的浓度均有不同程度的升高,Fe和Sn元素的增幅最大。水溶样品中,参与对比元素的含量均下降。文中对含量相对较高的Cr、Mn、Fe、Cu、Zn、Cd、Sn和Pb元素进行了源解析,分析得出采样点附近的交通源及地面扬尘是这些元素的主要来源。     

基于长时间序列的北京PM2.5浓度日变化及气象条件影响分析

基于2005~2014年北京宝联(城区)和上甸子大气成分本底站(郊区)监测结果得到了PM_(2.5)质量浓度日变化特征,并且讨论了气象条件的影响.结果表明,北京城区PM_(2.5)质量浓度10年平均值的日变化呈双峰分布,对应早晚出行高峰.但是,该特征在2007年以后才比较明显.月际(季节)变化表现为单峰与双峰之间、日最大值在早高峰与晚高峰之间的转换.一年中早峰值浓度在5~8月最高,与地面风速小、相对湿度以及水汽压(空气绝对含水量)较高有关,该季节晚高峰期间浓度变化相对较小主要受混合层较厚、地面风速大、降雨天气发生频繁的影响.11~12月和1~2月的16:00以后浓度明显升高,混合层顶高度在14:00~17:00大幅度下降是重要的影响因素.此外,严重和重度污染日09:00以后污染加重,与年平均值和中度污染日不同.边界层偏南风对来自周边地区高架源的污染物输送是其重要的影响机制.PM_(2.5)质量浓度日变化幅度随污染加重而增大.日最大风速和相对湿度日变化对浓度日变化幅度有影响,而且午后地面出现4~6 m·s-1的偏南风也会加大日变化幅度.北京郊区PM_(2.5)质量浓度多年平均值日变化呈单峰分布,日最大值超前于城区.而且,昼间的浓度在5~7月高于冬季.本研究结果将有助于细化不利扩散条件下的污染减排方案.     

北京市秋季大气气溶胶质量浓度谱分布特征的观测研究

为了研究不同天气形势和气象要素对不同粒径段的大气气溶胶质量浓度谱分布的影响,2010年秋季在北京市采用空气动力学粒径仪对0.5 ～20 μm的大气颗粒物进行了为期2个月的连续观测.结果表明,在不同天气形势和气团运动下,质量浓度谱分布差异明显.受到西北气流影响,在质量浓度较小的清洁天气,谱分布主要集中在粗粒径段(清洁天气).当天气以静稳为主,颗粒物质量浓度值中等偏高时,粗细粒径气溶胶分布中出现谱值相近的高峰(中等浑浊天气).在受到西南气流主要影响的高质量浓度的观测日中,细粒径气溶胶在谱分布中占主要地位(高浑浊天气).在相同气团影响的天气下,昼夜间质量浓度谱分布的谱型变化趋势一致.清洁天气保持了粗粒径段的单峰分布,中等浑浊和高浑浊天气呈双峰分布.清洁天气细粒径段谱值受光化学反应影响在日间略高于夜间.中等浑浊天气中质量浓度的谱值在夜间受相对湿度和温度变化影响有显著增加.高浑浊天气下,昼夜温湿差别小,谱分布未出现明显变化.     

Quantification, morphology and source of humic acid, kerogen and black carbon in offshore marine sediments from Xiamen Gulf, China

Three types of macromolecular organic matters (MOMs), i.e. humic acid (HA), kerogen+black carbon (KB), and black carbon (BC) were extracted from marine sediments of Xiamen Gulf, southeast of China. The chemical composition, morphological property and source of the three extractions were characterized by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) and scanning electron microscope (SEM). The results showed that KB was the predominant fraction in MOMs, which accounted for 61.79%-89.15% of the total organic content (TOC), while HA consisted less than 5%. The relative high contents of kerogen and BC, and low contents of HA in the samples indicated that anthropogenic input might be the major source of organic matter in marine sediments near the industrial regions. The characterization of SEM, not only revealed morphological properties of the three fractions, but also allowed a better understanding of the source of MOMs. The δ 13 C values of the three fractions suggested that materials from terrestrial C 3 plants were predominant. Furthermore, the anthropogenic activities, such as the discharge of sewage, coal and biomass combustion from industry nearby and agricultural practices within drainage basin of the Jiulong River, were remarkably contributed to the variations in δ 13 C values of MOMs in the offshore marine sediments.