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High concentrations of certain nutrients, including phosphate, are known to lead to undesired algal growth and low dissolved oxygen levels, creating deadly conditions for organisms in marine ecosystems. The rapid and robust detection of these nutrients using a colorimetric, paper-based system that can be applied on-site is of high interest to individuals monitoring marine environments and others affected by marine ecosystem health. Several techniques for detecting phosphate have been reported previously, yet these techniques often suffer from high detection limits, reagent instability, and the need of the user to handle toxic reagents. In order to develop improved phosphate detection methods, the commonly used molybdenum blue reagents were incorporated into a paper-based, colorimetric detection system. This system benefited from improved stabilization of the molybdenum blue reagent as well as minimal user contact with toxic reagents. The colorimetric readout from the paper-based devices was analyzed and quantified using RGB analyses (via ImageJ), and resulted in the detection of phosphate at detection limits between 1.3 and 2.8 ppm in various aqueous media, including real seawater.
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Coral skeleton P/Ca proxy for seawater phosphate: Multi-colony calibration with a contemporaneous seawater phosphate record
- Award ID(s):
- 0610487
- PAR ID:
- 10214844
- Date Published:
- Journal Name:
- Geochimica et Cosmochimica Acta
- Volume:
- 74
- Issue:
- 4
- ISSN:
- 0016-7037
- Page Range / eLocation ID:
- 1282 to 1293
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Nutrient pollution remains one of the greatest threats to water quality and imposes numerous public health and ecological concerns. Phosphate, the most common form of phosphorus, is one of the key nutrients necessary for plant growth. However, phosphate concentration in water should be carefully monitored for environmental protection requirements. Hence, an easy-to-use, field-deployable, and reliable device is needed to measure phosphate concentrations in the field. In this study, an inexpensive dip strip is developed for the detection of low concentrations of phosphate in water and seawater. In this device, ascorbic acid/antimony reagent was dried on blotting paper, which served as the detection zone, and was followed by a wet chemistry protocol using the molybdenum method. Ammonium molybdate and sulfuric acid were separately stored in liquid form to significantly improve the lifetime of the device and enhance the reproducibility of its performance. The device was tested with deionized water and Sargasso Sea seawater. The limits of detection and quantification for the optimized device using a desktop scanner were 0.134 ppm and 0.472 ppm for phosphate in water and 0.438 ppm and 1.961 ppm in seawater, respectively. The use of the portable infrared lightbox previously developed at our lab improved the limits of detection and quantification by a factor of three and were 0.156 ppm and 0.769 ppm for the Sargasso Sea seawater. The device’s shelf life, storage conditions, and limit of detection are superior to what was previously reported for the paper-based phosphate detection devices.more » « less
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High-resolution, autonomous monitoring of phosphate and silicate in the marine environment is essential to understand their complex dynamics and implications for the functioning of marine ecosystems. In the absence of dependable reagent-less sensors for these nutrients, leveraging established colorimetric techniques using miniaturized analyzers, such as programmable Flow Injection (pFI), offers the best immediate solution to meet oceanographic accuracy and precision standards. In this work, we further optimize the phosphomolybdate and silicomolybdate assays recently adapted for use with pFI, laying the groundwork for the technique’s use for long-term, autonomous operations. For both assays, we show that only a narrow range of acidities and molybdate concentrations can maximize sensitivity while minimizing salt effects. In addition, we demonstrate the stability of our optimized colorimetric reagent formulations, ensuring that analytical sensitivity remains within 10% of initial levels for at least 35 days of continuous use. We then applied our optimized protocols to produce oceanographically consistent phosphate and silicate profiles at the Hawaii Ocean Time Series (HOTS) and Southern Ocean Time Series (SOTS), respectively, which compared favorably against a reference method and historical data. Using certified reference materials for nutrients in seawater, we show that our pFI protocols, optimized for long-term operations, achieve a shipboard precision better than 6% and a relative combined uncertainty (k=1) of 4.5% for phosphate (0.45 - 2.95 µmol L-1) and 6.2% for silicate (2.2 to 103 µmol L-1). To demonstrate pFI’s potential as a versatile tool for autonomous monitoring, we report a five-day hourly phosphate time series at a coastal shore station in central California (n=121 analyses), examine phosphate uptake by seaweed at five-minute intervals at a seaweed aquaculture facility (n=103), and discuss a unique, high-resolution surface silicate transect spanning multiple frontal zones in the Australian sector of the Southern Ocean (n=249). These data, obtained using a commercially available pFI analyzer, confirm that pFI is a viable technology for autonomous monitoring of phosphate and silicate, paving the way for more ambitious, long-term deployments in a variety of settings.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.gca.2009.11.002
