Tag Archives: Konrad Hungerbühler

Nanoparticle behaviour in the environment unpredictable

These Swiss researchers took on a fairly massive project according to an April 19, 2017 news item on ScienceDaily,

The nanotech industry is booming. Every year, several thousands of tonnes of man-made nanoparticles are produced worldwide; sooner or later, a certain part of them will end up in bodies of water or soil. But even experts find it difficult to say exactly what happens to them there. It is a complex question, not only because there are many different types of man-made (engineered) nanoparticles, but also because the particles behave differently in the environment depending on the prevailing conditions.

Researchers led by Martin Scheringer, Senior Scientist at the Department of Chemistry and Applied Biosciences, wanted to bring some clarity to this issue. They reviewed 270 scientific studies, and the nearly 1,000 laboratory experiments described in them, looking for patterns in the behaviour of engineered nanoparticles. The goal was to make universal predictions about the behaviour of the particles.

An April 19, 2017ETH Zurich press release by Fabio Bergamin (also on EurekAlert), which originated the news item, elaborates,

Particles attach themselves to everything

However, the researchers found a very mixed picture when they looked at the data. “The situation is more complex than many scientists would previously have predicted,” says Scheringer. “We need to recognise that we can’t draw a uniform picture with the data available to us today.”

Nicole Sani-Kast, a doctoral student in Scheringer’s group and first author of the analysis published in the journal PNAS [Proceedings of the National Academy of Sciences], adds: “Engineered nanoparticles behave very dynamically and are highly reactive. They attach themselves to everything they find: to other nanoparticles in order to form agglomerates, or to other molecules present in the environment.”

Network analysis

To what exactly the particles react, and how quickly, depends on various factors such as the acidity of the water or soil, the concentration of the existing minerals and salts, and above all, the composition of the organic substances dissolved in the water or present in the soil. The fact that the engineered nanoparticles often have a surface coating makes things even more complicated. Depending on the environmental conditions, the particles retain or lose their coating, which in turn influences their reaction behaviour.

To evaluate the results available in the literature, Sani-Kast used a network analysis for the first time in this research field. It is a technique familiar in social research for measuring networks of social relations, and allowed her to show that the data available on engineered nanoparticles is inconsistent, insufficiently diverse and poorly structured.

More method for machine learning

“If more structured, consistent and sufficiently diverse data were available, it may be possible to discover universal patterns using machine learning methods,” says Scheringer, “but we’re not there yet.” Enough structured experimental data must first be available.

“In order for the scientific community to carry out such experiments in a systematic and standardised manner, some kind of coordination is necessary,” adds Sani-Kast, but she is aware that such work is difficult to coordinate. Scientists are generally well known for preferring to explore new methods and conditions rather than routinely performing standardized experiments.

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Distinguishing man-made and natural nanoparticles

In addition to the lack of systematic research, there is also a second tangible problem in researching the behaviour of engineered nanoparticles: many engineered nanoparticles consist of chemical compounds that occur naturally in the soil. So far it has been difficult to measure the engineered particles in the environment since it is hard to distinguish them from naturally occurring particles with the same chemical composition.

However, researchers at ETH Zurich’s Department of Chemistry and Applied Biosciences, under the direction of ETH Professor Detlef Günther, have recently established an effective method that makes such a distinction possible in routine investigations. They used a state-of-the-art and highly sensitive mass spectrometry technique (called spICP-TOF mass spectrometry) to determine which chemical elements make up individual nanoparticles in a sample.

In collaboration with scientists from the University of Vienna, the ETH researchers applied the method to soil samples with natural cerium-containing particles, into which they mixed engineered cerium dioxide nanoparticles. Using machine learning methods, which were ideally suited to this particular issue, the researchers were able to identify differences in the chemical fingerprints of the two particle classes. “While artificially produced nanoparticles often consist of a single compound, natural nanoparticles usually still contain a number of additional chemical elements,” explains Alexander Gundlach-Graham, a postdoc in Günther’s group.

The new measuring method is very sensitive: the scientists were able to measure engineered particles in samples with up to one hundred times more natural particles.

The researchers have produced a visualization of their network analysis,

The researchers evaluated the experimental data published in the scientific literature using a network analysis. This analysis reveals which types of nanoparticles (blue) have been studied under which environmental conditions (red). (Visualisations: Thomas Kast)

Here are links and citation for two papers associated with this research,

A network perspective reveals decreasing material diversity in studies on nanoparticle interactions with dissolved organic matter by Nicole Sani-Kast, Jérôme Labille, Patrick Ollivier, Danielle Slomberg, Konrad Hungerbühler, and Martin Scheringer. PNAS 2017, 114: E1756-E1765, DOI: 10.1073/pnas.1608106114

Single-particle multi-element fingerprinting (spMEF) using inductively-coupled plasma time-of-flight mass spectrometry (ICP-TOFMS) to identify engineered nanoparticles against the elevated natural background in soils by Antonia Praetorius, Alexander Gundlach-Graham, Eli Goldberg, Willi Fabienke, Jana Navratilova, Andreas Gondikas, Ralf Kaegi, Detlef Günther, Thilo Hofmann, and Frank von der Kammer. Environonmental Science: Nano 2017, 4: 307-314, DOI: 10.1039/c6en00455e

Both papers are behind a paywall.

New model to track flow of nanomaterials through our air, earth, and water

Just how many tons of nanoparticles are making their way through the environment? Scientists at the Swiss Federal Laboratories for Materials Science and Technology (Empa) have devised a new model which could help answer that question. From a May 12, 2016 news item on phys.org,

Carbon nanotubes remain attached to materials for years while titanium dioxide and nanozinc are rapidly washed out of cosmetics and accumulate in the ground. Within the National Research Program “Opportunities and Risks of Nanomaterials” (NRP 64) a team led by Empa scientist Bernd Nowack has developed a new model to track the flow of the most important nanomaterials in the environment.

A May 12, 2016 Empa press release by Michael Hagmann, which also originated the news item, provides more detail such as an estimated tonnage for titanium dioxide nanoparticles produced annually in Europe,

How many man-made nanoparticles make their way into the air, earth or water? In order to assess these amounts, a group of researchers led by Bernd Nowack from Empa, the Swiss Federal Laboratories for Materials Science and Technology, has developed a computer model as part of the National Research Program “Opportunities and Risks of Nanomaterials” (NRP 64). “Our estimates offer the best available data at present about the environmental accumulation of nanosilver, nanozinc, nano-tinanium dioxide and carbon nanotubes”, says Nowack.

In contrast to the static calculations hitherto in use, their new, dynamic model does not just take into account the significant growth in the production and use of nanomaterials, but also makes provision for the fact that different nanomaterials are used in different applications. For example, nanozinc and nano-titanium dioxide are found primarily in cosmetics. Roughly half of these nanoparticles find their way into our waste water within the space of a year, and from there they enter into sewage sludge. Carbon nanotubes, however, are integrated into composite materials and are bound in products such as which are immobilized and are thus found for example in tennis racquets and bicycle frames. It can take over ten years before they are released, when these products end up in waste incineration or are recycled.

39,000 metric tons of nanoparticles

The researchers involved in this study come from Empa, ETH Zurich and the University of Zurich. They use an estimated annual production of nano-titanium dioxide across Europe of 39,000 metric tons – considerably more than the total for all other nanomaterials. Their model calculates how much of this enters the atmosphere, surface waters, sediments and the earth, and accumulates there. In the EU, the use of sewage sludge as fertilizer (a practice forbidden in Switzerland) means that nano-titanium dioxide today reaches an average concentration of 61 micrograms per kilo in affected soils.

Knowing the degree of accumulation in the environment is only the first step in the risk assessment of nanomaterials, however. Now this data has to be compared with results of eco-toxicological tests and the statutory thresholds, says Nowack. A risk assessment has not been carried out with his new model so far. Earlier work with data from a static model showed, however, that the concentrations determined for all four nanomaterials investigated are not expected to have any impact on the environment.

But in the case of nanozinc at least, its concentration in the environment is approaching the critical level. This is why this particular nanomaterial has to be given priority in future eco-toxicological studies – even though nanozinc is produced in smaller quantities than nano-titanium dioxide. Furthermore, eco-toxicological tests have until now been carried out primarily with freshwater organisms. The researchers conclude that additional investigations using soil-dwelling organisms are a priority.

Here are links to and citations for papers featuring the work,

Dynamic Probabilistic Modeling of Environmental Emissions of Engineered Nanomaterials by Tian Yin Sun†, Nikolaus A. Bornhöft, Konrad Hungerbühler, and Bernd Nowack. Environ. Sci. Technol., 2016, 50 (9), pp 4701–4711 DOI: 10.1021/acs.est.5b05828 Publication Date (Web): April 04, 2016

Copyright © 2016 American Chemical Society

Probabilistic environmental risk assessment of five nanomaterials (nano-TiO2, nano-Ag, nano-ZnO, CNT, and fullerenes) by Claudia Coll, Dominic Notter, Fadri Gottschalk, Tianyin Sun, Claudia Som, & Bernd Nowack. Nanotoxicology Volume 10, Issue 4, 2016 pages 436-444 DOI: 10.3109/17435390.2015.1073812 Published online: 10 Nov 2015

The first paper, which is listed in Environmental Science & Technology, appears to be open access while the second paper is behind a paywall.