咖啡因在河流沉积物中吸附的影响因素及模拟研究

咖啡因是一种在环境中广泛存在的药物,其在水系环境的迁移和分布主要受到吸附行为的影响.在实验室条件下,近似模拟自然河流水/泥界面,应用中心复合实验设计,考察了温度、pH、有机质含量和转速等对咖啡因吸附的影响;利用实验所得数据,分别拟合和验证了基于线性方程和神经网络的咖啡因吸附模型,通过对比拟合和验证结果得到适用于自然河流的咖啡因吸附模型.实验结果表明,咖啡因在沉积物中的吸附呈现先快速后缓慢的过程,30 h内吸附比例超过90%;咖啡因的吸附是放热反应,低温有利于咖啡因的吸附;而转速增大能促进咖啡因的吸附反应;pH和有机质含量的影响较小.模型模拟结果表明,两种模型均能较好地拟合吸附实验结果,但神经网络模型的拟合程度和精度均优于线性方程模型;且交叉验证结果表明,利用不同组数据进行训练,神经网络模型均取得了优于线性方程的拟合结果.因此,在所考察的因素和浓度范围内,神经网络模型较好地预测了自然河流沉积物中咖啡因的吸附行为.     

溶解性有机质对铁铝土吸附2,4-D的影响

以动力学吸附和等温吸附实验研究了2,4-D在铁铝土中的吸附特征,并比较了不同亲/疏水性溶解性有机质（DOM）对此的影响.结果表明：2,4-D在铁铝土中的动力学吸附符合伪一级动力学方程,等温吸附符合Henry,Freundlich方程,是一个物理作用主导的,自发的,放热的非均质吸附过程.吸附系数K_d为0.61~2.02L/kg,是一种难吸附有机污染物,对地下水存在环境风险.吸附量受土壤pH值影响显著,与土壤中矿物含量,粘粒组成等也密切相关.DOM共存条件下,高疏水性DOM,中疏水性DOM抑制了2,4-D在铁铝土的吸附,使K_d值下降10.7%~58.8%.低疏水性DOM对铁铝土吸附2,4-D作用不明显.DOM对铁铝土吸附2,4-D的作用效应与土壤理化性质和DOM性质密切相关.土壤矿物组分越多,粘粒含量越高,堵孔效应越大.DOM疏水性越大,对2,4-D吸附作用的增溶作用,堵孔作用也越大,其中HOA,HON是关键组分.     

生物炭墙对紫色土坡耕地中氟苯尼考迁移影响

采用实验室批量平衡实验,研究紫色土坡耕地土壤中氟苯尼考吸附-解吸特征及生物炭施用的影响,此外,开展野外坡底生物炭（重量占比5%）可渗透反应墙的构建试验,观测自然降雨条件下该反应墙对坡耕地小区中氟苯尼考随地表径流与下渗水迁移的影响.结果表明,氟苯尼考在紫色土中的等温吸附行为符合Freundlich方程,在低浓度范围内（<2mg/L）,生物炭的施用一方面提高了其在紫色土中的吸附量,吸附过程可能以内扩散为主,另一方面,显著降低其解吸量;紫色土坡耕地中的淋溶作用是氟苯尼考的主要迁移方式;坡底生物炭（5%）渗透墙的构建有效地减控了其在紫色土中的淋溶迁移以及深层侧向迁移.     

十六烷基三甲基季铵盐-乙硫醇铵盐复合改性膨润土吸附性能研究

用十六烷基三甲基季铵盐(HDTMA)和乙硫醇铵盐(AET)双阳离子同时复合改性内蒙钙基膨润土(NMB),制得新型吸附材料HDTMA-AET-NMB.利用X射线衍射(XRD)、热分析(TG-DTA)、红外光谱(FT-IR)及N2-BET等测定发现,复合改性膨润土的表面性质和层间结构已发生显著改变.对重金属离子Cd2+和对硝基苯酚(PNP)的吸附研究表明,HDTMA-AET-NMB能协同吸附混合水溶液中的目标污染物,对水中重金属离子的吸附机理是膨润土层间的AET与被吸附的Cd2+形成了稳定的配合物;对水中对硝基苯酚的吸附源于其在长碳链疏水介质中的分配.复合改性膨润土可望应用于重金属-有机物混合废水的处理.     

Selective sorption of perfluorooctane sulfonate on molecularly imprinted polymer adsorbents

Perfluorooctane sulfonate (PFOS), as a potential persistent organic pollutant, has been widely detected in water environments, and has become a great concern in recent years. PFOS is very stable and difficult to decompose using conventional techniques. Sorption may be an attractive method to remove it from water. In this study, the molecularly imprinted polymer (MIP) adsorbents were prepared through the polymerization of 4-vinylpyridine under different preparation conditions in order to remove perfluorooctane sulfonate (PFOS) from water. The MIP adsorbents using perfluorooctanoic acid (PFOA) as the template had good imprinting effects and could selectively remove PFOS from aqueous solution. The sorption behaviors including sorption kinetics, isotherms, and effect of pH, salt, and competitive anions were investigated. Experimental results showed that the sorption of PFOS on the MIP adsorbents was very fast, pH-dependent, and highly selective. The achieved fast sorption equilibrium within 1 h was attributed to the surface sorption on the fine adsorbents. The sorption isotherms showed that the sorption selectivity of PFOS on the MIP adsorbents decreased at high PFOS concentrations, which may be due to the double-layer sorption and the formation of PFOS micelles on the sorbent surface. The sorption of PFOS on the MIP adsorbents was mainly dominated by the electrostatic interaction between the protonated vinylpyridine on the adsorbent surface and the anionic PFOS. The prepared MIP adsorbents can potentially be applied in water and wastewater treatment for selective removal of PFOS.     

植物角质层的蜡质组分对甲萘酚的吸附作用

采用批量平衡法,比较研究了苹果角质结合蜡质、分离蜡质和重建蜡质对极性有机污染物甲萘酚的吸附作用,并探讨了不同负载量的重建蜡质的吸附性能,以期为准确预测有机污染物在不同状态蜡质组分上的吸附行为提供依据.结果表明,甲萘酚在苹果角质层、脱蜡角质层、分离蜡质(IW)、重建蜡质(BW)上的等温吸附线呈非线性,符合Freundlich方程.植物蜡质对甲萘酚的吸附作用与蜡质所处状态密切相关,吸附能力(Koc)大小顺序为:重建蜡质(321.2) > 分离蜡质(190.4) > 角质结合蜡质(128.4),表明植物角质层进入土壤后发生演化过程中,其中不易降解的蜡质的吸附能力逐渐增大.重建蜡质(BW)的吸附系数(Kd)与甲萘酚的浓度呈负相关,与蜡质的负载量呈正有关.在低浓度时,甲萘酚的有机碳标化吸附系数Koc值随有机碳含量(foc)增大先增大后减小,存在一些强的特殊作用;而高浓度时, Koc-基本为一常数,不随蜡质负载量而变化,主要吸附机理为分配作用.角质结合蜡质(CW)对角质层的总吸附作用的贡献较小,但随甲萘酚平衡浓度的增大而逐渐增大,并于高浓度时, CW的吸附能力与IW相当.     

Enhanced and irreversible sorption of pesticide pyrimethanil by soil amended with biochars

Biochar derived from partial combustion of vegetation is ubiquitous and potentially effective in sequestration of environmental contaminants.Biochars were prepared by burning of red gum(Eucalyptus spp.) woodchips at 450 and 850°C(labeled as BC450 and BC850).These two biochars were found to possess markedly different properties in terms of surface area and porosity.Short-term equilibration tests(24 hr) were conducted to assess the sorption-desorption behavior of pyrimethanil in the soil amended with various amounts of biochar of each type,with a special focus on the desorption behavior of the sorbed pesticide through four times successive desorption by dilution.Sorption coefficient and isotherm nonlinearity of the amended soils progressively increased with the content of biochar in the soil.Biochar BC850 with higher surface area and microporosity showed a stronger effect on the reversibility of sorption pesticide.The soils amended with 5% BC450 and 1% BC850 had nearly the same sorption capacity for pyrimethanil;however,their desorption processes were very different with 13.65% and 1.49% of the sorbed pesticide being released,respectively.This study suggested that biochar in soil could be an important factor for immobilization of a pesticide and thus affecting its environment fate in soil.     

壳聚糖吸附酸性大红及Cu2+对吸附的增强作用

采用壳聚糖去除水中酸性大红,对壳聚糖吸附酸性大红的动力学、热力学以及溶液pH、盐浓度、外来Cu2+对吸附的影响进行了研究.准二级吸附动力模型、Langmuir、Freundlich及Dubinin-Radushkevich (D-R)方程分别用来对吸附动力学和等温线进行分析.结果表明,酸性大红在壳聚糖上的吸附是一个化学吸附控制的准二级动力学过程.Langmuir、Freundlich和D-R方程都能较好地描述吸附等温线.溶液pH和温度对吸附有较大影响,而氯化钠浓度对吸附的影响较小.对吸附热力函数的计算结果显示ΔH0<0,表明吸附是一个放热过程.由D-R方程计算的吸附自由能E为9.5~10.7 kJ.mol-1,表明吸附过程为离子交换化学吸附.Cu2+对吸附的影响结果显示Cu2+能显著提高壳聚糖对酸性大红的吸附容量,另外建立了Cu2+浓度与吸附量增加之间的数学模型.     

苯噻草胺在土壤中的吸附与解吸行为研究

采用批量平衡实验方法,研究了除草剂苯噻草胺在5种不同性质土壤中的吸附与解吸行为,并探讨了土壤有机质及溶液pH值对吸附的影响.结果表明,线性方程与Freundlich方程均能较好地拟合苯噻草胺在土壤中的吸附等温线.计算得到苯噻草胺在5种土壤中的碳标化分配系数K_oc在849.5～1?818.8 L·kg^-1之间,说明土壤对苯噻草胺有较强的吸附能力.苯噻草胺在土壤中的分配系数K_d、Freundlich常数K_f以及K_f(1/n)与土壤有机质含量均呈显著正相关.通过过氧化氢去除有机质后,土壤对苯噻草胺的吸附大大降低,说明土壤有机质是影响苯噻草胺在土壤中吸附的主要因素.对于同种土壤而言,苯噻草胺的吸附量随pH值的增大而减小.解吸实验表明,苯噻草胺在土壤中的解吸过程具有一定的滞后性,推测其在土壤中的迁移能力较差.     

Synthesis and kinetics investigation of meso-microporous Cu-SAPO-34 catalysts for the selective catalytic reduction of NO with ammonia

A series of meso-microporous Cu-SAPO-34 catalysts were successfully synthesized by a one-pot hydrothermal crystallization method, and these catalysts exhibited excellent NH_3-SCR performance at low temperature. Their structure and physic chemical properties were characterized by means of X-ray diffraction patterns(XRD), Scanning electron microscopy(SEM), Transmission electron microscopy(TEM), N_2 sorption-desorption, nuclear magnetic resonance(NMR), Inductively Coupled Plasma-Atomic Emission spectrometer(ICP-AES), X-ray absorption spectroscopy(XPS),Temperature-programmed desorption of ammonia(NH_3-TPD), Ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS) and Temperature programmed reduction(TPR).The analysis results indicate that the high activities of Cu-SAPO-34 catalysts could be attributed to the enhancement of redox property, the formation of mesopores and the more acid sites. Furthermore, the kinetic results verify that the formation of mesopores remarkably reduces diffusion resistance and then improves the accessibility of reactants to catalytically active sites. The 1.0-Cu-SAPO-34 catalyst exhibited the high NO conversion( 90%) among the wide activity temperature window in the range of 150–425℃.