Lipid biomarkers and metal pollution in the Holocene record of Cartagena Bay (SE Spain): Coupled natural and human induced environmental history in Punic and Roman times.

We reconstructed the palaeoenvironmental conditions of Cartagena Bay during the Holocene after a multidisciplinary study to identify natural variations and the anthropic processes of this coastal area. A total of 119 samples were recovered for amino acid racemization dating, 3 for radiocarbon dating (14C), and four sets of 80 samples for sedimentological and palaeontological determination, mineralogical content, biomarker and trace elements quantification. Two natural scenarios were identified from the variations of n-alkane indices and palaeobiological content. The first period (6650-5750 yr cal BP) was marked by the development of euhaline marine conditions with strong inputs from aquatic macrophytes and high biodiversity. After a hiatus, the area underwent a profound change, becoming a paucispecific brackish marsh environment with increasing inputs from land plants, with possible episodes of emersion with a greater presence from terrestrial gastropods (3600-300 cal yr BP). By combining trace element abundance and stanol distributions, our study also provides a novel approach to identify the predominant influence of anthropogenic factors in the last three millennia in the coastal record of Cartagena Bay. Findings confirmed that Pb mining and metallurgy began during the Bronze Age, with considerable inputs of this heavy metal into the atmosphere during Phoenician, Punic and particularly Roman times compared to the Middle Ages. Pollution by Cu and Zn was also observed during Punic and Roman times, and was first documented in the Middle Ages. In addition, faecal stanols, such as coprostanol, derived mainly from humans, and 24-ethylcoprostanol from herbivores were present, thereby indicating for the first time a continuous presence of human populations and significant pollution input since 3600 yr cal BP, this being greater in the late Bronze Age and Phoenician, Punic and Roman times than during Late Antiquity and the Middle Ages, when the city was in decline.

Keys to discern the Phoenician, Punic and Roman mining in a typical coastal environment through the multivariate study of trace element distribution.

Trace element concentrations in the Cartagena Bay coastal record reveal a contribution of natural processes. However, the influence of anthropogenic factors predominates in the last three millennia, particularly aerosol deposition linked to mining and industrial activities in the area. The coastal record of Cartagena can be considered a preserved environment, suitable to search for regional human activity fingerprinting, specifically that related to the deposition of heavy metals such as Pb and Cu. A multivariate statistical analysis was carried out to clarify the geochemical behaviour of trace and major elements. Our study design represents a novel approach to assign natural contributions, such as eolian and riverine input, to coastal deposits, and organic matter preservation under anoxic environments. Therefore, synergies obtained by the simultaneous study of multivariate statistics and enrichment factors allow robust conclusions about palaeoenvironmental evolution and human activities. Anthropogenic influence suggested that Pb mining and metallurgy began during the Chalcolithic period, with considerable inputs of Pb and Cu to atmospheric pollution during Phoenician, Punic and Roman times.

Early metal pollution in southwestern Europe: the former littoral lagoon of El Almarjal (Cartagena mining district, S.E. Spain).A sedimentary archive more than 8000 years old.

A borehole drilling campaign has allowed the study of a former littoral lagoon located next to the harbour city of Cartagena in South-East Spain (close to the Sierra de Cartagena polymetallic ore deposits). This lagoon, which developed during the Holocene, was first a shallow sedimentary marine environment and later evolved into a swampy semi-endorheic basin named "Almarjal" (after the Arab term from the fourteenth century). The lagoon eventually dried out and at present forms part of the substratum of the modern sector of the city urban area. The basin representative sediments are sapropelic black silty facies forming a continuous sedimentary archive, accounting for more than 8000 years of depositional phenomena. The geochemical study of these sediments, together with their absolute calibrated dating by 14C, allows definition of successive stages of mining and metallurgical activities in the area. In turn, this information provides a more comprehensive perspective regarding metal pollution, particularly lead contamination during different periods of the Recent Prehistory and the Classical Age. The results indicate that the beginning of contamination by lead and other heavy metals occurred as early as 4500 years ago, when the Final Chalcolithic period was taking place in the South-East of the Iberian Peninsula. This finding provides further insights regarding the debate on the origins of lead mining and metallurgy in SE Spain.