Theoretical comparison of how soil processes affect uptake of metals by diffusive gradients in thinfilms and plants

The theoretical basis for using measurements of metal uptake by the technique of diffusive gradients in thinfilms (DGT) to mimic processes in soils that affect uptake of metals by plants is examined. The uptake of metals by plants and DGT were compared conceptually and quantitatively by using the classic Barber model of plant uptake and the DIFS (DGT-induced fluxes in soils) model of uptake by DGT. For most metals and plants considered, uptake fluxes were similar to those induced by DGT using the most common gel layer thicknesses of 0.2 to 2 mm. Consequently DGT perturbs the chemical equilibrium of metals in the soil solution and between soil solution and solid phase, to a similar extent to plants, and therefore induces a similar balance in supply by diffusion and by release from the solid phase. DIFS was used to show that desorption kinetics, which are not considered by the plant uptake model, are likely important for uptake when the capacity of the soil solid phase is large. Model calculations showed that mass flow into a plant root would only contribute appreciably to the total flux of metal under circumstances when the solid phase reservoir of metal was very low. Generally, however, DGT is likely to emulate supply processes from the soil that govern uptake of metal by plants. Exceptions are likely to be found in poorly buffered soils (typically sandy and/or low pH), and at very high concentrations of metals in soil solution, such that the soil solution concentration at the plant root interface is higher than the Michaelis-Menten constant (Km).     

Enhancing phytoextraction: the effect of chemical soil manipulation on mobility, plant accumulation, and leaching of heavy metals

For heavy metal-contaminated agricultural land, low-cost, plant-based phytoextraction measures can be a key element for a new land management strategy. When agents are applied into the soil, the solubility of heavy metals and their subsequent accumulation by plants can be increased, and, therefore, phytoextraction enhanced. An overview is given of the state of the art of enhancing heavy metal solubility in soils, increasing the heavy metal accumulation of several high-biomass-yielding and metal-tolerant plants, and the effect of these measures on the risk of heavy metal leaching. Several organic as well as inorganic agents can effectively and specifically increase solubility and, therefore, accumulation of heavy metals by several plant species. Crops like willow (Salix viminalis L.), Indian mustard [Brassica juncea (L.) Czern.], corn (Zea mays L.), and sunflower (Helianthus annuus L.) show high tolerance to heavy metals and are, therefore, to a certain extent able to use the surpluses that originate from soil manipulation. More than 100-fold increases of lead concentrations in the biomass of crops were reported, when ethylenediaminetetraacetic acid (EDTA) was applied to contaminated soils. Uranium concentrations could be strongly increased when citric acid was applied. Cadmium and zinc concentrations could be enhanced by inorganic agents like elemental sulfur or ammonium sulfate. However, leaching of heavy metals due to increased mobility in soils cannot be excluded. Thus, implementation on the field scale must consider measures to minimize leaching. So, the application of more than 1 g EDTA kg(-1) becomes inefficient as lead concentration in crops is not enhanced and leaching rate increases. Moreover, for large-scale applications, agricultural measures as placement of agents, dosage splitting, the kind and amount of agents applied, and the soil properties are important factors governing plant growth, heavy metal concentrations, and leaching rates. Effective prevention of leaching, breeding of new plant material, and use of the contaminated biomass (e.g., as biofuels) will be crucial for the acceptance and the economic breakthrough of enhanced phytoextraction.     

Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.     

Evaluation of heavy metals accumulation by two emergent macrophytes from the polluted soil: an experimental study

The concentrations of copper (Cu) and lead (Pb) in, and the biomass of, the different parts of Persicaria glabra (Willd.) Gamez and Juncellus alopecuroides (Rottb.) C.B.Cl. were evaluated while grown in pots under laboratory conditions. Cu and Pb were added as sulphates (50, 100, 200, 400 mg/kg) to the pots. Heavy metal concentrations in the plants were measured by atomic absorption spectrometry. Results reveal that the biomass of J. alopecuroides (particularly roots) was higher than P. glabra, and that the growth tendency of macrophytes decreased with increasing heavy metal concentration in the soil, while in P. glabra, biomass went on increasing with the increase in copper concentration. Heavy metal accumulation in the roots was more than in aerial parts, and, therefore, barring two exceptions, the transfer factor of heavy metals from roots to aerial parts showed as less than 1, suggesting less transfer of heavy metals from roots to aerial parts. Thus, these macrophytes are efficient accumulators of trace elements, particularly J. alopecuroides, which can be recommended for biofiltration of heavy metals from contaminated soils.     

Field reconnaissance and estimation of petroleum hydrocarbon and heavy metal contents of soils affected by the Ebocha-8 oil spillage in Niger Delta, Nigeria

Field reconnaissance of the Ebocha-8 oil spill-affected site at Obiobi/Obrikom in the Niger Delta region of Nigeria was carried out to assess the extent of damage to the terrestrial ecosystem and delimit the epicenter of oil spillage. Following three successive reconnaissance surveys, the area to be sampled was delimited (200 x 200 m2), and soil samples were collected using the grid method from three replicate quadrats at two depths, surface (0-15 cm) and subsurface (15-30 cm). A geographically similar area located 50 m adjacent to the oil-polluted area was used as a reference (control) site. Total hydrocarbon content (THC) and heavy metal concentrations were later determined in the laboratory by extraction and spetrophotemetric techniques. Generally, the THC of soils at surface and subsurface depths of the oil-polluted plots was 2.06 x 10(4) +/- 4.97 x 10(3) mg/kg and 1.67 x 10(3) +/- 3.61 x 10(2) mg/kg soil, respectively, (no overlap in standard errors at 95% confidence limit) while concentrations of heavy metals(Pb, Cd, V, Cu and Ni) were enhanced, especially at the surface. The high levels of THC and heavy metals may predispose the site, which hitherto served as arable agricultural land, to impaired fertility and possible conflagration. When concentrations of heavy metals reach the levels obtained in this study, they may become toxic to plants or possibly bio-accumulate, thus leading to toxic reactions along the food chain. While the spilled-oil may have contributed to the enhanced levels of the metals in the affected soils, physico-chemical properties of the soils, mobility of metals, and the intense rainfall and flooding that preceded the period of study may have also contributed in part to their enhanced concentrations. The presence of high hydrocarbon content may cause oxygen deprivation, which may result in the death of soil fauna by asphyxiation. There is, therefore, an urgent need to clear the affected site of these excess hydrocarbon deposits so as to enhance the rehabilitation process of the affected mat layer of soils. Other appropriate mitigating measures, such as subsequent monitoring of hydrocarbon levels at suitable intervals after the clean up activities, are also recommended, with reference to the findings of this study, for effective management of the affected area.     

超声波去除农用污泥中重金属的试验研究

污水处理厂污泥中的重金属浓度高是污泥农用的主要障碍。为了降低农用污泥中的重金属含量,以Cu、Zn、Ni、Pb为对象,研究了超声波对其的影响。结果表明:超声对污泥中重金属有一定的溶出作用。当超声时间为30min时,溶解状态Cu、Zn、Ni、Pb的析出率分别为42.1%、37.5%、12.7%、14.7%;总的析出率分别为52.7%、44.7%、23.6%、71%。其中析出的Pb大部分以胶体状态存在,而溶解状态只占很少一部分。其他几种金属则以溶解状态为主。     

Hazard and Effects of Pollution by Lead on Vegetable Crops

Lead (Pb) contamination of the environment is an important human health problem. Children are vulnerable to Pb toxicity; it causes damage to the central nervous system and, in some extreme cases, can cause death. Lead is widespread, especially in the urban environment, and is present in the atmosphere, soil, water and food. Pb tends to accumulate in surface soil because of its low solubility, mobility, and relative freedom from microbial degradation of this element in the soil. Lead is present in soil as a result to weathering and other pedogenic processes acting on the soil parent material; or from pollution arising caused by the anthropogenic activities; such as mining, smelting and waste disposal; or through the adoption of the unsafe and unethical agricultural practices such as using of sewage sludge, and waste water in production of vegetable crops or cultivation of vegetables near highways and industry regions. Lead concentrations are generally higher in the leafy vegetables than the other vegetables. Factors affecting lead uptake included its concentration in the soil, soil pH, soil type, organic matter content, plant species, and unsafe agriculture practices. Generally, as Pb concentration increased; dry matter yields of roots, stems and leaves as well as total yield decreased. The mechanism of growth inhibition by lead involve: a decrease in number of dividing cells, a reduction on chlorophyll synthesis, induced water stress to plants, and decreased NO ₃ ^- uptake, reduced nitrate and nitrite reductase activity, a direct effect of lead on protein synthesis, a decrease on the uptake and concentration of nutrients in plants. The strategies to minimize Pb hazard can be represented in: (a) Phytoremediation, through natural plants are able to bio-accumulate Pb in their above–ground parts, which are then harvested for removal such as, using Indian Mustard (Brassica juncea), Ragweed (Ambrosia artemisiifolia), Hemp Dogbane (Apocynum cannabium), or Poplar trees, which sequester lead in its biomass. (b) Good and ethical agricultural practices such as cultivation of vegetables crops as far from busy streets or highways and industry regions as well as nonuse of sewage sludge and waste water in cultivated soils. (c) Increasing the absorptive capacity of the soil by adding organic matter and humic acid. (d) Growing vegetable crops and cultivars with a low potential to accumulate lead, especially in soils exposed to atmospheric pollution. (e) Washing of leafy vegetables by water containing 1 % vinegar or peeling roots, tubers, and some fruits of vegetables before consumption may be an important factor in reducing the lead concentration.     

Metals in vineyard soils of the Penedès area (NE Spain) after compost application

The application of organic wastes to improve soil physical characteristics in mechanized vineyards planted after land levelling is becoming a common practice in Mediterranean areas. It may be useful as an additional source of organic matter and nutrients, but these wastes could also have negative effects due to their metal content. The aim of the study was to evaluate the influence of compost application on soil metal contents in mechanized vineyard soils of the Spanish Mediterranean area, where this practice is repeated every three years. The study was carried out in a ten-year-old vineyard where the main soil type is Typic Calcixerept. Composted cattle manure was applied in alternate rows, at a rate of 40 Mgha(-1) dry-weight. Nine sampling points were located along the slopes of two plots: a levelled plot prepared for mechanization with large soil disturbance movements within the plot, and a plot of undisturbed soil. At each location, soil samples were taken in both treated and untreated soils. Total concentrations (digestion with aqua regia) and the extractable DTPA (Diethylene-triaminepentacetic)-CaCl2-TEA (Triethanolamine) fractions of Cu, Zn and Mn were analyzed in each sample. For Cu and Zn, the initial concentration was higher in the undisturbed plot. In both cases, total Cu and total Zn were positively affected by manure input and the concentration in treated soils was significantly higher than in untreated soil. For Mn, the initial concentration was higher in disturbed soils than in undisturbed ones, and although in both scenarios the concentrations increased with manure, no significant differences were found between treated and untreated soils. The extractable fraction also increased in treated versus untreated soils, although for Cu and Mn the extractable/total metal ratio was similar in treated and untreated soils. After one compost application, total metal contents increased significantly, particularly for Zn. Most of those metals are accumulated in the soil, due to the soil characteristics.     

Cadmium and zinc in vegetation and litter of a voluntary woodland that has developed on contaminated sediment-derived soil

Vegetation that develops spontaneously on metal-contaminated soils presents an opportunity to evaluate both metal bioavailability and the risks posed to biota. The behavior of Cd and Zn in the species of a spontaneously developed woodland, colonizing a canal embankment, has been investigated. Nitric-acid-extractable metal concentrations in the sediment-derived substrate ranged between 5.0 to 376 mg kg(-1)dry wt. Cd and 83.0 to 784 mg kg(-1)dry wt. Zn. The woodland is dominated by Willow (Salix) species. Salix caprea selectively accumulated Cd in all stem tissues, in contrast to S. viminalis, which regulated tissue Cd content. Both species showed an effective regulation of tissue Zn. Cadmium uptake by S. caprea was correlated with differences in soil pH, while Zn uptake was not. There was no relationship between tissue metal concentrations and soil metal nitric acid-extractable concentrations. Other aspects of ecosystem function appeared unaffected by the elevated Cd flux in S. caprea; leaf litter organisms present represented all major groups and there was no accumulation of organic matter. The woodland represents a potentially sustainable option for remediating a low value site with difficult access that does not involve removal of the contaminated material to a landfill or making a permanent inert cover.     

Effect of Cadmium on Microbial Activity and a Ryegrass Crop in Two Semiarid Soils

Soil pollution with Cd is an environmental problem common in the world, and it is necessary to establish what Cd concentrations in soil could be dangerous to its fertility from toxicity effects and the risk of transference of this element to plants and other organisms of the food chain. In this study, we assessed Cd toxicity on soil microorganisms and plants in two semiarid soils (uncultivated and cultivated). Soil ATP content, dehydrogenase activity, and plant growth were measured in the two soils spiked with concentrations ranging from 3 to 8000 mg Cd/kg soil and incubated for 3 h, 20 days, and 60 days. The Cd concentrations that produced 5%; 10%;, and 50%; inhibition of each of the two soil microbiological parameter studied (ecological dose, ED, values) were calculated using two different mathematical models. Also, the effect of Cd concentration on plant growth of ryegrass (Lolium perenne, L.) was studied in the two soils. The Cd ED values calculated for soil dehydrogenase activity and ATP content were higher in the agricultural soils than in the bare soil. For ATP inhibition, higher ED values were calculated than for dehydrogenase activity inhibition. The average yields of ryegrass were reduced from 5.03 to 3.56 g in abandoned soil and from 4.21 to 1.15 g in agricultural soil with increasing concentrations of Cd in the soil. Plant growth was totally inhibited in abandoned and agricultural soils at Cd concentrations above 2000 and 5000 mg/kg soil, respectively. There was a positive correlation between the concentration of Cd in the plants and the total or DTPA-extractable concentrations of Cd in the soil.     

Heavy metals in an urban watershed in southeastern Michigan

The occurrence of heavy metals in the soil was measured over a period of several years to determine background concentrations in a heavily urbanized watershed in southeastern Michigan. A spatially dispersed sample was collected to capture the inherent variability of the soils and historic land use. The analysis focused on 14 metals (antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, thallium, and zinc) that are part of the USEPA's list of the 129 most common pollutants. Metal concentrations were measured at three depths: near-surface (<0.5 m), shallow subsurface (0.5-10 m), and depths greater than 10 m across six soil units in glacial terrain. Additional analyses assessed the metal concentrations in each depth profile across three general land use categories: residential, commercial, and industrial. Metal concentrations were the highest in the near-surface with Pb present at concentrations averaging 15.5 times that of background in industrial areas and approximately 16 times background in residential areas. Cadmium, Hg, and Zn were also present in surface soils at levels of several times that of background. The highest concentrations of each of these metals were present in the clay-rich soils located in the eastern, more urbanized and industrialized part of the watershed. Metals detected at elevated concentrations decreased in concentration with increasing depth and distance from the urbanized and industrialized center of the watershed. Statistically significant differences in the concentrations of heavy metals were also noted between the land use categories, with Cd, Cr, Cu, Pb, Ni, and Zn observed within industrial areas at mean concentrations several times greater than background levels.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

Response of soil microbiological activities to cadmium,lead, and zinc salt amendments

Heavy metal pollution of soil has been recognized as a major factor impeding soil microbial processes. From this perspective, we studied responses of the soil biological activities to metal stress simulated by soil amendment with Zn, Pb, and Cd chlorides. The amounts of heavy metal salts added to five metal-polluted soils and four nonpolluted soils were selected to match the total metal concentrations typically found in polluted soils of the Silesia region of Poland. From the perspective of soil quality, metal mobility in amended soils could not be described by simple functions of pH or organic matter. Reaction of Pb with the soil caused strong immobilization with less than 1% of the Pb amendment recovered by 0.01 M CaCl2 extractions. Immobilization of Cd was also significant, whereas immobilization of the Zn amendment was much weaker than that of Cd or Pb. The Zn amendment had substantial inhibitory effect on soil dehydrogenase, acid and alkaline phosphatase, arylsulfatase, urease, and nitrification potential. Generally, Cd and Pb had limited or stimulatory effect on most of these biological activities, with an exception of Pb strongly inhibiting soil urease. The effect of the metal amendments on biological activities could not be satisfactorily accounted for by metal toxicity because no strong relationship was observed between extractable metal content and the degree of inhibition. The Zn amendment had a significant effect on soil pH, resulting in confounding effects of pH and Zn toxicity on activities. Metal amendment experiments seem to be of limited utility for meaningful assessment of metal contamination effects on soil quality.     

Phytoremediation of Soil Polluted by Nickel Using Agricultural Crops

Soil pollution due to heavy metals is widespread; on the world scale, it involves about 235 million hectares. The objectives of this research were to establish the uptake efficiency of nickel by some agricultural crops. In addition, we wanted to establish also in which part of plants the metal is stored for an eventual use of biomass or for recycling the metal. The experiments included seven herbaceous crops such as: barley (Hordeum vulgaris), cabbage (Brassica juncea), spinach (Spinacea oleracea), sorghum (Sorgum vulgare), bean (Phaseolus vulgaris), tomato (Solanum lycopersicum), and ricinus (Ricinus communis). We used three levels of treatment (150, 300, and 600 ppm) and one control. At the end of the biological cycle of the crops, the different parts of plants, i.e., roots, stems, leaves, fruits, or seeds, were separately collected, oven dried, weighed, milled, and separately analysed. The leaves and stems of spinach showed a very good nickel storage capacity. The ricinus too proved to be a very good nickel storer. The ability of spinach and ricinus to store nickel was observed also in the leaves of cabbage, even if with a lower storage capacity. The bean, barley, and tomato, in decreasing order of uptake and storage capacity, showed a high concentration of nickel in leaves and stems, whereas the sorghum evidenced a lesser capacity to uptake and store nickel in leaves and stems. The bean was the most efficient in storing nickel in fruits or grains. Tomato, sorghum, and barley have shown a storage capacity notably less than bean. The bean appeared to be the most efficient in accumulating nickel in the roots, followed in decreasing order by sorghum, ricinus, and tomato. With regard to the removal of nickel, spinach was the most efficient as it contains the highest level of this metal per gram of dry matter. The ricinus, cabbage, bean, sorghum, barley, and tomato evidenced a progressively decreasing efficiency in the removal of nickel.     

Adsorption of 2,4-dichlorophenoxyacetic acid by an Andosol

To identify the important soil components involved in 2,4-dichlorophenoxyacetic acid (2,4-D) adsorption on Andosols, 2,4-D adsorption on a surface horizon of an Andosol was compared with that on hydrogen peroxide (H2O2)-treated (soil organic matter [SOM] was removed), acid-oxalate (OX)-treated (active metal hydroxides and SOM were removed), and dithionite-citrate-bicarbonate (DCB)-treated (free and active metal [hydr]oxides and SOM were removed) soil samples at equilibrium pHs ranging from 4 to 8. Although the untreated soil contained a large amount of organic C (71.9 g kg-1), removal of SOM had little effect on 2,4-D adsorption. Active surface hydroxyls, which were attached to the active and free metal (hydr)oxides and metal SOM complexes, were identified as the most important soil functional group for 2,4-D adsorption. The dominant mechanism of the 2,4-D adsorption was a ligand exchange reaction in which the carboxylic group of 2,4-D displaced the active surface hydroxyl associated with metals and formed a strong coordination bond between the 2,4-D molecule and soil solid phase. The ligand exchange reaction reasonably accounted for the selective adsorption of 2,4-D over Cl-, competitive adsorption of phosphate over 2,4-D, reduction in plant-growth-inhibitory activity of soil-adsorbed 2,4-D, and the high 2,4-D adsorption ability of Andosols. Although a humic acid purified from the soil did not adsorb 2,4-D, the presence of the humic acid increased 2,4-D adsorption on Al and Fe, probably by inhibiting the hydrolysis and polymerization of Al and Fe resulting in the preservation of available adsorption sites on these metals. The adsorption behavior of 2,4-D on soils could be a good index for predicting the adsorption behavior of other organic acids in soils.     

Effects of spent engine oil on the growth parameters, chlorophyll and protein levels of Amaranthus hybridus L.

The susceptibility of Amaranthus hybridus L. seedlings to spent engine oil was investigated in soil supplemented with concentrations of oil ranging from 1–5 percent v/w. Parameters considered were relative growth rate (RGR), leaf area ratio (LAR), whole plant height, leaf area, leaf number, chlorophyll and protein levels. A relationship was found to exist between the inhibitory effects and the treatment concentrations. After seventy days growth in the treated soils, the mean height and leaf area of plants in soils treated with 5 percent spent engine oil were 27.0±1.25 cm and 5.63±0.36 cm². These were significantly different (at p=0.05) from the respective values of 41.4±0.8 cm and 13.44±0.22 cm² for the control plants. Levels of total chlorophyll (per gram fresh weight of leaves) and protein (per gram dry weight of whole plant) were higher in the control plants compared with those grown in oil treated soil. Results obtained from the growth analysis showed the inhibitory effects of spent engine oil on Amaranthus hybridus L.     

Stability constants for the complexation of various metals with a rhamnolipid biosurfactant

The presence of toxic metals in natural environments presents a potential health hazard for humans. Metal contaminants in these environments are usually tightly bound to colloidal particles and organic matter. This represents a major constraint to their removal using currently available in situ remediation technologies. One technique that has shown potential for facilitated metal removal from soil is treatment with an anionic microbial surfactant, rhamnolipid. Successful application of rhamnolipid in metal removal requires knowledge of the rhamnolipid-metal complexation reaction. Therefore, our objective was to evaluate the biosurfactant complexation affinity for the most common natural soil and water cations and for various metal contaminants. The conditional stability constant (log K) for each of these metals was determined using an ion-exchange resin technique. Results show the measured stability constants follow the order (from strongest to weakest): Al3+ > Cu2+ > Pb2+ > Cd2+ > Zn2+ > Fe3+ > Hg2+ > Ca2+ > Co2+ > Ni2+ > Mn2+ > Mg2+ > K+. These data indicate that rhamnolipid will preferentially complex metal contaminants such as lead, cadmium, and mercury in the presence of common soil or water cations. The measured rhamnolipid-metal stability constants were found in most cases to be similar or higher than conditional stability constants reported in the literature for metal complexation with acetic acid, oxalic acid, citric acid, and fulvic acids. These results help delineate the conditions under which rhamnolipid may be successfully applied as a remediation agent in the removal of metal contaminants from soil, as well as surface waters, ground water, and wastestreams.     

The effect of pH on metal accumulation in two Alyssum species

Nickel phytoextraction using hyperaccumulator plants offers a potential for profit while decontaminating soils. Although soil pH is considered a key factor in metal uptake by crops, little is known about soil pH effects on metal uptake by hyperaccumulator plants. Two Ni and Co hyperaccumulators, Alyssum murale and A. corsicum, were grown in Quarry muck (Terric Haplohemist) and Welland (Typic Epiaquoll) soils contaminated by a Ni refinery in Port Colborne, Ontario, Canada, and in the serpentine Brockman soil (Typic Xerochrepts) from Oregon, USA. Soils were acidified and limed to cover pH from strongly acidic to mildly alkaline. Alyssum grown in both industrially contaminated soils exhibited increased Ni concentration in shoots as soil pH increased despite a decrease in water-soluble soil Ni, opposite to that seen with agricultural crop plants. A small decrease in Alyssum shoot Ni concentration as soil pH increased was observed in the serpentine soil. The highest fraction of total soil Ni was phytoextracted from Quarry muck (6.3%), followed by Welland (4.7%), and Brockman (0.84%). Maximum Ni phytoextraction was achieved at pH 7.3, 7.7, and 6.4 in the Quarry, Welland, and Brockman soils, respectively. Cobalt concentrations in shoots increased with soil pH increase in the Quarry muck, but decreased in the Welland soil. Plants extracted 1.71, 0.83, and 0.05% of the total soil Co from Welland, Quarry, and Brockman, respectively. The differences in uptake pattern of Ni and Co by Alyssum from different soils and pH were probably related to the differences in organic matter and iron contents of the soils.     

Changes in the rhizosphere of metal-accumulating plants evidenced by chemical extractants

The plants Salix viminalis L. (common osier) and Thlaspi caerulescens J. Presl & C. Presl have been studied often because of their high potential to extract heavy metals from soils. The soil properties favoring this phytoextraction are not yet fully known. In this study we compared three frequently used single-extracting agents (NaNO3, diethylenetriaminepentaacetic acid [DTPA], and ethylenediaminetetra-acetic acid [EDTA]) with a sequential extraction procedure to describe changes in the different Cd, Cu, and Zn pools in the rhizosphere of S. viminalis and T. caerulescens grown on calcareous and acidic Swiss soils in a pot experiment. The sequential extraction was used to assess the chemical affinities of these heavy metals (HM) in the soil whereas the single extractants were used for estimating the bioavailable HM pools in the soils. Cadmium depletion in several pools was most apparent in the acidic soil, with a significant decrease observed in the NaNO3-, DTPA-, and EDTA-extractable fractions following T. caerulescens growth compared with control pots. The sequential extraction showed that most Cd extracted by the plant from the acidic soil originated from the organic pool, which implies that heavy metals bound to organic matter may constitute a significant part of the bioavailable Cd pool in soils. In the calcareous soil only a small amount of Cd was taken up by T. caerulescens, and this came mainly from the carbonate-bound fraction. This study shows that T. caerulescens, and to a lesser extent S. viminalis, can alter the heavy metal distribution in different soil pools within 90 d.     

Using Mediterranean shrubs for the phytoremediation of a soil impacted by pyritic wastes in Southern Spain: a field experiment

Re-vegetation is the main aim of ecological restoration projects, and in Mediterranean environments native plants are desirable to achieve successful restoration. In 1998, the burst of a tailings dam flooded the Guadiamar river valley downstream from Aznalcóllar (Southern Spain) with sludges that contained elevated concentrations of metals and metalloids, polluting soils and waters. A phytoremediation experiment to assess the potential use of native shrub species for the restoration of soils affected by the spillage was performed from 2005 to 2007, with soils divided into two groups: pH < 5 and pH > 5. Four native shrubs (Myrtus communis, Retama sphaerocarpa, Rosmarinus officinalis and Tamarix gallica) were planted and left to grow without intervention. Trace element concentrations in soils and plants, their extractability in soils, transfer factors and plant survival were used to identify the most-interesting species for phytoremediation. Total As was higher in soils with pH < 5. Ammonium sulphate-extractable zinc, copper, cadmium and aluminium concentrations were higher in very-acid soils, but arsenic was extracted more efficiently when soil pH was >5. Unlike As, which was either fixed by Fe oxides or retained as sulphide, the extractable metals showed significant relationships with the corresponding total soil metal concentration and inverse relationships with soil pH. T. gallica, R. officinalis and R. sphaerocarpa survived better in soils with pH > 5, while M. communis had better survival at pH < 5. R. sphaerocarpa showed the highest survival (30%) in all soils. Trace element transfer from soil to harvestable parts was low for all species and elements, and some species may have been able to decrease trace element availability in the soil. Our results suggest that R. sphaerocarpa is an adequate plant species for phytostabilising these soils, although more research is needed to address the self-sustainability of this remediation technique and the associated environmental changes.