Compilation of reaction kinetics parameters determined in the Key Development Project for Air Pollution Formation Mechanism and Control Technologies in China

A compilation of new advances made in the research field of laboratory reaction kinetics in China's Key Development Project for Air Pollution Formation Mechanism and Control Technologies was presented. These advances are grouped into six broad, interrelated categories, including volatile organic compound (VOC) oxidation, secondary organic aerosol (SOA) formation, new particle formation (NPF) and gas-particle partitioning, ozone chemistry, model parameters, and secondary inorganic aerosol (SIA) formation, highlighting the laboratory work done by Chinese researchers. For smog chamber applications, the current knowledge gained from laboratory studies is reviewed, with emphasis on summarizing the oxidation mechanisms of long-chain alkanes, aromatics, alkenes, aldehydes/ketones in the atmosphere, SOA formation from anthropogenic emission sources, and oxidation of aromatics, isoprene, and limonene, as well as SIA formation. For flow tube applications, atmospheric oxidation mechanisms of toluene and methacrolein, SOA formation from limonene oxidation by ozone, gas-particle partitioning of peroxides, and sulfuric acid-water (H₂SO₄-H₂O) binary nucleation, methanesulfonic acid-water (MSA-H₂O) binary nucleation, and sulfuric acid-ammonia-water (H₂SO₄-NH₃-H₂O) ternary nucleation are discussed.     

济南市夏季环境空气中PBDEs的浓度分布及潜在风险分析

为准确评估济南市夏季环境空气中PBDEs（多溴联苯醚）的污染情况,利用气相色谱-负化学离子源-质谱（GC-NCI-MS）方法,对采集到的大气颗粒物滤膜和气相样品进行了分析,得到不同粒径颗粒相和气相PBDEs在济南市夏季环境空气中的质量浓度.结果表明:观测期间,济南市环境空气中TSP（总悬浮颗粒物）、PM₁₀和PM_2.5中的ρ（PBDEs）分别为（224.1±14.0）（156.5±43.7）（110.2±27.4）pg/m3,质量浓度较高的3种PBDEs单体分别为BDE209、BDE99、BDE183;气相中ρ（PBDEs）为（54.8±13.2）pg/m3,其中,质量浓度较高的单体分别为BDE209、BDE47、BDE99.通过主因子分析发现,不同粒径颗粒物上吸附的PBDEs特征单体不同,TSP中以五溴联苯醚为主,PM₁₀中以八溴联苯醚和五溴联苯醚为主,PM_2.5中则以五溴联苯醚、八溴联苯醚、十溴联苯醚为主.通过将2种模型的预测值和实测值进行比较发现,稳衡态模型比K_OA（辛醇-空气分配系数）模型更好地模拟了PBDEs的气-粒分配情况.在稳衡态模型下,PBDEs在气-粒分配中接近于平衡状态.高溴代PBDEs主要分布于颗粒相中,而低溴代PBDEs的真实情况不同于理论预测结果,BDE99及BDE47在颗粒相的分配比高于50%,说明济南市低溴代PBDEs也容易吸附在颗粒相中.根据计算的PBDEs呼吸暴露水平可知,PM_2.5上PBDEs呼吸暴露量占TSP呼吸暴露量的49.1%,儿童约是成人的1.5倍.济南市普通儿童和成人对BDE99最高总摄入量分别为234.78和169.57 pg/（kg·d）,均低于BDE99最大允许摄入量260 pg/（kg·d）.根据US EPA（美国环境保护局）发布的PBDEs健康风险评价方法（EPA/540/R/070/002）,利用国内外相关参数分别计算空气吸入致癌风险指数发现,济南市夏季环境空气中PBDEs的致癌风险处于较低水平.研究显示,济南市夏季环境空气中不同粒径颗粒物PBDEs的质量浓度处于较低污染水平,其产生的潜在健康风险也较低.      

深圳冬季大气气态硝酸和硝酸盐气粒分配特征

利用双通道在线气体和气溶胶分析仪（MARGA）在深圳冬季同时观测了PM_2.5和PM₁₀中水溶性无机离子及气态前体物浓度变化,以探究气态硝酸（HNO₃）和颗粒态硝酸盐（pNO₃^-）的气粒分配特征.结果表明,气态硝酸和颗粒态硝酸盐总和TNO₃（TNO₃=HNO₃+pNO₃^-）中,气态HNO₃、细颗粒NO₃^-和粗颗粒NO₃^-三个部分的占比分别为9.6%、56.8%和33.6%.TNO₃浓度日变化呈现双峰特征,上午峰值来自于细颗粒态NO₃^-增加,由交通早高峰排放NO_x转化生成所致;白天光化学反应使TNO₃的3个部分浓度均增加,TNO₃在下午17：00达到全天峰值.相关分析表明,低温有利于NO₃^-以NH₄NO₃存在于细颗粒态;TNO₃浓度较高时,细颗粒态NO₃^-占比亦升高.     

Insights into measurements of water-soluble ions in PM2.5 and their gaseous precursors in Beijing

To better understand the characteristics and transformation mechanisms of secondary inorganic aerosols, hourly mass concentrations of water-soluble inorganic ions (WSIIs) in PM_2.5 and their gaseous precursors were measured online from 2016 to 2018 at an urban site in Beijing. Seasonal and diurnal variations in water-soluble ions and gaseous precursors were discussed and their gas-particle conversion and partitioning were also examined, some related parameters were characterized. The (TNH₃) _Rich was also defined to describe the variations of the excess NH₃ in different seasons. In addition, a sensitivity test was carried out by using ISORROPIA II to outline the driving factors of gas-particle partitioning. In Beijing, the relative contribution of nitrate to PM_2.5 has increased markedly in recent years, especially under polluted conditions. In the four seasons, only a small portion of NO₂ in the atmosphere was converted into total nitrate (TNO₃)_, and more than 80% of TNO₃ occurred in the form of nitrate due to the abundant ammonia. The concentration of total ammonia (TNH₃) was much higher than that required to neutralize acid gases, and most of the TNH₃ occurred as gaseous NH₃. The nitrous acid (HONO) concentration was highly correlated with NH₃ concentration and had increased significantly in Beijing compared with previous studies. The total chloride (TCl) was the highest in winter, and ε(Cl^?) was more sensitive to variations in the ambient temperature (T) and relative humidity (RH) than ε(NO₃^?).     

Sorption of metals onto natural organic matter as a function of complexation and adsorbent-adsorbate contact mode

The effect of complexing anion and adsorbate-adsorbent contact mode (static equilibrium or dynamic non-equilibrium) on binding and partition of Cu(2+), Cd(2+) and Zn(2+) onto organic matter (exemplified in a low-moor peat) was studied. The study comprised comparative batch and column flow-through sorption experiments on monometallic solutions of Me-Cl and Me-SO(4) salts, at pH 4.0, and sequential fractionation of sorbed metals with respect to binding strength. Both the presence of an anion having complexing properties (Cl(-)) as well as a contact mode was found to quantitatively and qualitatively affect the sorption capacity and binding strength of organic matter (peat) for metal ions. Complexing effect of Cl(-) on metal ions resulted mostly in reduction of metal ability to form strongly bound metal-organic compounds, in accordance with the order of stability constant of complex ions log K: Cd>Zn>Cu. Flow-through (dynamic) contact mode, which is the most appropriate to simulate environmental conditions, appeared to strongly attenuate the complexing effect of chloride ions on Cd and Zn sorption, and significantly enhance sorption capacity also in the absence of complexing ions. For Cd, it was mainly due to the enrichment in the strongly bound "insoluble organic" fraction, while for Zn the quantitative increase of sorption capacity did not alter significantly its partitioning. Neither a quantitative nor qualitative effect of contact mode on Cu binding was observed. Complex and diverse effects of different environmental parameters on metal sorption capacity and binding strength onto organic matter, which strongly influence metal mobility, leads to the conclusion that the correct simulation of these parameters for ecotoxicological testing is crucial for the reliable predicting of metal bioavailability under actual terrestrial environmental conditions.     

Improved atmospheric mercury simulation using updated gas-particle partition and organic aerosol concentrations

The gaseous or particulate forms of divalent mercury (Hg^II) significantly impact the spatial distribution of atmospheric mercury concentration and deposition flux (FLX). In the new nested-grid GEOS-Chem model, we try to modify the Hg^II gas-particle partitioning relationship with synchronous and hourly observations at four sites in China. Observations of gaseous oxidized Hg (GOM), particulate-bound Hg (PBM), and PM_2.5 were used to derive an empirical gas-particle partitioning coefficient as a function of temperature (T) and organic aerosol (OA) concentrations under different relative humidity (RH). Results showed that with increasing RH, the dominant process of Hg^II gas-particle partitioning changed from physical adsorption to chemical desorption. And the dominant factor of Hg^II gas-particle partitioning changed from T to OA concentrations. We thus improved the simulated OA concentration field by introducing intermediate-volatility and semi-volatile organic compounds (I/SVOCs) emission inventory into the model framework and refining the volatile distributions of I/SVOCs according to new filed tests in the recent literatures. Finally, normalized mean biases (NMBs) of monthly gaseous element mercury (GEM), GOM, PBM, WFLX were reduced from −33%–29%, 95%–300%, 64%–261%, 117%–122% to −13%–0%, −20%–80%, −31%–50%, −17%–23%. The improved model explains 69%–98% of the observed atmospheric Hg decrease during 2013–2020 and can serve as a useful tool to evaluate the effectiveness of the Minamata Convention on Mercury.     

哈尔滨市大气中多环芳烃的初步研究

利用改进型的大流量主动采样器,于2008年5月7~20日对哈尔滨市大气样品进行采集,并检测了气相和颗粒相中的多环芳烃(PAHs)的浓度.结果表明,哈尔滨市大气中总PAHs的浓度为8.1~37.2ng/m3,平均值为18.2ng/m3.通过特征分子比值法推断出哈尔滨市大气中PAHs主要来自于煤的燃烧.低环PAHs主要集中在气相,而高环PAHs则吸附在颗粒相上.气粒分配系数与过冷饱和蒸气压具有很好的相关性,但PAHs并没有达到气粒分配平衡,这可能与冬季取暖用煤燃烧产生的新多环芳烃有关.     

两相分配生物反应器处理高浓度有机废水研究进展

随着化学化工及其相关产业的高速发展,高浓度难降解有机废水日益增多,其新型适用的处理工艺技术研发具有迫切性和必要性。就现有废水处理工艺技术而言,生物处理工艺具有彻底矿化降解污染物、处理费用低、二次污染风险低等优点,但对浓度高、毒性大及疏水性强的有机污染物的处理受到限制。近期发展的两相分配生物反应器(two-phase partitioning bioreactor,即TPPB)法则在高浓度难降解有机污水处理中显现出显著的应用效果。综述了TPPB的工作原理、研究现状以及存在的问题,并展望了TPPB技术的应用前景。     

Metal partitioning in sediment pore water from the Ondo coastal region,Nigeria

Distribution and equilibrium partitioning of metals (Cd, Cu, Cr, Fe, Ni, Pb, Mn, and Zn) between pore water and surface sediments at the Ilaje coast of Ondo State, Nigeria, were studied. The Ilaje River can be one of the interesting research locations because of its economic nature and history of oil pollution. Seasonal variations were observed to investigate possible variations in the availability of metals for organisms throughout the year. The concentrations in both sediments and pore water during the dry and wet seasons were as follows: Cu?>?Fe???Mn?>?Pb?>?Ni?>?Cr?>?Cd?>?Zn. The pore water–sediment partition coefficient (K _p) showed that Zn and Cd were highly mobile while Fe and Cu have restricted mobility. Dissolved organic carbon (DOC) in pore water had a strong influence on mobility and bioavailability of all the metals (p?K _oc), increased levels of Fe and Cu were linked to lithological origin. Concentrations of Pb and Ni were associated with petroleum-related sources. The significance of the field-based techniques for ecotoxicological purposes is discussed.     

两相分配生物反应器中苍白杆菌PW对芘的降解效果

为降低PAHs对微生物的毒性,促进PAHs的降解,采用TPPB技术(two-phase patitioning bioreactor,两相分配生物反应器)对芘进行降解,研究了不同有机相(硅油、十二烷、十一醇、癸烷、十六烷、十八烷)、ρ(芘)、φ(有机相)和扰动速率对芘降解的影响. 结果表明:当φ(有机相)为10.0%、ρ(芘)为100~1 000 mg/L时,T0(纯水相)及T1(水-硅油)、T2(水-癸烷)、T3(水-十二烷)、T4(水-十一醇)、T5(水-十六烷)和T6(水-十八烷)体系中芘的降解率分别为92.5%~13.9%、69.3%~20.1%、79.6%~23.3%、81.9%~26.9%、86.7%~28.1%、87.7%~34.1%、89.6%~27.4%. ρ(芘)较低时,TPPB抑制了芘的降解;ρ(芘)较高时,TPPB则能促进芘的降解. 6种有机相中,十六烷对芘降解的促进效果最优. 最优φ(有机相)的确定和ρ(芘)有关,ρ(芘)为200 mg/L时,最优φ(十八烷)、φ(十六烷)、φ(十一醇)分别为5.0%、2.5%和5.0%;ρ(芘)为1 000 mg/L时,其均为20.0%. 液体扰动速率的提高能促进芘的降解,液体扰动速率为50~200 r/min时,T6和T5体系中的芘的降解率分别为50.1%~75.6%和54.1%~79.1%. 研究显示,TPPB技术是一种潜在治理高浓度PAHs污染的有效途径,TPPB的优化是多种影响因素综合作用的结果.