Detailed history of atmospheric trace elements from the Quelccaya ice core (Southern Peru) during the last 1200 years

The recent increase in trace element concentrations, for example Cr, Cu, Zn, Ag, Pb, Bi, and U, in polar snow and ice has provided compelling evidence of a hemispheric change in atmospheric composition since the nineteenth century. This change has been concomitant with the expansion of the Industrial Revolution and points towards an anthropogenic source of trace elements in the atmosphere. There are very few low latitude trace element ice core records and these are believed to be sensitive to perturbations of regional significance. To date, these records have not been used to document a preindustrial anthropogenic impact on atmospheric composition at low latitudes. Ice cores retrieved from the tropical Andes are particularly interesting because they have the potential to reveal detailed information about the evolution and environmental consequences of mineral exploitation related to the Pre Inca Civilizations, the Inca Empire (1438-1533 AD) and the subsequent Spanish invasion and dominance (1532-1833 AD). The chemical record preserved in the ice of the Quelccaya ice cap (southern Peruvian Andes) offers the exceptional opportunity to geochemically constrain the composition of the tropical atmosphere at high resolution over the last ~1200 years. Quantification of twenty trace elements (Ag, Al, As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Rb, Sb, Sn, Ti, Tl, U, V, and Zn) was performed by ICP-SFMS over 105 m of the Quelccaya North Dome core (5600 m asl, 128.57 m) by analyzing 2450 samples. This provides the first atmospheric trace element record in South America spanning continuously and at high resolution for the time period between 1990 and 790 AD. Ag, As, Bi, Cd, Cr, Co, Cu, Mn, Mo, Sb, Sn, Pb and Zn show increases in concentration and crustal enrichment factor starting at different times between 1450 and 1550 AD, in concomitance with the expansions of the Inca Empire and, subsequently, the Spanish Empire well before the inception of the Industrial Revolution. This indicates that there have been additional anthropogenic sources that have impacted the South American atmosphere during the past ~550 years. Furthermore, As, Bi and Pb record shows, the two most significant increases have occurred in the 20th century, one beginning in ~1905 AD and peaking in the 1920s and the second beginning in ~1955 AD and peaking in the 1970s. Comparison with other trace element records from Greenland and Antarctica reveals concomitant peaks of different amplitude in Pb concentration and crustal enrichment factor, possibly pointing to an unexpected larger than regional scale significance for the Quelccaya ice core record during the last century. In conclusion, the Quelccaya ice core indicates that societal and industrial development influenced the atmospheric composition in South America, from different large scale sources, during the last ~550 years. This is the first time that a low latitude ice core record has been used to reconstruct pre-industrial anthropogenic forcing on the atmosphere.