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

研究了在室内空气中氙灯照射下，1-硝基并(1-NP)与氯离子的混合反应产物在三种金属氧化物上的土壤组成。用苯：乙醇(4：1，v/v)提取1-NP，并进行GC/MS分析。随着辐照时间的延长，3种金属氧化物[二氧化钛(TiO2)、二氧化硅(SiO_2)和氧化铝(Al_2O_3)]上的1-NP含量逐渐减少。尤其是在整个辐照时间内，与其他两种金属氧化物相比，1-NP在TiO_2中的还原程度较高。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，除2，4-DNP外，其余6种DNPs均被检测到；在SiO_2中，除2，4-DNP外，还存在5种DNPs。与其他两种金属氧化物相比，在所有红外…中，1，7-dnp在二氧化钛中生成的量较多更多的休息时间。我们推测1-NP通过OH自由基光化学反应生成4-和2-NPs，这些异构体连续硝化生成2，4-，1，2-和1，7-DNPs。首次证实了1-NP-NOx-CI离子光化学反应体系在金属氧化物表面生成了2，4-，1，2-和1，7-DNPs。室内空气中的NOx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的产率和形成模式不同。因此，形成DNPs的光化学反应的性质因金属氧化物类型的不同而不同。在SiO_2中，辐照至6h，致突变性逐渐增强，6h时的致突变性为260万个/总浸出物，12h时降至150万个/样品。在Al_2O_3中，随着辐照时间的延长，致突变性逐渐增强(164万个回复子/样品)。在二氧化钛中，10min时致突变性迅速降至60%。12h后逐渐下降至22%。反应混合物中产生了三种氯代硝基吡喃(CNP)。在日本京都采集的表层土壤中检测到1-氯-3-硝基并(1，3-CNP)、1，6-CNP和1，8-CNP。首先，以1-硝基吡喃为原料，通过氯化反应合成了1，3-，1，6-和1，8-碳纳米管。采集了日本京都的表层土壤，用二维液相色谱-荧光检测和锌在线催化柱分析了1，3-，1，6-和1，8-GNPs。1，3-CNP、1，6-CNP和1，8-CNP的检出量分别为9.2-13.8、3.4-4.6和4.3-5.0pg/g土壤(n=2)。较少

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