Sorption and cosorption of organic contaminant on surfactant-modified soils

Three kinds of soils were modified with the cationic surfactants, hexadecyltrimethylammonium (HDTMA) bromide and tetramethylammonium (TMA) bromide to increase their sorptive capabilities. Sorption of chlorobenzene in simulated groundwater by these soils was investigated. HDTMA-modified soil has a higher ability to sorb chlorobenzene from simulated groundwater than unmodified soil. TMA-modified soil did not show the superiority. HDTMA thus can be used to modify soil to improve its sorption capability. Cosorption of chlorobenzene in simulated groundwater in the absence or presence of nitrobenzene and dichloromethane on HDTMA-modified soil was also investigated. Nitrobenzene facilitated sorption of chlorobenzene on all HDTMA-modified soil. Dichloromethane did not influence the sorption of chlorobenzene by HDTMA-modified soil. The results suggest that HDTMA-modified soil is a highly effective sorbent for chlorobenzene and multiple organic compounds did not impede the uptake of chlorobenzene.     

Sorption of hydrophobic organic compounds onto organoclays

The behavior and fate of nonionic hydrophobic organic compounds (HOCs) in the environment are mainly controlled by their interactions with various components of soils and sediments. Due to their large surface area and abundance in many soils, smectites may greatly influence the fate and transport of the contaminants in the environment. In our experiments, HOC sorption by hexadecyltrimethylammonium (HDTMA)-modified smectite linearly increased with the amount of HDTMA added to the clay. However, tetramethylammonium (TMA)- and dodecyltrimethylammonium (DTMA)-modified smectites showed not only inferiority in their sorption of HOC compared with the HDTMA-smectite, but also a partially decreased HOC sorption at specific surfactant loading levels. This means that the sorption of organoclays for organic contaminants was significantly influenced by the amount and size of the surfactants added on the clay. In addition, it seems that the interlayer structure (e.g., pore size) formed at each surfactant loading level plays an important role to adsorb HOC in different amount.     

Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient (K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.     

Influence of modified soils on the removal of diesel fuel oil from water and the growth of oil degradation micro-organism

Three soils were modified with two kinds of cationic surfactants in order to increase their sorptive capabilities for organic contaminants. Sorption of diesel fuel oil in water by these modified soils had been investigated. Modified soils can effectively sorb diesel fuel oil from water. The sorption capability of modified soils is: HDTMA-black soil > HDTMA-yellow brown soil > HDTMA-red soil > TMA-black soil > TMA-yellow brown soil > TMA-red soil. Sorption of diesel fuel oil by natural soils and HDTMA modified soils is via partition, the sorption isotherms can be expressed by Henry equation, and logK(SOM) is 2.42-2.80, logK(HDTMA) is 3.37-3.60. Sorption isotherms of TMA modified soils can be expressed by Langmuir equation, the saturation sorption capacities are 1150 (TMA-black soil), 750 (TMA-yellow-brown soil), 171 mg/kg (TMA-red soil), respectively. A diesel fuel oil degradation micro-organism (Pseudomonas sp.) was isolated in the lab. To test the influence of the modified soils on the micro-organism, various growth curves of Pseudomonas in different conditions were drawn. Pseudomonas can grow very well with natural soils and TMA modified soils. The acclimation period of Pseudomonas is reduced. As to HDTMA modified soils, HDTMA loading amount is very important. When HDTMA loading amount is no higher than 0.5 CEC, the micro-organism can grow very well after a long acclimation period.     

Efficient removal and mechanisms of water soluble aromatic contaminants by a reduced-charge bentonite modified with benzyltrimethylammonium cation

A novel strategy utilizing the phenyls interaction and the hydrophobic affinity of available siloxane surface in the interlayer of bentonite was proposed to improve the sorption capabilities of organobentonites for water soluble aromatic contaminants. A unique organobentonite (65BTMA) was synthesized by intercalating benzyltrimethylammonium cation (BTMA⁺) into the interlayer of a reduced-charge bentonite with cation exchange capacity (CEC) of 65 cmol kg⁻¹. Phenol, aniline and toluene were used as model compounds of water soluble aromatic contaminants. Their respective removal efficiencies by 65BTMA were achieved at 83.3%, 89.2% and 97.3% at the initial concentration of 20 mg l⁻¹. To reveal the sorption mechanism, sorption characteristics of aromatic contaminants to 65BTMA were compared with that of aliphatic contaminants in similar molecular size. And various organobentonites were prepared by combining TMA⁺ (tetramethylammonium), BTMA⁺, HTMA⁺ (heptyltrimethylammonium) and CTMA⁺ (cetyltrimethylammonium) with two bentonites (CEC = 108 and 65 cmol kg⁻¹). To 65BTMA, sorption magnitudes of aromatic contaminants were much greater than that of aliphatic compounds with similar size; and dramatically higher than those to other organobentonites at low pollutant concentrations. These observations revealed that the strong phenyls interactions contributed significantly to sorb the aqueous soluble aromatic contaminants to 65BTMA (>90%), and which favored to design uniquely powerful sorbents.     

Preparations of organobentonite using nonionic surfactants

Due to hydrophilic environment at its surface, natural bentonite is an ineffective sorbent for nonpolar nonionic organic compounds in water even though it has high surface area. The surface properties of natural bentonite can be greatly modified by simple ion-exchange reactions with large organic cations (cationic surfactants) and this organobentonite is highly effective in removing nonionic organic compounds from water. Cationic surfactant derived organobentonites have been investigated extensively for a wide variety of environmental applications. In this study, the preparation of organobentonite using nonionic surfactants has been investigated for the first time. Results indicate that nonionic surfactants intercalates into the interlamellar space of bentonite and may demonstrate higher sorption capacity than cationic surfactant. It is possible to create large interlayer spacing and high organic carbon content organobentonite by use of nonionic surfactants with suitable balance between the hydrocarbon and ethylene oxide chain lengths. In addition, nonionic surfactant derived organobentonites are more chemically stable than cationic surfactant derived organobentonites.     

Sorption and reduction of tetrachloroethylene with zero valent iron and amphiphilic molecules

Effects of surfactants and natural organic matter (NOM) on the sorption and reduction of tetrachloroethylene (PCE) with zero valent iron (ZVI) were examined in this study. PCE reduction by ZVI depended on the ionic type of the surfactants. The removal of PCE and production of TCE with non-ionic Triton X-100 and cationic hexadecyltrimethyl-ammonium (HDTMA) at one-half and two times the critical micelle concentration (CMC) were 1.2-1.8 times higher than without surfactants because of the enhanced PCE partitioning and surface concentration by the sorbed surfactants. When anionic sodium dodecyl benzene sulfonate (SDDBS) at one-half and two times CMC and NOM at 20 mg l(-1) and 50 mg l(-1) concentrations were used, the removal of PCE doubled and TCE production decreased. In the presence of SDDBS, TCE production by ZVI was lower than with HDTMA and Triton X-100 while PCE removal was higher than with the other surfactants.     

Fenuron sorption on homoionic natural and modified smectites

The adsorption isotherms of fenuron (1,1-dimethyl-3-phenylurea) on three smectites (SWy and SAz montmorillonites and SH hectorite) differing in their layer charge (SH相似文献   

Removal of phenols from water accompanied with synthesis of organobentonite in one-step process

A novel technology of wastewater treatment was proposed based on simultaneously synthesis of organobentonite and removal of organic pollutants such as phenols from water in one-step, which resulted that both surfactants and organic pollutants were removed from water by bentonite. The effects of contact time, pH and inorganic salt on the removal of phenols were investigated. Kinetic results showed that phenols and cetyltrimethylammonium bromide (CTMAB) could be removed by bentonite in 25 min. The removal efficiencies were achieved at 69%, 92% and 99%, respectively, for phenol, p-nitrophenol and beta-naphthol at the initial amount of CTMAB at about 120% cation exchange capacity of bentonite. Better dispersion property and more rapid bentonite sedimentation were observed in the process. The results indicated that the one-step process is an efficient, simple and low cost technology for removal of organic pollutants and cationic surfactants from water. The proposed technology made it possible that bentonite was applied as sorbent for wastewater treatment in industrial scale.     

固定化改性蒙脱土对苯酚吸附性能的研究

利用十六烷基三甲基溴化铵对天然蒙脱土进行改性,并用聚乙烯醇对改性蒙脱土进行固定化处理,然后进行柱状吸附和振荡条件的吸附试验。研究结果表明,HDTMA改性蒙脱土固定化后能有效吸附苯酚,不同环境条件对苯酚的柱状吸附能力产生不同的影响。在pH4~8的范围内,固定化改性蒙脱土对苯酚的吸附效果无显著性差异,pH在10以上,其吸附能力明显下降;温度对吸附效果影响不大;进水苯酚浓度越高,改性蒙脱土对苯酚的吸附量越大,但出水苯酚浓度也高;苯酚的流速越小,吸附容量越高,吸附效果越好。     

Comparison of modified montmorillonite adsorbents. Part II: The effects of the type of raw clays and modification conditions on the adsorption performance

This paper builds on the preceding researches to study the effects of the type of clays (montmorillonites K10, KSF) and modifying conditions on the structure and adsorption behavior of resulting clay adsorbents. The raw clays were modified by polymeric Al/Fe species, hexadecyl-trimethylammonium (HDTMA) surfactant and a complex of polymeric Al/Fe-HDTMA. X-ray diffraction spectra was applied to analyze the structure of the raw and modified clays. After modification, the basal spacing of the clays varied, depending on the types of raw clay and modification conditions. Copper and phenol were selected as adsorbates for evaluating the adsorption performance of various clays, which was affected significantly by the types of raw clay and modification conditions. In general the inorganic contaminant (e.g., Cu) tend to be adsorbed by the polymeric Al/Fe modified clay and the organic impurities (e.g., phenol) will be preferably captured by the surfactant modified clay; both due to the specific surface properties resulting from introducing the modifiers. The complex modified clays possessed the ability of adsorbing both inorganic and organic contaminants. In addition, the d 0 0 1 spacing of modified KSF was greater than that of K10; the adsorption performance with modified KSF was thus greater than that with the modified K10. Finally, the ratio of modifiers to the clay (metal:surfactant:clay) has been observed to affect the adsorption performance; the optimal conditions have been defined.     

Fenuron sorption on homoionic natural and modified smectites

Abstract

The adsorption isotherms of fenuron (l, l‐dimethyl‐3‐phenylurea) on three smectites (SWy and SAz montmorillonites and SH hectorite) differing in their layer charge (SH<SWy<SAz) and saturated with several inorganic and organic cations were determined. The isotherms and sorption parameters from Freundlich equation indicate low adsorptivity on inorganic clays, but medium sorption in organoclays (OCls). Fenuron adsorption on homoionic smectites increases with decreasing layer charge and hydratation power of the inorganic exchangeable cation (except Fe³⁺), indicating that fenuron adsorbs as neutral molecule on uncharged siloxane surface by hydrophobic bonding, with some contribution of polar bond (fenuron C=O group and water associated to exchangeable cation). In the case of Fe³⁺‐saturated smectite fenuron protonation, provided by the interlayer acidic environment, promotes further sorption of fenuron as cationic form. The sorption on organoclays is enhanced via hydrophobic interaction with organocations, which is favoured for high layer charge and basal spacing and organocation saturation close to CEC. Quaternary alkylamonium is more efficient in high layer charge smectite, whereas primary alkylammonium is more efficient in medium charge smectite. The low values of the maximum sorption obtained with homoionic inorganic and organic smectites (100 and 5000 μmol/Kg) represent one fenuron molecule for each 2000–200 exchange sites and indicate that fenuron sorption is mainly associated to the outer exchange sites. This low adsorptivity of fenuron, as consequence of its high water affinity (high water solubility) would suggest high mobility of fenuron in natural soil and water systems.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

Quantifying the sorption of organic chemicals on sediments

The use of a reference compound to quantify the sorption of nonpolar organic chemicals is proposed. This is because organic carbon normalized sorption coefficients (K_OC) do appear to be dependent on the type of sediment, and are thus not generally applicable to characterize the sorption properties of chemicals. Therefore, in this paper the hypothesis that nonpolar chemicals sorb in a constant ratio, independent of the sediment, has been investigated. Evidence for this hypothesis is shown with data from the literature. This enables one to compare sorption properties of nonpolar compounds on different sediments, if the differences between the sediments are normalized with a reference chemical rather than with the organic carbon content. Sediments with an organic carbon content of less than 0.1% seem to be unsuitable, because the compounds do not sorb mainly on the organic carbon, but also on other parts of the sediment. Sorption coefficients of compounds with aqueous solubilities in the μg per liter range or octan-1-ol water partition coefficients of more than 10⁵ are strongly influenced by the experimental techniques used. For these compounds the sorption coefficients measured by different techniques are less comparable. To enable comparison of sorption coefficients of hydrophobic chemicals, the use of a chlorobenzene as a reference compound in sorption experiments is suggested.     

Sorption of imidazolium-based ionic liquids to aquatic sediments

Ionic liquids (ILs) have received much attention as "green" alternatives to traditional solvents because they do not evaporate, eliminating concerns over fugitive emissions. However, if ionic liquids are used in industrial applications, they may enter aquatic systems via effluent, and their fate and transport may be influenced by sorption to sediments. In this study, we conducted batch mixing experiments with four alkylmethylimidizolium-based ILs and four types of aquatic sediments to asses the capacity for natural aquatic sediments to remove these chemicals from the water column. The concentration isotherms were non linear with point estimates of the distribution coefficient (K(d)) decreasing with increasing concentration. Apparent distribution coefficients ranged from 7.9 to 95.7l kg(-1) at an initial concentration of 0.5mM and were positively related to sediment organic matter (SOM) content. These K(d) values indicate that the ILs did not sorb strongly to the tested sediments. Increased alkyl chain length did not lead to increased sorption suggesting that hydrophobic interactions were not the most important sorption mechanism. We conclude that aquatic sediments have a limited capacity to sorb alkylmethylimidazolium ILs and that the transport of these contaminants in aquatic systems will not be strongly attenuated by sediments.     

Study of the contaminant transport into granite microfractures using nuclear ion beam techniques

Hydrated bentonite is a very plastic material and it is expected to enter in the rock microfractures at the granite/bentonite boundary of a deep geological high-level waste repository. This process is enhanced by the high swelling pressure of the clay. Since bentonite has a very good sorption capability for many radionuclides, the displacement of the clay might lead to a "clay-mediated" contaminant transport into the rock. The aim of this work is to study the contaminant transport into granite microfractures using nuclear ion beam techniques, and to determine to what extent the clay can favour it. To do so, bentonite previously doped with uranium, cesium and europium was put in contact with the surface of granite sheets. Granite sheets contacted with non-doped bentonite and with radionuclide solutions were also prepared as references. This allowed analysing the differences in the diffusion behaviour of the three systems: clay, radionuclides and clay plus radionuclides. A combination of Rutherford backscattering spectrometry (RBS) and other nuclear ion-beam techniques such as particle-induced X-ray emission (PIXE) and microPIXE was used to study the depth and lateral distribution of clay and contaminants inside granite. It was also tried to evaluate not only the diffusion depth and diffusion coefficients but also the different areas of the granite where the diffusants have a preferential access.     

改性膨润土对垃圾填埋场渗滤液吸附效果

通过制备不同组分改性膨润土,研究其对苯酚的吸附效果,结果表明,十六烷基三甲基溴化铵+十二烷基磺酸钠+硫酸铝-改性膨润土>十六烷基三甲基溴化铵+十二烷基磺酸钠-改性膨润土>十六烷基三甲基溴化铵-改性膨润土。通过改性膨润土对实际复杂组分渗滤液的吸附研究,结果表明,使用活性炭改性的膨润土吸附COD和NH4+-N最为理想,单位质量COD吸附量最高为26.8 mg/g,NH4+-N最高为3.92 mg/g,其中,COD最高去除率为77.3%,氨氮为28.9%;十六烷基三甲基溴化铵+十二烷基磺酸钠+硫酸铝-改性膨润土对COD和NH4+-N均有去除效果,两者对于渗滤液实际处理工程具有应用价值。     

Suitability of dye-clay complexes for removal of non-ionic organic compounds from aqueous solutions

Aqueous sorption of phenol, atrazine and naphthalene was measured on complexes formed from Na-montmorillonite (Fischer bentonite) and the organic cationic dyes crystal violet and rhodamine-B. Sorption isotherms were found to be non-linear. This agrees well with the rigid nature of the dye-clay organic coverage, which provides a finite surface for adsorption. High values of organic carbon-normalized distribution coefficients reached 20,000-25,000 for atrazine on rhodamine-B-montmorillonite, 7000 for atrazine on crystal violet-montmorillonite, and 1500 for phenol on crystal violet-montmorillonite. As such, dye-clays may significantly extend the variety of organoclay sorbents that effectively reduce aqueous concentrations of non-ionic organic compounds.     

Sulfamethoxazole sorption by sediment fractions in comparison to pyrene and bisphenol A

The environmental behavior of antibiotics has attracted great research attention. However, their sorption mechanisms in soils/sediments are still unknown. Comparison of the sorption properties between the widely-studied hydrophobic organic contaminants (HOCs) and antibiotics may provide valuable insight to antibiotic sorption mechanisms. Thus, in this study batch experiments for pyrene (PYR), bisphenol A (BPA), and sulfamethoxazole (SMX) sorption were conducted on a sediment sample and its separated fractions. Our results showed the high sorption of PYR on black carbon and organic matter. Although high sorption of SMX was observed for both separated organic fractions (humic acids) and inorganic mineral particles, the original sediment particles showed relatively low sorption. Competitive sorption between SMX and dissolved humic acid on mineral particles was observed in this study. This competitive interaction is a unique process for antibiotic sorption in soils/sediments compared with apolar HOCs and may be one of the important factors controlling the antibiotic sorption.