夏、冬季降雨中溶解性有机质(DOM)光谱特征及来源辨析

利用紫外-可见光谱与三维荧光光谱,结合拉格朗日混合单粒子轨道模型及火点图,研究了重庆2013年夏、冬两季雨水DOM光谱特征,并对其来源进行解析.结果表明,雨水DOM与水体、土壤DOM具有类似性质光谱特征,证明降雨DOM也是陆地及水环境中DOM地化特征的重要贡献者.雨水DOM中DOC含量为0.88~12.80 mg·L-1,CDOM含量在3.17~21.11m-1之间,夏、冬两季降雨DOM差异明显(P0.05).与夏季相比,冬季降雨DOM分子量较小,芳香性程度较低,腐殖化程度也更低,输入主要以本地和短距离输送为主;而夏季DOM来源较分散.尽管吸收和荧光光谱可用于解析雨水DOM组成和来源,但在光谱特征的解析和来源识别上与其他来源DOM有所区别,传统"内、外源区分"并不适用于雨水DOM.     

天津冬季一次重污染过程颗粒物中水溶性离子粒径分布特征

为研究天津冬季重污染天气过程中颗粒物水溶性离子的粒径谱分布及二次离子生成机制,于2014年1月利用Anderson撞击式分级采样器在中国气象局天津大气边界层观测站内采集颗粒物样品,并使用离子色谱仪分析Na~+、NH_4~+、K~+、Mg~(2+)、Ca~(2+)、Cl~-、NO_3~-、SO_4~(2-)等8种水溶性无机离子(TWSII).结果表明,采样期间PM_(2.5)和PM_(10)质量浓度均值分别为(138±100)μg·m~(-3)和(227±142)μg·m~(-3),粗、细粒子中TWSII的平均浓度分别为(34.07±6.16)μg·m~(-3)和(104.16±51.76)μg·m~(-3).细粒子中SO_4~(2-)、NO_3~-和NH_4~+这3种离子的浓度远高于其他离子,且相关性较好,粗粒子中NO_3~-、SO_4~(2-)、Cl~-浓度较高.随着污染程度加剧,细粒子中TWSII浓度增加明显,粗粒子中则变化不大.水溶性离子的粒径谱分布显示,SO_4~(2-)以单模态分布,优良天峰值出现在0.43~0.65μm,NO_3~-在优良日呈现三模态分布,峰值分别出现在0.43~0.65、2.1~3.3和5.8~9.0μm,NH_4~+呈双模态分布,优良日峰值出现在0.43~0.65μm和4.7~5.8μm,污染日3种二次离子峰值均以0.65~1.1μm的单模态分布为主,与三者之间的热动力平衡过程有关.细粒子中NH_4~+除与SO_4~(2-)和NO_3~-结合外,还与部分Cl~-结合,粗粒子中NH_4~+全部与NO_3~-和SO_4~(2-)结合后,剩余的NO_3~-和SO_4~(2-)与其他阳离子结合.     

西大海湖沉积物营养盐垂直分布特征变化分析

通过对西大海湖心柱状沉积岩芯有机质(OM)、总氮(TN)、总磷(TP)、磷形态和粒度指标的测试和分析,探讨其垂向分布特征及影响因素.结果表明,营养盐中OM、TN和TP的含量分别为0.633%~2.756%、0.150%~0.429%和648.00~1 480.67 mg·kg-1.Ca-P是TP的主要部分,占TP含量66.04%.1843~1970年间,Ca-P、IP、OM含量变化较小,Fe/Al-P、OP、TP、TN含量波动较大;1970~1996年间,Ca-P、IP、TP含量变化均呈减小趋势,Fe/Al-P、OP、OM含量不同程度上先减少后增加,TN波动较大;1996~2009年营养元素含量相对波动较大,Fe/Al-P、OP和OM的平均含量是3个阶段中最高的.西大海湖沉积岩芯营养元素污染来源以工业废水、生活污水和化肥农药的流失为主.沉积物中C/N比值显示有机质主要来源于水生生物.沉积物粒度组成以黏土和细粉砂为主.相关性研究表明,Ca-P、IP与TP均呈显著的正相关关系,表明Ca-P对IP、TP的增长贡献大.     

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。