土壤中镉、锌离子的单一及竞争吸附研究

采用等温吸附法探讨了重金属镉、锌在青岛地区3种主要土壤(棕壤、潮土和砂浆黑土)中的吸附特征.结果表明,在质量浓度为20～500 mg/L的单一重金属等温吸附试验中,棕壤和潮上对Cd~(2+)、Zn~(2+)的吸附量相近,而黑土对Cd~(2+)、Zn~(2+)的吸附量明显高于棕壤和潮土.Cd~(2+)、Zn~(2+)的双组分竞争吸附表明,3种上壤对Cd~(2+)、Zn~(2+)的吸附量与其单独存在下的情形相比都有所下降.质量浓度分别为20～500mg/L的两种重金属元索等馈竞争吸附时,这3种土壤对Cd2+的吸附量比对Zn~(2+)的大.非等量竞争吸附试验的结果表明,3种土壤中,500mg/L的Zn~(2+)对100 mg/L的Cd~(2+)吸附量的影响均比同浓度的Cd~(2+)对Zn~(2+)的影响大.用Langmuir和Freundlich方程对这两种重金属离子的等温吸附试验数据进行拟合,均呈极显著相关关系.     

Oxidative stress and DNA damages induced by cadmium accumulation

Experimental evidence shows that cadmium （Cd） could induce oxidative stress and then causes DNA damage in animal cells, however, whether such effect exists in plants is still unclear. In the present study, Vicia faba plants was exposed to 5 and 10 mg/L Cd for 4 d to investigate the distribution of Cd in plant, the metal effects on the cell lipids, antioxidative enzymes and DNA damages in leaves. Cd induced an increase in Cd concentrations in plants. An enhanced level of lipid peroxidation in leaves and an enhanced concentration of H2O2 in root tissues suggested that Cd caused oxidative stress in Vicia faba. Compared with control, Cd-induced enhancement in superoxide dismutase activity was significant at 5 mg/L than at 10 mg/kg in leaves, by contrast, catalase and peroxidaseactivities were significantly suppressed by Cd addition. DNA damage was detected by neutral/neutral, alkaline/neutral and alkaline/alkaline Comet assay. Increased levels of DNA damages induced by Cd occurred with reference to oxidative stress in leaves, therefore, oxidative stress induced by Cd accumulation in plants contributed to DNA damages and was possibly an important mechanism of Cd-phytotoxicity in Vicia faba plants.     

Thermodynamics and kinetics of cadmium adsorption onto oxidized granular activated carbon

Cadmium sorption behavior of granular activated carbon oxidized with nitric acid was systematically studied by sets of the equilibrium and time-based experiments under various conditions.The cadmium adsorption capacity of oxidized granular activated carbon enlarged with an increase in pH,and reduced with an increase in ionic strength.Experimental data were evaluated to find out kinetic characteristics.Adsorption processes were found to follow pseudo-second order rate equation.Adsorption isotherms correlate well with the Langmuir isotherm model and the maximum sorption capacity of cadmium evaluated is 51.02μmol/g.Thermodynamic parameters were calculated based on Van't Hoff equation.Equilibrium constant Kd was evaluated from Freundlich isotherm model constants,Langmnir isotherm model constants,and isotherms,respectively.The average change of standard adsorption heatΔH~0 was -25.29 kJ/mol.NegativeΔH~0 andΔG~0 values indicate the adsorption process for cadmium onto the studied activated carbon is exothermic and spontaneous.The standard entropyΔS~0 was also negative,which suggests a decrease in the freedom of the system.     

Metal contents of marine turtle eggs (Chelonia mydas; Lepidochelys olivacea) from the tropical eastern pacific and the implications for human health

Concentrations of eight elements were measured in Chelonia mydas and Lepidochelys olivacea eggs collected along the Pacific coast of Panama. Manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd), and mercury (Hg) concentrations were similar to previous reports of these species from around the world, while lead (Pb) was lower than previous reports. Cd posed the highest health risk to people who regularly eat the eggs, with average consumption rates leading to target hazard quotients (THQ) of up to 0.35 ± 0.15. Our conclusions indicate that current turtle egg consumption in isolated, coastal Pacific communities may pose a health concern for young children, and that youth and young adults should limit their consumption of turtle eggs to reduce their total intake of nonessential metals.     

聚(丙烯酸-co-丙烯酰胺)/膨润土/腐植酸钠三维网络凝胶吸附剂对Cd2+吸附性能研究

制备了一种聚(丙烯酸-co-丙烯酰胺)/膨润土/腐植酸钠三维网络凝胶吸附剂,重点考察了吸附剂对Cd2+吸附的pH依赖性、吸附动力学和吸附等温线.结果表明,Cd2+溶液pH值对吸附容量有较大影响.在pH=8、吸附时间30 min、Cd2+溶液初始浓度0.02 mol/L和吸附剂用量0.10 g的条件下,吸附剂对Cd2+的饱和吸附量可达294.7 mg/g.与膨润土相比,三维网络凝胶吸附剂具有更高的吸附容量和更快的吸附速率.     

碳酸镁与镉离子的吸附和沉淀作用研究

以碳酸镁为吸附剂,在镉离子初始浓度为0~6 mmol/L,初始pH值为4和7的条件下,研究了碳酸镁与镉离子的吸附与沉淀作用。结果表明,由于碳酸镁的溶解及与体系中氢离子的中和,碳酸镁—镉体系的最终pH值为10.4左右;体系的平衡pH值随着镉离子初始浓度的增加而减小;体系中镉的平衡浓度随着初始镉离子浓度的增加缓慢上升;碳酸镁对镉的吸附等温线为折线型,不符合Freundlich和Langmuir模型,符合伪二阶吸附动力学模型。结合碳酸镁吸附镉前后固相表征的结果,说明碳酸镁与镉离子的作用机制随着镉离子浓度的增加,从离子交换发展为离子交换和表面配位反应并存,最后表现为表面沉淀。     

3种镉超富集植物毛状根体系对镉胁迫响应的比较

近年来,转基因毛状根组织被越来越多地应用于重金属和有机污染物的植物修复技术研究中,已成为进行污染物毒性响应机制研究的便捷的实验室工具。为了探究龙葵、油菜、芥菜3种镉(cadmium,Cd)超富集植物对Cd毒性胁迫响应的差异,以诱导出的3种植物毛状根为研究材料,从毛状根的生长状态、富集Cd的能力、根组织细胞的凋亡程度和抗氧化酶活性等方面进行了探讨。结果表明:Cd浓度为0~50μmol·L-1时,龙葵、油菜、芥菜毛状根受Cd毒害的影响都不明显;Cd浓度为75~100μmol·L-1时,龙葵、油菜、芥菜毛状根均表现出对Cd胁迫的防御响应。在较高的Cd浓度(100μmol·L-1)下,龙葵毛状根的生物量受Cd毒害的影响最小,芥菜次之,油菜受影响最大;同时龙葵毛状根富集的Cd含量最高(745.0μg·g-1),芥菜次之(681.4μg·g-1),油菜最差(505.2μg·g-1)。龙葵、油菜、芥菜毛状根在Cd胁迫下的细胞凋亡水平均随Cd浓度的升高而升高,当Cd浓度为100μmol·L-1时,龙葵毛状根比油菜和芥菜毛状根的细胞凋亡程度均低。同时3种植物毛状根在不同浓度Cd处理下抗氧化酶活性的变化有一定差异。从上述结果综合来看,龙葵毛状根受Cd毒害的影响最小、富集Cd的能力最好,是进一步开展Cd超富集植物转基因改造研究的较好的实验室载体。     

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。     

铜、镉联合胁迫对羊角月牙藻的自由基氧化损伤影响研究

分析了铜和镉联合胁迫对羊角月牙藻(Selenastrum capricornutum)的影响,运用国内应用较少的新型技术——叶绿素荧光技术检测了胁迫下微藻的最大光能转化效率(Fv/Fm)受到的影响,并尝试通过膜脂过氧化损伤产物丙二醛(MDA)和其他指标在胁迫下的变化,对铜、镉联合胁迫机制进行初步探究。结果表明:(1)羊角月牙藻在铜、镉联合胁迫下生长受到抑制,表现出明显的浓度-效应关系。铜、镉的联合胁迫的相加指数为-1.63,表现为典型的拮抗作用。(2)通过叶绿素荧光技术的应用,探明Fv/Fm随毒性浓度的变化表现为浓度-效应关系,毒性浓度越大,羊角月牙藻的Fv/Fm越低,但在低毒性浓度刺激时随胁迫时间延长有回升迹象。(3)随毒性浓度的增加,羊角月牙藻的MDA增加,表现为显著的浓度-效应关系;可溶性蛋白质大体呈先升后降的趋势。(4)铜、镉联合胁迫下,MDA与羊角月牙藻生物量、Fv/Fm呈显著负相关。脂质过氧化是导致生物量下降和Fv/Fm受抑制的原因之一。(5)在微藻体内铜、镉发生拮抗作用的机制也可能与重金属的脂质过氧化作用由于拮抗受到抑制有关。     

冻融循环及有机肥配施对黑土中镉形态的影响

以黑龙江黑土为对象,研究了冻融循环及有机肥配施量对黑土中镉形态分布的影响。对配施不同有机肥的土壤样品进行5次冻融循环,采用电感耦合等离子质谱仪(ICP-MS)分析土壤样品中镉的赋存形态。结果表明,冻融循环数及有机肥的配施有助于降低黑土中的总镉量;冻融循环会促使黑土中的镉由交换态、碳酸盐结合态、有机结合态向铁锰氧化物结合态和残渣态转化,而增加有机肥配施量会使黑土中的镉由交换态向其他形态转化。因此,冻融循环及有机肥配施有助于降低土壤中镉的生物有效性,进而降低其环境风险。