零价铁-氧化剂联合降解土壤中硝基氯苯及土壤性质变化

硝基氯苯是重要的化工原料和中间体,其在土壤中的不断积累对生态环境和人体健康构成了严重威胁.高级氧化修复技术可以将有机污染物直接或间接矿化为CO_2和H_2O,从而成为近年来研究的重点.本文针对南京某化工厂搬迁遗留的硝基氯苯污染的场地土壤,研究了零价铁还原与氧化剂氧化的联合体系对硝基氯苯的降解率,并对反应过程的中间产物和动力学进行了分析,研究了降解后土壤性质的变化.结果表明,当采用KMnO_4、Fenton试剂、30%H_2O_2和Na_2S_2O_44种氧化剂直接氧化时,土壤中硝基氯苯的降解率分别为75.0%、62.9%、58.1%和41.5%;经零价铁还原1 h后,再施加氧化剂氧化处理,硝基氯苯降解率大幅提高,分别达到91.5%、88.5%、87.4%和70.4%.零价铁还原体系中间产物氯代苯胺浓度4 h时达到最大,施加氧化剂后迅速下降,4 h后下降至最低并维持较稳定水平;硝基氯苯氧化反应在单一氧化剂反应体系符合一级动力学方程,但在零价铁与氧化剂联合反应体系符合二级动力学方程;降解后的土壤性质有较大变化,CEC、TOC和土壤养分显著下降,Eh和EC显著增加,土壤pH除施加Na2S2O4下降显著外,施加KMnO_4、Fenton试剂、30%H_2O_2时下降较小,但同时添加零价铁土壤pH下降显著;土壤全N、全P、全K变化不显著,这些可为修复后土壤的再利用提供数据参考.     

不同铁营养状况下根系特征及蒸腾对黄瓜幼苗吸收镉的影响

采用营养液培养方法,研究了不同铁营养状况下的根系形态变化及蒸腾作用对不同品种黄瓜幼苗吸收镉的影响.结果表明,不加铁处理对地上部生物量的影响大于对根系的影响,并且不同品种间生物量差异显著.不加铁处理和低水平铁处理时,黄瓜根长变长、根表面积变大.与不加铁处理相比,加铁处理显著抑制了黄瓜根系对镉的吸收,中农5号(缺铁敏感黄瓜品种)和津春4号(缺铁不敏感黄瓜品种)每克根对镉的吸收量分别降低了25.5%~45.5%和28.8%~55.0%;但却增加了镉向地上部的转运,镉在叶中的分配系数分别增加了2.2~3.6倍(中农5号)和2.6~3.7倍(津春4号).缺铁敏感的中农5号吸镉总量与根长、根表面积都呈显著正相关性,而缺铁不敏感的津春4号吸镉总量与根长、根表面积之间的关系不显著.不管是中农5号还是津春4号,其蒸腾速率与每克根吸收镉的量均呈显著的正相关关系.不同铁营养状况影响了黄瓜幼苗的根系形态和蒸腾速率,从而影响了根系对镉的吸收,高铁水平显著抑制了黄瓜根系对镉的吸收.     

溶解氧和温度对地下水除铁、锰效果的影响

研究锰砂滤层去除铁、锰过程中温度、溶解氧两个因素对去除效果的影响,为生物法除铁、锰的实际运行提供了参考依据。从经济性和微生物角度考虑,原水DO维持在3mg／L左右即可满足运行要求,采用跌水曝气的方式去除效果优于管道混合器。当铁锰共存时最适宜的处理环境温度为20℃。     

Selective extraction and separation of Fe, Mn oxides and organic materials in river surficial sediments

In order to investigate the adsorption mechanism of trace metals to surficial sediments （SSs）, a selective extraction procedure was improved in the present work. The selective extraction procedure has been proved to selectively remove and separate Fe, Mn oxides and organic materials （OMs） in the non-residual fraction from the SSs collected in Songhua River, China. After screening different kinds of conventional extractants of Fe and Mn oxides and OMs used for separation of heavy metals in the soils and sediments, NH2OH .HCl （0.1 mol/L） ＋ HNO3 （0.1 mol/L）, （NH4）2C2O4 （0.2 mol/L） ＋ H2C2O4 （pH 3.0）, and 30% of H2O2 were respectively applied to selectively extract Mn oxides, Fe/Mn oxides and OMs. After the extraction treatments, the target components were removed with extraction efficiencies between 86.09%--3.36% for the hydroxylamine hydrochloride treatment, 80.63%- 101.09% for the oxalate solution extraction, and 94.76%-102.83% for the hydrogen peroxide digestion, respectively. The results indicate that this selective extraction technology was effective for the extraction and separation ofFe, Mn oxides and OMs in the SSs, and important for further mechanism study of trace metal adsorption onto SSs.     

聚硅酸铝铁/羧基壳聚糖复合絮凝剂处理硫化黑染料废水的研究

用聚硅酸铝铁/羧基壳聚糖复合絮凝剂对硫化黑染料废水进行了处理,研究了影响絮凝剂处理硫化黑染料废水的影响因素。结果表明,较佳的条件为转速50 r/min、聚硅酸铝铁和羧基壳聚糖的质量配比为3、废水pH值为9.0、絮凝剂用量为60 mg/L。在该条件下,复合絮凝剂对硫化黑染料废水的COD、色度、浊度去除率分别为92.1%,88.6%,96.3%。     

Oxidative degradation of phenol by sulfidated zero valent iron under aerobic conditions: The effect of oxalate and tripolyphosphate ligands

After adding either organic or inorganic ligands, sulfidated nano-zero-valent iron (SnZVI) was used for aerobic degradation of phenol, and the effect of the ligand species on oxidation performance was investigated. We found that SnZVI hardly degraded phenol in the absence of ligand addition. Ligands initiated and promoted the degradation of pollutants by SnZVI. The data herein show that a characteristic inorganic ligand, tripolyphosphate (TPP), is more effective in enhancing oxidation than a characteristic organic ligand oxalate. In addition to the scavenging of reactive oxidants by the organic ligand, more ferrous ion (Fe(II)) dissolution from SnZVI in the TPP system is another cause for the superior enhancement by the inorganic ligand. In the oxalate system, as the sulfur content of SnZVI increased, the oxidation efficiency increased because FeS shell promoted the transfer of electrons to produce more reactive oxygen species (ROS). In TPP system, the effect of sulfur content on oxidation performance is more complex. The SnZVI with low sulfur content showed poor oxidation performance compared with that of nZVI. Further experiments proved that sulfidation might weaken the complexation of TPP with surface bound Fe, which would slow down the ionic Fe(II) dissolution rate. Therefore, sulfidation has the dual effects of enhancing electron transfer and inhibiting the complexation of inorganic ligands. In addition, the mechanisms of ROS generation in different ligand systems were investigated herein. Results showed that the critical ROS in both the oxalate and TPP systems are hydroxyl radicals, and that they are produced via one-electron activation of O₂.     

含有机物铁泥的超临界水氧化法资源化

氨基染料生产过程中产生大量含有机物的铁泥,对环境造成严重污染并造成资源的极大浪费.利用超临界水氧化法对含有机物铁泥进行资源化处理研究,并对产物进行了X射线衍射分析(XRD)、色差实验与电子探针分析.研究结果显示,用超临界水氧化法处理铁泥可以将铁泥中所含的有机物完全氧化,真正实现环境友好;超临界水首先将铁泥氧化成α-Fe2O3与γ-Fe2O3,再经过800℃煅烧后可以作为氧化铁红颜料使用;超临界反应压力对样品的晶型与颜色影响不大.     

纳米级铁粉脱氯降解四氯化碳

四氯化碳的生产和使用,给人类带来了较大危害.为此,采用纳米铁粉这一新方法对其进行脱氯处理.试验以纳米级铁粉对四氯化碳的脱氯率为考察指标,选用L25(56)正交试验方案,考察了降解介质的初始pH值、纳米铁粉的质量、降解温度、摇床转速和脱氯时间5个影响因素.结果表明,pH值这一因素有极显著影响;在得出的纳米铁粉对四氯化碳脱氯的最佳工艺条件下,获得了99.5%的脱氯率,为有机氯化物脱氯开辟了一条新途径.     

铁矿石对脱除烧结废气中NOx的催化效应

向混合料中加添加剂能够在烧结过程中脱除烧结废气中的NO。实验研究了铁矿石对NO脱除反应的催化效应。在900℃下,分别以5种不同铁矿石作为填料层,用2种标准气体和压缩空气配制的混合气体模拟烧结废气。试验结果表明,铁矿石种类对铁矿石的催化能力有重要影响。D型铁矿的催化能力最强而且不会发生弱化,NO转化率接近100%;其它几种铁矿石的催化能力较差,随着反应时间的延长有明显的弱化现象,但很快即基本趋于稳定状态,NO转化率达到了60%~70%。     

某市给水管网中铁释放现象影响因素与控制对策分析

针对某市管网水中铁浓度的变化规律进行了系统的研究,确定了管垢向管网水中释放出的铁是管网水中铁超标的主要原因.研究中发现铸铁管和镀锌钢管中管垢的主要化学组分为铁.在给水管网中,管网水的溶解氧和余氯浓度低时,对应的管网水中铁释放现象严重,其原因是还原条件使管垢表面的致密钝化层被破坏,造成二价铁的大量释放.根据试验结果提出了给水管网中铁释放和“红水”现象的控制对策.