Inorganic hydrogeochemistry, hydrogeology and geology of the Stuarts Point aquifer system : a process analysis of the natural occurrences of enriched As(III) and As(V) in an Australian coastal groundwater system

摘要

Arsenic (As) in groundwater systems is a problem in many parts of the world owing to ever-increasing extraction of groundwater resources to meet the needs of growing populations. Surprisingly, the occurrence of elevated As concentrations in coastal sandy aquifers has only recently been published as a result of this research. Sandy aquifers are commonly used as a clean and reliable source of water for domestic, agricultural and industrial needs due to their high recharge rates and the filtering capacity of sands. Water quality monitoring in Australian sandy aquifers is usually limited to a small suite of major elements and salinity measurements to determine the quality of groundwater and to identify any potential problems from seawater intrusion as a result of over extraction. Minor and trace elements, particularly toxic elements, have largely been ignored in regular monitoring programs. Prompted by an emerging pattern of human health problems in a community reliant on groundwater, hydrogeochemical investigations of the Stuarts Point coastal sand aquifer, on the North Coast of New South Wales, Australia, identified elevated As concentrations of up to 337 μg/L in the catchment's Pleistocene barrier sands. These concentrations are well in excess of the World Health Organisation and the Australian National Health and Medical Research Council water quality criteria of 10 and 7 μg/L respectively. From research into the Stuarts Point geology, geochemistry, geomorphology, hydrogeology and hydrogeochemistry, and with the assistance of environmental isotopes, the spatial distribution, occurrence and mobilisation processes of As were determined. The presence and distribution of elevated As concentrations in the regional coastal aquifer system are sporadic and involve a series of complex hydrogeochemical processes. No single hydrogeochemical process can describe the release of As from solid phase to groundwater system on the regional scale. Processes of competitive exchange with PO43- and HCO3-, reductive dissolution of Fe oxyhydroxides and arsenical pyrite oxidation, though not forming dominant correlations, are still evident and influence As chemistry at this scale.Detailed investigations of the hydrogeochemistry on the vertical scale have identified two main processes as causing As to be released and mobilised. The first process is associated with the oxidation of arsenical pyrite in Acid Sulphate Soils and metal hydrolysis reactions which mobilise As in the acidic environment. In the absence of dissolved oxygen (DO), NO3- acts as the oxyanion facilitating arsenical pyrite oxidation and releasing As into solution. The second process that mobilises As from the sediments is the liberation of As from metal-oxyhydroxides in the carbon-rich environment, where HCO3- originates from the dissolution of shell material in the Pleistocene barrier sands. The marine influenced depositional history and geomorphology of the aquifer provide opportunities for As to become incorporated into the aquifers matrix in a variety of mineral forms, which is an occurrence not considered to be unique to the Stuarts Point catchment.The findings presented here are amongst the first detailed studies of naturally occurring As in an Australian groundwater system as well as in the Pleistocene coastal sand aquifer environment. The understanding of As accumulation and mobilisation identified as a result of this research emphasises the need for potential As occurrences in similar groundwater systems in other coastal environments in Australia, and globally, to be considered.