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Analytical chemistry of chromium species in the environment, and interpretation of results.

Valence-selective species determination of chromium in environmental and biological material presents intricacies primarily due to the complex nature of the samples and the instability of the oxidation states of chromium. In particular organic matter ubiquitously present in environmental samples introduces the risk of chromium(VI) reduction during analysis which takes place preferably in acidic solution. Also chromium(III) oxidation may occur in alkaline medium. Hence analytical methods should be adequately adapted to the reliable determination of chromium(VI) in blood, natural water, effluents, sediments and soil. It can be shown that polarography is most effectually suitable to the determination of chromium(VI) compounds. Chromium(VI) is electrochemically active over the entire pH range, so that medium pH can be selected for measuring, thus protecting samples most effectively from undergoing redox reactions during the analytical procedure. Other established methods such as spectrophotometry or valence-specific extraction are more crucial, because these generally require acidic medium. In some cases sample pre-treatment can be employed to eliminate reductants prior to final measurement. Very few methods are available to selectively measure chromium(III). Indirect determination is therefore preferred. Optimum conditions for the determination of total chromium by AAS are shortly outlined.

Chromium↗

Chromium, exercise, and body composition.

Chromium is an essential trace element involved in the metabolism of carbohydrates, lipids, and proteins mainly by increasing the efficiency of insulin. Chromium deficiency affects the maintenance of normal glucose tolerance and healthy lipid profiles. The Estimated Safe and Adequate Daily Dietary Intake for chromium is 50 to 200 microg/d for adults. However, the dietary intake of chromium in humans is often suboptimal. Chromium assessment has proven to be a challenge due to the low amounts of chromium present in biological materials and the absence of a reliable indicator of chromium status. Recently, chromium has been touted as an agent for increasing lean body mass and decreasing percent body fat. This article reviews the various studies that have been conducted to investigate the relationship of chromium with exercise and body composition.

Biological Transport↗

Elevated levels of DNA-protein crosslinks and micronuclei in peripheral lymphocytes of tannery workers exposed to trivalent chromium.

DNA-protein crosslinks (DPC) are a promising biomarker of exposure to hexavalent chromium, a known human carcinogen. Although trivalent chromium is considered to have much lower toxicity, the risk involved in chronic exposure is uncertain. DPC may be a useful tool in clarifying this risk, by signaling an exposure of body tissues to biologically active forms of chromium. DPC quantification was carried out in lymphocytes of a group of tannery workers exposed to trivalent chromium, a small group of manual metal arc stainless steel welders exposed to hexavalent chromium and a control group. This biomarker was compared with the frequency of micronuclei in cytokinesis blocked peripheral lymphocytes as a biomarker of cytogenetic lesions and total plasma and urine chromium levels as an index of exposure. The results indicate a significant increase in the formation of DPC in tannery workers compared with controls (0.88 +/- 0.19 versus 0.57 +/- 0.21%, P < 0.001, Mann-Whitney test) and an even higher level of DPC in welders (2.22 +/- 1.12%, P = 0.03). Tanners showed a significant increase in micronucleated cells compared with controls (6.35 +/- 2.94 versus 3.58 +/- 1.69 per thousand, P < 0.01), whereas in welders this increase was not significant (5.40 +/- 1.67 per thousand ). Urinary chromium was increased in both groups, with a greater increase observed in tanners compared with controls (2.63 +/- 1.62 versus 0.70 +/- 0.38 microg/g creatinine, P < 0.001) than in welders (1.90 +/- 0.37 microg/g creatinine, P < 0.005). Plasma chromium was also increased in both groups (tanners 2.43 +/- 2.11 microg/l, P < 0.001, welders 1.55 +/- 0.67 microg/l, P < 0.005 versus controls 0.41 +/- 0.11 microg/l). In summary, chronic occupational exposure to trivalent chromium can lead to a detectable increase in lymphocyte DNA damage which correlates with a significant exposure of the cells to the metal.

Adult↗

A study on the clinical application of a direct leukocyte migration test in chromium contact allergy.

A capillary tube leukocyte migration inhibition assay has been adopted as an in vitro method for the demonstration of chromium hypersensitivity in twenty-two subjects with clinically proven or suspected chromium allergy. Two complexes of trivalent chromium and human serum albumin, exerting different migration inhibitory effects, have been prepared and used as the antigen. In the presence of the chromium-albumin complex with strong inhibitory activity, sensitivity to chromium was demonstrated independent of the clinical condition of the skin in all the patch test positive subjects. An additional positive response to the second chromium-albumin complex was observed only in those patients who were clinically in a state of exacerbation of an allergic contact dermatitis in which chromium allergy was an active causative factor. The results were not influenced by skin allergic reactivity to compounds other than chromium and the method was found to be of practical clinical value for diagnosing chromium allergy.

Albumins↗

Effect of processing cement to concrete on hexavalent chromium levels.

Hexavalent chromium sensitization is known to occur from exposure to cement. Concrete is a mixture of cement, sand, rock, and water. Admixtures are compounds used to retard or accelerate concrete setting time. Some countries use ferrous sulfate to reduce hexavalent chromium in cement. We evaluated and compared hexavalent chromium levels in cement, rock (aggregate), and wet and dry concrete in samples from Singapore, Ireland, Denmark, Australia, and the United States. Cement from Denmark contains ferrous sulfate. The effect of representative admixtures on hexavalent chromium concentration in concrete was also evaluated, but technical limitations made evaluation difficult. Soluble chromium levels in cement ranged from 0.225 mg/kg in the US sample to 0.036 mg/kg in the Singapore sample. Aggregate chromium levels ranged from 0.083 mg/kg in the Denmark sample to < 0.002 mg/kg in the Ireland sample. Fresh US concrete, with 1.27 mg/kg hexavalent chromium, contained the highest level. The Denmark sample, with ferrous sulfate added, was lowest (< 0.01 mg/kg). Hardened concrete levels ranged from 0.104 mg/kg from the Ireland sample to 0.002 mg/kg from the Singapore sample. Therefore, hexavalent chromium levels do appear to be influenced by admixtures and by processing from powdered cement to dry concrete. Ferrous sulfate significantly reduced hexavalent chromium levels in fresh cement.

Carcinogens, Environmental↗

Effects of chromium on body composition and weight loss.

Chromium is an essential nutrient involved in the regulation of carbohydrate and lipid metabolism. Normal dietary intake of chromium in humans and farm animals is often suboptimal. In addition to its effects on glucose, insulin, and lipid metabolism, chromium has been reported to increase lean body mass and decrease percentage body fat, which may lead to weight loss in humans. The effects of chromium on body composition are controversial but are supported by animal studies, which increase their validity. A subject's response to chromium depends on his or her chromium status, diet consumed, type and amount of supplemental chromium, and study duration. There have been no confirmed negative effects of chromium in nutritional studies. Chromium is only a small part of the puzzle in the control of weight loss and body composition, and its effects, if present, will be small compared with those of exercise and a well-balanced diet.

Body Composition↗

Half life of chromium in serum and urine in a former plasma cutter of stainless steel.

For 8 years chromium in serum and urine has been followed up in a former plasma cutter of stainless steel who was exposed to airborne dust and fumes containing chromium during this work. After the first examination for serum chromium the exposure ended. Serum chromium concentration has been measured seven times during the period and was initially very high and has subsequently dropped slowly. The half life was 40 months in serum. Urinary chromium has been measured five times. The half life was 129 months in urine. The study shows that exposure to airborne dust and fumes containing chromium may cause accumulation of chromium in the body, and that when exposure ends, elimination of chromium is very slow. Previous studies suggest that chromium mainly accumulates in the lungs.

Chromium↗

The carcinogenicity of chromium.

The carcinogenicity of chromium compounds is reviewed with specific attention to the gaps in knowledge for risk estimation and research needs. The most important problems at present are whether trivalent chromium compounds cause cancer, and whether there is a difference in cancer causing effects between the soluble and the slightly soluble hexavalent compounds in the practical exposure situation. Dose estimates for risk estimation based on epidemiological investigations are also lacking. Present evidence indicates that the trivalent chromium compounds do not cause cancer although high concentrations in some in vitro systems have shown genetic toxicity. Hexavalent chromium compounds cause cancer in humans, in experimental animals and exert genetic toxicity in bacteria and in mammalian cells in vitro. Epidemiological evidence and animal experiments indicate that the slightly soluble hexavalent salts are the most potent carcinogens, but proper identification and characterization of exposure patterns in epidemiological work are lacking. Workers also tend to have mixed exposures. Soluble and slightly soluble salts are equally potent genotoxic agents in vitro. Further work for establishing dose estimates for risk evaluation in epidemiological work is important. In vitro systems should be applied for further identification of the mechanism of the carcinogenic effects, and animal experiments are urgent for comparison of the carcinogenic potency of the different hexavalent salts. Hexavalent chromium salts must be regarded as established carcinogens, and proper action should be taken in all industries with regard to such exposure. At present the carcinogenic risk to the general population caused by chromium compounds seems to be negligible, chromium in cigarettes, however, is an uncertainty in this respect. The amount of chromium and the type of chromium compounds inhaled from cigarettes is not known.

Animals↗

Skin permeation and cutaneous hypersensitivity as a basis for making risk assessments of chromium as a soil contaminant.

A literature review of experimental and human exposure studies of skin permeation and cutaneous hypersensitivity reactions evoked by chromium was carried out to provide a basis for making a risk assessment of chromium as a soil contaminant. In vitro and in vivo studies demonstrated that 1 to 4% of the applied dose of hexavalent and trivalent chromium to guinea pig skin penetrated skin within 5 to 24 hr after application. Ultrastructural investigations showed that hexavalent chromium localized intracellularly and extracellularly in the upper layers of guinea pig epidermis. Only minute quantities of hexavalent chromium are required to elicit a positive hypersensitivity reaction in susceptible individuals; using a patch dose of 20 micrograms, only 2 micrograms were required to evoke a positive skin reaction in hypersensitive subjects. The potential of hexavalent chromium to produce a skin sensitization reaction is readily demonstrated using animal models. The incidence and characteristics of chromium-induced skin hypersensitivity as a clinical entity are described. A health effects survey of populations exposed to chromium slag in soil in Tokyo, Japan extending over 8 years indicated a tendency toward symptoms characterized as headache, chronic fatigue, and gastrointestinal complaints, positive occult blood tests, minute hematuria and albuminuria suggestive of incipient renal disease, and a tendency toward an increase in contact dermatitis that was seasonally related. Multicenter patch test titration studies in human subjects using an incidence of positive patch tests of 10% or less showed that the threshold for skin hypersensitivity reactions to hexavalent chromium was determined to be of the order 0.001%, equivalent to 10 ppm or 10 mg/kg or 10 mg/L.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

The inter-relationship between insulin and chromium in hyperinsulinaemic euglycaemic clamps in healthy volunteers.

Evidence in the literature suggests that the trace element chromium may have a role in glucose homeostasis through the regulation of insulin action. We have previously reported a significant reduction in plasma chromium levels in healthy individuals, following a 75 g oral glucose load, and after meals and glucose-dependent uptake of chromium in insulin-dependent tissues in vitro. However, in vivo it is unclear whether the changes in plasma chromium relate to changes in plasma glucose or insulin. The present study describes a series of euglycaemic hyperinsulinaemic clamps designed to attempt to define the initiator of changes in plasma chromium levels in ten healthy individuals. The data showed a significant (P < 0.01) reduction in fasting plasma chromium levels following glucose infusion and an initial bolus of insulin. Significant (P < 0.02) increases in post-clamp urinary chromium excretion were insufficient to explain the decrease in plasma levels. During the recovery phase of an extended two-phase clamp protocol we found plasma insulin levels decreased by 70% within 10 min, associated with an increase in plasma chromium levels of 30% and no significant change in plasma glucose level. These data indicate that alterations in plasma glucose are unlikely to be directly related to changes in plasma chromium, whilst supporting the hypothesis that plasma insulin may influence plasma levels of this trace element. In contrast, plasma zinc was unaffected throughout these clamp studies.

Adult↗

Synergism of ascorbic acid and glutathione in the reduction of hexavalent chromium in vitro.

The reduction of 20 microM hexavalent chromium [chromium(VI)] in single-reductant solutions of 0.02-2 mM L-ascorbic acid (L-AsA) or 2 mM reduced glutathione (GSH), and in mixed solutions of 2 mM GSH containing L-AsA of the above-described concentrations was investigated at physiological pH (37 degrees C). The reduction of chromium(VI) in the L-AsA solutions of higher concentrations showed pseudo-first-order kinetics in a single phase with respect to chromium(VI). In the lower L-AsA concentrations, pseudo-first-order processes appeared only in an early stage of the reaction. The reduction in the GSH solution was characterized by a two-phase process. In the first phase, which appeared in very short duration, the reaction rate was much higher than that in the second, but resulted in a decrease of only 7% of the initial chromium(VI) level. The second phase showed the main process of the reduction. This indicated pseudo-first-order kinetics. The half-life values of chromium(VI) depended on the initial levels of the reductants and ranged from seconds to hours. The chromium(VI)-reducing ability of L-AsA was markedly higher than that of GSH. In the mixed solutions of L-AsA and GSH, synergistic effect on the reduction of chromium(VI) was observed, especially in earlier stages of the processes. The synergism was more conspicuous in the mixed solutions containing lower L-AsA levels. These results suggest that although AsA possesses higher reducing ability than GSH, their coexistence is of importance for the reduction of chromium(VI) in biological systems because of their synergism.

Ascorbic Acid↗

Effect of long-term ingestion of chromium compounds on aggression, sex behavior and fertility in adult male rat.

The effects of long-term ingestion of chromium chloride (trivalent compound) and potassium dichromate (hexavalent compound) was investigated on sexual behavior, aggressive behavior and fertility in male rats. Adult male rats were exposed to chromium chloride and potassium dichromate in drinking water at a concentration of 1000 ppm for 12 weeks. The exposure of male rats to chromium chloride and potassium dichromate reduced the number of mounts. The exposure of male rats to potassium dichromate increased the time to ejaculation. On the other hand, the exposure of male rats to chromium chloride and potassium dichromate increased the post ejaculatory interval. The number of animals ejaculating were reduced in chromium chloride and potassium dichromate exposed male rats. The exposure of male rats to chromium chloride and potassium dichromate decreased lateralizations, boxing bouts and fights with stud male. The exposure of male rats to chromium chloride and potassium dichromate had no effect on fertility. Testes, seminal vesicle and preputial gland weights were significantly reduced in chromium chloride- and potassium dichromate-exposed males. In conclusion, the long-term ingestion of chromium chloride and potassium dichromate would have adverse effects on sexual behavior and territorial aggression in adult male rat.

Animals↗

Mechanisms of chromium carcinogenicity and toxicity.

Chromium, like many transition metal elements, is essential to life at low concentrations yet toxic to many systems at higher concentrations. In addition to the overt symptoms of acute chromium toxicity, delayed manifestations of chromium exposure become apparent by subsequent increases in the incidence of various human cancers. Chromium is widely used in numerous industrial processes, and as a result is a contaminant of many environmental systems. Chromium, in its myriad chemical forms and oxidation states, has been well studied in terms of its general chemistry and its interactions with biological molecules. However, the precise mechanisms by which chromium is both an essential metal and a carcinogen are not yet fully clear. The following review does not seek to embellish upon the proposed mechanisms of the toxic and carcinogenic actions of chromium, but rather provides a comprehensive review of these theories. The chemical nature of chromium compounds and how these properties impact upon the interactions of chromium with cellular and genetic targets, including animal and human hosts, are discussed.

Animals↗

Elimination of chromium in urine after stainless steel welding.

Nine retired (on an average of four years) stainless steel welders had higher (p less than 0.001) urinary chromium levels [mean 7 (range 3-13) mumol/mol of creatinine] than 21 nonexposed referents [mean less than or equal to 1.5 (range less than 0.6-7) mumol/mol of creatinine] but did not differ in this respect from 14 active welders studied at the end of a 31-d vacation (mean 9, range 4-17). This result shows the existence of a slow compartment for chromium in the body. Urinary chromium on time after the end of exposure was analyzed mathematically by use of an exponential two-compartment model. Good fits were obtained, showing the existence of a fast compartment in addition to the slow one. For four welders followed for 31 d, the biological half-time of the slow compartment ranged from 14 d to infinity. For 12 welders followed for 60 h, the fast compartment had a median half-time of 7 (range 4-35) h. For 19 welders there was a significant (p less than 0.01) correlation between chromium in air (total and soluble hexavalent) and urinary chromium (rs = 0.68 and 0.64). However, the variation of urinary chromium on chromium in air was considerable, especially at chromium air levels at or below the hygienic standards. Correction for urinary chromium levels on Monday morning did not decrease the variation.

Adult↗

Co-removal of hexavalent chromium during copper precipitation.

In our recent study using the nucleated precipitation technology to treat plating wastewater, it was found that about one half of hexavalent chromium was co-removed with copper, nickel and zinc. Since hexavalent chromium could not react with either hydroxide or carbonate to from precipitates, this study was undertaken to evaluate the mechanism(s) involved in the chromium co-removal. Batch tests were conducted with synthetic solutions containing either only copper or both copper and hexavalent chromium. Metal precipitation was induced by adding Na2CO3 to different pH, and the quantitative removal of copper and chromium was determined. Besides, the [Cr]/[Cu] molar ratio of produced precipitates were also assessed in conjunction with the EDAX analysis to determine their compositions. Experimental results indicate that for pure copper solution, precipitation begins at pH 6.0, and completes at pH 7.0. The chemical forms of the precipitates are copper carbonates [CuCO3 x Cu(OH)2 and CuCO3 x 2Cu(OH)2]. On the other hand, in a bi-metal solution of copper plus chromium, precipitation of copper begins at about pH 5.0, and copper precipitation is always accompanied by some chromium removal. From the removal stoichiometry of the two metals, it is found that at low pH, the co-removal is a result of "co-precipitation" which results in the formation of CuCrO4 crystallites. Once such crystallites are formed, they provide a heterogeneous environment which enhances an early formation of copper carbonate at a lower pH (below 5.5). It is further found that once copper carbonate precipitates are produced, the remaining soluble will precipitate in such form, and at this stage further removal of copper is no longer accompanied by additional chromium removal. The test data also reflect that the produced copper carbonates are positively charged, as verified by zeta potential measurement, at pH below 7.5. Thus they are able to adsorb some anionic chromium (existing as chromate) through electrostatic attraction and/or inorganic ligand exchange. At pH of 6 to 10, the extent of adsorption decreases with increasing pH, and the adsorption capacity seems to coincide with the progressive reduction of positive zeta potentials of the precipitated particles.

Adsorption↗

Distribution, origin and fate of chromium in soils in Guanajuato, Mexico.

Total, hexavalent and trivalent chromium were determined in surface and 30-cm depth soil samples from a highly chromium-polluted area in Guanajuato state, central México. Four samples were also analyzed by a sequential extraction procedure. Nearly 0.9 km(2) out of the 8 km(2) area sampled was polluted with chromium, at concentrations up to 12960 mg kg(-1), mostly as Cr(III). Concentrations of Cr(VI) were lower than 0.5 mg kg(-1) in most sampled points, with the exception of one, where the concentration was found to be 65.14 mg kg(-1). Chromiumcontaining dust from a chromate factory accounted for most of the contamination. The highest concentrations of hexavalent chromium in soil, were in the bottom sediments of an abandoned water reservoir used to store polluted water from a well, before use of the water in the factory process. Tannery wastes, dust from a sanitary landfill of chromate compounds and the transport of chromium products are the sources of chromium at other sites. Chromium is fixed preferentially in the hydrous Fe and Mn oxides in the more polluted soils. Less polluted soils have a high proportion of chromium associated with the sulfide and organic fraction. Cr(III) is retained preferentially in the superficial soil layer. Variations in the physical characteristics of the soil, relative abundance of the various soil components and characteristics of the contaminant source, give rise to differences in chromium soil concentrations with depth.

Journal Article↗

Chromium picolinate, rather than biotin, alleviates performance and metabolic parameters in heat-stressed quail.

1. The effects of chromium picolinate and biotin supplementation alone and in combination on performance, carcase characteristics, malondialdehyde (MDA), vitamin C, vitamin E, glucose and cholesterol levels were evaluated in Japanese quail exposed to high ambient temperature. 2. Two hundred and forty quails (10d old) were assigned randomly to 4 dietary treatments at room temperature (22 degrees C; thermoneutral, TN) or ambient (34 degrees C for 8 h/d; heat stress, HS). Both TN and HS were fed either on a basal (control) diet or the basal diet supplemented with 400 microg of Cr/kg (Cr group), 0.5 mg of biotin/kg of diet (biotin group) or both (Cr + Biotin group). 3. Supplementing the diet of heat-stressed quails with chromium picolinate improved live weight gain, feed intake, feed efficiency and carcase traits. Biotin supplementation during TN and HS conditions did not have any beneficial effects on body weight gain, feed intake, feed efficiency or carcase traits. 4. Either in combination or alone, chromium picolinate increased serum concentrations of vitamins C and E, but decreased MDA, glucose and cholesterol concentrations in birds kept at high ambient temperature. There was no difference in vitamins C and E and MDA concentrations between birds given chromium picolinate and birds receiving chromium picolinate plus biotin, while glucose and cholesterol levels were significantly lower in all groups. The lowest concentrations of cholesterol and glucose were found in the combination group under both TN and HS conditions. An interaction between diet and temperature was detected for glucose and cholesterol concentrations. 5. Excretion rates for zinc, iron and chromium were lower in TN groups than in the corresponding HS groups. Supplementing diet with chromium picolinate and chromium picolinate plus biotin decreased excretion of minerals while biotin alone did not effect excretion of minerals. 6. Chromium supplementation, but not biotin supplementation, attenuated the decline in performance and antioxidant status resulting from heat stress.

Animals↗

Chromium picolinate supplementation and resistive training by older men: effects on iron-status and hematologic indexes.

Chromium competes with iron for binding to transferrin, and high-dose chromium supplementation has been hypothesized to adversely affect iron status. This study examined the effects of chromium picolinate supplementation on hematologic indexes and selected indexes of iron status in 18 men aged 56-69 y who participated in an introductory resistive training program. The men were randomly assigned (double-blind design) to groups (n = 9) that consumed either 17.8 mumol Cr/d (924 micrograms Cr/d) as chromium picolinate or a low-chromium placebo for 12 wk while engaging in resistive training twice weekly (3 sets of 8-12 repetitions at 80% of one repetition maximum for 5 exercises). Hematocrit, hemoglobin, red blood cell (erythrocyte) count, mean corpuscular volume, mean corpuscular hemoglobin, mean corpuscular hemoglobin concentration, red blood cell distribution width, platelet count, and mean platelet volume were within normal clinical ranges and were unchanged by either chromium picolinate supplementation or resistive training. Resistive training decreased total-iron-binding capacity from 38.4 +/- 9.3 to 27.3 +/- 5.6 mumol/L (P < 0.0001) and increased transferrin saturation from 35.7 +/- 16.3% to 45.4 +/- 16.9% (P = 0.050). Chromium picolinate supplementation did not influence these responses. Serum iron concentrations and serum ferritin concentrations were unchanged by either resistive training or chromium picolinate supplementation. These data suggest that high-dose chromium picolinate supplementation for 12 wk did not influence hematologic indexes or indexes of iron metabolism or status in older men. The decrease in total-iron-binding capacity and increase in transferrin saturation (%) with resistive training are largely opposite to changes associated with iron depletion and suggest a novel effect of resistive training on iron transport.

Aged↗