Dataset of natural metal background levels inferred from pre-industrial palaeochannel sediment cores along the Rhône River (France).

Natural metal background levels in sediments are critical to assess spatial and temporal trends of contamination in hydrosystems and to manage polluted sediments. This is even more sensitive that multi-factors such as geogenic basement, depositional context, and past or long-term pollution can affect the level of metals in sediments. This article provides natural metal background levels and ancillary data (location, chronology, grain-size, total organic carbon - TOC) in pre-industrial sediments along the Rhône River (France). Two distinct areas were selected to take into account the geological variability of the watershed: the Dauphiné Lowlands (Upper Rhône River) and the Tricastin Floodplain (Middle Rhône River). On each area, the sediment cores were retrieved from palaeochannel sequences and the sampled sections were dated by radiocarbon from the Roman to the Modern Times (AD 3-1878). Regulatory metals (Al, Fe, Cd, Cr, Cu, Ni, Pb, and Zn) and other trace elements (Ba, Co, Li, Mg, Mn, Na, P, Sr, Ti, V) were analysed following both Aqua Regia (AR) and Total Extraction (TE) procedures. Classically, TE provides metal concentrations greater than AR because TE includes crystalline lattice, while AR is close to the potentially bio-accessible part of metals (used for ecotoxicological purposes). Due to the small number of samples and to the non-normal distribution of the results, a median-based approach was chosen to establish the geochemical background values and ranges (MGB) for each sample and area. These MGBs are valuable to identify pollution sources, to characterise a contamination (spread and timing), and to estimate the state of rivers regarding pollution legacy. Along the Rhône River, these two continental MGBs were used to reconstruct the metal geo-accumulation trajectories in river sediments from 1965 to 2018 [1].

Hydro-climatic drivers of land-based organic and inorganic particulate micropollutant fluxes: The regime of the largest river water inflow of the Mediterranean Sea.

Land-based micropollutants are the largest pollution source of the marine environment acting as the major large-scale chemical sink. Despite this, there are few comprehensive datasets for estimating micropollutant fluxes released to the sea from river mouths. Hence, their dynamics and drivers remain poorly understood. Here, we address this issue by continuous measurements throughout the Rhône River basin (∼100,000 km2) of 1) particulate micropollutant concentrations (persistant organic micropollutants: polychlorobiphenyls [PCBi] and polycyclic aromatic hydrocarbons [PAHs]; emerging compounds: glyphosate and aminomethylphosphonic acid [AMPA]; and trace metal elements [TME]), 2) suspended particulate matter [SPM], and 3) water discharge. From these data, we computed daily fluxes for a wide range of micropollutants (n = 29) over a long-term period (2008-2018). We argue that almost two-thirds of annual micropollutant fluxes are released to the Mediterranean Sea during three short-term periods over the year. The watershed hydro-climatic heterogeneity determines this dynamic by triggering seasonal floods. Unexpectedly, the large deficit of the inter-annual monthly micropollutant fluxes inputs (tributaries and the Upper Rhône River) compared to the output (Beaucaire station) claims for the presence of highly contaminated missing sources of micropollutants in the Rhône River watershed. Based on a SPM-flux-averaged micropollutant concentrations mass balance of the system and the estimates of the relative uncertainty of the missing sources concentration, we assessed their location within the Rhône River catchment. We assume that the potential missing sources of PAHs, PCBi and TME would be, respectively, the metropolitan areas, the alluvial margins of the Rhône River valley, and the unmonitored Cevenol tributaries.

Metal pollution trajectories and mixture risk assessed by combining dated cores and subsurface sediments along a major European river (Rhône River, France).

In European rivers, research and monitoring programmes have targeted metal pollution from bed and floodplain sediments since the mid-20th century by using various sampling and analysis protocols. We propose to characterise metal contamination trajectories since the 1960s based on the joint use of a large amount of data from dated cores and subsurface sediments along the Rhône River (ca. 512 km, Switzerland-France). For the reconstruction of spatio-temporal trends, enrichment factors (EF) and geo-accumulation (Igeo) approaches were compared. The latter index was preferred due to the recurrent lack of grain-size and lithogenic elements in the dataset. Local geochemical backgrounds were established near (1) the Subalps and (2) the Massif Central to consider the geological variability of the watershed. A high contamination (Igeo = 3-5) was found for Cd, Cu and Zn from upstream to downstream over the period 1980-2000. This pattern is consistent with long-term emissions from major cities and the nearby industrial areas of the Upper Rhône (Geneva, Arve Valley), and Middle Rhône (Lyon, Chemical Corridor, Gier Valley). Hotspots due to Cu and Zn leaching from vineyards, mining, and highway runoff were also identified, while Pb was especially driven by industrial sources. The recovery time of pollution in sediment varied according to the metals and was shorter upstream of Lyon (15-20 years) than downstream (30-40 years). More widely, it was faster on the Rhône than along other European rivers (e.g. Seine and Rhine). Finally, the ecotoxicological mixture risk of metal with Persistent Organic Pollutants (POPs) for sediment-dwelling organisms showed a medium "cocktail risk" dominated by metals upstream of Lyon, although it is enhanced due to POPs downstream, and southward to the delta and the Mediterranean Sea. Overall, this study demonstrates the heterogeneity of the contamination trends along large fluvial corridors such as the Rhône River.

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.

Rome's urban history inferred from Pb-contaminated waters trapped in its ancient harbor basins.

Heavy metals from urban runoff preserved in sedimentary deposits record long-term economic and industrial development via the expansion and contraction of a city's infrastructure. Lead concentrations and isotopic compositions measured in the sediments of the harbor of Ostia-Rome's first harbor-show that lead pipes used in the water supply networks of Rome and Ostia were the only source of radiogenic Pb, which, in geologically young central Italy, is the hallmark of urban pollution. High-resolution geochemical, isotopic, and 14C analyses of a sedimentary core from Ostia harbor have allowed us to date the commissioning of Rome's lead pipe water distribution system to around the second century BC, considerably later than Rome's first aqueduct built in the late fourth century BC. Even more significantly, the isotopic record of Pb pollution proves to be an unparalleled proxy for tracking the urban development of ancient Rome over more than a millennium, providing a semiquantitative record of the water system's initial expansion, its later neglect, probably during the civil wars of the first century BC, and its peaking in extent during the relative stability of the early high Imperial period. This core record fills the gap in the system's history before the appearance of more detailed literary and inscriptional evidence from the late first century BC onward. It also preserves evidence of the changes in the dynamics of the Tiber River that accompanied the construction of Rome's artificial port, Portus, during the first and second centuries AD.

A lead isotope perspective on urban development in ancient Naples.

The influence of a sophisticated water distribution system on urban development in Roman times is tested against the impact of Vesuvius volcanic activity, in particular the great eruption of AD 79, on all of the ancient cities of the Bay of Naples (Neapolis). Written accounts on urbanization outside of Rome are scarce and the archaeological record sketchy, especially during the tumultuous fifth and sixth centuries AD when Neapolis became the dominant city in the region. Here we show that isotopic ratios of lead measured on a well-dated sedimentary sequence from Neapolis' harbor covering the first six centuries CE have recorded how the AD 79 eruption was followed by a complete overhaul of Neapolis' water supply network. The Pb isotopic signatures of the sediments further reveal that the previously steady growth of Neapolis' water distribution system ceased during the collapse of the fifth century AD, although vital repairs to this critical infrastructure were still carried out in the aftermath of invasions and volcanic eruptions.

Lead in ancient Rome's city waters.

It is now universally accepted that utilization of lead for domestic purposes and water distribution presents a major health hazard. The ancient Roman world was unaware of these risks. How far the gigantic network of lead pipes used in ancient Rome compromised public health in the city is unknown. Lead isotopes in sediments from the harbor of Imperial Rome register the presence of a strong anthropogenic component during the beginning of the Common Era and the Early Middle Ages. They demonstrate that the lead pipes of the water distribution system increased Pb contents in drinking water of the capital city by up to two orders of magnitude over the natural background. The Pb isotope record shows that the discontinuities in the pollution of the Tiber by lead are intimately entwined with the major issues affecting Late Antique Rome and its water distribution system.