Adsorption–desorption behavior of atrazine on agricultural soils in China

Adsorptionanddesorptionareimportantprocessesthataffectatrazinetransport,transformation,andbioavailabilityinsoils.Inthisstudy,theadsorption–desorptioncharacteristicsofatrazinein three soils (laterite, paddy soil and alluvial soil) were evaluated using the batch equilibrium method. The results showed that the kinetics of atrazine in soils was completed in two steps: a “fast” adsorption and a “slow” adsorption and could be well described by pseudo-second-order model.In addition,the adsorption equilibrium isotherms were nonlinear and were well fitted by Freundlich and Langmuir models. It was found that the adsorption data on laterite, and paddy soil were better fitted by the Freundlich model;as for alluvial soil,the Langmuir model described it better. The maximum atrazine sorption capacities ranked as follows: paddy soil > alluvial soil > laterite. Results of thermodynamic calculations indicated that atrazine adsorption on three tested soils was spontaneous and endothermic. The desorption data showed that negative hysteresis occurred. Furthermore, lower solution pH value was conducive to the adsorptionofatrazineinsoils.Theatrazineadsorptioninthesethreetestedsoilswascontrolled by physical adsorption, including partition and surface adsorption. At lower equilibrium concentration, the atrazine adsorption process in soils was dominated by surface adsorption;while with the increase of equilibrium concentration, partition was predominant.     

Adsorption and desorption of herbicide monosulfuron-ester in Chinese soils

Monosulfuron-ester is a new, low rate, sulfonylurea herbicide that is being promoted for annual broadleaf and gramineal weed control; however, there is a lack of published information on its behavior in soils. The adsorption and desorption of monosulfuronester by seven type soils were measured using a batch equilibrium technique. The results showed that the Freundlich equation fitted its adsorption and desorption well, and the Freundlich constant values (Kf-ads) ranged from 0.88 to 5.66. Adsorption isotherms were nonlinear with 1/nf-ads values < 1. Soil pH, organic matter (OM), and clay content were the main factors influencing its adsorption and desorption. Adsorption and desorption were negatively correlated with pH 4.0–8.0 while positively correlated with OM and clay content. The adsorption of monosulfuron-ester was mainly a physical process, because its free energy (ΔG) in seven soils was less than 40 kJ/mol. Monosulfuron-ester adsorption by three soils increased with increasing CaCl2 concentration using CaCl2 as a background electrolyte. Monosulfuron-ester desorption was hysteretic in all tested soils.     

Adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ) in paddy soils cultivated for various years in the subtropical China

The adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ) on upland red soil,and paddy soils which were originated from the upland soil and cultivated for 8,15,35 and 85 years,were investigated using the batch method.The study showed that the organic matter content and cation exchange capacity (CEC) of the soils are important factors controlling the adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ).The 15-Year paddy soil had the highest adsorption capacity for Pb(Ⅱ),followed by the 35-Year paddy soil.Both the 35-Year paddy soil and 15-Year paddy soil adsorbed more Cu(Ⅱ) than the upland soil and other paddy soils.The 15-Year paddy soils exhibited the highest desorption percentage for both Cu(Ⅱ) and Pb(Ⅱ).These results are consistent with the trend for the CEC of the soils tested.The high soil CEC contributes not only to the adsorption of Cu(Ⅱ) and Pb(Ⅱ) but also to the electrostatic adsorption of the two heavy metals by the soils.Lower desorption percentages for Cu(Ⅱ) (36.7% to 42.2%) and Pb(Ⅱ) (50.4% to 57.9%) were observed for the 85-Year paddy soil.The highest content of organic matter in the soil was responsible for the low desorption percentages for the two metals because the formation of the complexes between the organic matter and the metals could increase the stability of the heavy metals in the soils.     

Adsorption behavior of ammonium by a bioadsorbent – Boston ivy leaf powder

The adsorption behaviors of ammonium ions from aqueous solution by a novel bioadsorbent, the Boston ivy (Parthenocissus tricuspidata) leaf powder (BPTL) were investigated. The SEM images and FT-IR spectra were used to characterize BPTL. The mathematical models were used to analyze the adsorption kinetics and isotherms. The optimum pH range for ammonium adsorption by BPTL was found to be 5–10. The adsorption reached equilibrium at 14 hr, and the kinetic data were well fitted by the Logistic model. The intraparticle di usion was the main rate-controlling step of the adsorption process. The high temperature was favorable to the ammonium adsorption by BPTL, indicating that the adsorption was endothermic. The adsorption equilibrium fitted well to both the Langmuir model and Freundlich model, and the maximum monolayer adsorption capacities calculated from Langmuir model were 3.37, 5.28 and 6.59 mg N/g at 15, 25 and 35°C, respectively, which were comparable to those by reported minerals. Both the separation factor (RL) from the Langmuir model and Freundlich exponent (n) suggested that the ammonium adsorption by BPTL was favorable. Therefore, the Boston ivy leaf powder could be considered a novel bioadsorbent for ammonium removal from aqueous solution.     

Effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils

Glyphosate （GPS） is a non-selective, post-mergence herbicide that is widely used throughout the world. Due to the similar molecular structures of glyphosate and phosphate, adsorption of glyphosate on soil is easily affected by coexisting phosphate, especially when phosphate is applied at a significant rate in farmland. This paper studied the effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils including two variable charge soils and one permanent charge soil. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients（0.990-0.998） with K values of 2751, 2451 and 166 for the zhuanhong soil（ZH soil, Laterite）, red soil（ RS, Udic Ferrisol） and Wushan paddy soil（WS soil, Anthrosol）, respectively. The more the soil iron and aluminum oxides and clay contained, the more glyphosate adsorbed. The presence of phosphate significantly decreased the adsorption of glyphosate to the soils by competing with glyphosate for adsorption sites of soils. Meanwhile, the effects of phosphate on adsorption of glyphosate on the two variable charge soils were more significant than that on the permanent charge soil. When phosphate and glyphosate were added in the soils in different orders, the adsorption quantities of glyphosate on the soils were different, which followed GPS-soil 〉 GPS-P-soil = GPS-Soil-P 〉 P-soil-GPS, meaning a complex interaction occurred among glyphosate, phosphate and the soils.     

Adsorption and desorption characteristics of diphenylarsenicals in two contrasting soils

Diphenylarsinic acid(DPAA) is formed during the leakage of aromatic arsenic chemical weapons in soils,is persistent in nature,and results in arsenic contamination in the field.The adsorption and desorption characteristics of DPAA were investigated in two typical Chinese soils,an Acrisol(a variable-charge soil) and a Phaeozem(a constant-charge soil).Their thermodynamics and some of the factors influencing them(i.e.,initial pH value,ionic strength and phosphate) were also evaluated using the batch method in order to understand the environmental fate of DPAA in soils.The results indicate that Acrisol had a stronger adsorption capacity for DPAA than Phaeozem.Soil DPAA adsorption was a spontaneous and endothermic process and the amount of DPAA adsorbed was affected significantly by variation in soil pH and phosphate.In contrast,soil organic matter and ionic strength had no significant effect on adsorption.This suggests that DPAA adsorption may be due to specific adsorption on soil mineral surfaces.Therefore,monitoring the fate of DPAA in soils is recommended in areas contaminated by leakage from chemical weapons.     

Effects of bile salts and divalent cations on the adsorption of norfloxacin by agricultural soils

The effects of bile salts （sodium cholate and sodium deoxycholate, 0-20 mmol/L）, divalent cations （Ca^2＋, Mg^2＋, Cu^2＋ and Zn^2＋, 0-20 mmol/L） or pH （3.0-10.0） on the adsorption of norfloxacin by three selected soils （Paddy_H, Paddy_G and Red_J） were systematically studied. Soil adsorption of norfloxacin follows a pseudo second-order kinetics model, and the maximum adsorption capacity has been determined from the nonlinear fit of the Langmuir isotherm model to be 88.8, 88.1 and 63.0 μmol/g for the adsorption onto Paddy_H, Paddy_G and Red_J, respectively. The results indicate that norfloxacin has a high adsorption affinity for the agricultural soils tested and that the organic content of these soils have at least a slight influence on this adsorption. The adsorption of norfloxacin to soils was strongly dependent on pH and exhibited a maximum at approximately pH 6. The presence of divalent cations prominently suppressed the adsorption of norfloxacin by paddy soils, which followed an order of Cu^2＋ 〉 Mg^2＋ 〉 Ca^2＋ 〉 Zn^2＋, and by red soil, which followed an order of Cu^2＋ 〉 Zn^2＋ 〉 Ca^2＋ 〉 Mg^2＋. The adsorption of norfloxacin （by the soils studied） sharply decreased as the amount of bile salts was increased. For uncharged norfloxacin at environmentally relevant pH values, such factors as soil type, exogenous divalent cations and macromolecules significantly altered the environmental fate and transport of norfloxacin between aquatic and soil interfaces.     

Adsorption of dyes onto activated carbon prepared from olive stones

Activated carbon was produced from olive stones（OSAC） by a physical process in two steps. The adsorption character of this activated carbon was tested on three colour dyes molecules in aqueous solution： Methylene blue（MB）, Rhodamine B（RB） and Congo Red（CR）. The adsorption equilibrium was studied through isotherms construction at 30℃, which were well described by Langmuir model. The adsorption capacity on the OSAC was estimated to be 303 mg/g, 217 mg/g and 167 mg/g respectively for MB, RB and CR. This activated carbon has a similar adsorption properties to that of commercial ones and show the same adsorption performances. The adsorption kinetics of the MB molecule in aqueous solution at different initial concentrations by OSAC was also studied. Kinetic experiments were well fitted by a simple intra-particle diffusion model. The measured kinetics constant was influenced by the initial concentration and we found the following correlation： Kid = 1.55 C0^0.51.     

Effects of dissolved organic matter from sewage sludge on sorption of tetrabromobisphenol A by soils

Sorption of tetrabromobisphenol A (TBBPA) by soil influences its fate and transport in the environment. The presence of dissolved organic matter (DOM) may complicate the sorption process in soil. The effects of DOM from sewage sludge on TBBPA sorption by three soils were investigated using batch equilibration experiments in the study. DOM was observed to be sorbed on the soils and the isotherms could be fitted by the Langmuir model. The effects of DOM on TBBPA sorption were dependent on the characteristics ...     

Effect of an eco-friendly o/w emulsion stabilized with amphiphilic sodium alginate derivatives on lambda-cyhalothrin adsorption–desorption on natural soil minerals

The effects of amphiphilic O/W emulsions,stabilized by the alkyl polyglycoside(APG)or cholesterol-grafted sodium alginate(CSAD)/APG systems,on lambda-cyhalothrin adsorption/desorption mechanisms on natural soil minerals(i.e.,illite and kaolinite)were investigated.Sorption and desorption of lambda-cyhalothrin onto soil minerals was studied via batch equilibration to give insight into the adsorption equilibrium,kinetics,and thermodynamics of lambda-cyhalothrin adsorption onto minerals.The results indicate the following:(i)The adsorption processes for the APG system and CSAD/APG system include:rapid adsorption,slow adsorption,and adsorption equilibrium.The adsorption kinetics of pesticide on illite and kaolinite are in accordance with the Ho and McKay model,and the adsorption isotherm conforms to the Freundlich model.In addition,the adsorption processes of pesticide for the two systems on minerals were spontaneous and feasible(ΔG~00),endothermic(ΔH~00),and mainly involved chemical bonding(ΔH~060).(ii)The equilibrium adsorption percentages of the pesticide on illite for the APG system and CSAD/APG system were 42.4%and 64.8%,and the corresponding equilibrium adsorption percentages on kaolinite were 40.8%and 61.8%,respectively.Moreover,the pesticide adsorption rate K_(2-CSAD/APG)was faster than K_(2-APG),and its adsorption capacity K_(f-CSAD/APG )was greater than K_(f-APG).Meanwhile,the pesticide desorption K_(fd)in the CSAD/APG system was smaller than that in the APG system.As a result,this eco-friendly O/W emulsion based on amphiphilic sodium alginate derivatives might provide a green pesticide formulation,since it could reduce the amount of lambda-cyhalothrin entering aquatic systems to threaten non-target fish and invertebrate species.     

Adsorption kinetics of the herbicide safeners, benoxacor and furilazole, to activated carbon and agricultural soils

Chloroacetamide herbicides, namely acetochlor and metolachlor, are common herbicides used on corn and soybean fields. Dichloroacetamide safeners, namely benoxacor and furilazole, are commonly used in formulations containing chloroacetamide herbicides. Extensive reports on adsorption of chloroacetamide herbicides are available, yet little information exists regarding adsorption potential of co-applied safeners. Herein, the adsorption and desorption characteristics of selected herbicide safeners to granular activated carbon (GAC) and in agricultural soils are reported. Further, soil column studies were performed to understand the leaching behaviour of the herbicide Dual II Magnum. Equilibrium sorption experiments of safeners to three agricultural soils and one GAC showed that adsorption was best fitted by the Freundlich isotherm. The Freundlich adsorption constant, K_f, for benoxacor and furilazole sorption onto three agricultural soils ranged from 0.1 to 0.27 and 0.1 to 0.13 (mg/g) × (mg/L)?(1/n), respectively. The K_f for benoxacor and furilazole to GAC was 6.4 and 3.4 (mg/g) × (mg/L)?(1/n), respectively, suggesting more favorable sorption of benoxacor to GAC than furilazole to GAC. The sorption to soils was reversible as almost 40%–90% of both safeners was desorbed from three soils. These results were validated in four replicated soil column studies, where S-metolachlor was shown to leach similarly to the safener benoxacor, originating from the herbicide formulation. The leaching of S-metolachlor and benoxacor was influenced by soil texture. Cumulatively, these results show that safeners will move through the environment to surface waters similarly to the active ingredients in herbicides, but may be removed during drinking water treatment via GAC.     

Effect of ionic strength on adsorption of As（Ⅲ） and As（Ⅴ） on variable charge soils

The study was to investigate the adsorption behavior of arsenite (As(Ⅲ)) and arsenate (As(Ⅴ)) on two variable charge soils, i.e., Haplic Acrisol and Rhodic Ferralsol at different ionic strengths and pH with batch methods. Results indicated that the amount of As(Ⅲ) adsorbed by these two soils increased with increasing solution pH, whereas it decreased with increasing ionic strength under the acidic condition. This suggested that As(Ⅲ) was mainly adsorbed on soil positive charge sites through electrostatic attraction under the acidic condition. Moreover, intersects of As(Ⅴ) adsorption-pH curves at different ionic strengths (a characteristic pH) are obtained for both soils. It was noted that above this pH, the adsorption of As(Ⅴ) was increased with increasing ionic strength, whereas below it the reverse trend was true. Precisely the intersect pH was 3.6 for Haplic Acrisol and 4.5 for Rhodic Ferralsol, which was near the values of PZSE (soil point of zero salt effect) of these soils. The effects of ionic strength and pH on arsenate adsorption by these soils were interpreted by the adsorption model. The results of zeta potential suggested that the potential in adsorption plane becomes less negative with increasing ionic strength above soil PZSE and decreases with increasing ionic strength below soil PZSE. These results further supported the hypothesis of the adsorption model that the potential in the adsorption plane changes with ionic strength with an opposite trend to surface charge of the soils. Therefore, the change of the potential in the adsorption plane was mainly responsible for the change of arsenate adsorption induced by ionic strength on variable charge soils.     

Adsorption leaching of l-(2-chlorobenzoyl)-3-(4-chlorophenyl)urea in soil

A study of adsorption of l-(2-chlorobenzoyl)-3-(4-chlorophenyl)urea(ccu)on fourtypes of soil was performed by using the batch slurry method．Freundlich adsorption isotherm equations of CCU in each soil were obtained and the method and the procedure were described in detail．At the same time，Freundlich adsorption coeffacient(K_{d)and organic carbon adsorption coefficient(Koc)were given for each soil．The leaching of CCU on different soils was also investigated under laboratory conditions．The results showed that CCU possesses a weak tendency of leaching to the deep layer of soil or contaminating the underground water．}     

Adsorption behavior of Azo Dye C. I. Acid Red 14 in aqueous solution on surface soils

Azo dyes have received considerable attention because of their association with various human health problems. The aim of the investigation is to determine the adsorption behavior ofazo dyes in aqueous solution on DG06, GSE17200, and GSE17201 soils using C. I. Acid Red 14 （AR14） as example. The experimental results indicate that the Freundlich model expresses the adsorption isotherm better than the Langmuir model and the pseudo-second-order model achieves adsorption of AR14 on the three soils well. Based on the pseudo-second-order model, the adsorption thermodynamic of AR14 on DG06 soil have been studied and the thermodynamics parameter of AGO is determined and AGO value shows the adsorption process of AR14 on DG06 is mainly physical in nature. Furthermore, the effects of temperature, pH and salinity （NaC1） on adsorption have been investigated. The decrease in pH or the increase in salinity enhances the adsorption of AR14 by DG06, GSE17200, and GSE17201.     

Sources of nitrous and nitric oxides in paddy soils：Nitrification and denitrification

Rice-paddies are regarded as one of the main agricultural sources of N 2O and NO emissions. To date, however, specific N2O and NO production pathways are poorly understood in paddy soils. ^15N-tracing experiments were carded out to investigate the processes responsible for N2O and NO production in two paddy soils with substantially different soil properties. Laboratory incubation experiments were carried out under aerobic conditions at moisture contents corresponding to 60% of water holding capacity. The relative importance of nitrification and denitrification to the flux of NaO was quantified by periodically measuring and comparing the enrichments of the N2O, NH~-N and NO3-N pools. The results showed that both N2O and NO emission rates in an alkaline paddy soil with clayey texture were substantially higher than those in a neutral paddy soil with silty loamy texture. In accordance with most published results, the ammonium N pool was the main source of N2O emission across the soil profiles of the two paddy soils, being responsible for 59.7% to 97.7% of total N2O emissions. The NO3-N pool of N2O emission was relatively less important under the given aerobic conditions. The rates of N2O emission from nitrification （N2On） among different soil layers were significantly different, which could be attributed to both the differences in gross N nitrification rates and to the ratios of nitrified N emitted as NzO among soil layers. Furthermore, NO fluxes were positively correlated with the changes in gross nitrification rates and the ratios of NO/N2O in the two paddy soils were always greater than one （from 1.26 to 6.47）. We therefore deduce that, similar to N2O, nitrification was also the dominant source of NO in the tested paddy soils at water contents below 60% water holding capacity.     

Effect of biosurfactant on the sorption of phenanthrene onto original and H2O2-treated soils

The objective of this study was to examine the effect of biosurfactant on the sorption of phenanthrene (PHE) onto the original or H2O2-treated black loamy soil (typic isohumisols) and red sandy soil (typic ferralisols). The sorption isotherms were performed with the original and “soft” carbon-removed soils in the presence and absence of biosurfactant (200 mg/L). The sorption and degradation of biosurfactant were investigated. The result showed that organic matter played an important role in PHE sorption onto the black loamy and red sandy soils, and the PHE sorption isotherms on the “soft” carbon-removed soils exhibited more nonlinearity than those on the original soils. The values of partition coe cient (Kd) on the original black loamy soil with or without 200 mg/L biosurfactant were 181.6 and 494.5 mL/g, respectively. Correspondingly, in the red sandy soil, Kd was 246.4 and 212.8 mL/g in the presence or absence of biosurfactant, respectively. The changes of Kd suggested that biosurfactant inhibited PHE sorption onto the black loamy soil, but facilitated PHE sorption onto the red sandy soil. The nonlinearity of PHE sorption isotherm was decreased in the presence of biosurfactant. Site specific sorption might occur during PHE sorption onto both the original and the “soft” carbon-removed soils in the presence of biosurfactant. It was noted that biosurfactant could also be sorbed onto soils. The maximal sorption capacity of the red sandy soil for biosurfactant was (76.9 0.007) g/g, which was 1.31 times that of black loamy soil. Biosurfactant was degraded quickly in the two selected soils, and 92% of biosurfactant were mineralized throughout the incubation experiment for 7 d. It implied that biosurfactant should be added frequently when the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils was conducted through PAH desorption approach facilitated by biosurfactant.     

Removal of phenol by activated carbons prepared from palm oil mill effluent sludge

The study was attempted to produce activated carbons from palm oil mill effluent （POME） sludge. The adsorption capacity of the activated carbons produced was evaluated in aqueous solution of phenol. Two types of activation were followed, namely, thermal activation at 300, 500 and 800%, and physical activation at 150% （boiling treatment）. A control （raw POME sludge） was used to compare the adsorption capacity of the activated carbons produced. The results indicated that the activation temperature of 800℃ showed maximum absorption capacity by the activated carbon （POME 800） in aqueous solution of phenol. Batch adsorption studies showed an equilibrium time of 6 h for the activated carbon of POME 800. It was observed that the adsorption capacity was higher at lower values ofpH （2--3） and higher value of initial concentration of phenol （200--300 mg/L）, The equilibrium data were fitted by the Langmuir and Freundlich adsorption isotherms. The adsorption of phenol onto the activated carbon POME 800 was studied in terms of pseudo-first and second order kinetics to predict the rate constant and equilibrium capacity with the effect of initial phenol concentrations. The rate of adsorption was found to be better correlation for the pseudo-second order kinetics compared to the first order kinetics.     

Removal of Methyl Violet from aqueous solutions using poly （acrylic acid.co-acrylamide）/attapulgite composite

The adsorption of Methyl Violet (MV) cationic dye from aqueous solution was carried out by using crosslinked poly (acrylic acid-co-acrylamide)/attapulgite (Poly(AA-co-AM)/ATP) composite as adsorbent. The factors influencing adsorption capacity of the composite such as pH, concentration of the dye, temperature, contact time, adsorbent dosage, ionic strength and surfactant were systematically investigated. The equilibrium data fitted very well to the Langmuir isotherm and the maximum adsorption capacity reached 1194 mg/g at 30°C. The thermodynamic parameters including G0, △H0 and △S 0 for the adsorption processes of MV on the composite were also calculated, and the negative △H0 and △G0 confirmed that the adsorption process was exothermic and spontaneous. The kinetic studies showed that the adsorption process was consistent with the pseudo second-order kinetic model and the desorption studies revealed that the regeneration of the composite adsorbent can be easily achieved.     

Quantifying hysteresis of atrazine desorption from a sandy loam soil

Batch experiments were carried out to investigate the effects of initial atrazine concentrations and consecutive desorption steps on the desorption characteristics of atrazine from a sandy loam soil.As initial atrazine concentration increased,the average percentage of atrazine desorption on the sandy loam soil ranged gradually from 23.1% to 38.5% after five consecutive desorption steps.The values of the Freundlich capacity parameter,kdes,derived from the initial concentration and time-dependent desorption isotherm were consistently higher than those associated with sorption.The opposite trend was observed only for the values of nonlinear parameter,ndes,from the initial concentration-dependent desorption isotherms.Atrazine hydrolysis to hydroxyatrazine and bound residue formation were mainly responsible for the observed hysteresis in its sorption and desorption isotherms.For the initial concentration-dependent desorption isotherms,as initial atrazine concentration increased,the values of hysteretic coefficients ω and λ decreased,and H values increased.However,the relationships between initial atrazine concentration and hysteretic coefficients were not pronounced for ω,H,or λ.For the time-dependent desorption isotherms,λ and H values increased as the atrazine desorption step proceeded.The correlation between hysteretic coefficient and desorption step was highly significant for λ (P 0.0001),but not for H.