Migration of trace elements from pyrite tailings in carbonate soils

In the carbonate soils contaminated by a toxic spill from a pyrite mine (Aznalcóllar, southern Spain), a study was made of a thin layer (thickness = 4 mm) of polluted soil located between the pyrite tailings and the underlying soil. This layer, reddish-yellow in color due to a high Fe content, formed when sulfates (from the oxidation of sulfides) infiltrated the soil, causing acidification (to pH 5.6 as opposed to 8.0 of unaffected soil) and pollution (in Zn, Cu, As, Pb, Co, Cd, Sb, Bi, Tl, and In). The less mobile elements (As, Bi, In, Pb, Sb, and Tl) concentrated in the uppermost part of the reddish-yellow layer, with concentration decreasing downward. The more mobile elements (Co, Cd, Zn, and Cu) tended to precipitate where the pH was basic, toward the bottom of the layer or in the upper part of the underlying soil. The greatest accumulations occurred within the first 6 mm in overall soil depth, and were negligible below 15 mm. In addition, the acidity of the solution from the tailings degraded the minerals of the clay fraction of the soils, both the phyllosilicates as well as the carbonates. Also, within the reddish-yellow layer, gypsum formed autigenically, together with complex salts of sulfates of Fe, Al, Zn, Ca, and Mn, jarosite, and oxihydroxides of Fe.     

Spatiotemporal evolution of soil pH and zinc after the Aznalcollar mine spill

The residual pollution after the Aznalcóllar (southwestern Spain) pyrite mine spill is still a threat due to the continuing oxidation of sulfuric minerals. The objective of this paper was to analyze the combined effect of pyrite oxidation, sugar beet foam applications, and meteorological conditions on the spatiotemporal evolution of the pH and EDTA-extractable Zn concentration, using non co-located data from 11 sampling dates between June 1999 and March 2002. Median pH values ranged from 4.4 at the beginning of the monitoring period to 7.6 at the end, although values near 2.5 were observed throughout the entire period, despite of two sugar beet foam (SBF) applications. Zinc distributions were positively skewed and median concentrations ranged from 17 to 94 mg kg(-1). The inverse relationship between pH and Zn became weaker toward the end of the monitoring period as a consequence of the precipitation and posterior dissolution of newly formed minerals from the reaction products of the pyrite oxidation. Normal score maps showed that after the SBF applications only 0.5% of the monitored area was below the pH = 4 threshold, while on other dates up to one-third of the area remained below this value. The better performance of the second SBF application could be explained in terms of pyrite oxidation pathways and environmental conditions. From this analysis, with data obtained under uncontrolled field conditions, it is concluded that SBF should be applied before or during the wet and cold season to alleviate acidification, caused by the oxidation of pyrite or other sulfuric minerals.     

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.     

Prediction of trace element mobility in contaminated soils by sequential extraction

The modified three-step sequential extraction procedure proposed by the Community Bureau of Reference (or Bureau Communautaire de Reference, BCR) was used to predict trace element mobility in soils affected by an accidental spill comprising arsenopyrite- and heavy metal-enriched sludge particles and acid waste waters. The procedure was used to obtain the distribution of both the major (Al, Ca, Fe, Mg, and Mn) and trace elements (As, Bi, Cd, Cu, Pb, Tl, and Zn) in 13 soils of contrasting properties with various levels of contamination and in the sludge itself. The distributions of the major elements enabled us to confirm the main soil fractions solubilized in each of the three steps, and, in turn, to detect the presence of pyritic sludge particles by the high Fe extractability obtained in the third step. Cadmium was identified as being the most mobile of the elements, having the highest extractability in the first step, followed by Zn and Cu, Lead, Tl, Bi, and As were shown to be poorly mobile or nonmobile. In the case of some of the trace elements, the residual fractions decreased at higher levels of contamination, which was attributed to the anthropogenic contributions to the polluted samples. Comparison with soil-plant transfer factors, calculated in plants growing in the affected area, indicated that a relative sequence of trace element mobility was well predicted from data of the first step.     

Mapping residual pyrite after a mine spill using non co-located spatiotemporal observations

Monitoring of soil chemical properties for pollution assessment generally requires destructive soil sampling and results in spatiotemporal datasets where data from different sampling dates are non co-located. The objective of this study was to assess the spatial distribution of residual pyrite sludge at a reclaimed site, using temporally non co-located data on pH; soil oxidizable fraction (SOF); and EDTA-extractable Fe, Zn, and Cu from six different sampling dates over a period of 2 yr. During this period spatially averaged pH and Zn concentrations ranged, respectively, from 4.4 to 6.6 and from 60 to 140 mg kg(-1), with minimum pH values of below 2.7. The data were merged into a single dataset for each chemical property after applying a normal score (ns) transform. Normal score pH was significantly negatively correlated with the ns metal concentrations. A principal component analysis (PCA) showed that normal score pH, Zn, and Fe were associated with the residual contamination, while ns Cu, SOF, and elevation were related with historic contamination. The spatial dependence between the properties was found to be scale-dependent. The best ns estimates were produced by ordinary kriging with an anisotopic variogram model, for the properties related with Principal Component (PC) I, while those associated with PC II were best estimated using simple kriging with varying local means. A classified ns pH map showed that 33% of the study area reached at least once values of below 4 during the 2-yr period. This part of the area should be excluded to ensure successful revegetation.     

MODELING ACID MINE DRAINAGE ON A WATERSHED SCALE FOR TMDL CALCULATIONS1

ABSTRACT: The Cheat River of West Virginia is impaired by acid mine drainage (AMD). Fifty‐five of its river segments were placed on the 303(d) list, which required calculations of total maximum daily load (TMDL) to meet the water quality criteria for pH, total iron, aluminum, manganese, and zinc. An existing watershed model was enhanced to simulate AMD as nonpoint source load. The model divided a watershed into a network of catchments and river segments. Each catchment was divided into soil layers, which could contain pyrite, calcite and other minerals. A kinetic expression was used to simulate pyrite oxidation as a function of oxygen in the soil voids. Oxygen in the soil voids was consumed by pyrite oxidation and replenished by earth breathing. The by‐products of pyrite oxidation were calculated according to its mass action equations. Chemical equilibrium was used to account for the speciation of ferrous and ferric irons and precipitation of metal hydroxides. Simulated hydrology and water quality were compared to available data. The USEPA used the calibrated model to calculate the TMDLs in the Cheat River Watershed.     

Zinc distribution in soils amended with different kinds of sewage sludge

Sewage sludge (SS) can be applied to cropland to supply and recycle nutrients and organic carbon. Potentially toxic elements in the sludge, however, are of environmental concern. This study evaluates the changes in chemical speciation of Zn in three representative pristine soils of the Pampas Region, Argentina, measured with sequential extraction over a one-year period. Pure SS or SS containing 30% (DM) of its own incineration ash (AS) was applied to the soils at an application rate of 150Mgha(-1). Zn was sequentially fractionated into exchangeable, organically bound, inorganic and residual fractions. The application of the SS and AS amendments significantly increased Zn concentration in all soil fractions at each sampling date. At day 1, Zn was mainly found in the residual fraction. A year after the application of the amendments, redistribution towards the inorganic fraction was observed (41-76% of total Zn content). Zn found in exchangeable and inorganic fractions depended on soil pH rather than on the type of soil used. A negative and significant correlation was found between exchangeable Zn concentrations and soil pH (r=0.94), and a positive and significant correlation between inorganic Zn concentrations and soil pH (r=0.92). For each amended soil and sampling date, no significant differences were observed between SS or AS treatments for the exchangeable fraction. Moreover, the use of AS did not cause significant differences in Zn concentration in the other soil fractions compared to SS. Based on these results, land spreading of AS may be similar to SS diaposal in terms of Zn mobility.     

Inorganic pigments made from the recycling of coal mine drainage treatment sludge

Continuous industrial development increases energy consumption and, consequently, the consumption of fossil fuels. Coal mineral has been used in Brazil as a solid fuel for thermoelectric generators for several years. However, coal exploitation affects the environment intensely, mainly because Brazilian coal contains excess ash and pyrite (iron disulfide). According to the local coal industry syndicate, the average annual coal run per mine is 6 million ton/year; 3.5 million ton/year are rejected and disposed of in landfills. Besides pyrite, Brazilian coal contains Mn, Fe, Cu, Pb, Zn, Ge, Se, and Co. Additionally, the water used for coal beneficiation causes pyrite oxidation, forming an acid mine drainage (AMD). This drainage solubilizes the metals, transporting them into the environment, making treatment a requirement. This work deals with the use of sedimented residue from treated coal mine drainage sludge to obtain inorganic pigments that could be used in the ceramic industry. The residue was dried, ground and calcined ( approximately 1250 degrees C). The calcined pigment was then micronized (D(50) approximately 2mum). Chemical (XRF), thermal (DTA/TG), particle size (laser), and mineralogical (XRD) analyses were carried out on the residue. After calcination and micronization, mineralogical analyses (XRD) were used to determine the pigment structure at 1250 degrees C. Finally, the pigments were mixed with transparent glaze and fired in a laboratory roller kiln (1130 degrees C, 5min). The results were promising, showing that brown colors can be obtained with pigments made by residues.     

Agricultural recycling of treatment-plant sludge: a case study for a vegetable-processing factory

The present study evaluated the possibility of using the sludge produced by a vegetable-processing factory in agriculture. The sludge was amended with a soil mixture (i.e., a mixture of sand, soil, and manure) and was applied at 0, 165, 330, 495 and 660 t/ha to promote the growth of cucumbers. The effects of various sludge loadings on plant growth were assessed by counting plants and leaves, measuring stem lengths, and weighing the green parts and roots of the plants. We also compared heavy metal uptake by the plants for sludge loadings of 330, 495, and 660 t/ha with various recommended standards for vegetables. Our results showed that plant growth patterns were influenced to some extent by the sludge loadings. In general, the number of leaves, stem length, and dry weight of green parts exhibited a pronounced positive growth response compared with an unfertilized control, and root growth showed a lesser but still significant response at sludge loadings of 165 and 330 t/ha. The sludge application caused no significant increase in heavy metal concentrations in the leaves, though zinc (Zn) and iron (Fe) were found at elevated concentrations. However, despite the Zn and Fe accumulation, we observed no toxicity symptoms in the plants. This may be a result of cucumber's tolerance of high metal levels.     

Evaluation of leachates from coal refuse blended with fly ash at different rates

There is great interest in returning coal combustion products to mining sites for beneficial reuse as liming agents. A column study examined the effects of blending two coal fly ashes with an acid-forming coal refuse (4% pyritic S). Both fly ashes were net alkaline, but had relatively low neutralizing capacities. One ash with moderate alkalinity (CRF) was bulk blended with coal refuse at 0, 20, and 33% (w/w), while another lower alkalinity ash (WVF) was blended at 0, 5, 10, 20, and 33% (w/w). The columns were leached (unsaturated) weekly with 2.5 cm of simulated precipitation for >150 wk. Where high amounts of ash alkalinity (>20% w/w) were mixed with the coal refuse, pyrite oxidation was controlled and leachate pH was >7.0 with low metal levels throughout the study. At lower rates of alkalinity loading, trace metals were sequentially released from the WVF ash as the 5, 10, and 20% treatments acidified due to pyrite oxidation. Lechate metals increased in proportion to the total amounts applied in the ash. In this strongly acidic environment, metals such as Mn, Fe, and Cu were dissolved and leached from the ash matrix in large quantities. If ash is to be beneficially reused in the reclamation of acid-producing coal refuse, the alkalinity and potential acidity of the materials must be balanced through the appropriate addition of lime or other alkaline materials to the blend. Highly potentially acidic refuse material, such as that used here, may not be suitable for ash/refuse codisposal scenarios.     

Improvement of soil quality after "alperujo" compost application to two contaminated soils characterised by differing heavy metal solubility

Reclamation of trace element polluted soils often requires the improvement of the soil quality by using appropriate organic amendments. Low quality compost from municipal solid waste has been tested for reclamation of soils, but these materials can provide high amounts of heavy metals. Therefore, a high-quality compost, with low levels of heavy metals, produced from the main by-product of the Spanish olive oil extraction industry ("alperujo") was evaluated for remediation of soils affected by a pyritic mine sludge. Two contaminated soils were selected from the same area: they were characterised by differing pH values (4.6 and 7.3) and total metal concentrations, which greatly affected the fractionation of the metals. Compost was applied to soil at two rates (equivalent to 48 and 72 Tm ha(-1)) and compared with an inorganic fertiliser treatment. Compost acted as an available nutrient source (C, N and P) and showed a low mineralisation rate, suggesting a slow release of nutrients and thus favouring long term soil fertility. In addition, the liming effect of the compost led to a significant reduction of toxicity for soil microorganisms in the acidic soil and immobilisation of soil heavy metals (especially Mn and Zn), resulting in a clear increase in both soil microbial biomass and nitrification. Such positive effects were clearly greater than those provoked by the mineral fertiliser even at the lowest compost application rate, which indicates that this type of compost can be very useful for bioremediation programmes (reclamation and revegetation of polluted soils) based on phytostabilisation strategies.     

Effect of organic matter oxidation on the fractionation of copper, zinc, lead, and arsenic in sewage sludge and amended soils

Long-term land application of sewage sludge (SS) has caused concern over the potential release of trace metals into the environment following the degradation of organic matter (OM). This study was performed to assess the impact of OM degradation on the relative distribution of Cu, Zn, Pb, and As in SS and SS-amended soils. Three SSs of different ages and two soils treated with SS were subjected to incubation and direct chemical oxidation using diluted HO, followed by a sequential extraction. The majority of Cu, Pb, and As were bound to OM, whereas the majority of Zn was bound with Fe/Mn oxides for all three SSs. Incubation of SS for 6 mo did not result in a substantial decrease in OM content or a change in the relative distribution of Cu, Zn, Pb, and As. Direct OM oxidation to 30 and 70% by diluted HO resulted in a significant decrease in organically bound Cu but increased its exchangeable, carbonate-bound, and Fe/Mn-bound fractions. Oxidation of OM slightly decreased organically bound Zn but significantly increased exchangeable Zn in all SSs. Oxide- and carbonate-bound Zn also decreased following OM oxidation. Exchangeable fractions of As and Pb were minute before and after OM degradation, indicating that release into the environment would be unlikely. The relative distribution of Cu, Zn, Pb, and As in SS-treated soils was similar to that of SS, suggesting a dominant role of SS properties in controlling metal distribution following OM oxidation. Overall, OM oxidation increased the mobility and bioavailability of Zn and Cu, whereas it had less impact on Pb and As.     

Mobility of oil and other sludge constituents during oily sludge treatment by landfarming

Five levels of oily sludge application were made to the surface layer of a desert sandy soil in Kuwait. The migration of the constituents of the sludge to subsurface soil layers was investigated at intervals over a period of 29 months. The data show very limited mobility to subsurface soil layer (40–70 cm depth) but not to 70–90 cm depth. The environmental impact of the added sludge is related to soil pH and to the Zn equivalent value of the sludge. Zn equivalent for the soil treated with oily sludge was 612 mg kg⁻¹, which is much lower than permissible limits. This soil can accept more than 1000 t ha⁻¹ from this type of sludge. However, due to the heterogeneous composition of sludge the Zn equivalent value should be calculated for each batch. Addition of oily sludge to the desert soil susceptible to wind erosion had a significant effect on minimizing soil loss under wind tunnel conditions. This effect is attributed to aggregation of the soil particles in the surface soil layers.     

Bioproduction of ferric sulfate used during heavy metals removal from sewage sludge

Toxic metals removal from wastewater sewage sludge can be achieved through microbial processes involving Acidithiobacillus ferrooxidans. The oxidation of ferrous ions by A. ferrooxidans, cultured in sewage sludge filtrate, was studied in both batch and continuous flow stirred tank reactors. Sewage sludge filtrate containing natural nutrients (phosphorus and nitrogen) was recovered as effluent following the dehydration of a primary and secondary sludge mixture. Batch and continuous flow stirred tank reactor tests demonstrated that A. ferrooxidans were able to grow and completely oxidize ferrous iron in a culture medium containing more than 80% (v v(-1)) sewage sludge filtrate with 10 g Fe(II) L(-1) added. Toxic levels were reached when total organic carbon in the sewage sludge filtrate exceeded 250 mg L(-1). The ferric iron solution produced in the sludge filtrate by A. ferrooxidans was used to solubilize heavy metals in primary and secondary sludge. The solubilization of Cu, Cr, and Zn yielded 71, 49, and 80%, respectively. This is comparable with the yield percentages obtained using a FeCl(3) solution. The cost of treating wastewater sewage sludge by bioproducing a ferric ion solution from sewage sludge is three times less expensive than the conventional method requiring a commercial ferric chloride solution.     

Mineralogical characteristics and transformations during long-term operation of a zerovalent iron reactive barrier

Design and operation of Fe0 permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe0 filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe0 filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe0 section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants.     

Passive treatment of acid mine drainage with high metal concentrations using dispersed alkaline substrate

Passive treatment systems based on the dissolution of coarse calcite grains are widely used to remediate acid mine drainage (AMD). Unfortunately, they tolerate only low metal concentrations or acidity loads, because they are prone to passivation (loss of reactivity due to coating) and/or clogging (loss of permeability) by precipitates. To overcome these problems, a dispersed alkaline substrate (DAS) composed of a fine-grained alkaline reagent (calcite sand) mixed with a coarse inert matrix (wood chips) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate, whereas the dispersion of nuclei for precipitation on the inert surfaces retards clogging. Chemical and hydraulic performance of DAS was investigated in two laboratory columns fed at different flow rates with natural AMD of pH 2.3 to 3.5 and inflow net acidity 1350 to 2300 mg/L as CaCO(3). The DAS columns removed 900 to 1600 mg/L net acidity, 3 to 4.5 times more than conventional passive treatment systems. Regardless of the flow rate employed, Al, Fe(III), Cu, and Pb were virtually eliminated. Minor Zn, Ni, and Cd were removed at low flow rates. High acidity removal is possible because these metals accumulate intentionally in DAS, and their precipitation promotes further calcite dissolution. During 15 mo, DAS operated without clogging at 120 g acidity/m(2).d, four times the loading rate recommended for conventional passive systems; DAS may therefore be capable of treating AMD at sites where influent chemistry precludes the use of other passive systems.     

RUNOFF OF METALS FROM ALUM-TREATED HORSE MANURE AND MUNICIPAL SLUDGE1

ABSTRACT: Land application of organic soil amendments can increase runoff concentrations of metals such as Fe and Zn, metalbids such as B and As, and non-metals such as P and S that have the potential for causing adverse environmental impacts. Aluminum sulfate, or alum (Al₂(SO₄)3*(14H₂O), can reduce concentrations of some materials in runoff from sites treated with organic amendments. The objectives of this study were to (a) quantify concentrations of selected constituents (Al, As, B, Ca, Cd, Co, Fe, K, Mg, Mn, Mo, Na, P, Pb, 5, Se, Ti, and Zn) in runoff from plots treated with horse manure (mixed with stall bedding) and municipal sludge, (b) assess runoff quality effects of alum addition to those treatments, and (c) determine time variations in concentrations of the constituents. Horse manure and municipal sludge were applied to twelve 2.4 by 6.1 m fescue plots (six each for the manure and sludge). Alum was added to three of the manure-treated and three of the sludge-treated plots. Simulated rainfall (64 mm/h) was applied to the 12 treated plots and to three control (no treatment) plots. The first 0.5 h runoff was sampled and analyzed for the constituents described above. Addition of manure or sludge had no effect on runoff concentrations of the majority of constituents. In some cases (e.g., Al, As, Fe, Zn), however, concentrations were near or in excess of threshold values recommended for marine wildlife protection. Alum addition increased runoff of Al, Ca, K, and 5, due likely to its composition and by the addition of lime to counteract the acidity of alum. Concentration decreases of more than 50 percent were noted for P for the horse manure treatment. No alum effect was detected for P in runoff from the sludge-treated plots, possibly due to relatively stable P forms in the sludge. Runoff concentrations of Al, As, Fe, K, Mn, and P followed an approximately first-order decline with respect to time. Runoff concentrations of Ca and 5, however, peaked during the second runoff sample (four minutes following initiation of runoff), suggesting that differences in mobility and/or transport mechanisms exist among the materials investigated.     

Vertical distribution and speciation of trace metals in weathering flotation residues of a zinc/lead sulfide mine

Sulfide-bearing mine tailings are a serious environmental problem around the world. In this study, the vertical distribution and speciation of Zn and Pb in the fine-grained flotation residues of a former sulfide ore mine in Germany were investigated to assess the inorganic weathering processes that effect the environmental risk arising from this site. Total metal contents were determined by X-ray fluorescence spectroscopy (XRF). Mobilizable fractions of Zn, Pb, Fe, and Mn were quantified by sequential chemical extractions (SCE). Furthermore, the speciation of Zn was analyzed by Zn K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) to identify the residual Zn species. The variations in pH and inorganic C content show an acidification of the topsoil to pH 5.5. EXAFS results confirm that Zn is mainly bound in sphalerite in the subsoil and weathering reactions lead to a redistribution of Zn in the topsoil. A loss of 35% Zn and S from the topsoil compared with the parent material with 10 g kg-1 Zn and neutral pH has been observed. If acidification proceeds it will lead to a significant release of Zn, S, and Pb to the ground water. In contrast to Zn, Pb is enriched in the mobile fraction of the topsoil by more than a factor of two compared with the subsoil which contains a total of 2 g kg-1 Pb. Thus, the high bioavailability of Pb and the potential for Pb uptake by plants and animals currently represent the most severe threat for environmental health.     

Effect of cobalt sorption on metal fractionation in anaerobic granular sludge

A sequential extraction procedure was applied to two anaerobic methanogenic sludges (Eerbeek and Nedalco) to examine the speciation of micro- and macronutrients in the sludges after cobalt sorption by exposing the sludge to a 1 mM Co solution for 4 d at pH 7 and 30 degrees C. The effect of different physicochemical conditions on cobalt sorption was studied as well: effect of pH (6-8), effect of competition by a second trace element (Ni or Fe), modification of the granular matrix by glutaraldehyde or heat treatment, and EDTA (ethylenediaminetetraacetic acid) addition. Sorbed Co was found to distribute between the carbonates, organic matter + sulfides, and residual fractions. Cobalt adsorption resulted in an antagonistic interaction with other metals present in the granular matrix, evidenced by the solubilization of other trace elements (e.g., Ni, Cu, and Zn) as well as macronutrients (especially Ca and Fe). Modification of the sludge matrix by glutaraldehyde or heat treatment, or exposure to EDTA, led to serious modifications of the Co sorption capacity and strong interactions with multivalent cations (i.e., Ca(2+) and Fe(2+)).     

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.