Microscopic and Spectroscopic Methods Applied to the Measurements of Nanoparticles in the Environment

Abstract: Currently, thousands of commercially available products contain engineered nanoparticles (ENPs). Because numerous nanoparticles (NPs) are being used in products that will be in contact with water or directly used in water treatment processes, these materials will undoubtedly reside, at least temporarily, in bodies of water. Given the widespread use of NPs and ENPs in consumer goods, a large portion of these materials will soon go into the waste stream, potentially to soil and sediments or added directly to agricultural lands via biosolids. Possible impacts of ENPs on aquatic and terrestrial ecosystems are of great concern. Preliminary data from several research groups have shown that ENPs may have a direct impact on food safety and the food chain. However, our knowledge about detection and characterization of NPs in the environment, especially aquatic environments, is still in its infancy. This review includes the most recent literature about the methods applied to the measurement of NPs and ENPs in the environment. The review covers methods to determine size distribution, shape, structure, surface charge, chemical composition, surface area, agglomeration, surface chemistry, porosity, and solubility.     

Workplace exposure to nanoparticles and the application of provisional nanoreference values in times of uncertain risks

Nano reference values (NRVs) for occupational use of nanomaterials were tested as provisional substitute for Occupational Exposure Limits (OELs). NRVs can be used as provisional limit values until Health-Based OELs or derived no-effect levels (DNEL) become available. NRVs were defined for 8?h periods (time weighted average) and for short-term exposure periods (15?min-time weighted average). To assess the usefulness of these NRVs, airborne number concentrations of nanoparticles (NPs) in the workplace environment were measured during paint manufacturing, electroplating, light equipment manufacturing, non-reflective glass production, production of pigment concentrates and car refinishing. Activities monitored were handling of solid engineered NPs (ENP), abrasion, spraying and heating during occupational use of nanomaterials (containing ENPs) and machining nanosurfaces. The measured concentrations are often presumed to contain ENPs as well as process-generated NPs (PGNP). The PGNP are found to be a significant source for potential exposure and cannot be ignored in risk assessment. Levels of NPs identified in workplace air were up to several millions of nanoparticles/cm³. Conventional components in paint manufacturing like CaCO₃ and talc may contain a substantial amount of nanosized particulates giving rise to airborne nanoparticle concentrations. It is argued that risk assessments carried out for e.g. paint manufacturing processes using conventional non-nano components should take into account potential nanoparticle emissions as well. The concentrations measured were compared with particle-based NRVs and with mass-based values that have also been proposed for workers protection. It is concluded that NRVs can be used for risk management for handling or processing of nanomaterials at workplaces provided that the scope of NRVs is not limited to ENPs only, but extended to the exposure to process-generated NPs as well.     

Evaluation of environmental filtration control of engineered nanoparticles using the Harvard Versatile Engineered Nanomaterial Generation System (VENGES)

Applying engineering controls to airborne engineered nanoparticles (ENPs) is critical to prevent environmental releases and worker exposure. This study evaluated the effectiveness of two air sampling and six air cleaning fabric filters at collecting ENPs using industrially relevant flame-made engineered nanoparticles generated using a versatile engineered nanomaterial generation system (VENGES), recently designed and constructed at Harvard University. VENGES has the ability to generate metal and metal oxide exposure atmospheres while controlling important particle properties such as primary particle size, aerosol size distribution, and agglomeration state. For this study, amorphous SiO₂ ENPs with a 15.4 nm primary particle size were generated and diluted with HEPA-filtered air. The aerosol was passed through the filter samples at two different filtration face velocities (2.3 and 3.5 m/min). Particle concentrations as a function of particle size were measured upstream and downstream of the filters using a specially designed filter test system to evaluate filtration efficiency. Real time instruments (FMPS and APS) were used to measure particle concentration for diameters from 5 to 20,000 nm. Membrane-coated fabric filters were found to have enhanced nanoparticle collection efficiency by 20–46 % points compared to non-coated fabric and could provide collection efficiency above 95 %.     

Reciprocal Response of Human Oral Epithelial Cells to Internalized Silica Nanoparticles

Silica nanoparticles (SiO₂ NPs) are one of the most widely used engineered nanoparticles and can been found in a wide range of consumer products. Despite their massive global production scale, little is known about their potential effects in the context of unintended exposure or ingestion. Using TR146 cells as an in vitro model of the human oral buccal mucosa, the uptake, spatial intracellular distribution, reactive oxygen species (ROS) production, inflammatory response, and cytotoxic effects of commercial SiO₂ NPs are examined. SiO₂ NPs are shown to dock and cross the cellular membrane barrier in a dose–time‐dependent manner. Confocal sectioning reveals translocation of SiO₂ NPs into the cell nucleus after 12 h of exposure. A concentration threshold of more than 500 × 10^?6 m is observed, above which SiO₂ NPs are shown to exert significant oxidative stress with concomitant upregulation of inflammatory genes IL6 and TNFA. Further analysis of the p53 pathway and a series of apoptotic and cell cycle biomarkers reveals intracellular accumulation of SiO₂ NPs exert marginal nanotoxicity. Collectively, this study provides important information regarding the uptake, intracellular distribution, and potential adverse cellular effects of SiO₂ NPs commonly found in consumer products in the human oral epithelium.     

Bottom-up processing of thermoelectric nanocomposites from colloidal nanocrystal building blocks: the case of Ag2Te–PbTe

Nanoscale ZnO materials have been largely used in many products due to their distinct properties. However, ZnO nanoparticles (NPs) are hazardous to human health and the ecosystem. The characteristics and the stability of ZnO NPs are relevant to their fate in the environment and their potential toxicities. In this study, a stable commercial ZnO NP suspension was chosen to investigate its aggregation under various salt additions. Different concentrations of NaCl, KCl and CaCl₂ were chosen to represent various environmental conditions. Under pH 8?C9, the surface charge of commercial ZnO NPs was negative. The behavior of the stabilized ZnO NPs in water was affected by ionic combinations and ionic strength; that is, divalent cations were more effective than monovalent ones in promoting aggregation formation. The attachment efficiencies of ZnO aggregates were calculated based upon the aggregation kinetics. The critical coagulation concentration values for this commercial ZnO NPs were higher than previous reported for ZnO NPs, indicating this ZnO NP could be stable in the aquatic environment and might have increased hazardous potentials. Based upon the Derjaguin?CLandau?CVerwey?COverbeek theory, interactions between ZnO NPs in the presence of different ions were evaluated to illustrate the aggregation mechanism. Our results indicated that critical ionic type and concentration promote the aggregation of stable ZnO NPs. These understandings also can facilitate the design of the precipitation treatment to remove NPs from water.     

The effects of surface modification on the electrical properties of p–n + junction silicon nanowires grown by an aqueous electroless etching method

Journal of Nanoparticle Research - Applying engineering controls to airborne engineered nanoparticles (ENPs) is critical to prevent environmental releases and worker exposure. This study evaluated...     

Generation of AuGe nanocomposites by co-sparking technique and their photoluminescence properties

Inhalation exposure to airborne nanoparticles (NPs) has been reported during manual activities using typical fume hoods. This research studied potential inhalation exposure associated with the manual handling of NPs using two new nanoparticle-handling enclosures and two biological safety cabinets, and discussed the ability to contain NPs in the hoods to reduce environmental release and exposure. Airborne concentrations of 5 nm to 20 μm diameter particles were measured while handling nanoalumina particles in various ventilated enclosures. Tests were conducted using two handling conditions and concentrations were measured using real-time particle counters, and particles were collected on transmission electron microscope grids to determine particle morphology and elemental composition. Airflow patterns were characterized visually using a laser-light sheet and fog. The average number concentration increase at breathing zone outside the enclosure was less than 1,400 particle/cm³ for each particle size at all tested conditions and the estimated overall mass concentration was about 83 μg/m³ which was less than the dosage of typical nanoparticle inhalation exposure studies. The typical front-to-back airflow was used in the studied hoods, which could potentially induce reverse turbulence in the wake region. However, containment of NPs using studied hoods was demonstrated with excellent performance. Smoke tests showed that worker’s hand motion could potentially cause nanoparticle escape. The challenge of front-to-back airflow can be partially overcome by gentle motion, low face velocity, and front exhaust to reduce nanoparticle escape.     

Occupational safety and health criteria for responsible development of nanotechnology

In this study we investigated the release of titanium dioxide (TiO₂), silver (Ag) and silica (SiO₂) engineered nanoparticles (ENPs) from three different paints by using standardized water immersion test for coatings. Fibre-cement panels were coated with paints containing ENPs and then exposed to UV light and abraded to simulate weathering. After the static water immersion test, we observed a very low release of Ti (4–8 μg/l), while the Ag measured in leachates was under detection limit (0.1 μg/l). A small release of Si was measured in leachates, with 73 mg/l of Si released from paints containing SiO₂ ENPs after 120 h of water immersion. The cumulative loss of Si was about 1.8 % with respect to initial amount of Si in paint. Microscopic results highlighted that SiO₂ ENPs are mainly released in form of agglomerates with other particles, and only very few single SiO₂ ENPs were found in leachates. The results confirmed that Si migration is related to immersion cycles (wetting and drying cycles) of tested paints.     

Influence of titanium dioxide nanoparticles on cadmium and lead bioaccumulations and toxicities to <Emphasis Type="Italic">Daphnia magna</Emphasis>

Titanium dioxide nanoparticles (TiO₂ NPs) have attracted considerable concerns due to the increasing production and widespread applications, while their influences on other co-existing pollutants in real environment are not well studied. In this paper, the colloidal stability of TiO₂ NPs in the exposure medium was first evaluated, and then, the medium was modified so that TiO₂ NP suspension remained stable over the exposure period. Finally, using the optimized exposure medium, the effects of cadmium (Cd) and lead (Pb) on Daphnia magna both in the absence and presence of TiO₂ NPs were investigated. Results showed that 2 mg L^?1 of TiO₂ NPs was well dispersed in 1:20 diluted Elendt M7 medium without EDTA, and no immobility was observed. The presence of the nanoparticles increased the bioaccumulation and toxicity of Cd to the daphnias. On the contrary, while Pb bioaccumulation was enhanced by three to four times, toxicity of Pb was reduced in the presence of TiO₂ NPs. The decreased toxicity of Pb was more likely attributed to the decreased bioavailability of free Pb ion due to adsorption and speciation change of Pb in the presence of TiO₂ NPs. Additionally, surface-attached TiO₂ NPs combined with adsorbed heavy metals caused adverse effects on daphnia swimming and molting behavior, which is supposed to lead to chronic toxicity.     

Silver nanoparticles in soil–plant systems

Silver nanoparticles (AgNPs) have broad spectrum antimicrobial/biocidal properties against all classes of microorganisms and possess numerous distinctive physico-chemical properties compared to bulk Ag. Hence, AgNPs are among the most widely used engineered NPs in a wide range of consumer products and are expected to enter natural ecosystems including soil via diverse pathways. However, despite: (i) soil has been considered as a critical pathway for NPs environmental fate, (ii) plants (essential base component of all ecosystems) have been strongly recommended to be included for the development of a comprehensive toxicity profile for rapidly mounting NPs in varied environmental compartments, and (iii) the occurrence of an intricate relationship between “soil–plant systems” where any change in soil chemical/biological properties is bound to have impact on plant system, the knowledge about AgNPs in soils and investigations on AgNPs–plants interaction is still rare and in its rudimentary stage. To this end, the current paper: (a) overviews sources, status, fate, and chemistry of AgNPs in soils, AgNPs-impact on soil biota, (b) critically discusses terrestrial plant responses to AgNPs exposure, and (c) illustrates the knowledge-gaps in the current perspective. Based on the available literature critically appraised herein, a multidisciplinary integrated approach is strongly recommended for future research in the current direction aimed at unveiling the rapidly mounting AgNPs-fate, transformation, accumulation, and toxicity potential in “soil–plant systems,” and their cumulative impact on environmental and human health.     

Electrosynthesis and characterization of poly aniline/garnet nanoparticles for high-performance electrochemical capacitors

In this work, supercapacitive performance of polyaniline/yttrium aluminum garnet (YAG: Y₃Al₅O₁₂) nanoparticles (PANI/YAGNPs) was studied. YAG nanoparticles were synthesized by pulse electro-deposition method and after that, PANI/YAGNPs electrodeposited on the surface of glassy carbon electrodes through cyclic voltammetry. Morphological studies show that YAG nanoparticles were distributed in the structure of PANI filaments uniformly. XRD and FTIR were used to perform a structural study of materials. Different electrochemical techniques such as cyclic voltammetry (CV), galvano static charge discharge (CD), and impedance spectroscopy (EIS) were used to evaluate the applicability of using PANI/YAGNPs as an active material for supercapacitors. The specific capacitance (SC) of PANI and PANI YAG NPs electrodes calculated using CV technique are 240 and 440 F/g, respectively. Increasing the conductivity and stability of composite electrodes during continuous CD cycles compared to PANI ones are some features of using YAG NPs in the structure of polymer electrodes. Stability of composite electrodes remains about 98% through 1000 continuous cycles whereas the polymeric electrode loses about 91% of its capacitance during this time range.     

Mechanisms of effective gold shell on Fe3O4 core nanoparticles formation using sonochemistry method

Sonochemical synthesis (sonochemistry) is one of the most effective techniques of breaking down large clusters of nanoparticles (NPs) into smaller clusters or even individual NPs, which ensures their dispersibility (stability) in a solution over a long duration. This paper demonstrates the potential of sonochemistry becoming a valuable tool for the deposition of gold (Au) shell on iron oxide nanoparticles (Fe₃O₄ NPs) by explaining the underlying complex processes that control the deposition mechanism. This review summarizes the principles of the sonochemistry method and highlights the resulting phenomenon of acoustic cavitation and its associated physical, chemical and thermal effects. The effect of sonochemistry on the deposition of Au NPs on the Fe₃O₄ surface of various sizes is presented and discussed. A Vibra-Cell ultrasonic solid horn with tip size, frequency, power output of ½ inch, 20 kHz and 750 W respectively was used in core@shell synthesis. The sonochemical process was shown to affect the surface and structure of Fe₃O₄ NPs via acoustic cavitation, which prevents the agglomeration of clusters in a solution, resulting in a more stable dispersion. Deciphering the mechanism that governs the formation of Au shell on Fe₃O₄ core NPs has emphasized the potential of sonication in enhancing the chemical activity in solutions.     

Interference of Metal Oxide Nanoparticles with Coagulation Cascade and Interaction with Blood Components

Metal oxide nanoparticles (NPs) are increasingly used for different purposes, showing a potential risk on human health. The analysis of the interaction of these metal oxide NPs with blood components is a crucial step in the characterization of their biocompatibility, but information available of comparative studies with several doses and different metal oxide NPs is really scarce. In this study, six different metal oxide NPs (TiO₂, CeO₂, Al₂O₃, Y₂O₃, and two different types of ZnO NPs) at different concentrations are used, and their potential adverse effects on blood are determined. Both, prothrombin time (PT) and activated partial thromboplastin time (aPTT), are assessed to understand particle influence on the plasma coagulation cascade. Additional hematocompatibility tests include assessment of thrombin coagulation time, platelet aggregation, leukocyte procoagulant activity (PCA), hemolysis, and complement activation. The results demonstrate that only the ZnO and TiO₂ NPs affect the coagulation cascade by increasing the aPTT in a dose‐dependent manner. Moreover, ZnO NPs increase PT, while TiO₂ NPs induce a decrease in the PT. In addition to affecting coagulation time, ZnO NPs also induce platelet aggregation and leukocyte PCA. All tested metal oxide NPs do not affect hemolysis and complement activation.     

Stimuli-sensitive nanoparticles for multiple anti-HIV microbicides

This study is aimed to develop and evaluate an advanced intravaginal formulation for the delivery of multiple anti-HIV microbicides. Novel stimuli-sensitive nanoparticles (NPs) which protected the encapsulated drugs from being degraded in acidic pH conditions were made of Eudragit S-100^® (ES100^®), a pH-sensitive polymer. ES100^® NPs were prepared using the quasi-emulsion solvent diffusion technique and loaded with two microbicides namely Tenofovir (TNF) and Etravirine (ETV). The effects of various fabrication parameters on the formulation properties were evaluated for the optimization of ES100^® NPs. The morphology of the ES100^® NPs was examined by scanning electron microscopy. The cytotoxicity of NPs containing microbicides individually or in a combination was assessed using cell viability and trans-epithelial electrical resistance (TEER) measurements. The cellular uptake rates of the model microbicides by human vaginal epithelial cells, VK2 E6/E7 cells, were evaluated using confocal microscopy and florescence-assisted cell sorting technique. ES100^® NPs had a spherical shape, smooth surface, and uniform texture with a little aggregation. The average particle size for NPs loaded with TNF ranged from 125 to 230 nm, whereas those for ETV-loaded NPs ranged from 160 to 280 nm. ES100^® NPs had zeta potential in the range of ?5 to ?10 mV. In-vitro release studies displayed the potential benefits of ES100^® NPs in retaining and protecting the loaded microbicides at vaginal pH (acidic), but immediately releasing them as the pH changes to neutral or 7.4 (physiological pH). Cell viability studies demonstrated that ES100^® NPs did not exert any cytotoxicity individually or in a combination of both microbicides. TEER measurements confirmed that ES100^® NPs loaded with TNF and ETV did not cause any changes in the barrier integrity of VK2 E6/E7 cell monolayer. The cellular uptake study revealed that ES100^® NPs were taken by vaginal epithelial cells through the endocytosis process and that the uptake rate of the model microbicides loaded in nanoparticles was greater than that in the solution. The ES100^® NPs whose degradation rates are dependent on environmental pH would serve as an efficient platform for targeted delivery of multiple microbicides to protect women from sexually transmitted diseases including HIV-1 infection.     

Use of nanomaterials in the European construction industry and some occupational health aspects thereof

In the European construction industry in 2009, the use of engineered nanoparticles appears to be confined to a limited number of products, predominantly coatings, cement and concrete. A survey among representatives of workers and employers from 14 EU countries suggests a high level of ignorance about the availability and use of nanomaterials for the construction industry and the safety aspects thereof. Barriers for a large-scale acceptance of products containing engineered nanoparticles (nanoproducts) are high costs, uncertainties about long-term technical material performance, as well as uncertainties about health risks of nanoproducts. Workplace measurements suggest a modest exposure of construction workers to nanoparticles (NPs) associated with the use of nanoproducts. The measured particles were within a size range of 20–300 nm, with the median diameter below 53 nm. Positive assignment of this exposure to the nanoproduct or to additional sources of ultrafine particles, like the electrical equipment used was not possible within the scope of this study and requires further research. Exposures were below the nano reference values proposed on the basis of a precautionary approach.     

Chronic exposure to zinc oxide nanoparticles increases ischemic-reperfusion injuries in isolated rat hearts

The use of zinc oxide nanoparticles (ZnO NPs) in numerous products is increasing, although possible negative implications of their long-term consumption are not known yet. Our aim was to evaluate the chronic, 6-week oral exposure to two different concentrations of ZnO NPs on isolated rat hearts exposed to ischemic-reperfusion injury and on small intestine morphology. Wistar rats of both sexes (n = 18) were randomly divided into three groups: (1) 4 mg/kg ZnO NPs, (2) 40 mg/kg ZnO NPs, and (3) control. After 6 weeks of treatment, the hearts were isolated, the left ventricular pressure (LVP), the coronary flow (CF), the duration of arrhythmias and the lactate dehydrogenase release rate (LDH) were measured. A histological investigation of the small intestine was performed. Chronic exposure to ZnO NPs acted cardiotoxic dose-dependently. ZnO NPs in dosage 40 mg/kg maximally decreased LVP (3.3-fold) and CF (2.5-fold) and increased the duration of ventricular tachycardia (all P < 0.01) compared to control, whereas ZnO NPs in dosage 4 mg/kg acted less cardiotoxic. Goblet cells in the small intestine epithelium of rats, treated with 40 mg ZnO NPs/kg, were enlarged, swollen and numerous, the intestinal epithelium width was increased. Unexpectedly, ZnO NPs in both dosages significantly decreased LDH. A 6-week oral exposure to ZnO NPs dose-dependently increased heart injuries and caused irritation of the intestinal mucosa. A prolonged exposure to ZnO NPs might cause functional damage to the heart even with exposures to the recommended daily doses, which should be tested in future studies.     

A fluorescent probe for detecting thiamine using the luminescence intensity of nanoparticles

Determination of molecules and biomolecules using nanoparticles is promising in the development of analytical techniques. Modified Eu-doped Y₂O₃ nanoparticles (Y₂O₃:Eu NPs) by captopril have been used as a probe for thiamine (vitamin B₁) determination. According to the fluorescence enhancement of modified Eu-doped Y₂O₃ nanoparticles caused by thiamine, a simple and sensitive method were proposed for its detection. The increase in modified Y₂O₃:Eu NPs fluorescence signal as a function of thiamine concentration was found to be linear in the concentration range of 0–44 μM. The limit of detection (LOD) of thiamine by this method was 0.144 μM. All the measurements were performed in natural pH, at the room temperature under ambient conditions. Possible interaction mechanism was discussed.     

Safety Issue of Changed Nanotoxicity of Zinc Oxide Nanoparticles in the Multicomponent System

When nanomaterials are exposed to complex systems, such as food, they may cause significant changes in physical and chemical properties and even toxicity. The toxicity evaluation of complex systems is urgent. Unfortunately, so far, there is no database established about the toxicity changes of nanoparticles in composite systems. In this paper, the changes and toxicity mechanism of zinc oxide nanoparticles (ZnO NPs) in a composite system are studied. The results show that the dissolution of zinc ions (Zn²⁺) in acidic systems (vitamin C, tartaric acid, or citric acid) increases the toxicity of ZnO NPs. However, the toxicity of ZnO NPs is reduced by the complexation effect with Zn²⁺ in phosphoric acid, phosphate, and glutathione systems. The influence of titanium dioxide nanoparticles (TiO₂ NPs) on the toxicity of ZnO NPs depends on size and surface properties. In brief, the intracellular Zn²⁺ homeostasis level is the decisive factor in determining the toxicity change in complex systems. The results indicate that the toxicity changes are very different in combined systems, which may have potential food safety issues, especially for unstable nanoparticles.     

Structural and crystal growth kinetics studies for SnO2 nanoparticles prepared via hydrothermal route

Tin oxide nanoparticles with crystallite size (1.9–3 nm) were synthesized via hydrothermal route. The role of autoclave temperature (T_A) on the structural parameters and surface morphology of the as-synthesized SnO₂ nanoparticles (NPs) was followed using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The thermal behavior of the as-synthesized SnO₂ NPs was carried out using thermogravimetric and differential thermal analysis (TGA/DTA) techniques under non-isothermal conditions. The effect of T_A on the activation energy of crystal growth (E_c) and the Avrami exponent (n) of SnO₂ NPs were determined by different methods. The reaction mechanism controlling the growth process was discussed in terms of the results obtained using different iso-conversional methods to determine the local E_c(α) and n(α).