Particle release and control of worker exposure during laboratory-scale synthesis,handling and simulated spills of manufactured nanomaterials in fume hoods

Fume hoods are one of the most common types of equipment applied to reduce the potential of particle exposure in laboratory environments. A number of previous studies have shown particle release during work with nanomaterials under fume hoods. Here, we assessed laboratory workers’ inhalation exposure during synthesis and handling of CuO, TiO₂ and ZnO in a fume hood. In addition, we tested the capacity of a fume hood to prevent particle release to laboratory air during simulated spillage of different powders (silica fume, zirconia TZ-3Y and TiO₂). Airborne particle concentrations were measured in near field, far field, and in the breathing zone of the worker. Handling CuO nanoparticles increased the concentration of small particles (<?58 nm) inside the fume hood (up to 1?×?10⁵ cm^?3). Synthesis, handling and packaging of ZnO and TiO₂ nanoparticles did not result in detectable particle release to the laboratory air. Simulated powder spills showed a systematic increase in the particle concentrations inside the fume hood with increasing amount of material and drop height. Despite powder spills were sometimes observed to eject into the laboratory room, the spill events were rarely associated with notable release of particles from the fume hood. Overall, this study shows that a fume hood generally offers sufficient exposure control during synthesis and handling of nanomaterials. An appropriate fume hood with adequate sash height and face velocity prevents 98.3% of particles release into the surrounding environment. Care should still be made to consider spills and high cleanliness to prevent exposure via resuspension and inadvertent exposure by secondary routes.     

Aerosol characterization and lung deposition of synthesized TiO2 nanoparticles for murine inhalation studies

This study presents a novel exposure protocol for synthesized nanoparticles (NPs). NPs were synthesized in gas phase by thermal decomposition of metal alkoxide vapors in a laminar flow reactor. The exposure protocol was used to estimate the deposition fraction of titanium dioxide (TiO₂) NPs to mice lung. The experiments were conducted at aerosol mass concentrations of 0.8, 7.2, 10.0, and 28.5 mg m^?3. The means of aerosol geometric mobility diameter and aerodynamic diameter were 80 and 124 nm, and the geometric standard deviations were 1.8 and 1.7, respectively. The effective density of the particles was approximately from 1.5 to 1.7 g cm^?3. Particle concentration varied from 4 × 10⁵ cm^?3 at mass concentrations of 0.8 mg m^?3 to 12 × 10⁶ cm^?3 at 28.5 mg m^?3. Particle phase structures were 74% of anatase and 26% of brookite with respective crystallite sized of 41 and 6 nm. The brookite crystallites were approximately 100 times the size of the anatase crystallites. The TiO₂ particles were porous and highly agglomerated, with a mean primary particle size of 21 nm. The specific surface area of TiO₂ powder was 61 m² g^?1. We defined mice respiratory minute volume (RMV) value during exposure to TiO₂ aerosol. Both TiO₂ particulate matter and gaseous by-products affected respiratory parameters. The RMV values were used to quantify the deposition fraction of TiO₂ matter by using two different methods. According to individual samples, the deposition fraction was 8% on an average, and when defined from aerosol mass concentration series, it was 7%. These results show that the exposure protocol can be used to study toxicological effects of synthesized NPs.     

Green synthesis of Au nanoparticles using potato extract: stability and growth mechanism

Airborne particle release during the spray application of coatings was analyzed in the nanometre and micrometre size range. In order to represent realistic conditions of domestic and handcraft use, the spray application was performed using two types of commercial propellant spray cans and a manual gravity spray gun. Four different types of coatings doped with three kinds of metal-oxide tracer nanoparticle additives (TNPA) were analyzed. Depending on the used coating and the kind of spray unit, particulate release numbers between 5 × 10⁸ and 3 × 10¹⁰ particles per gram ejection mass were determined in the dried spray aerosols. The nanoparticulate fraction amounted values between 10 and 60 no%. The comparison between nanoparticle-doped coatings with non-doped ones showed no TNPA-attributed differences in both the macroscopic spray process characteristics and the particle release numbers. SEM, TEM and EDX-analyzes showed that the spray aerosols were composed of particles made up solely from matrix material and sheathed pigments, fillers and TNPAs. Isolated ZnO- or Fe₂O₃-TNPAs could not be observed.     

A fast and sensitive nanosensor based on MgO nanoparticle room-temperature ionic liquid carbon paste electrode for determination of methyldopa in pharmaceutical and patient human urine samples

In this study, we describe an ionic liquid–MgO nanoparticle modified carbon paste electrode (MgO/NPs/IL/CPE) was used as a simple, fast, and sensitive tool for the investigation of the electrochemical oxidation of methyldopa (MDOP) using voltammetric methods. The MgO/NPs was characterized with different methods such as TEM, SEM, and XRD. The oxidation peak potential of the MDOP at a surface of MgO/NPs/IL/CPE appeared at 450 mV that was about 100 mV lower than the oxidation peak potential at the surface of the traditional carbon paste electrode (CPE) under similar conditions. The electro-oxidation of MDOP occurred in a pH-dependent 2e^? and 2H⁺ process, and the electrode reaction followed a diffusion-controlled pathway. Under optimal conditions at pH 7.0, the anodic peak currents increased linearly with the concentration of MDOP in the range of 0.08–380 μmol L^?1 with a detection limit of 0.03 μmol L^?1 (3σ). The proposed sensor was successfully applied to the determination of MDOP in real samples such as drug and urine.     

Airborne nanoparticle exposures associated with the manual handling of nanoalumina and nanosilver in fume hoods

Manual handling of nanoparticles is a fundamental task of most nanomaterial research; such handling may expose workers to ultrafine or nanoparticles. Recent studies confirm that exposures to ultrafine or nanoparticles produce adverse inflammatory responses in rodent lungs and such particles may translocate to other areas of the body, including the brain. An important method for protecting workers handling nanoparticles from exposure to airborne nanoparticles is the laboratory fume hood. Such hoods rely on the proper face velocity for optimum performance. In addition, several other hood design and operating factors can affect worker exposure. Handling experiments were performed to measure airborne particle concentration while handling nanoparticles in three fume hoods located in different buildings under a range of operating conditions. Nanoalumina and nanosilver were selected to perform handling experiments in the fume hoods. Air samples were also collected on polycarbonate membrane filters and particles were characterized by scanning electron microscopy. Handling tasks included transferring particles from beaker to beaker by spatula and by pouring. Measurement locations were the room background, the researcher’s breathing zone and upstream and downstream from the handling location. Variable factors studied included hood design, transfer method, face velocity/sash location and material types. Airborne particle concentrations measured at breathing zone locations were analyzed to characterize exposure level. Statistics were used to test the correlation between data. The test results found that the handling of dry powders consisting of nano-sized particles inside laboratory fume hoods can result in a significant release of airborne nanoparticles from the fume hood into the laboratory environment and the researcher’s breathing zone. Many variables were found to affect the extent of particle release including hood design, hood operation (sash height, face velocity), work practices, type and quantity of the material being handled, room conditions, and the adequacy of the room exhaust.

Nanoparticle transport in water-unsaturated porous media: effects of solution ionic strength and flow rate

This paper presents the influence of ionic strength and flow on nanoparticle (NP) retention rate in an unsaturated calcareous medium, originating from a heterogeneous glaciofluvial deposit of the region of Lyon (France). Laboratory columns 10 cm in diameter and 30 cm in length were used. Silica nanoparticles (Au-SiO₂-FluoNPs), with hydrodynamic diameter ranging from 50 to 60 nm and labeled with fluorescein derivatives, were used to simulate particle transport, and bromide was used to characterize flow. Three flow rates and five different ionic strengths were tested. The transfer model based on fractionation of water into mobile and immobile fractions was coupled with the attachment/detachment model to fit NPs breakthrough curves. The results show that increasing flow velocity induces a decrease in nanoparticle retention, probably as the result of several physical but also geochemical factors. The results show that NPs retention increases with ionic strength. However, an inversion of retention occurs for ionic strength >5.10^?2 M, which has been scarcely observed in previous studies. The measure of zeta potential and DLVO calculations show that NPs may sorb on both solid-water and air-water interfaces. NPs size distribution shows the potential for nanoparticle agglomeration mostly at low pH, leading to entrapment in the soil pores. These mechanisms are highly sensitive to both hydrodynamic and geochemical conditions, which explains their high sensitivity to flow rates and ionic strength.     

Uptake of silver nanoparticles by monocytic THP-1 cells depends on particle size and presence of serum proteins

Human health risks by silver nanoparticle (AgNP) exposure are likely to increase due to the increasing number of NP-containing products and demonstrated adverse effects in various cell lines. Unfortunately, results from (toxicity) studies are often based on exposure dose and are often measured only at a fixed time point. NP uptake kinetics and the time-dependent internal cellular concentration are often not considered. Macrophages are the first line of defense against invading foreign agents including NPs. How macrophages deal with the particles is essential for potential toxicity of the NPs. However, there is a considerable lack of uptake studies of particles in the nanometer range and macrophage-like cells. Therefore, uptake rates were determined over 24 h for three different AgNPs sizes (20, 50 and 75 nm) in medium with and without fetal calf serum. Non-toxic concentrations of 10 ng Ag/mL for monocytic THP-1 cells, representing realistic exposure concentration for short-term exposures, were chosen. The uptake of Ag was higher in medium without fetal calf serum and showed increasing uptake for decreasing NP sizes, both on NP mass and on number basis. Internal cellular concentrations reached roughly 32/10 %, 25/18 % and 21/15 % of the nominal concentration in the absence of fetal calf serum/with fetal calf serum for 20-, 50- and 75-nm NPs, respectively. Our research shows that uptake kinetics in macrophages differ for various NP sizes. To increase the understanding of the mechanism of NP toxicity in cells, the process of uptake (timing) should be considered.     

Silver nanoparticles generated by pulsed laser ablation in supercritical CO2 medium

Pulsed laser ablation (PLA) has been widely employed in industrial and biological applications and in other fields. The environmental conditions in which PLA is conducted are important parameters that affect both the solid particle cloud and the deposition produced by the plume. In this work, the generation of nanoparticles (NPs) has been developed by performing PLA of silver (Ag) plates in a supercritical CO₂ medium. Ag NPs were successfully generated by allowing the selective generation of clusters. Laser ablation was performed with an excitation wavelength of 532 nm under various pressures and temperatures of CO₂ medium. On the basis of the experimental result, both surface of the irradiated Ag plate and structure of Ag NPs were significantly affected by the changes in supercritical CO₂ pressure and temperature. With increasing irradiation pressure, plume deposited in the surrounding crater created by the ablation was clearly observed. In Field Emission Scanning Electron Microscopy (FE-SEM) the image of the generated Ag NPs on the silicon wafer and the morphology of Ag particles were basically a sphere-like structure. Ag particles contain NPs with large-varied diameter ranging from 5 nm to 1.2 μm. The bigger Ag NPs melted during the ablation process and then ejected smaller spherical Ag NPs, which formed nanoclusters attached on the molten Ag NPs. The smaller Ag NPs were also formed around the bigger Ag NPs. Based on the results, this new method can also be used to obtain advanced nano-structured materials.     

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.     

Effects of particle size of silica aerogel on its nano-porous structure and thermal behaviors under both ambient and high temperatures

Silica aerogel as the most commonly used aerogel has attracted increasing attention from both academia and industries due to its extraordinary performances and potentials. Through this study, influences of the particle size (38–880 μm) on its nano-porous structure and thermal behaviors were addressed based on a series of experimental tests under both ambient and high temperatures (i.e., 1000 °C). It was known from the experimental results that the fractional densities of samples with particle sizes of 270–880 μm were similar, which were about 40% of the sample with a particle size of 38 μm. The ratio of densification was found decrease to about 10–40% when heating time increased from 10 to 90 min. For those samples with 150 μm or finer particles, SiC crystal with 70.8 nm particles was generated, and the pore shape was slit in the silica aerogel. The Brunauer–Emmett–Teller (BET) surface area, cumulative pore volume, and average pore diameter of those heated samples with over 75 μm diameter were about 40%, 20%, and 50% of those unheated (virgin) samples, respectively. Virgin samples showed 18% lower thermal conductivity for 75 μm particles compared to that of 38 μm, while for the heated samples, 38 μm particles showed a 28% lower thermal conductivity than that with 880 μm. Mixture of silica aerogel and other inorganic material particles are recommended for high-temperature applications, while the silica aerogel with different-sized particles are observed better for applications under ambient temperature.     

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

The potential for using hydroxyl radical (OH^?) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H₂O₂ addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80–100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H₂O₂ by NP surface generated OH^? were investigated. Depending on the ratio of iron and H₂O₂, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.     

Dustiness behaviour of loose and compacted Bentonite and organoclay powders: What is the difference in exposure risk?

Single-drop and rotating drum dustiness testing was used to investigate the dustiness of loose and compacted montmorillonite (Bentonite) and an organoclay (Nanofil^®5), which had been modified from montmorillonite-rich Bentonite. The dustiness was analysed based on filter measurements as well as particle size distributions, the particle generation rate, and the total number of generated particles. Particle monitoring was completed using a TSI Fast Mobility Particle Sizer (FMPS) and a TSI Aerosol Particle Sizer (APS) at 1 s resolution. Low-pressure uniaxial powder compaction of the starting materials showed a logarithmic compaction curve and samples subjected to 3.5 kg/cm² were used for dustiness testing to evaluate the role of powder compaction, which could occur in powders from large shipments or high-volume storage facilities. The dustiness tests showed intermediate dustiness indices (1,077–2,077 mg/kg powder) in tests of Nanofil^®5, Bentonite, and compacted Bentonite, while a high-level dustiness index was found for compacted Nanofil^®5 (3,487 mg/kg powder). All powders produced multimodal particle size-distributions in the dust cloud with one mode around 300 nm (Bentonite) or 400 nm (Nanofil^®5) as well as one (Nanofil^®5) or two modes (Bentonite) with peaks between 1 and 2.5 μm. The dust release was found to occur either as a burst (loose Bentonite and Nanofil^®5), constant rate (compacted Nanofil^®5), or slowly increasing rate (compacted Bentonite). In rotating drum experiments, the number of particles generated in the FMPS and APS size-ranges were in general agreement with the mass-based dustiness index, but the same order was not observed in the single-drop tests. Compaction of Bentonite reduced the number of generated particles with app. 70 and 40% during single-drop and rotating drum dustiness tests, respectively. Compaction of Nanofil^®5 reduced the dustiness in the single-drop test, but it was more than doubled in the rotating drum test. Physically relevant low-pressure compaction may reduce the risk of particle exposure if powders are handled in operations with few agitations such as pouring or tapping. Repeated agitation, e.g., mixing, of these compacted powders, would result in reduced (app. 20% for Bentonite) or highly increased (app. 225% for Nanofil^®5) dustiness and thereby alter the exposure risk significantly.     

One-step synthesis of intrinsically functionalized fluorescent carbon nanoparticles by hydrothermal carbonization from different carbon sources

Nuclepore filter collection with subsequent electron microscopy analysis for nanosized agglomerates (20–500 nm in mobility diameter) was carried out to examine the feasibility of the method to assess the personal engineered nanoparticle exposure. The number distribution of the nanoparticles collected on the filter surface was obtained by visual counting and converted to the distribution in the air using validated capillary tube models. The model was validated by studying the overall penetrations of nanoparticles (Ag and soot) with different agglomeration degrees through 1 μm pore diameter Nuclepore filters at different face velocities (2–15 cm/s). In the model, the effects of the maximum length of agglomerates on interception deposition and the dynamic shape factor on impaction deposition were taken into account. Results showed that the data of the overall penetration were in very good agreement with the properly applied models. A good agreement of filter surface collection between the validated model and the SEM analysis of this study was obtained, indicating a correct particle number distribution in the air can be converted from the Nuclepore filter surface collection and this method can be applied for quantitative engineered nanoparticle exposure assessment.     

Measurement of filtration efficiency of Nuclepore filters challenged with polystyrene latex nanoparticles: experiments and modeling

Membrane filtration has been demonstrated to be effective for the removal of liquid-borne nanoparticles (NPs). Such technique can be applied to purify and disinfect drinking water as well as remove NPs in highly pure chemicals used in the industries. This study aims to study the filtration process of a model membrane filter, the Nuclepore filter. Experiments were carried out using standard filtration tools and the nanoparticle tracking analysis (NTA) technique was used to measure particle (50–500 nm) concentration upstream and downstream of the filter to determine the filtration efficiency. The NTA technique has been calibrated using 150-nm polystyrene latex particles to determine its accuracy of particle concentration measurement. Measurements were found reliable within a certain concentration limit (about 10⁸–10¹⁰ particles/cm³), which is dependent on the camera settings during the measurement. Experimental results are comparable with previously published data obtained using the aerosolization method, validating the capability of the NTA technique. The capillary tube model modified from that developed for aerosol filtration was found to be useful to represent the experimental results, when a sticking coefficient of 0.15 is incorporated. This suggests that only 15% of the particle collisions with the filter results in successful attachment. The small sticking coefficient found can be explained by the unfavorable surface interactions between the particles and the filter medium.     

Structuring of micro line conductor using electro-hydrodynamic printing of a silver nanoparticle suspension

The generation of a fine pattern of metallic materials from suspensions is gaining significant interest because it is the key in the fabrications of displays and printed circuit boards. In our experiments, a silver nanoparticle suspension was first deposited onto a Kapton® polyimide film by using an electro-hydrodynamic printing system, including a guide ring and pin (nozzle)-to-pin (ground) electrodes. Then after thermal curing of the particles deposited, a conductor line as fine as 32 μm in width and 0.3 μm in thickness was obtained onto the film. The resistivity of the line was about 13 μΩ?cm. The pin type ground electrode was helpful in the deposit of the silver nanoparticle suspension along a specific direction. The guide ring repressed the chaotic motion of the jet and prevented the jet from digressing from the centerline. With the electro-hydrodynamic printing method, a nozzle (inner diameter: 140 μm, outer diameter: 320 μm) much larger than an ink jet nozzle could be used.     

The time-dependent cellular response mechanism upon exposure to zinc oxide nanoparticles

Zinc oxide nanoparticle is one of the nanomaterials people engaged most in their life and its health effect has been taken into concern. In this work, A549 cell line was used as cell model, and the cytotoxicity of zinc oxide nanoparticles was revealed to be concentration-dependent. Through the measurement of cellular proteome, much more differentially expressed proteins were observed after the cells being treated for 9 h than 24 h. Also, most of these proteins expressed in the pattern which showed a significant decrease after exposure to zinc oxide nanoparticles and then an increase at 24 h. Intracellular reactive oxygen species and glutathione determination indicated that high level of oxidative stress was presented in cell after treatment with zinc oxide nanoparticles for 9 h. It can be observed from western blot analysis that the expression of NF-κB p65, PNPase, and HSP90 rose significantly after 9 h of exposure. Thus, a deduction was reached that toxicity of nanoparticles consists both of particle toxicity and ion toxicity, and a long-time treatment may conceal the toxicity induced by particles. The conclusion we made highlighted the importance of exposure time in the study of nanoparticle toxicity and would provide a new perspective for studying toxicity mechanism of nanoparticles.     

Effect of Al particle size on the reaction kinetics and densification of TiAl intermetallics

The present investigation deals with response of the particle size of aluminum on the reactive sintering of Ti–Al intermetallics and subsequently on their reaction kinetics and densification behavior. Aluminum powders of initial average particle size of 44 μm were milled for various durations in a planetary ball mill to produce average particles sizes of 100, 28 and 7 μm. These aluminum powders of various particle sizes i.e. 100, 28 and 7 μm were mixed with titanium powder of average particles size of 44 μm in the ratio of 1:1 corresponding to the Ti–Al intermetallic composition. The reactive sintering temperatures of the mixtures were determined by DTA and the effect of change in particle Al particle size has been determined for the activation energy ofthe self-propagating reaction. The effect of Al particle size on the sintering was determined by studying density and microstructure.     

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.     

Stability of polyvinyl alcohol-coated biochar nanoparticles in brine

This paper reports on the dispersion stability of 150 nm polyvinyl alcohol coated biochar nanoparticles in brine water. Biochar is a renewable, carbon based material that is of significant interest for enhanced oil recovery operations primarily due to its wide ranging surface properties, low cost of synthesis, and low environmental toxicity. Nanoparticles used as stabilizing agents for foams (and emulsions) or in nanofluids have emerged as potential alternatives to surfactants for subsurface applications due to their improved stability at reservoir conditions. If, however, the particles are not properly designed, they are susceptible to aggregation because of the high salinity brines typical of oil and gas reservoirs. Attachment of polymers to the nanoparticle surface, through covalent bonds, provides steric stabilization, and is a necessary step. Our results show that as the graft density of polyvinyl alcohol increases, so too does the stability of nanoparticles in brine solutions. A maximum of 34 wt% of 50,000 Da polyvinyl alcohol was grafted to the particle surface, and the size of the particles was reduced from ~3500 nm (no coating) to 350 nm in brine. After 24 h, the particles had a size of ~500 nm, and after 48 h completely aggregated. 100,000 Da PVA coated at 24 wt% on the biochar particles were stable in brine for over 1 month with no change in mean particle size of ~330 nm.     

Workplace air measurements and likelihood of exposure to manufactured nano-objects,agglomerates, and aggregates

Workplace exposure to nanoparticles from gas metal arc welding (GMAW) process in an automobile manufacturing factory was investigated using a combination of multiple metrics and a comparison with background particles. The number concentration (NC), lung-deposited surface area concentration (SAC), estimated SAC and mass concentration (MC) of nanoparticles produced from the GMAW process were significantly higher than those of background particles before welding (P < 0.01). A bimodal size distribution by mass for welding particles with two peak values (i.e., 10,000–18,000 and 560–320 nm) and a unimodal size distribution by number with 190.7-nm mode size or 154.9-nm geometric size were observed. Nanoparticles by number comprised 60.7 % of particles, whereas nanoparticles by mass only accounted for 18.2 % of the total particles. The morphology of welding particles was dominated by the formation of chain-like agglomerates of primary particles. The metal composition of these welding particles consisted primarily of Fe, Mn, and Zn. The size distribution, morphology, and elemental compositions of welding particles were significantly different from background particles. Working activities, sampling distances from the source, air velocity, engineering control measures, and background particles in working places had significant influences on concentrations of airborne nanoparticle. In addition, SAC showed a high correlation with NC and a relatively low correlation with MC. These findings indicate that the GMAW process is able to generate significant levels of nanoparticles. It is recommended that a combination of multiple metrics is measured as part of a well-designed sampling strategy for airborne nanoparticles. Key exposure factors, such as particle agglomeration/aggregation, background particles, working activities, temporal and spatial distributions of the particles, air velocity, engineering control measures, should be investigated when measuring workplace exposure to nanoparticles.