Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof. (C) 2005 Elsevier Ltd. All rights reserved.

Comparison of EDTA and EDDS as potential soil amendments for enhanced phytoextraction of heavy metals

Phytoextraction has been proposed as an alternative remediation technology for soils polluted with heavy metals or radionuclides, but is generally conceived as too slow working. Enhancing the accumulation of trace pollutants in harvestable plant tissues is a prerequisite for the technology to be practically applicable. The chelating aminopolycarboxylic acid, ethylene diamine tetraacetate (EDTA), has been found to enhance shoot accumulation of heavy metals. However, the use of EDTA in phytoextraction may not be suitable due to its high environmental persistence, which may lead to groundwater contamination. This paper aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposes. A laboratory experiment was conducted to examine mobilisation of Cd, Cu, Cr, Ni, Pb and Zn into the soil solution upon application of EDTA or EDDS. The longevity of the induced mobilisation was monitored for a period of 40 days after application. Estimated effect half lives ranged between 3.8 and 7.5 days for EDDS, depending on the applied dose. The minimum observed effect half life of EDTA was 36 days, while for the highest applied dose no decrease was observed throughout the 40 day period of the mobilisation experiment. Performance of EDTA and EDDS for phytoextraction was evaluated by application to Helianthus annuus. Two other potential chelators, known for their biodegradability in comparison to EDTA, were tested in the plant experiment: nitrilo acetic acid (NTA) and citric acid. Uptake of heavy metals was higher in EDDS-treated pots than in EDTA-treated pots. The effects were still considered insufficiently high to consider efficient remediation. This may be partly due to the choice of timing for application of the soil amendment. Fixing the time of application at an earlier point before harvest may yield better results. NTA and citric acid induced no significant effects on heavy metal uptake. (C) 2004 Elsevier Ltd. All rights reserved.

An inventory of heavy metals inputs to agricultural soils in England and Wales

An inventory of heavy metal inputs (Zn, Cu, Ni, Pb, Cd, Cr, As and Hg) to agricultural soils in England and Wales in 2000 is presented, accounting for major sources including atmospheric deposition, sewage sludge, livestock manures, inorganic fertilisers and lime, agrochemicals, irrigation water, industrial by-product 'wastes' and composts. Across the whole agricultural land area, atmospheric deposition was the main source of most metals, ranging from 25 to 85% of total inputs. Livestock manures and sewage sludge were also important sources, responsible for an estimated 37-40 and 8-17% of total Zn and Cu inputs, respectively. However, at the individual field scale sewage sludge, livestock manures and industrial wastes could be the major source of many metals where these materials are applied. This work will assist in developing strategies for reducing heavy metal inputs to agricultural land and effectively targeting policies to protect soils from long-term heavy metal accumulation. (C) 2003 Elsevier Science B.V. All rights reserved.

Mesoporous concentric magnetic FePt core-shells nanoparticle with functionalized surfaces for capturing metal ions and DNA molecules

It is demonstrated that monodisperse magnetic FePt nanoparticle can be engineered into a protective dense silica layer, followed by concentric outer mesoporous silica layers with tailored -SH, -SO3H and -NH2 surface groups, these new materials can be used to capture heavy metal ions and DNA molecules from solution specifically by their internal or/and external functionalised surfaces by magnetic means.

Mesoporous concentric magnetic FePt core-shells nanoparticle with functionalized surfaces for capturing metal ions and DNA molecules

It is demonstrated that monodisperse magnetic FePt nanoparticle can be engineered into a protective dense silica layer, followed by concentric outer mesoporous silica layers with tailored -SH, -SO3H and -NH2 surface groups, these new materials can be used to capture heavy metal ions and DNA molecules from solution specifically by their internal or/and external functionalised surfaces by magnetic means.

Ultrasensitive SERS nanoprobes for hazardous metal ions based on trimercaptotriazine-modified gold nanoparticles

Trimercaptotriazine-modified gold nanoparticles exhibit strong SERS effects,(1) yielding vibrational profiles very sensitive to the presence of heavy metal ions. Because of the contrasting response observed for selected vibrational bands in the SERS profiles, they provide useful nanoprobes for Hg2+ and Cd2+ ions, allowing direct quantitative assays by employing relative peak intensity ratios instead of using internal standards.

Automated two-dimensional separation flow system with electrochemical preconcentration, stripping, capillary electrophoresis and contactless conductivity detection for trace metal ion analysis

This paper describes the automation of a fully electrochemical system for preconcentration, cleanup, separation and detection, comprising the hyphenation of a thin layer electrochemical flow cell with CE coupled with contactless conductivity detection (CE-C(4)D). Traces of heavy metal ions were extracted from the pulsed-flowing sample and accumulated on a glassy carbon working electrode by electroreduction for some minutes. Anodic stripping of the accumulated metals was synchronized with hydrodynamic injection into the capillary. The effect of the angle of the slant polished tip of the CE capillary and its orientation against the working electrode in the electrochemical preconcentration (EPC) flow cell and of the accumulation time were studied, aiming at maximum CE-C(4)D signal enhancement. After 6 min of EPC, enhancement factors close to 50 times were obtained for thallium, lead, cadmium and copper ions, and about 16 for zinc ions. Limits of detection below 25 nmol/L were estimated for all target analytes but zinc. A second separation dimension was added to the CE separation capabilities by staircase scanning of the potentiostatic deposition and/or stripping potentials of metal ions, as implemented with the EPC-CE-C(4)D flow system. A matrix exchange between the deposition and stripping steps, highly valuable for sample cleanup, can be straightforwardly programmed with the multi-pumping flow management system. The automated simultaneous determination of the traces of five accumulable heavy metals together with four non-accumulated alkaline and alkaline earth metals in a single run was demonstrated, to highlight the potentiality of the system.

Study on soluble heavy metals with preconcentration by using a new modified oligosilsesquioxane sorbent

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Heavy metals in a degraded soil treated with sludge from water treatment plant

A aplicação do lodo de estação de tratamento de água (LETA) em solos degradados é uma alternativa tanto para disposição desse resíduo como para a recuperação do solo. Neste trabalho avaliaram-se os efeitos do LETA nos teores de metais pesados em um Latossolo degradado por mineração de cassiterita na Floresta Nacional do Jamari, RO, Brasil. Utilizou-se delineamento experimental inteiramente casualizado com cinco tratamentos: testemunha (n = 4); testemunha química, que recebeu apenas calagem (n = 4) e doses D100, D150 e D200 (respectivamente 100, 150 e 200 mg de N kg-1 solo na forma de LETA), aplicadas antes da calagem (n = 20). Após 30 dias da calagem, período em que o solo contido nos vasos foi mantido com teor de umidade próximo à capacidade de retenção, coletaram-se amostras de solo, que foram analisadas com relação aos teores totais e extraíveis de Fe, Cu, Mn, Zn, Cd, Pb, Ni e Cr. A aplicação de LETA aumentou os teores dos metais pesados do solo. A aplicação deste tipo de lodo em áreas degradadas pode causar impacto ambiental e, portanto, deve ser monitorada.

Tolerance to copper and zinc of Acidithiobacillus thiooxidans isolated from sewage sludge

The effect of copper and zinc ions on sulphur oxidation by Acidithiobacillus thiooxidans, strain SFR01, isolated from anaerobic sewage sludge was assessed, resulting in tolerance levels up to 20 and 200 mmol l(-1) for copper and zinc, respectively. The tolerance levels obtained were higher than the concentration of copper and zinc usually found in the collected sewage sludge. The tolerance levels obtained indicate no constraints for sludge bioleaching of those metals due to their toxicities to the indigenous A. thiooxidans.

Aquatic humus from an unpolluted Brazilian dark-brown stream: general characterization and size fractionation of bound heavy metals

The main pool of dissolved organic carbon in tropical aquatic environments, notably in dark-coloured streams, is concentrated in humic substances (HS). Aquatic HS are large organic molecules formed by micro-biotic degradation of biopolymers and polymerization of smaller organic molecules. From an environmental point of view, the study of metal-humic interactions is often aimed at predicting the effect of aquatic HS on the bioavailability of heavy metal ions in the environment. In the present work the aquatic humic substances (HS) isolated from a dark-brown stream (located in an environmental protection area near Cubatao city in São Paulo-State, Brazil) by means of the collector XAD-8 were investigated. FTIR studies showed that the carboxylic carbons are probably the most important binding sites for Hg(II) ions within humic molecules. C-13-NMR and H-1-NMR studies of aquatic HS showed the presence of constituents with a high degree of aromaticity (40% of carbons) and small substitution. A special five-stage tangential-flow ultrafiltration device (UF) was used for size fractionation of the aquatic HS under study and for their metal species in the molecular size range 1-100 kDa (six fractions). The fractionation patterns showed that metal traces remaining in aquatic HS after their XAD-8 isolation have different distributions. Generally, the major percentage of traces of Mn, Cd and Ni (determined by ICP-AES) was preferably complexed by molecules with relatively high molecular size. Cu was bound by fractions with low molecular size and Co showed no preferential binding site in the various humic fractions. Moreover, the species formed between aquatic HS and Hg(II), prepared by spiking (determined by CVAAS), appeared to be concentrated in the relatively high molecular size fraction F-1 (> 100 kDa).

2-Mercaptobenzothiazole clay as matrix for sorption and preconcentration of some heavy metals from aqueous solution

2-Mercaptobenzothiazole loaded on previously polystyrene treated clay was prepared, characterized and used for sorption and preconcentration of Hg(II) Pb(II), Zn(II) and Cd(II) from an aqueous solution. The support used was a natural clay previously treated with sulphuric acid solution. Adsorptiou isotherms of metal ions from aqueous solutions as function of pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The chemically treated clay was very selective to Hg(II) in solution in which Zn(II), Cd(II), Pb(II) and some transition metal ions were also present.

Non-nutrient heavy metals in tomato plants cultivated in soil amended with biosolid and sugar-cane bagasse compost

In this study, non-nutrient heavy metal concentrations (Cd, Cr, Ni and Pb) were measured in composts during the composting process, in compost/Red-yellow Latosol mixtures, and in tomato plants. Composts were produced using sugar-cane bagasse, biosolids and cattle manure in the proportions 75-0-25, 75-12.5-12.5, 75-25-0, 50-50-0 or 0-100-0 (composts with 0, 12.5, 25, 50 and 100% biosolids). The composts were applied to the soil, in 6 treatments and a control (mineral fertilization). Control and the 0% biosolids treatments received inorganic nitrogen and all the treatments received the same amount of N, P and K. Tomato plants were cultivated in 24-L pots, in a green house in Jaboticabal, SP, Brazil. The experiment had a split plot design, in randomized blocks. Cadmium, Cr, Ni and Pb concentrations were determined during the composting process (7, 27, 57, 97 and 127 days after compost mounting), in soil (0 and 164 days after mixing) and plants. The samples were subjected to digestion with HNO 3, H2O2 and HCl and the metals were determined by AAS. Negative correlations were observed between Cd, Cr and Pb in the compost and Cd, Cr and Pb plant uptake, as well as Ni in the compost and Ni concentration in the plants. The concentrations of Cd, Cr, Ni and Pb increased during composting. Only Cd levels increased when compost was applied to the soil. The roots accumulated Cr, Ni and Pb, the stems and leaves, Cd and Ni and the fruits did not accumulate any of the metals studied. The composts with biosolids did not increase Cd, Cr, Ni and Pb uptake by plants.

Preparation of a silica gel modified with 2-amino-1,3,4-thiadiazole for adsorption of metal ions and electroanalytical application

Silica gel with a specific area of 382 m2 g-1 and an average pore diameter of 60 Å was chemically modified with 2-amino-1,3,4-thiadiazole, for the purpose of selective adsorption of heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). The following properties of this functionalized silica gel are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II). The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination. ©2006 Sociedade Brasileira de Química.

Heavy metals availability and fractions in soil amended with biosolid composts

The heavy metals when linked to organic matter have a behavior in the soil that is still little known. This study aimed to evaluate the effect of sewage-sludge-based composts when incorporated in the soil, in relation to heavy metals availability. Five composts were incorporated using sugar-cane bagasse, sewage sludge and cattle manure in the respective proportions: 75-0-25, 75-12.5-12.5, 75-25-0, 50-50-0 and 0-100-0 (composts with 0, 12.5, 25, 50 and 100% sewage sludge). The experiment consisted of 6 treatments (5 composts and a control with mineral fertilization) in randomized blocks with a split-plot design. The control and the treatment of 0% sewage sludge received inorganic nitrogen (N). All the treatments received the same amount of N (8.33 g) K (5.80 g) and K (8.11 g) per pot. Tomato plants were cultivated in 24.0 L pots in a greenhouse in Jaboticabal, SP, Brazil. The concentrations of heavy metals were determined in the soil samples at day 0 after compost incorporation. The higher the sewage sludge doses, the higher heavy metal contents in the soil. Among extractants, Melhlich-1 extracted the highest amount of heavy metals, while DTPA extracted the lowest one. The residual fraction presented the highest heavy metal content, followed by Fe oxides crystalline and amorphous to Cu, Cr and Mn, and Mn oxides, and Fe amorphous to Zn, indicating strong associations to oxides and clays. There were significant positive correlations between Mn contents in the plant and Mn linked to Fe oxide amorphous and crystalline.