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1.
传统的卤代烃自然衰减研究主要关注生物降解过程,然而近年有研究发现卤代烃可以被地层中的活性矿物还原降解.对天然活性矿物介导下卤代烃非生物自然衰减的研究进展总结显示,可以还原降解卤代烃的天然矿物主要包括铁硫矿物、铁氧矿物和含铁黏土矿物等,其中铁硫矿物在含水层中分布最为广泛.常见的反应机制包括还原消除、氢解、自由基加成、自由基偶联、脱卤化氢、水解,其中还原消除和氢解是其中最重要的两种反应机制,常见于卤代烷烃和卤代烯烃的非生物降解.卤代烃的非生物降解产物主要取决于还原降解途径和母体卤代烃.不同矿物对卤代烃的降解活性大致表现为马基诺矿?黄铁矿>黑云母>蛭石≈绿锈>磁铁矿≈蒙脱石.卤代烃的降解速率除受矿物种类影响外,还受到卤代烃种类、pH、硫化物浓度、共存金属离子、天然有机物、矿物形态等因素的影响.现有的研究已经确证活性矿物的还原降解是卤代烃自然衰减的重要机制,但该领域中仍然有一些重要知识点有待进一步研究.关于活性铁矿物Fe(Ⅱ)类型和反应能力之间的关系、还原卤代烃过程中Fe(Ⅱ)的结构变化以及结构态Fe(Ⅱ)向卤代烃的电子转移方式等仍然不清楚,建议进行更深入的研究;现有研究大都基于实验室小试装置,实际场地的研究不多,建议今后进一步探究实验室发现的规律是否符合场地中的实际情况;地下水位波动导致活性矿物间歇性暴露在溶解氧中,可能产生羟自由基(·OH)实现并导致卤代烃的氧化降解,这方面的研究目前尚存在不足,建议给予更多关注.   相似文献   

2.
The chemical composition of smog-chamber aerosol generated during the photo-oxidation of isoprene and β-pinene was probed using infrared (i.r.) microscopy interfaced with a low pressure impactor. The low-pressure impactor employed ZnSe impaction surfaces which allowed direct analysis, with no extraction, using i.r. microscopy. The low detection limits of this technique, coupled with direct sample analysis, permitted the chemical analysis of aerosol generated at low to moderate hydrocarbon and ozone loadings. The quantitative analysis of the i.r. spectra is limited, in part, by the absence of calibration standards, however, it is clear that the biogenic aerosols generated in this work were liquid mixtures containing ketone, aldehyde, alcohol and organonitrate functional groups. Molar loadings of each of these functional groups were estimated for nine smog-chamber experiments. For aerosol formed in isoprene photo-oxidation, aldehyde and ketone groups dominated (1.8 groups per average molecule) while for aerosol formed in β-pinene photo-oxidation, alcohols and ketones dominated (a combined 2.7 groups per average molecule).  相似文献   

3.
The levels of semi-volatile aldehydes with 4–10 carbon atoms and a ketone identified as 6-methyl-5-hepten-2-one by mass spectrometry have been measured in some urban, suburban and forest areas together with important hydrocarbons emitted by man-made (benzene, toluene) and biogenic sources (α-pinene). The results obtained show the ubiquitous occurrence of these carbonyl compounds in the atmospheric environment. Diurnal profiles obtained at various sites and a vertical gradient measured in a pine forest seem to be consistent with their natural origin. Direct emission from plants seems to be a major source for these components in the atmospheric boundary layer. The levels measured indicate that they are among the most abundant gaseous organic components present in natural environments.  相似文献   

4.
A biogenic hydrocarbon emission inventory system, developed for acid deposition and regional oxidant modeling, is described, and results for a U.S. emission inventory are presented. For deciduous and coniferous forests, scaling relationships are used to account for canopy effects upon solar radiation temperature, humidity and wind speed as a function of height through the canopy. Leaf temperature is calculated iteratively from a leaf energy balance as a function of height through the canopy. The predicted light and temperature levels are used with mean emprical emission rate factors and laboratory emission algorithms to predict hydrocarbon emission rates. For application to a U.S. inventory, diurnal emission fluxes of isoprene, α-pinene, other monoterpenes adn otehr hydrocarbons are predicted for eight land cover classes by state climatic division by month. The total U.S. emissions range from 22 to 50 Tg yr−1 depending upon the formulation of different emission rate factors. In the case where the forest canopy model is not used, the isoprene emissions increase by 50% and terpene emissions increase by 6%. In case study analyses, the predicted leaf temperatures were within 1–2°C of observed for a deciduous forest, and predicted emissions were within a factor of two of observations. Further evaluation of the inventory using field measurements is required to determine the overall accuracy of the emission estimates.  相似文献   

5.
多环芳烃作为一类典型的持久性有毒物质,一直是环境领域关注的热点和重点,有关多环芳烃衍生物的报道,尤其是有关大气中烷基和硝基多环芳烃的研究报道仍非常缺乏。本研究选取莱州湾刁龙嘴为采集区域,对大气颗粒相样品中16种母体多环芳烃(PAHs)、12种烷基多环芳烃(A–PAHs)和25种硝基多环芳烃(N–PAHs)进行分析。结果表明,16种母体多环芳烃(Σ16PAHs)的浓度范围为517.2 ~ 64124.8 pg/m3;12种烷基化多环芳烃(Σ12A–PAHs)的浓度范围为273.6 ~ 5897.3 pg/m3;25种硝基化多环芳烃(Σ25N–PAHs)的浓度范围为113.5 ~ 1032.3 pg/m3。3种类型多环芳烃的浓度和污染模式均表现出明显的季节变化特征,其中,夏季,2环、3环的PAHs、A–PAHs和N–PAHs比例相对较高,而冬季4环及以上单体的比例偏高。PAHs的特征比值表明,莱州湾刁龙嘴地区PAHs的来源主要以柴油、煤及生物质燃烧为主。Σ16PAHs、Σ12A–PAHs和Σ25N–PAHs与温度均呈现出显著的负相关性(R2 = 0.94,p < 0.01;R2 = 0.61, p < 0.01;R2 = 0.74,p < 0.01),说明温度是影响颗粒相吸附芳烃类物质的一个主要因素。此外,三者之间Pearson相关关系表明,PAHs及其衍生物表现出相同的污染来源和相似的环境行为。  相似文献   

6.
分别运用吹扫捕集和三级低温预浓缩系统与气-质联用的方法,测定了2014年11月黄渤海表层海水和大气中主要的C2~C5非甲烷烃(NMHCs)的浓度,研究其分布特征及海-气通量,并评价了它们的大气化学反应活性.海水中乙烷、丙烷、异丁烷、正丁烷、乙烯、丙烯、1-丁烯、异丁烯和异戊二烯的浓度平均值分别为53.0,49.4,26.4,29.2,186,62.7,35.6,89.9,42.4pmol/L.大气中乙烷、丙烷、异丁烷、正丁烷、乙烯、丙烯、1-丁烯、异丁烯和异戊二烯的体积分数平均值分别为0.043,21,0.36,6.7,7.5,0.71,0.12,0.16,0.085×10-9.大气中乙烷、丙烷、异丁烷、正丁烷、乙烯、丙烯、1-丁烯和异丁烯具有较好的相关性,均与异戊二烯没有相关性.海-气通量的计算结果表明,近岸陆架海域可能是大气中C2~C5NMHCs重要的源.通过计算C2~C5NMHCs的臭氧生成潜势和OH·消耗速率,表明乙烯、丙烯、丙烷和正丁烷是黄渤海大气C2~C5NMHCs的关键活性组分.  相似文献   

7.
VOCs在大气中主要是与OH自由基、NO3自由基和O3等反应氧化去除,部分OVOCs的自身光解也是重要的化学去除途径.本研究基于2018年和2019年秋季在珠三角地区的城市和区域站点的外场观测实验,使用VOCs、常规痕量气体及气象参数的观测数据,对烷烃、烯烃、芳香烃和OVOCs等VOCs组分不同化学去除途径的去除速率进行分析.结果表明,烷烃和芳香烃主要通过与OH自由基反应去除,最高占比超过99%.与NO3自由基和O3的反应可贡献烯烃去除速率的80%以上,特别是一些天然源的烯烃(如单萜烯)与NO3自由基的氧化去除是贡献最大的氧化途径.光解是甲醛最重要的去除途径,在两个站点均达到了50%以上,酮类的光解贡献会高于其他OVOCs类物质.OH自由基的氧化去除途径在城市和区域站点的人为源及天然源VOCs去除中占主导地位.区域站点,烯烃尤其是天然源的烯烃物种,与NO3自由基和O3反应的贡献要高于城市站点.本研究对促进不同VOCs物种在大气中的去除途径以及其空间差异的认识有重要意义.  相似文献   

8.
Aerosols and environmental pollution   总被引:2,自引:0,他引:2  
The number of publications on atmospheric aerosols has dramatically increased in recent years. This review, predominantly from a European perspective, summarizes the current state of knowledge of the role played by aerosols in environmental pollution and, in addition, highlights gaps in our current knowledge. Aerosol particles are ubiquitous in the Earth’s atmosphere and are central to many environmental issues; ranging from the Earth’s radiative budget to human health. Aerosol size distribution and chemical composition are crucial parameters that determine their dynamics in the atmosphere. Sources of aerosols are both anthropogenic and natural ranging from vehicular emissions to dust resuspension. Ambient concentrations of aerosols are elevated in urban areas with lower values at rural sites. A comprehensive understanding of aerosol ambient characteristics requires a combination of measurements and modeling tools. Legislation for ambient aerosols has been introduced at national and international levels aiming to protect human health and the environment.  相似文献   

9.
Biofiltration is considered an effective method to control volatile organic compounds (VOCs) pollution. This study was conducted to evaluate the potential use of a bacterial biofilter packed with wood chips and peat for the removal of hydrophobic α-pinene. When inoculated with two pure degraders and adapted activated sludge, a removal efficiency (RE) of more than 95% was achieved after a start-up period of 11 days. The maximum elimination capacity (EC) of 50 g/(m3. hr) with RE of 94% was obtained at empty bed retention time (EBRT) of 102 sec. When higher α-pinene concentrations and shorter EBRTs were applied, the REs and ECs decreased significantly due to mass-transfer and biological reaction limitations. As deduced from the experimental results, approximately 74% of α-pinene were completely mineralized by the consortiums and the biomass yield was 0.60 g biomass/g α-pinene. Sequence analysis of the selected bands excised from denaturing gradient gel electrophoresis revealed that the inoculated pure cultures could be present during the whole operation, and others were closely related to bacteria being able to degrade hydrocarbons. The kinetic results demonstrated that the whole biofiltration for α-pinene was diffusion-limit controlled owing to its hydrophobic characteristics. These findings indicated that this bacterial biofiltration is a promising technology for the remediation of hydrophobic industrial waste gases containing α-pinene.  相似文献   

10.
为探究鲁南地区大气中VOCs污染情况及二次生成转化特征,采用PTR-ToF-MS (质子转移反应飞行时间质谱仪)对鲁南某城市下辖6个行政区初夏(2021年5月19—27日)大气中挥发性有机物(VOCs)进行走航观测,研究该城市不同区域的VOCs浓度水平、组成特征以及对臭氧和SOA的生成贡献. 结果表明:①该市大气VOCs平均浓度为190.96 μg/m3,主要由含氧化合物、烃类、卤代烃、苯系物和含硫化合物组成,其中对VOCs组成贡献最大的物种包括乙酸乙烯酯、丙醛、环己酮、戊烯等. ②含氧化合物和烃类是该城市(除A区外)最主要的臭氧前体有机物,对OFP的贡献率分别达50%和40%. ③除甲苯是C区SOAFP (二次有机气溶胶生成潜势)贡献最大的VOCs物种外,二甲苯是其他各区SOAFP贡献最大的VOCs物种,贡献率在30%以上. ④因存在较多大型化工企业,A区与其他区大气VOCs组成差异较大,乙酸乙烯酯和二甲苯是其VOCs主要组分,苯系物、含氧有机物、卤代烃和烃类等四类物种OFP贡献相当,均约占25%;A区大气中VOCs的SOAFP较高,约是其他区的1.5~2.0倍. ⑤通过特征物种比值及走航观测分析发现,A区大气VOCs主要来源于溶剂挥发及燃烧过程,C区VOCs主要源于交通,其他区VOCs主要源于燃烧及工业生产过程;同时,食物加工过程(如油烟)排放也是该市大气VOCs的重要来源. 研究显示,降低大气中含氧有机物、烃类、苯系物浓度是控制该市大气臭氧、二次有机气溶胶生成的有效途径.   相似文献   

11.
Seven polycyclic aromatic hydrocarbons (PAHs) in atmospheric particulates were determinated by high performance liquid chromatography (HPLC) with fluorescence detector using direction injection and an on-line enrichment trap column.The method simplified the sample pretreatment,saved time and increased the efficiency.With the on-line trap column,PAHs were separated availably even underground injecting 1.0 ml sample with relatively high column efficiency.The recoveries of the seven PAHs were from 85% to 120% for spiked atmospheric particulate sample.The limit of detection was 15.3-39.6 ng/L (S/N=3.3).There were good linear correlations between the peak areas and concentrations of the seven kinds of PAHs in the range of 1-50 ng/ml with the correlation coefficients over 0.9970.Furthermore,it also indicated that the method is available to determine PAHs in atmospheric particulates well.  相似文献   

12.
环境空气中多环芳烃的来源包括自然源和人为源,本文根据化学质量平衡(CMB)受体模型对邯郸市大气颗粒物中多环芳烃进行源解析,测定邯郸市非采暖季和采暖季可吸入颗粒物中多环芳烃的浓度,对其污染水平进行比较分析。根据污染源调查结果,确定市区多环芳烃的主要排放源类,并建立相应的源成分谱。应用化学质量平衡受体模型解析邯郸市可吸入颗粒物上多环芳烃主要来源的分担率,并根据分析结果针对性提出了多环芳烃污染防治对策。  相似文献   

13.
BTEX(苯系物)作为空气中的一种痕量组分,主要包括苯、甲苯、乙苯、间-二甲苯、对-二甲苯、邻二甲苯,这些物质可影响人体健康和环境空气质量.分析和探讨了环境空气中BTEX常用的采样、前处理和检测方法,并列举了各方法的国内外应用实例.BTEX采样方法主要包括以下2种:①吸附管采样法,其采样器体积小、便于携带,但易造成穿透现象,样品易损失.②空气采样法,其操作简单、重复使用率高,但清洗复杂、价格较高.BTEX前处理方法主要包括以下3种:①固相微萃取法,其可减少样品与空气接触的机会,自动化程度较高,但难以实现样品的多次分析.②溶剂解析法,因其对环境影响较大,所以应用较少.③热脱附法,其常采用二级热脱附实现样品富集和浓缩,操作过程简单,设备体积相对较大,其升温和降温系统是影响前处理速度和效果的关键.BTEX检测方法主要包括:①质子转移反应质谱法,其灵敏度高,但因其价格昂贵应用较少.②气相色谱-光离子化检测法,其设备体积小巧常用于外场监测中.③差分吸收光谱法、直接空气进样质谱法、低压化学电离质谱法、大气压化学电离质谱法、固相微萃取-气相色谱法、吸附/热脱附-气相色谱-火焰离子检测法/质谱检测法等.研究显示,空气中BTEX的分析方法应根据实际应用条件来确定,在保证分析仪器灵敏度和精确度的基础上,开发外场检测的便携式自动在线分析仪器,提高仪器便携性、自动化、智能化,更好地满足各项标准和部门管理的需求.   相似文献   

14.
For the determination of regionally averaged fluxes and budgets of atmospheric trace constituents, the ultimate goal of the European Environment Research EUROTRAC, several ecosystems must be investigated, each representative of larger areas. One of the most wide-spread vegetation type is the coniferous forest, in which several compartments exist such as soil, trunk space, canopy and ‘free’ atmosphere above, which differ considerably in biology, chemistry and meteorology, but increase strongly by feedback processes caused by turbulent mixing and chemical reactions. To understand forest/atmosphere relations in detail, measurements are needed which provide concentrations, emission and deposition data of various chemical compounds as well as micrometeorological quantities. These measurements have to be carried out simultaneously in all storeys of a forest over extended periods and must be highly resolved with respect to time and space. In a first step detailed small-scale studies must be performed. This paper describes the scientific approach for integrated multi-disciplinary studies at Schachtenau, a research site in Central Europe's largest continuous forest, and presents first results from joint experiments.  相似文献   

15.
总结了环境大气中半/中等挥发性有机物(S/IVOCs)的主要测量技术及其进展,重点介绍了基于气相色谱技术和化学电离质谱技术的测量方法.S/IVOCs的测量主要由气相色谱技术开始发展,并随着质谱技术的发展而不断发展.基于气相色谱技术的测量方法,能够直接测量非极性化合物,但在面对组分多达千万种的复杂体系时,传统的一维色谱相对耗时,而且由于峰容量不够,峰重叠现象十分严重,难以实现全组分的准确分离.新近发展的多维分离系统如全二维气相色谱,通过正交的分离系统,能够实现复杂体系中物种组分的准确、快速分离.目前基于化学电离质谱技术的在线测量方法已经逐渐应用于S/IVOCs的测量,虽然在物种定性方面相对较弱,但其可提供高时间分辨率的测量结果,帮助分析S/IVOCs在大气中的快速变化.在未来的研究中,高时间分辨率和全组分准确测量是S/IVOCs研究的关键.  相似文献   

16.
总结了环境大气中半/中等挥发性有机物(S/IVOCs)的主要测量技术及其进展,重点介绍了基于气相色谱技术和化学电离质谱技术的测量方法.S/IVOCs的测量主要由气相色谱技术开始发展,并随着质谱技术的发展而不断发展.基于气相色谱技术的测量方法,能够直接测量非极性化合物,但在面对组分多达千万种的复杂体系时,传统的一维色谱相对耗时,而且由于峰容量不够,峰重叠现象十分严重,难以实现全组分的准确分离.新近发展的多维分离系统如全二维气相色谱,通过正交的分离系统,能够实现复杂体系中物种组分的准确、快速分离.目前基于化学电离质谱技术的在线测量方法已经逐渐应用于S/IVOCs的测量,虽然在物种定性方面相对较弱,但其可提供高时间分辨率的测量结果,帮助分析S/IVOCs在大气中的快速变化.在未来的研究中,高时间分辨率和全组分准确测量是S/IVOCs研究的关键.  相似文献   

17.
Generation of hydrocarbons in source rocks is controlled by their temperature history with burial, as well as by quantity, type and structure of their kerogens. The degree to which hydrocarbon generation processes have advanced in a given source rock can be recognized on the basis of elemental analysis of kerogens (H/C-O/C diagrams), as well as by analysis of yield and composition of extractable hydrocarbons. The “liquid window” or main phase of petroleum generation corresponds to a subsurface temperature interval of 60–150 °C. The overall chemical evolution of kerogens and their reaction products in this interval are exemplified here for several source rock series on the basis of organic carbon mass balance calculations. In this way the changes of the ratio of “reactive carbon” to “dead carbon” with maturity increase become obvious.  相似文献   

18.
目的对临近空间大气中性风场进行监测与分析。方法借助法布里-珀罗干涉仪(Fabry-Perot Interferometer,FPI)观测临近空间顶层的大气中性风场。针对北极黄河站(78.92°N,11.93°E)临近空间顶层的大气中性风场,介绍全天空FPI测风的基本原理,通过对2016年11月25日全天空FPI设备观测的OI557.7 nm气辉干涉图进行分析,反演得到极光亚暴期间的内5级环的水平风场和视线风场。结果极地地区临近空间顶层的水平风速基本保持在-200~200 m/s之间,极光亚暴使得中性风场呈现出一定的方向性,并且风场增大的方向垂直于极光弧。结论利用全天空FPI设备可以对临近空间顶层的大气中性风场进行探测和分析,有助于认识和理解临近空间大气环境。  相似文献   

19.
对马里亚纳海槽弧后扩张脊上所采集的玄武岩样品进行了系统的K -Ar定年 ,同时结合研究玄武岩的微量元素以及稀土元素特征后指出 ,马里亚纳海槽的张开及与之伴随发生的玄武岩浆活动自晚中新世以来一直都在进行 ,其主活动期为 2~ 4Ma。海槽玄武岩年龄在空间上具有从南到北逐渐变新的演化规律。据此 ,推断该海槽的扩张演化可能受控于该区内热区的迁移及运动规律  相似文献   

20.
This review surveys the present state of knowledge of the nitrate (NO3 radical. Laboratory data on the physics and chemistry of the radical and atmospheric determination of the concentrations of the radical are both considered. One aim of the review is to highlight the relationship between the laboratory and the atmospheric studies. Although the emphasis of the review is on gas-phase processes, relevant studies conducted in condensed phases are mentioned because of their potential importance in the interpretation of cloud and aerosol chemistry.The spectroscopy, structure, and photochemistry of the radical are examined. Here, the object is to establich the spectroscopic basis for detection of the radical and measurement of its concentration in the laboratory and in the atmosphere. Infrared, visible, and paramagnetic resonance spectra are considered. An important quantity discussed is the absorption cross section in the visible region, which is required for quantitative measurements. Interpretation of the spectroscopic features requires an understanding of the geometrical and electronic structure of the radical in its ground and excited states; there is still some controversy about the groundstate geometry, but the most recent experimental evidence 9eg from laser induced fluorescence) and theoretical calculations suggest that the radical has D3h symmetry. Photodissociation of the radical is important in the atmosphere, and the product channels, quantum yields, and dissociation dynamics are discussed. A short examination of the thermodynamics (heat and entropy of formation) of the radical is presented.The main exposition of laboratory studies of the chemistry of the nitrate radical is preceded by a consideration of the techniques used for kinetic and mechanistic studies. Methods for the generation and detection of the radical and the kinetic tools employed are all presented. The exact nature of the technique used in individual studies has some relevance to the way in which data must be analysed, and to the type of mechanistic information that can be extracted. Continuous and stopped flow, flash photolysis and pulse radiolysis, molecular modulation, and static reactor techniques can all provide absolute kinetic data, while relative rate measurements have been a further rich source of information.The treatment of the chemical reactions of the nitrate radical is formally divided into the interactions with non-radical inorganic (deemed to include NO and NO2) and organic species, and with atoms and free radicals. In general, the reactions with open-shell species are much more rapid than those with closed-shell reactants. With the closed-shell partners, addition reactions are faster than abstraction reactions. An attempt is made to consider critically the published data on most reactions of importance, and to tabulate rate constants and temperature dependences where possible. However, it is not the objective of this review to provide recommendations for rate parameters. Evidence for the products of the reactions is sought, and for the branching ratios into the various channels where more than one exists. One theme of this part of the review is the elucidation of correlations of reactivity with structure and with the reactions of other radical species such as OH.The review turns next to a consideration of the role of NO3 in the atmosphere, of its atmospheric sources and sinks, and of field measurements of concentrations of the radical. Long-path visible-absorption spectroscopy and matrix-isolation ESR have both been used successfully in field measurements in the troposphere as well as the stratosphere. Balloon-borne instruments and ground-based remote sensing have been used to obtain stratospheric concentrations. Two of the most important implications of the measurements are that the stratospheric profiles are consistent with accepted chemistry (and, in particular, do not require the postulation of an unidentified scavenging mechanism that had, at one stage, been proposed), and that the highly variable night-time tropospheric concentrations imply that NO3 is a reactive tropospheric constituent. The inter-relation between laboratory studies and atmospheric observations, and the problems in extrapolating laboratory data to atmospheric conditions, are both explored. Initiation of night-time chemical transformations by NO3 and the possible production of OH are considered. The available information is then brought together to see how far NO3 is a sensitive indicator of the state of the atmosphere, and some speculations are presented about the involvement of NO3 (or N2O5) in damage to trees and plants.The final section of the review suggests some issues that remain unresolved concerning the NO3 radical which is directly or indirectly relevant to a better knowledge of the part played by the radical in the atmosphere. Amongst the requirements noted are improved data for the heat of formation of the radical, its absorption cross section in the visible region (and, especially, the temperature dependence of the cross section), and the details of its photochemistry. There is also still a need for a definitive determination of the equilibrium constant and its temperature dependence for the association with NO2 and the reverse dissociation of N2O5. A series of chemical reactions deserves further investigation, especially with regard to elucidation of product channels, and overall oxidation mechanisms also need to be defined better. Future atmospheric studies that are desirable include study of basic NO3 chemistry in the field to understand the influence of humidity on the conversion (probably on surfaces) of N2O5 to HNO3, and thus on NO3 concentrations. In addition, a study of the chemistry of NO3 in the presence of volatile organic compounds and at elevated concentrations of the oxides of nitrogen should help in the understanding of, for example, polluted marine coasts, forests, and urban areas.  相似文献   

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