Tag Archives: titanium dioxide nanoparticles

Methylene Blue-based sunscreen—anti-aging and coral reef safe

In any event, it’s time to start thinking about sunscreens (for those of us in the Northern Hemisphere.) One other thing, this is informational; it is not an endorsement. A March 1, 2022 Mblue Labs product announcement on EurekAlert (also on EIN Presswire) describes some of the research that went into this new sunscreen,

(Bethesda, MD – March 1, 2022) Mblue Labs releases the first sunscreen based on a recent study that found Methylene Blue, a century old medicine, to be  a highly effective, broad-spectrum UV irradiation protector that absorbs UVA and UVB, repairs ROS (Free Radicals) and UV irradiation induced DNA damages, and is safe for coral reefs. The research paper, “Ultraviolet radiation protection potentials of Methylene Blue for human skin and coral reef health ” was published in Nature’s Scientific Reports (5/28/2021) https://www.nature.com/articles/s41598-021-89970-2 [open access].

80% of today’s sunscreens use Oxybenzone as a chemical UV blocker, despite multiple studies that have shown it expedites the destruction of coral reefs. Several states and countries have now banned the use of Oxybenzone and its derivatives to stop the devastating effects on the world’s marine ecosystem. In addition, consumers focus primarily on the Sun Protection Factor (SPF) to prevent sunburns and potentially dangerous long-term health issues. However, SPF only measures UVB exposure, leaving sunscreen users vulnerable to UVA-triggered oxidative stress and photo-aging.

Our peer-reviewed study demonstrates that Methylene Blue is an effective UV blocker with a number of highly desired characteristics as a novel ingredient to be included in sunscreens. It shows a broad spectrum absorption of both UVA and UVB rays, promotes DNA damage repair, combats reactive oxygen species (ROS) induced by UVA, and most importantly, poses no harm to coral reefs.” says the study’s senior author Dr. Kan Cao, Founder of Mblue Labs, Bluelene Skincare and a Professor at the University of Maryland Department of Cell Biology and Molecular Genetics.

Mblue Labs and the University of Maryland have a pending patent on the property of Methylene Blue as an effective UV blocking agent that also delays skin aging and promotes DNA damage repair. The company’s first anti-aging sunscreen called “Bluevado SunFix”, contains the FDA approved, safe active ingredients Zinc Oxide and Titanium Dioxide, together with an optimized dosage of Methylene Blue. 

“Our Vision for this novel multifunctionsunscreen is deeply rooted in our concern for coral reefs – the rainforest of the ocean. We look forward to working with the industry and the FDA to get Methylene Blue included in the sunscreen monograph. We are confident that Bluevado SunFix not only delivers broad spectrum UVB/UVA protection and post sun repair, but also provides the full anti-aging benefits of our Bluelene Moisturizer with the same cosmetic elegance.”  says Jasmin EL Kordi, CEO Mblue Labs.

This research was supported by a National Science Foundation (NSF) Small Business Technology Transfer Grant (Grant: 1842745). This press release does not necessarily represent the views of the NSF. This study was conducted jointly by researchers at Mblue Labs and the University of Maryland.

About Mblue Labs + Bluelene

MBlue Labs provides revolutionary anti-aging technology to consumers around the world.  The company’s clinical skincare brand Bluelene uses patented ingredient Methylene Blue to repair and protect skin on the mitochondrial level. Mblue Labs’ recent research demonstrates Methylene Blue as the new retinol challenger for anti-aging treatments, in addition to its exciting properties as a new UV sunscreen.

I went looking for the new sunscreen (Bluevado SunFix) and found this,

$58.00

Bluevado SunFix is the first FDA-approved anti-aging sunscreen with Methylene Blue. Methylene Blue’s unique ability to promote skin cell health, repair/delay skin aging and protect against UVA and UVB radiation, is now captured in the bravado of this revolutionary SPF Day Cream.

Our innovative formulation blends Methylene Blue with proven minerals to outperform Oxybenzone, deliver cosmetic elegance, and protect our precious coral reefs from harmful substances. 

Methylene Blue is a preferred alternative to retinol for sensitive skin sufferers and with SunFix there is no retinol sun sensitivity.

Bluevado SunFix is proudly made in the USA and is formulated for ALL skin types.

Preorder now to reserve your SunFix. First shipments are available in mid-March [2022].

Application:

Use as a daily SPF Moisturizer. For sun protection apply 15mins before sun exposure and reapply after 40 minutes of swimming or sweating.

Benefits:

Broad-spectrum UVA/UVB sun protection 

Prevents pre-mature aging 

Repairs photo-aging DNA damage caused by UVA exposure

Reduces fine lines, crows feet, and wrinkles

Improves skin elasticity & firmness

Provides all-day skin hydration

Protects coral reefs

Free USPS shipping for all domestic orders over $34!

Ingredients:

Active Ingredients: Zinc Oxide 8.2%, Titanium Dioxide 2.8%   

Inactive Ingredients: Water (Aqua), Caprylic/Capric Triglyceride, C13-15 Alkane, Cetearyl Alcohol, Glycerin, Oryza Sativa (Rice) Bran Oil, Heptyl Undecylenate, Cetyl Alcohol, Argania Spinosa (Argan) Kernel Oil, Tocopheryl Acetate, Glyceryl Stearate, PEG-100 Stearate, Capryloyl Glycerin/Sebacic Acid Copolymer, Sorbitan Laurate, Butyrospermum Parkii (Shea) Butter, Cocos Nucifera (Coconut) Oil, Bisabolol, Xanthan Gum, Polyhydroxystearic Acid, Jojoba Esters, Polysorbate 60, Ascorbyl Palmitate, Citrus Aurantium Bergamia (Bergamot) Peel Oil, Pelargonium Graveolens (Geranium) Leaf Oil, Citrus Grandis (Grapefruit) Peel Oil, Lavandula Angustifolia (Lavender) Oil, Phenoxyethanol, Caprylyl Glycol, Methylene Blue. [emphasis mine]

Caution: For external use only. Keep out of reach of children. In case of irritation or allergic reaction, discontinue use and consult your physician.

There’s 3 fl oz or 90 mL of product in the tube and it’s SPF 21. (If memory serves, Methylene Blue’s placement at the end of the list ingredients means that it’s the ingredient that weighs the least.)

Again, I am not endorsing this product. That said, it does look interesting.

Caption: Corals exposed to Methylene Blue remain healthy. Credit: Mblue Labs

BTW, Finding a product announcement on EurekAlert (online science news service sponsored by the American Association for the Advancement of Science [AAAS]) was a little unexpected but only because I was ignorant of their Content Eligibility Guidelines (scroll down to Business Announcements). Duly noted.

Oxygen-deficient nanotitania (titanium dioxide nanoparticles) for whiter teeth without the damage

A September 8, 2021 news item on phys.org announces research that could make the process of whitening teeth safer,

Most people would like to flash a smile of pearly whites, but over time teeth can become stained by foods, beverages and some medications. Unfortunately, the high levels of hydrogen peroxide in dentists’ bleaching treatments can damage enamel and cause tooth sensitivity and gum irritation. Now, researchers reporting in ACS Applied Materials & Interfaces have developed a gel that, when exposed to near infrared (NIR) light, safely whitens teeth without the burn.

Caption: A new bleaching gel whitened tooth samples by six shades, using a low level of hydrogen peroxide (12%). Credit: Adapted from ACS Applied Materials & Interfaces 2021, DOI: 10.1021/acsami.1c06774

A September 8, 2021Amercian Chemical Society (ACS) news release (also on EurekAlert), which originated the news item, provides more detail,

The growing demand for selfie-ready smiles has made tooth whitening one of the most popular dental procedures. Treatments at a dentist’s office are effective, but they use high-concentration hydrogen peroxide (30–40%). Home bleaching products contain less peroxide (6–12%), but they usually require weeks of treatment and don’t work as well. When a bleaching gel is applied to teeth, hydrogen peroxide and peroxide-derived reactive oxygen species (mainly the hydroxyl radical) degrade pigments in stains. The hydroxyl radical is much better at doing this than hydrogen peroxide itself, so researchers have tried to improve the bleaching capacity of low-concentration hydrogen peroxide by boosting the generation of powerful hydroxyl radicals. Because previous approaches have had limitations, Xingyu Hu, Li Xie, Weidong Tian and colleagues wanted to develop a safe, effective whitening gel containing a catalyst that, when exposed to NIR light, would convert low levels of hydrogen peroxide into abundant hydroxyl radicals.

The researchers made oxygen-deficient titania nanoparticles that catalyzed hydroxyl radical production from hydrogen peroxide. Exposing the nanoparticles to NIR light increased their catalytic activity, allowing them to completely bleach tooth samples stained with orange dye, tea or red dye within 2 hours. Then, the researchers made a gel containing the nanoparticles, a carbomer gel and 12% hydrogen peroxide. They applied it to naturally stained tooth samples and treated them with NIR light for an hour. The gel bleached teeth just as well as a popular tooth whitening gel containing 40% hydrogen peroxide, with less damage to enamel. The nanoparticle system is highly promising for tooth bleaching and could also be extended to other biomedical applications, such as developing antibacterial materials, the researchers say.

The authors acknowledge funding from the National Natural Science Foundation of China, the National Key R&D Program of China and the Key Technologies R&D Program of Sichuan Province.

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

Photothermal-Enhanced Fenton-like Catalytic Activity of Oxygen-Deficient Nanotitania for Efficient and Safe Tooth Whitening by Xingyu Hu, Li Xie, Zhaoyu Xu, Suru Liu, Xinzhi Tan, Ruojing Qian, Ruitao Zhang, Mingyan Jiang, Wenjia Xie, and Weidong Tian. ACS Appl. Mater. Interfaces 2021, 13, 30, 35315–35327 Publication Date: July 22, 2021 DOI: https://doi.org/10.1021/acsami.1c06774 Copyright © 2021 American Chemical Society

This paper is behind a paywall.

Converting carbon dioxide into fuel with blinking nanocrystals

A July 16, 2020 news item on Nanowerk announces some work from Rutgers University (New Jersey, US) where carbon dioxide could one day be converted into fuel or perhaps be used in quantum computers,

Imagine tiny crystals that “blink” like fireflies and can convert carbon dioxide, a key cause of climate change, into fuels.

A Rutgers-led team has created ultra-small titanium dioxide crystals that exhibit unusual “blinking” behavior and may help to produce methane and other fuels, according to a study in the journal Angewandte Chemie (“A Blinking Mesoporous TiO2-x Composed of Nanosized Anatase with Unusually Long-Lived Trapped Charge Carriers”).

The crystals, also known as nanoparticles, stay charged for a long time and could benefit efforts to develop quantum computers.

I don’t think I have the imagination necessary for this image, which illustrates the work according to the researchers,

The arrows point to titanium dioxide nanocrystals lighting up and blinking (left) and then fading (right). Images: Tewodros Asefa and Eliska Mikmekova

A July 16, 2020 Rutgers University news release (also on EurekAlert), which originated the news item, delves further into the topic,

“Our findings are quite important and intriguing in a number of ways, and more research is needed to understand how these exotic crystals work and to fulfill their potential,” said senior author Tewodros (Teddy) Asefa, a professor in the Department of Chemistry and Chemical Biology in the School of Arts and Sciences at Rutgers University-New Brunswick [in New Jersey]. He’s also a professor in the Department of Chemical and Biochemical Engineering in the School of Engineering.

More than 10 million metric tons of titanium dioxide are produced annually, making it one of the most widely used materials, the study notes. It is used in sunscreens, paints, cosmetics and varnishes, for example. It’s also used in the paper and pulp, plastic, fiber, rubber, food, glass and ceramic industries.

The team of scientists and engineers discovered a new way to make extremely small titanium dioxide crystals. While it’s still unclear why the engineered crystals blink and research is ongoing, the “blinking” is believed to arise from single electrons trapped on titanium dioxide nanoparticles. At room temperature, electrons – surprisingly – stay trapped on nanoparticles for tens of seconds before escaping and then become trapped again and again in a continuous cycle.

The crystals, which blink when exposed to a beam of electrons, could be useful for environmental cleanups, sensors, electronic devices and solar cells, and the research team will further explore their capabilities.

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

A Blinking Mesoporous TiO2−x Composed of Nanosized Anatase with Unusually Long‐Lived Trapped Charge Carriers by Dr. Tao Zhang, Dr. Jingxiang Low, Prof. Jiaguo Yu, Dr. Alexei M. Tyryshkin, Dr. Eliška Mikmeková, Prof. Tewodros Asefa. Angewandte Chemie DOI: https://doi.org/10.1002/anie.202005143 First published [online]: 22 May 2020

This paper is behind a paywall.

Sunscreens 2020 and the Environmental Working Group (EWG)

There must be some sweet satisfaction or perhaps it’s better described as relief for the Environmental Working Group (EWG) now that sunscreens with metallic (zinc oxide and/or titanium dioxide) nanoparticles are gaining wide acceptance. (More about the history and politics EWG and metallic nanoparticles at the end of this posting.)

This acceptance has happened alongside growing concerns about oxybenzone, a sunscreen ingredient that EWG has long warned against. Oxybenzone has been banned from use in Hawaii due to environmental concerns (see my July 6, 2018 posting; scroll down about 40% of the way for specifics about Hawaii). Also, it is one of the common sunscreen ingredients for which the US Food and Drug Administration (FDA) is completing a safety review.

Today, zinc oxide and titanium dioxide metallic nanoparticles are being called minerals, as in, “mineral-based” sunscreens. They are categorized as physical sunscreens as opposed to chemical sunscreens.

I believe the most recent sunscreen posting here was my 2018 update (uly 6, 2018 posting) so the topic is overdue for some attention here. From a May 21, 2020 EWG news release (received via email),

As states reopen and Americans leave their homes to venture outside, it’s important for them to remember to protect their skin from the sun’s harmful rays. Today the Environmental Working Group released its 14th annual Guide to Sunscreens.  

This year researchers rated the safety and efficacy of more than 1,300 SPF products – including sunscreens, moisturizers and lip balms – and found that only 25 percent offer adequate protection and do not contain worrisome ingredients such as oxybenzone, a potential hormone-disrupting chemical that is readily absorbed by the body.

Despite a delay in finalizing rules that would make all sunscreens on U.S. store shelves safer, the Food and Drug Administration, the agency that governs sunscreen safety, is completing tests that highlight concerns with common sunscreen ingredients. Last year, the agency published two studies showing that, with just a single application, six commonly used chemical active ingredients, including oxybenzone, are readily absorbed through the skin and could be detected in our bodies at levels that could cause harm.

“It’s quite concerning,” said Nneka Leiba, EWG’s vice president of Healthy Living science. “Those studies don’t prove whether the sunscreens are unsafe, but they do highlight problems with how these products are regulated.”

“EWG has been advocating for the FDA to review these chemical ingredients for 14 years,” Leiba said. “We slather these ingredients on our skin, but these chemicals haven’t been adequately tested. This is just one example of the backward nature of product regulation in the U.S.”

Oxybenzone remains a commonly used active ingredient, found in more than 40 percent of the non-mineral sunscreens in this year’s guide. Oxybenzone is allergenic and a potential endocrine disruptor, and has been detected in human breast milk, amniotic fluid, urine and blood.

According to EWG’s assessment, fewer than half of the products in this year’s guide contain active ingredients that the FDA has proposed are safe and effective.

“Based on the best current science and toxicology data, we continue to recommend sunscreens with the mineral active ingredients zinc dioxide and titanium dioxide, because they are the only two ingredients the FDA recognized as safe or effective in their proposed draft rules,” said Carla Burns, an EWG research and database analyst who manages the updates to the sunscreen guide.

Most people select sunscreen products based on their SPF, or sunburn protection factor, and mistakenly assume that bigger numbers offer better protection. According to the FDA, higher SPF values have not been shown to provide additional clinical benefit and may give users a false sense of protection. This may lead to overexposure to UVA rays that increase the risk of long-term skin damage and cancer. The FDA has proposed limiting SPF claims to 60+.

EWG continues to hone our recommendations by strengthening the criteria for assessing sunscreens, which are based on the latest findings in the scientific literature and commissioned tests of sunscreen product efficacy. This year EWG made changes to our methodology in order to strengthen our requirement that products provide the highest level of UVA protection.

“Our understanding of the dangers associated with UVA exposure is increasing, and they are of great concern,” said Burns. “Sunburn during early life, especially childhood, is very dangerous and a risk factor for all skin cancers, but especially melanoma. Babies and young children are especially vulnerable to sun damage. Just a few blistering sunburns early in life can double a person’s risk of developing melanoma later in life.”

EWG researchers found 180 sunscreens that meet our criteria for safety and efficacy and would likely meet the proposed FDA standards. Even the biggest brands now provide mineral options for consumers.  

Even for Americans continuing to follow stay-at-home orders, wearing an SPF product may still be important. If you’re sitting by a window, UVA and UVB rays can penetrate the glass.  

It is important to remember that sunscreen is only one part of a sun safety routine. People should also protect their skin by covering up with clothing, hats and sunglasses. And sunscreen must be reapplied at least every two hours to stay effective.

EWG’s Guide to Sunscreens helps consumers find products that get high ratings for providing adequate broad-spectrum protection and that are made with ingredients that pose fewer health concerns.

The new guide also includes lists of:

Here are more quick tips for choosing better sunscreens:

  • Check your products in EWG’s sunscreen database and avoid those with harmful ingredients.
  • Avoid products with oxybenzone. This chemical penetrates the skin, gets into the bloodstream and can affect normal hormone activities.
  • Steer clear of products with SPF higher than 50+. High SPF values do not necessarily provide increased UVA protection and may fool you into thinking you are safe from sun damage.
  • Avoid sprays. These popular products pose inhalation concerns, and they may not provide a thick and uniform coating on the skin.
  • Stay away from retinyl palmitate. Government studies link the use of retinyl palmitate, a form of vitamin A, to the formation of skin tumors and lesions when it is applied to sun-exposed skin.
  • Avoid intense sun exposure during the peak hours of 10 a.m. to 4 p.m.

Shoppers on the go can download EWG’s Healthy Living app to get ratings and safety information on sunscreens and other personal care products. Also be sure to check out EWG’s sunscreen label decoder.

One caveat, these EWG-recommended products might not be found in Canadian stores or your favourite product may not have been reviewed for inclusion, as a product to be sought out or avoided, in their database. For example, I use a sunscreen that isn’t listed in the database, although at least a few other of the company’s sunscreen products are. On the plus side, my sunscreen doesn’t include oxybenzone or retinyl palmitate as ingredients.

To sum up the situation with sunscreens containing metallic nanoparticles (minerals), they are considered to be relatively safe but should new research emerge that designation could change. In effect, all we can do is our best with the information at hand.

History and politics of metallic nanoparticles in sunscreens

In 2009 it was a bit of a shock when the EWG released a report recommending the use of sunscreens with metallic nanoparticles in the list of ingredients. From my July 9, 2009 posting,

The EWG (Environmental Working Group) is, according to Maynard [as of 20202: Dr. Andrew Maynard is a scientist and author, Associate Director of Faculty in the ASU {Arizona State University} School for the Future of Innovation in Society, also the director of the ASU Risk Innovation Lab, and leader of the Risk Innovation Nexus], not usually friendly to industry and they had this to say about their own predisposition prior to reviewing the data (from EWG),

When we began our sunscreen investigation at the Environmental Working Group, our researchers thought we would ultimately recommend against micronized and nano-sized zinc oxide and titanium dioxide sunscreens. After all, no one has taken a more expansive and critical look than EWG at the use of nanoparticles in cosmetics and sunscreens, including the lack of definitive safety data and consumer information on these common new ingredients, and few substances more dramatically highlight gaps in our system of public health protections than the raw materials used in the burgeoning field of nanotechnology. But many months and nearly 400 peer-reviewed studies later, we find ourselves drawing a different conclusion, and recommending some sunscreens that may contain nano-sized ingredients.

My understanding is that after this report, the EWG was somewhat ostracized by collegial organizations. Friends of the Earth (FoE) and the ETC Group both of which issued reports that were published after the EWG report and were highly critical of ‘nano sunscreens’.

The ETC Group did not continue its anti nanosunscreen campaign for long (I saw only one report) but FoE (in particular the Australian arm of the organization) more than made up for that withdrawal and to sad effect. My February 9, 2012 post title was this: Unintended consequences: Australians not using sunscreens to avoid nanoparticles?

An Australian government survey found that 13% of Australians were not using any sunscreen due to fears about nanoparticles. In a country with the highest incidence of skin cancer in the world and, which spent untold millions over decades getting people to cover up in the sun, it was devastating news.

FoE immediately withdrew all their anti nanosunscreen materials in Australia from circulation while firing broadsides at the government. The organization’s focus on sunscreens with metallic nanoparticles has diminished since 2012.

Research

I have difficulty trusting materials from FoE and you can see why here in this July 26, 2011 posting (Misunderstanding the data or a failure to research? Georgia Straight article about nanoparticles). In it, I analyze Alex Roslin’s profoundly problematic article about metallic nanoparticles and other engineered nanoparticles. All of Roslin’s article was based on research and materials produced by FoE which misrepresented some of the research. Roslin would have realized that if he had bothered to do any research for himself.

EWG impressed me mightily with their refusal to set aside or dismiss the research disputing their initial assumption that metallic nanoparticles in sunscreens were hazardous. (BTW, there is one instance where metallic nanoparticles in sunscreens are of concern. My October 13, 2013 posting about anatase and rutile forms of titanium dioxide at the nanoscale features research on that issue.)

EWG’s Wikipedia entry

Whoever and however many are maintaining this page, they don’t like EWG at all,

The accuracy of EWG reports and statements have been criticized, as has its funding by the organic food industry[2][3][4][5] Its warnings have been labeled “alarmist”, “scaremongering” and “misleading”.[6][7][8] Despite the questionable status of its work, EWG has been influential.[9]

This is the third paragraph in the Introduction. At its very best, the information is neutral, otherwise, it’s much like that third paragraph.

Even John D. Rockeller’s entry is more flattering and he was known as the ‘most hated man in America’ as this show description on the Public Broadcasting Service (PBS) website makes clear,

American Experience

The Rockefellers Chapter One

Clip: Season 13 Episode 1 | 9m 37s

John D. Rockefeller was the world’s first billionaire and the most hated man in America. Watch the epic story of the man who monopolized oil.

Fun in the sun

Have fun in the sun this summer. There’s EWG’s sunscreen database, the tips listed in the news release, and EWG also has a webpage where they describe their methodology for how they assess sunscreens. It gets a little technical (for me anyway) but it should answer any further safety questions you might have after reading this post.

It may require a bit of ingenuity given the concerns over COVID-19 but I’m constantly amazed at the inventiveness with which so many people have met this pandemic. (This June 15, 2020 Canadian Broadcasting Corporation article by Sheena Goodyear features a family that created a machine that won the 2020 Rube Goldberg Bar of Soap Video challenge. The article includes an embedded video of the winning machine in action.)

Norwegian Institute for Water Research (NIVA) releases study on silver and titanium nanomaterials in wastewater

It turns out that silver and titanium nanomaterials (e.g. silver nanoparticles washed out of athletic clothing) in wastewater may have ‘negative’ and ‘positive’ effects on freshwater and marine life depending on the species.

A November 18, 2019 news item on Nanowerk provides an introduction to the research (Note: Links have been removed),

You may not always think about it when you do your laundry or flush the toilet; but whatever you eat, wear or apply on your skin ends up in wastewater and eventually reaches the environment. The use of nanoparticles in consumer products like textiles, foods and personal care products is increasing.

What is so special about nanoparticles, is their tiny size: One nanometer is one billionth of a meter. The small size gives nanoparticles unique and novel properties compared to their bigger counterparts and may for example reach locations that bigger particles cannot reach.
Further, pristine nanoparticles behave differently from nanoparticles in the environment. In the environment, nanoparticles are transformed by interacting and forming aggregates with other particles, elements or solids, and thereby obtain other physicochemical properties.

The transformation of these tiny particles in wastewater treatment processes and their effect on freshwater and marine organisms, have largely been unknown.
Increased mortality of marine crustaceans.

In a study (“Ecotoxicological Effects of Transformed Silver and Titanium Dioxide Nanoparticles in the Effluent from a Lab-Scale Wastewater Treatment System”) conducted at the Norwegian Institute for Water Research (NIVA), Anastasia Georgantzopoulou and colleagues from NIVA and SINTEF investigated how silver and titanium dioxide nanoparticles behave in wastewater treatment plants, and how marine and freshwater organisms are affected by them.

Exposure to treated wastewater did not have any adverse effects on the freshwater crustacean Daphnia magna. (Photo: NIVA)

A November 18, 2019 NIVA press release, which originated the news item, fills in the details,

The researchers made a laboratory-scale wastewater treatment plant, using sludge from a wastewater treatment plant in Norway. They added environmentally relevant concentrations of silver (Ag) and titanium dioxide (TiO2) nanoparticles over a 5-week period and used the treated wastewater to assess the effects of transformed nanoparticles on freshwater and marine organisms, as well as on gill cells from rainbow trout.

The experiment demonstrated contrasting effects on the two crustacean species. For the marine copepod (Tisbe battagliai), mortality increased by 20-45%, whereas exposure to ttreated wastewater did not have any adverse effects on the freshwater crustacean (Daphnia magna).

“These differences are probably due, at least partly, to the two species’ different feeding habits, in combination with the fact that the nanoparticles showed a strong association to solids present in the wastewater”, Georgantzopoulou says, and explains:

“Daphnia magna is an organism that filters water for food, whereas the marine copepod feeds on bottom surfaces – like effluent solids that have settled out from the water. The bottom feeding crustacean is therefore more likely to ingest nanoparticles, and thereby be affected by solid-associated nanoparticles”. 

Effects on algal species

Nanoparticle-containing treated wastewater also affected algal growth, but the two algae species did not have a common response: The marine algae (Skeletonema pseudocostatum) responded with a 20-40 % growth inhibition, while the algal growth of the freshwater algae (Raphidocelis subcapitata) was actually stimulated, by a 40 % increase, accompanied by increased cell aggregation. The latter is probably some kind of a defense mechanism, aiming to decrease the surface area exposed to toxic particles.

“The results from our study indicate that algal responses to the treated wastewater exposure are species-dependent. This is possibly due to differences in algal cell size, surface area, and cell wall composition”, the NIVA researcher explains.

Increased permeability of fish gill cells

The researchers also found effects of silver and titanium nanoparticles on fish gill cells using an in vitro gill cell line model. As large amounts of water are passing through the gills, and they constitute a barrier to the external environment, this organ is highly exposed to water-borne contaminants, including nanoparticles.

“Exposure to nanoparticle-containing wastewater lead to an increase in reactive oxygen species, a group of molecules that can easily react with and damage cells. This was followed by increased permeability of the gill cells, leading to a compromised barrier function”, Georgantzopoulou says.

“However, the concentrations of silver and titanium nanoparticles in the treated wastewater were too low to fully account for the effects on cell permeability alone. The wastewater effluent is a complex mixture of materials, and the permeability response is probably caused by a combination of the presence of nanoparticles and other stressors”, Georgantzopoulou adds.

Wastewater treatment-transformation of nanoparticles

“We carried out this study on wastewater treatment plant-transformed nanoparticles, and compared them to pristine nanoparticles, as the former is more relevant to what is actually happening in the environment. The increased toxicity of the transformed nanomaterials observed in the study indicates that the effects cannot be predicted by assessing the effects of nanomaterials in their pristine form and highlights the importance of understanding their behavior, environmental transformation and interaction with organisms. Future studies should take nanoparticle transformation into account and focus on a more relevant experimental exposure conditions incorporating transformed nanoparticles in more long-term impact studies to provide a better understanding of their potential impacts”, Georgantzopoulou concludes.

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

Ecotoxicological Effects of Transformed Silver and Titanium Dioxide Nanoparticles in the Effluent from a Lab-Scale Wastewater Treatment System by Anastasia Georgantzopoulou, Patricia Almeida Carvalho, Christian Vogelsang, Mengstab Tilahun, Kuria Ndungu, Andy M. Booth, Kevin V. Thomas, Ailbhe Macken. Environ. Sci. Technol. 2018, 52, 16, 9431-9441 DOI: https://doi.org/10.1021/acs.est.8b01663 Publication Date:July 26, 2018 Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Algae outbreaks (dead zones) in wetlands and waterways

It’s been over seven years since I first started writing about Duke University’s  Center for the Environmental Implications of Nanotechnology and mesocosms (miniature ecosystems) and the impact that nanoparticles may have on plants and water (see August 11, 2011 posting). Since then, their focus has shifted from silver nanoparticles and their impact on plants, fish, bacteria, etc. to a more general examination of metallic nanoparticles and water. A June 25, 2018 news item on ScienceDaily announces some of their latest work,

The last 10 years have seen a surge in the use of tiny substances called nanomaterials in agrochemicals like pesticides and fungicides. The idea is to provide more disease protection and better yields for crops, while decreasing the amount of toxins sprayed on agricultural fields.

But when combined with nutrient runoff from fertilized cropland and manure-filled pastures, these “nanopesticides” could also mean more toxic algae outbreaks for nearby streams, lakes and wetlands, a new study finds.

A June 25, 2018 Duke University news release (also on EurekAlert) by Robin A. Smith, which originated the news item, provides more detail,

Too small to see with all but the most powerful microscopes, engineered nanomaterials are substances manufactured to be less than 100 nanometers in diameter, many times smaller than a hair’s breadth.

Their nano-scale gives them different chemical and physical properties from their bulk counterparts, including more surface area for reactions and interactions.

Those interactions could intensify harmful algal blooms in wetlands, according to experiments led by Marie Simonin, a postdoctoral associate with biology professor Emily Bernhardt at Duke University.

Carbon nanotubes and teeny tiny particles of silver, titanium dioxide and other metals are already added to hundreds of commercial products to make everything from faster, lighter electronics, self-cleaning fabrics, and smarter food packaging that can monitor food for spoilage. They are also used on farms for slow- or controlled-release plant fertilizers and pesticides and more targeted delivery, and because they are effective at lower doses than conventional products.

These and other applications have generated tremendous interest and investment in nanomaterials. However the potential risks to human health or the environment aren’t fully understood, Simonin said.

Most of the 260,000 to 309,000 metric tons of nanomaterials produced worldwide each year are eventually disposed in landfills, according to a previous study. But of the remainder, up to 80,400 metric tons per year are released into soils, and up to 29,200 metric tons end up in natural bodies of water.

“And these emerging contaminants don’t end up in water bodies alone,” Simonin said. “They probably co-occur with nutrient runoff. There are likely multiple stressors interacting.”

Algae outbreaks already plague polluted waters worldwide, said Steven Anderson, a research analyst in the Bernhardt Lab at Duke and one of the authors of the research.

Nitrogen and phosphorous pollution makes its way into wetlands and waterways in the form of agricultural runoff and untreated wastewater. The excessive nutrients cause algae to grow out of control, creating a thick mat of green scum or slime on the surface of the water that blocks sunlight from reaching other plants.

These nutrient-fueled “blooms” eventually reduce oxygen levels to the point where fish and other organisms can’t survive, creating dead zones in the water. Some algal blooms also release toxins that can make pets and people who swallow them sick.

To find out how the combined effects of nutrient runoff and nanoparticle contamination would affect this process, called eutrophication, the researchers set up 18 separate 250-liter tanks with sandy sloped bottoms to mimic small wetlands.

Each open-air tank was filled with water, soil and a variety of wetland plants and animals such as waterweed and mosquitofish.

Over the course of the nine-month experiment, some tanks got a weekly dose of algae-promoting nitrates and phosphates like those found in fertilizers, some tanks got nanoparticles — either copper or gold — and some tanks got both.

Along the way the researchers monitored water chemistry, plant and algae growth and metabolism, and nanoparticle accumulation in plant tissues.

“The results were surprising,” Simonin said. The nanoparticles had tiny effects individually, but when added together with nutrients, even low concentrations of gold and copper nanoparticles used in fungicides and other products turned the once-clear water a murky pea soup color, its surface covered with bright green smelly mats of floating algae.

Over the course of the experiment, big algal blooms were more than three times more frequent and more persistent in tanks where nanoparticles and nutrients were added together than where nutrients were added alone. The algae overgrowths also reduced dissolved oxygen in the water.

It’s not clear yet how nanoparticle exposure shifts the delicate balance between plants and algae as they compete for nutrients and other resources. But the results suggest that nanoparticles and other “metal-based synthetic chemicals may be playing an under-appreciated role in the global trends of increasing eutrophication,” the researchers said.

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

Engineered nanoparticles interact with nutrients to intensify eutrophication in a wetland ecosystem experiment by Marie Simonin, Benjamin P. Colman, Steven M. Anderson, Ryan S. King, Matthew T. Ruis, Astrid Avellan, Christina M. Bergemann, Brittany G. Perrotta, Nicholas K. Geitner, Mengchi Ho, Belen de la Barrera, Jason M. Unrine, Gregory V. Lowry, Curtis J. Richardson, Mark R. Wiesner, Emily S. Bernhardt. Ecological Applications, 2018; DOI: 10.1002/eap.1742 First published: 25 June 2018

This paper is behind a paywall.

What helps you may hurt you (titanium dioxide nanoparticles and orthopedic implants)

From a Sept. 16, 2017 news item on Nanotechnology Now,

Researchers from the Mayo Clinic have proposed that negative cellular responses to titanium-based nanoparticles released from metal implants interfere in bone formation and resorption at the site of repair, resulting in implant loosening and joint pain. [emphasis mine]Their review of recent scientific evidence and call for further research to characterize the biological, physical, and chemical interactions between titanium dioxide nanoparticles and bone-forming cells is published in BioResearch Open Access, a peer-reviewed open access journal from Mary Ann Liebert, Inc., publishers. The article is available free on theBioResearch Open Access website.

A Sept. 14, 2017 Mary Anne Liebert (Publishing) news release, which originated the news item,  mentions the authors,

Jie Yao, Eric Lewallen, PhD, David Lewallen, MD, Andre van Wijnen, PhD, and colleagues from the Mayo Clinic, Rochester, MN and Second Affiliated Hospital of Soochow University, China, coauthored the article entitled “Local Cellular Responses to Titanium Dioxide from Orthopedic Implants The authors examined the results of recently published studies of titanium-based implants, focusing on the direct and indirect effects of titanium dioxide nanoparticles on the viability and behavior of multiple bone-related cell types. They discuss the impact of particle size, aggregation, structure, and the specific extracellular and intracellular (if taken up by the cells) effects of titanium particle exposure.

“The adverse effects of metallic orthopedic particles generated from implants are of significant clinical interest given the large number of procedures carried out each year. This article reviews our current understanding of the clinical issues and highlights areas for future research,” says BioResearch Open Access Editor Jane Taylor, PhD, MRC Centre for Regenerative Medicine, University of Edinburgh, Scotland.

Before getting to the abstract, here’s a link to and a citation for the paper,

Local Cellular Responses to Titanium Dioxide from Orthopedic Implants by Yao, Jie J.; Lewallen, Eric A.; Trousdale, William H.; Xu, Wei; Thaler, Roman; Salib, Christopher G.; Reina, Nicolas; Abdel, Matthew P.; Lewallen, David G.; and van Wijnenm, Andre J.. BioResearch Open Access. July 2017, 6(1): 94-103. https://doi.org/10.1089/biores.2017.0017 Published July 1, 2017

This paper is open access.

Findings on oral exposure to nanoscale titanium dioxide

It’s been a while since I’ve run a piece on health concerns and nanoparticles. The nanoparticles in question are titanium dioxide and the concerns centre on oral exposure to them according to a Jan. 24, 2017 news item on Nanowerk,

Researchers from INRA [French National Institute for Agricultural Research] and their partners have studied the effects of oral exposure to titanium dioxide, an additive (E171) commonly used in foodstuffs, especially confectionary. They have shown for the first time that E171 crosses the intestinal barrier in animals and reaches other parts of the body.

Immune system disorders linked to the absorption of the nanoscale fraction of E171 particles were observed. The researchers also showed that chronic oral exposure to the additive spontaneously induced preneoplastic lesions in the colon, a non-malignant stage of carcinogenesis, in 40% of exposed animals.

Moreover, E171 was found to accelerate the development of lesions previously induced for experimental purposes. While the findings show that the additive plays a role in initiating and promoting the early stages of colorectal carcinogenesis, they cannot be extrapolated to humans or more advanced stages of the disease. [emphasis mine]

A Jan. 20, 2017 IINRA press release, which originated the news item,  provides more detail about European use of titanium dioxide as a food additive and about the research,

Present in many products including cosmetics, sunscreens, paint and building materials, titanium dioxide (or TiO2), known as E171 in Europe, is also widely used as an additive in the food industry to whiten or give opacity to products. It is commonly found in sweets, chocolate products, biscuits, chewing gum and food supplements, as well as in toothpaste and pharmaceutical products. Composed of micro- and nanoparticles, E171 is nevertheless not labelled a “nanomaterial”, since it does not contain more than 50% of nanoparticles (in general it contains from 10-40%). The International Agency for Research on Cancer (IARC) evaluated the risk of exposure to titanium dioxide by inhalation (occupational exposure), resulting in a Group 2B classification, reserved for potential carcinogens for humans.

Today, oral exposure to E171 is a concern, especially in children who tend to eat a lot of sweets. INRA researchers studied the product as a whole (that is, its mixed composition of micro- and nanoparticules), and have also evaluated the effect of the nanoscale particle fraction alone, by comparing it to a model nanoparticle.

Titanium dioxide crosses the intestinal barrier and passes into the bloodstream

The researchers exposed rats orally to a dose of 10mg of E171 per kilogram of body weight per day, similar to the exposure humans experience through food consumption (data from European Food Safety Agency, September 20162). They showed for the first time in vivo that titanium dioxide is absorbed by the intestine and passes into the bloodstream. Indeed, the researchers found titanium dioxide particles in the animals’ livers.

Titanium dioxide alters intestinal and systemic immune response

Titanium dioxide nanoparticles were present in the lining of the small intestine and in the colon, and entered the nuclei of the immune cells of Peyer’s patches, which induce immune response in the intestine. The researchers showed an imbalance in immune response, ranging from a defect in the production of cytokines in Peyer’s patches to the development of micro-inflammation in colon mucosa. In the spleen, representative of systemic immunity, exposure to E171 increases the capacity of immune cells to produce pro-inflammatory cytokines when they are activated in vitro.

Chronic oral exposure to titanium dioxide plays a role in initiating and promoting early stages of colorectal carcinogenesis

The researchers exposed rats to regular oral doses of titanium dioxide through drinking water for 100 days. In a group of rats previously treated with an experimental carcinogen, exposure to TiO2 led to an increase in the size of preneoplastic lesions. In a group of healthy rats exposed to E171, four out of eleven spontaneously developed preneoplastic lesions in the intestinal epithelium. Non-exposed animals presented no anomalies at the end of the 100-day study. These results indicate that E171 both initiates and promotes the early stages of colorectal carcinogenesis in animals.

These studies show for the first time that the additive E171 is a source of titanium dioxide nanoparticles in the intestine and the entire body, with consequences for both immune function and the development of preneoplastic lesions in the colon. These first findings justify a carcinogenesis study carried out under OECD [Organization for Economic Cooperation and Development] guidelines to continue observations at a later stage of cancer. They provide new data for evaluating the risks of the E171 additive in humans.

These studies were carried out within the framework of the Nanogut project, financed by the French Agency for Food, Environmental and Occupational Health & Safety (ANSES) within the French national programme for research related to the environment, health and the workplace (PNR EST) and coordinated by INRA. Sarah Bettini’s university thesis contract was financed by the French laboratory of excellence LabEx SERENADE.

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

Food-grade TiO2 impairs intestinal and systemic immune homeostasis, initiates preneoplastic lesions and promotes aberrant crypt development in the rat colon by Sarah Bettini, Elisa Boutet-Robinet, Christel Cartier, Christine Coméra, Eric Gaultier, Jacques Dupuy, Nathalie Naud, Sylviane Taché, Patrick Grysan, Solenn Reguer, Nathalie Thieriet, Matthieu Réfrégiers, Dominique Thiaudière, Jean-Pierre Cravedi, Marie Carrière, Jean-Nicolas Audinot, Fabrice H. Pierre, Laurence Guzylack-Piriou, & Eric Houdeau. Scientific Reports 7, Article number: 40373 (2017) doi:10.1038/srep40373 Published online: 20 January 2017

This paper is open access.

The research is concerning but they don’t want to draw any conclusions yet, which explains the recommendation for further research.

Nanosunscreen in swimming pools

Thanks to Lynn L. Bergeson’s Sept. 21, 2016 posting for information about the US Environmental Protection Agency’s (EPA) research into what happens to the nanoparticles when your nanosunscreen washes off into a swimming pool. Bergeson’s post points to an Aug. 15, 2016 EPA blog posting by Susanna Blair,

… It’s not surprising that sunscreens are detected in pool water (after all, some is bound to wash off when we take a dip), but certain sunscreens have also been widely detected in our ecosystems and in our wastewater. So how is our sunscreen ending up in our environment and what are the impacts?

Well, EPA researchers are working to better understand this issue, specifically investigating sunscreens that contain engineered nanomaterials and how they might change when exposed to the chemicals in pool water [open access paper but you need to register for free] … But before I delve into that, let’s talk a bit about sunscreen chemistry and nanomaterials….

Blair goes on to provide a good brief description of  nanosunscreens before moving onto her main topic,

Many sunscreens contain titanium dioxide (TiO2) because it absorbs UV radiation, preventing it from damaging our skin. But titanium dioxide decomposes into other molecules when in the presence of water and UV radiation. This is important because one of the new molecules produced is called a singlet oxygen reactive oxygen species. These reactive oxygen species have been shown to cause extensive cell damage and even cell death in plants and animals. To shield skin from reactive oxygen species, titanium dioxide engineered nanomaterials are often coated with other materials such as aluminum hydroxide (Al(OH)3).

EPA researchers are testing to see whether swimming pool water degrades the aluminum hydroxide coating, and if the extent of this degradation is enough to allow the production of potentially harmful reactive oxygen species. In this study, the coated titanium dioxide engineered nanomaterials were exposed to pool water for time intervals ranging from 45 minutes to 14 days, followed by imaging using an electron microscope.  Results show that after 3 days, pool water caused the aluminum hydroxide coating to degrade, which can reduce the coating’s protective properties and increase the potential toxicity.  To be clear, even with degraded coating, the toxicity measured from the coated titanium dioxide, was significantly less [emphasis mine] than the uncoated material. So in the short-term – in the amount of time one might wear sunscreen before bathing and washing it off — these sunscreens still provide life-saving protection against UV radiation. However, the sunscreen chemicals will remain in the environment considerably longer, and continue to degrade as they are exposed to other things.

Blair finishes by explaining that research is continuing as the EPA researches the whole life cycle of engineered nanomaterials.

Nanotechnology in the house; a guide to what you already have

A July 4, 2016 essay by Cameron Shearer of Flinders University (Australia) on The Conversation website describes how nanotechnology can be found in our homes (Note: Links have been removed),

All kitchens have a sink, most of which are fitted with a water filter. This filter removes microbes and compounds that can give water a bad taste.

Common filter materials are activated carbon and silver nanoparticles.

Activated carbon is a special kind of carbon that’s made to have a very high surface area. This is achieved by milling it down to a very small size. Its high surface area gives more room for unwanted compounds to stick to it, removing them from water.

The antimicrobial properties of silver makes it one of the most common nanomaterials today. Silver nanoparticles kill algae and bacteria by releasing silver ions (single silver atoms) that enter into the cell wall of the organisms and become toxic.

It is so effective and fashionable that silver nanoparticles are now used to coat cutlery, surfaces, fridges, door handles, pet bowls and almost anywhere else microorganisms are unwanted.

Other nanoparticles are used to prepare heat-resistant and self-cleaning surfaces, such as floors and benchtops. By applying a thin coating containing silicon dioxide or titanium dioxide nanoparticles, a surface can become water repelling, which prevents stains (similar to how scotch guard protects fabrics).

Nanoparticle films can be so thin that they can’t be seen. The materials also have very poor heat conductivity, which means they are heat resistant.

The kitchen sink (or dishwasher) is used for washing dishes with the aid of detergents. Detergents form nanoparticles called micelles.

A micelle is formed when detergent molecules self-assemble into a sphere. The centre of this sphere is chemically similar to grease, oils and fats, which are what you want to wash off. The detergent traps oils and fats within the cavity of the sphere to separate them from water and aid dish washing.

Your medicine cabinet may include nanotechnology similar to micelles, with many pharmaceuticals using liposomes.

A liposome is an extended micelle where there is an extra interior cavity within the sphere. Making liposomes from tailored molecules allows them to carry therapeutics inside; the outside of the nanoparticle can be made to target a specific area of the body.

Shearer’s essay goes on to cover the laundry, bathroom, closets, and garage. (h/t July 5, 2016 news item on phys.org)