Nanoscience and the Environment

Preface

Jamie R. Lead; Eugenia Valsami-Jones

Nanoscience, generally defined as the science of materials ranging between approximately 1 and 100 nm in at least one dimension, has become a hugely important area of research and development (R&D) in recent years. In this range, novel size-dependent properties manifest themselves and many exciting technological applications have emerged with perhaps more yet to come. As a result, there has been an exponential explosion in R&D funding (see Chapter 1), along with publications, patent applications, products on the market, and other metrics which capitalize on the novel uses of nanoscience. Interestingly, many of the commercial uses are currently fairly low technology, but the increasing sophistication in development and application means that there is potential for growth in more sophisticated nanomaterials, nanosystems, and nanodevices in a range of sectors including medicine and health, energy production, environmental remediation, and elsewhere. These sophisticated materials will tend to be more highly structured, more tightly constrained, and often smaller and dispersible; these properties will tend to increase mobility, bioavailability, and toxicity. Such properties will therefore likely increase the use and importance of nanomaterials as a social and economic driver, but will also likely lead to greater potential hazard and exposure to humans and to the environment.

The trade-off between utility and benefit of nanotechnology and its potential implications for human and environmental health is often seen as a major complication and potential limitation on the spread and general acceptance of the technology. For instance, potential hazards and risks might be perceived, misunderstood, and inflated. The consequent fallout might retard acceptance and uptake of new and important technologies. However, it is also possible to see this problem as illusory, except in the very short term; long-term sustainability of a technology depends upon its safety (however defined) and that this safety is seen to be openly investigated. Environmental and health issues which might arise are hopefully of less importance because knowledge is greater and, as there is greater transparency, general distrust is reduced. Therefore, it is possible to argue convincingly that commercial sustainability is increased by open research into environmental and human health consequences. In addition, the development of new knowledge and understanding is an important good in its own right, quite separate from the pragmatic gains produced.

From all of these arguments, it is clear that research into the fate and effects of nanomaterials in the environment is essential in both health and technology sectors. This book aims to summarize the current state of the art in relevant areas. Chapter 1 gives a grounding and overview of the many issues involved in a broadly defined environmental nanoscience including discussions of history, nomenclature and definitions, environmental processes, and related areas, setting the scene for the more detailed chapters that follow, on topics of particular current interest. Chapter 2 gives an account of the chemical, physical, and biological transformations which might occur once nanomaterials are released into the environment. The persistence of nanomaterials is governed by the nature of the particle and the nature of the environmental conditions, but changes might occur via processes such as microbial degradation, agglomeration, and dissolution. Chapter 3 surveys the current knowledge regarding the modeling of fate and behavior processes in the environment, a particularly important theme, considering the logistical difficulties of experimentally determining all potential behaviors, while Chapter 4 examines a particular transformation process relevant to fate and behavior, the development of an eco-corona. In human toxicology, the development of a more widely known protein corona is important on nanomaterial contact with biological macromolecules and alters protein and nanomaterial behavior. In the environment, development of an eco-corona, primarily due to natural organic macromolecules, is an important process which may significantly alter physicochemical processes (e.g., aggregation, dissolution, sulfidation), while also altering biouptake processes. Chapter 4 therefore nicely leads into Chapter 5, which considers biouptake and bioaccumulation mechanisms of nanomaterials, giving evidence of nanospecific uptake of metal-based nanomaterials, separate from that of dissolution. Finally, Chapter 6 discusses the potential mechanisms of toxicity, taking this slightly unusual perspective on toxicology to attempt to draw out more fundamental understanding of toxicity. Taken as a whole, the book serves as an introduction to environmental nanoscience and nanoecotoxicology and a detailed discussion of some of its key current issues.

We would like to thank various funding bodies for supporting the editors specifically for this book and in their general research, equally important to the quality of this volume. In particular, the UK Natural Environment Research Council, the European Union Framework Programs, and the Center for Environmental Nanoscience and Risk, USA have played a pivotal role in the editors’ research. In addition, we would like to thank the authors for their interest, timely submissions, and great effort in producing the individual chapters that form this book. Lastly, we would like to thank the publishing team whose patience and help was essential to completion of this book.

Chapter 1

Overview of Environmental Nanoscience

Mohammed Baalousha*,†; William How*; Eugenia Valsami-Jones*; Jamie R. Lead*,†    * School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham, United Kingdom

† Center for Environmental Nanoscience and Risk, Department of Environmental Health Sciences, Arnold School of Public Health, University of South Carolina, Columbia, South Carolina, USA

Abstract

Nanomaterials have always been present in our environment, though the ability to control material properties at the nanoscale and to incorporate these nanomaterials in consumer products at large scale is relatively new. Consequently, nanomaterials are likely to be released to the environment during manufacturing, transport or at the end of the life of the nano-enabled products, resulting in increased exposure of nanomaterials in the environment, where they are likely to cause concerns to environmental and human health. Exposure modeling estimates suggest that environmental concentrations of nanomaterials are likely to be in the range of ng/L to μg/L. Some nanomaterials are likely to be hazardous; however, risk posed by these nanomaterials is still unknown due to the lack of information on exposure and on bioavailability and toxicity. Several environmental processes specific to nanomaterials such as aggregation, disaggregation, dissolution, surface coating, and phase transformation control the fate of nanomaterials in the environment and impact their level toxicity. These transformations may increase the level of hazard posed by nanomaterials in certain cases and mitigate such hazard in other cases. Some progress has been made in understanding the environmental health and safety of nanomaterials, but many issues still need further progress and more work is required, in particular to advance our understanding fundamentals of science nano(eco)toxicology and environmental health and safety of nanomaterials.

Keywords

Nanoscience

Nanotechnology

Environment

Health and safety

Fate

Behavior and transformations of nanomaterials

1 Introduction

Nanoscience involves the understanding of processes and properties occurring at the lowest size range possible for matter to exist before reaching atomic dimensions. In its current form, where technological advances have enabled imaging, manipulation, and control of matter at the nanoscale, it is a relatively new field of science and can be dated to a number of key events including the discovery of the electron microscope in the 1930s, the scanning probe microscope in the 1970s, and the later discoveries of the carbon-based nanomaterials (NMs) such as C60, carbon nanotubes (CNTs) and, most recently, graphene. In addition to these technological developments, the concepts of nanoscience have been developed, and the Richard Feynman essay (there is a plenty of room at the bottom; Feynman, 1992) is often cited as a key staging post. Nanotechnology is generally defined as the spatial scale of 1–100 nm where novel, size-dependent properties are often exhibited. The products of such manipulations are often small structures within the nanoscale range, known as NMs or nanoparticles (NPs). Matter at the nanoscale often displays novel properties, and thus finds new applications in a wide range of consumer products to enhance efficiency, reduce harmful emission, and reduce waste (see examples in Table 1.1). Nanotechnology is expected to bring huge benefits to humans and the environment in areas such as medicine, clean energy, and environmental remediation, but not without potential risks. Understanding the environmental and human health impacts of NMs is therefore important for two reasons, in addition to the fundamental importance of curiosity-led scientific discovery. First, understanding the risks will help to ensure the protection of the environment and health, and second, such knowledge will safeguard the sustainable development of the nanotechnology industry, which is expected to be a significant global economic driver.

Table 1.1

Examples of Nanomaterials, Their Novel Properties, and Their Potential Applications

Taken from Piccinno et al. (2012).

Understanding the environmental and human health impacts of NMs is a highly multidisciplinary area of research requiring knowledge of physics, chemistry, biology, and social sciences. The purpose of this book is to provide a critical analysis of the state of the art of NMs in the environment including synthesis, characterization, fate, behavior and transformations, exposure, biouptake, and toxicity. This chapter gives an overview of our knowledge on NMs in the environment as a preamble to the more detailed analysis in subsequent chapters. Chapter 2 discusses the currently available knowledge on the transformations of NMs in environmental systems including processes such as interactions with natural organic macromolecules, sulfidation, oxidation, and aggregation. Chapter 3 reviews the current efforts on modeling the environmental fate and exposure of NMs. Chapter 4 reviews the available knowledge on the formation and characterization of natural organic matter and protein macromolecular corona and its implications in nano(eco)toxicology. Chapter 5 discusses the biouptake and bioaccumulation of NPs, while Chapter 6 discusses mechanisms of nanotoxicity as they are currently understood.

2 History: From Empirical Use to Discoveries

This section discusses the key events in the development of NMs and nanotechnologies and for more details the readers are referred to other sources (DiscoverNano, 2014; NNI, 2014; Tolochko, 2009).

NMs have been used early in known human history, well before the current development of nanotechnology, but without the understanding and control that characterizes our current technological and intellectual capabilities. Such NMs were based on craftsman's empirical understanding and manipulation of materials. For instance, soluble gold appeared around the fifth to fourth century B.C. in Egypt and China and has been used for both aesthetic and curative purposes. Colloidal gold and silver were used in a range of artifacts, a notable example being the Lycurgus Cup, a fourth century drinking vessel, possibly made in Rome, of dichroic glass, that is, a glass which looks opaque green in normal light, but translucent red when lit from the inside. The effect is thought to be the result of light scattering by the dispersed gold and silver NPs within the glass. In the sixth to fifteenth centuries, stained glass windows in European cathedrals were colored by gold chloride and other metal oxide and chloride NPs. Later on, Luster ceramic glazes were used in the Islamic world during the ninth to seventeenth centuries, and later in Europe, and contained silver, copper, or other metallic NPs (DiscoverNano, 2014; NNI, 2014). During the thirteenth to eighteenth centuries, Damascus saber blades contained CNTs and cementite nanowires—an ultrahigh carbon steel formulation that gave them strength, resilience, the ability to hold a keen edge and visible moire pattern in the steel that give the blades their name (Reibold et al., 2006).

More recently (seventeenth to twenty-first centuries), the advancement in colloidal chemistry laid out the basics for the synthesis of NMs and consequently enabled the development of nanotechnology in the shape we now know and provided the fundamental understanding of nanoscience and nanotechnology. For instance, the philosopher and medical doctor Francisci Antonnii published a book (1618) which is considered as the first book about colloidal (nanoparticulate) gold. The German chemist Johann Kunckel published a book (1676) where he talked about drinkable gold that contains metallic gold in neutral, slightly pink solution that exert curative properties for several diseases and concluded that gold must be present in such a degree of comminution that it is not visible to the human eye (using phosphorus in CS2 (DiscoverNano, 2014; Faraday, 1857; NNI, 2014). Shortly after that, in 1861, the term colloid (of which NPs are the smallest fraction) was coined by Thomas Graham, who is known as the founder of colloidal chemistry (Graham, 1861; Mokrushin, 1962).

The basic concept of nanotechnology, as we know and practice it today, was first introduced in 1959 by the Nobel Prize winner physicist Richard Feynman. In his talk at the 29th annual meeting of the American Physical Society, Richard Feynman said the principles of physics as far as I can see, do not speak against the possibility of manoeuvring things atom by atom. It is not an attempt to violate any laws; it is something, in principle, that can be done; but in practice it has not been done because we are too big (Feynman, 1992). However, the term nanotechnology was not used until 1974 when Norio Taniguchi, Tokyo Science University Professor, used the term nanotechnology to describe the precision of manufacture of materials at the nanometer scale (Taniguchi, 1974). Then in 1980, Eric Drexler published his book Engines of Creation, which brought the term nanotechnology into the popular public domain.

Alongside the conceptual and popular understanding of nanoscience, scientific and technological progress during the twentieth century paved the way toward the development of nanotechnology as we know it today. In particular, the development of microscopy techniques and the scientific understanding of the nature of electrons and electron optics played a major role in advancing our understanding of matter. In 1872, Ernst Abbe suggested that resolving detail in an object is limited approximately by the wavelength of the light used in imaging in optical microscopes, which limits the resolution of an optical microscope to few hundreds of nanometers. The development of ultraviolet microscope in the early twentieth century by August Köhler and Moritz Rohr improved resolving power by about a factor of two because of the shorter wavelength of UV light compared to visible light used in optical microscopes.

In 1926, the physicist Han Busch laid out the foundations of geometrical electron optics after demonstrating that electric and magnetic fields could act as particle lenses. Nearly at the same time, the French physicist de Broglie introduced the concept of corpuscle waves; a frequency and hence a wavelength was associated with charged particles. Following these two discoveries in electron optics, the idea of an electron microscope began to take shape (Bogner et al., 2007). The German physicist Ernst Ruska and the electrical engineer Max Knoll constructed the first prototype of electron microscope in 1931, capable of 400-fold magnification. Two years later, in 1933, Ruska built an electron microscope that exceeded (7000 ×) the resolution of attainable with optical (light) microscope (2000 ×). The first commercial TEM was produced by Siemens in 1939, where TEM started to become standard equipment in labs, hospitals, and universities around the world. Ruska was a joint recipient of the Nobel Prize for Physics in 1986 for his invention. The prize was shared with Heinrich Rohrer and Gerd Binning for the invention of scanning tunneling microscopy. Since then, the resolution and capabilities of TEM microscopy have improved constantly. In recent years, a number of new developments have been made in high-resolution TEM (HRTEM) for nanotechnology such as in situ microscopy for observing dynamic processes (e.g., thermally induced surface dynamic processes and electric transport in nanotubes) at the nanoscale, measurement techniques that directly correlate physical properties with structures, holographic imaging of electric and magnetic fields, quantitative chemical mapping (when coupled with energy dispersive spectroscopy and electron energy loss spectroscopy) at subnanometer resolution, and ultrahigh-resolution imaging techniques (Wang, 2003). HRTEM is one of the most powerful tools used for the characterization of NMs and it is indispensable for nanotechnology. HRTEM helped in making several discoveries in nanotechnologies. For instance, CNTs were first identified by HRTEM (Iijima, 1991; Tibbetts, 1984).

The foundations of scanning electron microscopy (SEM) were first laid out by Max Knoll during the 1930s, who first obtained scanned electron images from the surface of a solid and by Manfred von Ardenne, who established the principles underlying the SEM. Further work was reported by Vladimir K. Zworykin at the RCA Research Laboratories, followed by Charles Oatley in the 1950s–1960s at the Cambridge University Engineering Department led to the production of a commercial instrument by the Cambridge Scientific Instrument Company known as the Stereoscan in 1965 and was delivered to DuPont.

The invention of the scanning tunneling microscope in 1981 and atomic force microscope in 1986 enabled first observations and imaging of atom clusters (Binnig et al., 1982, 1986). Furthermore, the invention of scanning tunneling microscopy has enabled the control (displacement) of atoms, and John Foster of IBM Almaden labs was able to spell IBM out of 35 xenon atoms on a nickel surface using a scanning tunneling microscope to push the atoms into place.

In 1985, Harold Kroto, James R. Heath, Sean O’Brien, Robert Curl, and Richard Smalley discovered the C60 fullerene (Kroto et al., 1985). Kroto, Curl, and Smalley were awarded the 1996 Nobel Prize in Chemistry for their roles in the discovery of this class of NMs: C60 and other fullerenes (C60, C70, C76, C82, and C84). It is currently believed that minute quantities of the fullerenes are produced in nature, hidden in soot, and formed by lightning discharges in the atmosphere.

In 1991, CNTs were discovered in the soot of arc discharge by the Japanese researcher Sumio Ijima (Iijima, 1991). However, Monthioux and Kuznetsov (2006) suggested that the Russian scientists Radushkevich and Lukyanovich should be credited for the discovery of multiwalled CNTs. Radushkevich and Lukyanovich published what is believed to be the first evidence for the tubular nature of nanosized carbon filaments in 1952 in the Journal of Physical Chemistry of Russia. CNTs have unique properties and are starting to be used widely for many processes, although with concerns around their fiber-like nature.

Graphene, sheets of graphite that are one atom thick, was discovered in 2004 by Andre Geim and Konstantin Novoselov at The University of Manchester (Novoselov et al., 2004), who were awarded the 2010 Nobel Prize of Physics for their work. Little work has been performed on graphene and associated structures in terms of environment and health.

This brief discussion of recent advances in nanotechnology demonstrates that, in its short existence, it has revolutionized science and technology by opening up what is an important frontier in miniaturization. In addition to harvesting the benefits of smaller materials and devices, nanotechnology also led to the discovery of uniquely new functionalities of matter at the nanoscale, resulting from properties that may be described as hybrids between atomic and bulk. We are still in the process of discovering what these properties may altogether entail. The technological advancement nowadays is the scale of research and industry and the ability to precisely manipulate and design materials at the nanoscale to create tiny structures with fundamentally new properties and functions. Such development of nanotechnology is believed to have the potential to lead to unprecedented understanding and control of the properties of materials to discover further novel phenomena, processes, and tools. Thus, nanotechnology is likely to enable a wide range of discoveries in the near future in all major scientific areas including physical, biological, and engineering sciences as well as others.

Since 1999, consumer products making use of nanotechnology and containing NMs began appearing in the marketplace and are increasing year-on-year. Some examples are lightweight nanotechnology enabled automobile bumpers that resist denting and scratching, golf balls with improved performance, tennis rackets that are stiffer, nanosilver antibacterial socks, clear sunscreens, improved displays for televisions, cell phones, and digital cameras, and many other examples (Table 1.1 and Figure 1.1). As we move into the future, it is likely that significant new and high-technology applications of nanotechnology will be introduced and exploited and indeed this is currently occurring.

Figure 1.1 Applications of NMs. http://networksandservers.blogspot.co.uk/2011/01/nanotechnology.html .

3 Definitions

3.1 Nanometer and Nanoscale

The prefix nano was derived from the Greek word, nânos, which means dwarf. One of the prefix earliest uses in the scientific literature was in the term nanometer (nm), which was approved as a measurement standard with a multiplying factor of 10− 9, in the International Systems of Units in 1960 (Thompson and Taylor, 2008). This physical scale ranges upward from 1 to 999 nm before the graduation to the micrometer scale (1000 nm or 10− 6 m). This clear-cut definition of nanometer stands in contrast to the present situation where there is a plethora of nano words and its associated concepts in the scientific literature. Three words in particular, nanotechnology, nanoscience, and NMs, deserve special treatment.

In the context of nanotechnology, nano refers to the length scales involved, where a nanometer is 0.000000001 m. Figure 1.2 compares the nanometer to more tangible objects. For instance, the width of a human hair is 40,000–60,000 nm; viruses are about 75–100 nm (the upper range of most definition on NMs, see discussion in Section 3.3); DNA strands are about 2–12 nm in diameter, similar to the size of single-walled CNTs; and the size of a single atom is of the order of several Angstroms (0.1 nm).

Figure 1.2 Comparison of the nanoscale with tangible objects. From Office of Basic Energy Sciences. Office of Science. U.S. DOE. Version 05-26-06 pmd.

3.2 Nanoscience and Nanotechnology

Nanoscience is the scientific investigation and understanding of the phenomena that occur at the nanoscale as a result of the manipulation and control of matter at this scale (Table 1.1). Within the nanoscale (and occasionally outside), properties of materials differ significantly compared with those at a larger scale (see discussion in Section 4).

We currently define nanotechnology/nanotechnologies in a number of ways (see Table 1.2). In a wider context, nanotechnologies are the set of technologies that enable the manipulation, control, and design of matter within the nanoscale range in order to develop new applications/products or enhance the capabilities of existing applications/products. Nanotechnology benefits from the scientific advances made in nanoscience to exploit the discoveries of novel properties and functionalities of NMs and utilize them to develop such novel applications/products.

Table 1.2

Summary of Definitions of Nanomaterials