Fabrice Monna

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.

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.

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.

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.

The first 40Ar–39Ar date from Oxfordian ammonite-calibrated volcanic layers (bentonites) as a tie-point for the Late Jurassic

Eight volcanic ash layers, linked to large explosive events caused by subduction-related volcanism from the Vardar Ocean back-arc, interbedded with marine limestones and cherts, have been identified in the Rosso Ammonitico Veronese Formation (northeastern Italy). The thickest ash layer, attributed to the Gregoryceras transversarium ammonite Biozone (Oxfordian Stage), yields a precise and reliable 40 Ar– 39 Ar date of 156.1 ± 0.89 Ma, which is in better agreement with GTS2004 boundaries than with the current GTS2012. This first biostratigraphically well-constrained Oxfordian date is proposed as a new radiometric tie-point to improve the Geologic Time Scale for the Late Jurassic, where ammonite-calibrated radiometric dates are particularly scarce.

Landuse and soil degradation in the southern Maya lowlands, from Pre-Classic to Post-Classic times: The case of La Joyanca (Petén, Guatemala)

This work focuses on the impact of Maya agriculture on soil degradation. In site and out site studies in the area of the city of La Joyanca (NW Petén) show that “Maya clays” do not constitute a homogeneous unit, but represent a complex sedimentary record. A high resolution analysis leads us to document changes in rates and practices evolving in time in relation with major socio-political and economic changes. It is possible to highlight extensive agricultural practices between Early Pre-classical to Late Pre-classical times. Intensification occurs in relation with reduction of the fallow duration during Pre-classic to Classic periods. The consequences of these changes on soil erosion are discussed. However, it does not seem that the agronomic potential of the soils was significantly degraded before the end of the Classic period.

7000 years of vegetation history and land-use changes in the Morvan Mountains (France): a regional synthesis.

This paper aims to reconstruct the vegetation history of a middle mountain – the Morvan (Burgundy, France) – since the Neolithic (i.e. 7000 years). The results of palynological and non-pollen palynomorphs (NPPs) analysis performed on 10 peat cores document the main phases of human agro-pastoral practices and natural resources management which drove the formation of the cultural landscape of the Morvan Massif over time. To document the history of human activities at a regional scale, particular attention was given to the determination, the characterization and the graphical depiction of phrases of human impact. Both the quantification of the impact of human pressure and the chronological uncertainty of the different phases identified by pollen and NPP analysis were taken into account. This study reveals a clear human presence during periods that were formerly poorly documented, such as the onset of the Neolithic period, the Bronze Age, the early Iron Age and the early Middle Ages. It also sheds new light over periods for which there is better archaeological and historical knowledge, such as the widespread occupation of the massif in the late Iron Age, the cultivation of chestnut from the 11th to the 16th century and the impact of modern firewood exploitation on the forest.

Impact of nickel mining in New Caledonia assessed by compositional data analysis of lichens

The aim of this study is to explore the use of lichens as biomonitors of the impact of nickel mining and ore treatment on the atmosphere in the New Caledonian archipelago (South Pacific Ocean); both activities emitting also Co, Cr and possibly Fe. Metal contents were analysed in thirty-four epiphytic lichens, collected in the vicinity of the potential sources, and in places free from known historical mining. The highest Ni, Co, and Cr concentrations were, as expected, observed in lichens collected near ore deposits or treatment areas. The elemental composition in the lichens was explored by multivariate analysis, after appropriately transforming the variables (i.e. using compositional data analysis). The sample score of the first principal component (PC1) makes the largest (positive) multiplicative contribution to the log-ratios of metals originating from mining activities (Ni, Cr, Co) divided by Ti. The PC1 scores are used here as a surrogate of pollution levels related to mining and metallurgical activity. They can be viewed as synthetic indicators mapped to provide valuable information for the management and protection of ecosystems or, as a first step, to select locations where air filtration units could be installed, in the future, for air quality monitoring. However, as this approach drastically simplifies the problem, supplying a broadly efficient picture but little detail, recognizing the different sources of contamination may be difficult, more particularly when their chemical differences are subtle. It conveys only relative information: about ratios, not levels, and is therefore recommended as a preliminary step, in combination with close examination of raw concentration levels of lichens. Further validation using conventional air-monitoring by filter units should also prove beneficial.

Trace metals from historical mining sites and past metallurgical activity remain bioavailable to wildlife today.

Throughout history, ancient human societies exploited mineral resources all over the world, even in areas that are now protected and considered to be relatively pristine. Here, we show that past mining still has an impact on wildlife in some French protected areas. We measured cadmium, copper, lead, and zinc concentrations in topsoils and wood mouse kidneys from sites located in the Cévennes and the Morvan. The maximum levels of metals in these topsoils are one or two orders of magnitude greater than their commonly reported mean values in European topsoils. The transfer to biota was effective, as the lead concentration (and to a lesser extent, cadmium) in wood mouse kidneys increased with soil concentration, unlike copper and zinc, providing direct evidence that lead emitted in the environment several centuries ago is still bioavailable to free-ranging mammals. The negative correlation between kidney lead concentration and animal body condition suggests that historical mining activity may continue to play a role in the complex relationships between trace metal pollution and body indices. Ancient mining sites could therefore be used to assess the long-term fate of trace metals in soils and the subsequent risks to human health and the environment.