Formation of chloronitropyrenes and dinitropyrenes in metallic oxides as scil components in the presence of indoor air wth 1-nilropyrene and sodium chloride under xenon lamp irradiation

在室内空气存在的条件下，氙灯照射下，研究了1-硝基芘（1-NP）与Cl离子混合物的反应产物对三种金属氧化物土壤组分的影响。用苯：乙醇（4:1,v/v）提取含1-NP的化学物质，并进行GC/MS分析。在三种金属氧化物(二氧化钛（TiO_2）、二氧化硅（SiO_2）和氧化铝（Al_2O_3）上，随着辐照时间的延长，1-NP的含量逐渐减少。特别是在TiO_2中，与其他两种金属氧化物相比，1-NP在整个辐照时间内都有较大幅度的降低。另一方面，从反应产物中检测到6种DNP（1,3-、2,4-、1,2-、1,6-、1,8-和1,7- DNP）。在TiO_2和Al_2O_3中，检测到6种DNPs，在SiO_2中，除2,4- dnp外，检测到5种DNPs。特别是在TiO_2中，与其他两种金属氧化物相比，1,7- dnp在所有辐照时间内都形成了丰富的量。我们推测4- np和2- np是由1- np通过OH自由基的光化学反应生成的，通过这些同分异构体的硝化作用连续生成2,4-、1,2-和1,7- dnps。利用1- np - nox - ci离子的光化学反应体系，首次在金属氧化物上证实了2,4-、1,2-和1,7- dnps的生成。室内空气中的氮氧化物被证明是这些金属氧化物中形成DNPs的氮源。随着辐照时间的延长，三种金属氧化物中DNPs的产率和形成模式有所不同。因此，形成DNPs的光化学反应的性质取决于金属氧化物的类型。在SiO_2中，致突变性在照射6 h后逐渐增强，6 h时的致突变性为260万回物/总提取物，12 h时的致突变性为150万回物/样品。在Al_2O_3中，随着辐照时间的延长，致突变性逐渐增强（164万回物/样品）。在TiO_2中，致突变性在10分钟迅速下降到60%，在12小时逐渐下降到22%。在反应混合物中制备了三种氯硝基芘（CNP）。在日本京都采集的表层土壤中检测到1-氯-3-硝基芘（1,3- cnp）、1,6- cnp和1,8- cnp。首先，1-硝基芘氯化合成1,3-、1,6-和1,8- cnps。采用二维高效液相色谱-荧光检测和锌在线催化柱分析了日本京都表层土壤中1,3-、1,6-和1,8- gnps的含量。土壤中1,3- cnp、1,6- cnp和1,8- cnp含量分别为9.2 ~ 13.8、3.4 ~ 4.6和4.3 ~ 5.0 pg / g （n=2）。少

The reaction products obtained from the mixture of 1-nitropyrene (1-NP) and Cl ion were investigated on three metallic oxides as soil components under xenon lamp irradiation in the presence of indoor air. These chemicals including 1-NP were extracted with benzene:ethanol (4:1, v/v) and analyzed by GC/MS. The amounts of 1-NP gradually decreased as the irradiation time elapsed on three metallic oxides [titanium dioxide (TiO_2), silicon dioxide (SiO_2) and aluminum oxide (Al_2O_3)). Especially, in TiO_2, 1-NP was decreased at high levels in comparison with the other two sorts of metallic oxides in all irradiation time. On the other side, six sorts of DNPs (1,3-, 2,4-, 1,2-, 1,6-, 1,8- and 1,7- DNP) were detected from the reaction products. In TiO_2 and Al_2O_3, all of six sorts of DNPs were detected, in SiO_2, five sorts of DNPs were confirmed except for 2,4-DNP. Especially, in TiO_2, 1,7-DNP was formed in rich amounts in comparison with the other two sorts of metallic oxides in all irrad … More iation time. We presumed that 4- and 2-NPs were generated from 1-NP by the photochemical reaction of OH radical, continuously 2,4-, 1,2- and 1,7-DNPs were formed by the nitration of these isomers. The formation of 2,4-, 1,2- and 1,7-DNPs was confirmed for the first time on the metallic oxides by photochemical reaction system of the 1-NP-NOx-CI ion. NOx in the indoor air was shown to be a nitrogen source to form DNPs in these metallic oxides. The yields and the formation patterns of DNPs differed in three metallic oxides as the irradiation time was extended. Hence, the nature of the photochemical reaction in the formation of DNPs differed depending on the type of metallic oxides. In SiO_2, mutagenicity was gradually increased up to 6 hrs irradiation and the mutagenic potency was exhibited 2.6 million revertants/total extract at 6 hr and then decreased to 1.5 million revertants/sample at 12 hrs. In Al_2O_3, mutagenicity was gradually increased as the irradiation time elapsed (1.64 million revertants/sample). In TiO_2, mutagenicity was rapidly decreased to 60 % at 10 min. and gradually decreased to 22% at 12 hrs. Three chloronitropyrenes (CNP) were produced in the reaction mixture. 1-Chloro-3-nitropyrene (1,3-CNP), 1,6-CNP and 1,8-CNP were detected in surface soil collected in Kyoto, Japan. First, 1,3-, 1,6- and 1,8-CNPs were synthesized by chlorination of 1-nitropyrene. Surface soil was collected in Kyoto, Japan and analyzed for 1,3-, 1,6- and 1,8-GNPs by two-dimensional high-performance liquid chromatography with fluorescence detection and a zinc on-line catalytic column. 1,3-CNP, 1,6-CNP and 1,8-CNP were detected in the ranges 9.2-13.8, 3.4-4.6 and 4.3-5.0 pg per gram of soil (n=2), respectively. Less