Removal of Mercury Ions from Mixed Aqueous Metal Solutions by Natural and Modified Zeolitic Minerals

Research works on the removal of mercury from water by zeolitic mineralshow that small quantities of this element are sorbed. In this work the mercury sorption from aqueous solutions in the presence and absence of Cu(II), Ni(II) and Zn(II) onto a Mexican zeolitic mineral unmodified and modified with cysteamine hydrochloride or cystamine dihydrochloride was investigated in acidic pH. The zeolitic minerals were characterized by thermogravimetric analysis, scanning electron microscopy, X-ray diffraction and FTIR. The sorption kinetics behavior and the retention isotherms for mercury were determined in the natural and treated zeolitic mineral samples. It was found that the amounts of sulfur on the modified zeolitic minerals were 0.375 (cysteamine hydrochloride) and 0.475 (cystamine dihydrochloride) mmol g^-1, which were not saturated to their total capacities of adsorption for the maximum concentration used (0.310 mM). Under the experimental conditions, the retention of mercury was the highest for the zeolitic minerals treated with the organic compounds, with adsorption capacities ranging from 0.0107 to 0.0509 mmol Hg g^-1.The retention was not affected by the presence of others heavy metals studied in this work as expected.     

Zinc Removal from the Aqueous Solutions by the Chemically Modified Biosorbents

Biosorbents are the natural origin adsorbents, which popularity in environmental engineering is steadily increasing due to their low price, ease of acquisition, and lack of the toxic properties. Presented research aimed to analyze the possibility of chemical modification of the straw, which is a characteristic waste in the Polish agriculture, to improve its biosorption properties with respect to removal of selected metals from aquatic solutions. Biosorbents used during the tests was a barley straw that was shredded to a size in the range of 0.2–1.0 mm. The biosorption process was performed for aqueous solutions of zinc at a pH 5. Two different modifications of straw were analyzed: esterification with methanol and modification using the citric acid at elevated temperature. The results, obtained during the research, show a clear improvement in sorption capacity of the straw modified by the citric acid. In the case of straw modified with methanol, it has been shown that the effectiveness of zinc biosorption process was even a twice lower with respect to the unmodified straw. Moreover, it was concluded that the removal of analyzed metals was based mainly on the ion-exchange adsorption mechanism by releasing a calcium and magnesium ions from the straw surface to the solution.

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Preparation of High Surface Area Oxidized Activated Carbon from Peanut Shell and Application for the Removal of Organic Pollutants and Heavy Metal Ions

A peanut shell-derived oxidized activated carbon (OAC) with high surface area was prepared by zinc chloride (ZnCl₂) chemical activation and subsequent nitric acid oxidation. OAC was characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and N₂ adsorption-desorption. The results showed that OAC had the surface area of 1807 m² g^?1, with the total pore volume of 0.725 cm³ g^?1 and average pore diameter of 3.8 nm. More importantly, when OAC acted as an adsorbent, it exhibited high efficiency to remove basic blue 41 (BB-41), congo red (CR), phenol, Cr(VI), and Pb(II) from aqueous solution due to its universality in adsorption. Batch adsorption experiments were carried out to study the effect of various parameters such as pH, initial concentration, temperature, and contact time. Also, the isotherms, kinetic models, and thermodynamics of adsorption process were investigated. The equilibrium data for CR and Pb(II) were fitted to Langmuir isotherm model, while Freundlich model was suitable for the equilibrium isotherm of BB-41, phenol, and Cr(VI), respectively. As the result indicated, peanut shell was a suitable raw material to synthesize OAC which could be employed as an efficient and universal adsorbent for removing organic pollutants and heavy metal ions from wastewater.     

Evaluation of the 15Nitrogen Isotope Dilution Technique for Estimating Crop Nitrogen Uptake from Organic Residues

Abstract

A field experiment was conducted to test the new approach for estimating crop nitrogen (N) uptake from organic inputs. The soil was prelabeled with ¹⁵N by applying ¹⁵N fertilizer to sunflower crop (Helianthus annuus L. var. Viki). The ¹⁴N plots, which received unlabelled fertilizer, were also set up. At harvest, ¹⁵N labeled residues were added to the unlabeled soils at a rate of 73 kg N ha^?1 (direct technique) and unlabeled residues were added to the ¹⁵N‐labeled soils at the same rate (indirect technique). Control plots without residues were also established. All plots were sown with the wheat (Triticum aestivum L. var merchouch)–fababean (Vicia faba L.)–wheat (Triticum aestivum L. var merchouch) cropping sequence.

In the cropping sequence, the first, second and third crop derived respectively 12.01, 2.4, and 1.93 kg N ha^?1 from crop residues estimated by the direct method and 14.77, 3.3, and 1.85 kg N ha^?1 estimated by the indirect method. The results showed no significant difference between the two techniques, which suggests that the new soil prelabeling technique compares well with the direct technique.     

Zirconium-Modified Activated Sludge as a Low-Cost Adsorbent for Phosphate Removal in Aqueous Solution

A highly effective zirconium-modified activated sludge (Zr(IV)-AS) adsorbent was prepared from activated sludge and applied to remove phosphate from aqueous solutions by batch and column experiments. Characterized results revealed that zirconium was successfully loaded onto the activated sludge (AS), and the specific surface area and pore volume were substantially improved after zirconium loading on the AS. Zr(IV)-AS exhibited a high adsorption affinity for phosphate and the maximum adsorption amount was 27.55 mg P·g^?1 at 25 °C. Adsorption isotherms of phosphate could be described by the Langmuir model, and the adsorption kinetics were well described by the pseudo-second-order model. Phosphate adsorption on Zr(IV)-AS increased monotonically with decreasing solution pH. The presence of SO₄^2? in water resulted in slightly decreased phosphate adsorption on the adsorbent even at a high concentration (25 mmol/L), and a greater influence of HCO₃^? on adsorption could be ascribed to the increased solution pH with the addition of the HCO₃^?. Column adsorption experimental results showed that the adsorbent has excellent phosphate adsorption properties and that the effluent can meet the requirement of phosphorus in the national wastewater discharge standard of China. Phosphate-saturated Zr(IV)-AS can be effectively desorbed in 0.1 mol L^?1 NaOH solution, and the regenerated adsorbent still possessed the high capacity. The adsorption between the adsorbent and the phosphate is due to the electrostatic interaction and anionic exchange at the surface of the Zr(IV)-AS. Furthermore, this approach provides a possibility of treating wastewater with waste and has the potential for industrial applications for the removal of phosphate from wastewater.     

Effective Removal of Toxic Heavy Metal Ions from Aqueous Solution by CaCO<Subscript>3</Subscript> Microparticles

Heavy metals are a common contaminant in water supplies and pose a variety of serious health risks to nearby human populations. A promising approach to heavy metal decontamination is the sequestration of heavy metal ions in porous materials; however, current technologies involve materials which can be difficult to synthesize, are high-cost, or are themselves potentially toxic. Herein, we demonstrate that rapidly synthesized calcium carbonate (CaCO₃) microparticles can effectively remove high quantities of Pb²⁺, Cd²⁺, and Cu²⁺ ions (1869, 1320, and 1293 mg per gram of CaCO₃ microparticles, respectively) from aqueous media. The CaCO₃ microparticles were characterized with powder X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and Brunauer–Emmett–Teller (BET) N₂ sorption–desorption. It was found that the Ca²⁺ ions of the microparticles were replaced by the heavy metal ions, leading to partially recrystallized nanoparticles of new compositional phases such as cerussite (PbCO₃). The adsorption, surface dissolution/re-precipitation, and nucleation/crystal growth mechanisms were determined by investigating the Ca²⁺ released, along with the changes to particle morphology and crystal structure. Importantly, this study demonstrates that the porous CaCO₃ microparticles performed well in a system with multiple heavy metal ion species: 100% of Cu²⁺, 97.5% of Pb²⁺, and 37.0% Cd²⁺ were removed from an aqueous solution of all cations with initial individual metal concentrations of 50 mg/L and 1.5 g/L of CaCO₃ microparticles. At this concentration, the CaCO₃ microparticles significantly outperformed activated carbon. These results help to establish CaCO₃ microparticles as a promising low-cost and scalable technology for removing heavy metal ions from contaminated water.

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Effectiveness of Conventional and Low-Cost Wastewater Treatments in the Removal of Pharmaceutically Active Compounds

In the present work, the effectiveness of conventional wastewater treatments (activated sludge and oxidation ditches) and low-cost wastewater treatments (trickling filter beds, anaerobic lagooning and constructed wetlands) in the removal of pharmaceutically active compounds has been studied. To evaluate the efficiency of removal, 16 pharmaceutically active compounds belonging to seven therapeutic groups (anti-inflammatory drugs, antibiotics, antiepileptic drugs, ??-blockers, nervous stimulants, estrogens and lipid regulators) have been monitored during 1-year period in influent and effluent wastewater from 11 wastewater treatment plants of Spain. Mean removal rates of pharmaceutically active compounds achieved in conventional wastewater treatments were slightly higher than those achieved in low-cost treatments, being 64% and 55%, respectively. Ibuprofen, naproxen, salicylic acid and caffeine were the pharmaceutical compounds most efficiently removed, regardless the wastewater treatment applied, with removal rates up to 99%. Anaerobic lagooning was the less effective treatment for the removal of the most persistent compounds: carbamazepine and propranolol.     

A Model for Evaluating the Feasibility of an Extraction Procedure for Heavy Metal Removal from Contaminated Soils

A model was developed that allowed for the evaluation of a soil metal cleaning technique in a rapid and cost effective manner. Metal flow (Pb, Cu, Zn, and Cd) during a counter-current soil-acid extraction procedure, consisting of a decarbonation, solubilisation, and washing step, was determined. Required input data are total soil metal content and metal equilibrium distribution coefficients, derived from batch equilibration experiments. The model was calibrated and validated against experimentally obtained results. Model predictions adequately described metal behaviour and removal in each of the extraction steps. Based on the results, optimum operating conditions for the steps involved in the extraction procedure were determined and the feasibility of the counter-current extraction procedure for heavy metal removal from a contaminated soil evaluated.     

三种无机萃取剂去除土壤中PbCd的条件研究

通过对重金属污染土壤的萃取实验,比较了HCl、Na2S2O3、CaCl2 3种常用无机萃取剂对重金属Ph和cd的萃取效果,并通过改变萃取条件（萃取剂浓度、时间、固液比、萃取次数和温度）,以期找到各种萃取剂达到最大萃取效率时所需的萃取条件。结果表明,萃取剂浓度对于萃取效率的影响最大,随着浓度的提高,3种萃取剂对Ph、Cd的去除作用增强;固液比和萃取次数对Ph、Cd的去除率也有较大的影响;时间对两金属的去除率也有一定的影响,但在本实验条件下,达到萃取平衡所需时间很短;温度对萃取效率的影响很小。本实验中,HCl去除Pb、Cd的能力远远大于其他两种萃取剂。对Cd进行萃取时,需增加萃取次数才能达到较好的萃取效果。     

Polydopamine Nanoparticles as a New and Highly Selective Biosorbent for the Removal of Copper (II) Ions from Aqueous Solutions

The adsorption and desorption of copper (II) ions from aqueous solutions were investigated using polydopamine (PD) nanoparticles. The nanoscale PD nanoparticles with mean diameter of 75?nm as adsorbent were synthesized from alkaline solution of dopamine and confirmed using scanning electron microscopy and X-ray diffraction analysis. The effects of pH (2?C6), adsorbent dosage (0.2?C0.8?g?L^?1), temperature (298?C323?K), initial concentration (20?C100?mg?L^?1), foreign ions (Zn²⁺, Ni²⁺, Cd²⁺, Fe²⁺, and Ag⁺), and contact time (0?C360?min) on adsorption of copper ions were investigated through batch experiments. The isotherm adsorption data were well described by the Langmuir isotherm model. The maximum uptake capacity of Cu²⁺ ions onto PD nanoparticles was found to 34.4?mg/g. The kinetic data were fitted well to pseudo-second-order model. Moreover, the thermodynamic parameters of the adsorption (the Gibbs free energy, entropy, and enthalpy) were studied.     

Effectiveness of a Full-Scale Constructed Wetland for the Removal of Metals from Domestic Wastewater

The mobility of fluorescein and bromide used as tracers in packed soil columns was investigated. Five different soils were used in two application methods: soil surface application and soil incorporation, both of which simulate accepted methods of soil application of termiticides to prevent structural infestation. The breakthrough of bromide and fluorescein in column eluates were measured. The absorbance of fluorescein at 492 nm was pH dependent, and proper adjustments were made after measuring the eluate pH. Although high recoveries of bromide from the soil columns were observed, the breakthrough was different among the soil types, indicating that bromide behaves differently in different soils. Recovery of fluorescein, a weak acid, varied depending upon the pH of the soil used, and was only observed in the eluates of two of the five soils tested. Soil treated with bromide and fluorescein followed by soaking extraction showed high recovery of bromide but low recovery of fluorescein, except for in the most alkaline of the soils tested. If fluorescein is used as a conservative tracer in pesticide soil mobility studies, mobility can be underestimated in acidic soils because the active ingredient might travel more quickly than does the fluorescein.     

Residual Organic Compound Removal from Aqueous Solution Using Commercial Coconut Shell Activated Carbon Modified by a Mixture of Seven Metal Salts

The modified activated carbon (MAC) derived from commercial coconut shell activated carbon (AC) with mixture of seven metal salts was used as an adsorbent to remove target residual organic compound (sucrose) from aqueous solutions in batch modes. The results indicated that the highest adsorption capacity of sucrose onto MAC reached when the AC was modified at the ratio of impregnation of AC with mixture of seven metal salts, including nitrate silver (AgNO₃), manganese nitrate (Mn (NO₃)₂), potassium bichromate (K₂Cr₂O₇), nitrate cobalt (Co (NO₃)₂·6H₂O), nitrate copper (Cu (NO₃)₂·3H₂O), nitrate nickel (Ni (NO₃)₂·6H₂O) and nitrate iron (Fe (NO₃)₂·9H₂O) of 3% (w/w). The most appropriate conditions for sucrose adsorption onto MAC in batch experiments obtained at pH 7, contact time of 120 min, 800 mg MAC/50 mL of sucrose solution with initial concentration of 1500 mg/L. At this condition, the highest adsorption capacity of sucrose onto MAC reached 28.28 mg/g. The Langmuir, Freundlich, and Sips adsorption isothermal equilibrium models can adequately describe the adsorption properties of sucrose on MAC. The adsorption kinetic of sucrose onto MAC obeyed pseudo-first-order and pseudo-second-order models with the chemical sorption process. The saturated MAC was recovered by heat from an oven. The highest recovery efficiency of saturated MAC obtained at 180 °C in 120 min. The highest adsorption capacity of sucrose onto recovered MAC was 24.31 mg/g, appropriately adsorption capacity of initial MAC.     

Removal of Cu(II) Ions from Aqueous Solution by Magnetic Chitosan-Tripolyphosphate Modified Silica-Coated Adsorbent: Characterization and Mechanisms

A magnetic chitosan-modified Fe₃O₄@SiO₂ with sodium tripolyphosphate adsorbent (MTPCS) was synthesized by surface modification of Fe₃O₄@SiO₂ with chitosan using sodium tripolyphosphate (STPP) as the cross-linker in buffer solution for the adsorption of Cu(II) ions from aqueous solution. The structure and morphology of this magnetic nanoadsorbent were examined by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), BET surface area measurements, Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). The effects of initial pH, adsorbent amount, and initial concentration of heavy metal ions were investigated by batch experiments. Moreover, adsorption isotherms, kinetics, and thermodynamics were studied to understand the mechanism of adsorbing metal ions by synthesized MTPCS. The results revealed that adsorption kinetics was best depicted by the pseudo-second-order rate mode and intraparticle-diffusion models. The adsorption isotherm fitted well to the Langmuir model. Moreover, thermodynamic study verified the adsorption process was endothermic and spontaneous in nature. The maximum adsorption occurred at pH 5 ± 0.1, and the adsorbent could be used as a reusable adsorbent with convenient conditions.     

Effect of Organic Ligands on Copper(II) Removal from Metal Plating Wastewater by Orange Peel-based Biosorbents

A neutrophilic, autotrophic bacterium that couples iron oxidation to nitrate reduction (iron-oxidizing bacteria [IOB]) under anoxic conditions was isolated from a working bioremediation site in Trail, British Columbia. The site was designed and developed primarily to treat high concentrations of Zn and As that originate from capped industrial landfill sites. The system consisted of two upflow biochemical reactor cells (BCR) followed by three vegetated wetland polishing cells with sub-surface flow and a holding pond. During a 5-year period (2003–2007), the system treated more than 19,100 m³ of contaminated water, removing and sequestering more than 10,700 kg of As, Zn and sulfate at average input water concentrations of: As, 58.6 mg?l^?1 (±39.9 mg?l^?1); Zn, 51.9 mg?l^?1 (±35.4 mg?l^?1) and SO₄ ^2?, 781.5 mg?l^?1 (±287.8 mg?l^?1). The bacterium was isolated in order to better understand the mechanisms underlying the consistent As removal that took place in the system. Analysis using Basic Local Alignment Search Tool (BLAST) database showed that the closest homologies are to Candidatus accumulibacterphosphatis (95 % homology), Dechloromonas aromatica (94 %), and Sideroxydans lithotrophicus ES-1 (92 %) Within the BCR cells, the IOB oxidized Fe²⁺ generated by iron-reducing bacteria (IRB); the source of the iron was most likely biosolids and coatings of iron oxide on locally available sand used in the matrix. We have provisionally designated the novel bacterium as TR1.     

Removal of Cationic Dyes,Heavy Metal Ions,and CO<Subscript>2</Subscript> Capture by Adsorption on Mesoporous Silica HMS

Mesoporous silica with wormhole framework structure (HMS-OH) and its amine-functionalized material (HMS-NH₂) were prepared through an electrically neutral assembly pathways, post-grafting process of 3-aminopropyltriethoxysilane (APTES), respectively. Their adsorption behaviors toward cationic dyes as well as heavy metal ions in aqueous system and the capture capacities for CO₂ molecules all have been investigated. As-synthesized HMS-OH showed a high removal efficiency and rapid sorption rate to cationic dyes because of large surface area and versatile pore structure. HMS-NH₂ exhibited better heavy metal ions and more CO₂ gas sorption capacities due to the intrinsic property of amine groups grafted on the surface. The adsorption isotherms of methylene blue (MB) onto HMS-OH, Cu(II) onto HMS-NH₂ were fitted with Langmuir model and kinetic processes followed well the pseudo-second order pattern. There results revealed that both HMS-OH and HMS-NH₂ had a potential application in the treatment of cationic dyes, heavy metal ions, and greenhouse gas CO₂.     

Application of Pilot-Scale-Constructed Wetland as Tertiary Treatment System of Wastewater for Phosphorus and Nitrogen Removal

This paper presents the results of using a pilot-scale-constructed wetland as a tertiary system to simulate the treatment conditions of wastewater effluents from the metal-mechanical industry, aiming to achieve the Brazilian legal standards of phosphorus and nitrogen emission. The macrophytes were placed in 1 m³ polyethylene tanks, daily estimating the treatment of 2 m³ of effluents. The effluents were circulated in a horizontal subsurface flow through a porous matrix of thick sand and gravel, in which the roots of the macrophytes of the species Reed (Scirpus sp.) and Cattail (Typha sp.) were fixed. Monitoring of the pilot plant was performed through a battery of physical?Cchemical and biological analyses. Despite the load variations and operational problems, the system presented a positive degree of pollutant efficiency removal, especially for phosphorus (73% medium), TKN (61% medium), and NH₄?CN (56% medium). Peak results were achieved during the last 3 months of monitoring. The chemical analysis of the support layer, plus the root system and aerial portion of the plants, revealed that these wastes could be used as fertilizer.     

Development of an Environmentally Friendly Adsorbent for the Removal of Toxic Heavy Metals from Aqueous Solution

An effective adsorbent for the removal of heavy metals was manufactured by immobilization of jujube powder. The adsorptions of Cd, Zn and Cu from aqueous solutions by jujube complex beads (Type 1 and Type 2) were studied in a batch adsorption system. The adsorption data were fitted well with the Langmuir isotherm models. The adsorption capacities (β) for Cd, Zn and Cu were 4.23, 2.93 and 3.64 mg/g in Type 1 and 1.24, 0.70 and 1.35 mg/g in Type 2 beads. The removal efficiencies of the Type 2 beads, with a larger unit surface area, were lower than those of the Type 1 due to part of the casein or cyclic AMP being destroyed during the drying process of the Type 1. These values for Type 1 beads were higher than those of all other adsorbents for each heavy metal. A comparison of the kinetic models on the overall adsorption rate showed that the adsorption system was best described by pseudo-first-order kinetics. The removal efficiencies of Cd, Zn and Cu exhibited similar tendencies to those observed in the equilibrium tests. This indicates that the jujube complex beads developed in this study can be used as promising adsorbents for the removal of heavy metals from wastewater.     

Modification Effects of Hematite with Aluminum Hydroxide on the Removal of Fluoride Ions from Water

The modification effects of hematite with aluminum hydroxide were investigated on the removal of fluoride ions from water using batch experiments. The effects of pH, contact time, fluoride concentration, and the dose of sorbent on the sorption of fluoride ions by a modified hematite were studied. Characterization of hematite before and after the modification with aluminum hydroxide was studied by X-ray diffraction, scanning electron microscope, and Brunauer–Emmett–Teller. Equilibrium was reached in 48 h of contact time and the maximum sorption of fluoride was found in the pH_eq range between 2.34 and 6.26. The Elovich model described the kinetic sorption processes and the Langmuir–Freundlich model, the sorption isotherm process. These results indicated that the sorption mechanism was chemisorption on a heterogeneous material.     

On the Use of Different Efficiency Criteria for the Validation of a Heavy Metal Balancing Tool

The validation of metal balancing tools is usually based on the comparison of simulated versus observed data. In our study, we applied a set of different relative and absolute criteria to evaluate the performance of the model Assessment Tool for Metals in Soils. In this process, the uncertainty of the model output and the sensitivity of model parameters were also assessed. The study includes data from 123 agricultural used top soils which are characterized by the application of different fertilizers (mineral and farmyard fertilizers, sewage sludge) resulting in diverse metal inputs into the soil. Although the most common validation criteria (coefficient of determination, error ratio between prediction and observation) indicated a good model performance in predicting the metal contents over a simulation period, the absolute measure (mean absolute difference between prediction and observation) showed that the informational value of the validation results was limited for several sites. Therefore sites with short simulation periods and/or low metal inputs are not suitable for validation, because the model uncertainty covers the metal concentration changes. Excluding such sites from the validation statistics led to evaluable and quite better validation results. Although the calculated output uncertainty was low, a further reduction can be realized by improving the database for the identified sensitive parameters (initial soil metal content and fertilizers metal concentration).