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Effect of chromium salts on invertase immobilization onto carboxymethyl-cellulose-gelatine carrier system.

The carboxymethylcellulose-gelatine carrier system was investigated for invertase immobilization. Chromium (III) acetate, chromium (III) sulphate and potassium chromium (III) sulphate were used as cross-linking agents. Effect of carboxymethylcellulose-gelatine ratio and cross-linker concentration on immobilized enzyme activity were analysed. Reusability of immobilized enzyme was also investigated. Maximum immobilized enzyme activities were obtained with cross-linkers chromium (III) sulphate (0.004 mol dm-3) and potassium chromium (III) sulphate (0.001 mol dm-3) for a carrier composition of carboxymethylcellulose-gelatine ratio 0.111 (w/w) as 78%.

Carboxymethylcellulose Sodium↗

A comparison of the mutagenicity of soluble trivalent chromium compounds with that of potassium chromate.

The mutagenic potential of water soluble complexes of trivalent chromium with five different amino acids in Salmonella typhimurium strains TA92, TA94, TA98, and TA100 was studied. All complexes were nonmutagenic at concentrations up to 50 mumol/plate in the strains used. In contrast, trivalent chromium chloride was slightly mutagenic in TA98 and a considerable increase in numbers of revertants was observed in TA94. Hexavalent chromium was nonmutagenic in TA98. Strong mutagenic effects were found in TA92, TA94, and TA100. The large difference in mutagenicity between trivalent and hexavalent chromium is discussed with respect to affinity to extracellular phosphate, diffusability through membranes and reactivity with DNA. More definitive statements about the toxicological risks of the water soluble chromium complexes requires additional studies with well defined compounds in test systems specially suited to study metal complexes.

Chemical Phenomena↗

Studies on uptake of trivalent and hexavalent chromium by maize (Zea mays).

Pot culture experiments were carried out to study the uptake and translocation of chromium from irrigation water when supplied in its trivalent and hexavalent states to maize plants grown in soil and sand culture. The uptake of chromium was observed to increase with increase in the concentration for both oxidation states of chromium. For the root, the observed order of uptake was CrIII sand > CrVI sand > CrIII soil > CrVI soil, whereas in the lower shoot, upper shoot and fruit the order was CrVI sand > CrVI soil > CrIII sand > CrIII soil. Significantly high uptake of chromium by roots in the sand culture (CrIII treatment) is attributed to the effect of root exudates and degradation products on the mobilization of CrIII. In aerial parts of the plants a higher uptake was observed when the initial supply was CrVI. The trends observed are explained on the basis of the redox behaviour of chromium.

Chromium↗

Uptake of chromium by rat liver mitochondria.

Isolated rat liver mitochondria rapidly accumulate chromate (1.2 microM 51CrO4(2-)) to about 0.25-0.30 nmol Cr/mg protein. The relative uptake decreases with increasing chromate doses. Chromate uptake decreases when pH is raised from 7.0 to 7.5.N-ethylmaleimide (0.25 mM) and butylmalonate (5 mM) inhibit chromate uptake to 70% and 30% of control values, respectively, whereas mersalyl (40 nmol/mg protein) causes an inhibition of greater than 95%. Both sulphate and phosphate decrease mitochondrial chromate uptake, the former being more effective in lower doses (5 mM). These results indicate that transport of chromate is mediated both on the dicarboxylate and the phosphate carrier. The extensive mitochondrial chromium accumulation can be explained by trapping of chromium, probably by reduction of chromate to the trivalent form, within the mitochondria. Release of chromium after chromate loading was seen after 15 min. Added after chromate loading, mersalyl partly prevents this release. Trivalent chromium as 51CrCl3 is taken up to a much lower degree than hexavalent chromium as 51CrO4(2-). The presence of glutathione (5 mM) reduces the uptake both of 51Cr-III and 51Cr-VI, indicating extramitochondrial reduction of Cr-VI to Cr-III and subsequent binding to GSH.

Animals↗

Isolation and process parameter optimization of Aspergillus sp. for removal of chromium from tannery effluent.

Five morphologically different fungi were isolated from leather tanning effluent in which Aspergillus sp. and Hirsutella sp. had higher potential to remove chromium. The potential of Aspergillus sp. for removal of chromium was evaluated in shake flask culture in different pH, temperature, inoculums size, carbon and nitrogen source. The maximum chromium was removed at pH 6, temperature 30 degrees C, sodium acetate (0.2%) and yeast extract (0.1%). Aspergillus sp. was applied in 2l bioreactor for removal of chromium, and it was observed that 70% chromium was removed after 3 days.

Aspergillus↗

Combined effect of vanadium(V) and chromium(III) on lipid peroxidation in liver and kidney of rats.

Since chromium(III) was demonstrated to have antioxidative action, we have decided to study the effect of this element on V-induced LPO in liver and kidney of rats. Outbred 2-month-old, albino male Wistar rats received daily, for a period of 12 weeks: group I (control), deionized water to drink; group II, sodium metavanadate (SMV) solution at a concentration of 0.100mgV/mL; group III, chromium chloride (CC) solution at a concentration of 0.004mgCr/mL and group IV, SMV-CC solution at a concentration of 0.100mgV and 0.004mgCr/mL. The particular experimental groups took up with drinking water about 8.6mgV/kg b.w./24h (group II), 0.4mgCr/kg b.w./24h (group III), 9mgV and 0.36mgCr/kg b.w./24h (group IV). The V- or Cr-treated groups had higher concentrations of these two elements in liver and kidney compared to the controls. The administration of vanadium alone caused a significant decrease in fluid intake and in body weight gain compared to the controls. In liver supernatants obtained from all tested rats a statistically significant increase in MDA concentration was demonstrated in spontaneous LPO in comparison with the control rats. Moreover, in rats intoxicated with vanadium alone a statistically significant increase in liver MDA level was observed in the presence of 100microM NaVO(3). Instead, in supernatants of liver received from rats treated with chromium alone, a statistically significant increase in MDA concentration in comparison with the controls was found in the presence of 400microM NaVO(3). In kidney supernatants obtained from rats treated with chromium alone, a statistically significant increase in lipid peroxidation was shown in the presence of 30microM FeSO(4) and 400microM NaVO(3). These results show that the tested doses of vanadium(V) and chromium(III) ingested by rats with their drinking water caused significant alterations in internal organs, especially in liver. Under the conditions of our experiment, Cr(III) did not demonstrate antioxidant action, it rather had an oxidant effect.

Animals↗

Chromium uptake by rice and accumulation in soil amended with municipal solid waste compost.

Effect of addition of municipal solid waste compost (MSWC) on chromium (Cr) content of submerged rice paddies was studied. Experiments were conducted during the three consecutive wet seasons from 1997 to 1999 on rice grown under submergence, at the Experimental Farm of Calcutta University, India. A sequential extraction method was used to determine the various chromium fractions in MSWC and cow dung manure (CDM). Chromium was significantly bound to the organic matter and Fe and Mn oxides in MSWC and CDM. Chromium content in rice straw was higher than in rice grain. Chromium bound with organic matter in MSWC best correlated with straw Cr (r=0.99**) followed by Fe and Mn oxides (r=0.97*) and water soluble as well as exchangeable fractions (r=0.96*). The water soluble and the exchangeable fractions in MSWC best correlated with grain Cr (r=0.98*). The Cr content of rice grain had the highest correlation with water soluble and exchangeable Cr (r=0.99**) while the straw Cr best correlated with the Fe and Mn oxides (r=0.98*). Both the carbonate bound and residual fractions in MSWC and CDM did not significantly correlate with rice straw and grain Cr. MSWC would be a valuable resource for agriculture if it can be used safely, but long-term use may require the cessation of the dumping by the leather tanneries and other major contributors of pollutants.

Animals↗

Sorption studies of mixed chromium and chlorinated ethenes at the field and laboratory scales.

The sorption and desorption behavior of hexavalent chromium and chlorinated ethenes in a sandy ground water aquifer with a low reduction capacity was evaluated by performing a variety of analyses and experiments at the laboratory (batch and column studies) and field (in situ injection-withdrawal experiment) scales. The partitioning coefficients determined from the field and laboratory experiments are generally similar. Both sets of experiments yielded relatively low partition coefficients for chromium and chlorinated ethenes. The column studies and injection-withdrawal experiment indicate that chromium has the potential to leach from aquifer sediments and act as a secondary source of contamination. However, the magnitude of the secondary source effect is not significant due to low concentrations of leachable contamination. The chromium sorption isotherm data were also simulated using the triple layer surface complexation model (TLM). The isotherm data were modeled using the TLM, illustrating the applicability of geochemical modeling for sorption of chromium to these sediments under variable pE-pH conditions.

Adsorption↗

Implication of chromium speciation on disposal of discarded CCA-treated wood.

The wood preservative chromated copper arsenate (CCA) contains hexavalent chromium [Cr(VI)] and the conversion of Cr(VI) to trivalent chromium [Cr(III)] drives fixation of the treatment chemicals to the wood fibers. Since the toxicity of Cr depends on its valence state, an assessment of the Cr species occurring in CCA-treated wood, as well as leachates and ashes from CCA-treated wood, is helpful when assessing implications for disposal. In this study, both new and weathered wood samples of CCA-treated wood and their ashes were evaluated for total Cr and Cr(VI) within the solid matrices and within leachates. Results show that for both new and weathered CCA-treated wood, Cr(VI) occurred in the range of 0.7-4% of the total Cr. Greater Cr leaching occurred at the pH extremes, with Cr(VI) only measured under alkaline pH values (pH > 9.0). Total chromium concentrations from synthetic precipitation leaching procedure (SPLP) leachates from CCA-treated wood were consistently less than 3mg/L with Cr(VI) below detection limits. The results suggest that leaching of Cr(VI) from discarded CCA-treated wood should not be a concern in most landfill environments. One exception would be disposal in landfills with alkaline leachate; Cr(VI) was observed to leach from CCA-treated wood in the presence of alkaline leachate from crushed concrete. When CCA-treated wood is combusted, chromium becomes concentrated in the ash. Cr(VI) in ash from the combustion of CCA-treated wood was found between 4 and 7% of the total chromium. In ash from the combustion of wood recovered from construction and demolition (C&D) debris (which contained some CCA-treated wood), Cr(VI) accounted for as much as 43% of the total Cr. Nearly, all of the Cr in SPLP leachates produced from the ash was in the Cr(VI) form. The degree of Cr(VI) leaching from the ash was highly dependent upon the alkalinity of the ash, with higher ash leachate pH resulting in greater concentrations of Cr(VI).

Arsenates↗

Chromium speciation in environmental samples by solid phase extraction on Chromosorb 108.

In the present work, a solid phase extraction system has been proposed for speciation of Cr(III) and Cr(VI) in the real samples. The procedure based on the adsorption of chromium(III) as dithizonate chelate on the Chromosorb 108 resin. After reduction of Cr(VI) by concentrated H2SO4 and ethanol, the system was applied to the total chromium. Cr(VI) was calculated as the difference between the total Cr content and the Cr(III) content. The influences of the analytical parameters including pH of the aqueous solution, amounts of dithizone, eluent type, sample volume and flow rates of the sample and eluent solution were investigated. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The adsorption capacity of sorbent was 4.50 mg/g Cr(III). The detection limit of Cr(III) is 0.75 microg/L. The proposed method was applied to the speciation of chromium in environmental samples including natural waters and total chromium preconcentration in microwave digested Turkish tobacco, coffee and soil samples with satisfactory results. In order to verify the accuracy of the method, two certified reference materials (NIST SRM 1573a Tomato Leaves and RTC-CRM 025-050 Metals on Soil) were analyzed and the results obtained were in good agreement with the certified values. The relative errors and relative standard deviations were below 5% and 9%, respectively.

Adsorption↗

Removal of chromium and toxic ions present in mine drainage by Ectodermis of Opuntia.

This work presents conditions for hexavalent and trivalent chromium removal from aqueous solutions using natural, protonated and thermally treated Ectodermis of Opuntia. A removal of 77% of Cr(VI) and 99% of Cr(III) can be achieved. The sorbent material is characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, infrared spectroscopy, thermogravimetric analysis, before and after the contact with the chromium containing aqueous media. The results obtained from the characterization techniques indicate that the metal ion remains on the surface of the sorbent material. The percentage removal is found to depend on the initial chromium concentration and pH. The Cr(VI) and Cr(III) uptake process is maximum at pH 4, using 0.1g of sorbent per liter of aqueous solution. The natural Ectodermis of Opuntia showed a chromium adsorption capacity that was adequately described by the Langmuir adsorption isotherm. Finally, an actual mine drainage sample that contained Cd, Cr, Cu, Fe Zn, Ni and Pb was tested under optimal conditions for chromium removal and Ectodermis of Opuntia was found to be a suitable sorbent material. The use of this waste material for the treatment of metal-containing aqueous solutions as well as mine drainage is effective and economical.

Adsorption↗

Solid phase extraction of chromium(VI) from aqueous solutions by adsorption of its ion-association complex with cetyltrimethylammoniumbromide on an alumina column.

A simple approach has been developed for the solid phase extraction of chromium(VI) based on the adsorption of its ion-association complex with cetyltrimethylammoniumbromide (CTABr) on an alumina column. The effect of various parameters such as acidity, stability of the column, sample volume, effect of diverse ions, etc. have been studied in detail. The adsorbed complex could be eluted using sodium hydroxide and the concentration of chromium has been established using visible spectrophotometry after complexation with diphenyl carbazide. The calibration graph was linear in the range 0-0.5 microg mL(-1) chromium(VI) with a detection limit of 5 microg L(-1). A highest preconcentration factor of 25 could be obtained for 250 mL sample volume. The data from the column studies were also studied using the Thomas model of adsorption. The experimental results obtained were correlated with the proposed model of adsorption. The Thomas rate constant k was found to be 0.0025 L/min mg and the maximum adsorption capacity q(o) was found to be 0.36 mgCr/g alumina at an initial chromium(VI) concentration of 1 mg L(-1). The validity of the method has been checked by applying it to study the recovery of chromium in spiked water samples and electroplating wastewater.

Adsorption↗

Fluorescence resonance energy transfer from tryptophan to a chromium(III) complex accompanied by non-specific cleavage of albumin: a step forward towards the development of a novel photoprotease.

A chromium(III) complex, transdiaqua [N, N'-propylenebis(salicylideneimino)chromium(III)]perchlorate ([Cr(salprn)(H2O)(2)]ClO(4)) in the presence of sodium azide and upon photoexcitation was found to bring about non-selective cleavage of bovine serum albumin (BSA). Electron paramagnetic resonance (EPR) evidence has been obtained for the formation of a Cr(V) species upon photolysis of a solution containing the chromium(III) complex and sodium azide. This Cr(V) species non-selectively cleaves BSA. The fluorescence excitation spectrum of BSA-[Cr(salprn)(H2O)(2)]+ adduct showed a band at lambda(max)(ex) nm due to charge transfer transition of the chromium(III) complex as well as a prominent band at 290 nm attributable to tryptophan absorption. This indicated an efficient Forster type fluorescence energy transfer (FRET) from the tryptophan residues to the chromium(III) complex indicating that the Cr(III) complex binds in the vicinity of the tryptophan residue.

Animals↗

Mechanisms of DNA damage and insight into mutations by chromium(VI) in the presence of glutathione.

The mechanisms of hexavalent chromium(VI) induced DNA damage were unveiled by detecting products of single- and double-stranded DNA in the presence of glutathione. The absence of a detectable hydroxyl radical in the reactions indicates that DNA damage was exclusively by hypervalent chromium species. Polyacrylamide gel electrophoresis (PAGE) experiments with 32-mer single-stranded oligonucleotide and its complementary duplex revealed cleavages largely at purine bases with significant enhancement of such cleavages in the presence of a base. Quantitative estimations of bases released by HPLC before and after enzymatic digestion with exonucleases unequivocally established the excessive release of purine bases. This release was accompanied by the concomitant formation of phosphoglycolate as characterized by liquid chromatography-mass spectrometry (LC-MS). These data connote that the preponderance DNA damage is due to an oxidation specifically at H4' of the ribose moiety leading to the formation of apurinic sites. In addition to the oxidation at H4', DNA oxidation was also initiated through H5' site as evidenced by the identification of furfural. This pathway appears to be non-selective and more abundant for ssDNA as cleavages were observed at both purine and pyrimidine bases. Finally, the detection of guanidinohydantoin as a minor product points the involvement of an oxygen activated hypervalent chromium species, perhaps a peroxo-chromium species. Both major and minor pathways lead to cleavages at purine sites for ds-DNA and are consistent with the observation that DNA cleavage was enhanced in the presence of a base. In contrast, when hydrogen peroxide was added to the reactions, random DNA cleavages were apparent indicating involvement of multiple species including a hydroxyl radical. These data pinpoint mutation mechanisms induced by chromium(VI) in the presence of glutathione due to transversion either by inserting the wrong bases opposite to the apurinic sites during replication or by purine-purine mismatch.

Base Sequence↗

Effects of hexavalent chromium on the plasma membranes of sensitive and tolerant mutants of Schizosaccharomyces pombe. An EPR study.

The interactions of chromium(VI) with the plasma membranes of chromium-sensitive (chr-51S) and chromium-tolerant (chr1-66T) mutants and their parental strain (6chr(+)) of a Schizosaccharomyces pombe strain were studied by electron paramagnetic resonance (EPR) spectroscopy. 5-doxylstearic acid (5-SASL) and 3-doxylbutyric acid (HO-185) spin probes were used to label the membranes. The order parameter S from the EPR spectra was calculated at different temperatures (0-25 degrees C) in order to characterize the internal dynamics of the membranes. In control experiments, both mutants exhibited differences in structural transitions in the both 5-SASL- and the HO-185-labeled membranes in comparison with their parental strain, suggesting differences in the membrane composition and/or rotational dynamics of these mutants. Addition of K(2)Cr(2)O(7) (225 microM) induced small decreases in the phase transition temperatures of the 5-SASL-labeled membranes of the parental and chromium-sensitive strains. More pronounced effects of the chromium compound on the HO-185-labeled membranes were detected as evidence that the membrane perturbations are mostly localized in the environment of the lipid-water interface.

Cations↗

Determination of hexavalent chromium at the level of the California Public Health Goal by ion chromatography.

Chromium is a primary drinking water contaminant in the USA with hexavalent chromium, Cr(VI), being the most toxic form of the metal. As a required step in developing a revised state drinking water standard for chromium, the California Department of Health Services recently issued a new Public Health Goal (PHG) of 2.5 microg/l for total chromium and 0.2 microg/l for Cr(VI). Hexavalent chromium can be determined (as chromate) by ion chromatography, as described in US Evironmental Protection Agency Method 218.6; however, the method as originally published does not allow sufficient sensitivity for analysis at the California PHG level of 0.2 microg/l. Modification of the conditions described in Method 218.6, including the use of a lower eluent flow-rate, larger reaction coil, and larger injection volume, significantly increases the method sensitivity. The modified method, which uses IonPac NG1 and AS7 guard and analytical columns, an eluent of 250 mM ammonium sulfate-100 mM ammonium hydroxide operated at 1.0 ml/min, a 1000 microl injection volume, and postcolumn reaction with 2 mM diphenylcarbazide-10% methanol-0.5 M sulfuric acid (using a 750 microl reaction coil) followed by UV-Vis detection at 530 nm, permits a method detection limit for chromate of 0.02 microg/l. This results in a quantitation limit of 0.06 microg/l, which is more than sufficient for analysis at the California PHG level. Calibration is linear over the range of 0.1-10 microg/l and quantitative recoveries (>80%) are obtained for chromate spiked at 0.2 microg/l in drinking water. The modified method provides acceptable performance, in terms of chromate peak shape and recovery, in the presence of up to 1000 mg/l chloride or 2000 mg/l sulfate.

Calibration↗

Speciation of chromium by in-capillary reaction and capillary electrophoresis with chemiluminescence detection.

A sensitive method for the simultaneous determination of chromium(III) (Cr3+) and chromium(VI) (CrO4(2-)) using in-capillary reaction, capillary electrophoresis (CE) separation and chemiluminescence (CL) detection was developed. The chemiluminescence reaction was based on luminol oxidation by hydrogen peroxide in basic aqueous solution catalyzed by Cr3+ ion followed by capillary electrophoresis separation. Based on in-capillary reduction, chromium(VI) can be reduced by acidic sodium hydrogensulfite to form chromium(III) while the sample is running through the capillary. Before the electrophoresis procedure, the sample (Cr3+ and CrO4(2-)), buffer and acidic sodium hydrogensulfite solution segments were injected in that order into the capillary, followed by application of an appropriate running voltage between both ends. As both chromium species have opposite charges, Cr3+ ions migrate to the cathode, while CrO4(2-) ions, moving in the opposite direction toward the anode, react with acidic sodium hydrogensulfite which results in the formation of Cr3+ ions. Because of the migration time difference of both Cr3+ ions, Cr(III) and Cr(VI) could be separated. The running buffer was composed of 0.02 mol l(-1) acetate buffer (pH 4.7) with 1 x 10(-3) mol l(-1) EDTA. Parameters affecting CE-CL separation and detection, such as reductant (sodium hydrogensulfite) concentration, mixing mode of the analytes with CL reagent, CL reaction reagent pH and concentration, were optimized. The limits of detection (LODs) of Cr(III) and Cr(VI) were 6 x 10(-13) and 8 x 10(-12) mol l(-1) (S/N=3), respectively. The mass LODs for Cr(III) and Cr(VI) were 1.2 x 10(-20) mol (12 zmol) and 3.8 x 10(-19) mol (380 zmol), respectively.

Buffers↗

Phytotoxic lesions of chromium in maize.

Chromium (Cr) is fairly abundant in the earth's crust and ranks fourth among the 29 elements of biological importance. Besides natural sources, Cr enters biotic components of the ecosystem in various ways. Of other major industrial sources, tanning and chrome-plating industries are prominent sources. Cr(VI) form of chromium is highly reactive and influences both plants and animals. Due to Mn present in soil, Cr(III) is oxidized to Cr(VI) which remains in soil for a long time and can affect plant growth and development. Since maize is an important food and fodder plant for human beings and cattle, a study was conducted to investigate the effects of Cr on some metabolic activities of maize (Zea mays L. cv. Ganga 5). Chromium caused visible lesions of interveinal chlorosis. Young leaves showed vein clearing. Also, a papery appearance was observed in leaves. Margins of leaves were curled and the leaves appeared pale at greater Cr exposure. Concentrations of both chlorophyll a and b were reduced by exposure to Cr, the activities of ribonuclease and phenyl phosphatase were greater while the activity of iron-porphyrin enzyme catalase was less and the activity of amylase was also much less in plants exposed to Cr. Chromium also caused retardation of soluble protein. Accumulation of Cr in roots was much at all the levels of chromium supply. Exposure to Cr resulted in reduction in grain production and quality.

Chlorophyll↗