Fe-Rich Fossil Vents as Mars Analog Samples: Identification of Extinct Chimneys in Miocene Marine Sediments Using Raman Spectroscopy, X-Ray Diffraction, and Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy.

On Earth, the circulation of Fe-rich fluids in hydrothermal environments leads to characteristic iron mineral deposits, reflecting the pH and redox chemical conditions of the hydrothermal system, and is often associated with chemotroph microorganisms capable of deriving energy from chemical gradients. On Mars, iron-rich hydrothermal sites are considered to be potentially important astrobiological targets for searching evidence of life during exploration missions, such as the Mars 2020 and the ExoMars 2022 missions. In this study, an extinct hydrothermal chimney from the Jaroso hydrothermal system (SE Spain), considered an interesting geodynamic and mineralogical terrestrial analog for Mars, was analyzed using Raman spectroscopy, X-ray diffraction, and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. The sample consists of a fossil vent in a Miocene shallow-marine sedimentary deposit composed of a marl substrate, an iron-rich chimney pipe, and a central space filled with backfilling deposits and vent condensates. The iron crust is particularly striking due to the combined presence of molecular and morphological indications of a microbial colonization, including mineral microstructures (e.g., stalks, filaments), iron oxyhydroxide phases (altered goethite, ferrihydrite), and organic signatures (carotenoids, organopolymers). The clear identification of pigments by resonance Raman spectroscopy and the preservation of organics in association with iron oxyhydroxides by Raman microimaging demonstrate that the iron crust was indeed colonized by microbial communities. These analyses confirm that Raman spectroscopy is a powerful tool for documenting the habitability of such historical hydrothermal environments. Finally, based on the results obtained, we propose that the ancient iron-rich hydrothermal pipes should be recognized as singular terrestrial Mars analog specimens to support the preparatory work for robotic in situ exploration missions to Mars, as well as during the subsequent interpretation of data returned by those missions.

Economic resilience of Carthage during the Punic Wars: Insights from sediments of the Medjerda delta around Utica (Tunisia).

While the Punic Wars (264-146 BC) have been the subject of numerous studies, generally focused on their most sensational aspects (major battles, techniques of warfare, geopolitical strategies, etc.), curiously, the exceptional economic resilience of the Carthaginians in the face of successive defeats, loss of mining territory, and the imposition of war reparations has attracted hardly any attention. Here, we address this issue using a newly developed powerful tracer in geoarchaeology, that of Pb isotopes applied to paleopollution. We measured the Pb isotopic compositions of a well-dated suite of eight deep cores taken in the Medjerda delta around the city of Utica. The data provide robust evidence of ancient lead-silver mining in Tunisia and lay out a chronology for its exploitation, which appears to follow the main periods of geopolitical instability at the time: the Greco-Punic Wars (480-307 BC) and the Punic Wars (264-146 BC). During the last conflict, the data further suggest that Carthage was still able to pay indemnities and fund armies despite the loss of its traditional silver sources in the Mediterranean. This work shows that the mining of Tunisian metalliferous ores between the second half of the fourth and the beginning of the third century BC contributed to the emergence of Punic coinage and the development of the Carthaginian economy.

High-resolution reconstruction of atmospheric deposition of trace metals and metalloids since AD 1400 recorded by ombrotrophic peat cores in Hautes-Fagnes, Belgium.

The objective of our study was to determine the trace metal accumulation rates in the Misten bog, Hautes-Fagnes, Belgium, and assess these in relation to established histories of atmospheric emissions from anthropogenic sources. To address these aims we analyzed trace metals and metalloids (Pb, Cu, Ni, As, Sb, Cr, Co, V, Cd and Zn), as well as Pb isotopes, using XRF, Q-ICP-MS and MC-ICP-MS, respectively in two 40-cm peat sections, spanning the last 600 yr. The temporal increase of metal fluxes from the inception of the Industrial Revolution to the present varies by a factor of 5-50, with peak values found between AD 1930 and 1990. A cluster analysis combined with Pb isotopic composition allows the identification of the main sources of Pb and by inference of the other metals, which indicates that coal consumption and metallurgical activities were the predominant sources of pollution during the last 600 years.

Reconstructing historical atmospheric mercury deposition in Western Europe using: Misten peat bog cores, Belgium.

Four sediment cores were collected in 2008 from the Misten ombrotrophic peat bog in the Northern part of the Hautes Fagnes Plateau in Belgium. Total mercury (Hg) concentrations were analyzed to investigate the intra-site variability in atmospheric Hg deposition over the past 1,500 years. Mercury concentrations in the four cores ranged from 16 to 1,100 µg kg(-1), with the maxima between 840 and 1,100 µg kg(-1). A chronological framework was established using radiometric (210)Pb and (14)C dating of two cores (M1 and M4). Pollen horizons from these two cores were correlated with data from two additional cores, providing a consistent dating framework between all the sites. There was good agreement between atmospheric Hg accumulation rates in the four cores over time based on precise age dating and pollen chronosequences. The average Hg accumulation rate before the influence of human activities (from 500 to 1,300 AD) was 1.8 ± 1 µg m(-2)y(-1) (2SD). Maximum Hg accumulation rates ranged from 90 to 200 µg m(-2)y(-1) between 1930 and 1980 AD. During the European-North American Industrial Revolution, the mean Hg accumulation rate exceeded the pre-Industrial values by a factor of 63. Based on comparisons with historical records of anthropogenic activities in Europe and Belgium, the predominant regional anthropogenic sources of Hg during and after the Industrial Revolution were coal burning and smelter Hg emissions. Mercury accumulation rates and chronologies in the Misten cores were consistent with those reported for other European peat records.

Anthropogenic impacts in North Poland over the last 1300 years--a record of Pb, Zn, Cu, Ni and S in an ombrotrophic peat bog.

Lead pollution history over Northern Poland was reconstructed for the last ca. 1300 years using the elemental and Pb isotope geochemistry of a dated Polish peat bog. The data show that Polish Pb-Zn ores and coal were the main sources of Pb, other heavy metals and S over Northern Poland up until the industrial revolution. After review of the potential mobility of each element, most of the historical interpretation was based on Pb and Pb isotopes, the other chemical elements (Zn, Cu, Ni, S) being considered secondary indicators of pollution. During the last century, leaded gasoline also contributed to anthropogenic Pb pollution over Poland. Coal and Pb-Zn ores, however, remained important sources of pollution in Eastern European countries during the last 50 years, as demonstrated by a high (206)Pb/(207)Pb ratio (1.153) relative to that of Western Europe (ca. 1.10). The Pb data for the last century were also in good agreement with modelled Pb inventories over Poland and the Baltic region.

Atmospheric lead and heavy metal pollution records from a Belgian peat bog spanning the last two millenia: human impact on a regional to global scale.

Europe has been continuously polluted throughout the last two millennia. During the Roman Empire, these pollutions were mainly from ore extraction and smelting across Europe. Then, during the Middle Ages and the Early times of Industrial revolution (i.e. 1750), these pollutions extended to coal burning and combustion engine. Belgian ombrotrophic peat bogs have proved an effective archive of these pollutants and provide the opportunity to reconstruct the history of atmospheric deposition in NW Europe. The results of recent and past trace metal accumulation and Pb isotopes from a one-meter peat core (in the Misten peat bog) have been derived using XRF and Nu-plasma MC-ICP-MS. Combined with (14)C and (210)Pb dates these data have enabled us to trace fluxes in anthropogenic pollution back to original Roman times. Several periods of well-known Pb pollution events are clearly recorded including the Early and Late Roman Empire, the Middle Ages and the second industrial revolution. Also recorded is the introduction of leaded gasoline, and more recently the introduction of unleaded gasoline. Lead isotopes in this site have also enabled us to fingerprint several regional and global sources of anthropogenic particles.