Tag Archives: Sharon L. Walker

Metal nanoparticles and gut microbiomes

What happens when you eat or drink nanoparticles, metallic or otherwise? No one really knows. Part of the problem with doing research now is there are no benchmarks for the quantity we’ve been ingesting over the centuries. Nanoparticles do occur naturally, as well, people who’ve eaten with utensils made of or coated with silver or gold have ingested silver or gold nanoparticles that were shed by those very utensils. In short, we’ve been ingesting any number of nanoparticles through our food, drink, and utensils in addition to the engineered nanoparticles that are found in consumer products. So, part of what researchers need to determine is the point at which we need to be concerned about nanoparticles. That’s trickier than it might seem since we ingest our nanoparticles and recycle them into the environment (air, water, soil) to reingest (inhale, drink, eat, etc.) them at a later date. The endeavour to understand what impact engineered nanoparticles in particular will have on us as more are used in our products is akin to assembling a puzzle.

There’s a May 5, 2015 news item on Azonano which describes research into the effects that metallic nanoparticles have on the micriobiome (bacteria) in our guts,

Exposure of a model human colon to metal oxide nanoparticles, at levels that could be present in foods, consumer goods, or treated drinking water, led to multiple, measurable differences in the normal microbial community that inhabits the human gut. The changes observed in microbial metabolism and the gut microenvironment with exposure to nanoparticles could have implications for overall human health, as discussed in an article published in Environmental Engineering Science, a peer-reviewed journal from Mary Ann Liebert, Inc., publishers. The article is available free on the Environmental Engineering Science website until June 1, 2015.

A May 4, 2015 Mary Ann Liebert publisher news release on EurekAlert, which originated the news item, describes the research in more detail (Note: A link has been removed),

Alicia Taylor, Ian Marcus, Risa Guysi, and Sharon Walker, University of California, Riverside, individually introduced three different nanoparticles–zinc oxide, cerium dioxide, and titanium dioxide–commonly used in products such as toothpastes, cosmetics, sunscreens, coatings, and paints, into a model of the human colon. The model colon mimics the normal gut environment and contains the microorganisms typically present in the human microbiome.

In the article “Metal Oxide Nanoparticles Induce Minimal Phenotypic Changes in a Model Colon Gut Microbiota” the researchers described changes in both specific characteristics of the microbial community and of the gut microenvironment after exposure to the nanoparticles.

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

Metal Oxide Nanoparticles Induce Minimal Phenotypic Changes in a Model Colon Gut Microbiota by Alicia A. Taylor, Ian M. Marcus Ian, Risa L., Guysi, and Sharon L. Walker. Environmental Engineering Science. DOI:10.1089/ees.2014.0518 Online Ahead of Print: April 24, 2015

I’ve taken a quick look at the research while it’s still open access (till June 1, 2015) to highlight the bits I consider interesting. There’s this about the nanoparticle (NP) quantities used in the study (Note: Links have been removed),

Environmentally relevant NP concentrations were chosen to emulate human exposures to NPs through ingestion of both food and drinking water at 0.01 μg/L ZnO NP, 0.01 μg/L CeO2 NP, and 3 mg/L TiO2 NP (Gottschalk et al., 2009; Kiser et al., 2009, 2013; Weir et al., 2012; Keller and Lazareva, 2013). Recent work has also indicated that adults in the USA ingest 5 mg TiO2 per day, half of which is in the nano-size range (Lomer et al., 2000; Powell et al., 2010). Exposure routes and reliable dosing information of NPs that are embedded in solid matrices are difficult to predict, and this is often a limitation of analytical techniques (Nowack et al., 2012; Yang and Westerhoff, 2014). The exposure levels used in this study were predominately selected from literature values that give predictions on amount of NPs in water and food sources (Gottschalk et al., 2009; Kiser et al., 2009; Weir et al., 2012; Keller and Lazareva, 2013; Keller et al., 2013).

For anyone unfamiliar with chemical notations, ZnO NP is zinc oxide nanoparticle, 0.01 μg/L is one/one hundredth of a microgram per litre,  CeO2 is cesisum dioxide NP, and TiO2 is titanium dioxide NP while 3 mg/L, is 3 milligrams per litre.

After assuring the quantities used in the study are the same as they expect humans to be ingesting on a regular basis, the researchers describe some of the factors which may affect the interaction between the tested nanoparticles and the bacteria (Note: Links have been removed),

It is essential to note that interactions between NPs and bacteria in the intestines may be dependent on numerous factors: the surface charge of the NPs and bacteria, the chemical composition and surface charge of the digested food, and variability in diet. These factors may ultimately correlate to effects seen in humans on an individual basis. In fact, similar work has demonstrated that exposing common NPs found in food to stomach-like conditions will change their surface chemistry from negative to neutral or positive, causing the NPs to interact with negatively charged mucus proteins in the gastrointestinal tract and, in turn, affecting the transport of NPs within the intestine (McCracken et al., 2013). The purpose of this work was to measure responses of the microbial community during the NP exposures. Based on previous research, it is anticipated that the NPs altered by stomach-like conditions would also cause changes in the gut environment (McCracken et al., 2013).

Here’s some of what they discovered,

Our initial hypothesis, that NPs induce phenotypic changes in a gut microbial community, was affirmed through significant measurable effects seen in the data. Tests that supported that NPs caused changes in the phenotype included hydrophobicity, EPM, sugar content of the EPS, cell size, conductivity, and SFCA (specifically butyric acid) production. Data for cell concentration and the protein content of the EPS demonstrated no significant results. Data were inconclusive for pH. With such a complex biological system, it is very likely that the phenotypic and biochemical changes observed are combinations of responses happening in parallel. The effects seen may be attributed to both changes induced by the NPs and natural phenomena associated with microbial community activity and other metabolic processes in a multifaceted environment such as the gut. Some examples of natural processes that could also influence the phenotypic and biochemical parameters are osmolarity, active metabolites, and electrolyte concentrations (Miller and Wood, 1996; Record et al., 1998).

Here’s the concluding sentence from the abstract,

Overall, the NPs caused nonlethal, significant changes to the microbial community’s phenotype, which may be related to overall health effects. [emphasis mine]

This research like the work I featured in a June 27, 2013 posting points to some issues with researching the impact that nanoparticles may have on our bodies. There was no cause for immediate alarm in 2013 and it appears that is still the case in 2015. However, that assumes quantities being ingested don’t increase significantly.

Copper nanoparticles, toxicity research, colons, zebrafish, and septic tanks

Alicia Taylor, a graduate student at UC Riverside, surrounded by buckets of effluent from the septic tank system she used for her research. Courtesy: University of California at Riverside

Alicia Taylor, a graduate student at UC Riverside, surrounded by buckets of effluent from the septic tank system she used for her research. Courtesy: University of California at Riverside

Those buckets of efflluent are strangely compelling. I think it’s the abundance of orange. More seriously, a March 2, 2015 news item on Nanowerk poses a question about copper nanoparticles,

What do a human colon, septic tank, copper nanoparticles and zebrafish have in common?

They were the key components used by researchers at the University of California, Riverside and UCLA [University of California at Los Angeles] to study the impact copper nanoparticles, which are found in everything from paint to cosmetics, have on organisms inadvertently exposed to them.

The researchers found that the copper nanoparticles, when studied outside the septic tank, impacted zebrafish embryo hatching rates at concentrations as low as 0.5 parts per million. However, when the copper nanoparticles were released into the replica septic tank, which included liquids that simulated human digested food and household wastewater, they were not bioavailable and didn’t impact hatching rates.

A March 2, 2015 University of California at Riverside (UCR) news release (also on EurekAlert), which originated the news item, provides more detail about the research,

“The results are encouraging because they show with a properly functioning septic tank we can eliminate the toxicity of these nanoparticles,” said Alicia Taylor, a graduate student working in the lab of Sharon Walker, a professor of chemical and environmental engineering at the University of California, Riverside’s Bourns College of Engineering.

The research comes at a time when products with nanoparticles are increasingly entering the marketplace. While the safety of workers and consumers exposed to nanoparticles has been studied, much less is known about the environmental implications of nanoparticles. The Environmental Protection Agency is currently accessing the possible effects of nanomaterials, including those made of copper, have on human health and ecosystem health.

The UC Riverside and UCLA [University of California at Los Angeles] researchers dosed the septic tank with micro copper and nano copper, which are elemental forms of copper but encompass different sizes and uses in products, and CuPRO, a nano copper-based material used as an antifungal agent to spray agricultural crops and lawns.

While these copper-based materials have beneficial purposes, inadvertent exposure to organisms such as fish or fish embryos has not received sufficient attention because it is difficult to model complicated exposure environments.

The UC Riverside researchers solved that problem by creating a unique experimental system that consists of the replica human colon and a replica two-compartment septic tank, which was originally an acyclic septic tank. The model colon is made of a custom-built 20-inch-long glass tube with a 2-inch diameter with a rubber stopper at both ends and a tube-shaped membrane typically used for dialysis treatments within the glass tube.

To simulate human feeding, 100 milliliters of a 20-ingredient mixture that replicated digested food was pumped into the dialysis tube at 9 a.m., 3 p.m. and 9 p.m. for five-day-long experiments over nine months.

The septic tank was filled with waste from the colon along with synthetic greywater, which is meant to simulate wastewater from sources such as sinks and bathtubs, and the copper nanoparticles. The researchers built a septic tank because 20 to 30 percent of American households rely on them for sewage treatment. Moreover, research has shown up to 40 percent of septic tanks don’t function properly. This is a concern if the copper materials are disrupting the function of the septic system, which would lead to untreated waste entering the soil and groundwater.

Once the primary chamber of the septic system was full, liquid began to enter the second chamber. Once a week, the effluent was drained from the secondary chamber and it was placed into sealed five-gallon containers. The effluent was then used in combination with zebrafish embryos in a high content screening process using multiwall plates to access hatching rates.

The remaining effluent has been saved and sits in 30 five-gallon buckets in a closet at UC Riverside because some collaborators have requested samples of the liquid for their experiments.

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

Understanding the Transformation, Speciation, and Hazard Potential of Copper Particles in a Model Septic Tank System Using Zebrafish to Monitor the Effluent* by Sijie Lin, Alicia A. Taylor, Zhaoxia Ji, Chong Hyun Chang, Nichola M. Kinsinger, William Ueng, Sharon L. Walker, and André E. Nel. ACS Nano, 2015, 9 (2), pp 2038–2048 DOI: 10.1021/nn507216f
Publication Date (Web): January 27, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

* Link added March 10, 2015.

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.

Soybeans and nanoparticles

They seem ubiquitous today but there was a time when hardly anyone living in Canada  knew much about soybeans.  There’s a good essay about soybeans and their cultivation in Canada by Erik Dorff for Statistics Canada, from Dorff’s soybean essay,

Until the mid-1970s, soybeans were restricted by climate primarily to southern Ontario. Intensive breeding programs have since opened up more widespread growing possibilities across Canada for this incredibly versatile crop: The 1.2 million hectares of soybeans reported on the Census of Agriculture in 2006 marked a near eightfold increase in area since 1976, the year the ground-breaking varieties that perform well in Canada’s shorter growing season were introduced.

Soybeans have earned their popularity, with the high-protein, high-oil beans finding use as food for human consumption, animal rations and edible oils as well as many industrial products. Moreover, soybeans, like all legumes, are able to “fix” the nitrogen the plants need from the air. This process of nitrogen fixation is a result of a symbiotic interaction between bacteria microbes that colonize the roots of the soy plant and are fed by the plant. In return, the microbes take nitrogen from the air and convert it into a form the plant can use to grow.

This means legumes require little in the way of purchased nitrogen fertilizers produced from expensive natural gas-a valuable property indeed.

Until reading Dorff’s essay, I hadn’t early soybeans had been introduced to the Canadian agricultural sector,

While soybeans arrived in Canada in the mid 1800s-with growing trials recorded in 1893 at the Ontario Agricultural College-they didn’t become a commercial oilseed crop in Canada until a crushing plant was built in southern Ontario in the 1920s, about the same time that the Department of Agriculture (now Agriculture and Agri-Food Canada) began evaluating soybean varieties suited for the region. For years, soybeans were being grown in Canada but it wasn’t until the Second World War that Statistics Canada began to collect data showing the significance of the soybean crop, with 4,400 hectares being reported in 1941. In fact, one year later the area had jumped nearly fourfold, to 17,000 hectares…

As fascinating as I find this history, this bit about soybeans and their international importance explain why research about soyboans and nanoparticles is of wide interest (from Dorff’s essay),

The soybean’s valuable characteristics have propelled it into the agricultural mix in many parts of the world. In 2004, soybeans accounted for approximately 35% of the total harvested area worldwide of annual and perennial oil crops according to the Food and Agriculture Organization of the United Nations (FAO) but only four countries accounted for nearly 90% of the production with Canada in seventh place at 1.3% (Table 2). Soymeal-the solid, high-protein material remaining after the oil has been extracted during crushing-accounts for over 60% of world vegetable and animal meal production, while soybean oil accounts for 20% of global vegetable oil production.

There’s been a recent study on the impact of nanoparticles on soybeans at the University of California at Santa Barbara (UC Santa Barbara) according to an Aug. 20, 2012 posting by Alan on the Science Business website, (h/t to Cientifica),

Researchers from University of California in Santa Barbara found manufactured nanoparticles disposed after manufacturing or customer use can end up in agricultural soil and eventually affect soybean crops. Findings of the team that includes academic, government, and corporate researchers from elsewhere in California, Texas, Iowa, New York, and Korea appear online today in the Proceedings of the National Academy of Sciences.

The research aimed to discover potential environmental implications of new industries that produce nanomaterials. Soybeans were chosen as test crops because their prominence in American agriculture — it is the second largest crop in the U.S. and the fifth largest crop worldwide — and its vulnerability to manufactured nanomaterials. The soybeans tested in this study were grown in greenhouses.

The Aug. 20, 2012 UC Santa Barbara press release has additional detail abut why the research was undertaken,

“Our society has become more environmentally aware in the last few decades, and that results in our government and scientists asking questions about the safety of new types of chemical ingredients,” said senior author Patricia Holden, a professor with the Bren School [UC Santa Barbara’s Bren School of Environmental Science & Management]. “That’s reflected by this type of research.”

Soybean was chosen for the study due to its importance as a food crop –– it is the fifth largest crop in global agricultural production and second in the U.S. –– and because it is vulnerable to MNMs [manufactured nanomaterials]. The findings showed that crop yield and quality are affected by the addition of MNMs to the soil.

The scientists studied the effects of two common nanoparticles, zinc oxide and cerium oxide, on soybeans grown in soil in greenhouses. Zinc oxide is used in cosmetics, lotions, and sunscreens. Cerium oxide is used as an ingredient in catalytic converters to minimize carbon monoxide production, and in fuel to increase fuel combustion. Cerium can enter soil through the atmosphere when fuel additives are released with diesel fuel combustion.

The zinc oxide nanoparticles may dissolve, or they may remain as a particle, or re-form as a particle, as they are processed through wastewater treatment. At the final stage of wastewater treatment there is a solid material, called biosolids, which is applied to soils in many parts of the U.S. This solid material fertilizes the soil, returning nitrogen and phosphorus that are captured during wastewater treatment. This is also a point at which zinc oxide and cerium oxide can enter the soil.

The scientists noted that the EPA requires pretreatment programs to limit direct industrial metal discharge into publicly owned wastewater treatment plants. However, the research team conveyed that “MNMs –– while measurable in the wastewater treatment plant systems –– are neither monitored nor regulated, have a high affinity for activated sludge bacteria, and thus concentrate in biosolids.”

The authors pointed out that soybean crops are farmed with equipment powered by fossil fuels, and thus MNMs can also be deposited into the soil through exhaust.

The study showed that soybean plants grown in soil that contained zinc oxide bioaccumulated zinc; they absorbed it into the stems, leaves, and beans. Food quality was affected, although it may not be harmful to humans to eat the soybeans if the zinc is in the form of ions or salts, in the plants, according to Holden.

In the case of cerium oxide, the nanoparticles did not bioaccumulate, but plant growth was stunted. Changes occurred in the root nodules, where symbiotic bacteria normally accumulate and convert atmospheric nitrogen into ammonium, which fertilizes the plant. The changes in the root nodules indicate that greater use of synthetic fertilizers might be necessary with the buildup of MNMs in the soil.

At this point, the researchers don’t know how zinc oxide nanoparticles and cerium oxide nanoparticles currently used in consumer products and elsewhere are likely to affect agricultural lands. The only certainty is that these nanoparticles are used in consumer goods and, according to Holden, they are entering agricultural soil.

The citation for the article,

Soybean susceptibility to manufactured nanomaterials with evidence for food quality and soil fertility interruption by John H. Priester, Yuan Ge, Randall E. Mielke, Allison M. Horst Shelly Cole Moritz, Katherine Espinosa, Jeff Gelb, Sharon L. Walker, Roger M. Nisbet, Youn-Joo An, Joshua P. Schimel, Reid G. Palmer, Jose A. Hernandez-Viezcas, Lijuan Zhao, Jorge L. Gardea-Torresdey, Patricia A. Holden. Published online [Proceedings of the National Academy of Sciences {PNAS}] before print August 20, 2012, doi: 10.1073/pnas.1205431109

The article is open access and available here.