Long Peng

In situ detection of the chemistry of individual fog droplet residues in the Pearl River Delta region, China

We use a single-particle aerosol mass spectrometer (SPAMS) coupled with a ground-based counterflow virtual impactor (GCVI) to measure the chemical compositions of individual submicron fog droplet residues. This is the first report of single-particle mass spectrometry measurements of fog droplet residual particles at ground level in an urban area. We show that most of the fog droplet residues were composed of elemental carbon (EC) (67.7%), followed by K-rich (19.2%) and mineral dust/metal (12.3%) particles. The predominance of EC-containing particles demonstrated that these particles could be effective fog nuclei and highlights the important influence of anthropogenic emissions on regional climate system. Compared with interstitial and ambient aerosols, nitrate was enhanced, sulfate was depressed, and ammonium- and organics-containing particles were hardly found in the fog droplet residues during fog events, suggesting that dust and metal particles containing nitrate may be preferentially activated and that ammonium and organics may not play important roles in fog formation in Guangzhou. We also present direct observational evidence that trimethylamine (TMA) and hydroxymethanesulfonate (HMS) are not found within fog droplet residues, although we previously observed enhanced gas-to-particle partitioning of these compounds by fog processing. Additionally, higher fraction or intensities of [K]+, [Fe]+ and [SiO3]- were found in fog droplet residues than in ambient and interstitial particles.

Insight into the in-cloud formation of oxalate based on in situ measurement by single particle mass spectrometry

While ground-based works suggest the significance of in-cloud production (or aqueous formation) to oxalate, direct evidence is rare. With the in situ measurements performed at a remote mountain site (1690 m above sea level) in southern China, we first reported the size-resolved mixing state of oxalate in the cloud droplet residual (cloud RES), the cloud interstitial (cloud INT), and ambient (cloud-free) particles by single particle mass spectrometry. The results support the growing evidence that in-cloud aqueous reactions promote the formation of oxalate, with ∼ 15 % of the cloud RES and cloud INT particles containing oxalate in contrast to only ∼ 5 % of the cloud-free particles. Furthermore, individual particle analysis provides unique insight into the formation of oxalate during in-cloud processing. Oxalate was predominantly (> 70 % in number) internally mixed with the aged biomass-burning particles, highlighting the impact of biomass burning on the formation of oxalate. In contrast, oxalate was underrepresented in aged elemental carbon particles, although they represented the largest fraction of the detected particles. It can be interpreted by the individual particle mixing state that the aged biomass-burning particles contained an abundance of organic components serving as precursors for oxalate. Through the analysis of the relationship between oxalate and organic acids (−45[HCO2], −59[CH3CO2],−71[C2H3CO2],−73[C2HO3]), the results show that in-cloud aqueous reactions dramatically improved the conversion of organic acids to oxalate. The abundance of glyoxylate associated with the aged biomassburning particles is a controlling factor for the in-cloud production of oxalate. Since only limited information on oxalate is available in the free troposphere, the results also provide an important reference for future understanding of the abundance, evolution, and climate impacts of oxalate.

Oxalate Formation Enhanced by Fe-Containing Particles and Environmental Implications

We used a single particle mass spectrometry to online detect chemical compositions of individual particles over four seasons in Guangzhou. Number fractions (Nfs) of all the measured particles that contained oxalate were 1.9%, 5.2%, 25.1%, and 15.5%, whereas the Nfs of Fe-containing particles that were internally mixed with oxalate were 8.7%, 23.1%, 45.2%, and 31.2% from spring to winter, respectively. The results provided the first direct field measurements for the enhanced formation of oxalate associated with Fe-containing particles. Other oxidized organic compounds including formate, acetate, methylglyoxal, glyoxylate, purivate, malonate, and succinate were also detected in the Fe-containing particles. It is likely that reactive oxidant species (ROS) via Fenton reactions enhanced the formation of these organic compounds and their oxidation product oxalate. Gas-particle partitioning of oxalic acid followed by coordination with Fe might also partly contribute to the enhanced oxalate. Aerosol water content likely played an important role in the enhanced oxalate formation when the relative humidity is >60%. Interactions with Fe drove the diurnal variation of oxalate in the Fe-containing particles. The study could provide a reference for model simulation to improve understanding on the formation and fate of oxalate, and the evolution and climate impacts of particulate Fe.