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.     

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.     

An inventory of trace element inputs to agricultural soils in China

It is important to understand the status and extent of soil contamination with trace elements to make sustainable management strategies for agricultural soils. The inputs of trace elements to agricultural soils via atmospheric deposition, livestock manures, fertilizers and agrochemicals, sewage irrigation and sewage sludge in China were analyzed and an annual inventory of trace element inputs was developed. The results showed that atmospheric deposition was responsible for 43–85% of the total As, Cr, Hg, Ni and Pb inputs, while livestock manures accounted for approximately 55%, 69% and 51% of the total Cd, Cu and Zn inputs, respectively. Among the elements concerned, Cd was a top priority in agricultural soils in China, with an average input rate of 0.004 mg/kg/yr in the plough layer (0–20 cm). Due to the spatial and temporal heterogeneity of the sources, the inventory as well as the environmental risks of trace elements in soils varies on a regional scale. For example, sewage sludge and fertilizers (mainly organic and phosphate-based inorganic fertilizers) can also be the predominant sources of trace elements where these materials were excessively applied. This work provides baseline information to develop policies to control and reduce toxic element inputs to and accumulation in agricultural soils.     

Zinc fractionation in contaminated soils by sequential and single extractions: influence of soil properties and zinc content

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.     

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.     

三峡库区土壤中微量元素有效态含量及其特征

本文研究了微量元素在三峡库区土壤中的有效态含量以及丰缺程度，发生频率等特征，同时，初步探讨了有效态微量元素之间及其与土壤ｐＨ值，有机质含量的相关关系。     

Effect of liming on the distribution of heavy metals in untreated industrial sewage sludge produced in Pakistan for the cultivation of <Emphasis Type="Italic">Sorghum bicolor</Emphasis> (L.)

The recycling of sewage sludge on agriculture land represents an alternative, advantageous, disposal of this waste material. The aim of the present study was to evaluate the feasibility of using industrial sewage sludge, produced in Pakistan, as a fertiliser. Agricultural soil amended with 25% (w/w) sewage sludge with or without lime treatment was used for growing a variety of sorghum (PARC-SS-1). The mobility of the heavy metals (HMs) (Cd, Cu, Cr, Ni, Pb and Zn) and metalloid (As) in the untreated industrial waste water sewage sludge (UIWS) samples were assessed by applying a modified BCR (Community Bureau of Reference) sequential extraction procedure. The single extraction procedure comprised of the application of mild extractant (CaCl₂) and water for the estimation of the proportion of easily soluble metal fractions. The precision and accuracy of BCR was evaluated by using a certified reference material of soil amended with sewage sludge BCR 483. The plant available metal contents, as extracted by the deionised water and 0.01 M CaCl₂ solution and exchangeable fraction of BCR sequential, decreased with lime application in the range of 10–44% for As, Cr, Ni, Pb and Zn, except in the cases of Cd and Cu, where their mobility was increased by 10% and 24%, respectively. Sludge amendment enhanced the dry weight yield of sorghum and the increase was more obvious after liming up to 25%. The uptake of HMs were lower in test samples (3.2–21.8%), except for Cu and Cd, which was higher (4%), while they were below the permissible limit of these metals. The present experiment demonstrates that liming was important in factors facilitating the growth of sorghum in sludge-amended soil.     

Characteristics of slag, fly ash and deposited particles during melting of dewatered sewage sludge in a pilot plant

This study examines slag, fly ash, and deposited particles during melting of dewatered sewage sludge in a pilot plant. In addition, the chemical composition of particles in flue gas was simulated using a thermodynamics program, namely FACTSage 5.2. The results showed that the main components of slag were Al, Fe, Ca, P and Si; the minor components were Na, K, Mg, Cu, and Zn. The main chemical compound of slag was Ca4(Mg,Fe)5(PO4)6. For fly ash particles, heavy metals with the highest concentrations were in the order of Zn and As, Pb, Cu, and Cd, respectively. For non-heavy metals, Al, Fe and P were also found in significant amounts. The majority of deposited particles were composed of elements of Zn, P, S, Na, Fe, Al, Si, and Ca and such chemical compounds as Zn3(PO4)2, AlPO4, FePO4 and Fe(OH)3 while the minority consisted of elements of As, Cu, and Pb. Moreover, the compositions of deposited particles in each chamber differed due to different flue gas temperatures inside. In the secondary chamber at 760 degrees C, the amounts of Fe and Al were higher than Zn, whereas, in the other chambers (600-400 degrees C), the amount of Zn was higher. In other words, at the lower temperature the deposition of Zn was higher than the deposition of Fe and Al. In the water cooling section, volatile elements (i.e. Zn, As, Cu, Pb) were found in the highest concentrations due to a big difference in temperature between the wall surface and flue gas. From the simulation results, most of the elements in the gas phase were found to be chloride compounds, whereas those in the solid phase were in the form of oxide, sulfate, and phosphate compounds.     

Fractionation and mobility of copper, lead, and zinc in soil profiles in the vicinity of a copper smelter

Four soil profiles located near a copper smelter in Poland were investigated for the distribution and chemical fractions of Cu, Pb, and Zn and their mobility in relation to soil properties. Contamination with heavy metals was primarily restricted to surface horizons and the extent of contamination was 7- to 115-fold for Cu, 30-fold for Pb, and 6-fold for Zn as compared with subsurface horizons. In the less-contaminated fine-textured soil, the metals were distributed in the order: residual > Fe-Mn oxides occluded > organically complexed > exchangeable and specifically adsorbed, while the order for sandy soils was: residual > organically complexed > Fe-Mn oxides occluded > exchangeable and specifically adsorbed. The contaminated surface horizons of these profiles showed no consistent pattern of metal distribution. However, the common features of highly contaminated soils were very low percentage of residual fraction and the dominance of the NH4OAc extractable fraction. The sum of mobile metal fractions was generally < 10% in subsurface horizons, while in the contaminated surface horizons these fractions made up 50% of the total metal contents. Soil properties contributed more to the relative distribution of the metal fractions in the studied profiles than did the distance and direction to the source of pollution. The amounts of metal extracted by 0.01 M CaCl2 accounted for only a small part of the same metals extracted by NH4OAc. The mobility indexes of metals correlated positively and significantly with the total content of metals and negatively with the clay content.     

三峡库区土壤中有效态微量元素含量的区划

本文建立了三峡库区土壤中有效态微量元素含量的区划原则。根据确立的有效态微量元素含量丰缺的指标，运用等值线图法，采用微机处理，最后将库区划分为八个土壤亚区。     

Dissolution of trace element contaminants from two coastal plain soils as affected by pH

Trace element mobility in soils depends on contaminant concentration, chemical speciation, water movement, and soil matrix properties such as mineralogy, pH, and redox potential. Our objective was to characterize trace element dissolution in response to acidification of soil samples from two abandoned incinerators in the North Carolina Coastal Plain. Trace element concentrations in 11 soil samples from both sites ranged from 2 to 46 mg Cu kg(-1), 3 to 105 mg Pb kg(-1), 1 to 102 mg Zn kg(-1), 3 to 11 mg Cr kg(-1), < 0.1 to 10 mg As kg(-1), and < 0.01 to 0.9 mg Cd kg(-1). Acidified CaCl2 solutions were passed through soil columns to bring the effluent solution to approximately pH 4 during a 280-h flow period. Maximum concentrations of dissolved Cu, Pb, and Zn at the lowest pH of an experiment (pH 3.8-4.1) were 0.32 mg Cu L(-1), 0.11 mg Pb L(-1), and 1.3 mg Zn L(-1) for samples from the site with well-drained soils, and 0.25 mg Cu L(-1), 1.2 mg Pb L(-1), and 1.4 mg Zn L(-1) for samples from the site with more poorly drained soils. Dissolved Cu concentration at pH 4 increased linearly with increasing soil Cu concentration, but no such relationship was found for Zn. Dissolved concentrations of other trace elements were below our analytical detection limits. Synchrotron X-ray absorption near edge structure (XANES) spectroscopy showed that Cr and As were in their less mobile Cr(III) and As(V) oxidation states. XANES analysis of Cu and Zn on selected samples indicated an association of Cu(II) with soil organic matter and Zn(II) with Al- and Fe-oxides or franklinite.     

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.     

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.     

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.     

Trace metals in river bed sediments: An assessment of their partitioning and bioavailability by using multivariate exploratory analysis

In this study, river bed sediments were submitted to a BCR sequential extraction, together with three bioavailability tests: a weak acid elutriate (HCl), a physiologically based extraction test (PBET) and a toxicity characteristic leaching procedure (TCLP). The most remarkable features of the BCR procedure were: i) Mn and Zn showed the highest proportion of the F1 exchangeable fraction; ii) in addition to Fe, Pb and Zn were the metals with the higher percentages in the F2 reducible fraction; iii) Fe and Cu were the elements with the highest proportion of the F3 oxidizable fraction; iv) the application of Principal Component Analysis to the metals in each of the three fractions did not show clear associations between metals and sediment components considered as metal scavengers, v) considering the sum of the three BCR fractions, the elements showed a decreasing availability of: Fe > Pb > Zn > Cu > Mn > Ni > Cr. The single extractions followed a decreasing extractability order of: HCl > PBET > TCLP and they were far from the extractability deduced from the sum of fractions in the BCR extraction.     

Major and trace elements of selected pedons in the USA

Few studies of soil geochemistry over large geographic areas exist, especially studies encompassing data from major pedogenic horizons that evaluate both native concentrations of elements and anthropogenically contaminated soils. In this study, pedons (n = 486) were analyzed for trace (Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Zn) and major (Al, Ca, Fe, K, Mg, Na, P, Si, Ti, Zr) elements, as well as other soil properties. The objectives were to (i) determine the concentration range of selected elements in a variety of U.S. soils with and without known anthropogenic additions, (ii) illustrate the association of elemental source and content by assessing trace elemental content for several selected pedons, and (iii) evaluate relationships among and between elements and other soil properties. Trace element concentrations in the non-anthropogenic dataset (NAD) were in the order Mn > (Zn, Cr, Ni, Cu) > (Pb, Co) > (Cd, Hg), with greatest mean total concentrations for the Andisol order. Geometric means by horizon indicate that trace elements are concentrated in surface and/or B horizons over C horizons. Median values for trace elements are significantly higher in surface horizons of the anthropogenic dataset (AD) over the NAD. Total Al, Fe, cation exchange capacity (CEC), organic C, pH, and clay exhibit significant correlations (0.56, 0.74, 0.50, 0.31, 0.16, and 0.30, respectively) with total trace element concentrations of all horizons of the NAD. Manganese shows the best inter-element correlation (0.33) with these associated total concentrations. Total Fe has one of the strongest relationships, explaining 55 and 30% of the variation in total trace element concentrations for all horizons in the NAD and AD, respectively.     

DISTRIBUTION AND GRAIN-SIZE PARTITIONING OF METALS IN BOVFOM SEDIMENTS OF AN EXPERIMENTALLY ACIDIFIED WISCONSIN LAKE1

ABSTRACT: A study of concentrations and distribution of major and trace elements in surficial bottom sediments of Little Rock Lake in northern Wisconsin included examination of spatial variation and grain-size effects. No significant differences with respect to metal distribution in sediments were observed between the two basins of the lake, despite the experimental acidification of one of the basins from pH 6.1 to 4.6. The concentrations of most elements in the lake sediments were generally similar to soil concentrations in the area and were well below sediment quality criteria. Two exceptions were lead and zinc, whose concentrations in July 1990 exceeded the criteria of 50 μg/g and 100 μg/g, respectively, in both littoral and pelagic sediments. Concentrations of some elements, particularly Cu, Pb, and Zn, increased along transects from nearshore to midlake, following a similar gradient of sedimentary organic carbon. In contrast, Mn, Fe, and alkali/alkaline-earth elements were at maximum concentrations in nearshore sediments. These elements are less likely to partition to organic particles, and their distribution is more dependent on mineralogical composition, grain size, and other factors. Element concentrations varied among different sediment grain-size fractions, although a simple inverse relation to grain size was not observed. Fe, Mn, Pb, and Zn were more concentrated in a grain-size range 20–60 tm than in either the very fine or the coarse fractions, possibly because of the aggregation of smaller particles cemented together by organic and Fe/Mn hydrous-oxide coatings.     

A novel continuous-flow sequential extraction procedure for metal speciation in solids

A continuous-flow extraction system was developed to speed up, facilitate, and improve the accuracy of the chemical fractionation of metals in solid materials. A three-step sequential extraction scheme was used to evaluate the novel system by analyzing calcium (Ca), iron (Fe), manganese (Mn), copper (Cu), and zinc (Zn) in a soil certified reference material (National Institute of Standards and Technology [NIST] SRM 2710). In the proposed system, extraction occurred in a closed chamber through which extractants were passed sequentially. The extracts were collected in a number of subfractions for subsequent name atomic absorption analysis. Apart from the advantages of simplicity, speed, and less risk of the contamination that flow analysis systems usually possess, the continuous-flow system can improve the accuracy of chemical fractionation of metals by sequential extraction. The system ensures that extraction is performed at designated pH values without any need of adjustment. Variation of sample weight to chamber volume ratios from 1:12 to 1:40 had no effect on the extractability of the metals studied. In the extraction of the acid soluble fraction, concentrations of acetic acid in the range 0.11 to 0.5 mol L(-1) had no significant effect on the amounts of metals extracted, except Fe. Increasing the concentration of hydroxylamine in the reducible fraction step from 0.04 to 0.5 mol L(-1) affected the extraction efficiency for Fe, Mn, and Zn. The extraction profile, rather than a single value of extracted concentration, of each element offers additional information about the kinetics of leaching processes and chemical associations between elements in the solid materials.     

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.