Study of sorption kinetics of some ionic liquids on different soil types

In the present contribution sorption kinetics experiments under static conditions were utilized in three selected ionic liquids cations (1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium chlorides) study with five type of soil, differing in total organic carbon (TOC) content. The experimental results indicate the sorption capacity growth with increase in TOC content and hydrophobicity of ionic liquid cation. The obtained kinetic sorption parameters as well as distribution coefficients (K_d) were used to estimate the sorption properties of the soil types towards the ionic liquids in question. The Gibbs free energy values indicate that ionic liquid cations sorption on soils could be generally considered as a physical adsorption with exothermic effect. But the values of −dG for studied cations sorption on soil with very high of TOC content in soil (45%) may testify to nature of chemical adsorption. Sorption of the analyzed compounds occurs probably by means of hydrogen bonds, electrostatic and π  π interaction with the organic matter and the clay minerals of the soils.     

Experimental and modeling studies on sorption and diffusion of radium in bentonite

The sorption and desorption behavior of radium on bentonite and purified smectite was investigated as a function of pH, ionic strength and liquid to solid ratio by batch experiments. The distribution coefficients (Kd) were in the range of 10(2) to > 10(4) ml g-1 and depended on ionic strength and pH. Most of sorbed Ra was desorbed by 1 M KCl. The results for purified smectite indicated that Ra sorption is dominated by ion exchange at layer sites of smectite, and surface complexation at edge sites may increase Ra sorption at higher pH region. Reaction parameters between Ra and smectite were determined based on an interaction model between smectite and groundwater. The reaction parameters were then used to explain the results of bentonite by considering dissolution and precipitation of minerals and soluble impurities. The dependencies of experimental Kd values on pH, ionic strength and liquid to solid ratio were qualitatively explained by the model. The modeling result for bentonite indicated that sorption of Ra on bentonite is dominated by ion exchange with smectite. The observed pH dependency was caused by changes of Ca concentration arising from dissolution and precipitation of calcite. Diffusion behavior of Ra in bentonite was also investigated as a function of dry density and ionic strength. The apparent diffusion coefficients (Da) obtained in compacted bentonite were in the range of 1.1 x 10(-11) to 2.2 x 10(-12) m2 s-1 and decreased with increasing in dry density and ionic strength. The Kd values obtained by measured effective diffusion coefficient (De) and modeled De were consistent with those by the sorption model in a deviation within one order of magnitude.     

Changes in water-extractability of soil inorganic phosphate induced by chloride and sulfate salts

GOAL, SCOPE AND BACKGROUND: One of the principal experimental variables which effect the results of phosphorus (P) sorption studies is the ionic composition, in addition to both species and concentrations of the contacting solution. In spite of the realization that ionic species, concentrations and their compositions effect P sorption and/or desorption, most of the salt-related studies are confined to Cl- (anion) in association with different cations. While the knowledge about the comparative response of P to Cl- and SO4(2-) ions was lacking, the current study was conducted to evaluate the comparative effects of anions (in association with cations) on inorganic P release and P fractions in the soil. METHODS: The test soil was amended with livestock compost manure (OP); KH2PO4 (IPk) or Ca(H2PO4)2 (IPc) at a rate of 1ppm. Soil was subjected to one salt and nine subsequent water extractions and different P fractions were measured. Four salt types, NaCl, Na2SO4, KCl and K2SO4, were used at levels of 0.5 M. RESULTS: Irrespective of P sources, P release was substantially increased in the salt-pretreated soil as compared to the non-saline soil. Sulfate salts released more P in subsequent water extractions than Cl-. Phosphorus release decreased for salt types with Na2SO4 > NaCl > K2SO4 > KCl and for P sources with OP approximately IPk > Control (without P application) > IPc, respectively. DISCUSSION: No previous study was found to compare the results of more P release by SO4(2-) than Cl- salt. Most of the previous studies focused on anion sorption capacities, but the mechanism for their adsorption is not fully known. Most of the authors suggested that the mechanisms of SO4(2-) and PO4(3-) adsorption are similar, and that both ions compete for the same sorption sites (Kamprath et al. 1956, Couto et al. 1979, Pasricha and Fox 1993). Although adsorbed SO4(2-) does not compete strongly with PO4(3-), there is likely to be some competition for sorption between these anions which may cause comparatively more P release by SO4(2-) than Cl- salts. Higher P release by Na-saturation could be due to the release of P associated with oxide surfaces or due to dissolution of Ca-P phases (Curtin et al. 1987). CONCLUSIONS: Study clearly showed that not only cations species differ for P desorption capacity, but associated anions also play a vital role in the fate of P under saline environments. Synergetic effects exist between Na and SO4(2-) ions which enhanced the P release. This study has also confirmed the fact that P from organic sources is available as well as from inorganic P sources. However, P release depends more on the type of P source applied than on total P. RECOMMENDATIONS AND PERSPECTIVES: It is highly recommended that more than one anion species must be used in the research plans for evaluating the P response in a saline environment. The results have important implications from the point of view of research, as most of the researchers focus on different cations only for evaluating P response to salts from an environmental point of view. However, our study has made it clear that anions in association with cations differed for their effects on P release.     

Biodegradation of oxygenated and non-oxygenated imidazolium-based ionic liquids in soil

Aerobic biodegradation of ionic liquids in soil was monitored for the first time. The tests, followed over six months according to ASTM D 5988-96, were carried out on the four ionic liquids obtained from 1-R-3-methylimidazolium cations, with R=CH(3)(CH(2))(3) and CH(3)O(CH(2))(2), and the tetrafluoroborate and dicyanamide counter anions. The n-butyl derivatives, after an induction period of about two months, were found to be degradable, although the degradation rate with the dicyanamide anion was smaller. In contrast, no significant production of CO(2) was observed in the tests with the methoxyethyl derivatives. Calculations at the B3LYP/6-31G(d) level were carried out to characterize the atomic charge distributions and frontier orbital structures of 1-alkyl-3-methylimidazolium cations and point out the changes caused by replacement of a CH(2) group of the alkyl chain with an oxygen atom. The calculations predict an overall negative charge on the nitrogen atoms of the imidazolium-based cations. The energies of the highest occupied (pi) MO and lowest empty (pi( *)) MO are only slightly perturbed by the length and nature of the alkyl chain. However, the electron-donor properties of the oxy derivatives are radically increased. The HOMO becomes a lone pair orbital mainly localized on the oxygen atom, and its ionization energy is sizeably smaller than that of the outermost ring pi MO.     

Soil solution nitrogen and cations influenced by (NH4)2SO4 deposition in a coniferous forest

The effects of chronically enhanced (NH(4))(2)SO(4) deposition on ion concentrations in soil solution and ionic fluxes were investigated in a Picea abies plot at Grizedale forest, NW England. Soil cores closed at the base and containing a ceramic suction cup sampler were 'roofed' and watered every 2 weeks with bulk throughfall collected in the field. Treatments consisted of the inclusion of living roots from mature trees in the lysimeters and increasing (NH(4))(2)SO(4) deposition (NS treatment) to ambient + 75 kg N ha(-1) a(-1). Rainfall, throughfall and soil solutions were collected every 2 weeks during 18 months, and analysed for major cations and anions. NO(3)(-) fluxes significantly increased following NS treatment, and were balanced by increased Al(3+) losses. Increased SO(4)(2-) concentrations played a minor role in controlling soil solution cation concentrations. The soil exchange complex was dominated by Al and, during the experimental period, cores of all treatments 'switched' from Ca(2+) to Al(3+) leaching, leading to mean [Formula: see text] molar ratios in soil solution of NS treated cores of 0.24. The experiment confirmed that the most sensitive soils to acidification (through deposition or changing environmental conditions) are those with low base saturation, and with a pH in the lower Ca, or Al buffer ranges.     

Studies on the sorption and desorption characteristics of Zn(II) on the surface soils of nuclear power plant sites in India using a radiotracer technique

Zinc adsorption was studied in the soils of three nuclear power plant sites of India. 65Zn was used as a radiotracer to study the sorption characteristics of Zn(II). The sorption of zinc was determined at 25 and 45 degrees C at pH 7.8+/-0.2 in the solution of 0.01 M Ca(NO3)2 as supporting electrolyte. The sorption data was tested both in Freundlich and Langmuir isotherms and could be described satisfactorily. The effect of organic matter and other physico-chemical properties on the uptake of zinc was also studied in all the soil samples. The results showed that the cation exchange capacity, organic matter, pH and clay content were the main contributors to zinc sorption in these soils. The adsorption maximum was found to be higher in the soil on Kakarpara Atomic Power Plant sites soils having high organic matter and clay content. The zinc supply parameters of the soils are also discussed. In the desorption studies, the sequential extraction of the adsorbed zinc from soils showed that the diethylene triamine penta acetic acid extracted maximum amount of adsorbed zinc than CaCl2 and Mg(NO3)2. The zinc sorption on the soil and amount of zinc retention after extractants desorption shows a positively correlation with vermiculite and smectite mineral content present in the clay fraction of the soil. The amount desorbed by strong base (NaOH) and demineralised water was almost negligible from soils of all the sites, whereas the desorption by strong acid (HNO3) was 75-96% of the adsorbed zinc.     

Sorption of acidic organic solute onto kaolinitic soils from methanol-water mixtures

The fate of the acidic organic solute from the soil-water-solvent system is not well-understood. In this study, the effect of the acidic functional group of organic solute in the sorption from cosolvent system was evaluated. The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) by three kaolinitic soils and two model sorbents (kaolinite and humic acid) were measured as functions of the methanol volume fractions (f (c) ≤ 0.4) and ionic compositions (CaCl(2) and KCl). The solubility of 1-NAPA was also measured in various ionic compositions. The sorption data were interpreted using the cosolvency-induced sorption model. The K (m) values (= the linear sorption coefficient) of NAP with kaolinitic soil for both ionic compositions was log linearly decreased with f (c). However, the K (m) values of 1-NAPA with both ionic compositions remained relatively constant over the f (c) range. For the model sorbent, the K (m) values of 1-NAPA with kaolinite for the KCl system and with humic acid for both ionic compositions decreased with f (c), while the sorption of 1-NAPA with kaolinite for the CaCl(2) system was increased with f (c). From the solubility data of 1-NAPA with f (c), no significant difference was observed with the different ionic compositions, indicating an insignificant change in the aqueous activity of the liquid phase. In conclusion, the enhanced 1-NAPA sorption, greater than that predicted from the cosolvency-induced model, was due to an untraceable interaction between the carboxylate and hydrophilic soil domain in the methanol-water system. Therefore, in order to accurately predict the environmental fate of acidic pesticides and organic solutes, an effort to quantitatively incorporate the enhanced hydrophilic sorption into the current cosolvency-induced sorption model is required.     

Sorption of ionic liquids onto soils: experimental and chemometric studies

Chemometric analyses are a great tool to support typical experimental studies of the interactions of xenobiotics with natural environment. Such interpretations are able to determine statistically significant correlations and finally lead to identification of the major sorption factors. However, to effectively use chemometrics a bigger data set is required. Even though the ionic liquids are intensively studied, their complete fate or prediction of their behavior in the natural environment is still unclear. Therefore, to evaluate and distinguish the patterns of interactions of ILs in soil environment by chemometrics, sorption of nine ionic liquids (imidazolium and pyridinium chlorides) on 11 types of various soils was tested. Experimental studies indicated that compounds with longer alkyl side chains were sorbed far more strongly than weakly lipophilic ones. Moreover, salts with short and/or hydroxylated derivatives were more mobile in soils/sediments and thus, might cause a danger of contamination of surface or ground waters. Cluster analysis revealed that ionic liquids form two major clusters according to interaction with soil surface - one grouping compounds with short and hydroxylated alkyl side chains and the second with the rest of compounds. Pairwise scatterplots for correlations between soil variables and sorption coefficients indicated that the main soil parameter responsible for the sorption was cation exchange capacity. Correlation of sorption coefficients, K(d), with pH indicated the existence of lower sorption potency in lower pH values.     

Evaluation of accelerated dechlorination of p,p'-DDT in acidic paddy soil

The reductive dechlorination and behavior of p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) was investigated in a paddy soil. Treatment with 5% (w/w) metallic iron (Fe(0)) resulted in sharp decrease of p,p'-DDT, whereas there was no extra effect when 2% (w/w) aluminum sulfate (Al(2)(SO(4))(3)) was added to the Fe(0) treatment. These results suggest that Fe(0) could effectively promote the reductive dechlorination of p,p'-DDT and its metabolites while Al(2)(SO(4))(3) did not show any effect on those processes. Furthermore, p,p'-DDT and its daughter compounds inhibited holistic soil respiration greatly at first but could be metabolized by certain species of indigenous microorganisms after a period of adaptation time in the soil. When treated with Fe(0), the polluted soil produced much less CO(2) while the addition of Al(2)(SO(4))(3) counteracted its negative effect to much extent.     

Sorption-desorption of atrazine and diuron in soils from southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of 14C-atrazine and 14C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L(-1)). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R2 >or= 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06-0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.     

Sorption of acidic organic solute onto kaolinitic soils from methanol-water mixtures

The fate of the acidic organic solute from the soil-water-solvent system is not well-understood. In this study, the effect of the acidic functional group of organic solute in the sorption from cosolvent system was evaluated. The sorption of naphthalene (NAP) and 1-naphthoic acid (1-NAPA) by three kaolinitic soils and two model sorbents (kaolinite and humic acid) were measured as functions of the methanol volume fractions (f _c ≤ 0.4) and ionic compositions (CaCl₂ and KCl). The solubility of 1-NAPA was also measured in various ionic compositions. The sorption data were interpreted using the cosolvency-induced sorption model. The K _m values (= the linear sorption coefficient) of NAP with kaolinitic soil for both ionic compositions was log linearly decreased with f _c. However, the K _m values of 1-NAPA with both ionic compositions remained relatively constant over the f _c range. For the model sorbent, the K _m values of 1-NAPA with kaolinite for the KCl system and with humic acid for both ionic compositions decreased with f _c, while the sorption of 1-NAPA with kaolinite for the CaCl₂ system was increased with f _c. From the solubility data of 1-NAPA with f _c, no significant difference was observed with the different ionic compositions, indicating an insignificant change in the aqueous activity of the liquid phase. In conclusion, the enhanced 1-NAPA sorption, greater than that predicted from the cosolvency-induced model, was due to an untraceable interaction between the carboxylate and hydrophilic soil domain in the methanol-water system. Therefore, in order to accurately predict the environmental fate of acidic pesticides and organic solutes, an effort to quantitatively incorporate the enhanced hydrophilic sorption into the current cosolvency-induced sorption model is required.     

离子液体R_3NANR_3的制备及其脱硫性能

以二元酸和短链叔胺为原料,合成了已二酸三乙胺盐离子液体———R3NANR3。对该离子液体进行SO2气体的循环吸收和解吸行为的研究。实验结果表明,R3NANR3离子液体能对SO2气体进行有效的化学吸收。该吸收过程分二步进行,以第一步吸收为主。室温下（20℃）该离子液体在3 h以内吸收速率较快,3 h后吸收速率减慢并逐渐达到平衡。R3NANR3离子液体与SO2气体饱和吸收量的物质的量之比为1.08。较高温度将导致SO2气体的解吸,在90℃时饱和吸收液能较充分地解吸,残留量为0.0010 mol/L。多次吸收和解吸测试表明,R3NANR3离子液体能实现对SO2气体的循环吸收和分离,将成为烟气中SO2气体的脱除和利用的重要循环吸收剂。     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg(-1) degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg(-1) application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to >70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of (14)C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative (14)CO(2) was less than 1.5% of applied (14)C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

Toxicity of imidazolium- and pyridinium-based ionic liquids and the co-metabolic degradation of N-ethylpyridinium tetrafluoroborate

We examined the effects of the ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF₆], N-ethylpyridinium tetrafluoroborate [EtPy][BF₄], and N-ethylpyridinium trifluoroacetate [EtPy][CF₃COO] on Pseudomonas fluorescens, a ubiquitous soil bacterium. In the presence of 0.5- and 1% of [BMIM][PF₆] or [EtPy][CF₃COO] the growth of bacteria was inhibited, whereas exposing them to 1% [EtPy][BF₄] increased the lag period wherein bacteria adapt to growth conditions before continuing to grow. However, at higher concentrations (5% and 10%), no growth was observed. The inhibitory effects were evident by a decrease in the optical density of the culture, a decline in the consumption of the carbon source, citric acid, and a change in the size of the bacterium. At concentrations below 1%, [EtPy][BF₄] was metabolized by P. fluorescens in the presence of citric acid. Oxidation of the side alkyl-chain of [EtPy][BF₄] caused the accumulation of N-hydroxylethylpyridinium and pyridinium as major degradation products.     

Determination of solid-liquid partition coefficients (Kd) for the herbicides isoproturon and trifluralin in five UK agricultural soils

Isoproturon and trifluralin are herbicides of contrasting chemical characters and modes of action. Standard batch sorption procedures were carried out to investigate the individual sorption behaviour of 14C-isoproturon and 14C-trifluralin in five agricultural soils (1.8-4.2% OC), and the soil solid-liquid partition coefficients (Kd values) were determined. Trifluralin exhibited strong partitioning to the soil solid phase (Kd range 106-294) and low desorption potential, thus should not pose a threat to sensitive waters via leaching, although particle erosion and preferential flow pathways may facilitate transport. For isoproturon, soil adsorption was low (Kd range 1.96-5.75) and desorption was high, suggesting a high leaching potential, consistent with isoproturon being the most frequently found pesticide in UK surface waters. Soil partitioning was directly related to soil organic carbon (OC) content. Accumulation isotherms were modelled using a dual-phase adsorption model to estimate adsorption and desorption rate coefficients. Associations between herbicides and soil humic substances were also shown using gel filtration chromatography.     

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.     

The impact of contact time on pyrene sorptive behavior by a sandy-loam soil

Batch experiments with pyrene (PYR) were conducted to quantify the effect of contact time on its sorption and desorption behavior by a sandy-loam soil. Twenty-four and 48 h contact times were chosen for the nonequilibrium conditions and 240 h for the pseudoequilibrium study. All times was selected based on the kinetic results. The nonlinear, pseudoequilibrium sorption isotherm was fit to a two-stage Freundlich model: 3-7 mg/l for the first stage and 7-15 mg/l for the second stage. A substantial fraction of the sorbed PYR was not desorbed within the given desorption time. The reason of hysteresis was found to be a sorption enhancement due to soil hydration which provided more sorption sites. A desorption enhancement at 240-h desorption steps was attributed to the increased dissolved organic matter evolution. This study also found that both soil organic matter and clay materials had an equal role in PYR sorption enhancement and desorption resistance.     

Sorption-Desorption of Atrazine and Diuron in Soils from Southern Brazil

The objective of this study was to investigate the behavior of sorption and desorption of the herbicides atrazine (6-chloro-N ²-ethyl-N ⁴-isopropyl-1,3,5-triazine-2,4-diamine) and diuron [3-(3,4-dichlorophenyl)-1,1-dimethyleurea] in soil samples from a typical lithosequence located in the municipality of Mamborê (PR), southern Brazil. Five concentrations of ¹⁴C-atrazine and ¹⁴C-diuron were used for both herbicides (0.48, 0.96, 1.92, 3.84, and 7.69 mg L^?1). Sorption of both herbicides correlated positively with the organic carbon and clay content of the soil samples. Sorption isotherms were well described by the Freundlich model. The slope values of the isotherm (N) ranged from 0.84 to 0.90 (atrazine) and from 0.75 to 0.79 (diuron) for the lithosequence samples. Sorption of diuron was high regardless of the soil texture or the concentration added. The desorption isotherms for atrazine and diuron showed good fit to the Freundlich equation (R ² ≥ 0,87). Atrazine slope values for the desorption isotherms were similar for the different concentrations and were much lower than those observed for the sorption isotherms. Significant hysteresis was observed in the herbicide desorption. When the two herbicides were compared, it was found that diuron (N = 0.06–0.22) presented more pronounced hysteresis than atrazine. The results showed that, quantitatively, a greater atrazine fraction applied to these soils remains available to be leached in the soil profile, as compared to diuron.     

Bioavailability and mass balance studies of a commercial pentabromodiphenyl ether mixture in male Sprague-Dawley rats

Cyanogenic glycosides are common plant toxins. Toxic hydrogen cyanide originating from cyanogenic glycosides may affect soil processes and water quality. In this study, hydrolysis, degradation and sorption of dhurrin (4-hydroxymandelonitrile-beta-d-glucoside) produced by sorghum has been studied in order to assess its fate in soil. The log K(ow) of dhurrin was -1.18+/-0.08 (22 degrees C). Hydrolysis was a first-order reaction with respect to dhurrin and hydroxyl ion concentrations. Half lives ranged from 1.2h (pH 8.6; 25 degrees C) to 530d (pH 4; 25 degrees C). The activation energy of hydrolysis was 112+9kJ. At pH 5.8 and room temperature, addition of humic acids (50gl(-1)) increased the rate of hydrolysis tenfold, while addition of kaolinite or goethite (100-250gl(-1)) both decreased the rate considerably. No significant sorption to soil components could be observed. The degradation rates of dhurrin in top and subsoils of Oxisols, Ultisols, Alfisols and Mollisols were studied at 22 degrees C (25mgl(-1), soil:liquid 1:1 (w:V), pH 3.8-8.1). Half-lives were 0.25-2h for topsoils, and 5-288h in subsoils. Hydrolysis in solution explained up to 45% of the degradation in subsoils whereas the contribution in topsoils was less than 14%, indicating the importance of enzymatic degradation processes. The highest risk of dhurrin leaching will take place when the soil is a low activity acid shallow soil with low content of clay minerals, iron oxides and humic acids.     

Sorption and Desorption Behavior of Chloroanilines and Chlorophenols on Montmorillonite and Kaolinite

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.0 g of clay were equilibrated with 100.0 mL solutions of each chemical at concentrations ranging from 10.0 to 200.0 mg/L. The uptake of the compounds was deduced from the results of HPLC-UV-Vis analysis. The lipophilic species were best retained by both clay materials. The most lipophilic chemical used in the study, 2,4,6-trichloroaniline, was also the most strongly retained, with sorption of up to 8 mg/g. In desorption experiments, which also relied on HPLC-UV-Vis technique, 2,4,6-trichloroaniline was the least desorbed from montmorillonite. However, on kaolinite all of the compounds under study were irreversibly retained. The experimental data have been modelled according to the Langmuir and Freundlich isotherms. A hypothesis is proposed concerning the sorption mechanism and potential applications of the findings in remediation strategies have been suggested.