Hair analysis and the early detection of imbalances in trace elements for members of expeditions in Antarctica

In the framework of the Human Biology and Medicine Project of the National Program for Research in Antarctica (Programma Nazionale di Ricerche in Antartide, PNRA) a study was undertaken to explore the suitability of trace element determination in human hair as a tool for the early detection of the impact of extreme environmental conditions on the health of members of the Italian and French expeditions. This study included three campaigns, namely, the 1995–1996 expedition to the Italian base of Terra Nova Bay, as well as the 1997–1998 and 1998–1999 expeditions to both the Italian base of Terra Nova Bay and the Italian–French base of Dome C. Sampling of hair of participants in the expeditions was carried out both prior to departure and at the end of the period spent at the bases. As regards storage, pre-treatment and analysis of hair samples they were performed in accordance with previously established procedures. Acid-assisted microwave digestion was adopted as the best approach for preparing solutions for subsequent analysis by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. In the first part of this study, only the elements Ca, Cu, Fe, Mg and Zn were selected, while at a later stage it was decided to also include Co, Cr, Mn, Mo and Ni. Experimental results were subjected to basic statistical analysis to detect possible significant differences in element concentrations that occurred during the sojourn at the bases, with a view to identify possible remedial action to minimize adverse consequences.     

A study of trace elements in scalp hair and fingernails of industrial workers of Ontario,Canada

Instrumental neutron activation analysis was performed on scalp hair and fingernail samples collected randomly from a group of heavily exposed healthy male industrial workers living in the cities of Hamilton and Toronto (Ont.), Canada. The concentrations of trace elements (Ag, Au, Br, Cd, Co, Cr, Cs, Fe, Hg, Lu, Mn, Mo, Rb, Ru and T₃) were evaluated and compared for scalp hair and fingernails. Various trace elements show similar variations in the two kinds of samples. The results have also been compared with those for normal subjects from USA (scalp hair) and Canada (fingernails).     

Comparison of selenium content in human hair from different individuals in different countries,by76Se(n,γ)77mSe reaction

Samples of hair from 370 subjects were analysed by neutron activation. The samples were taken from residents of nine different countries: Japan, France, Ivory Coast, Brasil, Paraguay, Canary Islands, Papua New Guinea, Italy and New Zealand. The selenium determination was made using the⁷⁶Se(n,)^77mSe reaction.It was found that the average selenium concentration in the hair of Japanese subjects, both those living in Japan and those living in foreign countries was higher (total average: 0.59±0.14 mg/kg) than those of subjects from other countries (total average: 0.42±0.13 mg/kg).Our results from the determination of the selenium concentration in the hair of individuals from different countries show significant differences between different countries, nevertheless, the selenium content in human hair was small amounts. Since this is likely due to differences in diet. This method was able to analyze quickly for many samples.     

Carbon isotope analysis of bulk keratin and single amino acids from British and North American hair

The reconstruction of ancient diets using isotopic measurements of bone collagen, and other tissues, which survive in archaeological contexts, relies on known isotopic relationships between diet and body tissues. Examination of these relationships often requires the study of modern human and animal subjects. While hair keratin can act as a useful proxy for bone collagen in isotopic studies on living humans, where it is inappropriate to sample tissues such as collagen, it can, in addition, act as a chronological indicator of dietary change. This study investigates hair keratin delta13C values from current residents of the UK and the USA. Residents in the USA showed a clear bulk hair delta13C enrichment of approximately 3 per thousand over UK individuals, attributed to an elevated C4 dietary input from maize fed to livestock in North America. The keratin delta13C of subjects who moved between the UK and USA showed a pronounced change after relocation, taking approximately 4 months to reach isotopic equilibrium. To investigate these differences further, we measured delta13C values of dispensable and indispensable amino acids as a group, and selected individual amino acids. As a group, enrichment of dispensable amino acids compared with indispensable amino acids occurred in samples from both continents, averaging 7.2 per thousand in the UK and 7.9 per thousand in the USA. Dispensable and indispensable amino acids, as well as all individual amino acids measured, were enriched in samples from the USA compared with those from the UK.     

Determination of trace element levels in human scalp hair in occupationally exposed subjects by XRF

Trace element levels in hair of individuals living in urban areas were determined by energy dispersive XRF. Two groups of subjects were investigated, the first group was assumed to be from a healthy environment, the other one was exposed to a high level of contamination due to working conditions. The results were compared to data reported in the literature. The concentrations of Ca, Fe, Cu, Zn and Pb in the scalp hair were determined and the correlation between hair trace element levels and environmental effects was discussed. The results given by the second group show that environmental exposure effects hair trace element levels which are related to body trace element concentrations.     

Vertical Distribution of137 Cs in The Lacustrine Areas and Preliminary Results of 7Be Activity in Snow Samples at Terra Nova Bay (ANTARCTICA)

Abstract

¹³⁷ Cs activity in samples from lacustrine areas around the Italian base in Antarctica is reported as an integration of a previous work. Preliminary data of cosmogenic ⁷ Be activity determined in snowfalls, total atmospheric depositions, soil and air particulate collected during the 1990–91 and 1991–92 Italian expeditions in Antarctica is presented. The results obtained point out the efficiency of snow in the processes of air particulate scavenging and provide useful information for the development of research in Antarctica in the study of air/snow transfer processes by means of natural radionuclides.     

Multiple stable isotope (18O, 13C, 15N and 34S) analysis of human hair to identify the recent migrants in a rural community in SW England

Relationships between recent migration and hair delta(18)O values were examined for 40 people living in a rural community in SW England. The isotopic contents of 35 'local' hair samples were compared with those of 5 recently arrived individuals (from Australia, Canada, Chile, Germany and the USA). The hair delta(18)O values of these 'visitors' were +7.9 (Omaha, USA), +11.2 (Jena, Germany), +12.1 (Osorno, Chile), +12.6 (Montreal, Canada) and +14.3 per thousand (Adelaide, Australia). The hair value for the USA visitor (+7.9 per thousand) fell outside the range for the 33 local adult residents, +10.5 to +14.3 per thousand (+12.7 +/- 0.8 per thousand). Hair delta(18)O values did not identify the individuals from Adelaide, Montreal and Osorno as 'visitors', but hair delta(13)C or delta(34)S data did. Combining the hair delta(18)O, delta(13)C and delta(34)S values using principal components analysis (two components explained 89% of the overall variation among the 40 subjects) helped to more clearly distinguish European from non-European individuals, indicating the existence of global overall isotope (geo-origin) relationships.     

Stable isotope (13C, 15N and 34S) analysis of the hair of modern humans and their domestic animals

Relationships between dietary status and recent migration were examined by delta(13)C, delta(15)N and delta(34)S analysis of hair samples from 43 modern humans living in a rural community in SW England. The isotopic content of 38 'local' hair samples was compared with that of five recently arrived individuals (from Canada, Chile, Germany and the USA). Hair samples from domestic animals (i.e. mainly cats, dogs, cows and horses) were analysed to examine the difference in delta(13)C, delta(15)N and delta(34)S values between herbivores and carnivores. Generally, modern human hair data from the triple stable isotope (delta(13)C, delta(15)N and delta(34)S) provided enough information to confirm the dietary status and origin of the individual subjects. The dietary intake was generally reflected in the animal hair delta(15)N and delta(13)C values, i.e. highest in the carnivores (cats). However, a non-local origin of food sources given to domesticated omnivores (i.e. dogs) was suggested by their hair delta(34)S values.     

Short term and long term variations of Ca-concentration in beard

The Ca-concentration has been measured in daily shaven beard samples over a seven-year period. The Ca-concentration range in beard of single individuals is the same as that in the head hair of different groups. Inviduals belonging to the group with low Ca-level (Ca<700 ppm) in hair (endangered group from ischaemic heart diseases) may increase the Ca-level in their hair and get into the group with high Ca-level (Ca>700 ppm; defended group).     

Trace,Alkaline and Alkaline-Earth Elements in Sea Water Samples from Terra Nova Bay - Ross Sea (ANTARCTICA): A Three-Year Period of Observation

Abstract

This report concerns the correlation of the analytical results relevant to some elements obtained in filtered sea water samples collected in Terra Nova Bay and the Ross Sea (Antarctica) during three Italian expeditions. The following ranges of variability of the medians of total concentrations (ng/l) - which include time effect among expeditions and bias effect among participant groups - were found for trace elements (single values refer to elements which were only determined once by one laboratory): Sb (260), As (1.2 10³), Cd (5–50), Cr (120), Co (4), Cu (110–230), Fe (435–445), Pb (6–52), Mn (15–88), Hg (3), Ni (185–580), Se (30) and Zn (242–265). Speciation studies pointed out that 10–40% of Cd, 15–60% of Cu and 20–50% of Pb were present in the samples as an ASV-labile fraction.

As for alkaline and alkaline-earth elements, the following concentration ranges in surface sea waters, expressed in mM, were found: Li ([1.4–3.0] 10^?2), Na (394–480), K(5.1–9.9), Ca (6.4–14.7), Mg (46.2–59.0) and Sr ([7.6–10] 10^?2).

Inter- and intra-laboratory data comparison, incorrect results, local variations of concentration, including pollution effects and pack melting effect, are discussed in detail.     

Trends of volatile chlorinated hydrocarbons and trihalomethanes in Antarctica

In order to understand behaviour and environmental fate of manmade chemicals in remote and cold areas, during the XXVII Italian Expedition carried out in Antarctica throughout the austral summer 2011/2012, superficial snow and lake water were sampled along the Ross Sea's South coast and their content of some low-molecular weight volatile halogenated hydrocarbons was evaluated. In consideration of their important role in stratospheric ozone chemistry, some volatile chlorinated hydrocarbons (VCHCs) and trihalomethanes (THMs) were investigated. The analyses were realised with a dedicated system composed by a purge-and-trap injector coupled to a gas chromatograph with a mass spectrometer (PTI-GC-MS) operating in SIM mode. The investigated VCHCs (chloroform; 1,1,1-trichloroethane; tetrachloromethane; trichloroethylene and tetrachloroethylene) were present in all analysed samples, and concentration levels ranged from units to hundreds of ng L^?1 according to considered matrix. For the first time, THMs (bromoform; dibromochloromethane; bromodichloromethane), were measured in Antarctic lake waters and freshly deposited snow; their concentration levels ranged from units to tens of ng L^?1. In order to assess eventual temporal variations, VCHC content in aqueous Antarctic matrices was compared with levels occurring in the past Italian Antarctic expeditions: for some banned substances, a decrease in concentration was observed, probably due to worldwide use restrictions. Finally, current Antarctic and Italian VCHC and THM levels in snow and lake water samples were compared and were found to be quite similar, differing at most by one order of magnitude, corroborating the hypothesis of an accumulation of halogenated compounds in Antarctic aqueous matrices.     

Neutron activation analysis of hair failure of a mission

The presence and the concentration of trace elements in hair are subject to variations according to a number of factors. The primary investigations consist in a statistical interpretation of (1) the distribution of the oligo-elements in a homogeneous hair sample, (2) the distribution over one particular head, (3) the evolution in samples taken at successive intervals, (4) the distribution over a population. Our study was mainly concerned in the influence of the time factor, and revealed an unpredictable behaviour of the elements under investigation (As, Sb, Au, Mn, Hg, Cu). There was only one exception: Zn. This unpredictable behaviour of most of the oligo-elements is due to their being influenced by such external conditions as environment, washing, hair dyes, diet and drug intake. The identification of hair samples on the basis of concentrations so inconstant and easily influenced, is a most impromising endeavour. Furthermore the irregularity in distribution of the oligo-elements over the head of one and the same person is not of a nature to make things easier. The existence of these factors not only wellnigh excludes the possibility of an identification, but they furthermore make it difficult to confirm unequivocally that a hair specimen belongs to a given person, to the exclusion of any other.     

Investigation of elemental models in senile dementia and depressives using neutron activation analysis

Instrumental neutron activation analysis has been used to determine the concentration of a range of elements in hair and blood samples, separated into erythrocytes and plasma, obtained from two groups of women, senile demented (9) and depressives (16), and their respective controls (17 and 9). The results suggest that the senile dementia group has significantly higher Al concentrations in erythrocytes and hair relative to the controls but no significant correlation between the aluminium content of hair and that of blood exists. Further, Zn concentrations determined in the erythrocytes and plasma of these subjects were lower compared to the control values. Vanadium levels above our detection limit for the element were found in seven cases out of a total of sixteen in the depressive group. Vanadium was also found to be at higher concentration in the hair of the depressive group compared to the controls. Again no significant correlation was found to exist between the concentration of vanadium in hair and in erythrocyte sample for these seven subjects.     

Arsenic, antimony and bismuth in human hair from potentially exposed individuals in the vicinity of antimony mines in Southwest China

To study the effect of the environmental pollution in exposed population, human hair samples of residents were collected from two typical antimony mines (Xikuangshan antimony mine and Qinglong antimony mine, Southwest China) and one non-mining city (Guiyang, Southwest China), and the concentrations of arsenic, antimony and bismuth in these samples were analyzed by hydride generation-atomic fluorescence spectrometry. Arsenic concentrations for Xikuangshan, Qinglong, and Guiyang ranged 0.236-48.4 (mean 4.21), 0.130-16.1 (mean 2.96), and 0.104-0.796 (mean 0.280) μg/g, respectively. Antimony concentrations for Xikuangshan, Qinglong, and Guiyang ranged 0.250-82.4 (mean 15.9), 0.060-45.9 (mean 5.15), and 0.065-2.87 (mean 0.532) μg/g, respectively. Bismuth contents were found to be greater than the limit of detection (LOD > 0.016 μg/g) in all the human hair samples collected from residents from Qinglong antimony mine, 95.5% samples from Xikuangshan mine and only 22.7% samples from Guiyang. There were no significant differences in both arsenic and antimony concentrations between hair samples from male and female individuals in the same area (P > 0.05). Arsenic and bismuth were mainly present in samples from children (5-9 years) and adults aged 41-51 years. Relatively high antimony contents (≥ 3 μg/g) were detected mainly in samples from children and adults aged ≥ 41 years. Significant correlation was found between the concentrations of arsenic and antimony in the human hair samples (r = 0.523, P < 0.05). The results indicate that arsenic and antimony in antimony mining area may significantly affect human health.     

Deposition of JWH-018, JWH-073 and their metabolites in hair and effect of hair pigmentation

Analysis of drugs in hair is often used as a routine method to obtain detailed information about drug ingestion. However, few studies have been conducted on deposition of synthetic cannabinoids and metabolites in hair. The first purpose of this study was to establish and validate an analytical method for detection of JWH-018, JWH-073, and their metabolites in hair, by use of UHPLC–MS–MS, for forensic application. The second purpose was to investigate the distribution of synthetic cannabinoids metabolites in hair and the effect of hair pigmentation, by use of an animal model. For this, JWH-073 was chosen as a representative synthetic cannabinoid. Finally, the developed method was applied to hair samples from 18 individuals suspected of synthetic cannabinoids use. JWH-018, JWH-073, and their metabolites were extracted from hair with methanol. The extract was then filtered and analyzed by UHPLC–MS–MS with an electrospray ion source in positive-ionization mode. Validation proved the method was selective, sensitive, accurate, and precise, with acceptable linearity within the calibration ranges. No significant variations were observed when different sources of both human and rat hair were used. The animal study demonstrated that JWH-073 N-COOH M was the major metabolite of JWH-073 in rat hair, and hair pigmentation did not have a significant effect on incorporation of JWH-073 and its metabolites into hair. In the analysis of 18 authentic hair samples, only JWH-018, JWH-018 N-5-OH M, and JWH-073 were detected, with wide variation in concentrations.     

Glyphosate and aminomethylphosphonic acid in human hair quantified by an LC-MS/MS method

An LC-MS/MS method for hair testing of glyphosate and aminomethylphosphonic acid (AMPA), its main biodegradation product, has been developed. After decontamination, 50 mg of hair was ground and sonicated in water for 2 h. The method was fully validated in the 5–500 pg/mg range for glyphosate and 10–500 pg/mg for AMPA, and the limits of detection were 2 and 5 pg/mg, respectively. Matrix effect for glyphosate and AMPA was compensated by an isotope-labeled internal standard. Hair samples from four farmers who regularly used glyphosate and one farmer who used glyphosate but not his wife and 14 hair samples from nonoccupationally exposed subjects were tested. Glyphosate was found in head hair of three farmers, with concentration in the range 14–188 pg/mg. The fourth was found negative but with hair colored in red. Glyphosate was detected in 10 of 14 hair samples from nonoccupationally exposed subjects at concentrations of 11.5 pg/mg or lower and only in one segment (0–3 cm) of the farmer's spouse (6 pg/mg). AMPA was detected in five subjects, above the limit of quantification only in two of three occupationally exposed subjects with positive glyphosate. Further studies should be conducted to validate this potential new biomarker that could be useful for assessing long-term exposure to glyphosate.     

Persistent organic pollutants (POPs) at Ross Sea (Antarctica)

The most significant findings on the presence of persistent organic pollutants (POPs) in the marine ecosystem at Ross Sea are presented. Seawater samples were collected in many sampling sites located in a large area of the Ross Sea during various Italian expeditions in Antarctica. Two classes of POPs were considered, namely polychlorobiphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). The results highlighted the presence of these compounds in seawater samples at a total concentration level of about 50 pg/l for PCBs, and 220 pg/l for PAHs. Moreover, seawater samples showed low to high molecular weight PAHs (LMW/HMW) and phenanthrene to anthracene (PHE/ANT) ratios higher than 1 and 5, respectively, which may suggest the predominance of a petrogenic source (i.e. petroleum product contamination). Results were also obtained on the POP depth profile in the water column at Cape Adere, where two water masses converge and mix, i.e. the Modified Circumpolar Deep Water (MCDW) and the High Salinity Shelf Water (HSSW). According to both the PAH and temperature profiles a two-fold higher PAH and PCB concentration was observed for MCDW samples with respect to HSSW. This result represents the first experimental evidence of the external input of pollutants in this area of the Ross Sea coming from the outer oceanic circulation.     

The University of Surrey database of elemental composition of human hair

The elemental composition of human hair obtained from different studies at Surrey University over a period of 25 years has been recorded and forms part of a database, for biological and environmental samples, which is being developed. Instrumental neutron activation analysis (INAA), using reactor neutrons, was the principal method employed and from which reported data are presented.Elemental concentrations of Br, Ca, Ce, Cl, Co, Cr, Cs, F, Fe, Hf, K, Mg, Mn, Na, Rb, Sb, Sc, Se, V and Zn were obtained and recorded in the database. Chronological variations in two sets of subjects separated by a period of time of 16 years are also given. Variations in the concentration values of some elements related to the state of health and disease were reported for hair samples collected from subjects suffering from manic depression, senile dementia and breast cancer. Concentration values of some elements with relation to the nationality of subjects from Bulgaria, England, Kenya, Nigeria and Wales are presented and compared. This study is part of on-going research in the analysis of biomedical and bioenvironmental materials. The database is still in its infancy. This revised version was published online in August 2006 with corrections to the Cover Date.     

Stable carbon isotope analysis of different tissues of beef animals in relation to their diet

As part of a larger experiment, 31 young bulls, divided into three groups, were given different diets containing either C(3) plants or a combination of C(3) and C(4) plant-based feeds in three feeding periods before slaughter. Variation in the proportion of C(4) plant material in the diets was made by including or not maize or maize-derived ingredients, whereas the other dietary constituents were from C(3) plants. Analysis of stable carbon isotope ratios (delta(13)C value) was performed on different tissues taken at slaughter: blood, plasma, liver, kidney fat, hair, muscle and ruminal contents. Blood and plasma samples were also taken at the beginning of each period. A highly significant difference was found in the delta(13)C values of blood and plasma samples taken from animals that had received a diet of only C(3) plants or with 59% C(4) material for 70 days. The delta(13)C values of all different samples taken at slaughter were highly significantly different between the three feeding groups that had received diets with 0, 13.5 or 35% C(4) material for on average 137, 139 and 83 days, respectively. For the three groups, samples of hair, muscle, plasma, whole blood and liver were significantly enriched in (13)C compared with the diet (except for liver in one group), whereas kidney fat was significantly depleted. The proportion of C(4) plant material could be accurately estimated from the delta(13)C values of different tissue samples. Stable carbon analysis of different tissues from beef animals can be used to trace back diets containing variable proportions of C(3) and C(4) plant material.     

Trace element intake and excretion in the italian population

The content of the following trace elements, Ag, Co, Cr, Cs, Fe, Hg, Rb, Sb, Se and Zn has been evaluated in the diets, excretion (urines and feces), blood and hair samples taken from different groups of subjects. Each population group is composed by five or more individuals selected in order to be representative of the adult population living in a well defined community. Some communities, with different socio-economical living habits, and displaced in different regions of Italy, have been considered in order to detect the variability, if any, of the trace element distribution among the Italian population. The data obtained seem to show a reasonable uniformity of the average trace element daily intakes in different regions of Italy. Beside the individual variability, very significant differences among the groups studied have not been found, as the trace element contents in excreta, blood and hair samples are concerned. All data are compared with similar data referred to population living in other countries.