Aging effect on the mobility and bioavailability of copper in soil

Aging effect on the mobility and bioavailability of copper (Cu) was investigated using a spiked soil with different incubation periods from 3 to 56 d. Wheat was planted and earthworm was cultured separately in the incubated soils. The mobility of Cu in soil was evaluated by a chemical fractionation scheme and the toxicity and bioavailability were assessed by measuring the biomass and Cu concentration in tissues. Results showed that aging had a significant effect on Cu fraction distribution, of which Cu tended to incorporate from the exchangeable into more stable fractions such as the reducible and oxidisable fractions. However, aging had little effect on Cu bioavailability to wheat and earthworms. Comparing the soil being incubated for 3 d and 56 d, Cu concentration in wheat roots decreased from 14.5 to 12.8 mg/kg, and no significant changes in Cu concentration were observed in both wheat shoots and earthworms. The Cu concentration was around 2.0 and 50 mg/kg for wheat shoots and earthworms, respectively, irrespective of soil incubation time. The CaCl2-extractable Cu had a linear relationship with Cu concentration in wheat roots (R2 = 0.65, P < 0.05), but no linear relationship can be found for wheat shoots and earthworms. Biological control may be more crucial for Cu accumulation in organism than the changes in soil Cu fraction caused by aging.     

苄嘧磺隆对Cu2+在粘土矿物上吸附-脱附的影响

选择两种粘土矿物Ca－蒙脱石和高岭石作为吸附体，研究Cu^2 的吸附－脱附行为，以及苄嘧磺隆对Cu^2 吸附－脱附的影响，结果表明，Cu62 在比表面积、CEC大的Ca－蒙脱石上吸附量较高；而在比表面积、CEC小的高岭石上吸附量较低，蒙脱石对Cu^2 的吸附主要是静电吸附，吸附的Cu^2 较易脱附；高岭石主要通过专性吸附机制而吸附Cu^2 ，吸附的Cu^2 较难脱附，苄嘧磺隆对Cu^2 在粘土矿物上吸附－脱附的影响显著，苄嘧磺隆增加了Cu^2 在Ca-蒙脱石上的吸附，苄嘧磺隆作为桥而连接Ca-蒙脱石和Cu^2 ，苄嘧磺隆的浓度越高，Cu^2 的吸附量越大，解吸量赵低，苄嘧磺隆对Cu^2 在高岭石上吸附的影响，则是低pH值增加Cu^2 吸附，高pH值时降低Cu^2 吸附，解吸率的变化相反。     

Release behavior of copper and zinc from sandy soils

The concentrations and chemical forms of copper(Cu) and zinc(Zn) in surface soils directly influence the movement of Cu and Zn. In this study, thirteen sandy soil samples with a wide range of total Cu and Zn concentrations were collected for evaluating the relationships between Cu and Zn release and extraction time, ratio of soil to water, pH and electro;yte types. The results indicated that Cu released in batch extraction that represents long-term leaching was mainly from exchangeable, and carbonate bound Cu fractions, and Zn released in the batch extraction was mainly from its carbonate bound fraction. However, the Cu and Zn leached from the soils using the column leaching that represents short-term leaching were mainly from their exchangeable fractions. Soil column leaching at different pH values indicated that the amounts of leached Zn and Cu were greatly affected by pH. The Cu and Zn release experiments with varying extraction times and ratio of soil to water suggest that long-term water-logging in the soils after rain may increase contact time of the soils with water and the release of Cu and Zn to water from the soils, and total amounts of Cu or Zn released from the soils increase, but the Cu or Zn concentration in the surface runoff decrease with increasing rainfall intensity. The increased Ca concentration in soil solution increased stability of organic matter-mineral complexes and might decrease the dissolution of organic matter, and thus decreased the release of Cu-binding component of organic matter. However, high concentration of Na in the soil solution increased the dispersion of the organic matter-mineral complexes and increased dissolution of organic matter and the release of Cu from the soils.     

不同磷肥对棕壤吸附铜的影响

采用等温平衡法研究3种性质不同的磷肥（磷酸二铵,钙镁磷肥和磷矿粉）对棕壤铜吸附量的影响,并应用Freundlich方程Cs=KfCen分析土壤铜的吸附特征。结果表明,与不施磷肥处理（对照）相比,当n（磷）：n（铜）=1：1时,钙镁磷肥和磷矿粉增加棕壤对铜的吸附量,分别增加107%和158%;不同用量的磷酸二铵均会降低棕壤对铜的吸附能力;增加非水溶性磷肥（钙镁磷肥和磷矿粉）的施用量,能增加棕壤对铜的吸附量,提高棕壤的吸附能力;高量磷矿粉的作用效果最为明显。由此可知,为降低农产品质量安全风险,铜污染棕壤上不宜施用磷酸二铵,但可选用磷矿粉作为肥源。     

微波消解-原子吸收/原子荧光光度法测定活性污泥中的Cd、Pb、Ni、Cu、 Zn、Cr、K、As、Hg

通过实验,建立了活性污泥中金属和重金属的测定方法。活性污泥样品经硝酸—氢氟酸或硝酸—高氯酸微波消解处理后,Pb、Ni、Cu、Zn、Cr、K选用火焰原子吸收分光光度法测定,Cd用石墨炉原子吸收分光光度法测定,As、Hg用原子荧光光度法测定。该方法操作简单,结果准确,重现性好。样品加标回收率为93%-108%,相对标准偏差〈5%。     

铁粉还原-Fenton氧化处理络合铜废水的研究

采用铁粉还原-Fenton氧化工艺处理含络合铜工业废水,研究了联合工艺对络合铜的破络效果,重点考察了常温下H2O2投加量、初始pH值、反应时间、Cu(Ⅱ)初始浓度以及铁粉粒径等因素对该工艺处理效果的影响,同时探讨了相关机理。结果表明:在初始Cu(Ⅱ)浓度为50 mg/L,初始pH=3的体系中,加入过量铁粉,H2O2投加量控制在H2O2∶COD=1.5∶1(质量比),反应30 min后在pH=9的条件下沉淀,废水的COD去除率为86.5%,Cu(Ⅱ)去除率为99.9%,处理水达到《电镀污染物排放标准》(GB21900-2008)要求。研究还表明:铁粉粒径对处理效率的影响较小,采用工业级铁粉即可达到理想效果。     

电极-生物膜法处理铜酸洗废水

采用自行设计的反应器,用电极-生物膜法对铜酸洗废水进行了直接处理.结果表明,经过铜离子梯度驯化的反硝化微生物可以适应铜离子的存在并有效完成反硝化过程,在最佳工艺条件(电流密度为0.1mA/cm²,C/N为1.07)时,出水中总无机氮(TN)去除率达到98%以上,铜离子浓度<1mg/L,pH值在7左右,且不存在二次污染.电极-生物膜法可同步高效地实现中和、反硝化及铜离子的去除.验证了通过交换电极回收铜的可行性.     

高分子重金属絮凝剂SSXA对Cu2+的捕集性能研究

以淀粉-丙烯酰胺接枝共聚物、NaOH、CS2为原料,在一定条件下合成了一种新型高分子重金属絮凝剂--淀粉基黄原酸酯-丙烯酰胺接枝共聚物.研究了该絮凝剂的除Cu2 、去浊机理,并对硫酸铝浓度、初始Cu2 浓度、pH值、浊度等影响其除铜及去浊效能的因素作了考察.实验结果表明:(1)该絮凝剂对Cu2 有很好的捕集功能,但需要与硫酸铝复配以提高其沉降性能,适合复配使用.Al3 与初始Cu2 的体积摩尔浓度比值为0.3较为适宜,此时Cu2 去除率大于98%;(2)pH值对复配体系的除Cu2 、去浊效果影响不大;(3)Cu2 和致浊物质共存时,会互相促进彼此的去除.对初始Cu2 浓度为25 mg·L-1、浊度为5～300NTU的水样,处理后出水Cu2 浓度小于0.5mg·L-1、浊度小于3NTU.     

农用污泥中铜的生态安全阈值研究

本论文采用污泥和土壤外源铜的活性差异系数法研究了农用污泥中铜的生态安全阈值。首先通过比较确定不同土壤条件下污泥中铜和水溶性铜的活性差异的系数,然后利用系数法得到相应土壤条件下污泥铜HC5值(即能够保护95%物种的浓度),并建立了土壤理化性质参数与污泥铜HC5值的量化关系和预测模型。最后与我国现行污泥农用标准值进行了比较,提出了修改建议。结果表明,土壤中来源污泥的铜活性均值约为来源水溶性盐的40%左右。土壤阳离子交换量(CEC)是影响土壤中污泥源铜的毒性的主控因子,可影响污泥铜HC5值变异的84.6%,而土壤pH值和有机碳含量(OC)分别可影响污泥铜HC5值变异的8.4%和1.8%。基于土壤pH、OC和CEC的三因子模型进行预测优于基于土壤pH和CEC的两因子模型,其相关性达到94.8%。与模型预测值相比,我国现行污泥农用标准GB4284-84与CJ/T309-2009中对铜限值的规定均存在着不同程度的保护不足或保护过度问题。     

蜈蚣草生长对其根际铜尾矿土壤酶活性的影响

通过盆栽模拟试验,研究了蜈蚣草(Pteris vittata)生长对其根际铜尾矿土壤酶活性的影响。结果表明,蜈蚣草根际土壤中过氧化氢酶、脲酶、多酚氧化酶和蔗糖酶活性均随着植物的生长而呈现不同程度的升高,其中过氧化氢酶和脲酶活性均与植物生长时间之间呈显著正相关,多酚氧化酶和蔗糖酶活性在植物生长旺盛期达到峰值,分别为对照组的3.59和2.58倍,随后逐渐下降;而磷酸酶活性却随着植物的生长而显著降低。过氧化氢酶、脲酶和磷酸酶活性与蜈蚣草地下部分干质量的相关性大于其地上部分,且5种土壤酶活性与土壤有机质含量之间相关显著。蜈蚣草生长可有效改善根际铜尾矿的基质环境和根际土壤肥力水平,因此,在铜尾矿废弃地恢复实践中具有较大的应用潜力。