Contrasting mobility of arsenic and copper in a mining soil: A comparative column leaching and pot testing approach.

The remediation of legacy metal(loid) contaminated soils in-situ relies on the addition of [organic] amendments to reduce the mobility and bioavailability of metal(loid)s, improve soil geochemical parameters and restore vegetation growth. Two vermicomposts of food and animal manure waste origin (V1 and V2) were amended to an arsenic (As) and copper (Cu) contaminated mine soil (≤1500 mg kg-1). Leaching columns and pot experiments evaluated copper and arsenic in soil pore waters, as well as pH, dissolved organic carbon (DOC) and phosphate (PO43-) concentrations. The uptake of As and Cu to ryegrass was also measured via the pot experiment, whilst recovered biochars from the column leaching test were measured for metal sorption at the termination of leaching. Vermicompost amendment to soil facilitated ryegrass growth which was entirely absent from the untreated soil in the pot test. All amendment combinations raised pore water pH by ∼4 units. Copper concentrations in pore waters from columns and pots showed steep reductions (∼1 mg L-1), as a result of V1 & V2 compared to untreated soil (∼500 mg L-1). Combined with an increase in DOC and PO43-, As was mobilised an order of magnitude by V1. Biochar furthest reduced Cu in pore waters from the columns to <0.1 mg L-1, as a result of surface sorption. The results of this study indicate that biochar can restrict the mobility of Cu from a contaminated mine soil after other amendment interventions have been used to promote revegetation. However, the case of As, biochar cannot counter the profound impact of vermicompost on arsenic mobility.

Comparative effect of compost and technosol enhanced with biochar on the fertility of a degraded soil.

A large number of studies on the reclamation of mine soils focused on the problem caused by metals and did not explore in depth the issue of nutrients and vegetation after the application of organic materials. The aim of this study was to compare the effect of two treatments made of wastes and vegetated with Brassica juncea L. on the fertility of a settling pond mine soil. The first treatment was compost, biochar, and B. juncea (SCBP) and the second treatment was technosol, biochar, and B. juncea (STBP). This study evaluated the effect of the treatments on the soil nutrient concentrations and fertility conditions in the soil amendment mixtures, after 11 months of greenhouse experiment. Total carbon and nitrogen concentrations were higher in treatment SCBP than in treatment STBP after 7 months but, after 11 months, carbon concentration was higher in STBP. The used technosol could have forms of carbon more stable than compost, which could be released slower than in the compost-amended soils. Both compost and technosol mixed with biochar also increased the concentration of calcium, potassium, magnesium, and sodium in exchangeable form in the mine soil.

Recovering a copper mine soil using organic amendments and phytomanagement with Brassica juncea L.

A 3-month greenhouse experiment was carried out for evaluating the effect of an amendment mixture and mustards on the chemical characteristics of a mine soil and the metal uptake by plants. A settling pond soil was amended with increasing percentages of a technosol and biochar mixture and vegetated with Brassica juncea L. Adding amendments and planting mustards increased the soil pH from 2.83 to 6.18 and the TSC from u.l to 131 g kg(-1) and generally reduced the CaCl2-extractable metal concentrations in the soil. However, the amendments increased the pseudo-total soil concentration of Ni from 9.27 to 31.9 mg kg(-1), Pb from 27.9 to 91.6 mg kg(-1) and Zn from 46.5 to 577 mg kg(-1). The technosol and biochar mixture increased the shoot biomass from 0.74 to 2.95 g and generally reduced the metal concentrations in plants, meaning B. juncea as a potential candidate for phytostabilization of mine soils.

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.

Pyrolysis temperature influences the capacity of biochar to immobilize copper and arsenic in mining soil remediation.

Biochar is a promising material used for multiple remediation approaches, mainly in polluted soils. Its properties can differ depending on feedstock and pyrolysis temperature. In this context, we tested the capacity of three biochar products made from corncob, pyrolyzed at different temperatures (350, 500, and 650 °C), to remediate a mining soil affected by high levels of Cu and As. We performed an exhaustive characterization of the biochar. We found that biochar showed a higher surface area with increasing pyrolysis temperature, whereas high molecular weight PAHs were detected in biochar produced at the maximum temperature, thus indicating potential ecotoxicological risks. After the application of biochar to the soil, Cu was partially immobilized, especially when using that obtained at 500 °C. This effect is attributed to the structure of this material and an increase in soil pH and organic matter content. Conversely, As was increased in the soluble fraction for all three types of biochar but in a proportion that lacks relevance. On the whole, given its lower PAH content, higher Cu immobilization ratio, and an almost negligible increase in As availability, biochar obtained at 500 °C outperformed the other two products with respect to soil recovery. Of note, data on Cu and As availability were doubled-checked using two extraction methodologies. We propose that this operational approach for determining the most suitable pyrolysis temperature will find application in other soil remediation actions.

Using compost and technosol combined with biochar and Brassica juncea L. to decrease the bioavailable metal concentration in soil from a copper mine settling pond.

One of the most important sources of pollution caused by metals, if not the most important, is mining. Metal pollution is covert, persistent and irreversible. For this reason, soil metal pollution has become a severe problem in many parts of the world. The aim of this study was to observe which combination of amendments (compost + biochar or technosol + biochar) combined with Brassica juncea L. was best at reducing the assimilable contents of Cu, and which also increased to a lesser extent the contents of other metals (Ni, Pb, Zn) found in these amendments. We also studied the phytoremediation capacity of brassicas in these amendments. The experiment was carried out using 45-cm-deep cylinders over and 11-month period, with soil from the settling pond in the depleted copper mine located in Touro (Galicia, north-west Spain). At depth 0-15 cm, the settling pond soil (S) had a higher CaCl2-extractable Cu, Pb, and Ni concentration, at the three time periods measured (time 1 = 3 months, time 2 = 7 months, time 3 = 11 months). The settling pond soil + technosol + biochar and vegetated with Brassica juncea L. (STBP) had the highest CaCl2-extractable concentrations of Zn over time. In general terms, the most effective treatment for reducing the phytoavailable contents of Cu, Pb, Ni and Zn was the treatment using compost +b iochar + Brassica juncea L. In the two treatments applied, Brassica juncea L. had a good phytostabilisation capacity.

Effects of compost and technosol amendments on metal concentrations in a mine soil planted with Brassica juncea L.

Mining activities often cause important impacts on soil and water quality. The main objective of this study was to evaluate the effect of amendments (compost and technosol made from waste) on metal concentrations in a mine soil planted with Brassica juncea. A greenhouse experiment with cylinder pots was carried out during 11 months. The mine soil was collected from the settling pond of the depleted copper mine of Touro (Galicia, Northwest Spain). A series of characteristics were analysed including soil pseudototal metal concentrations, soil CaCl2-extractable (phytoavailable) metal concentrations and metal concentrations in soil pore water. The results showed that at depth 0-15 cm SCP (mine soil + compost, grown with B. juncea) had a significantly lower CaCl2-extractable Cu, Pb, Ni and Zn concentration than STP (mine soil + technosol, grown with B. juncea) over the time (P < 0.05). At depths 15, 30 and 45 cm, STP and SCP had lower Cu pore water concentration than S over the time. The highest translocation factor (TF) values for all metals (Cu, Pb, Ni and Zn) were observed at time 1 (3 months) in the settling pond soils treated with technosol and B. juncea L. The conclusions of this experiment revealed that SCP compared to STP caused a higher reduction on Cu, Pb, Ni and Zn phytoavailable concentrations in the first depths.

Predicting Cu and Zn sorption capacity of biochar from feedstock C/N ratio and pyrolysis temperature.

Biochars have been proposed for remediation of metal-contaminated water due to their low cost, high surface area and high sorption capacity for metals. However, there is a lack of understanding over how feedstock material and pyrolysis conditions contribute to the metal sorption capacity of biochar. We produced biochars from 10 different organic materials by pyrolysing at 450 °C and a further 10 biochars from cedar wood by pyrolysing at 50 °C intervals (250-700 °C). Batch sorption experiments were conducted to derive the maximum Cu and Zn sorption capacity of each biochar. The results revealed an exponential relationship between Cu and Zn sorption capacity and the feedstock C/N ratio and a sigmoidal relationship between the pyrolysis temperature and the maximum Cu and Zn sorption capacity. FTIR analysis revealed that as temperature increased, the abundance of functional groups reduced. We conclude that the high sorption capacity of high temperature biochars is due to an electrostatic attraction between positively charged Cu and Zn ions and delocalised pi-electrons on the greater surface area of these biochars. These findings demonstrate a method for predicting the maximum sorption capacity of a biochar based on the feedstock C/N ratio and the pyrolysis temperature.

Phytoremediating a copper mine soil with Brassica juncea L., compost and biochar.

The soils at a depleted copper mine in Touro (Galicia, Spain) are chemically degraded. In order to determine the effect of amendments and vegetation on the chemical characteristics of a mine soil and on the plant uptake of metals, a greenhouse experiment was carried out for 3 months. A settling pond soil was amended with different percentages of a compost and biochar mixture and vegetated with Brassica juncea L. The results showed that the untreated settling pond soil was polluted by Cu. Amendments and planting mustards decreased the pseudototal concentration of this metal, reduced the extreme soil acidity and increased the soil concentrations of C and TN. Both treatments also decreased the CaCl2-extractable Co, Cu and Ni concentrations. However, the amendments increased the pseudototal concentration of Zn in the soil, provided by the compost that was used. The results also showed that mustards extracted Ni efficiently from soils, suggesting that B. juncea L. is a good phytoextractor of Ni in mine soils.

Effect of salinity on zinc uptake by Brassica juncea.

Salinity is a major worldwide problem that affects agricultural soils and limits the reclamation of contaminated sites. Despite the large number of research papers published about salt tolerance in Brassica juncea L., there are very few accounts concerning the influence of salinity on the uptake of trace metals. In this study, B. juncea plants divided through soil sets comprising 0, 900 and 1800 mg Zn kg(-1), were treated with solutions containing 0, 60 and 120 mmol L(-1) of NaCl, with the purpose of observing the effect of salt on Zn uptake, and some physiological responses throughout the 90 days experiment. Increasing concentrations of NaCl and Zn produced a decline in the ecophysiological and biochemical properties of the plants, with observable synergistic effects on parameters like shoot dry weight, leaf area, or photochemical efficiency. Nevertheless, plants treated with 60 mmol L(-1) of NaCl accumulated striking harvestable amounts of Zn per plant that largely exceed those reported for Thlaspi caerulescens. It was concluded that salinity could play an important role on the uptake of Zn by B. juncea. The potential mechanisms behind these results are discussed, as well as the implications for phytoremediation of Zn on saline and non-saline soils.

Soil management of copper mine tailing soils--sludge amendment and tree vegetation could improve biological soil quality.

Mine soils at the depleted copper mine in Touro (Northwest Spain) are physico-chemically degraded and polluted by chromium and copper. To increase the quality of these soils, some areas at this mine have been vegetated with eucalyptus or pines, amended with sludges, or received both treatments. Four sites were selected at the Touro mine tailing in order to evaluate the effect of these different reclamation treatments on the biological soil quality: (1) Control (untreated), (2) Forest (vegetated), (3) Sludge (amended with sludges) and (4) Forest+Sludge (vegetated and amended). The new approach of the present work is that we evaluated the effect of planting trees or/and amending with sludges on the biological soil quality of mine sites polluted by metals under field conditions. The addition of sludges to mine sites recovered the biological quality of the soil, while vegetating with trees did not increase microbial biomass and function to the level of unpolluted sites. Moreover, amending with sludges increased the efficiency of the soil's microbial community to metabolize C and N, which was indicated by the decrease of the specific enzyme activities and the increase in the ratio Cmic:Nmic (shift towards predominance of fungi instead of bacteria). However, the high Cu and Cr concentrations still have negative influence on the microorganisms in all the treated soils. For the future remediation of mine soils, we recommend periodically adding sludge and planting native legume species.

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.

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.

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.

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.

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.

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.