In situ stabilization of soil lead using phosphorus and manganese oxide: influence of plant growth

In situ stabilization of Pb contaminated soils can be accomplished by adding P and Mn(IV) oxide. However, the long-term efficacy of in situ stabilization under continual P removal through plant growth is unknown. Moreover, the effects these treatments have on phytoavailability of other metals (Cd and Zn) commonly associated with Pb in soil are not well understood. Greenhouse experiments using sudax [Sorghum vulgare (L.) Moench] and Swiss chard [Beta vulgaris (L.) Koch] were carried out to evaluate the effects of plant growth on soil Pb bioavailability to humans after addition of P and other amendments, and the effects of these treatments on Pb, Cd, and Zn phytoavailability in three metal-contaminated soils. Eight treatments were used: zero P; 2500 mg of P as triple superphosphate (TSP); 5000 mg of P as TSP or phosphate rock (PR); 5000 mg of Mn oxide/kg; and combinations of Mn oxide and P as TSP or PR. The addition of P and/or Mn oxide significantly reduced bioavailable Pb, as measured by the physiologically based extraction test (PBET), in soils compared with the control even after extensive cropping. The PBET data also suggested that removal of P from soluble P sources by plants could negate the beneficial effects of P on bioavailable Pb, unless sufficient soluble P was added or soluble P was combined with Mn oxide. In general, Ph, Cd, and Zn concentrations in shoot tissues of sudax and Swiss chard were reduced significantly by TSP and did not change with the addition of PR. The combination of PR and Mn oxide significantly reduced Pb concentrations in plants compared with the control.     

Treatment of contaminated soil with phosphorus and manganese oxide reduces lead absorption by Sprague-Dawley rats

This study was conducted to determine the extent of Pb absorption into young rats (Rattus norvegicus var. Sprague-Dawley) fed untreated Pb-contaminated soil or Pb-contaminated soil treated with two different sources of P and P + Mn oxide. Data were compared from an in vitro, physiologically based extraction test (PBET) with the animal data to support the validity of the in vitro test to assess bioavailable Pb from a treated Pb-contaminated soil. Soil with a total Pb concentration of 2290 mg kg(-1) was used. Rats were fed 19 different test diets for 21 consecutive days. The test diets represented 95 g AIN93G rat meal kg(-1) diet with varying proportions of silica sand or soil to provide low, medium, or high doses of Pb from either Pb acetate, treated, or untreated soil. Blood, liver, kidney, and bone Pb concentrations were examined. For all four tissues, Pb concentrations for the Pb acetate groups were significantly higher than concentrations for all the soil groups. In general, either triple superphosphate (TSP) or phosphate rock (PR) treatments resulted in significant reductions in tissue Pb concentrations compared with untreated soil. Blood and kidney Pb concentrations for the PR + Mn oxide group were significantly lower than those of the PR group at the low and high doses. Relative bioavailability of Pb, as measured in all tissues, was significantly reduced when comparing untreated with amended soil. Correlation between the in vitro and in vivo tests, based on bone and liver tissue, showed that the in vitro test is successful at predicting Pb bioavailability.     

Application methods affect phosphorus-induced lead immobilization from a contaminated soil

Phosphate rock (PR) and phosphoric acid (PA) are an effective combination of P sources for immobilizing Pb in contaminated soils. This column experiment examined the effectiveness of different application methods on Pb immobilization in a contaminated soil. Phosphate was applied at a P/Pb molar ratio of 4 with half as PR and half PA. While PR was mixed with the soil or placed as a layer, aqueous PA was applied from the top of the column as one or two applications. After 4 wk of incubation, total and soluble Pb and P, TCLP-Pb (toxicity characteristic leaching procedure) and PBET-Pb (physiologically-based extraction test) in the P-treated soil were determined. Phosphate addition effectively reduced leachable Pb to below the EPA drinking water standard of 15 microg L(-1) in all treatments. Mixing both PA and PR with the soil was the most effective method in Pb immobilization, reducing TCLP-Pb by up to 95% and PBET-Pb by 25 to 42%. Application of PR as a layer in the soil column was the most effective in reducing Pb migration (by 73-79%) and minimizing soil acidification and P entrophication, potential drawbacks of PA. Applying PA in two applications was less effective than one application. Mixing PR and PA with the soil plus placing PR as a layer can be employed for effective remediation of Pb-contaminated soils, reducing Pb leachability, bioavailability, and mobility while minimizing soil acidification and P entrophication.     

Spectroscopic speciation and quantification of lead in phosphate-amended soils

The immobilization of Pb in contaminated soils as pyromorphite [Pb(5)(PO(4))(3)Cl, OH, F] through the addition of various phosphate amendments has gained much attention in the remediation community. However, it is difficult to fully determine the speciation and amount of soil Pb converted to pyromorphite by previously employed methods, such as selective sequential extraction procedures and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, which often lead to erroneous results in these non-equilibrated and heterogeneous systems. Statistical analysis by linear combination fitting (LCF) applied to X-ray absorption fine structure (XAFS) spectroscopic data of Pb-contaminated soil samples relative to known Pb reference material provides direct, in situ evidence of dominate Pb species in the amended soils without chemical or physical disruption to the Pb species as well as a weighted quantification output. The LCF-XAFS approach illustrated that pyromorphite concentration ranged from 0% (control soil) to 45% (1% phosphoric acid amendment, residence time of 32 mo) relative to the total Pb concentration. The Pb speciation in the nonamended control soil included Pb-sulfur species (galena + angelsite = 53%), adsorbed Pb (inner-sphere + outer-sphere + organic-bound = 45%), and Pb-carbonate phases (cerussite + hydrocerussite = 2%). The addition of P promoted pyromorphite formation and the rate of formation increased with increasing P concentration (up to 45%). The supplemental addition of an iron amendment as an iron-rich byproduct with triple superphosphate (TSP) enhanced pyromorphite formation relative to independent TSP amendment of like concentrations (41 versus 29%). However, the amendment of biosolids and biosolids plus TSP observed little pyromorphite formation (1-16% of total Pb), but a significant increase of sorbed Pb was determined by LCF-XAFS.     

Assessment of metal availability in smelter soil using earthworms and chemical extractions

Chemical immobilization is a relatively inexpensive in situ remediation method that reduces soil contaminant solubility, but the ability of this remediation treatment to reduce heavy metal bioavailability and ecotoxicity to soil invertebrates has not been evaluated. Our objectives were to (i) assess the ability of chemical immobilization amendments (municipal sewage sludge biosolids and rock phosphate) to reduce metal bioavailability and toxicity in a toxic metal-contaminated smelter soil and (ii) evaluate soil extraction methods using Ca(NO3)2 solution or ion-exchange membranes coated with diethylenetriaminepentaacetic acid (DTPA) as surrogate measures of metal bioavailability and ecotoxicity. We treated a soil contaminated by Zn and Pb milling and smelting operations and an uncontaminated control soil with lime-stabilized municipal biosolids (LSB), rock phosphate (RP), or anaerobically digested municipal biosolids (SS) and evaluated lethality of the remediated soils to earthworm (Eisenia fetida Savigny). Lime-stabilized municipal biosolids was the only remediation amendment to successfully immobilize lethal levels of Zn in the smelter soil (14-d cumulative mortality < or = 15%). Calcium nitrate-extractable Zn in the lethal Zn smelter soil-amendment combinations was 11.5 to 18.2 mmol/kg, compared with the nonlethal LSB amended soil (0.62 mmol/kg). The Ca(NO3)2-extractable Zn-based median lethal concentration (LC50) of 6.33 mmol/kg previously developed in Zn-spiked artificial soils was applicable in the remediated smelter soils despite a 14-fold difference in total Zn concentration. Chelating ion-exchange membrane uptake among the soils was highly variable (mean CV = 39%) compared with the Ca(NO3)2-extraction (mean CV = 1.9%) and not well related to earthworm toxicity.     

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.     

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.     

Validation of the in vitro gastrointestinal (IVG) method to estimate relative bioavailable lead in contaminated soils

The effect of the dosing vehicle (e.g., dough) on the ability of an in vitro gastrointestinal (IVG) method to predict relative bioavailable Pb associated with soil ingestion was evaluated. Bioaccessible Pb determined by the IVG method was compared with relative bioavailable Pb measured from dosing trials using juvenile swine for 18 contaminated soils ranging from 1270 to 14200 mg Pb kg(-1). Bioaccessible Pb was measured in the IVG gastric extraction (GE) and intestinal extraction (IE) solutions. Mean bioaccessible Pb values were 32.2% for GE without dough, 23.0% for GE with dough, 1.06% for IE without dough, and 0.56% for IE with dough. It is possible that phytic acid associated with the dough addition decreased bioaccessible Pb. In vivo relative bioavailable Pb ranges for different swine tissues were 1 to 87% for blood, 0 to 110% for liver, 1 to 124% for kidney, and 0.04 to 94% for bone. Strong linear relationships between IVG GE Pb with dough (r > 0.76, P < 0.0002), IVG IE Pb with dough (r > 0.56, P < 0.015), and IVG GE Pb without dough (r > 0.81, P < 0.0001) and in vivo bioavailable Pb as estimated with blood, kidney, liver, and bone were found. Inexpensive in vitro methods may be useful in providing an estimate of the variability in relative bioavailable Pb at a single study site. The IVG method can be used to estimate relative bioavailable Pb, As, and Cd in contaminated soil.     

Decreasing lead bioaccessibility in industrial and firing range soils with phosphate-based amendments

In-situ stabilization using phosphate (P) amendments, such as P-based fertilizers and rock, are a potentially cost-effective and minimally disruptive alternative for stabilizing Pb in soils. We examined the effect of time (0-365 d), in vitro extraction pH (1.5 vs. 2.3), and dosage of three P-based amendments on the bioaccessibility (as a surrogate for oral bioavailability) of Pb in 10 soils from U.S. Department of Defense facilities. Initial untreated soil bioaccessibility consistently exceeded the U.S. Environmental Protection Agency default value of 60% relative bioavailability, with higher bioaccessibility consistently observed at an in vitro extraction pH of 1.5 vs. 2.3. Although P-based amendments statistically (P < 0.05) reduced bioaccessibility in many instances, with reductions dependent on the amendment and dosage, large amendment dosages (approximately 20-25% by mass to yield 5% P by mass) were required to reduce average bioaccessibility by approximately 25%. For most amendment combinations, reductions continued to occur for periods up to 1 yr, indicating that the observed reductions were not merely experimental artifacts of the in vitro extraction procedure. Although our results indicated that reductions in Pb bioaccessibility with P amendments are technically feasible, relatively large amendment masses were required to achieve relatively modest reductions in bioaccessibility. The cost and potential environmental implications of adding such large amounts of P may limit the practicality of in situ immobilization for some Pb-contaminated soils, industrial and firing range soils in particular.     

Temporal changes in soil partitioning and bioaccessibility of arsenic, chromium, and lead

The hazard imposed by trace element contaminants within soils is dependent on their ability to migrate into water systems and their availability for biological uptake. The degree to which a contaminant may dissociate from soil solids and become available to a target organism (i.e., bioaccessibility) is therefore a determining risk factor. We used a physiologically based extraction test (PBET) to estimate the bioaccessible fraction of arsenic-, chromium-, and lead-amended soil. We investigated soils from the A and B horizons of the Melton Valley series, obtained from Oak Ridge National Laboratory site, to address temporal changes in bioaccessibility. Additionally, common extractions that seek to define reactive pools of metals were employed and their correlation to PBET levels evaluated. With the exception of Pb amended to the A horizon, all other treatments exhibited an exponential decrease in bioaccessibility with incubation time. The bioaccessible fraction was less than 0.2 mg kg(-1) within 30 d of incubation for As and Cr in the A horizon and for As and Pb within the B horizon; Cr in the B horizon declined to nearly 0.3 mg kg(-1) within 100 d of aging. The exchangeable fraction declined with incubation period and, with the exception of Pb, was highly correlated with the decline in bioaccessibility. Our results demonstrate limited bioaccessibility in all but one case and the need to address both short-term temporal changes and, most importantly, the soil physiochemical properties. They further reveal the importance of incubation time on the reactivity of such trace elements.     

Risk assessment test for lead bioaccessibility to waterfowl in mine-impacted soils

Due to variations in soil physicochemical properties, species physiology, and contaminant speciation, Pb toxicity is difficult to evaluate without conducting in vivo dose-response studies. Such tests, however, are expensive and time consuming, making them impractical to use in assessment and management of contaminated environments. One possible alternative is to develop a physiologically based extraction test (PBET) that can be used to measure relative bioaccessibility. We developed and correlated a PBET designed to measure the bioaccessibility of Pb to waterfowl (W-PBET) in mine-impacted soils located in the Coeur d'Alene River Basin, Idaho. The W-PBET was also used to evaluate the impact of P amendments on Pb bioavailability. The W-PBET results were correlated to waterfowl-tissue Pb levels from a mallard duck [Anas platyrhynchos (L.)] feeding study. The W-PBET Pb concentrations were significantly less in the P-amended soils than in the unamended soils. Results from this study show that the W-PBET can be used to assess relative changes in Pb bioaccessibility to waterfowl in these mine-impacted soils, and therefore will be a valuable test to help manage and remediate contaminated soils.     

Concomitant rock phosphate dissolution and lead immobilization by phosphate solubilizing bacteria (Enterobacter sp.)

This paper examines the potential value of phosphate solubilizing bacteria (Enterobacter cloacae) in the dissolution of rock phosphate (RP) and subsequent immobilization of lead (Pb) in both bacterial growth medium and soils. Enterobacter sp. showed resistance to Pb and the bacterium solubilized 17.5% of RP in the growth medium. Enterobacter sp. did not enhance Pb immobilization in solution because of acidification of bacterial medium, thereby inhibiting the formation of P-induced Pb precipitation. However, in the case of soil, Enterobacter sp. increased Pb immobilization by 6.98, 25.6 and 32.0% with the RP level of 200, 800 and 1600 mg P/kg, respectively. The immobilization of Pb in Pb-spiked soils was attributed to pyromorphite formation as indicated by XRD analysis. Inoculation of phosphate solubilizing bacteria with RP in soil can be used as an alternative technique to soluble P compounds which can cause eutrophication of surface water.     

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.     

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.     

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.     

Effect of biosolids processing on lead bioavailability in an urban soil

The potential for biosolids products to reduce Pb availability in soil was tested on a high Pb urban soil with biosolids from a treatment plant that used different processing technologies. High Fe biosolids compost and high Fe + lime biosolids compost from other treatment plants were also tested. Amendments were added to a Pb-contaminated soil (2000 mg kg(-1) Pb) at 100 g kg(-1) soil and incubated for 30 d. Reductions in Pb bioavailability were evaluated with both in vivo and in vitro procedures. The in vivo study entailed feeding a mixture of the Pb-contaminated soil and AIN93G Basal Mix to weanling rats. Three variations of an in vitro procedure were performed as well as conventional soil extracts [diethylenetriaminepentaacetic acid (DTPA) and Ca(NO3)2] and sequential extraction. Addition of the high Fe compost reduced the bioavailability of soil Pb (in both in vivo and in vitro studies) by 37 and 43%, respectively. Three of the four compost materials tested reduced Pb bioavailability more than 20%. The rapid in vitro (pH 2.3) data had the best correlation with the in vivo bone results (R = 0.9). In the sequential extract, changes in partitioning of Pb to Fe and Mn oxide fractions appeared to reflect the changes in in vivo Pb bioavailability. Conventional extracts showed no changes in metal availability. These results indicate that addition of 100 g kg(-1) of high Fe and Mn biosolids composts effectively reduced Pb availability in a high Pb urban soil.     

Runoff and leachate losses of phosphorus in a sandy Spodosol amended with biosolids

Florida Spodosols are sandy, inherently low in Fe- and Al-based minerals, and sorb phosphorus (P) poorly. We evaluated runoff and leachate P losses from a typical Florida Spodosol amended with biosolids and triple superphosphate (TSP). Phosphorus losses were evaluated with traditional indoor rainfall simulations but used a double-deck box arrangement that allowed leaching and runoff to be determined simultaneously. Biosolids (Lakeland, OCUD, Milorganite, and Disney) represented contrasting values of total P, percent water-extractable P (PWEP), and percentage of solids. All P sources were surface applied at 224 kg P ha(-1), representing a soil P rate typical of N-based biosolids application. All biosolids-P sources lost less P than TSP, and leachate-P losses generally dominated. For Lakeland-amended soil, bioavailable P (BAP) was mainly lost by runoff (81% of total BAP losses). This behavior was due to surface sealing and drying after application of the slurry (31 g kg(-1) solids) material. For all other P sources, BAP losses in leachate were much greater than in runoff, representing 94% of total BAP losses for TSP, 80% for Milorganite, 72% for Disney, and 69% for OCUD treatments. Phosphorus leaching can be extreme and represents a great concern in many coarse-textured Florida Spodosols and other coastal plain soils with low P-sorption capacities. The PWEP values of P sources were significantly correlated with total P and BAP losses in runoff and leachate. The PWEP of a source can serve as a good indicator of potential P loss when amended to sandy soils with low P-retention capacities.     

Source-related transport of phosphorus in surface runoff

Continual application of mineral fertilizer and manures to meet crop production goals has resulted in the buildup of soil P concentrations in many areas. A rainfall simulation study was conducted to evaluate the effect of the application of P sources differing in water-soluble P (WSP) concentration on P transport in runoff from two grassed and one no-till soil (2 m(2) plots). Triple superphosphate (TSP)-79% WSP, low-grade single superphosphate (LGSSP)-50% WSP, North Carolina rock phosphate (NCRP)-0.5% WSP, and swine manure (SM)-30% WSP, were broadcast (100 kg total P ha(-1)) and simulated rainfall (50 mm h(-1) for 30 min of runoff) applied 1, 7, 21, and 42 d after P source application. In the first rainfall event one d after fertilizer application, dissolved reactive P (DRP) and total P (TP) concentrations of runoff increased (P < 0.05) for all soils with an increase of source WSP; with DRP averaging 0.27, 0.50, 14.66, 41.69, and 90.47 mg L(-1); and total P averaging 0.34, 0.61, 19.05, 43.10, and 98.06 mg L(-1) for the control, NCRP, SM, LGSSP, and TSP, respectively. The loss of P in runoff decreased with time for TSP and SM, such that after 42 d, losses from TSP, SM, and LGSSP did not differ. These results support that P water solubility in P sources may be considered as an indicator of P loss potential.     

Weathering of lead bullets and their environmental effects at outdoor shooting ranges

Lead contamination at shooting range soils is of great environmental concern. This study focused on weathering of lead bullets and its effect on the environment at five outdoor shooting ranges in Florida, USA. Soil, plant, and water samples were collected from the ranges and analyzed for total Pb and/or toxicity characteristic leaching procedure (TCLP) Pb. Selected bullet and berm soil samples were mineralogically analyzed with X-ray diffraction and scanning electron microscopy. Hydrocerussite [Pb3(CO3)2(OH)2] was found in both the weathered crusts and berm soils in the shooting ranges with alkaline soil pH. For those shooting ranges with acidic soil pH, hydrocerussite, cerussite (PbCO3), and small amount of massicot (PbO) were predominantly present in the weathered crusts, but no lead carbonate mineral was found in the soils. However, hydroxypyromorphite [(Pb10(PO4)6(OH)2] was formed in a P-rich acidic soil, indicating that hydroxypyromorphite can be a stable mineral in P-rich shooting range soil. Total Pb and TCLP Pb in the soils from all five shooting ranges were significantly elevated with the highest total Pb concentration of 1.27 to 4.84% (w/w) in berm soils. Lead concentrations in most sampled soils exceeded the USEPA's critical level of 400 mg Pb kg(-1) soil. Lead was not detected in subsurface soils in most ranges except for one, where elevated Pb up to 522 mg kg(-1) was observed in the subsurface, possibly due to enhanced solubilization of organic Pb complexes at alkaline soil pH. Elevated total Pb concentrations in bermudagrass [Cynodon dactylon (L.) Pers.] (up to 806 mg kg(-1) in the aboveground parts) and in surface water (up to 289 microg L(-1)) were observed in some ranges. Ranges with high P content or high cation exchange capacity showed lower Pb mobility. Our research clearly demonstrates the importance of properly managing shooting ranges to minimize adverse effects of Pb on the environment.     

Application of two organic wastes in a soil polluted by lead: effects on the soil enzymatic activities

The effects of adding a crushed cotton gin compost (CCGC) and a poultry manure (PM) on the enzymatic activities of a Typic Xerofluvent soil polluted with Pb were studied in the laboratory. Three hundred grams of sieved soil (<2 mm) were mixed with PM at a rate of 10% or CCGC at a rate of 17.2%, applying to the soil the same amount of organic matter with each organic amendment. Urease, protease-BBA, beta-glucosidase, alkaline phosphatase, and arylsulfatase activities were measured at four different incubation times (1, 7, 15, and 45 d) in soils containing seven concentrations (100, 250, 500, 1000, 2500, 5000, and 8000 mg kg-1) of Pb, and in the same soils amended with CCGC and PM. In all treatments and incubation times, the inhibition percentage of soil enzyme activities by Pb was lower in soils amended with the PM and CCGC than in nonamended soils, and it differed with the organic amendment. In this respect, the in the 8000 mg Pb kg-1 treatment at the end of the incubation period, the protease-BBA activity inhibition percentage was lower (14.7 and 33.9% lower, respectively) in CCGC- than in PM-amended soils. Since the adsorption capacity of Pb was higher in CCGC- than the PM-amended soils, the addition of organic wastes with higher humic acid concentration is more beneficial for remediation of soils polluted with Pb.