Combined zinc-lead isotope and trace-metal assessment of recent atmospheric pollution sources recorded in Irish peatlands.

Atmospherically-fed Earth surface archives such as ombrotrophic peatlands, lake sediments, and ice consistently show an upward increase in Zn concentrations of hitherto unclear origin. Here, we present a combined stable Zn isotope and trace element (Zn, Cd, Ni, Cu, Cr, V, Ta, Pb) dataset for a historically polluted, near-urban bog (Liffey Head) from the east coast of Ireland. This peat record is compared to an archive from a rural site at the west coast of Ireland (Brackloon Wood). Both archives show a clear near-surface increase in Zn deposition, accompanied by periodic deposition in Cr, Ni, Mo, and V suggesting a co-genetic origin of these elements. In the Liffey Head site, biologic upward distillation of nutrients can be excluded as the origin of the elemental enrichments. The differences in the excess metal ratios between the two sites (e.g., Zn/Cd of 426-1564, east, and 77-106, west) are attributed to a higher contribution from traffic emissions (diesel, petrol) and oil-burning at the near-urban site, and dominant atmospheric influence from solid fossil fuel combustion emissions (e.g., mixed fuel, coal and wood) at the rural site. The Zn isotope composition in the historically-polluted Liffey Head bog evolved from δZn values of 0.72 ± 0.03‰ in the peat accumulated during the 19 century to lighter ratios (0.18 ± 0.03‰) towards the top of the monolith (i.e., recent). Zinc-isotope ratios are positively correlated with excess metal/Cd ratios and also with Pb/Pb, collectively fingerprinting the gradual change from a mining-dominated to a traffic-dominated atmospheric pollution at the east coast over the past century. A prevalent input, interpreted to represent combustion emissions from diesel engines, is observed for the past 15 years. Combined with trace elements and radiogenic Pb isotopes, the information obtained with the Zn isotope systematics adds towards an in-depth characterisation of the pollution signals.