Bioaccessibility of lead sequestered to corundum and ferrihydrite in a simulated gastrointestinal system

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (alpha-Al(2)O(3)) and ferrihydrite (Fe(5)HO(8).4H(2)O). The Pb-sorbed minerals were placed in a simulated gastrointestinal tract (in vitro) to simulate ingestion of Pb-contaminated soil. The changes in Pb speciation were determined using extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES). Both corundum (sorption maximum of 2.13 g kg(-1)) and ferrihydrite (sorption maximum of 38.6 g kg(-1)) have been shown to sorb Pb, with ferrihydrite having a very high affinity for Pb. The gastric bioaccessible Pb for corundum was >85% for corundum when the concentration of Pb was >200 mg kg(-1). Bioaccessible Pb was not detectable at 4. However, much of the sorbed Pb will become bioaccessible under gastric conditions (pH 1.5-2.5) if this soil is ingested. Caution should be used before using these materials to remediate a soil where soil ingestion is an important exposure pathway.     

Enhanced transformation of lead speciation in rhizosphere soils using phosphorus amendments and phytostabilization: an x-ray absorption fine structure spectroscopy investigation

To formulate successful phytostabilization strategies in a shooting range soil, understanding how heavy metals are immobilized at the molecular level in the rhizosphere soil is critical. Lead (Pb) speciation and solubility in rhizosphere soils of five different plant species were investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical extraction. The EXAFS analysis indicated that Pb occurred as PbCO (37%), Pb sorbed to organic matter (Pb-org: 15%), and Pb sorbed to pedogenic birnessite and/or ferrihydrite (Pb-ox: 36%) in the bulk soil. Comparison of the EXAFS spectra between bulk and rhizosphere soils demonstrated notable differences in fine structure, indicating that Pb species had been modified by rhizosphere processes. The estimated proportion of PbCO (25%) in the buckwheat soil was smaller than the other rhizosphere soils (35-39%). The addition of P significantly reduced Pb solubility in the bulk and rhizosphere soil except in the rhizosphere of buckwheat, for which the Pb solubility was 10-fold greater than in the other P-amended soils. This larger solubility in the buckwheat rhizosphere could not be explained by the total Pb speciation in the soil but was presumably related to the acidifying effect of buckwheat, resulting in a decrease of the soil pH by 0.4 units. The reduced Pb solubility by P amendment resulted from the transformation of preexisting PbCO (37%) into Pb(PO)Cl (26-32%) in the bulk and rhizosphere soils. In the P-amended rhizosphere soils, Pb-org species were no longer detected, and the Pb-ox pool increased (51-57%). The present study demonstrated that rhizosphere processes modify Pb solubility and speciation in P-amended soils and that some plant species, like buckwheat, may impair the efficiency of Pb immobilization by P amendments.     

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.     

Speciation of phosphorus in phosphorus-enriched agricultural soils using X-ray absorption near-edge structure spectroscopy and chemical fractionation

Knowledge of phosphorus (P) species in P-rich soils is useful for assessing P mobility and potential transfer to ground water and surface waters. Soil P was studied using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy (a nondestructive chemical-speciation technique) and sequential chemical fractionation. The objective was to determine the chemical speciation of P in long-term-fertilized, P-rich soils differing in pH, clay, and organic matter contents. Samples of three slightly acidic (pH 5.5-6.2) and two slightly alkaline (pH 7.4-7.6) soils were collected from A or B horizons in two distinct agrosystems in the province of Québec, Canada. The soils contained between 800 and 2100 mg total P kg(-1). Distinct XANES features for Ca-phosphate mineral standards and for standards of adsorbed phosphate made it possible to differentiate these forms of P in the soil samples. The XANES results indicated that phosphate adsorbed on Fe- or Al-oxide minerals was present in all soils, with a higher proportion in acidic than in slightly alkaline samples. Calcium phosphate also occurred in all soils, regardless of pH. In agreement with chemical fractionation results, XANES data showed that Ca-phosphates were the dominant P forms in one acidic (pH 5.5) and in the two slightly alkaline (pH 7.4-7.6) soil samples. X-ray absorption near-edge structure spectroscopy directly identified certain forms of soil P, while chemical fractionation provided indirect supporting data and gave insights on additional forms of P such as organic pools that were not accounted for by the XANES analyses.     

Effect of organic amendment and plant roots on the solubility and mobilization of lead in soils at a shooting range

Lead (Pb) dissolving gradually from spent pellets constitutes a serious environmental risk in and near shooting ranges, and remediation measures are necessary to prevent its movement to deeper soil layers and ground water. In this study, the effectiveness of organic amendment and plant roots in stabilizing Pb was assessed in a microcosm experiment. Planted (Scots pine, Pinus sylvestris L.) and unplanted microcosms consisting of coarse-textured mineral soil covered with Pb-contaminated humic topsoil were coated with uncontaminated peat layers of 1 to 3 cm and incubated for 77 d. In a percolation test, the microcosms were washed with ultra pure water to simulate heavy rain so as to rinse water-soluble lead (Pbw) from the topsoil layer. Although Pbw remained below detection limits in the mineral soils in all test units, acid-soluble lead (Pba) increased. Peat amendment diminished Pba in the mineral soil layer, this effect being more pronounced in planted soils, indicating that Pb was taken up by the plants. The percolation test showed that the effect of Scots pine seedlings on Pb movement was minor when peat was added. A long-term dissolution test revealed that considerably more Pb was released from old pellets into soil extracts than from new ones, whereas only traces of Pb, if any, were dissolved in sterilized pure water.     

Phosphate treatment of firing range soils: lead fixation or phosphorus release?

Phosphate treatment of lead (Pb)-contaminated soils relies on the premise that Pb converts to the thermodynamically stable, insoluble mineral class of pyromorphites. Recent research showed that treatment performance is kinetically controlled and strongly dependent on soil pH; this study employed an acidic phosphate (P) form, monobasic calcium phosphate (MCP), to investigate treatment performance of Pb occurring in an alkaline-buffered and an acidic firing range soil. The results of leaching, X-ray powder diffraction (XRPD), and modeling analyses showed that P and Pb dissolution in the alkaline soil and transformation reactions were kinetically controlled, so that: (i) TCLP (toxicity characteristic leaching procedure) and SPLP (synthetic precipitation leaching procedure) results were poor to marginal even at high MCP dosages; (ii) brushite (Ca(HPO(4)).2H(2)O) and cerussite (PbCO(3)) persisted in XRPD patterns; and, (iii) geochemical modeling failed to predict leaching and phase assemblages. In the acidic soil, Pb-P reactions promoted further soil acidification, improved TCLP performance, and generated better agreement with the equilibrium-based model; however, SPLP and modeling results showed that Pb concentrations could not be reduced below 15 microg/L mainly due to the low soil pH. The marginal or inadequate Pb immobilization was observed in both soils despite the elevated MCP dosages, which were well in excess of the pyromorphite stoichiometric ratio (P/Pb = 0.6). Additionally, P leaching concentrations and rates were extremely high (>300 mg/L), under both SPLP and deionized (DI) water extraction conditions, and as predicted by thermodynamic equilibrium. The performance and sustainability of phosphate-based treatment therefore seem questionable.     

Soil solid-phase controls lead activity in soil solution

Lead pollution of the environment is synonymous with civilization. It has no known biological function, and is naturally present in soil, but its presence in food crops is deemed undesirable. The concern regarding Pb is mostly due to chronic human and animal health effects, rather then phytotoxicity. However, not much is known about the chemistry and speciation of Pb in soils. We determined the activity of Pb2+, in near neutral and alkaline soils, representative of alluvial, desertic and calcareous soils of Egypt, using the competitive chelation method. Lead activity ranged from 10(-6.73) to 10(-4.83) M, and was negatively correlated with soil and soil solution pH (R2 = -0.92, P < 0.01 and R2 = -0.89, P < 0.01, respectively). It could be predicted in soil solution from the equation: log(Pb2+) = 9.9 - 2pH. A solubility diagram for the various Pb minerals found in soil was constructed using published thermodynamic data obtained from the literature, and our measured Pb2+ activities compared with this information. The measured Pb2+ activities were undersaturated with regard to the solubility of PbSiO3 in equilibrium with SiO2 (soil). However, they were supersaturated with regard to the solubilities of the Pb carbonate minerals PbCO3 (cerussite) and Pb3(CO3)2(OH)2 in equilibrium with atmospheric CO2 and hydroxide Pb(OH)2. They were also supersaturated with regard to the solubilities of the Pb phosphate minerals Pb3(PO4)2, Pb5(PO4)3OH, and Pb4O(PO4)2 in equilibrium with tricalcium phosphate and CaCO3. The activity of Pb2+ was not regulated by any mineral of known solubility in our soils, but possibly by a mixture of Pb carbonate and phosphate minerals.     

Characterization of lead removal from contaminated soils by nontoxic soil-washing agents

Few effective strategies exist for remediating and restoring metal-contaminated soils. We have evaluated the potential of two environmentally compatible, nondestructive, biological soil-washing agents for remediating aged, lead-contaminated soils. Two contaminated soils were washed with 10 mM rhamnolipid biosurfactant and 5.3% carboxymethyl-beta-cyclodextrin (CMCD). The metal removal efficiency of these agents was compared with 10 mM diethylenetriamine pentaacetic acid (DTPA) and 10 mM KNO3. Lead removal rates by both soil-washing agents exceeded the removal by KNO3, but were an order of magnitude less than removal by the synthetic chelator, DTPA. Analysis of soil extractions revealed that the Pb in the first soil (3780 mg kg(-1)) was primarily associated with the soluble, exchangeable, oxide, and residual fractions while the Pb in the second soil (23 900 mg kg(-1)) was found in the soluble, exchangeable, carbonate, and residual fractions. After 10 consecutive washes, rhamnolipid had removed 14.2 and 15.3% of the Pb from the first and second soils, respectively, and CMCD had removed 5 and 13.4% from the same two soils. The Pb removal rate by both agents either increased or was consistent throughout the 10 extractions, indicating a potential for continued removal with extended washing. Significant levels of Cu and Zn in both soils did not prevent Pb removal by either agent. Interestingly, the effectiveness of each agent varied as a function of Pb speciation in the soil. Rhamnolipid was more effective than CMCD in removing Pb bound to amorphous iron oxides, while both agents demonstrated similar potential for removing soluble, exchangeable, and carbonate-bound Pb. Neither agent demonstrated potential for the complete remediation of metal-contaminated soils.     

Assessment of contamination from arsenical pesticide use on orchards in the Great Valley region, Virginia and West Virginia, USA

Lead arsenate pesticides were widely used in apple orchards from 1925 to 1955. Soils from historic orchards in four counties in Virginia and West Virginia contained elevated concentrations of As and Pb, consistent with an arsenical pesticide source. Arsenic concentrations in approximately 50% of the orchard site soils and approximately 1% of reference site soils exceed the USEPA Preliminary Remediation Goal (PRG) screening guideline of 22 mg kg(-1) for As in residential soil, defined on the basis of combined chronic exposure risk. Approximately 5% of orchard site soils exceed the USEPA PRG for Pb of 400 mg kg(-1) in residential soil; no reference site soils sampled exceed this value. A variety of statistical methods were used to characterize the occurrence, distribution, and dispersion of arsenical pesticide residues in soils, stream sediments, and ground waters relative to landscape features and likely background conditions. Concentrations of Zn, Pb, and Cu were most strongly associated with high developed land density and population density, whereas elevated concentrations of As were weakly correlated with high orchard density, consistent with a pesticide residue source. Arsenic concentrations in ground water wells in the region are generally <0.005 mg L(-1). There was no spatial association between As concentrations in ground water and proximity to orchards. Arsenic had limited mobility into ground water from surface soils contaminated with arsenical pesticide residues at concentrations typically found in orchards.     

TCLP法评价钢铁工业区周边土壤重金属生态环境风险

采用土壤随机布点法,采集某钢铁工业区周边34个土壤样品,利用美国TCLP法对钢铁工业区周边土壤重金属（Cu、 Zn、 Pb、 Cd）有效态进行实验分析和生态风险评价。结果表明, Cu、 Zn、 Pb、 Cd有效态含量分别在0.87~57.7 mg/kg、5.20~1338 mg/kg、1.09~379 mg/kg、1.15×10-3~69.9×10-3 mg/kg之间,钢铁工业区土壤不同程度地受到重金属的污染,其中以Zn污染最为严重。内梅罗污染指数评价中,处于安全水平的点位仅占17.6%,受到污染的点位占55.9%。其中,轻污染占20.6%,中污染占2.9%,重污染占32.4%。     

Antimony impurity in lead arsenate insecticide enhances the antimony content of old orchard soils

Lead arsenate was a commonly used insecticide during the first half of the 20th century, particularly in deciduous tree fruit orchards. Antimony is cotransported with As during the ore refining process and could occur as an impurity in commercial lead arsenate products. The total concentrations of As and Sb in eight soil samples collected from eight orchards located throughout central Washington State were analyzed by neutron activation analysis. Total soil Sb concentrations ranged between 0.4 and 1.5 mg kg(-1), while total soil As concentration ranged from 1 to 170 mg kg(-1). Total soil Sb and As concentrations were positively related. Total Pb and As concentrations in four of the soils were substantially higher than natural background, while the Sb to As concentration ratios in these soils were consistent with values measured in three lead arsenate insecticide products. These results confirm that Sb impurity is present in lead arsenate insecticide and has contributed to Sb enrichment of soils on which lead arsenate-treated plants were grown. Although higher than in uncontaminated soils from the same region, the Sb concentrations in the affected soils fall within the normal range observed worldwide and are substantially lower than values associated with impaired human or environmental health.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

Ecotoxic effect of phenanthrene on nitrifying bacteria in soils of different properties

Information on ecotoxicity of organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), in terrestrial environment is needed for establishing soil quality criteria and for risk assessment purposes. An ecotoxic effect of a model PAH compound (phenanthrene) toward soils microorganisms (nitrifying bacteria) was evaluated in 50 different soils. The soil samples were collected from agricultural land in four regions of Poland with varying levels of industrialization (Slaskie, Dolnoslaskie, Podlaskie, and Lubelskie voievodeships). Soils were characterized for basic physicochemical properties (texture, organic matter content, pH(KCl), total nitrogen content, total sorption capacity) and the content of contaminants including PAHs (73-800 microg kg(-1)), Pb (6-720 mg kg(-1)), and Zn (9-667 mg kg(-1)). Ecotoxicity of phenanthrene (applied at 10, 100, 500, and 1000 mg kg(-1)) to soils microorganisms was evaluated in laboratory studies in control conditions (incubation of soils for 7 d at 20 +/- 2 degrees C). Nitrification potential was used as the ecotoxicity measurements end point. The EC50 values (146-1670 mg kg(-1)) calculated from the square root-X linear regression model differed significantly in various soils, although it was difficult to establish a causative relationship between soil physicochemical characteristic and phenanthrene toxicity. A significant factor in the assessment of soils vulnerability to the effect of phenanthrene was level of soil contamination, particularly with PAHs. Soils with previous contamination were more susceptible (mean EC50, 325 mg kg(-1)) than soils from uncontaminated, rural areas (mean EC50, 603 mg kg(-1)).     

In situ treatment of metals in contaminated soils with phytate

Batch experiments were conducted to evaluate the ability of various forms of phytate, the hexaphosphoric form of myo-inositol (IP6), to immobilize U, Ni, and other inorganic contaminants in soils and sediments. A Ca-phytate precipitate (Ca(n)-IP6), dodeca sodium-phytate (Na12-IP6), and hydroxyapatite (HA) were added to contaminated soil at rates of 0, 10, 25, and 50 g kg(-1) and equilibrated in 0.001 M CaCl2. The samples were then centrifuged, the solution pH was measured, and the supernatants were filtered prior to analysis for dissolved organic carbon (DOC), U, Ni, P, and other inorganic contaminants, such as As, Cr, Se, and Pb. The residual sediments were air-dried prior to characterization by analytical electron microscopy and extraction with the Toxicity Characteristic Leaching Procedure (TCLP). The solubility of several metals (e.g., U, Pb, Cu) increased with increasing Na12-IP6 when compared with the nonamended control. In some cases immobilization was observed at the lowest Na12-IP6 application rate (10 g kg(-1)) with an increase in solubility observed at the higher rates, demonstrating the importance of metal to ligand ratio. In contrast, Ca(n)-IP6 and HA decreased the solubility of U, Ni, Al, Pb, Ba, Co, Mn, and Zn. For example, soluble U decreased from 2242 to 76 microg kg(-1) and Ni from 58 to 9.6 mg kg with the Ca(n)-IP6 addition, similar to the results observed for HA. Arsenic and Se solubility increased for HA and both forms of IP6, but to a much greater degree for Na12-IP6, suggesting that the increase in pH observed for HA and Na12-IP6, combined with added competition from PO4 and IP6 for sorption sites, resulted in the release of sorbed oxyanion contaminants. The analytical electron microscopy results indicated that metals such as U and Ni were closely associated with secondary Al-rich precipitates in the HA-treated soils, rather than unreacted HA. The analytical electron microscopy results were less definitive for the Ca(n)-IP6-treated soil, although the residual P-containing material was enriched in Al, with lesser amounts of U and Ni.     

Lead phytoextraction from contaminated soil with high-biomass plant species

In this study, cabbage [Brassica rapa L. subsp. chinensis (L.) Hanelt cv. Xinza No 1], mung bean [Vigna radiata (L.) R. Wilczek var. radiata cv. VC-3762], and wheat (Triticum aestivum L. cv. Altas 66) were grown in Pb-contaminated soils. Application of ethylenediaminetetraacetic acid (EDTA) (3.0 mmol of EDTA/kg soil) to the soil significantly increased the concentrations of Pb in the shoots and roots of all the plants. Lead concentrations in the cabbage shoots reached 5010 and 4620 mg/kg dry matter on Days 7 and 14 after EDTA application, respectively. EDTA was the best in solubilizing soil-bound Pb and enhancing Pb accumulation in the cabbage shoots among various chelates (EDTA, diethylenetriaminepentaacetic acid [DTPA], hydroxyethylenediaminetriacetic acid [HEDTA], nitrilotriacetic acid [NTA], and citric acid). Results of the sequential chemical extraction of soil samples showed that the Pb concentrations in the carbonate-specifically adsorbed and Fe-Mn oxide phases were significantly decreased after EDTA treatment. The results indicated that EDTA solubilized Pb mainly from these two phases in the soil. The relative efficiency of EDTA enhancing Pb accumulation in shoots (defined as the ratio of shoot Pb concentration to EDTA concentration applied) was highest when 1.5 or 3.0 mmol EDTA/kg soil was used. Application of EDTA in three separate doses was most effective in enhancing the accumulation of Pb in cabbage shoots and decreased mobility of Pb in soil compared with one- and two-dose application methods. This approach could help to minimize the amount of chelate applied in the field and to reduce the potential risk of soluble Pb movement into ground water.     

Decontamination of Fly Ash and Used Lime from Municipal Waste Incinerator Using Thiobacillus ferrooxidans

Thiobacillus ferrooxidans to leach metals from APCR to render them nonhazardous. The multistage solubilization process involves an alkaline aqueous phase that removes some Pb. In the second phase, the APCR are acidified to pH 4 with H₂SO₄, then inoculated with a bacterial culture that has been acclimated in the presence of 2% Fe (FeCl₃). Several rinses and decantings achieve removal of the leachable metals. The final step involves the addition of Ca(H₂PO₄)₂ and an increase in the treatment pH prior to the final filtration. Viability of thiobacilli in APCR was poor. Despite this problem, the removal of Pb was 35.9%, 46.0%, and 68.7% (for APCR containing 1594, 3026, and 5038 mg Pb/kg, respectively), which demonstrates greater metal removal with increased APCR contamination. Zn removal varied from 68.2% (8273 mg Zn/kg APCR) to 79.5% (16,873 mg Zn/kg APCR), which was positively correlated to the level of residue contamination, whereas Cu was removed in the proportions of 26.9% (495 mg Cu/kg APCR) to 68.2% (465 mg Cu/kg APCR). Cadmium removal appeared to be independent of the level of Cd in the APCR; Cd was removed to the greatest degree, with a variation of 92.0% (129 mg Cd/kg APCR) to 94.7% (267 mg Cd/kg APCR). The treated APCR were tested using four different leachate tests. The APCR released 43 mg Pb/liter during contact with water, and 7.40 mg Cd/liter during TCLP [the toxicity characterization leaching procedure of the United States Environmental Protection Agency (US EPA)]. After biological treatment, the leachate from TCLP was within the acceptance criteria of the US EPA, if the pH of the APCR was increased to pH 5 after the biological treatment. In the case of the Transport Canada leaching test, a betterment of the process is required in order to satisfy the stringent regulatory level of 0.5 mg Cd/liter (0.68 and 0.57 mg/liter).     

Sorption of dissolved lead from shooting range soils using hydroxyapatite amendments synthesized from industrial byproducts as affected by varying pH conditions

For immobilization technologies to be successful, the use of readily available and cost advantageous amendment is important when the remediation targets vast amounts of contaminated soils. The objectives of this study were to investigate whether the byproduct-synthesized hydroxyapatite can be used as an immobilizing amendment for dissolved Pb from a shooting range soil, and to model the kinetic data collected from dissolution experiments. A soil–solution kinetic experiment was conducted under fixed pH conditions as a function of time. A Pb-contaminated soil was reacted with various hydroxyapatite amendments to determine the dissolution rate and mineral products of soil Pb. Three types of amendments used were pure hydroxyapatite (HA), and poorly crystalline hydroxyapatites synthesized from gypsum waste (CHA), and synthesized from incinerated poultry litter (PHA). The dissolved Pb concentration decreased with the addition of amendments at pH 3–7. Both CHA and PHA were more effective than HA for attenuating Pb dissolution at pH 6 and above. According to the thermodynamic calculation at pH 6, the dissolved Pb concentration for CHA and PHA treatments was predicted to be 66% and 50% lower than that of HA treatment, respectively. A better Pb immobilization effect demonstrated by CHA and PHA resulted in their greater solubility at higher pH, which may promote the formation of chloropyromorphite precipitates. Dissolution kinetics of soil Pb was adequately explained by pseudo-first order and pseudo-second order equations in acid pH ranges. According to the ion exchange model, an adequate agreement between the experimental data and regression curves was shown in the initial 40 min of the reaction process, but the accuracy of model predictability decreased thereafter. According to kinetic models and dissolution phenomena, CHA and PHA amendments had better Pb sorption capacity with rapid kinetics than pure hydroxyapatite at weak acid to neutral pH.     

Heavy metals distribution in an Iowa suburban landscape

This study investigated the degree to which human activities through urbanization influence heavy metal concentrations in a suburban landscape in Ankeny, IA. Residential areas from different years in nine time periods of development were identified from aerial photos. Soil cores were collected from the center of the front yard of 10 randomly selected homes. Cores were subdivided into 0- to 5-, 5- to 10-, and 10- to 20-cm increments from a composite of five cores. The soils were analyzed for organic C, pH, and total Cd, Co, Cr, Cu, Ni, Pb, and Zn. Results showed that organic C increased and pH decreased with time, and that there was a general decreasing trend in heavy metal concentrations from the pre-1939 period until 1983-1990, after which there was a sharp increase in the concentrations of most of the metals. The mean Cu concentration ranged from 21 mg kg(-1) for the pre-1939 time period of development to 14.9 mg kg(-1) for the recent period of development (2003-2005). Nickel concentrations increased significantly with depth with means of 21.3 mg kg(-1) at depth 0 to 5 cm, 22.5 mg kg(-1) at depth 5 to 10 cm, and 23.0 mg kg(-1) at depth 10 to 20 cm. The concentrations of heavy metals were significantly intercorrelated, except Zn, suggesting their coexistence as mineral constituents or common contamination source. The concentrations of Cu and Pb in some locations could be due to anthropogenic inputs or higher organic matter content in soils adjacent to older homes. There appears to have been a source that caused an increase in Cd, Cr, Co, Cu, Pb, and Ni concentrations in soil adjacent to homes built between 1983 and 1990.     

Lead transport into Bayou Trepagnier wetlands in Louisiana, USA

Establishment of a petroleum refinery in 1916 near the headwaters of Bayou Trepagnier with subsequent dredging of the bayou resulted in spoil banks containing high levels of Pb. A large swamp abuts the eastern bank of the bayou. Cores were taken from 15 baldcypress [Taxodium distichum (L.) Richard] trees growing in the swamp along a 610-m transect (nine trees) and a 183-m transect (six trees) running perpendicular from the spoil bank. The cores were crossdated, annual rings were measured, and 5-yr segments of the cores were prepared and analyzed for heavy metals. Soil samples were collected along one transect and analyzed for metals. Levels of Pb in Bayou Trepagnier swamp trees were compared to levels in nine baldcypress trees growing along Stinking Bayou, a reference area. During the last 100 yr, Pb in growth rings of swamp baldcypress trees averaged 8.6 mg/kg (SD 4.88) along one transect and 7.9 mg/kg (SD 5.39) along the other. Lead in the soil along the first transect dropped from >2700 mg/kg (spoil bank) to 10 mg/kg at 420 m into the swamp. Baldcypress trees growing near the refinery on the spoil bank along Bayou Trepagnier (covered in an earlier study) averaged 4.5 mg/kg Pb, and trees along Stinking Bayou averaged 2.1 mg/kg. Trees in the swamp soil with 10 to 425 mg/kg Pb concentrated much more Pb than trees growing on the heavily polluted bank. Greater uptake of Pb by trees in the swamp is discussed in terms of soil dynamics and Pb sources.     

Chemical immobilization of lead, zinc, and cadmium in smelter-contaminated soils using biosolids and rock phosphate

Chemical immobilization, an in situ remediation method where inexpensive chemicals are used to reduce contaminant solubility in contaminated soil, has gained attention. We investigated the effectiveness of lime-stabilized biosolid (LSB), N-Viro Soil (NV), rock phosphate (RP), and anaerobic biosolid (AB) to reduce extractability and plant and gastrointestinal (GI) bioavailability in three Cd-, Pb-, and Zn-contaminated soils from smelter sites. Treated (100 g kg(-1) soil) and control soils were incubated at 27 degrees C and -0.033 MPa (0.33 bar) water content for 90 d. The effect of soil treatment on metal extractability was evaluated by sequential extraction, on phytoavailability by a lettuce bioassay (Lactuca sativa L.), on human GI availability of Pb from soil ingestion by the Physiologically Based Extraction Test. The largest reductions in metal extractability and phytoavailability were from alkaline organic treatments (LSB and NV). Phytotoxic Zn [1188 mg Zn kg(-1) extracted with 0.5 M Ca(NO3)2] in Blackwell soil (disturbed soil) was reduced by LSB, NV, and RP to 166, 25, and 784 mg Zn kg(-1), respectively. Rock phosphate was the only treatment that reduced GI-available Pb in both gastric and intestinal solutions, 23 and 92%, respectively. Alkaline organic treatments (LSB, NV) decreases Cd transmission through the food chain pathway, whereas rock phosphate decreases risk from exposure to Pb via the soil ingestion pathway. Alkaline organic treatments can reduce human exposure to Cd and Pb by reducing Zn phytotoxicity and revegetation of contaminated sites.