基于NO+ PTR-QMS在线观测评估广州市夏季大气VOCs的光化学损失及二次环境效应

doi:10.16258/j.cnki.1674-5906.2026.01.010

生态环境学报 ›› 2026, Vol. 35 ›› Issue (1): 112-123.DOI: 10.16258/j.cnki.1674-5906.2026.01.010

• 研究论文【环境科学】 • 上一篇下一篇

基于NO⁺ PTR-QMS在线观测评估广州市夏季大气VOCs的光化学损失及二次环境效应

杜若愚(), 马潇瑶, 陈江耀^*()

广东工业大学环境科学与工程学院，广东广州 510006

收稿日期:2025-04-24 修回日期:2025-09-15 接受日期:2025-10-20 出版日期:2026-01-18 发布日期:2026-01-05
通讯作者: * E-mail: chenjiangyao@gdut.edu.cn
作者简介:杜若愚（2000年生），男，硕士研究生，主要研究方向为大气环境。E-mail: 852709866@qq.com
基金资助:
国家自然科学基金项目(42577424);国家自然科学基金项目(42177354)

Photochemical Loss and Secondary Environmental Effects of Summer Atmospheric VOCs in Guangzhou: An Assessment via NO⁺ PTR-QMS Online Observations

DU Ruoyu(), MA Xiaoyao, CHEN Jiangyao^*()

School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, P. R. China

Received:2025-04-24 Revised:2025-09-15 Accepted:2025-10-20 Online:2026-01-18 Published:2026-01-05

摘要/Abstract

摘要： 挥发性有机物（VOCs）作为臭氧（O₃）和二次有机气溶胶（SOA）的关键前体物，其在大气中的光化学行为对城市空气质量影响至关重要。然而，传统基于观测体积分数（VOC_M）的环境效应评估方法因忽略VOCs的光化学损耗，往往导致其环境贡献被低估。于2024年8－10月在广州大学城采用NO⁺ PTR-QMS技术对VOCs进行了高时间分辨率的在线监测，克服了传统PTR-MS对烷烃检测的局限性。结果表明，观测期间广州市大气VOCs平均体积分数为（29.0±0.73）×10⁻⁹，主要组分为烷烃（33.6%）、芳香烃（26.6%）和OVOCs（24.7%），其日间变化呈现与早晚交通高峰活动一致的双峰型特征。VOCs的整体光化学损失率（VOC_L）高达22.3%，其中烯烃损失率最高（50.5%）。考虑光化学损失后，基于VOC_M的传统评估方法显著低估了VOCs的真实环境效应：臭氧生成潜势（OFP）被低估了35.5%，主要由高活性烯烃（丁二烯44.2%、丁烯17.5%）驱动；二次有机气溶胶生成潜势（SOAP）被低估了33.7%，主要由高SOA产率芳烃（苯乙烯73.4%、C9/C8芳香烃）驱动。研究强调，准确评估VOCs环境效应需考虑光化学损失，优先控制高活性烯烃可有效削减O₃生成，而控制高产率芳香烃是降低SOA污染的关键，这为广州市制定精准VOCs减排策略及O₃与PM_2.5协同控制提供了科学依据。

关键词: 广州市, 挥发性有机物, 光化学损失, 二次污染物生成潜势, NO⁺ PTR-QMS

Abstract:

Volatile organic compounds (VOCs) are key precursors of ozone (O₃) and secondary organic aerosols (SOA) and play a crucial role in urban air quality owing to their photochemical behavior in the atmosphere. However, traditional methods for assessing the environmental effects of VOCs based on measured concentrations (VOC_M) often underestimate photochemical losses. This study utilized NO⁺ PTR-QMS for high-time-resolution online monitoring of VOCs in Guangzhou University City during the of 2024 (August-October), overcoming the limitations of traditional PTR-MS in alkane detection. The results showed that during the observation period, the average volume fraction of atmospheric VOCs in Guangzhou was (29.0±0.73)×10⁻⁹, with alkanes (33.6%), aromatics (26.6%), and OVOCs (24.7%) being the main components. The 12h daytime variation in VOCs exhibited a bimodal pattern consistent with the morning and evening traffic peaks. The overall photochemical loss rate of VOCs (VOC_L) was as high as 22.3%, with the highest loss rate observed for alkenes (50.5%). After considering photochemical losses, traditional assessment methods based on VOC_M significantly underestimated the true environmental effects of VOCs: the Ozone Formation Potential (OFP_L) was underestimated by 35.5%, mainly driven by the highly reactive alkenes (butadiene 44.2%, butene 17.5%); the Secondary Organic Aerosol Potential (SOAP_L) was underestimated by 33.7%, mainly driven by high-SOA-yield aromatics (styrene 73.4%, C9/C8 aromatics). This study highlights that an accurate assessment of the environmental effects of VOCs requires consideration of photochemical loss. Prioritizing the control of highly reactive alkenes can effectively reduce O₃ formation, whereas controlling high-yield aromatics is key to reducing SOA pollution, which provides a scientific basis for the development of accurate VOCs emission reduction strategies and synergistic control of O₃ and PM_2.5 in Guangzhou City.

Key words: Guangzhou City, volatile organic compounds, photochemical loss, secondary pollutant formation potential, NO⁺ PTR-QMS

中图分类号:

杜若愚, 马潇瑶, 陈江耀. 基于NO⁺ PTR-QMS在线观测评估广州市夏季大气VOCs的光化学损失及二次环境效应[J]. 生态环境学报, 2026, 35(1): 112-123.

DU Ruoyu, MA Xiaoyao, CHEN Jiangyao. Photochemical Loss and Secondary Environmental Effects of Summer Atmospheric VOCs in Guangzhou: An Assessment via NO⁺ PTR-QMS Online Observations[J]. Ecology and Environmental Sciences, 2026, 35(1): 112-123.

图/表 8

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参数	2024-08-06－2024-08-13	2024-09-24－2024-09-30	2024-10-15－2024-10-21
AQI	44.76±9.55	39.13±12.57	40.92±9.96
PM_2.5质量浓度/(μg∙m⁻³)	29.33±9.37	21.44±7.87	22.84±6.69
PM₁₀质量浓度/(μg∙m⁻³)	48.33±8.02	36.63±12.26	40.37±11.29
NO₂质量浓度/(μg∙m⁻³)	29.05±10.46	28.82±10.94	26.60 ±11.61
SO₂质量浓度/(μg∙m⁻³)	5.75±0.55	6.24±0.85	6.27±0.68
O₃质量浓度/(μg∙m⁻³)	70.79±47.54	63.77±51.45	67.28±40.10
CO质量浓度/(μg∙m⁻³)	0.72±0.08	0.72±0.09	0.71±0.05
温度/℃	31.51±3.03	30.66±2.78	29.67±2.53
相对湿度/%	74.51±13.05	82.48±10.63	79.51±12.54
紫外线强度/(W∙m⁻²)	12.55±15.58	9.05±11.66	10.33±13.35
大气压/hPa	1002.86±3.03	1004.56±1.75	1003.63±3.27
风速/(m∙s⁻¹)	0.86±0.42	0.96 ± 0.63	0.91±0.54

参数	2024-08-06－2024-08-13	2024-09-24－2024-09-30	2024-10-15－2024-10-21
AQI	44.76±9.55	39.13±12.57	40.92±9.96
PM_2.5质量浓度/(μg∙m⁻³)	29.33±9.37	21.44±7.87	22.84±6.69
PM₁₀质量浓度/(μg∙m⁻³)	48.33±8.02	36.63±12.26	40.37±11.29
NO₂质量浓度/(μg∙m⁻³)	29.05±10.46	28.82±10.94	26.60 ±11.61
SO₂质量浓度/(μg∙m⁻³)	5.75±0.55	6.24±0.85	6.27±0.68
O₃质量浓度/(μg∙m⁻³)	70.79±47.54	63.77±51.45	67.28±40.10
CO质量浓度/(μg∙m⁻³)	0.72±0.08	0.72±0.09	0.71±0.05
温度/℃	31.51±3.03	30.66±2.78	29.67±2.53
相对湿度/%	74.51±13.05	82.48±10.63	79.51±12.54
紫外线强度/(W∙m⁻²)	12.55±15.58	9.05±11.66	10.33±13.35
大气压/hPa	1002.86±3.03	1004.56±1.75	1003.63±3.27
风速/(m∙s⁻¹)	0.86±0.42	0.96 ± 0.63	0.91±0.54

序号	质荷比（m/z）	VOCs组分	离子式	类别	灵敏度（cps）	相关性（r²）	背景值（cps）	检测限/(μg∙m⁻³)
1	54	丁二烯	C₄H₆⁺	烯烃	70.68	0.999	11.30	0.021
2	56	丁烯	C₄H₈⁺	烯烃	131.23	0.998	5.13	0.011
3	57	丁烷	C₄H₉⁺	烷烃	540.16	0.991	11.82	0.003
4	59	异丙醇	C₃H₇O⁺	OVOCs	202.97	0.951	21.70	0.007
5	70	戊烯	C₅H₁₀⁺	烯烃	94.49	0.999	4.07	0.015
6	71	戊烷	C₅H₁₁⁺	烷烃	330.59	0.993	16.96	0.005
7	78	苯	C₆H₆⁺	芳香烃	44.16	0.994	2.72	0.034
8	83	甲基环戊烷	C₆H₁₁⁺	烷烃	32.77	0.988	3.23	0.046
9	84	己烯	C₆H₁₂⁺	烯烃	10.77	0.997	2.41	0.139
10	85	甲基戊烷	C₆H₁₃⁺	烷烃	95.8	0.989	4.31	0.016
11	88	丙酮	C₃H₆NO₂⁺	OVOCs	16.36	0.982	3.76	0.092
12	92	甲苯	C₇H₈⁺	芳香烃	81.19	0.995	3.44	0.018
13	97	甲基环己烷	C₇H₁₃⁺	烷烃	35.86	0.998	4.27	0.042
14	99	甲基己烷	C₇H₁₅⁺	烷烃	13.51	0.974	4.00	0.111
15	102	丁酮	C₄H₈NO₂⁺	烯烃	15.59	0.995	2.57	0.096
16	104	苯乙烯	C₈H₈⁺	芳香烃	33.02	0.998	4.04	0.045
17	106	C₈芳香烃	C₈H₁₀⁺	烷烃	312.17	0.991	5.64	0.005
18	113	甲基庚烷	C₈H₁₇⁺	OVOCs	13.47	0.985	2.94	0.111
19	120	C₉芳香烃	C₉H₁₂⁺	芳香烃	479.03	0.990	12.94	0.003
20	130	己酮	C₆H₁₂NO₂⁺	OVOCs	31.02	0.998	2.16	0.048
21	134	C₁₀芳香烃	C₁₀H₁₄⁺	芳香烃	59.2	0.995	2.45	0.025

序号	质荷比（m/z）	VOCs组分	离子式	类别	灵敏度（cps）	相关性（r²）	背景值（cps）	检测限/(μg∙m⁻³)
1	54	丁二烯	C₄H₆⁺	烯烃	70.68	0.999	11.30	0.021
2	56	丁烯	C₄H₈⁺	烯烃	131.23	0.998	5.13	0.011
3	57	丁烷	C₄H₉⁺	烷烃	540.16	0.991	11.82	0.003
4	59	异丙醇	C₃H₇O⁺	OVOCs	202.97	0.951	21.70	0.007
5	70	戊烯	C₅H₁₀⁺	烯烃	94.49	0.999	4.07	0.015
6	71	戊烷	C₅H₁₁⁺	烷烃	330.59	0.993	16.96	0.005
7	78	苯	C₆H₆⁺	芳香烃	44.16	0.994	2.72	0.034
8	83	甲基环戊烷	C₆H₁₁⁺	烷烃	32.77	0.988	3.23	0.046
9	84	己烯	C₆H₁₂⁺	烯烃	10.77	0.997	2.41	0.139
10	85	甲基戊烷	C₆H₁₃⁺	烷烃	95.8	0.989	4.31	0.016
11	88	丙酮	C₃H₆NO₂⁺	OVOCs	16.36	0.982	3.76	0.092
12	92	甲苯	C₇H₈⁺	芳香烃	81.19	0.995	3.44	0.018
13	97	甲基环己烷	C₇H₁₃⁺	烷烃	35.86	0.998	4.27	0.042
14	99	甲基己烷	C₇H₁₅⁺	烷烃	13.51	0.974	4.00	0.111
15	102	丁酮	C₄H₈NO₂⁺	烯烃	15.59	0.995	2.57	0.096
16	104	苯乙烯	C₈H₈⁺	芳香烃	33.02	0.998	4.04	0.045
17	106	C₈芳香烃	C₈H₁₀⁺	烷烃	312.17	0.991	5.64	0.005
18	113	甲基庚烷	C₈H₁₇⁺	OVOCs	13.47	0.985	2.94	0.111
19	120	C₉芳香烃	C₉H₁₂⁺	芳香烃	479.03	0.990	12.94	0.003
20	130	己酮	C₆H₁₂NO₂⁺	OVOCs	31.02	0.998	2.16	0.048
21	134	C₁₀芳香烃	C₁₀H₁₄⁺	芳香烃	59.2	0.995	2.45	0.025

基于NO⁺ PTR-QMS在线观测评估广州市夏季大气VOCs的光化学损失及二次环境效应

Photochemical Loss and Secondary Environmental Effects of Summer Atmospheric VOCs in Guangzhou: An Assessment via NO⁺ PTR-QMS Online Observations

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