Distribution and fractionation of cadmium, copper, lead, nickel, and zinc in a calcareous sandy soil receiving municipal solid waste

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.     

Tetracycline removal enhancement with Fe-saturated nanoporous montmorillonite in a tripartite adsorption/desorption/photo-Fenton degradation process

The adsorption and photo-Fenton degradation of tetracycline (TC) over Fe-saturated nanoporous montmorillonite was analyzed. The synthesized samples were characterized using XRD, FTIR, SEM, and XRF analysis, and the adsorption and desorption of TC onto these samples, as well as the antimicrobial activity of TC during these processes, were analyzed at different pH. Initially, a set of adsorption/desorption experiments was conducted, and surprisingly, up to 50% of TC adsorbed was released from Mt structure. Moreover, the desorbed TC had strong antibacterial activity. Then, an acid treatment (for the creation of nanoporous layers) and Fe saturation of the montmorillonite were applied to improve its adsorption and photocatalytic degradation properties over TC. Surprisingly, the desorption of TC from modified montmorillonite was still high up to 40% of adsorbed TC. However, simultaneous adsorption and photodegradation of TC were detected and almost no antimicrobial activity was detected after 180 min of visible light irradiation, which could be due to the photo-Fenton degradation of TC on the modified montmorillonite surface. In the porous structures of modified montmorillonite high, ˙OH radicals were created in the photo-Fenton reaction and were measured using the Coumarin technique. The ˙OH radicals help the degradation of TC as proposed in an oxidation process. Surprisingly, more than 90% of antimicrobial activity of the TC decreased under visible light (after 180 min) when desorbed from nanoporous Fe-saturated montmorillonite compared to natural montmorillonite. To the best of our knowledge, this is the first time that such a high TC desorption rate from an adsorbent with the least residual antimicrobial activity is reported which makes nanoporous Fe-saturated montmorillonite a perfect separation substance of TC from the environment.

     

Sunflower stalk, an agricultural waste, as an adsorbent for the removal of lead and cadmium from aqueous solutions

Sunflower residue, an agricultural waste material for the removal of lead (Pb) and cadmium (Cd) from aqueous solutions were investigated using a batch method. Adsorbent was prepared by washing sunflower residue with deionized water until the effluent was colorless. Batch mode experiments were carried out as a function of solution pH, adsorbent dosage, initial concentration and contact time. The results indicated that the adsorbent showed good sorption potential and maximum metal removal was observed at pH 5. Within 150 min of operation about 97 and 87 % of Pb and Cd ions were removed from the solutions, respectively. Lead and Cd sorption curves were well fitted to the modified two-site Langmuir model. The adsorption capacities for Pb and Cd at optimum conditions were 182 and 70 mg g^?1, respectively. The kinetics of Pb and Cd adsorption from aqueous solutions were analyzed by fitting the experimental data to a pseudo-second-order kinetic model and the rate constant was found to be 8.42 × 10^?2 and 8.95 × 10^?2 g mg^?1 min^?1 for Cd and Pb, respectively. The results revealed that sunflower can adsorb considerable amount of Pb and Cd ions and thus could be an economical method for the removal of Pb and Cd from aqueous systems.     

Phosphorus leaching from a sandy soil in the presence of modified and un-modified adsorbents

Phosphorus (P) leaching from a sandy soil was investigated in the presence of modified and unmodified clay minerals and nanoparticles (NPs). Compared with control soil, amended soil with NPs had the highest percentage of P retention than amended soil with clay minerals. Among the adsorbents used, the highest percentage of P retention was produced by Al₂O₃-chitosan while the lowest percentage of P retention was by zeolite. Data measured for P leaching after using adsorbents were used to predict P leaching using transport model. PHREEQC model was able to model P leaching from control and amended soil. After leaching, P values in control and amended soil were fractionated by a sequential extraction procedure. Concentration of P in Ca-bound fraction (HCl–P) after application of modified and unmodified clay minerals and NPs (except TiO₂ and Al₂O₃) increased and decreased, respectively. Saturation indices (SIs) and P speciation were assessed using the Visual MINTEQ version 2.3 program. According to the SIs, leaching P from control and amended soil with different adsorbent was controlled by dissolution of hydroxyapatite. The results indicated that used adsorbents can reduce P leaching from the sandy soil. Thus, retention of P by amended soil reduced a risk in terms of groundwater contamination with P.     

Measuring and modeling ammonium adsorption by calcareous soils

The aim of this study was assessment of ammonium (NH ₄ ⁺ ) adsorption isotherms in some agricultural calcareous soils and modeling of that by using the mechanistic exchange model. Ten surface soils (0–30 cm) were collected from areas covered with different land uses in Hamedan, western Iran. Isotherm experiments were carried out by concentrations of NH ₄ ⁺ prepared from NH₄Cl salt (0, 10, 20, 30, 40, 50, 100, and 150 mg NH ₄ ⁺ ?l^?1) in presence of 0.01 M CaCl₂ solution. The empirical models including simple adsorption isotherm and Freundlich equations were fitted well to the experimental data. The average amounts of adsorbed NH ₄ ⁺ in studied soils varied from 8.95 to 35.23 %. Adsorption percentage indicated positive correlation with pH, cation-exchange capacity (CEC), equivalent calcium carbonate, and clay content and had negative correlation with sand content. In order to predict and model NH ₄ ⁺ adsorption, cation-exchange model in PHREEQC program was used. The model could simulate the NH ₄ ⁺ adsorption very well in all studied soils. The values of CEC played the major role in modeling of NH ₄ ⁺ adsorption in this study indicating that cation-exchange process was the major mechanism controlling NH ₄ ⁺ adsorption in studied soils.     

Adsorption of ammonium from simulated wastewater by montmorillonite nanoclay and natural vermiculite: experimental study and simulation

In this research, montmorillonite nanoclay (MNC) and vermiculite were used to adsorb ammonium (NH₄ ⁺) from simulated wastewater. The effect of organic acids, cations, and anions on adsorption of NH₄ ⁺ was also studied using batch experiments. The presence of organic acids significantly decreased the NH₄ ⁺ adsorption using both adsorbents and the reduction followed the order of citric acid > malic acid > oxalic acid. The presence of cations in wastewater could decrease the adsorption of NH₄ ⁺ and the ion exchange selectivity on the MNC and vermiculite followed the orders Mg > Ca ≥ K > Na and Mg > > Ca > Na > K, respectively. Adsorption of NH₄ ⁺ by adsorbents in the presence of sulfate (SO₄) was higher than those in the presence of phosphate (PO₄) and chloride (Cl) anions. Results indicated that MNC and vermiculite had good potential for NH₄ ⁺ removal depending on adsorbent dosage, pH, contact time, and initial NH₄ ⁺ concentration. The effect of pH on removal of NH₄ ⁺ indicated that MNC would be more appropriate as the adsorbent than vermiculite at low pH values. Kinetic analysis demonstrated that the rate-controlling step adsorption for NH₄ ⁺ by MNC and vermiculite was heterogeneous chemisorption and followed the pseudo-second-order model. The desorption experiments indicated that the adsorption of NH₄ ⁺ by adsorbents was not fully reversible, and the total recovery of adsorbed NH₄ ⁺ for MNC and vermiculite varied in the range of 72 to 94.6% and 11.5 to 45.7%, respectively. Cation exchange model (CEM) in PHREEQC program was used to simulate NH₄ ⁺ adsorption. Agreement between measured and simulated data suggested that CEM was favored in simulating adsorption of NH₄ ⁺ by clay minerals. The results indicated that MNC and vermiculite have good performance as economic and nature-friendly adsorbents that can ameliorate the water and environment quality.     

Effect of organic and inorganic phosphorus fertilizers on phosphorus availability and its leaching over incubation time

Environmental Science and Pollution Research - The use of organic and inorganic phosphorus (P) fertilizers in agricultural soils is very common, and few studies have been conducted to...     

Competitive sorption of Cd, Cu, Mn, Ni, Pb and Zn in polluted and unpolluted calcareous soils

The objectives of this study were to investigate competitive sorption behaviour of heavy metals (Cd, Cu, Mn, Ni, Pb and Zn) under different management practices and identify soil characteristics that can be correlated with the retention and mobility of heavy metals using 65 calcareous soil samples. The lowest sorption was found for Mn and Ni in competition with the other metals, indicating the high mobility of these two cations. The Freundlich equation adequately described heavy metals adsorption. On the basis of Freundlich distribution coefficient, the selectivity sequence of the metal adsorption was Cu?>?Pb?>?Cd?>?Zn?>?Ni?>?Mn. The mean value of the joint distribution coefficient (K _dΣsp) was 182.1, 364.1, 414.7, 250.1, 277.7, 459.9 and 344.8 l kg^?1 for garden, garlic, pasture, potato, vegetables, wheat and polluted soils, respectively. The lowest observed K _dΣsp in garden soil samples was due to the lower cation exchange capacity and lower carbonate content. The results of the geochemical modelling under low and high metal addition indicated that Cd, Ni, Mn and Zn were mainly retained via adsorption, while Pb and Cu were retained via adsorption and precipitation. Stepwise forward regression analysis showed that clay, organic matter and CaCO₃ were the most important soil properties influencing competitive adsorption of Cd, Mn, Ni and Zn. The results in this study point to a relatively easy way to estimate distribution coefficient values.     

Effect of low-molecular-weight organic acids on kinetics release and fractionation of phosphorus in some calcareous soils of western Iran

Organic acid has been related to nutrient mobilization, mainly in phosphorus (P) insoluble utilization, and therefore enhances P bioavailability. In this study, we examined the effect of low-molecular-weight organic acids (malic, citric, and oxalic acids) on P release of some calcareous soils from western Iran. Fractionation and speciation of P in the soil solution were studied at the initial and final P release. Significantly different quantities of P were extracted by the organic acids. On average the maximum (1,554.9 mg kg^-1) and the minimum (1,260.5 mg kg^-1) P were extracted by 10 mM oxalic and malic acid, respectively. Power equation described well P release. In the initial stage of P release, the solution samples in soils were supersaturated with respect to hydroxyapatite and β-TCP. At the end of P release, all solutions were undersaturated with phosphate minerals. The percentage of Fe-Al oxide fraction generally increased after P release, while carbonate and residual P fractions were decreased in all organic acids. Compared with the native soils, adding malic and citric acids had no effect on Fe-Al oxide fraction, but oxalic acid significantly reduced this fraction.