固化/稳定化和软土加固污染土的强度和浸出特性研究

研究了固化/稳定化和软土加固两种土壤搅拌技术修复英国Yorkshire郡的重金属及有机物复合污染土的强度和浸出特性。使用的固化剂为氧化镁和高炉矿渣。选取现场固化/稳定化和软土加固处理后取回实验室分别养护1.5 a和1a的试样,开展了无侧限抗压强度和浸出试验,研究了场地深度对两种技术处理复合污染土的强度和浸出特性的影响。研究结果表明,氧化镁–高炉矿渣可以显著提升污染土强度,固化土无侧限抗压强度均值均超过英国的设计值350 kPa;浸出结果表明修复后除部分样中Ni不达标,Cu和Pb的浸出浓度均达到英国饮用水标准。氧化镁和高炉矿渣联合使用可以有效固化Ni。相较于软土加固技术,固化/稳定化技术修复污染土pH值更高、Ni浸出浓度和有机物浸出浓度更低,在固化重金属和有机物复合污染土方面效果更加显著。场地深度对修复后污染土的性质影响微弱。     

SPB和SPC固化稳定化镍锌污染土的强度及环境特性研究

以某汽配厂搬迁遗留电镀车间的镍(Ni)、锌(Zn)复合污染土为研究对象,研究2种新型固化剂SPB和SPC固化稳定化污染土的强度及环境安全特性。通过室内试验研究2种固化剂修复污染土的无侧限抗压强度(qu)、干密度(rd)、酸碱度(pH)、酸缓冲能力(ANC)及重金属浸出毒性、重金属形态分布等参数随固化剂掺量和养护龄期的变化规律。室内试验结果表明,污染土经固化剂SPB和SPC处理后q_u和rd显著提高,相同固化剂掺量、反应稳定(28 d)后,SPC固化土qu略高于SPB固化土,2种固化土rd基本相同;固化剂SPB和SPC使活性形态重金属转化为较稳定形态,重金属浸出浓度显著降低,但2种固化剂对重金属的固化稳定化效果存在差异,固化剂SPC固化稳定化Ni的效果优于固化剂SPB,而固化剂SPB固化稳定化Zn的效果更优;固化土pH显著提高,其中固化剂掺量10%、反应稳定后,SPB和SPC固化土pH分别为9.51和9.07;SPB和SPC固化土ANC均显著提高。另外,小试试验结果表明,SPC固化土pH低于PC固化土;固化剂SPC在短期养护(7 d)的固化效果优于PC。研究结果可以为固化剂SPB和SPC在实际工程的现场应用提供参考和建议。     

碱激发水泥固化稳定重金属污染土的强度和浸出特性试验研究

以固化重金属工业污染土为研究对象,采用两种碱激发水泥固化剂(A、B)对重金属污染土进行固化稳定处理。选用pH值、无侧限抗压强度试验、浸出和形态提取试验分别研究固化剂掺量和养护龄期对固化土强度、浸出及赋存形态的影响规律。强度和浸出试验结果表明:由火碱、偏高龄土或由消石灰、泡花碱组成的两种碱激发剂与普通硅酸盐水泥构成的固化剂(A、B)均可以改善污染土的强度特性,降低重金属Cd、Pb、As、Zn的溶出,随着固化剂掺量和养护龄期的增加,固化土A和B的强度、浸出及赋存形态均明显改善。但相同掺量和养护龄期条件下,固化土A的强度、溶出均好于固化土B。赋存形态试验结果表明:固化土A中Cd、Pb、As、Zn形态稳定性明显优于固化土B中的同类重金属,固化剂A可将污染土中的Cd、Pb、As、Zn从弱酸态向可氧化态和残渣态转化,而固化剂B可将污染土中的Cd、Pb、As、Zn从弱酸态向可还原态转化。固稳机制不同是固化土A、B的强度、浸出及赋存形态差异的根本原因。     

赤泥基固化剂固化/稳定铅锌镉污染土的强度及浸出特性研究

采用赤泥–磷石膏–水泥(RPPC)、赤泥–磷石膏–生石灰(RPCA)两种赤泥基固化剂以及普通水泥(PC)对人工制备的铅、锌、镉污染土进行固化/稳定化,进一步优化赤泥基固化剂的配比。对养护7和28d后的试样开展无侧限抗压强度、毒性浸出试验和pH梯度试验。研究发现,随着固化剂掺量和养护龄期的增加,赤泥基固化剂固化样的无侧限抗压强度逐渐增加,且强度间差值逐渐增加。三种固化剂的固化样浸出液pH值均分布在7～9范围内。28 d养护龄期后,15%掺量的赤泥基固化剂均有较好的强度和固化效果。相较而言,RPPC固化剂比RPCA固化剂具有更好的固化/稳定化效果,其无侧限抗压强度较高,重金属浸出浓度较低。pH梯度试验结果表明,pH=8时RPPC固化样的重金属浸出浓度最低。不同的浸提剂pH值下,浸出浓度仍满足随掺量增加而增加的趋势。     

有机物污染场地浅层异位固化稳定化试验研究

以某化工企业有机物污染浅层土为对象,应用4种固化药剂进行固化稳定化修复对比研究。通过现场异位固化稳定化结合室内无侧限抗压强度、毒性浸出等试验,讨论了固化剂组份、龄期对其物理力学性质和浸出特性影响,并对比分析了其固化稳定化效果及机理。结果表明:随着养护时间增长,修复土p H值、毒性浸出溶液的有机物浓度降低,其中pH值由0 d的12.76~13.11降至28 d时的12.11~12.69,而有机物浸出浓度14d降幅在65%~100%间;干密度及无侧限抗压强度qu则稳步提高,其中干密度28 d增幅达14.4%~23.2%,而强度最大增加到122 k Pa。固化剂3和4修复污染土干密度较大,28 d密度超过1.37 g/cm~3,密实作用明显;添加固化剂会立即显著增大污染土pH值,其中固化剂4(电石渣+凹凸棒土)各龄期pH值明显大于其他剂型;各固化剂对不同有机污染物的稳定效果有所差别,但均能有效固化稳定化苯胺、2-氯酚、萘、苯、甲苯、邻-二甲苯;就污染物总体固化稳定化效果而言,含活性炭组分的固化剂1效果最为突出,其总稳定率接近100%;含水泥组分的固化剂2,3对土体的增强作用较好,其28 d强度可达109 k Pa以上。相较其他药剂,固化剂4在成本、能耗及污染物排放方面表现最优,且能较好满足场地修复对有机物稳定率及强度的要求,综合效果最佳,为优选的最佳剂型。     

低碳固化剂修复重金属污染黏土的水动力参数测评

低碳修复剂研发与修复污染土的安全利用是推行污染场地绿色可持续修复的有效途径。以新型低碳钢渣基固化剂修复重金属镍（Ni）、锌（Zn）污染土为研究对象,通过柱状柔性壁渗透试验,采用溶质浸出质量比法测评了污染土修复前后的土水动力弥散系数。结果表明：固化土样渗透液重金属浓度显著低于污染土样,满足IV类地下水环境质量要求;与污染土相比,固化土的水动力弥散系数降低约2个数量级。研究成果为新型低碳钢渣基固化剂的固化稳定化效果评价及固化土作为土工材料安全性评估提供指导。     

活化钢渣在固化稳定化工业重金属污染土中的应用

针对钢渣基可持续型固化剂在工业重金属污染土固化稳定化的应用效果进行了试验研究,以重金属固定效率为评价标准,得到了磷酸盐活化钢渣的工艺参数。结果表明,磷酸二氢钾活化可以明显改善钢渣对重金属铅锌镉的固定效果。磷酸二氢钾和钢渣质量比为2%~4%时,通过湿法拌合、20℃风干制得的活化钢渣对重金属铅锌镉的固定效果最佳。并进一步以非活化钢渣作为对比,分析了活化钢渣固化铅锌镉污染土的环境安全及强度特性。结果表明,活化钢渣添加可以显著降低重金属铅锌镉的浸出浓度,提高污染土的pH值。活化钢渣的添加可以提高污染土的无侧限抗压强度,并随着固化剂的掺量的增加而增长;与未活化钢渣相比,钢渣的活化过程会削弱固化土的强度增加,而且固化剂掺加量越大削弱程度越大。     

生物炭修复高浓度铅锌污染土的试验研究

将5%、8%和10%的水稻秸秆制成的生物炭作为修复铅锌污染土的固化剂,水泥材料作为对比固化剂,对高浓度铅锌污染土场地进行修复试验。研究结果表明:土体修复完成并养护56 d龄期后,与水泥固化土相比,生物炭固化土的pH值呈中性、且土壤肥力更高;毒性浸出试验中生物炭对重金属固化效果更优;生物炭掺量为8%、10%的固化土,种子发芽率大于80%;试验用各掺量下水泥固化土的种子发芽率均低于80%,即水泥固化土无法使试验用种子发芽。这表明采用生物炭固化重金属污染土,更适合土体的种植再利用。     

新型磷基固化剂固化稳定化电镀工业污染黏土现场试验研究

针对某电镀工业重金属污染黏土固化稳定化修复工程开展了现场试验研究,分析养护1d、7d、28d后固化黏土的重金属浸出毒性、酸碱度(pH)、干密度(ρd)、贯入指数(DCPI)及回弹模量(EPFWD)等特性,并与水泥(PC)固化黏土进行比较,研究新型磷基固化剂SPC固化污染黏土的工程和环境特性。结果表明,SPC和PC能显著降低污染黏土重金属的浸出浓度,并满足地下水IV类质量标准(GB/T 14848-2017)的限制要求;相同龄期下SPC固化黏土的重金属浸出浓度低于PC固化黏土。SPC和PC能改善固化黏土的酸碱度,SPC固化黏土的pH值低于PC固化黏土;养护28d后,固化剂SPC和水泥固化黏土的pH分别为7.99和9.76。SPC和PC能显著提高污染黏土的强度和动态回弹模量,而SPC固化黏土的强度和动态回弹模量低于PC固化黏土。     

污染场地测试评价与处理技术

针对中国工业污染场地开发利用的岩土工程关键问题,全面总结了笔者及其课题组多年来的研究成果。主要包括5个方面:(1)污染场地土体工程性质变化基本规律和污染场地分类评价方法,阐明了重金属污染土和有机污染土的基本物理力学特性,在总结国内外已有污染场地风险评价和工程分类的基础上,提出了基于层次分析原理的污染场地指数分类法;(2)基于多功能孔压静力触探(CPTU)的污染场地原位测试方法,包括污染土的电阻率基本特征,基于电阻率CPTU的污染场地原位测试方法,基于CPTU的污染场地水力传导参数测试评价方法;(3)重金属污染场地固化/稳定化处理技术,揭示了重金属污染土固化/稳定化机理,阐明了水泥系固化剂固化/稳定重金属污染土的有效性与不足,提出了磷酸盐系固化剂和碱激发矿渣固化剂固化/稳定高浓度重金属污染土的方法,从工程与环境安全二方面提出了固化/稳定法的施工工艺;(4)有机污染场地曝气法处理技术,采用研发的一维二维曝气模拟装置,揭示了曝气法修复有机污染场地的气相运动规律、修复机理与效果,建立了基于集总参数的污染物去除效果评价方法,提出了曝气法工艺设计方法;(5)污染场地竖向隔离技术,提出了土–膨润土系竖向隔离墙材料设计关键参数确定方法,揭示了土–膨润土系竖向隔离墙的长期防渗防污性能和化学相容性特征,比较了隔离施工技术的特点,对SMC工法的效果进行了分析评价。研究成果对中国污染场地再开发利用和城市可持续发展具有重要意义。     

水泥固化重金属铅污染土的强度特性研究

污染场地中开挖出来的污染土利用水泥固化处理（S/S法）后,其污染物质的淋滤特性和土体的强度得到改善,可用于场地的回填和堤坝的填筑等。针对该项技术,对水泥固化稳定后的重金属铅污染土的强度特性进行了研究。试验所用的铅污染土通过将硝酸铅溶液加入干土中人工制备而成,并考虑了不同铅离子含量和水泥掺量对水泥固化污染土强度特性的影响。试验结果表明：水泥固化污染土的无侧限抗压强度随着水泥掺量以及龄期的增长而提高;与常规水泥土（不含重金属污染物）强度相比,污染土中铅离子含量较低时,强度略有提高,铅离子含量较高时,强度显著降低;不同铅含量水泥土试样的应力应变关系均表现为强度越高,破坏应变越小;试样28 d龄期的变形模量与强度呈较好的线性对应关系。     

Electrochemically enhanced oxidation reactions in sandy soil polluted with mercury

For remediation of soils contaminated with heavy metals, the electrodialytic remediation (EDR) method is a highly relevant method, see e.g. Hansen et al. (Hansen HK, Ottosen LM, Kliem BK, Villumsen A. Electrodialytic remediation of soils polluted with Cu, Cr, Hg, Pb, and Zn. J Chem Tech Biotechnol 1997;70:67-73). During the process the heavy metals are transferred to the pore water in dissolved form or attached to colloids and move within the applied electric field. The method is found to be useful in many soil types, but has its strength in fine-grained soils. It is exactly in such soils that other remediation methods fail. Four cell experiments were made in order to investigate how relevant the method is for a more sandy soil and if it is suitable for non-ionic heavy metals such as elemental mercury. The duration was 27 days for two of the experiments and two experiments lasted 54 days, and the mercury within the soil was initially 1200-1900 mg kg(-1), of which 84% was elemental Hg. To monitor the process the pseudo-total mercury concentration was distinguished between elemental mercury and non-metallic mercury species by thermodesorption. During the electrodialytic treatment an increase of the content of non-metallic mercury occurred and a corresponding decrease of the content of elemental mercury which indicates a transformation of the latter species into any other non-metallic species. Generally, oxidation of Hg by dissolved oxygen in a solution is kinetically inhibited and thus quite slow. The redistribution of Hg was closely connected to a decrease of soil pH during the experiments. This corresponds very well to the thermodynamic calculations from which it was found that a decrease in the pH of the soil will result in an increase in the oxidation rate of elemental Hg. Results from this investigation show that the electrodialytic remediation method alone is not efficient in situations with sandy soils containing elemental mercury. As a solution for this problem it is suggested to add chloride to the soil system. Chloride would act as a complexing agent avoiding precipitation and enhancing the dissolution of precipitates as well as elemental mercury.     

Assessment of fly ash-aided phytostabilisation of highly contaminated soils after an 8-year field trial: part 1. Influence on soil parameters and metal extractability

Sustainable management of large surface areas contaminated with trace elements is a real challenge, since currently applied remediation techniques are too expensive for these areas. Aided phytostabilisation appears to be a cost efficient technique to reduce metal mobility in contaminated soils and contaminated particle spread. In this context, this study aimed at evaluating the long-term efficiency of aided phytostabilisation on former agricultural soils highly contaminated with trace elements. The influence of afforestation and fly ash amendments to reduce metal mobility was investigated. Before being planted with a tree mix, the study site was divided into three plots: a reference plot with no amendment, the second amended with silico-aluminous fly ash and the third with sulfo-calcic fly ash. After eight years, some soil physico-chemical parameters, including cadmium (Cd), lead (Pb) and zinc (Zn) extractability were modified. In particular, pH decreased on the whole site while organic carbon content increased. The alteration of these parameters influencing trace element mobility is explained by afforestation. Over time, concentrations of CaCl₂-extractable metals increased and were correlated with the soil pH decrease. In the amended soils, extractable Cd, Pb and Zn concentrations were lower than in the reference soil. The results indicated that the two fly ashes buffered natural soil acidification due to vegetation development and limited trace element mobility and thus could limit their bioavailability. For long-term phytostabilisation, special attention should be focused on the soil pH, metal mobility and phytoavailability analysis.     

Evaluation of dissipation mechanisms by Lolium perenne L, and Raphanus sativus for pentachlorophenol (PCP) in copper co-contaminated soil

Though phytoremediation is widely studied in remediation of metal contaminated soils or organic contaminated soils, little information is available regarding the effectiveness and processes of phytoremediation of sites co-contaminated with organic and metal pollutants. Sites co-contaminated with organic and metal pollutants are common and considered to be a more complex problem as the two components often cause a synergistic effect on cytotoxicity as measured both by growth inhibition and colony-forming ability. In this paper, the dissipation mechanisms for pentachlorophenol (PCP) in copper co-contaminated soil by Lolium perenne L, and Raphanus sativus was investigated in a greenhouse experiment by monitoring the growth response of plants, evaluating the removal efficiency of extractable PCP, differentiating PCP residuals in strongly and loosely adhering rhizosphere soils, and analyzing the microbial activity in the rhizosphere. In copper co-contaminated soil with the initial PCP concentration of 50 mg/kg, plants grew better with the increment of soil Cu level (0, 150, 300 mg/kg), which implied that combinations of inorganic and organic pollutants sometimes exerted antagonistic effects on plant cytotoxicity. The observed higher PCP dissipation in soil spiked with 50 mg/kg PCP in the presence of Cu and the less difference of PCP residual between strongly and loosely adhering soils further suggests the occurrence of Cu-PCP interaction and the enhanced degradation and mass flow are two possible explanations. In copper co-contaminated soil with the initial PCP concentration of 100 mg/kg, however, both plant growth and microbial activity were inhibited with the increment of soil Cu level. The lowered degrading activity of microorganisms and the reduced mass flow were probably responsible for the significantly lower levels of PCP dissipation in copper co-contaminated soil. These results showed that remediation of sites co-contaminated with organic and metal pollutants is a complex problem and a more thorough understanding of the extent and mechanisms by which metals inhibit organic degradation is needed to develop phytoremediation of co-contaminated sites.     

Metal contamination at a wood preservation site: characterisation and experimental studies on remediation

The aim of this investigation was to determine the occurrence of As, Cu, Cr and Zn in the soil at an abandoned wood preservation unit and to examine some possible extractants for the contaminants in the soil. The mean As content of the contaminated surface soils (0-10 cm) was 186 mg kg(-1), where as the mean concentrations of Cu, Cr and Zn in soils from the contaminated area were 26, 29 and 91 mg kg(-1), respectively. The elevated As content in the mineral soils is related to adsorption of inorganic As phases in the fine grained fractions, which are characterised by large surface area and high positive surface charge under the current acidic conditions. Cu and Cr were found to be rather mobile, which is reflected in their lower abundance in soils and significant accumulation in sediments in the drainage leaving the area. The fine fraction of the soil (<0.125 mm) has an average metal content increased by nearly 34% as compared to the <2-mm fraction conventionally used for the analysis and assessment of soil contamination. The <2-mm fraction constitutes approximately 65% of the total weight while the fine fraction (<0.125 mm) constitutes approximately 10%. These facts, taken together, are essential for the choice of remediation measures. Oxalate solutions have been tested as extractants for soil remediation. Dark acid oxalate extraction dissolves the amorphous Al- and Fe-oxides and hydroxides and mobilises the adsorbed inorganic As species. Oxalate also acts as a ligand for the cationic heavy metals, releasing them from exchangeable sites. With a three-step sequential leaching, up to 98-99% of the metals could be removed. At lower concentrations and higher pH, the leaching decreased to approximately 70%.     

水泥固化稳定重金属污染土的工程性质试验研究

随着社会的快速发展,因工业生产以及人类活动引起的地基土重金属污染现象越来越严重。地基土受到重金属污染后,其工程性质会发生改变。固化稳定法是处理重金属污染土地基的常用方法之一。以人工制备的铅或锌重金属污染土为研究对象,通过系统的室内试验,着重研究水泥固化稳定重金属污染土的工程性质。试验结果表明,土体受到污染后,其强度降低;掺入水泥固化稳定的重金属污染土的强度随水泥掺入量以及养护龄期的增加显著增大。通过试验还发现,较低浓度重金属离子的存在可以促进水泥固化土抗剪强度的提高。     

Retention and release of Zn and Cd in spodic horizons as determined by pH(stat) analysis and single extractions

In the northern Campine in Belgium, large areas are contaminated by heavy metals such as Zn and Cd due to the (former) non-ferro metal industry. In the sandy soils, the heavy metal adsorption/attenuation in the spodic horizon represents the main retention mechanism of leached pollutants from the contaminated topsoils. In this study, the pH-dependent behaviour of the elements in these spodic horizons was tested by pH(stat) experiments and compared to sandy loam soils. Extractions with CaCl(2) 0.01 M and EDTA 0.05 M provided a further insight into the binding mechanisms. The results indicate that organic matter is the main factor responsible for the mobility of Cd, Zn and Ca in the spodic horizons. The binding of elements is not very strong, however, and highly dependent on pH. A slight decrease in pH can cause a significant release of metals from the spodic horizons, with up to 60% of Cd and 90% of Zn being released within a 1.5 unit change in pH (starting from the naturally occurring pH). This pH change can happen rapidly in these soils, due to the low buffering capacity, and is realistic given the acidification in Flanders. For the sandy loam soils, a pH decrease of 3 units is needed to release 40% of Cd and 20% of Zn, and the acid neutralization capacity is exhausted more gradually, suggesting that slower buffering mechanisms take place. For the sandy loam soils, Cd retention is mainly governed by organic matter, while for Zn other factors such as the clay minerals also play an important role. Despite the high potential mobility and pH dependence of the heavy metal retention in the spodic horizons, the actual risk for groundwater pollution is limited. For the diffusely contaminated areas, where traditional remediation is not an option, spodic horizons may therefore contribute to a natural attenuation of the soil contamination.     

有机氯农药污染土强度特性及微观机理分析研究

土体受到有机氯农药污染后,其工程性质会发生改变,农药成分也会给周围环境带来严重危害,尤其是持久性有机污染成分的危害更大。国内外对农药污染土体的研究主要关注场地修复技术,对其工程特性评价的研究鲜有报道。本文通过室内配制不同浓度的有机氯农药污染土样,在养护龄期为1 d、7 d、28 d、56 d、90 d时,分别进行了无侧限抗压强度试验、渗透试验、扫描电镜试验(SEM),分析了污染土体抗压强度、渗透系数、微观结构的变化规律,并采用微观解释宏观规律。试验结果表明,有机氯农药污染后的土体强度随农药浓度的增加而减小,随龄期增长呈先增大后减小的趋势,56 d龄期时的抗压强度最大;渗透系数随农药浓度的增大而减小,随龄期的增加而增大;土体微观结构表现为随农药浓度增大絮状结构增多,从而很好地解释了宏观力学特性变化规律。