The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.     

不同土壤重金属复合污染的有效态离子冲量表征

选择红壤、黄棕壤和潮土为对象，依据中国土壤环境质量二级和三级标准确定土壤重金属铜、锌、镉的污染浓度，通过生物盆裁试验研究在重金属Cu、Zn、Cd复合污染条件下牧草（黑麦草、紫花苜蓿）体内重金属含量和土壤中重金属有效态含量的相关性，结果表明，在3种不同性质的污染土壤上，牧草体内重金属的离子冲量与其对应土壤中重金属有效态的离子冲量之间均存在明显的相关性。校正土壤pH、牧草品种等因素后，土壤有效态离子冲量可以有效表征不同土壤-牧草系统的重金属复合污染。     

Potential use of Caulerpa fastigiata biomass for removal of lead: kinetics, isotherms, thermodynamic, and characterization studies

The present study attempts to analyze the biosorption trend of biosorbent Caulerpa fastigiata (macroalgae) biomass for removal of toxic heavy metal ion Pb (II) from solution as a function of initial metal ion concentration, pH, temperature, sorbent dosage, and biomass particle size. The sorption data fitted with various isotherm models and Freundlich model was the best one with correlation coefficient of 0.999. Kinetic study results revealed that the sorption data on Pb (II) with correlation coefficient of 0.999 can best be represented by pseudo-second-order. The biosorption capacity (q _e ) of Pb (II) is 16.11?±?0.32 mg g^?1 on C. fastigiata biomass. Thermodynamic studies showed that the process is exothermic (ΔH° negative). Free energy change (ΔG°) with negative sign reflected the feasibility and spontaneous nature of the process. The SEM studies showed Pb (II) biosorption on selective grains of the biosorbent. The FTIR spectra indicated bands corresponding to –OH, COO^?, –CH, C?=?C, C?=?S, and –C–C– groups were involved in the biosorption process. The XRD pattern of the C. fastigiata was found to be mostly amorphous in nature.     

Biosorption of Cr(VI) and Zn(II) ions from aqueous solution onto the solid biodiesel waste residue: mechanistic, kinetic and thermodynamic studies

In this present study, the biosorption of Cr(VI) and Zn(II) ions from synthetic aqueous solution on defatted J atropha oil cake (DJOC) was investigated. The effect of various process parameters such as the initial pH, adsorbent dosage, initial metal ion concentration and contact time has been studied in batch-stirred experiments. Maximum removal of Cr(VI) and Zn(II) ions in aqueous solution was observed at pH 2.0 and pH. 5.0, respectively. The removal efficiency of Cr(VI) and Zn(II) ions from the aqueous solution was found to be 72.56 and 79.81 %, respectively, for initial metal ion concentration of 500 mg/L at 6 g/L dosage concentration. The biosorbent was characterized by Fourier transform infrared, scanning electron microscopy and zero point charge. Equilibrium data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models and the best fit is found to be with the Freundlich isotherm for both Cr(VI) and Zn(II) metal ions. The kinetic data obtained at different metal ion concentration have been analysed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion models and were found to follow the pseudo-second-order kinetic model. The values of mass transfer diffusion coefficients (D _e) were determined by Boyd model and compared with literature values. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were analysed using the equilibrium constant values (K _e) obtained from experimental data at different temperatures. The results showed that biosorption of Cr(VI) and Zn(II) ions onto the DJOC system is more spontaneous and exothermic in nature. The results indicate that DJOC was shown to be a promising adsorbent for the removal of Cr(VI) and Zn(II) ions from aqueous solution.     

A review of toxicity and mechanisms of individual and mixtures of heavy metals in the environment

The rational for the study was to review the literature on the toxicity and corresponding mechanisms associated with lead (Pb), mercury (Hg), cadmium (Cd), and arsenic (As), individually and as mixtures, in the environment. Heavy metals are ubiquitous and generally persist in the environment, enabling them to biomagnify in the food chain. Living systems most often interact with a cocktail of heavy metals in the environment. Heavy metal exposure to biological systems may lead to oxidation stress which may induce DNA damage, protein modification, lipid peroxidation, and others. In this review, the major mechanism associated with toxicities of individual metals was the generation of reactive oxygen species (ROS). Additionally, toxicities were expressed through depletion of glutathione and bonding to sulfhydryl groups of proteins. Interestingly, a metal like Pb becomes toxic to organisms through the depletion of antioxidants while Cd indirectly generates ROS by its ability to replace iron and copper. ROS generated through exposure to arsenic were associated with many modes of action, and heavy metal mixtures were found to have varied effects on organisms. Many models based on concentration addition (CA) and independent action (IA) have been introduced to help predict toxicities and mechanisms associated with metal mixtures. An integrated model which combines CA and IA was further proposed for evaluating toxicities of non-interactive mixtures. In cases where there are molecular interactions, the toxicogenomic approach was used to predict toxicities. The high-throughput toxicogenomics combines studies in genetics, genome-scale expression, cell and tissue expression, metabolite profiling, and bioinformatics.     

Spatial and temporal organic and heavy metal pollution at Mai Po Marshes Nature Reserve,Hong Kong

An intensive monthly sampling of water and sediments from 12 sites over 8 months covering wet and dry seasons at Mai Po Marshes Nature Reserve was conducted during June 1997-February 1998. Major organic (C, N and P) and heavy metal pollutants (Cd, Cr, Cu, Ni, Pb, Zn) water and sediment samples were examined. The results showed that Mai Po Marshes were severely polluted by organic matter and heavy metals, and the water from Deep Bay appeared to be the source of pollution. Up to 13-55% chance that the sediments of Mai Po Marshes were classified as moderately to seriously metal contaminated materials, according to the guideline set by Hong Kong Government. Empirical models describing organic matter and heavy metal spatial and seasonal dynamics in the water and sediments were formulated, based on data analysis. During wet season (June-October), more than 58% variations of total P can be explained by ortho-P in water, while ammonia-N explained up to 90% variations of total Kjeldahl nitrogen in water. Throughout the whole sampling period (June-February), there were significant correlations (p<0.01) between total organic C in water. pH in the sediments and salinity in water appeared to be important factors determining heavy metal mobility in sediments, while potential metal release from the sediments is a concern when any oxidizing processes such as flooding or dredging are imposed on sediments.     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

Sulfidation treatment of molten incineration fly ashes with Na2S for zinc, lead and copper resource recovery

The present study focuses on the conversion of heavy metals involved in molten incineration fly ashes to metal sulfides which could be thereafter separated by flotation. The sulfidation treatment was carried out for five molten incineration fly ashes (Fly ash-A to Fly ash-E) by contacting each fly ash with Na(2)S solution for a period of 10 min to 6h. The initial molar ratio of S(2-) to Me(2+) was adjusted to 1.20. The conversion of heavy metals to metal sulfides was evaluated by measuring the S(2-) residual concentrations using an ion selective electrode. The formation of metal sulfides was studied by XRD and SEM-EDS analyses. In the case of Fly ash-A to Fly ash-D, more than 79% of heavy metals of zinc, lead and copper was converted to metal sulfides within the contacting period of 0.5h owing to a fast conversion of metal chlorides to metal sulfides. By contrast, the conversion of about 35% was achieved for Fly ash-E within the same contacting period, which was attributed to a high content of metal oxides. Further, the S(2-) to Me(2+) molar ratio was reduced to 1.00 to minimize Na(2)S consumption and the conversions obtained within the contacting period of 0.5h varied from 76% for Fly ash-D to 91% for Fly ash-C. Finally, soluble salts such as NaCl and KCl were removed during the sulfidation treatment, which brought about a significant enrichment in metals content by a factor varying from 1.5 for Fly ash-D to 4.9 for Fly ash-A.     

Ecophysiological and seasonal variations in Cd, Pb, Zn, and Ni concentrations in the leaves of urban deciduous trees in Istanbul

The concentrations of Cd, Pb, Zn and Ni were measured in the leaves of 7 species of deciduous trees, from the urban sites of Istanbul, in both the Spring and Autumn seasons. We detected some differences in the heavy metal concentrations of the control and urban site samples of identical species. Highest concentrations of Cd were detected in Populus, Pb in Aesculus and Robinia, Zn in Populus, and Ni in Robinia and Fraxinus. Lowest chlorophyll content and highest peroxidase (POD) activity was found in the urban site samples of Acer. We have found a positive correlation between the increase in the POD activity and the Pb concentration in Populus. Generally, the tree species investigated in this study, are considered to have different tolerance levels to heavy metal pollution. The data obtained show that the chlorophyll content and the POD activity may be used as heavy metal stress biomarkers in the urban trees.     

污泥中重金属的去除及回收试验

论述了利用离子交换技术循环使用柠檬酸去除污泥中重金属,并置换回收重金属的适宜工艺条件.经柠檬酸处理后,污泥中90%以上的重金属被去除;柠檬酸处理液中的重金属用离子交换法回收,考察了树脂种类、流速、操作方式等因素对离子交换、再生效果的影响;在适宜工艺条件下,重金属的交换率均为100%,而洗脱率均接近90%;柠檬酸及离子交换树脂循环使用,重金属也得到回收,降低了处理成本.     

Soluble and insoluble fractions of heavy metals in wet and dry atmospheric depositions in Bologna,Italy

Atmospheric depositions were collected monthly using a modified wet and dry sampler (dry deposition was collected on a water surface) located in Bologna, a northern Italian urban area, to evaluate the impact of airborne heavy metals on the local pollution load. Wet deposition samples were filtered and heavy metal contents in soluble and insoluble fractions were determined. The same procedure was applied to the water samples which collected dry deposition. The entire procedure was tested using a certified reference material (CRM), which provided satisfying recovery results. The percentage of heavy metal soluble fraction in dry deposition was generally lower than in wet one; Cd, V, Cu and Zn showed a higher average solubility than Cr, Ni and Pb both in wet and dry deposition. Factor analysis, after a varimax rotation of principal components, suggested possible anthropogenic sources which explain different metal deposition patterns. This data analysis also allowed to distinguish different clusters formed by monthly fluxes of heavy metals.     

Evaluation of the effectiveness of phosphate treatment for the remediation of mine waste soils contaminated with Cd, Cu, Pb, and Zn

The effectiveness of phosphate treatment for Cd, Cu, Pb, and Zn immobilization in mine waste soils was examined using batch conditions. Application of synthetic hydroxyapatite (HA) and natural phosphate rock (FAP) effectively reduced the heavy metal water solubility generally by about 84-99%. The results showed that HA was slightly superior to FAP for immobilizing heavy metals. The possible mechanisms for heavy metal immobilization in the soil involve both surface complexation of the metal ions on the phosphate grains and partial dissolution of the phosphate amendments and precipitation of heavy metal-containing phosphates. HA and FAP could significantly reduce Cd, Cu, Pb, and Zn availability in terms of water solubility in contaminated soils while minimizing soil acidification and potential risk of eutrophication associated with the application of highly soluble phosphate sources.     

Accumulation of nutrients and heavy metals in Phragmites australis (Cav.) Trin. ex Steudel and Bolboschoenus maritimus (L.) Palla in a constructed wetland of the Venice lagoon watershed

A recently constructed wetland, located in the Venice lagoon watershed, was monitored to investigate growth dynamics, nutrient and heavy metal shoot accumulation of the two dominating macrophytes: Phragmites australis and Bolboschoenus maritimus. Investigations were conducted over a vegetative season at three locations with different distance to the inlet point to assess effects on vegetation. The distance from the inlet did not affect either shoot biomass or nutrients (N, P, K and Na) and heavy metals (Cr, Ni, Cu and Zn) shoot content. With the exception of Na, nutrient and heavy metal concentrations were higher in shoots of P. australis than in B. maritimus. Heavy metal concentration in the incoming water and in the soil was not correlated to the plant content of either species. Shoot heavy metal concentrations were similar to those reported in the current literature, but accumulation generally increased towards the end of the growing season.     

Heavy metals in urban soils of East St. Louis, IL. Part II: Leaching characteristics and modeling

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.     

pH对电解处理垃圾渗滤液的影响

在不同的pH值条件下对氯离子和重金属离子含量不同的渗滤液和邻硝基苯酚人工模拟废水进行了电解处理,着重考察了不同pH值条件下氯离子浓度和重金属离子种类对有机物电解去除效果的影响。结果表明,电解处理过程中, pH值对有机物电解去除效果的影响与渗滤液的水质有关,尤其与渗滤液中氯离子和重金属离子浓度以及重金属离子种类有关。在pH＝2的条件下电解处理氯离子和重金属离子含量均很低的渗滤液,有利于有机物的氧化去除;在pH=9的条件下电解处理氯离子和重金属离子浓度均较高的渗滤液,其COD的电解去除效果最好;在pH=2或pH=12的条件下电解处理氯离子浓度高而重金属离子浓度低的渗滤液,能促进有机物的氧化分解。在一定浓度范围内,渗滤液中无机变价离子的组成不同,电解处理垃圾渗滤液的最佳pH值也不同。     

The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants

The experiments were done to investigate the effect of soil pH and organic matter content on EDTA-extractable heavy metal contents in soils and heavy metal concentrations in rice straw and grains. EDTA-extractable Cr contents in soils and concentrations in rice tissues were negatively correlated with soil pH, but positively correlated with organic matter content. The combination of soil pH and organic matter content would produce the more precise regression models for estimation of EDTA-Cu, Pb and Zn contents in soils, demonstrating the distinct effect of the two factors on the availability of these heavy metals in soils. Soil pH greatly affected heavy metal concentrations in rice plants. Furthermore, inclusion of other soil properties in the stepwise regression analysis improved the regression models for predicting straw Fe and grain Zn concentrations, indicating that other soil properties should be taken into consideration for precise predicting of heavy metal concentrations in rice plants.     

Heavy Metals in Urban Soils of East St. Louis,IL Part II: Leaching Characteristics and Modeling

ABSTRACT

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.     

Seasonal variation of heavy metals in ambient air and precipitation at a single site in Washington, DC

Atmospheric samples of precipitation and ambient air were collected at a single site in Washington, DC, for 7 months (for ambient air samples) and 1 year (for wet deposition samples) and analyzed for arsenic, cadmium, chromium and lead. The ranges of heavy metal concentrations for 6-day wet deposition samples collected over the 1-year period were 0.20-1.3 microg/l, 0.060-5.1 microg/l, 0.062-4.6 microg/l and 0.11-3.2 microg/l for arsenic, cadmium, chromium and lead, respectively, with a precision better than 5% for more than 95% of the measurements. The ranges of heavy metal concentrations for the 6-day ambient air samples were 0.800-15.7 ng/m(3), 1.50-30.0 ng/m(3), 16.8-112 ng/m(3), and 2.90-137 ng/m(3) for arsenic, cadmium, chromium and lead, respectively, with a precision better than 10%. The spread in the heavy metal concentration over the observation period suggests a high seasonal variability for heavy metal content in both ambient air and wet deposition samples.     

Heavy metal concentrations in Mullus barbatus and Pagellus erythrinus in relation to body size,gender, and seasonality

Marine environments have been subjected to an increase in heavy metal pollution. Investigations were conducted in the bioaccumulation of heavy metals for both a benthic (Mullus barbatus) and a benthopelagic fish species (Pagellus erythrinus). The aim of this study was to examine the concentration levels of four metals in the body tissue of two fish species, in Pagasitikos Gulf in Greece, and to determine if metal concentration levels were affected by season, size, and species. Fish samples were collected monthly from September 2009 to August 2010. Chromium (Cr), Copper (Cu), Zinc (Zn), and Cadmium (Cd) concentrations were measured in muscle, gills, vertebral column, and in the “remaining fish sample.” Statistical analysis pinpointed substantial differences in metal concentration levels between some size classes. Significant differences were observed between two fish species’ tissues concerning Cu, Zn, and Cd concentrations. Cu and Zn concentrations varied amongst red mullet tissues as did Zn and Cd concentrations in common pandora. Ample variations were found seasonally in metal concentration levels; however, nonsignificant statistical differences were found among sexes.