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

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

Estimating soil phosphorus requirements and limits from oxalate extract data

Excessive fertilizer and manure phosphorus (P) inputs to soils elevates P in soil solution and surface runoff, which can lead to freshwater eutrophication. Runoff P can be related to soil test P and P sorption saturation, but these approaches are restricted to a limited range of soil types or are difficult to determine on a routine basis. The purpose of this study was to determine whether easily measurable soil characteristics were related to the soil phosphorus requirements (P(req), the amount of P sorbed at a particular solution P level). The P(req) was determined for 18 chemically diverse soils from sorption isotherm data (corrected for native sorbed P) and was found to be highly correlated to the sum of oxalate-extractable Al and Fe (R2 > 0.90). Native sorbed P, also determined from oxalate extraction, was subtracted from the P(req) to determine soil phosphorus limits (PL, the amount of P that can be added to soil to reach P(req)). Using this approach, the PL to reach 0.2 mg P L(-1) in solution ranged between -92 and 253 mg P kg(-1). Negative values identified soils with surplus P, while positive values showed soils with P deficiency. The results showed that P, Al, and Fe in oxalate extracts of soils held promise for determining PL to reach up to 10 mg P L(-1) in solution (leading to potential runoff from many soils). The soil oxalate extraction test could be integrated into existing best management practices for improving soil fertility and protecting water quality.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

Kinetics of carbon mineralization of biochars compared with wheat straw in three soils

Application of biochars to soils may stabilize soil organic matter and sequester carbon (C). The objectives of our research were to study in vitro C mineralization kinetics of various biochars in comparison with wheat straw in three soils and to study their contribution to C stabilization. Three soils (Oxisol, Alfisol topsoil, and Alfisol subsoil) were incubated at 25°C with wheat straw, charcoal, hydrothermal carbonization coal (HTC), low-temperature conversion coal (LTC), and a control (natural organic matter). Carbon mineralization was analyzed by alkali absorption of CO released at regular intervals over 365 d. Soil samples taken after 5 and 365 d of incubation were analyzed for soluble organic C and inorganic N. Chemical characterization of biochars and straw for C and N bonds was performed with Fourier transformation spectroscopy and with the N fractionation method, respectively. The LTC treatment contained more N in the heterocyclic-bound N fraction as compared with the biochars and straw. Charcoal was highly carbonized when compared with the HTC and LTC. The results show higher C mineralization and a lower half-life of straw-C compared with biochars. Among biochars, HTC showed some C mineralization when compared with charcoal and LTC over 365 d. Carbon mineralization rates were different in the three soils. The half-life of charcoal-C was higher in the Oxisol than in the Alfisol topsoil and subsoil, possibly due to high Fe-oxides in the Oxisol. The LTC-C had a higher half-life, possibly due to N unavailability. We conclude that biochar stabilization can be influenced by soil type.     

Sorption of the veterinary antimicrobials sulfadimethoxine and ormetoprim in soil

Currently, limited research on the fate of antimicrobials in the environment exists, once they are discharged in human and animal wastes. Sorption of two antimicrobials, sulfadimethoxine (SDM) and ormetoprim (OMP), was investigated in two soils and sand using a series of batch experiments. Because OMP and SDM are often administered in combination, their sorption was also investigated in combination as co-solutes. The rate of SDM and OMP sorption was rapid over the first few hours of the experiments, which then slowed considerably after 16 to 68 h. OMP sorption was enhanced at high concentrations when in combination with SDM, with linear sorption coefficients ranging from 1.3 to 58.3 L.kg(-1) in the single solute experiments and 4.96 to 89.7 L.kg(-1) in the co-solute experiments. Sorption of OMP as a single solute seems to provide a better fit with the Freundlich equation, which became more linear (n approached 1) when SDM was present. Overall, SDM sorbed less than OMP in the two soils and sand. SDM linear sorption coefficients ranged from 0.4 to 25.8 L.kg(-1) as a single solute and 2.5 to 22.1 L.kg(-1) as a co-solute. Sorption of SDM becomes more nonlinear (n < 1) when SDM is present in combination with OMP. Overall, sorption of both antimicrobials increased in the selected soils and sand as the organic matter, clay content, and cation exchange capacity increased. These experiments indicate relatively low sorption of SDM and OMP in natural soils, making them a potential threat to surface and ground water.     

Distribution and mobility of mercury in soils of a gold mining region, Cuyuni river basin, Venezuela

An extensive and remote gold mining region located in the East of Venezuela has been studied with the aim of assessing the distribution and mobility of mercury in soil and the level of Hg pollution at artisanal gold mining sites. To do so, soils and pond sediments were sampled at sites not subject to anthropological influence, as well as in areas affected by gold mining activities. Total Hg in regionally distributed soils ranged between 0.02 mg kg(-1) and 0.40 mg kg(-1), with a median value of 0.11 mg kg(-1), which is slightly higher than soil Hg worldwide, possibly indicating long-term atmospheric input or more recent local atmospheric input, in addition to minor lithogenic sources. A reference Hg concentration of 0.33 mg kg(-1) is proposed for the detection of mining affected soils in this region. Critical total Hg concentrations were found in the surrounding soils of pollutant sources, such as milling-amalgamation sites, where soil Hg contents ranged from 0.16 mg kg(-1) to 542 mg kg(-1) with an average of 26.89 mg kg(-1), which also showed high levels of elemental Hg, but quite low soluble+exchangeable Hg fraction (0.02-4.90 mg kg(-1)), suggesting low Hg soil mobility and bioavailability, as confirmed by soil column leaching tests. The vertical distribution of Hg through the soil profiles, as well as variations in soil Hg contents with distance from the pollution source, and Hg in pond mining sediments were also analysed.     

Removal of perchlorate from contaminated waters using surfactant-modified zeolite

We investigated the potential of using surfactant (hexadecyltrimethylammonium)-modified zeolite (SMZ) as an inexpensive sorbent for removing perchlorate (ClO(4)(-)) from contaminated waters in the presence of competing anions. In batch systems, the presence of 10 mM OH(-) (i.e., pH 12), CO(3)(2-), Cl(-), or SO(4)(2-) had little effect on the sorption of ClO(4)(-) by SMZ, indicating that the sorption of ClO(4)(-) by SMZ was very selective. The presence of 10 mM NO(3)(-), however, reduced the sorption of ClO(4)(-) at low initial concentrations. The maximum sorption capacity for ClO(4)(-) by the SMZ remained relatively constant (40-47 mmol kg(-1)), in the absence or presence of the competing ions. In flow-through systems, ClO(4)(-) broke through the SMZ columns much later than other anions present in an artificial ground water. The affinity of the anions for SMZ followed the sequence of ClO(4)(-) > > NO(3)(-) > SO(4)(2-) > Cl(-). Perchlorate loading under dynamic flow-through conditions was 34 mmol kg(-1), somewhat less than the maximum loading of 40 to 47 mmol kg(-1) determined by the batch method. Less than 1% of previously sorbed ClO(4)(-) was leached out by ultra-pure water, by extraction fluid #1 of the standard toxicity characteristic leaching procedure (TCLP), or by a solution of 0.28 M Na(2)CO(3)/0.5 M NaOH. About 40% of the previously sorbed ClO(4)(-) was leached out from SMZ by a 0.5 M NO(3)(-) solution. The exchange of ClO(4)(-) with NO(3)(-) corroborated results of the batch tests where NO(3)(-) was shown to compete with ClO(4)(-) sorption.     

A comparative study for the sorption of Cd(II) by K-feldspar and sepiolite as soil components, and the recovery of Cd(II) using rhamnolipid biosurfactant

This study investigated the sorption characteristics and recovery of selected heavy metal Cd(II) from K-feldspar and sepiolite, representative soil components, using rhamnolipid biosurfactant. Although the proposed technique was classified as a soil bioremediation process, it can also be applied to treatment of waste waters containing Cd(II) ions with minor modifications. The effect of initial Cd(II) concentration on sorption capacity was characterized by determining the sorption isotherms. Of the four models examined, the Freundlich model showed the best fit for the sorption of Cd(II) on K-feldspar, whereas the Langmuir-model was used successfully to characterize the sorption of Cd(II) on sepiolite. Although a high Cd(II) uptake of 7.49 mmol/kg by K-feldspar was obtained, sepiolite was a superior Cd(II) accumulater, with a maximum Cd(II) uptake of 24.66 mmol Cd(II)/kg. The presence of Cd(II) in the sepiolite or K-feldspar prior to addition of the rhamnolipid generally resulted in less rhamnolipid sorption to sepiolite or K-feldspar. The maximum Cd(II) desorption efficiency by rhamnolipid from K-feldspar was substantially higher than that of sepiolite and determined to be 96% of the sorbed Cd(II), whereas only 10.1% of the sorbed Cd(II) from sepiolite was recovered by rhamnolipid solution.     

Sorption interactions between imazaquin and a humic acid extracted from a typical Brazilian oxisol

Soil sorption of most hydrophobic organic compounds (e.g., nonpolar pesticides) is directly related to soil organic matter (SOM) content. Humic substances are the major SOM components, containing carboxylic, phenolic, amine, quinone, and other functional groups, and specific structural configurations. In this paper, sorption interactions between imazaquin (2-[4,5-dydro-4-methyl-4-(1-methylethyl)-5-oxo-1H- imidazol-2-yl]-3-quinoline-carboxylic acid) herbicide (IM) and a humic acid (HA) extracted from a typical Brazilian Oxisol were studied with electron paramagnetic resonance (EPR) and Fourier-transform infrared (FTIR) spectroscopic techniques. A polarographic technique was used to quantify sorption. The IM amount sorbed on the HA was much higher than that on the whole soil within the pH range studied, emphasizing the prominent role played by SOM on IM sorption. Moreover, IM sorption increased as the soil-solution pH decreased. This enhancement in sorption was attributed to the hydrophobic affinity of the herbicide by the HA and to the electrostatic interaction between the protonated quinoline group of IM and the negative sites of the HA. Hydrophobic regions in the HA's interior at low pH (< 5.0) were recently demonstrated by an EPR detectable spin-label molecule. The FTIR and EPR spectroscopy and polarography data indicated weak interaction between IM and the soil and its HA, involving hydrogen bonding, proton transfer, and cation exchange (at low pH), and mainly hydrophobic interactions. However, no strong reaction mechanism, such as charge transfer, was involved. In addition, this research suggested that soil amendment with organic material might increase magnitude of IM sorption, consequently avoiding leaching and carryover problems usually found for mobile and persistent herbicides such as imazaquin.     

Role of mycorrhizal fungi and phosphorus in the arsenic tolerance of basin wildrye

Revegetation of arsenic (As)-rich mine spoils is often impeded by the lack of plant species tolerant of high As concentrations and low nutrient availability. Basin wildrye [Leymus cinereus (Scribner & Merr.) A. L?ve] has been observed to establish naturally in soils with elevated As content and thus may be useful for the stabilization of As-contaminated soils. An experiment was conducted to evaluate how variable phosphorus (P) concentrations and inoculation with site-specific arbuscular mycorrhizal fungi influence As tolerance of basin wildrye. Basin wildrye was grown in sterile sand in the greenhouse for 16 weeks. Pots of sterile sand were amended to create one of four rates of As (0, 3, 15, or 50 mg As kg(-1)), two rates of P (3 or 15 mg P kg(-1)), and +/-mycorrhizal inoculation in a 2 x 4 x 2 factorial arrangement. After 16 weeks of growth, plants were harvested, shoots and roots thoroughly washed, and the tissue analyzed for total shoot biomass, total root and shoot As and P concentrations, and degree of mycorrhizal infection. Basin wildrye was found to be tolerant of high As concentrations allowing for vigorous plant growth at application levels of 3 or 15 mg As kg(-1). Arsenic was sequestered in the roots, with 30 to 50 times more As in the roots than shoots under low P conditions. Mycorrhizal infection did not confer As tolerance in basin wildrye nor did mycorrhizal fungi influence biomass production. Phosphorus concentrations of 15 mg kg(-1) effectively inhibited As accumulation in basin wildrye. Basin wildrye has the potential to be used for stabilization of As-rich soils while minimizing exposure to grazing animals following reclamation.     

Sorption of arsenic from soil-washing leachate by surfactant-modified zeolite

Post-treatment of leachate from soil-washing remedial actions may be necessary depending on the amounts of dissolved contaminants present. Uptake of arsenic species by surfactant-modified zeolite (SMZ) from a synthetic soil leachate (pH of approximately 12 [NaOH]) was measured as a test of SMZ as a post-treatment sorbent. Batch sorption isotherms were prepared using leachate to SMZ ratios from 40:1 to 4:1, and temperatures of 25 and 15 degrees C. Equilibrium levels of dissolved and total solution arsenic were similar. At each temperature, sorption appeared to reach a plateau or maximum, then decreased at the highest solution concentration, corresponding to the lowest amount of zeolite added (2.5 g). A maximum sorption value of 72.0 mmol of arsenic per kg of SMZ (5400 mg/kg) was observed at 25 degrees C, and 42.1 mmol/kg (3150 mg/kg) at 15 degrees C. Total arsenic recoveries varied from 74 to 125%. Surfactant-modified zeolite removed up to 97% of dissolved organic carbon and decolorized the leachate solutions. Excluding the points for the highest arsenic to SMZ ratio, the sorption isotherms were well described by the linearized form of the Langmuir equation, with coefficients of determination greater than 0.90 at both temperatures. Sorption of arsenic by SMZ is attributed to anion exchange with counterions on the surfactant head groups, and/or partitioning of organic carbon-complexed arsenic into the surfactant bilayer.     

Sorption of atmospheric ammonia by soil and perennial grass downwind from two large cattle feedlots

Livestock manure in feedlots releases ammonia (NH3), which can be sorbed by nearby soil and plants. Ammonia sorption by soil and its effects on soil and perennial grass N contents downwind from two large cattle feedlots in Alberta, Canada were investigated from June to October 2002. Atmospheric NH3 sorption was measured weekly by exposing air-dried soil at sampling points downwind along 1700-m transects. The amount of NH3 sorbed by soil was 2.60 to 3.16 kg N ha(-1) wk(-1) near the source, declining to about 0.25 kg N ha(-1) wk(-1) 1700 m downwind, reflecting diminishing atmospheric NH3 concentrations. Ammonia sorption at a control site away from NH3 sources was much lower: 0.085 kg N ha(-1) wk(-1). Based on these rates, about 19% of emitted NH3 is sorbed by soil within 1700 m downwind of feedlots. Field soil and grass samples from the transect lines were analyzed for total N (TN) and KCl-extractable N content (soil only). Nitrate N content in field soil followed a trend similar to that of atmospheric NH3 sorption. Soil TN contents, because of high background levels, showed no clear pattern. The TN content of grass, downwind of the newer feedlot, followed a pattern similar to that of NH3 sorption; downwind of the older feedlot, grass TN was correlated to soil TN. Our results suggest that atmospheric NH3 from livestock operations can contribute N to local soil and vegetation, and may need to be considered when determining fertilizer rates and assessing environmental impact.     

Phosphorus sorption and availability in soils amended with animal manures and sewage sludge

Soils that receive large applications of animal wastes and sewage sludge are vulnerable to releasing environmentally significant concentrations of dissolved P available to subsurface flow owing to the gradual saturation of the soil's P sorption capacity. This study evaluated P sorption (calculated from Langmuir isotherms) and availability of P (as CaCl2-P and resin P) in soils incubated for 20 d with poultry litter, poultry manure, cattle slurry, municipal sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)). All the P sources had a marked negative effect on P sorption and a positive effect on P availability in all soils. In the cattle slurry- and KH2PO4-treated soils, the decreases in P sorption maximum (19-66%) and binding energy (25-89%) were consistently larger than the corresponding decreases (7-41% and 11-30%) in poultry litter-, poultry manure-, and sewage sludge-treated soils. The effects of cattle slurry and KH2PO4 on P availability were, in most cases, larger than those of the other P sources. In the poultry litter, poultry manure, and sewage sludge treatments, the increase in soil solution P was inversely related (R2 = 0.75) to the input of Ca from these relatively high Ca (13.5-42 g kg(-1)) sources. Correlation analyses implied that the magnitude of the changes in P sorption and availability was not related to the water-extractable P content of the P sources. Future research on the sustainable application of organic wastes to agricultural soils needs to consider the non-P- as well as P-containing components of the waste.     

Sorption dynamics of organic and inorganic phosphorus compounds in soil

Phosphorus retention in soils is influenced by the form of P added. The potential impact of one P compound on the sorption of other P compounds in soils has not been widely reported. Sorption isotherms were utilized to quantify P retention by benchmark soils from Indiana, Missouri, and North Carolina when P was added as inorganic P (Pi) or organic P (beta-D-glucose-6-phosphate, G6P; adenosine 5'-triphosphate, ATP; and myoinositol hexaphosphate, IP6) and to determine whether soil P sorption by these organic P compounds and Pi was competitive. Isotherm supernatants were analyzed for pH and total P using standard protocols, while Pi and organic P compounds were assayed using ion chromatography. Under the controlled conditions of this study, the affinity of all soils for P sources followed the order IP6 > G6P > ATP > Pi. Each organic P source had a different potential to desorb Pi from soils, and the order of greatest to least Pi desorption was G6P > ATP > IP6. Glucose-6-phosphate and ATP competed more directly with Pi for sorption sites than IP6 at greater rates of P addition, but at the lesser rates of P addition, IP6 actually desorbed more Pi. Inositol hexaphosphate was strongly sorbed by all three soils and was relatively unaffected by the presence of other P sources. Decreased total P sorption due to desorption of Pi can be caused by relatively small additions of organic P, which may help explain vertical P movement in manured soils. Sorption isotherms performed using Pi alone did not accurately predict total P sorption in soils.     

Oxytetracycline sorption to organic matter by metal-bridging

The sorption of oxytetracycline to metal-loaded ion exchange resin and to natural organic matter by the formation of ternary complexes between polyvalent metal cations and sorbent- and sorbate ligand groups was investigated. Oxytetracycline (OTC) sorption to Ca- and Cu-loaded Chelex-100 resin increased with increasing metal/sorbate ratio at pH 7.6 (OTC speciation: 55% zwitterion, 45% anion). Greater sorption to Cu- than Ca-loaded resin was observed, consistent with the greater stability constants of Cu with both the resin sites and with OTC. Oxytetracycline sorption to organic matter was measured at pH 5.5 (OTC speciation: 1% cation, 98% zwitterion, 1% anion). No detectable sorption was measured for cellulose or lignin sorbents that contain few metal-complexing ligand groups. Sorption to Aldrich humic acid increased from "clean" < "dirty" (no cation exchange pretreatment) < Al-amended < Fe(III)-amended clean humic acid with K(d) values of 5500, 32000, 48000, and 250000 L kg(-1) C, respectively. Calcium amendments of clean humic acid suggested that a portion of the sorbed OTC was interacting by cation exchange. Oxytetracycline sorption coefficients for all humic acid sorbents were well-correlated with the total sorbed Al-plus-Fe(III) concentrations (r(2) = 0.87, log-log plot), suggesting that sorption by ternary complex formation with humic acid is important. Results of this research indicate that organic matter may be an important sorbent phase in soils and sediments for pharmaceutical compounds that can complex metals by the formation of ternary complexes between organic matter ligand groups and pharmaceutical ligand groups.     

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.     

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

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

Competitive mobilization of phosphate and arsenate associated with goethite by root activity

Arsenate (As V) is the predominant form of arsenic in soils under aerobic conditions and competes with the major plant nutrient phosphorus (P) in the form of phosphate (PV) not only for sorption sites on mineral surfaces in soil but also for root membrane transporters. Plants have evolved several mechanisms for the mobilization of PV in soils in response to P deficiency, such as the release of organic anions and protons. The aim of the present study was to test whether these mechanisms result in a simultaneous mobilization of arsenate and what would be the consequences for As transfer from soil to plant. The compartment system approach with Zea mays as model crop was chosen as an experimental setup. The system is equipped with micro suction cups and allowed us to investigate processes occurring in the vicinity of roots. As a case study, an artificial quartz substrate with well defined soil physical properties was fertilized, spiked with As V, and amended with increasing amounts of goethite (0, 1, and 4 g kg(-1) in treatments G-0, G-1, and G-4, respectively). The addition of goethite alleviated the As V-induced growth reduction and reduced As V transfer from the substrate to the plant but induced P deficiency at the same time. When low amounts of goethite (1 g kg(-1)) were added, plants mobilized PV but not As V, which might be related to differences in surface complexation reported for PV and As V. No mobilization of PV or As V was observed with the addition of higher amounts of goethite, probably because of decreasing competition between organic anions, PV, and As V for binding sites.     

Degree of phosphorus saturation thresholds in manure-amended soils of alberta

The risk of P losses from agricultural land to surface and ground water generally increases as the degree of soil P saturation increases. A single-point soil P sorption index (PSI) was validated with adsorption isotherm data for determination of the P sorption status of Alberta soils. Soil P thresholds (change points) were then examined for two agricultural soils after eight annual applications of different rates of cattle manure and for three agricultural soils after one application of different rates of cattle manure. Linear relationships were found between soil-test P (STP) levels up to 1000 mg kg(-1) and desorbed P in the five Alberta soils. Weak linear relationships were also found between STP and runoff dissolved reactive phosphorus (DRP) in three of these soils. Change points for the degree of P saturation (DPS) were detected in four of the five soils at 3 to 44% for water-extractable P (WEP) and at 11 to 51% for CaCl(2)-extractable P (CaCl(2)-P). Change points were not found for DPS or runoff DRP. Overall DPS thresholds for the five soils combined were 27% for WEP and 44% for CaCl(2)-P at a critical desorbable-P value of 1 mg L(-1). The corresponding STP levels (44 mg kg(-1) for WEP and 71 mg kg(-1) for CaCl(2)-P) are similar to agronomic thresholds for crops grown on Alberta soils. Soluble P losses in overland flow and leaching may be greater in soils with DPS values that exceed these thresholds than in soils with lower DPS values.     

Transport of phosphate through artificial macropores during film and pulse flow

Flow through artificial macropores may occur as a water film along the macropore walls (film flow) or as moving water segments separated by air bubbles (pulse flow). To investigate the effect of macropore flow pattern (i.e., film and pulse flow) on the interaction of solutes with macropore walls, we studied orthophosphate (P) transport and sorption in artificial macropores. The experimental setup consisted of a column (height = 20 cm, diameter = 20 cm) homogenously packed with glass beads and fitted at outflow with a vertical artificial macropore placed below the column. The artificial macropore consisted of ceramic tubes (3 or 8 mm i.d.; 31.5 cm long) coated on the inside with iron oxide serving as phosphate sorbents. An orthophosphate solution containing 0.04 mg P L(-1) was applied at a rate of 9 to 12 mm h(-1) to the column, eventually causing macropore flow. In the 8-mm-i.d. tubes only film flow occurred. Pulse flow was dominating in the 3-mm-i.d. tubes. Generally, the flow patterns were reproducible and seldom did pulse flow replaced film flow or vice versa. During film flow, a significantly larger decrease in macropore P concentration per tube was observed relative to that with pulse flow events. However, pulse and film flow lead to almost the same amounts of P sorbed per unit surface area when exposed to the same solute P concentration. Comparison with P sorption capacity experiments indicated that the sorption rate, rather than the sorption capacity, controls the amount of sorbed P during macropore flow in the studied system.