菲和镉单一及复合污染条件下在毛蚶体内的富集动力学研究

采用室内半静态双箱动力学模型实验,研究了菲和镉单一及复合污染条件下在毛蚶(Anadara subcrenata)体内的生物富集,通过对富集与释放过程中毛蚶体内菲和Cd的富集量进行非线性曲线拟合,获得了菲和Cd单一及复合污染条件下在毛蚶体内的吸收速率常数k1、释放速率常数k2、生物富集因子BCF、生物半衰期B1/2和平衡状态下最大富集量CA max等动力学参数。实验结果表明,菲和Cd在实验前期富集速率较高,8 d以后富集速率减缓,释放阶段与富集阶段相似。毛蚶对菲的BCF值为37.80,远大于Cd的BCF值13.12,且生物半衰期时间更长,菲更容易在生物体内富集。菲和Cd联合暴露条件下,在毛蚶体内的CA max和BCF值均大于单一作用,说明二者同时暴露时,毛蚶对菲和镉的吸收富集均有所增强。实验模型拟合度较好,输出值和实测值之间无显著性差异,拟合方程和拟合参数可信。     

Hydrolysis and photolysis of oxytetracycline in aqueous solution

Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day^{? 1} were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 10² to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca^{2 +} made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day^{? 1}, which is comparable to that of hydrolysis at 60°C. The presence of Ca^{2 +} accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca^{2 +}. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.     

多孔性Mn3O4的制备及其对水中镉的吸附

采用硫酸锰水解-氧化两步法制备了多孔性四氧化三锰,以X射线衍射、扫描电镜和氮吸附比表面仪对其进行了表征,研究了该多孔性Mn3O4在不同的溶液pH值、吸附时间、投加量和温度下对水中Cd(Ⅱ)的吸附行为,并测定了吸附过程的动力学和热力学参数。实验结果表明,该法合成的四氧化三锰属四方体心结构,一次晶粒尺寸为45.8 nm,颗粒间存在大量的孔洞,BET法比表面积为40.27 m2/g。在293 K,pH 5.5,吸附12 h时达到平衡,饱和吸附量为12.8 mg/g。该吸附过程符合准二级反应动力学模型,其反应的吸附活化能为2.743 kJ/mol,吸附等温线较好地符合Langmuir等温方程,吸附焓变和熵变均为正值,自由能变为负值,说明该吸附过程为自发的吸热过程。     

4种人工湿地基质对马拉硫磷的吸附特性

通过基质对马拉硫磷的等温吸附和吸附动力学实验,研究天然土壤、煤渣、沸石、砾石对马拉硫磷的吸附特性,为人工湿地处理含马拉硫磷废水提供理论依据.结果表明:马拉硫磷浓度为2.25 ～ 90 mg/L条件下,Langmuir和Freundlich方程均能较好地拟合4种基质对马拉硫磷的等温吸附过程,并且Freundlich方程的拟合效果要好于Langmuir方程.马拉硫磷的理论饱和吸附量大小依次为天然土壤(9.9304 mg/g)＞煤渣(1.6173 mg/g)＞沸石(0.6039 mg/g)＞砾石(0.3965 mg/g).4种基质对马拉硫磷的缓冲能力大小依次为天然土壤＞煤渣＞沸石＞砾石,即当进水马拉硫磷浓度波动较大时,作为湿地基质天然土壤使人工湿地系统维持稳定出水水质的能力最强.马拉硫磷浓度为4.5 mg/L条件下,吸附动力学模型Elovich方程能较好地拟合4种基质对马拉硫磷的吸附动力学特征,说明4种基质对马拉硫磷的吸附是表面吸附和内部扩散吸附共同作用的结果.因此,天然土壤和煤渣适宜作为处理含马拉硫磷废水的人工湿地基质.     

柠檬酸盐络合铜在污泥上的吸附

利用二沉池污泥进行吸附柠檬酸盐络合铜实验。研究了吸附动力学、热力学、液固比以及pH值对吸附的影响,同时对比污泥吸附前后FTIR光谱推测吸附主要基团。结果表明,吸附速率受多种机制共同影响;准二级动力学模型能较好地描述污泥吸附柠檬酸盐络合铜动力学数据;增加液固比,总铜去除率下降;偏酸性环境下污泥对络合铜吸附效果较优;吸附过程符合Langmuir等温模型;红外光谱特征分析表明,污泥含有的—OH、酰胺基、—COO-、硅酸盐物质可能是污泥吸附络合铜的主要活性基团。     

Adsorption of glyphosate on Brazilian subtropical soils rich in iron and aluminum oxides

Abstract

We investigated the adsorption of glyphosate onto five subtropical soils of Paraná and São Paulo states, Brazil, a region of intense agricultural activities, aiming at the determination of kinetic and isotherm adsorption parameters which enable the evaluation of the potential leaching of the herbicide. The adsorption was fast, being described by the pseudo-second order and intraparticle diffusion models, thus suggesting that mixed mechanisms are involved. The Oxisol containing the highest concentrations of metal oxides (209.5?g kg^?1 Fe₂O₃ and 160.2?g kg^?1 Al₂O₃) was the sample with the highest rate constant, indicating the adsorption sites are readily available. All the soils are rich in aluminum and iron oxides, explaining the Freundlich coefficients (K_F) between 642 and 1360?mg^1-1/n kg^?1 L^1/n, which are higher than most of the coefficients described for other soils around the world. The maximum desorption (15% of the adsorbed amount) was observed for the Oxisol. For the other soils, desorption ranged from 2 to 7%. These results suggest that the leaching of free glyphosate to nearby surface and groundwaters is unlikely unless excessive doses are used. The adsorption parameters are useful for managing the right doses applied to the crops, thus avoiding contamination of adjacent areas.     

改性粉煤灰对糖蜜废水的吸附效果及机理

采用改性粉煤灰(MCFA)吸附糖蜜废水中的有机污染物,对吸附行为和机理进行了考察和分析。结果表明,MCFA投加量为30 g/L及pH为5.0的优化条件下,COD去除率为88.6%,饱和吸附量为89.7 mg COD/g MCFA。准二级方程能更好地描述糖蜜废水在MCFA上的吸附动力学。颗粒内扩散方程结果表明孔扩散并非唯一的速度控制步骤。吸附平衡表明,Freundlich等温线最符合吸附模式,为优惠吸附。D-R模式中的吸附自由能Ea值推断更可能是物理吸附而不是化学吸附。吸附热力学参数ΔG0(<0)、ΔH0(5.130 kJ/mol)和ΔS0(19.936 J/(mol.K))表明MCFA对糖蜜废水的吸附过程为可行的,自发性的吸热反应。     

磁性海泡石吸附Cr(VI)特性及动力学

采用化学共沉淀法合成磁性海泡石,通过静态吸附实验研究磁性海泡石对Cr(Ⅵ)的吸附特性及其动力学。结果表明,磁性海泡石对Cr(Ⅵ)的吸附在90 min内即可达到平衡;体系的初始pH是影响磁性海泡石吸附Cr(Ⅵ)性能的重要因素;当废水中Cr(Ⅵ)的初始浓度为50 mg/L时,磁性海泡石的适宜投加量为10 g/L;随反应温度的升高,磁性海泡石对Cr(Ⅵ)的吸附量增加;温度为25、35和45℃时,磁性海泡石对Cr(Ⅵ)的饱和吸附量分别为3.32、3.72、4.08 mg/g;吸附动力学曲线可以用拟二级反应动力学模型拟合;内扩散和液膜扩散联合控制Cr(Ⅵ)在磁性海泡石上的吸附过程,其中内扩散的控速作用大于液膜扩散。     

Fe-MCM-41催化氧化2,4-二氯苯氧乙酸

采用水热法合成了Fe-MCM-41中孔分子筛,紫外、红外及XRD表征显示铁离子已进入中孔分子筛骨架。以H2O2为氧化剂形成类Fenton试剂,实验结果表明,在催化剂加入量为1 g/L、H2O2体积分数为6%、pH为4、反应时间为10h、反应温度为35℃的条件下,处理质量浓度为50 mg/L的2,4-D废水的降解率达94.95%。宏观动力学研究显示,该反应近似为一级反应,反应速率常数、表观活化能分别为0.21667 min-1和26.65 kJ/mol。     

羧甲基壳聚糖-膨润土复合吸附剂对Cu^2＋、Ni^2＋、Cr^3＋的吸附

用羧甲基壳聚糖和膨润土制备复合吸附剂,研究了复合吸附剂在不同参数下对Cu^2＋、Ni^2＋和Cr^3＋吸附的影响。结果表明,复合吸附剂对Ni^2＋的吸附可以很快达到吸附平衡,而对Cu^2＋和Cr^3＋的吸附分别在30min和180min时达到平衡;且pH值对吸附容量的影响很显著。通过计算不同温度下的热力学参数△G、△H和△S,3种金属的△G〈0,证实这3种金属吸附都是自发过程。Cu^2＋、Ni^2＋和Cr^3＋的吸附等温线较符合Langmuir型;反应动力学都更符合准二级吸附速率方程。