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中国物理学会期刊

基于MAX-DOAS的杭州湾BrO及臭氧前体物观测:人为与海洋耦合影响及潜在源贡献分析*

Observation of BrO and ozone precursors in Hangzhou Bay using MAX-DOAS: Anthropogenic-marine coupling and potential source contribution

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  • 活性卤素物种在大气边界层氧化能力调控中发挥着关键作用,但其在人为污染显著的复杂沿海环境中的物理化学行为仍缺乏系统的观测约束.本研究于2024年5月1日至6月15日,基于课题组自主研发的二维多轴差分光学吸收光谱仪(MAX-DOAS),在杭州湾海盐站点开展了一氧化溴(BrO),二氧化氮(NO2),甲醛(HCHO),臭氧(O3)及气溶胶的连续观测.采用SCIATRAN辐射传输模型及基于最优估算法的PriAM廓线反演算法,获取了BrO、NO2和HCHO的对流层垂直廓线及垂直柱浓度,气溶胶消光廓线和气溶胶光学厚度;并以O3 dSCD作为表征臭氧变化的辅助指标;结合后向轨迹与加权潜在源贡献函数(WPSCF)进一步分析了气团来源与潜在源区.结果表明:气溶胶,BrO及臭氧前体物的浓度峰值主要集中在近地面0-1 km层.清洁期(5月21-25日),0-2 km BrO平均体积混合比为5.15 ppt,其变化主要受东海海盐气溶胶非均相活化过程影响;在污染期(6月11-15日)该平均值升至6.69 ppt,并于6月11日达到日均峰值9.74 ppt;且与NO2,HCHO及气溶胶在西南风条件下协同增强.BrO与O3在全观测期呈中等程度负相关(r=-0.46),符合溴介导的臭氧损耗循环特征,但气团输送及O3背景变化对此可能也有贡献.BrO与NO2在0-2 km层整体呈较高正相关,特别是二者均位于0.4-1.6 km时(r=0.58-0.90),提示二者可能存在共同源或耦合反应路径.WPSCF分析表明,清洁期与BrO高值相对应的气团以海洋来源为主,污染期则叠加了来自东南沿海城市群与长三角西部内陆的人为污染输送影响.研究揭示了东亚季风气候下海洋与人为排放对沿海BrO的协同作用,可为复杂海岸环境中活性卤素遥感探测,边界层过程表征及相关物理机制研究提供观测依据.

     

    Reactive halogen species play a key role in regulating the oxidative capacity of the atmospheric boundary layer, yet their behavior in complex coastal environments affected by substantial anthropogenic pollution remains poorly constrained by observations. To address this issue, continuous multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations were conducted at a coastal site in Haiyan, Hangzhou Bay (120.96°E, 30.54°N), from 1 May to 15 June 2024, using a self-developed two-dimensional MAX-DOAS instrument. Bromine monoxide (BrO), NO2, HCHO, O3, and aerosols were simultaneously observed. Spectral fitting was performed with the QDOAS software using dedicated wavelength windows for BrO (346-359 nm), HCHO (336.5-359 nm), O3 (320-340 nm), and NO2/O4 (338-370 nm). Aerosol extinction (AE) profiles, aerosol optical depth (AOD), and the vertical profiles and vertical column densities of BrO, NO2 and HCHO were retrieved with the SCIATRAN radiative transfer model and the PriAM optimal-estimation algorithm. Quality control comprised wavelength calibration against mercury-lamp spectra, dark-current and electronic-offset correction, root-mean-square residual filtering of spectral fits, fitting-error weighting in the optimal estimation, AOD thresholding (AOD > 2), and interquartile-range outlier screening, leaving 26 valid observation days. The retrievals show that BrO, aerosols and ozone precursors were predominantly concentrated within 0-1 km. During the relatively clean period (21-25 May), BrO remained low with weak temporal variability, and its average volume mixing ratio (VMR) below 2 km was 5.15 ppt, comparable to the marine boundary-layer background of 2-10 ppt. During the relatively polluted period (11-15 June), the 0-2 km BrO VMR rose to 6.69 ppt and reached a daily-mean maximum of 9.74 ppt on 11 June (AE = 1.13 km-1), coinciding with elevated NO2, HCHO and AOD under weak southwesterly winds (wind direction ~210°, wind speed < 3 m/s); the vertical stratification was more pronounced than in the clean period. Over the whole campaign, the differential slant column densities (dSCDs) of BrO and O3 were moderately anticorrelated (r= -0.46, p < 0.001), consistent with brominemediated ozone depletion, although NO titration, air-mass transport, background O3 variability, aerosol heterogeneous reactions and boundary-layer photochemistry may also contribute. BrO and NO2 remained positively correlated throughout 0-2 km, most strongly at 0.4-1.6 km (r ≈ 0.58-0.90), suggesting shared sources or coupled reaction pathways. A stratified analysis based on near-surface AE terciles showed that the mean BrO concentration in the high-AE group was about 3.24 times that in the low-AE group, with a BrO-AE Pearson correlation of r= 0.84 (p < 0.001), indicating that aerosol loading co-varied consistently with BrO within each period. Weighted potential source contribution function (WPSCF) analyses of BrO, AE, NO2 and HCHO indicate that, during the clean period, the high-WPSCF regions were concentrated over the near-shore and marine areas east of the site, pointing to a predominantly marine origin of the associated air masses. During the pollution period, the high-WPSCF regions extended southwestward from Hangzhou Bay toward the Yangtze River Delta hinterland, especially above 500 m, consistent with the enhanced inland transport identified by the trajectory cluster analysis. The spatial overlap among the BrO, AE and NO2 WPSCF distributions across the 200-2000 m layers supports the interpretation that the pollution-period BrO enhancement was jointly modulated by transported aerosols and NO2 together with near-surface environments favorable for heterogeneous bromine activation. These findings highlight the synergistic influence of marine and anthropogenic emissions on coastal BrO chemistry under the East Asian monsoon climate, and provide observational constraints for understanding reactive halogen chemistry in industrialized coastal environments, with implications for regional atmospheric oxidative capacity and photochemical pollution control.

     

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