质子转移反应飞行时间质谱仪(PTR-ToF-MS)高时间分辨在线测定广州环境空气还原性硫化合物
High time resolution online detection of reduced sulfur compounds (RSCs) in ambient air in Guangzhou by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS)
-
摘要: 采用高分辨质子转移反应飞行时间质谱仪（PTR-ToF-MS）对环境空气中还原性含硫化合物（RSCs）进行高时间分辨率在线测量.时间分辨率为2 s时，硫化氢（H2S）、甲硫醇（MeSH）、二甲硫（DMS）和二甲二硫（DMDS）的检测限分别为25、26、22、80 ng·m-3；时间分辨率为10 min时，4种RSCs的检测限全面优于离线测量方法.标准样品10次重复测量表明，RSCs相对标准偏差3O+反应常数k值进行了校正.利用校正后k值对广州环境空气RSCs进行绝对定量，结果与外标法测量结果相对偏差2S、DMDS、DMS和MeSH的浓度水平分别为501±155、1026±388、215±35、120±25 ng·m-3.RSCs日变化呈现差异，H2S、MeSH和DMS浓度日变化规律不明显，而其DMDS则呈现出较为明显的日变化特征.Abstract: High time resolution ambient levels of reduced sulfur compounds(RSCs) were measured online with a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). With a time resolution of 2 s, detection limits of H2S, MeSH, DMS,and DMDS were 25, 26, 22 and 80 ng·m-3, respectively. And with a time resolution of 10 min,the detection limits were lower than those of other offline measurement methods. Ten repetitive trials of standard RSCs mixtures showed that the relative standard deviations were less than 3% while the relative deviations from the authentic concentrations were within 5%. The theoretical rate constants k for the reactions between RSCs and H3O+, were corrected by comparing the theoretically calculated results with those determined by the external standard method. The relative deviations between ambient levels of RSCs theoretically calculated with the corrected rate constants k and those determined by the external standard method were less than 4%. Preliminary one-week online measurements of the RSCs in ambient air in Guangzhou in February 2017 revealed that the average concentrations of H2S, DMDS, DMS and MeSH were 501±155, 1026±388, 215±35 and 120±25 ng·m-3, respectively. The diurnal variations of RSCs showed different patterns:the diurnal variations of H2S,MeSH and DMS were insignificant while DMDS showed distinctive diurnal changes.
-
-
[1] ANDREAE M O and RAEMDONCK H. Dimethyl sulfide in the surface ocean and the marine atmosphere:A global view[J]. Science, 1983, 221(4612):744-747. [2] CLINE J D and BATES T S. Dimethyl sulfide in the Equatorial Pacific Ocean:A natural source of sulfur to the atmosphere[J]. Geophysical Research Letters, 1983, 10(10):949-952. [3] KETTLE A J, KUHN U, VON HOBE M, et al. Global budget of atmospheric carbonyl sulfide:Temporal and spatial variations of the dominant sources and sinks[J]. Journal of Geophysical Research:Atmospheres, 2002, 107(D22):ACH 25-21-ACH 25-16. [4] ENGEL A, SCHMIDT U. Vertical profile measurements of carbonylsulfide in the stratosphere[J]. Geophysical research letters, 1994, 21(20):2219-2222. [5] JAESCHKE W, CLAUDE H and HERRMANN J. Sources and sinks of atmospheric H2S[J]. Journal of Geophysical Research:Oceans, 1980, 85(C10):5639-5644. [6] BENTLEY R, CHASTEEN T G. Environmental VOSCs--formation and degradation of dimethyl sulfide, methanethiol and related materials[J]. Chemosphere, 2004, 55(3):291-317. [7] CHARLSON R J, LOVELOCK J E, ANDREAE M O, et al. Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate[J]. Nature, 1987, 326(6114):655-661. [8] GLASS D. A review of the health effects of hydrogen sulphide exposure[J]. The Annals of occupational hygiene, 1990, 34(3):323-327. [9] MU Y, WU H, ZHANG X, et al. Impact of anthropogenic sources on carbonyl sulfide in Beijing City[J]. Journal of Geophysical Research:Atmospheres, 2002, 107(D24):ACH 13-1-ACH 13-7. [10] 牟玉静, 吴海, 宋文质, 等. 大气中还原态硫化合物的测定[J]. 环境化学, 2003, 22(1):32-37. MU Y J, WU H, SONG W Z, et al. Determinationofthereducedsulfurcompoundsintheair[J]. Environmental Chemistry, 2003, 22(1):32-37(in Chinese).
[11] MU Y J, WU H, WU P Z, et al. Vertical distributions of COS and CS2 in Beijing City[J]. Journal of Environmental Sciences, 2004, 16(2):226-229. [12] 易志刚, 王新明. 预浓缩/色谱-质谱测量大气中挥发性有机硫化合物[J]. 分析测试学报, 2006, z(1):124-126. YI Z G, WANG X M. Determination of volatile organic sulfur compounds in the atmosphere by a proconcentrator/GC-MS[J]. Journal of Instrument Analysis, 2006, z(1):124-126(in Chinese).
[13] 吴婷, 易志刚, 王新明. 吹扫捕集-GC-MS-SIM法测定水中挥发性硫化合物[J]. 分析试验室, 2007, 26(4):54-57. WU T, YI Z G, WANG X M. Determination of volatile sulfur compounds in water by purge and trap preconcentration and gas chromatography-mass spectrometry in SMI mode[J]. Chinese Journal of Analysis Labortory, 2007, 26(4):54-57(in Chinese).
[14] SHENG Y, CHEN F, YU Y, et al. Emission of volatile organic sulfur compounds from a heavily polluted river in Guangzhou, South China[J]. Environmental Monitoring and Assessment, 2008, 143(1):121-130. [15] GUO H, SIMPSON I, DING A, et al. Carbonyl sulfide, dimethyl sulfide and carbon disulfide in the Pearl River Delta of southern China:Impact of anthropogenic and biogenic sources[J]. Atmospheric Environment, 2010, 44(31):3805-3813. [16] BASHKOVA S, BAGREEV A and BANDOSZ T J. Adsorption/oxidation of CH3SH on activated carbons containing nitrogen[J]. Langmuir, 2003, 19(15):6115-6121. [17] ANDERSEN K B, HANSEN M J and FEILBERG A. Minimisation of artefact formation of dimethyl disulphide during sampling and analysis of methanethiol in air using solid sorbent materials[J]. Journal of Chromatography A, 2012, 1245(Supplement C):24-31. [18] LINDINGER W, HANSEL A and JORDAN A. On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research[J]. International Journal of Mass Spectrometry and Ion Processes, 1998, 173(3):191-241. [19] YUAN B, KOSS A R, WARNEKE C, et al. Proton-transfer-reaction mass spectrometry:Applications in atmospheric sciences[J]. Chemical Reviews, 2017, 117(21):13187-13229. [20] CAPPELLIN L, KARL T, PROBST M, et al. On quantitative determination of volatile organic compound concentrations using proton transfer reaction time-of-flight mass spectrometry[J]. Environmental Science & Technology, 2012, 46(4):2283-2290. [21] YI Z G, WANG X M, SHENG G Y, et al. Exchange of carbonyl sulfide (OCS) and dimethyl sulfide (DMS) between rice paddy fields and the atmosphere in subtropical China[J]. Agriculture, Ecosystems & Environment, 2008, 123(1):116-124. [22] WU T, WANG X M, LI D, et al. Emission of volatile organic sulfur compounds (VOSCs) during aerobic decomposition of food wastes[J]. Atmospheric Environment, 2010, 44(39):5065-5071. [23] KABIR E and KIM KH. Use of solid phase microextraction (SPME) in the analysis of the reduced sulfur compounds (RSC) and its experimental limitations[J]. Microchemical Journal, 2012, 103(Supplement C):42-48. [24] SON YS, LEE G, KIM JC, et al. Development of a pretreatment system for the analysis of atmospheric reduced sulfur compounds[J]. Analytical Chemistry, 2013, 85(21):10134-10141. [25] SUSAYA J, KIM K-H, PHAN N-T, et al. Assessment of reduced sulfur compounds in ambient air as malodor components in an urban area[J]. Atmospheric Environment, 2011, 45(20):3381-3390. [26] PERRAUD V, MEINARDI S, BLAKE D, et al. Challenges associated with the sampling and analysis of organosulfur compounds in air using real-time PTR-ToF-MS and off-line GC-FID[J]. Atmospheric Measurement Techniques Discussions, 2015, 8:13157-13197. [27] TANIMOTO H,KAMEYAMA S, IWATA T, et al. Measurement of air-sea exchange of dimethyl sulfide and acetone by PTR-MS coupled with gradient flux technique[J]. Environmental Science & Technology, 2014, 48(1):526-533. [28] 黄昆, 曾立民, 于雪娜, 等. 大气中二甲基硫在线监测技术研发[J]. 环境化学, 2013, 32(11):2162-2169. HUANG K, ZENG L M, YU X N, et al. Online monitoring technique for dimethyl Sulfide in the atmosphere[J]. Environmental Chemistry, 2013, 32(11):2162-2169(in Chinese).
[29] 马奇菊, 胡敏, 田旭东, 等. 青岛近岸海域二甲基硫排放和大气中二甲基硫浓度变化[J]. 环境科学, 2004, 23(1):20-24. MA Q, HU M, TIAN X D, et al. Dimethylsulfide emission in Qingdao near-shore waters and atmosphere dimethylsulfide concentration variation[J]. Environmental Science, 2004, 23(1):20-24(in Chinese).
-
点击查看大图
计量
- 文章访问数: 2739
- HTML全文浏览数: 2700
- PDF下载数: 101
- 施引文献: 0
下载:
