Application Of New Carbon And Polymer Materials In Pretreatment Technique And Detection Of Environmental Organic Micro-pollutants

Currently,the residues of organic micropollutants in water environment pose a serious threat to public safety and human health,so it is urgent and vital to establish and develop a rapid and efficient analytical technique.However,the concentrations of organic micro-pollutants in the water environment are usually at the trace level and their compositions are complex,which require sample pretreatment before analysis and determination.Sample pretreatment technique is considered as the most key step in the whole analytical process.In recent years,the appearance and development of miniaturization and micromation pretreatment technology greatly overcomes defects of traditional technologies such as the tedious and time-consuming,a large number of samples and organic solvents consumption.What is more,their advantages including simplicity,flexibility,easy operation and environmental friendliness also meet the development demand of environmental analytical chemistry.Based on this,a variety of new micro-extraction technologies based on new carbon and polymer materials have been constructed and applied in the analysis and detection of organic micro-pollutants in real water samples coupled with chromatography in this paper.These studies can promote the development of micro-pretreatment technology and expand the application of carbon and polymer materials.The main research work as follows:1.Carbon aerogel（CA）with large specific surface area and mesoporous structure was prepared by microwave technique,and then it used as sorbent for micro-solid phase extraction to detect the residual level of four plant growth regulators in environmental water samples coupled with high performance liquid chromatography（HPLC）.The results showed that satisfactory recoveries were 92-101%and low limits of detection（LODs）were 0.01-0.1μg/L,and the relative standard deviation was lower than 5.1%,meaning this method was suitable for the detection of the residue analysis of plant growth regulators in real water samples.In addition,the magnetic carbon aerogel（mCA）was further prepared,and the"green solvent"ionic liquid（IL）was loaded on the surface of mCA to form mCA-IL mixed hemimicelles,which was used as sorbent for mixed hemimicelles solid-phase extraction technique（MHSPE）to detect the residual level of triclosan（TCS）and triclocarban（TCC）in environmental water samples coupled with HPLC.The results showed that the limits of detection（LODs）were 0.005-0.01μg/L,and the recoveries were in the range of 95.6-97.2%.Therefore,this method can be used for the analysis and detection of TCS and TCC in real environmental water samples,which expanded the multi-functional application of CA in different pretreatment technologies.2.A hollow fiber liquid solid extraction technique based on a wormlike porous carbon was constructed for the detection of the residual level of four personal care products（PCPs）in environmental water samples by using agitation extraction mode and HPLC.Benefited from the introduction of wormlike porous carbon and stirring extraction mode,the extraction performance of this method was significantly improved.The better recoveries（88-98%）and lower limits of detection（LODs）（0.005-0.05 g/L）were obtained.So this method can provide a new idea for the detection of personal care products residues in water samples.3.The middle polar fiber cloth polymer adsorbent was used as the extraction medium,and two practical extraction methods,like stir bar of fabric phase sorbent（stir bar-FPSE）and magnetic stir（magnetic stir-FPSE）of fabric phase sorbent for three kinds of brominated flame retardants（BFRs）in water was designed.In the meantime,BFRs[tetrabromobisphenol A（TBBPA）,tetrabromobisphenol A bisallylether（TBBPA-BAE）,tetrabromobisphenol A bis（2,3-dibromopropyl）ether（TBBPA-BDBPE）]in water sample were selected as model analytes for the practical evaluation of the proposed stir bar-FPSE and magnetic stir-FPSE methods using HPLC.The results showed that the polymer adsorbent had good selectivity for the extraction of the target analytes,and the agitation extraction mode was helpful to improve the extraction efficiency.The two methods presented good analytical properties,high recoveries（93-99%）,low limits of detection（LODs）（0.01-0.05μg/L）and satisfactory reproducibility（RSDs,1.3-5.3%）were obtained.The results indicated that two pretreatment techniques were promising for monitoring of BFRs in the water sample.4.Microporous organic polymer materials（POF）were successfully prepared by microwave method.POF material not only has a large specific surface area and pore structure,but also has good electrical conductivity,so it was used for the determination of three trichlorobenzene（TCBs）and organophosphorus pesticides in water samples by dispersive solid-phase extraction（DSPE）-gas chromatography（GC）and AChE biosensor,respectively.The limits of detection（LODs）for three TCBs were 0.1-0.5ng/L,the RSDs were lower than 6.5%and high recoveries of 95-99%were achieved.And the developed biosensors had the detection limit of 1.5×10^-13 g/mL for methyl parathion,3.4×10^-14 g/m L for paraoxon,respectively,indicating potential valuable tool for monitoring of organophosphorus pesticides（OPs）in environmental samples.Moreover,porous carbon material was prepared by calcination of POF,and then magnetic porous carbon was prepared by co-precipitation method using magnetic nanoparticles,which were used as sorbent for magnetic solid-phase extraction technology（MSPE）.The residues level of fluronitrile,fenohydrazide and myclobutanil in environmental water samples were determined by MSPE coupled with GC technique.The results showed the detection limits were 0.01-0.1μg/L and the recoveries were88%-94%,which can be used for the residue analysis of fluronitrile,fenohydrazide and myclobutanil in real environmental water samples.