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Cellulose nanofibrils for slow-release fertilizer

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An October 17, 2022 news item on phys.org highlights nanocellulose research from Brazil, Note: A link has been removed,

A research team affiliated with the Laboratory of Polymeric Materials and Biosorbents at the Federal University of São Carlos (UFSCar) in Araras, São Paulo state, Brazil, has produced and is testing cellulose-based materials for enhanced-efficiency fertilizers to improve the supply of nutrients to crops and reduce the release of non-biodegradable chemicals [forever chemicals] into the ecosystem.

The studies were led by Roselena Faez, a professor at the Center for Agricultural Sciences (CCA-UFSCar). The findings have recently been reported in two publications. One is an article published in Carbohydrate Polymers, with Débora França as first author. Here [keep scrolling down] the researchers describe how they used modified nanocellulose to discharge the nutrients contained in fertilizer into the soil slowly and in a controlled manner, given that nitrogen, phosphorus and potassium are highly soluble.

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Caption: The first and third photos show the paper made from phosphorylated sugarcane cellulose. The second shows the 3D structure of the material comprising cellulose and nutrient. The fourth shows the microparticles in powder form and after molding into tablets. Credit: Lucas Luiz Messa/Débora França

An October 19, 2022 Fundação de Amparo à Pesquisa do Estado de São Paulo [FAPESP] press release (also on EurekAlert but published October 17, 2022) by Karina Ninni, originated the phys.org news item. The researchers explain (Note: Links have been removed),

“Potassium is rapidly washed away by rain because of its high ion mobility. It’s the hardest to release in a controlled manner. Nitrogen can be obtained from various sources, such as nitrates, ammonia and urea, but plants get the nitrogen they need most easily from nitrate, which is also easily washed away and doesn’t remain in the soil for long. Phosphorus [as phosphate] is a very large ion and less mobile than the other macronutrients,” said Faez, who coordinates the Polymeric Materials and Biosorbents Research Group at UFSCar Araras.

Controlled-release products are available on the market, she added, but most are made of synthetic polymers, which are non-biodegradable. “Fertilizer grains are about the size of grains of coarse sea salt. To make sure the nutrients are released slowly, they’re coated with layers of polymer that last about two months each, so the manufacturer applies two, three or four coats, according to the desired length of time for controlled release,” Faez explained, noting that the polymers in question are plastics and remain in the soil, eventually degrading into microparticles that last virtually forever.

The researchers at UFSCar developed an entirely different product in which the chemical reaction between the modified nanocellulose and mineral salts keeps the nutrients in the soil. “We focused on the worst problems, which are nitrate and potassium. The material we developed is totally biodegradable and releases these nutrients at about the same slow rate as the available synthetic materials,” Faez said.

The nanocellulose was obtained from pure cellulose donated by a paper factory. The nanofibrils were functionalized with positive and negative charges to enhance polymer-nutrient interaction. “Because the salts are also made up of positively or negatively charged particles and highly soluble, we hypothesized that negatively charged nanocellulose would react with positive ions in the salts, while positively charged nanocellulose would interact with negative ions, reducing the solubility of the salts. This proved to be the case, and the group succeeded in modulating nutrient release in accordance with the type of particle in the material,” França said.

Evaluation in soil

The group fabricated the product in the form of tablets and evaluated its performance in terms of nutrient release into the soil. Evaluation of release into water is the usual method, and water is a very different system from soil. This part of the research was conducted in partnership with Claudinei Fonseca Souza, a professor at CCA-UFSCar’s Department of Natural Resources and Environmental Protection in Araras.

“We evaluated nutrient release into the soil and biodegradation of the material at the site for 100 days. But we deliberately used very poor soil with little organic matter, because this enables us to see the physical effects of release more easily,” Faez said.

The researchers used two techniques to obtain tablets: atomization and spray drying to encapsulate the nutrients with the nanocellulose, followed by heat processing of the resulting powder, which was pressed in a mold. This work was completed with the help of colleagues at the Cellulose and Wood Materials Laboratory belonging to EMPA (Swiss Federal Laboratories for Materials Science and Technology) and in collaboration with UFSCar’s Water, Soil and Environment Engineering Research Group, led by Souza. França performed the cellulose modifications at EMPA while on an internship there with support from FAPESP. She was also supported by a doctoral scholarship in Brazil.

Self-fertilization

The second recent article by the group was published in Industrial Crops and Products, with chemist Lucas Luiz Messa as first author. The goal of the study was to extract cellulose from sugarcane bagasse and modify it with a surface negative charge by phosphorylation (addition of a phosphorus group) to allow controlled release of potassium. In theory, delivery of plant nutrition would be slowed by cellulose phosphorylation, which would create surface anionic charges that would bind to macronutrient and micronutrient cations. 

The group prepared three types of structure with the phosphorylated cellulose: oven-dried paper-like film; spray-dried powder; and freeze-dried porous bulk similar to polystyrene foam. Freeze drying, or lyophilization, was seen to leave nutrients in the voids left by water removal. 

“Technologically speaking, the paper-like structure was the best material we produced for controlled delivery of nutrients. Several products can be created using this paper,” Faez said.

The results obtained in the research led by Messa enabled the group to develop small propagation pots for seedling cultivation. When this material degrades, the phosphorus it contains is released. According to Faez, cellulose phosphorylation is cheap, and the cost of the end product is relatively low. “It’s more or less BRL 0.27 per gram of paper produced. The propagation pot must be about 1 gram. Unit cost is therefore about BRL 0.30 in terms of laboratory costs,” she said.

Biodegradable propagation pots are already available on the market. “But our product has built-in fertilizer, which is a major competitive advantage. Indeed, we’ve filed a patent application,” she said.

The pot is about to be trialed by a flower producer in Holambra, São Paulo state. Several batches produced in the laboratory have been shipped there. Nutrient release has so far been tested only in water. “We call this an accelerated ion release assessment method because it’s faster in water, but even in water we found the release rate to be 40%-50% slower compared with the behavior of the ion in the material and without the material. Even in water, therefore, we succeeded in retaining these ions. We assume delivery will be even slower in the substrate,” she said.

The research was also supported by FAPESP via a Doctoral Scholarship in Brazil and a Research Internship Abroad Scholarship awarded to Messa, and a Regular Research Grant awarded to Faez.

Messa was assisted by a colleague at the University of California Davis (USA), where he worked as a research intern.

About São Paulo Research Foundation (FAPESP)

The São Paulo Research Foundation (FAPESP) is a public institution with the mission of supporting scientific research in all fields of knowledge by awarding scholarships, fellowships and grants to investigators linked with higher education and research institutions in the State of São Paulo, Brazil. FAPESP is aware that the very best research can only be done by working with the best researchers internationally. Therefore, it has established partnerships with funding agencies, higher education, private companies, and research organizations in other countries known for the quality of their research and has been encouraging scientists funded by its grants to further develop their international collaboration. You can learn more about FAPESP at www.fapesp.br/en and visit FAPESP news agency at www.agencia.fapesp.br/en to keep updated with the latest scientific breakthroughs FAPESP helps achieve through its many programs, awards and research centers. You may also subscribe to FAPESP news agency at http://agencia.fapesp.br/subscribe

I have links and citations for both papers mentioned in the press release,

Sugarcane bagasse derived phosphorylated cellulose as substrates for potassium release induced by phosphates surface and drying methods by Lucas Luiz Messa, You-Lo Hsieh, Roselena Faez. Industrial Crops and Products Volume 187, Part A, 1 November 2022, 115350 DOI: https://doi.org/10.1016/j.indcrop.2022.115350 Available online 20 July 2022, Version of Record 20 July 2022

This paper is behind a paywall.

Charged-cellulose nanofibrils as a nutrient carrier in biodegradable polymers for enhanced efficiency fertilizers by Débora França, Gilberto Siqueira, Gustav Nyström, Frank Clemens, Claudinei Fonseca Souza, Roselena Faez. Carbohydrate Polymers Volume 296, 15 November 2022, 119934 DOI: https://doi.org/10.1016/j.carbpol.2022.119934 Available online 1 August 2022, Version of Record 3 August 2022

This paper is behind a paywall.

Plants as a source of usable electricity

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A friend sent me a link to this interview with Iftach Yacoby of Tel Aviv University talking about some new research into plants and electricity. From a June 8, 2020 article by Omer Kabir for Calcalist (CTech) on the Algemeiner website,

For years, scientists have been trying to understand the evolutionary capabilities of plants to produce energy and have had only partial success. But a recent Tel Aviv University [TAU] study seems to make the impossible possible, proving that any plant can be transformed into an electrical source, producing a variety of materials that can revolutionize the global economy — from using hydrogen as fuel to clean ammonia to replace the pollutants in the agriculture industry.

“People are unaware that their plant pots have an electric current for everything,” Iftach Yacoby, head of the Laboratory of Renewable Energy Studies at Tel Aviv University’s Faculty of Life Sciences said in a recent interview with Calcalist.

“Our study opens the door to a new field of agriculture, equivalent to wheat or corn production for food security — generating energy,” he said. However, Yacoby makes it clear that it will take at least a decade before the research findings can be transferred to the commercial level.

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At the heart of the research is the understanding that plants have particularly efficient capacities when it comes to electricity generation. “Anything green that is not dollars, but rather leaves, grass, and seaweed for example, contains solar panels that are completely identical to the panels the entire country is now building,” Yacoby explained. “They know how to take in solar radiation and make electrons flow out of it. That’s the essence of photosynthesis. Most people think of oxygen and food production, but the most basic phase of photosynthesis is the same as silicon panels in the Negev and on rooftops — taking in sunlight and generating electric current.”

… “At home, an electric current can be wired to many devices. Just plug the device into a power outlet. But when you want to do it in plants, it’s about the order of nanometers. We have no idea where to plug the plugs. That’s what we did in this study. In plant cells, we found they can be used as a socket for anything, at just a nanometer size. We have an enzyme, which is equivalent to a biological machine that can produce hydrogen. We took this enzyme, put it together so that it sits in the socket in the plant cell, which was previously only hypothetical. When he started to produce hydrogen, we proved that we had a socket for everything, though nanotermically-sized. Now we can take any plant or kelp and engineer it so that their electrical outlet can be used for production purposes,” Yacoby explained.

“If you attach an enzyme that produces hydrogen you get hydrogen, it’s the cleanest fuel that can be,” he said. “There are already electric cars and bicycles with a range of 150 km that travel on hydrogen. There are many types of enzymes in nature that produce valuable substances, such as ammonia needed for the fertilizer industry and today is still produced by a very toxic and harmful method that consumes a lot of energy. We can provide a plant-based alternative for the production of materials that are made in chemical manufacturing facilities. It’s an electric platform inside a living plant cell.”

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You might find it helpful to read Kabir’s article in its entirety before moving on to the news release about the work. The work was conducted with researchers from Arizona State University (ASU;US) and a researcher from Yogi Vemana University (India), as well as, Yacoby. There’s a May 7, 2020 ASU news release (also on EurekAlert but published on May 6, 2020) detailing the work,

Hydrogen is an essential commodity with over 60 million tons produced globally every year. However over 95 percent of it is made by steam reformation of fossil fuels, a process that is energy intensive and produces carbon dioxide. If we could replace even a part of that with algal biohydrogen that is made via light and water, it would have a substantial impact.

This is essentially what has just been achieved in the lab of Kevin Redding, professor in the School of Molecular Sciences and director of the Center for Bioenergy and Photosynthesis. Their research, entitled Rewiring photosynthesis: a Photosystem I -hydrogenase chimera that makes hydrogen in vivo was published very recently in the high impact journal Energy and Environmental Science.

“What we have done is to show that it is possible to intercept the high energy electrons from photosynthesis and use them to drive alternate chemistry, in a living cell” explained Redding. “We have used hydrogen production here as an example.”

“Kevin Redding and his group have made a true breakthrough in re-engineering the Photosystem I complex,” explained Ian Gould, interim director of the School of Molecular Sciences, which is part of The College of Liberal Arts and Sciences. “They didn’t just find a way to redirect a complex protein structure that nature designed for one purpose to perform a different, but equally critical process, but they found the best way to do it at the molecular level.”

It is common knowledge that plants and algae, as well as cyanobacteria, use photosynthesis to produce oxygen and “fuels,” the latter being oxidizable substances like carbohydrates and hydrogen. There are two pigment-protein complexes that orchestrate the primary reactions of light in oxygenic photosynthesis: Photosystem I (PSI) and Photosystem II (PSII).

Algae (in this work the single-celled green alga Chlamydomonas reinhardtii, or ‘Chlamy’ for short) possess an enzyme called hydrogenase that uses electrons it gets from the protein ferredoxin, which is normally used to ferry electrons from PSI to various destinations. A problem is that the algal hydrogenase is rapidly and irreversibly inactivated by oxygen that is constantly produced by PSII.

In this study, doctoral student and first author Andrey Kanygin has created a genetic chimera of PSI and the hydrogenase such that they co-assemble and are active in vivo. This new assembly redirects electrons away from carbon dioxide fixation to the production of biohydrogen.

“We thought that some radically different approaches needed to be taken — thus, our crazy idea of hooking up the hydrogenase enzyme directly to Photosystem I in order to divert a large fraction of the electrons from water splitting (by Photosystem II) to make molecular hydrogen,” explained Redding.

Cells expressing the new photosystem (PSI-hydrogenase) make hydrogen at high rates in a light dependent fashion, for several days.

This important result will also be featured in an upcoming article in Chemistry World – a monthly chemistry news magazine published by the Royal Society of Chemistry. The magazine addresses current developments in the world of chemistry including research, international business news and government policy as it affects the chemical science community.

The NSF grant funding this research is part of the U.S.-Israel Binational Science Foundation (BSF). In this arrangement, a U.S. scientist and Israeli scientist join forces to form a joint project. The U.S. partner submits a grant on the joint project to the NSF, and the Israeli partner submits the same grant to the ISF (Israel Science Foundation). Both agencies must agree to fund the project in order to obtain the BSF funding. Professor Iftach Yacoby of Tel Aviv University, Redding’s partner on the BSF project, is a young scientist who first started at TAU about eight years ago and has focused on different ways to increase algal biohydrogen production.

In summary, re-engineering the fundamental processes of photosynthetic microorganisms offers a cheap and renewable platform for creating bio-factories capable of driving difficult electron reactions, powered only by the sun and using water as the electron source.

Here’s a link to and a citation for the paper,

Rewiring photosynthesis: a photosystem I-hydrogenase chimera that makes H2in vivo† by Andrey Kanygin, Yuval Milrad, Chandrasekhar Thummala, Kiera Reifschneider, Patricia Baker, Pini Marco, Iftach Yacoby and Kevin E. Redding. Energy Environ. Sci., 2020, Advance DOI: https://doi.org/10.1039/C9EE03859K First published: 17 Apr 2020

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This image was used to illustrate the research,

A model of Photosystem 1 core subunits Courtesy: ASU

Nanoparticle fertilizer and dreams of a new ‘Green’ revolution

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There were hints even while it was happening that the ‘Green Revolution’ of the 1960s was not all it was touted to be. (For those who haven’t come across the term before, the Green Revolution was a better way to farm, a way that would feed everyone on earth. Or, that was the dream.)

Perhaps this time, they’ll be more successful. From a Jan. 15, 2017 news item on ScienceDaily, which offers a perspective on the ‘Green Revolution’ that differs from mine,

The “Green Revolution” of the ’60s and ’70s has been credited with helping to feed billions around the world, with fertilizers being one of the key drivers spurring the agricultural boom. But in developing countries, the cost of fertilizer remains relatively high and can limit food production. Now researchers report in the journal ACS Nano a simple way to make a benign, more efficient fertilizer that could contribute to a second food revolution.

A Jan. 25, 2017 American Chemical Society news release on EurekAlert, which originated the news item, expands on the theme,

Farmers often use urea, a rich source of nitrogen, as fertilizer. Its flaw, however, is that it breaks down quickly in wet soil and forms ammonia. The ammonia is washed away, creating a major environmental issue as it leads to eutrophication of water ways and ultimately enters the atmosphere as nitrogen dioxide, the main greenhouse gas associated with agriculture. This fast decomposition also limits the amount of nitrogen that can get absorbed by crop roots and requires farmers to apply more fertilizer to boost production. However, in low-income regions where populations continue to grow and the food supply is unstable, the cost of fertilizer can hinder additional applications and cripple crop yields. Nilwala Kottegoda, Veranja Karunaratne, Gehan Amaratunga and colleagues wanted to find a way to slow the breakdown of urea and make one application of fertilizer last longer.

To do this, the researchers developed a simple and scalable method for coating hydroxyapatite (HA) nanoparticles with urea molecules. HA is a mineral found in human and animal tissues and is considered to be environmentally friendly. In water, the hybridization of the HA nanoparticles and urea slowly released nitrogen, 12 times slower than urea by itself. Initial field tests on rice farms showed that the HA-urea nanohybrid lowered the need for fertilizer by one-half. The researchers say their development could help contribute to a new green revolution to help feed the world’s continuously growing population and also improve the environmental sustainability of agriculture.

Here’s a link to and a citation for the paper,

Urea-Hydroxyapatite Nanohybrids for Slow Release of Nitrogen by Nilwala Kottegoda, Chanaka Sandaruwan, Gayan Priyadarshana, Asitha Siriwardhana, Upendra A. Rathnayake, Danushka Madushanka Berugoda Arachchige, Asurusinghe R. Kumarasinghe, Damayanthi Dahanayake, Veranja Karunaratne, and Gehan A. J. Amaratunga. ACS Nano, Article ASAP DOI: 10.1021/acsnano.6b07781 Publication Date (Web): January 25, 2017

Copyright © 2017 American Chemical Society

This paper is open access.

Nanoparticles for sustainable ways to grow crops

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An April 29, 2016 news item on Nanowerk celebrates research into food production,

Scientists are working diligently to prepare for the expected increase in global population — and therefore an increased need for food production— in the coming decades. A team of engineers at Washington University in St. Louis has found a sustainable way to boost the growth of a protein-rich bean by improving the way it absorbs much-needed nutrients.

Ramesh Raliya, a research scientist, and Pratim Biswas, the Lucy & Stanley Lopata Professor and chair of the Department of Energy, Environmental & Chemical Engineering, both in the School of Engineering & Applied Science, discovered a way to reduce the use of fertilizer made from rock phosphorus and still see improvements in the growth of food crops by using zinc oxide nanoparticles.

The food under investigation is the mung bean,

Researchers at Washington University in St. Louis hope that nanoparticle technology can help reduce the need for fertilizer, creating a more sustainable way to grow crops such as mung beans. Courtesy: Washington University in St. Louis

Researchers at Washington University in St. Louis hope that nanoparticle technology can help reduce the need for fertilizer, creating a more sustainable way to grow crops such as mung beans. Courtesy: Washington University in St. Louis

An April 28, 2016 Washington University in St. Louis  news release (also on EurekAlert) by Beth Miller, which originated the news item, provides more detail,

The research was published April 7 [2016] in the Journal of Agricultural and Food Chemistry. Raliya said this is the first study to show how to mobilize native phosphorus in the soil using zinc oxide nanoparticles over the life cycle of the plant, from seed to harvest.

Food crops need phosphorus to grow, and farmers are using more and more phosphorus-based fertilizer as they increase crops to feed a growing world population. However, the plants can only use about 42 percent of the phosphorus applied to the soil, so the rest runs off into the water streams, where it grows algae that pollutes our water sources. In addition, nearly 82 percent of the world’s phosphorus is used as fertilizer, but it is a limited supply, Raliya says.

“If farmers use the same amount of phosphorus as they’re using now, the world’s supply will be depleted in about 80 years,” Raliya said. “Now is the time for the world to learn how to use phosphorus in a more sustainable manner.”

Raliya and his collaborators, including Jagadish Chandra Tarafdar at the Central Arid Zone Research Institute in Jodhpur, India, created zinc oxide nanoparticles from a fungus around the plant’s root that helps the plant mobilize and take up the nutrients in the soil. Zinc also is an essential nutrient for plants because it interacts with three enzymes that mobilize the complex form of phosphorus in the soil into a form that plants can absorb.

“Due to climate change, the daily temperature and rainfall amounts have changed,” Raliya said. “When they changed, the microflora in the soil are also changed, and once those are depleted, the soil phosphorus can’t mobilize the phosphorus, so the farmer applies more. Our goal is to increase the activity of the enzymes by several-fold, so we can mobilize the native phosphorus several-fold.”

When Raliya and the team applied the zinc nanoparticles to the leaves of the mung bean plant, it increased the uptake of the phosphorus by nearly 11 percent and the activity of the three enzymes by 84 percent to 108 percent. That leads to a lesser need to add phosphorus on the soil, Raliya said.

“When the enzyme activity increases, you don’t need to apply the external phosphorus, because it’s already in the soil, but not in an available form for the plant to uptake,” he said. “When we apply these nanoparticles, it mobilizes the complex form of phosphorus to an available form.”

The mung bean is a legume grown mainly in China, southeast Asia and India, where 60 percent of the population is vegetarian and relies on plant-based protein sources. The bean is adaptable to a variety of climate conditions and is very affordable for people to grow.

Raliya said 45 percent of the worldwide phosphorus use for agriculture takes place in India and China. Much of the phosphorus supply in developing countries is imported from the United States and Morocco-based rock phosphate mines.

“We hope that this method of using zinc oxide nanoparticles can be deployed in developing countries where farmers are using a lot of phosphorus,” Raliya said.

“These countries are dependent on the U.S. to export phosphorus to them, but in the future, the U.S. may have to help supply food, as well. If this crop can grow in a more sustainable manner, it will be helpful for everyone.”

“This is a broader effort under way at the nexus of food, energy and water,” Biswas said. “Nanoparticle technology enabled by aerosol science helps develop innovative solutions to address this global challenge problem that we face today.”

Here’s a link to and a citation for the paper,

Enhancing the Mobilization of Native Phosphorus in the Mung Bean Rhizosphere Using ZnO Nanoparticles Synthesized by Soil Fungi by Ramesh Raliya, Jagadish Chandra Tarafdar, and Pratim Biswas. J. Agric. Food Chem., 2016, 64 (16), pp 3111–3118 DOI: 10.1021/acs.jafc.5b05224 Publication Date (Web): April 07, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.