Tag Archives: Min Liu

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. …

Split some water molecules and save solar and wind (energy) for a future day

Professor Ted Sargent’s research team at the University of Toronto has a developed a new technique for saving the energy harvested by sun and wind farms according to a March 28, 2016 news item on Nanotechnology Now,

We can’t control when the wind blows and when the sun shines, so finding efficient ways to store energy from alternative sources remains an urgent research problem. Now, a group of researchers led by Professor Ted Sargent at the University of Toronto’s Faculty of Applied Science & Engineering may have a solution inspired by nature.

The team has designed the most efficient catalyst for storing energy in chemical form, by splitting water into hydrogen and oxygen, just like plants do during photosynthesis. Oxygen is released harmlessly into the atmosphere, and hydrogen, as H2, can be converted back into energy using hydrogen fuel cells.

Discovering a better way of storing energy from solar and wind farms is “one of the grand challenges in this field,” Ted Sargent says (photo above by Megan Rosenbloom via flickr) Courtesy: University of Toronto

Discovering a better way of storing energy from solar and wind farms is “one of the grand challenges in this field,” Ted Sargent says (photo above by Megan Rosenbloom via flickr) Courtesy: University of Toronto

A March 24, 2016 University of Toronto news release by Marit Mitchell, which originated the news item, expands on the theme,

“Today on a solar farm or a wind farm, storage is typically provided with batteries. But batteries are expensive, and can typically only store a fixed amount of energy,” says Sargent. “That’s why discovering a more efficient and highly scalable means of storing energy generated by renewables is one of the grand challenges in this field.”

You may have seen the popular high-school science demonstration where the teacher splits water into its component elements, hydrogen and oxygen, by running electricity through it. Today this requires so much electrical input that it’s impractical to store energy this way — too great proportion of the energy generated is lost in the process of storing it.

This new catalyst facilitates the oxygen-evolution portion of the chemical reaction, making the conversion from H2O into O2 and H2 more energy-efficient than ever before. The intrinsic efficiency of the new catalyst material is over three times more efficient than the best state-of-the-art catalyst.

Details are offered in the news release,

The new catalyst is made of abundant and low-cost metals tungsten, iron and cobalt, which are much less expensive than state-of-the-art catalysts based on precious metals. It showed no signs of degradation over more than 500 hours of continuous activity, unlike other efficient but short-lived catalysts. …

“With the aid of theoretical predictions, we became convinced that including tungsten could lead to a better oxygen-evolving catalyst. Unfortunately, prior work did not show how to mix tungsten homogeneously with the active metals such as iron and cobalt,” says one of the study’s lead authors, Dr. Bo Zhang … .

“We invented a new way to distribute the catalyst homogenously in a gel, and as a result built a device that works incredibly efficiently and robustly.”

This research united engineers, chemists, materials scientists, mathematicians, physicists, and computer scientists across three countries. A chief partner in this joint theoretical-experimental studies was a leading team of theorists at Stanford University and SLAC National Accelerator Laboratory under the leadership of Dr. Aleksandra Vojvodic. The international collaboration included researchers at East China University of Science & Technology, Tianjin University, Brookhaven National Laboratory, Canadian Light Source and the Beijing Synchrotron Radiation Facility.

“The team developed a new materials synthesis strategy to mix multiple metals homogeneously — thereby overcoming the propensity of multi-metal mixtures to separate into distinct phases,” said Jeffrey C. Grossman, the Morton and Claire Goulder and Family Professor in Environmental Systems at Massachusetts Institute of Technology. “This work impressively highlights the power of tightly coupled computational materials science with advanced experimental techniques, and sets a high bar for such a combined approach. It opens new avenues to speed progress in efficient materials for energy conversion and storage.”

“This work demonstrates the utility of using theory to guide the development of improved water-oxidation catalysts for further advances in the field of solar fuels,” said Gary Brudvig, a professor in the Department of Chemistry at Yale University and director of the Yale Energy Sciences Institute.

“The intensive research by the Sargent group in the University of Toronto led to the discovery of oxy-hydroxide materials that exhibit electrochemically induced oxygen evolution at the lowest overpotential and show no degradation,” said University Professor Gabor A. Somorjai of the University of California, Berkeley, a leader in this field. “The authors should be complimented on the combined experimental and theoretical studies that led to this very important finding.”

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

Homogeneously dispersed, multimetal oxygen-evolving catalysts by Bo Zhang, Xueli Zheng, Oleksandr Voznyy, Riccardo Comin, Michal Bajdich, Max García-Melchor, Lili Han, Jixian Xu, Min Liu, Lirong Zheng, F. Pelayo García de Arquer, Cao Thang Dinh, Fengjia Fan, Mingjian Yuan, Emre Yassitepe, Ning Chen, Tom Regier, Pengfei Liu, Yuhang Li, Phil De Luna, Alyf Janmohamed, Huolin L. Xin, Huagui Yang, Aleksandra Vojvodic, Edward H. Sargent. Science  24 Mar 2016: DOI: 10.1126/science.aaf1525

This paper is behind a paywall.