便携式SERS传感器的近岸海水中PAHs检测
|
摘要
为实现海水中痕量多环芳烃(Polycyclic Aromatic Hydrocarbons, PAHs)的现场快速、高灵敏度检测,研制了便携式高灵敏度表面增强拉曼散射(Surface-enhanced Raman Scattering, SERS)传感器,将倒置的望远镜结构应用于外置光路模块,使光路的效率提高到商业化光纤拉曼探头的3.7倍,光路全长约120 mm,系统尺寸为350 mm×300 mm×180 mm,质量约15 kg,功耗约30 W,满足现场探测便携式的要求。利用该传感器对青岛岸边海水中PAHs进行现场检测,发现了萘、菲、屈菲、苯并(k)荧蒽、苯并(b)荧蒽、苯并(a)芘等的信号,检测结果得到气相色谱(Gas Chromatography, GC)的证实,且检测到GC法难以检测到的易挥发性物质萘。对青岛近海石老人海域和麦岛海域的现场船载检测发现:石老人海域随离岸距离的增加,PAHs种类和含量分布稳定;麦岛海域PAHs随离岸距离的增加,种类和含量均明显减少。结果表明,自主研发的SERS传感器具有便携、快速、高灵敏度的特点,可为近岸海域有机污染物PAHs的监测提供依据。
To realise the on-site, rapid and high sensitivity detection of trace polycyclic aromatic hydrocarbons(PAHs) in coastal water, a portable high-sensitive surface-enhanced Raman scattering sensor was developed, and a high-efficiency outside optical path of spectrometer assembled with inverted telescope structure was applied, which optimized the collection efficiency around 3.7 times better than a commercial optical probe, and the optical path was about 120 mm long. A high sensitive surface-enhanced Raman scattering(SERS) sensor was also established with 350 mm ×300 mm ×180 mm, 15 kg quality and 30 W power consumption, which can satisfy the portable requirements in on-site detection.PAHs in coastal sea water were detected on-site using this sensor, and signals of naphthalene,acenaphthylene, phenanthrene, chrysene, benzo(k) fluoranthene, benzo(b) fluoranthene, benzo(a) pyrene and so on were recognized. Meanwhile, the results were confirmed by the gas chromatography(GC).Besides, volatile naphthalene was discriminated by SERS but wasn′ t recognized by GC. SERS detection of Shilaoren and Maidao area of Qingdao coastal area showed that in Shilaoren coastal area, with the increase of offshore distance, the contents and concentration of PAHs were similar, but in Maidao coastal area, the contents and concentration of PAHs reduced significantly. The results indicate that SERS sensor is portable, convenient and with high sensitivity, and can provide data for PAHs monitoring in the high pollution area.
To realise the on-site, rapid and high sensitivity detection of trace polycyclic aromatic hydrocarbons(PAHs) in coastal water, a portable high-sensitive surface-enhanced Raman scattering sensor was developed, and a high-efficiency outside optical path of spectrometer assembled with inverted telescope structure was applied, which optimized the collection efficiency around 3.7 times better than a commercial optical probe, and the optical path was about 120 mm long. A high sensitive surface-enhanced Raman scattering(SERS) sensor was also established with 350 mm ×300 mm ×180 mm, 15 kg quality and 30 W power consumption, which can satisfy the portable requirements in on-site detection.PAHs in coastal sea water were detected on-site using this sensor, and signals of naphthalene,acenaphthylene, phenanthrene, chrysene, benzo(k) fluoranthene, benzo(b) fluoranthene, benzo(a) pyrene and so on were recognized. Meanwhile, the results were confirmed by the gas chromatography(GC).Besides, volatile naphthalene was discriminated by SERS but wasn′ t recognized by GC. SERS detection of Shilaoren and Maidao area of Qingdao coastal area showed that in Shilaoren coastal area, with the increase of offshore distance, the contents and concentration of PAHs were similar, but in Maidao coastal area, the contents and concentration of PAHs reduced significantly. The results indicate that SERS sensor is portable, convenient and with high sensitivity, and can provide data for PAHs monitoring in the high pollution area.
引文
[1] Yang Renjie, Dong Guimei, Yang Yanrong, et al. Effect of soil particle size on fluorescence characteristics of anthracene and its correction[J]. Optics and Precision Engineering, 2016, 24(11):2665-2671.(in Chinese)
[2] Yuan Yuanyuan, Wang Shutao, Wang Yutian, et al.Denoising of polycyclic aromatic hydrocarbons spectra based on EMD and mathematical morphology[J]. Acta Optica Sinica, 2017, 37(6):303-312.(in Chinese)
[3] Jiang Hong, Fan Ye, Wang Jiageng, et al. Study on the test of rubber soles by X-Ray fluorescent spectrum[J]. Infrared and Laser Engineering, 2017, 46(10):1023002.(in Chinese)
[4] Fleischmann M, Hendra P J, McQuillan A J. Raman spectra of pyridine adsorbed at a silver electrode[J].Chemical Physics Letters, 1974, 26(2):163-166.
[5] Jeanmaire D L, Van Duyne R P. Surfa ce Raman spectroelectrochemistry:Part I. Heterocyclic, aromatic,and aliphatic amines adsorbed on the anodized silver electrode[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1977, 84(1):1-20.
[6] Zhang Ming, Zhu Shaoling, Gao Fei, et al. Breast cancer oxyhemoglobin surface enhanced Raman spectroscopy[J]. Infrared and Laser Engineering,2017, 46(4):0433001.(in Chinese)
[7] Chu Xueying, Sha Xue, Xu Mingze, et al. Application of Raman scattering properties of transition metal dichalcogenides in immunoassays[J]. Optics and Precision Engineering, 2017, 26(3):572-577.(in Chinese)
[8] Péron O, Rinnert E, Lehaitre M, et al. Towards in situ detection of PAH trace in seawater using SERS-active sensors[C]//SPIE, 2009, 7312:73120D.
[9] Kolomijeca A, Kwon Y H, Kronfeldt H D. Surfaceenhanced in-situ Raman-sensor applied in the arctic area for analyses of water and sediment[C]//SPIE, 2012,8366:83660A.
[10] Jia S, Li D, Fodjo E. K, et al. Simultaneous preconcentration and ultrasensitive on-site SERS detection of polycyclic aromatic hydrocarbons in seawater using hexanethiol-modified silver decorated graphene nanomaterials[J]. Analytical Methods, 2016,28(42):7587-7596.
[11] Shi X, Liu S, Han X, et al. High-sensitivity surfaceenhanced Raman scattering(SERS)substrate based on a gold colloid solution with a pH change for detection of trace-level polycyclic aromatic hydrocarbons in aqueous solution[J]. Applied Spectroscopy, 2015, 69(5):574-579.
[12] Lu Zhengwei, Shao Shuai, Ma Yakun. Design of a composite laser beam expander without block[J].Chinese Optics, 2018, 11(4):582-589.(in Chinese)
[13] Ma Jun, Liu Shu, Shi Xiaofeng, et al. Detection and analysia of polycyclic aromatic hydrocarbons using surface-enhanced Raman spectroscopy[J]. Spectroscopy and Spectral Analysis, 2012, 32(9):2452-2457.(in Chinese)
[14] Du J, Xu J, Sun Z, et al. Au nanoparticles grafted on Fe3O4as effective SERS substrates for label-free detection of the 16 EPA priority polycyclic aromatic hydrocar bons[J]. Analytica Chimica Acta, 2016, 915:81-89.
[2] Yuan Yuanyuan, Wang Shutao, Wang Yutian, et al.Denoising of polycyclic aromatic hydrocarbons spectra based on EMD and mathematical morphology[J]. Acta Optica Sinica, 2017, 37(6):303-312.(in Chinese)
[3] Jiang Hong, Fan Ye, Wang Jiageng, et al. Study on the test of rubber soles by X-Ray fluorescent spectrum[J]. Infrared and Laser Engineering, 2017, 46(10):1023002.(in Chinese)
[4] Fleischmann M, Hendra P J, McQuillan A J. Raman spectra of pyridine adsorbed at a silver electrode[J].Chemical Physics Letters, 1974, 26(2):163-166.
[5] Jeanmaire D L, Van Duyne R P. Surfa ce Raman spectroelectrochemistry:Part I. Heterocyclic, aromatic,and aliphatic amines adsorbed on the anodized silver electrode[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1977, 84(1):1-20.
[6] Zhang Ming, Zhu Shaoling, Gao Fei, et al. Breast cancer oxyhemoglobin surface enhanced Raman spectroscopy[J]. Infrared and Laser Engineering,2017, 46(4):0433001.(in Chinese)
[7] Chu Xueying, Sha Xue, Xu Mingze, et al. Application of Raman scattering properties of transition metal dichalcogenides in immunoassays[J]. Optics and Precision Engineering, 2017, 26(3):572-577.(in Chinese)
[8] Péron O, Rinnert E, Lehaitre M, et al. Towards in situ detection of PAH trace in seawater using SERS-active sensors[C]//SPIE, 2009, 7312:73120D.
[9] Kolomijeca A, Kwon Y H, Kronfeldt H D. Surfaceenhanced in-situ Raman-sensor applied in the arctic area for analyses of water and sediment[C]//SPIE, 2012,8366:83660A.
[10] Jia S, Li D, Fodjo E. K, et al. Simultaneous preconcentration and ultrasensitive on-site SERS detection of polycyclic aromatic hydrocarbons in seawater using hexanethiol-modified silver decorated graphene nanomaterials[J]. Analytical Methods, 2016,28(42):7587-7596.
[11] Shi X, Liu S, Han X, et al. High-sensitivity surfaceenhanced Raman scattering(SERS)substrate based on a gold colloid solution with a pH change for detection of trace-level polycyclic aromatic hydrocarbons in aqueous solution[J]. Applied Spectroscopy, 2015, 69(5):574-579.
[12] Lu Zhengwei, Shao Shuai, Ma Yakun. Design of a composite laser beam expander without block[J].Chinese Optics, 2018, 11(4):582-589.(in Chinese)
[13] Ma Jun, Liu Shu, Shi Xiaofeng, et al. Detection and analysia of polycyclic aromatic hydrocarbons using surface-enhanced Raman spectroscopy[J]. Spectroscopy and Spectral Analysis, 2012, 32(9):2452-2457.(in Chinese)
[14] Du J, Xu J, Sun Z, et al. Au nanoparticles grafted on Fe3O4as effective SERS substrates for label-free detection of the 16 EPA priority polycyclic aromatic hydrocar bons[J]. Analytica Chimica Acta, 2016, 915:81-89.