Second-order modeling of arsenite transport in soils

Rate limited processes including kinetic adsorption-desorption can greatly impact the fate and behavior of toxic arsenic compounds in heterogeneous soils. In this study, miscible displacement column experiments were carried out to investigate the extent of reactivity during transport of arsenite in soils. Arsenite breakthrough curves (BTCs) of Olivier and Windsor soils exhibited strong retardation with diffusive effluent fronts followed by slow release or tailing during leaching. Such behavior is indicative of the dominance of kinetic retention reactions for arsenite transport in the soil columns. Sharp decrease or increase in arsenite concentration in response to flow interruptions (stop-flow) further verified that non-equilibrium conditions are dominant. After some 40-60 pore volumes of continued leaching, 30-70% of the applied arsenite was retained by the soil in the columns. Furthermore, continued arsenite slow release for months was evident by the high levels of residual arsenite concentrations observed during leaching. In contrast, arsenite transport in a reference sand material exhibited no retention where complete mass recovery in the effluent solution was attained. A second-order model (SOM) which accounts for equilibrium, reversible, and irreversible retention mechanisms was utilized to describe arsenite transport results from the soil columns. Based on inverse and predictive modeling results, the SOM model successfully depicted arsenite BTCs from several soil columns. Based on inverse and predictive modeling results, a second-order model which accounts for kinetic reversible and irreversible reactions is recommended for describing arsenite transport in soils.     

Impact of sewage sludge spreading on nickel mobility in a calcareous soil: adsorption–desorption through column experiments

A soil column adsorption–desorption study was performed on an agricultural calcareous soil to determine the impact of sewage sludge spreading on nickel mobility. Ni adsorption experiments were followed by desorption tests involving the following liquid extractants: water, calcium (100 mg/L), oxalic acid (525 mg/L equivalent to 100 mg carbon/L), and sludge extracts (0.5 and 2.5 g/L). Desorption tests were also conducted after sewage sludge spreading at three application rates (30, 75, and 150 t/ha). According to the breakthrough curve, Ni adsorption was irreversible and occurred mainly through interactions with calcite surface sites. Nickel desorption from the soil column was promoted in presence of significant dissolved organic carbon (DOC) concentration as observed with oxalic acid elution and sludge extract at 2.5 g/L. In sludge-amended soil columns, the maximum Ni levels occurred in first pore volumes, and they were positively correlated to the sludge application rate. The presence of DOC in leaching waters was the main factor controlling Ni desorption from the sludge-amended soil columns. This finding implies that DOC generated by sludge applied on calcareous soils might facilitate the leaching of Ni due to the formation of soluble Ni–organic complexes. Thus, sludge application can have potential environmental impacts in calcareous soils, since it promotes nickel transport by decreasing Ni retention by soil components.     

Stability of titania nanoparticles in soil suspensions and transport in saturated homogeneous soil columns

The stability of TiO₂ nanoparticles in soil suspensions and their transport behavior through saturated homogeneous soil columns were studied. The results showed that TiO₂ could remain suspended in soil suspensions even after settling for 10 days. The suspended TiO₂ contents in soil suspensions after 24 h were positively correlated with the dissolved organic carbon and clay content of the soils, but were negatively correlated with ionic strength, pH and zeta potential. In soils containing soil particles of relatively large diameters and lower solution ionic strengths, a significant portion of the TiO₂ (18.8-83.0%) readily passed through the soils columns, while TiO₂ was significantly retained by soils with higher clay contents and salinity. TiO₂ aggregate sizes in the column outflow significantly increased after passing through the soil columns. The estimated transport distances of TiO₂ in some soils ranged from 41.3 to 370 cm, indicating potential environmental risk of TiO₂ nanoparticles to deep soil layers.     

Effects of pH and ionic strength on sulfamethoxazole and ciprofloxacin transport in saturated porous media

Many antibiotics regarded as emerging contaminants have been frequently detected in soils and groundwater; however, their transport behaviors in soils remain largely unknown. This study examined the transport of two antibiotics, sulfamethoxazole (SMZ) and ciprofloxacin (CIP), in saturated porous media. Laboratory columns packed with quartz sand was used to test the effects of solution pH and ionic strength (IS) on their retention and transport. The results showed that these two antibiotics behaved differently in the saturated sand columns. In general, SMZ manifested a much higher mobility than CIP for all experimental conditions tested. Almost all SMZ transported through the columns within one pore volume in deionized water (i.e., pH=5.6, IS=0), but no CIP was detected in the effluents under the same condition after extended column flushing. Perturbations in solution pH (5.6 and 9.5) and IS (0 and 0.1M) showed no effect on SMZ transport in the saturated columns. When pH increased to 9.5, however, ~93% of CIP was eluted from the sand columns. Increase of IS from 0 to 0.1M also slightly changed the distribution of adsorbed CIP within the sand column at pH 5.6, but still no CIP was detected in the effluents. A mathematical model based on advection-dispersion equation coupled with equilibrium and kinetic reactions successfully simulated the transport of the antibiotics in water-saturated porous media with R(2)=0.99.     

Effect of soil amendments on sorption and mobility of metribuzin in soils

Metribuzin (4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one), is weakly sorbed to soil therefore, leaches easily to lower soil profiles. Soil amendments play a significant role in the management of leaching losses of pesticides. Therefore, present study reports the effect of organic manure and fly ash amendments on metribuzin downward mobility in sandy loam soil columns. Application of animal manure [T-1(OM) and T-2(OM)] and fly ash [T-1(FA) and T-2(FA)] at 2.5% and 5.0% levels increased the metribuzin retention in the soil. Freundlich constant [K(f)(1/n)] values of metribuzin for treatments T-1(OM) and T-2(OM) were 0.70 and 1.11, respectively, which were significantly higher than the value (0.27) in natural soil (T-0). The respective values for treatments T-1(FA) and T-2(FA) were 1.80 and 4.61. Downward mobility of metribuzin was studied in packed soil columns [300 mm (l)x59 mm (i.d.)]. Both the amendments significantly reduced the downward mobility of metribuzin and affected breakthrough time and maximum concentration of metribuzin in the leachate. Leaching losses of metribuzin were decreased from 97% in natural soil (T-0) column to 64% [T-1(OM)] and 42% [T-2(OM)] for animal manure-amended columns and 26% [T-1(FA)] to 100% [T-2(FA)] for fly ash-amended columns, as metribuzin did not leach out of 5% fly ash-amended column. Study indicates that both animal manure and fly ash were quite effective in reducing the downward mobility of metribuzin in packed soil columns of a sandy loam soil.     

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag–Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag–PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72 h in freshwater (500–600 μg L⁻¹) and seawater (1300–1500 μg L⁻¹), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag⁺ (1.1, 400 and 0.11 μg L⁻¹, respectively), Ag–Cit (3.0, 2380 and 0.15 μg L⁻¹, respectively) and Ag–PVP (19.5, 3690 and 2.0 μg L⁻¹, respectively) varied widely, with toxicity in the order Ag⁺ > Ag–Cit > Ag–PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag⁺ or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.     

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lower fraction of equilibrium sorption sites.     

Experimental Zn(II) retention in a sandy loam soil by very small columns

The use of column experiments, usually performed to better approximate field conditions, may provide information that is not available from batch experiments. In such experiments heavy metals are often adsorbed until saturation followed by desorption experiments. When the affinity of the metal to soil is high, the retention factor (R) could be greater than thousands and the duration of experiments can become impractically long. In order to use reasonable laboratory time, the flow rate should be increased or the column size decreased. The increase in flow rate produces undesirable kinetic and dispersion effects, so we used very small soil columns (pore volume = 0.31–0.70 ml) and relatively high flow rates (0.03–0.12 ml min⁻¹) in studies of Zn(II) adsorption and retention in soils. Conservative tracer flow column experiments under saturation conditions were carried out to determine flow parameters for different flow rates. Column pore volume (V_p), Peclet numbers (Pe) and longitudinal dispersion coefficients (D_L) were determined from breakthrough curves. The effect of type of electrolyte and ionic strength on the Zn(II) retention onto soil was determined. The influence of flow rate and bed height on the retention coefficient and on the mass transfer zone was also studied. The effect of different influent Zn(II) concentrations on the R values obtained was analyzed. Freundlich parameters from column experiments were compared with batch ones. The leaching efficiency of different electrolytes, salts of weak organic acids and EDTA was also studied.     

Characterizing pesticide sorption and degradation in microscale biopurification systems using column displacement experiments

Biopurification systems treating pesticide contaminated water are very efficient, however they operate as a black box. Processes inside the system are not yet characterized. To optimize the performance, knowledge of degradation and retention processes needs to be generated. Therefore, displacement experiments were carried out for four pesticides (isoproturon, bentazone, metalaxyl, linuron) in columns containing different organic mixtures. Bromide, isoproturon and bentazone breakthrough curves (BTCs) were well described using the convection-dispersion equation (CDE) and a first-order degradation kinetic approach. Metalaxyl and linuron BTCs were well described using the CDE model expanded with Monod-type kinetics. Freundlich sorption, first-order degradation and Monod kinetics coefficients were fitted to the BTCs. Fitted values of the distribution coefficient K_f,column were much lower than those determined from batch experiments. Based on mobility, pesticides were ranked as: bentazone > metalaxyl - isoproturon > linuron. Based on degradability, pesticides were ranked as: linuron > metalaxyl - isoproturon > bentazone.     

Residence time effects on phase transformation of nanosilver in reduced soils

Residence time effects on phase transformation of silver nanoparticles (AgNPs) (15–50 nm, with and without polyvinylpyrrolidone (PVP) coating) were investigated in reducing soils using experimental geochemistry and synchrotron-based x-ray techniques. After 30 days of anaerobic incubation, a substantial fraction of PVP-coated AgNPs (15 nm) were transformed into Ag₂S and or humic acid (HA) complexed Ag(I), whereas only the HA fraction was dominant in uncoated AgNPs (50 nm). Several investigations recently reported that sulfidation of AgNPs to Ag₂S was the predominant mechanism controlling the fate of AgNP in soil–water environments. However, this investigation showed each AgNP underwent particle-specific chemical transformations to different end compounds after 30 days. Considering the small contribution of Ag(I) dissolution from all AgNPs (less than 5 %), we concluded that changes in solid-state chemical speciation of sorbed AgNPs was promoted by particle-specific interactions of NPs in soil chemical constituents, suggesting a critical role of soil absorbents in predicting the fate of AgNPs in terrestrial environments.     

Reduced downward mobility of metribuzin in fly ash-amended soils

Metribuzin, a triazine herbicide, is poorly sorbed in the soils, therefore leaches to lower soil profile. Fly ash amendment, which enhanced metribuzin sorption in soils, may play a significant role in reducing the downward mobility of herbicide. Therefore, the present study reports the effect of Inderprastha fly ash amendment on metribuzin leaching in three soil types. Fly ash was amended at 1, 2 and 5% levels in the upper 15 cm of 30 cm long packed soil columns. Results suggested a significant reduction in the leaching losses of metribuzin in fly ash-amended columns of all the three soil types and effect increased with increase in the level of fly ash. Even after percolating water equivalent to 362 mm rainfall no metribuzin was recovered in the leachate of 5% fly ash-amended columns. Fly ash application affected both metribuzin breakthrough time and its maximum concentration in the leachate. Further, it resulted in greater retention of metribuzin in the application zone and better effect was observed in the organic carbon poor soils.     

Persulfate oxidation of trichloroethylene with and without iron activation in porous media

In situ chemical oxidation with persulfate anion (S2O82*) is a viable technique for remediation of groundwater contaminants such as trichloroethylene (TCE). An accelerated reaction using S2O82* to destroy TCE can be achieved via chemical activation with ferrous ion to generate sulfate radicals (SO4*)(E degrees =2.6 V). The column study presented here simulates persulfate oxidation of TCE in porous media (glass beads and a sandy soil). Initial experiments were conducted to investigate persulfate transport in the absence of TCE in the column. The persulfate flushing exhibited a longer residence time and revealed a moderate persulfate interaction with soils. In TCE treatment experiments, the results indicate that the water or persulfate solution would push dissolved TCE from the column. Therefore, the effluent TCE concentration gradually increased to a maximum when about one pore volume was replaced with the flushing solution in the column. The presence of Fe2+ concentration within the column caused a quick drop in effluent TCE concentration and more TCE degradation was observed. When a TCE solution was flushing through the soil column, breakthrough of TCE concentration in the effluent was relatively slow. In contrast, when the soil column was flushed with a mixed solution of persulfate and TCE, persulfate appeared to preferentially oxidize soil oxidizable matter rather than TCE during transport. Hence, persulfate oxidation of soil organics may possibly reduce the interaction between TCE and soil (e.g., adsorption) and facilitate the transport of TCE through soil columns resulting in faster breakthrough.     

Transport of Escherichia coli through variably saturated sand columns and modeling approaches

A sand column leaching system with well-controlled suction and flow rate was built to investigate the effects on bacterial transport of air-water interface effects (AWI) correlated to water content, particle size, and column length. Adsorption of Escherichia coli strain D to silica sands was measured in batch tests. The average % adsorption for coarse and fine sands was 45.9+/-7.8% and 96.9+/-3.2%, respectively. However, results from static batch adsorption experiments have limited applicability to dynamic bacterial transport in columns. The early breakthrough of E. coli relative to bromide was clear for all columns, namely c. 0.15 to 0.3 pore volume earlier. Column length had no significant effects on the E. coli peak concentration or on total recovery in leachate, indicating retention in the top layer of sands. Tailing of breakthrough curves was more prominent for all fine sand columns than their coarse sand counterparts. Bacterial recovery in leachate from coarse and saturated sand columns was significantly higher than from fine and unsaturated columns. Observed data were fitted by the convection-dispersion model, amended for one-site and two-site adsorption to particles, and for air-water interface (AWI) adsorption. Among all models, the two-site+AWI model achieved consistently high model efficiency for all experiments. Thus it is evident from experimental and modeling results that AWI adsorption plays an important role in E. coli transport in sand columns.     

Ability of biosolids and a cationic surfactant to modify methidathion leaching. Modelling with pescol

Packed columns were prepared with an agricultural soil to examine the ability of two organic soil modifiers, biosolid and the cationic surfactant tetradecyl trimethyl ammonium bromide (TDTMA), to alter the leaching of the insecticide methidathion. Ion chloride was used as a tracer of water flow and the mathematical model PESCOL was selected to predict the mobility of the insecticide. The biosolid addition (SB column) delayed the breakthrough curves for methidathion with respect to the non-amended soil (S) column. The cationic surfactant TDTMA, alone or combined with the biosolid (SS and SBS) and previously incorporated in the soil column, caused the highest retardation of this pesticide in the soil columns. Theoretical retardation factors (TRf) were similar to the experimental Rf values for the S and SB columns, and predicted the high retention observed in the SBS and SS columns. The simulation with PESCOL predicted the experimental results.     

Determination of bromacil transport as a function of water and carbon content in soils

This study was conducted to determine the significance of bromacil transport as a function of water and carbon content in soils and to explore the implications of neglecting sorption when making assessments of travel time of bromacil through the vadose zone. Equilibrium batch sorption tests were performed for loamy sand and sandy soil added with four different levels of powdered activated carbon (PAC) content (0, 0.01, 0.05, and 0.1%). Column experiments were also conducted at various water and carbon contents under steady-state flow conditions. The first set of column experiments was conducted in loamy sand containing 1.5% organic carbon under three different water contents (0.23, 0.32, and 0.41) to measure breakthrough curves (BTCs) of bromide and bromacil injected as a square pulse. In the second set of column experiments, BTCs of bromide and bromacil injected as a front were measured in saturated sandy columns at the four different PAC levels given above. Column breakthrough data were analyzed with both equilibrium and nonequilibrium (two-site) convection-dispersion equation (CDE) models to determine transport and sorption parameters under various water and carbon contents. Analysis with batch data indicated that neglect of the partition-related term in the calculation of solute velocity may lead to erroneous estimation of travel time of bromacil, i.e. an overestimation of the solute velocity by a factor of R. The column experiments showed that arrival time of the bromacil peak was larger than that of the bromide peak in soils, indicating that transport of bromacil was retarded relative to bromide in the observed conditions. Extent of bromacil retardation (R) increased with decreasing water content and increasing PAC content, supporting the importance of retardation in the estimation of travel time of bromacil even at small amounts of organic carbon for soils with lower water content.     

Sorption and transport of trichloroethylene in caliche soil

Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co = 122-1300 mg L⁻¹) but Freundlich isotherm at the low concentration range (1-122 mg L⁻¹). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6 × 10⁻⁴ s⁻¹), then continued at a 100-fold slower rate (7.7 × 10⁻⁶ s⁻¹). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R = 1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r² = 0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co = 1300 mg L⁻¹). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L⁻¹), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.