Hair Copper Research Articles

Method of determination of low copper concentration in human hair and nails

A graphite furnace atomic absorption spectrometry (GF-AAS) method was developed for the determination of copper in selected alternative materials. The method is characterised by a low limit of detection, good accuracy and satisfactory precision, while the duration of a single measurement is approximately 80 s. It allowed an application of the developed method to determine copper in small samples of hair and nails with equipment available in most analytical laboratories. The developed GF-AAS method was successfully applied to routine analyses using samples collected from healthy humans. The study has shown similar concentration of copper in fingernails and toenails collected from women and men, which was 2–3 times lower than concentration of this element in hair of both genders. The correlation between concentration of copper in nails and hair allows one to use hair, fingernails and toenails as invariable materials for the evaluation of chronic exposure to copper.

Development and analytical validation of an Enzyme-Linked Immunosorbent Assay (ELISA) for the detection of copper in human hair and serum samples

An indirect competitive Enzyme-Linked Immunosorbent Assay (IC-ELISA) based on an anti-chelated copper monoclonal antibody DF4 was developed and analytically validated for Cu2+ detection in human hair and serum samples and its performance was compared with Atomic Absorption Spectrometry (AAS). The assay was validated by determination of the lower limit of detection, accuracy, linearity, precision, and reproducibility. The limits of detection were 0.029 μg mL−1 for human serum and 0.032 μg g−1 for human hair. The ratios for spiking recovery were from 80.2% to 108.6% for serum, and 95.3% to 106.79% from hair for two certified reference materials (CRM). The mean ratios of found to expected values for dilutional parallelism were 91.72 ± 3.39% for serum, and 97.28 ± 6.7% for hair. The coefficients of variation for intra- and inter-assay variability were <11.70% and <15.29% for serum, <14.02% and <16.40% for hair, respectively. The standardized IC-ELISA showed reliability and a high correlation with AAS of 0.983. We concluded that the ELISA described here was sufficiently sensitive, linear, accurate, precise, and reproducible for clinical evaluation. The availability of this assay may create a new research and diagnostic tool for copper measurement.

Determination of Copper in Water, Vegetables, Foodstuffs and Pharmaceuticals by Direct and Derivative Spectrophotometry

The quantification of copper in water, vegetables, foodstuffs, human hair and pharmaceutical samples was determined by a simple more sensitive and selective spectrophotometric method. Cu(II) forms an orange - red color complex with 5-{� -methyl-3-hydroxy benzylidene} rhodanine (5M, 3H-BR), at pH 5.5 in sodium acetate and acetic acid buffer. The maximum absorbance was measured at 430 nm. The Beer's law is obeyed in the range of (0.05 µg -13 µg/mL). The molar absorptivity ( �) and the Sandell's sensitivity of the complex were 0.6027 × 10 4 mol -1 cm -1 and 0.01054 µg cm -2 respectively. First, second and third derivative spectrophotometry were also proposed and employed successfully for the determination of copper in the supra. The performance of the present method was also evaluated in terms of RMSEP, REP and RSD, students t- test. This indicates the greater importance of the method than other methods reported in the literature.

Determination of copper in human hair and tea samples after dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO)

A simple method of dispersive liquid-liquid microextraction-solidified floating organic drop (DLLME-SFO) prior to flame atomic absorption spectrometry was successfully used for separating and preconcentrating copper in human hair and tea samples. The proposed method was simple, cheap, and has high precision. In this study, optimization of experimental parameters influencing the extraction, such as type and volume of extraction and disperser solvents, pH, the amount of chelating agent and extraction time was normally carried out using a step-by-step approach, in which each factor was varied sequentially. The effect of the interfering ions on the analytes recovery was also investigated. The calibration graph was linear in the range of 5-200 ng mL-1 with limit of detection of 3.4 ng mL-1. The relative standard deviation (RSD) was 0.7% (n = 10, C = 2 ng mL-1) and the enhancement factor was 28.

Heavy Metals in Hair of Wild Canids from the Brazilian Cerrado

In this study, we aimed to assess whether free-ranging wild canids are exposed to heavy metals in one of the most developed and populated regions of Brazil. Hair of 26 wild canids (maned wolves Chrysocyon brachyurus, crab-eating foxes Cerdocyon thous, and hoary foxes Lycalopex vetulus) from the Cerrado biome in Southeast Brazil were analyzed by spectrophotometry to detect cadmium, chromium, and lead, and also the essential copper, iron, manganese, and zinc traces. All samples showed traces of copper, iron, manganese, and zinc. Non-essential lead was detected in 57% (2.35 ± 0.99 mg/kg), and chromium in 88% (2.98 ± 1.56 mg/kg) of samples. Cadmium traces (detection limit 0.8 mg/kg) were not found. Crab-eating foxes had more copper, iron, and manganese in hair than maned wolves. Correlations among element levels differed between maned wolves and crab-eating foxes. Concentrations of chromium and lead were outstandingly higher than in wild canids from other areas. Addressing the causes of such levels and the impacts of the heavy metal pollution in Neotropical ecosystems is urgent for animal health and conservation purposes. We argue that heavy metal pollution should be considered as dangerous threats to wildlife health in Brazil and recommend hair sampling as a biomonitoring tool for heavy metals in Neotropical terrestrial mammals.

A Comparison of Levels of Select Minerals in Scalp Hair Samples with Estimated Dietary Intakes of These Minerals in Women of Reproductive Age

The objective of this study was to evaluate daily intake of minerals and concentrations of minerals in hair in women of reproductive age. The study included 77 menstruating women, aged 35.9 ± 9.7 years. Subjects were divided into three groups according to age. All women were healthy. Hair samples were taken from several points of the occipital scalp. The content of minerals in hair samples was determined by flame atomic absorption spectrometry. Dietary intake of the analysed minerals was assayed on the basis of dietary intake interviews from three preceding days and evaluated using the dietetic computer programme. It was shown that calcium and iron daily intake by the women was below the recommended value. Only few women had low concentrations (below reference values) of magnesium, copper and zinc in hair. Statistically significant differences were shown between age groups. Generally, the concentrations of minerals in hair in the younger (19–30 years) and the older women (41–50 years) were higher than in hair of middle-aged women (31–40 years). The content of calcium, magnesium, iron and zinc in daily diets of women correlated inversely with copper level in their hair. Food products with good bioavailability of iron and calcium should be recommended for women of childbearing age in all age groups.

A rapid solid sampling method for determination of nickel and copper along human hair by ETAAS

A procedure for copper and nickel determination in scalp hair by solid sampling electrothermal atomic absorption spectrometric method was described. The hair samples (0.02 to 0.4 mg) were inserted directly on the platforms of solid sampling autosampler. The effects of pyrolysis temperature, atomization temperature, the amount of sample as well as addition of a modifier (Pd/Mg) and/or auxiliary digesting agents (hydrogen peroxide and nitric acid) and/or a surfactant (Triton X-100) on the determination of copper and nickel by solid sampling atomic absorption spectrometry were investigated. After optimization of parameters, the average recoveries of copper in two different certified reference hair samples were 105.7 and 97.6%. The recoveries of nickel in the both certified reference hair samples were in 95.2 and 96.4%. The limits of detection (3σ, N = 10) for copper and nickel were 22 ng/g and 35 ng/g, respectively. Heterogenous distribution of analyte in microscale for segmental analysis could be determined which is important to know that analyte quantity and time of poisoning of a person was exposed. For this purpose, 0.5 cm of pieces were cut along one or a few close strands and analyzed by solid sampling. This process could not be performed by wet-digestion method because 50 mg of sample is needed each time. Finally, the method was applied for the determination of copper and nickel concentrations in the hairs of different persons.

Lead, cadmium, copper, zinc, iron, and calcium in human hair as a function of gender, age, smoking, and hair dyeing

Hair samples were collected randomly from 110 subjects (55 male and 55 female) ranging in age from (<15–60) years. Each subject was asked to complete a personal questionnaire describing his/her sex, age, general health, smoking, use of hair dyes, occupational area, and living habits. Concentrations of Pb, Cd, Cu, Zn, Fe, and Ca in human hair samples were evaluated using atomic absorption spectrometry. Results indicated that concentrations of Pb, Cd, Cu, and Zn in the hair of smokers were higher than those in the hair of non-smokers, whereas, Fe and Ca concentrations in hair of smokers were lower than those in hair of non-smokers. Moreover, the concentrations of these elements are higher in dyed hair compared with undyed hair.

Evaluation of Status of Zinc, Copper, and Iron Levels in Biological Samples of Normal Children and Children with Night Blindness with Age Groups of 3–7 and 8–12 Years

The causes of night blindness in children are multifactorial, and particular consideration has been given to childhood nutritional deficiency, which is the most common problem found in underdeveloped countries. Such deficiency can result in physiological and pathological processes that in turn influence hair composition. This study was designed to compare the levels of zinc (Zn), copper (Cu), and iron (Fe) in scalp hair, blood, and urine of both genders of children with night blindness with age range of 3-7 and 8-12 years, comparing them to sex- and age-matched controls. A microwave-assisted wet acid digestion procedure was developed as a sample pretreatment, for the determination of zinc, copper, and iron in biological samples of children with night blindness. The proposed method was validated by using conventional wet digestion and certified reference samples of hair, blood, and urine. The digests of all biological samples were analyzed for Cu, Fe, and Zn by flame atomic absorption spectrometry using an air/acetylene flame. The results indicated significantly lower levels of Fe, Cu, and Zn in the biological samples (blood and scalp hair) of male and female children with night blindness, compared with control subjects of both genders. These data present guidance to clinicians and other professionals investigating the deficiency of essential trace metals in biological samples (scalp hair and blood) of children with night blindness.

Low-Potential Electrochemiluminescent Sensing Based on Surface Unpassivation of CdTe Quantum Dots and Competition of Analyte Cation to Stabilizer

A novel electrochemiluminescent (ECL) sensing system was constructed for low-potential detection of metal ion by immobilizing surface-unpassivated CdTe quantum dots (QDs) on a glassy carbon electrode. The surface-unpassivated CdTe QDs were prepared using meso-2,3-dimercaptosuccinic acid (DMSA) as a stabilizer to cap CdTe QDs and characterized with scanning electron micrograph and X-ray photoelectron spectroscopy. The immobilized QDs showed a strong cathodic ECL emission peak at -0.87 V with an onset potential at -0.64 V (vs Ag/AgCl/saturated KCl) in air-saturated, pH 9.0 HCl-Tris buffer. On the basis of the competition of metal ion to the stabilizer, the quenching effect of metal ion on ECL emission was observed, which led to a sensitive chemical sensing application. Using cupric cation as a model analyte, the sensor showed a linear range from 5.0 nM to 7.0 muM with a detection limit of 3.0 nM and had been successfully applied in the detection of copper in human hair. It could be extended to detect other metal ions with stronger metal-S interaction than with the Cd-S bond. As an example, the sensor could be used to detect Hg(2+) down to 1.4 nM. The bidentate chelate QD-based sensor exhibited a promising platform for rapid detection of cations with strong metal-S interaction and could be further applied for development of other low-potential electrochemical sensing systems.

Copper and calcium uptake in colored hair

During hair coloring a number of disulfide bonds in cystine are oxidized (1) to create cysteic acid, forming binding sites for metal ions such as Ca(2+ )and Cu(2+ )from tap water (2). The increased uptake of these metals can have a detrimental impact on fiber properties-for example, reducing shine and causing a poor wet and dry feel (3). In addition, the increased uptake of copper can also contribute to further fiber damage during subsequent coloring due to its ability to take part in metal-induced radical chemistry (4). It is important to know where in the fibers these metals are located in order to either effectively remove these metals or control their chemistry. Nanoscale secondary ion mass spectrometry (NanoSIMS) has been used to locate the calcium and copper within hair that has been treated with a colorant and washed multiple times in tap water containing these ions. Untreated hair is used as a baseline standard material. Images with up to 50-nm spatial resolution of the preferential locations of calcium uptake were obtained, showing a high concentration of calcium in the cuticle region of colored hair, specifically in the sulfur-rich regions (A-layer and exocuticle).

Dietary Intake and Serum and Hair Concentrations of Minerals and their Relationship with Serum Lipids and Glucose Levels in Hypertensive and Obese Patients with Insulin Resistance

Inadequate minerals intake, as well as disruption of some metabolic processes in which microelements are cofactors, are suggested to lead to the development of hypertension. The role of minerals in the pathogenesis of hypertension still remains to be explained. In the present study, we sought to determine associations between serum and hair mineral concentrations and serum lipids and glucose levels. Forty obese hypertensive subjects with insulin resistance and 40 healthy volunteers were recruited in the study. Blood pressure, BMI, and insulin resistance were recorded in all subjects. Levels of lipids, glucose, sodium and potassium, iron, copper, zinc, magnesium, and calcium were assessed in serum. Iron, copper, zinc, magnesium, and calcium were assessed in hair. Dietary intake of the analyzed minerals was estimated. We found distinctly higher concentrations of serum iron and serum and hair calcium as well as markedly lower levels of hair zinc in the hypertensive subjects. The study group manifested also significantly lower daily intake of calcium, magnesium, and iron. We observed a relationship between the concentrations of iron, zinc, and copper in serum and hair and high and low range of cholesterol, triglycerides, and glucose serum levels in the studied patients. Moreover, this study demonstrated significant correlation between serum and hair concentrations of selected minerals and their dietary intake and levels of serum lipids and glucose and blood pressure in the study and the control groups. The obtained results seem to indicate the association between lipid and glucose metabolism and iron, copper, zinc, and calcium concentrations in blood and hair of hypertensive and obese patients with insulin resistance.

Accumulation of lead, cadmium, nickel and copper in hair of people living near heavy traffic area

Accumulation of Pb, Cd, Ni and Cu in the hair of 462 males living near heavy traffic area and less traffic area in various parts of Rajasthan (India) was studied. Out of 462, 231 lived near heavy traffic area and remaining lived near less traffic area. Head hair samples from nape were obtained from subject under study alongwith filling up of a questionnaire recommended by World Health Organisation. Hair samples were washed, digested to get a colourless and clear solution and then analysed by AAS for Pb, Cd, Ni and Cu concentration. Subjects were grouped into four age groups of 21 to 30 years, 31 to 40 years, 41 to 50 years, 51 to 60 years. While significant concentration of Pb was found in all age groups of people living near heavy traffic area as compared to people living near less traffic area, that of Ni was not significant. Difference in Cd and Cu concentration of hair of people living near heavy traffic area and less traffic area was not found significant in all age groups.

On-line solid phase extraction system using 1,10-phenanthroline immobilized on surfactant coated alumina for the flame atomic absorption spectrometric determination of copper and cadmium

An on-line solid phase extraction (SPE) preconcentration system coupled to flame atomic absorption spectrometer (FAAS) was developed for determination of copper and cadmium at μg L −1 level. The method is based on the on-line retention of copper and cadmium on a microcolumn of alumina modified with sodium dodecyl sulfate (SDS) and 1,10-phenanthroline and subsequent elution with ethanol and determination by FAAS. The effect of chemical and flow variables that could affect the performance of the system was investigated. The relative standard deviation ( n = 6) at 20 μg L −1 level for copper and cadmium were 1.4 and 2.2% and the corresponding limits of detection (based on 3σ) were 0.04 and 0.14 μg L −1, respectively. The method was successfully applied to determination of copper and cadmium in human hair and water samples.

Copper and Zinc Levels in Hair of Both Schizophrenic and Depressed Patients

The aim of this paper is to estimate hair copper and zinc levels in schizophrenic and depressed patients and to correlate these levels to the severity of schizophrenia and major depressive disorder. The study was carried on 80 male and female persons with their ages between 20 -40 years. Twenty of them were healthy and helped as control, 30 were suffering from schizophrenia (group I) and 30 were suffering from major depressive disorder (group II). Exclusion criteria included pregnancy, another co-morbid psychiatric disorders and drugs known to affect trace element metabolism. Approximately 100 mg of scalp hair samples were cut from each person. Zinc and copper levels in the hair samples were determined by atomic absorption spectrophotometry after wet ashing. The mean hair copper level was significantly higher in both schizophrenic patients (group I) and depressed patients (group II) when compared with their corresponding mean level in healthy control group. On the other hand, the mean hair zinc level was significantly lower in both schizophrenic patients (group I) and depressed patients (group II) when compared with its mean level in the healthy control group. In depressed patients, the mean hair copper level was insignificantly higher while, the mean hair zinc level was significantly lower when compared with their corresponding mean level in schizophrenic patients. From these results, it can be concluded that copper excess and zinc deficiency may have a role in the pathogenesis of either schizophrenia and/ or depressive disorders. It can also be concluded that zinc deficiency may have more important role in inducing depressive disorders. So, it is recommended to evaluate both copper and zinc hair and serum levels in schizophrenic and depressed patients especially in those resistant to the traditional therapy measures. Moreover, this may have a prognostic value. It is recommended also to use zinc supplementation during antidepressant therapy as it may improve response to therapy and/ or decrease the antidepressant dose that can minimize the side effects.

Changes of selenium, copper, and zinc content in hair and serum of patients with idiopathic scoliosis

Our work aimed at extending the search for abnormalities of trace elements in patients with idiopathic scoliosis to the content of zinc (Zn), copper (Cu), and selenium (Se) in these subject's hair and serum. A total of 59 patients (54 girls and 4 boys) with idiopathic scoliosis, aged 13 on the average (range, 10-18 years), were examined. The degree of spine curvature deformity ranged between 12 degrees and 82 degrees . The hair of scoliotic patients under examination showed significantly increased content of zinc 263 +/- 108 microg/g (p < 0.01) and copper 46.2 +/- 37.1 microg/g (p < 0.01), and decreased content of selenium 0.194 +/- 0.114 microg/g (p < 0.01) in comparison with the control group. In scoliotic patients, the Cu/Zn ratio in hair (0.186 +/- 0.139) did not differ significantly from the values found in the probands of the control group (0.115 +/- 0.09). The Cu/Se ratio in this group of patients (254.9 +/- 215.9) was significantly higher (p < 0.001) due to a higher Cu value and a lower Se value in comparison with the controls (47.9 +/- 23.7). In comparison with controls, the serum selenium concentration in the group of scoliotic patients was significantly decreased p < 0.05 (0.74 +/- 0.13 micromol/L and 0.98 +/- 0.12 micromol/L). Various changes in the content of trace elements in biological samples taken from patients with idiopathic scoliosis are not accidental. What might bring about a shift in our knowledge is speciation of various forms of trace elements in the organism in relation to idiopathic scoliosis.

Correlation of Calcium, Copper, Iron, Magnesium and Zinc Content in Hair with Basal Metabolic Rate and Bioelectrical Impedance in Adolescent Females

Objective The aim of this study was to investigate the correlation of calcium, copper, iron, magnesium and zinc content in hair with basal metabolic rate (BMR), expressed as kilocalories per body weight in kilograms (kcal/kg), and bioelectrical impedance percentage (BI%) in adolescent females. Materials and Methods One hundred and forty-eight adolescent females with differing BMR and BI% were randomly enrolled, and the calcium, copper, iron, magnesium and zinc content of their hair were simultaneously measured by an atomic absorption spectrophotometer. Results Positive correlations of iron β = 0.3326; p < 0.01) and zinc (β = 0.3519; p < 0.05) content in hair with BMR were found, while inverse correlations of zinc ( b = −0.4885; p < 0.01) and iron ( b = −0.2582; p < 0.05) content in hair with BI% were found. Conclusion Iron and zinc content in hair seems to have a close relationship with BMR and BI% in adolescent females. Exactly how iron and zinc affects BMR and BI% in these subjects is still unclear and warrants further study. [ Tzu Chi Med J 2008;20(1):58–62]

The Occurrence and Incorporation of Copper and Zinc in Hair and their Potential Role as Bioindicators: A Review

This article reviews evidence that suggests Cu and Zn concentrations are not altered significantly by exogenous processes and may be useful in applications of hair analysis. The review attempts to identify what Cu and Zn concentrations may actually indicate biogenically and investigates the mechanisms by which they are incorporated into hair. Associations with specific hair components are proposed and avenues for development as a bioindicator are identified. Areas of research that offer promise in application or confirming the use of Cu and Zn are also indicated. Correlations and relationships with other health disorders are reviewed. Endogenous blood concentrations may also explain alterations in hair structure relating to breast cancer.

Determination of nickel, copper, zinc and lead in human scalp hair in Syrian occupationally exposed workers by total reflection X-ray fluorescence

The concentrations of Ni, Cu, Zn, and Pb in human scalp hair of 281 individuals working in 10 Syrian industrial plants were determined using co-precipitation by ammoniumpyrolidinedithiocarbamate (APDC) method for total reflection X-ray fluorescence (TXRF) analysis. The results were compared to data obtained for a control group consisted of individuals working at the Syrian Atomic Energy Commission and also to data reported in the literature. The results given by the group of workers in battery plant showed that Pb concentration in human scalp hair samples were higher than those for control group, while some abnormal concentrations were obtained for Cu, Zn and Ni in cables, printing and battery plants, respectively. Normal concentrations of these elements were obtained for hair workers in olive oil, power stations, textile, and iron industrial plants. The relationships of Pb-Pb/Ni and Cu-Cu/Ni were plotted with correlation coefficients of 0.9937 and 0.9014, respectively. In general, the results showed that, the workers who were occupationally exposed to battery industrial pollution are at risk, followed by individuals in printing and cables industries, while the rest of workers in other industries are considered occupationally unexposed.

Determination of zinc and copper in human hair by slurry sampling employing sequential multi-element flame atomic absorption spectrometry

The present work proposes a direct method based on slurry sampling for the determination of zinc and copper in human hair samples by multi-element sequential flame atomic absorption spectrometry. The slurries were prepared by cryogenic grinding and sonication of the samples. The optimization step was performed using univariate methodology and the factors studied were: nature and concentration of the acid solution, amount sample/slurry volume, sonication time, and particle size. The established experimental conditions are the use of a sample mass of 50 mg, 2 mol L − 1 nitric acid solution, sonication time of 20 min and slurry volume of 10 mL. Adopting the optimized conditions, this method allows the determination of zinc and copper with detection limits of 88.3 and 53.3 ng g − 1 , respectively, and precision expressed as relative standard deviation (RSD) of 1.7% and 1.6% (both, n = 10) for contents of zinc and copper of 100.0 and 33.3 μg g − 1 , respectively. The accuracy was checked and confirmed by analysis of two certified reference materials of human hair. The procedure was applied for the determination of zinc and copper in two human hair samples. The zinc and copper contents varied from 100.0 to 175.6 and from 3.2 to 32.8 μg g − 1 , respectively. These samples were also analyzed after complete digestion in a closed system and determination by FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.