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Development of a Real Time In Situ Zinc Analyser and Water Sampler — Results From High Resolution Monitoring of a Stream Impacted by Acid Rock Drainage

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  • Historically, most investigations of biogeochemical cycling in acid rock drainage systems involved synoptic sampling over longer time periods (one sample per week or month) or intensive time series studies over a few hours or days. However, many important episodic loading events, such as seasonal meltwater and storm events occur on timescales that are rarely observed by these traditional sampling approaches. Monitoring these transient processes, which may contribute the bulk of the annual metal loading, is essential for accurate assessment in acid rock drainage areas. Recent work also has demonstrated dramatic diel (24 hour cycle) variations in trace metal concentrations in response to diel changes in temperature, pH, oxygen, and photochemical cycling (Brick and Moore, 1996; Nimick et al, in prep). To characterise a system that may respond to diel, seasonal, and episodic events, a monitoring program must sample at a frequency that captures the details of these major forcing events. We developed two novel instruments, the Zn-DigiScan and the DigiSampler to examine low and high frequency temporal changes in acid rock drainage areas. The Zn-DigiScan is a battery powered real time in situ chemical analyser designed for long-term deployments with hourly analyses of Zn. Stream physical parameters (temperature, conductivity, dissolved oxygen, pH, turbidity, etc) were measured every 15 minutes with a water quality sonde. The DigiSampler was developed for the long-term daily sampling of biogeochemically active elements and can take either discrete samples or samples integrated over 24 hours. The DigiSampler collects 2 ml samples in a Teflon coil which are separated by 0.2 ml nitrogen bubbles. The sample coil is returned to lab and the 2 ml samples are diluted 1:10 and analysed for trace metals by ICP-MS. Initial results from a three-day deployment at Fisher Creek, MT, USA have successfully demonstrated the ability of the Zn-DigiScan to record Zn concentrations at levels below 100 μg/L. Zinc concentrations measured at 30 minute intervals in Fisher Creek showed a diel cycle with low values of ~25 μg/L in the late afternoon and increasing to ~60 μg/L by early morning. Zn concentrations were inversely related to temperature and pH, suggesting that temperature and pH dependent adsorption was the main factor controlling diel Zn fluctuations. Initial deployment of the DigiSampler also was successful, revealing diel cycles in Zn, Cu, and Mn. Comparison of trace metal samples collected by the DigiSampler showed good agreement with samples collected by an Isco automated water sampler, demonstrating that the DigiSampler can collect clean samples for trace metal analysis at the low μg/L range.

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