水泥固化镉污染土的电阻率及强度试验研究

通过对水泥固化镉污染土进行电阻率和无侧限抗压强度试验,揭示了交流电频率对水泥固化镉污染土电阻率的影响,龄期和镉离子含量对水泥土电阻率和强度的影响规律以及电阻率与无侧限抗压强度的关系。结果表明:电阻率随电流频率的增加而明显降低,建议采用50kHz^1MHz的电流测试频率范围;水泥土的强度及电阻率均随龄期的增加呈对数增加;当镉离子质量分数为50mg/kg时,水泥土的强度和电阻率都达到最大值,随着镉离子质量分数的继续增加,强度和电阻率基本保持不变,且普遍高于无镉离子时的水泥土;水泥土强度同电阻率呈现出很好的线性关系。

碱激发粉煤灰-矿渣固化镉污染土的影响因素分析

为研究液固比与矿渣掺量对碱激发粉煤灰矿渣固化镉污染土强度与浸出特性的影响,以矿渣部分替代粉煤灰作为胶凝粉料,以NaOH与Na_(2)SiO_(3)溶液作为碱激发剂,采用无侧限抗压强度、毒性浸出与酸碱度试验分析了碱激发粉煤灰矿渣固化镉污染土的强度、Cd^(2+)浸出浓度和pH的变化规律,并基于扫描电镜能谱(SEM-EDS)、X射线衍射(XRD)与压汞(MIP)试验结果研究了固化污染土的微观特征.结果表明:固化污染土的强度随液固比增大先剧烈下降后保持稳定,随矿渣掺量增加缓慢上升;Cd^(2+)的浸出质量浓度在液固质量比为0.3~0.4时小于0.01 mg/L,但在液固质量比超过0.4后急剧上升,Cd^(2+)的浸出浓度随矿渣掺量增加而下降;碱激发粉煤灰矿渣对镉的固定机理主要是形成Cd(OH)_(2),Cd^(2+)的加入会降低体系的碱度,阻碍碱激发反应;固化污染土中孔径为1~10μm以及大于10μm的孔隙体积分数随液固比增大而增加,这与试样初始含水率的增加有关.

稻壳灰-水泥固化镉污染土性能及影响机制

为实现污染土和稻壳灰资源化利用,解决水泥固化材料高排放问题,采用稻壳灰-水泥为固化剂对重金属镉污染土进行固化处理。开展不同养护龄期、固化剂类型及镉含量下固化镉污染土无侧限抗压强度、毒性浸出、X射线衍射及扫描电镜试验,通过分析抗压强度、浸出质量浓度、破坏形态、微观形貌及矿物组成等宏微观特性,揭示稻壳灰-水泥固化镉污染土微观作用机制。结果表明:稻壳灰可以加速水泥水化过程,提高固化土无侧限抗压强度,低水泥掺量时加入5%~10%稻壳灰改善效果较优;固化土强度随镉含量增加而先升后降,存在临界值100~400 mg/kg;稻壳灰掺入后,土体脆性破坏特征减弱,镉污染下土体裂纹较多且破坏面不规则;固化土浸出质量浓度随龄期增加而降低,在镉含量为100 mg/kg时满足标准限值,稻壳灰部分替代水泥后浸出质量浓度相差不大;稻壳灰-水泥主要以水化硅铝酸钙聚合物凝胶(C-A-S-H)和钙矾石(AFt)共同支撑土体孔隙,不断团聚、胶结形成空间网状结构,形成骨架结构并吸附镉离子。

酸性干湿循环下赤泥-石灰固化镉铅污染土性能

为实现固废资源化利用并达到以废治废,变废为宝的目的,提出采用赤泥-石灰作为固化剂对镉、铅重金属污染土进行固化/稳定化处理,通过酸性干湿循环试验、无侧限抗压强度试验、毒性浸出试验以及微观结构分析,研究不同固化剂配比、污染物浓度、溶液pH值和干湿循环次数对赤泥-石灰固化剂固化污染土的质量损失率、强度变化、毒性浸出浓度以及微观形态的影响。结果表明:在各种条件下,R4C4固化土质量损失率最低;在溶液pH值为7、干湿循环下,固化土抗压强度随石灰掺量增加而增加,随循环次数的增加先增大后减小,在循环次数为两次时达到峰值;溶液pH值减小时,强度也随之减小;浸出浓度随循环次数以及溶液pH值的增大而增大,在初始浓度为M1时所有试样均满足标准要求;在多次酸性干湿循环后土体出现裂缝,且水化物减少导致结构被破坏。

重金属镉污染对土体力学特性的影响及机理分析

为了研究重金属镉(Cd)对土体力学特性的影响规律及其微观机理,开展了不同Cd含量污染土强度、渗透、剪切特性、压汞和扫描电镜试验研究。力学特性试验结果表明:重金属Cd会劣化土体力学特性;随着Cd含量的增加,土体的抗压强度、剪切强度和黏聚力显著降低;而渗透系数、内摩擦角明显增大。扫描电镜试验结果表明:Cd使土颗粒发生团聚,Cd污染土出现大的团聚体,大颗粒增多,土体表面变得比较粗糙,土颗粒之间的接触形式增多,出现点-面接触和边-面接触;且团聚体间的孔隙较大。压汞试验表明:随着Cd含量的增加,污染土中孔径大于1μm的孔隙体积明显增加。污染土的微观结构和孔隙分布的改变是Cd污染土力学特性变化的本质原因。

镉污染粉土电化学特性试验研究

基于电化学测试技术,将电化学阻抗谱(EIS)理论与测试技术应用于镉污染粉土内部结构和电化学特性的研究。通过试验得出镉污染粉土的Nyquist图表现为一个时间常数的容抗弧,Bode图中阻抗模值受污染介质含量和频率的影响;模拟分析得到镉污染粉土的等效电路模型,主要包括溶液电阻、固液界面电阻和固体颗粒表面双电层电容三个主要电学元件;通过拟合等效电路参数值后得出:溶液电阻随着污染介质含量的增大呈对数减小,固液界面电阻随着污染介质含量的增大呈线性减小;固体颗粒表面双电层电容随着污染介质含量的增大呈指数增大。

砷、镉复合污染土击实特性及微观结构试验研究

重金属污染土不仅破坏环境健康,同时威胁岩土工程安全。通过控制变量法对砷(As)、镉(Cd)单一污染土和复合污染土的土壤化学、土体微观结构和击实特性对比分析,研究了不同重金属污染源、不同重金属浓度对污染土的击实特性影响规律及作用机制。结果表明:单一污染土中,As使土壤扩散双电层变厚,土颗粒呈絮凝状,小孔隙增加,小颗粒含量先增后减,最优含水率升高5.90%,最大干密度降低1.02%;Cd的作用效应截然相反,Cd压缩土壤扩散双电层,土体呈堆积状,小孔隙减少,小颗粒含量减少,最优含水率降低8.03%,最大干密度增加1.00%。Cd对土体击实特性影响大于As。复合污染土中,As、Cd对土体最优含水率的影响呈协同作用,而对最大干密度无明显相互作用关系。污染土宏微观联系桥梁可以通过分形维数与最大干密度建立,二者拟合结果为二次函数关系。研究成果可为重金属污染土环境与工程灾害防控提供关键参数和理论支撑。

填埋场污泥灰改性黏土衬垫镉离子吸附与迁移特性

针对填埋场黏土衬垫受重金属离子侵蚀的现状，采用污泥焚烧灰掺入黏土中制成改性黏土，在室内模拟填埋场衬垫受Cd（Ⅱ）污染的工况，通过静态平衡吸附试验，评价改性黏土对Cd（Ⅱ）的吸附效果；通过低温氮气吸附试验，分析改性黏土吸附Cd（Ⅱ）后的孔隙结构变化规律；通过污染物阻滞试验评价改性黏土阻滞污染物下渗的能力．结果表明：改性黏土对Cd（Ⅱ）的吸附属于Langmuir吸附模型，含污泥灰的改性黏土对Cd（Ⅱ）的理想最大吸附量增加31．9％～47．5％；吸附Cd（Ⅱ）后的改性黏土吸附一脱附等温线属于Ⅳ型，并出现H3型滞回环，污泥灰掺量3％试样的比表面积为109．90m^2／g，比未掺污泥灰试样大14．9％；土层孔隙水中Cd（Ⅱ）的浓度随着土层深度的增加而减少，深度达到17cm时，孔隙水中已无法检出Cd（Ⅱ）的存在，在相同土层深度处，含污泥灰试样的孔隙水中Cd（Ⅱ）浓度低于未掺污泥灰试样．

固化重金属污染土电阻率与强度特性试验研究

为研究固化重金属污染土电阻率与强度关系特征,对稻壳灰-水泥固化镉污染土开展电阻率测试及无侧限抗压强度试验,通过单轴压缩-电阻率联合试验得到固化土单轴应力-应变-电阻率关系,分析了初始电阻率影响因素及其与强度的关联性,建立了基于电阻率的强度预测与力学损伤模型。研究结果表明:固化土应力-应变和电阻率-应变曲线呈一定负相关关系;初始电阻率随稻壳灰掺量增加而先升后降,在稻壳灰掺量为5%时初始电阻率达到峰值,水泥掺量较高时初始电阻率持续降低;固化土初始电阻率随其龄期增加而持续增加,随镉含量增加而波动式增大后减小,在镉含量为2000 mg/kg时降为最低;基于初始电阻率的强度预测模型可对固化土抗压强度进行预测;基于实时电阻率的力学损伤模型可对固化土单轴压缩过程中土体破坏前的损伤发展进行预测。

Effects of Red Mud on the Remediation of Pb, Zn and Cd in Heavy Metal Contaminated Paddy Soil

[Objective] To study the remediation efficiency of red mud on Pb, Zn and Cd in the heavy metal contaminated paddy soil of mine area, to clarify its remediation mechanism and fertilizer efficiency on heavy metal contaminated soil. [Method] The soil incubation experiment was conducted to study the effect of red mud on the pH values and electrical conductivity （EC）, and the remediation efficiency of red mud on lead （Pb）, zinc （Zn） and cadmium （Cd） in heavy metal contaminated soil. [Result] Red mud addition reduced the content of exchangeable Pb, Zn and Cd in the soil significantly. Compared with the control, when incubated for 30, 60 and 90 d with the red mud dosage of 4% （W/W）, the exchangeable Pb content was decreased by 39.25%, 41.38% and 50.19%; exchangeable Zn content was decreased by 49.26%, 57.32% and 47.16%; and exchangeable Cd content was decreased by 19.53%, 24.06% and 25.70%, respectively. The application of red mud had significant impact on the share of Pb, Zn and Cd contents in five forms, and different amounts of red mud application all reduced the proportion of exchangeable Pb, Zn and Cd to the total Pb, Zn and Cd. In addition, the proportion of exchangeable Pb, Zn and Cd to total Pb, Zn and Cd decreased with the increasing amount of red mud addition. [Conclusion] The study provided references for reasonable application of red mud and reduction of heavy metal pollution in paddy soil.

Effects of Cadmium Pollution in Soil on Physiological and Biochemical Index of Allium sativum L.

[Objective] The experiment aimed to study the effects of cadmium pollution in soil on physiological and biochemical index of Allium sativum L. and provided reference for the recovery of cadmium pollution in soil. [Method]By setting eleven Cd concentrations from 0.21 to 500 mg/kg in soil and the pot test, ecological corresponding mechanism of plant height, chlorophyll (Chl) content, catalase (CAT) activity and malondialdehyde (MDA) of Allium sativum L. was analyzed. [Result] The plant height had a strong tolerance to cadmium pollution in soil, while the total chlorophyll content and chlorophyll a content had no significant difference compared with control treatment, except Cd concentration was 500 mg/kg. The high Cd concentration would increase the damage to membrane of Allium sativum L. however with the regulation of physiological mechanism, the damage was gradually decreased.[Conclusion] Allium sativum L. had strong eco-physiological adaptability to Cd contaminated soil and it had potential for recovering Cd contaminated soil.

Status of Heavy Metal Contamination in Paddy Soil of Guangxi Province and Effect of Silicon Fertilization on Cd Content in Brown Rice

[Objective] To provide a scientific basis for the management of Cd contamination, the status of Cd contamination in paddy soil of Guangxi Province, as well as the effect of silicon fertilization on Cd content in brown rice, was investigated. [Method] A total of 157 topsoil（0-20 cm） samples were collected from the major rice-growing paddy fields in Guangxi Province. The Cd contents in the topsoil samples were determined. The paddy soil environment quality and potential ecological risk were evaluated by single factor index and potential ecological index methods. In addition, in the Cd-contaminated paddy fields, the effects of different silicon fertilization treatments（no application（CK）, soil application of 750 kg/hm^2 silicon fertilizer（S）, leaf application of 1 500 L/hm^2 0.2% nanometer silicon（L）, soil application of 750 kg/hm^2 silicon fertilizer ＋ leaf application of 1 500 L/hm^2 0.2% nanometer silicon（SL）） on Cd content in brown rice were investigated. [Result] The total Cd contents in the 157 topsoil samples from paddy fields of Guangxi Province ranged from 0.02 to 7.33 mg/kg with an average content of 0.53 mg/kg. The Cd contents in 35.03% of the topsoil samples exceeded the grade II of national soil environment quality standards, and the topsoil samples were dominated by moderate and mild Cd contamination. Different silicon fertilization treatment all significantly reduced the Cd content in brown rice（P〈0.05）. In the treatment III, the Cd content in brown rice was lowest. Compared with that in the CK group, the Cd content in brown rice in the treatment III was reduced by 73.45%, in the treatment II was reduced by 62.07%, and in the treatment I was reduced by 34.48%. [Conclusion] The Cd in paddy fields of Guangxi Province showed a moderate to high ecological risk,and rational application of silicon fertilizer could effectively reduce the Cd content in brown rice.

Cadmium Release in Contaminated Soils due to Organic Acids

There is limited information on the release behavior of heavy metals fromnatural soils by organic acids. Thus, cadmium release, due to two organic acids (tartrate andcitrate) that are common in the rhizosphere, from soils polluted by metal smeltersor tailings andsoils artificially contaminated by adding Cd were analyzed. The presence of tartrate or citrate at alow concentration (<= 6 mmol L^(-1) for tartrate and <= 0.5 mmol L^(-1) for citrate) inhibited Cdrelease, whereas the presence of organic acids in high concentrations (>= 2 mmol L^(-1) for citrateand >= 15 mmol L^(-1) for tartrate) apparently promoted Cd release. Under the same conditions, theCd release in naturally polluted soils was less than that of artificially contaminatedsoils.Additionally, as the initial pH rose from 2 to 8 in the presence of citrate, a sequentialvalley and then peak appeared in the Cd release curve, while in the presence of tartrate the Cdrelease steadily decreased. In addition, Cd release was clearly enhanced as the electrolyteconcentration of KNO_3 or KC1 increased in the presence of 2 mmol L^(-1) tartrate. Moreover, ahigher desorption of Cd was shown with the KCl electrolyte compared to KNO_3 for the sameconcentration levels. This implied that the bioavailability of heavy metals could be promoted withthe addition of suitable types and concentrations of organic acids as well as reasonable fieldconditions.

Preliminary bioleaching of heavy metals from contaminated soil employing indigenous Penicillium Chrysogenum strain F1

Bioleaching is an environment-friendly and economical technique to remove heavy metals from contaminated soil.The objective of this work is to find out an indigenous strain to remedy soil contaminated by Zn,Pb,Cu and Cd.A strain which was selected from the soil of a local smelting industry was found to be able to produce many organic acids and degrade pH value of the liquid medium.The fungus strain is identified as Penicillium Chrysogenum (P.Chrysogenum) by sequencing 18srDNA and ITS.Bioleaching condition using P.Chrysogenum is optimized.Glucose is the best carbon source for P.Chrysogenum and inorganic nitrogen is better than organic nitrogen.In addition,neutral solution and room temperature are fit for P.Chrysogenum to bioleach.In the one-step bioleaching,the bioleaching ratios are 39.95% for Zn,9.4% for Pb,34.89% for Cu and 49.59% for Cd,which are 53.89% for Zn,14.44% for Pb,55.53% for Cu and 62.81% for Cd in the two-step bioleaching.The efficiency of two-step bioleaching is better than the one-step bioleaching.P.Chrysogenum is effective in removing heavy metals from the contaminated soil.

Study on electrokinetic remediation of cadmium contaminated soils

Kaolinite from a lead-zinc mining district,which was spiked with cadmium,has been treated by electrokinetics to investigate effects of treatment time and applied voltage gradient.The results showed that the increased test duration had induced a higher removal rate of cadmium.Being treated for 7 days,cadmium was removed from kaolinite dramatically.It was also found that higher removal rate happened when a higher voltage gradient was applied and cadmium accumulated near the cathode because pH increased.Increase of pH near the cathode caused accumulation of cadmium.Moreover,it was observed that cation exchange membrane which was placed between kaolinite and cathode could make pH lower than the initial value and avoid the higher pH near the cathode.As a result,the high concentration accumulation of cadmium near the cathode was avoided.

Dynamics of Microbial Activity Related to N Cycling in Cd-Contaminated Soil During Growth of Soybean

The potential influences of cadmium (Cd) on the biochemical processes of the soil nitrogen (N) cycle, along with the dynamics of ammonification, nitrification, and denitrification processes in the rhizosphere and non-rhizosphere (bulk soil), respectively, were investigated in a Cd-stressed system during an entire soybean growing season. In terms of Cd pollution at the seedling stage, the ammonifying bacteria proved to be the most sensitive microorganisms, whereas the effects of Cd on denitrification were not obvious. Following the growth of soybeans, the influences of Cd on ammonification in the bulk soil were: toxic impacts at the seedling stage, stimulatory effects during the early flowering stage, and adaptation to the pollutant during the podding and ripening stages. Although nitrification and denitrification in the bulk soil decreased throughout the entire growth cycle, positive adaptation to Cd stress was observed during the ripening stage. Moreover, during the ripening stage, denitrification in the bulk soil under high Cd treatment (20 mg kg-1) was even higher than that in the control, indicating a probable change in the ecology of the denitrifying microbes in the Cd-stressed system. Changes in the activity of microbes in the rhizosphere following plant growth were similar to those in the non-rhizosphere in Cd treatments; however, the tendency of change in the rhizosphere seemed to be more moderate. This suggested that there was some mitigation of Cd stress in the rhizosphere.

Phytoremediation of Cd Contaminated Soil through Certain Weed and Crop Species

Phytoremediation is a relatively new approach in remediating ecosystems contaminated by ecotoxic pollutants such as herbicides or heavy metals and especially cadmium （Cd）. Certain indicators of phytoremediation, as plant growth, tolerance to Cd, and uptake, transfer factor （TF） and percent removal of Cd, were studied for 11 crops and 8 weed species in soil with varying levels of Cd （0-240 mg Cd kg＂ soil） under controlled environment. Cadmium accumulated mainly in roots （51%-86%, depending on the species）, while a 14%-49% was transferred to shoots （except for four species） the concentration being positively related to Cd level in soil. Highest concentration in the above ground plant part was measured in sugarbeets （41-101 mg Cd kg-1 DW） followed by Bromus sterilis （75）, Eruca sativa （32-82）, Cichorium intibus （35-80）, and maize （60 mg Cd kgl）. Based on the results it is concluded that sugarbeets, maize, C. intibus, B. sterilis, E. sativa, Apium graveolens, and Vicia sativa seem to have a potential in remediating Cd contaminated soils.

Enhancement of Cd Solubility and Bioavailability Induced by Straw Incorporation in Cd-Polluted Rice Soil

Of the factors affecting migration and bioavailability of toxic metals in heavy metal contaminated soil, DOC （dissolved organic carbon） provides binding sites for metal cations and reduces the fixation and adsorption of heavy metals by soil solid phase. Elevation of DOC level due to the direct incorporation of crop residues may lead to enhanced accumulation of toxic metals in crop body grown in polluted farmland. In this study, an incubation experiment and a pot experiment were conducted respectively to investigate the effects of wheat straw incorporation on DOC level, cadmium availability, and Cd accumulation in rice plant, and to establish the relation between Cd solubility and DOC level. A Cd-contaminated rice soil was used and incorporated with different rates （0%, 0.5% and 1%） of wheat straw in both experiments. Results showed that the change pattern of Cd in soil solution was very similar to that of DOC level. Wheat straw addition significantly elevated Cd and DOC level in soil solution while NH4NO3-extrated Cd was not affected. There existed a close linear correlation between soluble Cd and DOC level. Enhanced Cd accumulation in rice plant, grown in a Cd contaminated soil, induced by wheat straw incorporation was observed in this study.

Analysis of Cadmium in Water Extracts from Contaminated Soils with High Arsenic and Iron Concentration Levels

Cadmium （Cd） concentrations in the water extracts of ten contaminated soils by arsenic （As） with various iron （Fe） contents were measured using inductively coupled plasma atomic emission spectrometry （ICP-AES） and electrothermal atomic absorption spectrometry （ETAAS）, Due to the potential spectral interferences of As and Fe in the quantification of Cd, two methods were used for the background compensation. The first method was based on the use of a deuterium lamp （BGCD2 mode）. The second one required a Cd hollow cathode lamp pulsated with a current for which the intensity varies in the course of time （BGCSR mode）. The results showed that the choices of the analytical technique and the method used for the background compensation depend on the Cd, As and Fe concentrations in the solution and the concentration ratios As/Cd or/and Fe/Cd. In comparison with the ICP-AES and the ETAAS in combination with the BGCD2 mode, it was shown that the high-speed self-reversal method （HSSR） was a more appropriate method to correct As and Fe spectral interferences during the Cd measurements. On the other hand, depending on the Cd concentration, it was established that no significant Fe interference occurred during the Cd determination even if Fe concentration was 50 mg/L, reflecting the efficiency of the HSSR method to overcome the Fe interferences in the determination of Cd concentration by ETAAS without any matrix modifier in water extracts.

SORPTION AND DESORPTION CHARACTERISTICS OF CADMIUM BY FOUR DIFFERENT SOILS IN NORTHEAST CHINA

Four soils, phaeozem (PM), saline-alkali soil (SA), meadow albic bleached soil (MA) and dark brown forest soil (DB) from Northeast China were used to examine the sorption and desorption characteristics of Cd and pH influence on it. According to sorption experiment without pH control, the order of amount of absorbed Cd by soils was: SA>PM>DB>MA. The results from non-linear fitting method showed that Langmuir and Freundrich models were more adaptable than Temkin model in describing the sorption data. The maximum sorption amounts from Langmuir model were: PM>SA>MA>DB. Exponential equation for PM and SA and quadratic equation for MA and DB were suitable to fit the desorption data. The order of average desorption percentage was: MA>DB>PM>SA. The amounts of sorption by PM, DB and MA reached the maximum in pH 9.0, while sorption by SA was linearly increased in the experimental range of pH 3.3-11.4. In uniform pH, however, Cd sorption by SA was the minimum among four soils, which indicated that the more amounts of Cd absorbed by SA in isotherm sorption were ascribed to the higher soil pH. The higher sorption of Cd in PM resulted from the higher percentage of organic matter and clay components.