Strategies for quantifying C(60) fullerenes in environmental and biological samples and implications for studies in environmental health and ecotoxicology.

Fullerenes are sphere-like molecules with unique physico-chemical properties, which render them of particular interest in biomedical research, consumer products and industrial applications. Human and environmental exposure to fullerenes is not a new phenomenon, due to a long history of hydrocarbon-combustion sources, and will only increase in the future, as incorporation of fullerenes into consumer products becomes more widespread for use as anti-aging, anti-bacterial or anti-apoptotic agents.An essential step in the determination of biological effects of fullerenes (and their surface-functionalized derivatives) is establishment of exposure-assessment techniques. However, in ecotoxicological studies, quantification of fullerenes is performed infrequently because robust, uniformly applicable analytical approaches have yet to be identified, due to the wide variety of sample types. Moreover, the unique physico-chemistry of fullerenes in aqueous matrices requires reassessment of conventional analytical approaches, especially in more complex biological matrices (e.g., urine, blood, plasma, milk, and tissue).Here, we present a review of current analytical approaches for the quantification of fullerenes and propose a consensus approach for determination of these nanomaterials in a variety of environmental and biological matrices.

The use of environmental, health and safety research in nanotechnology research.

Environmental, health, and safety (EHS) concerns are receiving considerable attention in nanoscience and nanotechnology (nano) research and development (R&D). Policymakers and others have urged that research on nano's EHS implications be developed alongside scientific research in the nano domain rather than subsequent to applications. This concurrent perspective suggests the importance of early understanding and measurement of the diffusion of nano EHS research. The paper examines the diffusion of nano EHS publications, defined through a set of search terms, into the broader nano domain using a global nanotechnology R&D database developed at Georgia Tech. The results indicate that nano EHS research is growing rapidly although it is orders of magnitude smaller than the broader nano S&T domain. Nano EHS work is moderately multidisciplinary, but gaps in biomedical nano EHS's connections with environmental nano EHS are apparent. The paper discusses the implications of these results for the continued monitoring and development of the cross-disciplinary utilization of nano EHS research.

Detection of fullerenes (C60 and C70) in commercial cosmetics.

Detection methods are necessary to quantify fullerenes in commercial applications to provide potential exposure levels for future risk assessments of fullerene technologies. The fullerene concentrations of five cosmetic products were evaluated using liquid chromatography with mass spectrometry to separate and specifically detect C60 and C70 from interfering cosmetic substances (e.g., castor oil). A cosmetic formulation was characterized with transmission electron microscopy, which confirmed that polyvinylpyrrolidone encapsulated C60. Liquid-liquid extraction of fullerenes from control samples approached 100% while solid-phase and sonication in toluene extractions yielded recoveries of 27-42%. C60 was detected in four commercial cosmetics ranging from 0.04 to 1.1 µg/g, and C70 was qualitatively detected in two samples. A single-use quantity of cosmetic (0.5 g) may contain up to 0.6 µg of C60, demonstrating a pathway for human exposure. Steady-state modeling of fullerene adsorption to biosolids is used to discuss potential environmental releases from wastewater treatment systems.

Evaluation of extraction methods for quantification of aqueous fullerenes in urine.

There is a growing concern about the human and environmental health effects of fullerenes (e.g., C(60)) due to their increasing application in research, medicine, and industry. Toxicological and pharmacokinetic research requires standard methods for extraction and detection of fullerenes from biological matrices such as urine. The present study validates the use of liquid-liquid extraction (LLE) and solid-phase extraction (SPE) methods in conjunction with liquid chromatography-mass spectrometry (LC-MS) for the quantitative determination of C(60) in human and synthetic urine as compared with ultrapure water. Glacial acetic acid, which is necessary to prevent emulsions during LLE, inhibited C(60) detection by LC-MS, but this could be mitigated with evaporation. Aqueous C(60) aggregates (nC(60)) were spiked at 180 µg/L into the components of a synthetic urine recipe to determine their individual impacts on extraction and detection. Urea, creatinine, and a complex protein (i.e., gelatin) were found to impair SPE, leading to a low recovery rate of 43 ± 4% for C(60) spiked into human urine. In contrast, C(60) was consistently recovered from synthetic matrices using LLE, and recovery in human urine was 80 ± 6%. These results suggest that LLE combined with LC-MS is suitable for studying the clearance of fullerenes from the body. LLE is a robust technique that holds promise for extracting C(60) from other complex biological matrices (e.g., blood, sweat, amniotic fluid) in toxicological studies, enabling a better understanding of the behavior of fullerenes in human and animal systems and facilitating a more comprehensive risk evaluation of fullerenes.

The release of nanosilver from consumer products used in the home.

Nanosilver has become one of the most widely used nanomaterials in consumer products because of its antimicrobial properties. Public concern over the potential adverse effects of nanosilver's environmental release has prompted discussion of federal regulation. In this paper, we assess several classes of consumer products for their silver content and potential to release nanosilver into water, air, or soil. Silver was quantified in a shirt, a medical mask and cloth, toothpaste, shampoo, detergent, a towel, a toy teddy bear, and two humidifiers. Silver concentrations ranged from 1.4 to 270,000 microg Ag g product(-1). Products were washed in 500 mL of tap water to assess the potential release of silver into aqueous environmental matrices (wastewater, surface water, saliva, etc.). Silver was released in quantities up to 45 microg Ag g product(-1), and size fractions were both larger and smaller than 100 nm. Scanning electron microscopy confirmed the presence of nanoparticle silver in most products as well as in the wash water samples. Four products were subjected to a toxicity characterization leaching procedure to assess the release of silver in a landfill. The medical cloth released an amount of silver comparable to the toxicity characterization limit. This paper presents methodologies that can be used to quantify and characterize silver and other nanomaterials in consumer products. The quantities of silver in consumer products can in turn be used to estimate real-world human and environmental exposure levels.

Nanoparticle silver released into water from commercially available sock fabrics.

Manufacturers of clothing articles employ nanosilver (n-Ag) as an antimicrobial agent, but the environmental impacts of n-Ag release from commercial products are unknown. The quantity and form of the nanomaterials released from consumer products should be determined to assess the environmental risks of nanotechnology. This paper investigates silver released from commercial clothing (socks) into water, and its fate in wastewater treatment plants (WWTPs). Six types of socks contained up to a maximum of 1360 microg-Ag/g-sock and leached as much as 650 microg of silver in 500 mL of distilled water. Microscopy conducted on sock material and wash water revealed the presence of silver particles from 10 to 500 nm in diameter. Physical separation and ion selective electrode (ISE) analyses suggest that both colloidal and ionic silver leach from the socks. Variable leaching rates among sock types suggests that the sock manufacturing process may control the release of silver. The adsorption of the leached silver to WWTP biomass was used to develop a model which predicts that a typical wastewater treatment facility could treat a high concentration of influent silver. However, the high silver concentration may limitthe disposal of the biosolids as agricultural fertilizer.