两种生物炭的制备及其对水溶液中四环素去除的影响因素

以中药材三桠苦药渣和玉米秸秆为原料,分别在400、600和800℃下热解制备生物炭,并研究其对水溶液中四环素的去除及其影响因素.利用元素分析、傅里叶红外光谱(FT-IR)、比表面积分析(BET)、X射线衍射(XRD)、扫描电子显微镜(SEM)等方法对制备的生物炭进行表征;并探究热解温度、生物炭添加量、初始溶液浓度、吸附时间、溶液pH、离子强度、环境温度等因素对生物炭去除水溶液中四环素的影响;通过吸附动力学和等温吸附平衡探究两种原料制备的生物炭对溶液中四环素的吸附行为.结果表明,生物炭对四环素的吸附性能随制备温度的升高而增加,800℃制备的三桠苦药渣生物炭(EIBC800)具有最佳吸附性能.生物炭添加量、溶液pH、离子强度、吸附时间对800℃制备的三桠苦药渣生物炭(EIBC800)和玉米秸秆生物炭(CSBC800)吸附水溶液中四环素影响较大,吸附时环境温度对吸附的影响大小依赖于抗生素质量浓度.EIBC800和CSBC800对四环素的吸附行为均符合准二级动力学方程(R~2分别为0. 954 0和0. 835 5),等温吸附符合Freundlich方程(R~2分别在0. 899 1～0. 957 9和0. 973 6～0. 994 6之间),主要吸附过程为化学吸附,且吸附过程均是自发吸热的过程.通过以两种原料所制备的生物炭吸附性能对比,EIBC800吸附抗生素的能力比CSBC800更强,说明中药渣在制备生物炭去除水环境中的抗生素具有较好的应用前景.     

Semi-closed synthesis of nitrogen and oxygen Co-doped mesoporous carbon for selective aqueous oxidation

Heteroatom-doped meso/micro-porous carbon materials are conventionally produced by harsh carbonization under an inert atmosphere involving specific precursors, hard/soft templates, and heteroatom-containing agents. Herein, we report a facile synthesis of N and O co-doped meso/micro-porous carbon (NOMC) by template-free carbonization of a small-molecule precursor in a semi-closed system. The semi-closed carbonizaiton process yields hydrophilic NOMCs with large surface area in a high yield. The porous structure as well as the elemental composition of NOMCs can be modulated by changing the holding time at a particular temperature. NOMCs as metal-free heterogeneous catalysts can selectively oxidize benzyl alcohol and its derivatives into aldehydes/ketones with>85％conversion in aqueous solution, which is much higher than that of the control sample obtained in tube furnace (21％conversion), mainly due to their high N content, high percentage of pyridinic N, and large surface area. The presence of O-containing moieties also helps to improve the hydrophilicity and dispersion ability of catalysts and thus facilitates the mass transfer process during aqueous oxidation. The NOMC catalysts also dispayed excellent activity for a wide range of substrates with a selectivity of>99％.     

SO2在水和有机溶剂中的化学形态及其脂/水分配系数：SO2生理学研究新模式

为了探讨内源性SO2生理作用和毒理作用的化学机制,采用真空减压法、超声波法、通气法、光谱扫描法及摇瓶法等对SO2在水和有机溶剂中的化学形态及其脂/水分配系数进行了研究.研究结果表明:1)气态SO2不仅易溶于水,而且更易溶于有机溶剂;2)SO2在水和有机溶剂中的溶解主要是物理性溶解,其主要以SO2分子状态存在于溶液中,在饱和溶液中90%以上是以自由分子状态存在,在较低浓度下也有50%左右以自由分子状态存在;3)SO2的脂/水分配系数仅为0.16～0.20,使存在于生物膜(脂相)系统的内源性SO2很容易进入水相并转化为亚硫酸盐,这将导致其在组织细胞内的半寿期很短,这符合信号分子的特征.由此结论:1)以SO2生理盐水溶液作为SO2供体,可作为研究内源性SO2生理作用和毒理作用的新模式;2)内源性SO2在组织细胞内的失活途径是:SO2→SO32-/HSO3-→SO42-.此外,论文认为亚硫酸钠和亚硫酸氢钠混合液并不能作为"SO2供体"用以处理生物组织.     

砷酸钙化合物的溶解度及其稳定性随pH值的变化

通过混合沉淀和溶解实验详细研究了pH值和Ca/As摩尔比对石灰沉淀法处理高浓度含砷废水的影响.沉淀后溶液中的As浓度随pH值的变化趋势与混合液的Ca/As摩尔比有关,在Ca/As=1·50和1·67时,沉淀后溶液中的As浓度在pH=7附近达到最低,然后随pH值的升高而呈现出增大的趋势;在Ca/As=2·00和4·00时,沉淀后溶液中的As浓度随pH值的升高而降低,且2种Ca/As摩尔比条件下的实验结果基本一致.混合沉淀过程中生成的砷酸钙化合物的组成与结构取决于溶液的Ca/As摩尔比和pH值.在低pH值和低Ca/As摩尔比条件下形成的沉淀物要比在高pH值和高Ca/As摩尔比条件下形成的沉淀物的颗粒要大,而且结晶程度要好.在Ca/As摩尔比为1·0~4·0和不同pH值条件下,主要生成Ca_3(AsO_4)_2·3H_2O、Ca_3(AsO_4)_2·2·25H_2O、Ca_5(AsO-4)_3OH和Ca_4(OH)-2(AsO_4)2·4H_2O,溶度积分别等于10~(-21·14)、10~(-21·40)、10~(-40·12)和10~(-27·49).     

苯甲酰苯胺类化合物溶解度和分配系数的测定及定量结构—性质相关研究

本文采用摇瓶法测定了１４各甲酰苯胺类化合物的溶解度及正辛醇／水分配系数,二者之间具有较好的相关性,应用线性溶剂化相关方法获得的相关方程,能更好地预测测苯甲酰苯胺类化合物的的水溶解度和正辛醇／水分配系数。     

Lead(II) and cadmium(II) removal from aqueous solution using processed walnut shell: kinetic and equilibrium study

The biosorption potential of processed walnut shell for Pb(II) and Cd(II) ions from aqueous solutions was explored. The effects of pH, contact time, initial ion concentration, and amount of dried adsorbent were studied in batch experiments. The maximum adsorption was achieved within the pH range 4.0–6.0. The equilibrium data were well fitted by the Langmuir isotherm model. The maximum monolayer adsorption capacities were found to be 32?g?kg^?1 and 11.6?g?kg^?1 for Pb(II) and Cd(II) ions, respectively. Kinetic data were best described by the pseudo-second-order model. The structural features of the adsorbent were characterized by Fourier transform infrared spectroscopy, which confirmed the involvement of hydroxyl (–OH), carboxyl (–COO^–), and carbonyl (C=O) groups in metal sorption. This readily available adsorbent is efficient in the uptake of Pb(II) and Cd(II) ions from an aqueous solution and could be used for the treatment of wastewater streams bearing these metal ions.     

森林新近凋落叶溶出DOM的性质及其对菲增溶作用的影响

凋落叶作为森林凋落物的主要组成部分,其溶出的大量有机质也是森林土壤可溶性有机质（DOM）的主要来源之一。研究森林凋落叶溶出DOM对PAHs增溶作用的影响有利于合理预测及评价森林土壤中PAHs的环境行为和生态风险。本研究采集了南亚热带常绿阔叶人工林的4种常见树种--尾叶桉（Eucalyptus urophylla）、木荷（Schima superba）、大叶相思（Acacia auriculiformis）和湿地松（Pinus elliottii）的新近凋落叶为试验材料,研究其DOM含量、组成与性质,对比分析了不同凋落叶DOM对菲的増溶作用及其与DOM性质的相关关系。结果表明,4种凋落叶的可溶性有机碳（DOC）质量分数在C 11.61~36.25 mg·g-1之间,其中尾叶桉的含量最大,湿地松最小。尾叶桉和木荷DOM的主要组分是可溶性糖（SS）和可溶性酚（SP）,两者总C量占DOC的比例超过47%,而大叶相思和湿地松中SS和SP两者总量所占比例均低于30%。另外,4种凋落叶DOM的质量分数（以C计）与其电导率的线性关系图中有明显转折点,说明它们均具有表面活性剂的性质。凋落叶DOM在临界胶束浓度（CMC）之上对菲具有不同程度的増溶作用,其与菲的结合系数（logKDOC）的大小顺序为尾叶桉（3.05 L·kg-1）＞木荷（3.02 L·kg-1）＞大叶相思（2.79 L·kg-1）＞湿地松（2.54 L·kg-1）,这表明尾叶桉和木荷DOM的增溶作用明显高于大叶相思和湿地松DOM。经分析表明,logKDOC与各DOM在254、280 nm处的特征紫外吸光度值（SUV-A254、SUV-A280）及其SS、SP的相对含量均呈显著正相关（p＜0.01）,与A240/A420、A254/A400比值呈显著负相关（p＜0.01）,说明DOM的芳香化程度越高,分子量越大, SS与SP所占比例越高,其对菲的増溶效果越明显。     

Potassium carbonate-based ternary transition temperature mixture (deep eutectic analogues) for CO2 absorption: Characterizations and DFT analysis

•Addition of hindered amine increased thermal stability and viscosity of TTTM. •Addition of hindered amine improved the CO₂ absorption performance of TTTM. •Good the CO₂ absorption of recycled solvents after two regenerations. •Important role of amine group in CO₂ absorption of TTTM confirmed by DFT analysis. Is it possible to improve CO₂ solubility in potassium carbonate (K₂CO₃)-based transition temperature mixtures (TTMs)? To assess this possibility, a ternary transition-temperature mixture (TTTM) was prepared by using a hindered amine, 2-amino-2-methyl-1,3-propanediol (AMPD). Fourier transform infrared spectroscopy (FT-IR) was employed to detect the functional groups including hydroxyl, amine, carbonate ion, and aliphatic functional groups in the prepared solvents. From thermogravimetric analysis (TGA), it was found that the addition of AMPD to the binary mixture can increase the thermal stability of TTTM. The viscosity findings showed that TTTM has a higher viscosity than TTM while their difference was decreased by increasing temperature. In addition, Eyring’s absolute rate theory was used to compute the activation parameters (ΔG*, ΔH*, and ΔS*). The CO₂ solubility in liquids was measured at a temperature of 303.15 K and pressures up to 1.8 MPa. The results disclosed that the CO₂ solubility of TTTM was improved by the addition of AMPD. At the pressure of about 1.8 MPa, the CO₂ mole fractions of TTM and TTTM were 0.1697 and 0.2022, respectively. To confirm the experimental data, density functional theory (DFT) was employed. From the DFT analysis, it was found that the TTTM+ CO₂ system has higher interaction energy (|ΔE |) than the TTM+ CO₂ system indicating the higher CO₂ affinity of the former system. This study might help scientists to better understand and to improve CO₂ solubility in these types of solvents by choosing a suitable amine as HBD and finding the best combination of HBA and HBD.     

腐殖酸钠和表面活性剂对黄土中石油污染物解吸增溶作用

选用十二烷基苯磺酸钠(LAS)、十二烷基硫酸钠(SDS)和十二烷基磺酸钠(SAS)对污染的土壤进行解吸实验,研究了这3种阴离子表面活性剂和腐殖酸钠对黄土中柴油类污染物的协同增溶作用.结果表明,腐殖酸钠和3种阴离子表面活性剂对黄土中柴油的解吸均有显著增溶作用,使柴油的解吸量明显增加,柴油的去除率最高可达63%.SDS对柴油的解吸量随腐殖酸钠浓度增大呈线性增加关系;但腐殖酸钠浓度增加对 LAS和SAS的解吸曲线有突越点,超过此浓度后反而会抑制解吸作用.     

嗜盐菌群对菲的降解及萘双加氧酶基因的表达规律

从胜利油田富集了一个能够降解多环芳烃的嗜盐菌群,通过克隆文库技术解析了菌群萘双加氧酶(ndo)基因的多样性.结果表明,该嗜盐菌群有6种ndo基因型,其中3种主要基因型(占总克隆子92.7%)与经典nah-like基因的相似度为89%.采用real-time RT-PCR等技术分析了不同盐度下菲降解过程中ndo基因的表达量、降解速率、生长曲线以及菲的生物可利用度,探索了菌群对菲的降解及ndo基因的表达规律.结果表明,当盐度由10%升高到20%,菌群完全降解100mg/L菲的时间从6d延长到9d,菌群生长的迟滞期由1d延长为3d.溶解菲的浓度在菌群生长过程中呈增加的趋势.Ndo基因的表达量在降解过程中呈先降低后随溶解菲浓度升高而升高的趋势,表明高浓度菲在初始阶段可能抑制ndo基因的表达.单因素方差分析(n=3, P>0.05)表明溶解菲浓度在10%和20%盐度下没有显著差异,表明一定范围的盐度不会影响菌群降解过程中菲的溶解度.菌群ndo基因的相对表达量在10%盐度下较在20%盐度下高,说明盐度对嗜盐菌群功能基因的表达具有抑制作用.