FeSO4对铬污染土的稳定特性及风险评价试验研究

采用硫酸亚铁（FeSO4）对铬污染土进行稳定化处理。选用浸出试验、Cr(VI)残留值试验和形态提取试验,研究了粒径和有机质对铬污染土稳定特性的影响规律。试验结果表明,粒径和有机质对铬污染土稳定特性有较大影响。粒径的减小可显著降低稳定土中Cr(VI)和总Cr的浸出浓度及稳定土中Cr(VI)的含量;当污染土粒径小于2 mm时,Fe(II)/Cr(VI)摩尔比为3,稳定土中Cr(VI)和总Cr的浸出浓度分别为4.68、8.9 mg/L,均低于我国《危险废弃物鉴别标准 浸出毒性鉴别》（GB/T5085.3－2007）的限值。有机质添加量的增加可明显降低稳定土中Cr(VI)和总Cr的浸出浓度及Cr(VI)的含量。当Fe(II)/Cr(VI)摩尔比为3时,有机质的添加量为5%,稳定土中Cr(VI)的含量为28.3 mg/kg,低于我国《土壤环境质量标准》（GB15618－2008）中工业和商业用地限值（30 mg/kg）;当有机质的添加量为10%时,稳定土中Cr(VI)的含量为4.8 mg/kg,低于居住用地限值（5 mg/kg）。形态提取试验结果表明：粒径的减小可降低弱酸提取态的铬含量,增加可还原态的铬含量,而对可氧化态和残渣态的铬含量影响不大;有机质可促使弱酸提取态、可还原态的铬转化为可氧化态的铬,而残渣态的铬变化不大。稳定土中铬从活性态向较稳定态转化,是铬稳定土稳定特性和环境风险变化的根本原因。     

多种铁改性和未改性生物炭对模拟地下水中六价铬的去除

为了研究不同类型的生物炭对模拟地下水中去除Cr（Ⅵ）的影响，选用杨木、柳木、桃木和松木为原料，分别在300℃和600℃热解温度下，制备不同粒径、经氯化铁改性的和未改性的20种生物炭，设计了一系列批实验，探究不同种类的生物炭对模拟地下水中Cr（Ⅵ）的去除效果；并采用傅里叶变换红外光谱（FTIR）和X射线近边吸收光谱（XANES）研究了生物炭去除Cr（Ⅵ）的机理。结果表明：在300℃下热解制成的改性生物炭，对Cr（Ⅵ）去除率均达到了99.0%以上；和粒径2 mm的生物炭相比，粒径<0.5 mm的生物炭对Cr（Ⅵ）有更好的去除效果；拟一级动力学方程较好地描述了300℃热解温度下杨木铁改性生物炭（FeCl3BC300Y）对Cr（Ⅵ）的去除过程。XANES分析结果表明，FeCl3BC300Y中的铬以三价的形态（Cr（Ⅲ））存在，FTIR分析表明羟基和羧基参与了Cr（Ⅵ）的去除。生物炭通过氧化还原和络合作用去除Cr（Ⅵ）。铁改性生物炭有望作为可渗透反应墙的填充材料，成为修复Cr（Ⅵ）污染地下水的新型材料。     

FeSO4稳定铬污染土的铬赋存形态及浸出特性研究

采用硫酸亚铁（FeSO4）对Cr(VI)污染土进行稳定化处理。研究了Fe(II)/Cr(VI)摩尔比和养护龄期对污染土稳定过程中的铬赋存形态及浸出特性的影响规律。结果表明：随着Fe(II)/Cr(VI)摩尔比和养护龄期的增加,Cr(VI)和总Cr的浸出浓度降低,稳定土中Cr(VI)的含量降低,当摩尔比为3时,Cr(VI)和总Cr的浸出浓度均低于我国《危险废弃物鉴别标准 浸出毒性鉴别》（GB/T50853―2007）的限值;当摩尔比为10时,稳定土中Cr(VI)的含量低于我国《土壤环境质量标准》（GB15618―2008）中工业和商业用地的限值（30 mg/kg）;当摩尔比为20时,低于居住用地限值（5 mg/kg）。形态提取试验结果表明：FeSO4改变稳定土中铬的赋存形态,可促使铬从弱酸态向可还原态和可氧化态转化,而对残渣态的铬影响不大。Cr(VI)的浸出浓度与稳定土中的Cr(VI)含量均存在指数函数关系,且浸出试验不能全面、客观地评价铬污染土稳定效果。     

络合剂淋洗Cu污染粉土的土柱试验研究

以当前我国备受关注的土体污染为背景,通过土柱试验研究了不同络合剂对Cu的淋洗效果,结果表明:乙二胺四乙酸二钠二水合物（ethylenediaminetetraacetic acid disodium saltdihydrate,EDTA）淋洗效果最佳,柠檬酸（citric acid,CIT）次之,氨三乙酸三钠盐单水合物（nitrilotriacetic acid trisodium salt monohydrate, NTA）淋洗效果相对最差;使用不同浓度的EDTA淋洗负载量为150 mg/kg的Cu污染土,浓度增大并未有效促进Cu的解吸,而较小浓度（0.005 mol/L）的EDTA是有效且经济的浓度,其对Cu的去除率达84%;0.015 mol/L的EDTA淋洗不同负载量的Cu污染土,随负载量增加,淋洗率下降,最高去除率为84%,但去除量增加;研究结果可为重金属污染土的淋洗修复工艺提供理论参考依据。     

硫化纳米铁对模拟地下水中Cr(Ⅵ)的去除效果及影响因素

硫化纳米铁（S-nZVI）是一种具有壳核结构的新型纳米铁（nZVI）改性材料,在多种污染物的去除上表现出超越nZVI的反应活性。本文采用两步合成法制备了S-nZVI,并采用透射电镜-能量色散X射线（TEM-EDX）、X射线衍射（XRD）和X射线光电子能谱分析（XPS）方法对S-nZVI和nZVI进行表征,探讨了不同硫铁摩尔比（n（S）/n（Fe））、初始pH值、试剂投加量和地下水化学成分对nZVI及S-nZVI去除Cr（Ⅵ）的影响。结果表明：S-nZVI具有明显的壳核结构,其Fe⁰核外层包覆着非晶的硫化亚铁和多硫化物;S-nZVI去除Cr（Ⅵ）的最佳n（S）/n（Fe）为0.14;增加S-nZVI投加量会提高其对Cr（Ⅵ）的去除率,投加量相同时,S-nZVI对Cr（Ⅵ）的去除率显著高于nZVI;提高初始pH值时,S-nZVI和nZVI对Cr（Ⅵ）的去除率均逐渐降低,但在相同pH值条件下,S-nZVI对Cr（Ⅵ）的去除率和去除速率始终高于nZVI,尤其是在pH=5时,S-nZVI仍能去除100%的Cr（Ⅵ）,而nZVI只能去除85%;K⁺、Na⁺、Ca²⁺、Mg²⁺、SO₄^2-、NO₃^-和Cl^-对S-nZVI和nZVI去除Cr（Ⅵ）均有促进作用,但对S-nZVI体系的促进作用更强;HCO₃^-的存在会使溶液的pH值升高从而抑制S-nZVI和nZVI对Cr（Ⅵ）的去除,对nZVI的抑制作用强于S-nZVI。总体来说,S-nZVI对Cr（Ⅵ）的去除率在不同pH值和多种地下水化学组分影响条件下均高于nZVI,因此具有更广泛的应用前景。     

β-FeOOH的水热法合成及其去除Cr(Ⅵ)实验研究

采用水热法成功合成四方纤铁矿(β-FeOOH),并结合XRD、SEM、zeta电位分析等对合成物进行系列表征。重点考察Cr(Ⅵ)初始浓度、pH值以及不同光照条件等因素下,β-FeOOH对Cr(Ⅵ)去除效果的影响。实验结果表明:合成得到的β-FeOOH为纺锤形晶体,长径200nm~250nm,端面直径30nm~50nm。Cr(Ⅵ)初始浓度、pH值以及光照条件对β-FeOOH去除Cr(Ⅵ)均存在重要影响。随着Cr(Ⅵ)初始浓度的升高,β-FeOOH吸附Cr(Ⅵ)量呈先递增后降低的趋势,当Cr(Ⅵ)初始浓度为50.07 mg/L时,β-FeOOH吸附Cr(Ⅵ)量达到最大值12.05mg/g,且吸附特征符合Langmuir方程吸附模型,饱和吸附量为16.35mg/g;β-FeOOH宜在弱酸性环境下去除Cr(Ⅵ),随着污染液pH的升高,β-FeOOH对Cr(Ⅵ)去除率呈现先增加后减小的趋势,在pH为6.24时去除率达到最大,为96.67%;光照条件会影响β-FeOOH对Cr(Ⅵ)的去除,β-FeOOH对Cr(Ⅵ)的去除效率呈现出黑暗环境自然环境紫外光照射。     

黄原胶改性微米铁修复地下水中Cr(Ⅵ)污染的试验

为了解决微米铁的重力沉降问题,提高微米铁修复地下水Cr（Ⅵ）污染的原位修复效果,本文利用黄原胶对微米铁进行改性,并通过沉降实验探究改性微米铁浆液的稳定性,同时选择Cr（Ⅵ）作为目标污染物,探究黄原胶改性微米铁去除地下水Cr（Ⅵ）污染的降解能力。实验结果显示：当黄原胶的投加质量浓度分别为0.0、1.0、1.5、2.0、2.5、3.0、6.0 g/L时,改性微米铁浆液的悬浮稳定性逐渐得到加强,在5 h沉降实验结束时,对应的相对分光光度值分别为0.05、0.25、0.46、0.57、0.65、0.73和0.87;黄原胶具有抑制微米铁吸附Cr（Ⅵ）的能力,其可促进Cr（Ⅵ）的还原,提高Cr（Ⅵ）的去除率;随着黄原胶投加质量浓度的增加,对应的Cr（Ⅵ）去除率分别为33.4%、41.2%、47.4%、51.1%、53.0%、63.9%和64.1%;6.0 g/L黄原胶改性的微米铁浆液具有最佳的悬浮稳定性,黄原胶的投加提高了微米铁的反应活性,但当黄原胶投加质量浓度超过3.0 g/L时,其对Cr（Ⅵ）的去除率没有显著提高;黄原胶投加质量浓度越大,黄原胶的缓冲作用就越明显。     

淋洗剂乙二胺四乙酸对重金属污染土工程特性的影响

以重金属铅（Pb2+）污染土和淋洗剂乙二胺四乙酸（EDTA）为研究对象,通过批次试验研究了不同浓度EDTA的淋洗对Pb2+污染土的渗透特性、持水特性、压缩特性、抗剪强度等工程特性的影响,为淋洗修复后土壤的二次利用提供参数支持。基于矿物成分、孔隙结构等微观试验,揭示了土壤工程特性变化的内在机制。研究结果表明,当淋洗剂EDTA浓度从0增加到0.15 mol/L,经淋洗修复后的污染土壤pH值从7.94下降到5.12,渗透系数降低超过一个数量级,黏聚力降低50%以上,而内摩擦角增大,持水性能提高,孔隙比从0.81下降到了0.76。微观试验的结果表明,随着淋洗剂浓度的增大,土壤中的蒙脱石、钠长石和伊利石矿物含量减少,石英矿物含量增加,其中蒙脱石含量从7.87%下降到了0.07%,而石英矿物含量增加了11.09%;淋洗后土壤单位质量进汞量由0.22 ml/g降低到0.15 ml/g,土壤总孔隙体积减少。重金属污染土淋洗修复工程在考虑重金属去除率及经济性指标的同时,还应考虑淋洗剂对土壤工程特性的弱化。     

光照作用对水铁矿去除Cr(Ⅵ)的影响

Cr在环境中释放易导致重金属污染,其所造成的环境危害与Cr存在形态紧密相关。Cr(Ⅵ)多以CrO₄^2-或Cr₂O₇^2-形式存在,在水体中具有较高溶解度和迁移性,且具有较大的毒性。水铁矿具有大比表面积和高反应活性,是环境中Cr(Ⅵ)的重要吸附剂;同时,水铁矿也是一种天然半导体矿物,在光照诱导作用下可产生光电子并转移电子。然而,水铁矿表面的光化学反应对Cr(Ⅵ)地球化学行为的影响尚不清楚。因此,本研究探讨了光照对水铁矿去除Cr(Ⅵ)的影响。结果表明:在黑暗条件下,水铁矿通过吸附作用去除了57%的Cr(Ⅵ);在光照有氧条件下,水铁矿对Cr(Ⅵ)的去除率上升到67%;在厌氧条件下,光照效应的增强作用更加明显水溶液中Cr(Ⅵ)几乎完全被去除。结合傅里叶变换衰减全反射红外光谱(ATR-FTIR)和X射线光电子能谱(XPS)分析发现,水铁矿能够快速吸附Cr(Ⅵ),其中有62%的Cr在水铁矿表面被还原,占总去除率的41.5%。因此光照能够通过还原作用增强水铁矿对Cr(Ⅵ)的去除,从而降低Cr(...     

含铬方解石向磷灰石转化过程中铬的迁移和固定

为了研究含重金属方解石向磷灰石转化过程中重金属的迁移转化规律,通过共沉淀法制备了分别含Cr(Ⅲ)和Cr(Ⅵ)的方解石,在水热条件下研究其向磷灰石的转化过程,并用XRD、FT-IR、SEM、ICP-OES等手段对产物进行测试和表征。结果表明,含Cr(Ⅲ)和Cr(Ⅵ)的方解石均可在水热条件下转化为碳羟磷灰石,超过97%的铬被固定到磷灰石结构中,仅约0.18%～2.06%的Cr(Ⅲ)、0.10%～0.62%的Cr(Ⅵ)被释放到溶液中。反应温度介于120～200℃范围内,温度越高,释放到溶液中的铬越少。研究结果表明,通过方解石-磷灰石的转化可以将铬固定到磷灰石中,从而降低土壤中铬的生物可利用性。     

Interaction between Cr(VI) and a Fe-rich soil in the presence of oxalic and tartaric acids

This study examined the interaction between Cr(VI) and a Fe-rich soil in the presence of low-molecular-weight organic acids as a function of pH. Oxalic and tartaric acids were chosen since they existed in soils commonly. Batch experiments showed that adsorption of Cr(VI) by the soil within the pH range examined was inhibited in the presence of oxalic acid, which was more pronounced when the initial ratio of [oxalic acid]/[Cr(VI)] was raised from 1:1 to 2:1. With the addition of tartaric acid, concentration of Cr(VI) in equilibrium solutions was far less than that of single adsorbate system across the pH wide (2.5–5.5), which was noticeable especially at low pH. The results were attributed to Cr(VI) adsorption and, particularly, the soil surface catalyzed reduction of Cr(VI) to Cr(III) by tartaric acid. The data reported in this paper suggested that the mobility, the bioavailability, and the toxicity of Cr(VI) in soil environments might be greatly affected by pH, the presence and nature of low-weight-molecular organic acids (oxalic and tartaric acids).     

Interaction of organic acids and pH on multi-heavy metal extraction from alkaline and acid mine soils

Vegetation at mining sites can produce increased heavy metal leaching by the organic acids and protons originating from root secretion and litter degradation. Batch experiments were conducted to investigate the effects of organic acids and pH on the extraction of Pb, Cd, Zn and Cu from an alkaline mine soil (sampled from a mining site of Chenzhou City, Hunan Province) and an acid mine soil (sampled from a mining site of Daxin county, Guangxi Province). The results showed that in the presence of organic acids (acetic, oxalic, malic, fumaric, tartaric and citric acids) at pH 7, the extraction of Pb, Cd, Zn and Cu from the acid mine soil was much higher than that from the alkaline mine soil, in which only citric acid with higher concentration was capable of extracting some heavy metals. Citric acid had the strongest ability in extracting heavy metals, followed by oxalic acid. Heavy metal extraction dramatically decreased with increasing pH. Moreover, at low pH, oxalic acid promoted the risk of Cu leaching; at high pH, the leaching of Pb, Zn, Cd and Cu was enhanced by both oxalic and citric acids. This indicated that those plants, which can produce substantial citric acid or oxalic acid by root secretion and litter degradation, should not be selected for the revegetation of mining sites.     

Adsorption of heavy metals in glacial till soil

The charged sites on soil particles are important for the retention/adsorption of metals. Metallic counterions can neutralize the intrinsic charges on the surfaces of soil particles by forming complexes. In this study, efforts have been made to determine the effect of surface potential, pH, and ionic strength on the adsorption of four metal ions, hexavalent chromium Cr(VI), trivalent chromium Cr(III), nickel Ni(II) and cadmium Cd(II), in glacial till soil. Batch tests were performed to determine the effect of pH (2–12) and ionic strength (0.001–0.1 M KCl) on zeta potential of the glacial till soil. The point of zero charge (pH _PZC ) of glacial till was found to be 7.0±2.5. Surface charge experiments revealed the high buffering capacity of the glacial till. Batch adsorption experiments were conducted at natural pH (8.2) using various concentrations of selected metals. The adsorption data was described by the Freundlich adsorption model. Overall glacial till shows lower adsorption affinity to Cr(VI) as compared to cationic metals, Cr(III), Ni(II) and Cd(II).     

Speciation of Chromium in Artificially Contaminated Soil Reference Material GSJ JSO-2 Using XANES and Chemical Extraction Methods

The oxidation states of chromium in GSJ JSO-2 (artificially contaminated soil) and three other geochemical reference materials (GSJ JSO-1, JLS-1 and JMS-1) were observed using X-ray near edge structure (XANES). For comparison, other artificially contaminated soil materials (mimic-JSO-2) were prepared by adding Cr(VI) into JSO-1. Their oxidation states of chromium were determined using XANES. The chromium contents were 1118 μg g^-1 for JSO-2, 1352 μg g^-1 for mimic-JSO-2 and 69-113 μg g^-1 for the other reference materials. Most chromium was present as hexavalent in mimic-JSO-2. No hexavalent species were detected in other samples. These results for chromium oxidation state in JSO-2 and mimic-JSO-2 obtained with XANES resembled those obtained from a chemical extraction method. The present JSO-2 has no trace of Cr(VI), although Cr(VI) was added as a major species during preparation. On the other hand, the content of Cr(VI) obtained in mimic-JSO-2 agreed with the original Cr(VI) content. A time-elapse study showed that Cr(VI) contents in mimic-JSO-2 decreased gradually to 70% of the original abundance during 240-day preservation in dry conditions. Moreover, the abundance of Cr(VI) decreased markedly to 15% after 240 days in the wet mimic-JSO-2 containing 20% m/m of water. These experiments suggested that soil humidity enhanced the reduction of Cr(VI) and that Cr(VI) was reduced even in dry conditions. Consequently, it is reasonable to infer that Cr(VI) doped into JSO-2 was completely reduced to Cr(III) during the preservation period of 5 years. The certification of the long-term stability of the chemical form in reference materials will be much more important in future.     

Ultrasonically enhanced electrokinetic remediation for removal of Pb and phenanthrene in contaminated soils

Electrokinetic and ultrasonic remediation technologies were studied for the removal of heavy metal and polycyclic aromatic hydrocarbon (PAH) in contaminated soils. The study emphasized the coupled effects of electrokinetic and ultrasonic techniques on migration as well as clean-up of contaminants in soils. The laboratory soil flushing tests combined electrokinetic and ultrasonic technique were conducted using specially designed and fabricated devices to determine the effect of both techniques. The electrokinetic technique was applied to remove mainly the heavy metal and the ultrasonic technique was applied to remove mainly organic substance in contaminated soil. A series of laboratory experiments involving electrokinetic and electrokinetic and ultrasonic flushing tests were carried out. Natural clay was used as a test specimen and Pb and phenanthrene were used as contaminants. An increase in out flow, permeability and contaminant removal rate was observed in electrokinetic and ultrasonic tests. Some practical implications of these results are discussed in terms of technical feasibility of in situ implementation of electrokinetic ultrasonic remediation technique.     

Removal of hexavalent chromium from aqueous solution by lignocellulosic solid wastes

The batch removal of Cr(VI) from aqueous solution using lignocellulosic solid wastes such as sawdust and pine leaves under different experimental conditions was investigated in this study. The influence of pH, temperature, contact time, initial concentration of Cr(VI) and particle size on the chromium removal was investigated. Adsorption of Cr(VI) is highly pH-dependent and the results indicate that the optimum pH for the removal is 2. The capacity of chromium adsorption at equilibrium by these natural wastes increased with absorbent concentration. Temperature in the range of 20–60 °C showed a restricted effect on the adsorption capacity of pine leaves, but had a considerable effect on the adsorption capacity of sawdust. The capacity of chromium adsorption at the equilibrium increased with the decrease in particle sizes. The suitability of adsorbents was tested with Langmuir and Freundlich isotherms and their constants were evaluated. Results indicated that the Freundlich model gave a better fit to the experimental data in comparison with the Langmuir equation. The study showed that lignocellulosic solid wastes such as sawdust and pine leaves can be used as effective adsorbents for removal of Cr(VI) from wastewater.     

河道疏浚底泥堆土镉污染修复技术分析

城市生活垃圾中重金属Cd污染修复是我国亟待解决的环境问题之一。为了确定最佳Cd污染修复技术,探究了多种镉修复技术在河道治理中的适用性。以华东地区城市河道疏浚底泥堆土修复工程为例,对重金属镉污染土壤的修复工艺进行了对比和分析。拟选定土壤稳定化修复技术、土壤淋洗技术和植物修复技术三种修复工艺对受污染土壤进行治理。实验结果表明,稳定化修复技术可以使土壤中镉的浸出率从33.3%降低到14.3%,能有效降低其在环境中的生物毒性,但镉的总量并不会降低;采用柠檬酸和草酸的土壤淋洗技术,能够使镉的去除率达到90.1%和92.4%;相比而言,植物修复技术具有更为突出的高效性、易操作和二次污染少的特点,但修复周期较长。从技术、经济、环境安全等多方面出发,分别对三种修复工艺进行了分析讨论,综合考虑了研究场地的现状和未来规划,最终确定土壤淋洗技术为治理河道底泥堆土镉污染的最佳选择。      

Comparative study on adsorption of chromium(VI) from industrial wastewater onto nature-derived adsorbents (brown coal and zeolite)

The removal of hexavalent chromium from wastewater streams has received an considerable attention in recent years, since it can cause harmful effects on the environment. Several approaches, including adsorption, are recognized to tackle this problem, but unfortunately most of these processes are impressed with practical conditions of the experiments. The main objective of this study was to recognize applicable conditions for Cr(VI) removal from an industrial drainage using nature-derived adsorbents (brown coal and modified zeolite) and to make the process more adaptive by using adsorbents conjointly. Batch experiments were carried out by agitating Cr(VI) stock solution with adsorbents at room temperature. The influence of main operating parameters was explored, and the best proportion of the adsorbents was determined. Maximum sorption of Cr(VI) onto brown coal was observed at pH = 4 by adding 60 g L^?1 adsorbent to contaminated solution. In case of using zeolite, the modification process was required, and the pH indicated a weak influence in a wide range (2–8). Optimum dosage of modified zeolite for Cr(VI) removal was 10 g L^?1. The hybrid application of adsorbents with the mass ratio of brown coal/modified zeolite at (3:1) was capable of removing more than 99% of Cr(VI) from contaminated wastewater in the natural pH range of the wastewater. The adsorption of Cr(VI) by brown coal and modified zeolite followed Langmuir and Freundlich isotherm models, respectively. Sorption of Cr(VI) onto both brown coal and modified zeolite fitted well to pseudo-second-order rate reaction.