Life-cycle assessment of engineered nanomaterials: a literature review of assessment status

The filtration of airborne nanoparticles is an important control technique as the environmental, health, and safety impacts of nanomaterials grow. A review of the literature shows that significant progress has been made on airborne nanoparticle filtration in the academic field in the recent years. We summarize the filtration mechanisms of fibrous and membrane filters; the air flow resistance and filter media figure of merit are discussed. Our review focuses on the air filtration test methods and instrumentation necessary to implement them; recent experimental studies are summarized accordingly. Two methods using monodisperse and polydisperse challenging aerosols, respectively, are discussed in detail. Our survey shows that the commercial instruments are already available for generating a large amount of nanoparticles, sizing, and quantifying them accurately. The commercial self-contained filter test systems provide the possibility of measurement for particles down to 15 nm. Current international standards dealing with efficiency test for filters and filter media focus on measurement of the minimum efficiency at the most penetrating particle size. The available knowledge and instruments provide a solid base for development of test methods to determine the effectiveness of filtration media against airborne nanoparticles down to single-digit nanometer range.     

Emerging patterns for engineered nanomaterials in the environment: a review of fate and toxicity studies

A comprehensive assessment of the environmental risks posed by engineered nanomaterials (ENMs) entering the environment is necessary, due in part to the recent predictions of ENM release quantities and because ENMs have been identified in waste leachate. The technical complexity of measuring ENM fate and transport processes in all environments necessitates identifying trends in ENM processes. Emerging information on the environmental fate and toxicity of many ENMs was collected to provide a better understanding of their environmental implications. Little research has been conducted on the fate of ENMs in the atmosphere; however, most studies indicate that ENMs will in general have limited transport in the atmosphere due to rapid settling. Studies of ENM fate in realistic aquatic media indicates that in general, ENMs are more stable in freshwater and stormwater than in seawater or groundwater, suggesting that transport may be higher in freshwater than in seawater. ENMs in saline waters generally sediment out over the course of hours to days, leading to likely accumulation in sediments. Dissolution is significant for specific ENMs (e.g., Ag, ZnO, copper ENMs, nano zero-valent iron), which can result in their transformation from nanoparticles to ions, but the metal ions pose their own toxicity concerns. In soil, the fate of ENMs is strongly dependent on the size of the ENM aggregates, groundwater chemistry, as well as the pore size and soil particle size. Most groundwater studies have focused on unfavorable deposition conditions, but that is unlikely to be the case in many natural groundwaters with significant ionic strength due to hardness or salinity. While much still needs to be better understood, emerging patterns with regards to ENM fate, transport, and exposure combined with emerging information on toxicity indicate that risk is low for most ENMs, though current exposure estimates compared with current data on toxicity indicates that at current production and release levels, exposure to Ag, nZVI, and ZnO may cause toxicity to freshwater and marine species.     

Relaxation time: a proton NMR-based approach as a metric to measure reactivity of engineered nanomaterials

The toxicological impact of engineered nanoparticles in environmental or biological milieu is very difficult to predict and control because of the complexity of interactions of nanoparticles with the varied constituents in the suspended media. Nanoparticles are different from their bulk counterparts due to their high surface area-to-volume ratio per unit mass, which plays a vital role in bioavailability of these nanoparticles to its surroundings. This study explores how changes in the spin-spin nuclear relaxation time can be used to gauge the availability of surface area and suspension stability of selected nanoparticles (CuO, ZnO, and SiO₂), in a range of simulated media. Spin-spin nuclear relaxation time can be mathematically correlated to wetted surface area, which is well backed up by the data of hydrodynamic size measurements and suspension stability. We monitored the change in spin-spin relaxation time for all the nanoparticles, over a range of concentrations (2.5 –100 ppm) in deionized water and artificial seawater. Selective concentrations of nanoparticle suspensions were subjected for temporal studies over a period of 48 hrs to understand the concept of spin-spin nuclear relaxation time-based reactivity of nanoparticle suspension. The nanoparticles showed high degree of agglomeration, when suspended in artificial seawater. This was captured by a decrease in spin-spin nuclear relaxation time and also an increment in the hydrodynamic size of the nanoparticles.     

‘You caught me off guard’: Probing the futures of complex engineered nanomaterials

This paper applies principles and methods from the framework of anticipatory governance to the case of what the National Research Council calls “complex engineered nanomaterials” (CENM). This framework does not aim to generate crystal ball visions or definitive answers, but rather provides guidance for uncovering, understanding, and addressing social, ethical, environmental, and policy issues that stem from emerging technologies. Thus, in anticipation of increased CENM research, CENM products, and their different governance challenges, we aim to lay the groundwork for the anticipatory governance of CENMs by mapping out what—according to the engineers and scientists, we interviewed who are working at the research level of these CENMs—will be the main issues and themes that we need to pay attention to in the near future. The structured interviews focused on three groups of questions: (1) potential and/or actual applications and/or products from the participant’s research; (2) environmental health and safety issues pertaining to both the participant’s research and CENMs generally; and (3) the future of CENMs. Without a foundational understanding to build on, social scientists, policymakers, and regulatory agencies will be at a loss about how to govern CENMs before they are widely implemented in society.     

Fluorescence and ESR studies on membrane oxidative damage by gamma radiation

Oxidative damage to cellular membranes critically controls the manifestation of cellular response to ionizing radiation. To gain further insight into the damaging mechanisms, we have investigated the effects of γ-radiation-generated free-radical-mediated peroxidative damage in egg yolk lecithin unilamellar liposomal membranes by employing 1,6-diphenyl-1,3,5-hexatriene (DPH). Alterations in lipid bilayer fluidity and malondialdehyde (MDA) formation were measured in irradiated liposomal membranes as a function of radiation dose (0.1-1 kGy). A relationship seems to exist between the degree of radiation-induced peroxidative damage and the magnitude of DPH fluorescence decay in irradiated membranes. Radiation-induced membrane rigidization and MDA formation were significantly reduced when α-tocopherol, a natural membrane antioxidant, was present in the liposomes suggesting an involvement of lipid free radicals in the mechanism of the damage process. The results of the present study have been compared with those obtained by the electron spin resonance (ESR) technique on human erythrocyte ghost membranes with spin-labeled phospholipids having the unique capability to sensitively report on the dynamic state of the lipid environment inside the bilayer membrane. Iodoacetamide and N-ethylmaleimide spin labels were used to investigate alterations in membrane proteins. These results have contributed to our understanding of mechanisms involved in radiation membrane oxidative damage in terms of lipid peroxidation, fluidity changes and involvement of -SH groups of membrane proteins. Combined use of fluorescence and ESR spin-label techniques is of potential interest in probing the deeper molecular mechanisms of radiation injury in cellular membranes for developing strategies to modify the radiation damage to cells.     

The electron beam irradiation damage on nanomaterials synthesized by hydrothermal and thermal evaporation methods--an example of ZnS nanostructures

Using transmission electron microscopy-related techniques, we have compared the degradation behaviors of several different types of ZnS nanostructures, including the ZnS nanosheets synthesized by hydrothermal method (with different oxygen impurity concentration) and ZnS nanobelts grown using thermal evaporation. We have identified that displacement damage, sputtering, and oxidation mechanisms exist during the electron irradiation process. While oxidation of the nanostructure is always observed, displacement damage appears to be the dominant mechanism contributing to the final structural collapse of ZnS nanosheets (synthesized via hydrothermal methods), but sputtering mechanism becomes critical in changing the surface roughness of the ZnS nanobelts (grown by thermal evaporation). The specific damage mechanisms of these nanomaterials disclose that different synthesis process results in different structure quality (particularly impurity related interior defects) of the ZnS nanostructures, which determines their specific degradation behaviors under the electron beam irradiation.     

Mechanism and kinetics of the oxidative damage to ergosterol induced by peroxyl radicals in lipid media: a theoretical quantum chemistry study

In this work, we have studied the mechanisms and kinetics of the initial damage to ergosterol induced by ^?OOH and ^?OOCH₃ peroxyl radicals in a lipid media, using quantum chemistry and computational kinetics methods. The initial damage to ergosterol induced by these radicals occurs predominantly through the hydrogen transfer mechanism (HT) from the allylic position C14 of ergosterol. For the reaction of ergosterol with ^?OOH, the HT‐9 pathway represents ~90.8% of the overall rate constant, while in the case of ^?OOCH₃, the HT‐14 pathway represents more than ~97.2% of the overall rate constant. The calculated overall reaction rates for the initial damage to ergosterol caused by the ^?OOH and ^?OOCH₃ are 2.05 × 10⁶ and 6.26 × 10⁴ M^?1 s^?1, respectively, indicating that the oxidative damage to ergosterol initiated by these radicals, and probably other alkyl‐peroxyl radicals, could be significantly dangerous to their integrity. Taking into account the calculated values of the overall rate coefficients, we can conclude that ergosterol is more susceptible to damage produced by peroxyl radicals than cholesterol and fatty acids. This suggests that fungal cells might be more sensitive to these radicals than animal cells, coinciding with the fact that one of the targets in combating fungi is precisely ergosterol. Finally, theoretical calculations confirm the antioxidant potential of ergosterol and could help explaining the nutraceutical activity of edible and medicinal mushrooms. Copyright © 2015 John Wiley & Sons, Ltd.     

Precise fabrication of nanomaterials: a nonlinear dynamics approach

Modeling of the precise fabrication in the self-assembling of particles is studied using the nonlinear Langevin equation system. The numerical simulation showed a marked ordering of the particles as a function of time after some induction period. The abnormally enlarged fluctuation was found around the start of the evident ordering. After the fluctuation, a sudden increase of the cluster size was observed. The results corresponded well to the dynamics due to the formation of the critical cluster. The shape of the critical cluster around the enlarged fluctuation was not compact and showed fractal-like structures. The fluctuation of the cluster size around the formation of the critical cluster was explained by the anomalous fluctuation theorem for the generalized Langevin equation. The characterization of the stochastic dynamics of the critical clusters rationalized the concept of dynamic templating for the fabrication technique of the self-assembling of nanoparticles, that is, the structural constraint on the particle assembly by externally adding the resonance frequencies that match with the localized nonlinear vibrational modes of the target structures originating from thermal (Brownian) activation.     

Quantitative analysis of oxidative DNA damage induced by high-voltage pulsed discharge with cavitation

Pulsed discharge is used for sterilization and disinfection, but the details of the molecular mechanisms remain largely unknown. Since pulsed discharge generates reactive oxygen species (ROS), we analyzed the oxidative DNA damages after pulsed discharge treatment to consider the involvement of ROS in the damaging process. We applied pulsed discharge with cavitation to plasmid DNA molecules and estimated the yields of the damages by agarose gel electrophoresis. The treated DNA contained various oxidative DNA damages, including single and double strand breaks and base lesions. The yields of the damages increased in response to the energy used for pulsed discharge. We also measured the yield of 8-hydroxyguanine (8-OH-G), one of the major oxidative base lesions, in the treated plasmid DNA by mass spectrometry quantitatively and found that the yield of the oxidative base lesion corresponded to the increment of the applied energy. In addition, we observed the involvement of mutM gene, which is responsible for repair of 8-OH-G, in the increased sensitivity of Escherichia coli to pulsed discharge. Therefore, ROS seem to mediate the sterilization ability of pulsed discharge.     

Post-pneumonectomy evaluation of the chest: a prospective comparative study of MRI with CT

A comparative study of 11 pneumonectomized patients was undertaken in order to evaluate the respective advantages and drawbacks of MRI and CT in post-operative follow-up. Nine patients were healthy at the time of the study and two presented with tumor recurrence. MR examination included 500/40 ms axial, and frontal 800/40-80 ms or 1300/60-120 ms nongated spin echo sequences. MRI was slightly more efficient in identifying vascular stump and main nodal stations, and detected better than CT tumoral and metastatic spread in cancer recurrences. It was as informative as CT in evaluating postpneumonectomy space and bronchial stump. It was noncontributory in the detection of calcifications. Although clips were visible with MRI, their location was less definite than with CT, a potential pitfall when radiotherapy is planned.     

An overview of engineered porous material for energy applications: a mini-review

The ordered porous materials, developed using various templating materials, have generated huge interest among the electrochemist community due to their plenty of unique properties and functionalities that can be effectively applied in optoelectronic devices. Mesoporous materials possess excellent opportunities in energy storage and energy conversion applications due to their extraordinarily high surface area and large pore size. These properties may enhance the performance of porous materials in terms of lifetime and stability, energy and power density. In this review, we have tried to club the fields of optoelectronics and mesoporous materials. Also, we have summarised the primary methods for preparing mesoporous materials using various templates and described their applications as electrodes and catalysts in fuel cells, solar fuel production, dye-sensitised solar cells, perovskite, supercapacitors and rechargeable batteries. Finally, we have highlighted the research and development challenges of mesoporous materials those need to be overcome to enhance their contribution in renewable energy applications.     

船舶夜航光环境评价指标筛选

为了客观、全面地评价船舶夜航光环境质量,保障船舶夜航安全,从分析海上光污染的概念及其来源出发,提出了选取船舶夜航光环境评价指标应遵循“主导性、可操作性及覆盖面广”的原则;在遵循该指标选取原则的基础上,利用光学、色度学及系统工程理论,从驾驶人员视觉绩效、船舶避碰行为、通航光环境条件等3大方面筛选出19个评价指标,建立了海上光环境评价体系,并给出了通航光环境条件中背景光的亮度、背景光的色度、污染光源眩光以及污染光源闪烁度的评价标准,为船舶夜航光环境的测量与评价奠定了基础。     

Occupational exposure limits for nanomaterials: state of the art

Assessing the need for and effectiveness of controlling airborne exposures to engineered nanomaterials in the workplace is difficult in the absence of occupational exposure limits (OELs). At present, there are practically no OELs specific to nanomaterials that have been adopted or promulgated by authoritative standards and guidance organizations. The vast heterogeneity of nanomaterials limits the number of specific OELs that are likely to be developed in the near future, but OELs could be developed more expeditiously for nanomaterials by applying dose–response data generated from animal studies for specific nanoparticles across categories of nanomaterials with similar properties and modes of action. This article reviews the history, context, and approaches for developing OELs for particles in general and nanoparticles in particular. Examples of approaches for developing OELs for titanium dioxide and carbon nanotubes are presented and interim OELs from various organizations for some nanomaterials are discussed. When adequate dose–response data are available in animals or humans, quantitative risk assessment methods can provide estimates of adverse health risk of nanomaterials in workers and, in conjunction with workplace exposure and control data, provide a basis for determining appropriate exposure limits. In the absence of adequate quantitative data, qualitative approaches to hazard assessment, exposure control, and safe work practices are prudent measures to reduce hazards in workers.     

Vibration-based damage detection and evaluation of sheet materials using a remote acoustic excitation

A simple method of damage severity assessment on sheet materials is suggested and proved by theory and experiment. The investigated defect types are in forms of added mass and crack. The method is based on the frequency shift measurement of a material vibrating as a membrane subjected to static tension and irradiated by an acoustic wave. It is shown both theoretically and experimentally that the natural frequency of the damaged membrane is shifted relative to its position in the ideal material. A local increase in thickness (or addition of mass) shifts the natural frequency down, while a crack shifts the frequency up. The method can be considered as acoustic weighting through the frequency shift. The sensitivity of this method can be high because frequency measurement is one of the most accurate measurements in physics and metrology. Published in Russian in Akusticheskiĭ Zhurnal, 2008, Vol. 54, No. 1, pp. 147–155. The text was submitted by the authors in English.     

Ruthenium(III) catalysed and uncatalysed oxidative mechanisms of methylxanthine drug theophylline by copper(III) periodate complex in alkali media: a comparative approach

The kinetics of oxidation of methylxanthine drug, theophylline (TP), by diperiodatocuprate(III) (DPC) has been investigated in the absence and presence of ruthenium(III) (Ru(III)) as homogeneous catalyst in alkaline medium at a constant ionic strength of 0.21 mol dm^?3 spectrophotometrically. The reaction exhibits 1:4 stoichiometry ([TP] : [DPC]) in both the cases. The order of the reaction with respect to [DPC] was unity, while the order with respect to [TP] was less than unity over the concentration range studied in both the cases. The rate was increased with an increase in [OH^?] and decreased with an increase in [IO₄^?]. The order with respect to [Ru(III)] was unity. The ionic strength and dielectic constant of the medium did not affect the rate significantly. The main product 1‐methyl‐(3‐N‐formyl)‐2,4‐purinodione was identified by spot tests, Fourier transform infrared spectroscopy and liquid chromatography–mass spectrometry spectral studies. Based on the experimental results, the possible mechanisms were proposed. The reaction constants involved in the different steps of the mechanisms were evaluated. The catalytic constant (K_c) was also calculated for Ru(III) catalysis at different temperatures. The activation parameters with respect to the catalyst and slow step of the mechanisms were computed, and thermodynamic quantities were determined. Kinetic studies suggest that the active species of DPC and Ru(III) are found to be [Cu(H₂IO₆)(H₂O)₂] and [Ru(H₂O)₅OH]²⁺, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of processing parameters on nanomaterials synthesis efficiency by a carbothermal reduction process

In this work, the influence of synthesis parameters on the synthesis efficiency of tin oxide nanomaterials was studied by using the carbothermal reduction method in a sealed tube furnace. The parameters were the starting material, temperature and time of synthesis as well as the gas flux. The starting material was tin dioxide mixed with carbon black in a molar proportion of 1.5:1 and 1:1. The temperature range was from 950 to 1,125 °C with a step of 25 °C, and the synthesis times used were 15, 30, 45, 60, 75, 90, and 120 min. Using optimum values of the above parameters, the gas flux was changed to verify its influence. After completion of the syntheses, we found a grayish-black material inside the tube which was characterized by X-ray diffraction and scanning electron microscopy. The results showed that the collected material is composed of nanobelts (with width around 60 nm) and disks that grew preferentially in the SnO phase. A model based on the oxide vapor pressure was proposed to evaluate the efficiency of the process, and the results showed good agreement between experimental data and the proposed model. Based on the results obtained, the best conditions to obtain a homogeneous material with 95% efficiency is using a starting material in the molar proportion Sn:C of 1.5:1, a temperature of 1,132 °C for 75 min, and a N₂ gas flux of 80 sccm.