Biochar amendment affects leaching potential of copper and nutrient release behavior in contaminated sandy soils.

Copper (Cu) contamination to soil and water is a worldwide concern. Biochar has been suggested to remediate degraded soils. In this study, column leaching and chemical characterization were conducted to assess effects of biochar amendment on Cu immobilization and subsequent nutrient release in Cu-contaminated Alfisol and Spodosol. The results indicate that biochar is effective in binding Cu (30 and 41%, respectively, for Alfisol with and without spiked Cu; 36 and 43% for Spodosol) and reducing Cu leaching loss (from ∼47 to 10% for the Cu-spiked Alfisol and from 48 to 9% for the Cu-spiked Spodosol). Copper was likely retained on biochar surfaces through complexation, as suggested by Fourier-transform infrared spectra. Biochar amendment converts a portion of Cu from available pool to more stable forms, thus resulting in decreased activities of free Cu and increased activity of organic Cu complexes in leachate. Reduction of >0.45-µm solids and nanoparticles concentrations in leachate was also observed. In addition, biochar application rate was correlated negatively with P, Ca, Mg, Zn, Mn, and NH-N concentration ( < 0.05) but positively with K and Na concentration ( < 0.05) in leachates. These results documented the potential of biochar as an effective amendment for Cu immobilization and mitigation of leaching risk for some nutrients.

Orthophosphate Leaching in St. Augustinegrass and Zoysiagrass Grown in Sandy Soil under Field Conditions.

Phosphorus (P) is required to maintain healthy, high-quality, warm-season turf. However, excessive P applications to soils with poor P retention capabilities may lead to leaching losses to groundwater. This field study was conducted to determine the maximum P fertilizer application rate to (Walt.) [Kuntze] 'Floratam' St. Augustinegrass (St. Augustinegrass) and 'Empire' zoysiagrass (zoysiagrass) below which P leaching is minimized. Five P levels ranging from 0 to 5.0 g P m yr were surface applied as triple superphosphate. Turf was established on an uncoated, low-P sand with negligible P retention capacity. Leaf and root growth, tissue P concentration, soil P concentration, soil P saturation, leachate volume, and orthophosphate (P) concentration in leachates were measured. Mehlich 1-extractable soil P (M1-P) and soil P saturation ratio (PSR) increased with time as the P rate increased. Lower M1-P and PSR values were measured with St. Augustinegrass, which absorbed more P than did zoysiagrass. The root system of St. Augustinegrass was larger and deeper compared with zoysiagrass, promoting greater P uptake and less P leaching. If tissue analysis indicates that P fertilization is required and the soil has the capacity to retain additional P, application of 0.8 g P m yr to zoysiagrass and 1.07 g P m yr to St. Augustinegrass is appropriate and does not result in increased P leaching.

Pyrolysis-induced phosphorus transformations for biosolids from diverse sources.

Biosolids have been long used as a soil amendment to promote nutrient recovery. The readily releasable forms of nutrients present in this biowaste, such as phosphorus (P), along with their over application, can be detrimental to the environment, causing eutrophication. Pyrolysis, the thermal decomposition of organic materials at elevated temperature and low oxygen, seems to be a promising strategy to lower P release from biowastes such as biosolids. We pyrolyzed biosolids from various treatments and locations (Florida and Illinois; Galicia, Spain; and São Paulo, Brazil) to convert to biochar. Our objectives were (a) to use solid-state assessments, such as X-ray diffraction and scanning electron microscopy, and chemical assessments, such as water-soluble P (WSP), pH, Mehlich 3-extractable P (M3-P), total P (TP), and total Kjeldahl nitrogen, to evaluate changes caused by the conversion and (b) to compare P leaching potentials of biosolids and their corresponding biochars on two soils with varying P retention capacities. Pairwise comparisons indicated that biochar conversion significantly increased TP in the final material, but the absolute WSP decreased. However, M3-P remained the same after conversion to biochar. Cumulative P leached as a fraction of TP was greater for biosolids than their corresponding biochars. Two soils with contrasting P retention capacities predictably differed in P leaching behaviors as amended with biosolids and biochars. Differences suggest that future research could evaluate the efficacy of using mixtures of biosolids and biochar for a given soil to maintain soil fertility while reducing environmental P loss risk.

Soil property control of biogeochemical processes beneath two subtropical stormwater infiltration basins.

Substantially different biogeochemical processes affecting nitrogen fate and transport were observed beneath two stormwater infiltration basins in north-central Florida. Differences are related to soil textural properties that deeply link hydroclimatic conditions with soil moisture variations in a humid, subtropical climate. During 2008, shallow groundwater beneath the basin with predominantly clayey soils (median, 41% silt+clay) exhibited decreases in dissolved oxygen from 3.8 to 0.1 mg L and decreases in nitrate nitrogen (NO-N) from 2.7 mg L to <0.016 mg L, followed by manganese and iron reduction, sulfate reduction, and methanogenesis. In contrast, beneath the basin with predominantly sandy soils (median, 2% silt+clay), aerobic conditions persisted from 2007 through 2009 (dissolved oxygen, 5.0-7.8 mg L), resulting in NO-N of 1.3 to 3.3 mg L in shallow groundwater. Enrichment of δN and δO of NO combined with water chemistry data indicates denitrification beneath the clayey basin and relatively conservative NO transport beneath the sandy basin. Soil-extractable NO-N was significantly lower and the copper-containing nitrite reductase gene density was significantly higher beneath the clayey basin. Differences in moisture retention capacity between fine- and coarse-textured soils resulted in median volumetric gas-phase contents of 0.04 beneath the clayey basin and 0.19 beneath the sandy basin, inhibiting surface/subsurface oxygen exchange beneath the clayey basin. Results can inform development of soil amendments to maintain elevated moisture content in shallow soils of stormwater infiltration basins, which can be incorporated in improved best management practices to mitigate NO impacts.

Spectroscopic models of soil organic carbon in Florida, USA.

Soil organic carbon (SOC) is an indicator of ecosystem quality and plays a major role in the biogeochemical cycles of major nutrients and water. Shortcomings exist to estimate SOC across large regions using rapid and cheap soil sensing approaches. Our objective was to estimate SOC in 7120 mineral and organic soil horizons in Florida using visible/near-infrared diffuse reflectance spectroscopy (VNIRS) calibrated by committee trees and partial least squares regression (PLSR). The derived VNIRS models were validated using independent datasets and explained up to 71 and 38% of the variance of SOC in mineral and organic horizons, respectively. We stratified the mineral horizons into seven soil orders and derived PLSR models for each order, which explained from 32% (Histosols) to 75% (Ultisols) of the variance of SOC concentration in validation mode. Estimates of SOC from all models were highly scattered along the regression lines, especially for high SOC values, and the slopes of the regression lines were generally <1 because VNIRS models tended to underestimate high SOC values and overestimate low SOC. Despite the great scatter of estimates in the prediction plots, VNIRS models had reasonable explanatory power for mineral horizons, given the heterogeneity of soils and environmental conditions in Florida, and have potential for the rapid assessment of SOC, with implications for regional SOC assessments, modeling, and monitoring. However, VNIRS models for organic horizons were hampered by small sample size and had very limited explanatory power.

Valorization of farm pond biomass as fertilizer for reducing basin-scale phosphorus losses.

Long-term fertilizer phosphorus (P) inputs are causing phosphorous saturation of agricultural soils globally. The saturation is spreading to the edge-of-the-farm stormwater detention systems (SDSs) from where the legacy P is potentially being released to downstream surface waters. We use site-specific and literature data for P-saturated SDSs, to develop and evaluate the biogeochemical and economic feasibility of a P recycling program that targets both low (LIC, sugarcane) and high intensity cropping (HIC, fresh-produce) systems within a watershed. The focus is to close the P cycle loop to rejuvenate P sink function of SDSs. It involves harvesting and composting the SDS's biomass and it's on-farm use as an organic fertilizer for crops. Results showed that harvesting-composting can conservatively increase the P retention from 50% to 77% for HIC and almost complete treatment for LIC. Beyond potentially increasing yield and improving soil health, compost use can further increase in-field retention of P (and water). Additional costs incurred in harvesting and composting can be offset by the economic value of compost and the reduction in State's expenditure on regional P treatment systems. Treatment costs were $26/kg of P for HIC and $42/kg for LIC, 10 times less than the current state expenditure of $355-$909/kg P using constructed wetlands. We propose an incentivized, payment for services (PS) program, where producers are paid for P recycling. The PS program considers the intensity of cropping systems and their location along the drainage network from headwaters to the outlet, to achieve basin-scale P load reduction. The LIC SDSs recover regional P by passing the public water through them while recycling is implemented at the HIC. The estimated basin-scale P retention with harvest-compost approach was 854 metric tons, 5 times the P that entered the Everglades Protection Area in 2018, at 88%-93% less cost than the State treatment systems.

Bench-scale recovery of phosphorus from flushed dairy manure wastewater.

Recovery of phosphorus (P) from flushed dairy manure in an easily-dewatered form would enable farmers to manage P as a resource rather than land-apply it in excess at environmental risk. The purpose of this study was to evaluate (i) the feasibility of P recovery and (ii) the form of recovered P from flushed dairy manure wastewater using crystallization in a fluidized-bed reactor. Wastewater was pumped directly from a dairy farm reservoir and continuously fed in parallel through four bench-scale fluidized-bed reactors deployed on-site. Chemical additives (NaOH and MgSO4) required for recovery were injected directly into the zone of fluidization. Recovered P forms were assessed by X-ray diffraction, scanning electron microscopy, and micro-elemental analysis. Recovery of P as poorly-crystalline hydroxylapatite (HAP) was documented in coatings ultrasonically removed from quartz seed grains following fluidization at elevated pH in conjunction with MgSO4 injection. Addition of MgSO4 was required to prevent CaCO3 precipitation upon pH elevation and hence enable calcium phosphate precipitation. It is likely that MgSO4 inhibited CaCO3 via formation of MgCO3 (aq). Periclase (MgO), which also served as an effective seed material, generated sufficient alkalinity at grain surfaces to precipitate abundant CaCO3 and in some cases detectable Ca phosphate even without NaOH addition to elevate pH of bulk solution.

Inhibition of calcium phosphate precipitation under environmentally-relevant conditions.

Precipitation of Ca phosphates plays an important role in controlling P activity and availability in environmental systems. The purpose of this study was to determine inhibitory effects on Ca phosphate precipitation by Mg(2+), SO(4)(2-), CO(3)(2-), humic acid, oxalic acid, biogenic Si, and Si-rich soil clay commonly found in soils, sediments, and waste streams. Precipitation rates were determined by measuring decrease of P concentration in solutions during the first 60 min; and precipitated solid phases identified using X-ray diffraction and electron microscopy. Poorly-crystalline hydroxyapatite (HAP: Ca(5)(PO(4))(3)OH) formed in control solutions over the experiment period of 24 h, following a second-order dependence on P concentration. Humic acid and Mg(2+) significantly inhibited formation of HAP, allowing formation of a more soluble amorphous Ca phosphate phase (ACP), and thus reducing the precipitation rate constants by 94-96%. Inhibition caused by Mg(2+) results from its incorporation into Ca phosphate precipitates, preventing formation of a well-crystalline phase. Humic acid likely suppressed Ca phosphate precipitation by adsorbing onto the newly-formed nuclei. Presence of oxalic acid resulted in almost complete inhibition of HAP precipitation due to preemptive Ca-oxalate formation. Carbonate substituted for phosphate, decreasing the crystallinity of HAP and thus reducing precipitation rate constant by 44%. Sulfate and Si-rich solids had less impact on formation of HAP; while they reduced precipitation in the early stage, they did not differ from the control after 24 h. Results indicate that components (e.g., Mg(2+), humic acid) producing relatively soluble ACP are more likely to reduce P stability and precipitation rate of Ca phosphate in soils and sediments than are components (e.g., SO(4)(2-), Si) that have less effect on the crystallinity.

Time dependency and irreversibility of water desorption by drinking-water treatment residuals: implications for sorption mechanisms.

Drinking-water treatment residuals (WTRs) are being evaluated as cost-effective sorption media for use in environmental remediation. Data from previous work have suggested that intraparticle phosphorus (P) diffusion into micropores is the rate-limiting mechanism of P sorption by WTRs. We used isothermal thermogravimetric analysis (TG) to study water desorption/resorption dynamics as they relate to steric diffusion rate limitations for prospective sorbates. Results showed that air-dried WTR particles contain significant amounts of water. Only about 40% of water desorbed isothermally (70 degrees C) for 10 h was readsorbed when particles were reexposed to ambient temperature and moisture conditions. This hysteresis related closely with time dependency of water loss, suggesting steric diffusional hindrance of water re-adsorption by meso- and micropores. The irreversibly desorbed water may be the component requiring increased kinetic energy to overcome diffusional resistance. Another possible factor in irreversibility could be pore shrinkage. Samples incubated for 12 months at 70 degrees C prior to TG analysis showed no hysteresis at 70 degrees C. Isothermal water losses with time fit well (r2 = 0.95) the diffusion model of Kabai. These results are consistent with an aqueous pore network that would account for high phosphorus sorption capacity and hysteresis that has been recently documented for WTRs.

Arsenic release from Floridan Aquifer rock during incubations simulating aquifer storage and recovery operations.

While aquifer storage and recovery (ASR) is becoming widely accepted as a way to address water supply shortages, there are concerns that it may lead to release of harmful trace elements such as arsenic (As). Thus, mechanisms of As release from limestone during ASR operations were investigated using 110-day laboratory incubations of core material collected from the Floridan Aquifer, with treatment additions of labile or refractory dissolved organic matter (DOM) or microbes. During the first experimental phase, core materials were equilibrated with native groundwater lacking in DO to simulate initial non-perturbed anaerobic aquifer conditions. Then, ASR was simulated by replacing the native groundwater in the incubations vessels with DO-rich ASR source water, with DOM or microbes added to some treatments. Finally, the vessels were opened to the atmosphere to mimic oxidizing conditions during later stages of ASR. Arsenic was released from aquifer materials, mainly during transitional periods at the beginning of each incubation stage. Most As released was during the initial anaerobic experimental phase via reductive dissolution of Fe oxides in the core materials, some or all of which may have formed during the core storage or sample preparation period. Oxidation of As-bearing Fe sulfides released smaller amounts of As during the start of later aerobic experimental phases. Additions of labile DOM fueled microbially-mediated reactions that mobilized As, while the addition of refractory DOM did not, probably due to mineral sorption of DOM that made it unavailable for microbial utilization or metal chelation. The results suggest that oscillations of groundwater redox conditions, such as might be expected to occur during an ASR operation, are the underlying cause of enhanced As release in these systems. Further, ASR operations using DOM-rich surface waters may not necessarily lead to additional As releases.

Long-term phosphorus effects on evolving physicochemical properties of iron and aluminum hydroxides.

Iron (Fe) and aluminum (Al) hydroxides are highly reactive components in environmental processes, such as contaminant fate and transport. Phosphorus (P) sorption by these components can decrease environmental problems associated with excess accumulation of P in soils. The long-term stability of P sorbed by Fe/Al hydroxides is of major concern. Synthetic Fe and Al hydroxides coprecipitated with P (1:1 metal:P molar ratio) were incubated at 70 degrees C for 24 months to simulate natural long-term weathering processes that could influence the stability of sorbed P. Heat incubation (70 degrees C) of the untreated (no P) Al hydroxides resulted in drastic decreases (within the first month of incubation) in oxalate-Al extractability, specific surface area (SSA), and micropore volume with time. These changes were consistent with the formation of pseudoboehmite. Untreated Fe hydroxides showed no formation of crystalline components following heating (70 degrees C) for 24 months. Much smaller changes in oxalate-Al, P extractability, and SSA values were observed in the P-treated Al particles when compared with the untreated. Phosphorus treatment of both Fe and Al hydroxides stabilized the particle surfaces and prevented structural arrangements toward a long-range ordered phase. Slight reduction in SSA of the P-treated particles was related to dehydration phenomena during heating at 70 degrees C. Monitoring of physicochemical properties of the solids after heating at 70 degrees C for 2 years showed that sorbed P may be stable in the long-term. Understanding long term physicochemical properties may help engineers to optimize the Fe/Al hydroxides performance in several environmental/industrial applications.

Removal of arsenic by magnetic biochar prepared from pinewood and natural hematite.

There is a need for the development of low-cost adsorbents to removal arsenic (As) from aqueous solutions. In this work, a magnetic biochar was synthesized by pyrolyzing a mixture of naturally-occurring hematite mineral and pinewood biomass. The resulting biochar composite was characterized with X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDS). In comparison to the unmodified biochar, the hematite modified biochar not only had stronger magnetic property but also showed much greater ability to remove As from aqueous solution, likely because the γ-Fe2O3 particles on the carbon surface served as sorption sites through electrostatic interactions. Because the magnetized biochar can be easily isolated and removed with external magnets, it can be used in various As contaminant removal applications.

Physicochemical and sorptive properties of biochars derived from woody and herbaceous biomass.

It is unclear how the properties of biochar control its ability to sorb metals. In this work, physicochemical properties of a variety of biochars, made from four types of feedstock at three pyrolysis temperatures (300, 450 and 600°C) were compared to their ability to sorb arsenic (As) and lead (Pb) in aqueous solutions. Experimental results showed that both feedstock types and pyrolysis temperature affected biochar's production rate, i.e., ratio of mass of biochar and biomass, thermal stability, elemental composition, non-combustible component (NCC) content, pH values, surface areas and thus their sorption ability to the two metals in aqueous solution. In general, the high temperature biochars had low O/C and H/C ratios, were more carbonized with larger surface area, and were more concentrated with alkaline cations. In addition, biochars made from woody feedstocks had larger surface area, but lower NCC contents than that made from grasses under the same conditions. Although all the tested biochars removed both As and Pb from aqueous solutions, they showed different sorption abilities because of the variations in properties. Statistical analyses suggested that feedstock type affected the sorption ability of the biochars to both As and Pb significantly (p<0.001). Pyrolysis temperature, however, showed little influence on biochar sorption of Pb in aqueous solutions. Statistical analyses also showed that electrostatic interaction played an important role in controlling the sorption of both As(V) and Pb(II) onto the biochar. Other mechanisms, such as precipitation and surface complexation, could also control the sorption of Pb(II) onto the biochars.

Manganese oxide-modified biochars: preparation, characterization, and sorption of arsenate and lead.

This work explored two modification methods to improve biochar's ability to sorb arsenic (As) and lead (Pb). In one, pine wood feedstock was pyrolyzed in the presence of MnCl2·4H2O (MPB) and in the other it was impregnated with birnessite via precipitation following pyrolysis (BPB). The resulting biochars were characterized using thermogravimetry, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analyses. The dominant crystalline forms of Mn oxides in the MPB and BPB were manganosite and birnessite, respectively. Batch sorption studies were carried out to determine the kinetics and magnitude of As(V) and Pb(II) onto the biochars. As(V) and Pb(II) sorption capacities of MPB (0.59 and 4.91 g/kg) and BPB (0.91 and 47.05 g/kg) were significantly higher than that of the unmodified biochar (0.20 and 2.35 g/kg). BPB showed the highest sorption enhancement because of the strong As(V) and Pb(II) affinity of its birnessite particles.

Intraparticle phosphorus diffusion in a drinking water treatment residual at room temperature.

Phosphorus (P) has been recognized as one of the major limiting nutrients that are responsible for eutrophication of surface waters, worldwide. Efforts have been concentrated on reducing P loads reaching water bodies, via surface runoff and/or leaching through a soil profile. Use of drinking water treatment residuals (WTRs) is an emerging cost-effective practice to reduce soluble P in poorly P-sorbing soils or systems high in P. Literature suggests that WTRs have huge P sorption capacities. We hypothesized that P sorption would be limited by diffusional constraints imposed by the WTR particles. Selected chemical and physical (specific surface area, particle size distribution) characteristics of an iron-based WTR were measured. Sorption P isotherms at room temperature were constructed, and sorption kinetics were monitored. An intraparticle diffusion model was utilized to fit the kinetic data. Results showed that the WTR dramatically reduced soluble P, showing nonequilibrium characteristics, even after 80 d of reaction. Specific surface area (SSA) measured with CO2 gas was significantly greater than the traditional BET-N2 value (28 versus 3.5 m2 g(-1)), suggesting that a large amount of internal surfaces might be present in the WTR. The intraparticle P diffusion model was modified to include the wide particle size distribution of the WTR. The intraparticle diffusion model fitted the data well (r2 = 0.83). We calculated a maximum apparent P diffusion coefficient value of 4 x 10(-15) cm2 s(-1), which agrees with published values for intraparticle diffusion in microporous sorbents. This work may be useful for predicting long-term sorption characteristics of WTRs, since WTRs have been suggested as potential long-term immobilizers of sorbed P in P-sensitive ecosystems.

Lead contamination in shooting range soils from abrasion of lead bullets and subsequent weathering.

Contamination of shooting range soils from the use of Pb bullets is under increasing scrutiny. Past research on Pb contamination of shooting ranges has focused on weathering reactions of Pb bullets in soil. The objective of this study was to determine the significance of abrasion of Pb bullets in contributing to soil Pb contamination. This was accomplished by firing a known mass of bullets into sand and analyzing for total Pb after removing bullets, through field sampling of a newly opened shooting range, and a laboratory weathering study. Forty-one mg of Pb were abraded per bullet as it passed through the sand, which accounted for 1.5% of the bullet mass being physically removed. At a shooting range that had been open for 3 months, the highest Pb concentration from the pistol range berm soil was 193 mg/kg at 0.5 m height, and from the rifle range berm soil was 1142 mg/kg at 1.0 m height. Most soils from the field abrasion experiment as well as soil collected from the rifle range had SPLP-Pb >15 microg/l (Synthetic Precipitation Leaching Procedure). Typically, Pb concentration in the rifle range was greater than that of the pistol range. Based on a laboratory weathering study, virtually all metallic Pb was converted to hydrocerussite (Pb3(CO3)2(OH)2), as well as to a lesser extent cerussite (PbCO3) and massicot (PbO) within one week. Our study demonstrated that abrasion of lead bullets and their subsequent weathering can be a significant source of lead contamination in soils of a newly opened shooting range.

Lead transformation and distribution in the soils of shooting ranges in Florida, USA.

The use of lead bullets and shot at shooting ranges is under increasing scrutiny as a potentially significant source of Pb pollution. This study assessed Pb contamination in the soils of two shooting ranges (TRR and MPR) in Florida. Soil samples were collected from the two ranges and analyzed for total Pb to determine Pb contamination. Selected spent bullets and berm soil samples were mineralogically characterized to identify Pb transformation. Total Pb in the range soils was significantly elevated with the highest (up to 4.84% by weight) in the berm soils. Most soils failed the synthetic precipitation leaching procedure (SPLP) test. Also, at the MPR shooting range, a substantial amount of Pb migrated down in the subsurface soil, possibly due to the enhanced solubilization of organic Pb complexes at alkaline pH, whereas high cation exchange capacity of the profile soil may be responsible for Pb retention in the subsoil. The weathering products on the surface of the spent bullets were predominantly hydrocerussite [Pb(3)(CO(3))(2)(OH)(2)] and cerussite (PbCO(3)). Hydrocerussite was mainly found in the MPR range soils, whereas Pb was transformed into hydroxypyromorphite [Pb(5)(PO(4))(3)OH] in the TRR range soils because of the presence of more P. Sequential extraction and lead activity ratio modeling showed that the soil Pb solubility was controlled by Pb carbonate minerals in the MPR shooting range, and by less soluble Pb phosphate minerals in the TRR shooting range. This research suggests that it is important to develop and implement efficient management practices to minimize adverse impacts of Pb at shooting ranges. Phosphate-induced Pb immobilization may be an effective alternative for reducing Pb mobility in the shooting range soils.

Arsenic species and leachability in the fronds of the hyperaccumulator Chinese brake (Pteris vittata L.).

Arsenic speciation is important not only for understanding the mechanisms of arsenic accumulation and detoxification by hyperaccumulators, but also for designing disposal options of arsenic-rich biomass. The primary objective of this research was to understand the speciation and leachability of arsenic in the fronds of Chinese brake (Pteris vittata L.), an arsenic hyperaccumulator, with an emphasis on the implications for arsenic-rich biomass disposal. Chinese brake was grown for 18 weeks in a soil spiked with 50 mg As kg(-1) as arsenate (AsO4(3-)), arsenite (AsO3(3-)), dimethylarsinic acid (DMA), or methylarsonic acid (MMA). Plant samples were extracted with methanol/water (1:1) and arsenic speciation was performed using high performance liquid chromatography coupled with atomic fluorescence spectrometry. The impacts of air-drying on arsenic species and leachability in the fronds were examined in the laboratory. After 18 weeks, water-soluble arsenic in soil was mainly present as arsenate with little detectable organic species or arsenite regardless of arsenic species added to the soil. However, arsenic in the fronds was primarily present as inorganic arsenite with an average of 94%. Arsenite re-oxidation occurred in the old fronds and the excised dried tissues. Arsenic species in the fronds were slightly influenced by arsenic forms added to the soil. Air-drying of the fronds resulted in leaching of substantial amounts of arsenic. These findings can be of significance when looking at disposal options of arsenic-rich biomass from the point of view of secondary contamination.

Phosphate-induced metal immobilization in a contaminated site.

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.

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.