Distribution of organophosphate insecticides in a Thai biomass-water system

Sorption and leaching of the organophosphate (OP) pesticides chlorpyrifos, profenofos, methyl parathion and malathion were investigated with four different types of biomass: coconut husk, rice husk, peat moss and peanut shell. Organic carbon contents of the biomass were in the range of 35.4–45.4%. Sorption studies were carried out by the batch (equilibrium) method at 4 different OP spike concentrations and at pH 3–7. Sorption isotherms conformed to a linear Freundlich equation and the Freundlich constant or sorption coefficient (K_D) confirmed that biomass organic carbon content was the principal sorbent factor affecting OP sorption. For a given sorbent, correlation of the extent of sorption with sorbate chemical properties was examined. Column leaching experiments involving different masses of coconut husk and peanut shell pre-spiked with OPs at the level equivalent to actual spraying concentrations in some Thai tangerine orchards were conducted. These experiments included repeated spikings and leaching. A water flow rate of 20 mL min^?1 was employed corresponding to the current average watering regime. Retardation and biodegradation with these sorbents were also examined.     

Use of biomass sorbents for oil removal from gas station runoff

The use of biomass sorbents, which are less expensive and more biodegradable than synthetic sorbents, for oil removal from gas station runoff was investigated. A bench-scale flume experiment was conducted to evaluate the oil removal and retention capabilities of the biomass sorbents which included kapok fiber, cattail fiber, Salvinia sp., wood chip, rice husk, coconut husk, and bagasse. Polyester fiber, a commercial synthetic sorbent, was also experimented for comparison purpose. Oil sorption and desorption tests were performed at a water flow rate of 20 lmin-1. In the oil sorption tests, a 50 mgl(-1) of used engine oil-water mixture was synthesized to simulate the gas station runoff. The mass of oil sorbed for all sorbents, except coconut husk and bagasse, was greater than 70%. Cattail fiber and polyester fiber were the sorbents that provided the least average effluent oil concentrations. Oil selectivity (hydrophobic properties) and physical characteristics of the sorbents are the two main factors that influence the oil sorption capability. The used sorbents from the sorption tests were employed in the desorption tests. Results indicated that oil leached out of all the sorbents tested. Polyester fiber released the highest amount of oil, approximately 4% (mass basis) of the oil sorbed.     

Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells

Purpose

The sorption of sulfamethoxazole, a frequently detected pharmaceutical compound in the environment, onto walnut shells was evaluated.

Methods

The sorption proprieties of the raw sorbent were chemically modified and two additional samples were obtained, respectively HCl and NaOH treated. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric (TG/DTG) techniques were applied to investigate the effect of the chemical treatments on the shell surface morphology and chemistry. Sorption experiments to investigate the pH effect on the process were carried out between pH?2 and 8.

Results

The chemical treatment did not substantially alter the structure of the sorbent (physical and textural characteristics) but modified the surface chemistry of the sorbent (acid?Cbase properties, point of zero charge??pH_pzc). The solution pH influences both the sorbent??s surface charge and sulfamethoxazole speciation. The best removal efficiencies were obtained for lower pH values where the neutral and cationic sulfamethoxazole forms are present in the solution. Langmuir and Freundlich isotherms were applied to the experimental adsorption data for sulfamethoxazole sorption at pH?2, 4, and 7 onto raw walnut shell. No statistical difference was found between the two models except for the pH?2 experimental data to which the Freundlich model fitted better.

Conclusion

Sorption of sulfamethoxazole was found to be highly pH dependent in the entire pH range studied and for both raw and treated sorbent.     

Sorption and degradation of pharmaceuticals and personal care products (PPCPs) in soils

Pharmaceuticals and personal care products (PPCPs) are one class of the most urgent emerging contaminants, which have drawn much public and scientific concern due to widespread contamination in aquatic environment. Most studies on the environmental fate and behavior of PPCPs have focused on nonsteroidal anti-inflammatory drugs. Some other compounds with high concentrations were less mentioned. In this study, sorption and degradation of five selected PPCPs, including bisphenol A (BPA), carbamazepine (CBZ), gemfibrozil (GFB), octylphenol (OP), and triclosan (TCS) have been investigated using three different soils. Sorption isotherms of all tested PPCPs in soils were well described by Freundlich equation. TCS and OP showed moderate to strong sorption, while the sorption of GFB and CBZ in soils was negligible. Degradation of PPCPs in three soils was generally fitted first-order exponential decay model, with half-lives (t _1/2) varying from 9.8 to 39.1 days. Sterilization could prolong the t _1/2 of PPCPs in soil, indicating that microbial activity played an important role in the degradation of these chemicals in soils. Degradation of PPCPs in soils was also influenced by the soil organic carbon (f _oc) contents. Results from our data show that sorption to the soils varied among the different PPCPs, and their sorption affinity on soil followed the order of TCS > OP > BPA > GFB > CBZ. The degradation of the selected PPCPs in soil was influenced by the microbial activity and soil type. The poor sorption and relative persistence of CBZ suggest that it may pose a high leaching risk for groundwater contamination when recycled for irrigation.     

Long-term tillage effects on soil metolachlor sorption and desorption behavior

Sorption and desorption are two important processes that influence the amount of pesticides retained by soils. However, the detailed sorption mechanisms as influenced by soil tillage management are unclear. This study examined the sorption and desorption characteristics of metolachlor [2-chloro-N-(2-ethyl-6-methyphenyl)-N-(2-methoxy-1-methylethyl)-acetamide] using the soil samples collected from the long-term conservation tillage (CnT) and conventional tillage (CT) research plots established in 1979 in Darlinton, SC. Humic acid (HA) and humin were extracted from the soils and used in the sorption experiments along with the whole soil samples. The sorption experiments were conducted using a batch-equilibration method. Three sequential desorption rinses were carried out following the sorption experiments. By comparing metolachlor sorption and desorption results we observed hysteresis for all soil samples and their organic matter fractions. Sorption nonlinearity (N) and hysteresis were dependent on the structure and composition of soil organic matter (SOM), e.g., Freundlich isotherm exponents (N) of HA and humin from CnT were higher than those of CT treatment, which may be related to high aromaticity of SOM fractions in CT treatment. Sorption capacity (K'f) was positively correlated with soil organic carbon (SOC) content. These results show that long-term tillage management can greatly affect metolachlor sorption and desorption behavior probably by qualitative differences in the structural characteristics of the humic substances.     

Sorption kinetics and its effects on retention and leaching.

Sorption of pesticides to substrates used in biopurification systems is important as it controls the system's efficiency. Ideally, pesticide sorption should occur fast so that leaching of the pesticide in the biopurification system is minimized. Although modeling of pesticide transport commonly assumes equilibrium, this may not always be true in practice. Sorption kinetics have to be taken into account. This study investigated the batch sorption kinetics of linuron, isoproturon, metalaxyl, isoxaben and lenacil on substrates commonly used in a biopurification system, i.e. cow manure, straw, willow chopping, sandy loam soil, coconut chips, garden waste compost and peat mix. The first-order sorption kinetics model was fitted to the observed pesticide concentrations versus time resulting in an estimated kinetic rate constant alpha. Sorption appeared to be fast for the pesticides linuron and isoxaben, pesticides which were classified as immobile, while less mobile pesticides displayed an overall slower sorption. However, the substrate does not seem to be the main parameter influencing the sorption kinetics. Coconut chips, which is a substrate with a high organic matter content showed slow sorption for most of the pesticides. The effect of different estimated alpha values on the breakthrough of pesticides through a biopurification system was evaluated using the HYDRUS 1D model. Significant differences in leaching behavior were observed as a result of the obtained differences in sorption kinetics.     

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.     

Removal of Cu and Pb by tartaric acid modified rice husk from aqueous solutions

A study on the modification of rice husk by various carboxylic acids showed that tartaric acid modified rice husk (TARH) had the highest binding capacities for Cu and Pb. The carboxyl groups on the surface of the modified rice husk were primarily responsible for the sorption of metal ions. A series of batch experiments using TARH as the sorbent for the removal of Cu and Pb showed that the sorption process was pH dependent, rapid and exothermic. The sorption process conformed to the Langmuir isotherm with maximum sorption capacities of 29 and 108 mg/g at 27 +/- 2 degrees C for Cu and Pb, respectively. The uptake increased with agitation rate. Decrease in sorbent particle size led to an increase in the sorption of metal ions and this could be explained by an increase in surface area and hence binding sites. Metal uptake was reduced in the presence of competitive cations and chelators. The affinity of TARH for Pb is greater than Cu.     

纳米零价铁颗粒去除污染土壤HCl浸提液中的Pb

主要研究了纳米零价铁颗粒对土壤HCl浸提液中重金属Pb的去除效果。通过批实验探讨HCl浓度、纳米零价铁投入量以及处理时间对Pb去除率的影响。实验结果表明,纳米零价铁颗粒对浸提液中Pb的去除反应符合langmuir和freundlich等温吸附方程;反应遵循准一级反应动力学方程,标准化后的反应速率常数KSA=0.018 mL/(m2.min);反应30 min时,0.5 g纳米零价铁对1.0 mol/L的HCl所提取Pb(51.7 mg/L)的去除率达到91.8%。研究结果表明,纳米零价铁对土壤HCl浸提液中Pb具有良好去除效果,但相对于处理水溶液中的Pb,反应速率偏低。     

Sorption of Zn(II) in aqueous solutions by scoria

We conducted kinetic and equilibrium sorption experiments on removal of Zn(II) from aqueous solutions by scoria (a vesicular pyroclastic rock with basaltic composition) from Jeju Island, Korea, in order to examine its potential use as an efficient sorbent. The batch-type kinetic sorption tests under variable conditions indicated that the percentage of Zn(II) removal by scoria increases with decreasing initial Zn(II) concentration, particle size, and sorbate/sorbent ratio. However, the sorption capacity decreases with the decrease of the initial Zn(II) concentration and sorbate/sorbent ratio. Equilibrium sorption tests show that Jeju scoria has a larger capacity and affinity for Zn(II) sorption than commercial powdered activated carbon (PAC); at initial Zn(II) concentrations of more than 10mM, the sorption capacity of Jeju scoria is about 1.5 times higher than that of PAC. The acquired sorption data are better fitted to the Langmuir isotherm than the Freundlich isotherm. Careful examination of ionic concentrations in sorption batches suggests that the sorption behavior is mainly controlled by cation exchange and typically displays characteristics of 'cation sorption'. The Zn(II) removal capacity decreases when solution pH decreases because of the competition with hydrogen ions for sorption sites, while the Zn(II) removal capacity increases under higher pH conditions, likely due to hydroxide precipitation. At an initial Zn(II) concentration of 5.0mM, the removal increases from 70% to 96% with the increase of initial pH from 3.0 to 7.0. We recommend Jeju scoria as an economic and efficient sorbent for Zn(II) in contaminated water.     

Sorption of alkylphenols on Ebro River sediments: comparing isotherms with field observations in river water and sediments

This study reports sorption isotherms of the endocrine disruptors nonylphenol (NP) and octylphenol (OP) in three sediment samples from the Ebro River basin (NE Spain), with organic carbon fractions (f_OC) ranging from 0.0035 to 0.082 g_OC g⁻¹. All isotherms were fitted to the Freundlich model with slightly nonlinear exponents ranging from 0.80 to 0.94. The solubility of the compounds as well as the organic carbon (OC) content had the strongest influences on the sorption behavior of these compounds. Comparison of the laboratory-spiked samples with the native contamination of NP of 45 water and concurrent sediment samples resulted in reasonable matches between both data sets, even though the lowest concentrations in the field were not completely reached in laboratory tests. This good agreement indicates that sorption laboratory data can be extrapolated to environmental levels and therefore the distribution of nonylphenol between sediments and water can be predicted with a precision of one order of magnitude. Furthermore, laboratory experiments with simultaneous loading of NP and OP revealed negligible competition for sorption sites at low concentrations.     

Sorption and desorption kinetics of diuron, fluometuron, prometryn and pyrithiobac sodium in soils

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac-sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r2 value > 0.98. The herbicide sorption as measured by the distribution coefficient (Kd) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac-sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the Kd values were normalised to organic carbon content of the soils (Koc), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac-sodium < fluometuron < prometryn < or = diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac-sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step (omega = [nad/nde - 1] x 100). Soil type and initial concentration had significant effect on omega. The effect of sorption and desorption properties of these four herbicides on the off-site transport to contaminate surface and groundwater are also discussed in this paper.     

Low cost sorbents for the removal of methyl parathion pesticide from aqueous solutions

Sorptive potential of selected agricultural waste materials i.e. rice (Oryza sativa) bran (RB), bagasse fly ash (BFA) of sugarcane (Saccharum officinarum), Moringa oleifera pods (MOP) and rice husk (RH) for the removal of methyl parathion pesticide (MP) from surface and ground waters has been investigated. Optimization of operating parameters of sorption process, i.e. sorbent dose, agitation time, pH, initial concentration of sorbate, and temperature have been studied. The sorption data fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) sorption isotherms. The maximum capacities of RB, BFA, MOP and RH for MP were calculated to be 3.6+/-0.8, 5.3+/-1.4, 5.2+/-1.5 and 4.7+/-1.0 mmolg(-1) by Freundlich, 0.39+/-0.009, 0.39+/-0.005, 0.36+/-0.004 and 0.35+/-0.008 mmolg(-1) by Langmuir and 0.9+/-0.08, 1.0+/-0.10, 1.0+/-0.10 and 0.9+/-0.07 mmolg(-1) by D-R isotherms respectively, employing 0.1g of each sorbent, at pH 6, 90 min agitation time and at 303 K. Application of first order Lagergren and Morris-Weber equations to the kinetic data yielded correlation coefficients, close to unity. Thermodynamic parameters of sorption process, i.e. DeltaH, DeltaS and DeltaG were computed and their negative values indicated the exothermic and spontaneous nature of sorption process. The pesticide may be stripped by sonication with methanol, making the regeneration and reutilization of sorbents promising. The sorbents investigated exhibited their potential applications in water decontamination, treatment of industrial and agricultural waste waters.     

Sorption of 1-hydroxy-2-naphthoic acid to goethite, lepidocrocite and ferrihydrite: batch experiments and infrared study

The adsorption of naphthoic acids to iron oxides and hydroxides influences strongly their mobility in soils and sediments. Sorption of 1-hydroxy-2-naphthoic acid (HNA) to three iron oxides was examined over a wide range of conditions (pH, ionic strength, sorbate and sorbent concentrations). In the examination of HNA sorption, Tempkin model was performed to fit sorption data of HNA onto all iron oxides. The adsorption in the Henry law range increases in the order: goethite相似文献   

Effect of sediment properties on the sorption of C12-2-LAS in marine and estuarine sediments

Linear alkylbenzene sulfonates (LAS) are anionic high production volume surfactants used in the manufacture of cleaning products. Here, we have studied the effect of the characteristics of marine and estuarine sediments on the sorption of LAS. Sorption experiments were performed with single sediment materials (pure clays and sea sand), with sediments treated to reduce their organic carbon content, and with field marine and estuarine sediments. C₁₂-2-LAS was used as a model compound. Sorption to the clays montmorillonite and kaolinite resulted in non-linear isotherms very similar for both clays. When reducing the organic content, sorption coefficients decreased proportionally to the fraction removed in fine grain sediments but this was not the case for the sandy sediment. The correlation of the sediment characteristics with the sorption coefficients at different surfactant concentrations showed that at concentrations below 10 μg C₁₂-2-LAS/L, the clay content correlated better with sorption, while the organic fraction became more significant at higher concentrations.     

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.     

Sorption of imazaquin in soils with positive balance of charges

The herbicide imazaquin has both an acid and a basic ionizable groups, and its sorption depends upon the pH, the electric potential (psi0), and the oxide and the organic carbon (OC) contents of the soil. Sorption and extraction experiments using 14C-imazaquin were performed in surface and subsurface samples of two acric oxisols (an anionic "rhodic" acrudox and an anionic "xanthic" acrudox) and one non-acric alfisol (a rhodic kandiudalf), treated at four different pH values. Imazaquin showed low to moderate sorption to the soils. Sorption decreased and aqueous extraction increased as pH increased. Up to pH 5.8, sorption was higher in subsurface than in surface layers of the acric soils, due to the positive balance of charges resulted from the high Fe and Al oxide and the low OC contents. It favored electrostatic interactions with anionic molecules of imazaquin. For the subsurface samples of these highly weathered soils, where psi0 was positive and OC was low, it was not possible to predict sorption just by considering imazaquin speciation and its hydrophobic partition to the organic domains of the soil. Moreover, if Koc measured for thesurface samples were assumed to represent the whole profile in predictive models for leaching potential, then it would result in underestimation of sorption potential in subsurface, and consequently result in overestimation of the leaching potential.     

Sorption isotherms of brominated diphenyl ethers on natural soils with different organic carbon fractions

Sorption isotherms of BDE-28 and BDE-47 on natural soils with different contents of soil organic matter (SOM) were investigated. Due to low water solubility of BDEs and resulted narrow ranges of aqueous equilibrium concentration, the linear distribution model showed similar and good fitting efficiency to the linear portion of nonlinear Freundlich curve. For the same sample, the linear and nonlinear model fitting sorption coefficients were close. At the statistically significant level of 0.05 or 0.1, significant relationships of total organic carbon fraction (fOC) with the fitting sorption coefficients can be observed. As for BDE-28, the relationships of fOC and SOM fractions with the single point partition coefficients at different aqueous concentrations of BDEs were significant; while for BDE-47, the relationships became less significant or insignificant, especially at higher aqueous concentrations. The findings in this study may facilitate more understanding on transport and fate of studied BDEs in soil systems.     

Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC = 0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measurable reduction in sorption of PCE by the Eustis soil (OC = 0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components.