Biomedical subjects

Rainer Schulin

Publications and source records attributed to Rainer Schulin.

16 recordsLinked to original sources

PubMed2006

Growth of Lygeum spartum in acid mine tailings: response of plants developed from seedlings, rhizomes and at field conditions.

Lygeum spartum is a native species in semiarid Mediterranean areas that grows spontaneously on acid mine tailings. We aimed to study the suitability of this plant for phytostabilization. L. spartum was grown from both seeds and rhizomes in acid mine tailings with various fertilizer and lime treatments. Untreated soils had a solution pH of 2.9 with high concentrations of dissolved salts (Electrical Conductivity 25 dS m(-1)) and Zn (3100 mg L(-1)). Plants grown on untreated soil had high shoot metal concentrations (>4000 mg kg(-1)Zn). Liming increased the solution pH to 5.5 and reduced the dissolved salts by more than 75%, resulting in lower shoot metal accumulation. Plants grown from rhizomes accumulated less metal than those grown from seeds. Plants collected in the field had metal concentrations an order of magnitude less than plants raised in the growth chamber. These differences may be due to the higher moisture content and homogeneous nature of the soils used in the pot experiment.

Anions↗

PubMed2006

Critical assessment of chelant-enhanced metal phytoextraction.

Chelant-enhanced phytoextraction has received a lot of attention in the past decade. In theory, this technique could cleanse metal polluted soils by solubilizing contaminating metals, allowing them to be taken up by plants that would subsequently be removed from the site. We review the processes of metal solubilization, uptake by plants, and leaching during chelant-enhanced phytoextraction. A large excess of chelant is required to solubilize the target metal due to the co-solubilization of Ca and Fe. Chelated metals are taken up via the apoplastic pathway. Disruption of the Casparian Band is required to achieve the high shoot concentrations needed for phytoextraction. Therefore, adding chelants to a soil increases not only the total dissolved metal concentration but also changes the primary route of plant metal-uptake from the symplastic to the apoplastic pathway. Depending on metal, plant species, and chelant concentration, significant increases in metal uptake are likely. Soil solution chelate concentrations of at least several mM are required to induce appreciable shoot concentrations. A simple calculation reveals that at such soil solution concentrations plants will remove only a small fraction of the solubilized metals. Leaching, exacerbated by preferential flow processes, is unavoidable. Chelant-enhanced phytoextraction is therefore limited to areas where the connection with groundwater has been broken, orwhere leaching is unimportant. Chelant-enhanced phytoextraction may nonetheless have a role in enhancing the uptake of essential trace metals. Such a role warrants further investigations into the use of biodegradable chelants such as ethylenediaminedisuccinic acid (EDDS).

Chelating Agents↗

PubMed2006

In situ transformations of fine lead oxide particles in different soils.

We present a field application of a new in situ technique to analyze phase transformations of fine lead oxide particles (50-100mum) in different soils directly in the field over 18 months. After the first month of exposure to a calcareous sand we found newly precipitated secondary mineral phases on the lead oxide. The samples exposed to two loamy soils (Dystric Cambisol and Luvisol) showed only very few traces of new phases. We identified the new phases as mainly lead-hydroxy carbonates (hydrocerussite). Whereas the results confirm the transformation of lead phases to lead carbonates in calcareous soil, they also show that an easily soluble phase such as PbO may persist in soils virtually unweathered for more than one year. The formation of a weathering crust is therefore not necessarily needed for preservation of easily soluble phases. The use of experimental in situ methods is thus giving new information on contaminant mineral behavior under field conditions.

Carbonates↗

PubMed2006

Uptake of metals during chelant-assisted phytoextraction with EDDS related to the solubilized metal concentration.

The use of chelants to enhance phytoextraction is one method being tested to make phytoextraction efficient enough to be used as a remediation technique for heavy metal pollution in the field. We performed pot experiments with sunflowers in order to investigate the use of the biodegradable chelating agent SS-EDDS for this purpose. We used singly and combined contaminated soils (Cu, Zn) and multimetal contaminated field soils (Cu, Zn, Cd, Pb). EDDS (10 mmol kg(-10 soil) increased soil solution metals greatly for Cu (factor 840-4260) and Pb (factor 100-315), and to a lesser extent for Zn (factor 23-50). It was found that Zn (when present as the sole metal), Cu, and Pb uptake by sunflowers was increased by EDDS, butin multimetal contaminated soil Zn and Cd were not. EDDS was observed in the sunflower roots and shoots at concentrations equal to metal uptake. The different metal uptake in the various soils can be related to a linear relationship between Cu and Zn in soil solution in the presence of EDDS and plant uptake, indicating the great importance of measuring and reporting soil solution metal concentrations in phytoextraction studies.

Biodegradation, Environmental↗

PubMed2006

Effects of metal-contaminated soil on the performance of young trees growing in model ecosystems under field conditions.

Young Populus tremula, Salix viminalis, Betula pendula and Picea abies trees were grown together in large open-top chambers. The treatments were: without or with (Cu/Zn/Cd/Pb=640/3000/10/90 mg kg-1) metal contamination in the topsoil, irrigation pH 3.5 or 5.5, and acidic or calcareous subsoil. Growth, metal allocation to foliage and wood, as well as leaf gas exchange were measured. Biomass was reduced in P. tremula and B. pendula by the metal-contaminated topsoil relative to uncontaminated topsoil, whereas in P. tremula photosynthesis and transpiration were decreased. These effects were related to the elevated foliar Zn accumulation in P. tremula. S. viminalis showed a significant reduction in growth and an increased Zn and Cd accumulation on acidic vs. calcareous subsoil. Acidic irrigation produced only a few significant effects. P. abies showed the lowest metal uptake and no growth response to metal contamination.

Betula↗

PubMed2006

Bacterial community structure and activity in different Cd-treated forest soils.

In this study we compared indicators of Cd bioavailability (water extracts, Lakanen extracts, free ions) and ecotoxicity in forest soils with contrasting physico-chemical characteristics. Soil samples were treated with CdCl(2) solutions (0, 0.1, 1, 10 and 100 mM) and incubated for 30 days. Microbial activity indexes (acid phosphatase, beta-glucosidase, basal respiration) and changes in bacterial community structure using terminal restriction fragment length polymorphism (T-RFLP) fingerprinting were investigated. The Cd concentrations measured ranged from 1% to 37% of the total additions in water extracts, to higher levels in Lakanen extracts. Effects of Cd were observed at bioavailable concentrations exceeding United Nations/European Economic Commission UN/ECE guidelines for total Cd in the soil solution. Basal respiration was the most affected index, while enzymatic activities showed variable responses to the Cd treatments. We also noticed that soils with pH higher than 6.7 and clay content higher than 50% showed inhibition of basal respiration but no marked shift in bacterial community structure. Soils with lower pH (pH <5.8) with less clay content (<50%) showed in addition strong changes in the bacterial community structure. Our results provide evidence for the importance of relating the effects of Cd on the soil communities to soil properties and to bioavailability.

Acid Phosphatase↗

PubMed2005

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing.

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.

Chelating Agents↗

PubMed2005

Evaluation of immobilized metal-ion affinity chromatography for the fractionation of natural Cu complexing ligands.

An immobilized metal-ion affinity chromatography (IMAC) method has been developed and validated for the separation of copper complexing ligands from soil solution. We first investigated the retention behavior of simple model ligands on the IMAC column and found that the ability to form ternary complexes of the structure Cu-IDA-ligand was the dominant factor influencing ligand retention on the IMAC column. The logK value of the Cu-complex was found to have only a minor influence on the retention. Legends containing only carboxylic acid functional groups were not retained on the column. To optimize reproducibility and quantitative recovery of copper ligands from soil solution, different composition and pH values of eluting buffer were tested. Soil solution chromatograms exhibited one non-retained fraction and two retained fractions. The elution times of the retained fractions were characteristic of peptides and proteins (first peak) and for compounds containing aromatic amines (second peak). The results show that IMAC is an effective tool for the fractionation of copper complexing ligands that are capable of forming ternary complexes.

2,2'-Dipyridyl↗

PubMed2005

Column extraction of heavy metals from soils using the biodegradable chelating agent EDDS.

A possible remediation strategy for metal polluted soils is washing with chelants. Here, we compare the efficiency of batch and column extraction of Cu, Zn, and Pb from three soils using the biodegradable chelant EDDS. A total of 53-80% of Cu was extracted in batch and 18-26% in column extraction. For Zn, the extractability was 16-50% in batch and 20-64% in columns and for Pb 25-52 and 18-91%, respectively. Column leaching was therefore equally or better suited for Zn and Pb removal. The longer extraction time in the column resulted in more formations of Fe(III)EDDS by slow dissolution of iron oxides. Zn was uniformly washed from the column, while Cu and Pb were extracted in the top layers and deposited in the bottom layers, presumably by biodegradation of the metal-EDDS complexes and slow dissolution of iron oxides. Between 18 and 42% of the applied EDDS was lost through biodegradation after 7 weeks. In short time experiments, only 6% of EDDS was degraded. Using EDDS concentrations in excess of available heavy metals caused pronounced leaching of organic matter and clogging of the column. Our results prove that heap leaching using EDDS is a promising approach to reduce the heavy metal content of polluted soils.

Biodegradation, Environmental↗

PubMed2005

The influence of EDDS on the uptake of heavy metals in hydroponically grown sunflowers.

Phytoextraction is an environmentally friendly in situ technique for cleaning up metal contaminated land. Unfortunately, efficient metal uptake by remediation plants is often limited by low phytoavailability of the targeted metals. Chelant assisted phytoextraction has been proposed to improve the efficiency of phytoextraction. Phytoremediation involves several subsequent steps: transfer of metals from the bulk soil to the root surfaces, uptake into the roots and translocation to the shoots. Nutrient solution experiments address the latter two steps. In this context we investigated the influence of the biodegradable chelating agent SS-EDDS on uptake of essential (Cu and Zn) and non-essential (Pb) metals by sunflowers from nutrient solution. EDDS was detected in shoots and xylem sap for the first time, proving that it is taken up into the above ground biomass of plants. The essential metals Cu and Zn were decreased in shoots in the presence of EDDS whereas uptake of the non-essential Pb was enhanced. We suggest that in the presence of EDDS all three metals were taken up by the non-selective apoplastic pathway as the EDDS complexes, whereas in the absence of EDDS essential metal uptake was primarily selective along the symplastic pathway. This shows that synthetic chelating agents do not necessarily increase uptake of heavy metals, when soluble concentrations are equal in the presence and absence of chelates.

Biodegradation, Environmental↗

PubMed2005

Removal of heavy metals from mine waters by natural zeolites.

In this study, we investigated the removal of Fe, Pb, Cd, and Zn from synthetic mine waters by a natural zeolite. The emphasis was given to the zeolite's behavior toward a few cations in competition with each other. Pb was removed efficiently from neutral as well as from acidic solutions, whereas the uptake of Zn and Cd decreased with low pH and high iron concentrations. With increasing Ca concentrations in solution, elimination of Zn and Cd became poorer while removal of Pb remained virtually unchanged. The zeolite was stable in acidic solutions. Disintegration was only observed below pH 2.0. Forward- and back-titration of synthetic acidic mine water were carried out in the presence and absence of zeolite to simulate the effects of a pH increase by addition of neutralizing agents and a re-acidification which can be caused by subsequent mixing with acidic water. The pH increase during neutralization causes precipitation of hydrous ferric oxides and decreased dissolved metal concentrations. Zeolite addition further diminished Pb concentrations but did not have an effect on Zn and Cd concentrations in solution. During re-acidification of the solution, remobilization of Pb was weaker in the presence than in the absence of zeolite. No substantial differences were observed for Fe, Cd, and Zn immobilization. The immobilization of the metals during pH increase and the subsequent remobilization caused by re-acidification can be well described by a geochemical equilibrium speciation model that accounts for metal complexation at hydrous ferric oxides, for ion exchange on the zeolite surfaces, as well as for dissolution and precipitation processes.

Hydrogen-Ion Concentration↗

PubMed2005

Determination of [S,S']-ethylenediamine disuccinic acid (EDDS) by high performance liquid chromatography after derivatization with FMOC.

The paper describes a new HPLC method for the determination of ethylenediamine disuccinic acid (EDDS). EDDS is derivatized with FMOC reagent followed by HPLC separation on a reversed-phase column. The eluents consist of phosphate buffer at pH 6.8 and acetonitrile. Separation was carried out using gradient elution. The FMOC-EDDS derivative is detected with a fluorescence detector with an excitation wavelength of 265 nm and an emission wavelength of 313 nm. The detection limit is 0.01 microM. The method is applicable to the determination of the compound in water, soil solution and plant material at trace levels.

Chromatography, High Pressure Liquid↗

PubMed2005

A new in situ method to analyze mineral particle reactions in soils.

We developed a simple method to monitorthe transformation of particles in soils under in situ conditions. The particles were fixed on small polymer supports (2 cm x 2 cm) with a thin film of epoxy resin. Attached to these carriers, the particles could be put into close contact with soil at a chosen site and easily recovered after extended periods of time. The method was tested with lead oxide and copper concentrate in the field. Quartz and copper oxide particles were used in preliminary laboratory experiments. The used particles sizes ranged from 20 to 200 microm. Laboratory and field experiments with acidic and calcareous soils showed that the PbO and Cu concentrate coated polymer supports were stable under field conditions for at least one year. Nondestructive X-ray fluorescence spectroscopy was used to quantify the metals before and after exposure. Scanning electron microscopy combined with energy-dispersive X-ray spectroscopy as well as micro-Raman spectroscopy was used to identify signs of dissolution and newly formed mineral phases. The mineral dissolution rate could be determined under field conditions. The new method has the potential to be used in other environmental media such as sediments or water to study the reactions of a variety of particles larger than 20 microm.

Copper↗

PubMed2005

Adsorption of Pb and Cd by amine-modified zeolite.

Natural zeolites, known for their excellent sorption properties towards metal cations, are widely used for the purification of wastewaters. The selectivity of clinoptilolite, a common zeolite mineral, for Pb is known to be particularly high, whereas its selectivity for Cd is often lower. Extraordinarily high sorption capacities for soft metal cations were observed in the case of thiol-functionalized silica gels and clays. In order to enhance the zeolites' sorption capacity for Cd, we treated natural heteroionic and Na-clinoptilolite in aqueous suspensions with cysteamine and propylamine solutions and investigated the sorption of Cd and Pb to amine-modified zeolite by a series of batch experiments. Stability constants for amine sorption on all zeolite samples at room temperature and 50 degrees C were obtained. Partial dimerization of cysteamine explains the enhanced sorption of this compound. In contrast, amine treatment did not enhance the adsorption capacity or selectivity of the clinoptilolite towards Cd and Pb. Instead, the amounts of adsorbed heavy metals decreased stoichometrically with increasing sorption of cysteamine and propylamine. This reduction can be explained by the blockage of channels by amine molecules and revealed that the modification of zeolites with mercaptoamines does not enhance the sorption capacity of zeolite for Cd and Pb.

Adsorption↗

PubMed2004

Use of diffusive gradients in thin films (DGT) in undisturbed field soils.

The technique of diffusive gradients in thin films (DGT) has been shown to be a promising tool to assess metal bioavailability in soils under laboratory conditions. In this study we used DGT to investigate the resupply kinetics of Cu and Zn under in-situ conditions in a polluted lysimeter soil and compared the results with laboratory measurements using undisturbed soil cores at defined water contents as well as homogenized soil samples. Results differed considerably between these treatments, although the same soil material was used in all experiments. A small pool of rapidly available Zn was found in the field but not in the homogenized soil. Soil solution pH and dissolved metal concentrations also varied significantly between the soil treatments. In addition, we compared the DGT-measured effective concentration with the uptake of Cu and Zn into the shoots of Lolium perenne (Ryegrass) under the same three types of conditions, i.e., field, soil cores, and homogenized soil. A close relationship was found which was not linear but could be described by a saturation-type behavior. L. perenne is a metal excluder plant, and thus, metal accumulation is limited by translocation of metals from roots to shoots. DGT predicted plant metal uptake much better than the soil solution concentration or pH. The results of this study suggest that DGT may be successfully used under field conditions to study the kinetics of metal resupply. Plant metal concentrations were not well predicted in all cases by the effective concentration CE under field conditions. Some plants took up considerably more metals than estimated by CE. Variations in metal uptake independent of their bioavailability can be caused by local variations in microsite conditions, e.g. light, temperature, water, and nutrients. To some degree, such indetermination has to be expected as an inherent feature of the system and the concept of bioavailability.

Biological Availability↗

PubMed2004

Extraction of heavy metals from soils using biodegradable chelating agents.

Metal pollution of soils is widespread across the globe, and the clean up of these soils is a difficulttask. One possible remediation technique is ex-situ soil washing using chelating agents. Ethylenediaminetetraacetic acid (EDTA) is a very effective chelating agent for this purpose but has the disadvantage that it is quite persistent in the environment due to its low biodegradability. The aim of our work was to investigate the biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDSA), methylglycine diacetic acid (MGDA), and nitrilotriacetic acid (NTA) as potential alternatives and compare them with EDTA for effectiveness. Kinetic experiments showed for all metals and soils that 24 h was the optimum extraction time. Longer times only gave minor additional benefits for heavy metal extraction but an unwanted increase in iron mobilization. For Cu at pH 7, the order of the extraction efficiency for equimolar ratios of chelating agent to metal was EDDS > NTA> IDSA > MGDA > EDTA and for Zn it was NTA > EDDS > EDTA >MGDA > IDSA. The comparatively low efficiency of EDTA resulted from competition between the heavy metals and co-extracted Ca. For Pb the order of extraction was EDTA > NTA >EDDS due to the much stronger complexation of Pb by EDTA compared to EDDS. At higher concentration of complexing agent, less difference between the agents was found and less pH dependence. There was an increase in heavy metal extraction with decreasing pH, but this was offset by an increase in Ca and Fe extraction. In sequential extractions EDDS extracted metals almost exclusively from the exchangeable, mobile, and Mn-oxide fractions. We conclude that the extraction with EDDS at pH 7 showed the best compromise between extraction efficiency for Cu, Zn, and Pb and loss of Ca and Fe from the soil.

Biodegradation, Environmental↗