Laboratory Study of Simulated Atmospheric Transformations of Chromium in Ultrafine Combustion Aerosol Particles

While atmospheric particles can have adverse health effects, the reasons for this toxicity are largely unclear. One possible reason is that the particles can contain toxic metals such as chromium. Chromium exists in the environment in two major oxidation states: III, which is an essential nutrient, and VI, which is highly toxic and carcinogenic. Currently little is known about the speciation of chromium in airborne particles or how this speciation is altered by atmospheric reactions. To investigate the potential impacts of atmospheric aging on the speciation and toxicity of chromium-containing particles, we collected chromium and chromium-iron combustion ultrafine particles on Teflon filters and exposed the particles to a combination of light, ozone, water vapor, and, in some cases, basic or acidic conditions. After the aging process, the aged and not-aged samples were analyzed for Cr oxidation state using X-ray Absorption Near Edge Spectroscopy (XANES). We found that the aging process reduced Cr(VI) by as much as 20% in chromium particles that had high initial Cr(VI)/Cr(total) ratios. This reduction of Cr(VI) to Cr(III) appears to be due to reactions primarily with light and hydroperoxyl radical (HO ₂ ) in the chamber. Particles that had low initial Cr(VI)/Cr(total) ratios experienced no significant change in Cr oxidation states after aging. Compared to particles containing only Cr, the addition of Fe to the flame decreased the Cr(VI)/Cr(total) ratio in fresh Cr-Fe particles by ～60%. Aging of these Cr-Fe particles had no additional effects on the Cr(VI)/Cr(total) ratio.     

EXTRACTION STUDIES ON THE SYSTEM BETWEEN BIS(2-ETHYLHEXYL) PHOSPHORIC ACID AND CHROMIUM(III) IN SEVERAL AQUEOUS SOLUTIONS

The extraction of chromium(III) by carboxylic acids and acidic organophosphorus compounds has been investigated. In general, chromium(III) was not extracted by carboxylic acids but the organophosphorus compound, di-2-ethylhexyl phosphoric acid, was found to be particularly adequate for the extraction. The partition of chromium(III) in nitrate medium and solutions of di-2-ethylhexyl phosphoric acid in Shellsol-T was studied using a tracer of 51cr. Distribution measurements of the metal ion in a wide range of pH and organophosphoric acid concentrations have been performed. The experimental data treated by a graphical method have been explained assuming the presence in the organic phase of the species Cr(DEHP)₃(H₂O)²(HDEHP). Equilibrium constants for the different extraction reactions are given. The extraction of the monomeric species was found to be independent of Ac^?or SO⁼ ₄ions presence.     

Preconcentration and determination of chromium in water with flame atomic absorption spectrometry by thiourea-formaldehyde as chelating resin

Thiourea-formaldehyde chelating resin is synthesized simply and rapidly from thiourea and formaldehyde by condensation polymerization and characterized by IR spectra and studied for the preconcentration and determination of trace Cr(III) ion from solution samples. The optimum pH value for sorption of the metal ion was 6.5. The sorption capacity of resin for Cr(III) was determined. The chelating resin can be reused for 20 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 96% was obtained for the metal ion with 0.5M HNO₃ as eluting agent. The equilibrium adsorption data of Cr(III) on modified resin were analyzed by Langmuir, Freundlich and Temkin models. Based on equilibrium adsorption data the Langmuir, Freundlich and Temkin constants were determined as 0.016, 0.040 and 0.074 at pH 6.5 and 20°C. The method was applied for chromium ion determination from river water sample.     

The role of sulfide in the immobilization of Cr(VI) in fly ash geopolymers

The use of fly ash-based geopolymer binders to immobilize chromium is investigated in detail, with particular regard to the role of the sulfide ion as a reductant for Cr(VI) treatment. In the absence of sulfide, Cr added as Cr(VI) is highly leachable. However, addition of a small quantity of Na₂S reduces the Cr to Cr(III), and enables leaching efficiencies in excess of 99.9% to be reached after 90 days' exposure to deionized water, Na₂CO₃ or MgSO₄ solutions. Leaching in H₂SO₄ is somewhat greater than this, due most probably to the oxidation of the Cr(III) present. Addition of the Cr(VI) as a highly soluble salt is preferable to its addition as a sparingly soluble salt, because a higher salt solubility means the Cr(VI) is more available for reduction prior to geopolymeric setting. The potential value of geopolymer technology as an immobilization process for problematic heavy metal waste streams is highlighted by these results, and the need for a full understanding of binder chemistry in any immobilization system outlined.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 5 : THE EFFECT OF SOLUTION MATRIX ON ACTINIDES

ABSTRACT

The influence of commonly occurring matrix constituents on the uptake of representative actinides in the tri-, tetra-, and hexavalent oxidation states by a new chelating ion exchange resin, called Diphonix?, has been investigated. The effect of increasing concentrations of HF at three fixed HC1 concentrations on the retention of U(VI), Np(IV), and Am(III) was measured. All three actinides showed strong retention in HF even up to a concentration of 1 M The effect of sulfuric, oxalic and phosphoric acids at three fixed HNO₃ concentrations on the retention of Th(IV), U(VI), and Am(III) was also measured. Only when the concentration of the complexing acids was above 0.1 M was the retention of the actinides decreased significantly at 0.1 M HNO₃ The effect was much less pronounced at higher HNO₃ concentrations.

Sodium, calcium, aluminum and iron were selected to study the influence of cationic matrix constituents on the uptake of actinide ions by Diphonix. In the case of tetra- and hexavalent actinides (represented by Th and U, respectively) only the very highest concentrations of Fe(III) and Al(III) caused a significant decrease in the retention of the two higher valent actinides. On the other hand, Am(III) retention was significantly lowered by Al and Fe(III) concentrations above 10^?2 M The influence of Al and Fe(III) on the uptake of Am(III) may be minimized by use of fluoride ion to complex Al and by reducing Fe(III) to Fe(II). Macroconcentrations of sodium and calcium had only minimal influence on the uptake of actinides in all three oxidation states.     

Modulated Cr(III) oxidation in KOH solutions at a gold electrode: Competition between disproportionation and stepwise electron transfer

The electrochemical oxidation of aqueous Cr(III) was examined using cyclic voltammetry with a polycrystalline Au electrode in KOH solutions of varying pH and Cr(III) concentration. The mechanism and kinetics for the oxidation of Cr(III) is a quasi-reversible diffusion-controlled reaction and is largely dependent on the solution pH. The reaction mechanism is initiated by an irreversible electrochemical electron transfer to form Cr(IV) which is the rate-determining step (RDS). Following the RDS, subsequent oxidation of Cr to its hexavalent state occurs by the disproportionation of Cr(IV) at low KOH concentrations and electron transfer at high KOH concentrations due to the involvement of OH⁻ in the disproportionation reaction. As the solution pH increases, the Cr(III) oxidation peak potential shifts negatively owing to the involvement of OH⁻ in the RDS. The competitive adsorption of OH⁻ and CrO₂⁻ on the electrode surface also plays an important role in the oxidation behavior.     

Fate of Cr(III) during Ozonation of Secondary Municipal Wastewater Effluent

ABSTRACT

In the present study, the fate of trivalent chromium (Cr(III)) during ozonation of ultrapurified water and wastewater effluent was investigated. In experiments conducted in phosphate buffered ultrapurified water, O₃ alone in excess was inefficient to oxidize Cr(III) (only about 10–15% of total Cr(III) content), while in presence of the secondary oxidant, OH radical, almost all Cr(III) was oxidized to hexavalent chromium (Cr(VI)). In a wastewater effluent, spiked with Cr(III), only about 10–20% of Cr(III) was oxidized with specific ozone doses in the range 0.15–1.5 gO₃/gDOC, although O₃ and OH radical were both available for reaction. Cr(VI) formation was monitored in parallel with the abatement of some common micropollutants, reacting with differing apparent second-order rate constants with ozone, decreasing in the order carbamazepine>> benzotriazole> atrazine> p-chlorobenzoic acid (pCBA). Carbamazepine and benzotriazole were abated to >80% for specific O₃ doses of 0.3 gO₃/gDOC and 0.8 gO₃/gDOC, respectively. The more ozone-resistant compounds (atrazine and pCBA) required a specific ozone dose of about 1.25 gO₃/gDOC for the same relative abatement. At this specific ozone dose (i.e., 1.25 gO₃/gDOC), only about 20% of Cr(III) was oxidized to Cr(VI), whereas only 10% of Cr(III) was oxidized to Cr(VI) at a more realistic specific ozone dose for enhanced wastewater treatment for micropollutant abatement (0.5 gO₃/gDOC). Therefore, for typical Cr(III) levels in municipal wastewaters, effluent ozonation only leads to toxicologically insignificant Cr(VI) concentrations.     

Recovery of chromium from tannery effluents using a redox–adsorption approach

Adsorption isotherms for sodium and trivalent chromium uptake from aqueous solutions onto Amberlite resin were prepared at 18°C. Adsorption of each cation followed the Langmuir model. The rate of uptake of each cation was found to be film diffusion controlled with sodium showing the most rapid uptake. In aqueous solutions containing both chromium and sodium as the only cationic species, it was found that with increasing initial concentration of sodium, the trivalent chromium uptake on the resin decreased substantially. To overcome this difficulty a four step redox–adsorption system has been developed for the removal of Cr³⁺ from tannery effluents. The first step comprises the oxidation of trivalent chromium to the hexavalent form using selected common oxidising agents. The liquid effluent is then passed through an Amberlite cation-exchange resin in step 2 where the sodium in the waste stream is completely removed. The anionic hexavalent form of chromium (Cr₂O) passes unaltered through the resin along with the waste stream. In the third stage the dichromate is reduced back to the trivalent cationic form which is subsequently removed from the waste stream by a second Amberlite ion-exchange bed in stage 4. Each step in this process is assessed in batch and flow mode using simulated and real tannery effluents.     

The electrochemical study of a chromium plating bath. I. Reactions leading to solution-free species

The electrode reactions occurring at C, Cr, Cu and Ni cathodes in the standard electroplating solution for chromium, 200 g dm^?3 CrO₃ and 2 g dm^?3 H₂SO₄, have been reinvestigated. This paper emphasises the study of those reactions which lead to solution-free products; these occur at potentials positive to that necessary for film or metal deposition. For each cathode, theI-E curve shows a wave or peak for the reduction of chromium (VI) to chromium(III) and it is demonstrated that this process is mass transport controlled, apparently by the transport of sulphate ions to the electrode surface. At Cr, Ni and Cu, the potential of the chromium(VI)/chromium(III) couple is determined by the removal of an insulating oxide film which forms spontaneously when the metal is immersed in the bath. In certain conditions it is also possible to define a well formed wave for proton reduction.     

Functionalization of a multiepoxy resin by methacrylic compounds and study of its thermal properties

Summary Methacrylation of triglycidyl triphenyl methane (via methacrylic acid) has been done using three catalysts: dimethyl dodecyl amine (DMDA), tetrabutyl ammonium bromide (TBAB) and chromium (III) diisopropyl salicylate (Cr Dips). The reaction has been followed by epoxy colorimetric titration, CPG and ¹H NMR.This study has shown the superiority of chromium catalysis because of its rapidity and ease of process.Then, these cured products (TACTIX and methacrylated TACTIX) show homogeneous Tg values which are higher than 200°C.     

New pink ceramic pigment based on chromium (IV)-doped lutetium gallium garnet

Lutetium gallium garnet codoped with chromium and calcium (Ca,Cr:LGG) and lutetium gallium garnet with chromium as single dopant (Cr:LGG) have been studied. Samples with Ca_xCr_xLu_3−2xGa₅O₁₂ (x = 0, 0.05, 0.10, 0.15, 0.2, 0.4, 0.6,) and Cr_xLu_3−xGa₅O₁₂ (x = 0.15 and 0.6) compositions were prepared by solid state reaction and the fired samples (1250 °C/6 h) were characterised by XRD, lattice parameters determination, UV–vis–NIR spectroscopy, CIEL*a*b* measurements and SEM/EDX. Moreover, the samples with calcium were tested as ceramic pigments in a conventional glaze matrix. In the Ca,Cr:LGG system solid solutions incorporating both Cr(III) and Cr(IV) ions were obtained. Cr(IV) occupies basically dodecahedral sites substituting for Lu (III) and is the predominant oxidation state up to x = 0.20 composition, giving a pink colouration in the ceramic glaze matrix. In the Cr:LGG system, only Cr(III) enters in solid solution occupying octahedral positions and producing green shades.     

Foam Fractionation and Ion Flotation of Simple and Complex Anions with Cationic Surfactants

Experimental data are presented and interpreted on the foam fractionation of an extensive series of simple and complex anions from dilute (of the order 10⁻⁶−10⁻⁴ molar) aqueous solutions, utilizing a quaternary ammonium surfactant with which the anions form soluble ion pairs in competition with the surfactant's counterion. Selectivity coefficients, based on a bubble-interface, ion exchange model, are established in a single-equilibrium-stage, continuous-flow, foam fractionation unit for each of a series of 13 anions and oxyanions versus the surfactant's bromide counterion. Three additional series of batch experiments with multi-metal solutions establish the separation and concentration in the foam of the oxyanions of Re(VII), Mo(VI), Cr(VI), W(VI), and V(V); of the cyanide complex anions of Zn(II), Cd(II), Hg(II), and Au(III); and of the chloride complex anions of Zn(II), Cd(II), Hg(II), and Au(III). The metal oxyanions and metal cyanide and chloride complex anions can be separated from each other and from competing chloride, cyanide, or nitrate. Ion flotation of anionic species with a cationic surfactant involves an entirely different mechanism, in which a precipitation reaction occurs and particle flotation follows. Hexavalent chromium (primarily HCrO⁻₄) is ion-floated with each of a series of variable chain length quaternary ammonium surfactants, elucidating the effects of temperature, the surfactant/Cr(VI) feed ratio, mixing time, and surfactant chain length in terms of the roles of the surfactant as precipitant, dispersant, collector, and frother.     

Coals as sorbents for the removal and reduction of hexavalent chromium from aqueous waste streams

The aim of this study is to demonstrate the potential of coals as a low-cost reactive barrier material for environmental protection applications, with the ability to prevent leaching of toxic Cr(VI) and other transition metals. Depending upon the type of ion and the surface functionalities, the uptake can involve ion sorption, ion exchange, chelation and redox mechanisms with the surface functionalities being considered as partners in electron transfer processes. The capacity for Cr(VI) uptake of low rank coals and oxidized bituminous coals has been found to lie within the range 0.2-0.6 mM g⁻¹. Air oxidation of bituminous coals can increase their Cr(VI) removal capacities. The effect of air oxidation of coals on uptake capacity was more pronounced for Cr(VI) than Cr(III), but less than for Hg(II) and the other ions (Ca²⁺, Ba²⁺, Zn²⁺, Cd²) investigated. As previously found for Hg(II), redox mechanisms play an important role in Cr(VI) uptake, with sorption of the resultant Cr(III) being aided by the functionalities arising from oxidation of the coal surface. In acidic media, much of the resultant Cr(III) is exchanged back into solution by hydrogen ions, but some of the sorbed chromium is irreversibly bound to the coal. The reduction of Cr(VI) alone is often considered a satisfactory solution in view of Cr(III) being essentially non-toxic.     

Photocatalytic reduction of chromium and oxidation of organics by polyoxometalates

The photocatalytic reduction of Cr(VI) to the less toxic Cr(III) is presented in the presence of the polyoxometalates (POM) PW₁₂O₄₀³⁻ or SiW₁₂O₄₀⁴⁻ as photocatalyst and an organic substrate (salicylic acid or propan-2-ol) as electron donor. Cr(VI), as dichromate, is reduced to Cr(III), according to the 6:1 stoichiometry of PW₁₂O₄₀⁴⁻ versus Cr₂O₇²⁻ indicated from experiments in the dark. Increase of POM or salicylic acid (SA) concentration accelerates, till a saturation value, both the reduction of metal and the oxidation of the organic, suggesting that these two conjugate reactions act synergistically. The photocatalytic action of POM is not so important in the case of highly concentrated solutions of organics that exhibit direct photochemical reduction of Cr(VI), i.e. propan-2-ol (i-prOH), while it becomes important at low concentrations of i-prOH, especially for organics that do not react directly photochemically with Cr(VI), such as SA. Increase of Cr(VI) concentration enhances consumption of SA and Cr(VI) till an optimum value, due to inner filter effect. The method is suitable for a range of chromium concentration from 5–100 ppm achieving complete reduction of Cr(VI) to Cr(III) up to non-detected traces (>98%). The presence of oxygen does not influence the efficiency of SA and Cr(VI) consumption. In contrast to the semiconductor-based heterogeneous photocatalysis, the POM-based homogeneous process seems superior in the frame that: (i) it remains catalytic throughout illumination by providing more active sites and (ii) among the two POM used, the one that is more efficient in the degradation of the organic, that is PW₁₂O₄₀³⁻ compared to SiW₁₂O₄₀⁴⁻, is also more efficient in reducing Cr(VI), due to a kinetic effect, and a compromise is not needed.     

Removal of Chromium(VI) and Chromium(III) from Aqueous Solution by Grainless Stalk of Corn

Abstract

Grainless stalk of corn (GLSC) was tested for removal of Cr(VI) and Cr(III) from aqueous solution at different pH, contact time, temperature, and chromium/adsorbent ratio. The results show that the optimum pH for removal of Cr(VI) is 0.84, while the optimum pH for removal of Cr(III) is 4.6. The adsorption processes of both Cr(VI) and Cr(III) onto GLSC were found to follow first-order kinetics. Values of k _ads of 0.037 and 0.018 min^?1 were obtained for Cr(VI) and Cr(III), respectively. The adsorption capacity of GLSC was calculated from the Langmuir isotherm as 7.1 mg g^?1 at pH 0.84 for Cr(VI), and as 7.3 mg g^?1 at pH 4.6 for Cr(III), at 20°C. At the optimum pH for Cr(VI) removal, Cr(VI) reduces to Cr(III). EPR spectroscopy shows the presence of Cr(V) + Cr(III)-bound-GLSC at short contact times and adsorbed Cr(III) as the final oxidation state of Cr(VI)-treated GLSC. The results indicate that, at pH ≈ 1, GLSC can completely remove Cr(VI) from aqueous solution through an adsorption-coupled reduction mechanism to yield adsorbed Cr(III) and the less toxic aqueous Cr(III), which can be further removed at pH 4.6.     

Insights into the Sorption Mechanisms of Cr(III) by Chemically Modified Pine Bark

The mechanisms of Cr(III) sorption by pine bark treated chemically (MPB) with NaOH were investigated. The removal of Cr(III) was found to be strongly dependent on the initial pH. Thus, a model was developed for describing the adsorption as a function of this variable. The removal efficiencies as a function of the adsorbent dosage for different pH values were predicted. The equilibrium data were well fitted by the modified Langmuir isotherm. Ion exchange at equilibrium suggested chromium uptake and Ca²⁺ release occurs approximately according to the stoichiometry of the equilibrium reactions. Cr(III) desorption from MPB with chelating agents was not very effective while high efficiencies were achieved with HNO₃ solutions.     

Metal chelates with some cellulose derivatives. Part I. Preparation and characterization of chromium (III)–carboxymethyl cellulose complexes

A systematic spectrophotometric study on the complexation of chromium (III) ion with sodium carboxymethyl cellulose (CMC) was carried out. The effects of the degree of substitution (DS) of the polymer, the concentrations of Cr(III) and CMC solutions, the pH and temperature on the complex formation were studied in the aqueous state. CMC complexes with Cr(III) were characterized by elemental analysis, magnetic moment and spectral (Vis and IR) data. The results showed that CMC (L) chelated to the metal ion according to the formula CrL₂ · 2H₂O. The ligand field parameters, namely D_q, B and β were calculated; the β-values indicate strong covalency in the ligand σ bond. The IR spectra revealed that the chelating sites of CMC are not only the carboxymethyl groups, via the ether- and the carboxyl-oxygen atoms, but also the secondary hydroxyl groups.     

Extraction of Copper by Selective Ion Exchangers with Pendent Ethyleneimine Groups—Investigation of Active States

Abstract

Selective ion exchangers with pendent ethyleneimine groups of the type -(NHC₂H₄)n · NH₂, where n = 1 to 5, have been prepared, and their ability to extract cationic and anionic-chelated copper(II) ions has been evaluated. Copper has been extracted from aqueous solution, and the equilibrium capacities of extraction vary according to the active sites in the selective ion exchangers. The poor exchange properties of selective ion exchangers with short pendent groups have been related to the nature of the active coordination sites. The active sites on these selective ion exchangers change from two nitrogen atoms and two oxygen atoms (N₂O₂) with short chains (n = 1) to four nitrogens when n = 2 to 5. Those which have N₄ active sites appear to extract cationic copper(II) efficiently, but those with N₂O₂ sites have low capacities and copper is easily leached from the resin even when the loading of the resin is low. When copper is complexed to EDTA to form an anionic complex, a side chain like pentaethylene hexamine is required to extract the copper from aqueous solution. A macroporous polystyrene resin had a lower capacity for anionic chelated copper than a polystyrene gel resin with the same functional groups due to the poorer accessibility of the active (N₄) sites to the large anion.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 2: ACID DEPENDENCIES OF TRANSITION AND POST-TRANSITION METAL IONS*

ABSTRACT

Diphonix^(tm)is a new dual-mechanism polyfunctional resin containing sulfonic and gem-diphosphonic acid groups. In Part 1 of this series the effectiveness of Diphonix in removing actinide ions from very acidic solutions was demonstrated. In this paper we report on the uptake of various transition and post-transition metal ions with Diphonix and two other resins for comparison. The results show that Diphonix has a very high affinity for Fe(III) and Cr(III) in very acidic solutions. From neutral solutions Diphonix exhibits a high selectivity for lead and transition metals over calcium. Conditions for efficient stripping of the investigated ions have been found.     

Removal of Chlorophenols from Aqueous Solution by Anion-Exchange Resins

Abstract

The effects of pH value and chloride ion concentration on the removal of chlorophenols from aqueous solutions by Purolite A-510 resin [macroreticular polystyrene-divinylbenzene resin with R(CH₃)₂(C₂H₄OH)N⁺ group] are discussed by the species distributions of chlorophenols. Those chlorophenols include phenol, 2-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. The investigations showed that the chlorophenols could be removed effectively at alkaline conditions where the ion-exchange reaction was dominant. Also, the removal of chlorophenols increased with the number of chlorine atoms on the chlorophenols. The removal of chlorophenols via the ion-exchange reaction was hindered by the presence of chloride ions. The effect of chloride ions, however, was diminished in acidic solutions where the adsorption reaction was dominant. The proposed equilibrium model, which considers both adsorption and ion-exchange reactions, adequately describes the sorption behavior of chlorophenols. The partition constants of the protonated chlorophenols can be estimated from the octanol/water partition coefficients of the phenolic compounds.