Geochemical signatures of acidic drainage recorded in estuarine sediments after an extreme drought.

Extreme prolonged drought over south-eastern Australia a decade ago (the Millennium Drought, 1996-2010) triggered extensive acid sulfate soil oxidation and associated acidification. Whilst the significant release of metal-enriched drainage has been documented during this event, the fate of these elements in receiving systems is still largely unknown. Here we investigate the spatial distribution, chemical partitioning, and potential bioavailability of S, Fe, Mn, Al, trace metals (V, Cr, Co, Ni, Cu, Pb) and rare earth elements in the surficial sediments of Lake Albert, South Australia; a system that received prolonged (2007-2011) acidic drainage during the Millennium Drought. The highest concentrations of all metals (Enrichment Factors ranging from 1.06-1.97) were observed in the sediments closest to shorelines where sulfidic material were oxidised, generating metal-enriched acidic drainage. Localised enrichment indicates metals have not been completely redistributed across the system following their initial deposition by physical (wind-driven resuspension) or chemical (diagenetic and redox changes) processes. Based on selective extraction data, these metals are likely partitioned as discrete sulfides (Pb) or are with organic material (V, Cr, Cu, Pb, REEs), Fe monosulfides (V, Co, Ni), or pyrite (Co, Ni, Pb). Lake-wide enrichment of trace metals Cr (mean concentration 57 ppm), Ni (39 ppm), Cu (36 ppm), and Pb (24 ppm) relative to other Lower Murray River sites is also evident, suggesting that metal contamination associated with acidic drainage is not restricted to near-source sites. Importantly, the mobilisation, transport, and accumulation of metals is controlled by sediment transport pathways and system hydrology and will thus function differently under varying states of geomorphology, climate, and anthropogenic modification. Our study shows that extreme drought is recorded as a lasting geochemical signature in estuarine sediments, demonstrating that metal and rare earth element geochemistry provides insights into the distribution and behaviour of contaminants mobilised into dynamic, anthropogenically altered estuaries.

Metal enrichment in estuarine sediments proximal to acid sulfate soils as a novel palaeodrought proxy.

Persistent drought over eastern Australia at the turn of the last millennium reduced stream flow in Australia's largest and most economically important drainage basin. Low water levels in the basin's terminal lakes triggered widespread pyrite oxidation, which altered surface water chemistry and released metals into the environment. The frequency of these events, and the links between drought and acid sulfate soil activation, are not known because the historical and instrumental records are short. Here, we present a Holocene-aged record of trace metal enrichment from Lake Albert-part of the terminal Lower Lakes system of the Murray-Darling Basin, Australia-that demonstrates the potential of trace elements mobilised during acidification events for palaeodrought reconstructions. Symptomatic metals were measured from a core of clayey sediment to form a multi-element assemblage that reveals acidification events in the geological past. Correlation with regional climate proxies suggests that climate forcing is significant in driving metal flux to estuarine sinks in acid sulfate soil rich landscapes, although the intensity of a drought is not the only variable responsible for acidification intensity. The constructed record indicates that regional climate moved from a generally humid climate phase with intermittent droughts, to a more arid climate at ~5.2ka which prevailed until ~1.7ka. Following conditions were relatively wet with low climatic variability through till European Settlement. Enrichment is observed coincident with both the 1982-83 drought and Millennium Drought, the latter of which reaching an intensity unsurpassed in the last ~4.8ka, likely a product of anthropogenic changes to the Lower Murray-Darling Basin system.

Photocatalysis of fenoxycarb over silver-modified zeolites.

Two samples of silver doped into zeolite Y were prepared and characterized. ICP and SEM-EDS analysis indicate that the AgY1 sample contains twice the amount of silver compared to the AgY2 sample. Solid state luminescence spectroscopy shows variations in the emission modes of the site-selective luminescence where various luminophores might be excited upon selecting the proper excitation energy. The selected material effectively decomposed the pesticide fenoxycarb in aqueous solution. The photodecomposition of fenoxycarb reached 80 % upon irradiation for 60 min in the presence of the AgY1 catalyst. 2-(4-Phenoxy-phenoxy)ethyl] carbamic acid (1) and 1-amine-2-(phenoxy-4-ol) ethane (2) were identified as products for both uncatalyzed solution and the catalyzed fenoxycarb with AgY2 catalyst. Whereas, compound (2) was the only product identified in the catalyzed reaction with AgY1.