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The phosphine oxides Cyanex 921 and Cyanex 923 as carriers for facilitated transport of chromium (VI)-chloride aqueous solutions.

The behaviour of the phosphine oxides Cyanex 921 and Cyanex 923 in the facilitated transport of chromium (VI) from chloride solutions is described. Transport is studied as a function of several variables such as stirring speeds of the aqueous phases, membrane phase diluent, hydrochloric acid concentration in the source phase and chromium and carrier concentrations. The separation of chromium (VI) from other metals presented in the source phase as well as the behaviour of phosphine oxides with respect to other neutral organophosphorous derivatives (tri-n-butylphosphate (TBP) and dibutyl butylphosphonate (DBBP)) are also investigated. Moreover, by using hydrazine sulphate in the receiving phase, Cr(VI) is immediately reduced to the less toxic Cr(III).

Chromium↗

Both trivalent and hexavalent chromium strongly alter in vitro germination and ultrastructure of kiwifruit pollen.

Due to its widespread industrial use, chromium is considered a dangerous environmental pollutant. It is known to inhibit plant growth and development. The present study provides the first evidence of the toxicity of this metal on the male haploid generation of a higher plant. Both Cr(III) and Cr(VI) species, supplied as CrCl(3) and CrO(3), respectively, exerted a strong dose-dependent inhibitory effect on kiwifruit pollen tube emergence and growth. Cr(III) resulted more effective than Cr(VI) in the 16-75microM interval; moreover, complete inhibition of germination was attained at much lower doses than Cr(VI). Also tube morphology was affected. While the plasma membrane was still undamaged in the large majority of the treated pollen grains, dramatic ultrastructural alterations were induced by chromium including chromatin condensation, swelling of mitochondria, cytoplasmic vacuolization, and perturbed arrangement of endoplasmic reticulum cisternae. Thus, it seems that the impact of the two chromium species on kiwifruit pollen may result in severe compromission of both essential structures and functions of the male gametophyte.

Actinidia↗

Does plasma irradiation improve shear bond strength of acrylic resin to cobalt-chromium alloy?

OBJECTIVES: Plasma treatment leads to surface modification such as the improved wettability of dental materials. Studies have suggested that plasma treatment may bring about an improvement in the shear bond strength between cobalt-chromium alloy and self-curing acrylic resin. METHODS: Forty-eight cobalt-chromium alloy specimens were randomly divided into four groups (each of the groups consisted of 12 specimens); air abrasion, adhesive primer, adhesive primer after air abrasion, or after plasma irradiation. A self-curing acrylic resin, 2 mm thick and 3.6 mm in diameter, was processed on all specimens before storage in distilled water at 37 degrees C for 24 h. Shear bond strength values were determined at a crosshead speed of 0.5 mm/min. Data was statistically analyzed using Scheffé's test. RESULTS: Adhesive primer clearly increased the shear bond strength compared with air abrasion (p < 0.05). The synergy of air abrasion and adhesive primer greatly increased the shear bond strength, showing a five-fold increase over air abrasion, or one and a half-fold over adhesive primer. A similar tendency in increase was observed in the adhesive primer after plasma treatment, but to a lower degree. Adhesive primer after plasma treatment showed half the shear bond strength of the treatment of adhesive primer after air abrasion (p < 0.05). Moreover, adhesive primer after plasma treatment showed a lower shear bond strength than adhesive primer alone although the difference was not statistically significant. SIGNIFICANCE: Plasma treatment does not improve adhesion between cobalt-chromium alloy and self-curing acrylic resin.

Acrylic Resins↗

Acute and chronic activity of perchlorate and hexavalent chromium contamination on the survival and development of Culex quinquefasciatus Say (Diptera: Culicidae).

Effects of water contamination with perchlorate and hexavalent chromium [Cr (VI)] on the mosquito Culex quinquefasciatus were assessed. The chronic (10-day) LC50s values for perchlorate and chromium were 74+/-8.0 mg/L and 0.41+/-0.15 mg/L, respectively. Relative Growth Index, a measure of growth and mortality rates in a population, was significantly reduced within 5 days for levels of perchlorate as low as 25 mg/L and for levels of chromium as low as 0.16 mg/L. Neither compound altered wing length of surviving adults. In combination, contaminants were synergistic, causing 14% more mortality than predicted. Acute (24-h) LC50 values for perchlorate and Cr (VI) were 17,000+/-3200 and 38+/-1.3 mg/L, respectively. Effects on mosquito larvae in contaminated environments are likely to be observed for Cr (VI) but not for perchlorate, which generally does not occur at levels as high as those shown here to affect larval mosquitoes.

Animals↗

Protective effects of 17beta-estradiol and trivalent chromium on interleukin-6 secretion, oxidative stress, and adhesion of monocytes: relevance to heart disease in postmenopausal women.

Postmenopausal diabetic women are at greater risk for heart disease compared with men of similar age and with other risk factors. We examined the hypothesis that 17beta-estradiol and trivalent chromium inhibit secretion of the pro-inflammatory cytokine interleukin (IL)-6 and oxidative stress in monocytes exposed to high glucose (HG). U937 human monocytes were cultured with HG (30 mM) with and without 17beta-estradiol (0-1000 nM) and chromium chloride (Cr(3+), 0-10 muM) at 37 degrees C for 24 h. Results show that 17beta-estradiol inhibits IL-6 and adhesion to endothelial cells (p <. 05) by HG-treated monocytes. Treatment with 17beta-estradiol+Cr(3+) required a significantly lower dose of estradiol-17beta compared with 17beta-estradiol alone for IL-6 inhibition. 17beta-Estradiol+Cr(3+) also inhibited lipid peroxidation and the adhesivity to human endothelial cells in HG-treated monocytes. Thus, 17beta-estradiol+Cr(3+) inhibits oxidative stress, IL-6 secretion, and monocytic adhesion to endothelial cells, risk factors in the development of heart disease. The female body requires E but studies on some patients indicate side effects with increased amounts of 17beta-estradiol-supplementation. The potential benefit of a lower estrogen dose in combination with chromium is novel and needs to be explored in postmenopausal diabetic women.

Antioxidants↗

Use of analytical microscopy to analyze the speciation of copper and chromium ions onto a low-cost biomaterial.

In this paper, we present our study of the speciation of copper and hexavalent chromium sorbed onto a lignocellulosic substrate, using analytical microscopy. The lignocellulosic substrate constitutes a low-cost biomaterial that can be used in wastewater treatment. Transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDXS) was used to determine the speciation of the two metal ions on the constitutive moieties of the lignocellulosic substrate. The use of a staining agent sensitive to carbon unsaturation allowed us to differentiate between the microstructures rich in lignin entities and those rich in cellulose entities. The EDX analysis showed that metal ions are preferentially sorbed onto microstructures rich in lignin moieties. The energy electron loss spectroscopy (EELS) was used to determine the oxidation states of chromium in association with lignocellulosic moieties. We showed that the sorption process of hexavalent chromium requires the reduction of Cr(VI) into Cr(III) and the probable oxidation of lignin moieties.

Cellulose↗

Detoxification of chromium slag by chromate resistant bacteria.

This paper presented direct detoxification of chromium slag by using microorganisms. Our work showed that a bacterial consortium isolated from chromium slag can efficiently accelerate Cr(VI) leaching rate and remove it. The chromate resistant bacterial consortium consists of three strains. The detoxification efficiencies of the three respective strains follow the sequence: strain I > strain III > strain II. The detoxification capability of the bacterial consortium is far stronger than that of the respective strain, showing an excellent synergistic effect. The specific growth rates in pure and chromium-containing medium are 0.1475 and 0.1573 h(-1), respectively. The presence of Cr(VI) has little effect on growth rate of the bacterial consortium. Cr(VI) removal takes place in exponential growth period of the bacterial consortium; the detoxification time should be controlled in this phase for every run. The kinetics of detoxification process was studied and can be described as eta = 0.0615e(0.1573t), which can be used to predict Cr(VI) removal efficiency.

Bacteria↗

Removal of chromium from aqueous solution using cellulose acetate and sulfonated poly(ether ether ketone) blend ultrafiltration membranes.

A process for purifying aqueous solutions containing heavy and toxic metals such as chromium has been investigated. Chromium salts are largely used in various industries including leather-manufacturing industry. Ultrafiltration processes are largely being applied for macromolecular and heavy metal ion separation from aqueous streams. Cellulose acetate and sulfonated poly(ether ether ketone) blend ultrafiltration membranes were prepared by precipitation phase inversion technique in 100/0, 90/10, 80/20 and 70/30% polymer blend compositions and subjected to the rejection of chromium at different concentrations such as 200, 400, 600, 800 and 1000 ppm with a water-soluble macroligand (polyvinylalcohol). Factors affecting the percentage rejection and permeate flux such as pH, concentration of solute, concentration of PVA, transmembrane pressure and composition of blend membranes were investigated. It was found that percentage rejection improved at a pH 6 and a macroligand concentration of 2 wt.%. The transmembrane pressure and concentration of solute also have an effect on the separation and product rate efficiencies of the blend membranes.

Alcohols↗

Chromium removal from electroplating wastewater by coir pith.

Coir pith is a by-product from padding used in mattress factories. It contains a high amount of lignin. Therefore, this study investigated the use of coir pith in the removal of hexavalent chromium from electroplating wastewater by varying the parameters, such as the system pH, contact time, adsorbent dosage, and temperature. The maximum removal (99.99%) was obtained at 2% (w/v) dosage, particle size <75microm, at initial Cr(VI) 1647mgl(-1), system pH 2, and an equilibrium time of 18h. The adsorption isotherm of coir pith fitted reasonably well with the Langmuir model. The maximum Cr(VI) adsorption capacity of coir pith at 15, 30, 45 and 60 degrees C was 138.04, 197.23, 262.89 and 317.65mgCr(VI)g(-1) coir pith, respectively. Thermodynamic parameters indicated an endothermic process and the adsorption process was favored at high temperature. Desorption studies of Cr(VI) on coir pith and X-ray absorption near edge structure (XANES) suggested that most of the chromium bound on the coir pith was in Cr(III) form due to the fact that the toxic Cr(VI) adsorbed on the coir pith by electrostatic attraction was easily reduced to less toxic Cr(III). Fourier transform infrared (FT-IR) spectrometry analysis indicated that the carbonyl (CO) groups and methoxy (O-CH(3)) groups from the lignin structure in coir pith may be involved in the mechanism of chromium adsorption. The reduced Cr(III) on the coir pith surface may be bound with CO groups and O-CH(3) groups through coordinate covalent bonding in which a lone pair of electrons in the oxygen atoms of the methoxy and carbonyl groups can be donated to form a shared bond with Cr(III).

Adsorption↗

A Schiff base complex of chromium(III): an efficient inhibitor for the pathogenic and invasive potential of Shigella dysenteriae.

A Schiff base complex of chromium(III), transdiaqua[N,N'ethylenebis (salicylideneimine)chromium(III)]perchlorate, [Cr(salen)(OH(2))(2)](+), was found to have an inhibitory effect on the growth of Shigella dysenteriae. The chromium(III) complex was found to cure (remove) the invasive plasmid and thereby render the microbe more sensitive to the tested antibiotics. The loss in the catalytic activity of the isolated endo-alpha-N-acetyl galactosaminidase on mucin as a substrate was also observed in the presence of [Cr(salen)(OH(2))(2)](+). This suggests that [Cr(salen)(OH(2))(2)](+) is toxic to the microbe and could make the microbe non-pathogenic and non-invasive, thus establishing its role in microbiological applications to reduce the toxic potentials of a microbe.

Animals↗

Safety and toxicological evaluation of a novel niacin-bound chromium (III) complex.

Chromium is an essential trace element required for normal protein, fat and carbohydrate metabolism. It also helps in energy production and increasing lean body mass. Niacin-bound chromium (NBC) is a unique form of bioavailable chromium that promotes healthy lipid profile. This study was focused on determining the broad spectrum safety of NBC. Acute oral, acute dermal, primary dermal irritation and primary eye irritation toxicities of NBC were evaluated. Ames bacterial reverse mutation assay, mouse lymphoma test and a dose-dependent 90-day subchronic toxicity were also conducted. In safety studies, the acute oral LD(50) of NBC was found to be greater then 5000 mg/kg in both male and female Sprague-Dawley rats. No changes in body weight or adverse effects were observed following necropsy. The acute dermal LD(50) of NBC was found to be >2000 mg/kg. The primary skin irritation test was conducted with NBC on New Zealand Albino rabbits. NBC was classified as slightly irritating. The primary eye irritation test was conducted with NBC on rabbits. NBC was classified as practically non-irritating to the eye. NBC did not induce mutagenic effects in the bacterial reverse mutation test in five Salmonella typhimurium strains (TA1535, TA98, TA100, TA97a and TA102), either with or without metabolic activation. Similarly, NBC did not induce mutagenic effects in the mammalian cell gene mutation test in L5178Y mouse lymphoma cells TK (+/-), either with or without metabolic activation. A dose-dependent 90-day subchronic toxicity study demonstrated no significant changes in selected organ weights individually and as percentages of body and brain weights. NBC supplementation did not cause changes in hepatic lipid peroxidation or DNA fragmentation after 30, 60 or 90 days of treatment. Hematology, clinical chemistry and histopathological evaluations did not show any adverse effects in all organs tested. Taken together, the above results indicate a broad spectrum of safety for NBC.

Acute Disease↗

Breakdown kinetics of the tri-chromium(III) oxo acetate cluster ([Cr(3)O(OAc)(6)]+) with some ligands of biological interest.

Kinetics for the breakdown of the trinuclear chromium acetate cluster, [Cr(3)O(OAc)(6)](+), with a series of monoprotic and diprotic ligands in weakly acidic aqueous media (pH approximately 4 or approximately 5) have been investigated spectrophotometrically at 40-60 degrees C. The results point to an ion-pair equilibrium as the first step followed by associative interchange mechanism forming the mononuclear product of the reaction. Pseudo-first-order rates were determined from absorbance data and associated activation parameters were calculated using the Eyring equation. Enthalpy and entropy terms of the reactions (e.g., histidine, DeltaH(double dagger) = 75 +/- 15 kJ mol(-1), DeltaS(double dagger) = -130 +/- 25 J K(-1) mol(-1); lactic acid, DeltaH(double dagger) = 66 +/- 13 kJ mol(-1), DeltaS(double dagger) = -155 +/- 30 J K(-1) mol(-1); glycine, DeltaH(double dagger) = 31 +/- 6 kJ mol(-1), DeltaS(double dagger) = -225 +/- 45 J K(-1) mol(-1)) are consistent with an associative interchange (I(a)) mechanism, and produce a linear isokinetic plot (slope = 50 degrees C). Rates and activation parameters are comparable to those of substitution reactions of the chromium(III) hexaaqua cation. Other ligands studied included malonic acid and the amino acid, aspartic acid. Observed rates are faster than water exchange rates, but typically slower than anion substitution rates, and indicate that trinuclear chromium(III) clusters are expected to be kinetically stable in neutral to slightly acidic conditions.

Chromium↗

Nutritional supplement chromium picolinate generates chromosomal aberrations and impedes progeny development in Drosophila melanogaster.

Chromium picolinate, [Cr(pic)(3)], is a popular nutritional supplement found in a variety of consumer products. Despite its popularity, safety concerns over its use have arisen. The supplement has been shown to generate clastogenic damage, mitochondrial damage, oxidative damage, and mutagenic effects in cultured cells and oxidative DNA damage and lipid peroxidation in rats. Recently [Cr(pic)(3)] has been demonstrated to generate heritable genetic change and delays in progeny development in Drosophila melanogaster. Based on the damage to chromosomes of cultured cells and of animal models, similar chromosome damage appeared to be a likely source of the mutagenic effects of the supplement in Drosophila. The current three-part study examines the effects of several chromium-containing supplements and their components on hatching and eclosion rates and success of development of first generation progeny of adult Drosophila fed food containing these compounds. It further examines the effects of the compounds on longevity of virgin male and female adults. Finally, the chromosomes in the salivary glands of Drosophila late in the third instar larval stage, which were the progeny of Drosophila whose diets were supplemented with nutritional levels of [Cr(pic)(3)], are shown to contain on average over one chromosomal aberration per two identifiable chromosomal arms. No aberrations were observed in chromosomes of progeny of untreated flies. The results suggest that human consumption of the supplement should be a matter of concern and continued investigation to provide insight into the requirements of chromium-containing supplements to give rise to genotoxic effects.

Animals↗

Tensile strength and corrosion resistance of brazed and laser-welded cobalt-chromium alloy joints.

STATEMENT OF PROBLEM: The longevity of prosthodontic restorations is often limited due to the mechanical or corrosive failure occurring at the sites where segments of a metal framework are joined together. PURPOSE: The purpose of this study was to determine which joining method offers the best properties to cobalt-chromium alloy frameworks. Brazed and 2 types of laser-welded joints were compared for their mechanical and corrosion characteristics. MATERIAL AND METHODS: Sixty-eight cylindrical cobalt-chromium dental alloy specimens, 35 mm long and 2 mm in diameter, were cast. Sixteen specimens were selected for electrochemical measurements in an artificial saliva solution and divided into 4 groups (n=4). In the intact group, the specimens were left as cast. The specimens of the remaining 3 groups were sectioned at the center, perpendicular to the long-axis, and were subsequently rejoined by brazing (brazing group) or laser welding using an X- or I-shaped joint design (X laser and I laser groups, respectively). Another 16 specimens were selected for electrochemical measurements in a more acidic artificial saliva solution. These specimens were also divided into 4 groups (n=4) as described above. Electrochemical impedance spectroscopy and potentiodynamic polarization were used to assess corrosion potentials, breakdown potentials, corrosion current densities, total impedances at lowest frequency, and polarization charge-transfer resistances. The remaining 36 specimens were used for tensile testing. They were divided into 3 groups in which specimen pairs (n=6) were joined by brazing or laser welding to form 70-mm-long cylindrical rods. The tensile strength (MPa) was measured using a universal testing machine. Differences between groups were analyzed using 1-way analysis of variance (alpha=.05). The fracture surfaces and corrosion defects were examined with a scanning electron microscope. RESULTS: The average tensile strength of brazed joints was 792 MPa and was significantly greater (P<.05) than the tensile strength of both types of laser-welded joints (404 MPa and 405 MPa). When laser welding was used, successful joining was limited to the peripheral aspects of the weld. The welding technique did not significantly affect the joint tensile strength. Electrochemical measurements indicated that the corrosion resistance of the laser-welded joints was better than of the brazed ones, primarily due to differences in passivation ability. CONCLUSION: Laser welding provides excellent corrosion resistance to cobalt-chromium alloy joints, but strength is limited due to the shallow weld penetration. Brazed joints are less resistant to corrosion but have higher tensile strength than laser welds.

Chromium Alloys↗

Hexavalent chromium disrupts the actin cytoskeleton and induces mitochondria-dependent apoptosis in human dermal fibroblasts.

Exposure to hexavalent chromium causes various adverse effects including deep skin ulcerations and allergic dermatitis. Because of many potential intracellular targets for hexavalent chromium toxicity, its mechanisms of action are not entirely understood. To investigate the role of the cytoskeleton and mitochondria in this process, primary human dermal fibroblasts were exposed to various concentrations of potassium chromate for 24 h. The followed markers included cell motility, cytoskeletal organization, oxidative stress, mitochondrial activity and activation of the apoptotic cascade. Potassium chromate (1.5-45 microM) induced time- and concentration-dependent cell shrinkage, reorganization of cytoskeleton and loss of motile activity in fibroblasts. In some cells this was followed by membrane blebbing. Dynamic changes in cell morphology were accompanied with the loss of mitochondrial membrane potential, increased oxidative stress and release of cytochrome c. Apoptosis was confirmed by detection of activated caspase-3 and nuclear fragmentation. The results indicate that in fibroblasts hexavalent chromium-induced damage to cytoskeleton and mitochondria might occur concurrently at relatively early stages of exposure. Furthermore, alterations of these targets seem to activate mitochondria-dependent and- independent apoptosis.

Actins↗

Cytotoxicity of chromium and manganese to lung epithelial cells in vitro.

Chromium, nickel and manganese are the predominant metals in welding fumes and are associated through epidemiological studies with an increased risk for developing occupational asthma due to welding activities. Here, we show that chromium(VI) and manganese, but not nickel, are cytotoxic to normal human lung epithelial cells in vitro (SAEC and BEAS-2B), at concentration ranges of 0.2-200 microM. The toxic effect was associated with increased levels of intracellular phosphoprotein and subsequent release of inflammatory cytokines IL-6 and IL-8, while no release of TNF-alpha was observed. Changes in intracellular phosphoprotein levels occurred at concentrations below the cytotoxic effect. IL-6 and IL-8 production increased up to 4.4-fold relative to controls. IL-6 and IL-8 are released from lung epithelium to recruit cells of the immune system to sites of tissue damage. Therefore, the observed effects of chromium(VI) and manganese in lung epithelial cells demonstrate a mechanism through which the toxicity of these metals to epithelial cells can result in recruitment of cells of the immune system.

Cell Survival↗

Designing a purification process for chromium-, copper- and arsenic-contaminated wood.

The disposal of chromated copper arsenate (CCA)-treated wood is becoming a serious problem in many countries due to increasing levels of contamination by the hazardous elements, chromium, copper and arsenic. The present experiment was conducted as a preliminary step toward one-step solvent extraction of CCA-treated wood. Because chromium, copper and arsenic have different chemical characteristics, it is best to consider them separately prior to designing a one-step extraction process. As a basis, various two-step extraction processes were first designed and tested experimentally to determine feasibility. Among these combinations, the treatment combining oxalic acid as the 1st step and a sodium oxalate solution under acidic conditions (pH 3.2) as the 2nd step was found to be an effective way of extracting CCA elements from treated wood. Extraction efficiency reached 100% for arsenic and chromium and 95.8% for copper after a 3-h sodium oxalate treatment, following a 1-h pre-extraction process with oxalic acid. On the other hand, the same combination under alkaline conditions (pH 11.2) during the 2nd step was ineffective for copper removal, indicating that pH plays an important role in complexation with sodium oxalate solution. The present results suggest that the extraction of CCA elements using a combination of oxalic acid and acidic sodium oxalate solution is a promising basis for application to a one-step extraction method.

Arsenates↗

Mechanism of hexavalent chromium adsorption by persimmon tannin gel.

Mechanism of chromium adsorption by the persimmon tannin (PT) gel was examined. The PT gel can adsorb Cr highly effectively from aqueous solutions containing Cr(VI), while it adsorbed far smaller amounts of Cr from the solution containing Cr(III). The maximum Cr adsorption from the Cr(VI) solution occurred at pH 3. The Cr adsorption from the Cr(VI) solution by the PT gel was rapid, was faster than VO2+ and Fe3+ adsorptions, and was obeyed the Langmuir adsorption isotherm (Qe= 5.27 mmol g(-1) and K= 16.2 mM). The gel adsorbed Cr from the Cr(VI) solution (pH 1 and 3) showed no ESR signal of Cr(III), while the ESR signal of Cr(III) was observed in the residual solution at pH 1. Hexavalent chromium was, therefore, adsorbed on the PT gel through the esterification of chromate with catechol group. In other words, Cr(VI) should combine with catechol as a hard acid, CrO2(2+) cation. Through the treatment of a Cr(VI) solution with the PT gel, chromium should be recovered as a Cr(IV)-tannin complex at pH 3 or a Cr(III) solution at pH 1 or lower pH region.

Adsorption↗