Christina Szea,
Benjamin Wanga,
Jiale Xub,
Juan Rivas-Davilab and
Mark A. Cappelli*a
aStanford University, Department of Mechanical Engineering, Stanford, USA. E-mail: cap@stanford.edu
bStanford University, Department of Electrical Engineering, Stanford, USA
First published on 24th November 2021
We investigated the use of plasma-fixated nitrogen, which produces nitrates (NO3−) in water, as a possible nitrogen fertilizer for recreational turf such as rye grass and bent grass. Experiments were carried out to study the effects of nitrate concentration on growth, the further effects of adding phosphorous (P) and potassium (K) to the plasma nitrated solution to make an N–P–K complete fertilizer, and to compare the efficacy of plasma-fixated nitrogen to sodium nitrate (NaNO3) and potassium nitrate (KNO3). The results indicate that the growth and biomass of the plants were strongly dependent on the concentration of the plasma-fixated nitrogen. Adding P–K to the plasma-fixated nitrogen improved grass growth. Grass that was supplied plasma-fixated nitrogen had improved growth compared to those supplied with equal amounts of NaNO3 and KNO3. This work highlights the potential use of plasma-fixated nitrogen as a fertilizer source for commonly used turf grass.
A gas discharge plasma, when generated in a molecular gas such as air, is composed of electrons, positive and negative ions, excited and neutral atoms, and other reactive molecular species and radicals. Plasma fixation of nitrogen in water, sometimes referred to as "plasma-activated water", can be generated via air plasma treatment either above or directly in water (i.e., the water is exposed to a plasma stream, or a plasma is generated directly in the water). This results in the formation of numerous dissolved and chemically active species, often generalized as reactive oxygen and nitrogen species (RONS).3 The dissolved reactive species can include nitrates, which are naturally present in soil and can be absorbed by plants as a source of nitrogen to promote plant growth. In this paper, we are specifically interested in the fixation of nitrate ions (plasma-fixated nitrogen), produced in water from exposure to air plasmas, for use as an exogenous fertilizer source for commonly used turf grass.
The application of plasma-fixated nitrogen in agriculture has recently gained much attention because of its various interesting properties and potential for sustainable production. Plasma activated water has been shown to enhance seed germination,4 plant growth,5–7 and have antiseptic properties as a result of microbial reduction.8 However, most applications to agriculture have focused on its use as a fertilizer for crops such as corn,9 barley,10 and fresh produce such as lettuce.6
In this paper, we examine the use of plasma-fixated nitrogen in the fertilization of turf grass, specifically rye grass and bent grass. Turf grass is considered to be one of the largest irrigated crops in the United States, covering a greater surface area than even irrigated corn. Turf grass is commonly used in residential and commercial lawns, golf courses, and recreational and sports fields.11 As such, turf grass has the potential to sequester a large amount of excess carbon from the atmosphere and reduce greenhouse gas emissions.11,12 The use of sustainable energy in the production of plasma-fixated nitrogen for turf grass growth would further reduce its carbon footprint.
Air plasmas were generated using an atmospheric dielectric barrier discharge (DBD) reactor4,9,13 operating at 23 kHz driving frequency and with a sinusoidal peak to peak voltage of 7 kV. In a typical experiment, the discharge drew 450 watts of input power. Industrial water contained in a glass container is placed close to the surface of the DBD (<1 cm) and treated until the plasma-fixated nitrogen solution reached a desired pH and nitrate level.
The plasma-fixated nitrogen stock solution was diluted with industrial water to achieve solutions with lower nitrate concentrations. These solutions had dilution factors of 2:1, 5:1, 10:1, 20:1, and 100:1, respectively, and were compared for their efficacy in growth studies. The nitrate concentrations and pH of each solution were measured prior to administering the solutions, and the results are summarized in Table 1. The nitrate concentration of the diluted plasma-fixated nitrogen solutions was measured using a nitrate ion-selective electrode (Vernier GDX-NO3) as nitrates as nitrogen (NO3–N). The pH of the solution was measured using a glass bodied pH sensor (Vernier GDX-GPH).
Treatment | NO3–N (ppm) | pH |
---|---|---|
Water | 2.54 | 6.79 |
100:1 | 2.86 | 6.21 |
20:1 | 7.22 | 4.21 |
10:1 | 14.56 | 3.51 |
5:1 | 31.61 | 3.06 |
2:1 | 85.71 | 2.63 |
Stock | 168 | 2.36 |
e + N2(g) → N(g) + N(g) + e | (1) |
e + O2(g) → O(g) + O(g) + e | (2) |
N(g) + O(g) → NO(g) | (3) |
NO(g) + O(g) → NO2(g) | (4) |
NO(g) + O3(g) → NO2(g) + O2(g) | (5) |
NO2(g) + O3(g) ↔ NO3(g) + O2(g) | (6) |
NO(g) + NO3(g) ↔ NO2(g) + NO2(g) | (7) |
(8) |
(9) |
(10) |
(11) |
Here, eqn (1)–(7) represent homogeneous gas-phase reactions (gas phase species are represented by subscripts (g)), eqn (8) and (9) represent heterogeneous reactions of gas-phase species with water at the interface (subscript (s) indicates interfacial), and eqn (10) and (11) represent homogeneous reactions of dissolved species in the liquid (subscript (l)). The system of reactions proposed above will progress towards dissolved nitrates provided an over-pressure of nitrogen and oxygen radicals are maintained within the plasma discharge. One gas discharge design may be favored over another in its ability to efficiently produce these reactive species, such as N and O, and intermediate species such as NO2 and NO3. Key to achieving high yields also rely on the transport of these intermediates to the water interface before their destruction through thermodynamically favored reverse reactions, such as those described in eqn (6) and (7).
In the plasma-fixated nitrogen dilution study, 50 uniform rye grass seeds were placed in 250 mL plastic containers on top of approximately 70 cubic centimeters of coco coir and covered with approximately 20 cubic centimeters of coco coir. Equal volumes of water and fertilizer were added daily to each respective container. The amount of nitrate added to each treatment group over time was recorded (Fig. 2c), and final measurements were collected after 17 days following initial planting.
To test the effect of adding P–K to plasma-fixated nitrogen stock solution, liquid fertilizer containing only P–K (Liquid KoolBloom 0-10-10) was diluted by a factor of 1000 in industrial water. This solution was added to 168 ppm NO3–N of plasma-fixated nitrogen stock solution to form an N–P–K complete fertilizer solution. The diluted P–K fertilizer was also tested without the added plasma-fixated nitrogen in this study as a control. 25 uniformly spaced rye grass seeds were placed in 250 mL plastic containers on top of approximately 250 cubic centimeters of coco coir and covered with approximately a quarter inch (or about 40 cubic centimeters) of coco coir. Equal volumes of water and fertilizer solution were added daily to each respective container. The amount of nitrate added to each treatment group over time was recorded (Fig. 5b and d). Four replicates for each treatment group were used in this study. Measurements were recorded after 19 days following initial planting.
To compare the performance of plasma-fixated nitrogen against other sources of plant nitrogen, 5 seeds were placed in approximately 7 grams of coco coir with a quarter inch of coco coir over the seeds, and either 2.5 mL of water (control), 100 ppm NO3–N plasma-fixated nitrogen solution, 100 ppm sodium nitrate as nitrogen (NaNO3, ASI sensors), and 100 ppm potassium nitrate as nitrogen (KNO3, LabChem) were added daily to each respective growth container until germination. After germination, equal volumes of the solutions were added daily to each respective treatment group. The amount of nitrate added to each treatment group over time was recorded (Fig. 9). Six replicates for each treatment group were used. Final measurements were recorded after 13 days following initial planting.
For all of the growth studies, the seeds were placed in a custom climate-controlled (T = 22 °C) plant growth chamber with 24 hour light exposure during the germination period and 14 hour light exposure during post-germination and plant growth.
Germination yield was calculated by dividing the number of germinated seeds by the total number of seeds in each cup using the following equation:
G = nG/nT × 100% |
The mean grass height of every treatment group that received diluted plasma-fixated nitrogen fertilizer, except for the 100:1 dilution, was found to be significantly greater (ρ < 0.05) from the mean height value measured for the control group. The height distributions of the treatment groups are shown in a box plot in Fig. 3a with the mean height plotted in green. As the fertilizer and NO3–N concentration increases, the mean height and the height distribution also increases, particularly for the highest concentration (2:1 dilution) treatment group. Increasing fertilizer concentration was also shown to increase grass biomass (Fig. 3b). The greatest effect was seen in the 5:1 and 2:1 dilution treatment groups, which had a 38.3% and 59.57% increase in dry mass when compared to the control, respectively (Fig. 3c). It is apparent that adding even small amounts of plasma-fixated nitrogen (4.20 mg and 1.68 mg for the 2:1 and 5:1 groups) dramatically increased biomass. It is noteworthy that the germination yield was not affected by the application of the plasma-fixated nitrogen. The value of G for the control group was 78%, and G values for the diluted fertilizer groups were similar (G = 80%, 88%, 74%, 78%, and 78% for the 100:1, 20:1, 10:1, 5:1, and 2:1 dilutions, respectively).
Recent studies have found that the addition of nitrogen to Aceraceae, a deciduous shrub, improved plant growth and health through improved root morphology.16 While we have not examined the physical morphology of our grass roots in detail, we conjecture that the benefits of added nitrogen, seen here as an increase in height and biomass, may also be the result of changes to root morphology. It is noteworthy that the more concentrated, acidic fertilizers (2:1 and 5:1) did not appear to ∼ burn ∼ the grass or its root system, suggesting the coco coir acted as an effective buffer to counteract the acidity of the fertilizer, in addition to the relatively low amount of solution that was added compared to the growth medium.
In studying the effect of adding plasma-fixated nitrogen on the growth of the plants, we considered two other quantitative measures for comparison that represent an efficiency factor for the nitrates on growth. The first is the ratio of the total added nitrates (as nitrogen) for the ith sample, (NO3–N)i, measured as mg of nitrogen, to the mean grass height of the ith sample beyond that of the control, i.e.,
The second is the ratio of the total added nitrates as nitrogen to the dry mass of the ith sample beyond that of the control, i.e.,
These two ratios allowed us to further quantify the efficacy of the plasma nitrated water. Fig. 4a shows that the 100:1 dilution case only required 0.00587 mg of NO3–N per additional millimeter of height, indicating that the 100:1 dilution had the most efficient usage of nitrogen in increasing height. This efficiency of nitrogen usage decreased as NO3–N concentration increased, suggesting that more nitrogen was needed to increase grass height by the same amount. This inverse relationship between nitrate concentration and nitrate efficiency in increasing height suggests that it may be more economical to fertilize more often with smaller amounts of nitrogen, if grass height is desirable. Fig. 4b shows the amount of nitrates required to increase grass biomass by 1 mg. Similar to Fig. 4a, the 100:1 dilution had the most efficient usage of nitrogen in increasing biomass since it only required 0.32051 mg of NO3–N per additional mg of biomass (on a per plant basis). However, the inefficiency of nitrogen usage in increasing biomass appears to peak at the 10:1 dilution and again at the 2:1 dilution of the fertilizer.
Determining the optimal dilution for increasing nitrogen fertilizer efficiency is important toward reducing fertilizer costs and runoff, and adjusting the amount of nitrates we add to the plants over time is crucial for optimizing growth.13 While the 100:1 dilution had the best efficiency for increasing height and mass, the growth rate was slow, and there was not a significant difference (significance level α < 0.05) in height from the control group over the 17 day growth period. Therefore, the results suggest that the 20:1 dilution may be the best in terms of maximizing growth rate and nitrogen efficiency regarding height. Similarly, the 5:1 dilution is likely the best in terms of maximizing growth rate and nitrogen efficiency regarding biomass. Further exploration is needed to determine the precise relationship between nitrogen efficiency in increasing mass and nitrate concentration, and particularly why certain dilutions like the 10:1 dilution were very inefficient in using the added nitrogen to increase mass.
Fig. 6a and b show the measured germination yield for both the rye grass and bent grass experiments, respectively. Rye grass had an average germination yield of 87% for the control, 92% for the P–K solution, 88% for the N solution, and 90% for the N–P–K solution, as shown by the blue bars in Fig. 6a. Therefore, the addition of P–K did not noticeably affect germination yield between experimental groups for the rye grass. The bent grass had an average germination yield of 48% for the control, 54% for the P–K solution, 75% for the N solution, and 69% for the N–P–K solution, as shown by the green bars in Fig. 6b. The N and N–P–K treatment groups had higher germination yields compared to the control and P–K groups, suggesting that the plasma-fixated nitrogen improved bent grass seed germination.
The addition of phosphorus and potassium to water and the plasma-fixated nitrogen solution had a small effect on rye grass height, as shown in Fig. 7a. The mean height of each treatment group is plotted in dark blue. The P–K treatment group had a slightly lower height distribution compared to the control (water). However, this did not constitute a significant difference (significance level α < 0.05). In contrast, the addition of P–K to the plasma-nitrated solution (N–P–K group) significantly increased the height distribution in comparison to the treatment group that received only the plasma nitrate solution (N group; ρ < 0.05). The N–P–K height distribution also has a wider range and a higher maximum height than the N height distribution, as well as a more symmetrical distribution.
Adding phosphorus and potassium to water alone had a small effect on rye grass biomass. As shown in Fig. 7b, the control and P–K treatment group had approximately equal biomass with an average dry mass per plant of 1.44 mg and 1.40 mg, respectively. Similarly, the average dry masses per plant of the N and N–P–K treatment groups were 4.24 mg and 4.64 mg, respectively, suggesting the addition of P–K to the plasma-fixated nitrogen solution had a significant effect on increasing grass biomass.
The results from the creeping bent grass seeds followed the same trend with regards to P–K's effect on height and biomass when added to water and plasma-fixated nitrogen. The control (water) and P–K groups had approximately the same height distribution, and the N–P–K treatment group had an increase in its median and range of height in comparison to the N treatment group (Fig. 8a). The mean height of each treatment group is plotted in red (Fig. 8a). The control and P–K groups had an average dry mass per plant of 0.29 mg and 0.24 mg, and the N and N–P–K treatment groups had an average dry mass per plant of 0.75 mg and 0.87 mg, indicating P–K had only a small effect on grass biomass (Fig. 8b).
Our study suggests that adding phosphorous and potassium without plasma-fixated nitrogen has a small but insignificant effect on decreasing plant growth, while adding phosphorous and potassium along with plasma-fixated nitrogen had a significant effect in enhancing plant height and biomass. These results are consistent with previous literature that showed adding phosphorous and potassium alongside nitrogen enhances plant growth.16,17
The plasma-fixated nitrogen also produced a higher biomass compared to the KNO3 and NaNO3 solutions. The plasma NO3 had an average dry mass per plant of 1.18 mg, while the KNO3 and NaNO3 groups had an average dry mass per plant of 1.93 mg and 1.86 mg, respectively (see Fig. 10b). Germination yield was also roughly equal across the different nitrogen sources (G = 97%, 93%, and 96% for the plasma NO3−, KNO3, and NaNO3, respectively). This shows that the nitrate source from the plasma-fixated solution has a higher performance in terms of growth and biomass compared to KNO3 and NaNO3 solutions of equal nitrate levels. The KNO3 solution produced more biomass due to the availability of potassium nutrient, compared to the NaNO3 solution.
The use of plasma-fixated nitrogen systems will allow for the development of sustainable decentralized production on site. These decentralized plants would be able to be integrated into fertigation systems and produce and distribute fertilizer only when necessary. Economic analysis of the energy costs and efficiencies have been extensively studied for a variety of plasma fixation technologies.18,20 These past studies have shown potential in realizability of scalable production based on estimated capital expenses and operating costs. The current Haber–Bosch process has been fully optimized over the past century of its use, with an energy consumption of about 0.48 MJ mol−1 ammonia produced. The use of non-thermal plasmas such as those used here have a theoretical cost limitation of 0.2 MJ mol−1 for NOx synthesis.3 The system used here is not optimized for commercial production and is currently much lower in yield when compared to that of the Haber–Bosch method. The encouraging studies of plant uptake presented here provides motivation for further research into studies of the detailed gas and liquid phase chemistry to improve the overall efficiency of such low-temperature plasma processes.
Solutions of plasma-fixated nitrogen, phosphorous, and potassium were tested to investigate the interactions of the plasma-fixated nitrogen on the two other plant nutrients. Plasma-fixated nitrogen added with phosphorus and potassium were found to improve growth and dry mass compared to just plasma-fixated nitrogen and phosphorus and potassium alone.
Finally, the effect of plasma-fixated nitrogen on grass growth were compared to two commonly used nitrate sources (potassium nitrate and sodium nitrate), and was found to have improvements in growth height and dry mass with the same dosage of nitrates (100 ppm NO3–N), allowing for a more efficient nitrate fertilizer. It have been shown that reactive nitrogen and oxygen species found in the plasma-fixated nitrogen solution improved seedling growth,9 leading to improved height and mass of the plasma-fixated nitrogen fed grass.
To summarize, we have investigated the use of plasma-fixated nitrogen as an exogenous nitrate fertilizer source for two types of commonly used turf grass. Our findings indicate that plasma-fixated nitrogen fertilizer, which contains active nitrates (NO3−), appears to be a promising candidate for use as a sustainable and green exogenous nitrogen source for fertilizing turf grass.
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