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Over the past decades, contamination of terrestrial environments with antimony (Sb) has aroused a great deal of public concern. In this research, the efficacy of Fe(III)-modified montmorillonite (Mt) (Fe-Mt) for the removal of Sb(V) from aqueous solutions with Sb(V) concentration in the range of 0.2–1 mmol L−1 and immobilization of Sb(V) in soils spiked with 250 mg Sb(V) kg−1 was investigated. The immobilizing mechanisms of the modified clay were assessed by fitting the experimental sorption data with the Langmuir and Freundlich sorption models and a series of single and sequential extraction studies. The results showed that the adsorption data had a better fit with the Langmuir equation (R2: 0.99) and Fe-Mt could efficiently remove up to 95% of Sb(V) at lower concentration ranges. The concentrations of Sb(V) in exchangeable fraction of modified Community Bureau of Reference (BCR) sequential extraction and distilled water extracts of the amended soils decreased dramatically by up to 60% and 92%, respectively. Furthermore, the bioaccessibility of Sb(V) in simulated human gastric juice reduced remarkably by 52% to 60%, depending upon the soil fraction sizes. The results confirmed that Fe-Mt could be a promising candidate for the removal of Sb(V) from aqueous solutions and immobilization of Sb(V) in terrestrial environments.

Arsenic (As) and antimony (Sb) are metalloids that belong to group 15 of the periodic table and exhibit toxic properties in the environment. They mostly occur naturally at low concentrations in soil, although these can be significantly elevated in both aquatic and terrestrial food chains as a result of dispersion from anthropogenic sources, e.g., mining activities. The bioavailability, i.e., the proportion of the contaminant in soil and dust that is available for uptake by plants and other living organisms, presents the greatest risk to terrestrial ecosystems. Various in vivo and in vitro methods have been used to measure As and Sb bioaccessibility in soil and dust. In vivo measurement of bioavailability can be time consuming, expensive, and unethical; thus, in vitro methods are commonly preferred. However, there is considerable uncertainty around the efficacy of in vitro tools used to measure the bioavailable fractions of As and Sb. The results of these methods are dependent on many variables, e.g., soil characteristics, contaminant sources, and chemical composition of in vitro methods. Therefore, substantial variations are observed between in vitro and in vivo results obtained from different test animals and endpoints. In this paper, we review the literature on As and Sb bioavailability in terrestrial ecosystems and current in vivo and in vitro techniques used for assessing bioavailability and bioaccessibility of metalloids. This would reveal research gaps and allow scientists and environmental policy makers to gain a deeper understanding of the potential risks associated with these metalloids in the environment.

Clays modified by cationic surfactants have been widely used for the removal of organic and inorganic anionic contaminants. However, their suitability for the removal of antimonite from aqueous solutions has not been systematically studied. In this study, hexadecylpyridinium chloride modified montmorillonite (HDPy+-M) and hexadecylpyridinium bromide modified zeolite (HDPy+-Z) were used to measure Sb(III) uptake from solutions containing 0.5–2.5 mM antimonite. Adsorption isotherms of antimonite were studied using the Langmuir and Freundlich equations. Adsorption kinetics were investigated using pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion models. The results of X-ray diffraction showed a large interlayer expansion for HDPy+-M, whereas the X-ray patterns of HDPy+-Z remained unchanged. Uptake of Sb(III) by both HDPy+-M and HDPy+-Z could be fitted well to the Langmuir isotherm, while the kinetics of adsorption could be described well using the pseudo-second-order model. Maximum adsorption capacities for Sb(III) uptake by HDPy+-M and HDPy+-Z were calculated to be 108.7 and 61.34 mg g−1, respectively. The results of the kinetic studies revealed that Sb(III) adsorption to HDPy+-Z was found to be quite fast and the reaction reached equilibrium in 8 h, whereas for HDPy+-M equilibration was attained within 24 h. The adsorption of antimonite onto both HDPy+-M and HDPy+-Z was found to be selective in the presence of Cl−1 and SO4−2 competitive anions. Considering the high affinity for Sb(III) uptake from solutions containing high concentrations of antimonite, both HDPy+-M and HDPy+-Z could be used as promising adsorbents for environmental applications.

Assessing the bioavailability of various Sb substances plays a crucial role in human health and the ecological risk assessment of contaminated soils. However, fate, behaviour and bioavailability of different Sb compounds in soils are insufficiently known. Therefore, in this present study, the effects of soil properties and ageing on bioavailability of four different Sb compounds (C8H4K2O12Sb2, Sb2S3, Sb2O3 and Sb2O3 nanoparticles) were evaluated during 120 days ageing time. A black soil (BS) with approximately 12% organic matter (OM) and a red soil (RS) with less than 1% OM were amended with 1000 mg Sb kg−1 of different Sb compounds and subjected to single extractions with distilled (DI) water, 2M HNO3, Simplified Bioaccessibility Extraction Test (SBET) and a modified Community Bureau of Reference (BCR) sequential extraction method. The results revealed that there are substantial variations in dissolution rate of various Sb sources, depending upon soil type and Sb compound. The amounts of DI water extractability of Sb during the incubation time varied between

An organoclay was prepared using montmorillonite and hexadecylpyridinium chloride (HDPyCl) and tested for the removal of nitrate and perchlorate anions from aqueous solutions. The cationic surfactant modified organoclay was prepared at room temperature using HDPyCl corresponding to 4 times the cation exchange capacity (CEC) of Na-montmorillonite. Powder X-ray diffraction (XRD) analysis of the above organoclay showed a large basal spacing of 40.27 A with the intercalation of HDPy cations in the interlayers probably as a result of a paraffin-type bilayer arrangement. The adsorption data of nitrate and perchlorate were fitted to the Langmuir and Freundlich adsorption isotherms and pseudo-first order and pseudo-second order kinetic models to better understand their adsorption mechanisms. The nitrate and perchlorate uptakes by this organoclay could be described well using the Langmuir isotherm while their uptake kinetics fitted well to the pseudo-second order model. The maximum adsorption capacities of nitrate and perchlorate by the organoclay, HDPy-montmorillonite were calculated at 0.67 and 1.11 mmol g− 1, respectively. Nitrate and perchlorate uptake kinetics were found to be fast as equilibrium was reached within 4 h. Furthermore, the uptakes of nitrate and perchlorate by HDPy-montmorillonite were found to be highly selective in the presence of Cl−, SO42 − and CO32 −, the most abundant naturally occurring anions. Therefore, the HDPy-montmorillonite could be used as a highly efficient adsorbent for the separation of nitrate and perchlorate from drinking or waste water and ground water.

The main objective of the present study was to evaluate the effectiveness of synthetic Zn–Al–SO 4 layered double hydroxide (LDH) for the removal of arsenite and arsenate from a simulated soil solution. The Zn–Al–SO 4 was synthesized using a hydrothermal method and the adsorption of arsenic was studied using Langmuir and Freundlich models. Moreover, the kinetics of adsorption was tested using pseudo-first, pseudo-second, intraparticle diffusion and Elovich models. The results of the experiments revealed that the adsorption isotherms of arsenite and arsenate on the Zn–Al–SO 4 LDHs can be described well with Langmuir isotherm and maximum adsorption capacities were calculated to be 34.24 and 47.39 mg g − 1 for arsenite and arsenate, respectively. The adsorption kinetics of arsenate followed pseudo-second order while arsenite uptake showed better correlation with intra-particle diffusion model. Furthermore, the effects of two major coexisting and competing divalent anions such as SO 4 2 − and CO 3 2 − on the uptakes of arsenite and arsenate were studied and the results showed that CO 3 2 − had greater adverse effect on the uptakes of arsenite and arsenate by Zn–Al–SO 4 than SO 4 2 − . Based on X-ray diffraction results, the main underplaying adsorption mechanism of arsenite and arsenate might be the exchange on the external surfaces and edges of Zn–Al–SO 4 LDHs, but possibly some topotactic exchange may occur through the substitution of arsenic anions with sulfate in the interlayer region.

This study investigated the effectiveness of 6 different types of naturally occurring manganese, aluminum and iron oxides for stabilization of As and Sb in a calcareous soil spiked with 50mgkg(-1) of As or Sb and two dosages of treatments (2% and 5%). The resulting contaminated soils were subjected to a series of chemical extraction studies including sequential extraction, single step extraction with DTPA and Simplified Bioaccessibility Extraction Test (SBET) for estimation of bioaccessible fraction of As and Sb in soil and a greenhouse experiment using barley as the test crop. The results showed that Fe-associated and carbonate-bound fraction of As and Sb were predominant fractions. However, the amounts of labile fractions were higher in As contaminated soils, whereas the percentage of Sb associated with crystalline Fe-oxide and residual fractions were higher. The results revealed that application of natural metal oxides reduced DTPA and SBET extractable amounts and plant uptake of As and Sb. After application of amendments, the exchangeable fraction of As decreased dramatically by up to 82% while Sb exchangeable fraction decreased by up to 60% depending upon the additive. The results of chemical extractions and plant uptake confirmed that Sb had lower bioavailability, compared with As.

Over the past few decades, many countries have issued legislation for risk based management of contaminated soils, sediments and water. Establishing appropriate guidelines for risk based management of antimony contaminated environments is of great importance due to its toxicological properties. Antimony (Sb) is a toxic metalloid with a wide range of industrial applications that can cause adverse effects on natural ecosystems and human health. There are numerous soil and water national and international toxicity guidelines, legislation and clean up target values for evaluating the risks and health hazards associated with Sb contaminated soils and water. Although they are not accurate definitive indices of environmental hazards, they can be used as a surrogate tool for estimating harmful effects of contaminants. In this summary report, five common soil and sediment toxicity guidelines set by the USA, Canada, Australia, the Netherlands and Finland as well as some of water toxicity guidelines and their derivation methods are compared. There are, however, substantial variations between toxicity threshold values due to the different scientific bases, software models and ecotoxicological criteria used for developing these guidelines. It is evident from the literature that site specific factors e.g. redox potential, pH and ageing may greatly affect the environmental availability of Sb. Hence, establishing universally acceptable regulatory guidelines and toxicity essays with an array of bioavailability based approach and site specific considerations would greatly improve the reliability and robustness of the current techniques used for environmental management and remediation of contaminated soils.

The influence of initial uranium concentration, solution pH, contact time and adsorbent mass was investigated for removal of uranium from aqueous solutions by pine wood powder and wheat straw using a batch technique. The maximum removal efficiency of uranium achieved at pH 8 and 7 for pine wood powder and wheat straw, respectively. Langmuir and Freundlich adsorption isotherms and three kinetic models of adsorption including; Elovich, Lagergren pseudo-first and Lagergren pseudo-second order were used to describe the adsorption mechanisms. The uranium sorption onto wood and wheat straw powders followed a Freundlich isotherm. The kinetic studies showed that the data fitted very well to the pseudo-second order model in the studied concentration range of uranium for both adsorbents. Uranium desorption from loaded adsorbents also studied using batch techniques as a function of desorptive reagent, desorption time and desorptive reagent concentration. The results of the experiment indicated that the optimum desorption efficiency of uranium for wood powder and wheat straw occurred in 5 min shaking time, using 1.5 M HNO3 and 2 M Na2CO3 solutions, respectively.