苄嘧磺隆和芘在土壤中的吸附解吸行为

吸附是外源有机污染进入土壤后首先发生的最重要的过程,直接影响着有机物的生物可利用性。采用完全混合法研究了苄嘧磺隆和芘在土壤中的吸附一解吸动力学特征以及等温吸附解吸行为。结果表明,（1）苄嘧磺隆和芘在土壤中的吸附-解吸动力学过程存在两段行为,即初期快速反应阶段和经过一段时间后的慢速阶段,动力学特征表明供试有机物8h内能达到吸附-解吸平衡;（2）在试验浓度范围内,线性方程能很好地描述苄嘧磺隆和芘在土壤中的吸附解吸行为;（3）苄嘧磺隆和芘在土壤中存在解吸迟滞现象,解吸并不完全是吸附的可逆过程,土壤中存在不可逆吸附室是造成解吸滞后的主要原因。     

Desorption kinetics of arsenate from kaolinite as influenced by pH

Arsenic is highly toxic and therefore represents a potential threat to the environment and human health. The mobility and bioavailability of arsenic in soil is mostly controlled by adsorption and desorption reactions. Even though adsorption and traditional batch desorption experiments provide information about the environmental fate of As, the equilibrium conditions imposed in these studies would usually not be reached in the natural environment. Flow-through desorption techniques, where the desorbed species are removed from the substrate, can therefore be used to provide information about the rate and mechanisms of As desorption. The effect of pH on As adsorption reactions is relatively well understood; however, desorption of As and the effect of pH on As desorption remain unexplored. Desorption of As(V) (the most dominant arsenic species in aerated soils) was therefore investigated using batch and flow-through desorption experiments. Traditional batch desorption experiments underestimated the desorption rate of As(V) from kaolinite. The pH had a large effect on the amount of As(V) desorbed from kaolinite, with both an increase and a decrease in pH (from the initial pH 6.4) enhancing As(V) desorption. Modeling desorption over time revealed that the pH can influence As(V) desorption over extended periods of time.     

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 and fractionation of dissolved organic matter and associated phosphorus in agricultural soil

Mobility of dissolved organic matter (DOM) strongly affects the export of nitrogen (N) and phosphorus (P) from soils to surface waters. To study the sorption and mobility of dissolved organic C and P (DOC, DOP) in soil, the pH-dependent sorption of DOM to samples from Ap, EB, and Bt horizons from a Danish agricultural Humic Hapludult was investigated and a kinetic model applicable in field-scale models tested. Sorption experiments of 1 to 72 h duration were conducted at two pH levels (pH 5.0 and 7.0) and six initial DOC concentrations (0-4.7 mmol L(-1)). Most sorption/desorption occurred during the first few hours. Dissolved organic carbon and DOP sorption decreased strongly with increased pH and desorption dominated at pH 7, especially for DOC. Due to fractionation during DOM sorption/desorption at DOC concentrations up to 2 mmol L(-1), the solution fraction of DOM was enriched in P indicating preferred leaching of DOP. The kinetics of sorption was expressed as a function of how far the solution DOC or DOP concentrations deviate from "equilibrium." The model was able to simulate the kinetics of DOC and DOP sorption/desorption at all concentrations investigated and at both pH levels making it useful for incorporation in field-scale models for quantifying DOC and DOP dynamics.     

Modeling of sorption and biodegradation of parathion and its metabolite paraoxon in soil

To investigate the distribution of parathion [O,O-diethyl O-(4-nitrophenyl) phosphorothioate] and its highly toxic metabolite paraoxon [O,O-diethyl O-(4-nitrophenyl)phosphate] between the soluble and sorbed pools in the soil, batch experiments were conducted to evaluate the rate of adsorption and desorption of 14C-labeled parathion and paraoxon in soil. The mineralization and degradation of these products were also investigated during a 56-d experiment under controlled laboratory conditions. Adsorption patterns indicated initial fast adsorption reactions occurring within 4 h for both parathion and paraoxon. We also observed the formation of nonextractable residues. The paraoxon was more intensively degraded than the parathion, and production of p-nitrophenol and other metabolites was observed. A kinetic model was developed to describe the sorption and biodegradation rates of parathion, taking into account the production, retention, and biodegradation of paraoxon, the main metabolite of parathion. After fitting the parameters of the model we made a simulation of the kinetics of the appearance and disappearance of paraoxon. From the simulation we predicted a quantity of metabolite in the liquid phase amounting to 1% of the quantity of parathion initially applied. This is in agreement with the experimental data.     

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.     

Theoretical comparison of how soil processes affect uptake of metals by diffusive gradients in thinfilms and plants

The theoretical basis for using measurements of metal uptake by the technique of diffusive gradients in thinfilms (DGT) to mimic processes in soils that affect uptake of metals by plants is examined. The uptake of metals by plants and DGT were compared conceptually and quantitatively by using the classic Barber model of plant uptake and the DIFS (DGT-induced fluxes in soils) model of uptake by DGT. For most metals and plants considered, uptake fluxes were similar to those induced by DGT using the most common gel layer thicknesses of 0.2 to 2 mm. Consequently DGT perturbs the chemical equilibrium of metals in the soil solution and between soil solution and solid phase, to a similar extent to plants, and therefore induces a similar balance in supply by diffusion and by release from the solid phase. DIFS was used to show that desorption kinetics, which are not considered by the plant uptake model, are likely important for uptake when the capacity of the soil solid phase is large. Model calculations showed that mass flow into a plant root would only contribute appreciably to the total flux of metal under circumstances when the solid phase reservoir of metal was very low. Generally, however, DGT is likely to emulate supply processes from the soil that govern uptake of metal by plants. Exceptions are likely to be found in poorly buffered soils (typically sandy and/or low pH), and at very high concentrations of metals in soil solution, such that the soil solution concentration at the plant root interface is higher than the Michaelis-Menten constant (Km).     

Leachate characteristics,dry matter yield of Urochloa decumbens and properties of two contrasting soils irrigated with sludgewater in columns

Increasing demands on freshwater and challenges in disposal of wastewaters encourage their use for irrigation. The study evaluated the effects of irrigation of signal grass (Urochloa decumbens) with sludgewater on leaching, uptake and retention of a range of elements in two contrasting soils in columns. The grass was grown on a sandy loam and a clay soil packed in plastic columns and irrigated for 119 days with either undiluted, diluted sludgewater or tap water. The sludgewater had a pH of 6.9 and high aluminum (Al), manganese (Mn), iron (Fe), and boron (B). Analyses were conducted on leachates, above-ground plant biomass (two harvests), and soils at the end of the experiment. Sludgewater treatments increased grass biomass yield and uptake of nitrogen (N), phosphorus (P), potassium (K), and magnesium (Mg) in both soils with a greater nutrient uptake from the clay than the sandy loam. The application of sludgewater increased Mn and reduced P (sandy loam only) in the leachate with no effects on Al, Fe, or B. Uptake of Al, Fe, and B was increased by sludgewater application. Even when diluted, the sludgewater increased extractable Mn, particularly in the clay soil. The findings showed that irrigation of the soils with sludgewater increased Mn and B concentrations and uptake by signal grass, with no negative effects on biomass production. Leaching and accumulation in the soils of toxic elements were minimal in the short term. Sludgewater can therefore be used to grow signal grass in both soils although these effects need to be evaluated under field conditions.     

Phosphorus leaching at cold temperatures as affected by wastewater application and soil phosphorus levels

Land application of wastewater in the northern-tier United States during winter months has been suggested as a means to reduce cost of building storage lagoons. A study was initiated in 1996 to assess land application of potato-processing wastewater on a 120-ha field at Park Rapids, MN. One objective of this study was to evaluate the effects of soil P levels and temperature on P leaching in soil columns. In this paper, we report the P sorption, desorption, and leaching characteristics of a high-P (>200 mg kg(-1)) and a low-P (<25 mg kg(-1)) surface soil from the wastewater irrigation site. The leaching experiment was done with wastewater at 4 +/- 2 or 10 +/- 2 degrees C. The high-P soil resulted in an equilibrium P concentration of 8.0 mg L(-1) compared with 0.14 mg L(-1) for the low-P soil. When low-P wastewater was applied to the high-P soil, the soil acted as a P source, and the total phosphorus (TP) concentration in the leachate was 3.5 times higher than the input TP concentration (C0). When high-P wastewater was applied to the high-P soil, the soil acted as a P sink retarding the TP concentration in the leachate by 80%. Phosphorus desorption was higher at 10 degrees C compared with 4 degrees C. The results showed that depending on P levels of the soil and the wastewater, reduction or increase in leachate P will occur below the surface soil. However, further mobility of this P under field conditions will depend on the volume and rate of percolating water as well as the sorption-desorption characteristics of the subsoil.     

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.     

Kinetic modeling of bioavailability for sorbed-phase 2,4-dichlorophenoxyacetic acid

The degradation rate of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in silica-slurry systems to evaluate the bioavailability of sorbed-phase contaminant. After the silica particles were saturated with 2,4-D, the system was inoculated with the 2,4-D-degrading microorganism Flavorbacterium sp. strain FB4. The disappearance rate of 2,4-D was found to be greater than the rate predicted based upon liquid-phase 2,4-D concentrations. A kinetic formulation, termed the enhanced bioavailability model, was developed to describe the desorption and biodegradation processes in this batch system. The approach assumes that 2,4-D resides in both the liquid and solid phases and degradation occurs via both suspended and attached biomass. All biomass can degrade liquid-phase 2,4-D at one rate, while only attached biomass can degrade sorbed 2,4-D at another rate. An enhanced transformation factor (Ef) was introduced to express the increased biodegradation rate over that expected from the liquid phase only. This approach was able to account for the increased degradation rates observed experimentally. The results provide evidence that desorption to the bulk solution is not prerequisite to degradation, and that sorbed substrate may be available for degradation.     

Sorption-desorption of carbamazepine from irrigated soils

Th anti-seizure medication carbamazepine is often found in treated sewage effluent and environmental samples. Carbamazepine has been shown to be very persistent in sewage treatment, as well as ground water. Due to environmental persistence, irrigation with sewage effluent could result in carbamazepine contamination of surface and ground water. To determine the potential for leaching of carbamazepine, a series of adsorption and desorption batch equilibrium experiments were conducted on irrigated soils. It was found that carbamazepine adsorption to biosolid-amended (T) soils had a KD of 19.8 vs. 12.6 for unamended soil. Based on adsorption, carbamazepine leaching potential would be categorized as low. During desorption significant hysteresis was observed and KD increased for both soils. Desorption isotherms also indicate a potential for irreversibly bound carbamazepine in the T soil. Results indicate that initial removal of carbamazepine via adsorption from irrigation water is significant and that desorption characteristics would further limit the mobility of carbamazepine through the soil profile indicating that carbamazepine found in sewage effluent used for irrigation has a low leaching potential.     

Accumulation of rare earth elements in corn after agricultural application

Using both pot and plot experiments, the dose-dependent accumulation of rare earth elements (REs) in corn (Zea mays L.) after application of an agricultural REs mixture was measured. In the pot experiment, the dose-dependent accumulation of REs in corn root and stem was observed, but it could not be detected in corn leaf under the dosage of 20 mg REs kg(-1) soil (oven-dry mass). The non-observed effect concentration (NOEC) for accumulation of REs in corn seedling with the pot experiment was 1.0 mg REs kg(-1). In the plot experiment, the dose-dependent accumulation was observed at an early stage after application of REs and the NOEC value of 32 mg REs m(-2) was obtained. At harvest, no dose-dependent accumulation of REs was observed in any part of the corn. These results can be confirmed by the fingerprinting analysis based on the differences between La to RE ratios in the REs mixture and in pot or plot soil. We observed that the plant shows no preference on individual RE and the results of fingerprinting indicated clearly the incorporation of exogenous REs in plant tissues, in a similar manner as that observed in the dose-dependent distribution of RE concentrations. The results indicated also a translocation process of REs from plant root to leaf when applied to soil or from leaf to root when applied to leaf. A homeostatic regulation mechanism for excessive uptake of REs in plants is suggested to regulate the concentrations of REs in the plant.     

Adsorption and desorption of metolachlor and metolachlor metabolites in vegetated filter strip and cultivated soil

Previous studies have indicated that dissolved-phase metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(methoxy-1-methylethyl) acetamide] transported in surface runoff is retained by vegetative filter strips to a greater degree than either metolachlor oxanilic acid 12-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl)amino]-2-oxo-acetic acid] (OA) or metolachlor ethanesulfonic acid [2-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl-1)amino]-2-oxoethanesul-fonic acid] (ESA), two primary metabolites of metolachlor. Adsorption-desorption of ESA and OA in vegetated filter strip soil (VFSS) has not been evaluated, yet these data are required to assess the mobility of these compounds in VFSS. The objective of this experiment was to compare metolachlor, ESA, and OA adsorption and desorption parameters between VFSS and cultivated soil (CS). Adsorption and desorption isotherms were determined using the batch equilibrium procedure. With the exception of a 1.7-fold increase in organic carbon content in the VFSS, the evaluated chemical and physical properties of the soils were similar. Sorption coefficients for metolachlor were 88% higher in VFSS than in CS. In contrast, sorption coefficients for ESA and OA were not different between soils. Relative to metolachlor, sorption coefficients for ESA and OA were at least 79% lower in both soils. Metolachlor desorption coefficients were 59% higher in the VFSS than in the CS. Desorption coefficients for ESA and OA were not different between soils. Relative to metolachlor, desorption coefficients for ESA and OA were at least 66% lower in both soils. These data indicate that the mobility of ESA and OA will be greater than metolachlor in both soils. However, higher organic carbon content in VFSS relative to CS may limit the subsequent transport of metolachlor from the vegetated filter strip.     

Simulation of phytoremediation of a TNT-contaminated soil using the CTSPAC model

Knowledge of water movement in the plant-xylem system and contaminant bioavailability in the soil environment is crucial to evaluate the success of phytoremediation practices. This study investigated the removal of 2,4,6-trinitrotoluene (TNT) from a contaminated sandy soil by a single poplar (Populus fastigiata) tree through the examinations of temporal variations of xylem water potential, root water uptake, and soil TNT bioavailability. A mathematical model, CTSPAC (Coupled Transport of water, heat, and solutes in the Soil-Plant-Atmosphere Continuum), was modified for the purpose of this study. The model was calibrated using laboratory measurements before its application. Our simulations show that the xylem water potential was high in the roots and low in the leaves with a potential head difference of 3.55 cm H2O, which created a driving force for water flow and chemical transport upward from the roots through the stem to the leaves. The daily average root water uptake rate was 25 cm3 h(-1) when an equilibrium condition was reached after 24 h. Our simulations further reveal that no TNT was found in the stem and leaves and only about 1% of total TNT mass was observed in the roots due to the rapid biodegradation and transformation of TNT into its daughter products. About 13% of the soil TNT was removed by the poplar tree, resulting mainly from root uptake since TNT is a recalcitrant compound. In general, the soil TNT bioavailability decreased with time due to the depletion of soil solution TNT by the poplar tree. A constant bioavailability (i.e., 3.1 x 10(-6)) was obtained in 14 d in which the soil TNT concentration was about 10 mg L(-1). Our study suggests that CTSPAC is a useful model to simulate phytoremediation of TNT-contaminated sites.     

Influence of pyrene combination state in soils on its treatment efficiency by Fenton oxidation

Interactions of hydrophobic organic compounds (HOCs) with soil organic matter (SOM) determine their combination state in soils, and therefore strongly influence their mobility, bioavailability, and chemical reactivity. Contact time (aging) of an HOC in soil also strongly influences its combination state and environmental fate. We studied Fenton oxidation of pyrene in three different soils to reveal the influences of SOM, contact time, and combination state on the efficiency of vigorous chemical reactions. Pyrene degradation efficiency depended strongly on the dose of oxidant (H(2)O(2)) and catalyst (Fe(2+)); the greatest degradation was achieved at an oxidant to catalyst molar ratio of 10:1. Pyrene degradation differed among the three soils, ranging from 65.4% to 88.9%. Pyrene degradation efficiency decreased with increasing SOM content, and the aromatic carbon content in SOM was the key parameter. We hypothesize that pyrene molecules that combine with the compact net structure of aromatic SOM are less accessible to Fenton oxidation. Furthermore, pyrene degradation efficiency decreased considerably after aged for 30 days, but further aging to 60 and 180 days did not significantly change degradation efficiency. The Fenton oxidation efficiency of pyrene in both unaged and aged soils was greater than the corresponding desorption rate during the same period, perhaps because Fenton reaction can make pyrene more accessible to the oxidant through the enhancement of HOCs' desorption by generating reductant species or by destroying SOM through oxidation.     

Cadmium leaching from micro-lysimeters planted with the hyperaccumulator Thlaspi caerulescens: experimental findings and modeling

The use of heavy metal hyperaccumulating plants has the potential to become a promising new technique to remediate contaminated sites. We investigated the role of metal mobilization in the Cd hyperaccumulation of Thlaspi caerulescens (J. & C. Presl, 'Ganges'). In a micro-lysimeter experiment we investigated the dynamics of Cd concentration of leachate as well as Cd removal by plant uptake in four treatments: (i) Control (bare soil), (ii) T. caerulescens, (iii) nonhyperaccumulator Brassica juncea (L.) Czern. ('PI 426308'), and (iv) co-cropping of the hyperaccumulator and nonhyperaccumulator. The experimental findings were analyzed using one- and two-site rate-limited desorption models. Co-cropping of T. caerulescens and B. juncea did not enhance metal uptake by B. juncea. Although Cd uptake of T. caerulescens was 10 times higher than that of B. juncea, the Cd concentration of leachate of the T. caerulescens treatment did not decrease below that of the B. juncea treatment. The Cd depletion in leachate was well reproduced by the two-site rate-limited desorption model. The optimized desorption coefficient was three orders of magnitude higher in the rhizosphere than in the bulk soil. Our results indicate that T. caerulescens accelerates the resupply of Cd from soil pointing to an important role of kinetic desorption in the hyperaccumulation by T. caerulescens.     

Controlled application rate of water treatment residual for agronomic and environmental benefits

Water treatment residuals (WTR) are useful soil amendments to control excessive soluble phosphorus (P) in soils, but indiscriminate additions can result in inadequate control or excessive immobilization of soluble P, leading to crop deficiencies. We evaluated the influence of application rates of an Al-WTR and various P-sources on plant yields, tissue P concentrations, and P uptake and attempted to identify a basis for determining WTR application rates. Bahiagrass (paspalum notatum Fluggae) was grown in a P-deficient soil amended with four P-sources at two application levels (N- and P-based rates) and three WTR rates (0, 10, and 25 g kg(-1) oven dry basis) in a glasshouse pot experiment. The glasshouse results were compared with data from a 2-yr field experiment with similar treatments that were surface applied to an established bahiagrass. Soil P storage capacity (SPSC) values increased with application rate of WTR, and the increase varied with sources of P applied. Soil soluble P concentrations increased as SPSC was reduced, and a change point was identified at 0 mg kg(-1) SPSC in the glasshouse and the field studies. A change point was identified in the bahiagrass yields at a tissue P concentration of 2.0 g kg(-1), corresponding to zero SPSC. Zero SPSC was shown to be an agronomic threshold above which yields and P concentrations of plants declined and below which there is little or no yield response to increased plant P concentrations. Applying P-sources at N-based rates, along with WTR sufficient to give SPSC value of 0 mg kg(-1) SPSC, enhanced the environmental benefits (reduced P loss potential) without negative agronomic impacts.