| With the rapid development of the aquaculture scale in China,the use of veterinary drugs and fish feeds has greatly increased.At the same time,pesticides and veterinary drugs used in land-based agricultural production activities are inputting into aquaculture waters through many pathways.The nutrients and various pollutants in aquaculture waters frequently induce algae bloomings and red tides,and then cause the emergence of algae toxins and shellfish toxins,result in serious aquaculture water quality pollution,aquatic product safety and aquatic ecosystem balance,and may threaten human health through food chain.Therefore,the study on multi-residual analytical technique and combined pollution in aquaculture waters are of great significance and application value.In this study,a sensitive,accurate and high-throughput analytical method system was established with 362 pesticides,106 veterinary drugs and 39 toxins as target analytes in aquaculture waters,GC-MS and LC-MS/MS for detection and LLE/SPE as extraction/cleanup technique.Main research contents and results are as the followings:1.Establishment of a rapid detection system for target pesticides,veterinary drugs and biological toxins using chromatography-mass spectrometryIn this study,a rapid detection system for target pesticides,veterinary drugs and biological toxins using GC-MS and LC-MS/MS were established through optimizing chromatographic columns,chromatographic conditions,mass spectrometry parameters,bring-to-volume solvents and filter membranes.According to the polarity difference,245 medium-to-weakly polar pesticides were detected by GC-MS,and other 262 kinds of strong polar pesticides,veterinary drugs and toxins were detected by LC-MS/MS.Under optimal conditions,all target analytes showed good linearity within a certain concentration range with R2 between 0.9900 and 0.9999.The instrumental detection limits of GC-MS targets was between 0.5 and 10.0 μg/L,while the instrumental detection limit of LC-MS/MS target analytes between 0.005 and 1.0 μg/L.The detection system established in this study exhibited a wide application range,high sensitivity and fast detection speed,all targets in a sample can be completed within 10 hours.2.Establishment of pre-treatment methods for simultaneous determination of pesticides,veterinary drugs and biological toxins in typical aquaculture watersA pre-treatment method system for 507 pesticides,veterinary drugs and toxins in lake water and sea water was established through optimizing SPE cartridge,elution solvent,pH,Na2EDTA addition amount and breakthrough volume.An isotope surrogate method was evaluated for better quantification.Under the optimized conditions,matrix spiking recovery experiment were carried out at three different concentration levels(10 ng/L,50 ng/L and 100 ng/L)and matrix effect was investigated.For pesticides detected by GC-MS:(1)The percentages of target compounds with recovery between 60%and 120%in lake water were 84.9%,90.2%and 92.2%with RSDs(n=4)from 0.5%～21.1%,0.5%～14.0%and 0.8%～13.0%,respectively.(2)The percentages of target compounds with recovery between 60%～120%in seawater were 85.7%,89.4%,and 93.1%with RSDs(n=4)1.4%～27.0%,1.2%～24.2%and 0.4%～23.6%,respectively.The method detection limits(MDLs)were between 0.2 and 10.0 ng/L.For pesticides,veterinary drugs and toxins detected by LC-MS/MS:(1)The percentages of target compounds with recovery between 60%～120%in lake water were 95.0%,95.4%and 97.3%with relation standard deviations(RSDs,n=4)0.5%～21.1%,0.5%～14.0%and 0.8%～3.0%,respectively.84.0%of the total target analytes showed matrix effects between-50%and 50%.(2)The percentages of target compounds with recovery between 60%～120%in seawater were 96.6%,97.7%,and 96.9%,with RSDs(n=4)1.3%～15.6%,2.1%～19.3%and 1.5%～14.8%,respectively.80.9%of the total targets showed matrix effects between-50%～50%.The MDLs were between 0.01 and 2.0 ng/L.The pretreatment methods established in this study are sensitive,reliable and fast,and fully meets the requirements for the determination of trace pesticides,veterinary drugs and toxins in the waters.3.Preliminary application and efficiency evaluation of a high-throughput analysis method system for pesticides,veterinary drugs and biological toxins in a typical aquaculture water environmentThe high-throughput analysis method established above was applied to monitoring surface seawater samples collected in the aquaculture area of Qingshan Island,Ningde City,Fujian Province.Results showed that:(1)A total of 25 pesticides,9 veterinary drugs,1 algae toxins and 1 shellfish toxin were detected.(2)Both traditional pesticides including carbamates,pyrethroids,organophosphorus pesticides and some new pesticides with less attention including acrylates,hormones,neonicotinoids,azoles were detected at all stations.(3)Besides commonly used antibiotics such as sulfonamides,quinolones and tetracyclines,some noteworthy veterinary drugs such as amantadine and nitrofurazone metabolite derivatives and metronidazole were also widely detected.(4)This high-throughput analysis methods takes 13 hours to finish one water sample determination,and can complete the analysis of 6 aquaculture water samples within 24 hours,thus verifying the efficiency.The established high-throughput analysis methods for pesticides,veterinary drugs and biological toxins in typical aquaculture waters provide reliable determination techniques for organic combined pollution monitoring and scientific data for water quality risk assessment and sustainable fishery development. |
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