KOH活化小麦秸秆生物炭对废水中四环素的高效去除

活化是提高生物炭吸附性能的重要手段.以小麦秸秆为研究对象,KOH为活化剂,制备KOH活化生物炭（K-BC）,同时制备原状生物炭（BC）作为对照.对生物炭进行比表面积和孔径、元素分析、XPS、FTIR、Raman、XRD和pH_pzc等表征,考察KOH活化对生物炭理化性质的影响,并探究生物炭对水体中四环素的吸附性能和机制.结果表明,KOH活化之后生物炭的比表面积和孔体积可达996.4 m²·g^-1和0.45 cm³·g^-1.KOH活化会制造更多的碳结构缺陷,影响生物炭的官能团和表面电性.拟二级动力学和Langmuir模型可以较好地拟合生物炭吸附四环素的过程.环境温度升高能提高生物炭对四环素的吸附量.K-BC吸附四环素是自发、吸热和无序度增加的过程.K-BC对四环素的最大吸附量理论可达到491.19 mg·g^-1（实验温度为45℃）.结合吸附后生物炭的Raman、FTIR和XPS表征,发现孔隙填充和π-π作用是K-BC吸附四环素的主要机制,氢键和络合作用也发挥重要作用.此外,K-BC还具有良好的循环使用性能.综上所述,KOH活化小麦秸秆生物炭是有效和可行的,可用于废水中四环素的去除.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

棉秆基活性炭的制备及其对2,4-二硝基苯酚的吸附

以棉秆为原料，以KOH为活化剂，制备了高比表面棉秆基生物质活性炭。分析了制得的活性炭的元素组成、表面官能团、吸附能力等物化性能，探讨了浸渍比，活化温度，活化时间等工艺参数对制备活性炭得率、表面官能团、碘值、亚甲基蓝值等性能的影响，并通过静态吸附实验比较了不同条件下制备活性炭对2，4-二硝基苯酚的吸附性能，探讨了典型炭样品对2，4-二硝基苯酚的等温吸附特性。结果表明，KOH活化棉秆基生物质活性炭的表面物化性质随浸渍比、活化温度等工艺参数变化而变化，活化适宜条件为浸渍比1：3、活化温度800℃、活化时间90 min，在此条件下制得的炭样的碘值为1 251 mg/g，亚甲基蓝吸附值为478 mg/g，分别是国家一级品标准的1.25倍与3.54倍；对2，4-二硝基苯酚的Langmuir最大吸附量为747 mg/g，与Freundlich模型相比，Langmuir模型能较好地描述2，4-二硝基苯酚在炭样上的吸附行为，表明制备活性炭样品表面吸附位的能量分布较为均一。     

大气气溶胶中元素种态研究

应用化学逐级提取流程对国际原子能机构（简称IAEA）气溶胶、室内和室外气溶胶、煤飞灰中元素的组成和种态进行了分析，应用仪器中子活化法测定了各种态中元素的含量，计算出元素在各种态中的分配比例。按照气溶胶中元素不同种态的环境和生物活性以及主要来源来分类，评述了元素在环境和生态系统中的吸收和转化能力，并对气溶胶中元素对环境的影响作出了初步的探讨。实验数据表明，气溶胶中的不同元素在各种态中的分布是有差异的。地壳来源元素中，Sc,Al,Fe和Ti主要分布在不溶物态中，稀土元素主要分布在氧化物态和不溶物态；不溶物态沉降到地表后不易进行迁移和转化，对环境的影响较小；氧化物态性质比较活泼，可以在大气中发生化学反应。Mn在气溶胶中主要分布在水可溶态和氧化物态，环境可交换性要比Al,Fe,Ti等大得多。人为来源元素的环境可交换态的比例都比较高，这说明它们通过干、湿清除过程沉降到地表后，水可溶态可以直接进入水循环；碳酸盐、氧化物和有机物态可以在适当的条件下与环境中的其他物质发生化学反应，生成易溶于水的化合物进入生态环境中，对环境影响较大。     

Heavy metal bioaccumulation in selected medicinal plants collected from Khetri copper mines and comparison with those collected from fertile soil in Haridwar,India

Heavy metal distribution in medicinal plants is gaining importance not only as an alternative medicine, but also for possible concern due to effects of metal toxicity. The present study has been focused on emphasizing the heavy metal status and bioaccumulation factors of V, Mn, Fe, Co, Cu, Zn, Se (essential metals) and Cr, Ni, Cd, As and Pb (potentially toxic metals) in medicinal plants grown under two different environmental conditions e.g., near to Khetri copper mine and those in fertile soils of Haridwar, both in India, using Instrumental Neutron Activation Analysis (relative method) and Atomic Absorption Spectrometry. The copper levels in the medicinal plants from Khetri were found to be 3-4 folds higher (31.6–76.5 mg kg^?1) than those from Haridwar samples (7.40–15.3 mg kg^?1), which is correlated with very high copper levels (763 mg kg^?1) in Khetri soil. Among various heavy metals, Cr (2.60–5.92 mg kg^?1), Cd (1.47–2.97 mg kg^?1) and Pb (3.97–6.63 mg kg^?1) are also higher in concentration in the medicinal plants from Khetri. The essential metals like Mn (36.4–69.3 mg kg^?1), Fe (192–601 mg kg^?1), Zn (24.9–49.9 mg kg^?1) and Se (0.13–0.91 mg kg^?1) and potentially toxic metals like Ni (3.09–9.01 mg kg^?1) and As (0.41–2.09 mg kg^?1) did not show much variations in concentration in the medicinal plants from both Khetri and Haridwar. The medicinal plants from Khetri, e.g., Ocimum sanctum, Cassia fistula, Withania somnifera and Azadirachta Indica were found rich in Ca and Mg contents while Aloe barbadensis showed moderately high Ca and Mg. Higher levels of Ca-Mg were found to correlate with Zn (except Azadirachta Indica). The bioaccumulation factors (BAFS) of the heavy metals were estimated to understand the soil-to-plant transfer pattern of the heavy metals. Significantly lower BAF values of Cu and Cr were found in the medicinal plants from Khetri, indicating majority fraction of these metals are precipitated and were immobilized species unsuitable for plant uptake. Overall, Withania somnifera (Ashwagandha) showed very high metal bioaccumulation.     

废弃混凝土对C_3S形成动力学的影响

废弃混凝土中石灰石的含量比较稳定,适合取代天然石灰石作为钙质原料配制水泥生料,并含有少量的SiO2,可以起部分硅质原料的作用。硬化的水泥浆体在高温下脱水形成氧化钙、氧化铝和氧化铁等氧化物,都是制造水泥所必须的氧化物。实验室利用20%和40%的废弃混凝土代替部分石灰石制备水泥熟料。研究了废弃混凝土对硅酸盐水泥熟料形成动力学的影响。用快速滴定法测定了不同熟料中f-CaO含量,根据文章提出CaO反应生成C3S的转化率,并用Amhenius公式计算了熟料中C3S形成反应的表观活化能。研究表明:废弃混凝土能改善生料的易烧性,并能降低熟料的烧成温度。     

污泥基活性炭的制备、表征及其应用

以城市生活污水厂脱水车间污泥为原料,采用化学活化法(ZnCl2为活化剂)在活化剂浓度为45%、活化温度为600℃、浸渍温度为45℃、活化时间为50min条件下制备污泥基活性炭。对污泥基活性炭进行了孔结构、扫描电镜(SEM)、红外光谱(FTIR)、XRD等表征分析。结果表明:该条件下制备出的污泥基活性炭碘吸附值为427.51mg/g,比表面积为329.48m2/g,大孔、中孔、微孔容积分别为0.19,0.12,0.15cm3/g。平均孔径为3.953nm。将其应用于生活污水处理,考察了污泥基活性炭投加量、pH、吸附时间对其吸附性能的影响。     

零价铁和碱激发矿渣稳定/固定化处理铬渣研究

采用零价铁和碱激发矿渣对铬渣进行稳定/固定化处理,考察了处理后固化体的毒性浸出水平,矿物组成及Cr形态分布变化情况,并对铬渣的处置和利用的有效性进行评价.结果表明,还原固定化处理后的样品硫酸硝酸法浸出毒性可满足作为砖或砌块使用的标准,抗压强度均高于15 MPa,其中Cr主要以Fe/Mn氧化物结合态存在,可被用于采石场修复、封闭泻湖以及作为路基材料等一些特殊用途.     

HPO42-和H2PO4-对蒙脱石-胡敏酸胶体凝聚的影响

为探究HPO₄^2-和H₂PO₄^-界面行为对土壤胶体凝聚的影响,以蒙脱石和胡敏酸胶体为研究对象,采用动态光散射技术比较研究HPO₄^2-和H₂PO₄^-引发胶体颗粒凝聚过程的差异.结果表明,随着电解质离子强度的升高,HPO₄^2-和H₂PO₄^-体系蒙脱石-胡敏酸混合悬液从慢速凝聚（线性增长）转化为快速凝聚（幂函数增长）,但胶体凝聚过程对H₂PO₄^-体系离子强度的变化更敏感.HPO₄^2-和H₂PO₄^-作用下凝聚体有效粒径增长、总体平均凝聚速率（TAA）、临界聚沉离子强度（CCIS）和活化能均存在明显差异;其中,与HPO₄^2-相比,H₂PO₄^-体系中拥有更高的TAA、更低的CCIS和活化能,说明H₂PO₄^-离子引发蒙脱石-胡敏酸混合胶体凝聚的作用更强,HPO₄^2-体系中CCIS是H₂PO₄^-中的2.43倍.HPO₄^2-和H₂PO₄^-体系中离子特异性效应的差异（活化能差值）随离子强度的降低而增大,主要由强电场中离子非经典极化作用引发.胡敏酸的添加明显增加了HPO₄^2-体系中胶体的CCIS和活化能,而对H₂PO₄^-体系未产生明显影响;HPO₄^2-和H₂PO₄^-离子特异性效应的强弱在不同比例蒙脱石/胡敏酸体系中表现为96%蒙脱石+4%胡敏酸 >> 99%蒙脱石+1%胡敏酸 > 100%蒙脱石.以上结果表明HPO₄^2-和H₂PO₄^-对蒙脱石-胡敏酸混合胶体的凝聚存在强烈的离子特异性效应,胶体表面附近电场强度直接影响该效应的强弱.     

Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants

CNT-TiO₂ composite is used to activate PMS under UV-light assistance. Superior performance is due to the enhanced electron-transfer ability of CNT. SO₄•⁻, •OH and ¹O₂ play key roles in the degradation of organic pollutants. In this work, a UV-light assisted peroxymonosulfate (PMS) activation system was constructed with the composite catalyst of multi-walled carbon nanotubes (CNT) - titanium dioxide (TiO₂). Under the UV light irradiation, the photoinduced electrons generated from TiO₂ could be continuously transferred to CNT for the activation of PMS to improve the catalytic performance of organic pollutant degradation. Meanwhile, the separation of photoinduced electron-hole pairs could enhance the photocatalysis efficiency. The electron spin resonance spectroscopy (EPR) and quenching experiments confirmed the generation of sulfate radical (SO₄•⁻), hydroxyl radical (•OH) and singlet oxygen (¹O₂) in the UV/PMS/20%CNT-TiO₂ system. Almost 100% phenol degradation was observed within 20 min UV-light irradiation. The kinetic reaction rate constant of the UV/PMS/20%CNT-TiO₂ system (0.18 min⁻¹) was 23.7 times higher than that of the PMS/Co₃O₄ system (0.0076 min⁻¹). This higher catalytic performance was ascribed to the introduction of photoinduced electrons, which could enhance the activation of PMS by the transfer of electrons in the UV/PMS/CNT-TiO₂ system.