Analysis of chromium behaviour and speciation during the electrodialytic process

The interest in chromium (Cr) arises from the widespread use of this heavy metal in various industrial processes that cause its release as liquid, solid and gaseous waste into the environment. The impact of Cr on the environment and living organisms primarily depends on its chemical form, since Cr(III) is an essential micronutrient for humans, other animals and plants, and Cr(VI) is highly toxic and a known human carcinogen. This study aimed to evaluate if the electrodialytic process (ED) is an appropriate treatment for Cr removal, through a critical overview of Cr speciation, before and after the ED experiments, to assess possible Cr(III)-Cr(VI) interconversions during the treatment. ED was the treatment technique applied to two types of matrices containing Cr: chromate copper arsenate (CCA) contaminated soil and municipal solid waste incineration (MSWI) fly ash. In order to study Cr remediation, three EDR set-ups were used: a new set-up, the combined cell (2/3C or 3/2C), with three compartments, alternating current between two anodes and different initial experimental conditions, one set-up with three compartments (3C cell) and the other set-up with two compartments (2C cell). The Cr removal rates obtained in this study were between 10-36% for the soil, and 1-13% for the fly ash. The highest Cr removal rates were achieved in the 26 days experiments: 36% for the soil, 13% for the fly ash. Regarding the 13 days experiments, the highest Cr removal rates were attained with the 2/3C set-up: 24% for the soil, 5% for the fly ash. The analysis of Cr(VI) was performed before and after ED experiments to evaluate eventual changes in Cr speciation during the treatment. This analysis was conducted by two methods: USEPA Method 3060A, for the extraction of Cr(VI); and Hach Company Method 8023, for the detection of Cr(VI). Despite the differences in Cr total concentration, both matrices presented a similar speciation, with Cr(III) being the main species found and Cr(VI) less than 3% of Cr total, before and after the treatment. For fly ash, Cr(VI) was initially below the detection limit of the method and remained that way after the treatment. For soil, Cr(VI) decreased after the treatment. Oxidation of Cr(III) to Cr(VI) did not occur during the ED process since there was no increase in Cr(VI) in the matrices after the treatment. Hence, the results of this study indicate that ED is an appropriate technique to remediate matrices containing Cr because it contributes to Cr removal, without causing Cr(III)-Cr(VI) interconversions.

Avaluació de la toxicitat de metalls pesants i arsènic en diferents models biològics

En aquest estudi, la toxicitat de diversos metalls pesants i l'arsènic va ser analitzada utilitzant diferents models biològics. En la primera part d'aquest treball, el bioassaig de toxicitat Microtox, el qual està basat en la variació de l'emissió lumínica del bacteri luminiscent Vibrio fischeri, va ser utilitzat per establir les corbes dosi-resposta de diferents elements tòxics com el Zn(II), Pb(II), Cu(II), Hg(II), Ag(I), Co(II), Cd(II), Cr(VI), As(V) i As(III) en solucions aquoses. Els experiments es varen portar a terme a pH 6.0 i 7.0 per tal de mostrar que el pH pot influir en la toxicitat final mesurada d'alguns metalls degut als canvis relacionats amb la seva especiació química. Es varen trobar diferents tipus de corbes dosi-resposta depenent del metall analitzat i el pH del medi. En el cas de l'arsènic, l'efecte del pH en la toxicitat de l'arsenat i l'arsenit es va investigar utilitzant l'assaig Microtox en un rang de pHs comprès entre pH 5.0 i 9.0. Els valors d'EC50 determinats per l'As(V) disminueixen, reflectint un augment de la toxicitat, a mesura que el pH de la solució augmenta mentre que, en el cas de l'As(III), els valors d'EC50 quasi bé no varien entre pH 6.0 i 8.0 i només disminueixen a pH 9.0. HAsO42- i H2AsO3- es varen definir com les espècies més tòxiques. Així mateix, una anàlisi estadística va revelar un efecte antagònic entre les espècies químiques d'arsenat que es troben conjuntament a pH 6.0 i 7.0. D'altra banda, els resultats de dos mètodes estadístics per predir la toxicitat i les possibles interaccions entre el Co(II), Cd(II), Cu(II), Zn(II) i Pb(II) en mescles binàries equitòxiques es varen comparar amb la toxicitat observada sobre el bacteri Vibrio fischeri. L'efecte combinat d'aquests metalls va resultar ser antagònic per les mescles de Co(II)-Cd(II), Cd(II)-Zn(II), Cd(II)-Pb(II) i Cu(II)-Pb(II), sinèrgic per Co(II)-Cu(II) i Zn(II)-Pb(II) i additiu en els altres casos, revelant un patró complex de possibles interaccions. L'efecte sinèrgic de la combinació Co(II)-Cu(II) i la forta disminució de la toxicitat del Pb(II) quan es troba en presència de Cd(II) hauria de merèixer més atenció quan s'estableixen les normatives de seguretat ambiental. La sensibilitat de l'assaig Microtox també va ser determinada. Els valors d'EC20, els quals representen la toxicitat llindar mesurable, varen ser determinats per cada element individualment i es va veure que augmenten de la següent manera: Pb(II) < Ag(I) < Hg(II)  Cu(II) < Zn(II) < As(V) < Cd(II)  Co(II) < As(III) < Cr(VI). Aquests valors es varen comparar amb les concentracions permeses en aigues residuals industrials establertes per la normativa oficial de Catalunya (Espanya). L'assaig Microtox va resultar ser suficientment sensible per detectar els elements assajats respecte a les normes oficials referents al control de la contaminació, excepte en el cas del cadmi, mercuri, arsenat, arsenit i cromat. En la segona part d'aquest treball, com a resultats complementaris dels resultats previs obtinguts utilitzant l'assaig de toxicitat aguda Microtox, els efectes crònics del Cd(II), Cr(VI) i As(V) es varen analitzar sobre la taxa de creixement i la viabilitat en el mateix model biològic. Sorprenentment, aquests productes químics nocius varen resultar ser poc tòxics per aquest bacteri quan es mesura el seu efecte després de temps d'exposició llargs. Tot i això, en el cas del Cr(VI), l'assaig d'inhibició de la viabilitat va resultar ser més sensible que l'assaig de toxicitat aguda Microtox. Així mateix, també va ser possible observar un clar fenomen d'hormesis, especialment en el cas del Cd(II), quan s'utilitza l'assaig d'inhibició de la viabilitat. A més a més, diversos experiments es varen portar a terme per intentar explicar la manca de toxicitat de Cr(VI) mostrada pel bacteri Vibrio fischeri. La resistència mostrada per aquest bacteri podria ser atribuïda a la capacitat d'aquest bacteri de convertir el Cr(VI) a la forma menys tòxica de Cr(III). Es va trobar que aquesta capacitat de reducció depèn de la composició del medi de cultiu, de la concentració inicial de Cr(VI), del temps d'incubació i de la presència d'una font de carboni. En la tercera part d'aquest treball, la línia cel·lular humana HT29 i cultius primaris de cèl·lules sanguínies de Sparus sarba es varen utilitzar in vitro per detectar la toxicitat llindar de metalls mesurant la sobreexpressió de proteines d'estrès. Extractes de fangs precedents de diverses plantes de tractament d'aigues residuals i diferents metalls, individualment o en combinació, es varen analitzar sobre cultius cel·lulars humans per avaluar el seu efecte sobre la taxa de creixement i la capacitat d'induir la síntesi de les proteïnes Hsp72 relacionades amb l'estrès cel·lular. No es varen trobar efectes adversos significatius quan els components s'analitzen individualment. Nogensmenys, quan es troben conjuntament, es produeix un afecte advers sobre tan la taxa de creixement com en l'expressió de proteins d'estrès. D'altra banda, cèl·lules sanguínies procedents de Sparus sarba es varen exposar in vitro a diferents concentracions de cadmi, plom i crom. La proteïna d'estrès HSP70 es va sobreexpressar significativament després de l'exposició a concentracions tan febles com 0.1 M. Sota les nostres condicions de treball, no es va evidenciar una sobreexpressió de metal·lotioneïnes. Nogensmenys, les cèl·lules sanguínies de peix varen resultar ser un model biològic interessant per a ser utilitzat en anàlisis de toxicitat. Ambdós models biològics varen resultar ser molt adequats per a detectar acuradament la toxicitat produïda per metalls. En general, l'avaluació de la toxicitat basada en l'anàlisi de la sobreexpressió de proteïnes d'estrès és més sensible que l'avaluació de la toxicitat realitzada a nivell d'organisme. A partir dels resultats obtinguts, podem concloure que una bateria de bioassaigs és realment necessària per avaluar acuradament la toxicitat de metalls ja que existeixen grans variacions entre els valors de toxicitat obtinguts emprant diferents organismes i molts factors ambientals poden influir i modificar els resultats obtinguts.

Influence of pH on the incorporation and growth of Pb(2)CrO(5) crystallites in silica matrix

Pb(2)CrO(5) nanoparticles were embedded in an amorphous SiO(2) matrix by the sol-gel process. The pH and heat treatment effects were evaluated in terms of structural, microstructural and optical properties from Pb(2)CrO(5)/SiO(2) compounds. X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), and diffuse reflectance techniques were employed. Kubelka-Munk theory was used to calculate diffuse reflectance spectra that were compared to the experimental results. Finally, colorimetric coordinates of the Pb(2)CrO(5)/SiO(2) compounds were shown and discussed. In general, an acid pH initially dissolves Pb(2)CrO(5) nanoparticles and following heat treatment at 600 A degrees C crystallized into PbCrO(4) composition with grain size around 6 nm in SiO(2) matrix. No Pb(2)CrO(5) solubilization was observed for basic pH. These nanoparticles were incorporated in silica matrix showing a variety of color ranging from yellow to orange.

Conversion coatings of Mg-alloy AZ91D using trihexyl(tetradecyl) phosphonium bis(trifluoromethanesulfonyl)amide ionic liquid

This work reveals the performance of a trihexyl(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide ([P6,6,6,14][NTf2]) ionic liquid (IL) conversion coating upon AZ91D. Such conversion coatings represent a novel avenue for chromate replacement. An optimization of coating performance was pursued by careful alloy pretreatment to generate a surface on which the coating performs best, as the AZ91 substrate is distinctly different from pure or dilute Mg alloys. The results reveal that a functional conversion coating can be achieved, retarding anodic dissolution kinetics, causing a significant decrease in corrosion rate. The coating efficacy is closely tied to the pretreatment performed, which dictates both the microstructural and electrochemical heterogeneity of the surface. The resulting coatings were found to contain MgxFx and phosphonium cation related components, the proportions of which were dependent on the pretreatment.

A corrosion inhibition study of steel grinding balls in an oxygen and alkaline environment

The corrosion of steel grinding balls is a major recurrent cost for mill operators concerned with the production gold. Subsequently, the use of corrosion inhibitors in production fluids, which is typically at pH >9, is an attractive and economical option. This study reports on the corrosion wear of steel grinding balls under alkaline/oxygen conditions and in presence of cyanide. A fundamental study on the influence of several inorganic-based inhibitors (i.e., nitrite, chromate, silicate, hexametaphosphate) on the corrosion rate of carbon steel was undertaken. Subsequently, the corrosion performances of various inhibitors were evaluated in stirred vessels. Corrosion rates were determined via mass loss and electrochemical methods (i.e., linear polarisation, Tafel). It was observed that inhibitors based upon chromate provide superior protection under the conditions investigated in this study. In lime treated, high chloride waters, chromate gave over 80% protection at levels of 10 100 ppm with no evidence of pitting.

Recent developments in corrosion inhibitors based on rare earth metal compounds

Rare earth organic compounds can provide an environmentally safe and non-toxic alternative to chromates as corrosion inhibitors for some steel and aluminium applications. For steel lanthanum 4-hydroxy cinnamate offers corrosion protection and reduces the susceptibility to hydrogen embrittlement. Recent work has also indicated that it inhibits the corrosion of steel in environments containing high levels of carbon dioxide. For aluminium alloys, cerium diphenyl phosphate provides excellent corrosion inhibition in chloride environments, and reduces susceptibly to stress corrosion cracking. Furthermore, for both steel and aluminium alloys filiform corrosion can be suppressed when rare earth inhibitor compounds are added as pigments to polymer coatings. The levels of inhibition observed are thought to be due to synergistic effects between the rare earth and organic parts of these novel compounds, and are related to the various species that may be present in the complex chemical conditions that develop in solution close to a metal surface. This paper reviews some of the published research conducted by the group at Deakin University over recent years.©2014 Institute of Materials, Minerals and Mining.

Investigation of corrosion inhibition mechanisms of rare-earth mercaptoacetate inhibitors on AA2024-T3

 Corrosion inhibition mechanisms on the aerospace alloy, AA2024-T3, was investigated for the inhibitor combination of rare earth metals and mercaptoacetate. The inhibitor demonstrated synergistic protection for AA2024-T3 from localised corrosion. It is intended to be a more environmentally friendly alternative to toxic chromate-based inhibitors.

Rare earth 3-(4′-hydroxyphenyl)propionate complexes

The reaction of lanthanoid chlorides or nitrates with sodium 3-(4′-hydroxyphenyl)propionate (Na4hpp) in methanol or water has yielded complexes [La4(4hpp)12(H2O)6]·4H2O·MeOH (1), [Ce2(4hpp)6(H2O)3]·(H2O)·2.5(EtOH) (2a) (after crystallization from ethanol), [Ho(4hpp)3(H2O)2] (5), [Er(4hpp)3(H2O)2]·1.5(H2O) (6), and [Lu(4hpp)3]·H2O crystal composition (7), as well as heterobimetallics [NaCe2(4hpp)7(H2O)2]·3(H2O) (2b), [NaPr2(4hpp)7(H2O)2]·3(H2O) (3), and [NaNd2(4hpp)7(H2O)(MeOH)]·(H2O)·3(MeOH) (4). The structures of homometallic complexes 1, 2a, 6, and 7 reveal one-dimensional coordination polymers and vividly illustrate the effect of lanthanoid contraction with a decline in coordination numbers in the series from 9-11 (1), 9,10 (2a), 8 (6) to 7 (7) through variations in carboxylate coordination and ligation of water. Bimetallic complexes 2a and 4 each exhibit five different carboxylate binding modes as well as coordination of the 4-OH substituent of 4hpp to sodium thereby linking 1D polymer chains into a 2D network with both 9 and 10 coordinate Ln atoms and 6 coordinate sodium. Bulk products after drying lose solvent of crystallization in some cases (2a, 6), or exchange MeOH for water (4). X-ray powder diffraction indicates that bulk 2b and 3 are isotypic, as are bulk 5 and 6. In contrast to the excellent corrosion protection of lanthanum 4-hydroxycinnamate, compound 1 is ineffective in preventing the corrosion of mild steel, thereby establishing the importance of the -CHCH- structural unit of the former in its anti-corrosion properties. However the flexible -CH2-CH2- chain of the 4hpp ligand enables the crystal engineering of its lanthanoid complexes in a wide variety of structures as well as effective crystallization for structure determination, whereas the analogous 4-hydroxycinnamates have so far evaded structural characterization except for Ln = La, Ce owing to crystallization problems.

Recuperação do cromo contido nas cinzas provenientes da incineração de resíduos sólidos das indústrias coureira e calçadista visando a obtenção de cromato de sódio (VI)

O processo de transformação da pele em couro envolve uma seqüência complexa de reações químicas e processos mecânicos, no qual o curtimento representa fundamental estágio, por propiciar à pele características como qualidade, estabilidade hidrotérmica e excelentes propriedades para uso. O sulfato básico de cromo trivalente é o agente curtente predominantemente empregado no curtimento de peles em todo o mundo. É produzido a partir do cromato de sódio, industrialmente obtido do minério de cromo. Consideráveis quantidades de resíduos sólidos contendo cromo são geradas pelas indústrias coureira e calçadista. Estes resíduos tem sido motivo de preocupação constante, uma vez que são considerados perigosos devido a presença do cromo. O processo de incineração destes resíduos é uma importante alternativa a ser considerada, em decorrência de suas características de redução de massa, volume e possibilidade de aproveitamento da energia térmica dos gases de combustão. O processo de incineração dos resíduos das indústrias coureira e calçadista dá origem a cinzas contendo cerca de 40% de cromo que pode ser submetida a um processo de recuperação. Este trabalho apresenta os resultados da pesquisa sobre a utilização das cinzas, provenientes da incineração dos resíduos sólidos da indústria coureira e da indústria calçadista, para a produção de cromato de sódio(VI). No processo de planejamento e de condução dos experimentos foram utilizadas as técnicas de Planejamento Fatorial 2k, Metodologia de Superfície de Resposta e Análise de Variância na avaliação da produção de cromato de sódio(VI). Os fatores investigados foram: temperatura, taxa de aquecimento, tempo de reação, vazão de ar e quantidade de dolomita. A partir das variáveis selecionadas identificaram-se como parâmetros importantes a temperatura e a taxa de aquecimento. As superfícies de resposta tridimensionais obtidas a partir dos modelos de segunda ordem ajustados aos dados experimentais, apresentaram o comportamento do efeito conjugado dos fatores temperatura e taxa de aquecimento sobre a variável resposta grau de oxidação, desde a temperatura de inicio da reação química até a temperatura limite utilizada industrialmente. As condições de operação do processo de produção de cromato de sódio(VI) foram otimizadas. Os níveis ótimos dos fatores de controle aplicados as cinzas dos resíduos da indústria calçadista, geradas em uma planta piloto com incinerador de leito fixo, com tecnologia de gaseificação e combustão combinadas, apresentaram um grau de oxidação superior a 96% para as cinzas coletadas no ciclone e de 99,5% para as cinzas coletas no reator de gaseificação. Os resíduos sólidos, as cinzas e o produto de reação foram caracterizados por análises químicas, fluorescência de raio-X, microscopia eletrônica de varredura e difração de raio-X.

Avaliação e modelagem da absorção de H2S do gás natural em coluna de leito estagnado

Natural gas, although basically composed by light hydrocarbons, also presents contaminant gases in its composition, such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). The H2S, which commonly occurs in oil and gas exploration and production activities, causes damages in oil and natural gas pipelines. Consequently, the removal of hydrogen sulfide gas will result in an important reduction in operating costs. Also, it is essential to consider the better quality of the oil to be processed in the refinery, thus resulting in benefits in economic, environmental and social areas. All this facts demonstrate the need for the development and improvement in hydrogen sulfide scavengers. Currently, the oil industry uses several processes for hydrogen sulfide removal from natural gas. However, these processes produce amine derivatives which can cause damage in distillation towers, can cause clogging of pipelines by formation of insoluble precipitates, and also produce residues with great environmental impact. Therefore, it is of great importance the obtaining of a stable system, in inorganic or organic reaction media, able to remove hydrogen sulfide without formation of by-products that can affect the quality and cost of natural gas processing, transport, and distribution steps. Seeking the study, evaluation and modeling of mass transfer and kinetics of hydrogen removal, in this study it was used an absorption column packed with Raschig rings, where the natural gas, with H2S as contaminant, passed through an aqueous solution of inorganic compounds as stagnant liquid, being this contaminant gas absorbed by the liquid phase. This absorption column was coupled with a H2S detection system, with interface with a computer. The data and the model equations were solved by the least squares method, modified by Levemberg-Marquardt. In this study, in addition to the water, it were used the following solutions: sodium hydroxide, potassium permanganate, ferric chloride, copper sulfate, zinc chloride, potassium chromate, and manganese sulfate, all at low concentrations (»10 ppm). These solutions were used looking for the evaluation of the interference between absorption physical and chemical parameters, or even to get a better mass transfer coefficient, as in mixing reactors and absorption columns operating in counterflow. In this context, the evaluation of H2S removal arises as a valuable procedure for the treatment of natural gas and destination of process by-products. The study of the obtained absorption curves makes possible to determine the mass transfer predominant stage in the involved processes, the mass transfer volumetric coefficients, and the equilibrium concentrations. It was also performed a kinetic study. The obtained results showed that the H2S removal kinetics is greater for NaOH. Considering that the study was performed at low concentrations of chemical reagents, it was possible to check the effect of secondary reactions in the other chemicals, especially in the case of KMnO4, which shows that your by-product, MnO2, acts in H2S absorption process. In addition, CuSO4 and FeCl3 also demonstrated to have good efficiency in H2S removal

Adsorption of chromium(VI) by titanium(IV) oxide coated on a silica gel surface

Titanium(IV) oxide, coated on the surface of silica gel (surface area, 308 m2 g-1; amount of Ti(IV) per gram of modified silica gel, 1.8 x 10(-3) mol), was used to adsorb CrO4(2-) ions from acidic solutions. The exchange capacity increased at lower pH values and was affected to some extent by the acid used. The material was used to preconcentrate Cr(VI) from 0.5 ppm solutions of chromate very efficiently and virtually 100% recovery was achieved in every instance.

Indirect determination of chloride and sulfate ions in alcohol fuel by capillary electrophoresis

A capillary zone electrophoresis method using indirect UV detection for the analysis of chloride and sulfate in alcohol fuel samples was developed. The anions were analyzed in less than 3 min using an electrolyte containing 10 mmol 1(-1) chromate and 0.75 mmol 1(-1) hexamethonium bromide (HMB) as electroosmotic flow modifier. Coefficients of variation were better than 0.6% for migration time (n = 10) and between 2.05 and 2.82% for peak area repeatabilities. Analytical curves of peak area versus concentration in the range of 0.065-0.65 mg kg(-1) for chloride and 0.25-4.0 mg kg(-1) for sulfate were linear with coefficients of correlation higher than 0.9996. The limits of detection for sulfate and chloride were 0.033 and 0.041 mg kg(-1), respectively. Recovery values ranged from 85 to 103%. The method was successfully applied for the quantification of sulfate and chloride in five alcohol fuel samples. The concentration of sulfate varied from 0.45 to 3.12 mg kg(-1). Chloride concentrations were below the method's LOD.

Synthesis and characterization of β-RbSc(CrO4)2

Synthesis and crystallographic data are reported for the double rubidium-scandium chromate RbSc(CrO4)2. The parameters of the orthorhombic cell are a = 14.836(2) A ̊; b = 5.627(1) A ̊ and c = 8.835(4) A ̊, Z = 4. The compound is closely related to the lamellar double chromates with other alkali metal cations, iron, lanthanides and yttrium offering the advantage of obtaining inorganic materials for electronics. © 1995.

Pre-resonant Raman effect of CrO2- 4 in a metasilicate glass

Pre-resonant Raman effect of chromate ion, CrO2- 4, was observed in a metasilicate glass with molar composition 2Na2O · 1CaO · 3SiO2 containing 1.0 wt% of Cr2O3. Raman spectra were measured by the conventional 90° scattering geometry and by the microprobe Raman spectroscopic techniques. The presence of chromate ions in the glass is favoured by the glass composition and oxidizing conditions during the glass melting, and they are responsible for optical absorption bands at 370 and 250 nm. Raman spectrum of the undoped glass presents bands at 625, 860 and 980 cm-1, and the presence of chromate ions gives rise to additional bands at 365, 850 and a shoulder at 890 cm-1. An enhancement of the 850 cm-1 Raman band is observed with decreasing laser exciting wavelength. The exciting frequency dependence of the intensity of this band is discussed in terms of theoretical models given in the literature.

Influence of cerium (IV) ions on the inorganic and organic phase for preparation of a siloxane-PMMA based film on tin plate substrate

Tinplate is one of the most widely used food canning materials, however, there are significant problems related to the use of tinplate cans, such as alterations in sensory features affecting food quality and corrosion phenomena of the canning material. To avoid corrosion problems different methods have been used for the passivation of tinplate such protective lacquers or different kinds of corrosion inhibitors (chromate and dichromate). However, chromates and dichromates are extremely harmful to the environment and can cause carcinogenic tumors to humans. An option, protective coatings obtained by the sol-gel process, act as a physical barrier, which isolates the surface of metal protecting from the corrosive agents. The aim of this work is to study the influence of addition of cerium (IV) ions in the inorganic and organic part of sol-gel processing in the formation of hybrid coatings based on siloxane-PMMA on tin plate. The coatings were obtained by dip-coating technique and evaluated by open circuit and impedance measurements, linear polarization and polarization curves obtained in 3.5% NaCl solution. The results have clearly shown the improvement on the protective properties of the Ce 4+ modified film when added into the organic phase, which can be due to the formation of a more uniform and densely reticulated siloxane-PMMA film. © 2009 by NACE International.