Category Archives: risk

FOE, nano, and food: part three of three (final guidance)

The first part of this food and nano ‘debate’ started off with the May 22, 2014 news item on Nanowerk announcing the Friends of the Earth (FOE) report ‘Way too little: Our Government’s failure to regulate nanomaterials in food and agriculture‘. Adding energy to FOE’s volley was a Mother Jones article written by Tom Philpott which had Dr. Andrew Maynard (Director of the University of Michigan’s Risk Science Center) replying decisively in an article published both on Nanowerk and on the Conversation.

The second part of this series focused largely on a couple of  research efforts (a June 11, 2014 news item on Nanowerk highlights a Franco-German research project, SolNanoTox) and in the US (a  June 19, 2014 news item on Azonano about research from the University of Arizona focusing on nanoscale additives for dietary supplement drinks) and noted another activist group’s (As You Sow) initiative with Dunkin’ Donuts (a July 11, 2014 article by Sarah Shemkus in a sponsored section in the UK’s Guardian newspaper0).

This final part in the series highlights the US Food and Drug Administration’s (FDA) final guidance document on nanomaterials and food issued some five weeks after the FOE’s report and an essay by a Canadian academic on the topic of nano and food.

A July 9, 2014 news item on Bloomberg BNA sums up the FDA situation,

The Food and Drug Administration June 24 [2014] announced new guidance to provide greater regulatory clarity for industry on the use of nanotechnology in FDA-regulated products, including drugs, devices, cosmetics and food.

In this final guidance, the agency said that nanotechnology “can be used in a broad array of FDA-regulated products, including medical products (e.g., to increase bioavailability of a drug), foods (e.g., to improve food packaging) and cosmetics (e.g., to affect the look and feel of cosmetics).”

Also on the agency website, the FDA said it “does not make a categorical judgment that nanotechnology is inherently safe or harmful. We intend our regulatory approach to be adaptive and flexible and to take into consideration the specific characteristics and the effects of nanomaterials in the particular biological context of each product and its intended use.”

This July 18, 2014 posting by Jeannie Perron, Miriam Guggenheimm and Allan J. Topol of Covington & Burling LLP on the National Law Review blog provides a better summary and additional insight,

On June 24, 2014, the Food and Drug Administration (FDA) released three final guidance documents addressing the agency’s general approach to nanotechnology and its use by the food and cosmetics industries, as well as a draft guidance on the use of nanomaterials in food for animals.

These guidance documents reflect FDA’s understanding of nanomaterials as an emerging technology of major importance with the potential to be used in novel ways across the entire spectrum of FDA- regulated products.

The documents suggest that FDA plans to approach nanotechnology-related issues cautiously, through an evolving regulatory structure that adapts to manufacturers’ changing uses of this technology. FDA has not established regulatory definitions of “nanotechnology,” “nanomaterial,” “nanoscale,” or other related terms. …

The notion of an “evolving regulatory structure” is very appealing in situations with emerging technologies with high levels of uncertainty. It’s surprising that more of the activist groups don’t see an opportunity with this approach. An organization that hasn’t devised a rigid regulatory structure has no investment in defending it. Activist groups can make the same arguments, albeit from a different perspective, about an emerging technology as the companies do and, theoretically, the FDA has become a neutral party with the power to require a company to prove its products’ safety.

You can find the FDA final guidance and other relevant documents here.

Finally, Sylvain Charlebois, associate dean at the College of Business and Economics at the University of Guelph, offers a rather provocative (and not from the perspective you might expect given his credentials) opinion on the topic of ‘nano and food’  in a July 18, 2014 article for TheRecord.com,

Nanotechnology and nanoparticles have been around for quite some time. In fact, consumers have been eating nanoparticles for years without being aware they are in their food.

Some varieties of Dentyne gum and Jell-O, M&M’s, Betty Crocker whipped cream frosting, Kool-Aid, Pop-Tarts, you name it, contain them. Even food packaging, such as plastic containers and beer bottles, have nanoparticles.

While consumers and interest groups alike are registering their concerns about genetically modified organisms, the growing role of nanotechnology in food and agriculture is impressive. When considering the socio-economic and ethical implications of nanotechnology, comparisons to the genetic modification debate are unavoidable.

The big picture is this. For years, capitalism has demonstrated its ability to create wealth while relying on consumers’ willingness to intrinsically trust what is being offered to them. With trans fats, genetically modified organisms and now nanoparticles, our food industry is literally playing with fire. [emphasis mine]

Most consumers may not have the knowledge to fully comprehend the essence of what nanotechnology is or what it can do. However, in an era where data access in almost constant real-time is king, the industry should at least give public education a shot.

In the end and despite their tactics, the activist groups do have a point. The food and agricultural industries need to be more frank about what they’re doing with our food. As Charlebois notes, they might want to invest in some public education, perhaps taking a leaf out of the Irish Food Board’s book and presenting the public with information both flattering and nonflattering about their efforts with our food.

Part one (an FOE report is published)

Part two (the problem with research)

ETA Aug. 22, 2014: Coincidentally, Michael Berger has written an Aug. 22, 2014 Nanowerk Spotlight article titled: How to identify nanomaterials in food.

FOE, nano, and food: part two of three (the problem with research)

The first part of this roughly six week food and nano ‘debate’ started off with the May 22, 2014 news item on Nanowerk announcing the Friends of the Earth (FOE) report ‘Way too little: Our Government’s failure to regulate nanomaterials in food and agriculture‘. Adding energy to FOE’s volley was a Mother Jones article written by Tom Philpott which had Dr. Andrew Maynard (Director of the University of Michigan’s Risk Science Center) replying decisively in an article published both on Nanowerk and on the Conversation.

Coincidentally or not, there were a couple of news items about ‘nano and food’ research efforts during the ‘debate’. A June 11, 2014 news item on Nanowerk highlights a Franco-German research project into the effects that nanomaterials have on the liver and the intestines while noting the scope of the task researchers face,

What mode of action do nanomaterials ingested via food have in liver and intestine? Which factors determine their toxicity? Due to the large number of different nanomaterials, it is hardly possible to test every one for its toxic properties. [emphasis mine] For this reason, specific properties for the classification of nanomaterials are to be examined within the scope of the Franco-German research project “SolNanoTox”, which began on 1 March 2014. The [German] Federal Institute for Risk Assessment (BfR) requires data on bioavailability for its assessment work, in particular on whether the solubility of nanomaterials has an influence on uptake and accumulation in certain organs, such as liver and intestine. “We want to find out in our tests whether the criterion ‘soluble or insoluble’ is a determining factor for uptake and toxicity of nanomaterials,” says BfR President Professor Dr. Andreas Hensel.

A June 13, 2014 German Federal Institute for Risk Assessment (BfR) press release, which originated the news item, details the research and the participating agencies,

A risk assessment of nanomaterials is hardly possible at the moment and involves a very high degree of uncertainty, as important toxicological data on their behaviour in tissue and cells are still missing. [emphasis mine] The German-French SolNanoTox research project examines which role the solubility of nanomaterials plays with regard to their accumulation and potential toxic properties. The project is to run for three and a half years during which the BfR will work closely with its French sister organisation ANSES. Other partners are the Institut des Sciences Chimiques de Rennes and Universität Leipzig. The German Research Foundation and French Agence Nationale de la Recherche (ANR) are funding the project.

The tasks of the BfR include in vitro tests (e.g. the investigation of the influence of the human gastrointestinal system) and analysis of biological samples with regard to the possible accumulation of nanomaterials. In addition to this, the BfR uses modern methods of mass spectrometry imaging to find out whether nanoparticles alter the structure of biomolecules, e.g. the structure of the lipids of the cellular membrane. So far, these important tests, which are necessary for assessing possible changes in DNA or cellular structures caused by nanomaterials in food, have not been conducted.

Metallic nanoparticles are to be studied (from the press release),

In the project, two fundamentally different types of nanoparticles are examined as representatives for others of their type: titanium dioxide as representative of water insoluble nanoparticles and aluminium as an example of nanomaterials which show a certain degree of water solubility after oxidation. [emphases mine] It is examined whether the degree of solubility influences the distribution of the nanomaterials in the body and whether soluble materials may possibly accumulate more in other organs than insoluble ones. The object is to establish whether there is a direct toxic effect of insoluble nanomaterials in general after oral uptake due to their small size.

Different innovative analytical methods are combined in the project with the aim to elucidate the behaviour of nanomaterials in tissue and their uptake into the cell. The main focus is on effects which can trigger genotoxic damage and inflammation. At first, the effects of both materials are examined in human cultures of intestinal and liver cells in an artificial environment (in vitro). In the following, it has to be verified by animal experimentation whether the observed effects can also occur in humans. This modus operandi allows to draw conclusions on effects and mode of action of orally ingested nanomaterials with different properties. The goal is to group nanomaterials on the basis of specific properties and to allocate the corresponding toxicological properties to these groups. Motivation for the project is the enormous number of nanomaterials with large differences in physicochemical properties. Toxicological tests cannot be conducted for all materials.

In the meantime, a June 19, 2014 news item on Azonano (also on EurekAlert but dated June 18, 2014) features some research into metallic nanoparticles in dietary supplement drinks,

Robert Reed [University of Arizona] and colleagues note that food and drink manufacturers use nanoparticles in and on their products for many reasons. In packaging, they can provide strength, control how much air gets in and out, and keep unwanted microbes at bay. As additives to food and drinks, they can prevent caking, deliver nutrients and prevent bacterial growth. But as nanoparticles increase in use, so do concerns over their health and environmental effects. Consumers might absorb some of these materials through their skin, and inhale and ingest them. What doesn’t get digested is passed in urine and feces to the sewage system. A handful of initial studies on nanomaterials suggest that they could be harmful, but Reed’s team wanted to take a closer look.

They tested the effects of eight commercial drinks containing nano-size metal or metal-like particles on human intestinal cells in the lab. The drinks changed the normal organization and decreased the number of microvilli, finger-like projections on the cells that help digest food. In humans, if such an effect occurs as the drinks pass through the gastrointestinal tract, these materials could lead to poor digestion or diarrhea, they say. The researchers’ analysis of sewage waste containing these particles suggests that much of the nanomaterials from these products are likely making their way back into surface water, where they could potentially cause health problems for aquatic life.

This piece is interesting for two reasons. First, the researchers don’t claim that metallic nanoparticles cause digestion or diarrhea due to any action in the gastrointestinal tract. They studied the impact that metallic nanoparticles in supplementary drinks had on cells (in vitro testing) from the gastrointestinal tract. Based on what they observed in the laboratory, “… these materials could lead to poor digestion or diarrhea… .” The researchers also suggest a problem could occur as these materials enter surface water in increasing quantities.

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

Supplement Drinks and Assessment of Their Potential Interactions after Ingestion by Robert B. Reed, James J. Faust, Yu Yang, Kyle Doudrick, David G. Capco, Kiril Hristovski, and Paul Westerhoff. ACS Sustainable Chem. Eng., 2014, 2 (7), pp 1616–1624 DOI: 10.1021/sc500108m Publication Date (Web): June 2, 2014

Copyright © 2014 American Chemical Society

With Paul Westerhoff as one of the authors and the reference to metallic nanoparticles entering water supplies, I’m guessing that this research is associated with the LCnano (lifecycle nano) project headquartered at Arizona State university (April 8, 2014 posting).

Getting back to the Franco-German SolNanoTox project, scientists do not know what happens when the cells in your intestines, liver, etc. encounter metallic or other nanoparticles, some of which may be naturally occurring. It should also be noted that we have likely been ingesting metallic nanoparticles for quite some time. After all, anyone who has used silver cutlery has ingested some silver nanoparticles.

There are many, many questions to be asked and answered with regard to nanomaterials in our foods.  Here are a few of mine:

  • How many metallic and other nanoparticles did we ingest before the advent of ‘nanomaterials in food’?
  • What is the biopersistence of naturally occurring and engineered metallic and other nanoparticles in the body?
  • Is there an acceptable dose versus a fatal dose? (Note: There’s naturally occurring formaldehyde in pears as per my May 19, 2014 post about doses, poisons, and the Sense about Science group’s campaign/book, Making Sense of Chemical Stories.)
  • What happens as the metallic and other engineered nanoparticles are added to food and drink and eventually enter our water, air, and soil?

Returning to the ‘debate’, a July 11, 2014 article by Sarah Shemkus for a sponsored section in the UK’s Guardian newspaper highlights an initiative taken by an environmental organization, As You Sow, concerning titanium dioxide in Dunkin’ Donuts’ products (Note: A link has been removed),

The activists at environmental nonprofit As You Sow want you to take another look at your breakfast doughnut. The organization recently filed a shareholder resolution asking Dunkin’ Brands, the parent company of Dunkin’ Donuts, to identify products that may contain nanomaterials and to prepare a report assessing the risks of using these substances in foods.

Their resolution received a fair amount of support: at the company’s annual general meeting in May, 18.7% of shareholders, representing $547m in investment, voted for it. Danielle Fugere, As You Sow’s president, claims that it was the first such resolution to ever receive a vote. Though it did not pass, she says that she is encouraged by the support it received.

“That’s a substantial number of votes in favor, especially for a first-time resolution,” she says.

The measure was driven by recent testing sponsored by As You Sow, which found nanoparticles of titanium dioxide in the powdered sugar that coats some of the donut chain’s products. [emphasis mine] An additive widely used to boost whiteness in products from toothpaste to plastic, microscopic titanium dioxide has not been conclusively proven unsafe for human consumption. Then again, As You Sow contends, there also isn’t proof that it is harmless.

“Until a company can demonstrate the use of nanomaterials is safe, we’re asking companies either to not use them or to provide labels,” says Fugere. “It would make more sense to understand these materials before putting them in our food.”

As You Sow is currently having 16 more foods tested. The result should be available later this summer, Fugere says.

I wonder if As You Sow will address the question of whether the nanoscale titanium dioxide they find indicates that nanoscale particles are being deliberately added or whether the particles are the inadvertent consequence of the production process. That said, I find it hard to believe no one in the food industry is using engineered nanoscale additives as they claim  (the other strategy is to offer a nonanswer) in Shemkus’ article (Note: Links have been removed).,

In a statement, Dunkin’ Donuts argues that the titanium dioxide identified by As You Sow does not qualify as a nanomaterial according to European Union rules or draft US Food and Drug Administration regulations. The company also points out that there is no agreed-upon standard method for identifying nanoparticles in food.

In 2008, As You Sow filed nanomaterial labeling resolutions with McDonald’s and Kraft Foods. In response, McDonald’s released a statement declaring that it does not support the use of nanomaterials in its food, packaging or toys. Kraft responded that it would make sure to address health and safety concerns before ever using nanomaterials in its products.

While Shemkus’ article appears in the Guardian’s Food Hub which is sponsored by the Irish Food Board, this article manages to avoid the pitfalls found in Philpott’s nonsponsored article.

Coming next: the US Food and Drug Administration Guidance issued five weeks after the FOE kicks off the ‘nano and food’ debate in May 2014 with its ‘Way too little: Our Government’s failure to regulate nanomaterials in food and agriculture‘ report.

Part one (an FOE report is published)

Part three (final guidance)

FOE, nano, and food: part one of three (an FOE report is published)

It seems the food and nano debate of Spring/Summer 2014 has died down, for a while at least. The first volley (from my perspective) was the May 2014 release of ‘Way too little: Our Government’s failure to regulate nanomaterials in food and agriculture’ by the Friends of the Earth (FOE) Australia. Here’s how the report is described in a May 22, 2014 news item on Nanowerk,

Friends of the Earth’s new report, Way too little (pdf), looks at the now widespread presence of nanomaterials in our food chain and how little Food Standards Australia New Zealand (FSANZ) is doing to ensure our safety.

You can find the following passage on p. 6 of FOE’s report ‘Way too little: Our Government’s failure to regulate nanomaterials in food and agriculture‘,

This report will examine the changes since our 2008 report including the development of new food, food contact and agricultural products. It will review the current literature relating to the potential environmental, health and safety impacts associated with nanotechnology and summarise the Australian regulatory responses to date.

This updated report uncovers the:

•accelerating rate of commercialisation and rapidly increasing number of commercial products containing nanomaterials in the food and agricultural sectors;

•lack of information regarding which nanomaterials have been released and the likely exposure of humans and natural systems to these materials;

•lack of basic steps to allow us to track nanomaterials that have been released, such as
labelling and a register of products containing nanomaterials;

•growing gap between the pace of commercialisation and environmental, health and safety assessments;

•increasingly large body of peer reviewed evidence that certain nanomaterials may cause harm to human health or the environment;

•failure of regulators to respond to the growingevidence of risks;

•lack of basic knowledge that is critical in order to fully analyse the particular environmental, health and safety issues associated with nanotechnology.

Six years ago, inaction was based on a perceived lack of data. Inaction is still the norm but that is no longer an excuse our Government can use. Scientists and scientific bodies such as the US National Research Council have given us more than enough evidence to justify a pro-active regulatory regime and a properly funded R&D program that will effectively target those areas of greatest environmental and health concern.

Unfortunately, our Federal Government seems unwilling to provide the levels of funding required for such work or to adopt appropriate regulation. The notion of precaution has been replaced with an attitude that it is the obligation of industry to determine whether their products are safe and regulators will only act when harm is shown. While France, Belgium and Denmark are implementing a mandatory register for nanomaterials and the EU’s is in the process of implementing a nano food labelling regime, Australian consumers remain in the dark.

This needs to change.

One of the issues with increased regulation and labeling is whether the benefits outweigh disadvantages such as the increased difficulty of getting needed foodstuffs to the marketplace and, of course, cost.

Tom Philpott in a May 28, 2014 article for Mother Jones magazine titled ‘Big Dairy Is Putting Microscopic Pieces of Metal in Your Food’ is a strong proponent for FOE’s position, albeit his geographic focus is the US and he seems most concerned with metallic nanoparticles (Note: Links have been removed),

Examples include Silk Original Soy Milk, Rice Dream Rice Drink, Hershey’s Bliss Dark Chocolate, and Kraft’s iconic American Cheese Singles, all of which now contain nano-size titanium dioxide*. As recently as 2008, only eight US food products were known to contain nanoparticles, according to a recent analysis [May 2014 report] from Friends of the Earth—a more than tenfold increase in just six years.

Philpott goes on to mention the US Food and Drug Administration’s (FDA) 2012 draft guidance on nanomaterials and food,

Back in 2012, the FDA released a draft, pending public comment, of a proposed new framework for bringing nano materials into food. The document reveals plenty of reason for concern. For example: “so-called nano-engineered food substances can have significantly altered bioavailability and may, therefore, raise new safety issues that have not been seen in their traditionally manufactured counterparts.” The report went on to note that “particle size, surface area, aggregation/agglomeration, or shape may impact absorption, distribution, metabolism and excretion (ADME) and potentially the safety of the nano-engineered food substance.”

What FDA is saying here is obvious: If nanoparticles didn’t behave differently, the industry wouldn’t be using them in the first place.

So what’s the remedy? Rather than require rigorous safety studies before companies can lace food with nanoparticles, the FDA’s policy draft proposes “nonbinding recommendations” for such research. Even that rather porous safety net doesn’t yet exist—the agency still hasn’t implemented the draft proposal it released more than two years ago.[emphasis mine]

June 27, 2014, the FDA issued a final ‘food and nanotechnology’ guidance document (more on that later).

In the meantime, Dr. Andrew Maynard (Director of the University of Michigan’s Risk Science Center) strongly countered Philpott’s Mother Jones article with his own article published both on The Conversation (June 3, 2014) and on Nanowerk (June 4, 2014),

Recently the American publication Mother Jones published an article on the dangers of food laced with tiny metal oxide particles. The article, however, is laced with errors and misinformation.

The source material for the article came from a report by the environmental organisation Friends of the Earth, an online database of nanotechnology-based consumer products and a peer-reviewed paper published in 2012. However, the analysis of the information is flawed.

..

Bad journalism

The inventory Philpott cites is the Project on Emerging Nanotechnologies Consumer Products Inventory, which I helped establish in 2006 as a way better understand the increasing number of consumer products that were using engineered nanomaterials. It provides a useful but only qualitative sense of what was being used where, and relies on intermittent web searches and other sources of intelligence. The inventory was never meant to be comprehensive or authoritative.

Briefly, Andrew’s argument is that the FOE report (Way too little) which claims a tenfold increase since 2008 of food products with added nano titanium dioxide (and which Philpotts uses to build his case) is erroneous. In 2006, the inventory was voluntary and there was no oversight. At that time, eight food products had been added to the list. In 2013, the inventory was revived (Oct. 28, 2013 posting) and new information added from a 2012 academic paper. The products from the 2012 paper may have predated the 2006 inventory products, or not. There is no way to tell. Andrew notes this in his measured way,

As someone who works on the risks and benefits of nanotechnology, I can see how errors in translation crept into this story. The 2012 paper was addressing a legitimate concern that little is know about how much titanium dioxide is in the processed food chain. The Consumer Products Inventory provides important and unique insights into nanoparticles being used in products. Friends of the Earth have every right to ask what is known about the potential risks in what we’re eating. And reporters like Philpott have a professional obligation to highlight issues of concern and interest to their readers.

The problem with exaggerated and inflated claims is that FOE proves itself to be an unreliable source and Philpott’s failure to investigate adequately puts his own credibility into question. How can you trust either FOE’s materials or Philpott’s articles? The easiest way to begin rebuilding credibility is to admit one’s mistakes. To date, I have not seen any such attempts from FOE or Philpott.

Coming next: a research initiative into the health effects of nano and food and a research paper on nano in commercial drinks both of which help illustrate why there are concerns and why there is a reluctance to move too quickly.

Part two (the problem with research)

Part three (final guidance)

Two-organ tests (body-on-a-chip) show liver damage possible from nanoparticles

This is the first time I’ve seen testing of two organs for possible adverse effects from nanoparticles. In this case, the researchers were especially interested in the liver. From an Aug. 12, 2014 news item on Azonano,

Nanoparticles in food, sunscreen and other everyday products have many benefits. But Cornell [University] biomedical scientists are finding that at certain doses, the particles might cause human organ damage.

A recently published study in Lab on a Chip by the Royal Society of Chemistry and led by senior research associate Mandy Esch shows that nanoparticles injure liver cells when they are in microfluidic devices designed to mimic organs of the human body. The injury was worse when tested in two-organ systems, as opposed to single organs – potentially raising concerns for humans and animals.

Anne Ju’s Aug. 11, 2014 article for Cornell University’s Chronicle describes the motivation for this work and the research itself in more detail,

“We are looking at the effects of what are considered to be harmless nanoparticles in humans,” Esch said. “These particles are not necessarily lethal, but … are there other consequences? We’re looking at the non-lethal consequences.”

She used 50-nanometer carboxylated polystyrene nanoparticles, found in some animal food sources and considered model inert particles. Shuler’s lab specializes in “body-on-a-chip” microfluidics, which are engineered chips with carved compartments that contain cell cultures to represent the chemistry of individual organs.

In Esch’s experiment, she made a human intestinal compartment, a liver compartment and a compartment to represent surrounding tissues in the body. She then observed the effects of fluorescently labeled nanoparticles as they traveled through the system.

Esch found that both single nanoparticles as well as small clusters crossed the gastrointestinal barrier and reached liver cells, and the liver cells released an enzyme called aspartate transaminase, known to be released during cell death or damage.

It’s unclear exactly what damage is occurring or why, but the results indicate that the nanoparticles must be undergoing changes as they cross the gastrointestinal barrier, and that these alterations may change their toxic potential, Esch said. Long-term consequences for organs in proximity could be a concern, she said.

“The motivation behind this study was twofold: one, to show that multi-organ, in vitro systems give us more information when testing for the interaction of a substance with the human body, and two … to look at nanoparticles because they have a huge potential for medicine, yet adverse effects have not been studied in detail yet,” Esch said.

Mary Macleod’s July 3, 2014 article for Chemistry World features a diagram of the two-organ system and more technical details about the research,

Schematic of the two-organ system [downloaded from http://www.rsc.org/chemistryworld/2014/07/nanoparticle-liver-gastrointestinal-tract-microfluidic-chip]

Schematic of the two-organ system [downloaded from http://www.rsc.org/chemistryworld/2014/07/nanoparticle-liver-gastrointestinal-tract-microfluidic-chip]

HepG2/C3A cells were used to represent the liver, with the intestinal cell co-culture consisting of enterocytes (Caco-2) and mucin-producing (HT29-MTX) cells. Carboxylated polystyrene nanoparticles were fluorescently labelled so their movement between the chambers could be tracked. Levels of aspartate transaminase, a cytosolic enzyme released into the culture medium upon cell death, were measured to give an indication of liver damage.

The study saw that single nanoparticles and smaller nanoparticle aggregates were able to cross the GI barrier and reach the liver cells. The increased zeta potentials of these nanoparticles suggest that crossing the barrier may raise their toxic potential. However, larger nanoparticles, which interact with cell membranes and aggregate into clusters, were stopped much more effectively by the GI tract barrier.

The gastrointestinal tract is an important barrier preventing ingested substances crossing into systemic circulation. Initial results indicate that soluble mediators released upon low-level injury to liver cells may enhance the initial injury by damaging the cells which form the GI tract. These adverse effects were not seen in conventional single-organ tests.

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

Body-on-a-chip simulation with gastrointestinal tract and liver tissues suggests that ingested nanoparticles have the potential to cause liver injury by Mandy B. Esch, Gretchen J. Mahler, Tracy Stokol, and Michael L. Shuler. Lab Chip, 2014,14, 3081-3092 DOI: 10.1039/C4LC00371C First published online 27 Jun 2014

This paper is open access until Aug. 12, 2014.

While this research is deeply concerning, it should be noted the researchers are being very careful in their conclusions as per Ju’s article, “It’s unclear exactly what damage is occurring or why, but the results indicate that the nanoparticles must be undergoing changes as they cross the gastrointestinal barrier, and that these alterations may change their toxic potential … Long-term consequences for organs in proximity could be a concern … .”

Corporate influence, nanotechnology regulation, and Friends of the Earth (FoE) Australia

The latest issue of the newsletter, Chain Reaction # 121, July 2014, published by Friends of the Earth (FoE) Australia features an article by Louise Sales ‘Corporate influence over nanotechnology regulation‘ that has given me pause. From the Sales article,

I recently attended an Organisation for Economic Co-operation and Development (OECD) seminar on the risk assessment and risk management of nanomaterials. This was an eye-opening experience that graphically illustrated the extent of corporate influence over nanotechnology regulation globally. Representatives of the chemical companies DuPont and Evonik; the Nanotechnology Industries Association; and the Business and Industry Advisory Committee to the OECD (BIAC) sat alongside representatives of countries such as Australia, the US and Canada and were given equal speaking time.

BIAC gave a presentation on their work with the Canadian and United States Governments to harmonise nanotechnology regulation between the two countries. [US-Canada Regulatory Cooperative Council] [emphasis mine] Repeated reference to the involvement of ‘stakeholders’ prompted me to ask if any NGOs [nongovernmental organizations] were involved in the process. Only in the earlier stages apparently − ‘stakeholders’ basically meant industry.

A representative of the Nanotechnology Industries Association told us about the European NANoREG project they are leading in collaboration with regulators, industry and scientists. This is intended to ‘develop … new testing strategies adapted to innovation requirements’ and to ‘establish a close collaboration among authorities, industry and science leading to efficient and practically applicable risk management approaches’. In other words industry will be helping write the rules.

Interestingly, when I raised concerns about this profound intertwining of government and industry with one of the other NGO representatives they seemed almost dismissive of my concerns. I got the impression that most of the parties concerned thought that this was just the ‘way things were’. As under-resourced regulators struggle with the regulatory challenges posed by nanotechnology − the offer of industry assistance is probably very appealing. And from the rhetoric at the meeting one could be forgiven for thinking that their objectives are very similar − to ensure that their products are safe. Right? Wrong.

I just published an update about the US-Canada Regulatory Cooperation Council (RCC; in  my July 14, 2014 posting) where I noted the RCC has completed its work and final reports are due later this summer. Nowhere in any of the notices is there mention of BIAC’s contribution (whatever it might have been) to this endeavour.

Interestingly. BIAC is not an OECD committee but a separate organization as per its About us page,

BIAC is an independent international business association devoted to advising government policymakers at OECD and related fora on the many diversified issues of globalisation and the world economy.

Officially recognised since its founding in 1962 as being representative of the OECD business community, BIAC promotes the interests of business by engaging, understanding and advising policy makers on a broad range of issues with the overarching objectives of:

  • Positively influencing the direction of OECD policy initiatives;

  • Ensuring business and industry needs are adequately addressed in OECD policy decision instruments (policy advocacy), which influence national legislation;

  • Providing members with timely information on OECD policies and their implications for business and industry.

Through its 38 policy groups, which cover the major aspects of OECD work most relevant to business, BIAC members participate in meetings, global forums and consultations with OECD leadership, government delegates, committees and working groups.

I don’t see any mention of safety either in the excerpt or elsewhere on their About us page.

As Sales notes in her article,

Ultimately corporations have one primary driver and that’s increasing their bottom line.

I do wonder why there doesn’t seem to have been any transparency regarding BIAC’s involvement with the RCC and why no NGOs (according to Sales) were included as stakeholders.

While I sometimes find FoE and its fellow civil society groups a bit shrill and over-vehement at times, It never does to get too complacent. For example, who would have thought that General Motors would ignore safety issues (there were car crashes and fatalities as a consequence) over the apparently miniscule cost of changing an ignition switch. From What is the timeline of the GM recall scandal? on Vox.com,

March 2005: A GM project engineering manager closed the investigation into the faulty switches, noting that they were too costly to fix. In his words: “lead time for all solutions is too long” and “the tooling cost and piece price are too high.” Later emails unearthed by Reuters suggested that the fix would have cost GM 90 cents per car. [emphasis mine]

March 2007: Safety regulators inform GM of the death of Amber Rose, who crashed her Chevrolet Cobalt in 2005 after the ignition switch shut down the car’s electrical system and air bags failed to deploy. Neither the company nor regulators open an investigation.

End of 2013: GM determines that the faulty ignition switch is to blame for at least 31 crashes and 13 deaths.

According to a July 17, 2014 news item on CBC (Canadian Broadcasting Corporation) news online, Mary Barra, CEO of General Motors, has testified on the mater before the US Senate for a 2nd time, this year,

A U.S. Senate panel posed questions to a new set of key players Thursday [July 17, 2014] as it delves deeper into General Motors’ delayed recall of millions of small cars.

An internal report found GM attorneys signed settlements with the families of crash victims but didn’t tell engineers or top executives about mounting problems with ignition switches. It also found that GM’s legal staff acted without urgency.

GM says faulty ignition switches were responsible for at least 13 deaths. It took the company 11 years to recall the cars.

Barra will certainly be asked about how she’s changing a corporate culture that allowed a defect with ignition switches to remain hidden from the car-buying public for 11 years. It will be Barra’s second time testifying before the panel.

H/T ICON (International Council on Nanotechnology) July 16, 2014 news item. Following on the topic of transparency, ICON based at Rice University in Texas (US) has a Sponsors webpage.

An upcoming alternate testing strategies (ATS) for nanomaterials workshop and the quest to reduce animal testing

It’s too late to announce a call for poster abstracts or travel awards but that still leaves the possibility of attending a September 15-16, 2014 Workshop to Explore How a Multiple Models Approach can Advance Risk Analysis of Nanoscale Materials in Washington, DC. In a July 9, 2014 Nanowerk Spotlight article,, Jo Anne Shatkin (President, Vireo Advisors) and Lorraine Sheremeta (Assistant Director, Ingenuity Lab, University of Alberta) tout the workshop in the context of describing new approaches to nanotoxicology research (Note: A link has been removed),

Engineered nanoscale materials (ENM or ‘nanomaterials’) offer the potential to create safer and more effective products through the use of smaller quantities of improved performance materials. Currently nanomaterials are used to improve the performance of life-saving drugs and medical technologies, to make renewable energy more efficient, to make value added products from industrial waste streams, to improve food, packaging, to lightweight materials used in transportation systems, and to improve many of the personal care products that we use every day. Nanomaterial manufacture and use is expected to increase over the coming years and despite the widespread use of nanomaterials in a variety of consumer products, we are only beginning to understand the impacts of these emerging materials on our health and the environment. To this end, the University of Alberta’s Ingenuity Lab is collaborating with the Society for Risk Analysis to evaluate the potential to use alternative test strategies (ATS) to improve our ability to assess nanomaterial toxicity and environmental impact.

Shatkin and Sheremeta describe toxicology tests and explain the importance of refining and improving these tests (from the article),

Standard in vivo toxicology test methods that depend heavily on the use of animals have long been used to assess chemical safety. [emphasis mine*] Existing and novel in vitro and in silico test methods provide important alternatives to in vivo animal testing for chemicals and potentially for ENM. Genotoxicity tests, for example, are used to assess the mutagenic potential of chemicals or nanomaterials in the replication of DNA in cells. Driven in part by increasing market and regulatory requirements for safer and more sustainable products, large international infrastructure has developed for creating, testing and validating in vitro test methods, and its use is expanding to chemical and nanomaterial assessment (NSF, 2007). The goals of reducing, refining and replacing animal testing (the commonly cited ‘three Rs’) – resonate with key and diverse stakeholders including animal rights groups, the bioethics community, the pharmaceutical industry, regulatory agencies and the broader public. [emphasis mine*]

Despite nearly a decade of effort in the conduct toxicology and exposure research to inform the assessment of health and environmental risks of nanomaterials, major gaps remain in the ability to understand and quantify risks. While there is now a large body of published data on carbon nanotubes and metal oxide nanoparticles, concern has been raised that speculation about nanomaterial risk has hardened into an assumption that there are ‘as-yet-to-be-discovered risks’ that we must identify and manage (Maynard, 2014) that demands extensive testing.

The authors describe ATS (alternative test strategies) in greater detail,

ATS approaches are regarded by many to have the potential for rapid screening of large numbers and types of materials. They can include a breadth of techniques including high throughput screening methods (HTS), high content screening, computational approaches, toxicogenomics, cell-based methods, in vitro assays and non-mammalian whole animal models. The emergence of ATS raises questions about how the results of these methods may be used for assessing the potential risks of ENM. For instance, ATS could be used in combination in a multiple models approach to evaluate new ENM in a number of rapid assays and compare with well-studied substances using in vivo testing; thereby identifying ENM for additional testing in a more strategic fashion than is possible through conventional testing approaches.

They also describe the current state of affairs with ATS,

In the United States, the U.S. ToxCast program has, as part of their 21st century toxicity screening program (NRC, 2007), tested 29 NMs with 62 in vitro test methods (Wang et al. 2013). Many researchers, including several from the University of Alberta, have proposed and developed ATS to include a variety of methods, some which are standardized for chemicals, and others which take advantage of developments including advanced biological mechanistic understanding, genomics, metabolomics, automation and informatics. However, these existing as well as emerging ATS have a short history with nanomaterials, and have not yet proven to be reliable for quantitative estimation of ENM risk. Still, several international efforts have developed ATS that have potential to be used for screening purposes, and to guide further testing priorities for regulatory decision making. The goal of the September [2014] workshop by the Society for Risk Analysis is to explore ways in which distinct ATS may be used for screening and prioritizing the need for more extensive testing of novel ENM.

The parties (including the authors of the article) involved in developing this risk workshop are listed, also mentioned are members of the international testing scene,

Lori Sheremeta, the Assistant Director of Ingenuity Lab in Edmonton Alberta and past Chair of the Society for Risk Analysis (SRA) Emerging Nanoscale Materials Specialty Group (ENMSG), is collaborating with U.S.-based nanomaterials risk expert Jo Anne Shatkin (an SRA Councilor and co-founder of the SRA ENMSG), Environment Canada, Health Canada, the SRA ENMSG and others on a Pilot Project with the Organization for Economic Co-operation and Development (OECD) Working Party on Manufactured Nanomaterials (WPMN) to develop a report on the State of the Science for ATS for nanomaterials, catalogue of existing and emerging ATS methods in a database; and develop a case study to inform workshop deliberations and expert recommendations.

There are many international efforts to develop, as well as to validate and standardize, these methods for chemicals, including organizations such as the US National Toxicology Program Interagency Center for the Evaluation of Alternative Toxicological Methods (ICCVAM), the European Union Reference Laboratory European Centre for the Validation of Alternative Methods (EURL ECVAM), the Japanese Center for the Validation of Alternative Methods (JacVAM), the Korean Centre for the Validation of Alternative Methods (KoCVAM) and the OECD. There is wide recognition that the diversity of NMs renders it impractical to use traditional animal testing to evaluate safety, hence there is significant interest in assessing the performance of both existing and emerging alternative testing strategies for NMs. Further, the EU directive REACH (Directive 2006/121/EC) requires replacing in vivo testing, and there is widespread popular agreement about the desire to limit animal testing. Finally, there is a need for more biologically informative toxicology methods (Hartung, 2010; Silbergeld et al, 2011; Landsiedel et al, 2009).

A list of the workshop objectives is offered  in the article,

The main objectives of the workshop are to:

assess the state of the science on HTS and ATS from a ‘multiple models’ perspective to identify areas of common findings from differing approaches, areas of greatest uncertainty, and priorities for follow up in applied research toward risk assessment of ENM;
evaluate the ability to use data from ATS/HTS methods for screening purposes – combining suites of assays and comparing well-studied substances to novel ones;

assess the ability to use a suite of ATS methods to amplify the Weight of Evidence;

characterize uncertainty associated with predictive relationships and propose strategies to address uncertainties;

elicit the perspectives of diverse stakeholders about the use of HTS/ATS for screening purposes in risk analysis of ENM; and

develop a set of recommendations for these alternative approaches to become more widely adopted for environmental, health and safety decision making about ENM across the product life cycle. The output of the workshop holds potential for transformation through risk screening approaches that promote safer and more sustainable material and technology development.

You can find more about the September 15-16, 2014 Workshop to Explore How a Multiple Models Approach can Advance Risk Analysis of Nanoscale Materials in Washington, DC here.

The text in the article is a bit rough. Some of the ideas and topics don’t follow each other logically. So, be prepared to spend a little time reading, Happily, there are references included with the article.

I last mentioned Jo Anne Shatkin here in the context of a 2013 paper on alternative test strategies (ATS) in an Aug. 22, 2013 posting. I think the most recent mention of Lorraine Sheremeta here is in a Jan. 11, 2010 posting about Canada, nanotechnology, and food.

Final note, I am hoping to get some more information about the workshop and ATS scene from Lorraine Sheremeta to be published in a subsequent posting.

* I added the emphases at 0830 hours PDT July 10, 2014.

Fewer silver nanoparticles washed off coated textiles

This time I have two complementary tidbits about silver nanoparticles, their use in textiles, and washing. The first is a June 30, 2014 news item on Nanowerk, with the latest research from Empa (Swiss Federal Laboratories for Materials Science and Technology) on silver nanoparticles being sloughed off textiles when washing them,

The antibacterial properties of silver-coated textiles are popular in the fields of sport and medicine. A team at Empa has now investigated how different silver coatings behave in the washing machine, and they have discovered something important: textiles with nano-coatings release fewer nanoparticles into the washing water than those with normal coatings …

A June 30,  2014 Empa news release, which originated the news item, describes the findings in more detail,

If it contains ‘nano’, it doesn’t primarily leak ‘nano’: at least that’s true for silver-coated textiles, explains Bernd Nowack of the «Technology and Society» division at Empa. During each wash cycle a certain amount of the silver coating is washed out of the textiles and ends up in the waste water. [emphasis mine] Empa analysed this water; it turned out that nano-coated textiles release hardly any nano-particles. That’s quite the opposite to ordinary coatings, where a lot of different silver particles were found. Moreover, nano-coated silver textiles generally lose less silver during washing. This is because considerably less silver is incorporated into textile fabrics with nano-coating, and so it is released in smaller quantities for the antibacterial effect than is the case with ordinary coatings. A surprising result that has a transformative effect on future analyses and on the treatment of silver textiles. «All silver textiles behave in a similar manner – regardless of whether they are nano-coated or conventionally-coated,» says Nowack. This is why nano-textiles should not be subjected to stricter regulation than textiles with conventional silver-coatings, and this is relevant for current discussions concerning possible special regulations for nano-silver.

But what is the significance of silver particles in waste water? Exposed silver reacts with the (small quantities of) sulphur in the air to form silver sulphide, and the same process takes place in the waste water treatment plant. The silver sulphide, which is insoluble, settles at the bottom of the sedimentation tank and is subsequently incinerated with the sewage sludge. So hardly any of the silver from the waste water remains in the environment. Silver is harmless because it is relatively non-toxic for humans. Even if silver particles are released from the textile fabric as a result of strong sweating, they are not absorbed by healthy skin.

I’ve highlighted Nowack’s name as he seems to have changed his opinions since I first wrote about his work with silver nanoparticles in textiles and washing in a Sept. 8, 2010 posting,

“We found that the total released varied considerably from less than 1 to 45 percent of the total nanosilver in the fabric and that most came out during the first wash,” Bernd Nowack, head of the Environmental Risk Assessment and Management Group at the Empa-Swiss Federal Laboratories for Materials Testing and Research, tells Nanowerk. “These results have important implications for the risk assessment of silver textiles and also for environmental fate studies of nanosilver, because they show that under certain conditions relevant to washing, primarily coarse silver-containing particles are released.”

How did the quantity of silver nanoparticles lost in water during washing change from “less than 1 to 45 percent of the total nanosilver in the fabric” in a 2010 study to “Empa analysed this water; it turned out that nano-coated textiles release hardly any nano-particles” in a 2014 study? It would be nice to find out if there was a change in the manufacturing process and whether or not this is global change or one undertaken in Switzerland alone.

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

Presence of Nanoparticles in Wash Water from Conventional Silver and Nano-silver Textiles by Denise M. Mitrano, Elisa Rimmele, Adrian Wichser, Rolf Erni, Murray Height, and Bernd Nowack. ACS Nano, Article ASAP DOI: 10.1021/nn502228w Publication Date (Web): June 18, 2014

Copyright © 2014 American Chemical Society

This paper is behind a paywall.

The second tidbit is from Iran and may help to answer my questions about the Empa research. According to a July 7, 2014 news item on Nanowerk (Note: A link has been removed),

Writing in The Journal of The Textile Institute (“Effect of silver nanoparticles morphologies on antimicrobial properties of cotton fabrics”), researchers from Islamic Azad University in Iran, describe the best arrangement for increasing the antibacterial properties of textile products by studying various structures of silver nanoparticles.

A July 7, 2014 news release from the Iran Nanotechnology Initiative Council (INIC), which originated the news item, provides more details,

By employing the structure presented by the researchers, the amount of nanoparticles stabilization on the fabric and the durability of its antibacterial properties increase after washing and some problems are solved, including the change in the fabric color.

Using the results of this research creates diversity in the application of various structures of nanoparticles in the complementary process of cotton products. Moreover, the color of the fabric does not change as the amount of consumed materials decreases, because the excess use of silver was the cause of this problem. On the other hand, the stability and durability of nanoparticles increase against standard washing. All these facts result in the reduction in production cost and increase the satisfaction of the customers.

The researchers have claimed that in comparison with other structures, hierarchical structure has much better antibacterial activity (more than 91%) even after five sets of standard washing.

This work on morphology would seem to answer my question about the big difference in Nowack’s description of the quantity of silver nanoparticles lost due to washing. I am assuming, of course, that something has changed with regard to the structure and/or shape of the silver nanoparticles coating the textiles used in the Empa research.

Getting back to the work in Iran, here’s a link to and a citation for the paper,

Effect of silver nanoparticles morphologies on antimicrobial properties of cotton fabrics by Mohammad Reza Nateghia & Hamed Hajimirzababa. The Journal of The Textile Institute Volume 105, Issue 8, 2014 pages 806-813 DOI: 10.1080/00405000.2013.855377 Published online: 21 Jan 2014

This paper is behind a paywall.

The relationship between Valyrian steel (from Game of Thrones), Damascus steel, and nuclear nanotechnology

There’s a very interesting June 20, 2014 posting by Charles Day on his Dayside blog (located on the Physics Today website). Day manages to relate the Game of Thrones tv series to nuclear power and nanotechnology,

The military technology of A Song of Ice and Fire, George R. R. Martin’s series of fantasy novels, is medieval with an admixture of the supernatural. Dragons aside, among the most prized weapons are swords made from Valyrian steel, which are lighter, stronger, and sharper than ordinary steel swords.

Like many of the features in the rich world of the novels and their TV adaptation, Game of Thrones, Valyrian steel has a historical inspiration. Sometime before 300 BC, metalworkers in Southern India discovered a way to make small cakes of high-carbon steel known as wootz. Thanks to black wavy bands of Fe3C particles that pervade the metal, wootz steel was already strong. …

Perhaps because the properties of wootz and Damascus steels depended, in part, on a particular kind of iron ore, the ability of metallurgists to make the alloys was lost sometime in the 18th century. In A Song of Ice and Fire, the plot plays out during an era in which making Valyrian steel is a long-lost art.

Martin’s knowledge of metallurgy is perhaps shaky. …

Interestingly, the comments on the blog posting largely concern themselves with whether George RR Martin knows anything about metallurgy. The consensus being that he does and that the problems in the Game of Thrones version of metallurgy lie with the series writers.

I first came across the Damascus steel, wootz, and carbon nanotube story in 2008 and provided a concise description on my Nanotech Mysteries wiki Middle Ages page,

Damascus steel blades were first made in the 8th century CE when they acquired a legendary status as unlike other blades they were able to cut through bone and stone while remaining sharp enough to cut a piece of silk. They were also flexible which meant they didn’t break off easily in a sword fight. The secret for making the blades died (history does not record how) about 1700 CE and there hasn’t been a new blade since.

 The blades were generally made from metal ingots prepared in India using special recipes which probably put just the right amount of carbon and other impurities into the iron. By following these recipes and following specific forging techniques craftsmen ended up making nanotubes … When these blades were nearly finished, blacksmiths would etch them with acid. This brought out the wavy light and dark lines that make Damascus swords easy to recognize.3

 It turns out part of the secret to the blade is nanotechnology. Scientists discovered this by looking at a Damascus steel blade from 1700 under an electron microscope. It seems those unknown smiths were somehow encasing cementite nanowires in carbon nanotubes then forging them into the steel blades giving them their legendary strength and flexibility.

The reference information I used then seems to be no longer available online but there is this more than acceptable alternative, a Sept. 27, 2008 postiing by Ed Yong from his Not Exactly Rocket Science blog (on ScienceBlogs.com; Note: A link has been removed),

In medieval times, crusading Christian knights cut a swathe through the Middle East in an attempt to reclaim Jerusalem from the Muslims. The Muslims in turn cut through the invaders using a very special type of sword, which quickly gained a mythical reputation among the Europeans. These ‘Damascus blades‘ were extraordinarily strong, but still flexible enough to bend from hilt to tip. And they were reputedly so sharp that they could cleave a silk scarf floating to the ground, just as readily as a knight’s body.

They were superlative weapons that gave the Muslims a great advantage, and their blacksmiths carefully guarded the secret to their manufacture. The secret eventually died out in the eighteenth century and no European smith was able to fully reproduce their method.

Two years ago, Marianne Reibold and colleagues from the University of Dresden uncovered the extraordinary secret of Damascus steel – carbon nanotubes. The smiths of old were inadvertently using nanotechnology.

Getting back to Day, he goes on to explain the Damascus/Valyrian steel connection to nuclear power (Note: Links have been removed),

Valyrian and Damascus steels were on my mind earlier this week when I attended a session at TechConnect World on the use of nanotechnology in the nuclear power industry.

Scott Anderson of Lockheed Martin gave the introductory talk. Before the Fukushima disaster, Anderson pointed out, the principal materials science challenge in the nuclear industry lay in extending the lifetime of fuel rods. Now the focus has shifted to accident-tolerant fuels and safer, more durable equipment.

Among the other speakers was MIT’s Ju Li, who described his group’s experiments with incorporating carbon nanotubes (CNTs) in aluminum to boost the metal’s resistance to radiation damage. In a reactor core, neutrons and other ionizing particles penetrate vessels, walls, and other structures, where they knock atoms off lattice sites. The cumulative effect of those displacements is to create voids and other defects that weaken the structures.

Li isn’t sure yet how the CNTs resist irradiation and toughen the aluminum, but at the end of his talk he recalled their appearance in another metal, steel.

In 2006 Peter Paufler of Dresden University of Technology and his collaborators used high-resolution transmission electron microscopy (TEM) to examine the physical and chemical microstructure of a sample of Damascus steel from the 17th century.

The saber from which the sample was taken was forged in Isfahan, Persia, by the famed blacksmith Assad Ullah. As part of their experiment, Paufler and his colleagues washed the sample in hydrochloric acid to remove Fe3C particles. A second look with TEM revealed the presence of CNTs.

There’s still active interest in researching Damascus steel blades as not all the secrets behind the blade’s extraordinary qualities have been revealed yet. There is a March 13, 2014 posting here which describes a research project where Chinese researchers are attempting (using computational software) to uncover the reason for the blade’s unique patterns,

It seems that while researchers were able to answer some questions about the blade’s qualities, researchers in China believe they may have answered the question about the blade’s unique patterns, from a March 12, 2014 news release on EurekAlert,

Blacksmiths and metallurgists in the West have been puzzled for centuries as to how the unique patterns on the famous Damascus steel blades were formed. Different mechanisms for the formation of the patterns and many methods for making the swords have been suggested and attempted, but none has produced blades with patterns matching those of the Damascus swords in the museums. The debate over the mechanism of formation of the Damascus patterns is still ongoing today. Using modern metallurgical computational software (Thermo-Calc, Stockholm, Sweden), Professor Haiwen Luo of the Central Iron and Steel Research Institute in Beijing, together with his collaborator, have analyzed the relevant published data relevant to the Damascus blades, and present a new explanation that is different from other proposed mechanisms.

At the time the researchers were hoping to have someone donate a piece of genuine Damascus steel blade. From my March 13, 2014 posting,

Note from the authors: It would be much appreciated if anyone would like to donate a piece of genuine Damascus blade for our research.

Corresponding Author:

LUO Haiwen
Email: [email protected]

Perhaps researchers will manage to solve the puzzle of how medieval craftsman were once able to create extraordinary steel blades.

Tech worries: nanotechnology and nickel on Slate

Dr. Andrew Maynard’s May 20, 2014 article (Small Packages; A new case study on the health risks of nanotech doesn’t tell the whole story) for Slate magazine does much to calm any fears there might be in the wake of a recent case study about the consequences of handling nickel nanoparticles in the workplace,

… The report describes a chemist who developed symptoms that included throat irritation, nasal congestion, facial flushing, and skin reactions to jewelry containing nickel, after starting to work with a powder consisting of nanometer-sized nickel particles. According to the report’s lead author, this is “case one in our modern economy” of exposure to a product of nanotechnology leading to an individual becoming ill.

… And this is why the case of the nickel nanoparticles above needs to be approached with some caution. Many people have an allergic skin reaction to nickel, and research has shown that inhaling nickel particles can cause people to become sensitized to the metal. It’s also well known that fine powders will become airborne more easily than coarse ones when they’re handled, and that the finer the powder you inhale, the more potent it is in your lungs. So it shouldn’t come as a surprise that handling nickel nanopowder in an open lab without exposure controls is not a great idea. In other words, the reported incident was more a case of bad exposure management than nanoparticle risk.

That said, the case does highlight the level of respect with which any new or unusual material should be treated. …

Reinforcing Andrew’s comments about nickel sensitivities, there’s a recent report about smartphones and metal sensitivities. From a May 21, 2014 article by Sarah Knapton for The Telegraph (UK), Note: A link has been removed,

If you have ever noticed swelling, redness, itching or blistering near your cheekbones, ears, jaw or hands, you may be allergic to your phone.

A new study suggests the nickel, chromium and cobalt found in common phones made by BlackBerry, Samsung and LG among others, can cause skin irritations.

Danish and US researchers found at least 37 incidents since 2000 where contact dermatitis was caused by mobile phones.

Here are links to and citations for the nickel case study and to the smartphone paper,

Occupational handling of nickel nanoparticles: A case report by W. Shane Journeay, MD, and Rose H. Goldman, MD. American Journal of Industrial Medicine Article first published online: 8 MAY 2014 DOI: 10.1002/ajim.22344

Mobile Phone Dermatitis in Children and Adults: A Review of the Literature by Clare Richardson, Carsten R. Hamann, Dathan Hamann, and Jacob P. Thyssen. Pediatric Allergy, Immunology, and Pulmonology. Online Ahead of Print: March 5, 2014. doi:10.1089/ped.2013.0308.

The nickel paper is behind a paywall and the smartphone paper is open access.

One comment, the smartphone literature search yielded a small sample, on the other hand, if there isn’t category for the problem, it might not get into reports and be studied.

Getting back to Andrew’s article, it is illuminating and frustratingly opaque (perhaps there was an editing issue?),

Over a couple of days in London last summer, I found myself mulling over a very similar question with a small group of colleagues. We were a pretty eclectic group—engineers, designers, toxicologists, business leaders, academics, policy wonks—but we had one thing in common: We wanted get a better handle on how dangerous realistic products of nanotechnology might be, and how these dangers might be avoided.

… Our approach was to imagine products based on engineered nanomaterials that were technologically feasible and would also have a reasonable chance of surviving a cut-throat economy—products like active food packaging labels that indicated the presence of contaminants; helium-filled balloons with solar cell skins; and materials templated from viruses to generate hydrogen and oxygen from water. We then tried to imagine how these plausible products could potentially release dangerous materials into the environment.

To our surprise, we struggled to come up with scenarios that scared us.

It sounds like this session was organized as a think tank. It would have been nice to know who organized it, who were their invitees, and what was their expertise. On that note, there is this about Andrew at the end of the Slate article,

Andrew Maynard is a leading expert on the responsible development and use of emerging technologies and is the director of the U-M [University of Michigan] Risk Science Center.

Having stumbled across Andrew many times over the years within the ‘nano blogosphere’ and having him kindly answer my amateurish questions about reading research, I feel  confidence when reading his opinion pieces that he is well informed and has carefully considered not only questions I might ask but others as well.

While I might like to know more about that 2013 think tank session in London (UK), this section towards the end of the piece suggests that Andrew has not, in an excess of enthusiasm, thrown in his lot with some hype happy group,

… the case [nickel inhalation] does highlight the level of respect with which any new or unusual material should be treated. This was also one of the conclusions from those two days in London. Just because the risks of many nanotechnology products seem relatively small, doesn’t mean that we can afford to be complacent. There’s still the possibility that someone will create a particularly dangerous new material, or will use a material that seems safe in a dangerous way. As a society we need to be vigilant when it comes to advanced materials, whether they are branded with the nano insignia or not.

As for Knapton article and smartphone research, I haven’t come to any particular conclusions but I am going to keep an eye out for evidence, anecdotal or otherwise. A friend of mine, who sometimes suffers from skin sensitivities, just switched over to her first Blackberry.

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.