Abstract

We have developed a method for the determination of copper in natural waters at nanomolar levels. The use of a microplate-reader minimizes sample processing time (~25 s per sample), reagent consumption (~120 μL per sample), and sample volume (~700 μL). Copper is detected by chemiluminescence. This technique is based on the formation of a complex between copper and 1,10-phenanthroline and the subsequent emission of light during the oxidation of the complex by hydrogen peroxide. Samples are acidified to pH 1.7 and then introduced directly into a 24-well plate. Reagents are added during data acquisition via two reagent injectors. When trace metal clean protocols are employed, the reproducibility is generally less than 7% on blanks and the detection limit is 0.7 nM for seawater and 0.4 nM for freshwater. More than 100 samples per hour can be analyzed with this technique, which is simple, robust, and amenable to at-sea analysis. Seawater samples from Storm Bay in Tasmania illustrate the utility of the method for environmental science. Indeed other trace metals for which optical detection methods exist (e.g., chemiluminescence, fluorescence, and absorbance) could be adapted to the microplate-reader.

Highlights

  • Copper, like many trace metals, is an essential micronutrient at very low concentrations or availability, but may be toxic and have deleterious effects at elevated concentrations

  • Copper concentrations in natural waters vary greatly depending on water type and location

  • Current methods for low-level copper analysis in natural waters include flow injection analysis with chemiluminescence detection (Coale et al, 1992) based on the luminescence produced by the complexation of copper with 1,10-phenanthroline (Yamada and Suzuki, 1984), in-situ analysis using chemiluminescence (Holm et al, 2008) and colorimetry (Callahan et al, 2003), ICP-MS (Field et al, 1999) and electrochemical methods (Achterberg and Braungardt, 1999; Wang, 2002)

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Summary

INTRODUCTION

Like many trace metals, is an essential micronutrient at very low concentrations or availability, but may be toxic and have deleterious effects at elevated concentrations. Current methods for low-level copper analysis in natural waters include flow injection analysis with chemiluminescence detection (Coale et al, 1992) based on the luminescence produced by the complexation of copper with 1,10-phenanthroline (Yamada and Suzuki, 1984), in-situ analysis using chemiluminescence (Holm et al, 2008) and colorimetry (Callahan et al, 2003), ICP-MS (Field et al, 1999) and electrochemical methods (Achterberg and Braungardt, 1999; Wang, 2002) The complexity of these methods and their relatively large sample size requirements (generally at least 40 mL) has limited their use and contributes directly to the lack of regular monitoring of environmental copper concentrations. The small size of the instrument makes it practical for use at sea or in the field

MATERIALS AND METHODS
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Methods

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