Geochemical fractions of copper in soil chronosequences of selected European floodplains

The influence of soil formation on copper sorption is documented based on chronosequences of soils from three river floodplains in Europe (Danube, Ebro and Elbe). Sequential extraction was used to fractionate copper in original and spiked soils in order to study the long-term and short-term behaviour of copper retention. Copper partitioning among defined geochemical fractions was mainly determined by soil pH and the contents of carbonates, organic matter and Fe-/Mn-oxides and hydroxides. Copper extracted with NH(2)OH.HCl correlated well with the contents of crystalline Fe-oxides and hydroxides, demonstrating increasing retention capacity with progressing soil development. Copper retained in original soils was found in more strongly bound fractions, whereas sorption of freshly added copper was primarily influenced by the presence of carbonates. Beyond the effect of progressing soil formation, variations in organic carbon contents due to different land use history affected the copper retention capacity of the investigated soils.     

Copper activity in soil solutions of calcareous soils

Copper partitioning was studied in seven calcareous soils at moisture content corresponding to 1.2 times the field moisture content (soil water potential 7.84 J kg(-1)). Copper retention was accompanied by the release in soil solution of Ca(2+), Mg(2+), Na(+), and H(+), and the total amount of these cations released was 0.8 to 1.09 times the amount of Cu sorbed (mol(c):mol(c)). The relationships between Cu activity and pH, and the balance of cations in soils correspond with the surface precipitation of CuCO(3) as the main mechanism of Cu retention. The values of ion activity product of surface precipitate were close for all studied soils with the average log(IAP(CuCO(3)))=-15.51. The relationship between copper activity in soil solutions and soil properties is well fit by a regression relating pCu (-log copper ion activity) with soil pH, total Cu, and carbonate content.     

Phytoremediation of pyrene contaminated soils amended with compost and planted with ryegrass and alfalfa

Ryegrass (Lolium perenne) and alfalfa (Medicago sativa) were planted in pots to remediate pyrene contaminated quartz sand (as a control group), alluvial and red soils amended with and without compost. The pyrene degradation percentages in quartz sand, alluvial soil, and red soil amended with compost (5%, w/w) and planted with ryegrass and alfalfa for 90 d growth were 98-99% and 97-99%, respectively, while those of pyrene in the corresponding treatments amended without compost but planted with ryegrass and alfalfa were 91-96% and 58-89%, respectively. Further, those of pyrene in the respective treatments amended with and without compost but unplanted were 54-77% and 51-63%, respectively. Pyrene contents in both roots and aboveground parts of ryegrass and alfalfa after 90 d growth in quartz sand and the two soils amended with or without compost were trace amounts. Statistical analyses for the parameters of ryegrass planted in red and alluvial soils including the concentrations of total water-soluble volatile low molecular weight organic acids, microbial population, pyrene degradation percentage, and spiked pyrene concentration show significant correlations at 5% and mostly 1% probability levels, by the analysis of variance. It was thus suggested that the interactions among the consortia of plant root exudates, microorganisms, and amended compost in rhizosphere soils could facilitate bioavailability of pyrene and subsequently enhance its dissipation.     

Effects of copper concentration on methane emission from rice soils

Outdoor pot experiments with various paddy soils representing five soil types were conducted at Nanjing Agricultural University during the 2000 and 2001 rice-growing seasons. Eighteen soils and ten out of the eighteen soils were involved in the 2000 and the 2001 experiment, respectively. Two treatments were designed as mineral fertilization (MF) and mineral fertilizer + wheat straw incorporation (MF + WS) for the 2001 experiment. Seasonal average rate of CH4 emission from different soils ranged from 1.96 to 11.06 mg m(-2) h(-1) in the 2000 experiment, and from 0.89 to 5.92 mg m(-2) h(-1) for the MF treatment in the 2001 experiment, respectively. Incorporation of wheat straw enhanced considerably CH4 emission with an average increment of 7.09 mg m(-2) h(-1). CH4 emissions from the two-year experiment were negatively correlated to soil available and total copper concentration. A further investigation showed that CH4 emission from the MF treatment was positively related to the dissolved organic carbon (DOC) in the soil (r = 0.904, p < 0.001), and that the DOC was negatively correlated to the concentrations of available copper (r = -0.844, p < 0.01) and total copper (r = -0.833, p < 0.01), respectively. Nevertheless, the incorporation of wheat straw did not enhance the soil DOC, and the relationship between CH4 emission and soil DOC was not statistically significant (r = 0.470, p < 0.20). It was concluded that higher concentration of copper in the soils resulted in lower soil DOC and thus reduced CH4 emission when there was no additional organic matter input. Incorporation of wheat straw did not affect soil DOC and available copper concentration but enhanced CH4 emission.     

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.     

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

Bacterial stimulation of copper phytoaccumulation by bioaugmentation with rhizosphere bacteria

Copper contaminated areas pose environmental health risk to living organisms. Remediation processes are thus required for both crop production and industrial activities. This study employed bioaugmentation with copper resistant bacteria to improve phytoremediation of vineyard soils and copper mining waste contaminated with high copper concentrations. Oatmeal plant (Avena sativa L.) was used for copper phytoextraction. Three copper resistant bacterial isolates from oatmeal rhizosphere (Pseudomonas putida A1; Stenotrophomonas maltophilia A2 and Acinetobacter calcoaceticus A6) were used for the stimulation of copper phytoextraction. Two long-term copper contaminated vineyard soils (Mollisol and Inceptisol) and copper mining waste from Southern Brazil were evaluated. Oatmeal plants substantially extracted copper from vineyard soils and copper mining waste. As much as 1549 mg of Cu kg?1 dry mass was extracted from plants grown in Inceptisol soil. The vineyard Mollisol copper uptake (55 mg Cu kg?1 of dry mass) in the shoots was significantly improved upon inoculation of oatmeal plants with isolate A2 (128 mg of Cu kg?1 of shoot dry mass). Overall oatmeal plant biomass displayed higher potential of copper phytoextraction with inoculation of rhizosphere bacteria in vineyard soil to the extent that 404 and 327 g ha?1 of copper removal were respectively observed in vineyard Mollisol bioaugmented with isolate A2 (S. maltophilia) and isolate A6 (A. calcoaceticus). Results suggest potential application of bacterial stimulation of phytoaccumulation of copper for biological removal of copper from contaminated areas.     

Phytoextraction potential of two Rumex acetosa L. accessions collected from metalliferous and non-metalliferous sites: effect of fertilization

Metal tolerance and phytoextraction potential of two common sorrel (Rumex acetosa L.) accessions, collected from a Pb/Zn contaminated site (CS, Lanestosa) and an uncontaminated site (UCS, Larrauri), were studied in fertilized and non-fertilized pots prepared by combining soil samples from both sites in different proportions (i.e., 0%, 33%, 66% and 100% of Lanestosa contaminated soil). The original metalliferous mine soil contained 20480, 4950 and 14 mg kg(-1) of Zn, Pb and Cd, respectively. The microcosm experiment was carried out for two months under greenhouse controlled conditions. It was found that fertilization increased mean plant biomass of both accessions as well as their tolerance. However, only the CS accession survived all treatments even though its biomass decreased proportionally according to the percentage of contaminated mine soil present in the pots. This metallicolous accession would be useful for the revegetation and phytostabilization of mine soils. Due to its high concentration and bioavailability in the contaminated soil, the highest values of metal phytoextracted corresponded to Zn. The CS accession was capable of efficiently phytoextracting metal from the 100% mine soil, indeed reaching very promising phytoextraction rates in the fertilized pots (6.8 mg plant(-1) month(-1)), similar to the ones obtained with hyperaccumulator plants. It was concluded that fertilization is certainly worth being considered for phytoextraction and revegetation with native plants from metalliferous soils.     

Distribution and availability of arsenic in soils from the industrialized urban area of Beijing, China

Concentrations of arsenic (As) were determined in soils of 5 industrial sites in an urban area of Beijing, China. Fifty seven typical surface soils were sampled to determine total concentrations of metals, pH and dissolved organic carbon (DOC). One hundred and eight deep soils were submitted to a four-step, sequential extraction to assess the relative mobility and bioavailability of As in the soil profiles. Total concentrations of As in surface soils ranged from 5.7 to 2.3 x 10(1) mg kg(-1), dw with greater concentrations inside the perimeter of the chemical plant which had greater concentrations than did other plants. 75.4% of surface soil samples in the industrial area contained concentrations of As that were greater than was considered to be the background concentration of 7.8 mg kg(-1), dw for the region. The mean concentration (9.9 mg kg(-1), dw) in the industrial soils was greater than that soils from other type of land use. Concentrations of As were significantly and negatively correlated with soil pH and DOC in industrial soils. Although mean concentration of total As in the soils from all sites were less at greater depths, the entire range from 0 to 180 cm (especially 0-80 cm) contained concentrations of As that were greater than background. Sequential extractions of soil indicated that only some surface soils had relatively great amount of extractable fraction of As. Most soils had relatively great amount of residual As. This result suggests that most arsenic in Beijing industrial soils should be immobile and of limited bioavailability.     

Effect of copper on soil functional stability measured by relative soil stability index (RSSI) based on two enzyme activities

Copper can affect essential processes in soils, often for long periods. Enzyme activity is considered a sensitive indicator to evaluate soil health and the potential toxic impact of a soil contaminant. Nevertheless, there is heterogeneity in the responses from enzyme activity assays because of the influence of pH and other physicochemical parameters on both enzyme activity and metal speciation. This leads to complications when comparing soils and limits the validity of the results. To overcome these problems, this paper evaluates resistance and recovery, quantified by using a relative soil stability index (RSSI), of the beta-glucosidase and protease activities towards an additional heat disturbance (17 h at 60 degrees C) in soils where soil organic matter, pH and Cu content were modified in a factorial setup. Chemical analyses (dissolved Cu, pCu(2+), dissolved organic carbon, pH) were performed both before the heat-perturbation and after the enzyme activity monitoring period. Results show that soil pH did not interfere with the RSSI scores of both enzymes. beta-glucosidase RSSI scores were scarcely affected by copper, making it inappropriate for evaluating copper-induced stress to soils. Protease activity shows stimulations of up to 2.5 times the activity of the unperturbed control in uncontaminated samples only. Thus, the protease RSSI score seems a good indicator for soil health relative to copper contamination given that all samples were affected by the presence of copper and high correlations were observed between RSSI scores and the different copper forms.     

Copper bioavailability in the rhizosphere of maize (Zea mays L.) grown in two Italian soils

In this study, potentially bioavailable copper was estimated in two soils (a fungicide polluted and a natural soil) using a passive sampling technique, DGT. As plants can alter copper mobility and bioavailability in the soil, the rhizosphere properties of Zea mays L. were investigated using rhizoboxes.

Compared to the total concentration, the soluble and the potentially bioavailable copper concentration in the bulk soils were generally low (less than 0.20% and 0.06% respectively), with a sixfold increase in the rhizosphere of the polluted soil. Our results suggest that maize cultivation in a polluted vineyard soil could increase the potentially available fraction of copper. DGTs showed a good sensitivity to soil properties and to root-induced changes in the rhizosphere, but the potentially bioavailable copper could not be related to the copper concentration in the above ground parts of maize. The results suggest that DGT may be used to predict some effects of the cultivation of polluted soils, for example, metal mobility and increased availability, but they cannot mimic the uptake of a tolerant plant.

For both soils, dissolved organic carbon (DOC) concentrations were threefold higher in the rhizosphere than in the bulk soil, whilst bioaccumulation in leaves and roots was not significant. DOC production, usually effective in ion mobilization and assimilation, may help also in the reduction of Cu uptake at toxic concentrations. The sequestration of available Cu in soil and soil solution by DOC seems to contribute to maize tolerance.     

The effects of pH and soil type on concentrations of zinc, copper and nickel extracted by calcium chloride from sewage sludge-treated soils

The effects of pH on concentrations of zinc, copper and nickel extracted by calcium chloride from a clay loam and two sandy loam soils that had been treated with sewage sludge were studied. Concentrations of all the metals increased rapidly as pH decreased below a threshold value ranging from 6.2 to 7.0 for Zn, 6.2 to 7.2 for Ni and 4.7 to 5.7 for Cu. Both the total concentrations and the threshold pH values were influenced by differences in soil texture and (between the two light-textured soils) by differences in soil cation exchange capacity. The amount of zinc and copper extracted from the mixtures was considerably less than that extracted from the same quantity of sludge alone.     

Phytoremediation of an aged petroleum contaminated soil using endophyte infected and non-infected grasses

Phytoremediation is a promising technique for cleaning petroleum contaminated soils. In this study, the effects of two grass species (Festuca arundinacea Schreb. and Festuca pratensis Huds.), infected (E(+)) and non-infected (E(-)) by endophytic fungi (Neotyphodium coenophialum and Neotyphodium uncinatum, respectively) on the degradation of petroleum hydrocarbons in an aged petroleum contaminated soil was investigated. Plants were grown in the soil for 7 months and unplanted soil considered as control. At the end of the experiment, total and oil-degrading bacteria, dehydrogenase activity, water-soluble phenols, total petroleum hydrocarbons (TPH) and polycyclic aromatic hydrocarbons (PAHs) contents were measured in the soil. The results demonstrated that E(+) plants contained more root and shoot biomass than E(-) plants and created higher levels of water-soluble phenols and dehydrogenase activity in the soil, while there was no significant difference in bacterial counts of planted soils. Planting stimulated total and oil-degrading bacterial numbers, dehydrogenase activity and the soil content of water-soluble phenols. Regardless of endophyte infection, PAH and TPH removal in the rhizosphere of plants were 80-84 and 64-72% respectively, whereas the removals in controls were 56 and 31%, respectively. It was revealed that TPHs in retention time range of n-alkanes with C(10)-C(25) chain lengths and TPH were more degraded in the rhizosphere of E(+) plants compared to E(-) ones. Thus, grasses infected with endophytic fungi could be more efficient for removal of TPH from oil-contaminated soils.     

汞、铅、铬污染土壤的微生物修复

利用裂褶菌(Schizophyllum commune)GGHN08-116菌株,以棉籽壳、玉米秸等为固体发酵底物修复受汞、铅、铬污染的土壤。通过菌丝穿透重度重金属土壤实验,研究了菌丝在穿透土壤过程对交换态重金属的影响以及该菌株子实体对重金属离子的富集能力,同时,通过盆栽实验研究了在重度重金属污染土壤上,施用不同比例的固体发酵料对污染土壤中汞、铅、铬及其胡萝卜根茎质量、产量的影响,研究结果表明,该菌株能穿透厚度为5 cm的土壤,并有子实体生成,土壤pH值略有下降,与对照差异不显著;与对照相比,土壤中交换态汞、铬含量均显著下降,而交换态铅差异不显著,子实体中除汞含量符合标准外,铅、铬均超出了GB 7096-2003,GB 2762-2005规定标准。在固体发酵料处理下土壤中交换态汞、铅、铬含量均显著下降,胡萝卜根茎中均未检测到汞、铅含量,铬含量也符合GB 2762-2005规定标准。GGHN08-116菌株及其固体发酵产物具有修复受重金属污染土壤的能力。     

Copper bioavailability and extractability as related to chemical properties of contaminated soils from a vine-growing area

Vineyard soils have been contaminated by Cu as a consequence of the long-term use of Cu salts as fungicides against mildew. This work aimed at identifying which soil parameters were the best related to Cu bioavailability, as assessed by measuring the concentrations of Cu in shoots and roots of tomato cropped (in lab conditions) over a range of 29 (24 calcareous and five acidic) Cu-contaminated topsoils from a vine-growing area (22-398 mg Cu kg(-1)). Copper concentrations in tomato shoots remained in the adequate range and were independent of soil properties and soil Cu content. Conversely, strong, positive correlations were found between root Cu concentration, total soil Cu, EDTA- or K-pyrophosphate-extractable Cu and organic C contents in the 24 calcareous soils, suggesting a prominent role of organic matter in the retention and bioavailability of Cu. Such relations were not observed when including the five acidic soils in the investigated population, suggesting a major pH effect. Root Cu concentration appeared as a much more sensitive indicator of soil Cu bioavailability than shoot Cu concentration. Simple extractions routinely used in soil testing procedures (total and EDTA-extractable Cu) were adequate indicators of Cu bioavailability for the investigated calcareous soils, but not when different soil types were considered (e.g. acidic versus calcareous soils).     

The effect of pH, ion strength and reactant content on the complexation of Cu2+ by various natural organic ligands from water and soil in Hong Kong

The complexation constants for copper associated with different natural organic ligands, including dissolved organic carbon (DOC) extracted from water, water soluble organic carbon (WSOC), fulvic acid (FA) and humic acid (HA) from soil, were determined and then compared based on discrete single site model. Both ion-selective electrode (ISE) and anodic stripping voltammetry were used to determine the content of free copper ions, while the relative number of complexation sites was estimated using a fluorescence quenching (FQ) at the same time. ISE proved to be the most applicable technique when the concentration of copper was above 10(-7) moll(-1). The logk values for two WSOC sample sites (Song Ziyuan and Xin Niangtan) were 4.64 and 4.66; higher than both the DOC and HA values yet lower than the FA values, which were unusually high due to unavoidable pollution from the cation exchange resin used during the purification process. Binding affinities between the copper ions and the organic ligands obtained from streams in Yong Wei (DOC) and Song Ziyuan (WSOC) were influenced by pH, ion strength, and reactant concentration. Values for logk increased with increases in pH (ion strength of 0.1 N). At pH 4, the logk values decreased with increases in the supporting electrolyte concentration and total copper ion additions.     

Ashes from fluidized bed combustion of residual forest biomass: recycling to soil as a viable management option

Although bottom ash (BA) [or mixtures of bottom and fly ash (FA)] from clean biomass fuels is currently used as liming agent, additive for compost, and fertilizer on agricultural and forest soils in certain European countries, in several other countries most of the ashes are currently disposed in landfills. This is due to both a lack of a proper classification of the materials and of regulatory barriers.Chemical characterization including analysis of an array of potentially toxic elements (PTEs) proved that over 100,000 tons of BA currently landfilled every year in Portugal actually complied with legal limits for PTEs for soil fertilizers applied in other countries. Pot experiments were conducted, testing three dosages of BA and FA (1, 2.5, and 5%, in weight) in three mining soils with different properties. Additions of ash materials to soils led to an increase in the pore water pH relative to control pots (0% of ash added) and had a clear impact on DOC and on the solubilization of both macro- and micronutrients (notably Cu).The results from the case study using BA and FA from a Portuguese biomass thermal power plant demonstrate that it is imperative to further develop a regulatory framework to alleviate technological and environmental barriers for biomass ash utilization as raw material for fertilizers and/or soil liming agent, in accordance with the goals of the circular economy. A more harmonized view on how to assess the merits and risks of the re-use of these materials is also needed.     

Effects of biochar and greenwaste compost amendments on mobility, bioavailability and toxicity of inorganic and organic contaminants in a multi-element polluted soil

Applying amendments to multi-element contaminated soils can have contradictory effects on the mobility, bioavailability and toxicity of specific elements, depending on the amendment. Trace elements and PAHs were monitored in a contaminated soil amended with biochar and greenwaste compost over 60 days field exposure, after which phytotoxicity was assessed by a simple bio-indicator test. Copper and As concentrations in soil pore water increased more than 30 fold after adding both amendments, associated with significant increases in dissolved organic carbon and pH, whereas Zn and Cd significantly decreased. Biochar was most effective, resulting in a 10 fold decrease of Cd in pore water and a resultant reduction in phytotoxicity. Concentrations of PAHs were also reduced by biochar, with greater than 50% decreases of the heavier, more toxicologically relevant PAHs. The results highlight the potential of biochar for contaminated land remediation.     

Changes in the concentrations of phenolics and photosynthates in Scots pine (Pinus sylvestris L.) seedlings exposed to nickel and copper

Studies were done on the effects of elevated soil concentrations of copper (Cu) and (Ni) on foliar carbohydrates and phenolics in Scots pine (Pinus sylvestris L.). Four year-old seedlings were planted in pots filled with metal-treated mineral forest soil in early June. The experimental design included all combinations of four levels of Cu (0, 25, 40 and 50 mg kg(-1) soil dw) and Ni (0, 5, 15 and 25 mg kg(-1) soil dw). Current year needles were sampled for soluble sugar, starch and phenolics at the end of September. Ni increased sucrose concentration in the needles, indicating disturbances in carbohydrate metabolism. Trees exposed to Ni had higher concentrations of condensed tannins compared with controls. In contrast, concentrations of several other phenolic compounds decreased when seedlings were exposed to high levels of Cu or to a combination of Ni and Cu. The results suggest that concentrations of phenolics in Scots pine needles vary in their responses to Ni and Cu in the forest soil.     

Uptake of 134Cs in the shoots of Amaranthus tricolor and Amaranthus cruentus

Amaranthus tricolor L. and Amaranthus cruentus L. were grown in pots containing 7.5 kg soils artificially contaminated with three levels of 134Cs activity: 5.55 x 10(5) Bq pot-1, 1.11 x 10(6) Bq pot(-)1, and 1.665 x 10(6) Bq pot(-1), respectively. Forty-nine days after sowing and growth, plants were harvested. The plants growing in soils with increasing 134Cs concentrations showed increasing concentration of this radionuclide in shoots. There were significant differences in uptake of 134Cs applied to soils between and within the plant species, depending on the initial 134Cs concentrations. The plant species showed different responses to the addition of (NH4)2SO4 to soils. Biomass production of both species was reduced in pots treated with (NH4)2SO4. (NH4)2SO4 application decreased the uptake of 134Cs by A. tricolor but increased the accumulation of 134Cs by A. cruentus, showing that chemicals with the highest efficiency to enhance the desorption of 134Cs might play an unexpected role in transferring the radionuclide to shoots.