Perchlorate Depositional History as Recorded in North American Ice Cores from the Eclipse Icefield, Canada, and the Upper Fremont Glacier, USA

Abstract

Temporal depositional rates are important in order to understand the production and occurrence of perchlorate (ClO ⁻₄ ) as limited information exists regarding the impact of anthropogenic production or atmospheric pollution on ClO ⁻₄ deposition. Perchlorate concentrations in discrete ice core samples from the Eclipse Icefield (Yukon Territory, Canada) and Upper Fremont Glacier (Wyoming, USA) were analyzed using ion chromatography tandem mass spectrometry to evaluate temporal changes in the deposition of ClO₄ ⁻ in North America. The ice core samples cover a time period from 1726 to 1993 and 1970 to 2002 for the Upper Fremont Glacier (UFG) and Eclipse ice cores, respectively. The average ClO₄ ⁻ concentration in the Eclipse ice core for the time period from 1970 to 1973 was 0.6 ± 0.3 ng L⁻¹, with higher values of 2.3 ± 1.7 and 2.2 ± 2.0 ng L⁻¹ for the periods 1982–1986 and 1999–2002, respectively. All pre-1980 ice core samples from the UFG had ClO₄ ⁻ concentrations <0.2 ng L⁻¹, and the post-1980 samples ranged from <0.2 ng L⁻¹ to a maximum of 2.6 ng L⁻¹ for the year 1992. A significant positive correlation (R = 0.75, N = 15, p < 0.001) of ClO ⁻₄ with SO ²⁻₄ was found for the annual UFG ice core layers and of ClO₄ ⁻ with SO ²⁻₄ and NO ⁻₃ in sub-annual Eclipse ice samples (R > 0.3, N = 121, p < 0.002). The estimated yearly ClO ⁻₄ depositional flux for the Eclipse ice core ranged from 0.6 (1970) to 4.7 μg m⁻² year⁻¹ (1982) and the UFG from <0.1 (pre-1980) to 1.4 μg m⁻² year⁻¹ (1992). There was no consistent seasonal variation in the ClO ⁻₄ depositional flux for the Eclipse ice core, in contrast to a previous study on the Arctic region. The presence of ClO ⁻₄ in these ice cores might correspond to an intermittent source such as volcanic eruptions and/or any anthropogenic forcing that may directly or indirectly aid in atmospheric ClO ⁻₄ formation.