Tomasz Bajda

Immobilization and reduction of hexavalent chromium in the interlayer space of positively charged kaolinites.

This work was designed to investigate the sorption equilibrium and kinetics of modified kaolinites of different structural order toward Cr(VI). The key reaction of modification involved an iodomethane quaternization of the mineral previously interlayer grafted with triethanolamine. This induced positively charged centers (PCNs) associated with nitrogens of ammonium salt molecules formed in the interlayer space. The positive charge was compensated by mobile iodide anions which could be ion-exchanged. Results reveal a significant increase in sorption capacity as compared to raw kaolinites and show that the sorption takes place exclusively in the interlayer space which proved to be accessible for the Cr(VI). The amount of sorbed Cr(VI) depends on the PCN content resulting from the kaolinites reactivity influenced by their structural order. An ion-exchange mechanism followed by Cr(VI) to Cr(III) reduction by iodide is proposed. The amount of initially sorbed Cr(VI) and its anionic form is strongly influenced by the pH. Desorption experiments showed that only the Cr(VI) which was not reduced (~30%) was released to the solution.

Utilization of bog iron ores as sorbents of heavy metals

Sorption properties of bog iron ores with respect to Pb, Cu, Zn, Cr are evaluated at various pH. Maximum sorption determined in the experiments equals to 97.0, 25.2, 25.5, 55.0mg/g for lead(II), copper(II), zinc(II), and chromium(III), respectively. Chromium(VI) is bound in the amount of up to 10.0mg/g. The values of desorption indicate that most of the metals remain stably bound to the surface of bog iron ores, indicating that the chemisorption process prevails. The metals are sorbed as cations at the pH values from 4 to 9. Within this pH range up to 100% of the initial metal amount is immobilized. 90-100% of Cr(VI) is sorbed at pH between 3 and 5. Such properties, combined with favorable conditions of shallow mining and resultant low costs, may be regarded as an incentive for local utilization of bog iron ores in the environmental protection practice.

Solubility of mimetite Pb5(AsO4)3Cl at 5–55°C

Environmetal context.The mobility of toxic arsenic compounds in the environment can be controlled by the solubility of certain minerals. To predict and model the fate and behaviour of these contaminants, the solubility and related thermodynamic properties of the lead and arsenic mineral mimetite were determined. The data obtained in this study will be used to optimise and increase the effectiveness of remediation procedures that are already applied to contaminated sites. Abstract.The solubility of the synthesised mimetite was measured in a series of dissolution experiments at 5–55°C and at pH values between 2.00 and 2.75. The solubility product logKSP for the reaction Pb5(AsO4)3Cl ↔ 5Pb2+ + 3AsO43– + Cl– at 25°C is –76.35 ± 1.01. The free energy of formation ΔGf,2980 calculated from this measured solubility product equals –2634.3 ± 5.9 kJ mol–1. The temperature dependence of the logKSP is non-linear, indicating that the enthalpy of the reaction depends on the temperature. The enthalpy of the formation of mimetite ΔHf0, is –2965.9 ± 4.7 kJ mol–1, the entropy, ΔS0, is 39.5 J mol–1 K–1, and the heat capacity, ΔCp,f0 is –6172 ± 105 J mol–1 K–1. Hydrochemical modelling indicates that regardless of the composition of the background solution, Pb5(AsO4)3Cl is most stable at neutral to weakly alkaline pH.

Synchrotron-based X-ray diffraction of the lead apatite series Pb10(PO4)6Cl2–Pb10(AsO4)6Cl2

A number of compounds of the pyromorphite-mimetite solid solution series were synthesized at room temperature and analyzed with infrared spectroscopy and powder X-ray diffraction. High-resolution high-quality powder diffraction data were obtained by means of the state-of-the-art instrument at the 11-BM beamline of the Advanced Photon Source at Argonne National Laboratory, Argonne, IL, USA. The unit-cell dimensions, atomic position and atomic displacement parameters, as well as site occupancy for analyzed phases, were refined by the Rietveld method and reported herein for the first time. The results of this study indicate that the pyromorphite-mimetite series is continuous in near-Earth-surface environments. Detailed structural changes caused by P(5+)-As(5+) substitutions in minerals from the pyromorphite-mimetite solid solution series are reported.

Arsenate substitution in lead hydroxyl apatites: A Raman spectroscopic study.

A total of seven compounds of the hydroxylpyromorphite Pb10(PO4)6(OH)2 - hydroxylmimetite Pb10(AsO4)6(OH)2 (HPY-HMI) solid solution series were synthesized at 80°C from aqueous solutions and characterized using Raman spectroscopy. The positions of the bands in all spectra of the series depend on the content of arsenates and phosphates shifting to lower wavenumbers with substitution of (AsO4)(3-) for (PO4)(3-). This shift results from the decreasing bond strength of X-O (where X=P, As) and higher atomic mass of As than P. The position and intensity of major (PO4)(3-) and (AsO4)(3-) bands in Raman spectra exhibit linear correlation with As content, while the ratio of the intensities of these peaks shows exponential correlation. This results due to different polarizability of (PO4)(3-) and (AsO4)(3-) molecules. A small carbonate band develops with increasing As content indicating that hydroxyl lead apatites adopt the (CO3)(2-) ions, particularly at the arsenate end of the series.

Removal of chromium(VI) from aqueous solutions using zeolites modified with HDTMA and ODTMA surfactants

Abstract The removal of Cr(VI) from aqueous solutions under various conditions was investigated using a natural clinoptilolite and a synthetic zeolite derived from fly-ash (Na-P1), modified either with hexadecyltrimethylammonium bromide (HDTMA) or octadecyltrimethylammonium bromide (ODTMA). The study was focused mainly on the impact of the properties of the zeolite on the sorption capacity, the sorption mechanism, the influence of pH and the durability of the immobilization. The zeolites were modified with HDTMA and ODTMA surfactants up to 100% and 120% of their external cation exchange capacity. Batch and column studies were conducted to evaluate the influence of pH and the initial Cr(VI) concentration on their efficiencies for removing chromates. The organo-zeolites show a significant ability to remove Cr(VI) from aqueous solutions. The amount of Cr(VI) removed by organo-clinoptilolite and organo-zeolite Na-P1 is greater at low pH values, whereas the sorption efficiency decreased with increasing pH. Sorption of Cr(VI) was more efficient with the HDTMA-modified organo-clinoptilolite (150 mmol Cr(VI)/kg) than the ODTMA-modified clinoptilolite (132 mmol Cr(VI)/kg). The maximum sorption capacity was obtained with the 1.2 × ECEC ODTMA-modified clinoptilolite (237 mmol Cr(VI)/kg). The organozeolites Na-P1 adsorbed Cr(VI) from aqueous solutions more effectively and were much more durable than the organo-clinoptilolites.

Removal of lead and phosphate ions from aqueous solutions by organo-smectite

Smectite has been modified using hexadecyltrimethyl ammonium bromide in an amount of double cationic exchange capacity. This alteration makes it possible to use organo-smectite as a sorbent to remove anionic forms. The experiment consisted of the interchangeable sorption of phosphate(V) and lead(II) by organo-smectite. Research was carried out with varying pH (2–5) and various concentrations (0.1–5 mmol/L). Organo-smectite with previously adsorbed lead ions removed more phosphate than the untreated organo-smectite. Experimental data show that lead is more likely to absorb on the organo-smectite than on the organo-smectite with previously adsorbed phosphate ions. It follows that the most effective use of the organo-smectite is through the sorption of first – Pb cations and then PO4 anions. With an increasing concentration of Pb(II) or P(V), the sorption efficiency increases. The maximum sorption efficiency of lead and phosphate ions is observed at pH 5. This enables the removal of harmful lead and phosphorus compounds from waste water and immobilizes them on the sorbents surface. The alternating reactions of lead and phosphorus ions result in the crystallization of brompyromorphite Pb5(PO4)3Br.

Dissolution of mimetite Pb5(AsO4)3Cl in low-molecular-weight organic acids and EDTA

Due to its relatively low solubility, mimetite Pb(5)(AsO(4))(3)Cl may control Pb and As(V) solution levels at a low value in contaminated soils. The time-dependent dissolution of mimetite by low-molecular-weight organic acids (LMWOAs) such as acetic, lactic, citric, and ethylene diamine tetra-acetic acid (EDTA) was determined. At pH 3.5, the presence of citric acid or EDTA significantly increases the solubility of mimetite while acetic or lactic acids show little effect. The effect of all organic anions on the dissolution of mimetite increased with the increase in solution pH. The rate of mimetite dissolution depended on the kind and concentration of organic solvents in the sequence r(EDTA)>r(lactate)>r(acetate)>r(citrate). Soluble Pb and As(V) released in LMWOAs and EDTA were higher than the WHO guideline value for these elements in drinking water (10 μg As(V)L(-1), 10 μg Pb L(-1)). This suggests that soil organic acids in rhizosphere can potentially liberate Pb and As(V) from mimetite in contaminated soils.

Sorption of Chromate by Clinoptilolite Modified With Alkylammonium Surfactants

Sorption of Chromate by Clinoptilolite Modified With Alkylammonium Surfactants Clinoptilolite from Dylągówka (Poland) with an external cation exchange capacity (ECEC) of 16 meq/100 g determined by adsorption of alkylammonium ions was treated with hexadecyltrimethylammonium (C16) and dioctadecyldimethylammonium (2C18) bromides in amounts equivalent to 1.0 and 1.5 ECEC. The products were characterized using IR spectroscopy and C and N determinations. The sorption of chromate on the modified mineral was measured spectrophotometrically as a function of pH, concentration of Cr(VI) or the proportion of the sorbent to solution. The amount of chromate removed from the solution continuously decreased with increasing pH in the range 1.3-10. At pH 2.6-3.1, the maximum adsorption of Cr(VI) by the organo-zeolites (103 and 124 mmol/kg) was observed for the samples modified using a 1.5 ECEC surfactant concentration. Considerably lower adsorption values (37 and 46 mmol/kg) were obtained with sorbents prepared using a 1.0 ECEC concentration of the alkylammonium ions.

SEWAGE SLUDGE BIOCHARS MANAGEMENT – ECOTOXICITY, MOBILITY OF HEAVY METALS AND SOIL MICROBIAL BIOMASS

Production of biochar from sewage sludge may be a promising solution for sewage sludge management and improvement of soil properties, including carbon dioxide sequestration. The aim of the present study was to compare the effects of biochars derived from different sewage sludges on soil physicochemical and biological properties, ecotoxicity, and plant yield. Three biochars (produced at a temperature of 300 °C) were applied into sandy acid soil in doses of 0.5, 1, and 2% (w/w). Depending on the type and dose, the application of sewage sludge biochars into the soil caused diverse effects on the parameters of soil biological activity (microbial biomass [Cmic], soil respiration, and value of metabolic quotient). No correlation between the applied dose of biochars and inhibition of Vibrio fischeri luminescence was observed. The factor with a stronger impact on the activity of V. fischeri was the type of biochar. The use of the OSTRACODTOXKIT F test (MicroBioTests) showed that the addition of sewage sludge biochar (regardless of its dose) reduced the soil toxicity to Heterocypris incongruens compared with the control soil. A significant increase of Poa pratensis L. biomass was obtained in soils with 1 and 2% additions of each of the biochars. The addition of biochars in doses of 1 and 2% to the soil had greater effect on the content of mobile forms of Cu, Pb, and Cd than the 0.5% dose compared with the control. Environ Toxicol Chem 2018;37:1197-1207.