Category Archives: environment

Carbon capture with nanoporous material in the oilfields

Researchers at Rice University (Texas) have devised a new technique for carbon capture according to a June 3, 2014 news item on Nanowerk,

Rice University scientists have created an Earth-friendly way to separate carbon dioxide from natural gas at wellheads.

A porous material invented by the Rice lab of chemist James Tour sequesters carbon dioxide, a greenhouse gas, at ambient temperature with pressure provided by the wellhead and lets it go once the pressure is released. The material shows promise to replace more costly and energy-intensive processes.

A June 3, 2014 Rice University news release, which originated the news item, provides a general description of how carbon dioxide is currently removed during fossil fuel production and adds a few more details about the new technology,

Natural gas is the cleanest fossil fuel. Development of cost-effective means to separate carbon dioxide during the production process will improve this advantage over other fossil fuels and enable the economic production of gas resources with higher carbon dioxide content that would be too costly to recover using current carbon capture technologies, Tour said. Traditionally, carbon dioxide has been removed from natural gas to meet pipelines’ specifications.

The Tour lab, with assistance from the National Institute of Standards and Technology (NIST), produced the patented material that pulls only carbon dioxide molecules from flowing natural gas and polymerizes them while under pressure naturally provided by the well.

When the pressure is released, the carbon dioxide spontaneously depolymerizes and frees the sorbent material to collect more.

All of this works in ambient temperatures, unlike current high-temperature capture technologies that use up a significant portion of the energy being produced.

The news release mentions current political/legislative actions in the US and the implications for the oil and gas industry while further describing the advantages of this new technique,

“If the oil and gas industry does not respond to concerns about carbon dioxide and other emissions, it could well face new regulations,” Tour said, noting the White House issued its latest National Climate Assessment last month [May 2014] and, this week [June 2, 2014], set new rules to cut carbon pollution from the nation’s power plants.

“Our technique allows one to specifically remove carbon dioxide at the source. It doesn’t have to be transported to a collection station to do the separation,” he said. “This will be especially effective offshore, where the footprint of traditional methods that involve scrubbing towers or membranes are too cumbersome.

“This will enable companies to pump carbon dioxide directly back downhole, where it’s been for millions of years, or use it for enhanced oil recovery to further the release of oil and natural gas. Or they can package and sell it for other industrial applications,” he said.

This is an epic (Note to writer: well done) news release as only now is there a technical explanation,

The Rice material, a nanoporous solid of carbon with nitrogen or sulfur, is inexpensive and simple to produce compared with the liquid amine-based scrubbers used now, Tour said. “Amines are corrosive and hard on equipment,” he said. “They do capture carbon dioxide, but they need to be heated to about 140 degrees Celsius to release it for permanent storage. That’s a terrible waste of energy.”

Rice graduate student Chih-Chau Hwang, lead author of the paper, first tried to combine amines with porous carbon. “But I still needed to heat it to break the covalent bonds between the amine and carbon dioxide molecules,” he said. Hwang also considered metal oxide frameworks that trap carbon dioxide molecules, but they had the unfortunate side effect of capturing the desired methane as well and they are far too expensive to make for this application.

The porous carbon powder he settled on has massive surface area and turns the neat trick of converting gaseous carbon dioxide into solid polymer chains that nestle in the pores.

“Nobody’s ever seen a mechanism like this,” Tour said. “You’ve got to have that nucleophile (the sulfur or nitrogen atoms) to start the polymerization reaction. This would never work on simple activated carbon; the key is that the polymer forms and provides continuous selectivity for carbon dioxide.”

Methane, ethane and propane molecules that make up natural gas may try to stick to the carbon, but the growing polymer chains simply push them off, he said.

The researchers treated their carbon source with potassium hydroxide at 600 degrees Celsius to produce the powders with either sulfur or nitrogen atoms evenly distributed through the resulting porous material. The sulfur-infused powder performed best, absorbing 82 percent of its weight in carbon dioxide. The nitrogen-infused powder was nearly as good and improved with further processing.

Tour said the material did not degrade over many cycles, “and my guess is we won’t see any. After heating it to 600 degrees C for the one-step synthesis from inexpensive industrial polymers, the final carbon material has a surface area of 2,500 square meters per gram, and it is enormously robust and extremely stable.”

Apache Corp., a Houston-based oil and gas exploration and production company, funded the research at Rice and licensed the technology. Tour expected it will take time and more work on manufacturing and engineering aspects to commercialize.

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

Capturing carbon dioxide as a polymer from natural gas by Chih-Chau Hwang, Josiah J. Tour, Carter Kittrell, Laura Espinal, Lawrence B. Alemany, & James M. Tour. Nature Communications 5, Article number: 3961 doi:10.1038/ncomms4961 Published 03 June 2014

This paper is behind a paywall.

The researchers have made an illustration of the material available,

 Illustration by Tanyia Johnson/Rice University

Illustration by Tanyia Johnson/Rice University

This morning, Azonano posted a June 6, 2014 news item about a patent for carbon capture,

CO2 Solutions Inc. ( the “Corporation”), an innovator in the field of enzyme-enabled carbon capture technology, today announced it has received a Notice of Allowance from the U.S. Patent and Trademark Office for its patent application No. 13/264,294 entitled Process for CO2 Capture Using Micro-Particles Comprising Biocatalysts.

One might almost think these announcements were timed to coincide with the US White House’s moves.

As for CO2 Solutions, this company is located in Québec, Canada.  You can find out more about the company here (you may want to click on the English language button).

“I write in praise of air,” a catalytic poem absorbing air pollutants on a nanotechnology-enabled billboard

The poem ‘In Praise of Air’, which is on a billboard at the University of Sheffield (UK), is quite literally catalytic. From a May 15, 2014 news item on Nanowerk,

Simon [Armitage], Professor of Poetry at the University, and Pro-Vice-Chancellor for Science Professor Tony Ryan, have collaborated to create a catalytic poem called In Praise of Air – printed on material containing a formula invented at the University which is capable of purifying its surroundings.

Here’s what the billboard looks like,

Courtesy of the University of Sheffield

Courtesy of the University of Sheffield

A May 14, 2014 University of Sheffield news release, which originated the news item, has more details about the project from the scientist’s perspective,

This cheap technology could also be applied to billboards and advertisements alongside congested roads to cut pollution.

Professor Ryan, who came up with the idea of using treated materials to cleanse the air, said: “This is a fun collaboration between science and the arts to highlight a very serious issue of poor air quality in our towns and cities.

“The science behind this is an additive which delivers a real environmental benefit that could actually help cut disease and save lives.

“This poem alone will eradicate the nitrogen oxide pollution created by about 20 cars every day.”

He added: “If every banner, flag or advertising poster in the country did this, we’d have much better air quality. It would add less than £100 to the cost of a poster and would turn advertisements into catalysts in more ways than one. The countless thousands of poster sites that are selling us cars beside our roads could be cleaning up emissions at the same time.”

The 10m x 20m piece of material which the poem is printed on is coated with microscopic pollution-eating particles of titanium dioxide which use sunlight and oxygen to react with nitrogen oxide pollutants and purify the air.

Professor Ryan has been campaigning for some time to have his ingredient added to washing detergent in the UK as part of his Catalytic Clothing project. If manufacturers added it, the UK would meet one of its air quality targets in one step.

The news release also describes the arts component and poet’s perspective on this project,

The poem will be on display on the side of the University’s Alfred Denny Building, Western Bank, for one year and its unveiling also marks the launch of this year’s Sheffield Lyric Festival which takes place between 14-17 May 2014 at the University’s Firth Hall.

At a special celebratory event on Thursday (May 15 2014), Simon will read In Praise of Air for the first time in public and Professor Ryan will explain the technology behind the catalytic poem. Volunteers will be wearing catalytic T-shirts.

Dr Joanna Gavins, from the University’s School of English, project manager for the catalytic poem collaboration, who also leads the Lyric Festival, said: “This highlights the innovation and creativity at the heart of the University and its research excellence.

“We are delighted that such a significant event will help launch this year’s Lyric Festival which also features poetry readings by students of the MA in Creative Writing, alongside internationally renowned writers such as Sinead Morrissey and Benjamin Zephaniah, and music from celebrated Sheffield songwriter, Nat Johnson.”

Simon added: “There’s a legacy of poems in public places in Sheffield and, on behalf of the University, I wanted to be part of that dialogue to show what we could do.

“I wanted to write a poem that was approachable, that might catch the attention of the passer-by and the wandering mind, and one that had some local relevance too. But I also hope it’s robust and intricate enough to sustain deeper enquiries – the School of English looks towards it for one thing, and I’d like to think it’s capable of getting the thumbs up or at least a nod from their direction, and from the big-brained students walking up and down Western Bank, and from discerning residents in the neighbourhood.”

He added: “I’ve enjoyed working with the scientists and the science, trying to weave the message into the words, wanting to collaborate both conceptually and with the physical manifestation of the work.

“Poetry often comes out with the intimate and the personal, so it’s strange to think of a piece in such an exposed place, written so large and so bold. I hope the spelling is right!

For the curious, here’s a link to the In Praise of Air project website where you’ll find the poem and much more,

I write in praise of air.  I was six or five
when a conjurer opened my knotted fist
and I held in my palm the whole of the sky.
I’ve carried it with me ever since.

Let air be a major god, its being
and touch, its breast-milk always tilted
to the lips.  Both dragonfly and Boeing
dangle in its see-through nothingness…

Among the jumbled bric-a-brac I keep
a padlocked treasure-chest of empty space,
and on days when thoughts are fuddled with smog
or civilization crosses the street

with a white handkerchief over its mouth
and cars blow kisses to our lips from theirs
I turn the key, throw back the lid, breathe deep.
My first word, everyone’s  first word, was air.

I like this poem a lot and find it quite inspirational for one of my own projects.

Getting back to Tony Ryan, he and his Catalytic Clothing project have been mentioned here in a Feb. 24, 2012 posting (Catalytic Clothing debuts its kilts at Edinburgh International Science Festival) and in a July 8, 2011 posting featuring a collaboration between Ryan and Professor Helen Storey at the London College of Fashion (Nanotechnology-enabled Catalytic Clothes look good and clean the air). The 2012 posting has an image of two kilted gentlemen and the 2011 posting has a video highlighting one of the dresses, some music from Radiohead, and the ideas behind the project.

You can find out more about Catalytic Clothing and the Lyric Festival (from the news release),

Catalytic Clothing

To find out more about the catalytic clothing project visit http://www.catalytic-clothing.org

Lyric Festival

The Lyric Festival is the [University of Sheffield] Faculty of Arts and Humanities’ annual celebration of the written and spoken word. Each May the festival brings some of the UK’s most renowned and respected writers, broadcasters, academics, and performers to the University, as well as showcasing the talent of Faculty students and staff. For more information visit http://www.sheffield.ac.uk/lyric

One last note about the University of Sheffield, it’s the academic home for Professor Richard Jones who wrote one of my favourite books about nanotechnology, Soft Machines (featured in my earliest pieces here, a May 6, 2008 posting). He is the Pro-Vice-Chancellor – Research & Innovation at the university and a blogger on his Soft Machines blog where he writes about innovation and research in the UK and where you’ll also find a link to purchase his book.

ETA May 20, 2014: A May 19, 2014 article by JW Dowey for Earth Times offers more details about the technology,

Titanium dioxide coating on cars and aircraft have revolutionised protective nanotechnology. The University of Sheffield has set the target as absorbing the poisonous compounds from vehicle exhausts. Tony Ryan is the professor of physical chemistry in charge of adapting self-cleaning window technology to pollution solutions. The 10m x20m poster they now use on the Alfred Denny university building demonstrates how nitrogen oxides from 20 cars per day could be absorbed efficiently by roadside absorption.

There are more tidbits to be had in the article including the extra cost (£100) of adding the protective coating to the ‘poetic’ billboard (or hoarding as they say in the UK).

Dreaming of the perfect face mask?

Researchers at Hong Kong Polytechnic University have something for anyone who has ever dreamed of getting a face mask that offers protection from the finest of pollutant particles, according to a May 13, 2014 news item on phys.org,

Researchers at the Hong Kong Polytechnic University have developed a ground-breaking filter technology that guards against the finest pollutants in the air

Haze is usually composed of pollutants in the form of tiny suspended particles or fine mists/droplets emitted from vehicles, coal-burning power plants and factories. Continued exposure increases the risk of developing respiratory problems, heart diseases and lung cancer. Can we avoid the unhealthy air?

A simple face mask that can block out suspended particles has been developed by scientists from the Department of Mechanical Engineering at the Hong Kong Polytechnic University (PolyU). The project is led by Professor Wallace Woon-Fong Leung, a renowned filtration expert, who has spent his career understanding these invisible killers.

An article for Hong Kong Polytechnic University’s April 2014 issue of Technology Frontiers, which originated the news item, describes the research problem and Professor Leung’s proposed face mask in more detail,

In Hong Kong, suspended particles PM 10 and PM 2.5 are being monitored.  PM 10 refers to particles that are 10 microns (or micrometres) in size or smaller, whereas PM 2.5 measures 2.5 microns or smaller.  At the forefront of combating air pollution, Professor Leung targets ultra-fine pollutants that have yet been picked up by air quality monitors – particles measuring 1 micron or below, which he perceived to be a more important threat to human health.

“In my view, nano-aerosols (colloid of fine solid particles or liquid droplets of sub-micron to nano-sizes), such as diesel emissions, are the most lethal for three reasons.  First, they are in their abundance by number suspended in the air.  Second, they are too small to be filtered out using current technologies.  Third, they can pass easily through our lungs and work their way into our respiratory systems, and subsequently our vascular, nervous and lymphatic systems, doing the worst kind of harm.”

However, it would be difficult to breathe through the mask if it were required to block out nano-aerosols.  To make an effective filter that is highly breathable, a new filter that provides high filtration efficiency yet low air resistance (or low pressure drop) is required.

According to Professor Leung, pollutant particles get into our body in two ways – by the airflow carrying them and by the diffusion motion of these tiny particles.  As the particles are intercepted by the fibres of the mask, they are filtered out before reaching our lungs.

Fibres from natural or synthetic materials can be made into nanofibres around 1/500 of the diameter of a hair (about 0.1 mm) through nanotechnologies.  While nanofibres increase the surface area for nano-aerosol interception, they also incur larger air resistance.  Professor Leung’s new innovation aims to divide optimal amount of nanofibres into multiple layers separated by a permeable space, allowing plenty of room for air to pass through.

A conventional face mask can only block out about 25% of 0.3-micron nano-aerosols under standard test conditions.  Professor Leung said, “The multi-layer nanofibre mask can block out at least 80% of suspended nano-aerosols, even the ones smaller than 0.3 micron.  In the meantime, the wearer can breathe as comfortably as wearing a conventional face mask, making it superb for any outdoor occasions. Another option is to provide a nanofiber mask that has the same capture efficiency as conventional face mask, yet it is at least several times more breathable, which would be suitable for the working group.”

The new filtration technology has been well recognized.  Recently, Professor Leung and his team have won a Gold Medal and a Special Merit Award from the Romania Ministry of National Education at the 42nd International Exhibition of Inventions of Geneva held in Switzerland.

If the breakthrough is turned into tightly-fit surgical masks, they are just as effective against bacteria and viruses whose sizes are under 1 micron.  “In the future, medical professionals at the frontline can have stronger protection against deadly bacteria and viruses,” added Professor Leung.

I did not find any published research about this proposed face mask but there is a 2009 patent for a Multilayer nanofiber filter (US 8523971 B2), which lists the inventors as: Wallace Woon-Fong Leung and Chi Ho Hung and the original assignee as: The Hong Kong Polytechnic University.  The description of the materials in the patent closely resembles the description of the face mask materials.

Cleaner greener diesel by way of bi-functional nanoparticles

It’s always good to hear about cleaner greener diesel as per this May 13, 2014 news item on Azonano,

Ames Laboratory [US Dept. of Energy] scientists have developed a nanoparticle that is able to perform two processing functions at once for the production of green diesel, an alternative fuel created from the hydrogenation of oils from renewable feedstocks like algae.

The method is a departure from the established process of producing biodiesel, which is accomplished by reacting fats and oils with alcohols.

A May ??, 2014 Ames Laboratory news release,which originated the news item, describes the specifics of the problem the scientists are trying to solve,

“Conventionally, when you are producing biodiesel from a feedstock that is rich in free fatty acids like microalgae oil, you must first separate the fatty acids that can ruin the effectiveness of the catalyst, and then you can perform the catalytic reactions that produce the fuel,” said Ames Lab scientist Igor Slowing. “By designing multifunctional nanoparticles and focusing on green diesel rather than biodiesel, we can combine multiple processes into one that is faster and cleaner.” Contrary to biodiesel, green diesel is produced by hydrogenation of fats and oils, and its chemical composition is very similar to that of petroleum-based diesel. Green diesel has many advantages over biodiesel, like being more stable and having a higher energy density.

One of the research groups at Ames Laboratory stumbled across an exciting property while working with bi-functional nanoparticles (from the news release),

An Ames Lab research group, which included Slowing, Kapil Kandel, Conerd Frederickson, Erica A. Smith, and Young-Jin Lee, first saw success using bi-functionalized mesostructured nanoparticles. These ordered porous particles contain amine groups that capture free fatty acids and nickel nanoparticles that catalyze the conversion of the acids into green diesel. Nickel has been researched widely in the scientific community because it is approximately 2000 times less expensive as an alternative to noble metals traditionally used in fatty acid hydrogenation, like platinum or palladium.

Creating a bi-functional nanoparticle also improved the resulting green diesel. Using nickel for the fuel conversion alone, the process resulted in too strong of a reaction, with hydrocarbon chains that had broken down. The process, called “cracking,” created a product that held less potential as a fuel.

“A very interesting thing happened when we added the component responsible for the sequestration of the fatty acids,” said Slowing. “We no longer saw the cracking of molecules. So the result is a better catalyst that produces a hydrocarbon that looks much more like diesel. “

“It also leaves the other components of the oil behind, valuable molecules that have potential uses for the pharmaceutical and food industries,” said Slowing.

But Slowing, along with Kapil Kandel, James W. Anderegg, Nicholas C. Nelson, and Umesh Chaudhary, took the process further by using iron as the catalyst. Iron is 100 times cheaper than nickel. Using iron improved the end product even further, giving a faster conversion and also reducing the loss of CO2  in the process.

“As part of the mission of the DOE, [US Dept. of Energy] we are focused on researching the fundamental science necessary to create the process; but the resulting technology should in principle be scalable for industry,” he said.

Here”s a link to and a citation for the published research paper,

Supported iron nanoparticles for the hydrodeoxygenation of microalgal oil to green diesel by Kapil Kandel, James W. Anderegg, Nicholas C. Nelson, Umesh Chaudhary, Igor I. Slowing. Journal of Catalysis Volume 314, May 2014, Pages 142–148 http://dx.doi.org/10.1016/j.jcat.2014.04.009

This paper is behind a paywall.

There is a patent pending on this technology (from the news release),

A patent application has been filed for this technology; it is available for licensing from the Iowa State University Research Foundation. Further information can be obtained at [email protected].

Patent or not, it would be nice to see at least one of these technologies successfully commercialized.

Nickel-eating plant in the Philippines

For anyone interested in phytoremediation and/or phytomining, this news from the Philippines is quite exciting (from a May 9, 2014 news release on EurekAlert, Note: A link has been removed, (also on ScienceDaily),

Scientists from the University of the Philippines, Los Baños (UPLB) have discovered a new plant species with an unusual lifestyle — it eats nickel for a living — accumulating up to 18,000 ppm of the metal in its leaves without itself being poisoned, says Professor Edwino Fernando, lead author of the report. Such an amount is a hundred to a thousand times higher than in most other plants. The study was published in the open access journal PhytoKeys.

The new species is called Rinorea niccolifera, reflecting its ability to absorb nickel in very high amounts. Nickel hyperaccumulation is such a rare phenomenon with only about 0.5–1% of plant species native to nickel-rich soils having been recorded to exhibit the ability. Throughout the world, only about 450 species are known with this unusual trait, which is still a small proportion of the estimated 300,000 species of vascular plants.

A May 9, 2014 Penfold Publishers news release, which originated the items elsewhere, provides more details and an image of the nickel-eating plant,

The new species, according to Dr Marilyn Quimado, one of the lead scientists of the research team, was discovered on the western part of Luzon Island in the Philippines, an area known for soils rich in heavy metals.

“Hyperacccumulator plants have great potentials for the development of green technologies, for example, ‘phytoremediation’ and ‘phytomining'”, explains Dr Augustine Doronila of the School of Chemistry, University of Melbourne, who is also co-author of the report.

Phytoremediation refers to the use of hyperacccumulator plants to remove heavy metals in contaminated soils. Phytomining, on the other hand, is the use of hyperacccumulator plants to grow and harvest in order to recover commercially valuable metals in plant shoots from metal-rich sites. [emphasis mine]

In a previous piece about phytomining and in contrast to this news release, I suggested that phytoremediation could also function as phytomining (an idea I found elsewhere), my March 5, 2013 posting. There are also a November 22, 2012 posting and a Sept. 26, 2012 posting on the topic of phyto-mining (anyone keen to read everything here on this topic, may want to search the term both with and without hyphens).

Here is the nickel-eating plant,

Caption: This photo shows the newly described metal-eating plant, Rinorea niccolifera. Credit: Dr. Edwino S. Fernando Usage Restrictions: CC-BY 4.0

Caption: This photo shows the newly described metal-eating plant, Rinorea niccolifera.
Credit: Dr. Edwino S. Fernando
Usage Restrictions: CC-BY 4.0

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

Rinorea niccolifera (Violaceae), a new, nickel-hyperaccumulating species from Luzon Island, Philippines by Edwino Fernando, Marilyn Quimado, and Augustine Doronila. PhytoKeys 37: 1–13. doi: 10.3897/phytokeys.37.7136

This paper is open access.

In a burst of curiosity I checked out the University of Philippines website and found some research bearing similarity to today’s (May 9, 2014) piece although in this case the metal being discussed is gold and the researchers are investigating the possibility of using bacteria to produce gold nanoparticles. From an April 16, 2014 article written by Miguel Victor T. Durian for the university’s Horizon magazine,

A pioneering nanotechnology study conducted by scientists at the UPLB National Institute of Molecular Biology and Biotechnology (BIOTECH) is exploring the potentials of plantgrowth- promoting bacteria (PGPB) in the biosynthesis of nanogold.

Dr. Lilia M. Fernando, Dr. Florinia E. Merca, and Dr. Erlinda S. Paterno are looking at how nanogold could be produced in large quantities using PGPB as this could bring down medical diagnostic and treatment costs especially against a dreaded disease – cancer.

“Our study primarily aimed to find a less expensive source of gold through the biosynthesis of the element by microorganisms.” Dr. Fernando explained. “Gold costs around 200 to 300 US dollars (or about Php9,000 to Php14,000), …,” Ms. Fernando added.

Furthermore, PGPB is abundantly available in the soils of the Philippines. In fact, the researchers carried out their collection of PGPB in Tarlac and Bohol. Moreover, cultivation of PGPB does not require any special incubation procedures in order to maintain its nano-size because it can survive at room temperature. This makes the cultivation of PGPB easier and less expensive compared to other microorganisms.

I look forward to hearing more about these projects as they develop.

Mopping up that oil spill with a nanocellulose sponge and a segue into Canadian oil and politics

Empa (Swiss Federal Laboratories for Materials Science and Technology or ,in German, Eidgenössische Materialprüfungs- und Forschungsanstalt) has announced the development of a nanocellulose sponge useful for cleaning up oil spills in a May 5, 2014 news item on Nanowerk (Note: A link has been removed),

A new, absorbable material from Empa wood research could be of assistance in future oil spill accidents: a chemically modified nanocellulose sponge. The light material absorbs the oil spill, remains floating on the surface and can then be recovered. The absorbent can be produced in an environmentally-friendly manner from recycled paper, wood or agricultural by-products (“Ultralightweight and Flexible Silylated Nanocellulose Sponges for the Selective Removal of Oil from Water”).

A May 2, 2014 Empa news release (also on EurekAlert*}, which originated the news item, includes a description of the potential for oil spills due to transport issues, Empa’s proposed clean-up technology, and a request for investment,

All industrial nations need large volumes of oil which is normally delivered by ocean-going tankers or via inland waterways to its destination. The most environmentally-friendly way of cleaning up nature after an oil spill accident is to absorb and recover the floating film of oil. The Empa researchers Tanja Zimmermann and Philippe Tingaut, in collaboration with Gilles Sèbe from the University of Bordeaux, have now succeeded in developing a highly absorbent material which separates the oil film from the water and can then be easily recovered, “silylated” nanocellulose sponge. In laboratory tests the sponges absorbed up to 50 times their own weight of mineral oil or engine oil. They kept their shape to such an extent that they could be removed with pincers from the water. The next step is to fine tune the sponges so that they can be used not only on a laboratory scale but also in real disasters. To this end, a partner from industry is currently seeked.

Here’s what the nanocellulose sponge looks like (oil was dyed red and the sponge has absorbed it from the water),

The sponge remains afloat and can be pulled out easily. The oil phase is selectively removed from the surface of water. Image: Empa

The sponge remains afloat and can be pulled out easily. The oil phase is selectively removed from the surface of water.
Image: Empa

The news release describes the substance, nanofibrillated cellulose (NFC), and its advantages,

Nanofibrillated Cellulose (NFC), the basic material for the sponges, is extracted from cellulose-containing materials like wood pulp, agricultural by products (such as straw) or waste materials (such as recycled paper) by adding water to them and pressing the aqueous pulp through several narrow nozzles at high pressure. This produces a suspension with gel-like properties containing long and interconnected cellulose nanofibres .

When the water from the gel is replaced with air by freeze-drying, a nanocellulose sponge is formed which absorbs both water and oil. This pristine material sinks in water and is thus not useful for the envisaged purpose. The Empa researchers have succeeded in modifying the chemical properties of the nanocellulose in just one process step by admixing a reactive alkoxysilane molecule in the gel before freeze-drying. The nanocellulose sponge loses its hydrophilic properties, is no longer suffused with water and only binds with oily substances.

In the laboratory the “silylated” nanocellulose sponge absorbed test substances like engine oil, silicone oil, ethanol, acetone or chloroform within seconds. Nanofibrillated cellulose sponge, therefore, reconciles several desirable properties: it is absorbent, floats reliably on water even when fully saturated and is biodegradable.

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

Ultralightweight and Flexible Silylated Nanocellulose Sponges for the Selective Removal of Oil from Water by Zheng Zhang, Gilles Sèbe, Daniel Rentsch, Tanja Zimmermann, and Philippe Tingaut. Chem. Mater., 2014, 26 (8), pp 2659–2668 DOI: 10.1021/cm5004164 Publication Date (Web): April 10, 2014

Copyright © 2014 American Chemical Society

This article is behind a paywall.

I featured ‘nanocellulose and oil spills’ research at the University Wisconsin-Madison in a Feb. 26, 2014 post titled, Cleaning up oil* spills with cellulose nanofibril aerogels (Note: I corrected a typo in my headline hence the asterisk). I also have a Dec. 31, 2013 piece about a nanotechnology-enabled oil spill recovery technology project (Naimor) searching for funds via crowdfunding. Some major oil projects being considered in Canada and the lack of research on remediation are also mentioned in the post.

Segue Alert! As for the latest on Canada and its oil export situation, there’s a rather interesting May 2, 2014 Bloomberg.com article Canada Finds China Option No Easy Answer to Keystone Snub‘ by Edward Greenspon, Andrew Mayeda, Jeremy van Loon and Rebecca Penty describing two Canadian oil projects and offering a US perspective,

It was February 2012, three months since President Barack Obama had phoned the Canadian prime minister to say the Keystone XL pipeline designed to carry vast volumes of Canadian crude to American markets would be delayed.

Now Harper [Canadian Prime Minister Stephen Harper] found himself thousands of miles from Canada on the banks of the Pearl River promoting Plan B: a pipeline from Alberta’s landlocked oil sands to the Pacific Coast where it could be shipped in tankers to a place that would certainly have it — China. It was a country to which he had never warmed yet that served his current purposes. [China's President at that time was Hu Jintao, 2002 - 2012; currently the President is Xi Jinping, 2013 - ]

The writers do a good job of describing a number of factors having an impact on one or both of the pipeline projects. However, no mention is made in the article that Harper is from the province of Alberta and represents that province’s Calgary Southwest riding. For those unfamiliar with Calgary, it is a city dominated by oil companies. I imagine Mr. Harper is under considerable pressure to resolve oil export and transport issues and I would expect they would prefer to resolve the US issues since many of those oil companies in Calgary have US headquarters.

Still, it seems simple, if the US is not interested as per the problems with the Keystone XL pipeline project, ship the oil to China via a pipeline through the province of British Columbia and onto a tanker. What the writers do not mention is yet another complicating factor, Trudeau, both Justin and, the deceased, Pierre.

As Prime Minister of Canada, Pierre Trudeau was unloved in Alberta, Harper’s home province, due to his energy policies and the formation of the National Energy Board. Harper appears, despite his denials, to have an antipathy towards Pierre Trudeau that goes beyond the political to the personal and it seems to extend beyond Pierre’s grave to his son, Justin. A March 21, 2014 article by Mark Kennedy for the National Post describes Harper’s response to Trudeau’s 2000 funeral this way,

Stephen Harper, then the 41-year-old president of the National Citizens Coalition (NCC), was a proud conservative who had spent three years as a Reform MP. He had entered politics in the mid-1980s, in part because of his disdain for how Pierre Trudeau’s “Just Society” had changed Canada.

So while others were celebrating Trudeau’s legacy, Harper hammered out a newspaper article eviscerating the former prime minister on everything from policy to personality.

Harper blasted Trudeau Sr. for creating “huge deficits, a mammoth national debt, high taxes, bloated bureaucracy, rising unemployment, record inflation, curtailed trade and declining competitiveness.”

On national unity, he wrote that Trudeau was a failure. “Only a bastardized version of his unity vision remains and his other policies have been rejected and repealed by even his own Liberal party.”

Trudeau had merely “embraced the fashionable causes of his time,” wrote Harper.

Getting personal, he took a jab at Trudeau over not joining the military during the Second World War: “He was also a member of the ‘greatest generation,’ the one that defeated the Nazis in war and resolutely stood down the Soviets in the decades that followed. In those battles however, the ones that truly defined his century, Mr. Trudeau took a pass.”

The article was published in the National Post Oct. 5, 2000 — two days after the funeral.

Kennedy’s article was occasioned by the campaign being led by Harper';s Conservative party against the  leader (as of April 2013) of the Liberal Party, Justin Trudeau.

It’s hard to believe that Harper’s hesitation over China is solely due to human rights issues especially  since Harper has not been noted for consistent interest in those issues and, more particularly, since Prime Minister Pierre Trudeau was one of the first ‘Western’ leaders to visit communist China . Interestingly, Harper has been much more enthusiastic about the US than Pierre Trudeau who while addressing the Press Club in Washington, DC in March 1969, made this observation (from the Pierre Trudeau Wikiquote entry),

Living next to you [the US] is in some ways like sleeping with an elephant. No matter how friendly and even-tempered is the beast, if I can call it that, one is affected by every twitch and grunt.

On that note, I think Canada is always going to be sleeping with an elephant; the only question is, who’s the elephant now? In any event, perhaps Harper is more comfortable with the elephant he knows and that may explain why China’s offer to negotiate a free trade agreement has been left unanswered (this too was not noted in the Bloomberg article). The offer and lack of response were mentioned by Yuen Pau Woo, President and CEO of the Asia Pacific Foundation of Canada, who spoke at length about China, Canada, and their trade relations at a Jan. 31, 2014 MP breakfast (scroll down for video highlights of the Jan. 31, 2014 breakfast) held by Member of Parliament (MP) for Vancouver-Quadra, Joyce Murray.

Geopolitical tensions and Canadian sensitivities aside, I think Canadians in British Columbia (BC), at least, had best prepare for more oil being transported and the likelihood of spills. In fact, there are already more shipments according to a May 6, 2014 article by Larry Pynn for the Vancouver Sun,

B.C. municipalities work to prevent a disastrous accident as rail transport of oil skyrockets

The number of rail cars transporting crude oil and petroleum products through B.C. jumped almost 200 per cent last year, reinforcing the resolve of municipalities to prevent a disastrous accident similar to the derailment in Lac-Mégantic in Quebec last July [2013].

Transport Canada figures provided at The Vancouver Sun’s request show just under 3,400 oil and petroleum rail-car shipments in B.C. last year, compared with about 1,200 in 2012 and 50 in 2011.

The figures come a week after The Sun revealed that train derailments jumped 20 per cent to 110 incidents last year in B.C., the highest level in five years.

Between 2011 and 2012, there was an increase of 2400% (from 50 to 1200) of oil and petroleum rail-car shipments in BC. The almost 300% increase in shipments between 2012 and 2013 seems paltry in comparison.  Given the increase in shipments and the rise in the percentage of derailments, one assumes there’s an oil spill waiting to happen. Especially so, if the Canadian government manages to come to an agreement regarding the proposed pipeline for BC and frankly, I have concerns about the other pipeline too, since either will require more rail cars, trucks, and/or tankers for transport to major centres edging us all closer to a major oil spill.

All of this brings me back to Empa, its oil-absorbing nanocellulose sponges, and the researchers’ plea for investors and funds to further their research. I hope they and all the other researchers (e.g., Naimor) searching for ways to develop and bring their clean-up ideas to market find some support.

*EurekAlert link added May 7, 2014.

ETA May 8, 2014:  Some types of crude oil are more flammable than others according to a May 7, 2014 article by Lindsay Abrams for Salon.com (Note: Links have been removed),

Why oil-by-rail is an explosive disaster waiting to happen
A recent spate of fiery train accidents all have one thing in common: highly volatile cargo from North Dakota

In case the near continuous reports of fiery, deadly oil train accidents hasn’t been enough to convince you, Earth Island Journal is out with a startling investigative piece on North Dakota’s oil boom and the dire need for regulations governing that oil’s transport by rail.

The article is pegged to the train that derailed and exploded last summer in  [Lac-Mégantic] Quebec, killing 47 people, although it just as well could have been the story of the train that derailed and exploded in Alabama last November, the train that derailed and exploded in North Dakota last December, the train that derailed and exploded in Virginia last week or — let’s face it — any future accidents that many see as an inevitability.

The Bakken oil fields in North Dakota are producing over a million barrels of crude oil a day, more than 60 percent of which is shipped by rail. All that greenhouse gas-emitting fossil fuel is bad enough; that more oil spilled in rail accidents last year than the past 35 years combined is also no small thing. But the particular chemical composition of Bakken oil lends an extra weight to these concerns: according to the Pipeline and Hazardous Materials Safety Administration, it may be more flammable and explosive than traditional crude.

While Abrams’ piece is not focused on oil cleanups, it does raise some interesting questions about crude oil transport and whether or not the oil from Alberta might also be more than usually dangerous.

Environmental impacts and graphene

Researchers at the University of California at Riverside (UCR) have published the results of what they claim is the first study featuring the environmental impact from graphene use. From the April 29, 2014 news item on ScienceDaily,

In a first-of-its-kind study of how a material some think could transform the electronics industry moves in water, researchers at the University of California, Riverside Bourns College of Engineering found graphene oxide nanoparticles are very mobile in lakes or streams and therefore may well cause negative environmental impacts if released.

Graphene oxide nanoparticles are an oxidized form of graphene, a single layer of carbon atoms prized for its strength, conductivity and flexibility. Applications for graphene include everything from cell phones and tablet computers to biomedical devices and solar panels.

The use of graphene and other carbon-based nanomaterials, such as carbon nanotubes, are growing rapidly. At the same time, recent studies have suggested graphene oxide may be toxic to humans. [emphasis mine]

As production of these nanomaterials increase, it is important for regulators, such as the Environmental Protection Agency, to understand their potential environmental impacts, said Jacob D. Lanphere, a UC Riverside graduate student who co-authored a just-published paper about graphene oxide nanoparticles transport in ground and surface water environments.

I wish they had cited the studies suggesting graphene oxide (GO) may be toxic. After a quick search I found: Internalization and cytotoxicity of graphene oxide and carboxyl graphene nanoplatelets in the human hepatocellular carcinoma cell line Hep G2 by Tobias Lammel, Paul Boisseaux, Maria-Luisa Fernández-Cruz, and José M Navas (free access paper in Particle and Fibre Toxicology 2013, 10:27 http://www.particleandfibretoxicology.com/content/10/1/27). From what I can tell, this was a highly specialized investigation conducted in a laboratory. While the results seem concerning it’s difficult to draw conclusions from this study or others that may have been conducted.

Dexter Johnson in a May 1, 2014 post on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website) provides more relevant citations and some answers (Note: Links have been removed),

While the UC Riverside  did not look at the toxicity of GO in their study, researchers at the Hersam group from Northwestern University did report in a paper published in the journal Nano Letters (“Minimizing Oxidation and Stable Nanoscale Dispersion Improves the Biocompatibility of Graphene in the Lung”) that GO was the most toxic form of graphene-based materials that were tested in mice lungs. In other research published in the Journal of Hazardous Materials (“Investigation of acute effects of graphene oxide on wastewater microbial community: A case study”), investigators determined that the toxicity of GO was dose dependent and was toxic in the range of 50 to 300 mg/L. So, below 50 mg/L there appear to be no toxic effects to GO. To give you some context, arsenic is considered toxic at 0.01 mg/L.

Dexter also contrasts graphene oxide with graphene (from his May 1, 2014 post; Note: A link has been removed),

While GO is quite different from graphene in terms of its properties (GO is an insulator while graphene is a conductor), there are many applications that are similar for both GO and graphene. This is the result of GO’s functional groups allowing for different derivatives to be made on the surface of GO, which in turn allows for additional chemical modification. Some have suggested that GO would make a great material to be deposited on additional substrates for thin conductive films where the surface could be tuned for use in optical data storage, sensors, or even biomedical applications.

Getting back to the UCR research, an April 28, 2014 UCR news release (also on EurekAlert but dated April 29, 2014) describes it  in more detail,

Walker’s [Sharon L. Walker, an associate professor and the John Babbage Chair in Environmental Engineering at UC Riverside] lab is one of only a few in the country studying the environmental impact of graphene oxide. The research that led to the Environmental Engineering Science paper focused on understanding graphene oxide nanoparticles’ stability, or how well they hold together, and movement in groundwater versus surface water.

The researchers found significant differences.

In groundwater, which typically has a higher degree of hardness and a lower concentration of natural organic matter, the graphene oxide nanoparticles tended to become less stable and eventually settle out or be removed in subsurface environments.

In surface waters, where there is more organic material and less hardness, the nanoparticles remained stable and moved farther, especially in the subsurface layers of the water bodies.

The researchers also found that graphene oxide nanoparticles, despite being nearly flat, as opposed to spherical, like many other engineered nanoparticles, follow the same theories of stability and transport.

I don’t know what conclusions to draw from the information that the graphene nanoparticles remain stable and moved further in the water. Is a potential buildup of graphene nanoparticles considered a problem because it could end up in our water supply and we would be poisoned by these particles? Dexter provides an answer (from his May 1, 2014 post),

Ultimately, the question of danger of any material or chemical comes down to the simple equation: Hazard x Exposure=Risk. To determine what the real risk is of GO reaching concentrations equal to those that have been found to be toxic (50-300 mg/L) is the key question.

The results of this latest study don’t really answer that question, but only offer a tool by which to measure the level of exposure to groundwater if there was a sudden spill of GO at a manufacturing facility.

While I was focused on ingestion by humans, it seems this research was more focused on the natural environment and possible future poisoning by graphene oxide.

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

Stability and Transport of Graphene Oxide Nanoparticles in Groundwater and Surface Water by Jacob D. Lanphere, Brandon Rogers, Corey Luth, Carl H. Bolster, and Sharon L. Walker. Environmental Engineering Science. -Not available-, ahead of print. doi:10.1089/ees.2013.0392.

Online Ahead of Print: March 17, 2014

If available online, this is behind a paywall.

Monitoring air pollution at home, at work, and in the car—the nano way

Meagan Clark, in an April 18, 2014  article for International Business Times, writes about a project in the EU (European Union) where researchers are working to develop nanotechnology-enabled sensors for air quality at home, at work, and in the car,

Poor indoor and outdoor air quality is linked to one in eight deaths worldwide or 7 million, making it the world’s most dangerous environmental health risk, according to a March [2014?] report by the World Health Organization.

That is the reasoning behind the European Union’s decision to fund a new nanotechnology project [IAQSENSE] that would allow people to gauge air quality real-time at home, work and in cars with low cost, mini sensor systems, the EU’s community research and development information service announced Friday [April 18, 2014].

“The control of indoor air quality and the related comfort it provides should have a huge societal impact on health, presence at work and economic-related factors,” Claude Iroulart, coordinator of IAQSENSE, said in a statement. …

The IAQSENSE homepage provides more details about itself,

The indoor air quality (IAQ) influences the health and well-being of people. For the last 20 years, there has been a growing concern regarding pollutants in closed environments and the difficulty in identifying these pollutants and their critical levels, without heavy, expensive equipment.

IAQSense aims to develop new nanotechnology based sensor systems that will precisely monitor the composition of the air in terms of both chemical and bio contaminants. This system will be miniaturized, low cost and adapted to mass production.

A major challenge consists of a gaz [sic] sensor system which must be at the same time low cost and highly sensitive and selective.  IAQSense relies on three patented technologies, of which one is based on surface ion mobility dynamics separating each gas component. Working like a spectrometer it allows high sensitivity fast multi-gas detection in a way never seen before.

IAQSense Project will characterize, monitor and improve indoor air quality in an innovative way.

The consortium is composed of 4 SMEs [small to medium enterprises[, 3 industrial companies and 3 research institutes. The project will last 3 years (01.09.2013 – 31.08.2016) and will deliver a complete sensor system.

The IAQSense research project has received funding from the European Community´s 7th Framework Programme under grant agreement n° 6043125.

As someone who has suffered from breathing problems from time to time, I wish them the best with this project .

Earth Day, Water Day, and every day

I’m blaming my confusion on the American Chemical Society (ACS) which seemed to be celebrating Earth Day on April 15, 2014 as per its news release highlighting their “Chemists Celebrate Earth Day” video series  while in Vancouver, Canada, we’re celebrating it on April 26, 2014 and elsewhere it seems to be on April 20, this year. Regardless, here’s more about how chemist’s are celebrating from the ACS news release,

Water is arguably the most important resource on the planet. In celebration of Earth Day, the American Chemical Society (ACS) is showcasing three scientists whose research keeps water safe, clean and available for future generations. Geared toward elementary and middle school students, the “Chemists Celebrate Earth Day” series highlights the important work that chemists and chemical engineers do every day. The videos are available at http://bit.ly/CCED2014.

The series focuses on the following subjects:

  • Transforming Tech Toys- Featuring Aydogan Ozcan, Ph.D., of UCLA: Ozcan takes everyday gadgets and turns them into powerful mobile laboratories. He’s made a cell phone into a blood analyzer and a bacteria detector, and now he’s built a device that turns a cell phone into a water tester. It can detect very harmful mercury even at very low levels.
  • All About Droughts - Featuring Collins Balcombe of the U.S. Bureau of Reclamation: Balcombe’s job is to keep your drinking water safe and to find new ways to re-use the water that we flush away everyday so that it doesn’t go to waste, especially in areas that don’t get much rain.
  • Cleaning Up Our Water – Featuring Anne Morrissey, Ph.D., of Dublin City University: We all take medicines, but did you know that sometimes the medicine doesn’t stay in our bodies? It’s up to Anne Morrissey to figure out how to get potentially harmful pharmaceuticals out of the water supply, and she’s doing it using one of the most plentiful things on the planet: sunlight.

Sadly, I missed marking World Water Day which according to a March 21, 2014 news release I received was being celebrated on Saturday, March 22, 2014 with worldwide events and the release of a new UN report,

World Water Day: UN Stresses Water and Energy Issues 

Tokyo Leads Public Celebrations Around the World

Tokyo — March 21 — The deep-rooted relationships between water and energy were highlighted today during main global celebrations in Tokyo marking the United Nations’ annual World Water Day.

“Water and energy are among the world’s most pre-eminent challenges. This year’s focus of World Water Day brings these issues to the attention of the world,” said Michel Jarraud, Secretary-General of the World Meteorological Organization and Chair of UN-Water, which coordinates World Water Day and freshwater-related efforts UN system-wide.

The UN predicts that by 2030 the global population will need 35% more food, 40% more water and 50% more energy. Already today 768 million people lack access to improved water sources, 2.5 billion people have no improved sanitation and 1.3 billion people cannot access electricity.

“These issues need urgent attention – both now and in the post-2015 development discussions. The situation is unacceptable. It is often the same people who lack access to water and sanitation who also lack access to energy, ” said Mr. Jarraud.

The 2014 World Water Development Report (WWDR) – a UN-Water flagship report, produced and coordinated by the World Water Assessment Programme, which is hosted and led by UNESCO – is released on World Water Day as an authoritative status report on global freshwater resources. It highlights the need for policies and regulatory frameworks that recognize and integrate approaches to water and energy priorities.

WWDR, a triennial report from 2003 to 2012, this year becomes an annual edition, responding to the international community’s expression of interest in a concise, evidence-based and yearly publication with a specific thematic focus and recommendations.

WWDR 2014 underlines how water-related issues and choices impact energy and vice versa. For example: drought diminishes energy production, while lack of access to electricity limits irrigation possibilities.

The report notes that roughly 75% of all industrial water withdrawals are used for energy production. Tariffs also illustrate this interdependence: if water is subsidized to sell below cost (as is often the case), energy producers – major water consumers – are less likely to conserve it.  Energy subsidies, in turn, drive up water usage.

The report stresses the imperative of coordinating political governance and ensuring that water and energy prices reflect real costs and environmental impacts.

“Energy and water are at the top of the global development agenda,” said the Rector of United Nations University, David Malone, this year’s coordinator of World Water Day on behalf of UN-Water together with the United Nations Industrial Development Organization (UNIDO).

“Significant policy gaps exist in this nexus at present, and the UN plays an instrumental role in providing evidence and policy-relevant guidance. Through this day, we seek to inform decision-makers, stakeholders and practitioners about the interlinkages, potential synergies and trade-offs, and highlight the need for appropriate responses and regulatory frameworks that account for both water and energy priorities. From UNU’s perspective, it is essential that we stimulate more debate and interactive dialogue around possible solutions to our energy and water challenges.”

UNIDO Director-General LI Yong, emphasized the importance of water and energy for inclusive and sustainable industrial development.

“There is a strong call today for integrating the economic dimension, and the role of industry and manufacturing in particular, into the global post-2015 development priorities. Experience shows that environmentally sound interventions in manufacturing industries can be highly effective and can significantly reduce environmental degradation. I am convinced that inclusive and sustainable industrial development will be a key driver for the successful integration of the economic, social and environmental dimensions,” said Mr. LI.

Rather unusually, Michael Bergerrecently published two Nanowerk Spotlight articles about water (is there theme, anyone?) within 24 hours of each other. In his March 26, 2014 Spotlight article, Michael Berger focuses on graphene and water remediation (Note: Links have been removed),

The unique properties of nanomaterials are beneficial in applications to remove pollutants from the environment. The extremely small size of nanomaterial particles creates a large surface area in relation to their volume, which makes them highly reactive, compared to non-nano forms of the same materials.

The potential impact areas for nanotechnology in water applications are divided into three categories: treatment and remediation; sensing and detection: and pollution prevention (read more: “Nanotechnology and water treatment”).

Silver, iron, gold, titanium oxides and iron oxides are some of the commonly used nanoscale metals and metal oxides cited by the researchers that can be used in environmental remediation (read more: “Overview of nanomaterials for cleaning up the environment”).

A more recent entrant into this nanomaterial arsenal is graphene. Individual graphene sheets and their functionalized derivatives have been used to remove metal ions and organic pollutants from water. These graphene-based nanomaterials show quite high adsorption performance as adsorbents. However they also cause additional cost because the removal of these adsorbent materials after usage is difficult and there is the risk of secondary environmental pollution unless the nanomaterials are collected completely after usage.

One solution to this problem would be the assembly of individual sheets into three-dimensional (3D) macroscopic structures which would preserve the unique properties of individual graphene sheets, and offer easy collecting and recycling after water remediation.

The March 27, 2014 Nanowerk Spotlight article was written by someone at Alberta’s (Canada) Ingenuity Lab and focuses on their ‘nanobiological’ approach to water remediation (Note: Links have been removed),

At Ingenuity Lab in Edmonton, Alberta, Dr. Carlo Montemagno and a team of world-class researchers have been investigating plausible solutions to existing water purification challenges. They are building on Dr. Montemagno’s earlier patented discoveries by using a naturally-existing water channel protein as the functional unit in water purification membranes [4].

Aquaporins are water-transport proteins that play an important osmoregulation role in living organisms [5]. These proteins boast exceptionally high water permeability (~ 1010 water molecules/s), high selectivity for pure water molecules, and a low energy cost, which make aquaporin-embedded membrane well suited as an alternative to conventional RO membranes.

Unlike synthetic polymeric membranes, which are driven by the high pressure-induced diffusion of water through size selective pores, this technology utilizes the biological osmosis mechanism to control the flow of water in cellular systems at low energy. In nature, the direction of osmotic water flow is determined by the osmotic pressure difference between compartments, i.e. water flows toward higher osmotic pressure compartment (salty solution or contaminated water). This direction can however be reversed by applying a pressure to the salty solution (i.e., RO).

The principle of RO is based on the semipermeable characteristics of the separating membrane, which allows the transport of only water molecules depending on the direction of osmotic gradient. Therefore, as envisioned in the recent publication (“Recent Progress in Advanced Nanobiological Materials for Energy and Environmental Applications”), the core of Ingenuity Lab’s approach is to control the direction of water flow through aquaporin channels with a minimum level of pressure and to use aquaporin-embedded biomimetic membranes as an alternative to conventional RO membranes.

Here’s a link to and a citation for Montemagno’s and his colleague’s paper,

Recent Progress in Advanced Nanobiological Materials for Energy and Environmental Applications by Hyo-Jick Choi and Carlo D. Montemagno. Materials 2013, 6(12), 5821-5856; doi:10.3390/ma6125821

This paper is open access.

Returning to where I started, here’s a water video featuring graphene from the ACS celebration of Earth Day 2014,

Happy Earth Day!

Good lignin, bad lignin: Florida researchers use plant waste to create lignin nanotubes while researchers in British Columbia develop trees with less lignin

An April 4, 2014 news item on Azonano describes some nanotube research at the University of Florida that reaches past carbon to a new kind of nanotube,

Researchers with the University of Florida’s [UF] Institute of Food and Agricultural Sciences took what some would consider garbage and made a remarkable scientific tool, one that could someday help to correct genetic disorders or treat cancer without chemotherapy’s nasty side effects.

Wilfred Vermerris, an associate professor in UF’s department of microbiology and cell science, and Elena Ten, a postdoctoral research associate, created from plant waste a novel nanotube, one that is much more flexible than rigid carbon nanotubes currently used. The researchers say the lignin nanotubes – about 500 times smaller than a human eyelash – can deliver DNA directly into the nucleus of human cells in tissue culture, where this DNA could then correct genetic conditions. Experiments with DNA injection are currently being done with carbon nanotubes, as well.

“That was a surprising result,” Vermerris said. “If you can do this in actual human beings you could fix defective genes that cause disease symptoms and replace them with functional DNA delivered with these nanotubes.”

An April 3, 2014 University of Florida’s Institute of Food and Agricultural Sciences news release, which originated the news item, describes the lignin nanotubes (LNTs) and future applications in more detail,

The nanotube is made up of lignin from plant material obtained from a UF biofuel pilot facility in Perry, Fla. Lignin is an integral part of the secondary cell walls of plants and enables water movement from the roots to the leaves, but it is not used to make biofuels and would otherwise be burned to generate heat or electricity at the biofuel plant. The lignin nanotubes can be made from a variety of plant residues, including sorghum, poplar, loblolly pine and sugar cane. [emphasis mine]

The researchers first tested to see if the nanotubes were toxic to human cells and were surprised to find that they were less so than carbon nanotubes. Thus, they could deliver a higher dose of medicine to the human cell tissue.  Then they researched if the nanotubes could deliver plasmid DNA to the same cells and that was successful, too. A plasmid is a small DNA molecule that is physically separate from, and can replicate independently of, chromosomal DNA within a cell.

“It’s not a very smooth road because we had to try different experiments to confirm the results,” Ten said. “But it was very fruitful.”

In cases of genetic disorders, the nanotube would be loaded with a functioning copy of a gene, and injected into the body, where it would target the affected tissue, which then makes the missing protein and corrects the genetic disorder.

Although Vermerris cautioned that treatment in humans is many years away, among the conditions that these gene-carrying nanotubes could correct include cystic fibrosis and muscular dystrophy. But, he added, that patients would have to take the corrective DNA via nanotubes on a continuing basis.

Another application under consideration is to use the lignin nanotubes for the delivery of chemotherapy drugs in cancer patients. The nanotubes would ensure the drugs only get to the tumor without affecting healthy tissues.

Vermerris said they created different types of nanotubes, depending on the experiment. They could also adapt nanotubes to a patient’s specific needs, a process called customization.

“You can think about it as a chest of drawers and, depending on the application, you open one drawer or use materials from a different drawer to get things just right for your specific application,” he said.  “It’s not very difficult to do the customization.”

The next step in the research process is for Vermerris and Ten to begin experiments on mice. They are in the application process for those experiments, which would take several years to complete.  If those are successful, permits would need to be obtained for their medical school colleagues to conduct research on human patients, with Vermerris and Ten providing the nanotubes for that research.

“We are a long way from that point,” Vermerris said. “That’s the optimistic long-term trajectory.”

I hope they have good luck with this work. I have emphasized the plant waste the University of Florida scientists studied due to the inclusion of poplar, which is featured in the University of British Columbia research work also being mentioned in this post.

Getting back to Florida for a moment, here’s a link to and a citation for the paper,

Lignin Nanotubes As Vehicles for Gene Delivery into Human Cells by Elena Ten, Chen Ling, Yuan Wang, Arun Srivastava, Luisa Amelia Dempere, and Wilfred Vermerris. Biomacromolecules, 2014, 15 (1), pp 327–338 DOI: 10.1021/bm401555p Publication Date (Web): December 5, 2013
Copyright © 2013 American Chemical Society

This is an open access paper.

Meanwhile, researchers at the University of British Columbia (UBC) are trying to limit the amount of lignin in trees (specifically poplars, which are not mentioned in this excerpt but in the next). From an April 3, 2014 UBC news release,

Researchers have genetically engineered trees that will be easier to break down to produce paper and biofuel, a breakthrough that will mean using fewer chemicals, less energy and creating fewer environmental pollutants.

“One of the largest impediments for the pulp and paper industry as well as the emerging biofuel industry is a polymer found in wood known as lignin,” says Shawn Mansfield, a professor of Wood Science at the University of British Columbia.

Lignin makes up a substantial portion of the cell wall of most plants and is a processing impediment for pulp, paper and biofuel. Currently the lignin must be removed, a process that requires significant chemicals and energy and causes undesirable waste.

Researchers used genetic engineering to modify the lignin to make it easier to break down without adversely affecting the tree’s strength.

“We’re designing trees to be processed with less energy and fewer chemicals, and ultimately recovering more wood carbohydrate than is currently possible,” says Mansfield.

Researchers had previously tried to tackle this problem by reducing the quantity of lignin in trees by suppressing genes, which often resulted in trees that are stunted in growth or were susceptible to wind, snow, pests and pathogens.

“It is truly a unique achievement to design trees for deconstruction while maintaining their growth potential and strength.”

The study, a collaboration between researchers at the University of British Columbia, the University of Wisconsin-Madison, Michigan State University, is a collaboration funded by Great Lakes Bioenergy Research Center, was published today in Science.

Here’s more about lignin and how a decrease would free up more material for biofuels in a more environmentally sustainable fashion, from the news release,

The structure of lignin naturally contains ether bonds that are difficult to degrade. Researchers used genetic engineering to introduce ester bonds into the lignin backbone that are easier to break down chemically.

The new technique means that the lignin may be recovered more effectively and used in other applications, such as adhesives, insolation, carbon fibres and paint additives.

Genetic modification

The genetic modification strategy employed in this study could also be used on other plants like grasses to be used as a new kind of fuel to replace petroleum.

Genetic modification can be a contentious issue, but there are ways to ensure that the genes do not spread to the forest. These techniques include growing crops away from native stands so cross-pollination isn’t possible; introducing genes to make both the male and female trees or plants sterile; and harvesting trees before they reach reproductive maturity.

In the future, genetically modified trees could be planted like an agricultural crop, not in our native forests. Poplar is a potential energy crop for the biofuel industry because the tree grows quickly and on marginal farmland. [emphasis mine] Lignin makes up 20 to 25 per cent of the tree.

“We’re a petroleum reliant society,” says Mansfield. “We rely on the same resource for everything from smartphones to gasoline. We need to diversify and take the pressure off of fossil fuels. Trees and plants have enormous potential to contribute carbon to our society.”

As noted earlier, the researchers in Florida mention poplars in their paper (Note: Links have been removed),

Gymnosperms such as loblolly pine (Pinus taeda L.) contain lignin that is composed almost exclusively of G-residues, whereas lignin from angiosperm dicots, including poplar (Populus spp.) contains a mixture of G- and S-residues. [emphasis mine] Due to the radical-mediated addition of monolignols to the growing lignin polymer, lignin contains a variety of interunit bonds, including aryl–aryl, aryl–alkyl, and alkyl–alkyl bonds.(3) This feature, combined with the association between lignin and cell-wall polysaccharides, which involves both physical and chemical interactions, make the isolation of lignin from plant cell walls challenging. Various isolation methods exist, each relying on breaking certain types of chemical bonds within the lignin, and derivatizations to solubilize the resulting fragments.(5) Several of these methods are used on a large scale in pulp and paper mills and biorefineries, where lignin needs to be removed from woody biomass and crop residues(6) in order to use the cellulose for the production of paper, biofuels, and biobased polymers. The lignin is present in the waste stream and has limited intrinsic economic value.(7)

Since hydroxyl and carboxyl groups in lignin facilitate functionalization, its compatibility with natural and synthetic polymers for different commercial applications have been extensively studied.(8-12) One of the promising directions toward the cost reduction associated with biofuel production is the use of lignin for low-cost carbon fibers.(13) Other recent studies reported development and characterization of lignin nanocomposites for multiple value-added applications. For example, cellulose nanocrystals/lignin nanocomposites were developed for improved optical, antireflective properties(14, 15) and thermal stability of the nanocomposites.(16) [emphasis mine] Model ultrathin bicomponent films prepared from cellulose and lignin derivatives were used to monitor enzyme binding and cellulolytic reactions for sensing platform applications.(17) Enzymes/“synthetic lignin” (dehydrogenation polymer (DHP)) interactions were also investigated to understand how lignin impairs enzymatic hydrolysis during the biomass conversion processes.(18)

The synthesis of lignin nanotubes and nanowires was based on cross-linking a lignin base layer to an alumina membrane, followed by peroxidase-mediated addition of DHP and subsequent dissolution of the membrane in phosphoric acid.(1) Depending upon monomers used for the deposition of DHP, solid nanowires, or hollow nanotubes could be manufactured and easily functionalized due to the presence of many reactive groups. Due to their autofluorescence, lignin nanotubes permit label-free detection under UV radiation.(1) These features make lignin nanotubes suitable candidates for numerous biomedical applications, such as the delivery of therapeutic agents and DNA to specific cells.

The synthesis of LNTs in a sacrificial template membrane is not limited to a single source of lignin or a single lignin isolation procedure. Dimensions of the LNTs and their cytotoxicity to HeLa cells appear to be determined primarily by the lignin isolation procedure, whereas the transfection efficiency is also influenced by the source of the lignin (plant species and genotype). This means that LNTs can be tailored to the application for which they are intended. [emphasis mine] The ability to design LNTs for specific purposes will benefit from a more thorough understanding of the relationship between the structure and the MW of the lignin used to prepare the LNTs, the nanomechanical properties, and the surface characteristics.

We have shown that DNA is physically associated with the LNTs and that the LNTs enter the cytosol, and in some case the nucleus. The LNTs made from NaOH-extracted lignin are of special interest, as they were the shortest in length, substantially reduced HeLa cell viability at levels above approximately 50 mg/mL, and, in the case of pine and poplar, were the most effective in the transfection [penetrating the cell with a bacterial plasmid to leave genetic material in this case] experiments. [emphasis mine]

As I see the issues presented with these two research efforts, there are environmental and energy issues with extracting the lignin while there seem to be some very promising medical applications possible with lignin ‘waste’. These two research efforts aren’t necessarily antithetical but they do raise some very interesting issues as to how we approach our use of resources and future policies.

ETA May 16, 2014: The beat goes on with the Georgia (US) Institute of Technology issues a roadmap for making money from lignin. From a Georgia Tech May 15, 2014 news release on EurekAlert,

When making cellulosic ethanol from plants, one problem is what to do with a woody agricultural waste product called lignin. The old adage in the pulp industry has been that one can make anything from lignin except money.

A new review article in the journal Science points the way toward a future where lignin is transformed from a waste product into valuable materials such as low-cost carbon fiber for cars or bio-based plastics. Using lignin in this way would create new markets for the forest products industry and make ethanol-to-fuel conversion more cost-effective.

“We’ve developed a roadmap for integrating genetic engineering with analytical chemistry tools to tailor the structure of lignin and its isolation so it can be used for materials, chemicals and fuels,” said Arthur Ragauskas, a professor in the School of Chemistry and Biochemistry at the Georgia Institute of Technology. Ragauskas is also part of the Institute for Paper Science and Technology at Georgia Tech.

The roadmap was published May 15 [2014] in the journal Science. …

Here’s a link to and citation for the ‘roadmap’,

Lignin Valorization: Improving Lignin Processing in the Biorefinery by  Arthur J. Ragauskas, Gregg T. Beckham, Mary J. Biddy, Richard Chandra, Fang Chen, Mark F. Davis, Brian H. Davison, Richard A. Dixon, Paul Gilna, Martin Keller, Paul Langan, Amit K. Naskar, Jack N. Saddler, Timothy J. Tschaplinski, Gerald A. Tuskan, and Charles E. Wyman. Science 16 May 2014: Vol. 344 no. 6185 DOI: 10.1126/science.1246843

This paper is behind a paywall.