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

在氙灯照射下，在室内空气中与 1-硝基芘和氯化钠存在下，金属氧化物中作为 scil 组分形成氯硝基芘和二硝基芘

• 批准号: 15590116
• 负责人: HIRAYAMA Teruhisa
• 金额: $ 1.98万
• 依托单位: Kyoto Pharmaceutical Universty
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15590116/
• 关键词: nitropyrene; dinitropyrene; nitration; xenon lamp irradiation; metallic oxides; soil components; mutaqenicity; Ames test

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

以3种金属氧化物为土壤组分，在氙灯照射下，研究了1-硝基芘（1-NP）与氯离子混合物在室内空气中的反应产物。用苯：乙醇（4：1，v/v）提取1-NP，用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，1-NP的含量随着照射时间的延长而逐渐减少。特别是在TiO_2中，1-NP在整个辐照时间内都比其它两种金属氧化物有很大程度的降低。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，6种DNP均被检测到;在SiO_2中，除2，4-DNP外，其它5种DNP均被检测到。特别是在TiO_2中，1，7-DNP的生成量比其它两种金属氧化物都要多 ...更多信息 行动时间。推测1-NP通过OH自由基的光化学反应生成4-和2-NP，这些异构体通过硝化反应连续生成2，4-、1，2-和1，7-DNPs。通过1-NP-NOx-Cl离子的光化学反应体系，首次证实了2，4-、1，2-和1，7-DNP在金属氧化物上的形成。室内空气中的NOx被证明是在这些金属氧化物中形成DNP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，DNP形成中的光化学反应的性质根据金属氧化物的类型而不同。在SiO_2中，致突变性逐渐增加，直至照射6小时，致突变效力在6小时时为260万回复突变体/总提取物，然后在12小时时降至150万回复突变体/样品。在Al_2O_3中，诱变性随着照射时间的延长而逐渐增加（164万回复突变体/样品）。在TiO_2中，致突变性在10分钟时迅速下降到60%，在12小时时逐渐下降到22%。在反应混合物中产生三种氯硝基芘（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，通过1-硝基芘的氯化来合成1，3-、1，6-和1，8-CNP。在日本京都采集表层土壤样品，通过二维高效液相色谱荧光检测和锌在线催化柱分析1，3-、1，6-和1，8-GNP。每克土壤中检测到的1，3-CNP、1，6-CNP和1，8-CNP的范围分别为9.2-13.8、3.4-4.6和4.3-5.0 pg（n=2）。少

项目成果

Mutagenic activity and quantification of nitroarenes in surface soil in the Kinki region of Japan

日本近畿地区表层土壤中硝基芳烃的诱变活性和定量

• 发表时间: 2003
• 期刊: Mutation Res. 538
• 作者: T.Watanabe;T.Hasei;Y.Takahashi;S.Otake;T.Murahashi;T.Takamura;T.Hirayama;K.Wakabayashi
• 通讯作者: K.Wakabayashi

Detection of Mutagenic 1-Chloro-3-,6-,and -8-Nitropyrenes in Surface Soil Collected in Kyoto, Japan

日本京都收集的表土中致突变 1-Chloro-3-,6-, 和 -8-硝基芘的检测

• 发表时间: 2004
• 期刊: Journal of Health Science 50・6
• 作者: Tsuyoshi Murahashi;Mitokazu Kawabata;Hidetoshi Sugiyama;Tomohiro Hasei;Tetsushi Watanabe;Teruhisa Hirayama
• 通讯作者: Teruhisa Hirayama

T.Watanabe, T.Hasei, Y.Takahashi, S.Otake, T.Murahashi, T.Takamura, T.Hirayama, K.Wakabayashi: "Mutagenic activity and quantification of nitroarenes in surface soil in the Kinki region of Japan"Mutation Res.. 538. 121-131 (2003)

T.Watanabe、T.Hasei、Y.Takahashi、S.Otake、T.Murahashi、T.Takamura、T.Hirayama、K.Wakabayashi：“日本近畿地区表层土壤中硝基芳烃的诱变活性和定量”突变

Detection of Mutagenic 1-Chloro-3-,-6-, and -8-Nitropyrenes in Surface Soil Collected in Kyoto, Japan

日本京都收集的表层土壤中致突变性 1-Chloro-3-、-6- 和 -8-硝基芘的检测

• 发表时间: 2004
• 期刊: Journal of Health Science 50
• 作者: Teruhisa Hirayama;et al.
• 通讯作者: et al.

H.Sugiyama, T.Watanabe, T.Murahashi, T.Hirayama: "Formation of 1,3-, 2,4-, 1,2-, 1,6-, 1,8- and 1,7-Dinitropyrenes in Metallic Oxides as Soil Components in the Presence of Indoor Air with 1-Nitropyrene and Sodium Chloride Under Xenon Lamp Irradiation"Jour

H.Sugiyama、T.Watanabe、T.Murahashi、T.Hirayama：“1,3-、2,4-、1,2-、1,6-、1,8- 和 1,7-二硝基芘的形成