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.     

Effects of wood bark and fertilizer amendment on trace element mobility in mine soils, Broken Hill, Australia: implications for mined land reclamation

Soil amendments can immobilize metals in soils, reducing the risks of metal exposure and associated impacts to flora, fauna and human health. In this study, soil amendments were compared, based on "closed system" water extracts, for reducing metal mobility in metal-contaminated soil from the Broken Hill mining center, Australia. Phosphatefertilizer (bovine bone meal, superphosphate, triple superphosphate, potassium orthophosphate) and pine bark (Pinus radiata) were applied to two soils (BH1, BH2) contaminated with mining waste. Both soils had near neutral to alkaline pH values, were sulfide- or sulfate-rich, and contained metal and metalloid at concentrations that pose high environmental risks (e.g., Pb = 1.25 wt% and 0.55 wt%, Zn = 0.71 wt% and 0.47 wt% for BH1 and BH2, respectively). The addition of fertilizers and/or pine bark to both soil types increased water extractable metals and metalloids concentrations (As, Cd, Cu, Fe, Mn, Pb, Sb, Zn) compared with nonamended soils. One or more of the elements As, Cd, Cu, Mn, Pb, and Zn increased significantly in extracts of a range of different soil+pine bark and soil+fertilizer+piner+pine bark tests in response to increased pine bark doses. By contrast, Fe and Sb concentrations in extracts did not change significantly with pine bark addition. Solution pH was decreased by phosphate fertilizers (except for bovine bone meal) and pine bark, and pine bark enhanced dissolved organic carbon. At least in the short-term, the application of phosphate fertilizers and pine bark proved to be an ineffective method for controlling metal and metalloid mobility in soils that contain admixtures of polymetallic, polymineralic mine wastes.     

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.     

Solubility of antimony and other elements in samples taken from shooting ranges

The aim of this study was to determine whether or not Sb and other elements (Ni, Cu, Bi, Tl, and Hg) originating from Pb alloy (2-5 wt. % Sb) bullets become more soluble as a result of weathering and what mechanisms possibly control their solubility. Samples were taken from bank material behind the targets at seven Swiss shooting ranges. The samples were dried, sieved, analyzed, and subjected to leaching experiments. Total average concentrations of Sb ranged from 0.5 to 13.8 g kg(-1). In the leaching experiments, Sb was almost exclusively present in solution as the oxidized species Sb(V) in concentrations of up to 5 mg L(-1). The Ca mineral Ca[Sb(OH)6]2 is suggested to control dissolved Sb(V) concentrations in soils at high concentrations. Oxalate extractions suggested that approximately 50% of Sb [predominantly Sb(V)] in the <0.5-mm fraction was adsorbed to Fe (hydr)oxides and possibly other minerals, such as calcite, that are soluble at pH 2. However, it is possible that only a fraction of the oxalate-extractable Sb(V) is reversibly bound to mineral surfaces. It was concluded that the release of Sb is significant and considerably higher than the other elements under investigation and that the mechanisms controlling Sb mobility should be further investigated.     

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.     

The characterization of total and leachable metals in foundry molding sands

Waste molding sands from the foundry industry have been successfully used as a component in manufactured soils, but concern over metal contamination must be addressed before many states will consider this beneficial use. Since there is little data available on this topic, the purpose of this study was to characterize total and leachable metals from waste molding sands. A total elemental analysis for Ag, Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, V, and Zn was conducted on 36 clay-bonded and seven chemically bonded molding sands. Total metal concentrations in the molding sands were similar to those found in agricultural soils. The leaching of metals (i.e. Ag, As, Ba, Be, Cd, Cr, Cu, Ni, Pb, Sb, and Zn) was assessed via the toxicity characteristic leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), and ASTM water leach test. Based on the TCLP data, none of the 43 molding sands would meet the Resource Conservation and Recovery Act (RCRA) characteristic for toxicity due to high Ag, As, Ba, Cd, Cr, and Pb. Compared to the TCLP results, the metal concentrations were generally lower in the SPLP and ASTM extracts, which is likely related to the buffering capacity of the extraction fluids.     

Sample drying effects on lead bioaccessibility in reduced soil

Risk-assessment tests of contaminated wetland soils often use experimental protocols that artificially oxidize the soils. Oxidation may impact bioavailability of contaminants from the soils, creating erroneous results and leading to improper management and remediation. The goal of this study was to determine if oxygenation of reduced sediments and soils influences Pb bioaccessibility measurements. The study site is located on the Coeur d'Alene River floodplain, downstream from the Silver Valley Mining District in Idaho. A physiologically based extraction test designed to simulate the gastrointestinal tract of waterfowl (W-PBET) was used to measure relative Pb bioavailability (bioaccessibility) from the soils. The soils were collected from a submerged wetland. One set of samples was allowed to air-dry, another set was freeze-dried, and a third set was analyzed wet. The wet soil showed decreased Pb bioaccessibility compared with the air- and freeze-dried soils. The changes in extractability of Fe and Mn on air-drying were opposite from each other: Fe extractability decreased while Mn increased. The results from this study show that redox changes may have significant impacts on Pb bioavailability, and should be considered when assessing Pb contamination risks in reduced soils.     

Solution chemistry influence on metal mobility in biosolids-amended soils

Many studies have implicated dissolved organic carbon (DOC) as an important contributor to the elevated mobility of trace metals in soils amended with biosolids. Few of these studies, however, have quantified both DOC and metal concentrations. We completed laboratory leaching column studies on a dryland Platner loam (fine, smectitic, mesic Aridic Paleustoll) and an irrigated Osgood sand (loamy, mixed, mesic Arenic Ustollic Haplargid), both with a history of biosolids application. The soils were neutral to slightly alkaline in pH prior to amendment. We performed an additional application of biosolids to one set of columns in the laboratory at a rate of 28 Mg ha(-1) to investigate the effect of time following application on metal mobility. The effect of electrolyte concentration was studied by using both distilled water and simulated irrigation water. Biosolids application increased both DOC and Cu in the column effluents resulting in a positive correlation between Cu and DOC across application treatments for both soils. Both Cu and Pb were mobilized under conditions of low electrical conductivity (EC). This may be the result of the release of a strong metal-binding component of DOC under these conditions. Conversely, Zn mobility was positively correlated with EC, suggesting that either cation exchange or the formation of inorganic complexes influences Zn mobility. Anodic stripping voltammetry measurements indicated that only a small percentage of the total dissolved metals existed as free ions or inorganic complexes; the remainder appears to be complexed to DOC.     

Phosphorus sequestration by chemical amendments to reduce leaching from wastewater applications

Phosphorus-immobilizing amendments can be useful in minimizing P leaching from high P soils that may be irrigated with wastewater. This study tested the P-binding ability of various amendment materials in a laboratory incubation experiment and then tested the best amendment in a field setup using drainage lysimeters. The laboratory experiment involved incubating 100-g samples of soil (72 mg kg(-1) water-extractable phosphorus, WEP) with various amendments at different rates for 63 d at field moisture capacity and 25 degrees C. The amendments tested were alum [Al2SO4)3.14H2O], ferric chloride (FeCl3), calcium carbonate (CaCO3), water treatment residual (WTR), and sugarbeet lime (SBL). Ferric chloride and alum at rates of 1.5 and 3.9 g kg(-1), respectively, were the most effective amendments that decreased WEP to 20 mg kg(-1), below which leaching has previously been shown to be low. Alum (1.3 kg m(-2)), which is less sensitive to redox conditions, was subsequently tested under field conditions, where it reduced WEP concentration in the 0- to 0.15-m layer from 119 mg kg(-1) on Day 0 to 36.1 mg kg(-1) (85% decrease) on Day 41. Lysimeter breakthrough tests using tertiary-treated potato-processing wastewater (mean total phosphorus [TP] = 3.4 mg L(-1)) showed that alum application reduced leachate TP and soluble reactive phosphorus (SRP) concentrations by 27 and 25%, respectively. These results indicate that alum application may be an effective strategy to immobilize P in high P coarse-textured soils. The relatively smaller decreases in TP and SRP in the leachate compared to WEP suggest some of the P may be coming from depths below 0.2 m. Thus, to achieve higher P sequestration, deeper incorporation of the alum may be necessary.     

Phosphorus release from a manure-impacted spodosol: effects of a water treatment residual

Long-term depositions of animal manures affect P dynamics in soils and can pose environmental risks associated with P losses. Laboratory studies were done on P solubility characteristics in a manure-impacted Immokalee soil (sandy, siliceous, hyperthermic Arenic Alaquod) and the effectiveness of water treatment residual (WTR) in controlling P leaching. Soil samples with contrasting initial total P concentrations were prepared by mixing samples of a manure-impacted surface A horizon and a minimally P-impacted E horizon. Effects of mixing various ratios of A and E horizons, WTR rates (0, 25, 50, and 100 g kg(-1)), and depths of WTR incorporation (mixed throughout the soil column or partially incorporated) on P leaching were determined. Between 62 and 77% of total P was released from the soil mixes by successive water extractions, suggesting a considerable buffering capacity of this manure-impacted soil to resupply P into solution. Between 224 and 408 mg kg(-1) P were leached during the 36-wk leaching period in the absence of WTR. Mixing WTRs with soil reduced soluble P concentration in leachates by as much as 99.8% compared with samples without WTR. Thoroughly mixing WTR with the entire soil column (15 cm) was much more efficient than mixing WTR with only the top 7.5 cm of soil. Calcium- and Mg-P forms appear to control P release in soils without WTR, whereas sorption-desorption reactions probably determine P leaching in WTR-treated samples. Soil P distribution in various chemical forms was affected by WTR additions. Data suggest that WTR-immobilized P is stable in the long term.     

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.     

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.     

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.     

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.     

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.     

Assessment of the use of industrial by-products to remediate a copper- and arsenic-contaminated soil

Two water treatment sludges (WTS-A, WTS-B), two red muds (RM), and red gypsum (RG), all rich in iron oxy-hydroxides, were added to a soil highly polluted with As and Cu at 2% (w/w) to reduce metal bioavailability. Because the amendments increased soil pH to approximately 6, a lime treatment to the same pH and an unamended treatment were included for comparison. All the amendments had significant positive effects on the soil microbial biomass and growth of ryegrass (Lolium multiflorum Lam. cv. Avance), but only WTS-A improved lettuce (Lactuca sativa L. cv. Tom Thumb) growth. The mineralization of added ammonium nitrogen was not significantly affected by the treatments, while a physiologically based extraction test (PBET) showed that bioaccessibility of As was low (< 5%) and decreased only in the WTS-A treatment. Concentrations of As in soil pore water and extractable As only decreased in the WTS and RG treatments. In contrast, Cu concentrations in soil pore water and extractable Cu decreased in all treatments, by more than 84% in the WTS, RM, and RG treatments. Non-isotopically exchangeable As and Cu were present in colloids in the soil pore water. Untreated soil had < 4% isotopically exchangeable As and this decreased by approximately 50%, with WTS, RM, and RG. The labile Cu pool represented a large proportion (34%) of the total Cu pool, and the isotopically exchangeable and soluble Cu were strongly correlated with soil pH. Acidification of the treated soils showed that the labile As and Cu both increased in the treated soils compared with untreated soils. The significance of the treatment effects on soil fertility and potential off-site transport of As and Cu to ground water are discussed.     

Organic manure and urea effect on metolachlor transport through packed soil columns

Application of organic manure (OM) amendments and nitrogen fertilizers can affect the sorption and movement of pesticides in soil. This study summarizes the sorption and leaching of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylphenyl) acetamide] in soils after cow (Bos taurus) manure (2.5 and 5.0%) and urea (60 and 120 kg N ha(-1)) amendments in batch and column experiments. Both cow manure and urea applications increased metolachlor sorption in soils. The values of the Freundlich adsorption parameter K(r)(1/n) for treatments T0, T1 (OM), and T2 (OM) were 2.31, 3.32, and 3.96 in Soil 1; 2.02, 2.77, and 3.32 in Soil 2; and 1.10, 1.46, and 2.02 in Soil 3, respectively. Similarly, K(f)(1/n) values for treatment T1 (urea) and T2 (urea) were 2.37 and 2.84 in Soil 1; 2.16 and 2.83 in Soil 2; and 1.50 and 1.70 in Soil 3, respectively. Column leaching studies using Soil 1 indicated that OM application drastically reduced the metolachlor leaching losses from 50% (natural soil) to < 1.0% (5.0% OM amendment). Likewise, urea application also decreased metolachlor mobility and leaching losses in columns treated with 60 and 120 kg N ha(-1) urea were 33 and 20%, respectively. The reduction in the metolachlor leaching losses was achieved through the increase in the sorption capability of the OM- and urea-amended soil. Therefore, coapplication of metolachlor with cow manure or urea fertilizers will not enhance metolachlor mobility and reduces metolachlor leaching losses in low-organic-matter soil.     

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.     

Salt additions alter short-term nitrogen and carbon mobilization in a coastal Oregon Andisol

Deposition of sea salts is commonly elevated along the coast relative to inland areas, yet little is known about the effects on terrestrial ecosystem biogeochemistry. We examined the influence of NaCl concentrations on N, C, and P leaching from a coastal Oregon forest Andisol in two laboratory studies: a rapid batch extraction (approximately 1 d) and a month-long incubation using microlysimeters. In the rapid extractions, salt additions immediately mobilized significant amounts of ammonium and phosphate but not nitrate. In the month-long incubations, salt additions at concentrations in the range of coastal precipitation increased nitrate leaching from the microcosms by nearly 50% and reduced the mobility of dissolved organic carbon. Our findings suggest that coupled abiotic-biotic effects increase nitrate mobility in these soils: exchange of sodium for ammonium, then net nitrification. Changes in sea salt deposition to land and the interactions with coastal soils could alter the delivery of N and C to sensitive coastal waters.     

Relative movement and soil fixation of soluble organic and inorganic phosphorus

There is considerable concern about pollution of surface waters with P. Although most of the research has focused on inorganic P in surface runoff, it has recently become possible to easily follow the fate of soluble organic P forms in soils and waters. Two experiments were performed to compare the relative mobility and soil fixation affinity of orthophosphate monoesters, orthophosphate diesters, and soluble inorganic P. We used three P substrates, 4-methylumbelliferyl phosphate (MUP), deoxyribonucleic acid (DNA), and KH(2)PO(4) in (i) a soil column experiment and (ii) a soil P adsorption test tube experiment. Shortly after columns were prepared, approximately two pore volumes of 0.005 M CaCl(2) were passed through 25 cm length columns containing 10 cm of loamy sand amended with approximately 10 mg P as MUP, DNA, or KH(2)PO(4) above 15 cm of nonamended loamy sand. The total net quantity of 757.8 microg P 2L(-1) of orthophosphate diesters in the leachate from the DNA columns exceeded the net quantity of orthophosphate monoesters in leachate from the MUP columns (4.6 microg P 2L(-1)) and soluble inorganic P from the KH(2)PO(4) columns (34.0 microg P 2L(-1)). Adsorption of soluble organic and inorganic P in the test tube experiment yielded similar results: DNA, containing orthophosphate diesters, had a relatively low affinity for soils. In both experiments, high concentrations of other P compounds were identified in samples treated with organic P substrates, suggesting enzymatic hydrolysis by native soil phosphatase enzymes. These findings indicate that repeated application of organic forms of P could lead to significant leaching of P to ground water.