Rapa Nui (Easter Island) Rano Raraku crater lake basin: Geochemical characterization and implications for the Ahu-Moai Period.

Rano Raraku, the crater lake constrained by basaltic tuff that served as the primary quarry used to construct the moai statues on Rapa Nui (Easter Island), has experienced fluctuations in lake level over the past centuries. As one of the only freshwater sources on the island, understanding the present and past geochemical characteristics of the lake water is critical to understand if the lake could have been a viable freshwater source for Rapa Nui. At the time of sampling in September 2017, the maximum lake depth was ~1 m. The lake level has substantially declined in the subsequent years, with the lake drying almost completely in January 2018. The lake is currently characterized by highly anoxic conditions, with a predominance of ammonium ions on nitrates, a high concentration of organic carbon in the water-sediment interface and reducing conditions of the lake, as evidenced by Mn/Fe and Cr/V ratios. Our estimates of past salinity inferred from the chloride mass balance indicates that it was unlikely that Rano Raraku provided a viable freshwater source for early Rapa Nui people. The installation of an outlet pipe around 1950 that was active until the late 1970s, as well as grazing of horses on the lake margins appear to have significantly impacted the geochemical conditions of Rano Raraku sediments and lake water in recent decades. Such impacts are distinct from natural environmental changes and highlight the need to consider the sensitivity of the lake geochemistry to human activities.

Lake sediment fecal and biomass burning biomarkers provide direct evidence for prehistoric human-lit fires in New Zealand.

Deforestation associated with the initial settlement of New Zealand is a dramatic example of how humans can alter landscapes through fire. However, evidence linking early human presence and land-cover change is inferential in most continental sites. We employed a multi-proxy approach to reconstruct anthropogenic land use in New Zealand's South Island over the last millennium using fecal and plant sterols as indicators of human activity and monosaccharide anhydrides, polycyclic aromatic hydrocarbons, charcoal and pollen as tracers of fire and vegetation change in lake-sediment cores. Our data provide a direct record of local human presence in Lake Kirkpatrick and Lake Diamond watersheds at the time of deforestation and a new and stronger case of human agency linked with forest clearance. The first detection of human presence matches charcoal and biomarker evidence for initial burning at c. AD 1350. Sterols decreased shortly after to values suggesting the sporadic presence of people and then rose to unprecedented levels after the European settlement. Our results confirm that initial human arrival in New Zealand was associated with brief and intense burning activities. Testing our approach in a context of well-established fire history provides a new tool for understanding cause-effect relationships in more complex continental reconstructions.

Development of a method for simultaneous analysis of PCDDs, PCDFs, PCBs, PBDEs, PCNs and PAHs in Antarctic air.

The development of a unique analytical method for the determination of five classes of persistent organic pollutants (POPs) in atmospheric gas and the particle phase through gas chromatography coupled to high-resolution mass spectrometry is presented. Every step of the pre-analytical and analytical optimization process is described. Great effort was put into simplifying the traditional techniques, with reference to EPA and literature methods. Automated instruments were used for sample extraction and cleanup in order to enhance repeatability and reduce contamination risks. Unlike most common approaches, no separation of the analytes was performed before the GC analysis in order to avoid sample fractionation and to save time and materials. This allowed low instrumental and method detection limits (pg to sub-pg) to be achieved. Accuracy and precision were tested by fortifying the matrix and analysing standard reference materials (NIST SRM 1649b Urban Dust and 2585 Organic Contaminants in House Dust). The method was applied to five samples from Terra Nova Bay, Antarctica. Concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) are presented. Lighter compounds dominate the distribution and are mainly present in the gaseous phase. The observed pattern may be attributable to long-range transport. Results are in general agreement with literature data, where available.