大气颗粒物及降尘中重金属的分布特征与人体健康风险评价

为了解PM_(2.5)、PM_(10)和降尘中Cu、Mn、Pb、Ti、V、Cd、Cr、Co、Mo、Ni等10种重金属元素的分布特征及人体健康风险,利用大流量颗粒物采样器采集了北京城区某地四季大气中PM_(2.5)、PM_(10)及降尘样品,用ICP-MS测定了上述10种金属元素的质量浓度.结果表明,PM_(2.5)和PM_(10)的年均质量浓度分别为153.40μg·m~(-3)和232.93μg·m~(-3),超出GB 3095-2012中二类环境功能区标准限值的5倍和3倍;PM_(2.5)/PM_(10)的均值为0.74,表明大气颗粒物中以粒径小于2.5μm的颗粒为主;后向轨迹分析结果表明外源颗粒物的来向随季节变化而改变,冬、春、夏、秋季主要来向为西北、北-东北、东南、东南-西北.PM_(2.5)和PM_(10)中10种元素的年均质量浓度从高到低依次为TiMnPbCuCrNiVCdMoCo,其中Ti、Mn、Pb、Cu和Cr这5种元素占10种目标元素总质量浓度的91.93%和92.49%.除PM_(10)中Cd年均质量浓度(6.53 ng·m~(-3))高于GB 3095-2012限定值(5.00 ng·m~(-3))外,其他元素的质量浓度均不超标.降尘中各元素的含量由高到低依次为TiMnPbCuNiCrVCoMoCd,Ti(2561.48μg·g~(-1))占所有元素的质量分数为72.57%,地累积指数(Igeo)结果表明,Cd(4.03)属重度污染,Pb(2.49)介于中度污染和重度污染之间,Cu(1.33)属中度污染,Ni(0.43)属轻微污染.重金属的致癌健康风险(10-4)和非致癌健康风险(1),均处于较低水平,短期内不会对人体健康造成威胁,但不能忽视长期处于此环境所带来的健康危害.     

传统北京烤鸭烤制过程中大气污染物的排放特征

烤鸭是具有北京特色的传统美食之一,制作过程采用果木炭火烤制方式,与其它食物烹饪过程存在明显的差异,国内还未对这类餐饮源的排放特征进行过系统研究,为掌握这类餐饮源排放特征,从而为污染控制提供技术依据,选取北京市具有代表性的烤鸭店,研究了其烤鸭烤制过程中大气污染物的排放特征.结果表明,传统烤鸭烤制过程中排放的油烟、颗粒物、挥发性有机物(VOCs)和醛酮类化合物的基准排放浓度分别为(0.74±0.45)、(15.32±7.93)、(7.60±3.41)和(1.22±0.59)mg·m~(-3);颗粒物排放浓度要远高于油烟排放浓度,VOCs组分构成相对复杂,既包括烷烃、烯烃、芳香烃等VOCs也包括醛酮类、醇类、酯类等含氧VOCs和卤代烃,其中3-甲基呋喃、乙醇和乙酸甲酯的浓度最高;醛酮类化合物的主要组分有乙醛、甲醛和丙烯醛等,其中C1~C3物质占72.27%.     

Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical

Sulfamethoxypyridazine(SMP) is one of the commonly used sulfonamide antibiotics(SAs).SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants.In this work,SMP was selected as a representative of SAs.We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter,i.e.,anions(Br~-,Cl~-,and NO~-_3) and cations ions(Ca~(2+),Mg~(2+),and Zn~(2+)) on SMP photodegradation mechanism by quantum chemical methods.In addition,the degradation mechanisms of SMP by hydroxyl radical(OH·) were also investigated.The creation of SO_2 extrusion product was accessed with two different energy pathways(pathway-1 and pathway-2) by following two steps(step-I and step-II) in the tripletsensitized photodegradation of SMP.Due to low activation energy,the pathway-1 was considered as the main pathway to obtain SO_2 extrusion product.Step-II of pathway-1 was measured to be the rate-limiting step(RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step.All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1.The estimated low activation energies of different degradation pathways of SMP with OH·radical indicate that OH·radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring.     

Impact of microbial communities from tropical soils on the mobilization of trace metals during dissolution of cinnabar ore

Biodissolution experiments on cinnabar ore(mercury sulphide and other sulphide minerals,such as pyrite) were performed with microorganisms extracted directly from soil. These experiments were carried out in closed systems under aerobic and anaerobic conditions with 2 different soils sampled in French Guyana. The two main objectives of this study were(1) to quantify the ability of microorganisms to mobilize metals(Fe, Al, Hg) during the dissolution of cinnabar ore, and(2) to identify the links between the type and chemical properties of soils, environmental parameters such as season and the strategies developed by indigenous microorganisms extracted from tropical natural soils to mobilize metals.Results indicate that microbial communities extracted directly from various soils are able to(1) survive in the presence of cinnabar ore, as indicated by consumption of carbon sources and,(2) leach Hg from cinnabar in oxic and anoxic dissolution experiments via the acidification of the medium and the production of low molecular mass organic acids(LMMOAs). The dissolution rate of cinnabar in aerobic conditions with microbial communities ranged from 4.8 × 10~(-4) to 2.6 × 10~(-3) μmol/m~2/day and was independent of the metabolites released by the microorganisms. In addition, these results suggest an indirect action by the microorganisms in the cinnabar dissolution. Additionally, because iron is a key element in the dynamics of Hg, microbes were stimulated by the presence of this metal,and microbes released LMMOAs that leached iron from iron-bearing minerals, such as pyrite and oxy-hydroxide of iron, in the mixed cinnabar ore.     

Simulated reaction of formaldehyde and ambient atmospheric particulate matter using a chamber

The reaction of HCHO with Beijing winter's real ambient particulate matter(PM) inside a 3.3 m~3 Teflon Chamber was conducted in this study. NO_2, O_3 and H_2O gases were removed from the ambient aerosol before entering into the chamber. The decays of HCHO were monitored(acetylacetone spectrophotometry method) during the reactions at different PM number concentrations(N_a) and relative humidities(RHs), and the formed particulate formate was detected by IC and XPS techniques. The results showed that when RH was10%–15%, the decay rate of HCHO in the chamber was higher with the existence of PM from relatively clean days(with number concentration(N_a) 200,000 particle/L, 0.35–22.5 μm)compared to dirty days(N_a 200,000 particle/L, 0.35–22.5 μm). When RH increased to 30%–45%, PM can hardly have significant influences on the decay of HCHO. The formations of formate on the reacted PM were consistent with the HCHO decay rates at different ambient PM N_aand RH conditions. This is a first study related to the "real" ambient PM reacted with HCHO and suggested that in the clean and low RH days, PM could be an effective medium for the conversion of HCHO to formate.     

重庆市夏秋季VOCs对臭氧和二次有机气溶胶生成潜势的估算

为估算重庆市夏秋季VOCs（挥发性有机物）对O₃和SOA（二次有机气溶胶）的生成潜势,利用在线GC-MS/FID在2015年8月22日-9月23日对重庆市区点和郊区点VOCs开展了为期一个月的实时观测,获得市区点和郊区点$ \varphi $（TVOCs）（总挥发性有机物）分别为41.35×10-9和22.72×10-9,其中市区点以烷烃（35.2%）和烯炔烃（25.2%）为主,郊区点以含氧挥发性有机物（oxygenated volatile organic compounds,OVOCs）（30.6%）和烷烃（26.0%）为主.结合最大增量反应活性量化市区点和郊区点VOCs的OFPs（臭氧生成潜势）分别为149.11×10-9和71.09×10-9,市区点OFPs最大的是乙烯、丙烯、甲苯、C8和C9的芳香烃等,郊区点OFPs最大的VOCs是丙烯醛、异戊二烯和甲基乙烯基酮.结合气溶胶生成系数量化郊区点和市区点VOCs对SOA的生成贡献分别为0.36和1.26 μg/m3,相比国内其余城市VOCs的SOAP（二次有机气溶胶生成潜势）较小,主要以甲基环己烷、正壬烷、正葵烷和十一烷等高碳烷烃,以及甲苯、苯、二甲苯和乙苯等芳香烃的SOAP为主.研究显示,控制烯炔烃和芳香烃的浓度有助于控制重庆市O₃的生成,控制高碳烷烃和芳香烃则有助于控制重庆市SOA的生成.      

覆盖金属氧化物对湖泊沉积物溶解性有机质特征的影响

为揭示不同金属氧化物对湖泊沉积物DOM（溶解性有机质）影响机制,通过室内模拟试验,在沉积物表层分别覆盖Fe、Al、Mn氧化物及湖沙后培养1 a,并利用三维荧光和紫外光谱方法进行表征.结果表明:① 覆盖Al、Fe、Mn氧化物和湖沙主要降低了0~3 cm沉积物的w（DOC）,降幅分别为8.61%、6.27%、22.38%和0.44%. ② 沉积物中DOM的类络氨酸峰（peak B₁）和类色氨酸峰（peak T₂）均产生较大变化.其中三种氧化物均显著降低了上层沉积物中DOM的peak T₂,使底层DOM的peakT₂显著增加. Mn氧化物使DOM的peak B₁降低,Fe和Al氧化物使DOM的peak B₁增加,湖沙则使两类峰均降低. ③ 覆盖金属氧化物改变了沉积物DOM结构特征,其中覆盖Fe氧化物增强了其芳香性,而覆盖Mn氧化物和Al氧化却降低其芳香性,但三者均使DOM腐质化程度及官能团数量增加,并使FI（Fluorescence Index,荧光指数）增大,表明DOM向生物源转化.研究显示,沉积物表层覆盖金属氧化物影响了沉积物中DOM迁移和转化,并促进了其降解,导致其分子量和腐殖化程度增加.      

浸没燃烧技术处理高浓度有机废水研究

针对现阶段高浓度有机废水处理困难的问题,提出了一种基于浸没燃烧技术的处理方法,设计制作了1台浸没燃烧装置,并开展了高浓度有机废水浸没燃烧实验研究,探究了过量空气系数、二次风量、燃烧温度等参数对燃烧尾气中CO、NOx排放的影响,以及浸没深度、燃烧温度对高浓度有机废水COD去除的影响。实验结果表明:该工艺对高浓度有机废水中的有机物去除效果明显,温度在900℃以上,浸没深度达到20 cm时,COD去除率可达90%以上。该方法可作为废水处理设备,与生物法等处理技术联用,应用前景广阔。     

进水有机负荷对三级生物滴滤池脱氮除磷的影响

试验采用三级(好氧/兼氧/好氧)多层组合填料生物滴滤池处理模拟生活污水,探索强化脱氮除磷工艺。考察了在相同水力负荷和布水周期下,改变进水有机负荷对COD、NH_4~+-N、TN和TP去除率的影响,并用扫描电镜和X射线衍射(XRD)对填料进行辅助分析。研究结果表明,三级串联生物滴滤池的组合相比传统的单级或两级生物滴滤池反应器处理效果更好。第1级和第2级生物滴滤池去除COD、NH_4~+-N和TN效果较好,贡献率合计分别为93.0%、91.2%和91.4%。第1级和第3级生物滴滤池除磷效果较好,贡献率合计91.4%。有机负荷为0.328~0.392 kg/(m~3·d)时,系统总体去除效果最好。     

Effects of Cu2+ and humic acids on degradation and fate of TBBPA in pure culture of Pseudomonas sp. strain CDT

Soil contamination with tetrabromobisphenol A(TBBPA) has caused great concerns;however, the presence of heavy metals and soil organic matter on the biodegradation of TBBPA is still unclear. We isolated Pseudomonas sp. strain CDT, a TBBPA-degrading bacterium, from activated sludge and incubated it with ~(14)C-labeled TBBPA for 87 days in the absence and presence of Cu~(2+)and humic acids(HA). TBBPA was degraded to organic-solvent extractable(59.4% ± 2.2%) and non-extractable(25.1% ± 1.3%) metabolites,mineralized to CO_2(4.8% ± 0.8%), and assimilated into cells(10.6% ± 0.9%) at the end of incubation. When Cu~(2+)was present, the transformation of extractable metabolites into non-extractable metabolites and mineralization were inhibited, possibly due to the toxicity of Cu~(2+)to cells. HA significantly inhibited both dissipation and mineralization of TBBPA and altered the fate of TBBPA in the culture by formation of HA-bound residues that amounted to 22.1% ± 3.7% of the transformed TBBPA. The inhibition from HA was attributed to adsorption of TBBPA and formation of bound residues with HA via reaction of reactive metabolites with HA molecules, which decreased bioavailability of TBBPA and metabolites in the culture. When Cu~(2+)and HA were both present, Cu~(2+)significantly promoted the HA inhibition on TBBPA dissipation but not on metabolite degradation. The results provide insights into individual and interactive effects of Cu~(2+)and soil organic matter on the biotransformation of TBBPA and indicate that soil organic matter plays an essential role in determining the fate of organic pollutants in soil and mitigating heavy metal toxicity.