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Consumer-level 3D printers emit ultrafine and fine particles, though little is known about their chemical composition or potential toxicity. We report chemical characteristics of the particles in comparison to raw filaments and assessments of particle toxicity. Particles emitted from polylactic acid (PLA) appeared to be largely composed of the bulk filament material with mass spectra similar to the PLA monomer spectra. Acrylonitrile butadiene styrene (ABS), extruded at a higher temperature than PLA, emitted vastly more particles and their composition differed from that of the bulk filament, suggesting that trace additives may control particle formation. In vitro cellular assays and in vivo mice exposure all showed toxic responses when exposed to PLA and ABS-emitted particles, where PLA-emitted particles elicited higher response levels than ABS-emitted particles at comparable mass doses. A chemical assay widely used in ambient air-quality studies showed that particles from various filament materials had comparable particle oxidative potentials, slightly lower than those of ambient particulate matter (PM2.5). However, particle emissions from ABS filaments are likely more detrimental when considering overall exposure due to much higher emissions. Our results suggest that 3D printer particle emissions are not benign and exposures should be minimized.

Particle emissions from consumer-fused deposition modeling 3D printers have been reported previously; however, the complex processes leading to observed aerosols have not been investigated. We measured particle concentrations and size distributions between 7 nm and 25 μm emitted from a 3D printer under different conditions in an emission test chamber. The experimental data was combined with a moment lognormal aerosol dynamic model to better understand particle formation and subsequent evolution mechanisms. The model was based on particles being formed from nucleation of unknown semivolatile compounds emitted from the heated filament during printing, which evolve due to condensation of emitted vapors and coagulation, all within a small volume near the printer extruder nozzle. The model captured observed steady state particle number size distribution parameters (total number, geometric mean diameter and geometric standard deviation) with errors nominally within 20%. Model solutions provided a range of vapor generation rates, saturation vapor pressures and vapor condensation factors consistent with measured steady state particle concentrations and size distributions. Vapor generation rate was a crucial factor that was linked to printer extruder temperature and largely accounted for differences between filament material and brands. For the unknown condensing vapor species, saturation vapor pressures were in the range of 10−3 to 10−1 Pa. The model suggests particles could be removed by design of collection surfaces near the extruder tip. Copyright © 2018 American Association for Aerosol Research

Dimethyl sulfide (DMS) is a major source of sulfur to the marine boundary layer (MBL), and methanesulfonic acid (MSA) is one of its two main final oxidation products. MSA can participate in the nucleation and growth of aerosol particles, thereby affecting clouds and climate, and is used as a tracer of biological sulfur inputs. Unlike MSA, the other major oxidation product of DMS, sulfate, has several other sources, including volcanic and anthropogenic inputs. As a result, MSA to non-sea-salt sulfate (nss-sulfate) ratios are often used as proxies for biological activity; i.e., the MSA to nss-sulfate ratio in aerosol particles is used to estimate the marine biological contribution to nss-sulfate in the MBL. We present here a determination of the reactive uptake coefficient, γ, for the heterogeneous oxidation of MSA by hydroxyl radicals within deliquesced ammonium sulfate aerosol particles with an MSA mass fraction of 0.16 (a typical marine value) at room temperature. We find γ = 0.05 ± 0.03. For high ambien...

Ambient levels of chlorinated gases and aerosol components were measured by on-line chemical ionization and aerosol mass spectrometers after an indoor floor was repeatedly washed with a commercial bleach solution. Gaseous chlorine (Cl_2, 10′s of ppbv) and hypochlorous acid (HOCl, 100′s of ppbv) arise after floor washing, along with nitryl chloride (ClNO_2), dichlorine monoxide (Cl2O) and chloramines (NHCl_2, NCl_3). Much higher mixing ratios would prevail in a room with lower and more commonly encountered air exchange rates than that observed in the study (12.7 h^(−1)). Coincident with the formation of gas-phase species, particulate chlorine levels also rise. Cl_2, ClNO_2, NHCl_2 and NCl_3 exist in the headspace of the bleach solution whereas HOCl was only observed after floor washing. HOCl decays away 1.4 times faster than the air exchange rate, indicative of uptake onto room surfaces and consistent with the well-known chlorinating ability of HOCl. Photochemical box modeling captures the temporal profiles of Cl_2 and HOCl very well, and indicates that the OH, Cl and ClO gas-phase radical concentrations in the indoor environment could be greatly enhanced (> 10^6 and 10^5 cm^(−3) for OH and Cl, respectively) in such washing conditions, dependent on the amount of indoor illumination.

Brown carbon (BrC) consists of those organic compounds in atmospheric aerosols that absorb solar radiation and may play an important role in planetary radiative forcing and climate. However, little is known about the production and loss mechanisms of BrC in the atmosphere. Here, we study how the light absorptivity of BrC from wood smoke and secondary BrC generated from the reaction of ammonium sulfate with methylglyoxal changes under photolytic aging by UVA radiation in the aqueous phase. Owing to its chemical complexity, BrC is separated by molecular weight using size exclusion chromatography, and the response of each molecular weight fraction to aging is studied. Photolytic aging induced significant changes in the light absorptivity of BrC for all molecular weight fractions; secondary BrC was rapidly photoblenched, whereas for wood smoke BrC, both photoenhancement and photobleaching were observed. Initially, large biomass burning BrC molecules were rapidly photoenhanced, followed by slow photolysis. As a result, large BrC molecules dominated the total light absorption of aged biomass burning BrC. These experimental results further support earlier observations that large molecular weight BrC compounds from biomass burning can be relatively long-lived components in atmospheric aerosols, thus more likely to have larger impacts on aerosol radiative forcing and could serve as biomass burning tracers.

Oxidative potential (OP), which is the ability of certain components in atmospheric particles to generate reactive oxidative species (ROS) and deplete antioxidants in vivo, is a prevailing toxicological mechanism underlying the adverse health effects associated with exposure to ambient aerosols. While previous studies have identified the high OP of fresh biomass burning organic aerosols (BBOA), it remains unclear how it evolves throughout atmospheric transport. Using the dithiothreitol (DTT) assay as a measure of OP, a combination of field observations and laboratory experiments is used to determine how atmospheric aging transforms the intrinsic OP (OPmassDTT) of BBOA. For ambient BBOA collected during the fire seasons in Greece, OPmassDTT was observed to increase by a factor of 2.1 +/- 0.9 for samples of atmospheric ages up to 68 h. Laboratory experiments indicate that aqueous photochemical aging (aging by UVB and UVA photolysis; as well as 01-1 oxidation), as well as aging by ozone and atmospheric dilution can transform the OPmassDTT of the water-soluble fraction of wood smoke within 2 days of atmospheric transport. The results from this work suggest that the air quality impacts of biomass burning emissions can extend beyond regions near fire sites and should be accounted for.

Biomass burning is a major source of atmospheric brown carbon (BrC) and through its absorption of UV/VIS radiation, it can play an important role on the planetary radiative balance and atmospheric photochemistry. The considerable uncertainty of BrC impacts is associated with its poorly constrained sources, transformations and atmospheric lifetime. Here we report laboratory experiments that examined changes in the optical properties of the water-soluble BrC fraction of biomass burning particles. Effects of direct UVB photolysis and OH oxidation in the aqueous phase on molecular weight-separated BrC were studied. Results indicated that low molecular weight (MW) BrC ( 10 hours) biomass burning emissions, poor linear correlations were found between light absorptivity and levoglucosan, consistent with other studies suggesting a short atmospheric lifetime for levoglucosan. However, a much stronger correlation between light absorptivity and total hydrous sugars was observed, suggesting that they may serve as more robust tracers for aged biomass burning emissions. Overall, the results from this study suggest that robust model estimates of BrC radiative impacts require consideration of the atmospheric aging of BrC and the stability of high-MW BrC.

This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are 5 times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions, assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloud water and aerosol chemistry.

As one aspect of the NETwork on Climate and Aerosols: addressing key uncertainties in Remote Canadian Environments (NETCARE), measurements of the cloud condensation nucleation properties of 50 and 100 nm aerosol particles were conducted at Ucluelet on the west coast of Vancouver Island in August 2013. The overall hygroscopicity parameter of the aerosol (κambient) exhibited a wide variation, ranging from 0.14 ± 0.05 to 1.08 ± 0.40 (where the uncertainty represents the systematic error). The highest κ values arose when the organic-to-sulfate ratio of the aerosol was lowest and when winds arrived from the west after transport through the marine boundary layer. The average κambient during this time was 0.57 ± 0.16, where the uncertainty represents the standard deviation. At most other times, the air was predominantly influenced by both marine and continental emissions, which had lower average PM1 κambient values (max value, 0.41 ± 0.08). The two-day average aerosol ionic composition also showed variation, but was consistently acidic and dominated by ammonium (18–56% by mole) and sulfate (19–41% by mole), with only minor levels of sodium or chloride. Average κorg (hygroscopicity parameter for the aerosol's organic component) values were estimated using PM1 aerosol composition data and by assuming that the ratio of aerosol organic to sulfate mass is related directly to the composition of the size-selected particles.

Fused filament fabrication (FFF) printers, the most common type of office, educational, and consumer-level 3D printers, emit complex mixture of volatile gases and ultrafine particles (UFPs) that can deteriorate indoor air quality (IAQ). It is important to understand their potential health risks as the technology becomes more prevalent. The developed method for characterizing and quantifying emissions from an operating FFF 3D printer measures particulate and volatile organic compound (VOC) concentrations over time using an environment controlled testing chamber. Characterization of 3D printer emissions is critical for understanding the chemical safety of this technology for providing guidance to minimize exposure to unintentional hazardous emissions. This study found 3D printers to be a source of numerous VOCs and particles that can be released into the indoor air with 216 individual VOCs identified. These VOCs were assessed for their indoor air and human exposure impact. The specific VOCs released during printing varied depending on the filament material. Filament monomers and degradation byproducts were identified in air samples. Total VOC emissions ranged from 147 μg h−1 for polyvinyl alcohol filament to 1660 μg h−1 for nylon filament. Nozzle temperature, filament material, filament brand, printer brand, and filament color all affected VOC and particle emissions. Personal exposure levels and room exposure levels in two indoor situations, a bedroom and a classroom, were predicted for certain VOCs known or suspected to be carcinogens or irritants. Some chemicals of concern exceeded recommended indoor levels linked to adverse health effects. Exposure levels could be minimized by operating verified low-emitting 3D printers and filaments, reducing the printer nozzle temperature when possible, increasing ventilation around the printer, and providing local exhaust.

A key mechanism for atmospheric secondary organic aerosol (SOA) formation occurs when oxidation products of volatile organic compounds condense onto pre-existing particles. Here, we examine effects of aerosol liquid water (ALW) on relative SOA yield and composition from α-pinene ozonolysis and the photooxidation of toluene and acetylene by OH. Reactions were conducted in a room-temperature flow tube under low-NOx conditions in the presence of equivalent loadings of deliquesced (∼20 μg m–3 ALW) or effloresced (∼0.2 μg m–3 ALW) ammonium sulfate seeds at exactly the same relative humidity (RH = 70%) and state of wall conditioning. We found 13% and 19% enhancements in relative SOA yield for the α-pinene and toluene systems, respectively, when seeds were deliquesced rather than effloresced. The relative yield doubled in the acetylene system, and this enhancement was partially reversible upon drying the prepared SOA, which reduced the yield by 40% within a time scale of seconds. We attribute the high relative y...

Motivated by the need to develop instrumental techniques for characterizing organic aerosol aging, we report on the performance of the Toronto Photo-Oxidation Tube (TPOT) and Potential Aerosol Mass (PAM) flow tube reactors under a variety of experimental conditions. The PAM system was designed with lower surface-area-to-volume (SA/V) ratio to minimize wall effects; the TPOT reactor was designed to study heterogeneous aerosol chemistry where wall loss can be independently measured. The following studies were performed: (1) transmission efficiency measurements for CO2, SO2, and bis(2-ethylhexyl) sebacate (BES) particles, (2) H2SO4 yield measurements from the oxidation of SO2, (3) residence time distribution (RTD) measurements for CO2, SO2, and BES particles, (4) aerosol mass spectra, O/C and H/C ratios, and cloud condensation nuclei (CCN) activity measurements of BES particles exposed to OH radicals, and (5) aerosol mass spectra, O/C and H/C ratios, CCN activity, and yield measurements of secondary organic aerosol (SOA) generated from gas-phase OH oxidation of m-xylene and α-pinene. OH exposures ranged from (2.0 ± 1.0) × 1010 to (1.8 ± 0.3) × 1012 molec cm−3 s. Where applicable, data from the flow tube reactors are compared with published results from the Caltech smog chamber. The TPOT yielded narrower RTDs. However, its transmission efficiency for SO2 was lower than that for the PAM. Transmission efficiency for BES and H2SO4 particles was size-dependent and was similar for the two flow tube designs. Oxidized BES particles had similar O/C and H/C ratios and CCN activity at OH exposures greater than 1011 molec cm−3 s, but different CCN activity at lower OH exposures. The O/C ratio, H/C ratio, and yield of m-xylene and α-pinene SOA was strongly affected by reactor design and operating conditions, with wall interactions seemingly having the strongest influence on SOA yield. At comparable OH exposures, flow tube SOA was more oxidized than smog chamber SOA, possibly because of faster gas-phase oxidation relative to particle nucleation. SOA yields were lower in the TPOT than in the PAM, but CCN activity of flow-tube-generated SOA particles was similar. For comparable OH exposures, α-pinene SOA yields were similar in the PAM and Caltech chambers, but m-xylene SOA yields were much lower in the PAM compared to the Caltech chamber.

The effects of particle-phase water and the acidity of pre-existing sulfate seed particles on the formation of isoprene secondary organic aerosol (SOA) was investigated. SOA was generated from the photo-oxidation of isoprene in a flow tube reactor at 70% relative humidity (RH) and room temperature in the presence of three different sulfate seeds (effloresced and deliquesced ammonium sulfate and ammonium bisulfate) under low NOx conditions. High OH exposure conditions lead to little isoprene epoxydiol (IEPOX) SOA being generated. The primary result is that particle-phase water had the largest effect on the amount of SOA formed, with 60% more SOA formation occurring with deliquesced ammonium sulfate seeds as compared to that on effloresced ones. The additional organic material was highly oxidized. Although the amount of SOA formed did not exhibit a dependence on the range of seed particle acidity examined, perhaps because of the low amount of IEPOX SOA, the levels of high-molecular-weight material increased with acidity. While the uptake of organics was partially reversible under drying, the results nevertheless indicate that particle-phase water enhanced the amount of organic aerosol material formed and that the RH cycling of sulfate particles may mediate the extent of isoprene SOA formation in the atmosphere.

Transition metal ions, such as water-soluble iron (WS-Fe), are toxic components of fine particles (PM2.5). In Atlanta, from 1998 to 2013, a previous study found that WS-Fe was the PM2.5 species most associated with adverse cardiovascular outcomes. We examined this data set to investigate the sources of WS-Fe and the effects of air quality regulations on ambient levels of WS-Fe. We find that insoluble forms of iron in mineral and road dust combined with sulfate from coal-fired electrical generating units were converted into soluble forms by sulfate-driven acid dissolution. Sulfate produced both the highly acidic aerosol (summer pH 1.5-2) and liquid water required for the aqueous phase acid dissolution, but variability in WS-Fe was mainly driven by particle liquid water. These processes were more pronounced in summer when particles were most acidic, whereas in winter the relative importance of WS-Fe from combustion emissions increased. Although WS-Fe constituted a minute fraction of PM2.5 mass (0.15%), the WS-Fe-PM2.5 mass correlation was high (r = 0.67) and may be explained by these formation routes, which, in part, could account for observed associations between PM2.5 mass and adverse health seen in past studies. Similar processes are expected in many regions, implying that these unexpected benefits from coal-burning reduction may be widespread.