Response of soil microbiological activities to cadmium,lead, and zinc salt amendments

Heavy metal pollution of soil has been recognized as a major factor impeding soil microbial processes. From this perspective, we studied responses of the soil biological activities to metal stress simulated by soil amendment with Zn, Pb, and Cd chlorides. The amounts of heavy metal salts added to five metal-polluted soils and four nonpolluted soils were selected to match the total metal concentrations typically found in polluted soils of the Silesia region of Poland. From the perspective of soil quality, metal mobility in amended soils could not be described by simple functions of pH or organic matter. Reaction of Pb with the soil caused strong immobilization with less than 1% of the Pb amendment recovered by 0.01 M CaCl2 extractions. Immobilization of Cd was also significant, whereas immobilization of the Zn amendment was much weaker than that of Cd or Pb. The Zn amendment had substantial inhibitory effect on soil dehydrogenase, acid and alkaline phosphatase, arylsulfatase, urease, and nitrification potential. Generally, Cd and Pb had limited or stimulatory effect on most of these biological activities, with an exception of Pb strongly inhibiting soil urease. The effect of the metal amendments on biological activities could not be satisfactorily accounted for by metal toxicity because no strong relationship was observed between extractable metal content and the degree of inhibition. The Zn amendment had a significant effect on soil pH, resulting in confounding effects of pH and Zn toxicity on activities. Metal amendment experiments seem to be of limited utility for meaningful assessment of metal contamination effects on soil quality.     

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

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

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.     

Leaching of dissolved organic carbon and carbon dioxide emission after compost application to six nutrient-depleted forest soils

The objective of this study was to assess the effect of compost application on soil respiration and dissolved organic carbon (DOC) output of nutrient-depleted forest soils. An amount of 6.3 kg m(-2) mature compost was applied to the forest floor of European beech (Fagus sylvatica L.), Norway spruce (Picea abies Karst.), and Scots pine (Pinus sylvestris L.) stands at Soiling and Unterlüss, Germany. Cumulative soil respiration significantly increased by 499 g C m(-2) in the spruce stand at Unterlüss and by 274 g C m(-2) in the beech stand at Soiling following compost application whereas soil respiration of the other four stands was not affected. The increases in soil respiration of the two stands were explained by improved microbial decomposition of soil organic matter. The DOC concentrations and fluxes in throughfall and seepage water at 10- and 100-cm depths were determined from August 1997 to March 2000. In the control plots, cumulative DOC outputs at 10 cm ranged between 57 and 95 g C m(-2), with the highest rates in the pine stands. Compost treatment significantly increased cumulative DOC outputs by 31 to 69 g C m(-2) at 10 cm and by 0.3 to 6.6 g C m(-2) at 100 cm. The mineral soils between the 10- and 100-cm depths acted as significant sinks for DOC, as shown by much lower cumulative outputs at 100 cm of 3 to 11 g C m(-2) in the control and 6 to 16 g C m(-2) in the compost plots. Our results suggest that a single, moderate application of mature compost to nutrient-depleted forest soils has little effect on C losses to the atmosphere and ground water.     

Pyrene degradation in forest humus microcosms with or without pine and its mycorrhizal fungus

The mineralization potential of forest humus and the self-cleaning potential of a boreal coniferous forest environment for polycyclic aromatic hydrocarbon (PAH) compounds was studied using a model ecosystem of acid forest humus (pH = 3.6) and pyrene as the model compound. The matrix was natural humus or humus mixed with oil-polluted soil in the presence and absence of Scots pine (Pinus sylvestris L.) and its mycorrhizal fungus (Paxillus involutus). The rates of pyrene mineralization in the microcosms with humus implants (without pine) were initially insignificant but increased from Day 64 onward to 47 microg kg(-1) d(-1) and further to 144 microg kg(-1) d(-1) after Day 105. In the pine-planted humus microcosms the rate of mineralization also increased, reaching 28 microg kg(-1) d(-1) after Day 105. The 14CO2 emission was already considerable in nonplanted microcosms containing oily soil at Day 21 and the pyrene mineralization continued throughout the study. The pyrene was converted to CO2 at rates of 0.07 and 0.6 microg kg(-1) d(-1) in the oily-soil implanted microcosms with and without pine, respectively. When the probable assimilation of 14CO2 by the pine and ground vegetation was taken into account the most efficient microcosm mineralized 20% of the 91.2 mg kg(-1) pyrene in 180 d. The presence of pine and its mycorrhizal fungus had no statistically significant effect on mineralization yields. The rates of pyrene mineralization observed in this study for forest humus exceeded the total annual deposition rate of PAHs in southern Finland. This indicates that accumulation in forest soil is not to be expected.     

ARE SOILS LIKE SPONGES?1

ABSTRACT: The purpose of this paper is to explore the validity of the old analogy that “soil is like a sponge.” Laboratory experiments were conducted to measure two hydrologic properties of porous media: drainage under gravity, and water potential curves. A tipping bucket rain gage connected to a data logger was used to measure the rate at which water drained under the force of gravity from a trough filled with four saturated porous media ‐ cellulose sponges, topsoil, peat, and a medium sand. Pressure plate techniques were used to determine water potential curves for soil materials and sponges. In terms of relative cumulative discharge from the trough, sponges were intermediate between peat and topsoil. Because of their tremendous water‐holding capacity, sponges discharged more than 2.5 times as much water as did peat. The water potential curve for sponges was fairly flat, like that of topsoil, but the high water content across all pressures (0.30–15.0 bars) indicated some similarity to peat. The results of these experiments suggest that the general patterns of water retention and release in soil materials and sponges are similar and vary only in degree.     

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.     

Effects of recreational use on forested sites

Impact of recreational activities on soil and vegetation was evaluated in eight forested camping and picnic areas in southern Rhode Island. Forest vegetation consists of mixed-oak and white pine stands. Soils are of granitic glacial till or outwash origin and textures range from loamy sand to find sandy loam. Recreational use resulted in significant compaction of soils as indexed by soil penetration resistance and bulk density. Evidence indicates that compaction influences bulk densities to a depth of about 12.7 cm. Rates of water infiltration are less on recreation areas. Soil water accretion and depletion during the growing season are less rapid on recreation sites than on control sites. Differences are attributed to reduced infiltration, percolation, and rooting activity. Much of the ground surface on recreation areas is devoid of vegetation. The surface consists primarily of bare mineral soil, rock, or litter. The plants most commonly present are grasses. Native ground cover vegetation including tree seedlings, ericaceous shrubs and herbs has been eliminated or greatly reduced by trampling. Damage to tree trunks is common in recreation areas. White pine radial growth and scarlet oak height growth were significantly less on recreation sites. Scarlet oak appears intolerant to heavy recreation use.     

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.     

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.     

Phosphorus leaching in relation to soil type and soil phosphorus content

Phosphorus losses from arable soils contribute to eutrophication of freshwater systems. In addition to losses through surface runoff, leaching has lately gained increased attention as an important P transport pathway. Increased P levels in arable soils have highlighted the necessity of establishing a relationship between actual P leaching and soil P levels. In this study, we measured leaching of total phosphorus (TP) and dissolved reactive phosphorus (DRP) during three years in undisturbed soil columns of five soils. The soils were collected at sites, established between 1957 and 1966, included in a long-term Swedish fertility experiment with four P fertilization levels at each site. Total P losses varied between 0.03 and 1.09 kg ha(-1) yr(-1), but no general correlation could be found between P concentrations and soil test P (Olsen P and phosphorus content in ammonium lactate extract [P-AL]) or P sorption indices (single-point phosphorus sorption index [PSI] and P sorption saturation) of the topsoil. Instead, water transport mechanism through the soil and subsoil properties seemed to be more important for P leaching than soil test P value in the topsoil. In one soil, where preferential flow was the dominant water transport pathway, water and P bypassed the high sorption capacity of the subsoil, resulting in high losses. On the other hand, P leaching from some soils was low in spite of high P applications due to high P sorption capacity in the subsoil. Therefore, site-specific factors may serve as indicators for P leaching losses, but a single, general indicator for all soil types was not found in this study.     

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

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

Effect of spent mushroom substrate applied to vineyard soil on the behaviour of copper-based fungicide residues

The effect of the addition of spent mushroom substrate (SMS) to the soil as an amendment on the distribution and/or fate of copper from a copper-based fungicide applied to a vineyard soil in La Rioja (N. Spain) was studied. The study was carried out on experimental plots amended or not with SMS at rates of 40 and 100 t ha(-1). The variation in total Cu content in the topsoil (0-10 cm) and in the soil profile (0-50 cm), and the distribution of Cu in different fractions of the topsoil were studied as a function of the dose of Cu added (5 and 10 kg ha(-1)) and of the time elapsed since application (0-12 months). In addition, the changes in the chemical properties (solid organic carbon (OC), dissolved organic carbon (DOC) and pH) of the soils were studied. A greater capacity for Cu retention by the amended soils than by the unamended one was observed only when the fungicide was applied at the high dose. No effect of the amendment rate was noted on this retention capacity. The metal content in the topsoil decreased over time in step with the disappearance of the OC in the amended soil due to its oxidation, mineralization and/or leaching. This decrease in total Cu content was possibly due to the formation of soluble Cu complexes with the DOC, which facilitated its transport through the soil. A re-distribution of Cu in the different soil fractions was also observed over time, mainly from the organic to the residual fraction. The results obtained indicate that the increase in OC due to the application of SMS at the rates used does not lead to any significant increase in the persistence of Cu in the soil over time. Of greater interest would be the assessment of the risk for groundwater quality, owing to possible leaching of the fungicide enhanced by the SMS when SMS and Cu-based fungicides are jointly applied to vineyard soils.     

Nutrient leaching in a Colombian savanna Oxisol amended with biochar

Nutrient leaching in highly weathered tropical soils often poses a challenge for crop production. We investigated the effects of applying 20 t ha biochar (BC) to a Colombian savanna Oxisol on soil hydrology and nutrient leaching in field experiments. Measurements were made over the third and fourth years after a single BC application. Nutrient contents in the soil solution were measured under one maize and one soybean crop each year that were routinely fertilized with mineral fertilizers. Leaching by unsaturated water flux was calculated using soil solution sampled with suction cup lysimeters and water flux estimates generated by the model HYDRUS 1-D. No significant difference ( > 0.05) was observed in surface-saturated hydraulic conductivity or soil water retention curves, resulting in no relevant changes in water percolation after BC additions in the studied soils. However, due to differences in soil solution concentrations, leaching of inorganic N, Ca, Mg, and K measured up to a depth of 0.6 m increased ( < 0.05), whereas P leaching decreased, and leaching of all nutrients (except P) at a depth of 1.2 m was significantly reduced with BC application. Changes in leaching at 2.0 m depth with BC additions were about one order of magnitude lower than at other depths, except for P. Biochar applications increased soil solution concentrations and downward movement of nutrients in the root zone and decreased leaching of Ca, Mg, and Sr at 1.2 m, possibly by a combination of retention and crop nutrient uptake.     

Predicting phosphorus losses with the PLEASE model on a local scale in Denmark and the Netherlands

To reduce losses from agricultural soils to surface water, mitigation options have to be implemented as a local scale. For a cost-effective implementation of these measures, an instrument to identify critical areas for P leaching is indispensable. In many countries, P-index methods are used to identify areas as risk for P losses to surface water. In flat areas, where losses by leaching are dominant, these methods have their limitations because leaching is often not described in detail, PLEASE, is a simple mechanistic model designed to stimulate P Losses by leaching at the field scale using a limited amount of local field data. In this study, PLEASE, was applied to 17 lowland sites in Denmark and 14 lowland sites in the Netherlands. Results show that the simple model simulated measured fluxes and concentrations in water from pipe drains, suction cups, and groundwater quite well. The modeling efficiency ranged from 0.92 for modeling total-P fluxes to 0.36 fr modeling concentrations in groundwater. Poor results were obtained for heavy clay soils and eutrophic peat soils, where fluxes and concentration were strongly underestimated by the model. The poot performance for the heavy clay soil can be explained by the transport of P through macropores to the drain pipes and the underestimation of overland flow on this heavy-textured soil. In the eutrophic peat soils, fluxes were underestimated due to the release of P from deep soil layers.     

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.     

ECONOMIC EFFECTS OF SOIL CONDITIONS ON FARM STRATEGIES TO REDUCE AGRICULTURAL POLLUTION1

ABSTRACT: Utilizing predictions of pollutant movement generated by the CREAMS model, the economics of reducing field losses of sediment and nitrate percolation were compared between two soil types on each of two slopes common to the Upper Eastern Shore of Maryland. The soils considered were Matapeake silt loam and Sassafras sandy loam textures on field slopes of 3.5 percent and 7.5 percent. A representative cash grain farm was used as a basis of comparison. Under assumptions of profit maximization, economic optimal cropping systems varied by slope. Results further indicated that relative cost-effectiveness of sediment or nitrate percolation control varied by soil type for both slopes considered. Unit costs of sediment control were less on silt loam soils, while unit costs of nitrate percolation control were less on sandy loam soils.     

Denitrification potential in relation to lithology in five headwater riparian zones

The influence of riparian zone lithology on nitrate dynamics is poorly understood. We investigated vertical variations in potential denitrification activity in relation to the lithology and stratigraphy of five headwater riparian zones on glacial till and outwash landscapes in southern Ontario, Canada. Conductive coarse sand and gravel layers occurred in four of the five riparian areas. These layers were thin and did not extend to the field-riparian perimeter in some riparian zones, which limited their role as conduits for ground water flow. We found widespread organic-rich layers at depths ranging from 40 to 300 cm that resulted from natural floodplain processes and the burial of surface soils by rapid valley-bottom sedimentation after European settlement. The organic matter content of these layers varied considerably from 2 to 5% (relic channel deposit) to 5 to 21% (buried soils) and 30 to 62% (buried peat). Denitrification potential (DNP) was measured by the acetylene block method in sediment slurries amended with nitrate. The highest DNP rates were usually found in the top 0- to 15-cm surface soil layer in all riparian zones. However, a steep decline in DNP with depth was often absent and high DNP activity occurred in the deep organic-rich layers. Water table variations in 2000-2002 indicated that ground water only interacted frequently with riparian surface soils between late March and May, whereas subsurface organic layers that sustain considerable DNP were below the water table for most of the year. These results suggest that riparian zones with organic deposits at depth may effectively remove nitrate from ground water even when the water table does not interact with organic-rich surface soil horizons.     

Evaluation of an acid ammonium oxalate extraction to determine fluoride resident concentrations in soils

Fluoride depositions near aluminum smelters and other fluoride-emitting plants can lead to fluoride accumulation in soils, which constitutes a risk for ground water contamination. This study was conducted to investigate the capacity of a 0.2 M acid ammonium oxalate solution to selectively and quantitatively extract fluoride accumulated in soils. The recovery of fluoride added to three soils was evaluated following 7- to 28-d incubations. Oxalate extraction was also compared with a total fluoride extraction method, using oxalate-extractable fluoride (Fox) and total fluoride (Ftot) accumulation profiles derived from column percolation experiments. To determine low-level fluoride concentrations without interference from high Al and Fe concentrations, an adapted ion chromatography method was used. Following soil incubations, oxalate extracted 42 to 86% of added fluoride. Recovery varied between soils and, in one soil, increased with added fluoride concentration. Recovery was unaffected by incubation time. Maximum recovery was obtained in a soil high in amorphous Fe and Al, low in clay, and free of carbonate. Lower recoveries were obtained in soils with higher clay or carbonate contents. Only 4 to 8% of Ftot was extracted in untreated samples using Fox, which suggests a high selectivity of this method for added fluoride. In percolation experiments, the use of Fox reduced considerably the background noise associated with Ftot for the evaluation of fluoride accumulation profiles. Because of its high selectivity and despite incomplete fluoride recovery, the use of Fox to determine fluoride resident concentrations in soils may improve environmental monitoring of fluoride accumulation and movement in contaminated soils.     

Potential negative consequences of adding phosphorus-based fertilizers to immobilize lead in soil

A study of the potential negative consequences of adding phosphate (P)-based fertilizers as amendments to immobilize lead (Pb) in contaminated soils was conducted. Lead-contaminated firing range soils also contained elevated concentrations of antimony (Sb), a common Pb hardening agent, and some arsenic (As) of unknown (possibly background) origin. After amending the soils with triple superphosphate, a relatively soluble P source, column leaching experiments revealed elevated concentrations of Sb, As, and Pb in the leachate, reflecting an initial spike in soluble Pb and a particularly dramatic increase in Sb and As mobility. Minimal As, Sb, and Pb leaching was observed during column tests performed on non-amended control soils. In vitro extractions tests were performed to assess changes in Pb, As, and Sb bioaccessibility on P amendment. Lead bioaccessibility was systematically lowered with increasing P dosage, but there was much less of an effect on As and Sb bioaccessibility than on mobility. Our results indicate that although P amendments may aid in lowering the bioaccessibility of soil-bound Pb, it may also produce an initial increase in Pb mobility and a significant release of Sb and As from the soil, dramatically increasing their mobility and to a lesser extent their bioavailability.