Total Contents and Sequential Extraction of Heavy Metals in Soils Irrigated with Wastewater,Akaki, Ethiopia

The Akaki River, laden with untreated wastes from domestic, industrial, and commercial sources, serves as a source of water for irrigating vegetable farms. The purpose of this study is to identify the impact of waste-water irrigation on the level of heavy metals and to predict their potential mobility and bioavailability. Zn and V had the highest, whereas Hg the lowest, concentrations observed in the soils. The average contents of As, Co, Cr, Cu, Ni, Zn, V, and Hg of both soils; and Pb and Se from Fluvisol surpassed the mean + 2 SD of the corresponding levels reported for their uncontaminated counterparts. Apparently, irrigation with waste water for the last few decades has contributed to the observed higher concentrations of the above elements in the study soils (Vertisol and Fluvisol) when compared to uncontaminated Vertisol and Fluvisol. On the other hand, Vertisol accommodated comparatively higher average levels of Cr, Cu, Ni, Zn, etc V, and Cd, whereas high contents of Pb and Se were observed in Fluvisol. Alternatively, comparable levels of Co and Hg were found in either soil. Except for Ni, Cr, and Cd in contaminated Vertisol, heavy metals in the soils were not significantly affected by the depth (0–20 and 30–50 cm). When the same element from the two soils was compared, the levels of Cr, Cu, Ni, Pb, Se, Zn, V, Cd at 0–20 cm; and Cr, Ni, Cu, Cd, and Zn at 30–50 cm were significantly different. Organic carbon (in both soils), CEC (Fluvisol), and clay (Vertisol) exhibited significant positive correspondences with the total heavy metal levels. Conversely, Se and Hg contents revealed perceptible associations with carbonate and pH. The exchangeable fraction was dominated by Hg and Cd, whereas the carbonate fraction was abounded with Cd, Pb, and Co. conversely, V and Pb displayed strong affinity to reducible fraction, where as Cr, Cu, Zn, and Ni dominated the oxidizable fraction. Cr, Hg, Se, and Zn (in both soils) showed preference to the residual fraction. Generally, a considerable proportion of the total levels of many of the heavy metals resided in non residual fractions. The enhanced lability is generally expected to follow the order: Cd > Co > Pb > Cu > Ni > Se > V and Pb > Cd > Co > Cu > Ni > Zn in Vertisol and Fluvisol, respectively. For the similar wastewater application, the soil variables influence the status and the distribution of the associated heavy metals among the different soil fractions in the study soils. Among heavy metals that presented relatively elevated levels and with potential mobility, Co, Cu, Ni (either soil), V (Vertisol), Pb, and Zn (Fluvisol) could pose health threat through their introduction into the food chain in the wastewater irrigated soils.     

Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.     

Evaluation of best management practice products in preventing discharge of metals: a laboratory evaluation

Heavy metal accumulation in soil poses serious environmental and health risks, as metals are carried with eroded soils. In this study, 17 different soil erosion and sediment control products were investigated for their effectiveness in controlling transport of particulate heavy metals (Cu, Zn, Pb, Cd). Among the treatments investigated, wood mulch and tackifiers were found to be the most effective in reducing total suspended solids (TSS) and total heavy metal losses. They reduced TSS to an undetectable level during short-term simulation tests. Paper mulch was the only treatment that had no significant reduction in both total metal loss and TSS. Fiber rolls, silt fences, and gravel bags were effective in reducing sediment loss. Although the netting/blanket treatments were not effective in reducing total metal discharge, they significantly reduced sediment loss compared with the control.     

The availability of copper in soils historically amended with sewage sludge, manure, and compost

Metals in soils amended with sewage sludge are typically less available compared with those in soils spiked with soluble metal salts. However, it is unclear if this difference remains in the long term. A survey of copper (Cu) availability was made in soils amended with sewage sludge, manure, and compost, collectively named organic amendments. Paired sets of amended and control soils were collected from 22 field trials where the organic amendments had aged up to 112 yr. Amended soils had higher total Cu concentrations (range, 2-220 mg Cu kg; median, 15 mg Cu kg) and organic C (range, 1-16 g kg; median, 4 g kg) than control soils. All samples were freshly spiked with CuCl, and the toxicity of added Cu to barley was compared between amended and control soils. The toxicity of added Cu was significantly lower in amended soils than in control soil in 15 sets by, on average, a factor of 1.4, suggesting that aged amendments do not largely increase Cu binding sites. The fraction of added Cu that is isotopic exchangeable Cu (labile Cu) was compared between control soils freshly spiked with CuCl and amended soils with both soils at identical total Cu concentrations. Copper derived from amendments was significantly less labile (on average 5.9-fold) than freshly added Cu in 18 sets of soils. This study shows that Cu availability after long-term applications of organic amendments is lower than that of freshly added Cu salts, mainly because of its lower availability in the original matrix and ageing reactions than because of increased metal binding sites in soil.     

Assessment of the use of industrial by-products to remediate a copper- and arsenic-contaminated soil

Two water treatment sludges (WTS-A, WTS-B), two red muds (RM), and red gypsum (RG), all rich in iron oxy-hydroxides, were added to a soil highly polluted with As and Cu at 2% (w/w) to reduce metal bioavailability. Because the amendments increased soil pH to approximately 6, a lime treatment to the same pH and an unamended treatment were included for comparison. All the amendments had significant positive effects on the soil microbial biomass and growth of ryegrass (Lolium multiflorum Lam. cv. Avance), but only WTS-A improved lettuce (Lactuca sativa L. cv. Tom Thumb) growth. The mineralization of added ammonium nitrogen was not significantly affected by the treatments, while a physiologically based extraction test (PBET) showed that bioaccessibility of As was low (< 5%) and decreased only in the WTS-A treatment. Concentrations of As in soil pore water and extractable As only decreased in the WTS and RG treatments. In contrast, Cu concentrations in soil pore water and extractable Cu decreased in all treatments, by more than 84% in the WTS, RM, and RG treatments. Non-isotopically exchangeable As and Cu were present in colloids in the soil pore water. Untreated soil had < 4% isotopically exchangeable As and this decreased by approximately 50%, with WTS, RM, and RG. The labile Cu pool represented a large proportion (34%) of the total Cu pool, and the isotopically exchangeable and soluble Cu were strongly correlated with soil pH. Acidification of the treated soils showed that the labile As and Cu both increased in the treated soils compared with untreated soils. The significance of the treatment effects on soil fertility and potential off-site transport of As and Cu to ground water are discussed.     

Natural attenuation of residual heavy metal contamination in soils affected by the Aznalcóllar mine spill, SW Spain

Non-amended soils affected by pyritic sludge residues were monitored for 7 years to assess the long-term natural attenuation ability of these soils. The decrease in both the total concentration of elements (particularly As) and (NH(4))(2)SO(4)-extractable fractions of Mn, and Zn, below the maximum permissible levels indicate a successful natural ability to attenuate soil pollution. Soil acidification by pyrite oxidation and rainfall-enhanced leaching were the largest contributors to the reduction of metals of high (Mn, Cu, Zn and Cd) and low (Fe, Al, and As) availability. Periodic use of correlation and spatial distribution analysis was useful in monitoring elemental dispersion and soil property/element relationships.     

Metals in vineyard soils of the Penedès area (NE Spain) after compost application

The application of organic wastes to improve soil physical characteristics in mechanized vineyards planted after land levelling is becoming a common practice in Mediterranean areas. It may be useful as an additional source of organic matter and nutrients, but these wastes could also have negative effects due to their metal content. The aim of the study was to evaluate the influence of compost application on soil metal contents in mechanized vineyard soils of the Spanish Mediterranean area, where this practice is repeated every three years. The study was carried out in a ten-year-old vineyard where the main soil type is Typic Calcixerept. Composted cattle manure was applied in alternate rows, at a rate of 40 Mgha(-1) dry-weight. Nine sampling points were located along the slopes of two plots: a levelled plot prepared for mechanization with large soil disturbance movements within the plot, and a plot of undisturbed soil. At each location, soil samples were taken in both treated and untreated soils. Total concentrations (digestion with aqua regia) and the extractable DTPA (Diethylene-triaminepentacetic)-CaCl2-TEA (Triethanolamine) fractions of Cu, Zn and Mn were analyzed in each sample. For Cu and Zn, the initial concentration was higher in the undisturbed plot. In both cases, total Cu and total Zn were positively affected by manure input and the concentration in treated soils was significantly higher than in untreated soil. For Mn, the initial concentration was higher in disturbed soils than in undisturbed ones, and although in both scenarios the concentrations increased with manure, no significant differences were found between treated and untreated soils. The extractable fraction also increased in treated versus untreated soils, although for Cu and Mn the extractable/total metal ratio was similar in treated and untreated soils. After one compost application, total metal contents increased significantly, particularly for Zn. Most of those metals are accumulated in the soil, due to the soil characteristics.     

Changes in the rhizosphere of metal-accumulating plants evidenced by chemical extractants

The plants Salix viminalis L. (common osier) and Thlaspi caerulescens J. Presl & C. Presl have been studied often because of their high potential to extract heavy metals from soils. The soil properties favoring this phytoextraction are not yet fully known. In this study we compared three frequently used single-extracting agents (NaNO3, diethylenetriaminepentaacetic acid [DTPA], and ethylenediaminetetra-acetic acid [EDTA]) with a sequential extraction procedure to describe changes in the different Cd, Cu, and Zn pools in the rhizosphere of S. viminalis and T. caerulescens grown on calcareous and acidic Swiss soils in a pot experiment. The sequential extraction was used to assess the chemical affinities of these heavy metals (HM) in the soil whereas the single extractants were used for estimating the bioavailable HM pools in the soils. Cadmium depletion in several pools was most apparent in the acidic soil, with a significant decrease observed in the NaNO3-, DTPA-, and EDTA-extractable fractions following T. caerulescens growth compared with control pots. The sequential extraction showed that most Cd extracted by the plant from the acidic soil originated from the organic pool, which implies that heavy metals bound to organic matter may constitute a significant part of the bioavailable Cd pool in soils. In the calcareous soil only a small amount of Cd was taken up by T. caerulescens, and this came mainly from the carbonate-bound fraction. This study shows that T. caerulescens, and to a lesser extent S. viminalis, can alter the heavy metal distribution in different soil pools within 90 d.     

Biosolid colloid-mediated transport of copper, zinc, and lead in waste-amended soils

Increasing land applications of biosolid wastes as soil amendments have raised concerns about potential toxic effects of associated metals on the environment. This study investigated the ability of biosolid colloids to transport metals associated with organic waste amendments through subsurface soil environments with leaching experiments involving undisturbed soil monoliths. Biosolid colloids were fractionated from a lime-stabilized, an aerobically digested, and a poultry manure organic waste and applied onto the monoliths at a rate of 0.7 cm/h. Eluents were monitored for Cu, Zn, Pb, and colloid concentrations over 16 to 24 pore volumes of leaching. Mass-balance calculations indicated significantly higher (up to 77 times) metal elutions in association with the biosolid colloids in both total and soluble fractions over the control treatments. Eluted metal loads varied with metal, colloid, and soil type, following the sequences Zn = Cu > Pb, and ADB > PMB > LSB colloids. Colloid and metal elution was enhanced by decreasing pH and colloid size, and increasing soil macroporosity and organic matter content. Breakthrough curves were mostly irregular, showing several maxima and minima as a result of preferential macropore flow and multiple clogging and flushing cycles. Soil- and colloid-metal sorption affinities were not reliable predictors of metal attenuation/elution loads, underscoring the dynamic nature of transport processes. The findings demonstrate the important role of biosolid colloids as contaminant carriers and the significant risk they pose, if unaccounted, for soil and ground water contamination in areas receiving heavy applications of biosolid waste amendments.     

Source-separated municipal solid waste compost application to Swiss chard and basil

A growth room experiment was conducted to evaluate the bioavailability of Cu, Mn, Zn, Ca, Fe, K, Mg, P, S, As, B, Cd, Co, Cr, Hg, Mo, Na, Ni, Pb, and Se from a sandy loam soil amended with source-separated municipal solid waste (SSMSW) compost. Basil (Ocimum basilicum L.) and Swiss chard (Beta vulgaris L.) were amended with 0, 20, 40, and 60% SSMSW compost to soil (by volume) mixture. Soils and compost were sequentially extracted to fractionate Cu, Pb, and Zn into exchangeable (EXCH), iron- and manganese-oxide-bound (FeMnOX), organic-matter (OM), and structurally bound (SB) forms. Overall, in both species, the proportion of Cu, Pb, and Zn levels in different fractions followed the sequence: SB > OM > FeMnOX > EXCH for Cu; FeMnOX = SB > OM > EXCH for Pb; and FeMnOX > SB = EXCH > OM for Zn. Application of SSMSW compost increased soil pH and electrical conductivity (EC), and increased the concentration of Cu, Pb, and Zn in all fractions, but not EXCH Pb. Basil yields were greatest in the 20% treatment, but Swiss chard yields were greater in all compost-amended soils relative to the unamended soil. Basil plants in 20 or 40% compost treatments reached flowering earlier than plants from other treatments. Additions of SSMSW compost to soil altered basil essential oil, but basil oil was free of metals. The results from this study suggest that mature SSMSW compost with concentrations of Cu, Pb, Mo, and Zn of 311, 223, 17, and 767 mg/kg, respectively, could be used as a soil conditioner without phytotoxic effects on agricultural crops and without increasing the normal range of Cu, Pb, and Zn in crop tissue. However, the long-term effect of the accumulation of heavy metals in soils needs to be carefully considered.     

Potential risks of copper, zinc, and cadmium pollution due to pig manure application in a soil-rice system under intensive farming: a case study of Nanhu, China

Heavy metal (copper [Cu], zinc [Zn], and cadmium [Cd]) pollution of soils from pig manures in soil-rice ( L.) systems under intensive farming was investigated, taking Nanhu, China, as the case study area. Two hundred pig manures and 154 rice straws, brown rice samples, and corresponding surface soil (0-15 cm) samples were collected in paddy fields from 150 farms in 16 major villages within the study area. The mean Cu and Zn concentrations in pig manures consistently exceeded the related standard. About 44 and 60% of soil samples exceed the Chinese Soil Cu and Cd Environmental Quality Standards, respectively. The concentration of Cu, Zn, and Cd in brown rice did not exceed the Chinese Food Hygiene Standard. There was a significant positive correlation between total Cu and Zn contents in soil and application rate of pig manures. Strong correlation was observed between the extractable Cu, Zn, and Cd in soil and the Cu, Zn, and Cd contents in the brown rice. The spatial distribution maps of Cu and Zn concentrations in brown rice, straw, and extractable soil Cu and Zn concentration also showed similar geographical trends. Further analyses on heavy metals loading flux and accumulation rates from pig manure applied suggested that Cu and Cd contents in soil currently have already exceeded the maximum permissible limit, and Zn, if still at current manure application rates, will reach the ceiling concentration limits in 9 yr. This study assists in understanding the risk of heavy metals accumulating from pig manure applications to agricultural soils.     

Effects of wood bark and fertilizer amendment on trace element mobility in mine soils, Broken Hill, Australia: implications for mined land reclamation

Soil amendments can immobilize metals in soils, reducing the risks of metal exposure and associated impacts to flora, fauna and human health. In this study, soil amendments were compared, based on "closed system" water extracts, for reducing metal mobility in metal-contaminated soil from the Broken Hill mining center, Australia. Phosphatefertilizer (bovine bone meal, superphosphate, triple superphosphate, potassium orthophosphate) and pine bark (Pinus radiata) were applied to two soils (BH1, BH2) contaminated with mining waste. Both soils had near neutral to alkaline pH values, were sulfide- or sulfate-rich, and contained metal and metalloid at concentrations that pose high environmental risks (e.g., Pb = 1.25 wt% and 0.55 wt%, Zn = 0.71 wt% and 0.47 wt% for BH1 and BH2, respectively). The addition of fertilizers and/or pine bark to both soil types increased water extractable metals and metalloids concentrations (As, Cd, Cu, Fe, Mn, Pb, Sb, Zn) compared with nonamended soils. One or more of the elements As, Cd, Cu, Mn, Pb, and Zn increased significantly in extracts of a range of different soil+pine bark and soil+fertilizer+piner+pine bark tests in response to increased pine bark doses. By contrast, Fe and Sb concentrations in extracts did not change significantly with pine bark addition. Solution pH was decreased by phosphate fertilizers (except for bovine bone meal) and pine bark, and pine bark enhanced dissolved organic carbon. At least in the short-term, the application of phosphate fertilizers and pine bark proved to be an ineffective method for controlling metal and metalloid mobility in soils that contain admixtures of polymetallic, polymineralic mine wastes.     

Fate of biosolids trace metals in a dryland wheat agroecosystem

Biosolids land application for beneficial reuse applies varying amounts of trace metals to soils. Measuring plant-available or total soil metals is typically performed to ensure environmental protection, but these techniques do not quantify which soil phases play important roles in terms of metal release or attenuation. This study assessed the distribution of Cd, Cr, Cu, Mo, Ni, Pb, and Zn associated with soluble/exchangeable, specifically adsorbed/carbonate-bound, amorphous Mn hydroxyoxide-bound, amorphous Fe hydroxyoxide-bound, organically complexed, and residual inorganic phases. Biosolids were applied every 2 yr from 1982 to 2002 (except in 1998) at rates of 0, 6.7, 13.4, 26.8, and 40.3 dry Mg biosolids ha(-)(1) to 3.6- by 17.1-m plots. In 2003, 0- to 20-cm and 20- to 60-cm soil depths were collected and subjected to 4 mol L(-1) HNO(3) digestion and sequential extraction. Trace metals were concentrated in the 0- to 20-cm depth, with no significant observable downward movement using 4 mol L(-1) HNO(3) or sequential extraction. The sequential extraction showed nearly all measurable Cd present in relatively mobile forms and Cr, Cu, Mo, Ni, Pb, and Zn present in more resistant phases. Biosolids application did not affect Cd or Cr fractionation but did increase relatively immobile Cu, Mo, and Zn phases and relatively mobile Cu, Ni, and Pb pools. The mobile phases have not contributed to significant downward metal movement. Long-term, repeated biosolids applications at rates considered several times greater than agronomic levels should not significantly contribute to downward metal transport and ground water contamination for soils under similar climatic conditions, agronomic practices, and histories.     

Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Multinuclear magnetic resonance analysis of two humic acid fractions from lowland rice soils

To determine the effects of intensive cropping of tropical lowland rice (Oryza sativa L.) and the associated long-term soil submergence on chemical properties of soil organic matter, we used solid-state 13C and 15N and solution 31P nuclear magnetic resonance (NMR) spectroscopy to analyze the labile mobile humic acid (MHA) and the more recalcitrant calcium humate (CaHA) fractions extracted from a series of soils supporting several long-term field experiments in the Philippines. The soils varied mainly in degree of submergence and cropping intensity, ranging from a rainfed rice field without soil submergence to irrigated double- and triple-cropped fields in which soil remains submerged almost all year long. As reported previously, all analyses associated increasing intensity of rice cropping with larger proportions of less humified material in the MHA and CaHA, such as diester phosphorus (P), amide nitrogen (N), and phenolic carbon (C). We established significant correlations between proportions of various spectral areas as well as between some spectral areas and other humic acid (HA) properties such as visible light absorption and free radical concentration (positive indices of humification) and hydrogen (H) concentration (negative index of humification). For example, spectral proportions of heterocyclic N were positively, and proportions of amide N and phenolic C negatively, correlated with visible light absorption and free radical concentration, and each of these spectral proportions had an opposite sign when correlated with H concentration. The correlations of N-alkyl C proportions were the strongest with these properties and with other functional group proportions.     

Time and moisture effects on total and bioavailable copper in soil water extracts

Environmental risk assessment of heavy metals in soil frequently involves testing of freshly spiked soils kept under stable humidity conditions, but it has been questioned whether these assessments are representative of the field situation. Furthermore, the poor correspondence that is often found between total metal content and metal toxicity calls for integrated chemical and biological analysis. The aim of this work was to determine time- and moisture-dependent changes in total water-extractable Cu as well as bioavailable Cu in soil water extracts. Measurements of total water-extractable copper ([Cu]tot) were performed using furnace atomic absorption spectrometry. An in vitro assay employing a Cu-specific Pseudomonas fluorescens reporter strain was used to estimate Cu that was biologically available to the reporter strain. We refer to this copper fraction as "bioavailable," [Cu]bio. We found a time-dependent decrease in [Cu]tot and [Cu]bio during incubation for up to 220 d at field capacity. Hence the [Cu]bio was reduced to between 32 and 40% of the initial values. Furthermore, the [Cu]bio to [Cu]tot ratio correlated positively with the amount of added Cu and tended to increase with time. The moisture content of the soil was important for Cu retention. Dry soil had higher [Cu]tot concentrations than humid soil, but the [Cu]bio to [Cu]tot, ratio was lower in the dry soil. Alternating drying and wetting did not lead to a more rapid Cu retention than observed under constant humid conditions. Our observations underline the need for considering both time and moisture effects when interpreting short-term toxicity studies and when making predictions concerning possible long-term effects of Cu in the soil environment.     

Solution chemistry influence on metal mobility in biosolids-amended soils

Many studies have implicated dissolved organic carbon (DOC) as an important contributor to the elevated mobility of trace metals in soils amended with biosolids. Few of these studies, however, have quantified both DOC and metal concentrations. We completed laboratory leaching column studies on a dryland Platner loam (fine, smectitic, mesic Aridic Paleustoll) and an irrigated Osgood sand (loamy, mixed, mesic Arenic Ustollic Haplargid), both with a history of biosolids application. The soils were neutral to slightly alkaline in pH prior to amendment. We performed an additional application of biosolids to one set of columns in the laboratory at a rate of 28 Mg ha(-1) to investigate the effect of time following application on metal mobility. The effect of electrolyte concentration was studied by using both distilled water and simulated irrigation water. Biosolids application increased both DOC and Cu in the column effluents resulting in a positive correlation between Cu and DOC across application treatments for both soils. Both Cu and Pb were mobilized under conditions of low electrical conductivity (EC). This may be the result of the release of a strong metal-binding component of DOC under these conditions. Conversely, Zn mobility was positively correlated with EC, suggesting that either cation exchange or the formation of inorganic complexes influences Zn mobility. Anodic stripping voltammetry measurements indicated that only a small percentage of the total dissolved metals existed as free ions or inorganic complexes; the remainder appears to be complexed to DOC.     

Traditional agricultural practices enable sustainable remediation of highly polluted soils in Southern Spain for cultivation of food crops

This study relates elemental content of a range of edible crops grown in soils severely polluted by metals and metalloids as affected by traditional smallholder management practices. Five agricultural plots close to a sulfidic waste dump were monitored. Soil analysis demonstrated elevated concentrations of As, Cu, Pb and Zn that were greatly in excess of maximum statutory limits for agricultural soils in the studied region. The main vegetables (lettuce, chard, onion, potatoes) and lemon, together with their associated soils, were measured for elemental content. Extractable soil element concentrations were very low. There were differences in elemental accumulation between crops, but none exceeded statutory concentrations in edible parts. Soil-plant transfer factors were uniformly low for all elements and crops. It is concluded that traditional soil management practices (annual liming and application of animal manures) have created conditions for sustainable long-term safety use, with potential for multiple end-use, of these highly polluted soils.     

Copper and zinc bioavailabilities to ryegrass (Lolium perenne L.) and subterranean clover (Trifolium subterraneum L.) grown in biosolid treated Chilean soils

The purpose of this study was assessing Cu and Zn availabilities in soils amended with a biosolid through the determination of their sequentially extracted chemical forms and their relationship with the contents of these metals in ryegrass (Lolium perenne L.) and subterranean clover (Trifolium subterraneum L.) plant tissues cultivated in a greenhouse using four soils classified as Aquic Xerochrepts and Ultic Haploxeralfs representatives of potential areas for biosolids application in the central zone of Chile. The soils were treated with sewage sludge at a rate of 0 and 30 Mg ha⁻¹. The greenhouse experiment was carried out through a completely randomized block design in a 2 × 4 (biosolid rate × soil) arrangement, considering three repetitions per treatment. The soils used in the greenhouse experiment before and after cultivation, were sequentially extracted with specific reagents and conditions in order to obtain the following fractions: exchangeable, sodium acetate-soluble, soluble in moderately reducing condition, K₄P₂O₇-soluble, soluble in reducing condition, and soluble in strongly acid and oxidizing condition. It was established that Cu and Zn were predominantly found in soils in less available forms, associated to organic matter, oxides and clay minerals. Zinc concentration in ryegrass plants was higher than that found in subterranean clover plants in biosolid-amended soils. Zinc contents in ryegrass shoot and root correlated with the exchangeable, bound-to-carbonate, and bound-to-FeOx metal forms in control soil. Copper and Zn bioavailabilities were estimated through satisfactorily fitted multiple linear regression models, with determination coefficients from 0.77 to 0.99, which showed a positive contribution of the labile metal forms in soils, especially in relation to Zn in both plant species.     

Distribution and movement of sludge-derived trace metals in selected Nigerian soils

Use of metal-rich sewage sludge as soil fertilizer may result in trace- metal contamination of soils. This study was conducted to evaluate the effects of long-term sludge application on trace-metal (Zn, Cu, Pb, and Ni) distribution and potential bioavailability in Nigerian soils under a tropical wet-dry climate. Total metal analyses, sequential chemical fractionation, and DTPA extractions were carried out on samples of control and sludge-amended pedons in Nigeria (a Rhodic Kandiustult and two Rhodic Kandiustalfs from Nigeria, respectively). The sewage sludge applied to the soils contained higher levels of Zn and Cu than Pb and Ni. The control pedon contained low levels of all four metals. Soil enrichment factors (EF) were calculated for each metal in the sludge-amended pedons. Compared with the control soil, the sludge-amended pedons showed elevated levels of Zn and Cu, reflecting the trace-metal composition of the sewage sludge. Zinc and Cu in the sludge-amended soils were strongly enriched at all depths in the profile, indicating that they had moved below the zone of sludge application. The sequential extraction and DTPA analyses indicated that the sludge-amended soils contained more readily extractable and bioavailable metal ions than the unamended soil.