Naturally produced organohalogens; Atmospheric simulation experiments on halogen activation in aerosol smog chamber facilities with sea salt and secondary organic aerosol (HALOSOA)

大陆和海洋气团的混合导致活性卤素与土壤中的腐殖化合物和类腐殖物质（HULIS）的相互作用，最近才发现这是一种普遍存在的气溶胶成分--众所周知的二次有机气溶胶（SOA），主要来自天然碳氢化合物的气体到颗粒的转化。来自海喷雾的卤化物通过涉及臭氧、OH自由基和其他光氧化剂的光化学、非均相相互作用被氧化成卤化化合物，其中氮的活性氧化物（NO、NO2、NO3、N2 O 5）和酸起决定性作用。所得的活化卤素（X、X2、XY、XO、HOX、XNO、XNO 2、XONO 2，其中卤素X、Y = Cl、Br和I）可形成有机卤素化合物，其中一些是气态的，其中一些保留在颗粒中。本研究的目的是模拟这种环境情况（涵盖从盐湖和火山羽流通过海洋边界层到北极条件的全部范围）进行气溶胶烟雾室实验，并通过各种技术进行研究，通过特定指示剂的时间曲线的自由基时钟和直接差分光腔增强吸收光谱（DOAS和CEAS），以及通过特定技术检测气相和颗粒相中的卤代有机物，例如GC-ECD、GC-HID、GC-MS、TPP-MS、直接气溶胶-MS、离子色谱和HPLC-DAD（包括来自外部合作者和活动嘉宾的ICR-FTMS、AMS和CIMS）。Cl、Br和I对这些地球化学循环的贡献由各种支持性实验解决，更不用说将外推到对流层边界层的室内实验中的观测结果的强制性模型计算。

Zusammenfassung (deutsch)Mixing of continental and marine air masses causes an interaction of activated halogens with humic compounds from soil and humic-like substances (HULIS), detected only recently as an ubiquitous aerosol constituent – the well-known secondary organic aerosol (SOA) from gas-to-particle conversion of mainly natural hydrocarbons. The halides from sea-spray are oxidized to halogenating compounds by photochemical, heterogeneous interactions involving ozone, OH radicals and other photooxidants, where reactive oxides of nitrogen (NO, NO2, NO3, N2O5) and acids play a decisive role. The resulting activated halogens (X, X2, XY, XO, HOX, XNO, XNO2 XONO2 with halogens X, Y = Cl, Br and I) may form organohalogen compounds, some of which are gaseous and some of which remain in the particles. The goal of the present study is to simulate this environmental situation (covering the full range from salt lakes and volcanic plumes via marine boundary layer to arctic conditions) in aerosol smog chamber experiments and to investigate it by a large variety of techniques, observing the activated halogens by the radical clock from time profiles of specific indicators and by direct, differential optical and cavity enhanced absorption spectroscopy (DOAS and CEAS), and detecting halogenated organics in gas and particle phase by specific techniques, such as GC-ECD, GC-HID, GC-MS, TPP-MS, direct aerosol-MS, ion chromatography and HPLC-DAD (including ICR-FTMS, AMS and CIMS from external collaborators and guests in campaigns). The contributions of Cl, Br and I to these geochemical cycles are settled by various supporting experiments, not to mention mandatory model calculations of the observations in the chamber experiments to be extrapolated to the boundary layer of the troposphere.