Category Archives: environment

Cellulose- and chitin-based biomaterial to replace plastics?

Although the term is not actually used in the news release, one of the materials used to create a new biomaterial could safely be described as nanocellulose. From a Sept. 20, 2017 Pennsylvania State University (Penn State) news release (also on EurekAlert) by Jeff Mulhollem,

An inexpensive biomaterial that can be used to sustainably replace plastic barrier coatings in packaging and many other applications has been developed by Penn State researchers, who predict its adoption would greatly reduce pollution.

Completely compostable, the material — a polysaccharide polyelectrolyte complex — is comprised of nearly equal parts of treated cellulose pulp from wood or cotton, and chitosan, which is derived from chitin — the primary ingredient in the exoskeletons of arthropods and crustaceans. The main source of chitin is the mountains of leftover shells from lobsters, crabs and shrimp consumed by humans.

These environmentally friendly barrier coatings have numerous applications ranging from water-resistant paper, to coatings for ceiling tiles and wallboard, to food coatings to seal in freshness, according to lead researcher Jeffrey Catchmark, professor of agricultural and biological engineering, College of Agricultural Sciences.

“The material’s unexpected strong, insoluble adhesive properties are useful for packaging as well as other applications, such as better performing, fully natural wood-fiber composites for construction and even flooring,” he said. “And the technology has the potential to be incorporated into foods to reduce fat uptake during frying and maintain crispness. Since the coating is essentially fiber-based, it is a means of adding fiber to diets.”

The amazingly sturdy and durable bond between carboxymethyl cellulose and chitosan is the key, he explained. The two very inexpensive polysaccharides — already used in the food industry and in other industrial sectors — have different molecular charges and lock together in a complex that provides the foundation for impervious films, coatings, adhesives and more.

The potential reduction of pollution is immense if these barrier coatings replace millions of tons of petroleum-based plastic associated with food packaging used every year in the United States — and much more globally, Catchmark noted.

He pointed out that the global production of plastic is approaching 300 million tons per year. In a recent year, more than 29 million tons of plastic became municipal solid waste in the U.S. and almost half was plastic packaging. It is anticipated that 10 percent of all plastic produced globally will become ocean debris, representing a significant ecological and human health threat.

crab shells

The material is comprised of cellulose pulp from wood or cotton, and chitosan, derived from chitin, the primary ingredient in the exoskeletons of arthropods and crustaceans. The main source of chitin is shells from lobsters, crabs and shrimp. Image: © iStock Photo OKRAD

The polysaccharide polyelectrolyte complex coatings performed well in research, the findings of which were published recently in Green Chemistry. Paperboard coated with the biomaterial, comprised of nanostructured fibrous particles of carboxymethyl cellulose and chitosan, exhibited strong oil and water barrier properties. The coating also resisted toluene, heptane and salt solutions and exhibited improved wet and dry mechanical and water vapor barrier properties.

“These results show that polysaccharide polyelectrolyte complex-based materials may be competitive barrier alternatives to synthetic polymers for many commercial applications,” said Catchmark, who, in concert with Penn State, has applied for a patent on the coatings.

“In addition, this work demonstrates that new, unexpected properties emerge from multi-polysaccharide systems engaged in electrostatic complexation, enabling new high-performance applications.”

Catchmark began experimenting with biomaterials that might be used instead of plastics a decade or so ago out of concerns for sustainability. He became interested in cellulose, the main component in wood, because it is the largest volume sustainable, renewable material on earth. Catchmark studied its nanostructure — how it is assembled at the nanoscale.

He believed he could develop natural materials that are more robust and improve their properties, so that they could compete with synthetic materials that are not sustainable and generate pollution — such as the low-density polyethylene laminate applied to paper board, Styrofoam and solid plastic used in cups and bottles.

“The challenge is, to do that you’ve got to be able to do it in a way that is manufacturable, and it has to be less expensive than plastic,” Catchmark explained. “Because when you make a change to something that is greener or sustainable, you really have to pay for the switch. So it has to be less expensive in order for companies to actually gain something from it. This creates a problem for sustainable materials — an inertia that has to be overcome with a lower cost.”

lab vials

The amazingly sturdy and durable bond between carboxymethyl cellulose and chitosan is the key. The two very inexpensive polysaccharides, already used in the food industry and in other industrial sectors, have different molecular charges and lock together in a complex that provides the foundation for impervious films, coatings, adhesives and more. Image: Penn State

Funded by a Research Applications for Innovation grant from the College of Agricultural Sciences, Catchmark currently is working to develop commercialization partners in different industry sectors for a wide variety of products.

“We are trying to take the last step now and make a real impact on the world, and get industry people to stop using plastics and instead use these natural materials,” he said. “So they (consumers) have a choice — after the biomaterials are used, they can be recycled, buried in the ground or composted, and they will decompose. Or they can continue to use plastics that will end up in the oceans, where they will persist for thousands of years.”

Also involved in the research were Snehasish Basu, post-doctoral scholar, and Adam Plucinski, master’s degree student, now instructor of engineering at Penn State Altoona. Staff in Penn State’s Material Research Institute provided assistance with the project.

The U.S. Department of Agriculture supported this work. Southern Champion Tray, of Chattanooga, Tennessee, provided paperboard and information on its production for experiments.

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

Sustainable barrier materials based on polysaccharide polyelectrolyte complexes by
Snehasish Basu, Adam Plucinski, and Jeffrey M. Catchmark. Green Chemistry 2017, 19, 4080-4092 DOI: 10.1039/C7GC00991G

This paper is behind a paywall. One comment, I found an anomaly on the page when I visited. At the top of the citation page, it states that this is issue 17 of Green Chemistry but the citation in the column on the right is “2017, 19 … “, which would be issue 19.

Substituting graphene and other carbon materials for scarce metals

A Sept. 19, 2017 news item on Nanowerk announces a new paper from the Chalmers University of Technology (Sweden), the lead institution for the Graphene Flagship (a 1B Euro 10 year European Commission programme), Note: A link has been removed,

Scarce metals are found in a wide range of everyday objects around us. They are complicated to extract, difficult to recycle and so rare that several of them have become “conflict minerals” which can promote conflicts and oppression. A survey at Chalmers University of Technology now shows that there are potential technology-based solutions that can replace many of the metals with carbon nanomaterials, such as graphene (Journal of Cleaner Production, “Carbon nanomaterials as potential substitutes for scarce metals”).

They can be found in your computer, in your mobile phone, in almost all other electronic equipment and in many of the plastics around you. Society is highly dependent on scarce metals, and this dependence has many disadvantages.

A Sept. 19, 2017 Chalmers University of Technology press release by Ulrika Ernstrom,, which originated the news item, provides more detail about the possibilities,

They can be found in your computer, in your mobile phone, in many of the plastics around you and in almost all electronic equipment. Society is highly dependent on scarce metals, and this dependence has many disadvantages.
Scarce metals such as tin, silver, tungsten and indium are both rare and difficult to extract since the workable concentrations are very small. This ensures the metals are highly sought after – and their extraction is a breeding ground for conflicts, such as in the Democratic Republic of the Congo where they fund armed conflicts.
In addition, they are difficult to recycle profitably since they are often present in small quantities in various components such as electronics.
Rickard Arvidsson and Björn Sandén, researchers in environmental systems analysis at Chalmers University of Technology, have now examined an alternative solution: substituting carbon nanomaterials for the scarce metals. These substances – the best known of which is graphene – are strong materials with good conductivity, like scarce metals.
“Now technology development has allowed us to make greater use of the common element carbon,” says Sandén. “Today there are many new carbon nanomaterials with similar properties to metals. It’s a welcome new track, and it’s important to invest in both the recycling and substitution of scarce metalsfrom now on.”
The Chalmers researchers have studied  the main applications of 14 different metals, and by reviewing patents and scientific literature have investigated the potential for replacing them by carbon nanomaterials. The results provide a unique overview of research and technology development in the field.
According to Arvidsson and Sandén the summary shows that a shift away from the use of scarce metals to carbon nanomaterials is already taking place.
“There are potential technology-based solutions for replacing 13 out of the 14 metals by carbon nanomaterials in their most common applications. The technology development is at different stages for different metals and applications, but in some cases such as indium and gallium, the results are very promising,” Arvidsson says.
“This offers hope,” says Sandén. “In the debate on resource constraints, circular economy and society’s handling of materials, the focus has long been on recycling and reuse. Substitution is a potential alternative that has not been explored to the same extent and as the resource issues become more pressing, we now have more tools to work with.”
The research findings were recently published in the Journal of Cleaner Production. Arvidsson and Sandén stress that there are significant potential benefits from reducing the use of scarce metals, and they hope to be able to strengthen the case for more research and development in the field.
“Imagine being able to replace scarce metals with carbon,” Sandén says. “Extracting the carbon from biomass would create a natural cycle.”
“Since carbon is such a common and readily available material, it would also be possible to reduce the conflicts and geopolitical problems associated with these metals,” Arvidsson says.
At the same time they point out that more research is needed in the field in order to deal with any new problems that may arise if the scarce metals are replaced.
“Carbon nanomaterials are only a relatively recent discovery, and so far knowledge is limited about their environmental impact from a life-cycle perspective. But generally there seems to be a potential for a low environmental impact,” Arvidsson says.


Carbon nanomaterials consist solely or mainly of carbon, and are strong materials with good conductivity. Several scarce metals have similar properties. The metals are found, for example, in cables, thin screens, flame-retardants, corrosion protection and capacitors.
Rickard Arvidsson and Björn Sandén at Chalmers University of Technology have investigated whether the carbon nanomaterials graphene, fullerenes and carbon nanotubes have the potential to replace 14 scarce metals in their main areas of application (see table). They found potential technology-based solutions to replace the metals with carbon nanomaterials for all applications except for gold in jewellery. The metals which we are closest to being able to substitute are indium, gallium, beryllium and silver.

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

Carbon nanomaterials as potential substitutes for scarce metals by Rickard Arvidsson, Björn A. Sandén. Journal of Cleaner Production (0959-6526). Vol. 156 (2017), p. 253-261. DOI:

This paper appears to be open access.

Measurably fewer nanoparticles in São Paulo’s (Brazil) air after ethanol use

An Aug. 28, 2017 news item on Nanotechnology Now features news about nanoparticles and the environment in São Paulo, Brazil,

When ethanol prices at the pump rise for whatever reason, it becomes economically advantageous for drivers of dual-fuel vehicles to fill up with gasoline. However, the health of the entire population pays a high price: substitution of gasoline for ethanol leads to a 30% increase in the atmospheric concentration of ultrafine particulate matter, which consists of particles with a diameter of less than 50 nanometers (nm).

An Aug. 23, 2017 Fundação de Amparo à Pesquisa do Estado de São Paulo (The São Paulo Research Foundation [FAPESP]) press release, which originated the news item, explains further,

The phenomenon was detected in São Paulo City, Brazil, in a study supported by FAPESP and published in July 2017 in Nature Communications.

“These polluting nanoparticles are so tiny that they behave like gas molecules. When inhaled, they can penetrate the respiratory system’s defensive barriers and reach the pulmonary alveoli, so that potentially toxic substances enter the bloodstream and may increase the incidence of respiratory and cardiovascular problems,” said Paulo Artaxo, Full Professor at the University of São Paulo’s Physics Institute (IF-USP) and a co-author of the study.

Levels of ultrafine particulate matter in the atmosphere are neither monitored nor regulated by environmental agencies not only in Brazil but practically anywhere in the world, according to Artaxo. The São Paulo State Environmental Corporation (CETESB), for example, routinely monitors only solid particles with diameters of 10,000 nm (PM10) and 2,500 nm (PM2.5) – as well as other gaseous pollutants such as ozone (O3), carbon monoxide (CO) and nitrogen dioxide (NO2).

“Between 75% and 80% of the mass of the nanoparticles we measured in this study corresponds to organic compounds emitted by motor vehicles – carbon in different chemical forms. What these compounds are exactly and how they affect health are questions that require further research,” Artaxo said.

He added that a consensus is forming in the United States and Europe based on recent research indicating that these emissions are a potential health hazard and should be regulated. Several US states, such as California, have laws requiring a 20%-30% ethanol blend in gasoline, which also helps reduce emissions of ultrafine particulate matter.


The data analyzed in the study were collected during the period of January-May 2011, when ethanol prices fluctuated sharply compared with gasoline prices, owing to macroeconomic factors such as variations in the international price of sugar (Brazilian ethanol is made from sugarcane).

Collection was performed at the top of a ten-story building belonging to IF-USP in the western part of São Paulo City. According to Artaxo, the site was chosen because it is relatively distant from the main traffic thoroughfares so that the aerosols there are “older” in the sense that they have already interacted with other substances present in the atmosphere.

“Generally speaking, the pollution we inhale every day at home or at work isn’t what comes out of vehicular exhaust pipes but particles already processed in the atmosphere,” he explained. “For this reason, we chose a site that isn’t directly impacted by primary vehicle emissions.”

The study was conducted during Joel Ferreira de Brito’s postdoctoral research, which Artaxo supervised. The model used to analyze the data was developed by Brazilian economist Alberto Salvo, a professor at the National University of Singapore and first author of the article. Franz Geiger, a chemist at Northwestern University in the US, also collaborated.

“We adapted a sophisticated statistical model originally developed for economic analysis and used here for the first time to analyze the chemistry of atmospheric nanoparticles,” Artaxo said. “The main strength of this tool is that it can work with a large number of variables, such as the presence or absence of rainfall, wind direction, traffic intensity, and levels of ozone, carbon monoxide and other pollutants.”

Analyses were performed before, during and after a sharp fluctuation in ethanol prices leading consumers to switch motor fuels in São Paulo City. While no significant changes were detected in levels of inhalable fine particulate matter (PM2.5 and PM10), the study proved in a real, day-to-day situation that choosing ethanol reduces emissions of ultrafine particles. To date, this phenomenon had only been observed in the laboratory.

“These results reinforce the need for public policies to encourage the use of biofuels, as they clearly show that the public lose in health what they save at the pump when opting for gasoline,” Artaxo said.

In São Paulo, a city with 7 million motor vehicles and the largest urban fleet of flexible-fuel cars, it would be feasible to run all buses on biofuel. “We have the technology for this in Brazil – and at a competitive price,” he said.

The fact that the city’s bus fleet still depends on diesel, Artaxo warned, creates an even worse health hazard in the shape of emissions of black carbon, one of the main components of soot and a pollutant that contributes to global warming. Alongside electricity generation, the transportation sector is the largest emitter of pollutants produced by the burning of fossil fuels.

For Artaxo, incentives for electric, hybrid or biofuel vehicles are vital to reduce greenhouse gas emissions. “By incentivizing biofuels, we could solve several problems at once,” he said. “We could combat climate change, reduce harm to health and foster advances in automotive technology by offering a stimulus for auto makers to develop more economical and efficient cars fueled by ethanol.”

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

Reduced ultrafine particle levels in São Paulo’s atmosphere during shifts from gasoline to ethanol use by Alberto Salvo, Joel Brito, Paulo Artaxo, & Franz M. Geiger. Nature Communications 8, Article number: 77 (2017) doi:10.1038/s41467-017-00041-5 Published online: 18 July 2017

This paper is open access.

Getting a more complete picture of aerosol particles at the nanoscale

What is in the air we breathe? In addition to the gases we learned about in school there are particles, not just the dust particles you can see, but micro- and nanoparticles too and scientists would like to know more about them.

An August 23, 2017 news item on Nanowerk features work which may help scientists in their quest,

They may be tiny and invisible, says Xiaoji Xu, but the aerosol particles suspended in gases play a role in cloud formation and environmental pollution and can be detrimental to human health.

Aerosol particles, which are found in haze, dust and vehicle exhaust, measure in the microns. One micron is one-millionth of a meter; a thin human hair is about 30 microns thick.

The particles, says Xu, are among the many materials whose chemical and mechanical properties cannot be fully measured until scientists develop a better method of studying materials at the microscale as well as the much smaller nanoscale (1 nm is one-billionth of a meter).

Xu, an assistant professor of chemistry, has developed such a method and utilized it to perform noninvasive chemical imaging of a variety of materials, as well as mechanical mapping with a spatial resolution of 10 nanometers.

The technique, called peak force infrared (PFIR) microscopy, combines spectroscopy and scanning probe microscopy. In addition to shedding light on aerosol particles, Xu says, PFIR will help scientists study micro- and nanoscale phenomena in a variety of inhomogeneous materials.

The lower portion of this image by Xiaoji Xu’s group shows the operational scheme of peak force infrared (PFIR) microscopy. The upper portion shows the topography of nanoscale PS-b-PMMA polymer islands on a gold substrate. (Image courtesy of Xiaoji Xu)

An August 22, 2017 Lehih University news release by Kurt Pfitzer (also on EurekAlert), which originated the news item, explains the research in more detail (Note: A link has been removed),

“Materials in nature are rarely homogeneous,” says Xu. “Functional polymer materials often consist of nanoscale domains that have specific tasks. Cellular membranes are embedded with proteins that are nanometers in size. Nanoscale defects of materials exist that affect their mechanical and chemical properties.

“PFIR microscopy represents a fundamental breakthrough that will enable multiple innovations in areas ranging from the study of aerosol particles to the investigation of heterogeneous and biological materials,” says Xu.

Xu and his group recently reported their results in an article titled “Nanoscale simultaneous chemical and mechanical imaging via peak force infrared microscopy.” The article was published in Science Advances, a journal of the American Association for the Advancement of Science, which also publishes Science magazine.

The article’s lead author is Le Wang, a Ph.D. student at Lehigh. Coauthors include Xu and Lehigh Ph.D. students Haomin Wang and Devon S. Jakob, as well as Martin Wagner of Bruker Nano in Santa Barbara, Calif., and Yong Yan of the New Jersey Institute of Technology.

“PFIR microscopy enables reliable chemical imaging, the collection of broadband spectra, and simultaneous mechanical mapping in one simple setup with a spatial resolution of ~10 nm,” the group wrote.

“We have investigated three types of representative materials, namely, soft polymers, perovskite crystals and boron nitride nanotubes, all of which provide a strong PFIR resonance for unambiguous nanochemical identification. Many other materials should be suited as well for the multimodal characterization that PFIR microscopy has to offer.

“In summary, PFIR microscopy will provide a powerful analytical tool for explorations at the nanoscale across wide disciplines.”

Xu and Le Wang also published a recent article about the use of PFIR to study aerosols. Titled “Nanoscale spectroscopic and mechanical characterization of individual aerosol particles using peak force infrared microscopy,” the article appeared in an “Emerging Investigators” issue of Chemical Communications, a journal of the Royal Society of Chemistry. Xu was featured as one of the emerging investigators in the issue. The article was coauthored with researchers from the University of Macau and the City University of Hong Kong, both in China.

PFIR simultaneously obtains chemical and mechanical information, says Xu. It enables researchers to analyze a material at various places, and to determine its chemical compositions and mechanical properties at each of these places, at the nanoscale.

“A material is not often homogeneous,” says Xu. “Its mechanical properties can vary from one region to another. Biological systems such as cell walls are inhomogeneous, and so are materials with defects. The features of a cell wall measure about 100 nanometers in size, placing them well within range of PFIR and its capabilities.”

PFIR has several advantages over scanning near-field optical microscopy (SNOM), the current method of measuring material properties, says Xu. First, PFIR obtains a fuller infrared spectrum and a sharper image—6-nm spatial resolution—of a wider variety of materials than does SNOM. SNOM works well with inorganic materials, but does not obtain as strong an infrared signal as the Lehigh technique does from softer materials such as polymers or biological materials.

“Our technique is more robust,” says Xu. “It works better with soft materials, chemical as well as biological.”

The second advantage of PFIR is that it can perform what Xu calls point spectroscopy.

“If there is something of interest chemically on a surface,” Xu says, “I put an AFM [atomic force microscopy] probe to that location to measure the peak-force infrared response.

“It is very difficult to obtain these spectra with current scattering-type scanning near-field optical microscopy. It can be done, but it requires very expensive light sources. Our method uses a narrow-band infrared laser and costs about $100,000. The existing method uses a broadband light source and costs about $300,000.”

A third advantage, says Xu, is that PFIR obtains a mechanical as well as a chemical response from a material.

“No other spectroscopy method can do this,” says Xu. “Is a material rigid or soft? Is it inhomogeneous—is it soft in one area and rigid in another? How does the composition vary from the soft to the rigid areas? A material can be relatively rigid and have one type of chemical composition in one area, and be relatively soft with another type of composition in another area.

“Our method simultaneously obtains chemical and mechanical information. It will be useful for analyzing a material at various places and determining its compositions and mechanical properties at each of these places, at the nanoscale.”

A fourth advantage of PFIR is its size, says Xu.

“We use a table-top laser to get infrared spectra. Ours is a very compact light source, as opposed to the much larger sizes of competing light sources. Our laser is responsible for gathering information concerning chemical composition. We get mechanical information from the AFM [atomic force microscope]. We integrate the two types of measurements into one device to simultaneously obtain two channels of information.”

Although PFIR does not work with liquid samples, says Xu, it can measure the properties of dried biological samples, including cell walls and protein aggregates, achieving a 10-nm spatial resolution without staining or genetic modification.

This looks like very exciting work.

Here are links and citations for both studies mentioned in the news release (the most recently published being cited first),

Nanoscale simultaneous chemical and mechanical imaging via peak force infrared microscopy by Le Wang, Haomin Wang, Martin Wagner, Yong Yan, Devon S. Jakob, and Xiaoji G. Xu. Science Advances 23 Jun 2017: Vol. 3, no. 6, e1700255 DOI: 10.1126/sciadv.1700255

Nanoscale spectroscopic and mechanical characterization of individual aerosol particles using peak force infrared microscopy by Le Wang, Dandan Huang, Chak K. Chan, Yong Jie Li, and Xiaoji G. Xu. Chem. Commun., 2017,53, 7397-7400 DOI: 10.1039/C7CC02301D First published on 16 Jun 2017

The June 23, 2017 paper is open access while the June 16, 2017 paper is behind a paywall.

Burning coal produces harmful titanium dioxide nanoparticles

It turns out that Canada has the fifth largest reserve of coal in the world, according to the Coal in Canada Wikipedia entry (Note: Links have been removed),

Coal reserves in Canada rank fifth largest in the world (following the former Soviet Union, the United States, the People’s Republic of China and Australia) at approximately 10 billion tons, 10% of the world total.[1] This represents more energy than all of the oil and gas in the country combined. The coal industry generates CDN$5 billion annually.[2] Most of Canada’s coal mining occurs in the West of the country.[3] British Columbia operates 10 coal mines, Alberta 9, Saskatchewan 3 and New Brunswick one. Nova Scotia operates several small-scale mines, Westray having closed following the 1992 disaster there.[4]

So, this news from Virginia holds more than the usual interest for me (I’m in British Columbia). From an Aug. 8, 2017 Virginia Tech news release (also on EurekAlert),

Environmental scientists led by the Virginia Tech College of Science have discovered that the burning of coal produces incredibly small particles of a highly unusual form of titanium oxide.

When inhaled, these nanoparticles can enter the lungs and potentially the bloodstream.

The particulates — known as titanium suboxide nanoparticles — are unintentionally produced as coal is burned, creating these tiniest of particles, as small as 100 millionths of a meter [emphasis mine], said the Virginia Tech-led team. When the particles are introduced into the air — unless captured by high-tech particle traps — they can float away from power plant stacks and travel on air currents locally, regionally, and even globally.

As an example of this, these nanoparticles were found on city streets, sidewalks, and in standing water in Shanghai, China.

The findings are published in the latest issue of Nature Communications under team leader Michael F. Hochella Jr., University Distinguished Professor of Geosciences with the College of Science, and Yi Yang, a professor at East China Normal University in Shanghai. Other study participants include Duke University, the University of Kentucky, and Laurentian University in Canada.

“The problem with these nanoparticles is that there is no easy or practical way to prevent their formation during coal burning,” Hochella said, adding that in nations with strong environmental regulations, such as the United States, most of the nanoparticles would be caught by particle traps. Not so in Africa [a continent not a nation], China, or India, where regulations are lax or nonexistent, with coal ash and smoke entering the open air.

“Due to advanced technology used at U.S.-based coal burning power plants, mandated by the Clean Air Act and the Environmental Protection Agency, most of these nanoparticles and other tiny particles are removed before the final emission of the plant’s exhaust gases,” Hochella said. “But in countries where the particles from the coal burning are not nearly so efficiently removed, or removed at all, these titanium suboxide nanoparticles and many other particle types are emitted into the atmosphere, in part resulting in hazy skies that plague many countries, especially in China and India.”

Hochella and his team found these previously unknown nanoparticles not only in coal ash from around the world and in the gaseous waste emissions of coal plants, but on city streets, in soils and storm water ponds, and at wastewater treatment plants.

“I could not believe what I have found at the beginning, because they had been reported so extremely rarely in the natural environment,” said Yang, who once worked as a visiting professor in Virginia Tech’s Department of Geosciences with Hochella. “It took me several months to confirm their occurrence in coal ash samples.”

The newly found titanium suboxide — called Magnéli phases — was once thought rare, found only sparingly on Earth in some meteorites, from a small area of rock formations in western Greenland, and occasionally in moon rocks. The findings by Hochella and his team indicate that these nanoparticles are in fact widespread globally. They are only now being studied for the first time in natural environments using powerful electron microscopes.

Why did the discovery occur now? According to the report, nearly all coal contains traces of the minerals rutile and/or anatase, both “normal,” naturally occurring, and relatively inert titanium oxides, especially in the absence of light. When those minerals are burned in the presence of coal, research found they easily and quickly converted to these unusual titanium suboxide nanoparticles. The nanoparticles then become entrained in the gases that leave the power plant.

When inhaled, the nanoparticles enter deep into the lungs, potentially all the way into the air sacs that move oxygen into our bloodstream during the normal breathing process. While human lung toxicity of these particles is not yet known, a preliminary biotoxicity test by Hochella and Richard Di Giulio, professor of environmental toxicology, and Jessica Brandt, a doctoral candidate, both at Duke University, indicates that the particles do indeed have toxicity potential.

According to the team, further study is clearly needed, especially biotoxicity testing directly relevant to the human lung. Partnering with coal-power plants either in the United States or China would be ideal, said Yang.

More troubling, the study shows that titanium suboxide nanoparticles are biologically active in the dark, making the particles highly suspect. Exact human health effects are yet unknown.

“Future studies will need to very carefully investigate and access the toxicity of titanium suboxide nanoparticles in the human lung, and this could take years, a sobering thought considering its potential danger,” Hochella said.

As the titanium suboxide nanoparticle itself is produced incidentally, Hochella and his team came across the nanoparticle by accident while studying a 2014 coal ash spill in the Dan River, North Carolina. During the study of the downstream movement of toxic metals in the ash in the Dan River, the team discovered and recognized the presence of small amounts of the highly unusual titanium suboxide.

The group later produced the titanium suboxide nanoparticles when burning coal in a lab simulation.

This new potential air pollution health hazard builds on already established findings from the World Health Organization. It estimates that 3.3 million premature deaths occur worldwide per year due to polluted air, Hochella said. In China, 1.6 million premature deaths are estimated annually due to cardiovascular and respiratory injury from air pollution. Most Chinese megacities top 100 severely hazy days each year with particle concentrations two to four times higher than WHO guidelines, Yang said.

Direct health effects on humans is only one factor. Findings of thousands of scientists have determined that the biggest driver of warming of the planet and the resulting climate change is industrial-scale coal burning. The impact of titanium suboxide nanoparticles found in the atmosphere, in addition to greenhouse gases, on animals, water, and plants is not yet known.

They’ve used an unusual unit of measurement, “100 millionths of a meter,” nanoparticles are usually described in nanometers.

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

Discovery and ramifications of incidental Magnéli phase generation and release from industrial coal-burning by Yi Yang, Bo Chen, James Hower, Michael Schindler, Christopher Winkler, Jessica Brandt, Richard Di Giulio, Jianping Ge, Min Liu, Yuhao Fu, Lijun Zhang, Yuru Chen, Shashank Priya, & Michael F. Hochella Jr. Nature Communications 8, Article number: 194 (2017) doi:10.1038/s41467-017-00276-2 Published online: 08 August 2017

This paper is behind a paywall.

This put me in mind of the famous London smog, which one doesn’t hear about much anymore. For anyone not familiar with that phenomenon, here’s more from the Great Smog of London Wikipedia entry (Note: Links have been removed),

The Great Smog of London, or Great Smog of 1952 sometimes called the Big Smoke,[1] was a severe air-pollution event [emphasis mine] that affected the British capital of London in December 1952. A period of cold weather, combined with an anticyclone and windless conditions, collected airborne pollutants – mostly arising from the use of coal [emphasis mine]– to form a thick layer of smog over the city. It lasted from Friday, 5 December to Tuesday, 9 December 1952 and then dispersed quickly when the weather changed.

It caused major disruption by reducing visibility and even penetrating indoor areas, far more severe than previous smog events experienced in the past, called “pea-soupers”. Government medical reports in the following weeks, however, estimated that up until 8 December, 4,000 people had died as a direct result of the smog and 100,000 more were made ill by the smog’s effects on the human respiratory tract. More recent research suggests that the total number of fatalities was considerably greater, about 12,000.[2]

London had suffered since the 1200s from poor air quality,[3] which worsened in the 1600s,[4][5] but the Great Smog is known to be the worst air-pollution event in the history of the United Kingdom,[6] and the most significant in terms of its effect on environmental research, government regulation, and public awareness of the relationship between air quality and health.[2][4] It led to several changes in practices and regulations, including the Clean Air Act 1956. …

Call for art (and possible donation) featuring amphibians for Precious Frogs Art Exhibit and fundraising effort

Thanks to the August 24, 2017 Opus Art Supplies newsletter (received via email), I got notice about this call for art (from the Opus Call for Submissions webpage),

Submission Deadline:

September 6, 2017

Date:  September 29, 2017December 15, 2017 [for Amphibian Art Exhibit at Science World in Vancouver, Canada]

Paint, draw, print, sculpt, design, photograph the province’s [British Columbia] frogs, toads and salamanders, and consider how art can combat threats to amphibian survival including habitat loss, pollution, invasive species, and disease. Because this is a fundraising event, we are hoping to engage artists to donate artwork for sale at the exhibition, with proceeds towards the long-term conservation of our native amphibians. However, you can choose to exhibit only. To submit, please download the call for artists for full details and instructions.

We encourage small pieces (for example: 5×7, 6×4, 8×8, 8×10 inches or other small size you enjoy working in) or small sculptures to ensure accessibility for all artists. We realize that artists are often asked to donate artwork for charity, and we respect and value the fact that artists have been very generous in supporting the causes they believe in. We hope you will consider ours.For more information and questions, contact us:

Precious Frog, the organization (the exhibition is Precious Frogs) requesting the art has more detail in its (On the spot webpage) June 12, 2017 initial call for submissions,

Are you an artist? Are you passionate about art and conservation? Are you interested in creatively exploring how to celebrate British Columbia’s amphibians through art?

This is your opportunity to submit a piece of art for a three-month long art exhibition to be launched at Science World in Vancouver on September 29, 2017.

We are very excited to announce that we are partnering with TELUS World of Science to bring you the first art exhibition in Vancouver entirely dedicated to the amphibians of the province. The Precious Frogs Art Exhibition will integrate art and conservation by showcasing a variety of visual and media art pieces combined with scientific and educational information on the challenges faced by amphibians in our province.

Elsewhere in North America, artists have already demonstrated their creativity to raise awareness about the global decline of amphibians. In North Carolina, artist Terry Thirion has initiated the Disappearing Frogs Project, in 2013.

But this is a first in Vancouver, and with the Precious Frogs art exhibition, we hope to inspire artists to be a bridge between scientists and the broader public and to promote awareness and action for the long-term conservation of all of our precious amphibians. Additional film screenings, educational events, and art workshops will be presented at Science World in the fall as part of the art exhibition.

To us, amphibians are intriguing, beautiful, complex, inspiring, unusual, and more. What do you see?

Paint, draw, print, sculpt, design, photograph the province’s  frogs, toads and salamanders, and consider how art can combat threats to amphibian survival including habitat loss, pollution, invasive species, and disease. Submit your most convincing art piece. Your work will support the Oregon Spotted Frog Recovery Team’s efforts to conserve amphibians in British Columbia.

To submit, please download the call for artists for full details and instructions. The submission deadline is September 6, 2017. For more information and questions, contact us:

And mark your calendar: the opening reception for the art exhibition will be on Tuesday, October 3 from 6 to 8 pm at Science World.

Frequently Asked Questions

Why are you organizing this event?

Amphibians serve an important role in ecosystems and are particularly sensitive to changes in the environment that ultimately affect us all. This volunteer-run project aims to promote awareness and raise funds for the long-term conservation of our native amphibians.

Why are you asking artists to donate artwork?

Because this is a fundraising event, we are hoping to engage artists to donate artwork for sale at the exhibition, with proceeds towards the long-term conservation of our native amphibians.  We encourage small pieces (for example: 5×7, 6×4, 8×8, 8×10 inches or other small size you enjoy working in) or small sculptures to ensure accessibility for all artists. We realize that artists are often asked to donate artwork for charity, and we respect and value the fact that artists have been very generous in supporting the causes they believe in. We hope you will consider ours.

I don’t want to donate my artwork. Can I still participate?

Yes absolutely! You can choose to have your artwork on display at the exhibition and marked “Not For Sale.” The artwork will be returned to you at the end of the exhibition, and you are then free to sell your piece as you wish. We encourage artists to consider a donation to the Precious Frogs Project on subsequent sales of amphibian-related artwork. The gesture will always be appreciated.

How much will the artwork be sold for?

Artwork will be sold at accessible, standardized prices ($20 – $50) for small works. Larger pieces will be sold at prices recommended by the artist.

Why should I participate?

We feel passionate about the conservation of amphibians, and we hope you will too. This project is part of a series of exhibits such as the Disappearing Frogs Project in the United States. If you participate in our project, you will become part of a larger context. Ultimately, this project is about opening people’s eyes on amphibian extinction, and artists have the capacity to express themselves and help change the views of people on these very important issues. Additionally, the publicity about the event and the public exposure artists will receive during the three-month long exhibition are factors that we hope artists will value, in addition to becoming active contributors to the long-term conservation of amphibians.

How do I find out more information about amphibians at risk in BC?

A good starting point is our Frog guide on our website, which lists all BC’s native amphibians — frogs, toads, and salamanders. If you would like to learn more or have specific questions, please do not hesitate to contact us at:

Do you accept volunteers?

Yes! Volunteers are welcome to help us with the different dimensions of this project and the events that we are planning during the three-month exhibition. Please check out our current volunteer position posting and contact us for additional opportunities.

Text: Isabelle Groc

Here’s a sample of what’s on’s call for submission webpage,

Artwork: Lord Byng Secondary School, Grade 10 Honours art class

I wish Precious Frog good luck with its fundraising efforts and greater exposure for any artists who participate.

US Dept. of Agriculture announces its nanotechnology research grants

I don’t always stumble across the US Department of Agriculture’s nanotechnology research grant announcements but I’m always grateful when I do as it’s good to find out about  nanotechnology research taking place in the agricultural sector. From a July 21, 2017 news item on Nanowerk,,

The U.S. Department of Agriculture’s (USDA) National Institute of Food and Agriculture (NIFA) today announced 13 grants totaling $4.6 million for research on the next generation of agricultural technologies and systems to meet the growing demand for food, fuel, and fiber. The grants are funded through NIFA’s Agriculture and Food Research Initiative (AFRI), authorized by the 2014 Farm Bill.

“Nanotechnology is being rapidly implemented in medicine, electronics, energy, and biotechnology, and it has huge potential to enhance the agricultural sector,” said NIFA Director Sonny Ramaswamy. “NIFA research investments can help spur nanotechnology-based improvements to ensure global nutritional security and prosperity in rural communities.”

A July 20, 2017 USDA news release, which originated the news item, lists this year’s grants and provides a brief description of a few of the newly and previously funded projects,

Fiscal year 2016 grants being announced include:

Nanotechnology for Agricultural and Food Systems

  • Kansas State University, Manhattan, Kansas, $450,200
  • Wichita State University, Wichita, Kansas, $340,000
  • University of Massachusetts, Amherst, Massachusetts, $444,550
  • University of Nevada, Las Vegas, Nevada,$150,000
  • North Dakota State University, Fargo, North Dakota, $149,000
  • Cornell University, Ithaca, New York, $455,000
  • Cornell University, Ithaca, New York, $450,200
  • Oregon State University, Corvallis, Oregon, $402,550
  • University of Pennsylvania, Philadelphia, Pennsylvania, $405,055
  • Gordon Research Conferences, West Kingston, Rhode Island, $45,000
  • The University of Tennessee,  Knoxville, Tennessee, $450,200
  • Utah State University, Logan, Utah, $450,200
  • The George Washington University, Washington, D.C., $450,200

Project details can be found at the NIFA website (link is external).

Among the grants, a University of Pennsylvania project will engineer cellulose nanomaterials [emphasis mine] with high toughness for potential use in building materials, automotive components, and consumer products. A University of Nevada-Las Vegas project will develop a rapid, sensitive test to detect Salmonella typhimurium to enhance food supply safety.

Previously funded grants include an Iowa State University project in which a low-cost and disposable biosensor made out of nanoparticle graphene that can detect pesticides in soil was developed. The biosensor also has the potential for use in the biomedical, environmental, and food safety fields. University of Minnesota (link is external) researchers created a sponge that uses nanotechnology to quickly absorb mercury, as well as bacterial and fungal microbes from polluted water. The sponge can be used on tap water, industrial wastewater, and in lakes. It converts contaminants into nontoxic waste that can be disposed in a landfill.

NIFA invests in and advances agricultural research, education, and extension and promotes transformative discoveries that solve societal challenges. NIFA support for the best and brightest scientists and extension personnel has resulted in user-inspired, groundbreaking discoveries that combat childhood obesity, improve and sustain rural economic growth, address water availability issues, increase food production, find new sources of energy, mitigate climate variability and ensure food safety. To learn more about NIFA’s impact on agricultural science, visit, sign up for email updates (link is external) or follow us on Twitter @USDA_NIFA (link is external), #NIFAImpacts (link is external).

Given my interest in nanocellulose materials (Canada was/is a leader in the production of cellulose nanocrystals [CNC] but there has been little news about Canadian research into CNC applications), I used the NIFA link to access the table listing the grants and clicked on ‘brief’ in the View column in the University of Pennsylania row to find this description of the project,


NON-TECHNICAL SUMMARY: Cellulose nanofibrils (CNFs) are natural materials with exceptional mechanical properties that can be obtained from renewable plant-based resources. CNFs are stiff, strong, and lightweight, thus they are ideal for use in structural materials. In particular, there is a significant opportunity to use CNFs to realize polymer composites with improved toughness and resistance to fracture. The overall goal of this project is to establish an understanding of fracture toughness enhancement in polymer composites reinforced with CNFs. A key outcome of this work will be process – structure – fracture property relationships for CNF-reinforced composites. The knowledge developed in this project will enable a new class of tough CNF-reinforced composite materials with applications in areas such as building materials, automotive components, and consumer products.The composite materials that will be investigated are at the convergence of nanotechnology and bio-sourced material trends. Emerging nanocellulose technologies have the potential to move biomass materials into high value-added applications and entirely new markets.

It’s not the only nanocellulose material project being funded in this round, there’s this at North Dakota State University, from the NIFA ‘brief’ project description page,


NON-TECHNICAL SUMMARY: Synthetic polymers are quite vulnerable to fire.There are 2.4 million reported fires, resulting in 7.8 billion dollars of direct property loss, an estimated 30 billion dollars of indirect loss, 29,000 civilian injuries, 101,000 firefighter injuries and 6000 civilian fatalities annually in the U.S. There is an urgent need for a safe, potent, and reliable fire retardant (FR) system that can be used in commodity polymers to reduce their flammability and protect lives and properties. The goal of this project is to develop a novel, safe and biobased FR system using agricultural and woody biomass. The project is divided into three major tasks. The first is to manufacture zinc oxide (ZnO) coated cellulose nanoparticles and evaluate their morphological, chemical, structural and thermal characteristics. The second task will be to design and manufacture polymer composites containing nano sized zinc oxide and cellulose crystals. Finally the third task will be to test the fire retardancy and mechanical properties of the composites. Wbelieve that presence of zinc oxide and cellulose nanocrystals in polymers will limit the oxygen supply by charring, shielding the surface and cellulose nanocrystals will make composites strong. The outcome of this project will help in developing a safe, reliable and biobased fire retardant for consumer goods, automotive, building products and will help in saving human lives and property damage due to fire.

One day, I hope to hear about Canadian research into applications for nanocellulose materials. (fingers crossed for good luck)

Cryopreserving and reviving fish embryos

Cryopreservation and the promise of animal revivification is not one of my favourite topics, from a July 13, 2017 news item on Nanowerk (Note: A link has been removed),

Scientists report for the first time the ability to both deep freeze and reanimate zebrafish embryos. The method, appearing in the journal ACS Nano (“Gold Nanorod Induced Warming of Embryos from the Cryogenic State Enhances Viability”), could potentially be used to bank larger aquatic and other vertebrate oocytes and embryos, too, for a life in the future.

It seems the science is more advanced than I’d realized. A July 13, 2017 American Chemical Society news release on EurekAlert, which originated the news item, describes cryopreservation and the technique the scientists used,

Cryopreservation has been used to save sperm, oocytes and even embryos of many species, including humans, cattle and lab animals. Preserving the embryos of most fishes, however, has remained an elusive goal. The embryos are relatively large with big yolks and are divided by multiple compartments. These traits make the embryos difficult to cool and warm uniformly without damage and ice formation. A few techniques, including microinjection of cryoprotectants and laser irradiation for re-warming, have shown promise toward achieving this long-sought goal. John Bischof and colleagues wanted to tweak the methods to see if they could finally make cryopreserving fish a reality.

The researchers injected a cryoprotectant, along with plasmonic gold nanoparticles to serve as a laser absorber, directly into zebrafish embryos. Plunging the embryos in liquid nitrogen rapidly cooled them to a cryogenically stable state in less than a second, according to modeling results. The researchers then used laser irradiation to heat up the nanoparticles, which were uniformly distributed inside the embryos, at an ultra-fast rate (1.4 x 107 degrees Celsius per minute). Not all of the embryos made it, but many were revived –a feat that is currently not possible by other techniques. Their hearts, eyes and nervous systems developed through at least the next 28 hours — and they started to wiggle. As more fish populations shrink and become threatened, the researchers say the cryopreservation method could help establish banks of frozen fish germ cells and embryos that could one day help replenish the oceans’ biodiversity. The technique could also be applied to amphibian, reptile and bird species with similar embryonic sizes and structures.

Here’s a video describing the work,

After watching that a video, I feel that I should revise my opinion of cryopreservation,

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

Gold Nanorod Induced Warming of Embryos from the Cryogenic State Enhances Viability by Kanav Khosla, Yiru Wang, Mary Hagedorn, Zhenpeng Qin, and John Bischof. ACS Nano, Article ASAP DOI: 10.1021/acsnano.7b02216 Publication Date (Web): July 13, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

DISCmini: world’s smallest handheld nanoparticle counter

DISCmini: a handheld diffusion size classifier for nanoparticle measurement Courtesy: Testo

They’/re claiming this is the world’s smallest in a July 12, 2017 news item on Nanowerk,

Testo, Inc., the world’s leading manufacturer of test and measurement instruments, announces the DiSCmini, the smallest handheld instrument for the measurement of nanoparticle. DiSCmini measures: particle number, average particle diameter and lung-deposited surface area (LDSA) with time resolution and logging at 1 second (1 Hz).

Testo’s DISCmini product page offers a video and more details,

Negative health effects due to nanoparticles appear to correlate particularly well with number concentration or surface. Epidemiological and toxicological studies are still mainly based on total mass, or they use fuzzy proxies like “distance from a busy road” to describe personal exposure, although the health-related effects of particle number concentration are well known. We believe that this contradictory situation is due to the lack of adequate sensors on the market.

This gap is now closed with Testo Particle´s handheld version of the “Diffusion Size Classifier”, testo DiSCmini.  The testo DiSCmini is a portable sensor for the measurement of particle number and average diameter with a time resolution of up to 1 second (1 Hz). The simultaneous capture of number concentration and particle size allows the specification of other characteristic parameters, such as the particles surface (Lung Deposited Surface Area, LDSA). The instrument is battery powered with a lifetime of up to 8 hours; data can be recorded on a memory card, and transferred to a external computer via USB cable.

The testo DiSCmini is particularly efficient for personal exposure monitoring in particle-loaded work space with toxic air contaminants such as diesel soot, welding fumes, or industrial nanomaterials.

The testo DiSCmini is based on the electrical charging of the aerosols. Positive air ions generated in a corona discharge are mixed with the aerosol. The charged particles are then detected in two stages by electrometers. The first detector stage is a pile of steel grids; small particles will preferably deposit on it by diffusion. The second stage is a high-efficiency particle filter which captures all the other particles. The mean particle size can be obtained by analysis of the two currents measured on the stages. The particle count is determined with the total current. The testo DiSCmini detects particles ranging in size from 10 to about 700 nm, while the modal value should lie below 300 nm. The concentration range is from about 1’000 to over 1’000’000 particles per cubic centimetre. The accuracy of the measurement depends on the shape of the particle size distribution and number concentration, and is usually around 15-20% compared to a reference CPC. The unit should be serviced and calibrated once a year.

Unlike other instruments the testo DiSCmini needs neither working liquid of any kind nor radioactive sources. Therefore, it can be operated in any position and over extended periods without requiring a liquid refill. Typical applications include the determination of personal exposure in particle-loaded jobs (diesel soot, welding fumes, industrial nanomaterials) or in vulnerable groups (asthmatics, COPD patients). The development of large area survey grids of ambient air is becoming possible. The small size of  the testo DiSCmini makes the instrument particularly suitable for personal carry-on measurement campaigns. The high measurement frequency of 1 Hz allows the instrument to monitor rapid changes in the aerosol. This feature is particularly interesting to local or defined sources of particle generation. The equipment is designed for situations and applications where quick and easy access to particle number concentration and average diameter is desired.

For anyone interested in the technical specifications, there’s the DISCmini product brochure.

Canada: Happy 150th anniversary!

There’s a bit of fun in the title for Jennifer Pascoe’s June 27, 2017 University of Alberta news release, (assuming you’re familiar with the opening words for Canada’s national anthem: “O Canada!”),


At just 32 atoms and visible only through a million-dollar scanning tunneling microscope, a tiny maple leaf created by UAlberta PhD student Roshan Achal illustrates the next wave of green technology, all while showing patriotic pride.

Invisible to the naked eye, the little leaf is pulling triple duty: celebrating Canada’s 150th birthday, attempting a world record, and—with critical implications for our technology-driven information society—providing critical steps towards the next generation of smaller and faster computers.

“It’s super cool and super Canadian and demonstrates our strength and skill in this niche of nanotechnology,” said Achal. “Almost no one else in the world can do it this well.”

Unlike other ultra-small atomic creations, this maple leaf retains its structure at room temperature.

A tiny act of patriotism

At ten nanometres in width, the leaf is roughly 100 times smaller than the world’s smallest national flag—created at the University of Waterloo in September 2016—10,000 times smaller than a human hair, and 53 million times smaller than the world’s largest maple leaf.

The leaf demonstrates the technique of building structures atom by atom (via something called scanning tunneling microscopy), which is being used to create and study circuitry to make smaller computational components while simultaneously speeding them up. In this particular niche of nanotechnology, Canada rates high on the international stage, with the University of Alberta leading the way.

“It’s hard to imagine, because it’s so small, but picture a surface almost like bubble wrap,” explained Achal of the silicon crystal wafer on which the leaf is patterned. “The bubbles are actually hydrogen atoms bonded to the surface, and we are able to pop those bubbles to create patterns.”

Nano pioneers

Achal is working on perfecting that patterning process to make atomic structures which will help revolutionize the next generation of computing by consuming less power. He’s using an ultra-sharp tool, a tip just one atom in width, which was perfected by his supervisor, UAlberta physics professor Robert Wolkow, whom Achal calls a “visionary.”

A pioneer in scanning tunneling microscopy technology, Wolkow already has a Guinness World Record for the nano-tip, the world’s sharpest man-made object, which provides unparalleled precision for patterning electronic circuits.

Achal explained the team wanted to do something to demonstrate their technological capabilities, but also something fun and meaningful to mark the occasion of Canada 150.

While they wait to hear back from Guinness World Records with an official nod to their small sculpture, the scientists continue to perfect their technique, with significant implications for next generation computing. This capability is now being put to commercial use by local spin-off Quantum Silicon Incorporated to make revolutionary ultra-fast and efficient silicon electronic devices.

It’s nice to see the enthusiasm although calling Wolkow ‘a visionary’ seems a little over the top especially with all of the other exuberance (super Canadian?). In any event, there are very few visionaries, maybe Wolkow could have been described as amazing, groundbreaking, and/or extraordinary?

Getting back to the point: Happy 150th Canada Day July 1, 2017!

h/t June 27, 2017 news item on Nanowerk.