饮用水源水中痕量有机物的分析方法研究和应用

发布时间：2018-04-16 08:21

本文选题：饮用水源水 + 痕量有机物　；参考：《山东建筑大学》2012年硕士论文

【摘要】：本论文在全面综述饮用水源水中痕量嗅味物质二甲基异冰片(2-MIB)和土臭素(GSM)以及痕量抗生素残留的前处理技术和仪器分析方法的基础上,建立了快速准确分析饮用水源水中痕量嗅味物质的固相微萃取-气相色谱/质谱联用方法(SPME-GC/MS)和痕量抗生素物质的固相萃取-快速分离液相/三重串联四极杆质谱法(SPE-RSLC/MS2)。将建立的两类物质的分析方法成功运用于济南市玉清水厂和鹊华水厂进、出水的分析,首次得到饮用水源水中痕量有机物的季节分布规律和臭氧-生物活性炭的深度水处理工艺对水样中痕量有机物的去除效果。论文主要研究内容与结论如下： (1)饮用水源水中痕量嗅味物质2-MIB和GSM的SPME-GC/MS分析方法的建立选用SPME技术高效提取水源水中的2-MIB和GSM,优化得到了SPME富集水样中2-MIB和GSM的最佳操作条件：萃取纤维头的类型：50/30μmDVB/CAR/PDMS;离子强度：25mL水样中加6gNaCl；萃取时间：15mmin；萃取温度80℃；搅拌速度1150rpm。选用GC/MS选择离子模式(SIM)进行定性定量分析,优化得到了仪器的操作条件：GC进样口的解吸时间2min；升温程序：在80℃保持2min后,以15℃/min升温至165℃；再以2℃/min,升温至170℃,并保持5min；采用SIM模式,确定特征离子m/z95、107和108,111、112和125分别作为2-MIB、GSM的定性离子, m/z95,112作为2-MIB和GSM的定量离子。方法的质量控制和质量保证实验结果表明：待测物质2-MIB和GSM在10-500ng/L范围内线性关系良好,相关系数均大于0.999；对标准样品和实际样品进行精密度分析,相对标准偏差分别在3.4%-5.9%和1.6%～3.2%之间；水样的加标回收率分别达到99.43%和97.37%,二者最低检出限分别为1.2和0.9ng/L。该方法分离快速、定性定量准确、灵敏度高,完全满足饮用水源水中痕量2-MIB和GSM的分析检测要求 (2)饮用水源水中痕量抗生素残留的SPE-RSLC/MS2分析方法的建玉采用SPE前处理技术高效富集水源水中的6种抗生素残留,优化得到了SPE富集水样中6种抗生素的最佳操作条件：固相萃取小柱的类型：Waters公司的Oasis HLB (200mg/6cc)；过样体积：500mL；过样流速：8mL/min;水样的pH值：2.8；Na2EDTA溶液的浓度：1μg；洗脱溶剂类型：甲醇；洗脱剂用量：9 mL。运用RSLC/MS2多反应选择监测离子模式(MRM)进行定性定量分析,优化得到了仪器的操作条件：流动相为A相：水(0.2%甲酸),B相：乙腈,流速为0.3mL/min。梯度淋洗程序：在1min内从85%A降至80%A(5min),1min降至75%A,再在3min内降至20%A(3min),然后在5min内回升至85%A。方法的质量控制和质量保证实验结果表明：6种抗生素在5～4000ng/L范围内具有良好的线性关系的,相关系数均大于0.9922～0.9999；水样加标回收率在85.1%-106.2%之间；相对标准偏差(n=6)为1.6%～11.5%；方法的检出限为0.8-3.2ng/L。该方法完全可以满足对饮用水源水中痕量抗生素残留的检测分析要求。 (3)饮用水源水中痕量有机物的分析方法在分布规律和处理工艺研究中的应用运用建立的水源水中痕量有机物的分析方法,分析检测玉清水厂和鹊华水厂2011年4月～2012年3月调查周期的进水水质,研究得到济南市饮用水源水中痕量有机物的季节分布规律。结果表明：痕量有机物的浓度水平呈明显的季节变化规律。痕量2-MIB和GSM在每年的8、9月份会达到其浓度峰值,而抗生素残留在雨量较少、疾病多发的冬、春季浓度值相对较高。与鹊华水厂相比,玉清水厂原水中嗅味物质含量低,但抗生素含量较高。这与它们的原水来源地鹊华水库和玉清湖水库中藻菌优势种类差异以及水库周边的工农业污水及医院废液的排放情况不同密切相关。运用建立的饮用水源水中痕量有机物的分析方法对2011年4月～2012年3月调查期内采集的玉清水厂和鹊华水厂的出水进行检测分析,结果显示：常规水处理工艺对痕量有机物的去除效果非常不理想,而增加了臭氧-生物活性炭的深度水处理工艺对原水中嗅味物质2-MIB和GSM的去除率可达90%以上,对6种抗生素的去除率可达70%以上。应用实践表明,本论文建立的饮用水源水中痕量有机物的分析方法可以满足例行监测和科研工作的要求
[Abstract]:In this paper, a comprehensive review of drinking water trace odor compounds (2-MIB) two MIB and Geosmin (GSM) and trace antibiotic residue pretreatment technique and instrument analysis method, a fast and accurate analysis of solid drinking water trace odor substances microextraction and gas chromatography / mass spectrometry a coupling method (SPME-GC/MS) and trace antibiotic substances by solid-phase extraction and rapid separation of liquid phase / three quadrupole mass spectrometry (SPE-RSLC/MS2) analysis method. Two kinds of substances will be established in Ji'nan City, the successful use of Yuqing waterworks and Quehua waterworks, water analysis, seasonal distribution and ozone - Biological for the first time of activated carbon in drinking water sources of trace organic compounds the depth of the water treatment process of trace organic compounds in water removal. The main research contents and conclusions are as follows:
(1) establishment of SPME-GC/MS analysis method for trace odor substances 2-MIB and GSM in drinking water source water
The efficient use of water extraction technology of SPME 2-MIB and GSM, 2-MIB and GSM were optimized by SPME preconcentration optimal operating conditions: extraction type fiber tip: 50/30 mDVB/CAR/PDMS; ionic strength: 25mL samples with 6gNaCl; extraction time: 15mmin; extraction temperature of 80 DEG C; stirring speed 1150rpm. with GC/MS selective ion mode (SIM) qualitative and quantitative analysis, obtained the optimum operating conditions of the instrument: 2min GC desorption time inlet; temperature program: at 80 degrees to 15 degrees 2min, /min is heated to 165 DEG C; and then to 2 DEG /min, is heated to 170 DEG C, and maintain 5min; using SIM model to determine the the characteristics of ion m/z95107 and 108111112 and 125 respectively as 2-MIB, qualitative ion GSM, m/z95112 2-MIB and GSM as quantitative ion. The quality control and quality assurance methods the experimental results show that the tested material of 2-MIB and GSM in 10 -500ng/L good linear range, the correlation coefficients were greater than 0.999; precision analysis of standard sample and actual sample, the relative standard deviations were between 3.4%-5.9% and 1.6% ~ 3.2%; the recovery of sample rate reached 99.43% and 97.37% respectively, the two lowest detection limit was 1.2 0.9ng/L. and the method of quick separation, qualitative quantitative accuracy, high sensitivity, fully meet the requirements of analysis and detection of trace 2-MIB and GSM in drinking water
(2) the SPE-RSLC/MS2 analysis method of trace antibiotic residues in drinking water source water
Using 6 kinds of antibiotic treatment in water efficient enrichment before SPE residues were optimized by 6 kinds of antibiotics SPE enriched the optimal operating conditions: type of solid phase extraction column: Waters Oasis HLB (200mg/6cc); a sample volume: 500mL; a sample flow rate: 8mL/min; water pH value: 2.8; Na2EDTA concentration: 1 G; elution solvent type: methanol; eluent dosage: 9 mL. RSLC/MS2 using multiple reaction monitoring mode (MRM) ion qualitative and quantitative analysis, obtained the optimum operating conditions of the instrument: the mobile phase of A phase: water (0.2% formic acid): acetonitrile, B, phase velocity 0.3mL/min. gradient elution: from 80%A to 85%A in 1min (5min), 1min to 75%A, then to 20%A in 3min (3min), and quality control and recovery in 5min 85%A. method to ensure the experimental results show that 6 kinds of antibiotics In the range of 5 ~ 4000ng/L has a good linear relationship, the correlation coefficients were greater than 0.9922 to 0.9999; the water recovery rate between 85.1%-106.2%; the relative standard deviation (n=6) ranged from 1.6% to 11.5%; the detection limit is 0.8-3.2ng/L.. This method can fully meet the detection of trace antibiotic residues in drinking water analysis.
(3) the application of the analytical method of trace organic matter in drinking water source in the study of distribution and treatment process
Use the analysis method of establishing water trace organic compounds, detection and analysis of Yuqing waterworks and Quehua Waterworks in April 2011 ~ March 2012 survey cycle the water quality of drinking water source in Ji'nan City, the water trace organic seasonal distribution. The results showed that the concentration of trace organic matter showed obvious seasonal variation of trace 2-MIB. And GSM will reach its peak density in the year 8,9 month, and antibiotic residues in less rainfall, disease prone winter, spring concentration is relatively high. Compared with the Quehua waterworks, Yuqing Waterworks in odorant content is low, but the antibiotic content is higher. The difference of species and the Dominant Algae bacteria in their raw water the source of Quehua reservoir and Yuqing lake reservoir and the reservoir surrounding areas of industrial and agricultural waste sewage and hospital discharge. Closely related to the different use of trace in drinking water established The analysis method of organic matter from April 2011 to March 2012 during the acquisition of Yuqing waterworks and Quehua waterworks were analyzed, results showed that the conventional water treatment process of trace organic removal effect is not ideal, and the increase of ozone biological activated carbon advanced water treatment process for raw water in odor substances 2-MIB and GSM removal rate can reach more than 90%, to 6 kinds of antibiotics removal rate can reach more than 70%. The practice shows that the analysis method of this paper is to establish the drinking water source of trace organics in water can meet the requirement of routine monitoring and scientific research work requirements

【学位授予单位】：山东建筑大学
【学位级别】：硕士
【学位授予年份】：2012
【分类号】：R123.1

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