Effect of heavy metals and organic matter on root exudates (low molecular weight organic acids) of herbaceous species: An assessment in sand and soil conditions under different levels of contamination.

Bioavailability of heavy metals can be modified by different root exudates. Among them, low molecular weight organic acids (LMWOAs) play an important role in this process. Three plant species (Poa annua, Medicago polymorpha and Malva sylvestris), potentially used for phytoremediation, have been assessed for both metal uptake and LMWOAs excretion in contaminated environments with different concentrations of Cd, Cu and Zn. The experiments have been carried out in washed sand and in three contaminated soils where two organic amendments were added (biosolid compost and alperujo compost). The most abundant LMWOAs excreted by all studied plants were oxalic and malic acids, although citric and fumaric acids were also detected. The general tendency was that plants responded to an increase of heavy metal stress releasing higher amounts of LMWOAs. This is an efficient exclusion mechanism reducing the metal uptake and allowing the plant growth at high levels of contamination. In the experiment using wash sand as substrate, the organic acids composition and quantity depended mainly on plant species and metal contamination. M. polymorpha was the species that released the highest concentrations of LMWOAs, both in sand and in soils with no amendment addition, whereas a decrease of these acids was observed with the addition of amendments. Our results established a clear effect of organic matter on the composition and total amount of LMWOAs released. The increase of organic matter and nutrients, through amendments, improved the soil quality reducing phytotoxicity. As a result, organic acids exudates decreased and were solely composed of oxalic acid (except for M. polymorpha). The release of LMWOAs has proved to be an important mechanism against heavy metal stress, unique to each species and modifiable by means of organic amendment addition.

Quality of trace element contaminated soils amended with compost under fast growing tree Paulownia fortunei plantation.

The use of fast growing trees could be an alternative in trace element contaminated soils to stabilize these elements and improve soil quality. In this study we investigate the effect of Paulownia fortunei growth on trace element contaminated soils amended with two organic composts under semi-field conditions for a period of 18 months. The experiment was carried out in containers filled with tree different soils, two contaminated soils (neutral AZ and acid V) and a non contaminated soil, NC. Three treatments per soil were established: two organic amendments (alperujo compost, AC, and biosolid compost, BC) and a control without amendment addition. We study parameters related with fertility and contamination in soils and plants. Paulownia growth and amendments increased pH in acid soils whereas no effect of these factors was observed in neutral soils. The plant and the amendments also increased organic matter and consequently, soil fertility. Positive results were also found in soils that were only affected by plant growth (without amendment). A general improvement of "soil biochemical quality" was detected over time and treatments, confirming the positive effect of amendments plus paulownia. Even in contaminated soils, except for Cu and Zn, trace element concentrations in leaves were in the normal range for plants. Results of this mid-term study showed that Paulownia fortunei is a promising species for phytoremediation of trace element polluted soils.

Long-term biomonitoring of soil contamination using poplar trees: accumulation of trace elements in leaves and fruits.

Phytostabilization aims to immobilize soil contaminants using higher plants. The accumulation of trace elements in Populus alba leaves was monitored for 12 years after a mine spill. Concentrations of As and Pb significantly decreased, while concentrations of Cd and Zn did not significantly over time. Soil concentrations extracted by CaCl2 were measured by ICP-OES and results of As and Pb were below the detection limit. Long-term biomonitoring of soil contamination using poplar leaves was proven to be better suited for the study of trace elements. Plants suitable for phytostabilization must also be able to survive and reproduce in contaminated soils. Concentrations of trace elements were also measured in P. alba fruiting catkins to determine the effect on its reproduction potential. Cadmium and Zn were found to accumulate in fruiting catkins, with the transfer coefficient for Cd significantly greater than Zn. It is possible for trace elements to translocate to seed, which presents a concern for seed germination, establishment and colonization. We conclude that white poplar is a suitable tree for long-term monitoring of soil contaminated with Cd and Zn, and for phytostabilization in riparian habitats, although some caution should be taken with the possible effects on the food web. Supplemental materials are available for this article. Go to the publisher's online edition of International Journal of Phytoremediation to view the supplemental file.

Growth of Populus alba and its influence on soil trace element availability.

The use of fast growing trees is a common practice for phytoremediation of contaminated soils. Plant roots can change trace element bioavailability in soils. We studied the effect of Populus alba on trace element bioavailability on two contaminated soils (one with neutral pH and other with acid pH) comparing two methods (0.01 M CaCl2-extractable in soil and concentration in soil pore water SPW), trace element accumulation in leaves and plant development over 36 months. Results were compared to those obtained with a non-contaminated soil. The experiment was carried out in containers (95 L of volume and 1m height). Half of the containers for each soil were planted with P. alba saplings and the others remained without plant. In neutral soils plant growth did not influence soil pH; the greatest effect due to plant growth was found in acid soil. Values of pH obtained by SPW showed a similar trend compared to those obtained after soil KCl extraction. Bioavailability of trace elements determined by both methods followed the same behavior in the three studied soils. Both methods for determining trace element bioavailability in soil were accurate to predict plant uptake. In non-contaminated soil, plants tended to increase micronutrients (Cu, Mn and Zn) availability. However, in case of contaminated soil, the growth of P. alba did not increase trace element availability. Moreover, results on height and diameter of the trunk of the trees, during 36 months, demonstrated that the presence of total trace elements in soil did not affect plant development.

Traditional agricultural practices enable sustainable remediation of highly polluted soils in Southern Spain for cultivation of food crops.

This study relates elemental content of a range of edible crops grown in soils severely polluted by metals and metalloids as affected by traditional smallholder management practices. Five agricultural plots close to a sulfidic waste dump were monitored. Soil analysis demonstrated elevated concentrations of As, Cu, Pb and Zn that were greatly in excess of maximum statutory limits for agricultural soils in the studied region. The main vegetables (lettuce, chard, onion, potatoes) and lemon, together with their associated soils, were measured for elemental content. Extractable soil element concentrations were very low. There were differences in elemental accumulation between crops, but none exceeded statutory concentrations in edible parts. Soil-plant transfer factors were uniformly low for all elements and crops. It is concluded that traditional soil management practices (annual liming and application of animal manures) have created conditions for sustainable long-term safety use, with potential for multiple end-use, of these highly polluted soils.

Phytostabilization of amended soils polluted with trace elements using the Mediterranean shrub: Rosmarinus officinalis.

We evaluate the mid-term effects of two amendments and the establishment of R. officinalis on chemical and biochemical properties in a trace element contaminated soil by a mine spill and the possible use of this plant for stabilization purposes. The experiment was carried out using containers filled with trace element polluted soil, where four treatments were established: organic treatment (biosolid compost, OAR), inorganic treatment (sugar beet lime, IAR), control with plant (NAR) and control without plant (NA). Amendment addition and plant establishment contributed to restore soil chemical (pH, total organic carbon, and water soluble carbon) and biochemical properties (microbial biomass carbon and the enzymatic activities: aryl-sulphatase and protease). The presence of rosemary did not affect soluble (0.01 M CaCl2) Cd and Zn and decreased trace element EDTA extractability in amended soils. There were no negative effects found on plant growth and nutrient content on polluted soils (NAR, OAR, and IAR). Trace element contents were within normal levels in plants. Therefore, rosemary might be a reliable option for successful phytostablization of moderate trace element contaminated soils.

Evaluation of pastures for horses grazing on soils polluted by trace elements.

Pasture established on polluted soil may pose a risk to grazing livestock creating a requirement for mechanical management which may affect biodiversity and expend energy. The risk associated with managing pasture by grazing horses (non-edible livestock) is being assessed in the Guadiamar Valley (SW Spain), where soils are polluted with trace elements following a major pollution incident. Soil pollution does not affect biomass production or floristic composition of pasture, although both variables influence trace element accumulation in herbage. Element concentrations in herbage are below maximum tolerable limits for horses. Faecal analysis showed regulated absorption of essential elements, while non-essential elements seemed preferentially excreted. Elemental content of horse hair did not differ in animals from polluted and control pastures. If pastures are managed by grazing, periodic monitoring is recommended in view of the long-term chronic trace element exposure in these systems.

Bioavailability and accumulation of trace elements in soils and plants of a highly contaminated estuary (Domingo Rubio tidal channel, SW Spain).

The Domingo Rubio tidal channel (Palos de la Frontera, Huelva, Spain) is an estuary located in the mouth of the Tinto River. The estuary is affected by different sources of pollution (waters of the Tinto River, contaminated with trace elements from the Iberian Pyrite belt, and effluent from the Huelva chemical industrial area). Soil and the most frequent plant species were collected in 2004 and 2006 at six different locations on the estuary. In general, N-Kjedahl, Total Organic Carbon values, salinity and contamination (total trace elements up to 1,000 mg kg(-1) As, 6 mg kg(-1) Cd, 2,500 mg kg(-1) Cu, 1,900 mg kg(-1) Pb and 1,300 mg kg(-1) Zn) tended to increase downstream of the tidal channel. Soil biochemical properties were not negatively affected either by the high salinity or by trace element contamination. Despite the high values of the trace elements, analysed plant samples showed that Cu was the only metal that could be a serious risk for the food chain.

Trace elements, pH and organic matter evolution in contaminated soils under assisted natural remediation: a 4-year field study.

A 4-year study was undertaken on the effect of three amendments (biosolid compost (BC), sugar beet lime (SL), and combination of leonardite plus sugar beet lime (LESL)) on reclamation of a moderately trace element-contaminated soil under field conditions. Results showed that organic C increased in BC and LESL treatments. BC and SL treatments increased soil pH and reduced CaCl(2)-extractable metal concentrations more efficiently. At the end of the experiment, CaCl(2)-extractable metal concentrations decreased and were similar in all treatments pointing out the importance of the natural remediation processes in contaminated soils. Addition of amendments showed no clear reduction in EDTA-extractable trace element concentrations, even, BC and LESL subplots showed some little increase of these elements with time. Amendments did not cause any change in total trace element concentration in soil. Addition of amendments could be a successful and reliable long term technique for stabilization of trace elements in contaminated soils at a field scale with minimum maintenance.

Trace elements in wild grasses: a phytoavailability study on a remediated field.

There have been significant efforts to establish a widely usable method for the prediction of trace element bioavailability in soil. In this work, we used extraction with 0.01 M CaCl2 and 0.05 M ethylenediaminetetraacetic acid (EDTA) to estimate bioavailable concentrations of As, Cd, Cu, Pb, and Zn in a soil moderately contaminated with trace elements 1 and 2 years after the application of three amendments. The experiment took place in a field plot of a soil affected by the toxic spill of the Aznalcóllar mine. Four treatments were established: three with amendments (biosolid compost, sugar beet lime, and a combination of leonardite plus sugar beet lime) and a control without amendment. Trace element concentrations of two representative species in each year (Lamarckia aurea and Poa annua in 2004 and Lamarckia aurea and Bromus rubens in 2005) were analyzed. The results showed a positive effect of the amendments both on soil and vegetation. Trace element concentrations in plants growing in the amended subplots were lower than those in plants from nonamended subplots. As a rule, concentrations of CaCl2-soluble Cd, Cu, and Zn in soil were positively correlated with trace elements in plants, whereas EDTA extraction was scarcely correlated with plant concentration. For species of grasses, especially L. aurea, CaCl2 seems to be a more suitable extractant to predict trace element bioavailability in this contaminated soil.

Mercury and other trace elements in soils affected by the mine tailing spill in Aznalcóllar (SW Spain).

The Aznalcóllar accident (28th April 1998) occurred because the collapse of the tailing-dam dike of the Aznalcóllar-Los Frailes mines. Soils were affected by a slurry of acidic water loaded with trace elements, finely divided metal sulphides, and materials used in the refining /floating process. Studies carried out before and after the soil restoration activities (sludge removal, amending, tilling, and afforestation) showed severe trace-element contamination (mainly As, Cd, Cu, Pb, Tl and Zn) in the superficial layer of the sludge-affected soils. Despite Hg being an important component of the Los Frailes ore and therefore of the contaminant sludge, data on Hg content of sludge-affected soils are scarce and sometimes controversial. The aim of this study was to determine the effect of the spill and of restoration measures on the Hg content of soils and how this related to other elements. Concentration of Hg immediately after the spill was 8-fold above background (0.061+/-0.012 mg kg(-1); mean+/-SD) at the surface (0-5 cm) and 3-4-fold greater in deeper layers (0-20; 0-50 cm). After the remediation measures, mean values of Hg and other elements (As, Cd, Cu, Pb and Zn) were very variable and remained above background values. These anomalies are due to the sludge left on the soil surface or buried during restoration operations, resulting in an irregular distribution of trace elements. The highest values for the less mobile elements (up to 176 mg kg(-1) As, 2.36 mg kg(-1) Hg and 1556 mg kg(-1) Pb) were observed in the area 1 km downstream of the tailings dam.

Factors affecting accumulation of thallium and other trace elements in two wild Brassicaceae spontaneously growing on soils contaminated by tailings dam waste.

Thallium is a scarce, highly toxic element. There are several investigations that report Tl accumulation in plants of the family Brassicaceae. These plants could pose a risk in areas where Tl is present at higher concentrations than normal soils. The present study reports analyses of two wild Brassicaceae, Hirschfeldia incana and Diplotaxis catholica, growing spontaneously at five sampling sites moderately polluted with Tl and other trace elements in the Green Corridor of the Guadiamar river, Seville, S. Spain. In general, trace element content was unremarkable in all part plants, despite the concentrations present in soil. Thallium was the only element whose concentration in both plant species was above normal for plants (maximum values of 5.00 mgkg(-1) in H. incana flowers). There were significant positive correlations between total Tl in soil and Tl in both plant species. Transfer Coefficients (TC) for all elements were, in general, <1 for both species, except for Tl in flowers and fruits at some sites. The highest Enrichment Factor (EF) was found for Tl in H. incana fruits (EF = 607) and D. catholica flowers (EF = 321). H. incana was studied in a previous growing season (2004) in the same area, although the rainfall was 3 times more than in the year of the present study (2005), giving a maximum Tl content of 46.5 mgkg(-1) in H. incana flowers. The data presented here show that Tl content of plants growing in semi-arid conditions can be significantly influenced by precipitation. In dry years, plant Tl accumulation may be significantly reduced.

Bioaccumulation of trace elements in a wild grass three years after the Aznalcóllar mine spill (South Spain).

In this paper, we surveyed the concentration of nine trace elements (As, Cd, Cu, Fe, Mn, Ni, Pb, Tl and Zn) in bermudagrass (Cynodon dactylon) 3 years after the mine spill in Aznalcóllar (south Spain). The results were compared with those that had been obtained for the same species in a previous study, 18 months after the accident. Three types of soil condition were determined: i) unaffected soils (UN, control); ii) cleaned up and amended soils (A, amended); and (iii) non-amended soils, inaccessible to the clean-up and remediation operations (NA, non-amended). The trace element concentrations in the plants were lower than those reported in the first sampling for both washed (plant tissues) and unwashed plants (as consumed by herbivores). Apart from Cd, trace elements concentrations (plant tissues) were similar in the A and the UN soils. In the NA soils, the Cd, Fe, Mn, Zn and Pb levels in unwashed plants were excessive for animal consumption. This wild grass seems to be suitable as a soil stabilizer for spill affected soils and as a biomonitor for soil pollution by some trace elements (As, Cu and Zn); however, its potential for phytoextraction is negligible.

Accumulation of As, Cd and selected trace elements in tubers of Scirpus maritimus L. from Doñana marshes (South Spain).

The collapse of a pyrite-mining, tailing dam on 1998 contaminated an area of 4286 ha along the Agrio and Guadiamar river valleys in southern Spain. Over 2700 ha of the Doñana marshes, an important wintering area for wetland European birds, were contaminated. This study reports analyses of the tubers of Scirpus maritimus (an important food for greylag geese, Anser anser) collected in 2000 in the "Entremuros" (spill-affected area) and in nearby unaffected Doñana marshes (control areas). In the spill-affected area mean tuber tissue concentrations of Cd (0.25 mg kg-1) and Zn (61 mg kg-1) were greater than in those tubers from the control area (0.02 mg kg-1 for Cd, and 22 mg kg-1 for Zn); values of Cd and Zn in "Entremuros" (samples collected two years after the mine spill) were much smaller than those reported only a few months after the accident. Trace elements (As, Fe, Mn and Tl, and to a lesser extent Cd and Pb) showed a preferential accumulation in the outer skin of tubers. Surprisingly, concentrations of As and Fe were greater in tubers from some marsh sites not affected by the mine-spill than in tubers from the "Entremuros". We suggest that relic river channels within the Doñana marshes may be contaminated by trace elements from historic mining activities. An exhaustive study of macrophytes and other plant species in this area is recommended to identify potential risks to wildlife.

Trace element and nutrient accumulation in sunflower plants two years after the Aznalcóllar mine spill.

The failure of a tailing pond dam at the Aznalcóllar pyrite mine (SW Spain) in April 1998 released a toxic spill affecting approximately 4300 ha along the Agrio and Guadiamar valleys. Two years later, we have studied yield and concentration of mineral nutrients and trace elements in sunflower plants grown in the spill-affected soil, and in an adjacent unaffected soil as comparison. The study has been carried out in plants at seedling (V4) and mature (R8) stages. Shoot and root biomass of sunflower seedlings was significantly smaller in the affected soil than in the unaffected soil, but there was no significant difference at the mature stage. Oil production was greater in the spill-affected plants. We have not detected any 'fertilising' effect caused by the acid waters of the spill on the main nutrient (N, P and Ca) acquisition, as documented in 1998 for sunflower plants flooded by the spill. Sunflower plants growing in the spill-affected soil reached adequate levels of nutrients. None of the trace elements measured-As, Cd, Cu, Pb and Tl-reached levels either phytotoxic or toxic for humans or animals in seeds and the above-ground part of the spill-affected plants. We evaluate the potential use of sunflower plants for phytoremediation. The potential for phytoextraction is very low; however, it may be used for soil conservation. The production of oil (usable for industrial purposes) may add some value to this crop.

Bioaccumulation of As, Cd, Cu, Fe and Pb in wild grasses affected by the Aznalcóllar mine spill (SW Spain).

The collapse of the tailing dam in the Aznalcóllar pyrite mine (SW Spain) occurred in April 1998 and affected approximately 4300 ha along the Agrio and Guadiamar valleys. An urgent soil cleaning up and remediation programme was started just after the accident. Eighteen months later, mineral nutrients and trace elements concentration in soil and two wild grasses--Cynodon dactylon and Sorghum halepense--have been studied. Three types of conditions are distinguished: (a) unaffected soils (control); (b) cleaned up and remediated soils (remediated); and (c) sludge-covered soils left in a fenced plot (non-remediated). As, Cd, Cu and Pb in grasses reached toxic levels for the food web in the non-remediated plot, while on remediated soils only Cd reached a toxic level in grass tissues. However, Pb and, to a lesser extent As and Fe, reached also toxic levels in unwashed plants (as they would be ingested by animals) in remediated soils. Both native grasses seem tolerant of trace elements pollution and suitable for stabilisation of spill-affected soils.