Competing esterification and oligomerization reactions of typical long-chain alcohols to secondary organic aerosol formation

Organosulfate (OSA) nanoparticles,as secondary organic aerosol (SOA) compositions,are ubiquitous in urban and rural environments.Hence,we systemically investigated the mechanisms and kinetics of aqueous-phase reactions of 1-butanol/1-decanol (BOL/DOL) and their roles in the formation of OSA nanoparticles by using quantum chemical and kinetic calculations.The mechanism results show that the aqueous-phase reactions of BOL/DOL start from initial protonation at alcoholic OH^(-)groups to form carbenium ions (CBs),which engage in the subsequent esterification or oligomerization reactions to form OSAs/organosulfites (OSIs) or dimers.The kinetic results reveal that dehydration to form CBs for BOL and DOL reaction systems is the rate-limiting step.Subsequently,about 18%of CBs occur via oligomerization to dimers,which are difficult to further oligomerize because all reactive sites are occupied.The rate constant of BOL reaction system is one order of magnitude larger than that of DOL reaction system,implying that relative short-chain alcohols are more prone to contribute OSAs/OSIs than long-chain alcohols.Our results reveal that typical long-chain alcohols contribute SOA formation via esterification rather than oligomerization because OSA/OSI produced by esterification engages in nanoparticle growth through enhancing hygroscopicity.

Insights into the formation of secondary organic carbon in the summertime in urban Shanghai

To investigate formation mechanisms of secondary organic carbon（SOC） in Eastern China,measurements were conducted in an urban site in Shanghai in the summer of 2015. A period of high O3 concentrations（daily peak 〉 120 ppb） was observed, during which daily maximum SOC concentrations exceeding 9.0 μg/（C·m^3）. Diurnal variations of SOC concentration and SOC/organic carbon（OC） ratio exhibited both daytime and nighttime peaks. The SOC concentrations correlated well with Ox（= O3＋ NO2） and relative humidity in the daytime and nighttime, respectively, suggesting that secondary organic aerosol formation in Shanghai is driven by both photochemical production and aqueous phase reactions. Single particle mass spectrometry was used to examine the formation pathways of SOC. Along with the daytime increase of SOC, the number fraction of elemental carbon（EC） particles coated with OC quickly increased from 38.1% to 61.9% in the size range of 250–2000 nm, which was likely due to gas-to-particle partitioning of photochemically generated semi-volatile organic compounds onto EC particles. In the nighttime, particles rich in OC components were highly hygroscopic, and number fraction of these particles correlated well with relative humidity and SOC/OC nocturnal peaks. Meanwhile, as an aqueous-phase SOC tracer, particles that contained oxalate-Fe（III） complex also peaked at night. These observations suggested that aqueous-phase processes had an important contribution to the SOC nighttime formation. The influence of aerosol acidity on SOC formation was studied by both bulk and single particle level measurements, suggesting that the aqueous-phase formation of SOC was enhanced by particle acidity.

四乙基愈创木酚液相·OH氧化SOA产率及特征分析:初始浓度的影响

液相化学过程作为二次有机气溶胶(SOA)形成的一种必不可少的途径,引起了学界对大气化学的广泛关注.由于其反应复杂性,反应机制、产物特性及对SOA质量的贡献还没有完全理解.本文选择四乙基愈创木酚(4-ethylguaiacol,EG)为前体物,系统地研究了初始浓度(0.03、0.3和3 mmol·L-1)的EG液相·OH氧化形成的液相二次有机气溶胶(aqSOA)特性的影响.用黑炭-气溶胶质谱(SP-AMS)测定aqSOA产率和氧化特性,气相色谱-质谱联用仪(GC/MS)、离子色谱(IC)测定产物和低分子有机酸.紫外分光光度计(UV-vis)和高效液相色谱测定了类腐殖质(HULIS)等表征光吸光产物的形成.结果表明,不同初始浓度(mmol·L-1)下aqSOA的O/C都表现为随着反应时间延长而升高,分别在0.42~0.61(0.03 mmol·L-1)、0.49~0.84(0.3 mmol·L-1)和0.49~0.63(3 mmol·L-1)之间变化.SP-AMS测定aqSOA组分发现高初始浓度时二聚体(C16H18O2+,m/z302)量明显高,说明高浓度下更容易发生聚合反应.UV-vis分析表明,随光氧化反应的进行,250 nm处吸光明显增强,可能是由于250 nm处新的吸光性产物生成所致.反应过程中生成的HULIS浓度不断升高,与UV-vis测定的300~400 nm区域内吸光度增强结论一致,说明水相反应形成了棕色碳.IC检测到产物中含有小分子有机酸:甲酸、乙醇酸和草酸其中甲酸浓度最高.GC/MS检测到aqSOA中含酮、单聚体和二聚体等,说明发生了官能团化和聚合化过程.