Speciation Analysis Of Tin And Lead In Marine Products And Environmental Waters By HPLC-ICP-MS

Tin and lead are highly toxic heavy metal pollutants,which are readily to accumulate in organisms.Their toxicity,migration,transformation and bioavailability vary greatly among chemical forms,therefore speciation analysis of tin and lead is more reasonable than total quantification.High performance liquid chromatography interfaced with inductively coupled plasma mass spectrometry（HPLC-ICP-MS）has the unique advantages including high sensitivity,high selectivity,and wide linear range（7-9 orders）,and hence it is one of the most attractive technologies for speciation analysis of tin and lead.In addition,preconcentration of ultra-trace tin and lead species in environmental water may be indispensable prior to speciation analysis.Solid phase extraction（SPE）is the right choice for the enrichment of heavy metal ions because of its advantages of high enrichment factors,low consumption of organic solvents,simple operation and easy automation.In this thesis,SPE was combined with HPLC-ICP-MS using a green,aqueous mobile phase to simultaneously enrich and analyze the various speciation of tin and lead in environmental water samples and seafood.The first chapter reviewed the toxicity of tin and lead and their main chemical species,advance on single-element and multi-elemental speciation analysis strategies,and enrichment techniques for Sn and Pb.In Chapter 2,an HPLC-ICP-MS method for simultaneous speciation analysis of tin and lead was established.A 10 cm Amphion II hydrophilic chromatographic column was selected from five stationary phases(C₁₈,C₈,SCX,SAX and Amphion II).By utilizing 4 m M sodium dodecyl benzene sulfonate（SDBS）at p H 2.0 as the mobile phase,five tin species（Sn（II）,TMT,TET,TBT and TPh T）and three lead species（Pb（II）,TML and TEL）can be analyzed within 16 min.Low detection limits(0.013-0.24μg L^–1)and good relative standard deviations（RSDs）of all the analytes（<5%）were achieved.The developed HPLC-ICP-MS method was successfully applied to the determination of tin and lead species in marine fish,shrimp,pond fish and sediment.In Chapter 3,an online SPE-HPLC-ICP-MS method for simultaneous enrichment and analysis of tin and lead species was developed on the basis of Chapter 2.Graphene oxide bonded silicon dioxide was used as the SPE adsorbent,8 m L of 1 m M benzoic acid as preconditioning agent,and mobile phase（4 m M SDBS,p H 2.0）as internal eluent for enriching tin and lead species from 10 m L of water samples without any p H adjustments at 10 m L min^–1 flow rate.High enrichment factors（552-2848）were obtained under these conditions,leading to satisfactory detection limits down to 0.002-0.008 ng L^–1.This method has been successfully applied to the determination of tin and lead compounds in seawater and aquaculture pond water.TBT and Pb（II）were detected in 13 seawater samples,and TMT,TBT and Pb（II）were found in 24 culture pond water samples.In Chapter 4,simultaneous speciation analysis of cadmium,tin,mercury and lead was preliminarily investigated by HPLC-ICP-MS.Simultaneous separation of Cd（II）,Sn（II）,TMT,TET,TBT,TPh T,Hg（II）,Me Hg,Et Hg,Pb（II）,TML and TEL was achieved in 23 minutes using 4 m M SDBS+0.1 m M Cys at p H 2.0 as mobile phase.Validation of analytical methods and other related experiments are on-going.This thesis focuses on the development of an HPLC-ICP-MS method for the simultaneous morphological analysis of tin and lead,using a green and environmentally friendly aqueous mobile phase to achieve the simultaneous separation of eight species of tin and lead in a short period of time.On this basis,the SPE-HPLC-ICP-MS method was developed for the simultaneous enrichment analysis of tin and lead species,which achieved high enrichment factors and low detection limits,and was successfully applied to the analysis and detection of seawater and aquaculture pond water.In the future,more methods for the separation and enrichment of metal species and their applications in food,environmental and biological fields can be explored.