Elemental contamination of Japanese women's hair from historical samples

Japanese women's hair, which had been cut in the past and preserved was examined for the presence of 12 elements (Na, K, Mg, Ca, Sr, Mn, Fe, Cu, Zn, Hg, Pb and P). Elevated levels of Fe, Mn, Cu, Pb and Hg (inorganic mercury) were conspicuous in the samples cut in the period 1880-1929 and used as hair pieces (kamoji). The effects of washing on element concentration depended on both the method of washing and the type of element. The least effective was washing with acetone and water, compared with two other methods involving anionic or non-ionic surface active agents. The most resistant elements to washing were Pb, Hg, Cu and Zn. From the intercorrelation of element content and factor analysis, by examining the diminution of contents by washing and by comparing the detected levels with the values measured on contemporary Japanese women's hair, the contribution of exogenous contamination to hair levels was found to be very strong for Fe, Mn, Cu, Hg (inorganic mercury), and Pb, moderate for Na and Zn, and negligible for Ca, Mg, Sr, K, Hg (organic mercury), and P.     

Scalp hair analysis as a tool in assessing human exposure to heavy metals (S. Domingos mine, Portugal)

Hair samples from the scalp were used in a preliminary assessment of heavy metals exposure (As, Cd, Cr, Cu, Mn and Zn) of the human population living near an abandoned cupric pyrite mine (Mina de S. Domingos, Southeast Alentejo, Portugal). In parallel with the collection of hair samples, individuals from two different communities at the South and North of the mine area answered a questionnaire designed to obtain information about potential exposure pathways to these elements. The questionnaire allowed data collection about the most frequently consumed foodstuffs, drinking water sources, smoking habits, alcohol consumption and health condition. Higher concentrations, and subsequently higher ranges, of Cd, Cu and As were recorded in individuals living near the mine (MSD group), in opposition to individuals living several kilometers apart. Additionally, the concentrations recorded in the hair of some individuals from the MSD group were above the reference values for non-exposed individuals, suggesting their enhanced exposure. However, no significant differences were found for the average concentration of these elements between villages. Individuals from the CP and SC groups presented significantly higher concentrations of Zn and Mn in scalp hair. These results were in agreement with the concentrations of these elements recorded in soil samples. The water supplies of the area do not seem to be potential sources of trace elements for human beings. In opposition, individuals that frequently consume milk and cheese obtained from cattle that usually breeds in the area presented significantly higher concentrations of As and Mn in their scalp hair. Our results suggest that the population of S. Domingos mine area and neighbour localities may be exposed to some of the elements analysed namely Mn and Zn. The most likely exposure pathways seemed to be animal foodstuffs, however, a more detailed analysis of these products, as well as garden vegetables and fruits, should be performed.     

河南焦作矿区煤矸石场地重金属对人体综合致病机理研究

煤矸石露天堆放有毒有害重金属的释放,对矿区自然生态环境造成污染的同时,也对人体健康产生严重危害。它们通过食物链进入人体,严重威胁人体的健康,导致人体发生多种的疾病。为查清煤矸石场地重金属对人体致病机理,本次分别取研究区接触组、对照组的人体血样、尿样、发样中Cu、Zn、Pb、Cd等重金属元素进行了人体健康医学检测。结果表明,除Cu外,接触组的重金属Pb、Cd、Zn平均检测值都明显较对照组高。导致这一状况与矿区采矿、选矿、洗矿等工业活动以及煤矸石山长期露天堆放造成周边环境污染存在一定的关系。     

Disposal of heavy metal‐contaminated sediment from Ulsan Bay,South Korea: treatment processes and legal framework

The effectiveness of two different management schemes to dispose of heavy metal‐contaminated sediments from Ulsan Bay, South Korea, soil washing and solidification/stabilization, were evaluated through a series of analyses. NaOH proved to be an effective washing reagent for As, extracting 75% of the As in sediment samples. EDTA was found to significantly enhance the extraction of Cu, Pb and Zn. However, complete removal of any metals was not achieved even after application of 100 mM concentrations of washing reagents. Therefore, a solidification/stabilization technique was applied to dredged sediment samples using ordinary Portland cement (1–40%) and fly ash (～20%). Solidified sediments did not release meaningful amount of the metals via leaching tests. Our results suggest that solidification/stabilization is a better option for effective disposal of heavy metal‐contaminated sediments than soil washing. A legal framework for the treatment of hazardous wastes and contaminated soils in Korea is discussed.     

Mobilization of some metals in water and animal tissue by NTA, EDTA and TPP

Parallel experiments were conducted under stagnant and flowing conditions to determine whether sodium tripolyphosphate (TPP), the conventional detergent builder, or two potential replacements, nitrilotriacetic acid (NTA) and ethylene—diaminetetraacetic acid (EDTA) significantly influenced the mobilization of major cations (Ca, Mg, Na, K) and some heavy metals (Fe, Mn, Zn, Cu, Pb, Cr). Water sediments and tissue of chironomid adults (Chironomus tentans Fabricius), crayfish (Orconectes virilis Hagen) and rainbow trout (Salmo gairdnerii Richardson) were examined. The results showed that the chelating agents applied in concentrations of 0.2–5.0 mg 1⁻¹ often increased the concentration of iron, manganese, lead and zinc in water above contaminated lake sediments. Other heavy metals were not affected significantly. EDTA was the most active mobilizing agent while NTA and TPP both had a less significant effect. The chelating agents generally had little effect on the rate of uptake of most metals by chironomids in aquaria. The role of chelating agents in flowing systems was even less pronounced. Zinc concentrations in water were significantly elevated by the treatment with 1 mg 1⁻¹ EDTA and manganese concentrations were significantly higher in trout from the pond treated with an intermediate level (1 mg 1⁻¹) of NTA. All other treatments yielded levels of major ions and heavy metals that were not significantly different from those in the control ponds.     

The effect of surfactants on the mixed chelate extraction-atomic absorption spectrophotometric determination of copper, nickel, iron, cobalt, cadmium, zinc and lead

Twelve surfactants representing pure cationic, anionic and non-ionic detergents, three commercial detergents, sodium pyrophosphate, sodium tripolyphosphate, a soap, nitrilotriacetic acid (NTA), EDTA, and humic acid were investigated for their effect on the extraction-atomic absorption spectrophotometric determination of copper, nickel, iron, cobalt, cadmium, zinc and lead. Cations were extracted into 10 ml of a solution containing diphenylthiocarbazone, 8-quinolinol and acetyl acetone in ethyl propionate. To avoid emulsion formation, the maximum concentration of linear alkylate sulphonate (LAS) was 10 mg l⁻¹ and for solid industrial LAS-type detergent was 50 mg l⁻¹, but washing powder did not interfere at 100 mg l⁻¹. Cationic and non-ionic detergents gave low recoveries for cobalt. Condensed phosphates at a concentration of 20 mg l⁻¹ did not cause significant interference. NTA interfered with nickel extraction and EDTA with all metals. Humic acid, however, gave no interference. A standard addition procedure can be used to correct the results.A comparison is made between the APDC-MIBK and the mixed chelate-ethyl propionate methods for the determination of trace metals in the presence of various surfactants in natural waters; the latter is preferable.     

Arsenic and other elements in hair, nails, and skin-scales of arsenic victims in West Bengal, India

For the first time, biological tissues (hair, nails, and skin-scales) of arsenic victims from an arsenic affected area of West Bengal (WB), India were analyzed for trace elements. Analysis was carried out by inductively coupled plasma-mass spectrometry (ICP-MS) for 10 elements (As, Se, Hg, Zn, Pb, Ni, Cd, Mn, Cu, and Fe). A microwave digester was used for digestion of the tissue samples. To validate the method, certified reference materials--human hair (GBW 07601) and bovine muscle (CRM 8414)--were analyzed for all elements. The W test was used to study the normal/log normal distribution for each element in the tissue samples. For hair (n=44) and nails (n=33), all elements show log-normal distribution. For skin-scale samples (n=11), data are not sufficient to provide the information about the trend. Geometric mean, standard error, and range for each element were presented and compared with literature values for other populations. This study reveals the higher levels of toxic elements As, Mn, Pb, and Ni in the tissue samples compared with available values in the literature. The elevated levels of these toxic metals in the tissues may be due to exposure of these elements through drinking water and food. The correlations of Mn and Ni with other essential elements, e.g. Fe, Cu, Zn, suggest that Mn and Ni may substitute for those elements in hair, nails, and skin-scales. However, correlation represents the relation between two elements only and does not take into consideration of the presence of other elements. Principle component analysis was applied to explain the behavior among the elements present in hair and nails. This study reveals that in the arsenic-affected areas of WB, the concentrations of other toxic elements in drinking water and foodstuff should be monitored to evaluate the arsenic poisoning.     

Relevance of hair and spines of the European hedgehog (Erinaceus europaeus) as biomonitoring tissues for arsenic and metals in relation to blood

Hair has been proven to be suitable for non-destructive and non-invasive exposure assessments in human and mammal populations. A previous study with European hedgehog (Erinaceus europaeus) showed that, for some metals, hair and spine metal concentrations were positively correlated to levels in liver, kidney and muscle. Although blood has been studied in a wide variety of species, the relationship between hair and blood metal concentrations has yet to be quantified in many mammalian species. Tissue concentrations from hedgehogs residing in a park with known metal pollution were compared with those from a reference park and correlations between contaminant levels in hair and blood, and spines and blood were studied. Moreover, the relative distribution of arsenic and metals in hair, spines and blood was determined. Elevated concentrations were found in hedgehogs residing in the polluted site for As (8.2 μg/g, 6.3 μg/g, 3.6 μg/ml), Cd (0.48 μg/g, 0.17 μg/g, 0.02 μg/ml) and Pb (7.6 μg/g, 7.3 μg/g, 54 μg/ml), in hair, spines and blood respectively. Positive correlations were identified for exposure levels between hair and blood as well as between spines and blood for three elements (As, Cd, and Pb), whereas a negative correlation was found between Cr concentrations in spines and blood. In conclusion, hair and spines can be used to monitor blood concentrations of some metals, although more data are needed on uptake from the food chain and on the incorporation dynamics of these contaminants.     

Trace element content of commercial shampoos: impact on trace element levels in hair.

Popular shampoos were screened for their contents in trace elements, using ICP-MS detection in a semi-quantitative mode. Hair samples from volunteers were analyzed before and after hair washing with selected shampoos to demonstrate the effect of the contamination and the impact on occupational medicine. While some shampoos showed high levels of certain elements, the degree of contamination on the hair was found to be negligible. Only one shampoo tested, formulated with selenium sulfide, was found to seriously contaminate the hair.     

Hair can be a good biomarker of occupational exposure to mercury vapor: simulated experiments and field data analysis

Generally, urine mercury (U-Hg) is widely used for assessment of inorganic mercury (I-Hg) exposure in humans. The reliability of scalp hair as an indicator of mercury vapor exposure is contentious. However, significant correlations were found between hair total mercury (T-Hg) and U-Hg and between hair I-Hg and total gaseous mercury (TGM) in ambient air in our previous studies. Simulated experiments were designed to assess the contribution of direct absorption/adsorption of mercury vapor in the hair. Results indicated that the increases of hair T-Hg concentrations were less than 1 μg/g, which was negligible compared with hair T-Hg concentrations in occupationally exposed workers. The β-mercaptoethanol washing can remove 30% of mercury (Hg) in the exposed hair samples. The inhaled Hg constituted the major fraction (97.4%) of I-Hg exposure for the artisanal Hg mining workers. From the simulated experiments and field data analysis, we can conclude that hair I-Hg can be a useful tool for monitoring occupational exposure to Hg vapor.     

Application of double focusing sector field ICP-MS for multielemental characterization of human hair and nails. Part II. A study of the inhabitants of northern Sweden

Double-focusing sector-field, inductively coupled plasma-mass spectrometry was used for the determination of 71 elements in scalp hair and fingernail samples from an urban population group living in the north-east of Sweden. Samples (n = 114 for hair and n = 96 for nails) were taken from subjects without known occupational exposure to metals. From these results, concentration ranges were calculated and compared with published intervals. Statistical analysis was used to elucidate differences according to sex, age and smoking habit. It was found that significant correlations exist between different elements in hair and nails, as well as between hair and nail concentrations for several elements. Strong positive correlation for Hg, Cd, Pb, Sb and Bi levels between these media confirms that both can be used for exposure assessment for these elements. Several examples on the use of distribution patterns for the rare-earth elements (REE) and of Pb isotope ratios for assessment of exposure are given.     

The effect of pH and hardness metal ions on the competitive interaction between trace metal ions and inorganic and organic complexing agents found in natural waters

The effect of pH and hardness metal ions on the interactions between trace metals and both inorganic and organic complexing agents has been studied under conditions simulating natural aquatic conditions, by employing anodic stripping voltammetric titration techniques. The complexation of Bi(III), Cd(II), Cu(II), Pb(II), and Tl(I) with the hydroxo- and carbonato-ligands found in a carbonate medium has been observed to generally increase with increasing pH. Both labile and nonlabile interactions have been observed. Nonlabile interactions are predominant at low pH and labile interactions generally increase with increasing pH. Neither calcium nor magnesium affects these interactions. The complexation of humic acids with trace metals in a carbonate medium was found to be more intense than metal ion-inorganic complexation. Both labile and nonlabile complexation was found; however, no generalizations can be made concerning the type and extent of complexation because of the individual nature of the interactions of each trace metal. Calcium was found to be more effective than magnesium in inhibiting trace metal-organic complexation. The effect of calcium is to inhibit labile complexation and is most pronounced with the cadmium-humic acid system.     

Application of double focusing sector field ICP-MS for multielemental characterization of human hair and nails. Part I. Analytical methodology

The capabilities of double focusing sector field inductively coupled plasma mass spectrometry (ICP-SMS) for the determination of 71 elements in hair and nails were studied. A microwave-assisted digestion procedure with nitric acid and hydrogen peroxide as well as direct sampling of the nails by laser ablation (LA) have been tested. Examples of spectral interferences are given and different correction procedures are discussed. Method detection limits below ng g⁻¹ were obtained for 39 elements investigated by using high-purity reagents and by taking special care to prevent contamination during preparation. However, these detection limits were insufficient for detection of some platinum group elements in the majority of the samples. The accuracy of the analytical procedure was estimated by analysis of the GBW07601 certified reference material as well as by participation in an interlaboratory comparison program. The reproducibility was assessed from replicate analysis (including sample preparation) and was found to be, as average values for all elements, 9–10% R.S.D. and 18–19% R.S.D. for hair and nails, respectively. Contribution from exogenous deposition was evaluated by analyzing samples before and after washing, as well as by studying spatial element distribution along hair and nails. It was found that even after sample washing, many elements are enriched in the surface of the nail.     

The biologic bases for using hair and nail for analyses of trace elements.

Sampling of human beings for trace element content can be a complex and costly procedure. The use of hair and nails simplifies the process and it is for this reason that such samples are extensively used. The primary consideration, however, is not how easily the samples can be collected nor even how accurately trace elements can be measured in hair and nails; rather, it is what do the values mean, i.e., to what extent does the measured level reflect the concentration and/or activity of the element in other parts of the body?The structure and histogenesis of hair and nails are discussed in relation to mechanisms by which trace elements are incorporated into these tissues. Problems of contamination in vivo are also considered.A résumé of current literature is presented, considering the trace elements that are appropriate for measurement in samples of human hair and nail and some of the problems involved in analysis.     

Effect of laundry activities on in-stream concentrations of linear alkylbenzene sulfonate in a small rural South African river

In many parts of the world clothes are washed near to or in rivers and streams. Little information is available on resulting concentrations of detergent ingredients or on any potential effects caused. In this study, the fate of a commonly used anionic surfactant, linear alkylbenzene sulphonate (LAS) was investigated in a reach of the Balfour River (Eastern Cape Province, South Africa) which was regularly used as a site for laundry activity. Samples of river water were collected upstream of the main washing site and at a number of locations downstream on several occasions in winter and summer. Sediment samples were also collected and analysed. In addition, a household survey was conducted to ascertain the amount of detergent used and the distribution of washing practices. The results of the survey suggested that the use of riverside locations for laundry activities was seasonal. Most washing tended to be done at home during the winter with riverside sites used more frequently during the summer months. The monitoring data showed that LAS concentrations in water were very variable. They were occasionally high in the immediate vicinity of the laundry site (up to 342 µg L^− 1) but were generally very low (< 11 µg L^− 1) at downstream monitoring stations, suggesting that LAS was rapidly dissipated by a combination of degradation, hydrodynamic dispersion and dilution. Concentrations in the immediate vicinity of the washing site were lower than expected on the basis of the household survey because most waste water was disposed of on the river bank rather than directly in the river. No ecological effects are expected from LAS emissions at this site.     

PBBs, PBDEs, and PCBs levels in hair of residents around e-waste disassembly sites in Zhejiang Province, China, and their potential sources

This study was conducted to explore the exposure potential of Chinese residents to PBBs, PBDEs, and PCBs in e-waste disassembly sites in Zhejiang province. The contents of 23 PBB congeners, 12 PBDE congeners, and 27 PCB congeners in hair and in their potential sources, including soil and e-waste, were measured via GC-MS. The levels of PHAHs in the three subfamilies (i.e., the PBBs, PBDEs, and PCBs) were all considerably higher (P<0.05) in hair samples collected from the disassembly sites than from the control site. The highest levels of PBBs (57.77 ng g(-1) dw), PBDEs (29.64 ng g(-1) dw), and PCBs (181.99 ng g(-1) dw) in hair were all found in those from the disassembly site Xinqiu, which are respectively 2, 2, and 10 times more than those observed in hair from the control site Yandang. Among the three subfamilies of PHAHs, PCBs were the most predominant pollutants detected. PBBs, which have very limited information available in China, can be detected at a comparable level with PBDEs in these samples in the study. Therefore, these observations suggested that more attention should be given over the potential for environmental or occupational exposure to PHAHs present in e-waste. By and large, the PHAH levels measured in the hair samples were consistent with those detected in the soil. Hair analysis could thus be a valid screening tool for assessing human PHAHs exposure in and around e-waste disassembly sites.     

Biomonitorization of cadmium, chromium, manganese, nickel and lead in whole blood, urine, axillary hair and saliva in an occupationally exposed population

Heavy metal contamination from occupational origin is a cause for concern because of its potential accumulation in the environment and in living organisms leading to long term toxic effects. This study was aimed to assess Cd, Cr, Mn, Ni and Pb levels in whole blood, urine, axillary hair and saliva from 178 individuals with occupational exposure to heavy metals. Levels of metal compounds were determined by atomic absorption spectrometry. We collected information on occupation, lifestyle habits and food intake by questionnaire. Multiple linear regression analyses for metal ion concentration in whole blood, urine, axillary hair and saliva were adjusted for age, gender, smoking and alcohol consumption, lifetime workplace exposure, residence area and food habits. Overall, blood and urine median concentrations found for the five metals analyzed do not exceed biological exposure indexes, so that they are very similar to a non-occupationally exposed population. Toxicokinetic differences may account for the lack of correlations found for metal levels in hair and saliva with those in blood or urine. For those heavy metals showing higher median levels in blood with respect to hair (Cd, Mn and Pb) indicating lesser hair incorporation from blood, the lifetime working experience was inversely correlated with their hair levels. The longer the lifetime working experience in industrial environments, the higher the Mn and Ni concentration in saliva. Axillary hair and saliva may be used as additional and/or alternative samples to blood or urine for biomonitoring hair Mn, and saliva Ni in subjects with occupational exposure.     

Mammalian hair as an accumulative bioindicator of metal bioavailability in Australian terrestrial environments

The current study represents the first investigation of the suitability of marsupial and eutherian mammalian hair as indicator tissue for metal exposure and accumulation within contaminated Australian terrestrial ecosystems. A soil metal contamination gradient was established across 22 sites at increasing distances from a decommissioned Lead/Zinc smelter in NSW, Australia. Within each site, soil and small mammal populations were sampled. An Australian native marsupial, the insectivorous Brown Antechinus, Antechinus stuartii: Dasyuridae, and introduced rodents, the omnivorous Brown or Norway Rat, Rattus norvegicus: Muridae and the Black Rat, Rattus rattus: Muridae were assessed for hair concentrations of Cadmium (Cd), Copper (Cu), Lead (Pb) and Zinc (Zn). Metals in soil were most elevated at sites within close proximity to the smelter, with soil metal concentrations decreasing with distance from the smelter. The non-essential metals Pb and Cd were accumulated in hair, both metals exhibiting positive linear relationships with environmental exposure (soil metal concentrations). When the variables of weight and snout-vent length were considered, no further contribution in terms of explaining the variability in hair Cd or Pb was observed for all species examined. The essential metals Cu and Zn were regulated in hair, remaining similar across the metal contamination gradient. A significant negative correlation between snout-vent length and hair Cu concentration was found for the Brown Rat; greater hair Cu concentrations were found in smaller individuals of this species. Accumulation of Pb to hair was similar among species while concentrations of Cd in Brown Rat hair were higher than both Black Rat and Brown Antechinus hair. As each of the three aforementioned species exhibit similar bioaccumulation relationships for Pb, we suggest that sampling hair from introduced rodents (pest species) may provide a suitable proxy for the assessment of Pb bioavailability for a range of small mammals within Australian urban remnants.     

The interpretation of human hair trace element concentrations

Scalp hair samples collected from 86 Canadian elderly, non-institutionalized women (mean age 66.6 +/- 6.2 y) on two separate occasions ten weeks apart, were analyzed for Zn, Cu and Mn content. Fasting blood samples were also collected and serum Zn, Cu and albumin content determined. Median hair Zn, Cu and Mn and mean serum Zn and albumin concentrations were not significantly different at the pre- and post-study periods. Furthermore, hair Zn concentrations at the two sampling times were positively and significantly correlated as were hair Cu, hair Mn, serum Zn and serum albumin values. In contrast no significant correlation related the hair and serum Zn values and hair and serum Cu values at any time. The constancy of the hair Zn, Cu and Mn concentrations at the two sampling periods may reflect the homeostatic regulation which controls absorption and hence body trace element content. In addition, results indicate that, after careful laboratory washing, the effects of adventitious contamination on hair trace element content are small, and can be effectively ignored.     

Trace elements in hair in the UK: results and interpretation in the preconception situation

The paper examines the high incidence of birth defects that still occur in the UK and suggests that it might be possible to reduce this by preparing prospective mothers for parenthood prior to conception. One test in particular is suggested as having a part to play in this preconception screening-that being the hair metals analysis. Such a screening test is useful in identifying both excesses of toxic metals and deficiencies of essential metals. The results from our studies seem to indicate a high proportion of potential mothers as having low levels of manganese, iron and possibly zinc in their hair. The significance of these findings is discussed in relation to the possible effect on birth defects and the possible routine use of hair metal testing in the pre-conception situation is suggested.