基于高质量分辨率质谱仪研究上海城区秋季大气亚微米级颗粒物化学特性

利用先进的高分辨飞行时间气溶胶质谱仪(High Resolution Time-of-Flight Aerosol Mass Spectrometer,HR-To F-AMS),于2017年9月8日—2017年10月8日对上海市城区开展了亚微米级颗粒物化学组分、粒径及其污染来源的在线测量.结果表明,观测期间上海城区亚微米颗粒物质量浓度平均为(22.0±17.2)μg·m-3;其中,有机物是PM1的主要贡献者,平均占总颗粒物浓度的49.3%,硫酸根、硝酸根和铵根的占比分别为24.2%、10.5%和9.7%.上海城区亚微米级颗粒物中无机盐组分类(硝酸根,硫酸根和铵根)具有较为一致的粒径分布,峰值粒径主要集中在空气动力学粒径500~600 nm.有机物的粒径分布峰值位于空气动力学粒径400~500 nm,且在小粒径范围内有较高的有机物浓度,表明存在一定程度的一次排放.观测期间有机气溶胶呈现明显的多峰分布,硫酸根、铵根和氯离子呈白天低、夜间高的特点,而硫酸根和黑碳的日变化并不明显.基于高分辨率有机质谱计算得到上海城区有机气溶胶氧碳比(O/C)的平均比值为0.37;有机物与有机碳(OM/OC)的平均比值1.65.利用正矩阵因子解析(PMF)模型对有机气溶胶高质量分辨率质谱进行来源解析,得到4类有机气溶胶:HOA(还原态有机气溶胶)、COA(餐饮源有机气溶胶)、MO-OOA(高氧化性有机气溶胶)和LO-OOA(低氧化性有机气溶胶),分别占有机气溶胶总量的15%、20%、32%和26%,说明观测期间上海城区有机气溶胶主要来自二次气溶胶的贡献.     

Effect of sulfur source on photocatalytic degradation performance of CdS/MoS2 prepared with one-step hydrothermal synthesis

Cd S/Mo S_2,an extremely efficient photocatalyst,has been extensively used in hydrogen photoproduction and pollutant degradation.Cd S/Mo S_2can be synthesized by a facile one-step hydrothermal process.However,the effect of the sulfur source on the synthesis of Cd S/Mo S_2via one-step hydrothermal methods has seldom been investigated.We report herein a series of one-step hydrothermal preparations of Cd S/Mo S_2using three different sulfur sources:thioacetamide,L-cysteine,and thiourea.The results revealed that the sulfur source strongly affected the crystallization,morphology,elemental composition and ultraviolet(UV)–visible-light-absorption ability of the Cd S/Mo S_2.Among the investigated sulfur sources,thioacetamide provided the highest visible-light absorption ability for Cd S/Mo S_2,with the smallest average particle size and largest surface area,resulting in the highest efficiency in Methylene Blue(MB)degradation.The photocatalytic activity of Cd S/Mo S_2synthesized from the three sulfur sources can be arranged in the following order:thioacetamideL-cysteinethiourea.The reaction rate constants(k)for thioacetamide,L-cysteine,and thiourea were estimated to be 0.0197,0.0140,and 0.0084 min~(-1),respectively.However,thioacetamide may be limited in practical application in terms of its price and toxicity,while L-cysteine is relatively economical,less toxic and exhibited good photocatalytic degradation performance toward MB.     

The selective catalytic reduction of NO over Ce0.3TiOx-supported metal oxide catalysts

A Ce_(0.3)TiO_xoxide carrier was synthesized via a sol–gel process,and Ce_(0.3)TiO_xsupported metal(M=Cd,Mn,Fe,W,Mo)oxide catalysts were prepared by the method of incipient-wetness impregnation.The catalysts were characterized by means of X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET)analysis,scanning electron microscopy(SEM),transmission electron microscopy(TEM),Fourier transform infrared(FT–IR)spectroscopy,UV–Visdiffusereflectancespectroscopy(UV–VisDRS),and Temperature-programmed reduction with H_2(H_2-TPR).The catalytic activities for de-NO_(x )were evaluated by the NH_3-SCR reaction.Among all the catalysts tested,the 2 wt.%Cd/Ce_(0.3)TiO_xcatalyst exhibited the best NH_3-SCR performance,with a wide temperature window of 250–450°C for NO conversion above 90%.Moreover,the catalyst showed N_2 selectivity greater than 99%from 200 to 450°C.     

Characteristics of microbial community involved in early biofilms formation under the influence of wastewater treatment plant effluent

Effluents from wastewater treatment plants (WWTPs) containing microorganisms and residual nutrients can influence the biofilm formation. Although the process and mechanism of bacterial biofilm formation have been well characterized, little is known about the characteristics and interaction of bacteria, archaea and eukaryotes in the early colonization, especially under the influence of WWTP effluent. The aim of this study was to characterize the important bacterial, archaeal and eukaryotic species in the early stage of biofilm formation downstream of the WWTP outlet. Water and biofilm samples were collected 24 and 48 hr after the deposition of bio-cords in the stream. Illumina Miseq sequencing of the 16S and 18S rDNA showed that, among the three domains, the bacterial biofilm community had the largest alpha and beta diversity. The early bacterial colonizers appeared to be “biofilm-specific”, with only a few dominant operational taxonomic units (OTUs) shared between the biofilm and the ambient water environment. Alpha-proteobacteria and Ciliophora tended to dominate the bacterial and eukaryotic communities, respectively, of the early biofilm already at 24 hr, whereas archaea played only a minor role during the early stage of colonization. The network analysis showed that the three domains of microbial community connected highly during the early colonization and it might be a characteristic of the microbial communities in the biofilm formation process where co-occurrence relationships could drive coexistence and diversity maintenance within the microbial communities.     

Dispersive liquid–liquid microextraction of silver nanoparticles in water using ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate

Using the ionic liquid(IL)1-octyl-3-methylimidazolium hexafluorophosphate as the extractant and methanol as the dispersion solvent,a dispersive liquid–liquid microextraction method was developed to extract silver nanoparticles(AgN Ps)from environmental water samples.Parameters that influenced the extraction efficiency such as IL concentration,pH and extraction time were optimized.Under the optimized conditions,the highest extraction efficiency for AgN Ps was above 90% with an enrichment factor of 90.The extracted AgN Ps in the IL phase were identified by transmission electron microscopy and ultraviolet–visible spectroscopy,and quantified by inductively coupled plasma mass spectrometry after microwave digestion,with a detection limit of 0.01 μg/L.The spiked recovery of AgN Ps was 84.4% with a relative standard deviation(RSD)of 3.8%(n = 6)at a spiked level of 5 μg/L,and 89.7% with a RSD of 2.2%(n = 6)at a spiked level of 300 μg/L,respectively.Commonly existed environmental ions had a very limited influence on the extraction efficiency.The developed method was successfully applied to the analysis of Ag NPs in river water,lake water,and the influent and effluent of a wastewater treatment plant,with recoveries in the range of 71.0%–90.9% at spiking levels of 0.11–4.7 μg/L.     

Structural and metabolic responses of microbial community to sewage-borne chlorpyrifos in constructed wetlands

Long-term use of chlorpyrifos poses a potential threat to the environment that cannot be ignored, yet little is known about the succession of substrate microbial communities in constructed wetlands(CWs) under chlorpyrifos stress. Six pilot-scale CW systems receiving artificial wastewater containing 1 mg/L chlorpyrifos were established to investigate the effects of chlorpyrifos and wetland vegetation on the microbial metabolism pattern of carbon sources and community structure, using BIOLOG and denaturing gradient gel electrophoresis(DGGE) approaches. Based on our samples, BIOLOG showed that Shannon diversity(HV) and richness(S) values distinctly increased after 30 days when chlorpyrifos was added. At the same time, differences between the vegetated and the non-vegetated systems disappeared. DGGE profiles indicated that H Vand S had no significant differences among four different treatments. The effect of chlorpyrifos on the microbial community was mainly reflected at the physiological level. Principal component analysis(PCA) of both BIOLOG and DGGE showed that added chlorpyrifos made a difference on test results.Meanwhile, there was no difference between the vegetation and no-vegetation treatments after addition of chlorpyrifos at the physiological level. Moreover, the vegetation had no significant effect on the microbial community at the genetic level. Comparisons were made between bacteria in this experiment and other known chlorpyrifos-degrading bacteria. The potential chlorpyrifos-degrading ability of bacteria in situ may be considerable.     

添加CaO对燃煤重金属元素富集效果的影响

选取CaO作为吸附剂,探究了不同燃烧温度下添加CaO对重金属元素在燃煤灰渣中富集效果的影响规律。实验结果表明:添加CaO对重金属元素Cr未起到富集作用,而对Mn,Ni,Cu,Zn,As,Cd,Pb 7种重金属元素的富集效果显著;随燃烧温度的升高,CaO对各赋存形态的Mn,Ni,Cu,Zn,As的富集效果先变好而后变差,对各赋存形态的Cd和Pb的富集效果越来越好;CaO添加比(预处理后的CaO颗粒与预处理后的原煤的质量比)越大,CaO对Mn,Ni,Cu,Zn,As,Cd,Pb的富集效果越好,燃烧温度为850℃时的最佳CaO添加比为4%。     

高效重金属捕集剂EDTC的结构表征及对酸性络合铜的去除特性研究

以乙二胺和二硫化碳为反应物,无水乙醇和去离子水的混合溶液为溶剂,制备了一种巯基类重金属捕集剂N,N-双(二硫代羧基)乙二胺(EDTC),采用紫外光谱、红外光谱和元素分析对其结构进行表征,重点研究了其对EDTA络合铜、柠檬酸络合铜和酒石酸铜3种酸性模拟络合铜的去除性能及螯合沉淀物的溶出特性,并探讨了EDTC脱除络合铜的机理.研究结果表明,处理50 mg·L-1的含铜废水,p H值范围为3~9,EDTC投加量为mEDTC/mCu=8(质量比),反应时间3 min,PAM投加量为1 mg·L-1,此时出水Cu2+浓度均低于0.25 mg·L-1,去除率达到99.5%以上.螯合沉淀物在弱酸性和弱碱性条件下很稳定,不易产生二次污染.红外光谱图分析结果表明,EDTC与Cu会发生螯合反应,即EDTC直接脱出络合铜中Cu2+,并与Cu2+生成难溶的螯合产物EDTC-Cu,进而有效地去除废水中Cu.     

Chemical characteristics of fine particles and their impact on visibility impairment in Shanghai based on a 1-year period observation

In this work, a one-year observation focusing on high time resolution characteristics of components in fine particles was conducted at an urban site in Shanghai. Contributions of different components on visibility impairment were also studied. Our research indicates that the major components of PM_2.5 in Shanghai are water-soluble inorganic ions and carbonaceous aerosol, accounting for about 60% and 30% respectively. Higher concentrations of sulfate (SO₄²⁻) and organic carbon (OC) in PM_2.5 occurred in fall and summer, while higher concentrations of nitrate (NO₃⁻) were observed in winter and spring. The mass concentrations of Cl⁻ and K⁺ were higher in winter. Moreover, NO₃⁻ increased significantly during PM_2.5 pollution episodes. The high values observed for the sulfate oxidizing rate (SOR), nitrate oxidizing rate (NOR) and secondary organic carbon (SOC) in OC indicate that photochemical reactions were quite active in Shanghai. The IMPROVE (Interagency Monitoring of Protected Visual Environments) formula was used in this study to investigate the contributions of individual PM_2.5 chemical components to the light extinction efficient in Shanghai. Both NH₄NO₃ and (NH₄)₂SO₄ had close relationships with visibility impairment in Shanghai. Our results show that the reduction of anthropogenic SO₂, NO_x and NH₃ would have a significant effect on the improvement of air quality and visibility in Shanghai.     

长春市净月大学城区PM2．5及PM10空间分布特征初步研究

为掌握长春市主城区净月大学城区PM2．5和PM10质量浓度的空间分布特征,选择了8处室外环境空间,使用YT－HPC3000 C型主动采样激光粉尘仪,对各样点进行了质量浓度监测。结果表明,与区域内室外8处样点的PM10质量浓度,以轻轨站处为最高,其他7处样点均好于二级标准;室内4处样点的PM2．5和PM10的质量浓度,食堂均未达标,其他3处样点均达标。在室内各样点,PM2．5与PM10的浓度空间分布呈现随高度升高而降低的趋势;在室外各样点,PM2．5与PM10的浓度分布与其所处垂向位置无明显相关关系。