上海市城区VOCs的年变化特征及其关键活性组分

2010年在上海市城区开展了为期一年的连续观测,采用自动在线GC-FID方法定量测试了大气中56个VOCs物种的浓度.结果发现,上海市城区大气VOCs的全年小时体积分数为(2.47~301.48)×10^-9,平均体积分数为(26.45±23.36)×10^-9,其中,烷烃占46.72%,芳香烃占33.18%,烯烃占11.33%,乙炔占8.76%.T/B(甲苯/苯)为3.51±2.40,表明气团除受机动车影响外,受溶剂、油气和LPG挥发等其他VOCs排放的影响也比较突出;E/E(乙烷/乙炔)为0.98±0.68,表明气团存在老化现象,且春冬季节气团光化学年龄相对较短,夏秋季节光化学年龄相对较长.VOCs的浓度水平和组成在不同风向风速影响下存在一定差异,西南部石化和化工企业排放的VOCs对城区的影响明显,其主要物种为芳香烃和烯烃;该地区气团的OH消耗速率常数(K^OH)为8.05×10^-12 cm³·分子^-1·s^-1,平均VOCs最大O₃增量反应活性(4.00 mol·mol^-1)与乙烯相当,平均反应活性较强;对OH消耗速率(L^OH)贡献率最大的是烯烃(42.21%)和芳香烃(40.83%),对臭氧生成潜势(OFP)贡献率最大的是芳香烃(62.75%)和烯烃(21.70%),VOCs的关键活性组分是二甲苯、甲苯、乙苯、乙烯、丙烯、反-2-丁烯及异戊二烯.     

Simultaneous elution of polycyclic aromatic hydrocarbons and heavy metals from contaminated soil by two amino acids derived from β-cyclodextrins

Two highly water-soluble amino acids, which derived from -CDs, i.e., glutamic acid- -cyclodextrin (GluCD) and ethylene-diamine- -cyclodextrin (EDCD), were synthesized and were examined for their e ect on solubilization of anthracene (ANT), complexation of cadmium (Cd2+), and elution removal of ANT and Cd2+ in soil. The results showed that GluCD and EDCD were powerful complexant for ANT and Cd2+. In the presence of 10 g/L GluCD and EDCD, the solubilization of ANT increased by 47.04 and 23.85 times compared to the control, respectively. GluCD resulted in approximately 90% complexation of Cd2+ while 70% complexation was observed for EDCD. Simultaneously, GluCD and EDCD could greatly enhance the elution removal of ANT and Cd2+ from soil. GluCD resulted in the highest elution e ciency of ANT and Cd2+.With the addition of 10 g/L GluCD, 53.5% of ANT and 85.6% of Cd2+ were eluted, respectively. The ANT had a negligible e ect on the Cd2+ removal due to di erent complexing sites of ANT and Cd2+, while Cd2+ enhanced the ANT removal under the addition of GluCD because Cd2+ neutralized the –COOH group of GluCD. Adversely, the removal of ANT was decreased with Cd2+ under the addition of EDCD, this was due to the fact that Cd2+ enhanced the polarity of EDCD molecule and inhibited the complexation between ANT and EDCD. The study suggested that GluCD could be preferred and be successfully applied to remediation of heavy metals or organic compounds in contaminated soil.     

溴离子和溴酸盐活性炭竞争吸附及溴酸盐生成影响

采用3种活性炭对水体中溴离子和溴酸盐的吸附去除规律进行了考察.结果表明,单吸附条件下溴离子和溴酸盐的吸附去除效率分别达到69%和88%以上,双吸附质条件时溴离子去除率减少到10%.溴酸盐去除率为60%以上;有机物与溴酸盐之间存在竞争吸附关系,AC-400的孔径分布条件更适合于有机物的吸附过程.而不利于溴酸盐的吸附,在低浓度平衡溶液条件下(ce＜72 mg·L-1),AC-100对有机物的吸附能力较高,在溶液平衡浓度72mg·L-1＜ce＜211 mg·L-1条件时,AC-150对有机物的吸附能力较强,影响程度取决于活性炭比表面积和粒度分布等因素;溴酸盐的去除效率同时受到水体中氨含量和pH的影响,氨含量超过200μg/L以上溴酸盐减少量变化不显著,较低pH值溴酸盐生成量较少.     

Chemical characteristics of haze particles in Xi'an during Chinese Spring Festival: Impact of fireworks burning

Fireworks burning releases massive fine particles and gaseous pollutants, significantly deteriorating air quality during Chinese Lunar New Year(LNY) period. To investigate the impact of the fireworks burning on the atmospheric aerosol chemistry, 1-hr time resolution of PM_(2.5) samples in Xi'an during the winter of 2016 including the LNY were collected and detected for inorganic ions, acidity and liquid water content(LWC) of the fine aerosols. PM_(2.5) during the LNY was 167 ± 87 μg/m~3, two times higher than the China National Ambient Air Quality Standard(75 μg/m~3). K~+(28 wt.% of the total ion mass) was the most abundant ion in the LNY period, followed by SO_4~(2-)(25 wt.%) and Cl-(18 wt.%). In contrast, NO_3~-(34 wt.%) was the most abundant species in the haze periods(hourly PM32-2.5 75 μg/m), followed by SO_4(29.2 wt.%) and NH_4~+(16.3 wt.%), while SO_4~(2-)(35 wt.%) was the most abundant species in the clean periods(hourly PM_(2.5) 75 μg/m~3), followed by NO_3~-(23.1 wt.%) and NH_4~+(11 wt.%). Being different from the acidic nature in the non-LNY periods, aerosol in the LNY period presented an alkaline nature with a pH value of 7.8 ± 1.3. LWC during the LNY period showed a robust linear correlation with K_2SO_4 and KCl, suggesting that aerosol hygroscopicity was dominated by inorganic salts derived from fireworks burning. Analysis of correlations between the ratios of NO--3/SO_4~(2-) and NH_4~+/SO_4~(2-) indicated that heterogeneous reaction of HNO_3 with NH_3 was an important formation pathway of particulate nitrate and ammonium during the LNY period.     

Electrokinetic movement of multiple chlorobenzenes in contaminated soils in the presence of β-cyclodextrin

This study investigated the electrokinetic (EK) behavior of multiple chlorobenzenes, including 1,2,3,4-tetrachlorobenzene (TeCB), 1,2,4,5-tetrachlorobenzene (i-TeCB), and 1,2,3-trichlorobenzene (TCB) in contaminated clayed soils. The effect of β-cyclodextrin (β-CD) on the EK removal of the chlorobenzenes was studied. The largest removal was obtained when Na2CO3/NaHCO3 buffer was used as anodic purging solution without β-CD. The removal efficiencies were related to the aqueous solubilities of chlorobenzenes. With the same cumulative electroosmotic flow, greater solubility led to higher removal efficiency. The addition of β-CD inhibited the EK removal efficiency of all chlorobenzenes. The inhibition increased with the increase of β-CD concentration. With the same β-CD concentration, the inhibition increased with the rise of electric potential. It was found that the inclusion compounds between β-CD and chlorobenzenzes were less soluble than chlorobenzenes. The formation of the less soluble inclusion compounds reduced the aqueous solubility of chlorobenzenes and led to the partial immobilization of the chlorobenzenes that desorbed from soil. It was feasible to use the EK technology to remove chlorobenzenes in contaminated soils using water as the anodic flushing solution. The addition of β-CD was not recommended for the EK removal of chlorobenzenes.     

成都市典型工艺过程源挥发性有机物源成分谱

选取成都市人造板、医药制造和化工制品等工艺过程源典型企业,通过采样瓶和SUMMA罐采样及GC-MS和国标分析方法,获取了人造板等行业各生产工艺环节的挥发性有机物(VOCs)排放组分特征.其中,人造板生产工艺分为制胶、调胶、分选和热压,医药制造分为生产车间和废水处理.结果表明,人造板和医药制造VOCs贡献组分以OVOCs为主,占VOCs总排放的50%以上.甲醛制造有组织和无组织排放组分差异较大,有组织以OVOCs为主而无组织以卤代烃为主.涂料制造VOCs排放与其原辅料相关性较高,VOCs排放组分以芳香烃和OVOCs为主.人造板各工艺环节除调胶外,最主要的VOCs组分均为甲醛,其排放占比达到50%以上.医药制造各工艺环节的首要VOCs组分均为乙醇,1,4-二烷、乙酸乙酯和甲苯等亦为主要组分.甲醛制造以丙酮和乙醇等组分为主.涂料制造主要以间,对-二甲苯等芳香烃为主.以臭氧生成潜势表征人造板、医药制造和化工的VOCs污染源反应活性,结果表明不同行业VOCs组分对反应活性的贡献类似,均主要以甲醛、乙醇等OVOCs和部分芳香烃等高活性组分为主.应对工艺过程源等行业分环节监管,并重点关注臭氧生成潜势较大的VOCs组分,分析行业排放特征和化学机制,从源头控制O3生成.     

郑州市春季大气挥发性有机物污染特征及源解析

对2018年春季郑州市5点位进行环境大气挥发性有机物(VOCs)罐采样及组分分析,开展其污染特征、臭氧生成潜势(OFP)、气溶胶生成潜势(AFP)和来源解析研究.结果表明,郑州市春季VOCs体积分数为(30. 66±13. 60)×10-9,烷烃占比最高(35. 3%),其次为OVOCs(25. 3%)、卤代烃(24. 1%)、芳香烃(10. 0%)和烯烃(5. 2%);总OFP为195. 53μg·m-3,烷烃、烯烃、芳香烃、卤代烃和OVOCs贡献率分别为25. 6%、17. 8%、38. 9%、5. 8%和11. 9%;总AFP为0. 95μg·m-3,芳香烃贡献率最高(87. 6%),其次为烷烃(12. 4%);秦岭路和经开区点位正戊烷、异戊烷、苯和甲苯受机动车影响较大,郑州大学点位主要受燃烧源影响;源解析显示机动车尾气及LPG挥发、溶剂使用源、工业过程源、区域老化气团和植物源对采样期间VOCs浓度贡献依次是30. 5%、27. 3%、22. 1%、14. 4%和5. 7%.     

2015～2017年上海郊区大气新粒子生成特征

本研究利用扫描电迁移率粒径谱仪(SMPS)对上海郊区2015～2017年期间大气新粒子生成进行长期连续观测,结合气象要素、气态污染物和PM_(2.5)化学组分等数据,分析上海郊区新粒子生成特征.结果表明,上海郊区新粒子生成天(NPF)为172 d,占有效天数(942 d)的18. 3%;其中典型新粒子生成天(Event)和新粒子增长-缩小天(Shrinkage)分别为150 d和32 d;NPF天占比春、夏季最高,秋季次之,冬季最低.高温低湿、太阳辐射强、风速大和降雨量少的气象条件有利于新粒子生成;南风、西南风和西风期间Event天占比高,气团主要来自环太湖流域植被覆盖和农业种植区,而Non-NPF和Shrinkage天主导风向为东北、东到东南风.与非新粒子生成天(Non-NPF)相比,Event天各季度SO_2和O_3均高,表明气态硫酸和光化学反应为新粒子生成的关键因素; PM_(2.5)浓度并不均低于Non-NPF天,但PM_(10)值均更高,可能与多相光催化反应有关.Shrinkage天除O_3外,其他污染物浓度均最低,较低的气态前体物导致新粒子增长程度有限.PM_(2.5)化学组分显示,Event天NH_4~+、SO_4~(2-)和NO_3~-无机组分秋季平均浓度高于Non-NPF天,其他季节则相反;有机碳各季节平均浓度均高于Non-NPF天; Shrinkage天各组分浓度最低,但春、夏、冬季有机碳占比均高于Non-NPF天;因此有机物在上海郊区新粒子生成及增长过程中有重要贡献.     

重庆市北碚城区大气中VOCs组成特征研究

2012年3月~2013年2月,使用特制的不锈钢钢瓶采集重庆市北碚城区大气样品,并采用三步预浓缩-气相色谱/质谱法对所采集的气体样品进行检测.本研究共检出78种挥发性有机物(volatile organic compounds,VOCs),其中烷烃25种,烯烃15种,芳香烃28种,卤代烃10种.结果表明,重庆市北碚大气中年均浓度最高的前7种VOCs分别为:二氯甲烷(3.08×10-9,体积分数,下同)、苯(2.09×10-9)、异戊烷(1.85×10-9)、甲苯(1.51×10-9)、丙烷(1.51×10-9)、间/对-二甲苯(1.43×10-9)、苯乙烯(1.39×10-9).北碚大气中总挥发性有机物(total volatile organic compounds,TVOCs)浓度为33.89×10-9,季节变化表现为:春季(42.57×10-9)>秋季(33.89×10-9)>冬季(31.91×10-9)>夏季(27.04×10-9).从组成来看,烷烃和芳香烃对TVOCs贡献最大,分别达到31.5%和30.7%;其次是卤代烃类,占27.4%;含量最少的组分是烯烃,所占比例仅为10.4%.采用臭氧生成潜势对VOCs组分活性分析结果表明,烯烃类和芳香烃类化合物是对北碚大气O3生成贡献最大的物质.利用主成分分析法对大气样品中VOCs来源进行分析,发现北碚大气VOCs主要源于机动车尾气排放,贡献比为50.41%.北碚大气中T/B年均值为0.73,表明大气中的苯类物质主要来源于机动车的尾气排放,受溶剂挥发的影响较小.     

移动源排放VOCs特征及臭氧生成潜势研究—以兰州市为例

高浓度近地面臭氧(O_3)污染是国内外许多城市面临的大气污染问题,且近年来O_3浓度呈逐渐升高的趋势.随着城市规模日益扩大,移动源成为VOCs的主要排放源之一,对移动源的O_3生成潜势进行评估,并识别其关键物种和重点污染区域,可为城市O_3控制对策的制定提供科学依据.本文以兰州市移动源为例,结合排放系数、交通流量及相关统计数据,建立兰州市VOCs移动源排放清单,并使用最大增量反应活性(MIR)估算移动源VOCs的臭氧生成潜势(OFP).结果表明,兰州市汽油车是移动源中最主要的OFP贡献源类,占移动源的71.12%;烯烃和芳香烃为移动源总OFP主要的贡献者,主要贡献物种为:乙烯、丙烯、甲醛、3-甲基-1-丁烯、甲苯、正丁烯、乙炔、间二甲苯、1,2,4-三甲基苯、邻二甲苯,这10个物种的OFP占移动源总OFP的67.29%;根据兰州市移动源VOCs排放的OFP贡献空间分布结果,移动源VOCs排放的重点控制区域为城关区和七里河区.