Abstract. The South Pole Ice Core (SPICEcore) was drilled in 2014–2016 to provide a detailed multi-proxy archive of paleoclimate conditions in East Antarctica during the Holocene and late Pleistocene. Interpretation of these records requires an accurate depth–age relationship. Here, we present the SPICEcore (SP19) timescale for the age of the ice of SPICEcore. SP19 is synchronized to the WD2014 chronology from the West Antarctic Ice Sheet Divide (WAIS Divide) ice core using stratigraphic matching of 251 volcanic events. These events indicate an age of 54 302±519 BP (years before 1950) at the bottom of SPICEcore. Annual layers identified in sodium and magnesium ions to 11 341 BP were used to interpolate between stratigraphic volcanic tie points, yielding an annually resolved chronology through the Holocene. Estimated timescale uncertainty during the Holocene is less than 18 years relative to WD2014, with the exception of the interval between 1800 to 3100 BP when uncertainty estimates reach ±25 years due to widely spaced volcanic tie points. Prior to the Holocene, uncertainties remain within 124 years relative to WD2014. Results show an average Holocene accumulation rate of 7.4 cm yr−1 (water equivalent). The time variability of accumulation rate is consistent with expectations for steady-state ice flow through the modern spatial pattern of accumulation rate. Time variations in nitrate concentration, nitrate seasonal amplitude and δ15N of N2 in turn are as expected for the accumulation rate variations. The highly variable yet well-constrained Holocene accumulation history at the site can help improve scientific understanding of deposition-sensitive climate proxies such as δ15N of N2 and photolyzed chemical compounds.

Perchlorate concentration ranges from a few to a few hundred ng kg−1 in surface and shallow‐depth snow at three Antarctic locations (South Pole, Dome A, and central West Antarctica), with significant spatial variations dependent on snow accumulation rate and/or atmospheric production rate. An obvious trend of increasing perchlorate since the 1970s is seen in South Pole snow. The trend is possibly the result of stratospheric chlorine levels elevated by anthropogenic chlorine emissions; this is supported by the timing of a similar trend at Dome A. Alternatively, the trend may stem from postdepositional loss of snowpack perchlorate or a combination of both. The possible impact of stratospheric chlorine is consistent with evidence of perchlorate production in the stratosphere. Additionally, perchlorate concentration appears to be directly affected by the springtime Antarctic ozone hole. Therefore, perchlorate variations in Antarctic snow are likely linked to stratospheric chemistry and ozone over the Antarctic.

An ion chromatography-electrospray ionization-tandem mass spectrometry (IC-ESI-MS/MS) method has been developed for rapid and accurate measurement of perchlorate in polar snow and ice core samples in which perchlorate concentrations are expected to be as low as 0.1 ng L(-1). Separation of perchlorate from major inorganic species in snow is achieved with an ion chromatography system interfaced to an AB SCIEX triple quadrupole mass spectrometer operating in multiple reaction monitoring mode. Under optimized conditions, the limit of detection and lower limit of quantification without pre-concentration have been determined to be 0.1 and 0.3 ng L(-1), respectively, with a linear dynamic range of 0.3-10.0 ng L(-1) in routine measurement. These represent improvements over previously reported methods using similar analytical techniques. The improved method allows fast, accurate, and reproducible perchlorate quantification down to the sub-ng L(-1) level and will facilitate perchlorate measurement in the study of natural perchlorate production with polar ice cores in which perchlorate concentrations are anticipated to vary in the low and sub-ng L(-1) range. Initial measurements of perchlorate in ice core samples from central Greenland show that typical perchlorate concentrations in snow dated prior to the Industrial Revolution are about 0.8 ng L(-1), while perchlorate concentrations are significantly higher in recent (post-1980) snow, suggesting that anthropogenic sources are a significant contributor to perchlorate in the current environment.

Snowpit samples collected at the West Antarctic Ice Sheet (WAIS) Divide location in January 2013 were analysed to investigate the levels and variations of perchlorate concentrations in Antarctic snow. During 2008–12, the perchlorate concentration in WAIS Divide snow ranged between 6–180 ng l–1 and followed a seasonal cycle. The highest concentrations appeared in the autumn, and the lowest in winter and spring. No apparent correlation was observed between perchlorate and nitrate or chloride concentrations in snow. Since perchlorate is believed to form in the atmosphere when chlorine species are oxidized in reactions involving ozone, perchlorate concentrations were hypothesized to be high during the spring, based on the assumption that stratospheric ozone depletion enhances tropospheric perchlorate production. The data show that perchlorate concentrations in snow were sharply reduced during stratospheric ozone depletion events; the evidence, therefore, does not support the hypothesis. Instead, the results suggest a stratospheric origin of perchlorate in Antarctic snow.

A 300-year (1700-2007) chronological record of environmental perchlorate, reconstructed from high-resolution analysis of a central Greenland ice core, shows that perchlorate levels in the post-1980 atm were two-to-three times those of the pre-1980 environment. While this confirms recent reports of increased perchlorate in Arctic snow since 1980 compared with the levels for the prior decades (1930-1980), the longer Greenland record demonstrates that the Industrial Revolution and other human activities, which emitted large quantities of pollutants and contaminants, did not significantly impact environmental perchlorate, as perchlorate levels remained stable throughout the 18, 19, and much of the 20 centuries. The increased levels since 1980 likely result from enhanced atmospheric perchlorate production, rather than from direct release from perchlorate manufacturing and applications. The enhancement is probably influenced by the emission of organic chlorine compounds in the last several decades. Prior to 1980, no significant long-term temporal trends in perchlorate concentration are observed. Brief (a few years) high-concentration episodes appear frequently over an apparently stable and low background (∼1 ng kg). Several such episodes coincide in time with large explosive volcanic eruptions including the 1912 Novarupta/Katmai eruption in Alaska. It appears that atmospheric perchlorate production is impacted by large eruptions in both high- and low-latitudes, but not by small eruptions and nonexplosive degassing.