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.     

北京市铺装道路降尘污染特征及来源

为研究北京市道路降尘在不同季节的污染特征及来源,选取北京市4条典型道路得到64个采样点的道路尘样品,采集的道路尘样品经过预处理得到75 μm以下的颗粒物,经过再悬浮及实验室分析得到PM_2.5的粒径分布和化学成分谱.结果表明:不同采样高度及不同道路类型的颗粒物粒径大体分布规律一致,颗粒物质量频率存在三个峰值,分别为0.75 μm（微粒径）、2.50 μm（小粒径）、4.50 μm（大粒径）;各季节的降尘颗粒物的化学组分中质量分数最大的是元素,主要元素（含量>1%）季节变化为冬季>春季>秋季>夏季,元素富集因子法得到污染元素为Cr、Cd、Sn、Cu、Zn、Pb、As,双重元素为Bi、Ti、Ni、W、Mg、Ca、TI、Mo、V、Fe、Zr、Ba,其余16种为非富集元素;颗粒物中离子质量分数在夏季最大为9.31%,春季、秋季、冬季的离子质量分数相差不大,其中Ca2+、NO₃-、Cl-、SO₄2-占总离子质量的80%左右;碳素中w（OC）和w（EC）的季节变化均为夏季>秋季>春季>冬季,OC/EC[w（OC）/w（EC）]的季节变化规律为冬季>春季>秋季>夏季.不同季节w（OC）和w（EC）的相关性大小为夏季>秋季>春季>冬季.对PM_2.5中化学组分来源分析表明,污染元素受机动车和建筑尘影响较大,与机动车尾气相比,机动车磨损造成的污染也不容小视;燃煤影响一直存在,但供暖期污染有所改善.机动车尾气、建筑尘及土壤尘对离子均有贡献,在夏季土壤尘、建筑尘、二次反应的综合影响较大,春季土壤尘影响更为突出.碳在夏秋季节受汽车尾气和建筑尘的影响较大,夏季二次反应影响不大;冬季除气象因素外,燃煤和生物质燃烧也不可忽视;春季土壤尘影响较为突出.      

Effect of lubricant sulfur on the morphology and elemental composition of diesel exhaust particles

This work investigates the effects of lubricant sulfur contents on the morphology, nanostructure, size distribution and elemental composition of diesel exhaust particle on a light-duty diesel engine. Three kinds of lubricant (LS-oil, MS-oil and HS-oil, all of which have different sulfur contents: 0.182%, 0.583% and 1.06%, respectively) were used in this study. The morphologies and nanostructures of exhaust particles were analyzed using high-resolution transmission electron microscopy (TEM). Size distributions of primary particles were determined through advanced image-processing software. Elemental compositions of exhaust particles were obtained through X-ray energy dispersive spectroscopy (EDS). Results show that as lubricant sulfur contents increase, the macroscopic structure of diesel exhaust particles turn from chain-like to a more complex agglomerate. The inner cores of the core-shell structure belonging to these primary particles change little; the shell thickness decreases, and the spacing of carbon layer gradually descends, and amorphous materials that attached onto outer carbon layer of primary particles increase. Size distributions of primary particles present a unimodal and normal distribution, and higher sulfur contents lead to larger size primary particles. The sulfur content in lubricants directly affects the chemical composition in the particles. The content of C (carbon) decreases as sulfur increases in the lubricants, while the contents of O (oxygen), S (sulfur) and trace elements (including S, Si (silicon), Fe (ferrum), P (phosphorus), Ca (calcium), Zn (zinc), Mg (magnesium), Cl (chlorine) and Ni (nickel)) all increase in particles.     

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.      

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.     

滴定分析法在土壤胡敏酸研究中的应用

胡敏酸是土壤有机质的重要组成部分,是研究土壤有机质物理化学性质的重要环节之一。本文综述了国内外在土壤胡敏酸研究中所采用的各种分析方法,详细论述了滴定分析方法在土壤胡敏酸官能团测定、土壤胡敏酸带电性质测定以及胡敏酸与金属相互作用研究中的应用,并使用滴定分析法测定了贵州喀斯特地区石灰土胡敏酸中酸性官能团及其与Ca2+形成络合物的稳定系数。通过总结对比滴定分析法在研究胡敏酸方面的应用,本文认为现代滴定分析法在表征土壤胡敏酸物化特性和研究土壤胡敏酸演化规律等方面具有广泛应用前景。     

基于质谱技术的在线大气颗粒物来源与污染过程解析研究——以江苏省淮安市为例

通过大气细颗粒物实时在线源解析技术(质谱直接测量法)采集录入淮安市市区部分特征污染源排放成分谱,对淮安市大气细颗粒物进行在线源解析,获取高时间分辨的颗粒物源解析结果,分析颗粒物来源、季度变化和重污染天气的污染过程,评估形成重污染过程的污染影响因子和影响程度,为区域大气污染综合整治提供重要目标指向,同时也为淮安环境空气PM2.5重度污染实时预警与监控、大气污染源减排方案评估、污染事件监控等提供有效的在线监测技术平台.     

川东北低山丘陵区细颗粒物主要相关因素和季节变化分析——以南充主城区为例

基于中国空气质量在线监测分析平台和全球天气精准预报网的大气质量和气象数据,以四川盆地东北低山丘陵区典型城市南充市主城区为例,检验了细颗粒物(PM_(2.5))浓度的概率密度分布,发现其接近对数正态分布,由相关分析确定了PM_(2.5)浓度的主要相关因素为CO、NO_2(相关系数r分别为0.76、0.55,P0.01),再通过对2014年1月—2016年6月的日数据的逐步回归筛选出最优的回归指标和模拟方程(决定系数R_(adj)~2为0.68,P0.05),2016年7月—2017年6月的数据验证表明模拟效果较好(拟合优度为0.64,相对误差15.48%);最后根据时序插值、浓度和IAQI(PM_(2.5))的时段均值发现PM_(2.5)浓度在年际上有降低趋势;在季节上由高到低依次为冬季、春季、秋季、夏季;PM_(2.5)浓度在1月和6月分别呈现出年内的峰值和谷值,5、10月出现了阶段性峰值,尤其是5月;IAQI(PM_(2.5))的季节变化与浓度变化规律相似;且PM_(2.5)与PM_(10)比值的均值为0.67,表明现阶段南充市主城区大气污染物中细颗粒物占有较大比重。     

典型水库型湖泊中CDOM吸收及荧光光谱变化特征:基于沿岸生态系统分析

为进一步了解水库型湖泊溶解性有机质(DOM)的地球化学特征,本文以三峡库区典型内陆水库型湖泊——长寿湖为研究对象,利用紫外-可见和三维荧光光谱,并结合湖区周边生态系统分析,讨论了长寿湖水体中CDOM的组成、来源和空间分布特征.结果表明,长寿湖不同采样点DOM浓度(DOC和CDOM)存在一定程度的空间分布差异,但各点FDOM分布较为稳定.回水区出现DOM累积,由于受陆源输入影响有限,水体内源活动主导,具有较明显"内源控制"特征,芳香性和分子量相对较低;而周边陆地以人工林兼旅游开发为主的采样点,陆源输入在带入较多腐殖化(高芳香性)组分的同时,人为活动排放也是导致其类蛋白组分丰富的重要原因;入湖区尽管周边果林和居民生活对水体DOM有一定影响,但上游河流输入的影响也不容忽视.另外,各采样点也出现了不受周边生态系统影响的独立的相关性特征,例如芳香性特征常数(SUVA280)和光谱斜率[S(275~295)]显著负相关、CDOM和FDOM极显著正相关、CDOM和S(275~295)负相关等.同时,长寿湖水体中CDOM的生色团主要由具有芳香性结构的大分子组分构成;至少51%的CDOM波动可以通过FDOM变化来进行解释,其中回水区荧光组分对CDOM变动的影响最为明显.在采用传统FI值无法区分DOM来源差异性时,结合采样点沿岸生态系统,综合紫外-可见和荧光光谱特征,有助于对DOM组成及来源进行解析.     

黄河口湿地土壤中正构烷烃分子指标及物源指示意义

对黄河口湿地表层土壤中的总有机碳、正构烷烃等进行了分析,计算了正构烷烃分子指标,探讨了其物源指示意义,并对不同采样区域和采样时间的结果进行了比较.结果表明,黄河口湿地土壤中正构烷烃以高碳奇数烷烃(C25～C33)为主,说明土壤中有机质主要来自于陆地高等植物,而样品中未分离混合物的存在表明土壤可能受到了油类污染.土壤中总的正构烷烃含量有明显的时间和区域差异,总的变化范围在0.57～3.90μg.g-1.在2009年4月(枯水期)总的正构烷烃含量相对6月(调水调沙期间)要高,以黄河口湿地核心恢复区最高,其次是黄河入海前最后一个浮桥下方的黄河北岸,最后是黄河故道区域,而6月的变化趋势与此相反.这一变化趋势与总有机碳是一致的,而与中值粒径的变化趋势相反,反映了两个不同的采样时间水环境条件的差异.基于正构烷烃的分子指标,如平均链长ACL、奇偶优势度OEP、烷烃指数AI、碳优势指数CPI和陆海比TAR等表明黄河口湿地土壤的有机质的成熟度较低,有较强的陆源高等植物输入优势,且主要来自于草本植物.与其他指标相比,陆海比指标TAR更好地反映了水环境条件的变化.