Evaluation of copper availability to plants in copper-contaminated vineyard soils

The repeated use of copper (Cu) fungicides to control vine downy mildew has led to long-term accumulation of Cu in vineyard soils which now raises the issue of the potential bioavailability of Cu for various living organisms including plant species. The bioavailable Cu can be defined as the portion of soil Cu that can be taken up by roots, for a given plant species. In order to evaluate the bioavailability of Cu to plants, a pot experiment was conducted in glasshouse conditions with a crop species (maize) and 12 soils sampled in the upper horizon of 10 vineyard plots (total Cu ranging from 38 to 251 mg kg-1) and two woodland plots (control soils that had not received any Cu application; total Cu amounting to 20-26 mg kg-1). These soils were selected for their diverse physical (large range of particle size distribution) and chemical (from acid to calcareous soils) properties. After 35 days of growth, plant shoots were harvested for analysis. The roots were separated from soil particles for further analysis. The concentrations of Cu in the roots and aerial parts of the maize were then compared with the amounts of Cu extracted from the soil by a range of conventional extractants. Observed Cu concentrations in maize roots which have grown in contaminated vineyard soils were very high (between 90 and 600 mg kg-1), whereas Cu concentrations in the aerial parts varied only slightly and remained low (< 18 mg kg-1). Root Cu concentrations observed for maize increased with increasing total Cu content in the soil and with decreasing soil CEC. Cu accumulation in maize roots may be as high in calcareous soils as in acid soils, suggesting that soil pH had little influence. In the case of the vineyard soils studied, the lack of correlation found for maize between Cu concentrations in roots and in the aerial parts, suggests that an analysis of the aerial parts would not be a good indicator of plant Cu uptake, as it provides no insight into the real amount of Cu transferred from the soil to the plant. For maize, our results show that extraction with organic complexing agents (EDTA, DTPA) and extraction with ammonium acetate seem to provide a reasonably good estimate of root Cu concentration.     

Effects of copper fungicide residues on the microbial function of vineyard soils

The use of copper-based fungicides leads to an accumulation of copper (Cu) in vineyard soils, potentially causing adverse effects to the microbial function and fertility of the soil. This study used a soil microcosm approach to assess the effects of Cu accumulation on microbial function in vineyard soils. Surface soil samples were collected from 10 vineyards and a number of un-impacted reference sites in each of three different viticultural regions of Australia. The field-collected soils were transferred to microcosms and maintained for up to 93 days in the laboratory at 20–22 °C and 60 % of their maximum water-holding capacity. The microbial function of the soils was indicated by measuring phosphomonoesterase, arylsulfatase, urease, and phenol oxidase activities. In general, the vineyard soils had greater concentrations of Cu and lower enzyme activities than in the reference soils, although a weak negative relationship between Cu and enzyme activity could only be found for phosphomonoesterase activity. The results show that soil physical–chemical properties (i.e., organic carbon, pH) are greater determinants of soil enzyme activity than increased soil Cu concentration at the Cu concentrations present in vineyard soils.     

Particulate copper in soils and surface runoff from contaminated sandy soils under citrus production

Soil contamination by copper (Cu) is a worldwide concern. Laboratory incubation and soil Cu characterization were conducted to examine the effects of external Cu loading and liming on Cu speciation in both bulk soil and particulates of an Alfisol and Spodosol under citrus production. Also, drainage water from the sites was evaluated for dissolved and particulate forms of Cu. Soil available Cu estimated by CaCl₂, NH₄OAc, or Mehlich-3 extraction significantly increased with external Cu loads and decreased with soil pH. Most increases in soil Cu occurred in the exchangeable and oxide-bound fractions. Organically bound Cu was the dominant fraction in both bulk soil and particulates, but more in particulates than bulk soil (P?≤?0.001). Organically bound Cu was highly correlated with total recoverable Cu (P?≤?0.01), increased significantly with external Cu loads (P?≤?0.001), and decreased with soil pH (P?≤?0.05). Lime addition converted part of Cu from available pools to more stable forms. Organically bound Cu complexes were found to dominate in soil solution or surface runoff. These results indicate that most Cu accumulated in the contaminated soils is highly mobile, and thus may impact citrus production and the environment.     

Potential and drawbacks of EDDS-enhanced phytoextraction of copper from contaminated soils

Incubation and pot experiments using poplar (Populus nigra L. cv. Wolterson) were performed in order to evaluate the questionable efficiency of EDDS-enhanced phytoextraction of Cu from contaminated soils. Despite the promising conditions of the experiment (low contamination of soils with a single metal with a high affinity for EDDS, metal tolerant poplar species capable of producing high biomass yields, root colonization by mycorrhizal fungi), the phytoextraction efficiency was not sufficient. The EDDS concentrations used in this study (3 and 6 mmol kg⁻¹) enhanced the mobility (up to a 100-fold increase) and plant uptake of Cu (up to a 65-fold increase). However, despite EDDS degradation and the competition of Fe and Al for the chelant, Cu leaching cannot be omitted during the process. Due to the low efficiency, further research should be focused on other environment-friendly methods of soil remediation.     

Influence of organic amendments on copper distribution among particle-size and density fractions in Champagne vineyard soils

The intensive use for over 100 years of copper sulfate (Bordeaux mixture) to fight against mildew in vineyard soils has led to an important, widespread accumulation of Cu (100 to 1500 mg Cu kg-1 soil). In Champagne vineyards, organic amendments are used currently to increase soil fertility and to limit soil erosion. Organic amendments may have a direct effect on the retention of Cu in the soil. To assess the influence of the organic management on the fate of Cu in calcareous Champagne vineyard soils, we studied Cu distribution (1) in the soil profile and (2) among primary soil particles, in vineyard parcels with different amendments. Amendments were oak-bark, vine-shoots and urban compost. The results were compared with the amount and the distribution of Cu in an unamended calcareous soil. Physical soil fractionations were carried out to separate soil primary particles according to their size and density. Cu has a heterogeneous distribution among soil particle fractions. Two fractions were mainly responsible for Cu retention in soils: the organic debris larger than 50 microns or coarse particulate organic matter (POM) issued from the organic amendments, and the clay-sized fraction < 2 microns. The POM contained up to 2000 mg Cu kg-1 fraction and the clay fraction contained up to 500 mg Cu kg-1 fraction. The clay-sized fraction was responsible for almost 40% of the total amount of Cu in the four parcels. POM was predominantly responsible for the differences in Cu contents between the unamended and the three amended parcels. Our results attested that methods of soil particle-size fractionation can be successfully used to assess the distribution of metal elements in soils.     

Linking plant tissue concentrations and soil copper pools in urban contaminated soils

Copper tissue concentrations of radish (Raphanus sativa cv. Cherry Belle), lettuce (Lactuca sativa cv. Buttercrunch) and ryegrass (Lolium perenne cv. Barmultra) grown in a greenhouse in urban contaminated soils are compared to total, soluble and free ion copper pools. The tissue concentrations of copper vary between 8.1 and 82.6 mg Cu kg(-1) dry tissue and the total soil copper content varies between 32 and 640 mg Cu kg(-1) dry soil. The linear regressions with cupric ion activity and total soil copper are both significant (p < 0.01), but cupric ion activity yields a higher level of statistical significance in every case. The results support the hypothesis that free metal in the soil solution is a better indicator of plant metal bioavailability than either total or soluble metal.     

Extractability and mobility of mercury from agricultural soils surrounding industrial and mining contaminated areas

This study focussed on a comparison of the extractability of mercury in soils with two different contamination sources (a chlor-alkali plant and mining activities) and on the evaluation of the influence of specific soil properties on the behaviour of the contaminant. The method applied here did not target the identification of individual species, but instead provided information concerning the mobility of mercury species in soil. Mercury fractions were classified as mobile, semi-mobile and non-mobile. The fractionation study revealed that in all samples mercury was mainly present in the semi-mobile phase (between 63% and 97%). The highest mercury mobility (2.7 mg kg(-1)) was found in soils from the industrial area. Mining soils exhibited higher percentage of non-mobile mercury, up to 35%, due to their elevated sulfur content. Results of factor analysis indicate that the presence of mercury in the mobile phase could be related to manganese and aluminium soil contents. A positive relation between mercury in the semi-mobile fraction and the aluminium content was also observed. By contrary, organic matter and sulfur contents contributed to mercury retention in the soil matrix reducing the mobility of the metal. Despite known limitations of sequential extraction procedures, the methodology applied in this study for the fractionation of mercury in contaminated soil samples provided relevant information on mercury's relative mobility.     

Extractability and mobility of mercury from agricultural soils surrounding industrial and mining contaminated areas

This study focussed on a comparison of the extractability of mercury in soils with two different contamination sources (a chlor-alkali plant and mining activities) and on the evaluation of the influence of specific soil properties on the behaviour of the contaminant. The method applied here did not target the identification of individual species, but instead provided information concerning the mobility of mercury species in soil. Mercury fractions were classified as mobile, semi-mobile and non-mobile.The fractionation study revealed that in all samples mercury was mainly present in the semi-mobile phase (between 63% and 97%). The highest mercury mobility (2.7 mg kg⁻¹) was found in soils from the industrial area. Mining soils exhibited higher percentage of non-mobile mercury, up to 35%, due to their elevated sulfur content.Results of factor analysis indicate that the presence of mercury in the mobile phase could be related to manganese and aluminium soil contents. A positive relation between mercury in the semi-mobile fraction and the aluminium content was also observed. By contrary, organic matter and sulfur contents contributed to mercury retention in the soil matrix reducing the mobility of the metal.Despite known limitations of sequential extraction procedures, the methodology applied in this study for the fractionation of mercury in contaminated soil samples provided relevant information on mercury’s relative mobility.     

Effects of incubation on solubility and mobility of trace metals in two contaminated soils

Much research has focused on changes in solubility and mobility of trace metals in soils under incubation. In this experiment, changes in solubility and mobility of trace metals (Pb, Cu and As) and Fe in two contaminated soils from Tampa, Florida and Montreal, Canada were examined. Soils of 30 g were packed in columns and were incubated for 3-80 days under water-flooding incubation. Following incubation, metal concentrations in pore water (water soluble) and in 0.01 M CaCl2 leachates (exchangeable+water soluble) were determined. While both soils were contaminated with Pb (1600-2500 mg kg(-1)), Tampa soil was also contaminated with As (230 mg kg(-1)). Contrast to the low pH (3.8) of Tampa soil, Montreal soil had an alkaline pH of 7.7 and high Ca of 1.6%. Concentrations of Fe(II) increased with incubation time in the Tampa soil mainly due to reductive Fe dissolution, but decreased in the Montreal soil possibly due to formation of FeCO3. The inverse relationship between concentrations of Pb and Fe(II) in pore water coupled with the fact that Fe(II) concentrations were much greater than those of Pb in pore water may suggest the importance of Fe(II) in controlling Pb solubility in soils. However, changes in concentrations of Fe(II), Pb, Cu and As in pore water with incubation time were similar to those in leachate, i.e. water soluble metals were positively related to exchangeable metals in the two contaminated soils. This research suggests the importance of Fe in controlling metal solubility and mobility in soils under water-flooded incubation.     

Chelating agent-assisted electrokinetic removal of cadmium, lead and copper from contaminated soils

An integrated experimental program was conducted to remove Cd, Pb and Cu from contaminated soil. The chelate agents nitrilotriacetic acid (NTA), diethylenetriamine pentaacetic acid (DTPA) and ethyleneglycol tetraacetic acid (EGTA) were used as washing solutions under different pH conditions and concentrations. Results showed that the extraction efficiency for Cd in decreasing order was NTA > EGTA > DTPA, while for Pb and Cu it was DTPA > NTA > EGTA. The use of higher chelate concentrations did not necessarily result in greater extraction efficiency. Electrokinetic remediation was applied by conditioning anolyte-catholyte pH to neutral values in order to avoid any potential alterations to the physicochemical soil properties. The removal efficiency for Cd was 65-95%, for Cu 15-60%, but for Pb was less than 20%. The phytotoxicity of the treated soil showed that the soil samples from the anode section were less phytotoxic than the untreated soil, but the phytotoxicity was increased in the samples from the cathode section.     

Deciphering biodegradable chelant-enhanced phytoremediation through microbes and nitrogen transformation in contaminated soils

Biodegradable chelant-enhanced phytoremediation offers an alternative treatment technique for metal contaminated soils, but most studies to date have addressed on phytoextraction efficiency rather than comprehensive understanding of the interactions among plant, soil microbes, and biodegradable chelants. In the present study, we investigated the impacts of biodegradable chelants, including nitrilotriacetate, S,S-ethylenediaminedisuccinic acid (EDDS), and citric acid on soil microbes, nitrogen transformation, and metal removal from contaminated soils. The EDDS addition to soil showed the strongest ability to promote the nitrogen cycling in soil, ryegrass tissue, and microbial metabolism in comparison with other chelants. Both bacterial community-level physiological profiles and soil mass specific heat rates demonstrated that soil microbial activity was inhibited after the EDDS application (between day 2 and 10), but this effect completely vanished on day 30, indicating the revitalization of microbial activity and community structure in the soil system. The results of quantitative real-time PCR revealed that the EDDS application stimulated denitrification in soil by increasing nitrite reductase genes, especially nirS. These new findings demonstrated that the nitrogen release capacity of biodegradable chelants plays an important role in accelerating nitrogen transformation, enhancing soil microbial structure and activity, and improving phytoextraction efficiency in contaminated soil.     

Arsenic mobility in contaminated lake sediments

An arsenic contaminated lake sediment near a landfill in Maine was used to characterize the geochemistry of arsenic and assess the influence of environmental conditions on its mobility. A kinetic model was developed to simulate the leaching ability of arsenic in lake sediments under different environmental conditions. The HM1D chemical transport model was used to model the column experiments and determine the rates of arsenic mobility from the sediment. Laboratory studies provided the information to construct a conceptual model to demonstrate the mobility of arsenic in the lake sediment. The leaching ability of arsenic in lake sediments greatly depends on the flow conditions of ground water and the geochemistry of the sediments. Large amounts of arsenic were tightly bound to the sediments. The amount of arsenic leaching out of the sediment to the water column was substantially decreased due to iron/arsenic co-precipitation at the water-sediment interface. Overall, it was found that arsenic greatly accumulated at the ground water/lake interface and it formed insoluble precipitates.     

Solid speciation and mobility of potentially toxic elements from natural and contaminated soils: a combined approach

The study area (Szklary Massif, SW Poland) comprises three sites of different soil provenance: (1) natural serpentine Cambisol, (2) anthroposol situated on waste dump and (3) cultivated Inceptisol developed on glacial tills next to the dump. Potentially toxic elements (PTE) have either lithogenic or anthropogenic origins in these sites. The chemical partitioning of Co, Cr, Cu, Ni, Pb and Zn among solid forms was determined by sequential extractions coupled with direct mineral identifications (SEM, electron microprobe analysis - EMPA, and XRD). Examination of solid residues after several extraction steps was conducted in order to discuss the indirect speciation obtained by the extraction method. Total concentrations of PTE having anthropogenic origin greatly exceed those of lithogenic origin. Mobility of studied PTE is variable in the different environments except for Cr which is always mostly found in residual fractions of extractions. Cu and Pb are more mobile than Cr and Co in all soils. Zn is more stable (Cu>Pb>Ni>Co>Zn>Cr) in the serpentine soil and cultivated epipedon (Pb>Cu>Zn>Ni>Co>Cr) than in the anthroposol (Zn>CuPb>Ni>Co>Cr). PTE of lithogenic origin are generally less mobile than those from anthropogenic origin except Ni which is more mobile in the serpentine soil. Nonetheless, mineral forms of metals better determine their mobility than metal origin. Identification by direct methods of the PTE mineral form was not possible for metals present at low concentrations (Cu, Pb). However, direct mineralogical examinations of the solid residues of several extractions steps improved the assessment of the PTE solid speciation and mobility, particularly for Cr, Ni and Zn.     

Ecological restoration of mine degraded soils,with emphasis on metal contaminated soils

This paper reviews the ecological aspects of mined soil restoration, with special emphasis on maintaining a long-term sustainable vegetation on toxic metal mine sites. The metal mined soils are man-made habitats which are very unstable and will become sources of air and water pollution. Establishment of a vegetation cover is essential to stabilize the bare area and to minimize the pollution problem. In addition to remediate the adverse physical and chemical properties of the sites, the choice of appropriate vegetation will be important. Phytostabilization and phytoextraction are two common phytoremediation techniques in treating metal-contaminated soils, for stabilizing toxic mine spoils, and the removal of toxic metals from the spoils respectively. Soil amendments should be added to aid stabilizing mine spoils, and to enhance metal uptake accordingly.     

Sorption of phenanthrene by soils contaminated with heavy metals

The fate of polycyclic aromatic hydrocarbons (PAHs) in soils with co-contaminants of heavy metals has yet to be elucidated. This study examined sorption of phenanthrene as a representative of PAHs by three soils contaminated with Pb, Zn or Cu. Phenanthrene sorption was clearly higher after the addition of heavy metals. The distribution coefficient (K(d)) and the organic carbon-normalized distribution coefficient (K(oc)) for phenanthrene sorption by soils spiked with Pb, Zn or Cu (0-1000 mg kg(-1)) were approximately 24% larger than those by unspiked ones, and the higher contents of heavy metals added into soils resulted in the larger K(d) and K(oc) values. The enhanced sorption of phenanthrene in the case of heavy metal-contaminated soils could be ascribed to the decreased dissolved organic matter (DOM) in solution and increased soil organic matter (SOM) as a consequence of DOM sorption onto soil solids. Concentrations of DOM in equilibrium solution for phenanthrene sorption were lower in the case of the heavy metal-spiked than unspiked soils. However, the decreased DOM in solution contributed little to the enhanced sorption of phenanthrene in the presence of metals. On the other hand, the sorbed DOM on soil solids after the addition of heavy metals in soils was found to be much more reactive and have far stronger capacity of phenanthrene uptake than the inherent SOM. The distribution coefficients of phenanthrene between water and the sorbed DOM on soil solids (K(ph/soc)) were about 2-3 magnitude larger than K(d) between water and inherent SOM, which may be the dominant mechanism of the enhanced sorption of phenanthrene by soils with the addition of heavy metals.     

Copper uptake by Elsholtzia splendens and Silene vulgaris and assessment of copper phytoavailability in contaminated soils

Tolerance and metal uptake are two essential characteristics required for phytoextraction of metals from contaminated soils. We compared tolerance and Cu uptake of Elsholtzia splendens (reported previously to be a Cu hyperaccumulator) with Silene vulgaris (the Imsbach population, a well-known Cu-tolerant excluder species), using 30 soils varying widely in total Cu concentration (19-8645 mg kg(-1)). We further investigated the effectiveness of different soil testing methods for predicting plant metal uptake. The results showed that both Elsholtzia splendens and Silene vulgaris were tolerant to Cu, especially Silene vulgaris. However, Elsholtzia splendens did not hyperaccumulate Cu, but behaved as a typical Cu excluder like Silene vulgaris. The concentrations of Cu in both plants correlated more closely with 1 M NH4NO3 extractable Cu, soil solution Cu, or effective Cu concentration determined using DGT, than with soil total Cu, EDTA extractable Cu or free Cu2+ activity. The relationships between soil solution properties and root Cu concentrations were further investigated using multiple regression. The results showed that increasing soil solution pH increased root Cu concentration when free Cu2+ activity was held constant, suggesting a higher phytoavailability of free Cu2+ at a higher pH. Soil solution DOC appeared to play two contrasting roles on the phytoavailability of Cu: (1) reducing Cu availability by complexing Cu; and (2) increasing Cu availability at the same level of free Cu2+ activity by providing a strong buffer for free Cu2+. The results are consistent with the intensity/capacity concept for phytoavailability of metals in soils.     

Arsenic and heavy metal mobility in iron oxide-amended contaminated soils as evaluated by short- and long-term leaching tests

Several iron-bearing additives were evaluated for their effectiveness in the attenuation of arsenic (As) in various contaminated soils. These were selected for their known or potential ability to adsorb As anions, thus changing the speciation of As in a soil system. Three soils with different sources of As contamination were investigated (canal dredgings, coal fly ash deposits, and low-level alkali waste). The amendments used were goethite (alpha-FeOOH), iron grit, iron (II) and (III) sulphates (plus lime), and lime, applied to the soils at a rate of 1% w/w. A series of leachate extraction tests (UKEA, ASTM and modified Dutch column leaching test) were conducted on the equilibrated amended soils. These were used to firstly evaluate the potential of the amendments as immobilising agents, and secondly to compare the short- and long-term durability of their effects. Column tests demonstrated the efficiency of iron oxides over the longer time scale; these treatments significantly reduced concentrations of arsenic in leachates from all treated soils. Amended soils were also observed to contain higher levels of lead (Pb) and cadmium (Cd) in their leachates, signifying that certain Fe-oxides potentially increased heavy metal mobility in treated soils. The conclusions were that whilst Fe-oxides may be used as effective in situ amendments to attenuate As in soils, their effects on other trace elements, such as Pb and Cd, require careful consideration.     

农药污染土壤的生物修复技术

本文综述了土壤农药有机污染的生物修复技术 ,重点分析了植物、微生物对土壤农药污染的修复机制以及影响因子 ,介绍了几种生物修复技术     

Speciation of zinc in contaminated soils

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100Lkg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.     

Multi-step leaching of Pb and Zn contaminated soils with EDTA

The efficiency of multi-step leaching of heavy metal contaminated soils was evaluated in a laboratory scale study. Four different soils contaminated with Pb (1136+/-16-4424+/-313mgkg(-1)) and Zn (288+/-5-5489+/-471mgkg(-1)) were obtained from industrial sites in the Mezica Valley, Slovenia and Príbram district, Czech Republic. Different dosages (2.5-40mmolkg(-1)) of ethylenediamine tetraacetate (EDTA) were used to treat soils in 1-10 leaching steps. Higher EDTA dosages did not result in a proportional gain in Pb and Zn removal. EDTA extracted Pb more efficiently than Zn from three of four tested soils. The percentage of removed Zn did not exceed 75% regardless of the soil, EDTA dosage and leaching steps. Significantly more Pb (in three of four soils) and Zn were removed from soils when the same amount of EDTA was applied in several leaching steps. The interference of major soil cations Fe and Ca with EDTA complexation as a possible factor affecting Pb and Zn removal efficiency with multi-step heap leaching was examined and is discussed. The results of our study indicate that, for some soils, using multi-step leaching instead of the more traditionally used single dose EDTA treatment could improve heavy metal removal efficiency and thus the economics of soil remediation.