Organobentonite for Sorption and Degradation of Phenol in the Presence of Heavy Metals

An experimental study was performed to determine the feasibility of usingorganobentonite modified with quarternary ammonium cations (QACs) as a reactive medium in immobilization and biodegradation barriers for mixed contaminants in the subsurface soil. Various factors, including interactions between heavy metals, organic contaminants, and soil microorganisms, were investigated when they coexisted with untreated bentonite and organobentonite. Batch sorption tests for cadmium and lead were conducted to quantify sorption selectivity of these metals on untreated bentonite and organobentonite. Metal concentrations of 50 × 10^-6 M slightly reduced the growth of soil microbes and partially interfered with the biodegradation of phenol. Soil microorganisms tested with untreated bentonite grew after approximately 25 hr of lag period and degraded phenol completely within 350 hr. The results from this study demonstrate that organobentonite could be used as a reactive medium for immobilization and biodegradation of organic contaminants in the presence of heavy metals in the subsurface soil.     

Interaction of naphthalene derivatives with soil: an experimental and theoretical case study

This study provides insight into the relevance of the chemical functional groups of soil organic matter (aromatic, paraffinic, O‐alkyl, carboxyl and carbonyl carbon), as determined by CPMAS ¹³C NMR, on adsorption processes. Batch adsorption experiments with eight naphthalene derivatives were conducted with soils from a long‐term field experiment and model sorbents. Although the adsorption of some derivatives was mainly affected by the paraffinic organic carbon content in soil, the relation between the C‐distribution and adsorption was complex. This casts doubt on the use of such NMR data to estimate sorption behaviour. Additionally, sorption experiments were performed with six model sorbents representing typical soil components. Considerable adsorption of naphthalene derivatives was observed for montmorillonite and lignin; the smallest values were for kaolinite and cellulose. A quantum chemical approach was used to calculate a local polarity parameter as a molecular property of the naphthalene derivatives. This parameter was correlated with the logarithm of the adsorption coefficients, logK_d. Here, clear trends were observed for three of the model sorbents (kaolinite, montmorillonite and lignin).     

Use of bentonite and activated carbon in controlled release formulations of carbofuran

Controlled release systems (CRS), unlike the conventional formulations, facilitate a gradual and controlled discharge of the pesticides, reducing the losses by evaporation and leaching and minimizing pesticide pollution. In this study, carbofuran-an insecticide-nematicide identified as a groundwater pollutant-was incorporated in alginate-based granules to obtain controlled release properties. The effect on carbofuran release rate caused by the incorporation of bentonite, activated carbon, and different mixtures of both sorbents in alginate basic formulation was studied by immersion of the granules in water. The water uptake, sorption capacity of the sorbent, permeability, and time taken for 50% of the active ingredient to be released into water, T(50), were calculated by the comparison of the preparations. T(50) values were higher for those formulations containing bentonite and/or activated carbon (T(50) values range from 14.76 h for the alginate formulation containing only bentonite as the sorbent to 29.5 weeks for the alginate formulation containing only activated carbon as the sorbent) than for the preparation without these sorbents (11.72 h). On the basis of a parameter of an empirical equation used to fit the insecticide-nematicide release data, it appears that the release of carbofuran from the various formulations into water is controlled by a diffusion mechanism. The sorption capacity of the sorbents for carbofuran was the most important factor modulating carbofuran release. In addition, it was observed that there is a linear correlation of the T(50) values and the content of activated carbon in dry granules.     

SORPTION OF INORGANIC PHOSPHATE BY IRON- AND ALUMINIUM- CONTAINING COMPONENTS

The amounts of inorganic P sorbed by a range of Fe- and Al- containing components varied appreciably and decreased in the order allophane > fresh Al gel > Fe gel pseudoboehmite > aged Al gel > dried Fe gel > Fe-coated kaolinite > haematite > goethite > akaganeite > gibbsite = ground kaolinite > dispersed kaolinite. Al gel sorbed 30 to 70 times more P than gibbsite, and Fe gel sorbed approximately 10 times more P than its crystalline analogues (haematite, goethite. and akaganeite). Despite large differences in the extent of P sorption, the form of the isotherm was essentially the same for each sorbent. The ability of freshly-prepared Al gel suspensions to sorb P decreased with ageing, a property not shown by Fe gel. Drying of Fe gel at 80°C, however, caused an approximately 4-fold decrease in P sorption. Precipitation of Fe gel (2% Fe) on the surface of kaolinite increased P sorption by a factor of 10. The occurrence of Fe gel as a coating apparently presents more sorption sites to solution per unit weight of Fe gel than Fe gel alone. A linear relationship (r= 0.98) was obtained between the amount OH^? sorbed per unit increase in pH value (‘hydroxyl buffering’) and the overall P sorption maximum for each sorbent. Hydroxyl buffering provided a better index of P sorption potential than specific surface area. Except for the crystalline Fe sorbents, isotherms obtained by plotting fractional sorption saturation against final solution P concentration for the sorbents were essentially coincident with those for several contrasting soils. For crystalline Fe components a lower relative amount of weaker sorption, as opposed to chemisorption, of the overall sorption maximum was obtained. Differences in the extent of P sorption. however, appear to be primarily related to the number of functional M-OH groups presented at the solid-solution interface.     

TIME-DEPENDENT SORPTION OF PHOSPHATE BY SOILS AND HYDROUS FERRIC OXIDES

The sorption of inorganic phosphate (P) by soils and hydrous ferric oxides was studied at times up to 192h. An initially rapid decrease in solution P concentration was followed by a much slower decrease between 48 and 192h with soils, Fe gel. and natural goethite, whereas synthetic goethite gave a well-defined equilibrium condition after only 48h. Resolution of the sorption isotherms showed that the increase in P sorption with time involved an appreciable shift of P from a more-physically sorbed form to a chemisorbed form. This was supported by chemical fractionation which showed that NaOH-extractable P was fairly constant with increasing sorption time, whereas the additional sorbed P was extracted by citrate-dithionite-bicarbonate from soils, and by HC1 from Fe gel and natural goethite. These sorbents contained short-range (amorphous) material, whereas synthetic goethite, from which all sorbed P was NaOH –extractable. did not. It is proposed that the time-dependent sorption of P and the associated shift of P to chemisorbed forms, involves the diffusion of P into “structurally porous”, short-range order material.     

ISOTOPIC EXCHANGE OF FIXED AMMONIUM

The isotope ¹⁵N was used to study the rate of exchange between unlabelled NH₄-hydrobiotite and labelled solution NH₄. Most of the isotopic dilution occurred within 10 minutes of adding the solution to the solid, but even after 13 days less mineral-NH₄ had exchanged with isotope than was removed by several extractions with KC1 solution. NH₄ remaining in the mineral after extraction with KC1, conventionally named ‘fixed ammonium’, contained some isotope which was sorbed without release of unlabelled NH₄; the fixed ammonium was, therefore, not isotopically exchangeable. The sorption was shown to result from incomplete ammonium saturation of hydrobiotite, isotope slowly replacing interlayer cations trapped by lattice collapse. The rate of sorption was initially controlled by a temperature-dependent diffusion process for which the activation energies were between 9 and 13 kcal/ mole. In the later stages of the reaction the rate became progressively slower than predicted by the diffusion equation, and analysis of the kinetics suggested that, ultimately, exchange of cations at the sorption sites was the rate-limiting process.     

Sorption of organic acids in acid soils and its implications in the rhizosphere

Organic acids have been implicated in many soil-forming and rhizosphere processes, but their fate in soil is poorly understood. We examined the sorption of four simple short-chain organic acids (citric, oxalic, malic and acetic) in five acid soils and on synthetic iron hydroxide (ferrihydrite). The results for both soils and ferrihydrite indicated that the sorption depended on concentration in the following order of strength: phosphate >> oxalate > citrate > malate >> acetate. The sorption reactions in soil were shown to be little influenced by pH, whereas for ferrihydrite, sorption of all ligands increased strongly with decreasing pH. The sorption of organic anions onto ferrihydrite was influenced to a lesser extent by the presence of metal cations in solution. From the results we calculated that when organic acids enter solution they rapidly become sorbed onto the soil's exchange complex (> 80% within 10 min), and we believe that this sorption will greatly diminish their effectiveness to mobilize nutrients from the rhizosphere.     

Use of activated bentonites in controlled-release formulations of atrazine

The herbicide atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) was incorporated in alginate-based granules to obtain controlled-release (CR) properties. The basic formulation [sodium alginate (1.40%)-atrazine (0.60%)-water] was modified by the addition of sorbents. The effect on atrazine release rate caused by the incorporation of acid-treated bentonite (0.5 and 2.5 M H2SO4) in alginate formulation was studied by immersion of the granules in water under static conditions. The water uptake, sorption capacity of the sorbent, permeability, and time taken for 50% of the active ingredient to be released into water, t50, were calculated for the comparison of the preparations. t50 values were longer for those formulations containing acid-treated bentonite (36.78 and 29.01 days for 0.5 and 2.5 M H2SO4 treatments, respectively) than for the preparation without bentonite (9.69 days). On the basis of a parameter of an empirical equation used to fit the herbicide release data, it appears that the release of atrazine from the various formulations into water is controlled by diffusion mechanism. The sorption capacity of the sorbents and the permeability of the formulations (ranging from 4.99 to 20.83 mg day(-1) mm(-1)) were the most important factors affecting herbicide release.     

Caesium sorption—desorption in clay—humic acid systems

Soaking for 7 d with 0.05 M NaCl resulted in less caesium being sorbed by bentonite and kaolinite, but more by illite, compared to soaking for 2 d prior to addition of Cs. Overall the amount of Cs sorbed by the three clays was in the order bentonite > illite > kaolinite. Addition of humic acid to the clays depressed the sorption of Cs by all three clays, with illite showing the greatest effect. Desorption of added Cs was not totally reversible. The presence of humic acid resulted in an enhanced desorption of Cs from bentonite and to a lesser extent kaolinite. This enhanced desorption in the presence of humic acid was not seen for illite. The order of Cs retention following desorption for both clay and clay/ humic-acid mixtures was illite > bentonite > kaolinite. A single K_d value could not describe the whole isotherm, but individual values were calculated at different Cs concentrations to cover the range of the isotherm. K_d values for desorption were higher than the corresponding K_d for sorption. For both sorption and desorption, the presence of humic acid resulted in lower K_d values than in its absence.     

Phosphate sorption by natural hematites

Iron (hydr)oxides are active phosphate sorbents in soils and sediments, but no information exists on phosphate (P) sorption by natural hematites. In this study, we characterized the chemical, mineralogical and P-sorption properties of 14 hematite-rich natural materials of different origins. Phosphate sorption was described by a modified Freundlich equation including a time term. Phosphate sorbed at 1d at an equilibrium concentration of 1 mg P dm^?3 ranged widely (0.2–1.7 μmol m^?2). After 1 d, hematites showed a marked slow sorption. At 75 d, and an equilibrium concentration of 6mg P dm^?3, the total amount of P sorbed ranged between 0.8 and 4.1 μmol mp^?2. Phosphate-sorption capacity was influenced by the morphology of the coherently scattering domains: the shorter the domains in the crystallographic c relative to the a direction, the lower the P-sorption capacity. This has been observed by other authors in synthetic hematites and agrees with the idea that the prismatic faces, which have singly co-ordinated Fe-OH groups, are more active in P-sorption than other faces. The average P sorption capacity of hematites was similar to that of natural goethites (2.6 μmol P m^?2) but, in contrast to these, variability among samples was high. In comparison with goethites, hematites show slower sorption and lower affinity for phosphate.     

Use of Industrial By-products to Sorb and Retain Phosphorus

The potential of six industrial by-products for use as phosphorus-sorbing materials (PSMs) in solutions was evaluated. These included two different acid mine drainage treatment residuals (AMDR1 and AMDR2), water treatment residual (WTR), fly ash, bauxite mining residual, and flue gas desulfurization product (FGD). Characterization of the by-products and their mechanisms for sorption and retention of inorganic phosphorus (P) from solution identified those PSMs that sorbed primarily by an iron and aluminum (Fe/Al) mechanism, those that sorbed primarily by a calcium and magnesium (Ca/Mg) mechanism, and those that sorbed by both mechanisms. Degree of P sorption and associated mechanisms were strongly influenced by the pH, buffer capacity, ionic strength, and common ion effects.     

Retention of cobalt by an oxisol in relation to the content of iron and manganese oxides

Abstract

The study aims at determining the cobalt retention properties of various soil components. Therefore, cobalt (Co) sorptions and extractions were carried out using an Oxisol sample before (untreated) and after successive removal of organic matter and active manganese (Mn) oxides (H₂O₂‐treated) and iron (Fe) oxides (H₂O₂+CBD‐treated). A synthetic goethite was included for comparison. Sorption of the four sorbents was determined over a range of Co concentrations (initially 10^‐8 M to 10^‐4 M), pH values (3 to 8) and reaction times (2 hours to 504 hours). The Co species sorbed was Co(ll), since oxygen exclusion during sorption had no effect on the amount sorbed. The pH‐dependent sorption curve (sorption edge) was shifted to lower pH at decreasing initial Co concentration and increasing reaction time. The displacements, in particular of the sorption edges corresponding to the lowest initial Co concentrations, to successively higher pH following removal of Mn oxides, organic matter and Fe oxides could be attributed to sorption onto sites of decreasing Co affinity [Mn oxides (and organic matter) > Fe oxides > kaolinite]. Extractions of sorbed Co at pH 5.5–7.5 with 2 M HCI showed that the extractability decreased with increasing sorption time and decreasing initial Co concentration. The untreated and H₂O₂‐treated soil samples retained sorbed Co at least as firmly as the synthetic goethite, whereas the H₂O₂+CBD‐treated sample (kaolinite) was clearly less effective. The results emphasized the importance of the soil Mn and Fe oxides for Co retention in soils but also the necessity of taken interior sorption sites into consideration.     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

Phosphate sorption by calcium‐bentonite as described by commonly used isotherms

Abstract

The one and two Langmuir, the Freundlich, and the Temkin isotherms were fitted to phsophorus (P) sorption data for P sorption by calcium (Ca)‐bentonite at different initial concentration and pH values of 3.8, 4.8, 6.0, 7.0, 8.0, and 9.0. Each was found to describe P sorption by Ca‐bentonite with comparable success. The effect of pH on P adsorption by Ca‐bentonite was studied and Langmuir, Temkin, and Freundlich isotherms were converted to the forms:

Langmuir: (Co‐X)X= 1/(0.0275–0.0025pH)(12.323–1.061pH) + (Co‐X)(12.323–1.016pH) Temkin: X = (2.45–0.211pH)In(AC) Freundlich: X = (1.324–0.146pH)C(^0.172+0044 _P ^H) where: X = (mmol P/kg) the amount of P sorbed per unit weight of soil, C = (μmol P/L) the P concentration in the equilibrium solution, and Co = ((μmol P/L) initial P concentration. It is noteworthy, that the maximum amount (Xm) of P that can be sorbed in a monolayer decreases by increasing of pH. Finally, the B constant of Temkin isotherms is indepented from pH changes.     

中试规模猪粪堆肥挥发性有机物排放特征

为监测堆肥过程挥发性有机物(volatile organic compounds,VOCs)排放情况,该文开展了猪粪堆肥现场试验,采用苏玛罐采样,气相色谱-质谱法分析了猪粪好氧堆肥过程中VOCs浓度。结果表明:猪粪好氧堆肥过程中可以检测出的VOCs有81种,包括烷烃类34种,芳香烃类21种,卤烃类19种,胺类1种,含硫化合物3种,氟利昂类3种;其中检出率高且浓度远远超过其嗅阈值的VOCs包括三甲胺、二甲基硫、二甲基二硫和二甲基三硫,VOCs排放主要发生在堆肥的前2周。该研究将为控制猪粪堆肥过程中VOCs气体排放提供科学数据支持。     

Sorption of As(V) Species from Aqueous Systems

Arsenic is of increasing environmental concern due to risk to plants, animal and human health. In aqueous systems arsenic is dominated by the As^V oxyanions H₂AsO₄ ^- and HAsO₄ ^2- under oxidizing conditions. The possibility to remove arsenic from aqueous solutions, using sorption processes, was studied with both inorganic and organic-based sorbents. Both of tested inorganic sorbents, calcined synthetic hydrotalcite and calcined natural boehmite, were acceptable for removal of As^V compounds from aqueous systems at laboratory temperature (20 °C) and neutral pH due to their crystal structure changes. They were able to remove more than 70% of As^V compounds from aqueous solution at low sorbent-solution ratios (1 g L^-1 and 2.6 g L^-1, respectively) and relatively high concentration of AsO₄ ^3- ions in the initial solution (about 2.10^-3 mol L^-1). Humic acid-type sorbents (i.e. pure humic acid and oxihumolite) efficiences remined low even at increased sorbent-solutionratios (about 20 g L^-1) and significantly lower concentrations of As in the initial solution. At higher pH values (about 9), the sorption process slightly improved due to solubility of humic substances in alkaline solutions. The sorption increment did not exceed 50% of the initial As content. These results were confirmed by infrared spectroscopy. Both the original calcined and the sorbed inorganic sorbent samples show significant As-O vibrations, while in spectra of original and sorbed oxihumolite no significant As-O vibrations were observed, due to negligible content of sorbed As compounts.     

萘和p,p′-DDE在典型包气带介质上的吸附动力学及吸附-解吸特征

选取3种典型包气带土壤为吸附剂,萘和p,p′-DDE为吸附质,研究了其吸附动力学特征及吸附解吸规律。实验结果显示,初始浓度越大,吸附到达平衡所需时间就越短。数据拟合结果表明,单一级次的动力学方程难以描述两种吸附质的吸附动力学特征,分析认为土壤对有机污染物的吸附过程不是单一反应,而是有机污染物在无机矿物、无定型有机碳和凝聚型有机碳上同时进行吸附反应的复合结果。萘与p,p′-DDE的吸附、解吸过程均表现出非线性,Freundlich方程的吸附指数n在不同程度上偏离1;两种污染物在土样中的吸附过程不完全可逆,Kow、初始浓度以及土壤有机碳含量（fo）c的差异都影响其在土壤不同组分上的吸附百分比,进而影响解吸率。萘更多地吸附在无机矿物表面及无定型有机碳上,随着初始浓度的增大（37.7~780.9μg.L-1）,解吸率可从10%左右增至近85%;而当初始浓度为37.7μg.L-1时,随foc的增大（0.01%~0.65%）,解吸率由12.39%降至3.90%。p,p′-DDE则更多地吸附在凝聚型有机碳上,解吸率随浓度的变化（11.0~275.1μg.L-1）仅在1%~5%内波动,当初始浓度为11.0μg.L-1时,解吸率随foc的增大由4.49%降至1.06%。两者解吸率都和foc呈负相关关系。     

Cosorption of atrazine and a lauryl polyoxyethylene oxide nonionic surfactant on smectite

Commercial atrazine formulations commonly contain nonionic surfactants that serve as solubilizing and wetting agents for enhancing the stability and efficacy of the herbicide. The fate of atrazine in soils has been extensively investigated; yet, few studies have considered the effects of formulation components on the fate of atrazine in soils. In this study, we investigated the influence of the nonionic surfactant, Brij 35 (Brij), on the sorption of atrazine on Ca- and K-saturated samples of a reference smectite, Panther Creek (PC). In general, Brij concentrations of 50 and 200 mg L(-1) had little effect on atrazine sorption, but sorption was substantially inhibited by Brij concentrations of 2100 mg L(-1). For Brij concentrations of 6300 mg L(-1), atrazine sorption was intermediate between that observed for the 200 and 2100 mg L(-1) Brij systems. Brij molecules themselves were very strongly sorbed by PC, with sorption maxima exceeding 200 g kg(-1). X-ray diffraction analysis of Brij-treated PC indicated that the sorbed Brij was intercalated into interlayers of the smectite. At Brij concentrations of 2100 mg L(-1), Brij competed with atrazine for interlayer sorption sites. In contrast, at the initial Brij concentration of 6300 mg L(-1), the clay interlayers were largely filled with Brij, and excess Brij probably accumulated on external surfaces of the clay as surface micelles. We hypothesize that atrazine partitioning into surfactant micelles on external surfaces of the clay led to enhanced retention by the solid phase.     

Controlled release of isoproturon, imidacloprid, and cyromazine from alginate-bentonite-activated carbon formulations

Different alginate-based systems of isoproturon, imidacloprid, and cyromazine have been investigated in order to obtain controlled release (CR) properties. The basic formulation [sodium alginate (1.50%), pesticide (0.30%), and water] was modified using different amounts of bentonite and activated carbon. The higher values of encapsulation efficiency corresponded to those formulations prepared with higher percentages of activated carbon, showing higher encapsulation efficiency values for isoproturon and imidacloprid than for cyromazine, which has a higher water solubility. The kinetic experiments of imidacloprid/isoproturon release in water have shown us that the release rate is higher in imidacloprid systems than in those prepared with isoproturon. Moreover, it can be deduced that the use of bentonite and/or activated carbon sorbents reduces the release rate of the isoproturon and imidacloprid in comparison with the technical product and with alginate formulation without modifying agents. The highest decrease in release rate corresponds to the formulations prepared with the highest percentage of activated carbon. The water uptake, permeability, and time taken for 50% of the active ingredient to be released into water, T50, were calculated to compare the formulations. On the basis of a parameter of an empirical equation used to fit the pesticide release data, the release of isoproturon and imidacloprid from the various formulations into water is controlled by a diffusion mechanism. The sorption capacity of the sorbents and the permeability of the formulations were the most important factors modulating pesticide release. Finally, a linear correlation of the T50 values and the content of activated carbon in formulations were obtained.     

Tree Response to Experimental Watershed Acidification

In this study, lead (Pb) and antimony (Sb) sorption experiments were conducted to elucidate the mechanisms of Pb and Sb sorption by combined applications using single or combined applications of hydroxyapatite (HAP) and ferrihydrite (FH), to evaluate the contribution of each material in Pb and Sb sorption, and to assess the chemical stability of the sorbed Pb and Sb. In the combined application, isotherms of Pb sorption and Sb sorption were well fitted to Langmuir and Freundlich isotherm models, respectively. The Pb and Sb amounts sorbed in the combined application were the same levels as the summed totals of those sorbed in the single applications, indicating that in the combined application, Pb sorption and Sb sorption were not suppressed. Pb was mainly sorbed on HAP in the combined application, at a 90 % level of the total adsorbed Pb. The HAP and FH contributions to Sb sorption were 32 and 68 % of the total adsorbed Sb, respectively, and Sb was sorbed on each material independently even in the combined application. The percentages of both Pb and Sb dissolved from the sorbed materials in the combined applications at pH 4 and 6 were the same levels as those in the single applications. However, the percentages of Sb dissolved in both combined and single applications were high at an alkaline pH. These results suggest that HAP and FH in a combined application would be useful for simultaneous Pb and Sb immobilization in soil with acidic to neutral pH, but not in soil with an alkaline pH.