Tag Archives: Center for the Environmental Implications of Nanotechnology (CEINT)

Gold nanoparticles not always always biologically stable

It’s usually silver nanoparticles (with a nod to titanium dioxide as another problem nanoparticle) which star in scenarios regarding environmental concerns, especially with water. According to an Aug. 28, 2018 news item on Nanowerk, gold nanoparticles under certain conditions could also pose problems,

It turns out gold isn’t always the shining example of a biologically stable material that it’s assumed to be, according to environmental engineers at Duke’s Center for the Environmental Implications of NanoTechnology (CEINT).

In a nanoparticle form, the normally very stable, inert, noble metal actually gets dismantled by a microbe found on a Brazilian aquatic weed.

While the findings don’t provide dire warnings about any unknown toxic effects of gold, they do provide a warning to researchers on how it is used in certain experiments.

Here’s an image of one of the researchers standing in the test bed where they made their discovery (the caption will help to make sense of the reference to mesocosms in the news release, which follows,,

Mark Wiesner stands with rows of mesocosms—small, manmade structures containing different plants and microorganisms meant to represent a natural environment with experimental controls. Courtesy: Duke University

An August 28, 2018 Duke University news release (also on EurekAlert) by Ken Kingery, which originated the news item, provides more detail about gold nanoparticle instability,

CEINT researchers from Duke, Carnegie Mellon and the University of Kentucky were running an experiment to investigate how nanoparticles used as a commercial pesticide affect wetland environments in the presence of added nutrients. Although real-world habitats often receive doses of both pesticides and fertilizers, most studies on the environmental effects of such compounds only look at a single contaminant at a time.

For nine months, the researchers released low doses of nitrogen, phosphorus and copper hydroxide nanoparticles into wetland mesocosms [emphasis mine]– small, manmade structures containing different plants and microorganisms meant to represent a natural environment with experimental controls. The goal was to see where the nanoparticle pesticides ended up and how they affected the plant and animal life within the mesocosm.

The researchers also released low doses of gold nanoparticles as tracers, assuming the biologically inert nanoparticles would remain stable while migrating through the ecosystem. This would help the researchers interpret data on the pesticide particles that partly dissolve by showing them how a solid metal particle acts within the system.

But when the researchers went to analyze their results, they found that many of the gold nanoparticles had been oxidized and dissolved.

“We were taken completely by surprise,” said Mark Wiesner, the James B. Duke Professor and chair of civil and environmental engineering at Duke. “The nanoparticles that were supposed to be the most stable turned out to be the least stable of all.”

After further inspection, the researchers found the culprit — the microbiome growing on a common Brazilian waterweed called Egeria densa. Many bacteria secrete chemicals to essentially mine metallic nutrients from their surroundings. With their metabolism spiked by the experiment’s added nutrients, the bacteria living on the E. densa were catalyzing the reaction to dissolve the gold nanoparticles.

This process wouldn’t pose any threat [emphasis mine] to humans or other animal species in the wild. But when researchers design experiments with the assumption that their gold nanoparticles will remain intact, the process can confound the interpretation of their results.

“The assumption that gold is inert did not hold in these experiments,” said Wiesner. “This is a good lesson that underscores how real, complex environments, that include for example the bacteria growing on leaves, can give very different results from experiments run in a laboratory setting that do not include these complexities.”

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

Gold nanoparticle biodissolution by a freshwater macrophyte and its associated microbiome by Astrid Avellan, Marie Simonin, Eric McGivney, Nathan Bossa, Eleanor Spielman-Sun, Jennifer D. Rocca, Emily S. Bernhardt, Nicholas K. Geitner, Jason M. Unrine, Mark R. Wiesner, & Gregory V. Lowry. Nature Nanotechnology (2018) DOI: https://doi.org/10.1038/s41565-018-0231-y Published

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.

Silver nanoparticles and wormwood tackle plant-killing fungus

I’m back in Florida (US), so to speak. Last mentioned here in an April 7, 2015 post about citrus canker and zinkicide, a story about a disease which endangers citrus production in the US, this latest story concerns a possible solution to the problem of a fungus, which attacks ornamental horticultural plants in Florida. From a May 5, 2015 news item on Azonano,

Deep in the soil, underneath more than 400 plant and tree species, lurks a lethal fungus threatening Florida’s $15 billion a year ornamental horticulture industry.

But University of Florida plant pathologist G. Shad Ali has found an economical and eco-friendly way to combat the plant destroyer known as phytophthora before it attacks the leaves and roots of everything from tomato plants to oak trees.

Ali and a team of researchers with UF’s Institute of Food and Agricultural Sciences, along with the University of Central Florida and the New Jersey Institute of Technology, have found that silver nanoparticles produced with an extract of wormwood, an herb with strong antioxidant properties, can stop several strains of the deadly fungus.

A May 4, 2015 University of Florida news release, which originated the news item, describes the work in more detail,

“The silver nanoparticles are extremely effective in eliminating the fungus in all stages of its life cycle,” Ali said. “In addition, it has no adverse effects on plant growth.” [emphasis mine]

The silver nanoparticles measure 5 to 100 nanometers in diameter – about one one-thousandth the width of a human hair. Once the nanoparticles are sprayed onto a plant, they shield it from fungus. Since the nanoparticles display multiple ways of inhibiting fungus growth, the chances of pathogens developing resistance to them are minimized, Ali said. Because of that, they may be used for controlling fungicide-resistant plant pathogens more effectively.

That’s good news for the horticulture industry. Worldwide crop losses due to phytophthora fungus diseases are estimated to be in the multibillion dollar range, with $6.7 billion in losses in potato crops due to late blight – the cause of the Irish Potato Famine in the mid-1800s when more than 1 million people died – and $1 billion to $2 billion in soybean loss.

Silver nanoparticles are being investigated for applications in various industries, including medicine, diagnostics, cosmetics and food processing.  They already are used in wound dressings, food packaging and in consumer products such as textiles and footwear for fighting odor-causing microorganisms.

Other members of the UF research team were Mohammad Ali, a visiting doctoral student from the Quaid-i-Azam University, Islamabad, Pakistan; David Norman and Mary Brennan with the University of Florida’s Plant Pathology-Mid Florida Research and Education Center; Bosung Kim with the University of Central Florida’s chemistry department; Kevin Belfield with the College of Science and Liberal Arts at the New Jersey Institute of Technology and the University of Central Florida’s chemistry department.

Ali’s comment about silver nanoparticles not having any adverse effects on plant growth is in contrast to findings by Mark Wiesner and other researchers at  Duke University (North Carolina, US). From my Feb. 28, 2013 posting (which also features a Finnish-Estonia study showing no adverse effects from silver nanoparticles  in crustaceans),

… there’s a study from Duke University suggests that silver nanoparticles in wastewater which is later put to agricultural use may cause problems. From the Feb. 27, 2013 news release on EurekAlert,

In experiments mimicking a natural environment, Duke University researchers have demonstrated that the silver nanoparticles used in many consumer products can have an adverse effect on plants and microorganisms.

The main route by which these particles enter the environment is as a by-product of water and sewage treatment plants. [emphasis] The nanoparticles are too small to be filtered out, so they and other materials end up in the resulting “sludge,” which is then spread on the land surface as a fertilizer.

The researchers found that one of the plants studied, a common annual grass known as Microstegium vimeneum, had 32 percent less biomass in the mesocosms treated with the nanoparticles. Microbes were also affected by the nanoparticles, Colman [Benjamin Colman, a post-doctoral fellow in Duke’s biology department and a member of the Center for the Environmental Implications of Nanotechnology (CEINT)] said. One enzyme associated with helping microbes deal with external stresses was 52 percent less active, while another enzyme that helps regulate processes within the cell was 27 percent less active. The overall biomass of the microbes was also 35 percent lower, he said.

“Our field studies show adverse responses of plants and microorganisms following a single low dose of silver nanoparticles applied by a sewage biosolid,” Colman said. “An estimated 60 percent of the average 5.6 million tons of biosolids produced each year is applied to the land for various reasons, and this practice represents an important and understudied route of exposure of natural ecosystems to engineered nanoparticles.”

“Our results show that silver nanoparticles in the biosolids, added at concentrations that would be expected, caused ecosystem-level impacts,” Colman said. “Specifically, the nanoparticles led to an increase in nitrous oxide fluxes, changes in microbial community composition, biomass, and extracellular enzyme activity, as well as species-specific effects on the above-ground vegetation.”

Getting back to Florida, you can find Ali’s abstract here,

Inhibition of Phytophthora parasitica and P. capsici by silver nanoparticles synthesized using aqueous extract of Artemisia absinthium by Mohammad Ali, Bosung Kim, Kevin Belfield, David J. Norman, Mary Brennan, & Gul Shad Ali. Phytopathology  http://dx.doi.org/10.1094/PHYTO-01-15-0006-R Published online April 14, 2015

This paper is behind a paywall.

For anyone who recognized that wormwood is a constituent of Absinthe, a liquor that is banned in many parts of the world due to possible side effects associated with the wormwood, here’s more about it from the Wormwood overview page on WebMD (Note: Links have been removed),

Wormwood is an herb. The above-ground plant parts and oil are used for medicine.

Wormwood is used in some alcoholic beverages. Vermouth, for example, is a wine beverage flavored with extracts of wormwood. Absinthe is another well-known alcoholic beverage made with wormwood. It is an emerald-green alcoholic drink that is prepared from wormwood oil, often along with other dried herbs such as anise and fennel. Absinthe was popularized by famous artists and writers such as Toulouse-Lautrec, Degas, Manet, van Gogh, Picasso, Hemingway, and Oscar Wilde. It is now banned in many countries, including the U.S. But it is still allowed in European Union countries as long as the thujone content is less than 35 mg/kg. Thujone is a potentially poisonous chemical found in wormwood. Distilling wormwood in alcohol increases the thujone concentration.

Returning to the matter at hand, as I’ve noted previously elsewhere, research into the toxic effects associated with nanomaterials (e.g. silver nanoparticles) is a complex process.