Environmental Science: Nano – the benefits!

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Describing Nanoparticle Behaviour

Will the use of partition coefficients during nanoparticle risk assessment generate errors?

This perspective, by Antonia Praetorius from ETH Zurich et al analyses the danger of using partition coefficients for the risk assessment of nanoparticles.

Nanoparticle Behaviour

Adequate fate descriptors are crucial to predict the behaviour and transport of a contaminant in the environment and determining environmental concentrations for risk assessment. The authors of this perspective argue that the application of equilibrium partition coefficients in the context of engineered nanoparticle (ENP) fate assessment, although frequently suggested, lacks scientific justification.

Theories underlying partitioning behaviour and colloidal science are well established concepts and demonstrate that when it comes to ENPs, the use of partition coefficients could be inappropriate.  In environmental media, ENPs form thermodynamically unstable dispersions as opposed to solutions. Therefore, Praetorius et al suggest that the use of any coefficient based on equilibrium partitioning is inadequate for ENPs and can lead to significant errors in ENP fate predictions and risk assessment.

Have you done research involving the use of equilibrium partition coefficients for nanoparticles? Read the full perspective now for free* and submit your comments below.

The road to nowhere: Equilibrium partition coefficients for nanoparticles
Antonia Praetorius,   Nathalie Tufenkji,   Kai-Uwe Goss,  Martin Scheringer,   Frank von der Kammer and  Menachem Elimelech
DOI: 10.1039/C4EN00043A

The question remains, what are the best ‘global descriptors’ when it comes to describing ENP behaviour?

*Access is free through a registered RSC account – click here to register

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Phytotoxicity of Cerium Oxide Nanoparticles

For the very first time, researchers from China evaluate the phytotoxicity of cerium oxide nanoparticles (CeO2 NPs) in a plant agar medium.

Plants: basic components of the ecosystem and vulnerable to nanoparticle exposure. It is important to understand the interactions between nanoparticles and plants, especially when herbivorous consumers introduce these plants into our food chain.

As CeO2 NPs are widely used in many applications, their interactions with the ecosystem are inevitable. It has previously been shown that CeO2 NPs can inhibit root elongation of plants in aqueous suspensions. Dr Zhiyong Zhang et al investigated the toxicity of CeO2 NPs on asparagus lettuce in a plant agar medium, a semisolid, soil-like medium which provides a more realistic environment for plant growth.

A variety of parameters were investigated to understand the plant’s defence and response to abiotic stress caused by CeO2 NPs. Although the agar medium limited the bioavailability of CeO2 NPs, they were still more toxic to asparagus lettuce in the agar medium than in aqueous solution. This could be caused by the production of excess reactive oxygen species causing oxidative stress to the plants.

The increased phytotoxicity of CeO2 NPs in a soil like medium can also be explained by the biotransformation of CeO2 NPs. It has previously been demonstrated that Ce3+ released from CeO2 NPs can cause species-specific toxicity. This study showed that in an agar medium more than 20% of the Ce in the roots was transformed to Ce3+, whereas in aqueous solution only 6% of CeO2 was reduced to Ce3+. It is therefore reasonable to postulate that the phytotoxicity of CeO2 NPs is also attributed to the release of Ce3+.

To read the full paper, download it for free* today!

Effect of Cerium Oxide Nanoparticles on Asparagus Lettuce Cultured in an Agar Medium
Di Cui,   Peng Zhang,   yuhui Ma,   Xiao He,   Yuanyuan Li,  Jing Zhang,   Yuechun Zhao and   Zhiyong Zhang
DOI: 10.1039/C4EN00025K

* Access is free through a registered RSC account – click here to register

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Nanoparticle detection in a microsecond

Improving nanoparticle detection techniques

Nanoparticles – they are really small; we can’t see them, hear them or feel them and therefore they are pretty hard to detect! Manuel David Montaño, from Colorado School of Mines, and colleagues have made improvements in the detection and characterization of engineered nanoparticles, simply by reducing the time of detection for each nanoparticle – the dwell time.

In order to determine the toxicity, fate and transport of nanoparticles in the environment, we first need to determine the size and quantity of nanoparticles in the environment. In order to determine the size and quantity of nanoparticles in the environment we need to be able to accurately detect these nanoparticles. Single particle ICP-MS (spICP-MS) is already a promising technique to detect and characterize low concentrations of engineered nanoparticles in biological and environmental matrices. Initially developed for aerosol particle analysis, spICP-MS uses time resolved analysis with dwell times of approximately 10miliseconds. So how does it work? A discrete pulse of intensity, origination from nanoparticle vaporization and ionization, can be detected – the signal generated by the ions can then be correlated to nanoparticle mass.

The problem – this method of detection only works on low concentrations of nanoparticles. In high concentrations of nanoparticles, two or more nanoparticles can be detected during the same dwell time giving invalid results. It appears that particles are larger in size and lower in concentration that they really would be in the environment. To overcome this problem, often samples have to be diluted considerably, making the results less environmentally relevant. In this study, instead of diluting the samples, researchers simply reduced the dwell time from milliseconds to microseconds. This improved the resolution and working range of spICP-MS, allowing a greater breadth of environmental samples to be analysed.

You can read the full paper for free* by clicking the link below

Improvements in the detection and characterization of engineered nanoparticles using spICP-MS with microsecond dwell times
M. D. Montaño, H. R. Badiei, S. Bazargan and J. F. Ranville
DOI: 10.1039/C4EN00058G

* Access is free through a registered RSC account – click here to register

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Nanoparticle Crystal Structure Affects Alkali and Acid Digestion

By Imali Mudunkotuwa, Postdoctoral Researcher Scholar at University of Iowa and web writer for the Royal Society of Chemistry Environmental Team

Titanium Oxide nanoparticles (TiO2 NPs) – given their wide applications, exposure scenarios and classification as a class 2B carcinogen (International Agency of Research on Cancer), it is high time for the precise and accurate quantitative analysis of TiO2 NP contamination in environmental samples. Being one of the metal oxides that is extremely hard to solubilize makes accurate and precise measurement of TiO2 a challenge. Recent investigations using mixed acid digestion and alkali potassium hydroxide (KOH) fusion has given improved recoveries of TiO2 when compared to the conventional methods. This is great news for all of us who struggle to quantify TiO2 nanoparticles in complex environmental matrices! However, as with all nanoscale materials there are complications arising from size and polymorph dependent thermodynamic stabilities as well as chemical reactions between Ti and other sample matrices, especially at elevated temperature and pressure. Thus, R. G. Silva and coworkers of United States Environmental Protection Agency (US-EPA) investigate the digestibility of different polymorphs of TiO2 NPs; anatase, rutile and brookite. These samples were used for spiking environmental matrices consisting of river sediment and clay minerals (bentonite and kaolinite). Furthermore, a portion of these were subjected to heat (300OC) and pressure (10.3 bar) treatment to investigate its impact on the Ti recovery from the TiO2 NPs.

Extensive characterization of all three nanoparticle samples with respect to size, shape, crystallinity and surface area before and after the heat and pressure treatments showed significant changes in the physicochemical properties of anatase and brookite. Rutile on the other hand was resistant to changes. In terms of digestion, acid digestion resulted in relatively lower Ti concentration for the pure TiO2 NP samples that underwent heat and pressure treatment. In contrast, alkali fusion resulted in increased levels of Ti. Nevertheless, when the TiO2 NP polymorphs were blended in the environmental matrices, for anatase and brookite the recoveries were similar for both types of digestions. However, for the recovery of rutile the alkali fusion method proved to be superior to that of the mixed acid method. Therefore, this work recommends using the alkali fusion method for the extraction of Ti from TiO2 NP contaminated unknown environmental samples.

To access the full article, download a copy for free* by clicking the link below.

Polymorph-dependent titanium dioxide nanoparticle dissolution in acidic and alkali digestions

R. G. Silva, M. N. Nadagouda, C. L. Patterson, Srinivas Panguluri, T. P. Luxton, E. Sahle-Demessieb and   C. A. Impellitterib
DOI: 10.1039/C3EN00103B

*Access is free through a registered RSC account – click here to register

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Environmental Effects of Nano International Conference

The 9th International Conference on the Environmental Effects of Nanoparticles and Nanomaterials – Columbia, South Carolina, USA.

The 9th International Conference on the Environmental Effects of Nanoparticles and Nanomaterials

September 7-11, 2014


The 9th International Conference on the Environmental Effects of Nanoparticles and Nanomaterials (Nano2014) aims to bring together researchers, regulators, and industry to discuss the potential hazards and risks of current and future applications in the key sector of nanotechnology, along with mechanisms to bring about risk reduction while maintaining economic and social benefits.

Human exposure and hazard will be key aspects of the conference and the program will contain multiple sessions related to:

1) physical and chemical properties of nanoparticles as related to the environment and health,

2) fate, behavior and transformations,

3) toxicology and ecotoxicology,

4) social and regulatory sciences,

5) innovation and applications of nanotechnology to environmental and health issues.

Don’t miss out – submit your abstracts by 15th June 2014!

Registration can be completed online and you must be registered by 30th June 2014 in order to attend this conference

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Illuminating the issue of real-time nanomaterial characterization

By Ian Keyte, Doctoral Researcher at University of Birmingham and web writer for the Royal Society of Chemistry Environmental Team

Fluorescence complexation could hold the key to more detailed monitoring of airborne nanomaterials. Researchers at Texas A&M University, USA describe the successful development of a new method of simultaneous online quantification and characterization.

Fluorescent Complexation

The increased manufacture and use of nanomaterials has led to increased concerns about their associated health risks, particularly in the occupational setting. One of the main barriers to addressing uncertainties in this field is a poor understanding of personal exposure levels. There is currently a lack of sufficient dynamic data regarding the main exposure routes for airborne nanomaterials so appropriate exposure guidelines, profiles and models cannot be established.

It is important, therefore to establish effective means of measuring the levels and chemical/physical properties of nanomaterials in real-time. Preferred traditional means of nanomaterial analysis e.g. mass spectrometry (MS) and electron microscopy (EM) cannot be easily adapted to use in an online capacity. This means exposure analysis is generally slow and can only be carried out for relatively short, unrepresentative time-frames.

In this study Fanxu Meng and co-workers introduce and demonstrate an integrated methodology that allows continuous online monitoring of the levels and characterization of airborne nanomaterials. This method combines ultra high flow sampling with a sensitive fluorescence-based detection system.

The sampling system comprised a modified wetted wall cyclone (WWC) collector which has an ultra high flow rate (>1000 L min-1) combined with a continuous flow microfluidic network allowing online detection capability. The detection system utilized florescence generated by the combination of a suspension of collected nanoparticles and a tracer dye solution. The resulting dye-nanoparticle complex produces an intense and easily detectible fluorescent signature, dependent on the quantity and the physical/chemical properties of the collected nanomaterials.

The integrated system was tested using prepared suspensions of Al2O3. A scanning mobility particle sizer (SMPS) was used to quantify the concentration and size distribution of nanoparticles inside the test chamber. It was shown that florescence displays a characteristic pattern, dependent on the concentration but also the size and particle surface area of the nanomaterials. A linear correlation between florescence intensity and airborne concentration of Al2O3 at concentrations up to 1.0-1.2 wt% at flow rates of 0.2 and 0.02 mL min-1 was observed.

This work provides a platform for continuous measurement of airborne nanomaterials. Simultaneous sampling and compound characterization can enable better time-resolved assessment of the transport and fate of released nanomaterials and identification of hazardous releases. The method described is capable of sampling a broad range of air volumes (representative of the work place environment) and allows online detection and analysis. The authors highlight potential further innovations for this work, possibly leading to more detailed exposure profiles for nanomaterials; establishing fluorescence “fingerprints” for a range of different nanoparticles; and analysis of biological material.

Download the full article for free* today!

Localized Fluorescent Complexation Enables Rapid Monitoring of Airborne Nanoparticles
Fanxu Meng, Maria D. King, Yassin A. Hassan, and Victor M. Ugaz
DOI: 10.1039/C4EN00017J

*Access is free through a registered RSC account – click here to register

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Most accessed ESNano articles in Q1 2014

Most accessed articles from January – March 2014

Recent advances in BiOX (X = Cl, Br and I) photocatalysts: synthesis, modification, facet effects and mechanisms 
Liqun Ye, Yurong Su, Xiaoli Jin, Haiquan Xie and Can Zhang    
Environ. Sci.: Nano, 2014,1, 90-112
DOI: 10.1039/C3EN00098B  
 
Green synthesis and formation mechanism of cellulose nanocrystal-supported gold nanoparticles with enhanced catalytic performance 
Xiaodong Wu, Canhui Lu, Zehang Zhou, Guiping Yuan, Rui Xiong and Xinxing Zhang    
Environ. Sci.: Nano, 2014,1, 71-79
DOI: 10.1039/C3EN00066D  
  
Natural water chemistry (dissolved organic carbon, pH, and hardness) modulates colloidal stability, dissolution, and antimicrobial activity of citrate functionalized silver nanoparticles 
Lok R. Pokhrel, Brajesh Dubey and Phillip R. Scheuerman    
Environ. Sci.: Nano, 2014,1, 45-54
DOI: 10.1039/C3EN00017F  
 
A minor lipid component of soy lecithin causes growth of triangular prismatic gold nanoparticles 
Benjamin R. Ayres and Scott M. Reed    
Environ. Sci.: Nano, 2014,1, 37-44
DOI: 10.1039/C3EN00015J  
 
Characterization of particle emissions and fate of nanomaterials during incineration 
Eric P. Vejerano, Elena C. Leon, Amara L. Holder and Linsey C. Marr    
Environ. Sci.: Nano, 2014,1, 133-143
DOI: 10.1039/C3EN00080J  
 
Effect of natural organic matter on the disagglomeration of manufactured TiO2 nanoparticles 
Frédéric Loosli, Philippe Le Coustumer and Serge Stoll    
Environ. Sci.: Nano, 2014,1, 154-160
DOI: 10.1039/C3EN00061C  
 
A chemical free, nanotechnology-based method for airborne bacterial inactivation using engineered water nanostructures 
Georgios Pyrgiotakis, James McDevitt, Andre Bordini, Edgar Diaz, Ramon Molina, Christa Watson, Glen Deloid, Steve Lenard, Natalie Fix, Yosuke Mizuyama, Toshiyuki Yamauchi, Joseph Brain and Philip Demokritou    
Environ. Sci.: Nano, 2014,1, 15-26
DOI: 10.1039/C3EN00007A  
  
Interactions between polybrominated diphenyl ethers and graphene surface: a DFT and MD investigation 
Ning Ding, Xiangfeng Chen and Chi-Man Lawrence Wu    
Environ. Sci.: Nano, 2014,1, 55-63
DOI: 10.1039/C3EN00037K  
  
Deposition of nanoparticles onto polysaccharide-coated surfaces: implications for nanoparticle–biofilm interactions 
Kaoru Ikuma, Andrew S. Madden, Alan W. Decho and Boris L. T. Lau    
Environ. Sci.: Nano, 2014,1, 117-122
DOI: 10.1039/C3EN00075C  
  
Quantitative assessment of inhalation exposure and deposited dose of aerosol from nanotechnology-based consumer sprays 
Yevgen Nazarenko, Paul J. Lioy and Gediminas Mainelis    
Environ. Sci.: Nano, 2014,1, 161-171
DOI: 10.1039/C3EN00053B  

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to ESNano? Then why not submit to us today or alternatively email us your suggestions.

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Nanoparticle sulfidation transformations

Sulfidation of CuO may increase its apparent solubility, resulting bioavailability and ecotoxicity attributed to toxic Cu2+

A study by Gregory Lowry and colleagues from Carnegie Mellon University suggests that Copper Oxide (CuO) nanoparticles (NPs) are sulfidized in the environment, affecting their resulting properties. Some of the affected properties, such as solubility are relevant to the toxicity of these nanoparticles in the environment.

Many nanoparticles are transformed in the environment; it is often the transformed materials which cause concern with regards to nanoparticle toxicity. There have been several papers highlighting how important it is to research the properties of nanoparticle transformations. A recent review by Nasia Von Moos provides an overview of what is currently known about environmental transformations of nanomaterials in freshwater systems, a recent paper by Julián A. Gallego-Urrea discusses the transformations which TiO2 nanoparticles undergo once they reach the aquatic environment and this research paper reports that sulfidation is an important transformation for some metal oxide nanoparticles, such as CuO NPs.

Why is sulfidation in the environment important?

Copper-based NPs are being used in semiconductors, heat transfer fluids, catalysts, batteries and many more products and technologies. Their wide spread uses will likely lead to subsequent release into the environment, raising concerns about their potential toxicity. It has already been demonstrated that CuO NPs are toxic to many organisms including crustaceans, algae and fish; although Cu2+ is more toxic to most of these organisms. It is therefore essential to determine what the products of sulfidized CuO NPs are and if they are more or less toxic to the environment when compared with pristine CuO.

Sulfidation of CuO

Cuo NPs were characterized and sulfidized in water by inorganic sulfide. Characterization of the resulting products showed that CuO is sulfidized to several copper sulphide species including crystalline CuS (covellite), amorphous (CuxSy) species and copper sulphate hydroxide species. In previous studies it has been demonstrated shown that sulfidation decreases the solubility and metal availability of Ag and ZnO NPs. This study however shows that the sulfidation of CuO NPs breaks the trend. Sulfidation actually increased the dissolved fraction of copper compared to pristine CuO NPs. This increased release of Cu2+ and CuS nanoclusters from sulfidized NPs compared to CuO suggests that toxicity studies with pristine CuO may be misleading in environments where sulfidation is likely to occur, demonstrating that it is prudent to use environmentally transformed nanoparticles in fate, transport and toxicitiy studies rather than focusing soley on the prisitne materials. Access the full article for free* by clicking the link below.

Sulfidation of copper oxide nanoparticles and properties of resulting copper sulfide
Rui Ma, John Stegemeier, Clement Levard, James Dale, Clinton W Noack, Tittany Yang, Gordon Brown and Gregory Lowry
DOI: 10.1039/C4EN00018H

*Access is free through a registered RSC account – click here to register

The author recommends further studies which are still needed to:

  1. Identify the nature of the CuxSy nanoclusters.
  2. Assess the toxicity of sulfidized CuO NPs and CuxSy nanoclusters.
  3. Assess the stability of very small metal sulphide clusters (Ag, Zn and Cu) against oxidation under environmental and biological conditions.
  4. Assess how sulfidation of CuO NPs occurs in situ at relevant CuO/S concentration ratios and how this affects their bioavailability under realistic exposure scenarios.
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Vicki Grassian is the 2014 John Jeyes Award Winner

John Jeyes 2014 Award WinnerProfessor Vicki Grassian, Chair of Environmental Science: Nano has won the 2014 John Jeyes Award for her pioneering contributions to the chemistry of environmental interfaces, heterogeneous atmospheric chemistry and the environmental implications of nanomaterials.

It is truly an honor to receive this award Grassian said.

The John Jeyes Award, founded in 1975, is a biennial award for chemistry in relation to the environment. Vicki Grassian, Founding Director of the Nanoscience and Nanotechnology Institute at the University of Iowa, has mentored over one hundred students and postdocs in her laboratory, many of them now having their own research programs focused on energy and the environment.

The John Jeyes Award is wonderful recognition of the research that has been done by the students and postdoctoral associates who have worked in my laboratoryGrassian said.

We would like to congratulate Vicki on her achievement and take this opportunity to thank Vicki for her pioneering contributions to Environmental Science: Nano, bringing together a variety of communities to publish their work on nanoscience and the implications for the environment, health and sustainability.

Vicki’s latest ES:Nano paper Iron oxide nanoparticles induce Pseudomonas aeruginosa growth, induce biofilm formation and inhibit antimicrobial peptide function (C3EN00029J) is included in a dedicated themed collection of papers celebrating the 2014 RSC Prize and Award winners. All articles in this collection are free* to access until 6th June.

*Access is free through a registered RSC account – click here to register

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Applications of porous nanomaterials

Sean Lehman and Sarah Larsen from the University of Iowa review zeolite and mesoporous silica nanomaterials with emphasis on connections to the environment.

In recent years, there has been a great deal of interest in zeolites and mesoporous silica nanomaterials (MSNs). Zeolites are widely used in industry for applications such as catalysis, separations and gas adsorption, however the authors believe that these porous nanomaterials have a largely unrealized commercial potential for environmental applications.

Structures of porous nanomaterials

This review article covers three major areas:

  1. Greener synthesis of zeolite and MSNs
  2. Potential of zeolite and MSNs for environmental applications
  3. The biological toxicity of zeolite and MSNs

Due to cost and reduced thermal stability MSNs are not as extensively applied as zeolite; however they are currently being investigated for potential environmental and biomedical applications. Their varied physiochemical properties open up a wide range of potential applications. The more applications that these porous nanomaterials have in industry, the greater the interested in developing greener synthesis for them and reducing their toxicity. With two measurements which are on the nanoscale, pore size as well as particle size, zeolites and MSN make very interesting nanomaterials.

This review describes both the environmental applications, including environmental catalysis and adsorption of environmental contaminants, and implications of zeolite and MSNs. Due to concerns that increased use of these materials translates to increased exposures, toxicity studies of both nanomaterials are also reviewed.

To read the full review for free* click the link below:

Zeolite and Mesoporous Silica Nanomaterials: Greener Syntheses, Environmental Applications and Biological Toxicity

Sean E Lehman and Sarah C Larsen
DOI: 10.1039/C4EN00031E, Critical Review

Zeolites and MSNs are silicate or aluminosilicate nanomaterials with well-defined pore networks; there are however some differences between the two porous nanomaterials.

Properties of zeolites:

  • Crystalline aluminosilicates (or silicates)
  • Regular arrangements of micropores
  • High surface areas
  • Exchangeable cations

Properties of MSN:

  • Amorphous silica materials
  • Regualr arrangement of mesopores
  • Very high surface area

The first area discussed in this review is the synthesis of zeolite and MSNs using green synthetic routes. The green strategies can be organized into three main categories: solvent, template and heating. The diagram below demonstrates the strategies for the greener synthesis of zeolites and mesoporous silica.

Greener synthesis of zeolites and mesoporous silica

*Access is free through a registered RSC account – click here to register

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