Tag Archives: sewage

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.

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.

Poopy gold, silver, platinum, and more

In the future, gold rushes could occur in sewage plants. Precious metals have been found in large quantity by researchers investigating waste and the passage of nanoparticles (gold, silver, platinum, etc.) into our water. From a Jan. 29, 2015 news article by Adele Peters for Fast Company (Note: Links have been removed),

One unlikely potential source of gold, silver, platinum, and other metals: Sewage sludge. A new study estimates that in a city of a million people, $13 million of metals could be collecting in sewage every year, or $280 per ton of sludge. There’s gold (and silver, copper, and platinum) in them thar poop.

Funded in part by a grant for “nano-prospecting,” the researchers looked at a huge sample of sewage from cities across the U.S., and then studied several specific waste treatment plants. “Initially we thought gold was at just one or two hotspots, but we find it even in smaller wastewater treatment plants,” says Paul Westerhoff, an engineering professor at Arizona State University, who led the new study.

Some of the metals likely come from a variety of sources—we may ingest tiny particles of silver, for example, when we eat with silverware or when we drink water from pipes that have silver alloys. Medical diagnostic tools often use gold or silver. …

The metallic particles Peters is describing are nanoparticles some of which are naturally occurring  as she notes but, increasingly, we are dealing with engineered nanoparticles making their way into the environment.

Engineered or naturally occurring, a shocking quantity of these metallic nanoparticles can be found in our sewage. For example, a waste treatment centre in Japan recorded 1,890 grammes of gold per tonne of ash from incinerated sludge as compared to the 20 – 40 grammes of gold per tonne of ore recovered from one of the world’s top producing gold mines (Miho Yoshikawa’s Jan. 30, 2009 article for Reuters).

While finding it is one thing, extracting it is going to be something else as Paul Westerhoff notes in Peters’ article. For the curious, here’s a link to and a citation for the research paper,

Characterization, Recovery Opportunities, and Valuation of Metals in Municipal Sludges from U.S. Wastewater Treatment Plants Nationwide by Paul Westerhoff, Sungyun Lee, Yu Yang, Gwyneth W. Gordon, Kiril Hristovski, Rolf U. Halden, and Pierre Herckes. Environ. Sci. Technol., Article ASAP DOI: 10.1021/es505329q Publication Date (Web): January 12, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

On a completely other topic, this is the first time I’ve noticed this type of note prepended to an abstract,

 Note

This article published January 26, 2015 with errors throughout the text. The corrected version published January 27, 2015.

Getting back to the topic at hand, I checked into nano-prospecting and found this Sept. 19, 2013 Arizona State University news release describing the project launch,

Growing use of nanomaterials in manufactured products is heightening concerns about their potential environmental impact – particularly in water resources.

Tiny amounts of materials such as silver, titanium, silica and platinum are being used in fabrics, clothing, shampoos, toothpastes, tennis racquets and even food products to provide antibacterial protection, self-cleaning capability, food texture and other benefits.

Nanomaterials are also put into industrial polishing agents and catalysts, and are released into the environment when used.

As more of these products are used and disposed of, increasing amounts of the nanomaterials are accumulating in soils, waterways and water-systems facilities. That’s prompting efforts to devise more effective ways of monitoring the movement of the materials and assessing their potential threat to environmental safety and human health.

Three Arizona State University faculty members will lead a research project to help improve methods of gathering accurate information about the fate of the materials and predicting when, where and how they may pose a hazard.

Their “nanoprospecting” endeavor is supported by a recently awarded $300,000 grant from the National Science Foundation.

You can find out more about Paul Westerhoff and his work here.

Silver nanoparticles, water, the environment, and toxicity

I am contrasting two very different studies on silver nanoparticles in water and their effect on the environment to highlight the complex nature of determining the risks and environmental effects associated with nanoparticles in general. One piece of research suggests that silver nanoparticles are less dangerous than other commonly used forms of silver while the other piece raises some serious concerns.

A Feb. 28, 2013 news item on Nanowerk features research about the effects that silver nanoparticles have on aquatic ecosystems (Note: A link has been removed),

According to Finnish-Estonian joint research with data obtained on two crustacean species, there is apparently no reason to consider silver nanoparticles more dangerous for aquatic ecosystems than silver ions.

The results were reported in the journal Environmental Science and Pollution Research late last year (“Toxicity of two types of silver nanoparticles to aquatic crustaceans Daphnia magna and Thamnocephalus platyurus”). Jukka Niskanen has utilised the same polymerisation and coupling reactions in his doctoral dissertation studying several hybrid nanomaterials, i.e. combinations of synthetic polymers and inorganic (gold, silver and montmorillonite) nanoparticles. Niskanen will defend his doctoral thesis at the University of Helsinki in April.

The University of Helsikinki Feb. 28, 2013 press release written by Minna Merilainen and which originated the new item provides details about the research,

“Due to the fact that silver in nanoparticle form is bactericidal and also fungicidal and also prevents the reproduction of those organisms, it is now used in various consumer goods ranging from wound dressing products to sportswear,” says Jukka Niskanen from the Laboratory of Polymer Chemistry at the University of Helsinki, Finland.A joint study from the University of Helsinki and the National Institute of Chemical Physics and Biophysics (Tallinn, Estonia), Toxicity of two types of silver nanoparticles to aquatic crustaceans Daphnia magna and Thamnocephalus platyurus, shows that silver nanoparticles are apparently no more hazardous to aquatic ecosystems than a water-soluble silver salt. The study compared the ecotoxicity of silver nanoparticles and a water-soluble silver salt.

“Our conclusion was that the environmental risks caused by silver nanoparticles are seemingly not higher than those caused by a silver salt. However, more research is required to reach a clear understanding of the safety of silver-containing particles,” Niskanen says.

Indeed, silver nanoparticles were found to be ten times less toxic than the soluble silver nitrate - a soluble silver salt used for the comparison.

The bioavailability of silver varies in different test media

To explain this phenomenon, the researchers refer to the variance in the bioavailability of silver to crustaceans in different tested media.

University lecturer Olli-Pekka Penttinen from the Department of Environmental Sciences of the University of Helsinki goes on to note that the inorganic and organic compounds dissolved in natural waters (such as humus), water hardness and sulfides have a definite impact on the bioavailability of silver. Due to this, the toxicity of both types of tested nanoparticles and the silver nitrate measured in the course of the study was lower in natural water than in artificial fresh water.

The toxicity of silver nanoparticles and silver ions was studied using two aquatic crustaceans, a water flea (Daphnia magna) and a fairy shrimp ( Thamnocephalus platyurus). Commercially available protein-stabilised particles and particles coated with a water-soluble, non-toxic polymer, specifically synthesised for the purpose, were used in the study. First, the polymers were produced utilising a controlled radical polymerization method. Synthetic polymer-grafted silver particles were then produced by attaching the water-soluble polymer to the surface of the silver with a sulfur bond.

Jukka Niskanen has utilised such polymerisation and coupling reactions in his doctoral dissertation. Polymeric and hybrid materials: polymers on particle surfaces and air-water interfaces, studying several hybrid nanomaterials , i.e., combinations of synthetic polymers and inorganic (gold, silver and montmorillonite) nanoparticles....

It was previously known from other studies and research results that silver changes the functioning of proteins and enzymes. It has also been shown that silver ions can prevent the replication of DNA. Concerning silver nanoparticles, tests conducted on various species of bacteria and fungi have indicated that their toxicity varies. For example, gram-negative bacteria such as Escherichia coli are more sensitive to silver nanoparticles than gram-positive ones (such as Staphylococcus aureus). The difference in sensitivity is caused by the structural differences of the cell membranes of the bacteria. The cellular toxicity of silver nanoparticles in mammals has been studied as well. It has been suggested that silver nanoparticles enter cells via endocytosis and then function in the same manner as in bacterial cells, damaging DNA and hindering cell respiration. Electron microscope studies have shown that human skin is permeable to silver nanoparticles and that the permeability of damaged skin is up to four times higher than that of healthy skin.

While this Finnish-Estonian study suggests that silver nanoparticles do not have a negative impact on the tested crustaceans in an aquatic environment, 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.”

As previously noted, these two studies show just how complex the questions of risk and nanoparticles can become.  You can find out more about the Finish-Estonian study,

Toxicity of two types of silver nanoparticles to aquatic crustaceans Daphnia magna and Thamnocephalus platyurus by  Irina Blinova, Jukka Niskanen, Paula Kajankari, Liina Kanarbik, Aleksandr Käkinen, Heikki Tenhu, Olli-Pekka Penttinen, and Anne Kahru. Environmental Science and Pollution Research published November 11, 2012 online

The publisher offers an interesting option for this article. While it is behind a paywall, access is permitted through a temporary window if you want to preview a portion of the article that lies beyond the abstract.

Meanwhile here’s the article by the Duke researchers,

Low Concentrations of Silver Nanoparticles in Biosolids Cause Adverse Ecosystem Responses under Realistic Field Scenario by Benjamin P. Colman, Christina L. Arnaout, Sarah Anciaux, Claudia K. Gunsch, Michael F. Hochella Jr, Bojeong Kim, Gregory V. Lowry,  Bonnie M. McGill, Brian C. Reinsch, Curtis J. Richardson, Jason M. Unrine, Justin P. Wright, Liyan Yin, and Emily S. Bernhardt. PLoS ONE 2013; 8 (2): e57189 DOI: 10.1371/journal.pone.0057189

This article is open access as are all articles published by the Public Library of Science (PLoS) journals.

For anyone interested in the Duke University/CEINT mesocosm project, I made mention of it in an Aug. 15, 2011 posting.

Latest on silver nanoparticle toxicity

Dr. Bernd Nowack has issued another report on nanosilver. His work was first mentioned in my Sept. 8, 2010 posting which focused on how washing silver nanoparticle-treated textiles releases silver nanoparticles into the wash water. Nowack’s latest work is a report recommending a more stringent approach to studying the risk that silver nanoparticles might pose to the environment. From the Nov. 22, 2010  news item by Lin Edwards on physrorg.com,

Dr. Nowack said one of the risks arises because some of the wastewater and sludge from sewage treatment plants ends up on farms in fertilizers, and could therefore enter the food chain. Another risk is that nanosilver could have a detrimental effect on the nitrifying bacteria that are vital to the effluent treatment processes, and could prevent treatment plants from working properly.

Nowack’s report said in earlier studies some nanosilver had been shown to bond with sulfur in sewage sludge to produce non-toxic silver sulfide nanoparticles, but it is not known how efficient sulfur is at removing biocidal silver.