Application of High-Performance Liquid Chromatography with A New Photometric Detection Method (Development of Analytical Methods for Environmental Pollutants)

(1)离子色谱（ion chromatography， IC）中保留峰和峰形成机理的理论研究：在前人研究的基础上，提出了“选择性增峰抑制电导率检测IC”理论。该理论有效地应用于污水样品中痕量正磷酸盐的测定。通过在胡佛模型的方程中引入一个新的参数“淋洗液分离因子”，从理论上评价了多价淋洗液体系的离子交换色谱行为。(2)光度检测的功能洗脱剂IC: [Cu(en)_2SO_4和[Cu(trien)]SO_4都是灵敏测定阳离子的有效洗脱剂。采用Na_2[Cu(edta)]- Na_2H_2 edta洗脱液，通过光度检测IC将阴离子和金属离子降解为金属-edta阴离子螯合物，可有效地用于环境水样中阳离子和阴离子的测定。采用铜-酒石酸络合洗脱液，基于配体交换形成机理，分光光度法测定了苹果酸对映体。用该法测定了苹果汁添加剂苹果酸的含量。(3)碳酸盐-碳的测定：通过氮气吹扫，可以有效地去除溶解在洗脱液中的干扰大气中的二氧化碳。使用该设备，可以通过光度检测IC和离子排除色谱（电导率检测）检测低至10^<-6> M的痕量碳酸盐碳。用该方法测定了雨水中的碳酸盐碳。(4)偏振光度检测：在吸光度检测器的流道两侧设置两个偏振片，通过偏振片和流道的自然光的强度根据通过的光活性化合物而变化。吸光度的变化与化合物的浓度成正比。非显色性的光学活性化合物，如糖，采用光度检测高效液相色谱法灵敏地测定，没有任何衍生化。(5)自动预处理/高效液相色谱系统：结合柱切换系统和切心技术有效去除IC中的干扰化合物，该系统用于光度检测IC测定河流和雨水样品中的阴离子，电导率检测IC测定污水样品中的正磷酸盐。(6)化学发光检测高效液相色谱法测定硝酸芘。建立了在线电化学还原后的高效液相色谱-化学发光法测定硝基、亚硝基和氨基芘的方法。建立了离线化学还原后的高效液相色谱-化学发光法测定1,3 -、1,6 -、1,8 -二硝基芘和1-硝基芘的方法。利用这些方法，测定了柴油和汽油发动机排气微粒中的二硝基芘和硝基芘。少

(1) Theoretical studies on the retention and peak formation mechanism in ion chromatography (IC) : Following on from our previous work, a new theory "selective peak enhancement and suppression of conductivity detection IC" was evaluated. This theory was effectively used in the determination of trace level orthophosphate in sewage samples. Ion exchange chromatographic behavior of polyvalent eluent systems was evaluated theoretically by introducing a new parameter "the intereluent separation factor" in equations for Hoover's model.(2) Functional eluents for photometric detection IC : Both[Cu(en)_2SO_4 and[Cu(trien)]SO_4 were effective eluents for the sensitive determination of cations. Using a Na_2[Cu(edta)]- Na_2H_2 edta eluent, not only anions but also metal ions were deterifined as metal-edta anion chelates by photometric detection IC. These methods were effectively used in the determination of cations and anions in environmental water samples. Malic acid enantiomers were separately d … More etermined by photometric detection IC using a copper - tartaric acid complex eluent, based on a ligand-exchange formation mechanism. Malic acid, an apple juice additive, was determined by this method.(3) Determination of carbonate-carbon : Interfering atmospheric carbon dioxide dissolved in eluents was removed effectively by nitrogen purging. Using this equipment, trace level carbonate carbon as low as 10^<-6> M could be determined by photomeric detection IC as well as ion exclusion chromatography (conductivity detection). Carbonate-carbon in rain water was determined by this method.(4) Polarized photometric detection : When two polarizers were set on both sides of the flow sell of an absorbance detector, the intensity of natural light transmitted through the polarizers and the flow cell was changed according to the optically active compounds if passed through. The change in absorbance was in proportion to the concentration of the compound. Nonchromophoric optically active compounds such as sugars were sensitively determined using photometric detection HPLC without any derivatization.(5) Automatic pretreatment/HPLC system : The combination of column-switching system and a heart-cutting technique effectively removed interfering compounds in IC. This system was used to determine anions in river and rain water samples by photometric detection IC and orthophosphate in sewage samples by conductivity detection IC.(6) Determination of nitopyrenes by HPLC with chemiluminescence detection : A method of determining nitro-, nitroso- and aminopyrenes has been developed using HPLC with chemiluminescence detection after on-line electrochemical reduction. Determination method of 1, 3-, 1, 6-, 1, 8-dinitropyrenes and 1-nitropyrene has also been developed using HPLC with chemiluminescence detection after off-line chemical reduction. Utilizing these methods, dinitropyrenes and nitropyrene were determined in diesel- and gasoline-engine exhaust particulates. Less