天津市区夏季碳气溶胶特征及改进的二次有机碳估算方法

为更加准确地估算环境受体PM_2.5中SOC（二次有机碳）的质量浓度,于2015年6-8月利用在线监测仪器同步采集小时分辨率的PM_2.5及OC（有机碳）和EC（元素碳）样品数据,分析碳气溶胶的变化特征,并尝试运用改进的EC示踪法估算ρ（SOC）.结果表明:天津市区夏季ρ（PM_2.5）为（70.9±46.0）μg/m3,ρ（OC）和ρ（EC）分别为（7.6±3.1）（2.2±1.5）μg/m3,占ρ（PM_2.5）的11.8%±4.6%和3.1%±1.4%,OC/EC（质量浓度之比,下同）的平均值为4.0±2.0.ρ（OC）与ρ（EC）之间的Pearson相关系数（R）仅为0.66,说明OC和EC的来源较为复杂,SOC的产生可能是重要影响因素.ρ（NO₂）与OC/EC呈显著负相关（R=-0.47,P < 0.01）,并且OC/EC（4.0）相对较低,说明天津市区机动车可能对碳气溶胶具有重要影响.ρ（SO₂）与ρ（OC）、ρ（EC）的相关性较低（R均为0.33,P均小于0.01）,说明天津市区碳气溶胶可能受燃煤源的影响较低.改进的EC示踪法主要是利用O₃和CO、EC作为光化学反应和一次源排放的指标,并结合ρ（OC）、ρ（EC）和OC/EC的变化特征,逐步筛选一次排放源主导的时间段的ρ（OC）和ρ（EC）数据,然后利用最小二乘法拟合获得ρ（OC）和ρ（EC）的线性方程,最后进行ρ（SOC）和ρ（POC）（POC为一次有机碳）的估算.天津市区夏季ρ（SOC）的平均值为（2.5±2.0）μg/m3,分别占ρ（OC）和ρ（PM_2.5）的28.8%±15.0%和3.7%±3.6%;ρ（POC）的平均值为（5.2±1.7）μg/m3,分别占ρ（OC）和ρ（PM_2.5）的71.2%±15.0%和8.1%±5.2%,说明天津市区夏季有机碳的主要来源是一次排放源.研究显示,相比于EC示踪法,改进的EC示踪法估算的ρ（SOC）明显降低,ρ（POC）明显升高.AT（大气温度）对ρ（SOC）的影响较为显著,而WS（风速）对ρ（POC）的影响较为显著.      

Characterization particulate matter from several Chinese cooking dishes and implications in health effects

Cooking fume produced by oil and food at a high temperature releases large amount of fine particulate matter(PM) which have a potential hazard to human health. This chamber study investigated particle emission characteristics originated from using four types of oil(soybean oil, olive oil, peanut oil and lard) and different kinds of food materials(meat and vegetable). The corresponding emission factors(EFs) of number, mass, surface area and volume for particles were discussed. Temporal variation of size-fractionated particle concentration showed that olive oil produced the highest number PM concentration for the entire cooking process. Multiple path particle dosimetry(MPPD) model was performed to predict deposition in the human respiratory tract. Results showed that the pulmonary airway deposition fraction was the largest. It was also found that particles produced from olive oil led to the highest deposition. We strongly recommend minimizing the moisture content of ingredients before cooking and giving priority to the use of peanut oil instead of olive oil to reduce human exposure to PM.     

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 O_3 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 O_x(= O_3+ NO_2) 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.     

Behaviors and kinetics of toluene adsorption‐desorption on activated carbons with varying pore structure

This work was undertaken to investigate the behaviors and kinetics of toluene adsorption and desorption on activated carbons with varying pore structure. Five kinds of activated carbon from different raw materials were selected. Adsorption isotherms and breakthrough curves for toluene were measured. Langmuir and Freundlich equations were fitted to the equilibrium data, and the Freundlich equation was more suitable for simulating toluene adsorption. The process consisted of monolayer, multilayer and partial active site adsorption types. The effect of the pore structure of the activated carbons on toluene adsorption capacity was investigated. The quasi-first-order model was more suitable for describing the process than the quasi-second-order model. The adsorption data was also modeled by the internal particle diffusion model and it was found that the adsorption process could be divided into three stages. In the external surface adsorption process, the rate depended on the specific surface area. During the particle diffusion stage, pore structure and volume were the main factors affecting adsorption rate. In the final equilibrium stage, the rate was determined by the ratio of meso-and macro-pores to total pore volume. The rate over the whole adsorption process was dominated by the toluene concentration. The desorption behavior of toluene on activated carbons was investigated,and the process was divided into heat and mass transfer parts corresponding to emission and diffusion mechanisms, respectively. Physical adsorption played the main role during the adsorption process.     

Impact of density of coating agent on antibacterial activity of silver nanoparticle impregnated plasma treated activated carbon

To use stabilized nanoparticles(NPs) in water as disinfectants over a very long period, the amount of coating agent(for NP stabilization) needs to be optimized. To this end, silver nanoparticles(Ag-NPs) with two different coating densities of tri-sodium citrate(12.05 and46.17 molecules/nm~2, respectively), yet of very similar particle size(29 and 27 nm, respectively)were synthesized. Both sets of citrate capped NPs were then separately impregnated on plasma treated activated carbon(AC), with similar Ag loading of 0.8 and 0.82 wt.%, respectively. On passing contaminated water(containing 10~4 CFU Escherichia coli/m L of water) through a continuous flow-column packed with Ag/AC, zero cell concentration was achieved in 22 and 39 min, with Ag-NPs(impregnated on AC, named as Ag/AC) having lower and higher coating density, respectively. Therefore, even on ensuring similar Ag-NP size and loading, there is a significant difference in antibacterial performance based on citrate coating density in Ag/AC.This is observed in lower coating density case, due to both:(i) higher Ag~+ ion release from Ag-NP and(ii) stronger binding of individual Ag-NPs on AC. The latter ensures that, Ag-NP does not detach from the AC surface for a long duration. TGA-DSC shows that Ag-NPs with a low coating density bind to AC with 4.55 times higher adsorption energy, compared to Ag/AC with a high coating density, implying stronger binding. Therefore, coating density is an important parameter for achieving higher antibacterial efficacy, translating into a faster decontamination rate in experiments, over a long period of flow-column operation.     

黄土高原成龄苹果园生态系统CO2通量特征

黄土高原地区是中国和世界苹果(Malus demestica)集中连片栽培面积最大的区域,在生态环境改善中发挥了重要作用,然而关于黄土高原地区苹果园生态系统尺度上的碳通量研究很少.在本研究中,利用涡度相关技术对我国陕西黄土高原地区成龄苹果园生态系统的CO_2通量和气象因素进行了观测.基于2016年1月到2016年12月的观测数据,定量分析了此苹果园净生态系统碳交换(NEE)、生态系统呼吸(R_(eco))和生态系统总初级生产力(GPP)不同时间尺度及主要气象因素的变化,探究了光合有效辐射(PAR)和不同层次土壤温度(T_s)、空气温度(T_a)对NEE的影响.结果表明,苹果园生态系统NEE月总量在非果树生长季12、1、2和3月为正值(表现为碳源),生长季(4~11月)均为负值(表现为碳汇),整体表现为强烈的碳汇.生长季NEE月平均日变化在8月出现最大吸收峰[-17.08μmol·(m~2·s)~(-1)],11月吸收峰最小[-4.47μmol·(m~2·s)~(-1)];在非生长季NEE的月平均日变化非常微弱,昼夜变化不明显.GPP、Reco和NEE日总量的最大值分别为11.12、5.04和-7.34 g·( m~2·d)~(-1).GPP、Reco和NEE月总量的最大值分别为238.97、105.38和-144.44 g·(m~2·月)~(-1),月GPP和NEE总量在5~8月保持相对稳定的高值.全年GPP、Reco和NEE分别为1 223.2、525.2和-698.0 g·(m2·a)-1,表明我国黄土高原地区的成龄苹果园生态系统具有相对较高的固碳能力.夜间生态系统呼吸Reco.n与不同层次土壤温度、空气温度之间呈正相关关系,相关系数表现为T_(s-5 cm)T_(s-10 cm)T_(a-4 m)T_(a-8 m);光合有效辐射PAR可以解释白天NEE变化的80%以上.     

13C脉冲标记法定量冬小麦光合碳分配及其向地下的输入

研究冬小麦生长向地下部分的输入对于土壤固碳和作物生产具有重要意义.分别在分蘖期、拔节期、花期和灌浆期,用~(13)CO2对冬小麦进行脉冲标记7 h,标记结束后28 d(示踪期)破坏性取样,测定冬小麦地上部、根、土壤和土壤呼吸中的~(13)C含量等指标.研究结果表明,在各标记时期,冬小麦光合固定的~(13)C大部分保留在地上部(51.6%~90.8%),且随小麦生长的进行而逐渐向地上部分配,向地下部分(根系、土壤和根际呼吸)的转移随生长进程的延续而降低.转移到地下部的~(13)C中,有22.9%~65.3%被根际呼吸消耗,24.3%~59.3%在根部保存,10.4%~17.8%通过根际沉积转化为土壤有机碳.示踪期28d内最后2 d呼吸产生的~(13)C只占整个示踪期根际呼吸~(13)C量的0.7%~2.7%,说明28 d的示踪期可以确保光合碳在各系统分配完全.在整个生育期内,冬小麦净吸收的光合碳分配到地上部、根部、土壤有机碳和根际呼吸的比例分别为78.5%、6.0%、3.1%和12.4%.结合当地生产方式估算,冬小麦在整个生育期内输入到地下的总碳量为1.72 t·hm~(-2),其中有0.99t·hm~(-2)被根际呼吸消耗,根部固持碳量为0.48 t·hm~(-2),0.25 t·hm~(-2)以有机碳沉积的形式进入土壤.     

三峡库区典型河流水-气界面CO2通量日变化观测及其影响因素分析

为研究河流水-气界面CO_2通量的季节和日变化特征;于2016年7月15～17日以及2017年11月4～6日对三峡库区嘉陵江支流竹溪河进行定点定时采集表层水样,并同步监测关键环境因子,采用亨利定律结合薄边界层模型计算其水-气界面CO_2通量F(CO_2).结果表明,竹溪河表层水CO_2分压p(CO_2)及界面CO_2脱气通量呈现出显著的日间和季节变化,以及明显的日内变化特征:在上午09:00前后达到释放高峰,随后波动下降;水-气界面CO_2通量日间均值分别为(100. 9±31. 6)、(78. 6±12. 1)、(83. 9±29. 7)、(137. 5±42. 1)、(147. 6±34. 0)、(132. 4±21. 7) mmol·(m~2·d)~(-1);并表现出夏季表层水体CO_2释放通量明显低于秋季,其均值分别为(87. 8±27. 5) mmol·(m~2·d)~(-1)和(139. 2±34. 0) mmol·(m~2·d)~(-1);总体表现出大气CO_2源的特征.竹溪河p(CO_2)和F(CO_2)受到诸多环境因子的影响,相关分析表明,pH、碱度、水温和气温是主要环境影响因子,CO_2释放通量可以用pH和碱度预测.     

过滤式碳纤维电极消毒效果比较与机理研究

过滤式电极消毒作为一种安全、高效的新型消毒技术备受关注,然而目前使用的电极材料比较单一,且稳定性和高效性难以兼备,制约了该技术的设备化发展.本文采用过滤式消毒方式,考察了几种高孔隙率的导电碳纤维毡的消毒效果.结果表明,碳纤维毡电极具有优异的消毒能力,活性碳纤维电极可在几伏的电压下使细菌死亡,与传统电化学消毒相比,电压降低了1~2个数量级.其中A-PCF(聚丙烯腈基活性碳纤维)电极在外接电压2 V,水力停留时间2 s时即可对大肠杆菌菌液实现6.5log的去除.当外接电压≤2 V时,流出物中未检测到氯,pH保持不变,排除了电化学产物的影响.A-PCF可作为过滤式电极消毒的优选电极材料.     

基于IVE模型和大数据分析的杭州市道路移动源主要温室气体排放清单研究

利用IVE模型和对杭州市机动车排放管理数据库大数据的分析,得到杭州市2015年各类机动车主要温室气体高分辨率排放清单,分析了排放分担情况及时间变化特征,并利用Arc GIS及杭州市路网信息建立了1 km×1 km网格化空间分布.结果表明,杭州市道路移动源温室气体排放中CO_2、CH_4和N_2O的年排放量分别为818.11×10~4、0.85×10~4和0.07×10~4t,合计856.79×10~4t(以CO2当量计).从温室气体种类来看,CO_2占道路移动源温室气体排放总量的绝大部分,为95.5%;从机动车类型来看,小微型客车对道路移动源温室气体排放的贡献率最大,占72.8%;从道路类型的排放情况来看,杭州市市中心、城区、城郊和郊区中温室气体合计CO_2当量贡献率最高的均为主干路,分别为43.4%、61.8%、58.0%和42.4%.杭州市道路移动源温室气体排放强度均呈现由城市中心向城市边缘递减的趋势,同时温室气体排放量日变化特征明显,均出现弱双峰现象.