水中土霉味化合物的鉴定与去除研究
摘要
目前,日益增多的污染物排放到饮用水水源中,造成了水体富营养化现象严重。由此导致了藻类的大量繁殖,藻类不仅会消耗了水中的溶解氧,同时还释放嗅味物质,引起饮用水异嗅问题的出现。反-1,10-二甲基-反-9-萘烷醇(土味素,Geosmin)和二甲基异冰片(MIB)则是饮用水体中最常见的两种不良气味化合物,常规的水处理技术不能将其去除。
研究运用比对实验、三角实验以及糖水对照实验对小组成员进行培训,建立了气味层次法(FPA),绘制出气味分析曲线,测定了在45℃的条件下,Geosmin和MIB的嗅阈值分别为5ng/L和8ng/L。同时,本研究还建立了固相微萃取—气质联用技术(SPME-GC/MS)分析水中的Geosmin和MIB,确定出最优化条件,在65℃的恒温水浴中,结合磁力搅拌萃取30min进样,脱附3min,该方法测定Geosmin的回收率为93.9%～99.2%,MIB的回收率为93.8%～96.2%,将这两种方法进行比较发现,两者之间吻合性较好,充分说明将FPA方法引入嗅味分析评价体系的可行性。
结合FPA与SPME-GC/MS,对一年中长江水系的四大水厂、太湖以及南京中山陵风景区四大湖泊进行了气味鉴定与评价。调查发现,在上述水体中均检测出Geosmin和MIB的存在,浓度在5ng/L～25ng/L,有明显的嗅味,并且春夏季节,水中Geosmin和MIB的浓度高于秋冬季节。
实验还探讨了余氯对FPA和SPME-GC/MS测定的影响。研究发现,当余氯的浓度达到0.8mg/L或以上时,土霉味将很难被感知,而余氯对Geosmin和MIB的SPME-GC/MS测定有11%～79%的掩蔽效应,使用硫代硫酸钠去除饮用水中的余氯的方法可以消除以上掩蔽效应。
本课题运用光化学降解法、活性炭吸附法以及活性炭臭氧联用技术,探讨了Geosmin和MIB的去除方法,并结合FPA,对处理效果进行了评价,研究表明,臭氧、紫外对Geosmin和MIB的去除都有一定的效果,但均达不到嗅阈值以下,而粉末活性炭虽然能够有效地将Geosmin和MIB去除至嗅阈值以下,但是粉末活性炭的再生等后续工作的繁琐因素,不建议广泛使用。颗粒活性炭臭氧联用技术对饮用水中土霉味化合物的去除效果显著,结果表明:30mg/L颗粒活性炭投加量与3g/h臭氧联用可将上述气味化合物去除至嗅阈值以下。
At present,along with more and more pollutants being discharged into drinking water source,eutrophication was one of popular environmental problems happened in waters. Blooming aglae consume dissolved oxygen in water,release some components smelling disgusting.Geosmin and MIB(G&M)are the most common unpleasant compounds in water, and they can not be removed by conventional water treatment processes.
Paired Comparison Test,Triangle Test and Sensitivity/Discrimination Test Ranking were used to train the panel of Flavor Profile Analysis(FPA)and the PFA method was established.Results showed that the olfactory threshold of Geosmin was 5ng/L,and the olfactory threshold of MIB was 8ng/L.At the same time,SPME-GC/MS was used to determine G&M in water,and the optimized operating condition was that the samples were extracted on a stirrer/hot plate schott for 30min at 65℃.The desorb time is 3min.The recovery rate of G&M can reach 93.9%～99.2%and 93.8%～96.2%repetively.
FPA was introduced to the system of the analysis and identification on earthy and musty odors.The water samples from four water treatment plants along Changjiang River,Tai Lake and four lakes in Nanjing Sun Yat-sen in a year,were detected by PFA panel and SPME-GC/MS.The research showed that the G&M concentration in the water samples above were 5ng/L～25ng/L,and it was higher in spring and summer than that in autumn and winter.
The impacts of residual chlorine on detecting G&M were studied.When the concentration of residual chlorine is more than 0.8mg/L,the earthy and musty odors can hardly been apperceived,and 11%～79%of reduction for G&M concentrations was observed in the presence of residual chlorine.The addition of sodium thiosulfate can effectively counteract the influence of chlorine.
Ozone,UV,and activated carbon were used to remove G&M in water.It was found that ozone and UV have a little effect on removing G&M,but they could not decrease G&M to the concentration below olfactory threshold.Powder activated carbon(PAC)could effectively get rid of G&M,but PAC could hardly been regenerated,and it was not suggested to be used on a large scale.The removal effect of G&M in water with hyphenated techniques of granular activated carbon(GAC)and ozone was researched.The results showed that GAC of 30mg/L and ozone of 3g/h could remove these compounds to the concentration below olfactory threshold.
研究运用比对实验、三角实验以及糖水对照实验对小组成员进行培训,建立了气味层次法(FPA),绘制出气味分析曲线,测定了在45℃的条件下,Geosmin和MIB的嗅阈值分别为5ng/L和8ng/L。同时,本研究还建立了固相微萃取—气质联用技术(SPME-GC/MS)分析水中的Geosmin和MIB,确定出最优化条件,在65℃的恒温水浴中,结合磁力搅拌萃取30min进样,脱附3min,该方法测定Geosmin的回收率为93.9%～99.2%,MIB的回收率为93.8%～96.2%,将这两种方法进行比较发现,两者之间吻合性较好,充分说明将FPA方法引入嗅味分析评价体系的可行性。
结合FPA与SPME-GC/MS,对一年中长江水系的四大水厂、太湖以及南京中山陵风景区四大湖泊进行了气味鉴定与评价。调查发现,在上述水体中均检测出Geosmin和MIB的存在,浓度在5ng/L～25ng/L,有明显的嗅味,并且春夏季节,水中Geosmin和MIB的浓度高于秋冬季节。
实验还探讨了余氯对FPA和SPME-GC/MS测定的影响。研究发现,当余氯的浓度达到0.8mg/L或以上时,土霉味将很难被感知,而余氯对Geosmin和MIB的SPME-GC/MS测定有11%～79%的掩蔽效应,使用硫代硫酸钠去除饮用水中的余氯的方法可以消除以上掩蔽效应。
本课题运用光化学降解法、活性炭吸附法以及活性炭臭氧联用技术,探讨了Geosmin和MIB的去除方法,并结合FPA,对处理效果进行了评价,研究表明,臭氧、紫外对Geosmin和MIB的去除都有一定的效果,但均达不到嗅阈值以下,而粉末活性炭虽然能够有效地将Geosmin和MIB去除至嗅阈值以下,但是粉末活性炭的再生等后续工作的繁琐因素,不建议广泛使用。颗粒活性炭臭氧联用技术对饮用水中土霉味化合物的去除效果显著,结果表明:30mg/L颗粒活性炭投加量与3g/h臭氧联用可将上述气味化合物去除至嗅阈值以下。
At present,along with more and more pollutants being discharged into drinking water source,eutrophication was one of popular environmental problems happened in waters. Blooming aglae consume dissolved oxygen in water,release some components smelling disgusting.Geosmin and MIB(G&M)are the most common unpleasant compounds in water, and they can not be removed by conventional water treatment processes.
Paired Comparison Test,Triangle Test and Sensitivity/Discrimination Test Ranking were used to train the panel of Flavor Profile Analysis(FPA)and the PFA method was established.Results showed that the olfactory threshold of Geosmin was 5ng/L,and the olfactory threshold of MIB was 8ng/L.At the same time,SPME-GC/MS was used to determine G&M in water,and the optimized operating condition was that the samples were extracted on a stirrer/hot plate schott for 30min at 65℃.The desorb time is 3min.The recovery rate of G&M can reach 93.9%～99.2%and 93.8%～96.2%repetively.
FPA was introduced to the system of the analysis and identification on earthy and musty odors.The water samples from four water treatment plants along Changjiang River,Tai Lake and four lakes in Nanjing Sun Yat-sen in a year,were detected by PFA panel and SPME-GC/MS.The research showed that the G&M concentration in the water samples above were 5ng/L～25ng/L,and it was higher in spring and summer than that in autumn and winter.
The impacts of residual chlorine on detecting G&M were studied.When the concentration of residual chlorine is more than 0.8mg/L,the earthy and musty odors can hardly been apperceived,and 11%～79%of reduction for G&M concentrations was observed in the presence of residual chlorine.The addition of sodium thiosulfate can effectively counteract the influence of chlorine.
Ozone,UV,and activated carbon were used to remove G&M in water.It was found that ozone and UV have a little effect on removing G&M,but they could not decrease G&M to the concentration below olfactory threshold.Powder activated carbon(PAC)could effectively get rid of G&M,but PAC could hardly been regenerated,and it was not suggested to be used on a large scale.The removal effect of G&M in water with hyphenated techniques of granular activated carbon(GAC)and ozone was researched.The results showed that GAC of 30mg/L and ozone of 3g/h could remove these compounds to the concentration below olfactory threshold.
引文
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