| The Multinitrophenols and its compositions, such as PA、TNR and TNPG, because of itshigh heat sensitivity and high flame sensitivity, easy to ignite, and the characteristics of highoutput energy of the flame, has been widely used in design and production of ignition powder.Environment safety concerns everyone’s health and has attracted more attention around theworld. With the expansion of nitrophenol industrial production, more and more toxicsubstances are expelled to the surroundings, introduced into food chains, and accumulated inhuman bodies. Many of these compounds are carcinogenic, teratogenic and mutagenic toanimals and human. Environment safety has posed a series of life risks for people. Hence, thedevelopment of analysis methods for the determination of toxic substance nitrophenolresidual in environment is necessary to contamination and ensure of environment safety.The main purpose of this thesis was to develop some simple, fast and Cost effectivesample pretreatment methods and analyte concentration methods to analysis of multi residuenitrophenol, The Details in the contents and results of the thesis are as follows:（1） Establish perfect ultrasonic assisted extraction gas chromatography massspectrometry (GC MS) determination of nitrophenol in environment samples, surfacesediments and soil nitrophenol residue analysis method, optimized the extraction method andinstrument analysis conditions. Eight kinds of nitrophenol in0.010～5.0mg/L respectively alinear relationship between concentration scope, correlation coefficient of0.9909, thedetection limit of0.010～0.050mg/kg respectively; Different samples between the averagerecovery was80.6%～115.3%, relative standard deviation is3.4%～10.8%, using thismethod in the water, soil, sediment, obtain the stable recovery.（2） A fast and cost effective method was developed for the determination of multiresidue nitrophenol in environment samples by solid phase extraction. Response surfacemethodology (RSM) and desirability function approach were used to optimize the extractioncondition and evaluate the interaction effect of different parameters in SPE. As a compromiseresult between nitrophenol recovery and pigment clean up degree. A Bond Elut Plexa solidphase extraction(SPE) was used for the extraction and purification of the compounds inenvironmental waste water, the sample loaded was5.0mL,and then eluted with5.0mLAcetonitrile, tetrahydrofuran (4: l), the elution was introduced into the instrument anddetermined by HPLC coupled with photodiode array detector at220nm. A good base line separation of target compounds was obtained in22minutes under the optimum condition ofdetermination. The calibration curves were linear in the concentration range of0.1mg/L～5.0mg/L with correlation coefficients of0.9973～0.9987. Over all recoveries were good(82.5%～105.4%),and the relative standard deviations ranged from3.2%to5.7%for thetarget compounds. The minimum detectable concentrations were0.02mg/kg～0.04mg/kg.This established method is convenient, sensitive and accurate, and was suitable for the routinedetection of trace amide contaminants in environmental samples.（3） A simple, rapid sensitive and accurate ultra performance liquid chromatographytandem mass spectrometry (UPLC MS/MS) method was developed for the simultaneousdetermination of14kinds of nitrophenol residues in environmental samples. The samplepreparation using the modified QuEChERS method completed the extraction and clean upsteps in one procedure. In this none buffer QuEChERS method, samples were cleaned up withprimary graphitized carbon black (GCB) and C18sorbent, then centrifuged and filtratedbefore detection. The pretreatment method was simple, rapid and effective and can meet thedetection requirements. The UPLC MS/MS method was performed on Waters Accucore PFP(2.1*150mm i. d.,2.6m) and the column temperature was30℃, the gradient elution withacetonitrile and ammonium acetate as the mobile phase and the flow rate was0.3mL/min. Thenegative electrospray ionization (ESI) source under the multiple reaction monitoring (MRM)mode and external standard method were used for quantification. The results showed that thecorrelation coefficients up to0.9914were obtained across a concentration range of0.005～0.5mg/L. The limits of detection (LOD) ranged0.002～0.005mg/kg. The method wasvalidated with soil samples spiked at three fortification levels (0.01mg/kg、0.1mg/kg and1mg/kg) and recoveries were in the range of76.3%～104.7%with relative standarddeviations (RSD) of3.7%～8.6%.（4） In this thesis, nitrophenol were chosen to study the ionization and dissociationrules by electron impact and Electro spray ionization tandem mass spectrometer(ESI MS／MS)．It demonstrated that：1) Nitrophenol are prone to form M'M+in EI mode．Fragment ions such as NO2、NO、CHO、CNO2、OH、CO are formed in the dissociation of C O bond, C N bond andrecomposition reaction can also be found．2) Nitrophenol in soft ionization electrospray ionization (ESI), usually more easily lose NO, CO, OH, CHO, CNO2, NO2fragment ions. Smaller molecular weight, molecularstructure relatively simple nitrophenol usually has lost the NO, CO, keep the benzene ringstructure. With the increase of the nitro and nitrophenol hydroxyl number, at the time oflosing NO and OH is often accompanied by ring opening reaction. Trinitrophenol in structureis more complex, because the bond energy and space effects, the influence of the loss of NO2fragment ions in turn.According to MS data, dissociation rule and dissociation characteristic of these14kindsof Nitrophenol chemicals were summarized，which will be a helpful theoretic reference tonitrophenol EI MS and ESI MS/MS analysis and to structural resolution of unknownchemicals．(5)2,4,6Trinitrophenol,2,4,6trinitroresorcinate,2,4,6trinitrophloroglucinol adsorptionheat and mass loss of desorption on stationary phase were tested by micro calorimetry andthermal analysis methods. Corresponding enthalpy and kinetic data were obtained. It was found that theinteraction of adsorption between PFP phase with benzene ring and2,4,6Trinitrophenol,2,4,6trinitroresorcinate,2,4,6Trinitrophloroglucinol were strong and adsorption heat werebig. The high temperature was not favorable to the adsorption of2,4,6Trinitrophenol,2,4,6trinitroresorcinate,2,4,6Trinitrophloroglucinol on phase and the monomolecular layeradsorption was occurred with lower adsorption rate and higher adsorption heat. Multimolecular layer adsorption was occurred with higher adsorption rate and lower adsorptionheat in low temperature environment. Liquid chromatography separate rate was affected byadsorption rate and separate character was decided by adsorption heat. |
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