寒冷地区活性氯化学对HONO生消的机理研究  

Mechanism study of active chlorine chemistry on the formation and loss ofHONO in cold regions

作　　者：谢胜金 齐虹[1,2] 修艾军 张学磊 卢露[1,2] 蒋金攀 刘一鸣 李思婷 XIE Shengjin;QI Hong;XIU Aijun;ZHANG Xuelei;LU Lu;JIANG Jinpan;LIU Yiming;LI Siting(State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology,Harbin 150090;School of Environment,Harbin Institute of Technology,Harbin 150090;Northeast Institute of Geography and Agroecology,Chinese Academy of Sciences,Changchun 130102;Guangdong Province Key Laboratory for Climate Change and Natural Disaster Studies,School of Atmospheric Sciences,Sun Yat-sen University,Guangzhou 510275)

机构地区：[1]哈尔滨工业大学城市水资源与水环境国家重点实验室,哈尔滨150090 [2]哈尔滨工业大学环境学院,哈尔滨150090 [3]中国科学院东北地理与农业生态研究所,长春130102 [4]中山大学大气科学学院,广东省气候变化与自然灾害重点实验室,广州510275

出　　处：《环境科学学报》2025年第2期405-417,共13页Acta Scientiae Circumstantiae

基　　金：国家自然科学基金(No.42371154,42171142,42305171);中国科学院青年促进会项目(No.2022230)。

摘　　要：亚硝酸(HONO)是OH自由基的重要前体,在大气化学中发挥着关键作用,但其来源和形成机制尚不明确.CAMx模型中化学机制仅考虑HONO的气相生成反应,导致HONO的模拟结果普遍被低估.东北地区由于冰雪覆盖期较长,可提供足够的气-雪界面,加速了地表非均相化学反应的发生.本研究纳入人为氯排放清单并耦合HONO非均相化学反应,基于CAMx模型探究了东北地区冰雪覆盖条件下活性氯对HONO生成和消耗的影响及其对二次污染的潜在作用.结果发现,哈尔滨和长春及其周边地区的人为氯排放在冬季较为集中,主要源于秸秆焚烧和燃煤供暖.将11个非均相反应纳入CAMx模型后,发现显著提高了模拟的准确性,并促进了颗粒物和臭氧的生成.通过模型敏感性分析揭示,冰雪表面吸附的氯化物(HCl)与HONO的非均相反应是HONO的一个重要汇.研究结果为揭示冰雪覆盖条件下区域尺度HONO生消机制提供了新的视角.Nitrous acid(HONO),a significant precursor to hydroxyl radicals,is pivotal in atmospheric chemistry,yet its sources and formation mechanisms remain elusive.The chemical mechanism embedded in the CAMx model predominantly accounts for the gas-phase generation of HONO,which often resulted in an underestimation of simulated HONO levels.The Northeast region of China with extended period of ice and snow cover,provided an abundance of air-snow interfaces conducive to heterogeneous chemical reactions.This study adopted the anthropogenic chlorine emission inventory and integrated it with the HONO related heterogeneous reactions.Utilizing the CAMx model,we investigated the influence of active chlorine on HONO production and consumption under the ice and snow conditions of Northeast China,as well as its potential contribution to secondary pollution.Our results indicated that anthropogenic chlorine emissions were particularly concentrated in the region of Harbin-Changchun during winter,predominantly from the incineration of straw and coal-burned heating.The incorporation of 11 new heterogeneous reactions into the CAMx model notably enhanced the simulation's accuracies of particulate matters and ozone.A sensitivity analysis of the model underscored that the heterogeneous interaction between ice and snow surface-adsorbed chloride(HCl)and HONO also was a significant HONO sink.These findings offered novel insights into the mechanisms of regional HONO production and consumption under ice and snow conditions.

关 键 词：活性氯化学 亚硝酸 非均相反应 冰雪界面 地表化学 CAMx模型 

分 类 号：X131.1[环境科学与工程—环境科学] X51