采用光谱学技术分析邻苯二甲酸酯与DNA互作机制

邻苯二甲酸酯(PAEs)作为增塑剂被广泛使用,易渗透到环境中产生环境毒性,多种PAEs已被美国环境保护署和中国环境监测中心列为优先控制污染物,其生态毒理学机制被广泛关注。本试验以小牛胸腺DNA(ct DNA)为供试材料,旨在通过光谱学技术探究PAEs与DNA的相互作用机制。在紫外可见光谱试验中,随着PAEs浓度的增加,DNA紫外光谱出现增色效应,证明DNA的部分碱基对被PAEs破坏,且PAEs与DNA通过嵌插作用结合。荧光光谱试验中,随着PAEs浓度的增加,EBct DNA体系荧光强度逐渐降低,邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)和邻苯二甲酸二丁酯(DBP)的最大荧光抑制率分别为55%、50%和36%;KI荧光猝灭试验中,在加入DNA之后KI对DMP、DEP和DBP的荧光猝灭常数Ksv分别从7.992(R2=0.9970)、10.270(R2=0.9960)和13.52(R2=0.9806)降低到6.721(R2=0.9963)、7.047(R2=0.9599)和11.03(R2=0.9803),荧光猝灭常数均降低,实验结果证明PAEs与DNA通过嵌插作用结合。盐离子试验中,随着Na Cl浓度的增加,PAEsct DNA的荧光强度没有发生变化。试验结果排除了PAEs与DNA分子之间沟槽作用的可能,确定了其结合方式为嵌插作用,随着PAEs侧链的逐渐增长,嵌插作用逐渐减弱。     

Diverse molecular compositions of dissolved organic matter derived from different composts using ESI FT-ICR MS

Dissolved organic matter (DOM) derived from various composts can promote significant changes of soil properties. However, little is known about the DOM compositions and their similarities and differences at the molecular level. In this study, the molecular compositions of DOM derived from kitchen waste compost (KWC), green waste compost (GWC), manure waste compost (MWC), and sewage sludge compost (SSC) were characterized by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The molecular formulas were classified into four subcategories: CHO, CHON, CHOS, and CHONS. The KWC, MWC, and SSC DOM represented the highest fraction (35.8%-47.4%) of CHON subcategory, while the GWC DOM represented the highest fraction (68.4%) of CHO subcategory. The GWC DOM was recognized as the nitrogen- and sulfur-deficient compounds that were less saturated, more aromatic, and more oxidized compared with other samples. Further analysis of the oxygen, nitrogen-containing (N-containing), and sulfur-containing (S-containing) functional groups in the four subcategories revealed higher organic molecular complexity. Comparison of the similarities and differences of the four samples revealed 22.8% ubiquitous formulas and 17.4%, 11.1%, 10.7%, and 6.3% unique formulas of GWC, KWC, SSC, and MWC DOM, respectively, suggesting a large proportion of ubiquitous DOM as well as unique, source-specific molecular signatures. The findings presented herein provide new insight into the molecular characterization of DOM derived from various composts and demonstrated the potential role of these different compounds for agricultural utilization.     

SEWAGE DISCHARGES FROM SHIPS TRANSITING COASTAL SALT WATERS1

ABSTRACT: A number of aspects of the discharging of non-oily wastewaters by transiting ships are treated in this overview paper. In the introduction, options to discharging (the use of holding tank, on board treatment) and the impact of changing regulations are discussed. Assessment of the effects of sewage discharges on coastal waters required that data, at first not available, be generated. An account is given of the characterization of Navy shipboard wastewaters and of experiments involving sewage discharges at sea, measurements of water quality before, during and after an amphibious operation, and fore and aft of transitting Navy ships. A better understanding of sewage dilution after discharge led to the verification of a method for controlled discharging of sewage (and other wastewaters). This method permits limiting the coliform bacteria count in the ship's wake to values below acceptable limits. The final sections contain information on long range effects of ships’sewage discharges, obtained in studies by the U.S. Navy and others, as well as public health considerations.     

新型低温CuO/AC脱硫剂制备——煅烧温度对脱硫活性的影响

首次将炭载型ＣｕＯ／ＡＣ用于烟气脱硫,在最经济的烟气脱硫温度窗口（１２０～２５０℃）显示出高的脱硫活性．考查了煅烧温度和煅烧后脱硫剂的预氧化对脱硫活性的影响,并对脱硫剂进行了ＴＰＤ和ＥＸＡＦＳ表征．结果表明：经２５０℃煅烧的ＣｕＯ／ＡＣ脱硫剂具有最高的脱硫活性．２００℃煅烧,前驱体Ｃｕ（ＮＯ₃）₂未完全分解;高于２５０℃煅烧,活性组分ＣｕＯ被载体Ｃ部分还原为金属Ｃｕ 微晶,从而发生烧结、聚集,以上均导致脱硫剂活性的下降．尽管不同温度煅烧的ＣｕＯ／ＡＣ表现出大的脱硫活性差异,但吸硫后均生成同一反应产物ＣｕＳＯ₄．２５０℃煅烧的ＣｕＯ／ＡＣ脱硫剂Ｃｕ 以ＣｕＯ和Ｃｕ₂Ｏ形态存在,其中的Ｃｕ₂Ｏ在２００℃很容易氧化成ＣｕＯ     

阳(阴)离子复配修饰两性磁性膨润土的表面特征差异及对苯酚吸附的影响

以膨润土(BT)为基质,采用共沉淀法制备负载Fe3O4的磁性膨润土(MBT),在两性表面活性剂十二烷基二甲基甜菜碱(BS-12)修饰(BS-MBT)的基础上,以阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)/阴离子表面活性剂十二烷基磺酸钠(SDS)为复配修饰剂,通过湿法分别制备2种两性复配修饰磁性膨润土(BS-CT-MBT/BS-SDS-MBT),采用扫描电镜、X-射线衍射、热重、红外光谱对样品进行表征,测定磁性、比表面积和孔容等性质,通过批处理实验法对比两性复配修饰磁性膨润土对苯酚的吸附.结果表明,两性复配修饰膨润土具有良好的磁分离性能.与BS-MBT相比,BS-CT-MBT的C、N质量分数增大,复配修饰剂质量分数增加,孔容和比表面积减小,BS-SDS-MBT的C、N质量分数减小,复配修饰剂质量分数减少,孔容减小,比表面积增大.在pH 6.0的0.1 mol·L~(-1)Na Cl溶液中各修饰剂的解吸率低于9%.各土样对苯酚的等温吸附数据符合Henry模型,以分配吸附为主,吸附量顺序为BS-CT-MBTBS-MBTBS-SDS-MBTBTMBT,修饰剂质量分数是影响苯酚吸附的决定性因素,CTMAB提升土样吸附苯酚能力的效果高于SDS.     

Chemical characterization and source apportionment of PM1 and PM2.5 in Tianjin, China: Impacts of biomass burning and primary biogenic sources

The submicron particulate matter (PM₁) and fine particulate matter (PM_2.5) are very important due to their greater adverse impacts on the natural environment and human health. In this study, the daily PM₁ and PM_2.5 samples were collected during early summer 2018 at a sub-urban site in the urban-industrial port city of Tianjin, China. The collected samples were analyzed for the carbonaceous fractions, inorganic ions, elemental species, and specific marker sugar species. The chemical characterization of PM₁ and PM_2.5 was based on their concentrations, compositions, and characteristic ratios (PM₁/PM_2.5, AE/CE, NO₃^?/SO₄^2?, OC/EC, SOC/OC, OM/TCA, K+/EC, levoglucosan/K⁺, V/Cu, and V/Ni). The average concentrations of PM₁ and PM_2.5 were 32.4 µg/m³ and 53.3 µg/m³, and PM₁ constituted 63% of PM_2.5 on average. The source apportionment of PM₁ and PM_2.5 by positive matrix factorization (PMF) model indicated the main sources of secondary aerosols (25% and 34%), biomass burning (17% and 20%), traffic emission (20% and 14%), and coal combustion (17% and 14%). The biomass burning factor involved agricultural fertilization and waste incineration. The biomass burning and primary biogenic contributions were determined by specific marker sugar species. The anthropogenic sources (combustion, secondary particle formation, etc) contributed significantly to PM₁ and PM_2.5, and the natural sources were more evident in PM_2.5. This work significantly contributes to the chemical characterization and source apportionment of PM₁ and PM_2.5 in near-port cities influenced by the diverse sources.     

KMnO4-PAC对高原喀斯特湖库DOM的DBPsFP控制

以云贵高原典型喀斯特湖库红枫湖取水口溶解性有机质（DOM）为研究对象,调查不同组合方式下高锰酸钾-聚合氯化铝（KMnO₄-PAC）对消毒副产物的生成潜能（DBPsFP）变化和平均组成分布,并通过红外光谱（FTIR）和三维荧光光谱（3D-EEM）对部分样品进行化学表征,推断其影响机制.结果表明：在0.1,0.2,0.4mg/L KMnO₄投加量下,DBPsFP降低17.5~73%,DOM的卤代活性化学结构和官能团部分被有效钝化;PAC的网捕和卷扫效应使DBPsFP进一步减少27.9~86.1%,组合工艺对DBPs的生成潜能影响大小为：三卤甲烷（THM₄） > 卤乙酸（HAA₉） > 卤乙腈（HAN₄）/卤代酮（HK₂）/三氯硝基甲烷（TCNM）.FTIR的结果表明预氧化后3300cm^-1处的透过率降低,指纹区1000~1300cm^-1处的峰频提升,表明分子中的O-H、COOH和C-O官能团增加,共轭不饱和结构在KMnO₄作用下部分消失.3D-EEM验证了外源有机物（腐殖酸）在DOM中占比随KMnO₄浓度梯度升高而下降,同时类蛋白结构的吸收峰强度增加,说明最终DBPs贡献可能源于DOM中剩余的小分子类蛋白（氨基酸）.     

秋冬交替季节白洋淀沉积物有机质特性研究

为了研究白洋淀沉积物中有机质释放对秋冬交替季节淀区水环境的影响.将白洋淀分为自然保护区、旅游区、村落密集区、淀中村区和出淀口区五部分,在20个代表性采样点采集沉积物样品,采用光谱学方法表征样品中有机质特性,并研究氮、磷的溶解释放特征.结果表明:①在自然保护区、淀中村区和出淀口区,沉积物中有机质的腐殖化和芳香化程度较高,主要为陆源可见光类腐殖酸组分（C1）、海源可见光类腐殖酸组分（C3）和紫外光类腐殖酸组分（C4）;而在旅游区和村落密集区,有机质的腐殖化和芳香化程度较低,主要为类色氨酸组分（C2）,表明这些区域受人为活动影响大.②紫外吸收光谱和荧光光谱参数具有很好的相关性,可用于表征沉积物中有机质特征;类色氨酸组分的荧光强度与沉积物中w（TN）和w（TP）具有良好的正相关关系,显示出同源性特征.③与以类腐殖酸为主要成分的沉积物样品相比,氮、磷更易从以类蛋白为主要成分的沉积物中释放.研究显示,秋冬交替季节白洋淀沉积物中有机质以类蛋白和类腐殖酸为主,且类蛋白具有促进共存氮、磷溶解释放的作用.      

Chemical characterization and source apportionment of atmospheric submicron particles on the western coast of Taiwan Strait, China

Taiwan Strait is a special channel for subtropical East Asian Monsoon and its western coast is an important economic zone in China. In this study, a suburban site in the city of Xiamen on the western coast of Taiwan Strait was selected for fine aerosol study to improve the understanding of air pollution sources in this region. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer(HR-To F-AMS) and an Aethalometer were deployed to measure fine aerosol composition with a time resolution of 5 min from May 1to 18, 2015. The average mass concentration of PM1 was 46.2 ± 26.3 μg/m~3 for the entire campaign. Organics(28.3%), sulfate(24.9%), and nitrate(20.6%) were the major components in the fine particles, followed by ammonium, black carbon(BC), and chloride. Evolution of nitrate concentration and size distribution indicated that local NOx emissions played a key role in high fine particle pollution in Xiamen. In addition, organic nitrate was found to account for 9.0%–13.8% of the total measured nitrate. Positive Matrix Factorization(PMF)conducted with high-resolution organic mass spectra dataset differentiated the organic aerosol into three components, including a hydrocarbon-like organic aerosol(HOA) and two oxygenated organic aerosols(SV-OOA and LV-OOA), which on average accounted for 27.6%,28.8%, and 43.6% of the total organic mass, respectively. The relationship between the mass concentration of submicron particle species and wind further confirmed that all major fine particle species were influenced by both strong local emissions in the southeastern area of Xiamen and regional transport through the Taiwan Strait.     

麦秸焚烧导致的北京市大气污染时空分布和化学组成特征分析

为了全面评价农田秸秆焚烧产生的污染事件,并为制定有效的管理措施提供依据,于2006年6月20日监测了西南风下北京南部农田麦秸焚烧产生的污染物向北京传输的过程.获得了SO2、CO、NOx以及可吸入颗粒物(PM10)质量浓度的数据.颗粒物的化学组分数据.数据分析结果表明,污染输送对北京市西南部地区空气质量影响最大(PM10小时浓度超过600μg·m-3),对北部山区影响较小(PM10浓度峰值在110μg·m-3).高浓度污染在市区持续时间最长.麦秸焚烧通过输送增加了PM10(尤其是PM1)、CO、NO2以及NMHC等污染物质,这使得与前一日相比污染物之间的相关关系发生了变化:SO2与其它污染物的相关性不显著,而CO与NO2、CH4与NO显著相关.因子分析进一步揭示,气象条件对污染物浓度变化具有主导作用,而由麦秸焚烧所产生的外来污染源属于次要地位.污染输送过程中,PM25中的硝酸盐类和有机碳、碳黑质量浓度增大.麦秸焚烧所输送的气态污染物和细小颗粒物对人体健康存在威胁,在不利扩散的气象条件下在大气中存留时间加长.研究结果表明,气象条件不利于污染扩散时必须禁止农田秸秆焚烧.