Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

Solute movement through an allophanic soil

Allophanic soils are widespread around the world, but little research has been done on their transport properties. This study reveals the effect of two soil water potential heads and two water-flow regimes of continuous and intermittent flow on solute transport through undisturbed soil columns of Horotiu silt loam (Typic Hapludand), an allophanic soil. Two different methods--breakthrough curves (BTCs) and time domain reflectometry (TDR)--were employed to determine the extent of preferential solute transport in the topsoil. The TDR data were also used to look at the depth dependence of the transport properties. The convection-dispersion equation (CDE) with the appropriate boundary conditions adequately described the movement of both Br and Cl under the various flow conditions. Although no preferential flow was found under the imposed unsaturated flow conditions, the flow of water and transport of solute became more uniform with depth. The results show that both Br and Cl are retarded in this allophanic soil. Retardation values range from 1.5 to 1.9, and, as the TDR data showed, increase from the depth of 5.0 to 10.0 cm. Intermittent leaching results showed that there was no effect on solute concentrations in the leachate following no-flow periods. This suggests that water and solute transport in this soil were either relatively uniform or that transverse mixing during flow was already fast enough to eliminate concentration gradients between regions of different "mobility."     

Sorption and transport behavior of naphthalene in an aggregated soil

Soil solution chemistry influences the sorption and transport behavior of hydrophobic organic compounds (HOCs) in soil. We used both batch and column studies to investigate the influence of ionic strengths (0.03 and 1.5 M) and flow velocities (12 and 24 cm h-1) on sorption and transport of naphthalene (NAP) in aggregated soil. Sorption parameters such as the Freundlich coefficient (Kf) and exponent (n) calculated from batch studies and column experiments were also compared. Retardation of NAP transport was greater at higher solution ionic strength, which may be attributed to greater sorption affinity due to enhanced aggregation of the sorbent. The effect of ionic strength on sorption of NAP observed in the batch study was consistent with the results from the column study. The Kf and n values obtained from the batch study for the two ionic strengths ranged from 7.8 to 13.7 and 0.68 to 0.80, respectively, whereas the Kf and n values obtained from the column study ranged from 7.9 to 9.9 and 0.73 to 0.85, respectively. The effluent breakthrough curve (BTC) of NAP at a flow rate of 24 cm h-1 showed significant chemical and physical nonequilibrium behavior, implying that a considerable amount of sorption in aggregated soil was time dependent when flow was relatively fast. The BTCs calculated with the parameters determined from batch studies compared poorly with the measured BTCs. The potential for nonequilibrium transport should be incorporated in models used for predicting the fate and transport of HOCs. Furthermore, caution is required when extrapolating the results from batch studies, especially for aggregated soils.     

A transport model with coupled ternary exchange and chemisorption retention for hydrazinium cations

A numerical model was developed to describe the fate and transport of hydrazinium (N2H5+) and competing Ca2+ and H+ cations applied in acidic solutions to columns of Ca2+/H+-saturated sandy soil during steady saturated flow conditions. Instantaneous ternary H+-Ca2+-N2H5+ cation exchange using the Gaines-Thomas approach was combined with second-order, irreversible, kinetic chemisorption of exchange-phase N2H5+ ions as major retention mechanisms for N2H5+. Exchange-mediated chemisorption is assumed to occur as chemical binding of N2H5+ ions located on carboxyl-group exchange sites to nearby carbonyl groups, consequently decreasing the effective soil cation exchange capacity (CEC). Comparison of simulated and observed breakthrough curves (BTCs) for concentrations of N2H5+ and Ca2+ ions in column effluent was used in model evaluation. The cation transport model with cation exchange coupled with exchange-mediated chemisorption provided a valid first approximation for N2H5+ transport.     

Transport and biodegradation of perchlorate in soils

Perchlorate (ClO4-) contamination of ground water and surface water is a widespread problem, particularly in the western United States. This study examined the effect of biodegradation on perchlorate fate and transport in soils. Solute transport experiments were conducted on two surface soils. Pulses of solution containing perchlorate and Br- were applied to saturated soil columns at steady state water flow. Perchlorate behaved like a nonreactive tracer in Columbia loam (coarse-loamy, mixed, superactive, nonacid, thermic Oxyaquic Xerofluvent) but was degraded in Yolo loam (fine-silty, mixed, superactive, nonacid, thermic Mollic Xerofluvent). Batch experiments demonstrated that perchlorate removal from solution in Yolo loam was caused by biodegradation. Other batch experiments with Yolo loam surface and subsurface soils, Columbia loam surface soil, and dredge tailings demonstrated that perchlorate biodegradation required anaerobic conditions, an adequate carbon source, and an active perchlorate-degrading microbial population. The sequential reduction of perchlorate and NO3- by an indigenous soil microbial community in Yolo loam batch systems was also studied. Nitrate reduction occurred much sooner than perchlorate reduction in soils that had not been previously exposed to perchlorate, but NO3- and perchlorate were simultaneously reduced in soils previously exposed to perchlorate. The results of this study have implications for in situ remediation schemes and for agricultural soils that have been contaminated by perchlorate-tainted irrigation water.     

Distribution of phosphorus in manure slurry and its infiltration after application to soils

Computer models help identify agricultural areas where P transport potential is high, but commonly used models do not simulate surface application of manures and P transport from manures to runoff. As part of an effort to model such P transport, we conducted manure slurry separation and soil infiltration experiments to determine how much slurry P infiltrates into soil after application but before rain, thus becoming less available to runoff. We applied dairy and swine slurry to soil columns and after both 24 and 96 h analyzed solids remaining on the soil surface for dry matter, total phosphorus (TP), and water-extractable inorganic (WEIP) and organic (WEOP) phosphorus. We analyzed underlying soils for Mehlich-3 and water-extractable P. We also conducted slurry separation experiments by sieving, centrifuging, and suction-filtering to determine which method could easily estimate slurry P infiltration into soils. About 20% of slurry solids and 40 to 65% of slurry TP and WEIP infiltrated into soil after application, rendering this P less available to transport in runoff. Slurry separation by suction-filtering through a screen with 0.75-mm-diameter openings was the best method to estimate this slurry P infiltration. Measured quantities of manure WEOP changed too much during experiments to estimate WEOP infiltration into soil or what separation method can approximate infiltration. Applying slurries to soils always increased soil P in the top 0 to 1 cm of soil, frequently in the 1- to 2-cm depth of soil, but rarely below 2 cm. Future research should use soils with coarser texture or large macropores, and slurry with low dry matter content (1-2%).     

Colloid mobilization and arsenite transport in soil columns: effect of ionic strength

Colloid generation and transport in soils is of significance because of suspected colloid-facilitated transport of contaminants to the groundwater. In this study, colloid mobilization and its effect on the transport of arsenite [As(III)] were investigated in Olivier (fine-silty, mixed, active, thermic Aquic Fraglossudalfs) and Windsor (mixed, mesic typic Udipsamments) soil columns. Input solution of 10 mg L(-1) As(III) in 0.01 M NaCl was applied to water-saturated columns, and followed by leaching with deionized water (DIW). Flow interruptions were performed during the As(III) input and DIW leaching phases. Turbidity, electrical conductivity (EC), and pH of column effluents were monitored with time. Total and dissolved concentrations of As, Fe, and Al were analyzed. Effluent results demonstrated that colloid-facilitated transport contributed little to arsenic movement when the solution ionic strength was maintained constant. Mobilization of colloidal amorphous material and enhanced transport of As(III) were observed as a result of changes in ionic strength of the input solution. The peak of colloid generation coincided with peak concentrations of Fe, suggesting mobilization of Fe oxides and facilitated transport of As(III) adsorbed on oxide surfaces. Colloid mobilization was enhanced due to flow interruption in the Olivier column, which suggests slow dissociation of aggregated colloidal particles. Moreover, effluent results indicate significant effect of organic matter in stabilizing aggregates of colloidal particles.     

Transport of Escherichia coli in sand columns with constant and changing water contents

Understanding how changes in volumetric water content (theta) affect bacterial adsorption could help reduce transport of pathogenic and indicator bacteria that may be present in infiltrating wastewater. Three flow regimes that simulated infiltration from a household septic system were evaluated: saturated, unsaturated with a constant volumetric water content theta (constant unsaturated flow), and unsaturated with cyclic changes in theta (variable unsaturated flow). Escherichia coli was suspended in artificial sewage (AS) and applied as step inputs to sand columns, with regular interruptions in input for variable unsaturated flow. A transport model was fit to the saturated and constant unsaturated flow breakthrough curves to determine retardation (R), the first-order filtration coefficient (mu), and the maximum outflow relative concentration (Cmax). The total cells transported as a fraction of input (tau) in all three flow regimes was calculated. Constant unsaturated flow resulted in a significantly lower Cmax (0.633) in comparison with saturated flow (0.803, P < or = 0.05), although unsaturated mu (0.0693 h(-1)) was not significantly different from saturated mu (0.0259 h(-1)). Constant unsaturated flow also resulted in a significantly smaller tau (0.617) than saturated (0.806) or variable unsaturated flow (0.734). In variable unsaturated flow, cell concentrations were out of phase with theta--as the column drained, cell concentrations in the outflow increased; and when a pulse of suspension was applied, cell concentrations decreased. Constant unsaturated flow is probably the best for removal of pathogenic bacteria because this regime resulted in lower maximum concentrations of E. coli and greater cell removal, in comparison with saturated and variable unsaturated flow.     

Transport of di(2-ethylhexyl)phthalate (DEHP) applied with sewage sludge to undisturbed and repacked soil columns

Municipal sewage sludge is often used on arable soils as a source of nitrogen and phosphorus, but it also contains organic contaminants that may be leached to the ground water. Di(2-ethylhexyl)phthalate (DEHP) is a priority pollutant that is present in sewage sludge in ubiquitous amounts. Column experiments were performed on undisturbed soil cores (20-cm depth x 20-cm diameter) with three different soil types: a sand, a loamy sand, and a sandy loam soil. Dewatered sewage sludge was spiked with 14C-labeled DEHP (60 mg kg(-1)) and bromide (5 g kg(-1)). Sludge was applied to the soil columns either as five aggregates, or homogeneously mixed with the surface layer. Also, two leaching experiments were performed with repacked soil columns (loamy sand and sandy loam soil). The DEHP concentrations in the effluent did not exceed 1.0 microg L(-1), and after 200 mm of outflow less than 0.5% of the applied amount was recovered in the leachate in all soils but the sandy loam soil with homogeneous sludge application (up to 3.4% of the applied amount recovered). In the absence of macropore flow, DEHP in the leachate was primarily sorbed to mobilized dissolved organic macromolecules (DOM, 30.3 to 81.3%), while 2.4 to 23.6% was sorbed to mobilized mineral particles. When macropore flow occurred, this changed to 16.5 to 37.4% (DOM) and 36.9 to 40.6% (mineral particles), respectively. The critical combination for leaching of considerable amounts of DEHP was homogeneous sludge application and a continuous macropore structure.     

Turfgrass thatch effects on pesticide leaching: a laboratory and modeling study

Process-based models are frequently used to assess the water quality impacts of turfgrass management emanating from proposed or existing golf courses. Thatch complicates the prediction of pesticide transport because surface-applied pesticides must pass through an organic-rich layer before entering the soil. This study was conducted to (i) compare the use of a linear equilibrium model (LEM) and two-site nonequilibrium (2SNE) model to predict pesticide transport through soil and thatch + soil columns, and (ii) evaluate thatch effects on pesticide transport through soil columns with a volume-averaging approach. Pesticide breakthrough curves were obtained for soil and thatch + soil columns from a 1 cm h(-1) flux applied one day after applying triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) and carbaryl (1-napthyl-methyl carbamate). Pesticide and bromide transport parameters indicated that nonequilibrium processes were affecting pesticide transport. Columns containing zoysiagrass (Zoysia japonica Steud.) thatch had lower triclopyr and carbaryl leaching losses than did soil-only columns, although total reductions attributable to thatch did not exceed 15% of the applied pesticide. When laboratory-based retardation factors were used, the 2SNE model explained 88 to 93% of the variability for triclopyr and 70 to 94% of the variability for carbaryl. Laboratory-based retardation factors performed well in a 2SNE model to predict the peak concentration and tailing behavior of triclopyr and carbaryl with a volume-averaging approach. These results suggest that separate representation of the thatch layer in process-based models is not a prerequisite to obtain reasonable estimates of pesticide transport under steady state flow conditions.     

TRANSPORT AND FATE OF ATRAZINE IN MIDWESTERN RIPARIAN BUFFER STRIPS1

ABSTRACT: The fate of pesticides entering the Riparian Buffer Strips (RBS) has not been well documented. This study compared the transport and fate of atrazine in soil of three‐, five‐, and nine‐year‐old switchgrass (Panicum virgatum L.) RBS to that in adjacent soils cropped to a corn‐soybean rotation or a grass‐alfalfa pasture. Undisturbed soil columns were collected from the RBS and cropped areas within the Bear Creek watershed, near Roland, Iowa. Atrazine and bromide breakthrough curves obtained using intact soil columns under saturated conditions were described by a two‐region, mobile‐immobile transport model. Preferential flow of bromide and atrazine was evident in five‐and nine‐year‐old RBS soil, but there was little difference in transport characteristics between these two RBS soils and the adjacent cropped soils. There was a trend towards an increase in dispersion coefficients between the five‐and nine‐year‐old RBS sites, which suggests an increased degree of preferential flow with increasing RBS age. Despite similar texture and organic C contents, atrazine sorption was significantly greater in RBS soil than the adjacent cropped soil. Cropped soil degraded atrazine faster than the RBS soil. The rapid degradation of atrazine in the corn‐soybean soil adjacent to the five‐year‐old RBS (atrazine half‐life of 19 days) appeared to be due to a larger population of atrazine‐degrading microorganisms. Atrazine‐degrading microorganisms in the corn‐soybean soil were 50,940 cells g^‐1 soil compared with 2,970 cells g^‐4 soil in 5‐year‐old RBS soil which resulted in 60 percent mineralization of [¹⁴C‐UL‐atrazine] in the corn‐soybean soil.     

Bromide and nitrate movement through undisturbed soil columns

Field experiments often assume that Br-, 14NO3(-)-N, and 15NO3(-)-N have similar leaching kinetics. This study tested this assumption. Twenty-four undisturbed soil columns (15-cm diameter) were collected from summit-shoulder, backslope, and footslope positions of a no-tillage field with a corn (Zea mays L.)-soybean [Glycine max (L.) Merr.] rotation. Each of the landscape positions had a different soil series. After conditioning the columns with 4 L of 0.01 M CaCl2 (2 pore volumes), 15N-labeled Ca(NO3)2 and KBr were applied to the soil surface and leached with 4 L of 0.01 M CaCl2. Leachate was collected, weighed, and analyzed for NO3(-)-N, NH4(+)-N, 15N, 14N, and Br-. The total amount of 15NO3(-)-N and 14NO3(-)-N collected in 1000, 2000, and 3000 mL of leachate was similar. These data suggest that 15N discrimination during leaching did not occur. Bromide leached faster through the columns than NO3(-)-N. The more rapid transport of Br- than NO3(-)-N was attributed to lower Br- (0.002 +/- 0.036 mg kg(-1)) than NO3(-)-N (0.17 +/- 0.03 mg kg(-1)) sorption. Results from this study suggest that (i) if Br- is used to estimate NO3(-)-N leaching loss, then NO3(-)-N leaching losses may be overestimated by 25%; (ii) the potential exists for landscape position to influence anion retention and movement in soil; and (iii) 15N discrimination was not detected during the leaching process.     

Developing risk models of Cryptosporidium transport in soils from vegetated, tilted soilbox experiments

Transport of Cryptosporidium parvum through macroporous soils is poorly understood yet critical for assessing the risk of groundwater contamination. We developed a conceptual model of the physics of flow and transport in packed, tilted, and vegetated soilboxes during and immediately after a simulated rainfall event and applied it to 54 experiments implemented with different soils, slopes, and rainfall rates. Using a parsimonious inverse modeling procedure, we show that a significant amount of subsurface outflow from the soilboxes is due to macropore flow. The effective hydraulic properties of the macropore space were obtained by calibration of a simple two-domain flow and transport model that accounts for coupled flow in the matrix and in the macropores of the soils. Using linear mixed-effects analysis, macropore hydraulic properties and oocyst attenuation were shown to be associated with soil bulk density and rainfall rate. Macropore flow was shown to be responsible for bromide and C. parvum transport through the soil into the underlying pore space observed during the 4-h experiments. We confirmed this finding by conducting a pair of saturated soil column studies under homogeneously repacked conditions with no macropores in which no C. parvum transport was observed in the effluent. The linear mixed-effects and logistic regression models developed from the soilbox experiments provide a basis for estimating macropore hydraulic properties and the risk of C. parvum transport through shallow soils from bulk density, precipitation, and total shallow subsurface flow rate. The risk assessment is consistent with the reported occurrence of oocysts in springs or groundwater from fractured or karstic rocks protected only by shallow overlying soils.     

Transport and retention of fullerene nanoparticles in natural soils

Commercial production and use of fullerene (C60) nanomaterials will inevitably lead to their release into the environment, where knowledge of C60 fate and transport is limited. In this study, a series of one-dimensional column experiments was conducted to assess the transport and retention of nanoscale fullerene aggregates (nC60) in water-saturated soils. Under the experimental conditions, complete retention of nC60 was observed in columns (2.5 cm inside diameter x 11 cm length) packed with Appling or Webster soil, which contain 0.75 and 3.33% organic carbon by weight, respectively. When the volume of aqueous nC60 suspension (approximately 4.5 mg L(-1)) applied to Appling soil was increased from 5 to 65 pore volumes, the travel distance increased from 3 to 8 cm, and the retention capacity approached a limiting value of 130 microg g(-1), although nC60 was not detected in the column effluent. The addition of 20 mg C L(-1) Suwannee River humic acid to the influent suspension increased the nC60 transport in Appling soil but did not resul in breakthrough. Attempts to simulate the experimental data using clean-bed filtration theory were not satisfactory, yielding retention profiles that failed to match observed data. Subsequent incorporation of a limiting retention capacity expression into the mathematical model resulted in accurate predictions of the measured nC60 retention profiles and transport behavior. The sizable retention capacities observed in this study suggest that transport of nC60 is limited in relatively fine-textured soils containing appreciable amounts of clay minerals and organic matter, with substantial accumulation of nC60 aggregates near the point of release.     

Dissolution of trace element contaminants from two coastal plain soils as affected by pH

Trace element mobility in soils depends on contaminant concentration, chemical speciation, water movement, and soil matrix properties such as mineralogy, pH, and redox potential. Our objective was to characterize trace element dissolution in response to acidification of soil samples from two abandoned incinerators in the North Carolina Coastal Plain. Trace element concentrations in 11 soil samples from both sites ranged from 2 to 46 mg Cu kg(-1), 3 to 105 mg Pb kg(-1), 1 to 102 mg Zn kg(-1), 3 to 11 mg Cr kg(-1), < 0.1 to 10 mg As kg(-1), and < 0.01 to 0.9 mg Cd kg(-1). Acidified CaCl2 solutions were passed through soil columns to bring the effluent solution to approximately pH 4 during a 280-h flow period. Maximum concentrations of dissolved Cu, Pb, and Zn at the lowest pH of an experiment (pH 3.8-4.1) were 0.32 mg Cu L(-1), 0.11 mg Pb L(-1), and 1.3 mg Zn L(-1) for samples from the site with well-drained soils, and 0.25 mg Cu L(-1), 1.2 mg Pb L(-1), and 1.4 mg Zn L(-1) for samples from the site with more poorly drained soils. Dissolved Cu concentration at pH 4 increased linearly with increasing soil Cu concentration, but no such relationship was found for Zn. Dissolved concentrations of other trace elements were below our analytical detection limits. Synchrotron X-ray absorption near edge structure (XANES) spectroscopy showed that Cr and As were in their less mobile Cr(III) and As(V) oxidation states. XANES analysis of Cu and Zn on selected samples indicated an association of Cu(II) with soil organic matter and Zn(II) with Al- and Fe-oxides or franklinite.     

Aging effects on the sorption-desorption characteristics of anthropogenic organic compounds in soil

Field studies have demonstrated that prolonged pesticide-soil contact times (aging) may lead to unexpected persistence of these compounds in the environment. Although this phenomenon is well documented in the field, there have been very few controlled laboratory studies that have tested the effects of long-term aging and the role of differing sorbates on contaminant sorption-desorption behavior and fate in soils. This study examines the sorption-desorption behavior of chlorobenzene, ethylene dibromide (1,2-dibromomethane), atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), and 2, 4-D (2,4-dichlorophenoxyacetic acid) on one soil type after 1 d, 30 d, and 14 mo of aging. Sorption isotherms were evaluated after each aging period to observe changes in the uptake of each compound by soil. Desorption kinetic data were generated after each aging period to observe changes in release from soil, and desorption parameters were evaluated using a three-site desorption model that includes equilibrium, nonequilibrium, and nondesorption sites. The data indicate no statistically significant increase in sorption for ethylene dibromide or chlorobenzene from 1 to 30 d, although sorption of 2,4-D increased slightly, and sorption of atrazine decreased slightly. Statistically significant increases in linear sorption coefficients (Kd), from 1 d to 14 mo of aging, were apparent for ethylene dibromide and 2,4-D. The Kd values for chlorobenzene, measured after 1 d, 30 d, and 14 mo of aging, were statistically indistinguishable. Aging affected the distribution of chemicals within sorption sites. With aging, the desorbable fraction decreased and the nondesorbable fraction, which was apparent after only 1 d of pesticide-soil contact, increased for all chemicals studied.     

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.     

Adsorption and transport of arsenic(V) in experimental subsurface systems

The adsorption and transport of As(V) in a heterogeneous, iron oxide-containing soil was investigated in batch and column laboratory experiments. The As(V) adsorbed rapidly to the soil over the first 48 h, but continued to adsorb slowly over the next several weeks, clearly indicating the potential for rate-limited transport. The equilibrium As(V) adsorption isotherm was markedly nonlinear, further indicating the potential for nonideal transport. A model developed for the adsorption of As(V) to hydrous ferric oxide (HFO) was able to predict the pH-dependent adsorption of As(V) to the soil in batch experiments within 0.116 to 0.726 root mean square error (RMSE). Arsenic(V) was significantly retarded in column transport experiments. The column transport experiments were modeled using the one-dimensional advection-dispersion equation, considering both linear and nonlinear adsorption equilibrium. Although the nonlinear local equilibrium model (NLLE, RMSE = 0.273) predicted the data better than the linear local equilibrium model (LLE, RMSE = 0.317), As(V) breakthrough occurred more rapidly than predicted by either model due to adsorption nonequilibrium. However, due to the presence of an irreversible or slowly desorbing fraction, the peak aqueous As(V) concentration (0.624 mg L(-1)) and the total amount of As(V) recovered (44%) was lower than predicted based on the two equilibrium models (NLLE and LLE). For the conditions used in this study [1 mg L(-1) As(V), pH 4.5 and 9,0-0.25 mM PO4, 0.53-1.6 cm min(-1) pore water velocity], the effect on As(V) mobility and recovery increased in the order pH < pore water velocity < PO4.