季铵盐的GC-MS和LC-MS检测及其在城市污水处理厂中的分布特征研究

发布时间：2018-03-14 03:10

本文选题：季铵盐　切入点：LC-MS　出处：《湖南大学》2015年硕士论文　论文类型：学位论文

【摘要】：季铵化合物(QACs)是一类最主要的阳离子表面活性剂,被广泛用于家庭,工业,农业及医疗应用领域作为木材防腐剂,杀虫剂,杀真菌剂,消毒剂和清洁剂。QACs普遍存在于全世界范围内的污水,工业废水,污泥,地表水以及水体沉积物中,对生物处理系统及环境系统构成威胁。现在,QACs的环境污染问题逐渐引起环境工作者的关注。因此,建立一种快捷、稳定、可靠的环境样品中QACs分析方法对环境中QACs的监测具有十分重要的意义。本实验首先探讨了经TMSH衍生运用GC-MS检测十六烷基三甲基氯化铵(ATMAC-C16)的分析方法。从优化衍生反应条件、GC-MS分析条件出发,研究了衍生剂用量对ATMAC-C16衍生产物检测的影响。然而,由于GC-MS需要先对QACs进行衍生化处理,较为复杂,本实验最终选定采用液相色谱质谱联用技术(LC-MS)结合正离子电喷雾电离(ESI+)方法检测季铵盐。首先,初步建立了LC-MS分析季铵盐的仪器方法。在选定色谱柱为C18柱,流动相为含有0.1%甲酸的甲醇/水(7:3)溶液的前提下,优化了液相色谱的梯度洗脱程序,梯度洗脱开始时流动相比例为30%A、70%B;0-4min时逐渐增加到100%B;4-6min时保持100%B;6-7min时又降低到30%A、70%B;7-8min时保持为30%A、70%B。该方法对十六烷基三甲基氯化铵(ATMAC-C16)、十八烷基苄基氯化铵(BAC-C18)、双十二烷基二甲基溴化铵(DADMAC C12:C12)以及双十八烷基二甲基溴化铵(DADMAC C18:C18)这四种季铵盐的检测限可达到5ng/m L;并建立了四种季铵盐的线性方程分别为y=2494.9956x+49182.4711,y=4525.7995x+50788.1729,y=760.6959x+35908.5828,y=2711.0139x+14566.4124,相关系数均大于0.99;相对标准偏差小于10%,方法的精密度较好。本文还采用LC-MS方法对长沙开福污水处理厂的进出水和各处理单元的污泥样品进行检测,通过索氏萃取和固相萃取方法提取、富集及纯化其中的季铵盐。检测结果表明进水中含有ATMAC-C16、BAC-C18、DADMAC C12:C12、DADMAC C18:C18这四种季铵盐,其中DADMAC C12:C12含量最高,为17.3093 ng/mL;其次是BAC-C18和DADMAC C18:C18,分别为15.5366 ng/mL和7.0409 ng/mL;ATMAC-C16含量最低,为5.2801 ng/mL。而出水样中只检测到ATMAC-C16,含量为1.0418 ng/mL;其它三种季铵盐均低于检测限,未被检出。由此可算出该污水处理厂对四种季铵盐的去除率均在80%以上。对该污水处理厂各处理单元的污泥样品的检测结果表明:所有污泥样品中都含有这四种季铵盐,但由于低于检测限无法被定量。
[Abstract]:Quaternary ammonium compounds (quaternary ammonium compounds) are the most important cationic surfactants that are widely used as wood preservatives, insecticides and fungicides in household, industrial, agricultural and medical applications. Disinfectants and detergents. QACs are found worldwide in sewage, industrial wastewater, sludge, surface water and sediments. Threat to biological treatment systems and environmental systems. Now the problem of environmental pollution of QACs has gradually attracted the attention of environmental workers. Therefore, to establish a fast, stable, Reliable QACs analysis method in environmental samples is of great significance for the monitoring of QACs in the environment. In this experiment, the analytical method for the detection of cetyltrimethylammonium chloride ATMAC-C16 by TMSH derivation and GC-MS was first discussed. The reaction conditions were analyzed by GC-MS. The effect of the amount of derivatives on the detection of ATMAC-C16 derivatives was studied. However, because of the need of GC-MS for the first derivative treatment of QACs, it is more complicated. In this experiment, the liquid chromatography-mass spectrometry (LC-MS) combined with positive ion electrospray ionization ionization (ESI) method was used to detect quaternary ammonium salts. Firstly, an instrument for the determination of quaternary ammonium salts by LC-MS was established. The chromatographic column was selected as C18 column. With the mobile phase of methanol / water 7: 3 solution containing 0.1% formic acid, the gradient elution procedure of liquid chromatography was optimized. The mobile phase ratio at the beginning of gradient elution was 30A70BC16, 18 alkyl benzyl ammonium chloride BAC-C18, bis#number1# dialkyl methyl bromide, and then decreased to 30A70B7min, 30A70B7min and 30A70B at the beginning of the gradient elution. The method was applied to the determination of hexadecyltrimethylammonium chloride ATMAC-C16, 18 alkyl benzyl ammonium chloride BAC-C18, bis-#number1# dialkyl methyl bromide. The detection limits of the four quaternary ammonium salts (DADMAC C12: C12) and bis 18 alkyl dimethyl ammonium bromide (DADMAC C18: C18) can reach 5ng / mL, and the linear equations of the four quaternary ammonium salts are established respectively as yy 2494.9956x 49182.4711y4525.7995x 50788.1729ynium 760.69x 35908.5828yU 2711.139x 14566.4124124.The correlation coefficients are all greater than 0.990.The relative standard deviations are higher than 0.994.The linear equations of the four quaternary ammonium salts are as follows: YY 2494.9956x 49182.4711y4525.7995x 50788.1729yr 760.69x 35908.5828yr. Less than 10, the precision of the method is better. The LC-MS method is also used to detect the inlet and outlet water of Changsha Kaifu sewage treatment plant and the sludge samples from each treatment unit. The quaternary ammonium salt was enriched and purified by Soxhlet extraction and solid phase extraction. The results showed that there were four quaternary ammonium salts, ATMAC-C16, BAC-C18, DADMAC, C12: C12, DADMAC, C18C18, in which the content of DADMAC C12: C12 was the highest. BAC-C18 and DADMAC C18: C18 were 15.5366 ng/mL and 7.0409 ng / mL respectively, the lowest ATMAC-C16 content was 5.2801 ng / mL. however, only ATMAC-C16 was detected in water samples with a content of 1.0418 ng / mL; the other three quaternary ammonium salts were all below the detection limit. The removal rates of the four quaternary ammonium salts in the sewage treatment plant are all above 80%. The results of the sludge samples from each unit of the sewage treatment plant show that all the sludge samples contain these four quaternary ammonium salts. However, it can not be quantified because it is below the detection limit.
【学位授予单位】：湖南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X703

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