Dunkin' Donuts ditches nano titanium dioxide - but is it actually harmful?

In response to pressure from the advocacy group As You Sow, Dunkin’ Brands has announced that it will be removing allegedly “nano” titanium dioxide from Dunkin’ Donuts’ powdered sugar donuts. As You Sow claims there are safety concerns around the use of the material, while Dunkin’ Brands cites concerns over investor confidence. It’s a move that further confirms the food sector’s conservatism over adopting new technologies in the face of public uncertainty. But how justified is it based on what we know about the safety of nanoparticles? donuts
Titanium dioxide (which isn’t the same thing as the metal titanium) is an inert, insoluble material that’s used as a whitener in everything from paper and paint to plastics. It’s the active ingredient in many mineral-based sunscreens. And as a pigment, is also used to make food products look more appealing.

Part of the appeal to food producers is that titanium dioxide is a pretty dull chemical. It doesn’t dissolve in water. It isn’t particularly reactive. It isn’t easily absorbed into the body from food. And it doesn’t seem to cause adverse health problems. It just seems to do what manufacturers want it to do – make food look better. It’s what makes the powdered sugar coating on donuts appear so dense and snow white. Titanium dioxide gives it a boost.


And you’ve probably been consuming it for years without knowing. In the US, the Food and Drug Administration allows food products to contain up to 1% food-grade titanium dioxide without the need to include it on the ingredient label. Help yourself to a slice of bread, a bar of chocolate, a spoonful of mayonnaise or a donut, and chances are you’ll be eating a small amount of the substance ("Titanium Dioxide Nanoparticles in Food and Personal Care Products").


Why does As You Sow want this substance gone from Dunkin' Donuts? The answer in part comes from the little prefix “nano.” For some years now, researchers have recognized that some powders become more toxic the smaller the individual particles are, and titanium dioxide is no exception . Pigment grade titanium dioxide – the stuff typically used in consumer products and food – contains particles around 200 nanometers in diameter, or around one five hundredth the width of a human hair. Inhale large quantities of these titanium dioxide particles (I’m thinking “can’t see your hand in front of your face” quantities), and your lungs would begin to feel it. If the particles are smaller though, it takes much less material to cause the same effect. But you’d still need to inhale very large quantities of the material for it to be harmful. And while eating a powdered donut can certainly be messy, it’s highly unlikely that you’re going to end up stuck in a cloud of titanium dioxide-tinted powdered sugar coating! This is the “nano” effect, where some particles smaller than 100 nanometers seem to be more “potent” – or capable of doing more damage in the body – than larger particles of the same material. It’s an effect that is particularly clear when particles like titanium dioxide deposit in the lungs. But it can also occur elsewhere in the body. Depending on what they are made of and what shape they are, research has shown that some nanoparticles are capable of getting to parts of the body that are inaccessible to larger particles. And some particles are more chemically reactive because of their small size. Some may cause unexpected harm simply because they are small enough to throw a nano-wrench into the nano-workings of your cells ("ARTIKEL"). This body of research is why organizations like As You Sow have been advocating caution in using nanoparticles in products without appropriate testing – especially in food. But the science about nanoparticles isn’t as straightforward as it seems. First of all, particles of the same size but made of different materials can behave in radically different ways. Assuming one type of nanoparticle is potentially harmful because of what another type does is the equivalent of avoiding apples because you’re allergic to oysters. Food grade titanium dioxide is really common and not so “nano” The titanium dioxide used by Dunkin’ Brands and many other food producers is not a new material, and it’s not really a “nanomaterial” either. Nanoparticles are typically smaller than 100 nanometers in diameter. Yet most of the particles in food grade titanium dioxide are larger than this. They have to be for the powder to be of any use in food products. Admittedly food grade titanium dioxide does contain a few nanoparticles, and this shouldn’t be dismissed. A 2012 study out of Paul Westerhoff’s lab at Arizona State University tested 89 off-the-shelf food products for the presence of titanium dioxide ("Titanium Dioxide Nanoparticles in Food and Personal Care Products"). The list included everything from gum and soy milk, to Twinkies and mayonnaise. As well as finding evidence for the substance in every product, the research also indicated that up to 5% of the titanium dioxide in some of these products could be in the form of nanoparticles. Yet there is little evidence that this small quantity of nanoparticles skews the safety of food grade titanium dioxide. In 2004 the European Food Safety Agency carried out a comprehensive safety review of the material. After considering the available evidence on the same materials that are currently being used in products like Dunkin’ Donuts, the review panel concluded that there no evidence for safety concerns. Most research on titanium dioxide nanoparticles has been carried out on ones that are inhaled, not ones we eat. Yet nanoparticles in the gut are a very different proposition to those that are breathed in. Studies into the impacts of ingested nanoparticles are still in their infancy, and more research is definitely needed. Early indications are that the gastrointestinal tract is pretty good at handling small quantities of these fine particles. This stands to reason given the naturally occurring nanoparticles we inadvertently eat every day, from charred foods and soil residue on veggies and salad, to more esoteric products such as clay-baked potatoes. There’s even evidence that nanoparticles occur naturally inside the gastrointestinal tract. Could there be a risk from titanium dioxide that we don’t know about yet? There’s a small possibility that we haven’t been looking in the right places when it comes to possible health issues. Maybe – just maybe – there could be long term health problems from this seemingly ubiquitous diet of small, insoluble particles that we just haven’t spotted yet. It’s the sort of question that scientists love to ask, because it opens up new avenues of research. It doesn’t mean that there is an issue, just that there is sufficient wiggle room in what we don’t know to ask interesting questions. It’s questions like this that are driving current toxicology research on nanoparticles. While there is no evidence of a causal association between titanium dioxide in food and ill health, some studies – but not all by any means – suggest that large quantities of titanium dioxide nanoparticles can cause harm if they get to specific parts of the body. For instance, there are a growing number of published studies that indicate nanometer sized titanium dioxide particles may cause DNA damage at high concentrations if it can get into cells . But while these studies demonstrate the potential for harm to occur, they lack information on how much material is needed, and under what conditions, for significant harm. And they tend to be associated with much larger quantities of material than anyone is likely to be ingesting on a regular basis. They are also counterbalanced by studies that show no effects, indicating that there is still considerable uncertainty over the toxicity or otherwise of the material ("Titanium dioxide nanoparticles: a review of current toxicological data"). It’s as if we’ve just discovered that paper can cause cuts, but we’re not sure yet whether this is a minor inconvenience or potentially life threatening. In the case of nanoscale titanium dioxide, it’s the classic case of “more research is needed.” Uncertainties like this – small as they are – are magnified when the perceived gains are low, which is why Dunkin’ Brands is reformulating its donut coating. They claim to be able to recreate the same visual effect without the titanium dioxide. Other opacity additives are available, although in this case Dunkin' Brands aren’t replacing the titanium dioxide with anything else. If substitutes are used however, there needs to be thorough safety testing if these alternative additives are to find favor. And this gets to the crux of the issue raised by Dunkin' Brands' decision – when there’s uncertainty around the science, how can food companies make smart decisions that don’t come back to bite them, either in the board room or in the court of public opinion?
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U.S. National Nanotechnology Initiative 2016 funding brings total to $22 billion

The President's Budget for Fiscal Year 2016 provides $1.5 billion for the National Nanotechnology Initiative (NNI), a continued Federal investment in support of the President's priorities and innovation strategy. Cumulatively totaling more than $22 billion since the inception of the NNI in 2001, this funding reflects nanotechnology's potential to significantly improve our fundamental understanding and control of matter at the nanoscale and to translate that knowledge into solutions for critical national needs. 2016 National Nanotechnology Initiative PCA Chart This is pie chart showing NNI Program Component Areas. (Image: NNCO) Nearly half of the requested budget is dedicated to applications-focused R&D and support for the Nanotechnology Signature Initiatives (NSIs), reflecting an increased emphasis within the NNI on accelerating the transition of nanotechnology-based discoveries from lab to market. The NSIs are multiagency initiatives designed to accelerate innovation in areas of national priority through enhanced interagency coordination and collaboration. Furthermore, the NNI has continued to grow its hallmark environmental, health, and safety (EHS) activities, which now account for more than 10% of the NNI's total budget (7% in dedicated EHS investments, plus approximately 3% in additional EHS-related investments within the NSIs). "Right now, the NNI is focused on innovations that support national priorities, while maintaining a strong foundation of fundamental research in nanoscience," says Dr. Michael Meador, Director of the National Nanotechnology Coordination Office. "Our goal is to create an environment to foster technology transfer and new applications today, while supporting the basic research that will provide a continuing pipeline of new discoveries to enable future revolutionary applications tomorrow." The President's 2016 Budget supports nanoscale science, engineering, and technology R&D at 11 agencies; another 9 agencies have nanotechnology-related mission interests or regulatory responsibilities. The NNI Supplement to the President's 2016 Budget documents activities of these agencies in addressing the goals and objectives of the NNI. To view the full document, visit http://1.usa.gov/1b3VPNm (pdf).
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New metal-organic framework material captures carbon at half the energy cost

UC Berkeley chemists have made a major leap forward in carbon-capture technology with a material that can efficiently remove carbon from the ambient air of a submarine as readily as from the polluted emissions of a coal-fired power plant. The material then releases the carbon dioxide at lower temperatures than current carbon-capture materials, potentially cutting by half or more the energy currently consumed in the process. The released CO2 can then be injected underground, a technique called sequestering, or, in the case of a submarine, expelled into the sea. "Carbon dioxide is 15 percent of the gas coming off a power plant, so a carbon-capture unit is going to be big," said senior author Jeffrey Long, a UC Berkeley professor of chemistry and faculty senior scientist at Lawrence Berkeley National Laboratory. "With these new materials, that unit could be much smaller, making the capital costs drop tremendously as well as the operating costs." The material, a metal-organic framework (MOF) modified with nitrogen compounds called diamines, can be tuned to remove carbon dioxide from the room-temperature air of a submarine, for example, or the 100-degree (Fahrenheit) flue gases from a power plant. "It would work great on something like the International Space Station," Long said. Diamine-Appended Metal-Organic Frameworks The diamine-appended metal-organic framework before and after binding of carbon dioxide. The view is a cross section through one of the pores of the MOF, showing diamine molecules (containing blue nitrogen atoms) attached to metal (manganese) atoms (green). Carbon dioxide molecules (grey carbon atoms with two red oxygen atoms) bind through a cooperative mechanism akin to a chain reaction along the pore surfaces. Some H atoms (white) are omitted for clarity. (Graphic by Thomas McDonald, Jarad Mason, Jeffrey Long/UC Berkeley) Though power plants are not now required to capture carbon dioxide from their emissions, it will eventually be necessary in order to slow the pace of climate change caused by fossil-fuel burning. If the planet's CO2 levels rise much higher than they are today, it may even be necessary to remove CO2 directly from the atmosphere to make the planet livable. Long and his colleagues describe how the new materials -- diamine-appended MOFs -- work in this week's issue of the journal ("Cooperative insertion of CO2 in diamine-appended metal-organic frameworks"). From flue gas to submarines Power plants that capture CO2 today use an old technology whereby flue gases are bubbled through organic amines in water, where the carbon dioxide binds to amines. The liquid is then heated to 120-150 degrees Celsius (250-300 degrees Fahrenheit) to release the gas, after which the liquids are reused. The entire process is expensive: it consumes about 30 percent of the power generated, while sequestering underground costs an additional though small fraction of that. The new diamine-appended MOFs can capture carbon dioxide at various temperatures, depending on how the diamines are synthesized, and releases the CO2 at only 50 C above the temperature at which CO2 binds, instead of the increase of 80-110 C required for aqueous liquid amines. Because MOFs are solid, the process also saves the huge energy costs of heating the water in which amines are dissolved. MOFs are composites of metals -- in this case, magnesium or manganese -- with organic compounds that, together, form a porous structure with microscopic, parallel channels. Several years ago, Long and his lab colleagues developed a way to attach amines to the metals in an MOF to produce pores of sufficient diameter to allow CO2 to penetrate rapidly into the material. They found that MOFs with attached diamines are very different from other carbon-capture materials, in that the CO2 seems to load into the material very quickly at a specific temperature and pressure, then come out quickly when the temperature is raised by 50 C. In the new paper, UC Berkeley graduate students Thomas McDonald and Jarad Mason, together with other co-workers, describe how this works. "This material is unique in that it binds CO2 in a cooperative mechanism," Long said. "When the first CO2 starts to adsorb at a very specific pressure, all of a sudden it facilitates more CO2 adsorption, and the MOF rapidly saturates. That is really a different property from any other CO2 adsorbent based on amines. "Then," he added, "if you raise the temperature by applying heat, at some temperature all the CO2 will come flooding off." Long's team found that the diamines bind to the metal atoms of the MOF and then react with CO2 to form metal-bound ammonium carbamate species that completely line the interior channels of the MOF. At a sufficiently high pressure, one CO2 molecule binding to an amine helps other CO2 molecules bind next door, catalyzing a chain reaction as CO2polymerizes with diamine like a zipper running down the channel. Increasing the temperature by 50 degrees Celsius makes the reaction reverse just as quickly. The pressure at which CO2 binds to the amines can be adjusted by changing the metal in the MOF. Long has already shown that some diamine-appended MOFs can bind CO2 at room temperature and CO2 levels as low as 300 parts per million. The current atmospheric concentration of CO2 is now 400 parts per million (ppm), and policy-makers in many countries hope to reduce this below 350 ppm to avoid the most severe impacts of climate change, from increasingly severe weather events and sea level rise to global average temperature increases of 10 degrees Fahrenheit. 'We got lucky' Last summer, Long co-founded a startup, Mosaic Materials, to use the new technology to radically reduce the cost of chemical separations, with plans in the works for a pilot study of CO2 separation from power plant emissions. This would involve creating columns containing millimeter-size pellets made by compressing a crystalline powder of MOFs. "We're also hoping to develop something that might be tested in a submarine," Long said. That would pave the way for eventual scale-up to capturing CO2 from natural gas plants, which produce emissions containing about 5 percent CO2, to the higher concentrations of coal-fired power plants. "We got lucky," he said. "We were just trying to find a simple way to attach these amines to our MOF surface, because they are one of the best compounds for selectively binding CO2 in the presence of water, which can be a problem in flue gas. And it just happens we got the right length in the amine to make these one-dimensional chains that bind CO2in a cooperative manner." Long suggested as well that the findings may have relevance for the fixation of CO2 by plants, owing to striking structural similarities between the magnesium-based MOF and the naturally occurring CO2-fixing photosynthetic enzyme RuBisCO.
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