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.     

Accumulation and fractionation of copper, iron, manganese, and zinc in calcareous soils amended with composts.

Amending soils with compost may lead to accumulation of metals and their fractions at various concentrations in the soil profile. The objectives of this study were to determine 1) the accumulation of Cu, Fe, Mn, and Zn with depth and 2) the distribution of water soluble, exchangeable, carbonate, Fe-Mn oxides, organic and residual forms of each metal in soils amended with MSW compost, co-compost, biosolids compost and inorganic fertilizer (as control). Total concentrations of Cu, Fe, Mn and Zn were concentrated in the 0-22 cm soil layer and scant in the rock layer. These metals were in the decreasing order of Fe > Mn > Zn > or = Cu. Copper, Fe, and Zn were predominantly in the residual form followed by fractions associated with Fe-Mn oxides, carbonate, organic, exchangeable and water soluble in all treatments except MSW compost amended soil where the organic fraction was higher than the carbonate fraction. In fertilizer, co-compost and biosolids compost treated soils Mn concentrated mainly in the Fe-Mn oxides form followed by residual, carbonate, and organic forms whereas, in MSW compost treated soil the same pattern occurred except that Mn organic fraction was higher than that in the carbonate form. The MSW compost has a greater potential to be used as a soil amendment to supply plants with Cu, Mn and Zn than other treatments in calcareous soils of south Florida.     

Response of kidney bean to concentration and chemical form of cadmium, zinc, and lead in polluted soils

Seven soils which had been polluted with heavy metals from a zinc smelter were sequentially extracted so that Cd, Zn, and Pb could be partitioned into five operationally defined geochemical fractions: exchangeable, carbonate, Fe-Mn oxide, organic, and residual fractions. Kidney beans were planted in the soils to examine the effect of concentration and chemical form of the metals in soil on the growth and metal uptake of the plants. The growth of kidney bean was restricted in heavy metal polluted soils compared with controls. Metal concentration and metal uptake by plants were correlated. The highest relationship was found between amount of metal uptake and the metal concentration in exchangeable + carbonate forms. The uptake of metals was according to their solubility sequence, i.e. Cd > Zn > Pb. The uptake rate of exchangeable + carbonate forms was the same for the three elements.     

A test of sequential extractions for determining metal speciation in sewage sludge-amended soils

Sequential extraction procedures are widely used to estimate the quantity of trace metals bound to different solid fractions in contaminated soils. However, reliability of speciation of trace metals by these procedures remains largely unexamined. In the present study, the selectivity of each extraction step was tested by observing the effect of reversing the extraction order in the procedure. Two different sequential extraction methods and their reversed modes were used for metal fractionation in sewage sludge-amended soils. Significantly increased amounts of extractable metals (Cd, Cu, Pb and Zn) were evident in the sludge-amended soils compared to control soil by all extraction schemes; however, the amounts of metals extracted by each step were strongly dependent on the order of extraction, the type of reagents and the nature of the individual metals. Caution is advised in deducing the forms of soil metals from sequential extraction results from metal-contaminated soils.     

Microbial indicators of heavy metal contamination in urban and rural soils

Urban soils and especially their microbiology have been a neglected area of study. In this paper, we report on microbial properties of urban soils compared to rural soils of similar lithogenic origin in the vicinity of Aberdeen city. Significant differences in basal respiration rates, microbial biomass and ecophysiological parameters were found in urban soils compared to rural soils. Analysis of community level physiological profiles (CLPP) of micro-organisms showed they consumed C sources faster in urban soils to maintain the same level activity as those in rural soils. Cu, Pb, Zn and Ni were the principal elements that had accumulated in urban soils compared with their rural counterparts with Pb being the most significant metal to distinguish urban soils from rural soils. Sequential extraction showed the final residue after extraction was normally the highest proportion except for Pb, for which the hydroxylamine-hydrochloride extractable Pb was the largest part. Acetic acid extractable fraction of Cd, Cu, Ni, Pb and Zn were higher in urban soils and aqua regia extractable fraction were lower suggesting an elevated availability of heavy metals in urban soils. Correlation analyses between different microbial indicators (basal respiration, biomass-C, and sole C source tests) and heavy metal fractions indicated that basal respiration was negatively correlated with soil Cd, Cu, Ni and Zn inputs while soil microbial biomass was only significantly correlated with Pb. However, both exchangeable and iron- and manganese-bound Ni fractions were mostly responsible for shift of the soil microbial community level physiological profiles (sole C source tests). These data suggest soil microbial indicators can be useful indicators of pollutant heavy metal stress on the health of urban soils.     

Impact of river overflowing on trace element contamination of volcanic soils in south Italy: part II. Soil biological and biochemical properties in relation to trace element speciation

The effect of heavy metal contamination on biological and biochemical properties of Italian volcanic soils was evaluated in a multidisciplinary study, involving pedoenvironmental, micromorphological, physical, chemical, biological and biochemical analyses. Soils affected by recurring river overflowing, with Cr(III)-contaminated water and sediments, and a non-flooded control soil were analysed for microbial biomass, total and active fungal mycelium, enzyme activities (i.e., FDA hydrolase, dehydrogenase, beta-glucosidase, urease, arylsulphatase, acid phosphatase) and bacterial diversity (DGGE characterisation). Biological and biochemical data were related with both total and selected fractions of Cr and Cu (the latter deriving from agricultural chemical products) as well as with total and extractable organic C. The growth and activity of soil microbial community were influenced by soil organic C content rather than Cu or Cr contents. In fact, positive correlations between all studied parameters and organic C content were found. On the contrary, negative correlations were observed only between total fungal mycelium, dehydrogenase, arylsulphatase and acid phosphatase activities and only one Cr fraction (the soluble, exchangeable and carbonate bound). However, total Cr content negatively affected the eubacterial diversity but it did not determine changes in soil activity, probably because of the redundancy of functions within species of soil microbial community. On the other hand, expressing biological and biochemical parameters per unit of total organic C, Cu pollution negatively influenced microbial biomass, fungal mycelium and several enzyme activities, confirming soil organic matter is able to mask the negative effects of Cu on microbial community.     

PCBs and DDT in the serum of juvenile California sea lions: associations with vitamins A and E and thyroid hormones

In order to better understand the fate of metals during the biodegradation of organic matter in soils, an in vitro incubation experiment was conducted with metal-rich and metal-free leaves of Arabidopsis halleri introduced in a non-contaminated soil. During incubation of these microcosms, we followed the partitioning of Zn and Cd between the solution and their solid components, by determining the metal contents of six soil fractions and dissolved metals after granulo-densimetric separations at selected times. Microbial biomass and exchangeable metals in K(2)SO(4) solutions were also determined at the same times, and two main stages were identified. The first one takes place after a fast abiotic transfer of Zn and Cd from readily soluble plant tissues onto fine soil constituents, keeping metals away from the liquid phase: during about 14 days, microbial biomass increased as well as metal contents of some soil fractions, particularly those rich in particulate organic matter. During the second stage, between 14 and 60 days and for the metal-rich microcosms, Zn and Cd contents in solution increased, while microbial biomass decreased instead of staying constant as in control. A change of Zn and Cd speciation is assumed, from non-toxic adsorbed forms to more toxic species in solution. Remaining metal-rich plant residues seem to create a stable organic C compartment in the soil.     

Mobility of Zn, Cd and Pb in soils as affected by poultry litter extract--II. Redistribution among soil fractions

The application of poultry litter to metal-contaminated soils may influence metal leaching and distribution of metals among soil fractions. Soil columns (one uncontaminated control, one metal-amended, and two metal-contaminated soils) were leached with H2O, CaCl2, EDTA, and poultry litter extract (PLE) solutions. After leaching, the soil samples in the columns were sequentially extracted for water soluble (WS), exchangeable (EXC), organic matter (OM), Mn oxide (MNO), amorphous Fe oxide (AFEO), crystalline Fe oxide (CFEO) and residual (RES) fractions. The OM fraction showed high retention for Zn from the PLE. The EDTA redistributed Zn, Cd and Pb from the EXC, OM and MNO fractions to the WS fraction. The PLE usually solubilized more Zn and Cd from the EXC fraction than CaCl2. Neither PLE nor CaCl2 mobilized Pb. The application of poultry litter on metal-contaminated soils might cause Zn and Cd redistribution from the EXC to the WS fraction and enhance metal mobility.     

Distribution and Fractionation of Phosphorus,Cadmium, Nickel,and Lead in Calcareous Soils Amended with Composts

Abstract

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe–Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0–22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P ? Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0–22 cm soil depths except for Cd in the 10–22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe–Mn oxides form in the 0–10 and 10–22 cm soil layers. Cadmium was predominantly in the Fe–Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0–10 cm soil layer.     

Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances

Effective phytoremediation of soils contaminated by heavy metals depends on their availability to plant uptake that, in turn, may be influenced by either the existing soil humus or an exogenous humic matter. We amended an organic and a mineral soil with an exogenous humic acid (HA) in order to enhance the soil organic carbon (SOC) content by 1% and 2%. The treated soils were further enriched with heavy metals (Cu, Pb, Cd, Zn, Ni) to a concentration of 0, 10, 20, and 40 microg/g for each metal and allowed to age at room temperature for 1 and 2 months. After each period, they were extracted for readily soluble and exchangeable (2.5% acetic acid), plant-available (DTPA, Diethylentriaminepentaacetic acid), and occluded (1 N HNO(3)) metal species. Addition of HA generally reduced the extractability of the soluble and exchangeable forms of metals. This effect was directly related to the amount of added HA and increased with ageing time. Conversely, the potentially plant-available metals extracted with DTPA were generally larger with increasing additions of exogenous HA solutions. This was attributed to the formation of metal-humic complexes, which ensured a temporary bioavailability of metals and prevented their rapid transformation into insoluble species. Extractions with 1 N HNO(3) further indicated that the added metals were present in complexes with HA. The observed effects appeared to also depend on the amount of native SOC and its structural changes with ageing. The results suggest that soil amendments with exogenous humic matter may accelerate the phytoremediation of heavy metals from contaminated soil, while concomitantly prevent their environmental mobility.     

Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Evaluation of remediation process with plant-derived biosurfactant for recovery of heavy metals from contaminated soils

A washing process was studied to evaluate the efficiency of saponin on remediating heavy metal contaminated soils. Three different types of soils (Andosol: soil A, Cambisol: soil B, Regosol: soil C) were washed with saponin in batch experiments. Utilization of saponin was effective for removal of heavy metals from soils, attaining 90-100% of Cd and 85-98% of Zn extractions. The fractionations of heavy metals removed by saponin were identified using the sequential extraction. Saponin was effective in removing the exchangeable and carbonated fractions of heavy metals from soils. In recovery procedures, the pH of soil leachates was increased to about 10.7, leading to separate heavy metals as hydroxide precipitates and saponin solute. In addition recycle of used saponin is considered to be effective for the subsequent utilization. The limits of Japanese leaching test were met for all of the soil residues after saponin treatment. As a whole, this study shows that saponin can be used as a cleaning agent for remediation of heavy metal contaminated soils.     

Chromium uptake by rice and accumulation in soil amended with municipal solid waste compost

Effect of addition of municipal solid waste compost (MSWC) on chromium (Cr) content of submerged rice paddies was studied. Experiments were conducted during the three consecutive wet seasons from 1997 to 1999 on rice grown under submergence, at the Experimental Farm of Calcutta University, India. A sequential extraction method was used to determine the various chromium fractions in MSWC and cow dung manure (CDM). Chromium was significantly bound to the organic matter and Fe and Mn oxides in MSWC and CDM. Chromium content in rice straw was higher than in rice grain. Chromium bound with organic matter in MSWC best correlated with straw Cr (r=0.99**) followed by Fe and Mn oxides (r=0.97*) and water soluble as well as exchangeable fractions (r=0.96*). The water soluble and the exchangeable fractions in MSWC best correlated with grain Cr (r=0.98*). The Cr content of rice grain had the highest correlation with water soluble and exchangeable Cr (r=0.99**) while the straw Cr best correlated with the Fe and Mn oxides (r=0.98*). Both the carbonate bound and residual fractions in MSWC and CDM did not significantly correlate with rice straw and grain Cr. MSWC would be a valuable resource for agriculture if it can be used safely, but long-term use may require the cessation of the dumping by the leather tanneries and other major contributors of pollutants.     

Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

氧化亚铁硫杆菌对电子垃圾焚烧迹地重金属形态的影响简

采用生物淋滤法处理电子垃圾焚烧迹地重金属严重污染的土壤。所用氧化亚铁硫杆菌是从矿坑废水中通过一系列培养、分离和纯化得到。实验结果表明,生物淋滤法可以有效地去除土壤中重金属Cu、Pb和Zn,去除率的大小顺序为Zn>Cu>Pb;采用五步连续提取法分析处理前后土壤中重金属的存在形态,结果表明,通过氧化亚铁硫杆菌处理受重金属污染的土壤,可以促使易移动的重金属结合态的溶解（可交换态、碳酸盐结合态和Fe-Mn氧化物结合态）,并使难移动的重金属结合态向易移动的重金属结合态转变。     

氧化亚铁硫杆菌对电子垃圾焚烧迹地重金属形态的影响

采用生物淋滤法处理电子垃圾焚烧迹地重金属严重污染的土壤。所用氧化亚铁硫杆菌是从矿坑废水中通过一系列培养、分离和纯化得到。实验结果表明,生物淋滤法可以有效地去除土壤中重金属Cu、Ph和Zn,去除率的大小顺序为Zn〉Cu〉Pb;采用五步连续提取法分析处理前后土壤中重金属的存在形态,结果表明,通过氧化亚铁硫杆菌处理受重金属污染的土壤,可以促使易移动的重金属结合态的溶解（可交换态、碳酸盐结合态和Fe—Mn氧化物结合态）,并使难移动的重金属结合态向易移动的重金属结合态转变。     

Effect of applying chemical fertilizers on forms of lead and cadmium in red soil

A three-month incubation study was undertaken to examine the influence of N, P and K on the various forms (soluble plus exchangeable (SE), weakly specifically adsorbed (WSA), Fe-Mn oxides bound (OX), organic matter complexed (OM) and residual fractions (RES)) of lead (Pb) and cadmium (Cd) in a red soil. Application of urea at the rate of 200 mg N/kg significantly lowered the SE fraction, but raised the WSA or OX fraction of both metals. Supply of 80 mg P/kg caused a decrease in the SE fraction of the two metals. The WSA fraction of Pb was reduced, whereas that of Cd increased by adding P. However, addition of 100 mg K/kg led to an increase in the SE fraction, but a decrease in the WSA fraction of Pb and Cd. Applying chemical fertilizers had no significant consistent influences on the other fractions of metals. These findings suggest that in heavy metal contaminated red soil, applying fertilizers does not only provide plant nutrients, but may also change the speciations and thus biovailability of heavy metals.     

Copper amendments and soil ph affect distribution of different chemical forms of metals and their uptake by Swingle citrumelo seedlings

Abstract

This study was conducted to evaluate the effects of various rates of Copper (Cu) amendments (as CuSO₄.5H₂O at either 0, 25, 50, 100, 200, or 400 mg Cu kg^‐1) to soils with different pH values on the distribution of various chemical forms of Zinc (Zn), Iron (Fe), Manganese (Mn), and Aluminum (Al) in soils and their uptake by Swingle citrumelo citrus rootstock seedlings. The soils included Myakka fine sand (pH 5.70), Candler fine sand (pH 6.45), and Oldsmar fine sand (pH 8.16). The chemical forms of metals evaluated in this study included exchangeable, sorbed, organically bound, precipitated, and residual forms. An increase in Cu rates, lowered the pH in the Myakka and Candler fine sands, but not in the Oldsmar fine sand. This, in turn, resulted in an increase in the proportion of the readily soluble forms (the exchangeable + sorbed forms) of Zn and Mn, and decreased that of Fe in the Myakka and Candler fine sands. In those two soils, the organically bound forms of Zn, Fe, and Mn decreased with an increase in Cu rates. However, the proportion of readily soluble forms was not significantly influenced by increasing Cu rates in the Oldsmar fine sand. The total content of Zn, Fe, and Mn in citrus roots and that of Zn and Fe in the leaves, significantly decreased with an increase in Cu rates in the Myakka and Candler fine sands. In the Oldsmar fine sand, Cu rates through the entire range had no significant effects on the total contents of Zn, Fe, and Mn in the leaves or in the roots of Swingle citrumelo rootstock seedlings.     

Distribution and fractionation of phosphorus, cadmium, nickel, and lead in calcareous soils amended with composts

Composts improve organic carbon content and nutrients of calcareous soils but the accumulation and distribution of phosphorus and heavy metals among various fractions in soil may vary under the south Florida conditions. The accumulation of P, Cd, Ni, and Pb with depth and the distribution of water soluble, exchangeable, carbonate, Fe-Mn oxides, organic and residual forms of each element were investigated in soils amended with municipal solid waste (MSW) compost, co-compost and biosolids compost and inorganic fertilizer (as control). Total concentrations of P, Cd, Ni, and Pb were higher in the 0-22 cm soil layers and decreased considerably in the rock layers. These elements were in the decreasing order of P > Pb > Ni > Cd. Amounts of water soluble and exchangeable forms of P, Cd, Ni and Pb were negligible at 0-22 cm soil depths except for Cd in the 10-22 cm depth. Amending calcareous soil with either organic or inorganic amendments rendered phosphorus, nickle and lead in the residual form followed by Fe-Mn oxides form in the 0-10 and 10-22 cm soil layers. Cadmium was predominantly in the Fe-Mn oxides fraction followed by the residual and carbonate forms in both soil layers. A significant positive correlation was found between various organic carbon fractions and organic forms of P, Cd and Pb in the surface soil layer. Soil amended with MSW compost had higher concentration of Cd in the organic fraction whereas, co-compost and MSW compost amended soil had higher concentrations of organic Ni fraction in the 0-10 cm soil layer.     

In situ fixation of metals in soils using bauxite residue: chemical assessment

Contamination of soils with heavy metals and metalloids is a widespread problem all over the world. Low cost, non-invasive, in situ technologies are required for remediation processes. We investigated the efficiency of a bauxite residue (red mud) to fix heavy metals in two soils, one contaminated by industrial activities (French soil), and one by sewage sludge applications (UK soil). This Fe-oxide rich material was compared with lime, or beringite, a modified aluminosilicate that has been used for in situ fixation processes. Four different crop species were successively grown in pots. Metal concentrations in the soil pore waters were analyzed during the growing cycles. At the end of the experiment fluxes of heavy metals were measured using a diffusive gradient in thin film technique (DGT). Furthermore, a sequential extraction procedure (SEP) and an acidification test were performed to investigate the mechanisms of metal fixation by different soil amendments. In both soils, the concentrations of metals in the soil pore water and metal fluxes were greatly decreased by the amendments. An application of 2% red mud performed as well as beringite applied at 5%. Increasing soil pH was a common mechanism of action for all the amendments. However, the red mud amendment shifted metals from the exchangeable to the Fe-oxide fraction, and decreased acid extractability of metals. The results suggest that specific chemisorption, and possibly metal diffusion into oxide particles could also be the mechanisms responsible for the fixation of metals by red mud.