Micro- and Mini-nitrate Sensors for Monitoring of Soils, Groundwater and Aquatic Systems (2009)

Inorganic nitrogen (nitrate, NO3-) is a major source of pollution in groundwater, surface water and the air. Application of nitrate-containing fertilizers can create distributed or non-point source pollution problems. Scalable nitrate sensors (sensors which are small and inexpensive) would enable us to better assess non-point source pollution processes in agronomic soils, groundwater and rivers. Sensor research groups in the CENS have been working toward high-performance scalable nitrate sensors using (1) potentiometric, (2) amperometric method, and the recent addition is (3) spectrochemical sensor. 1. Potentiometric Nitrate Sensor. This work describes the fabrication and testing of inexpensive PVC-membrane-based ion selective electrodes (ISEs) for monitoring nitrate levels in soil water environments. Over the past year, we emphasized testing of the in situ behavior of fabricated sensors in soils subject to irrigation with dairy manure water. Observed temporal responses for the nitrate sensors exhibit diurnal cycling with elevated nitrate levels at night and depressed levels during the day; these cycles are prominent even after rigorous temperature corrections. We have thus far concluded that while modern ISEs are not yet ready for long-term, unattended deployment, short-term installations (on the order of 2 to 4 days) are viable and may provide semi-quantitative insights into nitrogen dynamics in complex soil systems. 2. Amperometric Nitrate Sensor. A simple and sensitive amperometric nitrate sensor is microfabricated on the silicon chip and uses a nitrate-sensitive silver electrode. The concentration is determined by double-potential-step chronocoulometry because of high SNR and rejection of oxygen background current. The limit of detection ranges from 4 to 75 µM, and the upper limit of the linear range varies between 500 and 2000 µM. HPO42-/PO34- , Ca2+, and Sr2+ show significant interference (&gt; 20 % signal distortion). We proposed a compact sample-preparation system based on Donnan dialysis to minimize the interference. The novel dialyzer uses small-bore tubes in containing solutions and a peristaltic pump in circulating the solutions to promote agitation. By using an anion-exchange membrane (AEM), the dialyzer removes cations completely and reduces interfering anions significantly from groundwater samples. Major advantages of the novel dialyzer are (1) high dialysis efficiency (~ 90 %), (2) linear response, and (3) reasonable throughput (1 samples/hr).A numerical analysis based on the one-dimensional bi-ionic-system-in-series model provides a good prediction of dialyzer performance. 3. Spectrochemical Nitrate Sensor. A multiplexible, miniaturized, and spectrochemical sensor is proposed because optical methods usually provide superior long-term reliability. UV light is absorbed by nitrate while propagating through groundwater sample in a liquid-core capillary waveguide, and absorbance is analyzed to quantify nitrate using a fiber-optic spectrometer. Using fiber-optic cables and optical multiplexers, multiple sensors can be operated remotely by single spectrophotometer and light source. Multivariate analysis is used to compensate these interferences from ionic and neutral species and baseline from dissolved organic species in groundwater, and calculate nitrate concentration precisely. A series of numerical analyses were performed to assess effects of spectrometric noises and interferences. According to the analyses, a large sharp Gaussian noise with a peak located near the peak of nitrate spectra will generate a significant error. Using a bench-top spectrometer, nitrate spectra in wide concentration range (10-7 to 1-4 M) were recorded to obtain concentration. It is observed that spectra were linear over the range.