Determination Of Triazine Herbicides In Environmental Water Quality And Urine Samples By Tandem Mass Spectrometry

Objective Triazine herbicides were one of the most widely used herbicides in China,which were a kind of selective bud before and after bud herbicide.In order to control corn,sorghum,fruits and vegetables and other crops weeds,they were widely used in industrial and agricultural city and many other areas.They were used a great deal in agriculture and hard to be biodegraded,with high persistent ecological toxicity.Surface water was often polluted.Triazine herbicides were widely used,causing serious pollution to the environment,in the meantime analytical methods were few.Part 1 of this paper,a solid phase extraction-liquid chromatography-tandem mass spectrometry(SPE-MS)method for six kinds of triazine herbicides in environmental water quality was established to meet the simultaneous analysis and determination of six kinds of herbicides residues in water samples.Simazine was a six-member heterocyclic triazine herbicide,enters the body through the respiratory tract,digestive tract,skin and mucous membrane,long-term exposure can lead to birth defects,causing disruption of normal hormonal function and tumors of the reproductive system,etc.In animal experiments,rats were administered orally with radiologically labeleds simazine.After 96 hours,the excretion of radioactive simazine protoform in the urine of rats accounted for about49.3% of the total intake.Therefore,by measuring the prototype of simazine in urine,can effectively evaluate simazine exposure dose level.There were few studies on the detection methods of simazine prototype in urine at home and abroad.At present,the biological contact limit and biomaterial detection method of simazine have not been established in China.The second part of this paper was to establish a solid phase extraction-liquid chromatography-tandem mass spectrometry method for the determination of urinary metabolites in people with occupational exposure or low exposure to simazine.Methods(1)The Waters Oasis HLB column was selected as the solid phase extraction column,and methanol was selected as the eluent.The sample was enriched by activation of solid phase extraction column,sample loading,impurity washing,vacuum drying,elution and nitrogen blowing.Six triazine herbicides were extracted from environment water quality water.Optimization of spe conditions,including the exploration of the type of spe column,the type and amount of eluent,and the sample loading flow.Explored the methodological performance indexes.The established method was applied to test the water samples from 14 inner lakes,10 from outer lakes,10 from the Yangtze River and 10 from the end of the pipe network,a total of 47 samples,to further verify the practicability of the method.(2)Chose Waters Oasis HLB LP column as solid phase extraction column,acetonitrile as eluent,extraction simazine from urine.By rotation of single factor experiment,selected the highest enrichment ratio solid phase extraction column,explored the types of activation reagents,explored the type and dosage of eluent,sample velocity of flow,etc.The methodological performance indicators were studied.Urine samples from 20 college student volunteers were collected and tested using the established method.SD rats were fed with water samples containing 200.0μg/L simazine.Rat urine was collected in the animal metabolism cage to determine the simazine in urine.Results(1)The results of six triazine herbicides in environment water quality:all the six triazine herbicides had good linear relationships within the range of0～250.0μg/L concentrations,and the correlation coefficient were greater than 0.999.The detection limit were 0.54～1.44μg/L,the quantitative limit were 1.8～4.8μg/L,the average recovery were 75.0%～93.3% and precision ranges from 0.6% to 5.0%.According to the established method,14 water samples from the inner lake,10 from the outer lake,10 from the Yangtze River,and 10 servings tap water were determined.The results showed that the concentrations of cyanazine were 0.015～0.018μg/L,metribuzin concentrations were 0.017～0.041μg/L,and prometryn concentrations were 0.011～0.014μg/L.The concentrations of metribuzin in the outer lake were0.015～0.037μg/L.The concentrations of metribuzin in the Yangtze River water were0.008～0.019μg/L,and the other substances were not detected in the tap water.(2)The results of triazine herbicide simazine in the urine: There was a good linear relationship between the peak area of simazine in urine and its concentration in the range of 0～500.0μg/L,the linear correlation coefficient greater than 0.999,the detection limit was 0.91μg/L and the quantitative limit was 3.03μg/L,the recovery rates were 80.7%～83.6% and RSD ranged from 6.8% to 9.1%.None of the college student volunteers showed simazine in their urine.SD rats were fed with water samples containing 200.0μg/L simazine,Rat urine was collected in the animal metabolic cage,and about 5 m L urine samples were collected within 24 hours.Urine samples were determined on the same day,fed continuously for 10 days and measured 20 times.The concentration of simazine in rat urine ranged from 0.8 to61.6 μg/L.Conclusions(1)Solid phase extraction(SPE)liquid chromatography tandem mass spectrometry was developed for six triazine herbicides in environment water quality.The method was simple,efficient,high concentration,low detection limit and high sensitivity.It can meet the requirements of simultaneous analysis and determination of 6 herbicide residues in environment water quality water samples.A new method was provided for the simultaneous determination of 6 triazine herbicide residues in environment water quality water.(2)A new method of solid phase extraction(SPE)liquid chromatography tandem mass spectrometry(LC-MS)was developed for the determination of triazine herbicide simazine in urine.The new method is suitable for the determination of simazine in urine in occupational and non-occupational contact people.This method is simple in operation,high in enrichment efficiency,can eliminate the interference of complex matrix in the urine sample and environment water quality,and has high accuracy and precision.The method meet the requirements of the “Guidelines for the establishment of occupational health standards,Part 5: Methods for determination of chemical substances in biological materials”(GBZ/T 210.5-2008).The practicability and feasibility of the method were verified through the detection of rat metabolic urine samples and volunteer urine samples,which can provide technical support for the determination of simazine in urine.(3)A new method is established to detect the levels of external exposure and internal exposure of triazine herbicides by measuring the environmental water quality and urine.