Lead isotopic fingerprint in human scalp hair: The case study of Iglesias mining district (Sardinia, Italy).

The Sulcis-Iglesiente district (SW Sardinia, Italy) has been, until recently, one of the most important Italian polymetallic mining areas for the extraction of lead. Epidemiological studies conducted over several decades have indicated this site at high risk of environmental crisis with possible adverse effects on the public health. In the present paper we discuss Pb isotope signatures in human scalp hair and road dust collected from the Sulcis-Iglesiente area in order to trace the exposure of populations to potential Pb sources. A total of 23 determinations (20 on hair samples and 3 on road dust samples) of lead isotope ratios (206Pb/207Pb and 208Pb/206Pb) were carried out. The obtained results were integrate with literature data regarding the total content of Pb in hair samples from the same study area. Hair from children living in Sant'Antioco exhibited lead isotope ratios in the ranges 1.152-1.165 for 206Pb/207Pb and 2.101-2.108 for 208Pb/206Pb, while hair samples from Iglesias resulted less radiogenic: 206Pb/207Pb~1.147-1.154 and 208Pb/206Pb~2.106-2.118. These values pointed to a multi-source mixing between the less radiogenic sources, corresponding to the Pb ore deposits, and the more radiogenic sources identified in local background.

Perturbation vectors to evaluate air quality using lichens and bromeliads: a Brazilian case study.

Samples of one lichen species, Parmotrema crinitum, and one bromeliad species, Tillandsia usneoides, were collected in the state of Rio de Janeiro, Brazil, at four sites differently affected by anthropogenic pollution. The concentrations of aluminum, cadmium, copper, iron, lanthanum, lead, sulfur, titanium, zinc, and zirconium were determined by inductively coupled plasma-atomic emission spectroscopy. The environmental diagnosis was established by examining compositional changes via perturbation vectors, an underused family of methods designed to circumvent the problem of closure in any compositional dataset. The perturbation vectors between the reference site and the other three sites were similar for both species, although body concentration levels were different. At each site, perturbation vectors between lichens and bromeliads were approximately the same, whatever the local pollution level. It should thus be possible to combine these organisms, though physiologically different, for air quality surveys, after making all results comparable with appropriate correction. The use of perturbation vectors seems particularly suitable for assessing pollution level by biomonitoring, and for many frequently met situations in environmental geochemistry, where elemental ratios are more relevant than absolute concentrations.

Impact of trace metals from past mining on the aquatic ecosystem: a multi-proxy approach in the Morvan (France).

This study seeks to determine to what extent trace metals resulting from past mining activities are transferred to the aquatic ecosystem, and whether such trace metals still exert deleterious effects on biota. Concentrations of Cd, Cu, Pb and Zn were measured in streambed sediments, transplanted bryophytes and wild brown trout. This study was conducted at two scales: (i) the entire Morvan Regional Nature Park and (ii) three small watersheds selected for their degree of contamination, based on the presence or absence of past mining sites. The overall quality of streambed sediments was assessed using Sediment Quality Indices (SQIs). According to these standard guidelines, more than 96% of the sediments sampled should not represent a threat to biota. Nonetheless, in watersheds where past mining occurred, SQIs are significantly lower. Transplanted bryophytes at these sites consistently present higher trace metal concentrations. For wild brown trout, the scaled mass and liver indices appear to be negatively correlated with liver Pb concentrations, but there are no obvious relationships between past mining and liver metal concentrations or the developmental instability of specimens. Although the impact of past mining and metallurgical works is apparently not as strong as that usually observed in modern mining sites, it is still traceable. For this reason, past mining sites should be monitored, particularly in protected areas erroneously thought to be free of anthropogenic contamination.

Metals and metalloids in hair samples of children living near the abandoned mine sites of Sulcis-Inglesiente (Sardinia, Italy).

The Sulcis-Iglesiente district (SW Sardinia, Italy) is one of the oldest and most important polymetallic mining areas in Italy. Large outcrops of sulfide and oxide ores, as well as the products of the long-lasting mining activity, are present throughout the district releasing significant quantities of metals and metalloids into the surrounding environment. Here are reported concentrations of 21 elements determined in scalp hair samples from children (aged 11-13 years) living in different geochemical environments of southwestern Sardinia: Iglesias, hosting several abandoned mines, and the island of Sant׳Antioco, not affected by significant base metal mineralization events. Trace element determinations were performed by ICP-MS. Statistically significant differences (p<0.01) in elemental concentration levels between the two study sites were found. Hair of children from Iglesias exhibited higher concentration values for Ag, Ba, Cd, Cr, Ni, Pb, Rb, Sb, U, V, and Zn. Rubidium, V and U resulted more abundant at Sant׳Antioco. Hair samples from Iglesias showed gender-related differences for a larger number of elements (Ag, Ba, Cd, Co, Cu, Ni, Sr, U and Zn) than at Sant׳Antioco, where only U was significantly different. The above elemental concentrations in females were always higher than in male donors. Robust Principal Component Analysis operated on log-transformed elemental concentrations showed components indicative of a) sulfides ore minerals (PC1) reflecting the influence of the diffuse mineralization covering the entire study area, b) the presence of some bioavailable As sources (PC2) as As-rich pyrite and Fe-containing sphalerite and c) other sources of metals overlapping the diffuse mineralizations, as carbonate rocks and coal deposits (PC3). The results provided evidence of a potential risk of adverse effects on the health of the exposed population, with children living at Iglesias being greatly exposed to several metals and metalloids originated in mining tailings, enriched soils, waters and food.

Impact of historical mining assessed in soils by kinetic extraction and lead isotopic ratios.

The aim of this study is to estimate the long-term behaviour of trace metals, in two soils differently impacted by past mining. Topsoils from two 1 km(2) zones in the forested Morvan massif (France) were sampled to assess the spatial distribution of Cd, Cu, Pb and Zn. The first zone had been contaminated by historical mining. As expected, it exhibits higher trace-metal levels and greater spatial heterogeneity than the second non-contaminated zone, supposed to represent the local background. One soil profile from each zone was investigated in detail to estimate metal behaviour, and hence, bioavailability. Kinetic extractions were performed using EDTA on three samples: the A horizon from both soil profiles and the B horizon from the contaminated soil. For all three samples, kinetic extractions can be modelled by two first-order reactions. Similar kinetic behaviour was observed for all metals, but more metal was extracted from the contaminated A horizon than from the B horizon. More surprising is the general predominance of the residual fraction over the "labile" and "less labile" pools. Past anthropogenic inputs may have percolated over time through the soil profiles because of acidic pH conditions. Stable organo-metallic complexes may also have been formed over time, reducing metal availability. These processes are not mutually exclusive. After kinetic extraction, the lead isotopic compositions of the samples exhibited different signatures, related to contamination history and intrinsic soil parameters. However, no variation in lead signature was observed during the extraction experiment, demonstrating that the "labile" and "less labile" lead pools do not differ in terms of origin. Even if trace metals resulting from past mining and metallurgy persist in soils long after these activities have ceased, kinetic extractions suggest that metals, at least for these particular forest soils, do not represent a threat for biota.

Wild brown trout affected by historical mining in the Cévennes National Park, France.

In the protected area of the Cévennes National Park (Southern France), 114 wild brown trout (Salmo trutta fario) were captured at six locations affected to different extents by historical mining and metallurgy dating from the Iron Age to Modern Times. Cadmium and lead in trout livers and muscles reflect high sediment contamination, although an age-related effect was also detected for hepatic metal concentrations. Lead isotope signatures confirm exposure to drainage from mining and metallurgical waste. Developmental instability, assessed by fluctuating asymmetry, is significantly correlated with cadmium and lead concentrations in trout tissues, suggesting that local contamination may have affected fish development. Nowadays, the area is among the least industrialized in France. However, our results show that 60% of the specimens at one site exceed EU maximum allowed cadmium or lead concentration in foodstuffs. The mining heritage should not be neglected when establishing strategies for long-term environmental management.

Modeling of 137Cs migration in soils using an 80-year soil archive: role of fertilizers and agricultural amendments.

An 80-year soil archive, the 42-plot experimental design at the INRA in Versailles (France), is used here to study long-term contamination by 137Cs atmospheric deposition and the fate of this radioisotope when associated with various agricultural practices: fallow land, KCl, NH4(NO3), superphosphate fertilizers, horse manure and lime amendments. The pertinence of a simple box model, where radiocaesium is supposed to move downward by convectional mechanisms, is checked using samples from control plots which had been neither amended, nor cultivated since 1928. This simple model presents the advantage of depending on only two parameters: alpha, a proportional factor allowing the historical atmospheric 137Cs fluxes to be reconstructed locally, and k, an annual loss coefficient from the plow horizon. Another pseudo-unknown is however necessary to run the model: the shape of historical 137Cs deposition, but this function can be easily computed by merging several curves previously established by other surveys. A loss of approximately 1.5% per year from the plow horizon, combined with appropriate fluxes, provides good concordance between simulated and measured values. In the 0-25cm horizon, the residence half time is found to be approximately 18yr (including both migration and radioactive decay). Migration rate constants are also calculated for some plots receiving continuous long-term agricultural treatments. Comparison with the control plots reveals significant influence of amendments on 137Cs mobility in these soils developed from a unique genoform.

Anthropogenic lead distribution in soils under arable land and permanent grassland estimated by Pb isotopic compositions.

The role of land use on fate of metals in soils is poorly understood. In this work, we studied the incorporation of lead in two neighboring soils with comparable pedogenesis but under long-term different agricultural management. Distributions of anthropogenic Pb were assessed from concentrations and isotopic compositions determined on bulk horizon samples, systematical 5-10 cm increment samples, and on 24-h EDTA extracts. Minor amounts of anthropogenic lead were detected until 1-m depth under permanent grassland, linked to high earthworm activity. In arable land, exogenous Pb predominantly accumulated at depths < 60 cm. Although the proximity between the two sites ensured comparable exposition regarding atmospheric Pb deposition, the isotopic compositions clearly showed the influence of an unidentified component for the cultivated soil. This work highlights the need for exhaustive information on historical human activities in such anthropized agrosystems when fate of metal pollution is considered.

Immunolocalization of estrogen and androgen receptors and steroid concentrations in the stallion epididymis.

The presence of steroids and their receptors throughout development, specifically androgen receptor (AR), estrogen receptor alpha (ERalpha) and estrogen receptor beta (ERbeta), in the epididymis of a high estrogen producing species like the stallion has not been determined. Epididymal and testicular samples were collected for analysis of testosterone and estradiol-17beta (E(2)) concentrations and for immunolocalization of AR, ERalpha and ERbeta. The concentration of testosterone in the testis and epididymis were not different among age groups (P>0.05). AR was localized in the principal cells of the caput, corpus and cauda in all four age groups. This lack of change in testosterone concentration and receptor localization suggests that testosterone is important for both development and maintenance of epididymal function. There was an age-related increase in E(2) concentrations in all regions of the epididymis (P<0.05), suggesting that E(2) is also important for adult function. ERbeta was localized in the principal cells of the caput, corpus and cauda in all four age groups, but the localization of ERalpha was regional and age dependent. In peri-pubertal animals, ERalpha immunostaining was most prominent and estradiol was similarly present in all three epididymal regions; this suggests that estradiol also plays a key role in the maturation of the stallion epididymis during the pubertal transition when sperm first arrive in the epididymis. In conclusion, these results suggest that the stallion epididymis is regulated by both androgens and estrogens throughout development and that estradiol is more important to epididymal function in the stallion than previously believed.

A comparison of the effects of equine luteinizing hormone (eLH), equine growth hormone (eGH) and human recombinant insulin-like growth factor (hrIGF-I) on steroid production in cultured equine Leydig cells during sexual maturation.

There are several hormones and local testicular factors involved in the initiation and control of steroidogenesis and spermatogenesis during puberty. GH and its mediator, IGF-I, increase substantially during puberty, and in addition to LH, these growth-promoting hormones can have direct effects upon testicular function. The objective of this work was to investigate the effects of eLH, eGH and hrIGF-I upon Leydig cells derived from testes of colts and stallions representing different stages of development. Testes were obtained from 48 light horse colts and stallions at the time of routine castration, horses were categorized according to age group (prepubertal, pubertal and postpubertal) and a Leydig cell enriched preparation was utilized for cell culture. Cells derived from all 48 horses were treated with doses of eLH, and a subset of 21 horses received doses of eGH and hrIGF-I. Cells were plated at a concentration of 1 x 10(6) cells/ml and incubated for 24 h at 32 degrees C. Production of testosterone and estradiol was measured by validated RIA. Leydig cells from prepubertal colts secreted greater basal amounts of testosterone but lesser basal amounts of estradiol compared with the other age groups (p < 0.001). Pubertal stallions exhibited the greatest relative response to eLH (p < 0.05). Neither eGH nor hrIGF-I elicited a steroidogenic response over baseline concentrations in any of the three age groups.

Environmental impact of early Basque mining and smelting recorded in a high ash minerogenic peat deposit.

More than four metres of core, covering almost 5000 years of deposition, were collected in a high ash minerogenic peat deposit located in the High Aldudes valley (Basque country), an area well known for its mineral abundance, exploited from Roman Times at least. Although minerogenic peatlands are not generally considered as the best archives to reconstruct past atmospheric metal deposition history, lead isotopic geochemistry demonstrates the integrity of the Pb record at least within the three upper meters; that is to say over the last four millennia. Zn, Cd and Cu may have been widely redistributed either by biological cycling, advective groundwater movements, or diffusional processes. Anthropogenic lead input phases are clearly pinpointed by positive shifts in Pb/Sc ratios with concomitant sharp drops in (206)Pb/(207)Pb ratios. They are often accompanied by significant declines in tree taxa, interpreted as increasing demand for wood to supply energy for local mining and/or metallurgical operations. Periods of mining and/or smelting activity are identified during Antiquity and Modern Times, and are also confirmed by textual and field evidence. Inputs from the Rio Tinto (Southern Spain), often invoked as a major lead contributor to the European atmosphere during Roman Times, were not detected here. This remote source was probably masked by local inputs. Other mining and/or smelting phases, only suspected by archaeologists, are here identified as early as the Bronze Age. Although the durations of these phases are possibly overestimated because of detrital inputs consequent to the release of lead from polluted soils over a long period of time after major pollutant inputs, the periods at which pollution peaks occur are in good agreement with archaeological knowledge and palaeo-botanical data. The combination of geochemical and palaeo-botanical techniques with field archaeology, therefore provides a powerful tool in studying the interaction of early human societies with their environment, as regards early mining and smelting.

Modeling lead input and output in soils using lead isotopic geochemistry.

The aim of this study is to model downward migration of lead from the plow layer of an experimental site located in Versailles (about 15 km southwest of Paris, France). Since 1928, samples have been collected annually from the topsoil of three control plots maintained in bare fallow. Thirty samples from 10 different years were analyzed for their lead and scandium contents and lead isotopic compositions. The fluxes are simple because of the well-controlled experimental conditions in Versailles: only one output flux, described as a first-order differential function of the anthropogenic lead pool, was taken into account; the inputs were exclusively ascribed to atmospheric deposition. The combination of concentration and isotopic data allows the rate of migration from the plowed topsoil to the underlying horizon and, to a lesser extent, the atmospheric fluxes to be assessed. Both results are in good agreement with the sparse data available. Indeed, the post-depositional migration of lead appears negligible at the human time scale: less than 0.1% of the potentially mobile lead pool migrates downward, out of the first 25 cm of the soil, each year. Assuming future lead inputs equal to 0, at least 700 yr would be required to halve the amount of accumulated lead pollution. Such a low migration rate is compatible with the persistence of a major anthropogenic lead pool deposited before 1928. Knowledge of pollution history seems therefore to be of primary importance.

History and environmental impact of mining activity in Celtic Aeduan territory recorded in a peat bog (Morvan, France).

The present study aims to document historical mining and smelting activities by means of geochemical and pollen analyses performed in a peat bog core collected around the Bibracte oppidum (Morvan, France), the largest settlement of the great Aeduan Celtic tribe (ca. 180 B.C. to 25 A.D.). The anthropogenic Pb profile indicates local mining operations starting from the Late Bronze Age, ca. cal. 1300 B.C. Lead inputs peaked at the height of Aeduan civilization and then decreased after the Roman conquest of Gaul, when the site was abandoned. Other phases of mining are recognized from the 11th century to modern times. They have all led to modifications in plant cover, probably related in part to forest clearances necessary to supply energy for mining and smelting. Zn, Sb, Cd, and Cu distributions may result from diffusional and biological processes or from the influence of groundwater and underlying mineral soil, precluding their interpretation for historical reconstruction. The abundance of mineral resources, in addition to the strategic location, might explain why early settlers founded the city of Bibracte at that particular place. About 20% of the anthropogenic lead record was accumulated before our era and about 50% before the 18th century, which constitutes a troublesome heritage. Any attempts to develop control strategies in accumulating environments should take into account past human activities in order to not overestimate the impact of contemporary pollution.

Immunocytochemical localization of cytochrome P450 aromatase in the testis of prepubertal, pubertal, and postpubertal horses.

The large amount of testicular estrogens produced by the stallion is unique compared to the amounts found in other domestic species. Although the cellular locale of the cytochrome P450 aromatase (P450arom) enzyme that converts C19 androgens to C18 estrogens has been identified in the Leydig cell of adult equine testis, the location in the immature equine testis is not known. The goal of this work was to localize the enzyme in colts and stallions during sexual development. Testes were obtained from prepubertal (n=7), pubertal (n=6), and postpubertal (n=8) colts and stallions during both the breeding and non-breeding seasons. Tissue was fixed and prepared for immunocytochemistry (ICC), carried out with an antiserum against human placental P450arom. In prepubertal colts, there was distinct immunopositive staining of a similar degree within both the Leydig cell and the seminiferous tubule. Horses in the pubertal group had strong Leydig cell immunopositive staining and a slight degree of positive staining within the seminiferous tubules. Postpubertal stallions exhibited definitive immunopositive staining within Leydig cells but not within the seminiferous tubules. Therefore, P450arom is present within the Leydig cell throughout sexual development. In contrast, the presence of P450arom within the seminiferous tubule based upon ICC appeared to be gone by adulthood, suggesting that an age-dependent shift in the locale of this enzyme as the stallion matures.

Factors controlling 7Be and 210Pb atmospheric deposition as revealed by sampling individual rain events in the region of Geneva, Switzerland.

Bulk atmospheric deposition of 7Be and 210Pb has been measured at Versoix, close to Geneva, Switzerland. Collectors were continuously deployed from November 1997 through November 1998 for periods from 1 to 22 days depending on the frequency of rain. The activities of 7Be and 210Pb integrated over the sampling interval were moderately well correlated with rainfall (r2 of 0.66 and 0.55, respectively; p < 0.001) and well correlated one with the other (r2 of 0.91; p < 0.001). The 7Be/210Pb activity ratio is close to 13.5, except for samples collected in the periods of very low precipitation which have a distinctly lower ratio. A simple model accounting for rainfall, seasonal variations and reload of the local atmosphere after a rain event explains 90% of the variance of 7Be and 210Pb deposition. Concentrations of 210Pb and Ca++ in rain were correlated with transport time of air masses over the continent as indicated by reconstruction of air mass trajectories over three days.