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.     

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.     

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 role of glomalin, a protein produced by arbuscular mycorrhizal fungi, in sequestering potentially toxic elements

Naturally occurring soil organic compounds stabilize potentially toxic elements (PTEs) such as Cu, Cd, Pb, and Mn. The hypothesis of this work was that an insoluble glycoprotein, glomalin, produced in copious amounts on hyphae of arbuscular mycorrhizal fungi (AMF) sequesters PTEs. Glomalin can be extracted from laboratory cultures of AMF and from soils. Three different experiments were conducted. Experiment 1 showed that glomalin extracted from two polluted soils contained 1.6-4.3 mg Cu, 0.02-0.08 mg Cd, and 0.62-1.12 mg Pb/g glomalin. Experiment 2 showed that glomalin from hyphae of an isolate of Gigaspora rosea sequestered up to 28 mg Cu/g in vitro. Experiment 3 tested in vivo differences in Cu sequestration by Cu-tolerant and non-tolerant isolates of Glomus mosseae colonizing sorghum. Plants were fed with nutrient solution containing 0.5, 10 or 20 microM of Cu. Although no differences between isolates were detected, mean values for the 20 microM Cu level were 1.6, 0.4, and 0.3 mg Cu/g for glomalin extracted from hyphae, from sand after removal of hyphae and from hyphae attached to roots, respectively. Glomalin should be considered for biostabilization leading to remediation of polluted soils.     

Retention and distribution of heavy metals in mangrove soils receiving wastewater

The distribution and chemical fractionation of heavy metals retained in mangrove soils receiving wastewater were examined by soil column leaching experiments. The columns, filled with mangrove soils collected from two swamps in Hong Kong and the People's Republic of China, were irrigated three times a week for 150 days with synthetic wastewater containing 4 mg l(-1) Cu, 20 mg l(-1) Zn, 20 mg l(-1) Mn and 0.4 mg l(-1) Cd. Soil columns leached with artificial seawater (without any heavy metals) were used as the control. At the end of the leaching experiments, soil samples from each column were divided into five layers according to its depth viz. 0-1, 1-3, 3-5, 5-10 and > 10 cm, and analyzed for total and extractable heavy metal content. The fractionation of heavy metals in the surface soil samples (0-1 cm) was investigated by the sequential extraction technique. In both types of mangrove soils, the surface layer (0-1 cm) of the columns receiving wastewater had significantly higher concentrations of total Cu, Cd, Mn and Zn than the control. Concentrations declined significantly with soil depth. The proportion of exchangeable heavy metals in soils receiving wastewater was significantly higher than that found in the control, about 30% of the total heavy metals accumulated in the soil masses of the treated columns were extracted by ammonium acetate at pH 4. The sequential extraction results show that in native mangrove soils (the soils without any treatment), the major portion of Cu, Zn, Mn and Cd was associated with the residual and precipitated fractions with very low concentrations in more labile phases. However, in mangrove soils receiving wastewater, a significantly higher percentage of Mn, Zn and Cd was found in the water-soluble and exchangeable fractions. Copper appeared to be more strongly adsorbed in mangrove soils than the other heavy metals. In general, heavy metal accumulation in the surface mangrove soils collected in Hong Kong was higher than those in the PRC, although the metals in the latter soil type were more strongly bound. These findings suggest that whether the heavy metal retained in managrove soils becomes a secondary source or a permanent sink would depend on the kinds of heavy metals and also the types of mangrove soils.     

Soil pH and anion abundance affects on copper adsorption

Copper (Cu) input to agricultural soils results from Cu containing pesticides and or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2-9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0-100 mg L(-1) in the equilibration solution, 95-99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl2 or Ca(NO3)2 as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500-2000 mg L(-1), the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2-7.9. In a high pH soil (pH=9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

Distribution and Fractionation of Copper in Soils of Apple Orchards (5 pp)

Background Frequent application of Bordeaux mixture, which includes copper, as a fungicide in fruit and grape orchards may lead to copper accumulation in the soil, especially when orchard age and application times increase. The objectives of this study were: (i) to investigate the copper content and its spatial distribution in orchard soils; (ii) to identify the copper fractionation in soil and its relationship with plant uptake; (iii) to understand the characteristics of copper contamination in orchard soils. Materials and Methods Soil profile samples were taken in apple orchards with ages of 0, 5, 10, 20, 30 years and pot experiments were also carried out to study the effects of external copper input on copper fractionation. All soil samples were air-dried, ground and extracted with 0.43 mol L–1 HNO3 for the total absorbed copper. Fractionation determination was conducted following Tessier and Shuman sequential extraction methods, and copper was measured with AAS. Plant samples were first dry ashed, dissolved with 6 mol L–1 HCl and then copper and other elements were measured with ICP-MS.Results and Discussion Soil total Cu was higher in the apple orchards than that in non-orchard fields and was seen to have increased with orchard age. Soil Cu increased substantially with the average annual copper increase, ranging from 2.5 to 9 mg Cu kg–1. The distribution of copper in the soil profile was uneven, decreasing from surface to deeper layers, and the differences were significant, but the contents in every layer were also significantly correlated with those in the next layers. For all copper fractions, the organically bound, crystalline Mn oxide bound, and amorphous Fe bound fractions extracted with the Shuman method were much higher than the exchangeable and residual fractions. Using the Tessier method, organically bound, carbonate bound and Fe-Mn oxide bound fractions were much higher. With an increase in external copper input, the organically bound, crystalline Mn oxide bound and amorphous Fe bound fractions in the Shuman method and organically bound, carbonate bound and Fe-Mn oxide bound fractions in the Tessier method all increased significantly, while the changes in other fractions were not significant. Soil total copper and copper fractions were found to have good correlations with apple tree uptake. Copper in fruit flesh had significant correlations with soil total content in the 0–10 cm layer, all the copper fractions in the 0–5 cm layer, and some fractions in the deeper layers. Conclusion Copper content in orchard soils increased significantly with intensive application of Bordeaux mixtures and orchard age. Copper content decreased sharply from the topsoil to deeper soil layers. The copper contents in different layers also significantly correlated with those in the next layers. Dominant fractions of the copper in soil were mainly associated with organic matter, iron and manganese oxides and carbonates. A close relationship was found between the copper content in soils and in apple tree organs (which contained 8.9 to 66mg kg–1 Cu). Recommendation and Perspective Though most copper in the soil was specifically adsorbed or immobilized, and copper was mainly distributed in topsoil, which was essentially devoid of roots, the copper concentration of fruit still had significantly positive correlations with soil copper and most copper fractions. Therefore, measures must be taken to control copper accumulation in orchard soils and to make the apple fruit production sustainable.     

Toxicity of uranium and copper individually, and in combination, to a tropical freshwater macrophyte (Lemna aequinoctialis)

Copper (Cu) and uranium (U) are of potential ecotoxicological concern to tropical freshwater biota in northern Australia, as a result of mining activities. Few data are available on the toxicity of U, and no data are available on the toxic interaction of Cu and U, to freshwater biota. This study determined the toxicity of Cu and U individually, and in combination, to a tropical freshwater macrophyte, Lemna aequinoctialis (duckweed), in a synthetic soft water (27 degrees C; pH, 6.5; hardness, 40 mg CaCO3 l-1, alkalinity, 16 mg CaCO3 l-1), typical of many fresh surface waters in coastal northern Australia. The growth rate of L. aequinoctialis decreased with increasing Cu or U concentrations, with the concentration of Cu inhibiting growth by 50% (EC50) being 16+/-1.0 microg l-1, with a minimum detectable effect concentration (MDEC) of 3.2 microg l-1. The concentration of U inhibiting growth by 50% (EC50) was 758+/-35 microg l-1 with a MDEC of 112 microg l-1. The EC50 value for the exposure of L. aequinoctialis to equitoxic mixtures of Cu and U was significantly (P0.05) higher than one toxic unit (1.35; 95% confidence interval, 1.18-1.52), indicating that the combined effects of Cu and U are less than additive (antagonistic). Therefore, inhibition of the growth rate of L. aequinoctialis was reduced when Cu and U were present in equitoxic mixtures, relative to individual metal exposures. Since non-additive (e.g. antagonistic) interactions of metal mixtures cannot be predicted using current mixture models, these results have important potential implications for the protection of freshwater ecosystems through the derivation of national water quality guidelines.     

Heavy metal contamination from mining sites in South Morocco: 1. Use of a biotest to assess metal toxicity of tailings and soils

Our work was conducted to investigate the heavy metal toxicity of tailings and soils collected from five metal mines located in the south of Morocco. We used the MetPAD biotest Kit which detects the toxicity specifically due to the heavy metals in environmental samples. This biotest initially developed to assess the toxicity of aquatic samples was adapted to the heterogeneous physico-chemical conditions of anthropogenic soils. Contrasted industrial soils were collected from four abandoned mines (A, B, C and E) and one mine (D) still active. The toxicity test was run concurrently with chemical analyses on the aqueous extracts of tailings materials and soils in order to assess the potential availability of heavy metals. Soil pH was variable, ranging from very acidic (pH 2.6) to alkaline values (pH 8.0-8.8). The tailings from polymetallic mines (B and D) contained very high concentrations of Zn (38,000-108,000 mg kg(-1)), Pb (20,412-30,100 mg kg(-1)), Cu (2,019-8,635 mg kg(-1)) and Cd (148-228 mg kg(-1)). Water-extractable metal concentrations (i.e., soil extracts) were much lower but were highly toxic as shown by the MetPAD test, except for soils from mines A, E and site C3 from mine C. The soil extracts from mine D were the most toxic amongst all the soils tested. On this site, the toxicity of soil water extracts was mainly due to high concentrations of Zn (785-1,753 mg l(-1)), Cu (1.8-82 mg l(-1)) and Cd (2.0-2.7 mg l(-1)). The general trend observed was an increase in metal toxicity measured by the biotest with increasing available metal contents in tailings materials and soils. Therefore, the MetPAD test can be used as a rapid and sensitive predictive tool to assess the heavy metal availability in soils highly contaminated by mining activities.     

Spatial distribution of heavy metals in urban soils of Naples city (Italy)

Concentrations of surface and sub-surface soil Cu, Cr, Pb and Zn in the Naples city urban area were measured in 1999. Contourmaps were constructed to describe the metals spatial distribution. In the most contaminated soil samples, metals were speciated by means of the European Commission sequential extraction procedure. At twelve sites, Cu, Pb and Zn levels in soil were compared with those from a 1974 sampling. Many surface soils from the urban area as well as from the eastern industrial district contained levels of Cu, Pb and Zn that largely exceeded the limits (120, 100 and 150 mg kg(-l) for Cu, Pb and Zn, respectively) set for soils of public, residential and private areas by the Italian Ministry of Environment. Chromium values were never above regulatory limits(120 mg kg(-1)). Copper apparently accumulates in soils contiguous to railway lines and tramway. Cu and Cr existed in soil mainly inorganic forms (-68%), whereas Pb occurs essentially as residual mineral phases (77%). The considerable presence of Zn in the soluble, exchangeable and carbonate bound fraction (23%) suggests this element has high potential bioavailability and leachability through the soil. Concentrations of Cu, Pb and Zn have greatly increased since the 1974 sampling, with higher accumulation in soils from roadside fields.     

Isotherms and sequential extraction procedures for evaluating sorption and distribution of heavy metals in soils

Heavy metals are potentially toxic to human life and the environment. Their contaminating effect in soils depends on chemical associations. Hence, determining the chemical form of a metal in soils is important to evaluate its mobility and bioavailability. We utilized a sequential extraction procedure and sorption isotherms (monometal and competitive) to evaluate the mobility and distribution of Cd, Cu, Ni, Pb, and Zn in four soils differing in their physicochemical properties: Calcixerollic Xerochrepts (Cx1 and Cx2), Paralithic Xerorthent (Px) and Lithic Haplumbrept (Lh). Most of the metals retained under point B conditions of sorption isotherms were extracted from the more mobile fractions: exchangeable and carbonates, in contrast with the profiles of the original soils where metals were preferently associated with the residual fraction. In soils having carbonate concentration under 6% (Cx1 and Lh), the exchangeable fraction was predominant, whereas in calcareous soils (Cx2 and Px) metals extracted from carbonates predominated. Partitioning profiles were in accordance with the affinity sequences deduced from the initial slope of isotherms and showed that the soils had a greater number of surface sites and higher affinity for Pb and Cu than for Cd, Ni, or Zn. In general, the simultaneous presence of the cations under study increased the percentages of metals released in the exchangeable fraction. The tendency towards less specific forms was more noticeable in Cx2 and Px soils and for Ni, Zn, and Cd. The affinity of inorganic surfaces was larger for Zn than for Cd or Ni, but the affinity of organic surfaces was larger for Cd or Ni than for Zn.     

Aquatic arsenic: phytoremediation using floating macrophytes

Phytoremediation, a plant based green technology, has received increasing attention after the discovery of hyperaccumulating plants which are able to accumulate, translocate, and concentrate high amount of certain toxic elements in their above-ground/harvestable parts. Phytoremediation includes several processes namely, phytoextraction, phytodegradation, rhizofiltration, phytostabilization and phytovolatilization. Both terrestrial and aquatic plants have been tested to remediate contaminated soils and waters, respectively. A number of aquatic plant species have been investigated for the remediation of toxic contaminants such as As, Zn, Cd, Cu, Pb, Cr, Hg, etc. Arsenic, one of the deadly toxic elements, is widely distributed in the aquatic systems as a result of mineral dissolution from volcanic or sedimentary rocks as well as from the dilution of geothermal waters. In addition, the agricultural and industrial effluent discharges are also considered for arsenic contamination in natural waters. Some aquatic plants have been reported to accumulate high level of arsenic from contaminated water. Water hyacinth (Eichhornia crassipes), duckweeds (Lemna gibba, Lemna minor, Spirodela polyrhiza), water spinach (Ipomoea aquatica), water ferns (Azolla caroliniana, Azolla filiculoides, and Azolla pinnata), water cabbage (Pistia stratiotes), hydrilla (Hydrilla verticillata) and watercress (Lepidium sativum) have been studied to investigate their arsenic uptake ability and mechanisms, and to evaluate their potential in phytoremediation technology. It has been suggested that the aquatic macrophytes would be potential for arsenic phytoremediation, and this paper reviews up to date knowledge on arsenic phytoremediation by common aquatic macrophytes.     

Phytostabilization of a metal contaminated sandy soil. II: Influence of compost and/or inorganic metal immobilizing soil amendments on metal leaching

A lysimeter approach (under natural climatologic conditions) was used to evaluate the effect of four metal immobilizing soil treatments [compost (C), compost+cyclonic ashes (C+CA), compost+cyclonic ashes+steel shots (C+CA+SS)) and cyclonic ashes+steel shots (CA+SS)] on metal leaching through an industrially contaminated soil. All treatments decreased Zn and Cd leaching. Strongest reductions occurred after CA+SS and C+CA+SS treatments (Zn: -99.0% and -99.2% respectively; Cd: -97.2% and -98.3% respectively). Copper and Pb leaching increased after C (17 and >30 times for Cu and Pb respectively) and C+CA treatment (4.4 and >3.7 times for Cu and Pb respectively). C+CA+SS or CA+SS addition did not increase Cu leaching; the effect on Pb leaching was not completely clear. Our results demonstrate that attention should be paid to Cu and Pb leaching when organic matter additions are considered for phytostabilization of metal contaminated soils.     

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 contamination in paddy soils irrigated with wastewater

Copper (Cu) contamination was investigated in paddy soils where Cu-rich wastewater (12 mg Cu/l) was used for irrigation. The results showed that Cu contamination increased the soil Cu content from 17.0 mg Cu/kg in the non-wastewater irrigated soils (NWIS) to 101.2 mg Cu/kg in the wastewater irrigated soils (WIS), and Cu accumulated mostly in the surface layer (0-10 cm) of the paddy soil. The average Cu contents in brown rice, rice hull and rice straw from NWIS were 1.4, 7.3 and 14.5 mg Cu/kg, while those from WIS were 15.5, 133.2, and 101.4 mg Cu/kg, respectively. Correlation analysis revealed that the relationship between the Cu content in the rice straw and the rice hull with the total Cu content of the soil could be described by an exponential function (R2 = 0.921 and 0.831, respectively; P <0.01). Rice plants grown in the WIS showed symptoms of black roots, less effective tiller, etc. Subsequently, the rice yield decreased by 18-25%, compared with that grown in NWIS.     

Effect of plant growth on copper solubility and speciation in soil solution samples

The effect of plant growth on copper solubility and speciation was studied in a 10-week pot experiment. A copper-tolerant grass variety (Agrostis capillaris L. var. Parys Mountain) was grown in pots that contained either clean (copper-total approx. 30 mg kg(-1)) or copper contaminated soil (copper-total approx. 170 mg kg(-1)) at two pH levels (4.7 and 5.5). Also, similar pots without vegetation were included in the study. Due to the addition of NH(4)NO(3) fertilizer and subsequent nitrification of ammonia to nitrate, soil pH decreased from 4.7 to 3.5 and from 5.5 to 4, respectively. In the planted pots, soil pH recovered faster after depletion of NH(4)(+). This resulted in a decrease in the calcium solution concentrations and an increase in the dissolved organic carbon (DOC) concentrations in the planted pots. However, this was only observed in the clean soil; in the contaminated soil no difference in DOC levels between bare and planted pots was observed. Copper solubility in the contaminated soil was lower in the presence of plants; in the clean soil no differences were observed between the bare and planted pots. In the planted pots, copper activities in solution in both clean and contaminated soils were two orders of magnitude lower than in the bare pots. Copper activities in the non-planted contaminated soil reached potentially toxic levels ([Cu]+/-10(-5) to 10(-6) M) in contrast to the lower levels in the planted pots ([Cu]+/-10(-7) to 10(-10) M). Data and model results show that plant growth improves pH, DOC and calcium in solution to such an extent that both the total dissolved copper concentration and the free metal activity in soils can be reduced. This stresses the potential beneficial role of plants for the immobilization and detoxification of metals in contaminated soils.     

Dioxins, metals, and fish toxicity in ash residue from space heaters burning used motor oil

Ash residue, generated from burning used motor oil, is a complex and ubiquitous waste stream. Ash samples were collected from space heaters and analyzed for dioxins (N=10), expressed as toxic equivalents (TEQ), and heavy metals (N=9). TEQ averaged 148-164 ng kg(-1) (standard deviation [SD] 385-416 ng kg(-1)), depending on methods used for non-detects (NDs) and toxic equivalency factors (TEFs). It is notable that median TEQ (2.89-3.49 ng kg(-1)) was about 50 fold lower, reflecting the influence of several high end values on the mean. The proportion of NDs among 17 polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in each sample averaged 38.2% (range 0-94.1%). Total metals averaged 103,000 mg kg(-1) (SD 26,600 mg kg(-1)), with Zn, Cu, and Pb contributing 89.3%, 6.4%, and 3.0% of the total, respectively. Rainbow trout bioassays resulted in median mortalities of 3.2% and 42.0% (respective SD 25.3% and 43.2%) at ash concentrations of 10 and 100 mg l(-1), respectively. Nominal concentrations of several metals (e.g., Cu, Zn) in the fish bioassay exceeded their reported median lethal concentrations (LC50s) for the test species. Multiple regressions (Bonferroni P<0.05) demonstrated that most of the variance in fish mortality could be accounted for by pH, metals (e.g., As, Cd, Pb), and TEQ. Mean TEQ concentration in used oil ash ranked on the high end of TEQ content in other environmental matrices, including wood ash, cement kiln dust, biosolids, and soils. Overall, these results suggest that suitable disposal methods are needed for ash generated from burning used motor oil.     

Growth response and phytoextraction of copper at different levels in soils by Elsholtzia splendens

Phytoremediation is a promising approach for cleaning up soils contaminated with heavy metals. Information is needed to understand growth response and uptake mechanisms of heavy metals by some plant species with exceptional capability in absorbing and superaccumulating metals from soils. Greenhouse study, field trial, and old mined area survey were conducted to evaluate growth response and Cu phytoextraction of Elsholtzia splendens in contaminated soils, which has been recently identified to be tolerant to high Cu concentration and have great potential in remediating contaminated soils. The results from this study indicate that the plant exhibited high tolerance to Cu toxicity in the soils, and normal growth was attained up to 80 mg kg(-1) available soil Cu (the NH4OAc extractable Cu) or 1000 mg kg(-1) total Cu. Under the field conditions, a biomass yield of 9 ton ha(-1) was recorded at the soil available Cu level of 77 mg kg(-1), as estimated by the NH4OAc extraction method. Concentration-dependent uptake of Cu by the plant occurred mainly at the early growth stage, and at the late stage, there is no difference in shoot Cu concentrations grown at different extractable soil Cu levels. The extractability of Cu from the highly polluted soil is much greater by the roots than that by the shoots. The NH4OAc extractable Cu level in the polluted soil was reduced from 78 to 55 mg kg(-1) in the soil after phytoextraction and removal of Cu by the plant species for one growth season. The depletion of extractable Cu level in the rhizosphere was noted grown in the mined area, even at high Cu levels, the NH4OAc extractable Cu in the rhizosphere was 30% lower than that in the bulk soil. These results indicate that phytoextraction of E. splendens can effectively reduce the plant-available Cu level in the polluted soils.     

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.     

Copper chloride inhibits brush border membrane enzymes,alters antioxidant and metabolic status and damages DNA in rat intestine: a dose-dependent study

Environmental Science and Pollution Research - Copper (Cu) is an extensively used heavy metal and an indispensible micronutrient for living beings. However, Cu is also toxic and exerts multiple...