熟污泥改性黄土对铜的吸附解吸特征

为探明熟污泥改性黄土对重金属的容纳能力,以熟污泥改性黄土为供试土样,采用序批实验法研究了供试土样对铜(Cu)的吸附解吸特征,并分析了供试土样对铜的固定能力及影响因素.供试土样对铜的吸附量在铜添加浓度小于100mg/L时急剧增加,在铜添加浓度大于100mg/L时增加缓慢,而解吸量的变化趋势则恰恰相反.Langmuir型吸附等温式是描述供试土样对铜的吸附过程的最佳模型,而吸附量与解吸量的关系可以很好的用指数函数来描述.供试土样对铜的固定吸附量随熟污泥含量的增加而增加,有机质含量是决定性因素.     

施用有机物料对污染土壤水溶性有机物和铜活性的动态影响

采用黑麦草盆栽研究施用绿肥、污泥和猪粪后，对Cu污染土壤水溶性有机物(DOM)和土壤Cu环境行为动态的影响．施用有机物料后土壤DOM含量比对照增加0.4—7.5倍，尤以绿肥和猪粪最明显．但随时间延长DOM降解明显，尤其在第一周内．污染土壤中水溶性Cu浓度随DOM的降解而相应减少研究发现，施用污泥有利于降低污染土壤中水溶性Cu浓度和黑麦草对Cu的吸收量，这是污泥固相有机质对Cu吸持使其活性降低和污泥DOM使Cu活性提高二者综合作用的结果．与此相反，施用绿肥和猪粪后，黑麦草体内的Cu含量却明显提高，其中潮土上提高1．4～2．1倍，红壤上提高1．4-1．6倍．因此．施用有机物料改良重金属污染地需格外谨慎。     

植物多酚物质原位钝化污染土壤重金属的研究 I.对土壤Cu吸持与溶出的影响

研究了两种缩合类植物多酚L和Y对土壤中污染元素Cu的吸持解吸的影响．结果表明植物多酚具有明显促进土壤吸持Cu，抑制土壤Cu的溶出作用，而且在潮上上效果更大在所研究的Cu和多酚浓度范围内，多酚Y都比多酚L作用显著．Cu的吸持等温线可用Freundlich方程定量描述有多酚存在的条件下土壤对Cu的吸持量比对照处理(不加多酚)高3—6倍．两种土壤对Cu吸持率随着多酚溶液浓度增加也随之增加，特别是在0-400mg(C)/L的多酚溶液浓度范围内，多酚Y和多酚L的浓度每提高100mg(C)/L，可分别使红壤对Cu的吸持率提高33.3％和56．60%，而使潮土提高14．1％和21．4％在土壤对Cu的吸附率相对比较低时(如pH2—5)，添加植物多酚显著增加土壤对Cu吸附．随着多酚溶液浓度的提高，两种土壤中Cu的溶出率都随之降低。     

Effect of copper on phospholipid fatty acid composition of microbial communities in two red soils

The phospholipid fatty acid （PLFA） composition was analyzed in two red soils experimentally contaminated with copper at different concentrations. The total amounts ofphospholipid fatty acids （PLFAs） in both red soils were significantly correlated with soil microbial biomass C and N, which decreased consistently with increasing levels of copper. The relative quantities of the PLFAs 17：0 （10 Me）, i16：0, il 5：0 and 16：1w5c, decreased with increasing heavy metal concentration, while those of cyl7：0, which is an indicator of gram-negative bacteria, increased. The Shannon index calculated from the PLFA data indicated that Cu addition in the red soils decreased the population diversity of soil microbial communities. Multivariate analysis of PLFA data demonstrated that high levels of Cu application had a significant impact on microbial community structure and there is a threshold metal concentration for PLFA composition. Comparatively higher toxic effect on microbial biomass and community structure were found in the red sandy soil than those in the red clayey soil. The differential effect of Cu addition on microbial communities in the two soils may be due to differences in soil texture and cation exchange capacity.     

7个柳树无性系在Cu/Zn污染土壤中的生长及对Cu/Zn的吸收

通过盆栽试验来评价7个柳树无性系(旱柳?杞柳和金丝柳)修复Cu/Zn污染土壤或矿砂的潜力.研究了7个无性系在2种污染介质中的生长,叶绿素含量?根系形态及其对Cu、Zn的吸收转移.结果表明,150d后,7个柳树无性系在污染介质中都能生长,其中旱柳和金丝柳生长较好,其他无性系生长受到明显抑制.各无性系叶片出现黄化现象,叶绿素相对含量降低.根系发育受到一定程度的抑制.各无性系对Cu的积累主要在地下部,而对Zn的积累主要在地上部,特别是在叶片中.7个无性系在铜土中更容易积累重金属.各无性系生物富集系数(BCF)Cu.Cu的转移系数(TF)值均<1,Zn的TF值在1.36~2.49之间.旱10?旱34和金丝柳对Cu和Zn有较强的耐性和一定积累能力,适合在尾矿区造林和修复.     

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.     

小头蓼(P.Microcephalum)对矿区铜的吸收积累研究

调查并分析云南省铜矿区的植物区系及土壤理化特性，发现小头蓼（P.Microcephalum）在云南省高海拔铜矿区生长旺盛，是该地区的优势植物种，小头蓼生长的土壤基质富含铜，其它养分条件适中，研究表明小头蓼具有较强的富集铜的能力；随土壤中铜含量的增加，植物根系铜含量也相应增加，但叶部铜含量变人与土壤铜含量之间无相关性，研究认为该植物具有对铜污染土壤的植物固定潜能。此外，还指出最适于小头蓼富集铜的土壤条件为土壤有机质1％－1.5％，土壤pH为中性。     

Impacts of soil organic matter, pH and exogenous copper on sorption behavior of norfloxacin in three soils

Norfloxacin (Nor) sorption and the factors (soil organic matter (SOM), pH, and exogenous copper (Cu) influencing the sorption were investigated in a black soil (soil B), a fluvo-aquic soil (soil F), and a red soil (soil R). With increasing of Nor concentrations, sorption amount of norfloxacin increased in both the bulk soils and their SOM-removed soils, but the sorption capacity in SOM-removed soils was higher than that of their corresponding bulk soils, indicating that the process of norfloxacin sorption in soil was influenced by the soil properties including SOM. The sorption data in all bulk soils and SOM-removed soils were fitted to Freundlich and Langmuir models. The correlation coefficients suggested that the experimental data fitted better to Freundlich equation than to Langmuir equation. Furthermore, the data from soil F and SOM-removed F could not be described by Langmuir equation. The norfloxacin sorption amount decreased in soil B and soil F, whereas it increased in soil R as solution pH increased. The maximum KD and KOC were achieved in soil R when the equilibrium solution pH was 6. And the norfloxacin sorption was also influenced by the exogenous Cu2+ ions, which depended on the soil types and Cu2+ concentrations. With increasing of Cu2+ concentrations in solution, generally, sorption amount, KD and KOC for norfloxacin in soils increased and were up to a peak at 100 mg/L Cu2+, and then the sorption amount decreased regardless of norfloxacin levels.     

城市污泥中Cu回收研究：生物沥浸-溶剂萃取-电积沉Cu技术

城市污泥通常含有大量有机质但也存在数量不等有害金属,在不影响污泥有益成分的基础上,去除和回收污泥中金属,既使污泥无害化又产生经济效益,意义重大.针对苏州某工业园区污泥重金属含量较高,研究利用生物沥浸-溶剂萃取-电积技术回收城市污泥中重金属Cu的工艺,并探讨了采用5-壬基水杨醛肟萃取剂M5640从城市污泥生物沥浸液中萃取分离Cu和Fe的最佳工艺参数.结果表明,经过生物沥浸处理72 h后,城市污泥中重金属Cu溶出率高达90%.当最佳工艺条件为:萃取剂体积分数为2%,相比(有机相与水相体积比,以O/A表示)为1/3,沥浸液pH为2.0时,沥浸液中Cu的一级萃取率达到95%以上,而Fe的共萃率低于10%;反萃取试验结果表明,在反萃取相比为2/1的条件下用1.5 mol/L硫酸溶液进行反萃取,Cu的一级反萃取率达到80.07%;反萃取后的富集Cu溶液作为电解液,在槽电压为2.1 V、电解温度为55℃条件下电积6 h,Cu回收率达到90%以上.在整个工艺中萃余液和反萃液均可循环利用无废液排放,对含Cu高的污泥,利用生物沥浸-溶剂萃取-电积技术回收有良好的应用前景.     

Effects of free iron oxyhydrates and soil organic matter on copper sorption-desorption behavior by size fractions of aggregates from two paddy soils

Effects of free iron oxyhydrates (Fed) and soil organic matter (SOM) on copper (Cu2+) sorption-desorption behavior by size fractions of aggregates from two typical paddy soils (Ferric-Accumulic Stagnic Anthrosol (Soil H) and Gleyic Stagnic Anthrosol (Soil W)) were investigated with and without treatment of dithionite-citrate-bicarbonate and of H2O2. The size fractions of aggregates were obtained from the undisturbed bulk topsoil using a low energy ultrasonic dispersion procedure. Experiments of equilibrium sorption and subsequent desorption were conducted at soil water ratio of 1:20, 25℃. For Soil H, Cu2+ sorption capacity of the DCB-treated size fractions was decreased by 5.9% for fine sand fraction, by 40.4% for coarse sand fraction, in comparison to 2.9% for the bulk sample. However, Cu2+ sorption capacities of the H2O2-treated fractions were decreased by over 80% for the coarse sand fraction and by 15% for the clay-sized fraction in comparison to 88% for bulk soil. For Soil W, Cu2+ sorption capacity of the DCB-treated size fraction was decreased by 30% for the coarse sand fraction and by over 75% for silt sand fraction in comparison to 44.5% for the bulk sample. Cu2+ sorption capacities of the H2O2-treated fractions were decreased by only 2.0% for the coarse sand fraction and by 15% for the fine sand fraction in comparison to by 3.4% for bulk soil. However, Cu2+ desorption rates were increased much in H2O2-treated samples by over 80% except the clay-sized fraction (only 9.5%) for Soil H. While removal of SOM with H2O2 tendend to increase desorption rate, DCB- and H2O2-treatments caused decrease in Cu2+ retention capacity of size fractions. Particularly, there hardly remained Cu2+ retention capacity by size fractions from Soil H after H2O2 treatment except for clay-sized fraction. These findings supported again the dominance of the coarse sand fraction in sorption of metals and the preference of absorbed metals bound to SOM in differently stabilized status among the size fractions. Thus, enrichment and turnover of SOM in paddy soils may have great effects on metal retention and chemical mobility in paddy soils.     

Extraction of copper from sewage sludge using biodegradable chelant EDDS

[S,S]-Ethylenediaminedisuccinic acid(EDDS),a biodegradable chelant,was used to separate the heavy metals from the sewage sludge based on chemical extraction technology.Under various conditions,the extraction experiments were carried out for the sewage sludge from Shanghai Taopu Municipal Wastewater Plant,China.The influences ofpH and the concentration of EDDS on the extraction efficiency for copper(Cu)were discussed.The results showed that EDDS had higher extraction efficiency for Cu from the sewage slud...     

Free cupric ions in contaminated agricultural soils around a copper mine in eastern Nanjing City, China

To determine the environmental free metal ion activity was a recent hot issue. A method to measure low-level free cupric ion activity in soil solution extracted with 0.01 mol/L KNO3 was developed by using cupric ion-selective electrode （ISE） and calibrating with Cu-buffer solution. Three copper buffers including iminodiacetic acid （IDA）, ethylenediamine （EN）, and glycine （Gly） were compared for calibrating the Cu-ISE curves in the range of free cupric ions （pCu^2＋） 7-13. The Cu-EN buffer showed the best electrode response and thus was applied as the calibration buffer. The pCu^2＋ of 39 contaminated agricultural soils around a copper mine was measured, ranging from 5.03 to 9.20. Most Cu in the soil solutions was found to be complexed with dissolved soil organic matters, averaging 98.1%. The proportion of free Cu^2＋ ions in the soil solutions decreased with the increasing of solution pH. Soluble Cu and free Cu^2＋ ions concentrations were analyzed by multiple linear regressions to evaluate the effects of soil properties on metal levels and speciation. The results showed that soil solution pH was the most significant factor influencing pCu^2＋ （with R^2 value of 0.76）, while not important for the soluble Cu concentration.     

土壤性质对铜-芘复合污染土壤电动-氧化修复的影响研究

重金属-有机复合污染土壤的修复是污染土壤修复的难点之一.选取我国3种典型土壤（红壤、黄棕壤和黑土）,以铜和芘为模式污染物,分别代表典型的重金属和有机污染物,研究了不同土壤类型对电动-氧化技术处理铜和芘复合污染土壤的影响机制.试验中阴、阳极电解液的组分均为10%的羟丙基-β环糊精、12%H2O2和0.01 mol.L-1 NaNO3溶液,施加电压梯度为1V.cm-1.经过15 d电动修复后,红壤、黄棕壤和黑土中总芘去除率分别为38.5%、46.8%和51.3%,总铜去除率分别为85.0%、22.6%和24.1%.pH较高的黑土产生高电渗流,增加了氧化剂与污染物的接触,同时较低的黏粒含量也有利于芘的解吸.红壤的低pH和低有机质含量影响了重金属的形态分布,提高了铜去除率.研究表明不同土壤的pH、黏粒含量和重金属的形态分布等是影响不同类型土壤上铜和芘迁移和修复效率的主导因素.     

Growth and metal uptake of energy sugarcane (Saccharum spp.) in different metal mine tailings with soil amendments

A pot experiment was conducted to investigate the feasibility of growing energy sugarcane(Saccharum spp.) in three different metal mine tailings(Cu, Sn and Pb/Zn tailings) amended with uncontaminated soil at different mixing ratios. The results indicated that sugarcane was highly tolerant to tailing environments. Amendments of 20% soil to Sn tailings and 30% soil to Cu tailings could increase the biomass of cane-stem for use as the raw material for bioethanol production. Heavy metals were mostly retained in roots, which indicated that sugarcane was useful for the stabilization of the tailings. Bagasse and juice, as the most valuable parts to produce bioethanol, only accounted for 0.6%– 3% and 0.6%–7% of the total metal content. Our study supported the potential use of sugarcane for tailing phytostabilization and bioenergy production.     

Risk assessment of heavy metal contaminated soil in the vicinity of a lead/zinc mine

Heavy metal contamination of soils through anthropogenic activities is a widespread and serious problem confronting scientists and regulators throughout the world. In this study we investigated the distribution, chemical species and availability of lead, zinc, cadmium and copper in nine surface（0 to 20 cm） soils from near an abandoned lead/zinc mine tailings located in Shaoxing, Zhejiang, China. Total heavy metal contents ranged from 5271 to 16369 mg/kg for Pb, 387 to 1221 mg/kg for Zn, 3.0 to 9.3 mg/kg for Cd and 65 to 206 mg/kg for Cu. In general, all heavy metals exceeded China National Standards for Soil Environmental Quality of Heavy Metals by a factor of 3-65 times. Comparison of the heavy metal concentrations（Pb, Zn, Cd and Cu） with clay content revealed a strongly significant relationship while significant relationship（ P 〈 0.001 ） was also obtained between Cd ＋ Zn and Pb ＋ Cu. Solid phase speciation of the soils using Tessier procedure showed that the heavy metals were distributed in the order： residual 〉〉 organically complexed-Fe-Mn oxides occluded 〉 carbonate bound 〉 exchangeable 〉 water soluble. In the organic matter fraction, the ratio of Pb（29.1% ） to its total concentration in the soils was higher than those of Zn（4.70% ）, Cd（3.16% ） and Cu（9.50% ）. The percentages of the water soluble and the exchangeable fractions of Pb（1.80% ） and Cd（2.74% ） were markedly greater than those of Zn（0.10% ） and Cu（0.15% ）, suggesting that Pb and Cd are relatively more mobile and hence more toxic in the contaminated soils. Strongly significant relationships between H20-Pb, H20-Zn and H20-Cu, strong positive correlations between H20-Pb, H20-Zn, H20-Cu and organic matter in soil were found. The content of H20-Pb, H20-Zn, H20-Cu was negatively correlated with pH values. The similar negative relationships between pH values and exchangeable heavy metals were also recorded. It is suggested that increasing soil pH or liming the soil could decrease bioavailability of heavy metals in the soil.     

Clay mineralogy affects the efficiency of sewage sludge in reducing lead retention of soils

Recent studies have shown the feasibility of using of sewage sludge for the remediation of heavy metal-contaminated soils. However, there are no researches to check the influence of clay mineralogy on the efficiency of the sewage sludge to remediation of contaminated soils with heavy metals. For this purpose, we use two contrasting soils:Oxisol rich in hematite and gibbsite and Inceptisol rich in kaolinite. Thermal-treated sludge was applied to Pb-contaminated soil samples and incubated for 40 days. The soil samples were submitted to seven sequential extractions: soluble-Pb, exchangeable-Pb,precipitated-Pb, organic matter-Pb, Fe and Mn oxide-Pb, gibbsite and kaolinite-Pb, and residual-Pb. The reduction of soluble Pb forms by thermal sludge application was more pronounced in the Oxisol than in the Inceptisol because of the conversion of soluble-Pb into more stable forms, such as precipitated-Pb and oxides-Pb. For Inceptisol was necessary to apply high rates of thermal sludge to reach a significant reduction in soluble-Pb contents. The addition of humic fractions in the form of thermal sludge increased the concentration of organic matter-Pb. In confined area, the use of sewage sludge to reduce the heavy metals levels in soils must be better considered, mainly in more weathered soils.     

几种牧草对铜尾矿重金属的抗性及其微生物效应

铜尾矿是一类重金属含量极高 ,对植物生长产生毒害的生境 .盆栽试验结果表明 ,4种牧草在纯尾矿以及由尾矿和对照土壤组成的混合尾矿上都能生长 ,但植物的长势随尾矿中重金属含量的增加而减弱 ,4种牧草对重金属的抗性依次表现为百喜草 >苇状羊茅 >黑麦草 >狗芽根 .此外 ,Biolog结果显示 ,土壤微生物群落代谢剖面 (AWCD)及群落丰富度、多样性指数与牧草的长势密切相关 ,种植牧草后能明显地提高土壤微生物群落功能多样性 ,提高幅度表现为百喜草 >苇状羊茅 >黑麦草>狗芽根 ,百喜草可望成为金属尾矿植被恢复的先锋牧草 .     

污泥对樟子松生物量及其重金属积累和土壤重金属有效性的影响

采用盆栽试验研究了不同剂量污泥(体积分数,即污泥体积占污泥和沙土总体积的百分比,分别为:0、20%、33.3%、50%和100%)施用于风沙土条件下,污泥剂量对樟子松幼苗生物量及其对重金属的累积和土壤中重金属有效性的影响.结果表明,在养分含量低的风沙土中,施用污泥能够显著提高樟子松幼苗生物量,最适剂量为50%;污泥剂量的增加可促进樟子松植株对重金属的吸收和累积,在最适剂量(50%)条件下,樟子松植株中Cu、Cd、Pb、Zn的累积量分别是对照(不施污泥)的18.0、8.9、17.1、11.5倍;樟子松植株重金属吸收速率顺序为:ZnCuPbCd,而迁移系数顺序为:ZnCdCuPb;土壤中有效态重金属含量随污泥剂量的增加而增加,而植株收获后土壤中有效态重金属下降幅度均小于对照.     

Remediation of copper polluted red soils with clay materials

Attapulgite and montmorillonite were utilized to remediate heavy metal polluted red soils in Guixi City, Jiangxi Province, China. The e ects of clay minerals on availability, chemical distribution, and biotoxicity of Cu and Zn were evaluated. The results provided a reference for the rational application of clay materials to remediate heavy metal contaminated soils. From the sorption experiment, the maximum adsorbed Cu2+ by attapulgite and montmorillonite was 1501 and 3741 mg/kg, respectively. After polluted red soil was amended with attapulgite or montmorillonite and cultured at 30 and 60 days, soil pH increased significantly compared to the control. An 8% increase in the amount of montmorillonite in soil and 30 days incubation decreased acid exchangeable Cu by 24.7% compared to the control red soil. Acid exchangeable Cu decreased with increasing amounts of attapulgite and montmorillonite, with best remediation e ect reached at a dose of 8%. Results also showed that the Cu poisoning e ect on earthworms was reduced with the addition of attapulgite and montmorillonite. Montmorillonite showed the best e ect, with the addition of a 2% dose the mortality of earthworms decreased from 60% to zero compared to the control. Our results indicated that the bioavailability of Cu in soils was reduced more e ectively with the application of montmorillonite than attapulgite.     

我国几个工矿与污灌区土壤重金属污染状况及原因探讨

对我国几个重工业区、矿区、开发区以及污灌区土壤重金属污染状况的调查结果表明，土壤重金属含量绝大部分高于土壤背景值，Cd、Zn等明显超标，某些重金属元素含量间还存在着一定的伴生规律。土中浸提态Cd、Zn含量与土壤pH值呈负相关。土壤中的重金属主要来自于污灌、金属矿藏开采、污泥利用以及大气飘尘等。金属冶炼厂附近土壤中Pb、Zn、Cd含量皆与离污染源距离呈密切的指数相关（R^2＞0.9）。