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PubMed2006

Induction of hypericins in Hypericum perforatum in response to chromium.

Seedlings of Hypericum perforatum were grown with 0.01 and 0.1 mM of chromium added to the nutrient media. A treatment with 0.01 mM Cr(VI) for seven days resulted in an increased production of protopseudohypericin (+135%), hypericin (+38%) and pseudohypericin (+5%). Treatment with 0.1 mM Cr(VI) for two days also caused an increase of protopseudohypericin (+167%), hypericin (25%) and pseudohypericin (+5%). The greatest effect of chromium treatment was observed at a concentration of 0.1 mM for seven days: protopseudohypericin increased +404% and pseudohypericin to +379%. Hypericin was not affected by this treatment.

Analysis of Variance↗
PubMed2004

Treatment of humic acids with ferric, aluminum, and chromium ions in water.

The interaction of ferric, aluminum, and chromium ions with humic acids at different pH of mixture has been investigated. The concentration of metal ions, bound with humic acid is proportional to the concentration of metal ion in water solution at pH 3 at low metal ion concentrations. The ratio of the number of ferric ions, bound with humic acid, to the number of acidic groups in humic acid is more than 1.5 at high ferric ion concentration in solution. That is bound with the formation of dimers of ferric ions and their treatment with acidic groups of humic acid. The radius of particles formed in the reaction of humic acid with ferric ion does not depend on the pH and decreases in the reaction with chromium and aluminum ions at pH higher than 4. An increase of metal ion concentration leads to the increase of the particle radius at low metal ion concentration reaching the constant value at high metal ion concentration and pH 6.1.

Aluminum↗
PubMed2004

Adsorption properties of gases on mesoporous chromium silicate.

The properties of nitrogen, carbon dioxide, and nitrogen dioxide adsorption onto mesoporous chromium silicates were studied by measurements of both the adsorption isotherms and the IR spectra. The pore sizes of two types of chromium silicates, Cr-FSM-16 (Si/Cr=170 (Cr-FSM-16 [170]) and 390 (Cr-FSM-16 [390])), which contain different amount of Cr, were 2.75 nm. BET surface areas of Cr-FSM-16 were 590 m2/g and they were smaller than that onto FSM-16. The initial heat of adsorption of nitrogen onto Cr-FSM-16 was higher than that onto FSM-16. But the initial heat of adsorption of carbon dioxide onto Cr-FSM-16 was smaller than that onto FSM-16. These results indicated that Cr in Cr-FSM-16 decreased adsorption interaction with carbon dioxide. When nitrogen dioxide was adsorbed on FSM-16 and Cr-FSM-16 at 303 K under no light, an absorption band of nitrogen monoxide adsorbed was measured by IR spectroscopy. This decomposition of nitrogen dioxide by FSM-16 and Cr-FSM-16 was caused by SiOH and Cr, respectively.

Adsorption↗
PubMed2004

Biogeochemical influence on transport of chromium in manganese sediments: experimental and modeling approaches.

Hexavalent chromium (Cr(VI)) was reduced to immobile and nontoxic Cr(III) by a dissimilatory metal reducing bacteria, Shewanella alga Simidu (BrY-MT) ATCC 55627. A series of kinetic batch and dynamic column experiments were conducted to provide an understanding of Cr(VI) reduction by the facultative anaerobe BrY-MT. Reduction of Cr(VI) was rapid (within 1 h) in columns packed with quartz sand and bacteria, whereas Cr(VI) reduction by BrY-MT was delayed (57 h) in the presence of beta-MnO2-coated sand. A mathematical model was developed and evaluated against data obtained from column experiments. The model takes into account (1) advective-dispersive transport of Cr(III), Cr(VI), lactate, and protein (mobile and immobile bacteria); (2) first-order kinetic adsorption of Cr(III) and lactate; (3) conversion of solid phase beta-MnO2 to solid phase MnOOH due to oxidation of Cr(III); (4) dual-Monod kinetics, where Cr(VI) is the electron acceptor and lactate is the electron donor. The breakthrough data for Cr(III), Cr(VI), lactate, and protein (mobile and immobile bacteria) were fitted simultaneously. The breakthrough data are well described by the mathematical model that considers the above processes. This result demonstrates the ability of the coupled hydrobiogeochemical model to simulate chromium transport in complex reactive systems.

Biological Transport↗
PubMed2006

Spatial variability of arsenic and chromium in the soil water at a former wood preserving site.

Contamination of industrial sites by wood preservatives such as chromated copper arsenate (CCA) may pose a serious threat to groundwater quality. The objective of this study was to characterise the spatial variability of As and Cr concentrations in the solid phase and in the soil water at a former wood impregnation plant and to reveal the fundamental transport processes. The soil was sampled down to a depth of 2m. The soil water was extracted in situ from the vadose zone over a period of 10 months at depths of 1 and 1.5m, using large horizontally installed suction tubes. Groundwater was sampled from a depth of 4.5m. Results showed that arsenic and chromium had accumulated in the upper region of the profile and exhibited a high spatial variability (As: 21-621 mg kg(-1); Cr: 74-2872 mg kg(-1)). Concentrations in the soil water were high (mean As 167 microg L(-1); Cr: 62 microg L(-1)) and also showed a distinct spatial variability, covering concentration ranges up to three orders of magnitude. The variability was caused by the severe water-repellency of the surface soil, induced by the concurrent application of creosote wood preservatives, which leads to strong preferential flow as evident from a dye experiment. In contrast to soil water concentrations, only low As concentrations (<12 microg L(-1)) were detected in the groundwater. High Cr concentrations in the groundwater (approx. 300 microg L(-1)), however, illustrated the pronounced mobility of chromium. Our study shows that at sites with a heterogeneous flow system in the vadose zone a disparity between flux-averaged and volume-averaged concentrations may occur, and sampling of soil water might not be adequate for assessing groundwater concentrations. In these cases long-term monitoring of the groundwater appears to be the best strategy for a groundwater risk assessment.

Arsenates↗
PubMed2004

Bench- and field-scale evaluation of chromium and cadmium extraction by electrokinetics.

The results of bench-scale laboratory tests and in situ, pilot-scale demonstration of electrokinetic extraction of chromium and cadmium from contaminated soil are presented. The laboratory tests were conducted using 10 cm long samples under current density of 5A/m(2) for 1200 h. Tests were conducted with and without citric acid amendment at the cathode. The results showed that citric acid improved extraction, especially in the sections near the cathode. However, processing was not enough to result in complete cleanup. The field demo was conducted at the Naval Air Weapon Station (NAWS), Point Mugu, California. Three cathodes were centered between six anodes. The anode-cathode spacing was 4.45 m (15 ft). Constant voltage of 60 V ( approximately 13 V/m) was applied for 20 days and then was reduced to 45 V (10 V/m) for 6 months. Citric acid was used to maintain the cathode pH at 4. After 6 months of treatment, 78% of the soil volume has been cleared of chromium or treated to below natural background levels. The results also indicated that 70% of the soil between the electrodes had been cleared of cadmium contamination. A comparison between the bench-scale and field demo showed that the field process was more effective than the lab tests. This indicated that small sample size will induce a negative effect on the efficiency of the process due to an increased impact of the boundaries on the overall process.

Cadmium↗
PubMed2004

Evaluation and optimization of chromium removal from tannery effluent by microemulsion in the Morris extractor.

In this research a surfactant derived from a vegetable oil (coconut oil) was used to remove chromium from a tannery effluent. In the extraction process, a Morris extractor was used. Important variables used in assessing the optimization of the process included agitation speed, solvent rate and total flow rate. The experiments were conducted using a 2(3) factorial design. According to the response from the experimental design, the effects of each variable were calculated and the interactions between them determined. Response surface methodology was employed to study the effects of the studied variables. The optimum operational conditions were: agitation speed, 428 rpm; solvent rate, 0.37; total flow rate, 2.0 l h(-1). After extraction process, a re-extraction study was accomplished and the obtained results showed that chromium could be removed from the microemulsion phase by hydrochloric and sulphuric acidic solutions, what allows its reuse in the leather manufacturing process.

Algorithms↗
PubMed2005

Lifetime and regeneration of immobilized titania for photocatalytic removal of aqueous hexavalent chromium.

Immobilized titania (TiO2) batch reactors reduced hexavalent chromium (Cr(VI)) in the form of potassium dichromate (K2Cr2O7) to trivalent chromium (Cr(III)) in aqueous solution at pH 3 under 171 W/m2 light intensity. The light source was a 125-W ultraviolet (UV) lamp. The Cr(VI) reduction showed zero-order kinetics (k0), while the Cr(VI) adsorption fitted with first-order kinetics (k(1st)). Adsorption capacity increased with increasing initial Cr(VI) concentration, and the area of immobilized TiO2 limited the reduction efficiency. The lifetime of fresh immobilized TiO2 was approximately 14 h. In addition, the regeneration of TiO2 with 3M sodium hydroxide (NaOH) was necessary to improve adsorption reaction.

Adsorption↗
PubMed2005

Biological chromium(VI) reduction using a trickling filter.

A pilot-scale trickling filter was constructed and tested for biological chromium(VI) removal from industrial wastewater. Indigenous bacteria from industrial sludge were enriched and used as inoculum for the filter. Sodium acetate was used as carbon source and it was found to inhibit chromate reduction at high concentrations. Three different operating modes were used to investigate the optimal performance and efficiency of the filter, i.e. batch, continuous and SBR with recirculation. The latter one was found to achieve removal rates up to 530 g Cr(VI)/m2 d, while aeration was taking place naturally without the use of any external mechanical means. The low operating cost combined with the high hexavalent chromium reduction rates indicates that this technology may offer a feasible solution to a very serious environmental problem.

Biodegradation, Environmental↗
PubMed2005

Extraction and recovery of chromium from electroplating sludge.

This work reports a study of the extraction and recovery of chromium from the wastes (class I dangerous) generated by a galvanic manufacturer. Commercial HCl at room temperature was employed, and the conditions of the extraction process were optimized according to a sequential experimental design, which also included the acid concentration and contact time as variables. The best extraction conditions (80% v/v; 30 min; 97.6% Cr) for the chromic sludge were chosen in order to make the recovery process economically feasible. After each extraction, the residue was submitted to leaching essays, to assess environmental risks. It was found that sludge could be characterized as no longer dangerous. In the recovery study, a simple and low-cost technique was evaluated for selectivity based on an oxidation step with hydrogen peroxide. A 2(3) factorial design to assess the influence of oxidation time (min), temperature ( degrees C) and peroxide amount (mol/L) was employed. The best conditions, yielding a chromium recovery of about 92%, were a time of 60 min, a temperature of 60 degrees C and 2.1 mol/L peroxide. Additional essays revealed that the same result could be obtained with more economic conditions (40 min, 1.4 mol/L peroxide and 60 degrees C). This technique proved not only effective in comparison with existing alternatives, but also low costing.

Chromium↗
PubMed2006

Stabilization of chromium ore processing residue (COPR) with nanoscale iron particles.

Laboratory batch experiments were conducted on heavily contaminated groundwater and chromium ore processing residue (COPR) samples to determine the rate and extent of hexavalent chromium [Cr(VI)] reduction and immobilization by nanoscale iron particles. Laboratory synthesized nanoscale iron particles (<100 nm, specific surface area 35 m(2)/g) were used for this work. Groundwater ([Cr(VI)]=42.83 +/- 0.52 mg/L, pH 11.0+/-0.5) and COPR samples ([Cr(VI)] = 3280 +/- 90 mg/kg) were collected from an industrial site in New Jersey. Cr(VI) in the water and COPR samples was quickly reduced and precipitated out of the aqueous solution. The surface area normalized reaction rate constant of Cr(VI) reduction by nanoscale iron particles was 0.157 +/- 0.018 mg m(-2) min(-1), about 25 times greater than that by iron powders (100 mesh). One gram of nanoparticles can reduce 84.4-109.3mg Cr(VI) in the groundwater and 69.3-72.7 mg Cr(VI) in the COPR. This reduction capacity is 50-70 times greater than that of iron powders under the same experimental conditions.

Chromium↗
PubMed2006

Trivalent chromium removal from wastewater using low cost activated carbon derived from agricultural waste material and activated carbon fabric cloth.

An efficient adsorption process is developed for the decontamination of trivalent chromium from tannery effluents. A low cost activated carbon (ATFAC) was prepared from coconut shell fibers (an agricultural waste), characterized and utilized for Cr(III) removal from water/wastewater. A commercially available activated carbon fabric cloth (ACF) was also studied for comparative evaluation. All the equilibrium and kinetic studies were conducted at different temperatures, particle size, pHs, and adsorbent doses in batch mode. The Langmuir and Freundlich isotherm models were applied. The Langmuir model best fit the equilibrium isotherm data. The maximum adsorption capacities of ATFAC and ACF at 25 degrees C are 12.2 and 39.56 mg/g, respectively. Cr(III) adsorption increased with an increase in temperature (10 degrees C: ATFAC--10.97 mg/g, ACF--36.05 mg/g; 40 degrees C: ATFAC--16.10 mg/g, ACF--40.29 mg/g). The kinetic studies were conducted to delineate the effect of temperature, initial adsorbate concentration, particle size of the adsorbent, and solid to liquid ratio. The adsorption of Cr(III) follows the pseudo-second-order rate kinetics. From kinetic studies various rate and thermodynamic parameters such as effective diffusion coefficient, activation energy and entropy of activation were evaluated. The sorption capacity of activated carbon (ATFAC) and activated carbon fabric cloth is comparable to many other adsorbents/carbons/biosorbents utilized for the removal of trivalent chromium from water/wastewater.

Adsorption↗
PubMed2006

Mechanisms of the removal of hexavalent chromium by biomaterials or biomaterial-based activated carbons.

Three papers published during recent 2 years in Journal of Hazardous Materials made a mistake in analyzing chromium species in aqueous solution, resulting in incorrect elucidation of Cr(VI) biosorption; the Cr(VI) was removed from aqueous solution systems by 'anionic adsorption'. However, it has been proved that Cr(VI) is easily reduced to Cr(III) by contact with organic materials under acidic conditions because of its high redox potential value (above +1.3 V at standard condition). Therefore, it is strongly possible that the mechanism of Cr(VI) removal by biomaterials or biomaterial-based activated carbons is not "anionic adsorption" but "adsorption-coupled reduction". Thus, for researches of Cr(VI) biosorption, researchers have to analyze not only Cr(VI) but also total Cr in aqueous solution and to check the oxidation state of chromium bound on the biomaterials or activated carbons.

Biocompatible Materials↗
PubMed2006

Chromium(VI) adsorption from aqueous solution onto Moroccan Al-pillared and cationic surfactant stevensite.

Batch adsorption of the chromium(VI) onto Moroccan stevensite pillared by Keggin aluminium hydroxypolycation (Al-stevensite) and cationic surfactant cetyltrimethylammoniumbromide (CTA-stevensite) was investigated. The results showed that the CTA-stevensite has a higher affinity than that of Al-stevensite for chromium(VI) adsorption. The adsorption capacities for natural stevensite, Al-stevensite and CTA-stevensite calculated according to the Dubinin-Kaganer-Radushkevich isotherm (DKR) are 13.7, 75.4 and 195.6mmolkg(-1), respectively. The study of the pH effect showed that the optimal range corresponding to the Cr(VI) maximum adsorption on Al-stevensite is pH 3.5-6 and that on CTA-stevensite is pH 2-6. The adsorption rates evaluated according to the pseudo-second-order model are 7.2, 207.2 and 178.5mmolkg(-1)min(-1) for the natural stevensite, Al-stevensite and CTA-stevensite, respectively. The low values of the adsorption energy calculated by (DKR) suggest that anion exchange is the main mechanism that governs the chromate adsorption.

Adsorption↗
PubMed2004

Kinetics and mechanism of the reaction between chromium(III) and 3,4-dihydroxyphenylpropionic (dihydrocaffeic) acid in weak acidic aqueous solutions.

The reaction of 3,4-dihydroxyphenylpropionic acid (dihydrocaffeic acid, hydcafH3) with chromium(III) in weak acidic aqueous solutions has been shown to take place through various oxygen-bonded intermediates. The formation of the oxygen-bonded complexes upon substitution of water molecules of the chromium(III) coordination sphere takes place in at least three stages, the first of which has an observed rate constant k1(obs)=k1K0'[hydcafH3]/[H+] where K0' corresponds to the Cr(H2O)6(3+) complex dissociation equilibrium. The second and third stages are ligand concentration independent and are thus attributed to isomerisation and chelation processes. The corresponding activation parameters are DeltaH2(not equal)=78+/-3 kJmol(-1), DeltaS2(not equal)=-49+/-9 JK(-1)mol(-1), DeltaH3(not equal)=60+/-9 kJmol(-1) and DeltaS3(not equal)=-112+/-39 JK(-1)mol(-1). The kinetic results support associative mechanisms and the nature of the electronic spectra a catecholic-type of coordination at the pH and concentration range studied and reported in this paper. The associatively activated substitution processes are accompanied by proton release causing a pH decrease. At lower acid concentration oxidation of the ligand takes place with concomitant high increase in the UV and VIS absorbance.

Caffeic Acids↗
PubMed2006

Synthesis, characterization and properties of chromium(III) complex [Cr(SA)(en)2]Cl.2H2O.

The reaction of chromium(III) chloride, salicylic acid (SA) and ethylenediamine (en) led to the formation of chromium complex [Cr(SA)(en)(2)]Clx2H(2)O(1). The crystal structure belongs to monoclinic system with the space group P2(1), R(1)=0.0358. In this compound, Cr(III) atom is six-coordinated in octahedral coordination geometry by one phenolic hydroxyl oxygen, one carboxylate oxygen from the salicylic acid and four nitrogen atoms from two ethylenediamine molecules, respectively. The transfer manners of Cr(III) from the title compound to the low-molecular-mass chelator, ethylenediamine-N,N,N',N'-tetraacetic acid (EDTA) and the iron-binding protein apoovotransferrin (apoOTf) were followed by a combination of UV-visible (UV-Vis) and fluorescence spectra in 0.01M Hepes at pH 7.4. The results show that Cr(III) can be transferred from the complex to apoovotransferrin with the retention of the salicylate acted as a synergistic anion.

Chlorides↗
PubMed2004

Tolerance and accumulation of hexavalent chromium by two seaweed associated aspergilli.

Marine seaweed (Eucheuma sp.) associated strains of Aspergillus flavus and Aspergillus niger were tested for their Cr(VI) tolerance. Both the isolates showed luxuriant growth in different concentrations of Cr(VI), i.e., 25, 50 and 100 ppm. There was no marked variation in the dry weight of control and test isolates, which indicated that both the isolates can tolerate a wide range of hexavalent chromium and their application for bioremediation purpose can be envisaged as XRF data revealed both the isolates accumulated more than 25% of the chromium supplied. A. flavus invariably exhibited higher accumulation potential.

Aspergillus↗
PubMed2004

Accumulation of hexavalent chromium by an exopolysaccharide producing marine Enterobacter cloaceae.

An exopolysaccharide producing Enterobacter cloaceae (AK-I-MB-71a) was tested for its Cr (VI) tolerance. This isolate was not only resistant to this heavy metal but also showed enhanced growth and exopolysaccharide production in the presence of Cr (VI) at 25, 50 and 100 ppm concentrations. XRF analysis of both the biomass as well as the exopolysaccharide revealed that a sum total of about 60-70% chromium was accumulated by this bacterium. This indicated that this organism could prove to be a potential candidate in the field of bioremediation with respect to chromium removal.

Biomass↗