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).     

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.     

Small-scale spatial variability of atrazine and dinoseb adsorption parameters in an alluvial soil

Soil sorption processes largely control the environmental fate of herbicides. Therefore, accuracy of sorption parameters is crucial for accurate prediction of herbicide mobility in agricultural soils. A combined experimental and statistical study was performed to investigate the small-scale spatial variability of sorption parameters for atrazine and dinoseb in soils and to establish the number of samples needed to provide a value of the distribution coefficient (K(d)) next to the mean, with a given precision. The study explored sorption properties of the two herbicides in subsurface samples collected from four pits distributed along a transect of an alluvial soil; two to four samples were taken at about 30 cm apart at each sampling location. When considering all the data, the distribution coefficients were found to be normally and log-normally distributed for atrazine and dinoseb, respectively; the CVs were relatively high (close to 50% for dinoseb and 40% for atrazine). When analyzed horizon by horizon, the data revealed distribution coefficients normally distributed for both herbicides, whatever the soil layer, with lower CVs. The K(d) values were shown to vary considerably between samples collected at very short distance (a few centimeters), suggesting that taking a single soil sample to determine sorption properties through batch experiments can lead to highly unrepresentative results and to poor sorption/mobility predictions.     

Atrazine sorption-desorption hysteresis by sugarcane mulch residue

Sorption and desorption kinetics are essential components for modeling the movement and retention of applied agricultural chemicals in soils and the fraction of chemicals susceptible to runoff. In this study, we investigated the retention characteristics of sugarcane (Saccharum spp. hybrid) mulch residue for atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) based on studies of sorption-desorption kinetics. A sorption kinetic batch method was used to quantify retention of the mulch residue for a wide range of atrazine concentrations and reaction times. Desorption was performed following 504 h of sorption using successive dilutions, followed by methanol extraction. Atrazine retention by the mulch residue was well described using a linear model where the partitioning coefficient (K(d)) increased with reaction time from 10.40 to 23.4 cm3 g(-1) after 2 and 504 h, respectively. Values for mulch residue K(d) were an order of magnitude higher than those found for Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquepts) where the sugarcane crop was grown. A kinetic multireaction model was successful in describing sorption behavior with reaction time. The model was equally successful in describing observed hysteretic atrazine behavior during desorption for all input concentrations. The model was concentration independent where one set of model parameters, which was derived from all batch results, was valid for the entire atrazine concentration range. Average atrazine recovery following six successive desorption steps were 63.67 +/- 4.38% of the amount adsorbed. Moreover, a hysteresis coefficient based on the difference in the area between sorption and desorption isotherms was capable of quantifying hysteresis of desorption isotherms.     

Imazaquin adsorbed on pillared clay and crystal violet-montmorillonite complexes for reduced leaching in soil

Ground water pollution due to herbicide leaching has become a serious environmental problem. Imazaquin [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid] is an herbicide used to control broadleaf weeds in legume crops. Imazaquin is negatively charged at the basic pH of calcareous soils and exhibits high leaching potential in soils. Our aim was to design formulation of imazaquin to reduce herbicide leaching. Imazaquin sorption on pillared clay (PC) and crystal violet (CV)-montmorillonite complexes was studied. The CV-montmorillonite complexes become positively charged with adsorption of CV above the cation exchange capacity (CEC) of montmorillonite, and thus can sorb imazaquin. The Langmuir equation provides a good fit to isotherms of imazaquin sorption on PC and CV-montmorillonite complexes, but for charged complexes an equation that combines electrostatics with specific binding was preferred. Maximal imazaquin sorption was 17.3 mmol kg-1 for PC and 22.2 mmol kg-1 for CV-montmorillonite complexes. The extents of imazaquin desorption into water were 21% for PC and 5% for CV-clay complexes. The presence of anions decreased imazaquin sorption on both sorbents in the sequence phosphate > acetate > sulfate. Reduction of imazaquin sorption by the anions and the extent of its desorption in electrolyte solutions were higher for PC than for CV-clay complexes. Leaching of imazaquin from CV-montmorillonite formulations through soil (Rhodoxeralf) columns was two times less than from PC formulations and four times less than that of technical imazaquin. The CV-montmorillonite complexes at a loading above the CEC appear to be suitable for preparation of organo-clay-imazaquin formulations that may reduce herbicide leaching significantly.     

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.     

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.     

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.     

Measuring sorption of hydrophilic organic compounds in soils by an unsaturated transient flow method

Determination of sorption of hydrophilic, weakly sorbing organic compounds in soil by conventional batch methods using a slurried suspension is often prone to considerable errors because small changes in the solution concentration on equilibration must be accurately determined. This difficulty is exacerbated for compounds susceptible to degradation, which also decreases the solution concentration. The objective of this study was to determine sorption of hydrophilic pesticides by applying an unsaturated transient flow method, which enables determination of sorption at sufficiently small solution to soil ratios. The method makes use of piston-like displacement of the antecedent solution in equilibrium with sorbed phase when pesticide-free water is infiltrated into a soil column spiked with a pesticide. Pesticide sorption and the solution concentration are inferred from a plot of total pesticide content per unit mass of soil vs. water content in a region where the antecedent solution is accumulated. Thus, extraction of solution from relative dry soil is unnecessary. We tested this method for two hydrophilic pesticides, monocrotophos [dimethyl (E)-1-methyl-2-(methyl-carbamoyl) vinyl phosphate] and dichlorvos (2,2-dichlorovinyl dimethyl phosphate). The sorption coefficient, K(d), obtained for monocrotophos was slightly lower than that by batch method (K(d) = 0.10 vs. 0.19 L kg(-1)), whereas for dichlorvos, a compound highly susceptible to degradation, the unsaturated flow method yielded a much smaller K(d) (0.19 vs. 3.22 L kg(-1)). The K(d) values for both compounds were consistent with the observed retardation in the pesticide displacement in the columns. The proposed method is more representative of field conditions and particularly suitable for weakly sorbing organic compounds in soils.     

Sorption of MS2 bacteriophage to layered double hydroxides: effects of reaction time, pH, and competing anions

Batch sorption and column breakthrough studies were conducted to investigate the potential of layered double hydroxides (LDHs) to remove bacteriophage MS2 from contaminated waters. All four of the LDHs evaluated in this study had very high retention capacities for MS2. Sorption results showed that MS2 could be completely removed from 5.2 x 10(2) plaque-forming units (pfu)/mL solution by Mg-Al LDH 2 (i.e., 2:1 Mg to Al ratio LDH), with the highest sorption capacity observed in this study of 1.51 x 10(10) pfu/g. Attachment of MS2 to LDHs was a rapid process and reached quasi-equilibrium after a 1-h reaction time. Within the pH range studied (pH 4-9), Mg-Al LDH 2 showed high sorption potential for MS2 at all pH values but sorption decreased slightly with increasing solution pH. Background solution anions influenced virus sorption, with SO4(2-) and HPO4(2-) decreasing sorption significantly whereas the presence of NO3- had little effect on the attachment of MS2 to Mg-Al LDH 2. The addition of another virus (phiX174) only caused a slight decrease in the retention of MS2 by Mg-Al LDH 2, suggesting that there was insignificant competitive sorption between MS2 and phiX174 on LDH surfaces. Results from column experiments indicate that there was no MS2 breakthrough from columns packed with Mg-Al LDH 2-coated sand, suggesting complete MS2 retention at the virus concentration tested. The high mass recovery by beef extract solution revealed that the removal of viruses by the LDH was due to sorption of MS2 to LDH surfaces, rather than inactivation.     

Anionic polyacrylamide effects on soil sorption and desorption of metolachlor,atrazine, 2,4-D,and picloram

Polyacrylamide (PAM) treatment of irrigation water is a growing conservation technology in irrigated agriculture in recent years. There is a concern regarding the environmental impact of PAM after its application. The effects of anionic PAM on the sorption characteristics of four widely used herbicides (metolachlor, atrazine, 2,4-D, and picloram) on two natural soils were assessed in batch equilibrium experiments. Results showed that PAM treatment kinetically reduced the sorption rate of all herbicides, possibly due to the slower diffusion of herbicide molecules into interior sorption sites of soil particles that were covered and/or cemented together by PAM. The equilibrium sorption and desorption amounts of nonionic herbicides (metolachlor and atrazine) were essentially unaffected by anionic PAM, even under a high PAM application rate, while the sorption amounts of anionic herbicides (2,4-D and picloram) were slightly decreased and their desorption amounts increased little. The impact mechanisms of PAM were related to the molecular characteristics of PAM and herbicides. The negative effects of PAM on the sorption of anionic herbicides are possibly caused by the enhancement of electrostatic repulsion by presorbed anionic PAM and competition for sorption sites. However, steric hindrance of the large PAM molecule weakens its influence on herbicide sorption on interior sorption sites of soil particles, which probably leads to the small interference on herbicide sorption, even under high application rates.     

Role of soil sorption and microbial degradation on dissipation of mesotrione in plant-available soil water

Mesotrione is a carotenoid biosynthesis-inhibiting herbicide labeled for pre-emergence and postemergence weed control in corn production. Understanding the factors that influence the dissipation of mesotrione in soil and in the plant-available water (PAW) is important for the environmental fate assessment and optimal weed management practices. The present research investigated the role of soil properties and microbial activities on the interrelated sorption and degradation processes of mesotrione in four soils by direct measurements of PAW. We found that mesotrione bound to the soils time dependently, with approximately 14 d to reach equilibrium. The 24-h batch-slurry equilibrium experiments provided the sorption partition coefficient ranging from 0.26 to 3.53 L kg(-1), depending on soil organic carbon and pH. The dissipation of mesotrione in the soil-bound phase was primarily attributed to desorption to the PAW. Degradation in the PAW was rapid and primarily dependent on microbial actions, with half-degradation time (DT(50)) <3 d in all four soils tested. The rapid degradation in the PAW became rate limited by sorption as more available molecules were depleted in the soil pore water, resulting in a more slowed overall process for the total soil-water system (DT(50) <26 d). The dissipation of mesotrione in the PAW was due to microbial metabolism and time-dependent sorption to the soils. A coupled kinetics model calibrated with the data from the laboratory centrifugation technique provided an effective approach to investigate the interrelated processes of sorption and degradation in realistic soil moisture conditions.     

Macroscopic and molecular investigations of copper sorption by a steam-activated biochar

Excessive Cu concentrations in water systems can negatively affect biological systems. Because Cu can form strong associations with organic functional groups, we examined the ability of biochar (an O-C-enriched organic bioenergy by-product) to sorb Cu from solution. In a batch experiment, KOH steam-activated pecan shell biochar was shaken for 24 h in pH 6, 7, 8, or 9 buffered solutions containing various Cu concentrations to identify the effect of pH on biochar Cu sorption. Afterward, all biochar solids from the 24-h shaking period were air-dried and analyzed using X-ray absorption fine structure (XAFS) spectroscopy to determine solid-phase Cu speciation. In a separate batch experiment, biochar was shaken for 30 d in pH 6 buffered solution containing increasing Cu concentrations; the Cu sorption maximum was calculated based on the exponential rise to a maximum equation. Biochar sorbed increasing amounts of Cu as the solution pH decreased from 9 to 6. The XAFS spectroscopy revealed that Cu was predominantly sorbed onto a biochar organic phase at pH 6 in a molecular structure similar to Cu adsorbed on model humic acid (Cu-humic acid [HA]). The XAFS spectra at pH 7, 8, and 9 suggested that Cu was associated with the biochar as three phases: (i) a complex adsorbed on organic ligands similar to Cu-HA, (ii) carbonate phases similar to azurite (Cu(CO)(OH)), and (iii) a Cu oxide phase like tenorite (CuO). The exponential rise equation fit to the incubated samples predicted a Cu sorption maximum of 42,300 mg Cu kg. The results showed that KOH steam-activated pecan shell biochar could be used as a material for sorbing excess Cu from water systems, potentially reducing the negative effects of Cu in the environment.     

Fracture-controlled nitrate and atrazine transport in four Iowa till units

Fractures in till may provide pathways for agricultural chemicals to contaminate aquifers and surface waters. This study was conducted to quantify the influence of fractures on solute fate and transport using three conservative and two nonconservative tracers. The conservative tracers were potassium bromide (KBr), pentafluorobenzoic acid (PFBA), and 1,4-piperazinediethanesulfonic acid disodium salt (PIPES); the nonconservative tracers were nitrate and atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine]. Three sites in Iowa were investigated, including four late Wisconsinan and Pre-Illinoian tills. Laboratory tracer experiments were conducted using eight large (0.4-0.45 m long by 0.43 m in diameter), undisturbed columns of till collected from depths of 1 to 28 m. The tills were densely fractured, with fracture spacing ranging from 3.8 to 10.4 cm. First arrival velocities of Br- ranged from 0.004 to 64.8 m d(-1), 10 to 100 times faster than predicted for unfractured media. Nitrate behaved as a conservative tracer in weathered till columns, but degraded during experiments using deeper tills. Sorption caused retardation of atrazine in the shallowest four columns. Atrazine degradation occurred in deeper columns as demonstrated by deviations between atrazine and the conservative tracers. Mobile-immobile model (MIM) simulations estimated first-order exchange coefficients (alpha) ranging from 1 x 10(-8) to 1.7 x 10(-2) s(-1), sorption coefficients (K(d)) for atrazine ranging from 2.6 x 10(-5) to 1 x 10(-3) m3 kg(-1), and degradation half-lives ranging from 0.24 to 67 d (nitrate) and 1.6 to 277 d (atrazine). This study suggests that aquifers and surface waters associated with thin, fractured till units may be vulnerable to contamination, yet deeper aquifers may be protected by these materials due to increased residence times provided by matrix diffusion.     

Sorption kinetics of chlortetracyline and tylosin on sandy loam and heavy clay soils

Antibiotics may appear in the environment when manure, sewage sludge, and other organic amendments are added to soils. There is concern that the presence of antibiotics in soils may lead to the development of antibiotic-resistant bacteria which may spread to the rest of the environment. This paper aims at evaluating the sorption kinetics of two antibiotics frequently used in pig production. The results indicate that sorption of chlortetracycline (CTC) and tylosin (TYL) in sandy loam and clay occurs very fast. More than 95% of the CTC adsorption is completed within 10 min on both soils and of TYL within 3 h. These results suggest that 24-h soil and antibiotic solution mixtures is enough for sorption studies. Also, there is less likelihood that these antibiotics will leach through soil and appear in the ground water since their sorption on soils is very high unless they are carried by soil particles through preferential flow. There was also no effect of soil sterilization on sorption kinetics of these antibiotics thus suggesting that there is minimal probability of the antibiotics degrading by microorganisms during 24- to 48-h adsorption studies.     

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.     

Microbial reduction of hexavalent chromium under vadose zone conditions

Hexavalent chromium [Cr(VI)] is a common contaminant associated with nuclear reactors and fuel processing. Improper disposal at facilities in and and semiarid regions has contaminated underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those in the vadose zone, and to evaluate the potential for enhancing biological Cr(VI) reduction through nutrient addition. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic C (molasses). Nutrient amendments resulted in up to 87% reduction of the initial 67 mg L(-1) Cr(VI) in an unsaturated batch experiment. Molasses and nitrate additions to 15 cm long unsaturated flow columns receiving 65 mg L(-1) Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-d experiment. All of the immobilized Cr was in the form of Cr(III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy, and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.     

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.     

Organic manure and urea effect on metolachlor transport through packed soil columns

Application of organic manure (OM) amendments and nitrogen fertilizers can affect the sorption and movement of pesticides in soil. This study summarizes the sorption and leaching of metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylphenyl) acetamide] in soils after cow (Bos taurus) manure (2.5 and 5.0%) and urea (60 and 120 kg N ha(-1)) amendments in batch and column experiments. Both cow manure and urea applications increased metolachlor sorption in soils. The values of the Freundlich adsorption parameter K(r)(1/n) for treatments T0, T1 (OM), and T2 (OM) were 2.31, 3.32, and 3.96 in Soil 1; 2.02, 2.77, and 3.32 in Soil 2; and 1.10, 1.46, and 2.02 in Soil 3, respectively. Similarly, K(f)(1/n) values for treatment T1 (urea) and T2 (urea) were 2.37 and 2.84 in Soil 1; 2.16 and 2.83 in Soil 2; and 1.50 and 1.70 in Soil 3, respectively. Column leaching studies using Soil 1 indicated that OM application drastically reduced the metolachlor leaching losses from 50% (natural soil) to < 1.0% (5.0% OM amendment). Likewise, urea application also decreased metolachlor mobility and leaching losses in columns treated with 60 and 120 kg N ha(-1) urea were 33 and 20%, respectively. The reduction in the metolachlor leaching losses was achieved through the increase in the sorption capability of the OM- and urea-amended soil. Therefore, coapplication of metolachlor with cow manure or urea fertilizers will not enhance metolachlor mobility and reduces metolachlor leaching losses in low-organic-matter soil.     

On the interaction mechanisms of atrazine and hydroxyatrazine with humic substances

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) is retained against leaching losses in soils principally by sorption to organic matter, but the mechanism of sorption has been a matter of controversy. Conflicting evidence exists for proton transfer, electron transfer, and hydrophobic interactions between atrazine and soil humus, but no data are conclusive. In this paper we add to the database by investigating the role of (i) hydroxyatrazine (6-hydroxy-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and (ii) hydrophobicity in the sorption of atrazine by Brazilian soil humic substances. We demonstrate, apparently for the first time, that hydroxyatrazine readily forms electron-transfer complexes with humic substances. These complexes probably are the cause of the well-known strong adsorption by humic acids and they may be the undetected cause of apparent electron-transfer complexes between soil organic matter and atrazine, whose transformation to the hydroxy form is facile. We also present evidence that supports the important contribution of hydrophobic interactions to the pH-dependent sorption of atrazine by humic substances.