RESUMO
Constraining sources and site-specific processes of trace elements in speleothem geochemical records is key to an informed interpretation. This paper examines a 10-year data set of drip water solutes from Harrie Wood Cave, south-eastern Australia, and identifies the processes that control their response to El Niño-Southern Oscillation events which varies the site water balance. The contributions of aerosol and bedrock end-members are quantified via hydrochemical mass balance modelling. The parent bedrock is the main source for the drip water solutes: Mg, Sr, K and trace elements (Ba, Al, V, Cr, Mn, Ni, Co, Cu, Pb and U), while atmospheric aerosol inputs also contribute significantly to drip water trace elements and Na, K and Zn. A laboratory investigation evaluating water-soluble fractions of metals in soil samples and soil enrichment factors provided a basis for understanding metal retainment and release to solution and transport from the soil zone. These results identified the role of the soil as a sink for: trace metals, Na and K, and a secondary source for Zn. Further, soil processes including: cation exchange, K-fixation, metal adsorption to colloids and the release of Zn associated with organic matter degradation further modify the chemical composition of the resultant drip waters. This research is significant for the south-eastern Australian region, as well as other sites in a karst setting with clay-rich soil. In particular these results reveal that the response of drip water chemistry to hydroclimatic forcing is non-linear, with the greatest response observed when the long-term gradient in the cumulative water balance reverses. This longer-term drip water monitoring dataset is significant because it provides the pivotal framework required to reliably identify suitable trace element proxies for interpretation in geochemical speleothem records on multi-decadal timescales.
RESUMO
Characterisation of atmospheric aerosols is of major importance for: climate, the hydrological cycle, human health and policymaking, biogeochemical and palaeo-climatological studies. In this study, the chemical composition and source apportionment of PM2.5 (particulate matter with aerodynamic diameters less than 2.5µm) at Yarrangobilly, in the Snowy Mountains, SE Australia are examined and quantified. A new aerosol monitoring network was deployed in June 2013 and aerosol samples collected during the period July 2013 to July 2017 were analysed for 22 trace elements and black carbon by ion beam analysis techniques. Positive matrix factorisation and back trajectory analysis and trajectory clustering methods were employed for source apportionment and to isolate source areas and air mass travel pathways, respectively. This study identified the mean atmospheric PM2.5 mass concentration for the study period was (3.3±2.5)µgm-3. It is shown that automobile (44.9±0.8)%, secondary sulfate (21.4±0.9)%, smoke (12.3±0.6)%, soil (11.3±0.5)% and aged sea salt (10.1±0.4)% were the five PM2.5 source types, each with its own distinctive trends. The automobile and smoke sources were ascribed to a significant local influence from the road network and bushfire and hazard reduction burns, respectively. Long-range transport are the dominant sources for secondary sulfate from coal-fired power stations, windblown soil from the inland saline regions of the Lake Eyre and Murray-Darling Basins, and aged sea salt from the Southern Ocean to the remote alpine study site. The impact of recent climate change was recognised, as elevated smoke and windblown soil events correlated with drought and El Niño periods. Finally, the overall implications including potential aerosol derived proxies for interpreting palaeo-archives are discussed. To our knowledge, this is the first long-term detailed temporal and spatial characterisation of PM2.5 aerosols for the region and provides a crucial dataset for a range of multidisciplinary research.
