Cu、Cd、Pb、Zn、As复合污染对灯心草的生理毒性效应

通过盆栽试验,以现行土壤环境质量标准为浓度设置依据并结合实际污染土壤研究了不同处理水平的Cu、Cd、Pb、Zn、As5种重金属复合污染对灯心草生长、叶绿素含量及保护酶系统的影响。实验结果表明:5种重金属复合污染对灯心草地上部生长有一定程度的抑制作用,在土壤环境质量二级标准上限值处灯心草地上部生物量减产9.15%,<10%,但地下部生物量减产趋势不明显。复合重金属污染抑制灯心草的光合作用使叶绿素含量减少、叶绿素a/b值降低。在接近土壤环境质量标准低浓度设计范围内,灯心草3种保护酶有逐渐被激活的趋势,表现出一定的协调性共同抵制重金属的毒害。但在高浓度处理水平下,酶活性遭到抑制。生长在矿毒水和铅锌尾矿污染土壤中的灯心草地上部生物量分别下降28.23%和37.1%,但POD、SOD和CAT3种酶活性均高于对照。通过应用综合生态环境效益法,以灯心草为指示植物可以将土壤环境质量二级标准上限值设定为土壤中5种重金属的临界毒性效应值。     

Cd、Pb、Cu、Zn、As复合污染对龙须草生长的影响

本文研究了不同处理水平下Cd、Pb、Cu、Zn、As复合污染对龙须草生长的影响。结果表明,龙须草地下部对重金属的抗性大于地上部。在接近土壤环境质量二级标准上限值时,龙须草生长正常,减产幅度<10%;在含Cd5mgkg-1、Pb600mgkg-1、Cu125mgkg-1、Zn300mgkg-1、As50mgkg-1的复合污染土壤上,龙须草地下部干重与对照相比较差异性不显著(α=0.01);在含矿毒水河水污染土壤和尾矿砂污染水稻土壤上,龙须草地下部干重与对照相当,且地上部干重分别为对照的61.58%和40.64%。这些说明龙须草在土壤重金属复合污染修复中具有良好的应用前景。     

Cd、Pb、Cu、Zn、As复合污染对杂交水稻苗的联合生理毒性效应及临界值

通过室内土培试验,研究了不同浓度的Cd、Pb、Cu、Zn、As等5种重金属复合污染对水稻苗的联合生理毒性效应,并对其临界值进行了探讨。结果表明:5种重金属污染对水稻苗的联合生理毒性效应随其污染浓度的增加而显著增强,剂量—效应关系明显。除处理(1)外,其余各处理对水稻苗体的诸项生长指标的抑制均达到了极显著的程度(P<0.01),且对根长的抑制明显大于苗长。随着复合重金属污染浓度的增大,水稻苗叶片中叶绿素含量急剧减少;丙二醛(MDA)含量迅速增加;POD和SOD酶活性呈先升后降的变化趋势。铅锌尾矿和矿毒水污染对水稻苗生长和各项生理生化指标的影响也均达到了极显著程度,但在二者污染下,POD和SOD酶活性均高于对照,铅锌尾矿的毒性效应大于矿毒水。以酶活性为参考指标,可以将土壤环境质量二级标准上限值设定为土壤中Cd、Pb、Cu、Zn、As等5种重金属对该水稻品种的临界毒性效应值。     

Adsorption density,mobility and limit values of Cd,Zn, Cu and Pb in acid forest soils

To investigate Cd, Zn, Cu and Pb adsorption in acidified forest soils, six soil samples of the aluminium buffer range were selected and analyzed for their physical and chemical properties. Determination of the specific surface area using ethylene glycol monoethyl ether (EGME) adsorption yielded a characteristic value of the solid phases, which can parameterize the major properties of the various soil constituents with sufficient accuracy.

Traditional adsorption isotherms reveal the relation between the amount of a heavy metal adsorbed and the heavy metal concentration in the soil solution only for the soil under study and can therefore not be applied to other soils. To meet the aim of modelling heavy metal adsorption and mobility also for soils differing greatly in their properties, it was attempted to establish a generalizing adsorption isotherm for soils of entirely different composition of the solid phase. The generalizing adsorption density isotherms introduced in the following provide a useful mathematical model for the quantity/intensity relation of heavy metals in soils that differ greatly in their specific surface area and their composition.

It is also shown that limit values which take into account the major quantities influencing heavy metal adsorption and mobility in acid soils can be established from the regression equation between the adsorption density of a heavy metal (ions/m² specific surface area) and its concentration in the soil solution. In particular in view of the groundwater contamination to be expected if acid rain and, as a result, soil acidification continues, these limit values seem to provide considerably more information than the European limit values, given in mg heavy metal /kg soil, which are presently valid for any soil condition and property.     

绿化植物废弃物对重金属迁移的影响

采用土柱模拟实验,比较研究了覆盖绿化植物废弃物与土壤之上和绿化植物废弃物与土壤混合处理对城市绿地土壤中重金属淋溶的影响。结果表明,Zn、Pb和Cd均在80天后淋溶完全,而Cu有所不同,在80天后又有增加的趋势,原因可能跟重金属与有机质的结合能力有关。此外,绿化植物废弃物与土壤相混合能抑制Cu、Zn、Pb和Cd向下淋溶,而绿化植物废弃物覆盖于土壤之上则有促进Cu、Zn、Pb和Cd淋溶的趋势,且不论是混合处理还是覆盖处理,20cm厚绿化植物废弃物的处理均比10cm厚绿化植物废弃物处理对Cu、Zn、Pb和Cd的促进或抑制作用大。研究还得知,Cu、Zn、Pb和Cd的迁移还与土壤pH有关,低pH土壤有利于重金属的淋溶。     

绿化植物废弃物对土壤中Cu Zn Pb和Cd形态的影响

利用自制的Cu、Zn、Pb和Cd污染的灰潮土和黄泥土,通过室内培养实验研究了不同绿化植物废弃物添加量和不同培养时间对这两种污染土壤中这4种重金属形态的影响。结果表明,绿化植物废弃物的加入抑制了Cu的活化,且添加60%绿化植物废弃物时有机结合态Cu的含量最高;绿化植物废弃物与污染土培养2～3个月时,残余态Zn的含量最高,对植物的毒害最小;绿化植物废弃物添加量为60%时灰潮土中有效态Pb含量较低,而添加量为30%时黄泥土中有效态Pb含量最低;绿化植物废弃物添加量的多少对灰潮土Cd形态的影响较小,但黄泥土中的Cd则随绿化植物废弃物量的增加活性逐渐减弱,且两种土壤均在培养2～3个月时可交换态Cd的含量最低。     

Effects of pH and Ionic Strength on the Adsorption of Cs,Sr, Eu,Zn, Cd and Hg by Pseudomonas Putida

Bacterial metal accumulation may influence the mobility and chemical form (speciation) ofmetals in the environment. The passive adsorption of six metals (Cs, Sr, Eu, Zn, Cd and Hg) by asoil bacterium, Pseudomonas putida, was studied in the present work, using a radiotracerbatch-distribution technique. To replicate natural conditions, the adsorption was considered as afunction of pH (4-10) and ionic strength (0.01 M and 0.1 M KCl) at a low metal concentration(10-8 M). P. putida exhibited a total metal accumulating capacity of 200-1000 meq kg-1 bacteria(dry weight) (measured in 0.01 M KCl at pH 6.4). This capacity is comparable to that of manyorganic soil components and it is above the capacity of most inorganic constituents. The followingaffinity order of adsorption was observed: Hg>Eu>Cd,Zn,Sr>Cs. The results indicatethat the bacterial surface carries different sites that exhibit varying affinity and capacity for bindingmetal ions. It can be concluded that the overall adsorption of metals by P. putida is determined byseveral interacting processes related to the properties of both the metals and the bacterial surfaceand to the composition of the solution phase (pH as well as ionic strength).     

单一重金属胁迫对灯心草生长及生理生化指标的影响

通过盆栽试验研究了不同浓度处理水平的Cu、Cd、Pb、Zn、As五种重金属单一胁迫对灯心草生长及其生理生化特性的的影响。结果表明:种植灯心草土壤中的Cd、Pb、Cu三种重金属临界值可分别设定为10mg kg-1、100 mg kg-1、100mg kg-1。灯心草不适合在Zn污染的土壤中种植,土壤中As临界值尚需作进一步的研究来确定。各单一重金属胁迫对灯心草叶绿素的合成均有很大程度的抑制作用,剂量-效应关系明显。灯心草三种保护酶对于不同浓度处理水平重金属胁迫的响应不同:在土壤环境质量低浓度设置范围内三种酶有较好的协同效应能共同抵御重金属胁迫造成的膜伤害,表现出较强的自我调节能力。而在高浓度处理水平时,三种酶活性呈现不同的变化趋势。灯心草生理生化指标对重金属胁迫的响应存在元素种类之间的差异。各单一重金属对灯心草生长抑制及生理毒害效应大小排序为:Zn>As>Cu>Pb>Cd。     

重金属单一污染对龙须草叶绿素含量和抗氧化酶系统的影响

盆栽试验的结果表明:Cd、Pb、Cu、Zn和As单一污染处理时龙须草叶绿素含量随着重金属处理浓度的增加呈现先升后降的趋势,但其总叶绿素含量和叶绿素a/b比值均低于对照;龙须草SOD的活性随着Zn、As单一污染处理浓度增加呈现先升后降的趋势,而随着其它三种重金属处理浓度的增加呈现下降趋势;龙须草CAT和POD的活性随着As处理浓度的增加呈现出上升趋势,而随着其它四种重金属处理浓度的增加呈现先升后降趋势。     

Solubility control of Cu, Zn, Cd and Pb in contaminated soils

We developed a semiempirical equation from metal complextion theory which relates the metal activity of soil solutions to the soil's pH, organic matter content (OM) and total metal content (MT). The equation has the general form: where pM is the negative logarithm (to base 10) of the metal activity, and a, b and c are constants. The equation successfully predicted free Cu²⁺ activity in soils with a wide range of properties, including soils previously treated with sewage sludge. The significant correlation of pCu to these measured soil properties in long-contaminated soils suggests that copper activity is controlled by adsorption on organic matter under steady state conditions. An attempt was made from separate published data to correlate total soluble Cu, Zn, Cd and Pb in soils to soil pH, organic matter content and total metal content. For Cu, the total Cu content of the soil was most highly correlated with total soluble Cu. Similarly, total soluble Zn and Cd were correlated with total metal content, but were more strongly related to soil pH than was soluble Cu. Smaller metal solubility in response to higher soil pH was most marked for Zn and Cd, metals that tend not to complex strongly with soluble organics. The organic matter content was often, but not always, a statistically significant variable in predicting metal solubility from soil properties. The solubility of Pb was less satisfactorily predicted from measured soil properties than solubility of the other metals. It seems that for Cu at least, solid organic matter limits free metal activity, whilst dissolved organic matter promotes metal solubility, in soils well-aged with respect to the metal pollutant. Although total metal content alone is not generally a good predictor of metal solubility or activity, it assumes great importance when comparing metal solubility in soils having similar pH and organic matter content.     

Accumulation of As,Pb, Zn,Cd and Cu and arbuscular mycorrhizal status in populations of Cynodon dactylon grown on metal-contaminated soils

Metal(loid) accumulation and arbuscular mycorrhizal (AM) status of the dominant plant species, Cynodon dactylon, growing at four multi-metal(loid)s-contaminated sites and an uncontaminated site of China were investigated. Up to 94.7 As mg kg^?1, 417 Pb mg kg^?1, 498 Zn mg kg^?1, 5.8 Cd mg kg^?1 and 27.7 Cu mg kg^?1 in shoots of C. dactylon were recorded. The plant was colonized consistently by AM fungi (33.0–65.5%) at both uncontaminated site and metal-contaminated sites. Based on morphological characteristics, fourteen species of AM fungi were identified in the rhizosphere of C. dactylon, with one belonging to the genus of Acaulospora and the other thirteen belonging to the genus of Glomus. Glomus etunicatum was the most common species associated with C. dactylon growing at metal-contaminated sites. Spore abundance in the rhizosphere of C. dactylon growing at the metal-contaminated soils (22–82 spores per 25 g soil) was significantly lower than that of the uncontaminated soils (371 spores per 25 g soil). However, AM fungal species diversity in the metal-contaminated soils was significantly higher than that in the uncontaminated soils. This is the first report of AM status in the rhizosphere of C. dactylon, the dominant plant survival in metal-contaminated soils. The investigation also suggests that phytorestoration of metal-contaminated sites might be facilitated using the appropriate plant with the aid of tolerant AM fungi.     

低分子有机酸对土壤中重金属的解吸及影响因素

研究了柠檬酸、草酸、酒石酸和苹果酸对矿区土壤中重金属Pb、Cd、Cu和Zn的解吸行为,并探讨了介质pH值对其解吸土中重金属的影响。振荡解吸试验结果表明四种低分子有机酸对供试污染土壤中Pb、Cd、Cu和Zn都具有一定的解吸能力。由于土壤中重金属有效态含量较低,各重金属的解吸率都不高。在对Pb和Cd的解吸中,各低分子有机酸能力大小顺序为柠檬酸>酒石酸≈苹果酸>草酸;Cu的解吸顺序为柠檬酸>草酸>酒石酸≈苹果酸;Zn的解吸顺序为酒石酸>柠檬酸≈苹果酸>草酸。低分子有机酸随浓度的增加,其解吸能力提高。低分子有机酸对重金属的解吸量随pH值的降低而增加。     

The flux of Cd,Cu, Pb and Zn in mining polluted soils

The monitoring of heavy metal deposition onto soils surrounding old Pb-Zn mines in two locations in the UK has shown that relatively large amounts of Cd, Pb, Zn and, in one case, Cu are entering the soil annually. Small particles of ore minerals in windblown mine tailings were found to be contributing up to 1.46 g m^?2 yr^?1 of Pb, 1.41 g m^?2 yr^?1 of Zn and 0.027 g m^?2 yr^?1 of Cd. However, when these inputs from bulk deposition are compared with the concentrations of the same metals within the soil profiles it is apparent that relatively little long-term accumulation is occurring. Metals are being lost from the soil profiles, probably through leaching. A calculated relative retention parameter gave values that ranged from 0.01 to 0.17 for Cd, 0.11 to 0.19 for Zn, 0.32 to 0.63 for Cu and over 1 for Pb. These relative retention values were found to follow the order of electronegativity of the elements concerned: Pb>Cu>Zn>Cd. Distribution coefficient (Kd) values quantifying the adsorptive capacity of the mine soils for Cd and Pb showed marked differences for the two metals (12 to 69 cm³ g^?1 for Cd and 14 to 126 cm³ g^?1 for Pb) and may, in part, account for the two to one hundred-fold variation in the relative retention parameter for the different metals within these soils.     

Effect of Solid/Liquid Ratio on the Remobilization of Cu,Pb, Cd and Zn from Polluted River Sediment

The incidence of the solid/liquid ratio on thesolubilization of heavy metals from a polluted riversediment was assessed by batch experiments. Thepercentage of solubilized metal increases stronglywhen the concentration of the sediment-watersuspension decreases from 50 to 0.1 g L^-1. Thissolubilization behavior is described by a simpleequilibrium desorption model on the association of themetals and sediment. The association constantscalculated with this model indicate the affinitybetween the metals and the sediment (Pb > Cu > Zn> Cd). If polluted river sediments are in situresuspended, the decrease of the solid/liquid ratioassociated to this natural event could provoke theremobilization of metals trapped in sediments.     

Distribution of Zn, Cd, Pb and Cu Metals in Groundwater of the Guadiamar River Basin

Traditionally, the Guadiamar River Basin (Seville, SouthwestSpain) has received pollution from two different sources. Inits upper course, from a pyrite exploitation and, in itslower reaches, from untreated urban and industrial wastes aswell as wastes from intensive agricultural activity. In 1998,the accidental release in the river of about 6 million m³ of acid water and sludge from mine tailings contributedto worsen the pollution of an already contaminated area. Themain polluting agents of the spill were heavy metals. Itaffected a large number of wells either directly or as a consequence of infiltration from polluted soils. Assessment of the pollution by total metal determination does not revealthe true environmental impact of the spill and speciation studies showing the distribution of the main pollutants are required. There is a direct association between the physicochemical speciation of an element and its bioavailability, toxicity and mobility. This article describesa distribution study of the metals Zn, Cd, Pb and Cu by speciation analysis of groundwater in six wells of the GuadiamarRiver Basin; the samples were taken several weeks after the spill. The speciation analysis resulted in the definition ofthree species categories: a) labile metal (H⁺ exchangeable),b) metal strongly associated to dissolved organic matter and c) metal associated with suspended material. Analysis was carried out by anodic stripping voltammetry (ASV). Metal speciation ingroundwater of the Guadiamar River Basin allows a differentiationbetween: on the one hand, metals from the mining spill, andon the other hand a less recent pollution from accumulatedinfiltration of either mining or agricultural origin, the last one due to an abuse of phytosanitary products.     

Chemical speciation and bioavailability of Cd,Cu, Pb and Zn in Western Balkan soils

Abstract

Three thermal power plants in Serbia, Croatia and Bosnia of the Western Balkan region were expected to be metal polluting sources, and this study was performed to investigate the bioavailability and chemical speciation of trace metals in soils and soil water extracts, respectively. Surface (0–15 cm) soil samples along with maize and grass samples were collected at a gradient from the pollution source. The chemical speciation of metals was conducted using the Windereme Humic Aqueous Model (WHAM)/Model VI for water, whereas the Diffusion Gradient in Thin Films (DGT) technique was used to estimate plant availability. The chemical speciation indicated that more than 99% of all four metals in soil water extracts were complexed to fulvic acid. This is connected to relatively high soil pH (> 6.5) and high contents of soil organic matter in these soils. The accumulation of trace metals by DGT was not correlated to plant uptake. This is connected to the very low partitioning of free ions in solution, but also to the low variation in metal solubility and metal concentration in plant tissue between sites. In spite of active thermal power plants located in the areas, hardly any differences in concentration of soil metals between sites were seen and the partition of metals in soil waters was insignificant. The latter indicates that these soils have a large metal-retaining capacity. The only significant soil chemical variable affecting the variation in metal solubility was the soil pH. In a time with large infrastructure and industrial expansion in these areas, this investigation indicates the importance of protecting these high-quality soils from industrial use and degradation. High industrial activity has so far had insignificant effect on soil quality with respect to bioavailability of trace metals in these soils.     

Effect of pH on Removal of Cu,Cd, Zn,and Ni by Cement Kiln Dust in Aqueous Solution

A batch experiment was conducted to study the effect of pH on the sorption of copper (Cu), cadmium (Cd), zinc (Zn), and nickel (Ni) by cement kiln dust (CKD). The experiment was carried out by adding 25 mL of solutions containing concentrations of 200, 400, 600, 800, and 1000 mg/L of each of these heavy metal cations to 1.00 g of CKD. The pH of these suspensions was adjusted to 2, 5, and 7 as well as non-adjusted. The sorbed amount (Cs) and the sorption percentage of Cu, Cd, Zn, and Ni by CKD increased with increasing the suspension pH. The adsorption data of Cu, Cd, Zn, and Ni were generally well correlated with Langmuir model when the suspension pH was adjusted to 5, 7, non-adjusted and 7, respectively. However, they could be well described by Freundlich model when the suspension pH was adjusted to 5, 2, non-adjusted and 5, respectively.     

Distribution of As, Cd, Pb, and Zn in redox features of mine-waste impacted wetland soils

Purpose

Wetland soils of the Coeur d??Alene (CdA) River Basin of northern Idaho, USA are contaminated with toxic elements released during mining activities. In this paper, we report results from a multi-scale investigation of total As, Cd, Pb, and Zn distributions along a transect of these contaminated soils.

Materials and methods

Four sites along an 80-m transect were established at the Black Rock Slough wetland in CdA River Basin. The elevation difference between the upslope and lowland site was 1.1?m. Soils were sampled from three depths, down to 45?cm. Redoximorphic features were isolated from the soils and categorized into five types of cemented particles, and Fe-enriched and depleted soil masses. Soils and isolated soil separates were analyzed for total elemental concentration.

Results and discussion

Within soil profiles, contaminants are enriched in surface horizons as compared to the original depositional profiles. Enrichment was more dramatic in the upland sites than the lowland sites. Fe-enriched masses that ranged in size from a few millimeters to several centimeters were also enriched in As, Pb, and Zn. At the smallest scale investigated, five different soil aggregate types ranging in size from 1 to 2?mm in diameter had distinct contaminant associations: Fe-cemented aggregates were elevated in As and Zn; Mn-cemented aggregates had more than five times as much Pb as the bulk soil; root channels were elevated in As; and charcoal particles were elevated in all contaminants, particularly Pb and Cd.

Conclusions

Results show that in wetland soils pedogenic processes differentially distribute contaminants amongst the redoximorphic features. The distribution is affected by landscape position and water table influence. At the pedon scale, there is an enrichment of As, Cd, Pb, and Zn in surface horizons, suggesting that upward flux of contaminants is occurring. This contaminant redistribution should be considered in design of management and remediation strategies.     

Retention of Cd, Cu, Pb and Zn by Wood Ash, Lime and Fume Dust

Heavy metals are of interest due to their deleterious impacts on both human and ecosystem health. This study investigated the effectiveness of wood ash in immobilizing the heavy metals Pb, Cd, Cu and Zn from aqueous solutions. The effects of initial metal concentrations, solution pH, ash dose and reaction time on metal sorption, as well as the metal sorption mechanisms were studied. To investigate the effect of initial metal concentrations, solutions containing Cd, Zn (25, 50, 75, 100 or 125 mg L^?1), Cu (25, 50, 75, 100, 125, 150 or 175 mg L^?1) or Pb (250, 500, 750, 1000, 1250, or 1500 mg L^?1) were reacted with 10 g L^?1 ash for two hours. For the effect of pH, solutions containing 100 mg L^?1 of Cd, Cu or Zn or 1500 mg L^?1 of Pb were reacted with 15 g L^?1 ash over a pH range of 4 to 7. The wood ash was effective in immobilizing the four metals with a sorption range of 41–100 %. The amounts of metals retained by the ash followed the order of Pb > Cu > Cd > Zn. As expected, absolute metal retention increased with increasing initial metal concentrations, solution pH and ash dose. Metal retention by the ash exhibited a two-phase step: an initial rapid uptake of the metal followed by a period of relatively slow removal of metal from solution. Metal retention by the ash could be described by the Langmuir and Freundlich isotherms, with the latter providing a better fit for the data. Dissolution of calcite /gypsum minerals and precipitation of metal carbonate/sulfate like minerals were probably responsible for metal immobilization by the ash in addition to adsorption.