Soils from abandoned shooting range facilities as contamination source of potentially toxic elements: distribution among soil geochemical fractions.

Civilian and military shooting range facilities cause environmental issues in several countries due to the accumulation of Potentially Toxic Elements; as a result of weathering of ammunitions accumulated into the soils. The contents and distribution of Cu, Ni, Pb and Zn were analyzed in 12 soils in an abandoned clay target shooting range at two different depths (0-15 and 15-30 cm). Single extractions (CaCl2 and DTPA) and Tessier sequential extraction were conducted to assess the PTE mobility and the PTE distribution in the different soil geochemical fractions at both depths. High total contents of Pb were found at both soil depths, while Cu, Ni and Zn showed lower significance levels. Copper, Ni and Zn are mainly associated with the residual fraction (> 95% of total content in all cases). However, Pb was highly associated with exchangeable fractions (21-52%), showing a high mobility at both depths. With moderate-high contents of organic matter (6-12%), the studied soils have acidic values and low levels of Al, Fe and Mn oxides that favors the migration of Pb through the soil profile and potential transformation to more mobile forms (Pb0 to Pb2+ and Pb4+). Although Pb reduced downward mobility in soils, due to the specific conditions of these facilities and the lead source (weathering of ammunition), risk assessment studies on clay-target shooting and firing range facilities should study the potential migration of Pb through the soil profile.

Chemical availability versus bioavailability of potentially toxic elements in mining and quarry soils.

Abandoned mining and quarry areas are sources of potentially toxic elements (PTEs), through lixiviates or transfer processes of bioavailable fractions from mining wastes and tailings. In this study, earthworms (Eisenia fetida Savigny, 1826) were exposed for 28 days to two mining soils from a lead/zinc mine and two quarry soils from an old serpentine quarry. Despite their pseudo total metal contents, a previous characterization of these soils pointed out for a low chemical availability of PTEs. Therefore, a multibiomarker approach was used and the response of E. fetida to soils was assessed through the analysis of neurotoxic, oxidative stress, energy metabolism and DNA damage biomarkers (acetylcholinesterase, catalase, glutathione-s-transferase, lactate dehydrogenase, lipid peroxidation and DNA strand breaks). Metal bioaccumulation was also assessed to evaluate bioavailability and organism's exposure. Results showed that high contents of PTEs were recorded in the whole body of earthworms exposed to lead/zinc mine. However, the bioaccumulation factors for worms exposed to soils from both sampling sites were <1 due to the high PTEs contents in soils. Earthworms exposed to both types of soils displayed neurotoxic and energy metabolism effects. However, significant levels of oxidative stress and DNA damage were recorded only for earthworms exposed to lead/zinc mine soils. This study demonstrated that despite the low availability of PTEs showed by previous sequential chemical extractions, the results obtained from the direct toxicity assessment performed in this study, highlight the importance of a multibiomarker approach using soil organisms to provide a better evaluation of soils pollution.

Assessment of iron-based and calcium-phosphate nanomaterials for immobilisation of potentially toxic elements in soils from a shooting range berm.

Shooting range facilities in military areas have been indicated as a hotspot of land degradation with high contents of Potentially Toxic Elements (PTEs). Currently, based on the new nanomaterials with specific characteristics, nanoremediation technologies are used to immobilise and to reduce the availability of PTEs in field and laboratory conditions. In this study, the effects of nano-hydroxyapatite and/or hematite on PTEs immobilisation (As, Cd, Cu, Pb, Sb and Zn) in military shooting range soils were assessed through the measure of available and leachable forms with three single-extractions: calcium chloride (0.01M CaCl2), low molecular weight organic acids (10 mM LMWOAs) and toxicity characteristic leaching procedure (TCLP). A sequential chemical extraction was used to determine the distribution of the PTEs in the different geochemical phases of the soils before and after the nanomaterial treatments. Results showed that the availability of PTEs decreased, especially for Pb (40-95%) and Zn (50-99%) after nanomaterial treatments. When both nanomaterial (hydroxyapatite + hematite) were combined, the immobilisation rate improved. However, when each nanomaterial was added individually to the soils, some elements, such as, Cu or Sb, showed a slight increment of their mobilisation. The sequential chemical extraction showed that the highest percentage of PTEs were mainly in the residual fraction before and after adding nanomaterials, being even higher in soils after the nanomaterial treatments. Likewise, the mobile fractions decreased after the treatment with nanomaterials. Our findings suggest that nanoremediation techniques improve the soil conditions, but they should be used carefully to avoid mobilisation of non-target PTEs or unexpected potentially impacts for soil biota.

Ability of Cytisus scoparius for phytoremediation of soils from a Pb/Zn mine: Assessment of metal bioavailability and bioaccumulation.

Abandoned mining areas are an environmental concern for aquatic and terrestrial ecosystems due to their unfavourable soil properties and high levels of potentially toxic elements. Despite this, some plant species may grow spontaneously and colonise these areas; being suitable in many cases for restoration practices, since they may accumulate metals in their tissues. This study aims to assess the effectiveness of 14 chemical soil extractants to predict the bioavailability of toxic elements (Cd, Pb and Zn) in soils from the abandoned Pb/Zn mine of Rubiais (NW Spain), based on root and shoot metal contents in Cytisus scoparius (L.) Link, which grows spontaneously in this area. Afterwards, its potential for phytoremediation activities was assessed. Mine soils showed high contents Cd (1.77-14.38 mg kg-1), Pb (850-2137 mg kg-1) and Zn (1754-12090 mg kg-1). Cytisus scoparius grows in spite of these high metal contents; accumulating Zn and Pb in its roots, Zn in the aerial part and excluding mostly Cd from its tissues. None of the extractants used to determine the bioavailable content of Pb allow predicting its availability for C. scoparius. However, LMWOA was the most effective extractant to determine the bioavailability of Cd and Zn for this species. Besides, NH4NO3 and Ca(NO3)2 are also good indicators for Zn bioavailability. The analysis of bioconcentration and translocation factors suggest that C. scoparius behaves like a Zn accumulator plant, whereas alternatively, it behaves like a Pb phytostabiliser and as a Cd excluder species. Thus, C. scoparius can be used as a species for mine soil restoration, decreasing the mobility of metals and preventing their dispersion to another ecosystem compartments.

Pb pollution in soils from a trap shooting range and the phytoremediation ability of Agrostis capillaris L.

Pb pollution caused by shooting sport activities is a serious environmental problem that has increased considerably in recent decades. The aims of this study were firstly to analyze Pb pollution in soils from a trap shooting range abandoned in 1999, secondly to study the effectiveness of different extractants [CaCl2, DTPA, NH4OAc, low molecular weight organic acids (LMWOA), and bidistilled water (BDW)] in order to determine Pb bioavailability in these soils, and finally to evaluate the phytoremediation ability of spontaneous vegetation (Agrostis capillaris L.). To this end, 13 soils from an old trap shooting range (Galicia, NW Spain) were studied. It was found that Pb levels in the soils were higher than 100 mg kg(-1), exceeding the generic reference levels, and three of these samples even exceeded the USEPA threshold level (400 mg kg(-1)). In general, the reagent that best represents Pb bioavailability and has the greatest extraction efficiency was CaCl2, followed by DTPA, NH4OAc, LMWOA, and BDW. A. capillaris Pb contents ranged between 9.82 and 1107.42 mg kg(-1) (root) and between 6.43 and 135.23 mg kg(-1) (shoot). Pb accumulation in roots, as well as the presence of secondary mineral phases of metallic Pb in the adjacent soil, showed the phytostabilization properties of A. capillaris.

Validation of TOF-SIMS and FE-SEM/EDS Techniques Combined with Sorption and Desorption Experiments to Check Competitive and Individual Pb2+ and Cd2+ Association with Components of B Soil Horizons.

Sorption and desorption experiments were performed by the batch method on the B horizons of five natural soils: Umbric Cambisol, Endoleptic Luvisol, Mollic Umbrisol, Dystric Umbrisol, and Dystric Fluvisol. Individual and competitive sorption and desorption capacity and hysteresis were determined. The results showed that Pb2+ was sorbed and retained in a greater quantity than Cd2+ and that the hysteresis of the first was greater than that of the second. The most influential characteristics of the sorption and retention of Pb2+ were pH, ECEC, Fe and Mn oxides and clay contents. For Cd2+ they were mainly pH and, to a lesser extent, Mn oxides and clay content. The combined use of TOF-SIMS, FE-SEM/EDS and sorption and desorption analyses was suitable for achieving a better understanding of the interaction between soil components and the two heavy metals. They show the preferential association of Pb2+ with vermiculite, chlorite, Fe and Mn oxides, and of Cd2+ with the same components, although to a much lesser extent and intensity. This was due to the latter's higher mobility as it competed unfavourably with the Pb2+ sorption sites. TOF-SIMS and FE-SEM/EDS techniques confirmed the results of the sorption experiments, and also provided valuable information on whether the soil components (individually or in association) retain Cd2+ and/or Pb2+; this could help to propose effective measures for the remediation of contaminated soils.

Identifying sources of Pb pollution in urban soils by means of MC-ICP-MS and TOF-SIMS.

Lead pollution was evaluated in 17 urban soils from parks and gardens in the city of Vigo (NW Spain). The Pb isotope ratios ((207)Pb/(206)Pb, (208)Pb/(204)Pb, (206)Pb/(204)Pb and (208)Pb/(206)Pb) were determined after being measured by MC-ICP-MS. The association of the isotopes ((204)Pb, (206)Pb, (207)Pb and (208)Pb) with the different components of the soil was studied using TOF-SIMS. The isotopic ranges obtained for the samples were between 1.116 and 1.203 ((206)Pb/(207)Pb), 2.044-2.143 ((208)Pb/(206)Pb), 37.206-38.608 ((208)Pb/(204)Pb), 15.5482-15.6569 ((207)Pb/(204)Pb) and 17.357-18.826 ((206)Pb/(204)Pb). The application of the three-end-member model indicates that the Pb derived from petrol is the main source of Pb in the soils (43.51% on average), followed by natural or geogenic Pb (39.12%) and industrial emissions (17.37%). The emissions derived from coal combustion do not appear to influence the content of Pb in the soil. TOF-SIMS images show that the Pb mainly interacts with organic matter. This technique contributes to the understanding of the association of anthropogenic Pb with the components of the soil, as well as the particle size of these associations, thus allowing the possible sources of Pb to be identified.

Copper distribution in surface and subsurface soil horizons.

The horizons of four natural soils were treated with Cu(2+) in an acid medium to study the retention capacity of Cu. The possible mineralogical changes arising because of the treatment were also studied. The soil properties and characteristics with the greatest influence on the metal retention and its distribution among the different soil fractions were determined. Crystalline phases of each horizon were determined by X-ray diffraction (XDR). The morphology, structural distribution and particle chemical composition of soil samples were investigated using field emission scanning electron microscopy. Cu distribution in the different geochemical phases of the soil was studied using a sequential extraction. The treatment led to an increase in the amorphous phases and the formation of new crystalline phases, such as rouaite (Cu2(NO3)(OH)3) and nitratine (NaNO3). Cu was also found superficially sorbed on amorphous hydroxy compounds of Fe that interact with albite, muscovite and gibbsite, and also on spherical and curved particles of aluminium clays. The largest amount of Cu retained was in an exchangeable form, and the smallest amount associated with the crystalline Fe oxides and residual fraction. In the surface horizons, the predominant Cu retention process is complexation in organomineral associations, while in the subsurface horizons it is adsorption.

A soil quality index for reclaimed mine soils.

The quality of soils found in mines is low if they do not receive any reclamation treatment; yet, to the authors' knowledge, there are still no equations to evaluate the quality of metal-contaminated mine soils after the application of the most widely used reclamation treatments (planting vegetation and amending with wastes). Therefore, the purposes of the present study were 1) to propose a method for developing soil quality indexes (SQIs); 2) to develop the SQIs for 2 types of mine soils (settling pond and mine tailing) reclaimed by planting trees, amending with wastes, or both; and 3) to assess the quality of these soils under field conditions. The results obtained after the use of an SQI developed for reclaimed mine soils through the selection of an SQI with a factor analysis and the totaling of the scores of the selected variables revealed that this method is a valid tool for developing SQIs. Applying this index with reclaimed mine soils showed that the untreated sites had a very low quality and that the treatment that most improved the soils was amending with wastes (sewage sludges and paper mill residues). The authors recommend the periodic addition of sewage sludges and paper mill residues to degraded sites as they increase the quality of soils, but the effects decrease over time.

Modeling the plant-soil interaction in presence of heavy metal pollution and acidity variations.

On a mathematical interaction model, developed to model metal uptake by plants and the effects on their growth, we introduce a modification which considers also effects on variations of acidity in soil. The model relates the dynamics of the uptake of metals from soil to plants and also variations of uptake according to the acidity level. Two types of relationships are considered: total and available metal content. We suppose simple mathematical assumptions in order to get as simple as possible expressions with the aim of being easily tested in experimental problems. This work introduces modifications to two versions of the model: on the one hand, the expression of the relationship between the metal in soil and the concentration of the metal in plants and, on the other hand, the relationship between the metal in the soil and total amount of the metal in plants. The fine difference of both versions is fundamental at the moment to consider the tolerance and capacity of accumulation of pollutants in the biomass from the soil.

Speciation of heavy metals in River Rhine.

Chemical speciation of Zn, Cu, Ni, Cd and Pb in River Rhine was studied by measuring free ion concentration and distribution in nanoparticles, and by comparing the measurement with speciation modeling. Concentrations of free metal ions were determined in situ using Donnan Membrane Technique (DMT). The percentage of free over total (filtered) metal concentration is 52%, 33%, 2.6%, 0.48% and 0.12% for respectively Zn, Cd, Ni, Pb and Cu, i.e. the degree of metal complexation in the river is the lowest for Zn and the highest for Cu. Metals in 1-300 nm particles were analyzed using Asymmetric Flow Field Flow Fractionation (AsF-FFF), but the overall recovery is quite low. The nano-sized Cu detected is mainly associated with DOM of 1-5 nm, whereas Pb and Zn are dominantly associated with particles of iron hydroxides and clay of larger size (30-100 nm). Free ion concentrations calculated with the speciation modeling are in good agreement with the measurements, except for Pb. Based on the model, DOM-bound is the most important complexed form for Cu and Cd, whereas formation of (bi)carbonate and EDTA complexes are more important for Ni and Zn. Adsorption of Pb to DOM is probably overestimated by the model, whereas Pb adsorption to iron hydroxides is underestimated.

Effects of tree vegetation and waste amendments on the fractionation of Cr, Cu, Ni, Pb and Zn in polluted mine soils.

Soils at a depleted copper mine in Touro (Galicia, Spain) are physically and chemically degraded and have also polluted the surrounding area. Due to these environmental problems and the large area of these mine soils, the reclamation strategies carried out at Touro have consisted of planting trees (pine or eucalyptus), amending with waste material (sewage sludge and paper mill residues), or using both treatments. Tree planting has been carried out for 21 years and waste amending for 10. Two different zones were selected in the mine (the settling pond and mine tailing) in order to evaluate the effect of the different reclamation practices on the chemical fractions of Cr, Cu, Ni, Pb and Zn. The results showed that soils in the untreated sites were polluted by Cr and Cu. Planting pines and eucalyptus on mine soils decreased the concentration of these heavy metals in non-mobile soil fractions. Amendments also attenuated pollution by Cr and Cu as the wastes that were used had lower concentrations than the untreated mine soils. Planting trees increased Ni, Pb and Zn retention in the non-mobile fractions, preventing them from being leached into surrounding areas. However, caution should be exercised when adding organic wastes, as they can lead to increase concentrations of Ni, Pb and Zn and their phytoavailable form. The results also showed that changes in the chemical fractionation of heavy metals in soils was more influenced by the clay percentage and both dissolved and soil organic carbon (SOC and DOC) than by soil pH or cation exchange capacity.

Effects of vegetation on chemical and mineralogical characteristics of soils developed on a decantation bank from a copper mine.

Open cast mining has a strong impact on the environment, the intensity depending on the morphology of the deposit and on the nature of the minerals. At Touro mine (NW Spain) there is a large area covered by tailings, one of which, called the "sedimentation bank", was used to deposit sludge resulting from the extraction of copper in the flotation plant. Three zones were selected and the soils were sampled to analyse the changes brought about by vegetation on the chemical and mineralogical properties of the soils developed over the sedimentation bank and its development over time. The vegetation increased the pH, contents of organic material, nitrogen, clay and free oxides of Fe and Al, and the cationic exchange capacity of the soils. The decrease in the sulphide content, benefited by the vegetation process, led to a reduction in the total content of Cr and Cu. The vegetation also contributed towards the alteration of the primary minerals. The transformation of jarosite, the formation of nanocrystals of hematite, goethite, hydroxypolymers, and amorphous minerals that contained Cu, Cr and Pb were observed. Nevertheless the high Cu and Cr contents indicate that it is advisable to change the restoration process.

Development of a model to select plants with optimum metal phytoextraction potential.

PURPOSE: The aim of the present study is to propose a nonlinear model which provides an indicator for the maximum phytoextraction of metals to help in the decision-making process. Research into different species and strategies plays an important role in the application of phytoextraction techniques to the remediation of contaminated soil. Also, the convenience of species according to their biomass and pollutant accumulation capacities has gained important space in discussions regarding remediation strategies, whether to choose species with low accumulation capacities and high biomass or high accumulation capacities with low biomass. METHODS: The effects of heavy metals in soil on plant growth are studied by means of a nonlinear interaction model which relates the dynamics of the uptake of heavy metals by plants to heavy metal deposed in soil. RESULTS: The model, presented theoretically, provides an indicator for the maximum phytoextraction of metals which depends on adjustable parameters of both the plant and the environmental conditions. Finally, in order to clarify its applicability, a series of experimental results found in the literature are presented to show how the model performs consistently with real data. CONCLUSIONS: The inhibition of plant growth due to heavy metal concentration can be predicted by a simple kinetic model. The model proposed in this study makes it possible to characterize the nonlinear behaviour of the soil-plant interaction with heavy metal pollution in order to establish maximum uptake values for heavy metals in the harvestable part of plants.

Heavy metal concentrations in plants and different harvestable parts: a soil-plant equilibrium model.

A mathematical interaction model, validated by experimental results, was developed to modeling the metal uptake by plants and induced growth decrease, by knowing metal in soils. The model relates the dynamics of the uptake of metals from soil to plants. Also, two types of relationships are tested: total and available metal content. The model successfully fitted the experimental data and made it possible to predict the threshold values of total mortality with a satisfactory approach. Data are taken from soils treated with Cd and Ni for ryegrass (Lolium perenne, L.) and oats (Avena sativa L.), respectively. Concentrations are measured in the aboveground biomass of plants. In the latter case, the concentration of metals in different parts of the plants (tillering, shooting and earing) is also modeled. At low concentrations, the effects of metals are moderate, and the dynamics appear to be linear. However, increasing concentrations show nonlinear behaviors.

Enrichment of marsh soils with heavy metals by effect of anthropic pollution.

The impact of waste disposal on marsh soils was assessed in topsoil samples collected at eight randomly selected points in the salt marsh in Ramallosa (Pontevedra, Spain) at 4-month intervals for 2 years. Polluted soil samples were characterized in physico-chemical terms and their heavy metal contents determined by comparison with control, unpolluted samples. The results revealed a marked effect of waste discharges on the soils in the area, which have low contents in heavy metals under normal environmental conditions. In fact, the studied soils were found to contain substantial amounts of total and DTPA-extractable Cd, Cu, Pb and Zn. Based on the relationship of the redox potential with the DTPA-extractable Cd, Cu, Pb, and Zn contents of the soils, strongly reductive conditions raised the total contents in these elements by effect of their remaining in the soils as precipitated sulphides. Such contents, however, decreased as oxidative conditions gradually prevailed. The contents in DTPA-extractable metals increased with increasing Eh through the release of the metals in ionic form to the soil solution under oxidative conditions. The contents in heavy metals concentrating in the polluted soils were several times higher than those in the control soils (viz. 2 vs. 6 for Cd, 4 vs. 6 for Cu, 4 vs. 20 for Pb, and 2 vs. 15 for Zn, all in mgkg(-1)). This can be expected to influence the amounts of available heavy metals present in the soils, and hence the environmental quality of the area, in the near future. Based on its geoaccumulation index (Class >/=3 for Cd and Cu, and 1-4 for Pb and Zn), the Ramallosa marsh is highly polluted with Cd and moderately to highly polluted with Cu, Pb and Zn. The enrichment factors obtained confirm that the salt marsh is highly polluted (especially with Cd) as the primary result of anthropic activity.

Degradation of fuel oil in salt marsh soils affected by the Prestige oil spill.

We assessed natural degradation of fuel oil in three marshes from Galicia (Spain) affected by the Prestige oil spill (Baldaio, Barizo, and Muxía). Soil samples collected from polluted and unpolluted areas on four different dates were used to determine total petroleum hydrocarbon content and fuel-oil components. Natural degradation was monitored by analysing changes in the proportion of saturated hydrocarbons, aromatics, asphaltenes and resins in the soils, and also by evaluating the degree of depletion of saturated hydrocarbons on each sampling date. We additionally assessed the phytoremediation potential of Lolium perenne, L., Convolvulus arvensis L. and Raphanus raphanistrum L. All marsh soils exhibited natural degradation of saturated and aromatic hydrocarbons to between 85 and 95% in most cases. In contrast, asphaltenes and resins were degraded to a lesser extent (viz. 64-76% in Barizo 1, Muxía and Traba; 39-44% in Baldaio; and only 12% in Barizo 2, where flooding by the river continues to introduce balls of fuel oil into the soil). Monitoring analyses revealed natural degradation to be dependent on the thickness of the pollutant layer. Field plots sown with L. perenne L. exhibited no significant differences in fuel-oil degradation from untreated plots.

Influence of mineral and organic components on copper, lead, and zinc sorption by acid soils.

Sorption isotherms were constructed for the sorption of Cu, Pb and Zn by the surface horizons of three soils [a Humic Cambisol (G1), a Haplic Podzol (G2) and an Umbric Gleysol (G3)] and by fractions obtained by sequential removal of organic matter and oxides. All were of L-type except the H-type isotherms recorded for sorption of lead by whole G2, and all were fitted well by the Langmuir model, with determination coefficients > 0.91. Langmuir equation parameter beta correlated well (r(2) = 0.985) with experimentally maximum sorption capacity. For all soils, metal sorption capacities decreased in the order Zn > Cu > Pb. Sorption by organic matter was one of the main contributions to total sorption. Sorption by oxides was generally most substantial in G1, which had the largest total oxides content, while the sorption of lead by G3 was attributable to its high Mn oxides content. The clayey residue contributed significantly to sorption of zinc by G1, and G3 (due to their respective vermiculite and gibbsite contents) and to sorption of copper by G1 due to its vermiculite content.