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.     

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.     

Effect of biochar amendment on tylosin adsorption-desorption and transport in two different soils

The role of biochar as a soil amendment on the adsorption-desorption and transport of tylosin, a macrolide class of veterinary antibiotic, is little known. In this study, batch and column experiments were conducted to investigate the adsorption kinetics and transport of tylosin in forest and agricultural corn field soils amended with hardwood and softwood biochars. Tylosin adsorption was rapid at initial stages, followed by slow and continued adsorption. Amounts of adsorption increased as the biochar amendment rate increased from 1 to 10%. For soils with the hardwood biochar, tylosin adsorption was 10 to 18% higher than that when using the softwood biochar. Adsorption kinetics was well described by Elovich equation ( ≥ 0.921). As the percent of biochar was increased, the rates of initial reactions were generally increased, as indicated by increasing α value at low initial tylosin concentration, whereas the rates during extended reaction times were generally increased, as indicated by decreasing β value at high initial tylosin concentration. A considerably higher amount of tylosin remained after desorption in the corn field soil than in the forest soil regardless of the rate of biochar amendment, which was attributed to the high pH and silt content of the former. The breakthrough curves of tylosin showed that the two soils with biochar amendment had much greater retardation than those of soils without biochar. The CXTFIT model for the miscible displacement column study described well the peak arrival time as well as the maximum concentration of tylosin breakthrough curves but showed some underestimation at advanced stages of tylosin leaching, especially in the corn field soil. Overall, the results indicate that biochar amendments enhance the retention and reduce the transport of tylosin in soils.     

Sorption, mobility, and transformation of estrogenic hormones in natural soil

Potent estrogenic hormones are consistently detected in the environment at low concentration, yet these chemicals are strongly sorbed to soil and are labile. The objective of this research was to improve the understanding of the processes of sorption, mobility, and transformation for estrogens in natural soils, and their interaction. Equilibrium and kinetic batch sorption experiments, and a long-term column study were used to study the fate and transport of 17beta-estradiol and its primary metabolite, estrone, in natural soil. Kinetic and equilibrium batch experiments were done using radiolabeled 17beta-estradiol and estrone. At the concentrations used, it appeared that equilibrium sorption for both estrogens was achieved between 5 and 24 h, and that the equilibrium sorption isotherms were linear. The log K(oc) values for 17beta-estradiol (2.94) and estrone (2.99) were consistent with previously reported values. Additionally, it was found that there was rate-limited sorption for both 17beta-estradiol (0.178 h(-1)) and estrone (0.210 h(-1)). An approximately 42 h long, steady-flow, saturated column experiment was used to study the transport of radiolabeled 17beta-estradiol, which was applied in a 5.00 mg L(-1) solution pulse for 44 pore volumes. 17beta-estradiol and estrone were the predominant compounds detected in the effluent. The effluent breakthrough curves were asymmetric and the transport modeling indicated that sorption was rate-limited. Sorption rates and distributions of the estrogens were in agreement between column and batch experiments. This research can provide a better link between the laboratory results and observations in the natural environment.     

Sorption and transport of 17beta-estradiol and testosterone in undisturbed soil columns

Land-applied domestic animal wastes contain appreciable amounts of 17beta-estradiol (henceforth, estradiol) and testosterone. These sex hormones may be transported through soil to groundwater and streams, where they may adversely affect the environment. Previous column transport studies with these hormones used repacked soil and did not consider preferential flow. We, therefore, determined the sorption and transport characteristics of estradiol and testosterone in undisturbed soil columns (15-cm i.d. by 32-cm height). In the sorption experiment, isotherms for estradiol and testosterone were nonlinear with Freundlich exponents (n) less than one. Sorption of both hormones decreased with soil depth, and estradiol sorbed more strongly than testosterone. Average estradiol Freundlich sorption coefficients (K(f)) values were 36.9 microg(1 - n) mL(n) g(-1) for the 0- to 10-cm soil depth and 25.7 microg(1 - n) mL(n) g(-1) for the 20- to 30-cm soil depth. Average testosterone K(f) values were 26.7 microg(1 - n) mL(n) g(-1) for the 0- to 10-cm soil depth and 14.0 microg(1 - n) mL(n) g(-1) for the 20- to 30-cm soil depth. In the transport experiment, 27% of the estradiol and 42% of the testosterone leached through the soil columns. Approximately 50% of the remaining soil-bound hormones were sorbed in the top 10 cm of soil. In almost all instances, breakthrough concentrations of estradiol, testosterone, and a chloride tracer peaked simultaneously. Simultaneous breakthrough and HYDRUS-1D transport parameters indicated both chemical and physical nonequilibrium processes affected hormone transport. This suggests hormones placed on soil surfaces may contaminate groundwater under conditions of preferential flow.     

Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5.     

Dissolution and transport of TNT, RDX, and composition B in saturated soil columns

Low-order detonations and blow-in-place procedures on military training ranges can result in residual solid explosive formulations to serve as distributed point sources for ground water contamination. This study was conducted to determine if distribution coefficients from batch studies and transport parameters of pure compounds in solution adequately describe explosive transport where compounds are present as solid particles in formulations. Saturated column transport experiments were conducted with 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and the explosive formulation, Composition B (Comp B) (59.5 +/- 2.0% RDX, 39.5 +/- 2.3% TNT, and 1% wax) in solid and dissolved forms. The two soils used were Plymouth loamy sand (mesic, coated Typic Quartzipsamments) from Camp Edwards, MA and Adler silt loam (coarse-silty, mixed, superactive, thermic Fluvaquentic Eutrudepts) from Vicksburg, MS. Interrupted flow experiments were used to determine if explosives were at equilibrium distribution between soil and solution phases. The HYDRUS-1D code was used to determine fate and transport parameters. Results indicated that sorption of high explosives was rate limited. The behavior of dissolved Comp B was similar to the behavior of pure TNT and RDX. Behavior of solid Comp B was controlled by dissolution that depended on physical properties of the Comp B sample. Adsorption coefficients determined by HYDRUS-1D were different from those determined in batch tests for the same soils. Use of parameters specific to formulations will improve fate and transport predictions.     

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.     

Sorption and degradation of alachlor and metolachlor in ground water using green sands

Reactive barriers are used for in situ treatment of contaminated ground water. Waste green sand, a by-product of gray-iron foundries that contains iron particles and organic carbon, was evaluated in this study as a low-cost reactive material for treating ground water contaminated with the herbicides alachlor [2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide] and metolachlor [2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o-acetoluidide]. Batch and column tests were conducted with 11 green sands to determine transport parameters and reaction rate constants for the herbicides. Similar Fe-normalized rate constants (K(SA)) were obtained from the batch and column tests. The K(SA) values obtained for green sand iron were also found to be comparable with or slightly higher than K(SA) values for Peerless iron, a common reactive medium used in reactive barriers. Partition coefficients ranging between 3.6 and 50.2 L/kg were obtained for alachlor and between 1.0 and 54.8 L/kg for metolachlor, indicating that the organic carbon and clay in green sands can significantly retard the movement of the herbicides. Partition coefficients obtained from the batch and column tests were similar (+/-25%), but the batch tests typically yielded higher partition coefficients for green sands exhibiting greater sorption. Calculations made using transport parameters from the column tests indicate that a 1-m-thick reactive barrier will result in a 10-fold reduction in concentration of alachlor and metolachlor for seepage velocities less than 0.1 m/d provided the green sand contains at least 2% iron. This level of reduction generally is sufficient to reduce alachlor and metolachlor concentrations below maximum contaminant levels in the United States.     

Sorption kinetics and equilibria of organic pesticides in carbonatic soils from South Florida

A batch reactor was used to determine sorption kinetic parameters (k2, F, and K*) and the equilibrium sorption coefficient (K). The two-site nonequilibrium (TSNE) batch sorption kinetics model was used to calculate the kinetic parameters. Two probe organic pesticides, atrazine [2-chloro-4-ethylamino-6-isopropylamino-s-triazine] and diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were studied using three carbonatic soils from South Florida (Chekika, Perrine, and Krome), one noncarbonatic soil from Iowa (Webster), and one organic soil (Lauderhill) from South Florida. Carbonatic soils contained more than 600 g kg(-1) CaCO3. Sorption is initially very fast up to 3 h and then slowly reaches equilibrium. All soil-chemical combinations reached sorption equilibrium after about 24 h and all sorption isotherms were linear. The sorption kinetics data were well described by the TSNE model for all soil-chemical combinations except for the marl soil data (Perrine-Atrazine), which were better described by the one-site nonequilibrium (OSNE) model. Diuron, with higher K, undergoes slower sorption kinetics than atrazine. The Lauderhill soil containing organic carbon (OC) of 450 g kg(-1) exhibited slowest sorption kinetics for both pesticides. An inverse relationship between k3 and K was observed for atrazine and diuron separately in Chekika, Webster, and Lauderhill soils but not in Perrine and Krome soils. The sorption kinetic parameters were used to distinguish the sorption behavior between atrazine and diuron and to identify differences between soils. Normalizing the sorption coefficient (K) to OC showed that atrazine and diuron had K oc values in carbonatic soils that were a third of reported literature values for noncarbonatic soils. Using existing literature K oc values in solute transport models will most likely underestimate the mobility of atrazine, diuron, and other neutral organic chemicals in carbonatic soils.     

Transport of sulfadiazine in undisturbed soil columns: effects of flow rate, input concentration and pulse duration

Antibiotics reach soils via spreading of manure or sewage sludge. Knowledge on the transport behavior of antibiotics in soils is needed to assess their environmental fate. The effect of flow rate and applied mass, i.e., input concentration and pulse duration, on the transport of 14C-sulfadiazine (SDZ; 4-aminoN-pyrimidin-2-yl-benzenesulfonamide) was investigated with soil column experiments and numerical studies. Sulfadiazine was applied in pulses (6.8, 68 or 306 h) under steady-state (0.051 and 0.21 cm h(-1)) and intermittent flow conditions and at two input concentrations (0.57 and 5.7 mg L(-1)). Breakthrough curves (BTCs) of 14C were measured and for one experiment concentrations of SDZ, and its transformation products 4-(2-iminopyrimidin-1(2H)-yl)aniline (An-SDZ) and N(1)-2-(4-hydroxypyrimidinyl)benzenesulfanilamide (4-OH-SDZ) were determined. After finalizing the leaching experiments, 14C was quantified in different slices of the columns. A lower flow rate led to remarkably lower eluted masses compared with the higher flow rates. All BTCs could be described well using a three-site attachment-detachment model for which a common set of parameters was determined. However, the BTC obtained with the high input concentration was slightly better described with a two-site isotherm-based model. The prediction of the concentration profiles was good with both model concepts. The fitted sorption capacities decreased in the order SDZ > 4-OH-SDZ > An-SDZ. Overall, the experiments reveal the presence of similar mechanisms characterizing SDZ transport. The dependence of model performance on concentration implies that although the three-site attachment-detachment model is appropriate to predict the transport of SDZ in soil columns, not all relevant processes are adequately captured.     

Aging effects on cadmium transport in undisturbed contaminated sandy soil columns

Limited information is available on the effects of contaminant aging (i.e., the contact time of Cd with the soil) on Cd transport in soils. We conducted displacement experiments in which indigenous Cd and freshly applied Cd were leached simultaneously from undisturbed samples of three Spodosol horizons. Sorption of Cd was described using Freundlich isotherms, whereas transport was described as a convection-dispersion process. Parameter optimization analysis using a mobile-immobile transport model applied to nonsorbing tracer displacement data showed that 16 to 22% of the water in the columns was immobile. The low dimensionless mass transfer coefficients in the mobile-immobile model were indicative of diffusion-limited transfer between mobile and immobile water, and hence physical nonequilibrium. A two-site kinetic sorption model could be fitted closely to breakthrough curves of the non-aged Cd for three soil horizons. No conclusive evidence was found that contaminant aging in soil affects cadmium transport. On the one hand, predictions of aged Cd leaching, using parameters estimated from displacement experiments with nonaged Cd, differed from those for the aged Cd in the E horizon. On the other hand, no meaningful differences in transport behavior between aged and non-aged Cd were found for the humus Bh and Bh/C horizons. The two-site kinetic rate coefficient alphac was found to depend on water flux, further indicating that mass transfer between sorption sites and the liquid is limited by diffusion rather than by kinetic sorption.     

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.     

Enhanced biogeochemical cycling and subsequent reduction of hydraulic conductivity associated with soil-layer interfaces in the vadose zone

Biogeochemical dynamics in the vadose zone are poorly understood due to the transient nature of chemical and hydrologic conditions but are nonetheless critical to understanding chemical fate and transport. This study explored the effects of a soil layer on linked geochemical, hydrological, and microbiological processes. Three laboratory soil columns were constructed: a homogenized medium-grained sand, a homogenized organic-rich loam, and a sand-over-loam layered column. Upward and downward infiltration of water was evaluated during experiments to simulate rising water table and rainfall events, respectively. In situ collocated probes measured soil water content, matric potential, and Eh. Water samples collected from the same locations were analyzed for Br, Cl, NO, SO, NH, Fe, and total sulfide. Compared with homogeneous columns, the presence of a soil layer altered the biogeochemistry and water flow of the system considerably. Enhanced biogeochemical cycling was observed in the layered column over the texturally homogeneous soil columns. Enumerations of iron- and sulfate-reducing bacteria showed 1 to 2 orders of magnitude greater community numbers in the layered column. Mineral and soil aggregate composites were most abundant near the soil-layer interface, the presence of which likely contributed to an observed order-of-magnitude decrease in hydraulic conductivity. These findings show that quantifying coupled hydrologic-biogeochemical processes occurring at small-scale soil interfaces is critical to accurately describing and predicting chemical changes at the larger system scale. These findings also provide justification for considering soil layering in contaminant fate and transport models because of its potential to increase biodegradation or to slow the rate of transport of contaminants.     

The influence of nitrate on selenium in irrigated agricultural groundwater systems

Selenium (Se) contamination of groundwater is an environmental concern especially in areas where aquifer systems are underlain by Se-bearing geologic formations such as marine shale. This study examined the influence of nitrate (NO?) on Se species in irrigated soil and groundwater systems and presents results from field and laboratory studies that further clarify this influence. Inhibition of selenate (SeO?) reduction in the presence of NO? and the oxidation of reduced Se from shale by autotrophic denitrification were investigated. Groundwater sampling from piezometers near an alluvium-shale interface suggests that SeO? present in the groundwater was due in part to autotrophic denitrification. Laboratory shale oxidation batch studies indicate that autotrophic denitrification is a major driver in the release of SeO? and sulfate. Similar findings occurred for a shale oxidation flow-through column study, with 70 and 31% more reduced Se and S mass, respectively, removed from the shale material in the presence of NO? than in its absence. A final laboratory flow-through column test was performed with shallow soil samples to assess the inhibition of SeO? reduction in the presence of NO?, with results suggesting that a concentration of NO? of approximately 5 mg L or greater will diminish the reduction of SeO?. The inclusion of the fate and transport of NO? and dissolved oxygen is imperative when studying or simulating the fate and transport of Se species in soil and groundwater systems.     

Removal of mercury from aqueous solutions using activated carbon prepared from agricultural by-product/waste

Removal of mercury from aqueous solutions using activated carbon prepared from Ceiba pentandra hulls, Phaseolus aureus hulls and Cicer arietinum waste was investigated. The influence of various parameters such as effect of pH, contact time, initial metal ion concentration and adsorbent dose for the removal of mercury was studied using a batch process. The experiments demonstrated that the adsorption process corresponds to the pseudo-second-order-kinetic models and the equilibrium adsorption data fit the Freundlich isotherm model well. The prepared adsorbents ACCPH, ACPAH and ACCAW had removal capacities of 25.88 mg/g, 23.66 mg/g and 22.88 mg/g, respectively, at an initial Hg(II) concentration of 40 mg/L. The order of Hg(II) removal capacities of these three adsorbents was ACCPH > ACPAH > ACCAW. The adsorption behavior of the activated carbon is explained on the basis of its chemical nature. The feasibility of regeneration of spent activated carbon adsorbents for recovery of Hg(II) and reuse of the adsorbent was determined using HCl solution.     

A laboratory study of bacteria-facilitated cadmium transport in alluvial gravel aquifer media

Colloids, including bacteria, can dramatically accelerate the transport of heavy metals in ground water. Batch and column experiments were conducted to investigate adsorption of cadmium (Cd) onto Bacillus subtilis spores or Escherichia coli vegetative cells and Cd transport in alluvial gravel aquifer media in the presence of these bacteria. Results of the batch experiments showed that adsorption of Cd onto the bacteria was (i) positively related to solution pH, bacterial concentration, and negative surface charge, but inversely related to Cd concentration and (ii) a rate-limited nonlinear process, but adsorption onto E. coli was much less. For column influent Cd concentrations of about 4 mg/L and bacterial concentrations of > or = 10(5) colony-forming units (cfu)/mL, there was a significant increase in total Cd effluent concentrations. In comparison with controls that did not have bacteria-facilitated transport, Cd traveled 17 to 20 times faster when it traveled with mobile bacteria. However, Cd traveled mostly 2 to 3 times slower during the desorption phase under the influence of bacteria retained in the column. The difference between total and dissolved Cd concentrations was significant during Cd cotransport with B. subtilis spores, but this concentration difference was very small during Cd cotransport with E. coli, suggesting an adsorption-dominant mechanism during Cd cotransport with the spores and the possibility of Cd chelation by the dissolved membrane vesicles secreted from E. coli cell walls. Bacteria-facilitated transport of heavy metals may pose a threat to ground water quality in sites such as landfills and following land disposal of industrial and domestic effluent and sludge.     

The use of ion exchange membranes for isotope analyses on soil water sulfate: laboratory experiments

To investigate the potential use of anion exchange membranes (plant root simulator [PRS] probes) for isotope investigations of the soil sulfur cycle, laboratory experiments were performed to examine the sulfate exchange characteristics and to determine the extent of sulfur and oxygen isotope fractionation during sulfate sorption and desorption on the probes in aqueous solutions and simulated soil solutions. The sulfate-exchange tests in aqueous solutions under varying experimental conditions indicated that the amount of sulfate exchanged onto PRS probes increased with increasing reaction time, initial sulfate concentration, and the number of probes used (= surface area), whereas the percentage of removal of available sulfate was constant irrespective of the initial sulfate concentration. The competition of nitrate and chloride in the solution lowered the amount of exchanged sulfate. The exchange experiments in a simulated soil under water-saturated and water-unsaturated conditions showed that a considerable proportion of the soil sulfate was exchanged by the PRS probes after about 10 d. There was no evidence for significant sulfur and oxygen isotope fractionation between soil sulfate and sulfate recovered from the PRS probes. Therefore, we recommend the use of PRS probes as an efficient and easy way to collect soil water sulfate for determination of its isotope composition.     

Incubation time effects on imazaquin desorption as determined by nonequilibrium thin-soil disc flow

Because organic sorption in soil may never reach equilibrium, a thin-disc flow nonequilibrium method may be helpful in understanding herbicide-soil interactions. This research was conducted to (i) determine the influence of incubation time on imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] desorption from soil, (ii) examine the influence of solution flow velocities on desorption, and (iii) elucidate the most appropriate kinetic model to describe imazaquin leaching. Soil at 7.5% moisture w/w was treated with imazaquin and incubated for 24, 72, and 168 h. Treated soil was sealed in an in-line filter apparatus and rinsed with 5.0 mM CaCl2 at 0.33, 0.67, or 1.0 mL min(-1). Effluent was collected as 1.0-mL fractions for a total of 50 mL. Flow was stopped for 24 h. When flow resumed, fractions were collected for an additional 15 mL. After the initial desorption, 79% of the imazaquin incubated for 24 h was leached. Increasing incubation time beyond 24 h reduced imazaquin leaching. After both desorption events, 13% of the initially applied imazaquin remained in the soil incubated for 168 h, compared with 7% with soil incubated for 24 h. Elovich and Freundlich kinetics accounted for 98% of the variance observed in the imazaquin desorption curves. First-order and diffusion kinetics accounted for 91% of the variance. Incubating soil for 72 h before desorption reduced the rate of imazaquin desorption by approximately 12%, compared with the 24-h incubation treatment. Imazaquin desorption was not affected by wash solution flow rate. These data suggest that the kinetics of desorption in prolonged desorption events are limited by transport phenomena (i.e., particle and film diffusion).