ozonation

臭氧化
  • 文章类型: Journal Article
    金银花果实是维生素的丰富来源,有机酸,和酚类化合物,以其促进健康的特性为特征。该果实中生物活性化合物的含量可能因品种和收获日期而异。这项研究分析了在1、3和5分钟内施用5ppm气态臭氧对L.kamtschatica品种和新创建的L.emphyllocalyx克隆的化学性质的影响。从emphyllocalyx收获的果实,根据收获的年份,与L.kamtschatica相比,尺寸和重量明显更大。平均而言,L.emphyllocalyx克隆的酸度比其他测试品种高6%。在emphylloc无性系\'21-17\'-57.80mg·100g-1中,抗坏血酸的平均含量最高;收获年份会显著影响维生素C的含量,2022-53.92mg·100g-1达到最高水平。多酚的总含量显著依赖于种植年份;达到,平均而言,与其他年份相比,2022年增长了54.8%。使用FRAP的总抗氧化剂值,DPPH,和ABTS方法因品种而异;在每种情况下,暴露于臭氧都显着增加了抗氧化剂的价值。在研究的基础上,两种植物品种均可用于食品加工。气态臭氧暴露会显著影响化学成分,增加水果的健康促进价值。
    Lonicera caerulea L. fruits are a rich source of vitamins, organic acids, and phenolic compounds, which are characterised by their health-promoting properties. The content of bioactive compounds in this fruit may vary depending on the cultivar and the harvest date. This study analysed the effect of applying 5 ppm gaseous ozone for 1, 3, and 5 min on the chemical properties of L. kamtschatica varieties and newly created clones of L. emphyllocalyx for three years of cultivation. The fruits harvested from L. emphyllocalyx, depending on the year of harvest, had significantly larger size and weight compared to L. kamtschatica. On average, the acidity of the L. emphyllocalyx clones was 6% higher than other tested varieties. The average content of ascorbic acid was highest in L. emphyllocalyx clone \'21-17\'-57.80 mg·100 g-1; the year of harvest will significantly affect the content of vitamin C, reaching the highest level in 2022-53.92 mg·100 g-1. The total content of polyphenols was significantly dependent on the year of cultivation; reaching, on average, 54.8% more in 2022 compared to the rest of the years. The total antioxidant value using the FRAP, DPPH, and ABTS methods varied depending on the variety; exposure to ozone significantly increased the antioxidant value in each case. On the basis of the study, both botanical varieties can be used in food processing. Gaseous ozone exposure can significantly influence chemical composition, increasing the health-promoting value of fruit.
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  • 文章类型: Journal Article
    使用高级量子化学和动力学计算(M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G(d,P)理论水平)。三种不同机理下的臭氧(O3)引发的MTZ降解途径,即环加成,氧添加,和单电子转移(SET),在283-333K的温度范围和1atm的压力下进行了探索。因此,发现MTZ苯环C16C18双键处的环加成反应是大气中最主要的通道,标准吉布斯反应自由能(ΔrG0g)为-129.13kJmol-1,最高支化率为95.18%。在水相中,主反应通道转变为SET机制,具有最低的吉布斯活化能(ΔG#aq)73.8kJmol-1,占ktotal的87.8%。在283-333K的温度范围内,总速率常数(ktotal)在大气中从8.42显着增加到5.82×101M-1s-1,在水性环境中从4.10×102显着增加到2.40×104M-1s-1。值得注意的是,生态毒性评估表明,MTZ可能对鱼类有害,对水蚤慢性有害。相比之下,其主要臭氧分解产物没有急性或慢性毒性或诱变作用。
    The atmospheric and aqueous ozonolysis of metazachlor (MTZ) is investigated using high-level quantum chemical and kinetic calculations (M06-2X/6-311 +  + G(3df,3pd)//M06-2X/6-31 + G(d,p) level of theory). The ozone (O3)-initiated degradation pathways of MTZ under three different mechanisms, namely cycloaddition, oxygen-addition, and single electron transfer (SET), are explored in the temperature range of 283-333 K and 1 atm pressure. As a result, the cycloaddition reaction at the C16C18 double bond of the benzene ring of MTZ is found to be the most dominant channel in the atmosphere with the standard Gibbs free energy of reaction (ΔrG0g) of - 129.13 kJ mol-1 and the highest branching ratio of 95.18%. In the aqueous phase, the main reaction channel turns into the SET mechanism, which owns the lowest Gibbs free energy of activation (ΔG#aq) of 73.8 kJ mol-1 and contributes 87.8% to the ktotal. Over the temperature range of 283-333 K, the total rate constant (ktotal) significantly increases from 8.42 to 5.82 × 101 M-1 s-1 in the atmosphere and from 4.10 × 102 to 2.40 × 104 M-1 s-1 in the aqueous environment. Remarkably, the ecotoxicity assessment shows that MTZ may be harmful to fish and chronically harmful to daphnia. In contrast, its main ozonolysis products exhibit no acute or chronic toxicity or mutagenic effects.
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  • 文章类型: Journal Article
    臭氧化的有效性,从废水中破坏有机污染物的已知技术之一,取决于废水基质的组成。根据臭氧化过程中的目标化合物确定所需的臭氧(O3)剂量。使用探针化合物定量羟基自由基。对氯苯甲酸(pCBA)通常用作测量羟基的探针化合物。然而,实时测量是不可能的,因为分析过程消耗时间和资源。本研究旨在通过荧光激发-发射矩阵和平行因子分析来评估臭氧氧化废水中各种有机物质的光谱特征。研究还表明,可实时分析的色氨酸样荧光(TLF)可用作羟基自由基指数。重要的是,得出了对氯苯甲酸与TLF之间的相关性,结果显示高度相关(R2=0.91),证实了我们研究结果的可靠性。七种微量有机化合物,根据它们与O3和羟基自由基的反应性进行分类,选择作为目标化合物并用O3处理。TLF指数作为目标化合物去除率的模子因子。当O3剂量低于1.0gO3/gDOC(RMSE:0.0445~0.0895)时,实验值和模型值匹配。
    The effectiveness of ozonation, one of the techniques known for destroying organic contaminants from wastewater, depends on the composition of the wastewater matrix. The required ozone (O3) dose is determined based on the target compounds during ozonation. Hydroxyl radicals are quantified using a probe compound. The para-chlorobenzoic acid (pCBA) is typically used as a probe compound to measure hydroxyl radicals. However, real-time measurement is impossible, as the analysis process consumes time and resources. This study aimed to evaluate the spectroscopic characteristics of various organic substances in wastewater ozonation through fluorescence excitation-emission matrix and parallel factor analysis. The study also demonstrated that real-time analyzable tryptophan-like fluorescence (TLF) can be used as a hydroxyl radical index. Importantly, the correlation between para-chlorobenzoic acid and TLF was derived, and the results showed a high correlation (R2 = 0.91), confirming the reliability of our findings. Seven trace organic compounds, classified based on their reactivity with O3 and hydroxyl radicals, were selected as target compounds and treated with O3. The TLF index was used as a model factor for the removal rate of the target compounds. The experimental and model values matched when the O3 dose was below 1.0 g O3/g DOC (RMSE: 0.0445-0.0895).
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  • 文章类型: Journal Article
    通过测量分子臭氧(O3)和羟基自由基(•OH)的暴露量,可以准确地计算臭氧化对微污染物的减排量(即,取决于[O3]dt和取决于[•OH]dt)。在实际的臭氧化过程中,取决于[O3]dt值可以通过监测过程中的O3衰变来计算。然而,在该领域中,计算281[•OH]dt具有挑战性,这就需要开发模型来从可测量的参数中预测式[·OH]dt。本研究展示了机器学习模型的发展,可以从五个基本输入变量(pH,溶解的有机碳浓度,碱度,温度,和O3剂量)和两个可选的(取决于[O3]dt和瞬时臭氧需求,IOD)。为了开发模型,四种不同的机器学习方法(随机森林,支持向量回归,人工神经网络,和高斯过程回归)使用在130种不同的天然水样品中测量(或确定)的输入和输出变量。结果表明,将281[O3]dt作为输入变量显着提高了预测模型的准确性,总体R2增加0.01-0.09,具体取决于机器学习方法。这表明取决于[O3]dt作为反映溶解有机物的•OH产生特性的关键变量起着至关重要的作用。相反,IOD对预测模型的准确性影响最小。一般来说,基于机器学习的预测模型优于基于作为对照开发的响应面方法的预测模型。值得注意的是,利用高斯过程回归算法的模型在预测模型中显示出最高的确定系数(总体R2=0.91-0.95)。
    The abatement of micropollutants by ozonation can be accurately calculated by measuring the exposures of molecular ozone (O3) and hydroxyl radical (•OH) (i.e., ∫[O3]dt and ∫[•OH]dt). In the actual ozonation process, ∫[O3]dt values can be calculated by monitoring the O3 decay during the process. However, calculating ∫[•OH]dt is challenging in the field, which necessitates developing models to predict ∫[•OH]dt from measurable parameters. This study demonstrates the development of machine learning models to predict ∫[•OH]dt (the output variable) from five basic input variables (pH, dissolved organic carbon concentration, alkalinity, temperature, and O3 dose) and two optional ones (∫[O3]dt and instantaneous ozone demand, IOD). To develop the models, four different machine learning methods (random forest, support vector regression, artificial neural network, and Gaussian process regression) were employed using the input and output variables measured (or determined) in 130 different natural water samples. The results indicated that incorporating ∫[O3]dt as an input variable significantly improved the accuracy of prediction models, increasing overall R2 by 0.01-0.09, depending on the machine learning method. This suggests that ∫[O3]dt plays a crucial role as a key variable reflecting the •OH-yielding characteristics of dissolved organic matter. Conversely, IOD had a minimal impact on the accuracy of the prediction models. Generally, machine-learning-based prediction models outperformed those based on the response surface methodology developed as a control. Notably, models utilizing the Gaussian process regression algorithm demonstrated the highest coefficients of determination (overall R2 = 0.91-0.95) among the prediction models.
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  • 文章类型: Journal Article
    在这项研究中,探索了一种共催化途径来增强挥发性有机化合物(VOC)的光臭氧催化降解。将NiCo2O4负载到CeO2纳米颗粒的表面上以产生复合催化剂(10%NiCo2O4/CeO2)。NiCo2O4在CeO2上的集成增强了催化剂与甲苯之间的相互作用,代表性的VOC,导致甲苯吸附显着增加,而比表面积没有相应增加。这种集成还改善了电荷载体的利用和臭氧到O2的转化。在可见光照射下,H2O在10%NiCo2O4/CeO2表面积累电荷载流子,促进臭氧利用和甲苯吸附。NiCo2O4负载的另一个好处是其提高太阳能转换效率的能力。因此,与CeO2相比,10%NiCo2O4/CeO2的甲苯去除和矿化效率分别提高了182%和309%,与NiCo2O4相比分别提高了201%和357%。总的来说,这项研究证明了一种新型的助催化剂设计策略,用于增强VOCs的光臭氧催化降解。
    In this study, a co-catalytic route was explored to enhance the photo-ozone catalytic degradation of volatile organic compounds (VOCs). NiCo2O4 was loaded onto the surface of CeO2 nanoparticles to create a composite catalyst (10%NiCo2O4/CeO2). The integration of NiCo2O4 onto CeO2 enhanced the interaction between the catalyst and toluene, a representative VOC, resulting in significantly increased toluene adsorption without a corresponding increase in specific surface area. This integration also improved the utilization of charge carriers and conversion of ozone to O2-. Under visible light irradiation, H2O accumulated charge carriers at 10%NiCo2O4/CeO2\'s surface, facilitating both ozone utilization and toluene adsorption. Another benefit of NiCo2O4 loading was its ability to enhance the conversion efficiency of solar energy. Consequently, the toluene removal and mineralization efficiencies of 10%NiCo2O4/CeO2 were enhanced by 182% and 309% compared to CeO2, and by 201% and 357% compared to NiCo2O4, respectively. Overall, this study demonstrated a novel co-catalyst design strategy for enhancing the photo-ozone catalytic degradation of VOCs.
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  • 文章类型: Journal Article
    塑料已成为现代社会不可或缺的一部分;由于大多数塑料是不可生物降解的,因此废物的扩散已成为一个不容忽视的问题。在循环经济的背景下,通过可持续过程进行解聚/降解是紧迫的问题。多种类型的塑料材料的存在使得有必要研究每种材料的特定特性。这篇小型评论旨在概述技术方法及其对最广泛的塑料材料之一的解聚和/或降解的性能,聚丙烯(PP)。介绍了最先进的技术,描述了最相关的技术,重点是高级氧化技术(AOT)和迄今为止获得的一些方法的结果,如臭氧化,声化学,或光催化,最终目的是使PP解聚/降解过程更可持续。
    Plastics have become indispensable in modern society; however, the proliferation of their waste has become a problem that can no longer be ignored as most plastics are not biodegradable. Depolymerization/degradation through sustainable processes in the context of the circular economy are urgent issues. The presence of multiple types of plastic materials makes it necessary to study the specific characteristics of each material. This mini-review aims to provide an overview of technological approaches and their performance for the depolymerization and/or degradation of one of the most widespread plastic materials, polypropylene (PP). The state of the art is presented, describing the most relevant technologies focusing on advanced oxidation technologies (AOT) and the results obtained so far for some of the approaches, such as ozonation, sonochemistry, or photocatalysis, with the final aim of making more sustainable the PP depolymerization/degradation process.
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  • 文章类型: Journal Article
    原始CMK-3碳被臭氧化,然后被Zr和Fe化合物化学改性。用物理化学方法对合成的碳质材料进行了表征。获得的碳具有高比表面积(约800m2g-1)和酸性表面。研究了氧化和Zr/Fe改性碳的Cr(VI)吸附性能。在240分钟后,在pHeq=5.8时,对Zr/Fe改性的碳(50.1mgg-1)评估了对Cr(VI)离子的最高静态吸附能力。Elovich和Freundlich理论模型很好地拟合了Zr/Fe改性的CMK-3型碳上的Cr(VI)吸附动力学和等温线数据。作用于Zr/Fe改性碳的主要Cr(VI)吸附机理可能是基于Cr(VI)与碳质表面之间的氧化还原反应。在所研究的系统中,Cr(VI)吸附过程中也可能发生静电吸引和表面络合过程。竞争阴离子对浓度水平的影响,例如在电镀废水中,将Cr(VI)吸附到化学改性碳上,微不足道。HCl和HNO3介质不足以在Cr(VI)吸附后进行Zr/Fe改性的碳再生。Zr/Fe改性的碳被成功地应用于从模型的电镀废水中高效地(>90%)去除Cr(VI)。
    The pristine CMK-3 carbon was ozonized and then chemically modified by the Zr and Fe compounds. The synthesized carbonaceous materials were characterized with physicochemical methods. The obtained carbons had a high specific surface area (ca. 800 m2 g-1) and an acidic surface. The Cr(VI) adsorption properties of the oxidized and Zr/Fe-modified carbon were studied. The highest static adsorption capacity towards Cr(VI) ions was evaluated for Zr/Fe-modified carbon (50.1 mg g-1) at pHeq = 5.8 after 240 min. The Elovich and Freundlich theoretical models were well fitted to the Cr(VI) adsorption kinetic and isotherm data on the Zr/Fe-modified CMK-3-type carbon. The leading Cr(VI) adsorption mechanism acting on the Zr/Fe-modified carbon was probably based on the redox reactions between Cr(VI) and the carbonaceous surface. Electrostatic attraction and surface complexation processes could also occur during Cr(VI) adsorption in the studied system. The effect of the competitive anions on the concentration level, such as in the galvanic wastewater for Cr(VI) adsorption onto chemically modified carbon, was negligible. The HCl and HNO3 media were insufficient for the Zr/Fe-modified carbon regeneration after Cr(VI) adsorption. The Zr/Fe-modified carbon was successfully applied for the efficient (>90%) Cr(VI) removal from the model galvanic wastewater.
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  • 文章类型: Journal Article
    废水处理厂在控制污染物向环境的传输方面发挥着至关重要的作用,并且经常将诸如合成微塑料纤维(MF)之类的持久性污染物排放到生态系统中。在这项研究中,我们通过采用紧密模拟废水处理厂消毒过程的条件,研究了由商用布制成的聚对苯二甲酸乙二醇酯(PET)MF在消毒后二次废水中的命运和毒性。挑战传统假设,这项研究表明,氯化和臭氧化氧化处理对MF的表面形态没有明显的改变。此外,实验结果表明,原始和氧化的MF对废水和碱性水中新兴关注的污染物具有最小的吸附潜力。有限的吸附归因于MF的惰性性质和低表面积与体积比。观察到索他洛尔的轻微吸附,磺胺甲恶唑,和噻菌灵在碱性水中,其中主要的吸附相互作用被认为是氢键和静电力。对人类细胞的急性暴露实验显示没有立即的毒性;然而,应进一步调查暴露的慢性和长期后果。总的来说,尽管关注与MFs污染有关,这项工作证明了污水处理厂中MFs的整体冷漠(即,消毒对MFs表面性质的影响较小,对痕量有机污染物混合物的吸附潜力有限),不会改变它们对生命形式的急性毒性。
    Wastewater treatment plants play a crucial role in controlling the transport of pollutants to the environment and often discharge persistent contaminants such as synthetic microplastic fibers (MFs) to the ecosystem. In this study, we examined the fate and toxicity of polyethylene terephthalate (PET) MFs fabricated from commercial cloth in post-disinfection secondary effluents by employing conditions that closely mimic disinfection processes applied in wastewater treatment plants. Challenging conventional assumptions, this study illustrated that oxidative treatment by chlorination and ozonation incurred no significant modification to the surface morphology of the MFs. Additionally, experimental results demonstrated that both pristine and oxidized MFs have minimal adsorption potential towards contaminants of emerging concern in both effluents and alkaline water. The limited adsorption was attributed to the inert nature of MFs and low surface area to volume ratio. Slight adsorption was observed for sotalol, sulfamethoxazole, and thiabendazole in alkaline water, where the governing adsorption interactions were suggested to be hydrogen bonding and electrostatic forces. Acute exposure experiments on human cells revealed no immediate toxicity; however, the chronic and long-term consequences of the exposure should be further investigated. Overall, despite the concern associated with MFs pollution, this work demonstrates the overall indifference of MFs in WWTP (i.e., minor effects of disinfection on MFs surface properties and limited adsorption potential toward a mix of trace organic pollutants), which does not change their acute toxicity toward living forms.
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  • 文章类型: Journal Article
    蓝藻水华以增加的频率和强度发生,尤其是在淡水中。这导致引入其产品的复杂混合物,即,氰基代谢物,饮用水处理厂。为了评估臭氧化过程中氰基代谢物混合物的命运,提出了一种新的多化合物臭氧(O3)竞争动力学方法。应用了16种已知二阶速率常数的竞争者,它们与O3的反应在1至108M-1s-1之间,以覆盖广泛的O3反应性。表观二阶速率常数(kapp,在pH7下同时测定了31种氰基代谢物的O3)。卡普,含烯烃和苯酚的氰基代谢物的O3与它们的预期反应性(0.4-1.7×106M-1s-1)一致,而kapp,含色氨酸和硫醚的氰基代谢物的O3显着高于预期(3.4-7.3×107M-1s-1)。预计含有这些部分的氰基代谢物在臭氧化过程中会很好地减少。对于含有杂环的氰基代谢物,卡普,O3的变化范围从<102到5.0×103M-1s-1,首次了解了此类化合物的O3反应性。由于较低的O3反应性,含杂环和脂族胺的氰基代谢物可能仅在接近中性pH的直接O3反应中部分降解。羟基,它们是在臭氧化过程中形成的,可能对他们的减排更重要。这种新颖的多化合物动力学方法允许对臭氧化动力学进行高通量筛选。
    Cyanobacterial blooms occur at increasing frequency and intensity, notably in freshwater. This leads to the introduction of complex mixtures of their products, i.e., cyano-metabolites, to drinking water treatment plants. To assess the fate of cyano-metabolite mixtures during ozonation, a novel multicompound ozone (O3) competition kinetics method was developed. Sixteen competitors with known second-order rate constants for their reaction with O3 ranging between 1 and 108 M-1 s-1 were applied to cover a wide range of the O3 reactivity. The apparent second-order rate constants (kapp,O3) at pH 7 were simultaneously determined for 31 cyano-metabolites. kapp,O3 for olefin- and phenol-containing cyano-metabolites were consistent with their expected reactivity (0.4-1.7 × 106 M-1 s-1) while kapp,O3 for tryptophan- and thioether-containing cyano-metabolites were significantly higher than expected (3.4-7.3 × 107 M-1 s-1). Cyano-metabolites containing these moieties are predicted to be well abated during ozonation. For cyano-metabolites containing heterocycles, kapp,O3 varied from <102 to 5.0 × 103 M-1 s-1, giving first insights into the O3 reactivity of this class of compounds. Due to lower O3 reactivities, heterocycle- and aliphatic amine-containing cyano-metabolites may be only partially degraded by a direct O3 reaction near circumneutral pH. Hydroxyl radicals, which are formed during ozonation, may be more important for their abatement. This novel multicompound kinetic method allows a high-throughput screening of ozonation kinetics.
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  • 文章类型: Journal Article
    已经开发了高级氧化工艺(AOP)来分解有毒污染物以保护水生环境。AOP已被认为是废水处理的替代处理方法。溴存在于天然水中,对人体健康造成毒性影响,因此,必须将其从饮用水源中去除。在许多技术中,高级氧化包括在这篇综述中。这篇综述系统地研究了1997年至2024年4月发表的来自Scopus的文献,PubMed,科学直接,和WebofScience数据库,重点研究AOPs对含溴离子水溶液中污染物去除的功效,以研究溴离子对AOPs的影响。从有资格纳入审查的每篇文章中提取的数据和信息包括AOP的类型,污染物的类型,以及在存在和不存在溴离子的情况下AOP的去除效率。在筛选的1784份文件中,90项研究符合纳入标准,提供对各种AOP的见解,包括紫外线/氯,UV/PS,UV/H2O2,UV/催化剂,和可见光/催化剂过程。观察到的溴离子的存在对AOP过程的功效的影响,除了受到审查的AOP方法之外,取决于各种因素,如目标污染物的性质,催化剂类型,和溴离子浓度。这些考虑因素对于选择在规定条件下去除特定污染物的最佳方法至关重要。在结果分析期间遇到的挑战包括实验设置的变化,污染物类型和浓度的差异,以及报告AOP性能指标的不一致。在研究报告中解决这些参数将增强后续系统评论的连贯性和实用性。
    Advanced oxidation processes (AOPs) have been developed to decompose toxic pollutants to protect the aquatic environment. AOP has been considered an alternative treatment method for wastewater treatment. Bromine is present in natural waters posing toxic effects on human health and hence, its removal from drinking water sources is necessary. Of the many techniques advanced oxidation is covered in this review. This review systematically examines literature published from 1997 to April 2024, sourced from Scopus, PubMed, Science Direct, and Web of Science databases, focusing on the efficacy of AOPs for pollutant removal from aqueous solutions containing bromide ions to investigate the impact of bromide ions on AOPs. Data and information extracted from each article eligible for inclusion in the review include the type of AOP, type of pollutants, and removal efficiency of AOP under the presence and absence of bromide ion. Of the 1784 documents screened, 90 studies met inclusion criteria, providing insights into various AOPs, including UV/chlorine, UV/PS, UV/H2O2, UV/catalyst, and visible light/catalyst processes. The observed impact of bromide ion presence on the efficacy of AOP processes, alongside the AOP method under scrutiny, is contingent upon various factors such as the nature of the target pollutant, catalyst type, and bromide ion concentration. These considerations are crucial in selecting the best method for removing specific pollutants under defined conditions. Challenges were encountered during result analysis included variations in experimental setups, disparities in pollutant types and concentrations, and inconsistencies in reporting AOP performance metrics. Addressing these parameters in research reports will enhance the coherence and utility of subsequent systematic reviews.
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