大气臭氧被动采样方法及其Δ<sup>17</sup>O测定的研究

引用本文: 李裕文, 赵祝钰, 曹芳, 周雨辰, 周苇菁, 杨笑影, 俞浩然, 章炎麟. 大气臭氧被动采样方法及其Δ¹⁷O测定的研究[J]. 分析化学, 2022, 50(5): 801-809. doi: 10.19756/j.issn.0253-3820.210798 shu

Citation: LI Yu-Wen, ZHAO Zhu-Yu, CAO Fang, ZHOU Yu-Chen, ZHOU Wei-Jing, YANG Xiao-Ying, YU Hao-Ran, ZHANG Yan-Lin. Passive Sampling of Atmospheric Ozone and Determination of Δ¹⁷O[J]. Chinese Journal of Analytical Chemistry, 2022, 50(5): 801-809. doi: 10.19756/j.issn.0253-3820.210798 shu

大气臭氧被动采样方法及其Δ¹⁷O测定的研究

1.
南京信息工程大学应用气象学院, 南京 210044;
2.
南京信息工程大学教育部气候与环境变化国际合作联合实验室, 大气环境中心, 南京 210044

通讯作者: 曹芳,E-mail:caofang@nuist.edu.cn; 章炎麟,E-mail:dryanlinzhang@outlook.com

基金项目:
国家自然科学基金项目（Nos.41977305，41977185）、江苏省双创团队项目（2018）、江苏省自然科学基金项目（No.BK20180040）和江苏省"333人才工程"项目（No.RRA2020068）资助。

摘要: 基于被动采样方法，使用亚硝酸盐涂覆的被动采样器，对大气中臭氧（O₃）进行采集，采样周期为1周。将大气O₃转化为吸附膜上的硝酸盐，通过加入一定浓度的氨基磺酸将剩余的亚硝酸盐去除后，加入适量NaOH中和，调节溶液pH值，最后采用反硝化细菌法将硝酸盐转化为N₂O，进入800℃金管高温裂解为N₂和O₂，将测定的δ¹⁸O和δ¹⁷O值换算为Δ¹⁷O （Δ¹⁷O=δ¹⁷O-0.52δ¹⁸O），根据国际标准样品（USGS34和USGS35）建立的标准曲线获取硝酸盐的Δ¹⁷O真实值，并进一步换算为大气中O₃的Δ¹⁷O值。研究结果表明，加入0.5 mL氨基磺酸（1 mol/L），振荡15 min可完全去除亚硝酸盐，且对硝酸盐同位素值测定无影响；使用99.999% NaNO₂可更好地降低试剂中NO^-₃导致的空白效应，从而减小对同位素值测定的影响；O₃转化生成的硝酸盐含量应高于6 μg NO^-₃-N，此时测得Δ¹⁷O的标准偏差为0.29‰（n=3）。通过本方法对南京市春季的大气被动采集O₃样品进行分析，换算得到O₃的Δ¹⁷O=26.59‰±1.41‰，与主动采集样品的值基本一致。被动采集方法具有成本低、仪器便携性好、耗能小等优点，其同位素值测量结果表明，被动采样是一种可行性高的采样方法，可用于大气O₃氧同位素异常值研究。

关键词:

English

Passive Sampling of Atmospheric Ozone and Determination of Δ¹⁷O

1.
School of Applied Meteorology, Nanjing University of Information Science and Technology, Nanjing 210044, China;
2.
Atmospheric Environment Center, Joint Laboratory for International Cooperation on Climate and Environmental Change, Ministry of Education, Nanjing University of Information Science and Technology. Nanjing 210044, China

Corresponding author: CAO Fang, ; ZHANG Yan-Lin,

Received Date: 19 October 2021
Revised Date: 15 January 2022
Fund Project:
Supported by the National Natural Science Foundation of China (Nos.41977305, 41977185), the Jiangsu Innovation & Entrepreneurship Team (2018), the Provincial Natural Science Foundation of Jiangsu Province, China (No.812 BK20180040) and the "333 Talent Project" of Jiangsu Province, China (No.RRA2020068).

Abstract: As an air pollutant, tropospheric ozone (O₃) is also a precursor of atmospheric nitrate. Its oxygen isotope abnormal (Δ¹⁷O) can be used to trace atmospheric nitrate and other atmospheric chemical processes.This research was based on the passive sampling method, and the O₃ in the atmosphere was collected using a passive sampler coated with nitrite. The sampling period was one week. The atmospheric O₃ was converted into nitrate on the adsorption filter membrane, the remaining nitrite was removed by adding a certain concentration of sulfamic acid, and then the corresponding concentration of sodium hydroxide was added to neutralize the pH of the solution. Nitrate was converted into N₂O by the denitrifying bacteria method, and the produced N₂O entered the gold tube at 800℃ to be pyrolyzed into N₂ and O₂. The δ¹⁸O and δ¹⁷O values of oxygen were measured and converted to Δ¹⁷O (Δ¹⁷O=δ¹⁷O-0.52δ¹⁸O). With the help of international samples with known Δ¹⁷O values (USGS34 and USGS35), a Δ¹⁷O standard curve was established to convert the Δ¹⁷O of real nitrates, and finally converted to the value of Δ¹⁷O in atmospheric ozone. The research results showed that adding 0.5 mL of sulfamic acid (1 mol/L) to the reaction and shaking for 15 min could completely remove nitrite without affecting the isotope value of nitrate. The use of 99.999% sodium nitrite could better reduce the blank effect caused by nitrate in the drug, thereby reducing the impact on the isotope value. The content of nitrate generated by O₃ conversion should be higher than 6 μg of NO₃-N, and the standard deviation of Δ¹⁷O measured at this time was 0.29‰ (n=3). This method was used to analyze the passively collected O₃ samples in Nanjing spring, and the Δ¹⁷O value of O₃was 26.59‰±1.41‰, which was consistent with the actively collected value and similar to previous research results. Passive sampling method had many advantages such as low price, good portability and low energy consumption. Its isotope value measurement results showed that the passive sampling was a highly feasible sampling method and could be used in the study of atmospheric O₃ oxygen isotope abnormal values.

Key words:

1. [1]
  ALEXANDER B, SHERWEN T, HOLMES C D, FISHER J A, CHEN Q, EVANS M J, KASIBHATLA P. Atmos. Chem. Phys., 2020, 20(6):3859-3877.ALEXANDER B, SHERWEN T, HOLMES C D, FISHER J A, CHEN Q, EVANS M J, KASIBHATLA P. Atmos. Chem. Phys., 2020, 20(6):3859-3877.
2. [2]
  VICARS W C, BHATTACHARYA S K, ERBLAND J, SAVARINO J. Rapid Commun. Mass Spectrom., 2012, 26(10):1219-1231.VICARS W C, BHATTACHARYA S K, ERBLAND J, SAVARINO J. Rapid Commun. Mass Spectrom., 2012, 26(10):1219-1231.
3. [3]
  YU Hao-Ran, CAO Fang, ZHANG Wen-Qi, ZHAO Zhu-Yu, ZHANG Yan-Lin. Chin. J. Anal. Chem., 2021, 49(2):253-262. 俞浩然, 曹芳, 张雯淇, 赵祝钰, 章炎麟. 分析化学, 2021, 49(2):253-262.
4. [4]
  ZHAO Zhu-Yu, CAO Fang, ZHANG Wen-Qi, ZHAI Xiao-Yao, FANG Yan, FAN Mei-Yi, ZHANG Yan-Lin. Chin. J. Anal. Chem., 2019, 47(6):907-915. 赵祝钰, 曹芳, 张雯淇, 翟晓瑶, 方言, 范美益, 章炎麟. 分析化学, 2019, 47(6):907-915.
5. [5]
  HE P, XIE Z, CHI X Y, YU X W. Atmos. Chem. Phys., 2018, 18(19):14465-14476.HE P, XIE Z, CHI X Y, YU X W. Atmos. Chem. Phys., 2018, 18(19):14465-14476.
6. [6]
  ZONG Z, WANG X P, TIAN C G, CHEN Y J, FANG Y T, ZHANG F, LI C, SUN J Z, LI J, ZHANG G. Environ. Sci. Technol., 2017, 51(11):5923-5931.ZONG Z, WANG X P, TIAN C G, CHEN Y J, FANG Y T, ZHANG F, LI C, SUN J Z, LI J, ZHANG G. Environ. Sci. Technol., 2017, 51(11):5923-5931.
7. [7]
  ZHANG Wen-Qi, ZHANG Yan-Lin. Chin. Sci. Bull., 2019, 64(7):649-662. 张雯淇, 章炎麟. 科学通报, 2019, 64(7):649-662.
8. [8]
  ISHINO S, HATTORI S, SAVARINO J, JOURDAIN B, PREUNKERT S, LEGRAND M, CAILLON N, BARBERO A, KURIBAYASHI K, YOSHIDA N. Atmos. Chem. Phys., 2017, 17(5):3713-3727.ISHINO S, HATTORI S, SAVARINO J, JOURDAIN B, PREUNKERT S, LEGRAND M, CAILLON N, BARBERO A, KURIBAYASHI K, YOSHIDA N. Atmos. Chem. Phys., 2017, 17(5):3713-3727.
9. [9]
  SAVARINO J, BHATTACHARYA S K, MORIN S, BARONI M. J. Chem. Phys., 2008, 128(19):194303.SAVARINO J, BHATTACHARYA S K, MORIN S, BARONI M. J. Chem. Phys., 2008, 128(19):194303.
10. [10]
  JOHNSTON J C, THIEMENS M H. J. Geophys. Res.:Atmos., 1997, 102(D21):25395-25404.JOHNSTON J C, THIEMENS M H. J. Geophys. Res.:Atmos., 1997, 102(D21):25395-25404.
11. [11]
  KRANKOWSKY D, BARTECKI F, KLEES G G, MAUERSBERGER K, SCHELLENBACH K, STEHR J. Geophys. Res. Lett., 1995, 22(13):1713-1716.KRANKOWSKY D, BARTECKI F, KLEES G G, MAUERSBERGER K, SCHELLENBACH K, STEHR J. Geophys. Res. Lett., 1995, 22(13):1713-1716.
12. [12]
  BAO H, THIEMENS M H, FARQUHAR J, CAMPBELL D A, LEE C C, HEINE K, LOOPE D B. Nature, 2000, 406(6792):176-178.BAO H, THIEMENS M H, FARQUHAR J, CAMPBELL D A, LEE C C, HEINE K, LOOPE D B. Nature, 2000, 406(6792):176-178.
13. [13]
  BÖHLKE J K, ERICKSEN G E, REVESZ K. Chem. Geol., 1997, 136(1-2):135-152.BÖHLKE J K, ERICKSEN G E, REVESZ K. Chem. Geol., 1997, 136(1-2):135-152.
14. [14]
  GONG Yi-Ran, JING Wan-Jun. Environ. Prot. Circ. Econ., 2001, (3):46-48. 贡轶然, 荆万钧. 环境保护与循环经济, 2001, (3):46-48.
15. [15]
  TANG Can, ZENG Qing-Ru, JIANG Zhao-Hui, ZHOU Xi-Hong, ZHONG Ning. J. Saf. Environ., 2004, (4):13-16. 汤灿, 曾清如, 蒋朝晖, 周细红, 钟宁. 安全与环境学报, 2004, (4):13-16.
16. [16]
  ZHAO Yang, SHAO Min, WANG Chen, WANG Bo-Guang, LU Si-Hua, ZHONG Liu-Ju. Environ. Sci., 2011, 32(2):324-329. 赵阳, 邵敏, 王琛, 王伯光, 陆思华, 钟流举. 环境科学, 2011, 32(2):324-329.
17. [17]
  LUO Yu-Han, LIU Wen-Qing, BIAN Lin-Gen, LU Chang-Gui, XIE Pin-Hua, SI Fu-Qi, SUN Li-Guang. Spectrosc. Spectral Anal., 2011, 31(2):456-460. 罗宇涵, 刘文清, 卞林根, 逯昌贵, 谢品华, 司福祺, 孙立广. 光谱学与光谱分析, 2011, 31(2):456-460.
18. [18]
  CARMICHAEL G R, FERM M, THONGBOONCHOO N, WOO J H, CHAN L Y, MURANO K, VIET P H, MOSSBERG C, BALA R, BOONJAWAT J, UPATUM P, MOHAN M, ADHIKARY S P, SHRESTHA A B, PIENAAR J J, BRUNKE E B, CHEN T, JIE T, DING G, PENG L C, DHIHARTO S, HARJANTO H, JOSE A M, KIMANI W, KIROUANE A, LACAUX J P, RICHARD S, BARTUREN O, CERDA J C, ATHAYDE A, TAVARES T, COTRINA J S, BILICI E. Atmos. Environ., 2003, 37(9-10):1293-1308.CARMICHAEL G R, FERM M, THONGBOONCHOO N, WOO J H, CHAN L Y, MURANO K, VIET P H, MOSSBERG C, BALA R, BOONJAWAT J, UPATUM P, MOHAN M, ADHIKARY S P, SHRESTHA A B, PIENAAR J J, BRUNKE E B, CHEN T, JIE T, DING G, PENG L C, DHIHARTO S, HARJANTO H, JOSE A M, KIMANI W, KIROUANE A, LACAUX J P, RICHARD S, BARTUREN O, CERDA J C, ATHAYDE A, TAVARES T, COTRINA J S, BILICI E. Atmos. Environ., 2003, 37(9-10):1293-1308.
19. [19]
  SWARTZ J S, VAN ZYL P G, BEUKES J P, LABUSCHAGNE C, BRUNKE E G, PORTAFAIX T, GALY-LACAUX C, PIENAARJ J. Atmos. Environ., 2020, 222:117128.SWARTZ J S, VAN ZYL P G, BEUKES J P, LABUSCHAGNE C, BRUNKE E G, PORTAFAIX T, GALY-LACAUX C, PIENAARJ J. Atmos. Environ., 2020, 222:117128.
20. [20]
  ALBERTIN S, SAVARINO J, BEKKI S, BARBERO A, CAILLON N. Atmos. Chem. Phys., 2021, 21(13):10477-10497.ALBERTIN S, SAVARINO J, BEKKI S, BARBERO A, CAILLON N. Atmos. Chem. Phys., 2021, 21(13):10477-10497.
21. [21]
  VICARS W C, SAVARINO J. Geochim. Cosmochim. Acta, 2014, 135:270-287.VICARS W C, SAVARINO J. Geochim. Cosmochim. Acta, 2014, 135:270-287.
22. [22]
  SAVARD M M, COLE A S, VET R, SMIRNOFF A. Atmos. Chem. Phys., 2018, 18(14):10373-10389.SAVARD M M, COLE A S, VET R, SMIRNOFF A. Atmos. Chem. Phys., 2018, 18(14):10373-10389.
23. [23]
  GRANGER J, SIGMAN D M. Rapid Commun. Mass Spectrom., 2009, 23(23):3753-3762.GRANGER J, SIGMAN D M. Rapid Commun. Mass Spectrom., 2009, 23(23):3753-3762.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

大气臭氧被动采样方法及其Δ¹⁷O测定的研究

通讯作者: 曹芳,E-mail:caofang@nuist.edu.cn; 章炎麟,E-mail:dryanlinzhang@outlook.com

English

Passive Sampling of Atmospheric Ozone and Determination of Δ¹⁷O

Corresponding author: CAO Fang, ; ZHANG Yan-Lin,

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

大气臭氧被动采样方法及其Δ17O测定的研究

通讯作者: 曹芳,E-mail:caofang@nuist.edu.cn; 章炎麟,E-mail:dryanlinzhang@outlook.com

English

Passive Sampling of Atmospheric Ozone and Determination of Δ17O

Corresponding author: CAO Fang, ; ZHANG Yan-Lin,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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Passive Sampling of Atmospheric Ozone and Determination of Δ¹⁷O

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