Investigation of Two Magnetic Permanently Confined Micelle Array Sorbents Using Nonionic and Cationic Surfactants for the Removal of PAHs and Pesticides from Aqueous Media

Surfactants have been used for environmental remediation to remove hydrophobic organic compounds (HOCs) in water and soil. However, there are limited studies on the use of surfactants in confined micelle arrays to remove pesticides and polycyclic aromatic hydrocarbons from water. We studied the recovery of HOCs using two confined surfactants: nonionic Triton X-100 and cationic 3-(trimethoxysily)propyl-octadecyldimethyl-ammonium chloride (TPODAC). The micelle arrays were confined on a mesoporous silica matrix deposited onto a magnetic iron core. These magnetic, dispersible sorbents can be used to recover HOCs, minimizing the application of surfactants when compared to soil-washing techniques. The TPODAC-based sorbent had better average recovery of the HOCs studied compared to the Triton-X sorbent, and was, in general, comparable to activated carbon. It performed well with the chlorinated pesticides, in part due to additional interactions between the cationic sites and the polar compounds.     

土壤有机质对疏水性有机污染物的非线性吸附及其影响因素

土壤有机质(SOM)是土壤的重要组成部分,它对疏水性有机污染物(HOCs)的吸附作用对污染物在环境中的迁移转化有着至关重要的影响。近年来的一些研究表明,HOCs在SOM上的吸附行为并不严格地符合传统的线性分配模型。本文综述了近年来一些学者提出的SOM对HOCs的非线性吸附作用的机制及其影响因素,认为SOM的组成和结构均对HOCs的吸附有着重要的影响。SOM吸附在土壤矿物表面后,其结构或各组分的比例发生了改变,从而对其本身的吸附作用产生影响。溶液的化学环境(主要是阳离子)会对SOM的结构和吸附作用产生影响,特别是当溶液中存在一些过渡金属(如,铜或银)的离子时,共吸附的金属离子可能会与多环芳烃类分子形成阳离子-π键的作用,从而促进多环芳烃类物质在SOM上的吸附。     

Enhanced sorption of polycyclic aromatic hydrocarbons by soil amended with biochar

Purpose  

Polycyclic aromatic hydrocarbon (PAHs) are ubiquitous pollutants in agricultural soils in China. Biochar is the charred product of biomass pyrolysis, which is widely applied to soils to sequestrate atmospheric carbon dioxide and guarantees a long-term benefit for soil fertility. Knowledge about the impacts of various biochars on soil sorption affinity remains obscure. In this study, we evaluated the effects of various biochars on PAHs sorption to biochar-amended agricultural soil.     

表面活性剂与EDTA对紫色土镉的化学行为影响

Elemental composition and geochemical characteristics of iron-manganese nodules from nine main soils in China were studied by chemical and multivariate statistical analyses to better understand the reactions and functions of ironmanganese nodules in soils and sediment. Compared to the corresponding soils, Mn, Ba, Cd, Co and Pb had strong accumulation, Ni had moderate accumulation, while Ca, Cu, Fe, Na, P, Sr and Zn accumulated to a minor degree in the iron-manganese nodules. In contrast, Si, Al, K, Mg and Ti were reduced in the iron-manganese nodules. The contents of Ba, Cd, Co, Cu, Ni, Pb and Zn were positively and significantly correlated with that of MnO2 in the iron-manganese nodules, while the contents of Cr, Cu, Ni, Pb and Zn were positively and significantly correlated with that of Fe2O3 in soils. Based on a principle component analysis, the elements of iron-manganese nodules were divided into four groups： 1） Mn, Ba, Cd, Co, Cu, Li, Ni, Pb and Zn that were associated with Mn oxides, 2） Fe, Cr and P that were associated with Fe oxides, 3） Si, K, and Mg that were included in the elemental composition of phyllosilicate, and 4） Ca, Na, Al and Ti that existed in todorokite, birnessite, lithiophorite and phyllosilicate. It was suggested that accumulation, mineralization and specific adsorption were involved in the formation processes of soil iron-manganese nodules.     

Effect of SDBS–Tween 80 mixed surfactants on the distribution of polycyclic aromatic hydrocarbons in soil–water system

Purpose

Enhancing desorption of hydrophobic organic contaminants from soils is a promising approach for the effective remediation of soils contaminated with organic compounds. The desorption efficiency of chemical reagent, such as surfactant, should be evaluated. In this study, the effect of mixed anionic–nonionic surfactants sodium dodecylbenzene sulfonate (SDBS)–Tween 80 on the distribution of polycyclic aromatic hydrocarbons in soil–water system was evaluated.

Materials and methods

Batch desorption experiments were employed to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and surfactants in soil–water system. PAHs and SDBS were determined by high-performance liquid chromatography, Tween 80 by spectrophotometry, and total organic carbon with a carbon analyzer.

Results and discussion

Sorption of PAHs to soil was increased at low surfactant concentration due to the effective partition phase on soil formed by sorbed surfactants. The mixture of anionic and nonionic surfactants decreased the sorption of surfactants to soil, increasing the effective surfactant concentration in solution and thus decreasing the sorption of PAHs on soil. Anionic–nonionic mixed surfactant showed better performance on desorption of PAHs from soil than single surfactant. The greatest desorption efficiency was achieved with low proportions of SDBS (SDBS/Tween80?=?1:9).

Conclusions

SDBS–Tween 80 mixed surfactant showed the highest desorption rate with low proportion of SDBS, which indicated that the addition of relative low amount of anionic surfactant could significantly promote the desorption efficiency of PAHs by nonionic surfactants. Results obtained from this study did provide useful information in surfactant-enhanced remediation of soil and subsurface contaminated by hydrophobic organic compounds.     

Organic and inorganic phosphate interactions with soil hydroxy-interlayered minerals

Background  

Even though extensive work has been done on P interactions with free Al- and Fe-hydroxide minerals, limited or no information exists on sorption/desorption processes of organic and inorganic phosphate forms with soil hydroxy-interlayered minerals.     

Sorption of estrogens,triclosan, and caffeine in a sandy loam and a silt loam soil

Purpose  

Recently, pharmaceuticals and personal care products (PPCPs) have been identified in the environment. Concerns on the occurrence and fate of these compounds in soil and sediment have significantly increased. It is believed that these PPCPs sorb to soil and sediment; however, information on sorption of PPCPs is still limited. In this study, the sorption of estrone (E1), 17β-estradiol (E2), estriol (E3), 17α-ethynylestradiol (EE2), triclosan, and caffeine to two loam soils and Ottawa sand was assessed.     

Effect of soil pH on the sorption capacity of soil organic matter for polycyclic aromatic hydrocarbons in unsaturated soils

Sorption by soil organic matter (SOM) is considered the most important process affecting the bioavailability of hydrophobic organic chemicals (HOCs)in soil.The sorption capacity of SOM for HOCs is affected by many environmental factors.In this study,we investigated the effects of soil pH and water saturation level on HOC sorption capacity of SOM using batch sorption experiments.Values of soil organic carbon-water partition coefficient (K_OC) of six selected polycyclic aromatic hydrocar...     

Effects of ionic surfactants on the aggregate stability and water repellency of silt loam soil

Purpose

With the increase of surfactant usages, more and more concerns were paid on their effects on the physicochemical characteristics of soils. Up to now, only few researches have examined the effects of ionic surfactants on the stability of soil structure and soil water repellency.

Materials and methods

Cetyltrimethyl ammonium bromide (CTAB) as cationic surfactant and sodium dodecyl sulfate (SDS) as anionic surfactant were adopted to investigate their effects on the aggregate stability and water repellency of a silt loam soil which was sampled in Corn High-Tech Park, Huang-Huai-Hai region, China. (1) Aggregate stability: 50 g soil was mixture with 100 mL surfactant solution in a beaker. The concentrations of surfactant solutions were 0 (the blank), 200, 400, 600, 800, 1000, and 2000 mg L^?1, respectively. After 30 min, the soil was sieved and divided into four fraction aggregates. (2) Soil water repellency: the concentrations of surfactant solutions were the same as experiment 1. Forty grams of soil was blended with 80 mL surfactant solution in an aluminum specimen. Drying the water by oven of 40 °C firstly and then by air, the whole period was about 1 week. After that, soil water infiltration and sorptivity were measured.

Results and discussion

Compared to the blank, surfactants increased the amounts of 2–0.25 and <0.053 mm aggregates of the soil and decreased the amounts of 0.25–0.053 mm aggregates of the soil. Surfactants also increased the mean weight diameter (MWD) of the soil. Except the 200 mg L^?1 treatment, CTAB promoted the soil water infiltration. All SDS treatments impeded the soil water infiltration. The soil repellency factor (R) value of the blank was 1.22, lower than the critical value of 1.95, which implied that the soil of blank treatment was free of soil water repellency. For CTAB, only 200 and 400 mg L^?1 treatment’s R were higher than 1.95 while for SDS, all the treatment’s R were higher than 1.95.

Conclusions

Surfactants improved the stability of soil aggregates. Soil treated with CTAB did not show the repellency, whereas SDS treatment resulted in intense water repellency compared with the wettable blank soil. Findings of this study can be used to explain the role of ionic surfactants on soil structure stability as well as on the development of water repellency in lower soil depths.

     

Removal of trace and major metals by soil washing with Na<Subscript>2</Subscript>EDTA and oxalate

Background, aim, and scope  

Various metals such as cationic metals (Cu, Pb, Zn) and anionic metals (As, Cr) often coexist in real soils, and normal soil washing techniques for the removal of cationic metals with a single-washing reagent make it rather difficult to simultaneously remove all of them. Oxalate could effectively remove anionic As and EDTA could effectively remove the cationic metals, so it was possible to remove all coexisting cationic and anionic metals by washing with the combination of Na₂EDTA and oxalate. The objective of this study was to (1) discuss the possibility of removing five metals, As, Cd, Cu, Pb, and Zn, effectively from the soil by washing with Na₂EDTA-combined oxalate; (2) optimized through the consecutive washing.     

Competitive sorption of linear alkylbenzene sulfonate (LAS) surfactants and the antibiotics sulfamethoxazole and ciprofloxacin in wastewater-irrigated soils of the Mezquital Valley,Mexico

Purpose

The increasing reuse of wastewater for irrigation introduces surfactants and antibiotics into the environment. How these two kinds of compounds interact with regard to their sorption processes in soil is not clear.

Materials and methods

We performed batch experiments to investigate the sorption of linear alkylbenzene sulfonates (LAS) and its effect on sorption of sulfamethoxazole and ciprofloxacin in irrigated and non-irrigated soils with different organic matter (OM) contents.

Results and discussion

LAS sorption was non-linear in the presence of the antibiotics, and as general trend, it increased with rising OM content of soils. Free LAS was also removed from solution by complexation with Ca²⁺. Dissolved organic compounds released from soils with OM contents ≥18.4 g kg^?1 further reduced LAS sorption. Sorption of sulfamethoxazole was reduced by LAS sorption only in one soil with a small OM content of 9.5 g kg^?1.

Conclusions

The strong sorption of ciprofloxacin is not affected by LAS. Sulfamethoxazole sorption only competes with LAS sorption in organic matter-poor soils. Accumulation of organic matter in soils, for example due to long-term wastewater irrigation, provides extra sorption capacity for LAS and sulfamethoxazole so that competition for sorption sites is reduced.

     

表面活性剂对植物修复有机污染土壤的增效作用及原理

Phytoremediation is becoming a cost-effective technology for the in-situ clean up of sites polluted with hydrophobic organic contaminants （HOCs）. The major factors limiting phytoremediation are the mass transfer, rate of plant uptake, and microbial biodegradation of HOCs. This article discusses the potential of surfactants to enhance desorption, plant uptake, and biodegradation of HOCs in the contaminated sites. Positive effects of surfactants on phytoremediation have been recently observed in greenhouse studies. The presence of some nonionic surfactants including polyoxyethylene sorbltan monooleate （Tween 80） and polyoxyethylene（23）dodecanol （Brij35） at relatively low concentrations resulted in significant positive effects on phytoremediation for pyrene-contaminated soil. However, the anionic surfactant （sodium dodecyl sulfate, SDS） and the cationic surfactant （cetyltrimethylammonium bromide, CTMAB） were not useful because of their phytotoxicity or low efficiency for surfactant-enhanced phytoremediation （SEPR）. The mechanisms of SEPR for HOC-contaminated sites were evaluated by considering experimental observations. In view of concerns about the cost effectiveness and toxicity of surfactants to plants, more research is needed to enhance the use of SEPR technology.     

The use of a microbial contact toxicity test for evaluating cadmium bioavailability in soil

Background, Aims and Scope

Bioavailability of toxic compounds in soil can be defined as the fraction able to come into contact with biota and to cause toxic effects. The contact toxicity tests may detect the total toxic response of all bioavailable contaminants present in a sample. The objectives of this study were to evaluate the use of microbial contact toxicity tests for cadmium bioavailability assessment and to evaluate the relationship between sorption, soil characteristics and cadmium bioavailability.

Methods

A test soil bacterium,Bacillus cereus, was put in direct contact with the solid sample. Four unpolluted soils were selected to provide solid samples with a variety of physicochemical characteristics. The toxicity and sorption behaviour of cadmium spiked to the soil samples were determined.

Results, Discussion and Conclusions

A significant correlation between contact toxicity test results and partitioning of cadmium in the soil samples (r²= 0.79, p <0.05; n = 26) was found. The results confirm that the bioavailability of cadmium in soil depends on its sorption behaviour. Cadmium sorbed to the cation exchange sites associated with fulvic acids is non-bioavailable in the toxicity test employed in this study. It is concluded that the microbial contact toxicity test is a suitable tool for detecting cadmium bioavailablity in the soils used in this study.

Outlook

The application of microbial contact toxicity tests for bioavailability assessment can be very useful for the risk identification and remediation of soil-associated contaminants.     

Differences in sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid on artificial soils as a function of soil pre-aging

Purpose

The sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) to three different artificial soil mixtures was investigated. Artificial soils serve as model systems for improving understanding of sorption phenomena.

Materials and methods

The soils consisted of quartz, ferrihydrite, illite, montmorillonite, and charcoal. In a previous study, several selected mixtures had been inoculated with organic matter, and microbial aging (incubation) had been performed for different periods of time (3, 12, and 18?months) before conducting the sorption experiments. The effect of this pre-incubation time on the sorption behavior was determined. Interaction of MCPA with soil surfaces was monitored by aqueous phase sorption experiments, using high-performance liquid chromatography/ultraviolet and in selected cases Fourier-transformed infrared spectroscopy.

Results and discussion

The sorption behavior showed large differences between differently aged soils; Freundlich and linear sorption model fits (with sorption constants K _f , 1/n exponents, and K _d values, respectively) were given for pH?=?3 and the unbuffered pH of ??7. The largest extent of sorption from diluted solutions was found on the surfaces with a pre-incubation time of 3?months. Sorption increased at acidic pH values.

Conclusions

Regarding the influence of aging of artificial soils, the following conclusions were drawn: young artificial soils exhibit stronger sorption at lower concentrations, with a larger K _f value than aged soils. A correlation with organic carbon content was not confirmed. Thus, the sorption characteristics of the soils are more influenced by the aging of the organic carbon than by the organic carbon content itself.     

Kinetics and binding capacity of six soils for structurally defined hydrolyzable and condensed tannins and related phenols

Purpose  

We investigated tannin–soil interactions by assessing the kinetics of sorption and sorption capacities, and their relationship to the chemical properties of six polyphenolic compounds and the textures of six soils. We developed a new extraction procedure for recovering tannins from soil samples by successive extraction with solvents of decreasing polarity.     

Interactions of simazine, metsulfuron-methyl, and tetracycline with biochars and soil as a function of molecular structure

Purpose

Biochars are increasingly recognized as effective, inexpensive, and environmentally friendly sorbents for abating organic contaminants. In this study, the sorption and competitive sorption characteristics of simazine (SZ), metsulfuron-methyl (ME), and tetracycline (TC) to corn straw biochars and soil were examined to understand the interactions of herbicides and antibiotics with biochars and the potential role of biochars as engineered sorbents.

Materials and methods

Biochars were obtained by pyrolyzing corn straw at 400, 500, and 600 °C for 6 h under oxygen-limited conditions and were characterized via elemental analysis, N₂-BET surface area determination, ¹³C nuclear magnetic resonance spectroscopy, and Fourier transform infrared spectroscopy. Soil was collected from North Tanggu Farm in Tianjin, and its organic carbon, cation exchange capacity, and particle size distribution were analyzed. The batch sorption experiments were performed to obtain the sorption isotherms of SZ, ME, and TC to biochars and soil.

Results and discussion

The biochars that were pyrolyzed at higher temperatures had higher sorption affinities for SZ, ME, and TC, which may be due to the enhancement of hydrophobic interactions, charge transfer (π–π*) interactions, and pore-filling mechanism. The sorption affinities for these compounds to all biochars decreased in the order SZ?>?TC?>?ME, indicating that the neutral molecule with a stronger hydrophobicity is more easily adsorbed by biochars. For soil, the decrease of the sorption affinities followed the order TC?>?SZ?>?ME due to the high sorption affinity of TC with clays in the soil. Moreover, the sorption affinities of TC by biochars were lower than by soil, indicating that corn straw biochars may be not an ideal sorbent for the immobilization of TC. Biochars were much more effective in sorbing SZ and ME than soil, indicating that corn straw biochars can potentially prevent transport of the herbicides to surface and ground water. Nevertheless, the presence of TC significantly hinders biochar adsorption of SZ and ME, implying that the coexisting contaminants should be considered when developing biochars as engineered sorbents.

Conclusions

The observations in this study demonstrated that the sorption of organic contaminants by biochars is dependent on the properties of the biochars and the molecular structures of the contaminants. Corn straw biochars effectively retain SZ and ME and hinder their transportation to surface and ground water; however, the coexisting contaminants should be considered. Our results will be helpful for designing biochars as engineered sorbents for environmental applications.     

Availability of polycyclic aromatic hydrocarbons in aging soils

Purpose  

The soil contamination by hydrophobic organic contaminants (HOCs), such as polycyclic aromatic hydrocarbons (PAHs), poses great threats to human health and ecological security and attracts worldwide concerns. The total HOC concentrations overestimate its available fraction to the soil biota. Increased understanding of the availabilities of PAHs in soil environment will have considerable benefits for their risk assessment and be very instructive to food safety and remediation strategies in contaminated sites. However, the availability of PAHs in aging soils and particularly the correlations of the availabilities with their forms in soils have yet to be elucidated. In this work, the availabilities of PAHs in aging soils were evaluated using a sequential mild extraction technique.     

Evaluation of platinum distribution between different soil components

Purpose

More attention has been given to the determination of background levels of platinum group element (PGE) in an urban environment. But, few studies have been conducted for its environmental behaviour. The necessity to understand the PGE behaviour in environment increases due to the increase in platinum (Pt) emissions. The aim of the study is to evaluate the adsorption and the distribution of Pt within soil and sediment components. This study investigated the Pt adsorption on kaolinite, hematite and humic acid.

Materials and methods

A batch experiment was used to determine sorption of Pt. The experiments were carried out on the three solids and on two mixtures of iron oxide and kaolinite, with two ratios 25:75 and 75:25. An elemental distribution of Pt was determined on the mixtures iron oxide–kaolinite by micro-X-ray fluorescence.

Results and discussion

The highest concentrations of Pt were found on kaolinite, followed by hematite and humic acid. Kaolinite exhibited the highest adsorption capacity. The sorption capacity of both mixtures was lower than that of kaolinite and iron oxide. Moreover, the shape of isotherms, for both mixtures, tends towards that of kaolinite. The elemental distribution maps of mixtures showed, for both ratios, a high enrichment of kaolinite with Pt opposite to a slight enrichment of hematite.

Conclusions

The results showed that Pt is adsorbed mainly on kaolinite, which suggests that Pt was mainly associated with clay in soil. The results allowed the evaluation of the impact of the matrix of soil or sediment on the ability to retain or promote Pt dispersion in an urban environment.