北京市PM2.5中类腐殖质的生物氧化应激效应初探

为研究细颗粒物(PM_2.5)中类腐殖质(humic-like substances, HULIS)的生物氧化应激效应,对北京市区和郊区不同季节大气PM_2.5及其中碳质组分和金属元素浓度进行测定,并以大鼠肺泡巨噬细胞(NR8383)作为细胞模型,分析PM_2.5及其重要组分诱导产生内源性ROS的能力,研究了PM_2.5中HULIS对诱导产生内源性ROS的贡献. 结果表明:①冬季PM_2.5中碳质组分浓度及内源性ROS浓度(单位为μg zymosan/m3,以酵母聚糖(zymosan)表征的单位体积空气中内源性ROS的浓度)明显高于夏季,但夏季PM_2.5具有更高的生物氧化潜力(单位为μg zymosan/mg PM,以酵母聚糖(zymosan)表征的单位质量颗粒物的生物氧化潜力). ②PM_2.5中碳质组分和一些金属元素浓度均与PM_2.5生成的内源性ROS浓度之间具有较高的相关性. ③HULIS单独诱导生成的内源性ROS浓度也呈冬季〔市区和郊区分别为(55.46±22.69) (43.27±23.89) μg zymosan/m3〕高于夏季〔市区和郊区分别为(18.73±11.94) (7.88±3.63) μg zymosan/m3〕的特征. 在北京市区和郊区两个采样点,由HULIS单独诱导生成的内源性ROS浓度与PM_2.5诱导生成的总内源性ROS浓度之间具有较好的相关性. 研究显示,HULIS是PM_2.5中诱导ROS生成的关键组分,在北京市区和郊区两个采样点HULIS对PM_2.5诱导的内源性ROS的贡献率分别为42%和37%.      

几种重金属对皱纹盘鲍血细活性氧产生的影响

体外条件下利用化学发光法定量地研究了不同种类和不同浓度的重金属:Cr、Cd、Hg、Pb、C和Zn对皱纹盘鲍血细胞吞噬时活性氧产生的影响。结果表明,不同种类和不同浓度的重金属浸泡急性处理皱纹盘鲍血细胞都不同程度地抑制了血细胞吞噬时的化学发光,表明重金属能够抑制皱纹盘鲍血细胞吞噬活动中的活性氧(ROS)的产生,而且这种抑制作用随着重金属浓度的增加而加强。不同的重金属抑制强度不同,从强到弱以次为Hg>Cd>Cu>Pb>Cr>Zn。研究表明六种重金属中,Hg对皱纹盘鲍血细胞的免疫毒性最大。     

PM2.5中类腐殖质表面活性测定方法与实例分析

建立了大气细粒子中类腐殖质（HULIS）表面活性的动态表征方法,并以华北平原乡村站点冬季大气PM_2.5样品为例,对PM_2.5中HULIS的表面活性进行表征.HULIS碳质组分（HULIS-C）浓度为2.0~4.6μg C/m³,占水溶性有机碳和总有机碳的比例分别为31%~40%和20%~26%.浓度为88~200mg C/L的HULIS水溶液,其表面张力相对于纯水降低了18%~22%.HULIS-C浓度在低于70mg C/L时表面张力降低显著,在88~320mg C/L之间降低相对缓慢.动态表面张力随着时间变化逐渐降低,在液滴形成后200s以内表面张力下降迅速,之后趋于平缓,说明表面活性分子在液滴中扩散趋于稳定需要一定的时间,该特征时间可能影响表面活性物质在云凝结核活化时的作用.证实了在污染地区的大气PM_2.5中含有一定量的表面活性物质,这些物质可能对颗粒物活化为云滴、雾滴过程产生显著影响;表面活性物质的存在可能在外界湿度变化过程中导致颗粒物发生液-液相分离现象,在颗粒物表面形成有机膜,影响活性分子摄取以及半挥发性物质的气-粒分配过程,从而影响大气非均相反应过程.     

气溶胶中溶解性有机质(DOM)液相氧化

许多实验研究都关注大气凝聚相中单一有机化合物的液相光化学,对于实际大气液相环境中溶解性有机质（DOM）的液相光化学氧化的研究还很少.为此,本文报道了模拟太阳光和紫外光辐照下,大气气溶胶水相萃取的DOM直接或·OH氧化的实验结果.不同光解阶段的产物的吸光、氧化特性采用UV-vis和黑炭气溶胶质谱仪（SP-AMS）分析.结果表明,紫外光体系中DOM得到不断降解,相应的产物f44值远低于太阳光体系;液相光解时会生成多种羧酸,草酸的生成量最高.太阳光照反应条件下吸光度和HULIS浓度变化不大;而UV和UV+·OH条件下,HULIS浓度随反应时间不断增加,UV+·OH中反应23 h时HULIS浓度约为初始的4倍,说明含羧基、羟基和芳香基等官能团的棕色碳的形成.综合研究结果表明,太阳光作用下实际DOM液相氧化时吸光性和棕色碳的形成速率不是很快,而紫外光作用下大部分DOM不断分解为HULIS或小分子物质,剩余的有机物的吸光性可能比较强,导致最终产物的单位质量吸收效率（MAE）比较高.本文首次探讨了实际膜液相氧化过程,结果对厘清大气复合污染的形成机制提供重要依据.     

Study on superoxide and hydroxyl radicals generated in indirect electrochemical oxidation by chemiluminescence and UV-Visible spectra

The generation and transformation of radicals on the cathode of indirect electrochemical oxidation were studied by chemilumines- cence(CL)and UV-Visible spectra in the reactor with a salt bridge that connected the separated chambers.The CL intensity of 4×10~(-9)mol/L luminol on the cathode with bubbling oxygen was about seven times that of the intensity without it,which was because of the generation of reactive oxygen species(ROS).The existence of ROS,especially the generation of the superoxide radical,c...     

城市环境PM2.5空间分布监测方法研究进展

随着城市化和工业化的发展,城市环境中日益增多的PM_(2.5)对人类健康造成了严重威胁。本文旨在分析总结目前PM_(2.5)空间分布的相关监测方法以及空气质量预测模型。当下,PM_(2.5)浓度的监测不仅涉及大气化学、污染物的源解析、大气化学运输模型、线性及非线性空气质量模拟等方面,还涉及地理信息系统与卫星遥感等新技术的运用。本文在比较传统PM_(2.5)监测与新型监测方法不同的基础上,分析了各自的优劣,为空气质量监测提供建议和指导。     

Variation in levels of reactive oxygen species is explained by maternal identity, sex and body-size-corrected clutch size in a lizard

Many organisms show differences between males and females in growth rate and crucial life history parameters, such as longevity. Considering this, we may expect levels of toxic metabolic by-products of the respiratory chain, such as reactive oxygen species (ROS), to vary with age and sex. Here, we analyse ROS levels in female Australian painted dragon lizards (Ctenophorus pictus) and their offspring using fluorescent probes and flow cytometry. Basal level of four ROS species (singlet oxygen, peroxynitrite, superoxide and H₂O₂) measured with a combined marker, and superoxide measured specifically, varied significantly among families but not between the sexes. When blood cells from offspring were chemically encouraged to accelerate the electron transport chain by mitochondrial uncoupling, net superoxide levels were three times higher in daughters than sons (resulting in levels outside of the normal ROS range) and varied among mothers depending on offspring sex (significant interaction between maternal identity and offspring sex). In offspring, there were depressive effects on ROS of size-controlled relative clutch size, which relies directly on circulating levels of vitellogenin, a confirmed antioxidant in some species. Thus, levels of reactive oxygen species varies among females, offspring and in relation to reproductive investment in a manner that makes its regulatory processes likely targets of selection.     

广州冬季气溶胶中水溶性有机物和类腐殖质的吸光性和荧光光谱特性

利用紫外-可见光谱与三维荧光-平行因子分析法(EEM-PARAFAC),研究了广州市2014年12月～2015年1月大气气溶胶中水溶性有机物(WSOC)和类腐殖质(HULIS)的吸光性和荧光光谱特征.结果表明,广州冬季气溶胶中HULIS的芳香性(SUVA254)、腐殖化程度(HIX)和光吸收效率(MAE365)均高于WSOC.利用EEM-PARAFAC从WSOC和HULIS解析出了类富里酸(C1)、类腐殖酸(C2)和类蛋白(C3)这3种荧光组分.其中类腐殖质组分(C1+C2)分别占WSOC和HULIS中总荧光组分的78%和85%,说明类腐殖荧光组分是WSOC和HULIS的最主要组成,且HULIS富集了更多的WSOC中主要的类腐殖组分.另外,灰霾期的WSOC和HULIS表现出更高的芳香性、腐殖化程度和C2组分,说明灰霾期有助于大分子量吸光性有机质的形成.相关性分析结果显示,WSOC和HULIS的C1组分相对含量与HIX、MAE365、OCsec、K+、SO_4~(2-)和NH_4~+呈现极显著的负相关关系,而C2与它们之间存在极显著的正相关关系.由此说明,WSOC和HULIS中C1的降低和C2的增加会引起它们的腐殖化程度和光吸收能力的增强;同时生物质燃烧排放和二次气溶胶过程可能有助于C2组分的增加.     

铜与毒死蜱复合污染对淡水绿藻的毒性效应

重金属及农药残留在水环境中被频繁检测出,其复合污染对环境生物的联合毒性有别于单因子的生物效应.以淡水绿藻为受试生物,比较分析了有机磷农药毒死蜱（Chlorpyrifos）和重金属铜的单一及复合暴露对蛋白核小球藻急性毒性、细胞通透性及抗氧化应激的影响.铜、毒死蜱72小时单一暴露对小球藻的EC₅₀分别为0.68和12.71μmol/L,藻细胞叶绿素含量随污染物浓度的增大而降低,细胞通透性随污染物浓度的增大而增强,藻细胞活性氧和抗氧化酶被显著诱导.利用相加指数法（Additive Index,AI）确定铜、毒死蜱联合暴露对小球藻急性毒性的联合作用类型为拮抗作用,这与小球藻ROS产生量及抗氧化酶等指标的显著性水平分析结果一致.     

Review on recent progress in on-line monitoring technology for atmospheric pollution source emissions in China

Emissions from mobile sources and stationary sources contribute to atmospheric pollution in China, and its components, which include ultrafine particles (UFPs), volatile organic compounds (VOCs), and other reactive gases, such as NH₃ and NO_x, are the most harmful to human health. China has released various regulations and standards to address pollution from mobile and stationary sources. Thus, it is urgent to develop online monitoring technology for atmospheric pollution source emissions. This study provides an overview of the main progress in mobile and stationary source monitoring technology in China and describes the comprehensive application of some typical instruments in vital areas in recent years. These instruments have been applied to monitor emissions from motor vehicles, ships, airports, the chemical industry, and electric power generation. Not only has the level of atmospheric environment monitoring technology and equipment been improving, but relevant regulations and standards have also been constantly updated. Meanwhile, the developed instruments can provide scientific assistance for the successful implementation of regulations. According to the potential problem areas in atmospheric pollution in China, some research hotspots and future trends of atmospheric online monitoring technology are summarized. Furthermore, more advanced atmospheric online monitoring technology will contribute to a comprehensive understanding of atmospheric pollution and improve environmental monitoring capacity.     

邻苯二甲酸二丁酯对短裸甲藻活性氧自由基的影响

为揭示邻苯二甲酸二丁酯(dibutyl phthalate,DBP)对短裸甲藻(Gymnodinium breve)的抑制机制,采用荧光探针法和比色法研究了DBP对短裸甲藻活性氧(reactive oxygen species,ROS)、羟自由基.OH和过氧化氢H2O2含量以及超氧阴离子自由基O.2-产生速率的影响,同时观察了电子传递链抑制剂对DBP诱导ROS能力的影响.结果表明DBP诱导了短裸甲藻ROS的积累.随浓度的增大,DBP促进了.OH、H2O2的积累,如3 mg.L-1的DBP处理组,培养至48 h时.OH出现一个极大峰值33U.mL-1,约为对照组的2.4倍;H2 O2含量培养至72 h出现最大值,约为250 nmol.(107 cells)-1,约为对照组的5倍;但是DBP对O.2-产生速率的影响并没有显示出规律性.电子传递链选择性抑制实验表明DBP可能影响了藻细胞线粒体和细胞膜2个位点上电子传递,使.OH、H2O2含量和O.2-产生速率受到了不同的影响,最终诱导了短裸甲藻总ROS的积累.可见,DBP导致ROS的过量积累是其抑制藻细胞生长的主要机制.本研究结果对揭示化感物质抑制藻类的机制提供了科学依据.     

Oxidative degradation of phenol by sulfidated zero valent iron under aerobic conditions: The effect of oxalate and tripolyphosphate ligands

After adding either organic or inorganic ligands, sulfidated nano-zero-valent iron (SnZVI) was used for aerobic degradation of phenol, and the effect of the ligand species on oxidation performance was investigated. We found that SnZVI hardly degraded phenol in the absence of ligand addition. Ligands initiated and promoted the degradation of pollutants by SnZVI. The data herein show that a characteristic inorganic ligand, tripolyphosphate (TPP), is more effective in enhancing oxidation than a characteristic organic ligand oxalate. In addition to the scavenging of reactive oxidants by the organic ligand, more ferrous ion (Fe(II)) dissolution from SnZVI in the TPP system is another cause for the superior enhancement by the inorganic ligand. In the oxalate system, as the sulfur content of SnZVI increased, the oxidation efficiency increased because FeS shell promoted the transfer of electrons to produce more reactive oxygen species (ROS). In TPP system, the effect of sulfur content on oxidation performance is more complex. The SnZVI with low sulfur content showed poor oxidation performance compared with that of nZVI. Further experiments proved that sulfidation might weaken the complexation of TPP with surface bound Fe, which would slow down the ionic Fe(II) dissolution rate. Therefore, sulfidation has the dual effects of enhancing electron transfer and inhibiting the complexation of inorganic ligands. In addition, the mechanisms of ROS generation in different ligand systems were investigated herein. Results showed that the critical ROS in both the oxalate and TPP systems are hydroxyl radicals, and that they are produced via one-electron activation of O₂.     

Polymorphic ROS scavenging revealed by CCCP in a lizard

Ingestion of antioxidants has been argued to scavenge circulating reactive molecules (e.g., free radicals), play a part in mate choice (by mediating access to this important resource), and perhaps increase life span. However, recent work has come to question these relationships. We have shown elsewhere in the polychromatic lizard, Ctenophorus pictus, that diet supplementation of carotenoids as antioxidants does not depress circulating natural reactive oxygen species (ROS) levels and leads to no corresponding improvement of color traits. However, a much stronger test would be to experimentally manipulate the ROS levels themselves and assess carotenoid-induced ROS depression. Here, we achieve this by using carbonyl cyanide 3-chlorophenylhydrazone, which elevates superoxide (SO) formation approximately threefold at 10 μM in this model system. We then look for depressing effects on ROS of the carotenoids in order to assess whether ‘super-production’ of SO makes carotenoid effects on elevated ROS levels detectable. The rationale for this treatment was that if not even such elevated levels of SO are reduced by carotenoid supplementation, the putative link carotenoids, ROS depression, and mate quality (in terms of antioxidant capacity) is highly questionable. We conclude that there is no significant effect of carotenoids on mean SO levels even at the induced ROS levels. However, our results showed a significant interaction effect between carotenoid treatment and male color, with red males having higher ROS levels than yellow males. We suggest that this may be because different pigments are differently involved in the generation of the integumental colors in the two morphs with concomitant effects on ROS depletion depending on carotenoid uptake or allocation to coloration and antioxidation.     

Toxic effects of enrofloxacin on Scenedesmus obliquus

In this article, the toxic effects of Enrofloxacin (ENFX) on Scenedesmus obliquus were studied, through investigating the growth, photosynthetic pigments, and protein contents. The possible toxic mechanisms of ENFX were analyzed by determining the superoxide dismutase (SOD) activity, malondialdehyde (MDA) content, proline content, and superoxide anion (O₂⁻) generation rate. Results showed that the growth of algae was inhibited by ENFX and the 50% effective concentration (EC₅₀) values for 24, 48, 72, and 96 h of ENFX were 88.39, 63.86, 45.10, and 59.16 mg·L⁻¹, respectively. After treated with ENFX for 96 h, the contents of photosynthetic pigments decreased with the increase of ENFX concentration, the content of soluble protein and the activity of SOD increased and then decreased, and the generation rate of superoxide anion (O₂⁻) increased continually. The contents of MDA and proline changed little in lower ENFX concentration groups, but increased rapidly when treated with higher concentration groups. These results suggested that ENFX affected the growth of S. obliquus, and the main toxicity mechanism was that algal cells generated the reactive oxygen species under ENFX stress, and then the reactive oxygen species (ROS) induced the oxidation damages of biologic macromolecules and changed the biomembrane permeability further.     

水中萘普生的紫外光降解机制及其产物毒性研究

以120 W汞灯为紫外光光源,通过活性氧物种(ROS)的淬灭实验和溶解氧(DO)浓度实验和发光菌毒性实验,对水中萘普生(NPX)的降解机制、反应动力学及其产物毒性进行了研究.结果表明,NPX的紫外光降解过程包括了直接光解和ROS参与的自敏化光解两个过程,同时.OH、1O2、O.2-的自敏化光解贡献率分别为0.1%、80.2%、35.7%;溶解氧浓度实验表明,溶解氧对萘普生的降解具有抑制作用,而且浓度越大,抑制效果越明显;发光菌毒性实验表明,萘普生光降解生成了具有较萘普生更高风险的中间产物.本研究中萘普生的所有光解实验过程均符合准一级动力学方程.     

生物质燃烧源类腐殖质的臭氧老化特征

针对生物质燃烧排放类腐殖质（BC-HULIS）的臭氧（O₃）氧化开展模拟研究,利用总有机碳分析仪（TOC）、紫外-可见吸收光谱（UV-vis）、荧光激发发射矩阵光谱结合平行因子分析（EEM-PARAFAC）以及傅里叶变换红外光谱（FTIR）表征老化前后HULIS的光学性质和化学结构变化.研究表明,经臭氧氧化后BC-HULIS占相应的水溶性有机碳（WSOC）的比例降低,表明部分HULIS发生降解生成水溶性小分子化合物.此外经O₃老化后,HULIS的质量吸收指数（MAE₃₆₅）和芳香性指数（SUVA₂₅₄）分别从1.8~2.7和4.2~5.0m²/gC下降到1.1~1.3和3.7~4.1m²/gC,表明老化后HULIS的吸光能力和芳香度均呈现降低.EEM-PARAFAC解析结果显示,BB-HULIS中荧光发色团主要由类蛋白荧光组分（C2）和类腐殖质荧光组分（C1、C3、C4）组成.O₃老化后,BB-HULIS的总荧光强度显著降低,两种性质的荧光组分相对含量和荧光参数发生显著变化,如老化后HULIS中类腐殖质荧光组分的相对含量和腐质化指数（HIX）均显著高于老化前样品,表明老化过程发生类蛋白的降解和类腐殖质的聚合.另外,FTIR分析结果显示O₃老化后含氧官能团含量显著增强,表明了O₃老化对HULIS官能团的影响.     

海洋大气边界层内臭氧和氮氧化物浓度日变化的模拟研究

利用MECCA大气化学模式,考虑卤素类(Br,Cl和I)物质的化学过程,对海洋大气边界层内臭氧和NOx的日变化进行了模拟,并与实测数据进行了对比.结果表明,当考虑这些影响后,ψ(O3)略有降低并且产生峰值的时间提前,这主要是由于Br,BrO,Cl和ClO等物质浓度在日出后很快达到峰值所致,基于同样的原因,NO2变化也有类似的特点.在清洁环境下,海洋大气边界层内臭氧的消耗主要由HOx,O(1D)+H₂O和卤素控制,白天以卤素对臭氧的消耗为主.此外还模拟了不同ψ(NOx)下臭氧的日变化,得出在高ψ(NOx)情况下,边界层内臭氧可由净损耗变为净增长.      

中国区大气汞污染模型模拟初探

介绍并利用Community Multiscale Air Quality-Hg (CMAQ-Hg)多尺度大气汞污染模型,模拟研究了2005年6月24日—7月31日我国大气汞污染状况. 初步模拟结果表明:人为排放源高的地区(如有汞矿群分布、煤炭和火力发电厂及金属冶炼厂)的大气中ρ(汞)较高,大气中元素态汞(GEM)的月均ρ(汞)高于反应性气态汞(RGM)和颗粒汞(PHG),初步反映了我国大气汞污染的分布以及不同形态汞的浓度分布受汞排放源种类及其物理化学特性的影响特征. 在解决汞排放源清单不确定性较大的问题及将模型运行参数本地化后,CMAQ-Hg有望成为研究我国汞污染特点及其长程输送的有力工具.      

磷化氢生物净化体系及抑制作用机理

在PH₃生物净化体系中添加呼吸链电子传递抑制剂,对比分析微生物生长代谢、磷的迁移转化、活性氧（ROS）产生及氧化酶活性等变化规律.当鱼藤酮或抗霉素A分别添加至R1、R2PH₃生物反应器后,其微生物体O₂^-·含量在运行时间14~17d期间的平均值分别上升至0.68,0.96mmol/g,明显高于空白对照组R0反应器.除自由基O₂^-·外,另一类型的活性氧HO·也存在于PH₃净化系统中;受累积的活性氧影响,生物体内丙二醛（MDA）含量处于较高水平,PH₃净化效率通常不超过75%,添加抑制剂的R1与R2反应体系在15~17d期间PH₃平均去除率分别下降至65.1%、59.5%.pH值、ROS含量以及氧化酶活性等因素均明显影响PH₃生物净化效果,当Fe³⁺、Cu²⁺、Mg²⁺等金属阳离子迁移转运至微生物体内时,超氧化物歧化酶（SOD）与过氧化氢酶（CATase）活性得以不同程度的增强,可缓解活性物质O₂^-·或HO·导致的氧化胁迫作用,PH₃净化效能得以适度提升.     

磁性氧化石墨电催化活性及净化印染废水效能

采用高铁酸钾作为铁前驱体和氧化剂氧化石墨矿物,原位合成磁性氧化石墨(MGO)催化剂.磁性氧化石墨与碳黑(CB)混合在碳纤维布基底上制备阴极(MGO/CB),将溶解氧还原生成活性氧(ROS)氧化处理含活性红X-3B染料的模拟废水,并采用扫描电子显微镜、X-射线衍射仪、X-射线光电子能谱、电化学手段表征磁性氧化石墨催化剂的...