An official website of the United States government
Abstract Agricultural intensification has increased the use of chemical fertilizers, promoting plant growth and crop yield. Excessive use of nitrogen fertilizers leads to nutrient loss and low nitrogen use efficiency. Management of nitrogen fertilizer input requires close to real‐time information about the soil nitrate concentration. While there is extensive work developing nitrate ion sensing solutions for liquid media, few allow for in‐soil measurements. This study introduces inkjet‐printed potentiometric sensors, containing 2 electrodes, the reference electrode (RE) and the nitrate‐selective film‐encapsulated working electrode (WE). The interaction between the nitrate‐sensitive membrane and soil nitrate ions causes a change in potential across the RE and WE. Additionally, a hydrophilic Polyvinylidene Fluoride (PVDF) layer ensures the long‐term functionality of the sensor in wet soil environments by protecting it from charged soil particles while simultaneously allowing water to flow from the soil toward the sensor electrodes. The sensors are tested in sand and silt loam soil, demonstrating their versatility across soil types. The potential change can be related to the nitrate concentration in soil, with typical sensitivities of 45–55 mV decade−1. Overall, the use of the PVDF layer allows for direct sensing in moist soil environments, which is critical for developing soil nitrate sensors.
more »
« less
Fully‐Printed Ion Sensor Arrays for Measuring Agricultural Nitrogen and Potassium Concentrations Using Nernstian and AI Models
The chemical composition of growing media is a key factor for plant growth, impacting agricultural yield and sustainability. However, there is a lack of affordable chemical sensors for ubiquitous nutrient ion monitoring in agricultural applications. This work investigates using fully printed ion‐sensor arrays to measure the concentrations of nitrate, ammonium, and potassium in mixed‐electrolyte media. Ion sensor arrays composed of nitrate, ammonium, and potassium ion‐selective electrodes and a printed silver‐silver chloride (Ag/AgCl) reference electrode are fabricated and characterized in aqueous solutions in a range of concentrations that encompass what is typical for agricultural growing media (0.01 mm–1m). The sensors are also tested in mixed‐electrolyte solutions of NaNO3, NH4Cl, and KCl of varying concentrations, and the recorded potentials are input into Nernstian and artificial neural network models to compare the prediction accuracy of the models against ground truth. The artificial neural network models demonstrated higher accuracy over the Nernstian model, and the model using only ion‐sensor inputs is 7.5% more accurate than the Nernstian model under the same conditions. By enabling more precise and efficient fertilizer application, these sensor arrays coupled to computational models can help increase crop yields, optimize resource use, and reduce environmental impact.
more »
« less
- Award ID(s):
- 2329885
- PAR ID:
- 10625408
- Publisher / Repository:
- Advanced Sensor Research
- Date Published:
- Journal Name:
- Advanced Sensor Research
- Volume:
- 4
- Issue:
- 4
- ISSN:
- 2751-1219
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Current potentiometric sensing methods are limited to detecting nitrate at parts-per-billion (sub-micromolar) concentrations, and there are no existing potentiometric chemical sensors with ultralow detection limits below the parts-per-trillion (picomolar) level. To address these challenges, we integrate interdigital graphene ion-sensitive field-effect transistors (ISFETs) with a nitrate ion-sensitive membrane (ISM). The work aims to maximize nitrate ion transport through the nitrate ISM, while achieving high device transconductance by evaluating graphene layer thickness, optimizing channel width-to-length ratio (RWL), and enlarging total sensing area. The captured nitrate ions by the nitrate ISM induce surface potential changes that are transduced into electrical signals by graphene, manifested as the Dirac point shifts. The device exhibits Nernst response behavior under ultralow concentrations, achieving a sensitivity of 28 mV/decade and establishing a record low limit of detection of 0.041 ppt (4.8 × 10−13M). Additionally, the sensor showed a wide linear detection range from 0.1 ppt (1.2 × 10−12M) to 100 ppm (1.2 × 10−3M). Furthermore, successful detection of nitrate in tap and snow water was demonstrated with high accuracy, indicating promising applications to drinking water safety and environmental water quality control.more » « less
-
null (Ed.)We fabricated and evaluated multiplexed ion-selective electrodes (ISEs) by modifying printed circuit board (PCB). The multiplexed sensor consisted of all-solid-state K+ and NO3- ISEs, together with a Ag/AgCl reference. The sensor was further embedded in a microfluidic microchannel for in-line continuous analysis, and was characterized for up to one week of operation. Both ISEs showed a near-Nernstian response (~52 mV/dec) and reasonable stabilities (baseline drift ~2.9 mV/day). The sensor provides a versatile and low-cost tool for monitoring concentrations of different ions in many biomedical, environmental and agricultural applications.more » « less
-
Single particle electrochemical oxidation of polyvinylpyrrolidone-capped silver nanoparticles at a microdisk electrode is investigated as a function of particle shape (spheres, cubes, and plates) in potassium nitrate and potassium hydroxide solutions. In potassium nitrate, extreme anodic potentials (≥1500 mV vs Ag/AgCl (3 M KCl)) are necessary to achieve oxidation, while lower anodic potentials are required in potassium hydroxide (≥900 mV vs Ag/AgCl (saturated KCl)). Upon oxidation, silver oxide is formed, readily catalyzing water oxidation, producing a spike-step current response. The spike duration for each particle is used to probe effects of particle shape on the oxidation mechanism, and is substantially shorter in nitrate solution at the large overpotentials than in hydroxide solution. The integration of current spikes indicates oxidation to a mixed-valence complex. In both electrolytes, the rate of silver oxidation strongly depends on silver content of the nanoparticles, rather than the shape-dependent variable–surface area. The step height, which reflects rate of water oxidation, also tracks the silver content more so than shape. The reactivity of less-protected citrate-capped particles toward silver oxidation is also compared with that of the polymer-capped particles under these anodic conditions in the nitrate and hydroxide solutions.more » « less
-
Nitrate contamination of ground water is a serious problem due to the intensive agricultural activities needed to feed the world’s growing population. While effective, drinking water treatment using commercial ion exchange polymers is often too expensive to be employed. At the same time, lignocellulosic waste from crop production—an abundant source of the renewable polymer cellulose—is often burned to clear fields. This results in not only adverse health outcomes, but also wastes a valuable resource. In this study, wheat straw was pretreated to extract cellulose, then selectively oxidized with periodate, crosslinked with an alkyl diamine (1,7-diaminoheptane or 1,10-diaminodecane), and functionalized with a quaternary ammonium compound ((2-aminoethyl)trimethyl ammonium chloride) to generate a cellulose-based anion exchange polymer. This polymer lowered aqueous nitrate concentrations to health-based drinking water standards. Unlike commercial ion exchange polymers, its synthesis did not require the use of toxic epichlorohydrin or flammable solvents. The pretreatment conditions did not significantly affect nitrate uptake, but the crosslinker chain length did, with polymers crosslinked with 1,10-diaminodecane showing no nitrate uptake. Agricultural-waste-based anion exchange polymers could accelerate progress toward the sustainable development goals by providing low-cost materials for nitrate removal from water.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/adsr.202400121
