Size-distribution and driving factors of aerosol oxidative potential in rural kitchen microenvironments of northeastern India.

This study reports size-resolved dithiothreitol (DTT)-based oxidative potential (OP: total and water-soluble) in rural kitchens using liquefied petroleum gas (LPG), firewood (FW), and mixed biomass (MB) fuels in northeastern (NE) India. In comparison to LPG, volume-normalized total OP (OPtotal(v)DTT) was enhanced by a factor of ∼5 in biomass-using kitchens (74 ± 35 to 78 ± 42 nmol min-1 m-3); however, mass-normalized total OP (OPtotal(m)DTT) was similar between LPG and FW users and higher by a factor of 2 in MB-using kitchens. The water-insoluble OP (OPwi(v, m)DTT) fraction in OPtotal(v, m)DTT was greater than 50% across kitchens. Size distributions across kitchens and OPDTT categories ranged from unimodal to trimodal. OPws(v)DTT was driven by metals as well as organics across size fractions while OPwi(v)DTT was majorly constrained by metals with an increasing importance of organics in fine particles of biomass-using kitchens. Multiple linear regression analysis revealed that Cu and Ba explained 71% of the OPtotal(v)DTT variability in LPG-using kitchens, while water-soluble organic carbon (WSOC) and Ba were responsible for 44% variability in FW-using kitchens. Finally, the high internal dose of OPtotal(v)DTT (28-31 nmol min-1 m-3) in biomass-using kitchens established the severity of oxidative stress on the exposed population.

Strategies to Assess Occupational Exposure to Airborne Nanoparticles: Systematic Review and Recommendations.

In many industrial sectors, workers are exposed to manufactured or unintentionally emitted airborne nanoparticles (NPs). To develop prevention and enhance knowledge surrounding exposure, it has become crucial to achieve a consensus on how to assess exposure to airborne NPs by inhalation in the workplace. Here, we review the literature presenting recommendations on assessing occupational exposure to NPs. The 23 distinct strategies retained were analyzed in terms of the following points: target NPs, objectives, steps, "measurement strategy" (instruments, physicochemical analysis, and data processing), "contextual information" presented, and "work activity" analysis. The robustness (consistency of information) and practical aspects (detailed methodology) of each strategy were estimated. The objectives and methodological steps varied, as did the measurement techniques. Strategies were essentially based on NPs measurement, but improvements could be made to better account for "contextual information" and "work activity". Based on this review, recommendations for an operational strategy were formulated, integrating the work activity with the measurement to provide a more complete assessment of situations leading to airborne NP exposure. These recommendations can be used with the objective of producing homogeneous exposure data for epidemiological purposes and to help improve prevention strategies.

Understanding population exposure to size-segregated aerosol and associated trace elements during residential cooking in northeastern India: Implications for disease burden and health risk.

Mass-size distribution of respirable aerosol and 13 associated trace elements (TEs) were investigated in rural kitchens using liquefied petroleum gas (LPG), firewood and mixed biomass fuels across three northeastern Indian states. The averaged PM10 (particulate matter with aerodynamic diameter ≤ 10 µm) and ΣTE concentrations were 403 and 30 µg m-3 for LPG, 2429 and 55 µg m-3 for firewood, and 1024 and 44 µg m-3 for mixed biomass-using kitchens. Mass-size distributions were tri-modal with peaks in the ultrafine (0.05-0.08 µm), accumulation (0.20-1.05 µm), and coarse (3.20-4.57 µm) modes. Respiratory deposition, estimated using the multiple path particle dosimetry model, ranged from 21 % to 58 % of the total concentration across fuel types and population age categories. Head, followed by pulmonary and tracheobronchial, was the most vulnerable deposition region, and children were the most susceptible age group. Inhalation risk assessment of TEs revealed significant non-carcinogenic as well as carcinogenic risk, especially for biomass fuel users. The potential years of life lost (PYLL) was the highest for chronic obstructive pulmonary disease (COPD: 15.9 ± 3.8 years) followed by lung cancer (10.3 ± 0.3 years) and pneumonia (10.1 ± 0.1 years), while the PYLL rate was also highest for COPD, with Cr(VI) being the major contributor. Overall, these findings reveal the significant health burden faced by the northeastern Indian population from indoor cooking using solid biomass fuels.

Towards a surface metric to measure the dustiness of nanomaterial powders.

The relevance of dustiness methods is increasingly recognized in the preliminary exposure evaluation of workers handling nanomaterials in powder form, and should also be transposed to the assessment of environmental risk in the future. The methods currently recommended in the European standards are mainly based on determining a mass-based dustiness index [mg kg-1], whereas surface area is regularly put forward as a more appropriate determinant to assess the pulmonary toxicity of nanoparticles. In this study, we describe an operational methodology leading us to propose a surface metric to determine the dustiness index [m2 kg-1] of nanoparticulate matter. To this end, we demonstrate the equivalence between the external specific surface area of a nanopowder and that of its aerosol with five nanomaterials produced and used on an industrial scale, and covering a range of external specific surface areas from 35 to 230 m2 g-1. Compared to the conventional mass-based dustiness index, the surface-based dustiness index (1) is more discriminating, covering an additional order of magnitude, and (2) has an impact on the powder ranking with potential consequences on the preventive measures to be implemented. Finally, our proposal has the potential to be included in future revisions of European standards for workplace exposure and dustiness measurement, provided that further experimental results on surface-based dustiness indices support these preliminary data.

Retained particle surface area dose drives inflammation in rat lungs following acute, subacute, and subchronic inhalation of nanomaterials.

BACKGROUND: An important aspect of nanomaterial (NM) risk assessment is establishing relationships between physicochemical properties and key events governing the toxicological pathway leading to adverse outcomes. The difficulty of NM grouping can be simplified if the most toxicologically relevant dose metric is used to assess the toxicological dose-response. Here, we thoroughly investigated the relationship between acute and chronic inflammation (based on polymorphonuclear neutrophil influx (% PMN) in lung bronchoalveolar lavage) and the retained surface area in the lung. Inhalation studies were performed in rats with three classes of NMs: titanium dioxides (TiO2) and carbon blacks (CB) as poorly soluble particles of low toxicity (PSLT), and multiwall carbon nanotubes (MWCNTs). We compared our results to published data from nearly 30 rigorously selected articles. RESULTS: This analysis combined data specially generated for this work on three benchmark materials - TiO2 P25, the CB Printex-90 and the MWCNT MWNT-7 - following subacute (4-week) inhalation with published data relating to acute (1-week) to subchronic (13-week) inhalation exposure to the classes of NMs considered. Short and long post-exposure recovery times (immediately after exposure up to more than 6 months) allowed us to examine both acute and chronic inflammation. A dose-response relationship across short-term and long-term studies was revealed linking pulmonary retained surface area dose (measured or estimated) and % PMN. This relationship takes the form of sigmoid curves, and is independent of the post-exposure time. Curve fitting equations depended on the class of NM considered, and sometimes on the duration of exposure. Based on retained surface area, long and thick MWCNTs (few hundred nm long with an aspect ratio greater than 25) had a higher inflammatory potency with 5 cm2/g lung sufficient to trigger an inflammatory response (at 6% PMN), whereas retained surfaces greater than 150 cm2/g lung were required for PSLT. CONCLUSIONS: Retained surface area is a useful metric for hazard grouping purposes. This metric would apply to both micrometric and nanometric materials, and could obviate the need for direct measurement in the lung. Indeed, it could alternatively be estimated from dosimetry models using the aerosol parameters (rigorously determined following a well-defined aerosol characterization strategy).

Seasonal Evolution of Size-Segregated Particulate Mercury in the Atmospheric Aerosol Over Terra Nova Bay, Antarctica.

Size-fractionated particulate mercury (PHg) measurements were performed from November 2017 to January 2018 at Terra Nova Bay (Antarctica) for the first time. Samples were collected every 10 days by a six-stage high-volume cascade impactor with size classes between 10 µm and 0.49 µm. Total PHg concentrations were maxima (87 ± 8 pg m-3) in November, then decreased to values ~40% lower and remained almost constant until the end of the sampling period (~30 pg m-3). The trimodal aerosol mass distribution reveals that from 30% to 90% of the total PHg came in the size > 1.0 µm. Hg in the two coarse fractions was probably produced by the adsorption of oxidized Hg species transported by air masses from the Antarctic plateau or produced locally by sea ice edges. PHg in accumulation mode seemed to be related to gas-particle partitioning with sea salt aerosol. Finally, average dry deposition fluxes of PHg were calculated to be 0.36 ± 0.21 ng m-2 d-1 in the accumulation mode, 47 ± 44 ng m-2 d-1 in the first coarse mode, and 37 ± 31 ng m-2 d-1 in the second coarse mode. The present work contributed to the comprehension of the Hg biogeochemical cycle, but further research studies are needed.

What does ergonomics have to do with nanotechnologies? A case study.

Despite recent concerns for workers' health, exposure situations to nanoparticles can occur in numerous workplaces. Understanding how exposures occur considering human work in these transformations remains a crucial issue of nanotechnologies. The objective of this article is to understand exposure situations to nanoparticles, their determinants and the resources to act on them. This understanding was achieved by specific measurement of nanoparticles aerosols, combined with an analysis of work activity (actions performed and physical strain) in a rubber industry. The presentation of real time measurements, associated with the video of work situations, during confrontation interviews becomes a means of making exposing work activities visible, to analyze and transform them from the points of view formulated by the company's stakeholders. In this way, characterized "typical exposure situations" serve to trigger discussions and open up new spaces for debate highlighting how innovation affects work and gives rise to enhanced prevention projects.

Characterizing particle emissions from a direct energy deposition additive manufacturing process and associated occupational exposure to airborne particles.

This study aims to characterize airborne particles emitted from a metal additive manufacturing machine and related levels of occupational exposure. To achieve this, a complete measurement methodology was deployed around a direct energy deposition machine. Different operating conditions were investigated, based on configurations of two materials and two injection nozzles. Two replicates were performed for each condition. Airborne particles emitted during repeated manufacturing cycles were measured simultaneously at the source, in the near field, in the far field and on the operator. Real-time instruments were used to characterize the machine emissions (10 nm-10 µm) associated with respirable and inhalable samplers and cascade impactors. Measurements were made during both the manufacturing process and transient operating phases. In parallel, personal exposure to hexavalent chromium was assessed. The number of particles measured for the different machining phases show that high levels of particles (> 5 × 105 # cm-3, 0.3-1.3 mg m-3 inhalable particles, 0.2-6 µg m-3 CrVI) were emitted in the machine enclosure. The size distributions indicate that more than 90% of the particles are smaller than 250 nm. Occupational exposure to CrVI was found to be below the LOQ of 0.098 µg m-3 for the two alloys investigated. During the machining process, near-field number and mass concentrations were ∼ 104 # cm-3, and below 0.04 mg m-3, respectively. Far-field number concentrations were also on the order of 104 # cm-3 throughout the whole monitoring period. The transient phase of door opening was found to result in high levels of exposure (> 105 # cm-3), which were also detected in the near-field, confirming the need to implement preventative actions. To address this issue, a collective protective measure, consisting of setting a time delay of about 8 min between the end of the manufacturing process and opening of the door, could be employed. This collective measure should also be accompanied by the wearing of personal protective equipment by the operator when an intervention in the machine enclosure is necessary.

Pulmonary toxicity of two different multi-walled carbon nanotubes in rat: Comparison between intratracheal instillation and inhalation exposure.

Multi-walled carbon nanotubes (MWCNTs), which vary in length, diameter, functionalization and specific surface area, are used in diverse industrial processes. Since these nanomaterials have a high aspect ratio and are biopersistant in the lung, there is a need for a rapid identification of their potential health hazard. We assessed in Sprague-Dawley rats the pulmonary toxicity of two pristine MWCNTs (the "long and thick" NM-401 and the "short and thin" NM-403) following either intratracheal instillation or 4-week inhalation in order to gain insights into the predictability and intercomparability of the two methods. The deposited doses following inhalation were lower than the instilled doses. Both types of carbon nanotube induced pulmonary neutrophil influx using both exposure methods. This influx correlated with deposited surface area across MWCNT types and means of exposure at two different time points, 1-3 days and 28-30 days post-exposure. Increased levels of DNA damage were observed across doses and time points for both exposure methods, but no dose-response relationship was observed. Intratracheal instillation of NM-401 induced fibrosis at the highest dose while lower lung deposited doses obtained by inhalation did not induce such lung pathology. No fibrosis was observed following NM-403 exposure. When the deposited dose was taken into account, sub-acute inhalation and a single instillation of NM-401 and NM-403 produced very similar inflammation and DNA damage responses. Our data suggest that the dose-dependent inflammatory responses observed after intratracheal instillation and inhalation of MWCNTs are similar and were predicted by the deposited surface area.

Toward an operational methodology to identify industrial-scaled nanomaterial powders with the volume specific surface area criterion.

Nanoparticulate powders are increasingly found in the workplace. Inhalation exposure to airborne nanoparticles (NPs) is possible throughout the life-cycle of the powders. As the toxicity of NPs has never been demonstrated, it remains essential to evaluate the risks associated with NPs in order to propose preventative measures. The first step of a risk assessment strategy consists in the identification of the 'nano' nature of a material, which suffers from a lack of an operational methodology. Here, we present a simplified and operational strategy relying on the volume specific surface area (VSSA) for nanomaterial identification, based on the recommendation stemming from the European Commission and previous work on this topic from the European Project Nanodefine. The proposed strategy was tested on a set of 15 representative industrial powders (TiO2, SiO2, CuO, and ZnO), covering a wide range of properties, and previous published data. The VSSA classification was validated via a comparison with the particle size obtained by transmission electron microscopy (TEM). It was evidenced that the VSSA is in accordance with particle size for nanomaterial powder classification. The proposed methodology involves relatively accessible methods such as thermogravimetric analysis, nitrogen adsorption and helium pycnometry and limits the detection of false negatives. Moreover, it does not imply systematic confirmation of the results with the reference particle size criterion. Our results suggest that the VSSA is a promising parameter to be used for risk assessment and should be further investigated on powder mixings to confirm its relevancy to define nanomaterial powders.

Sampling Efficiency and Performance of Selected Thoracic Aerosol Samplers.

Measurement of worker exposure to a thoracic health-related aerosol fraction is necessary in a number of occupational situations. This is the case of workplaces with atmospheres polluted by fibrous particles, such as cotton dust or asbestos, and by particles inducing irritation or bronchoconstriction such as acid mists or flour dust. Three personal and two static thoracic aerosol samplers were tested under laboratory conditions. Sampling efficiency with respect to particle aerodynamic diameter was measured in a horizontal low wind tunnel and in a vertical calm air chamber. Sampling performance was evaluated against conventional thoracic penetration. Three of the tested samplers performed well, when sampling the thoracic aerosol at nominal flow rate and two others performed well at optimized flow rate. The limit of flow rate optimization was found when using cyclone samplers.

Inter-comparison of personal monitors for nanoparticles exposure at workplaces and in the environment.

Personal monitors based on unipolar diffusion charging (miniDiSC/DiSCmini, NanoTracer, Partector) can be used to assess the individual exposure to nanoparticles in different environments. The charge acquired by the aerosol particles is nearly proportional to the particle diameter and, by coincidence, also nearly proportional to the alveolar lung-deposited surface area (LDSA), the metric reported by all three instruments. In addition, the miniDiSC/DiSCmini and the NanoTracer report particle number concentration and mean particle size. In view of their use for personal exposure studies, the comparability of these personal monitors was assessed in two measurement campaigns. Altogether 29 different polydisperse test aerosols were generated during the two campaigns, covering a large range of particle sizes, morphologies and concentrations. The data provided by the personal monitors were compared with those obtained from reference instruments: a scanning mobility particle sizer (SMPS) for LDSA and mean particle size and a ultrafine particle counter (UCPC) for number concentration. The results indicated that the LDSA concentrations and the mean particle sizes provided by all investigated instruments in this study were in the order of ±30% of the reference value obtained from the SMPS when the particle sizes of the test aerosols generated were within 20-400nm and the instruments were properly calibrated. Particle size, morphology and concentration did not have a major effect within the aforementioned limits. The comparability of the number concentrations was found to be slightly worse and in the range of ±50% of the reference value obtained from the UCPC. In addition, a minor effect of the particle morphology on the number concentration measurements was observed. The presence of particles >400nm can drastically bias the measurement results of all instruments and all metrics determined.

Evaluation of the diffusion size classifier (meDiSC) for the real-time measurement of particle size and number concentration of nanoaerosols in the range 20-700 nm.

In the frame of assessing exposure to nanostructured particles, the aim of this work is to study the performance of a new device devoted to the real-time measurement of nanostructured aerosol: the meDiSC (Diffusion Size Classifier, Matter Engineering, Switzerland). This instrument is based on unipolar diffusion charging of particles which are then collected successively in diffusion and filtration stages. From currents measured in these stages, the instrument is capable of determining aerosol mean size and number concentration. These data were compared to reference measurements regarding monodisperse aerosols in a range from 20 to 700 nm; the relative biases were found unsatisfying. This led us to investigate the principle of the instrument. Consequently, the charging law of the diffusion charger was experimentally established, as well as the calibration curve allowing the determination of the mean size of the particles. The latter analysis was completed by a model based on diffusion theory. Our results indicate the possibility to improve the range of size measurement up to 350 nm. Measured particle size and number concentration were also used to calculate geometric surface-area concentration; the experimental data were compared to a reference calculated surface-area concentration. The results demonstrate the possibility to evaluate this parameter within acceptable uncertainty. In a second step, the meDiSC was challenged with polydisperse aerosols. It was observed that meDiSC overestimates particle size by a factor 1.7, while particle number concentrations are found within ±40% of the reference. The model applied to polydisperse aerosols indicates that polydispersity little influences particle size up to 300 nm while geometric standard deviation remains below 1.7.