Article

Organic compound and particle emissions of additive manufacturing with photopolymer resins and chemical outgassing of manufactured resin products

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Abstract

Photopolymer resins are applied at an increasing rate in additive manufacturing (AM) industry as vat photopolymerization (VP) and material jetting (MJ) methods gain more popularity. The aim of this study was to measure volatile organic compound (VOC), carbonyl compound, ultrafine particle (UFP), and particulate matter (PM10) air concentrations emitted in 3D printer operations. Individual chemicals were identified when multiple photopolymer resin feedstocks were used in various VP and MJ printers. The size distributions of UFPs, and indoor air parameters were also monitored. Finally, the VOC outgassing of the cured resin materials was determined over 84 days. The data demonstrated that 3D printer operators were exposed to low concentrations of airborne exposure agents as follows: average concentrations of VOCs were between 41 and 87 µg/m³, UFP number levels ranged between 0.19 and 3.62 × 10³ number/cm³; however, no impact was detected on air parameters or PM10 concentrations. A majority of the UFPs existed in the 10–45 nm size range. The identified compounds included hazardous species included sensitizing acrylates and carcinogenic formaldehyde. The outgassed products included similar compounds that were encountered during the AM processes, and post-processing solvents. Products heated to 37°C emitted 1.4‒2.9-fold more VOCs than at room temperature. Total emissions were reduced by 84‒96% after 28 days roughly from 3000–14000 to 100–1000 µg/m²/hr. In conclusion, resin printer operators are exposed to low concentrations of hazardous emissions, which might result in adverse health outcomes during prolonged exposure. Manufactured resin products are suggested to be stored for 4 weeks after their production to reduce potential consumer VOC hazards.

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... Previous studies of 3D printers have identified emissions of several hazardous VOCs, such as styrene [7,[22][23][24][25][26][27][28][29][30][31] methyl methacrylate [22,29,32,33] isopropanol [32], benzene [22][23][24]34], and toluene [22-24, 28, 30, 34]. Some of these VOCs have been linked to adverse health consequences after large exposure doses, including increased risk of some cancers [16][17][18][19][20][21]. ...
... Previous studies of 3D printers have identified emissions of several hazardous VOCs, such as styrene [7,[22][23][24][25][26][27][28][29][30][31] methyl methacrylate [22,29,32,33] isopropanol [32], benzene [22][23][24]34], and toluene [22-24, 28, 30, 34]. Some of these VOCs have been linked to adverse health consequences after large exposure doses, including increased risk of some cancers [16][17][18][19][20][21]. ...
... The laser scans the entire plane of the structure, focusing the light on the selected curing zone for each pass. Previous research by Väisänen et al. [32] identified and quantified a range of carbonyl compounds released during stereolithographic printing a Formlabs Form 2, resin 3D printer with clear and castable Formlabs wax resins. Dental resins were also examined. ...
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Background Three-dimensional (3D) printing is a technique by which materials are continually added in layers to form structures. The technique has grown in popularity over the past decade and affordable desktop 3D printers are now widely used in schools, universities, businesses, and hospitals. Objective Understanding the types of chemical emissions from these 3D printers and their potential health effects is essential to safely use this technology. Methods A scoping literature review on volatile organic compound (VOC) emissions from resin-bed and filament 3D printers has been conducted. Most of the published research has focused on emissions from filament 3D printers. Results VOC emissions from resin 3D printers have been reported mostly as carbonyl compounds or methacrylate monomers. Filament VOC emissions are more varied in composition reflecting the constituents in the filaments used in this printer. The published research reported that the airborne concentrations of specific VOCs from 3D desktop printers fell below the HSE British workplace exposure limits (WELs). This may suggest that VOC emissions from these printers do not present a risk to occupational health. However, caution is required in reaching this conclusion because most of these studies quantified specific VOC emissions using methods different to those required by workplace regulatory standards. Other exposure circumstances, such as the effect of total VOC emissions, need to be considered, particularly for vulnerable groups, including individuals with respiratory disease, the elderly, or young children. Variables that could increase exposure and risks to health include long print times, multiple 3D printers, and poor ventilation. Research on the VOC emissions from resin 3D printers is required using experimental emission chambers. Impact The research discussed in this review focused on VOC emissions from desktop 3D printers and the potential health impacts associated with exposure to these compounds. The review identifies circumstances when people may be exposed to 3D printer emissions for which no regulatory exposure limits apply. This circumstance is especially relevant to people working in small businesses and organisations and to vulnerable people, such as the young, elderly and those with pre-existing lung disease. Raising awareness of these potential health concerns from 3D printer emissions can help to inform actions to mitigate exposure, through policy and behavioural changes, as well as engineering control measures. To our knowledge, this is the first review discussing studies of VOC emission from resin and popular filament 3D printers, including exposure risks and health outcomes.
... Individual sample constituents were identified by comparing the mass spectral patterns and retention times of peaks in the samples to the mass spectral patterns and retention times of a standard curve (acetone, isopropyl alcohol, hexane, benzene, toluene, ethylbenzene, xylenes, and methyl acrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl methacrylate, glycidyl methacrylate, and hydroxypropyl methacrylate). Compounds in the standard curve were selected based on ingredient lists from Safety Data Sheets (SDS), prior characterization of vat resins (author's unpublished data), and available literature [5,[12][13][14][15][16][23][24][25][26]. Additionally, tentatively identified compounds were qualitatively identified from the remaining chromatographic peaks based on the mass spectral matches with mass spectral library software (Wiley Registry 8th Edition/NIST 2008 Mass Spectral Library, Wiley-Blackwell, New York, NY, USA) and a manual review by the analyst. ...
... This observation was consistent with Zhang et al. who reported that sub-micron size particle concentrations released during SLA printing were similar to the background [34]. In a series of studies, Väisänen et al. used a CNC to monitor emissions from several different VP machines and resins during printing [15,16]. In their studies, average particle concentrations during the operation of SLA and DLP printers were approximately 1200 to 3600 #/cm 3 . ...
... Though particle emission rates differed on a group-level basis in that study, for the specific SLA and DLP printers used in the current study, particle number concentrations were not significantly different [23]. Väisänen et al. reported that maximum particle number concentrations measured using a CNC instrument while printing with SLA and DLP printers were approximately 4000 to 13,500 #/cm 3 [15,16]; however, VP particle concentrations tend to be lower than fused filament fabrication (FFF). As heat is used to melt the polymer, particle concentrations can reach a maximum of 2 × 10 5 -1 × 10 6 #/cm 3 [3]. ...
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Vat photopolymerization (VP), a type of additive manufacturing process that cures resin to build objects, can emit potentially hazardous particles and gases. We evaluated two VP technologies, stereolithography (SLA) and digital light processing (DLP), in three separate environmental chambers to understand task-based impacts on indoor air quality. Airborne particles, total volatile organic compounds (TVOCs), and/or specific volatile organic compounds (VOCs) were monitored during each task to evaluate their exposure potential. Regardless of duration, all tasks released particles and organic gases, though concentrations varied between SLA and DLP processes and among tasks. Maximum particle concentrations reached 1200 #/cm3 and some aerosols contained potentially hazardous elements such as barium, chromium, and manganese. TVOC concentrations were highest for the isopropyl alcohol (IPA) rinsing, soaking, and drying post-processing tasks (up to 36.8 mg/m3), lowest for the resin pouring pre-printing, printing, and resin recovery post-printing tasks (up to 0.1 mg/m3), and intermediate for the curing post-processing task (up to 3 mg/m3). Individual VOCs included, among others, the potential occupational carcinogen acetaldehyde and the immune sensitizer 2-hydroxypropyl methacrylate (pouring, printing, recovery, and curing tasks). Careful consideration of all tasks is important for the development of strategies to minimize indoor air pollution and exposure potential from VP processes.
... No report of ventilation controls for BJ, VP, PBF, or DED machines was identified by the literature search. Väisänen et al. (2022) noted a LEV control for an MJ machine and 6 articles evaluated ventilation controls for ME-type FFF 3-D printers. Of these six articles, three evaluated LEV at or near to the extruder nozzle (Dunn et al. 2020;Kwon et al. 2017;Viitanen et al. 2021), one evaluated the efficacy of a room LEV system (Zontek, Scotto, and Hollenbeck 2021), one evaluated the efficacy of an air purifier equipped with different particulate and gas combination filters positioned near a printer , and one evaluated room GEV (Secondo et al. 2020). ...
... Of these six articles, three evaluated LEV at or near to the extruder nozzle (Dunn et al. 2020;Kwon et al. 2017;Viitanen et al. 2021), one evaluated the efficacy of a room LEV system (Zontek, Scotto, and Hollenbeck 2021), one evaluated the efficacy of an air purifier equipped with different particulate and gas combination filters positioned near a printer , and one evaluated room GEV (Secondo et al. 2020). Väisänen et al. (2022) measured particles, VOCs, and carbonyls emitted from an MJ printer. The printer had a built-in LEV duct, and samples were collected from the lab room air and from the printer exhaust ventilation duct (operating at 7 ACH) when using different resins. ...
Article
Additive manufacturing (AM) refers to several types of processes that join materials to build objects, often layer-by-layer, from a computer-aided design file. Many AM processes release potentially hazardous particles and gases during printing and associated tasks. There is limited understanding of the efficacy of controls including elimination, substitution, administrative, and personal protective technologies to reduce or remove emissions, which is an impediment to implementation of risk mitigation strategies. The Medline, Embase, Environmental Science Collection, CINAHL, Scopus, and Web of Science databases and other resources were used to identify 42 articles that met the inclusion criteria for this review. Key findings were as follows: 1) engineering controls for material extrusion-type fused filament fabrication (FFF) 3-D printers and material jetting printers that included local exhaust ventilation generally exhibited higher efficacy to decrease particle and gas levels compared with isolation alone, and 2) engineering controls for particle emissions from FFF 3-D printers displayed higher efficacy for ultrafine particles compared with fine particles and in test chambers compared with real-world settings. Critical knowledge gaps identified included a need for data: 1) on efficacy of controls for all AM process types, 2) better understanding approaches to control particles over a range of sizes and gas-phase emissions, 3) obtained using a standardized collection approach to facilitate inter-comparison of study results, 4) approaches that go beyond the inhalation exposure pathway to include controls to minimize dermal exposures, and 5) to evaluate not just the engineering tier, but also the prevention-through-design and other tiers of the hierarchy of controls.
... The severity of these hazards varies between different AM techniques, operation parameters, and materials used (Roth et al., 2019;Stefaniak et al., 2021;Romanowski et al., 2023). Most of the studies have concentrated on MEX printers, especially desktop printers (Stephens et al., 2013;Viitanen et al., 2021;Dunn et al., 2020;Du Preez et al., 2018;Azimi et al., 2016;Wojtyła et al., 2020;Zhang et al., 2017;Stabile et al., 2017;Floyd et al., 2017;Mendes et al., 2017), but some studies on PBF (Graff et al., 2017;Kangas et al., 2023;Jensen, A.C.0., Harboe, H., Brostrøm, A., Jensen, K.A., Fonseca, A.S., 2020), directed energy deposition DED (Bau et al., 2020;Ding and Ng, 2021), binder jetting BJT (Kangas et al., 2023;Afshar-Mohajer et al., 2015) and VPP (Zisook et al., 2020;Väisänen et al., 2022;Väisänen et al., 2019) have been published as well. ...
... These additives range from dyes, photopolymer resins, organometallic compounds, carbon nanomaterials, nanometal oxides to micrometer-scale particles such as copper, bronze, steel, tungsten, gold, and aluminum nitride (Vance et al. 2017). Several engineered nanomaterials were infused into PC filaments, such as silicon dioxide nanoparticles, titanium nitride nanoparticles (Vidakis et al. 2021), titanium carbide nanopowder (Vaisanen et al. 2022;Vidakis, Petousis, Grammatikos, et al. 2022), aluminum nitride nanoparticles (Vidakis, Petousis, Mangelis, et al. 2022), and carbon nanotubes (Potter et al. 2021). ...
Article
During fused filament fabrication (FFF) 3D printing with polycarbonate (PC) filament, a release of ultrafine particles (UFPs) and volatile organic compounds (VOCs) occurs. This study aimed to determine PC filament printing emission-induced toxicity in rats via whole-body inhalation exposure. Male Sprague Dawley rats were exposed to a single concentration (0.529 mg/m³, 40 nm mean diameter) of the 3D PC filament emissions in a time-course via whole body inhalation for 1, 4, 8, 15, and 30 days (4 hr/day, 4 days/week), and sacrificed 24 hr after the last exposure. Following exposures, rats were assessed for pulmonary and systemic responses. To determine pulmonary injury, total protein and lactate dehydrogenase (LDH) activity, surfactant proteins A and D, total as well as lavage fluid differential cells in bronchoalveolar lavage fluid (BALF) were examined, as well as histopathological analysis of lung and nasal passages was performed. To determine systemic injury, hematological differentials, and blood biomarkers of muscle, metabolic, renal, and hepatic functions were also measured. Results showed that inhalation exposure induced no marked pulmonary or systemic toxicity in rats. In conclusion, inhalation exposure of rats to a low concentration of PC filament emissions produced no significant pulmonary or systemic toxicity.
... Broekhuizen et al. suggested a nano reference value of 40,000 particles/cm 3 for nanoparticles with a density below 6 g/cm 3 (polymer particles have a density of 1-2 g/cm 3 ), which was exceeded in this study for all FDM and extrusion prints with no encapsulation or filter (23). Other techniques in this study, i.e., VP, PBF, and MJ, had concentrations below 20,000 particles/cm3 (PBF) or even below 5,000 particles/cm3 (VP and MJ), which is in agreement with other studies (24). ...
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Additive manufacturing (AM), or 3D printing, is a growing industry involving a wide range of different techniques and materials. The potential toxicological effects of emissions produced in the process, involving both ultrafine particles and volatile organic compounds (VOCs), are unclear, and there are concerns regarding possible health implications among AM operators. The objective of this study was to screen the presence of respiratory health effects among people working with liquid, powdered, or filament plastic materials in AM. Methods In total, 18 subjects working with different additive manufacturing techniques and production of filament with polymer feedstock and 20 controls participated in the study. Study subjects filled out a questionnaire and underwent blood and urine sampling, spirometry, impulse oscillometry (IOS), exhaled NO test (FeNO), and collection of particles in exhaled air (PEx), and the exposure was assessed. Analysis of exhaled particles included lung surfactant components such as surfactant protein A (SP-A) and phosphatidylcholines. SP-A and albumin were determined using ELISA. Using reversed-phase liquid chromatography and targeted mass spectrometry, the relative abundance of 15 species of phosphatidylcholine (PC) was determined in exhaled particles. The results were evaluated by univariate and multivariate statistical analyses (principal component analysis). Results Exposure and emission measurements in AM settings revealed a large variation in particle and VOC concentrations as well as the composition of VOCs, depending on the AM technique and feedstock. Levels of FeNO, IOS, and spirometry parameters were within clinical reference values for all AM operators. There was a difference in the relative abundance of saturated, notably dipalmitoylphosphatidylcholine (PC16:0_16:0), and unsaturated lung surfactant lipids in exhaled particles between controls and AM operators. Conclusion There were no statistically significant differences between AM operators and controls for the different health examinations, which may be due to the low number of participants. However, the observed difference in the PC lipid profile in exhaled particles indicates a possible impact of the exposure and could be used as possible early biomarkers of adverse effects in the airways.
... The emissions from these plastics were reported to produce adverse health effects in both aquatic and land species (Burgos-Aceves et al. 2022;Dmytriw 2020;Martín et al. 2018;Rubio, Marcos, and Hernandez 2020;Suhyun et al. 2019). Recently, the use of 3D printers has increased, and there are data demonstrating that 3D printers used in areas that are not properly ventilated might generate and release high concentrations of respirable particulate and volatile vapors that may also affect health (Chan et al. 2020, Yi et al. 2016Kim et al. 2015;Leso et al. 2021;Vaisanen et al. 2022). The exact characteristics of the exposure, and the physiological and biological effects of the exposure, are dependent upon the concentrations and types of PM and VOC released during the printing process (Farcas et al. 2019;MT et al. 2020). ...
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With the growing adoption of additive manufacturing (AM) technology across various industries, concerns regarding the possible release of hazardous volatile organic compound (VOC) emissions have surfaced, particularly in VAT photopolymerization (VPP) processes. This study investigates VOC emissions in VPP AM by implementing machine learning (ML) and advanced digital twins to monitor, predict, and mitigate VOC release. An Industrial Internet of Things (IIoT) sensor network, integrated with an Anycubic Mono X 6 K 3D printer, captured data on critical parameters, including layer thickness, exposure time, and light intensity. Subsequent ML model analysis identified exposure time as a principal factor influencing VOC emissions. A Unity-based digital twin was developed to support proactive process optimization, offering real-time visualization and predictive analytics of emission trends. The system aligns with Industry 4.0 objectives, showing considerable potential to enhance operational efficiency and environmental sustainability in VPP AM. This integrated approach significantly advances environmentally responsible AM practices in industrial settings.
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Three-dimensional (3D) printing of manufactured goods has increased in the last 10 years. The increased use of this technology has resulted in questions regarding the influence of inhaling emissions generated during printing. The goal of this study was to determine if inhalation of particulate and/or toxic chemicals generated during printing with polycarbonate (PC) plastic affected the neuroendocrine system. Male rats were exposed to 3D-printer emissions (592 µg particulate/m3 air) or filtered air for 4 h/day (d), 4 days/week and total exposures lengths were 1, 4, 8, 15 or 30 days. The effects of these exposures on hormone concentrations, and markers of function and/or injury in the olfactory bulb, hypothalamus and testes were measured after 1, 8 and 30 days exposure. Thirty days of exposure to 3D printer emissions resulted in reductions in thyroid stimulating hormone, follicle stimulating hormone and prolactin. These changes were accompanied by (1) elevation in markers of cell injury; (2) reductions in active mitochondria in the olfactory bulb, diminished gonadotropin releasing hormone cells and fibers as well as less tyrosine hydroxylase immunolabeled fibers in the arcuate nucleus; and (3) decrease in spermatogonium. Polycarbonate plastics may contain bisphenol A, and the effects of exposure to these 3D printer-generated emissions on neuroendocrine function are similar to those noted following exposure to bisphenol A.
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Background: While acrylates are well-known skin sensitisers, they are not classified as respiratory sensitisers although several cases of acrylate-induced occupational asthma (OA) have been reported. Objectives: The aim of this study was to evaluate the characteristics of acrylate-induced OA in a large series of cases and compare those with OA induced by other low-molecular-weight (LMW) agents. Methods: Jobs and exposures, clinical and functional characteristics, and markers of airway inflammation were analysed in an international, multicentre, retrospective cohort of subjects with OA ascertained by a positive inhalation challenge to acrylates (n= 55) or other LMW agents (n=418) including isocyanates (n=125). Results: Acrylate-containing glues were the most prevalent products and industrial manufacturing, dental work and beauty care were typical occupations causing OA. Work related rhinitis was more common in acrylate than isocyanate-induced asthma (p<0.001). The increase in post-challenge fractional exhaled nitric oxide (FeNO) was significantly greater in acrylate-induced OA (26.0, 8.2-38.0 ppb) than in OA induced by other LMW agents (3.0, -1.0-10.0 ppb, p<0.001) or isocyanates (5.0, 2.0-16.0 ppb, p=0.010). Multivariable models confirmed that OA induced by acrylates was significantly and independently associated with a post-challenge increase in FeNO (≥17.5 ppb). Conclusions: Acrylate-induced OA shows specific characteristics, concomitant work-related rhinitis and exposure-related increases in FeNO, suggesting that acrylates may induce asthma through different immunological mechanisms than other LMW agents. Our findings reinforce the need for a re-evaluation of the hazard classification of acrylates, and further investigation of the pathophysiological mechanisms underlying their respiratory sensitizing potential.
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Additive manufacturing (commonly referred to as 3D printing) created an attractive approach for regenerative medicine research in musculoskeletal tissue engineering. Given the high number of fabrication technologies available, characterized by different working and physical principles, there are several related risks that need to be managed to protect operators. Recently, an increasing number of studies demonstrated that several types of 3D printers are emitters of ultrafine particles and volatile organic compounds whose harmful effects through inhalation, ingestion and skin uptake are known. Confirmation of danger of these products is not yet final, but this provides a basis to adopt preventive measures in agreement with the precautionary principle. The purpose of this investigation was to provide a useful tool to the researcher for managing the risks related to the use of different kinds of three-dimensional printers (3D printers) in the lab, especiallyconcerning orthopedic applications, and to define appropriate control measures. Particular attention was given to new emerging risks and to developing response strategies for a comprehensive coverage of the health and safety of operators.
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The ISO 16000 standard series provide guidelines for emission measurements of volatile organic compounds (VOCs) from building materials. However, polymer‐based consumer products such as toys may also release harmful substances into indoor air. In such cases, the existing standard procedures are unsuitable for official control laboratories due to high costs for large emission testing chambers. This paper aims at developing and comparing alternative and more competitive methods for the emission testing of consumer products. The influence of the emission chamber size was investigated as smaller chambers are more suited to the common size of consumer products and may help to reduce the costs of testing. Comparison of the performance of a 203 l emission test chamber with two smaller chambers with the capacity of 24 l and 44 ml, respectively, was carried out by using a polyurethane reference material spiked with 14 VOCs during the course of 28 days. The area‐specific emission rates obtained in the small chambers were always similar to those of the 203 l reference chamber after a few hours. This implies that smaller chambers can provide at least useful numbers on the extent of polymer‐based consumer product emissions into indoor air, thereby supporting meaningful exposure assessments.
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Printing devices are known to emit chemicals into the indoor atmosphere. Understanding factors that influence release of chemical contaminants from printers is necessary to develop effective exposure assessment and control strategies. In this study, a desktop fused deposition modeling (FDM) 3-D printer using acrylonitrile butadiene styrene (ABS) or polylactic acid (PLA) filaments and two monochrome laser printers were evaluated in a 0.5 m³ chamber. During printing, chamber air was monitored for vapors using a real-time photoionization detector (results expressed as isobutylene equivalents) to measure total volatile organic compound (TVOC) concentrations, evacuated canisters to identify specific VOCs by off-line gas chromatography-mass spectrometry (GC-MS) analysis, and liquid bubblers to identify carbonyl compounds by GC-MS. Airborne particles were collected on filters for off-line analysis using scanning electron microscopy with an energy dispersive x-ray detector to identify elemental constituents. For 3-D printing, TVOC emission rates were influenced by a printer malfunction, filament type, and to a lesser extent, by filament color; however, rates were not influenced by the number of printer nozzles used or the manufacturer's provided cover. TVOC emission rates were significantly lower for the 3-D printer (49 to 3552 µg h⁻¹) compared to the laser printers (5782 to 7735 µg h⁻¹). A total of 14 VOCs were identified during 3-D printing that were not present during laser printing. 3-D printed objects continued to off-gas styrene, indicating potential for continued exposure after the print job is completed. Carbonyl reaction products were likely formed from emissions of the 3-D printer, including 4-oxopentanal. Ultrafine particles generated by the 3-D printer using ABS and a laser printer contained chromium. Consideration of the factors that influenced the release of chemical contaminants (including known and suspected asthmagens such as styrene and 4-oxopentanal) from a FDM 3-D printer should be made when designing exposure assessment and control strategies.
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UV printing inks are considered safer than the classical inks; however, despite being on the outer surface of the packaging material, their components can migrate into foodstuffs and can give rise to contamination. Photoinitiators are a part of the formulation of printing inks, being an important class of migrant, for which there have been more than 100 incidents of contamination of packaged food with photoinitiators reported through RASFF (Rapid Alert System for Food and Feed) alerts in the EU. In this review the process of photo-polymerisation is explained in depth to provide an insight into the complexity of the process, and the diversity of potential contaminants together with their degradation products. The critical factors affecting the migration process itself are reviewed, together with analytical methods and the current legislation in the EU and other parts of the world.
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Volatile organic compounds (VOCs) have shown potential as non-invasive breath biomarkers for lung cancer, but their unclear biological origin currently limits clinical applications. This systematic review explores headspace analysis of VOCs in patient-derived body fluids and lung cancer cell lines to pinpoint lung cancer-specific VOCs and uncover their biological origin. A search was performed in the databases MEDLINE and Web of Science. Twenty-two articles were included in this systematic review. Since there is no standardised approach to analyse VOCs, a plethora of techniques and matrices/cell lines were explored, which is reflected in the various VOCs identified. However, comparing VOCs in the headspace of urine, blood and pleural effusions from patients and lung cancer cell lines showed some overlapping VOCs, indicating their potential use in lung cancer diagnosis. This review demonstrates that VOCs are promising biomarkers for lung cancer. However, due to lack of inter-matrix consensus, standardised prospective trials will have to be conducted to validate clinically relevant biomarkers.
Article
The aim of this study was to determine concentrations of particulates and volatile organic compounds (VOCs) emitted from 3D printers using polylactic acid (PLA) filaments at a university workroom to assess exposure and health risks in an occupational setting. Under typical-case (one printer) and worst-case (three printers operating simultaneously) scenarios, particulate concentration (total and respirable), VOCs and formaldehyde were measured. Air samples were collected in the printing room and adjacent hallway. Size-resolved levels of nano-diameter particles were also collected in the printing room. Total particulate levels were higher in the worst-case scenario (0.7 mg/m³) vs. typical-case scenario (0.3 mg/m³). Respirable particulate and formaldehyde concentrations were similar between the two scenarios. Size-resolved measurements showed that most particles ranged from approximately 27 to 116 nm. Total VOC levels were approximately 6-fold higher during the worst-case scenario vs. typical situation with isopropyl alcohol being the predominant VOC. Airborne concentrations in the hallway were generally lower than inside the printing room. All measurements were below their respective occupational exposure limits. In summary, emissions of particulates and VOCs increased when multiple 3D printers were operating simultaneously. Airborne levels in the adjacent hallway were similar between the two scenarios. Overall, data suggest a low risk of significant and persistent adverse health effects. Nevertheless, the health effects attributed to 3D printing are not fully known and adherence to good hygiene principles is recommended during use of this technology.
Article
Despite the potential benefits of photopolymerization-based additive manufacturing, photochemical reactions in free-radical polymerization rarely proceed to completion, leading to the accumulation of residual monomer in polymer networks. In this novel study, we examined an array of methacrylate polymers for denture bases (>60 % Bis-EMA and 15–25 % proprietary methacrylic oligomer), orthodontic appliances (>70 % proprietary methacrylic oligomer, <20 % glycol methacrylate and <5 % pentamethyl-piperidyl sebucate) and implant surgical guides (≥75 % Bis-EMA and 30–50 % diurethane dimethacrylate, mixture of isomers) using headspace gas chromatography-mass spectrometry. Experimental data reported herein show that a substantial proportion of chemical compounds observed in the methacrylates decreased with post-illumination and the applied ethanol treatment. In the absence of residual methyl methacrylate, other potentially toxic acrylic esters were observed thus emphasizing the need to thoroughly scrutinize additively manufactured dental devices prior to their use. In the long term, standards for medical devices in dentistry could be revised to reflect the current trends in biomaterials and precursors they are generated from.
Article
Acrylates are synthetic thermoplastic resins used in a multitude of products, ranging from bone cement to artificial nails. They represent an important and increasing cause of both occupational and nonoccupational allergic contact dermatitis. Isobornyl acrylate, an acrylic monomer found within ultraviolet‐cured inks, adhesives and various medical devices for diabetes, has emerged as an important sensitizer. In addition, long‐lasting nail products have played a significant role in the increased prevalence of acrylate allergy. Sensitized individuals classically present with facial or eyelid dermatitis, and some patients experience associated fingertip and nail changes. This manuscript reviews these two important sources of acrylate allergy and summarizes other potential new exposures, including surgical glues and wound‐care products.
Article
Objectives Due to their small size, ultrafine particles (UFP) are believed to exert higher toxicity than larger particles. As numerous studies on health effects of UFP have been published since the last systematic review in 2013, we aim to systematically review the new literature. Methods We searched MEDLINE and the specialized LUDOK database for studies published between 01.01.2011 and 11.05.2017 investigating health effects of ambient air pollution-related UFP. We included epidemiologic studies containing UFP measures and quantifiable measures of associations. Relevant data were extracted on the basis of previously developed evaluation criteria. Results We identified 85 original studies, conducting short-term (n = 75) and long-term (n = 10) investigations. Panel (n = 32), scripted exposure with predefined settings (n = 16) or time series studies (n = 11) were most frequent. Thirty-four studies adjusted for at least one other pollutant. Most consistent associations were identified for short-term effects on pulmonary/systemic inflammation, heart rate variability and blood pressure. Conclusions The evidence suggests adverse short-term associations with inflammatory and cardiovascular changes, which may be at least partly independent of other pollutants. For the other studied health outcomes, the evidence on independent health effects of UFP remains inconclusive or insufficient.
Article
The aim of this study was to measure the concentrations of gaseous and particulate contaminants originated from additive manufacturing operations and post-processes in an occupational setting when plastics were used as feedstock materials. Secondary aims were to evaluate the concentration levels based on proposed exposure limits and target values and to propose means to reduce exposure to contaminants released in additive manufacturing processes. Volatile organic compounds were sampled with Tenax® TA adsorption tubes and analyzed with thermo desorption gas chromatography-mass spectrometry instrument. Carbonyl compounds were sampled with DNPH-Silica cartridges and analyzed with high-performance liquid chromatography device. Particles were measured with P-Trak instrument and indoor air quality was sampled with IAQ-Calc instrument. Dust mass concentrations were measured simultaneously with DustTrak DRX instrument and IOM-samplers. Particle concentrations were at highest (2070-81 890 #/cm³ mean) during manufacturing with methods where plastics were thermally processed. Total volatile organic compounds concentrations, in contrast, were low (113-317 µg/m³ mean) during manufacturing with such methods, and vat photopolymerization method. However, total volatile organic compounds concentrations of material jetting and multi jet fusion methods were higher (1114-2496 µg/m³ mean), perhaps because of material and binder spraying, where part of the spray can become aerosolized. Chemical treatment of manufactured objects was found to be a severe volatile organic compounds source as well. Formaldehyde was detected in low concentrations (3-40 µg/m³) in all methods except for material jetting method, in addition to several other carbonyl compounds. Notable dust concentrations (1.4-9.1 mg/m³) were detected only during post-processing of powder bed fusion and multi jet fusion manufactured objects. Indoor air quality parameters were not found to be notably impacted by manufacturing operations. Only low concentrations (below 2 ppm) of CO were detected during several manufacturing processes. All studied additive manufacturing operations emitted potentially harmful contaminants into their environments, which should be considered in occupational additive manufacturing and workplace design. According to the measured contaminant levels it is possible that adverse additive manufacturing related health effects may occur amongst exposed workers.
Article
Purpose This paper aims to measure exposures to airborne contaminants during three-dimensional (3-D) printing and post-processing tasks in an industrial workplace. Design/methodology/approach Contaminant concentrations were assessed using real-time particle number (0.007 to 1 µm) and total volatile organic compound (TVOC) monitors and thermal desorption tubes during various tasks at a manufacturing facility using fused deposition modeling (FDMTM) 3-D printers. Personal exposures were measured for two workers using nanoparticle respiratory deposition samplers for metals and passive badges for specific VOCs. Findings Opening industrial-scale FDMTM 3-D printer doors after printing, removing desktop FDMTM 3-D printer covers during printing, acetone vapor polishing (AVP) and chloroform vapor polishing (CVP) tasks all resulted in transient increases in levels of submicrometer-scale particles and/or organic vapors, a portion of which enter the workers’ breathing zone, resulting in exposure. Personal exposure to quantifiable levels of metals in particles <300 nm were 0.02 mg/m³ for aluminum, chromium, copper, iron and titanium during FDMTM printing. Personal exposures were 0.38 to 6.47 mg/m³ for acetone during AVP and 0.18 mg/m³ for chloroform during CVP. Originality/value Characterization of tasks provided insights on factors that influenced contaminant levels, and in turn exposures to various particles, metals < 300 nm and organic vapors. These concentration and exposure factors data are useful for identifying tasks and work processes to consider for implementation of new or improved control technologies to mitigate exposures in manufacturing facilities using FDMTM 3-D printers.
Chapter
Nanomaterials are invading our environment due to their increasing use in a very broad range of sectors making human exposure foreseeable during the life cycle of these materials. Inhalation is one of the most frequent routes of exposure in case of unintentional exposure and the small size of nanomaterials allows them to reach the deep lung. Understanding the fate and effects of nanomaterials is a great challenge for scientists as they exhibit a huge physico-chemical diversity that drives their biological reactivity. It is critical to determine the fate of nanomaterials at their route of entry in the organism as this will determine their local and/or systemic effects. In this review we will describe the epithelial barriers and the clearance processes of the respiratory tract. The mechanisms involved in the internalization of nanomaterials by respiratory cells and their ability to cross the epithelial barrier will be presented, highlighting methodologies and the role of the nanomaterial physico-chemical properties.
Article
Background: Dental technicians (DTs) are at increased risk for allergic contact sensitization. Objectives: To assess the current spectrum of occupational sensitization in DTs with occupational contact dermatitis (OCD). Methods: A retrospective analysis of Information Network of Departments of Dermatology patch test data from the years 2001-2015 concerning DTs with OCD was performed. Results: Patients of the study group (226 DTs with OCD) were significantly more often diagnosed with allergic contact dermatitis (37.6% versus 18.5%; p = 0.0002) than patients of the control group (124 DTs without OCD). In the study group, positive reactions were most frequently observed to methacrylates and/or acrylates (n = 67). Of these, 61 patients showed positive reactions to at least one of the five most frequent allergens in this group, namely 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, and/or ethylene glycol dimethacrylate. In contrast, no positive reactions to diurethane dimethacrylate (DUDMA) occurred. Among allergens of the German Contact Dermatitis Research Group series 'dental metals', positive reactions were less frequent and were mainly to palladium chloride (n = 6). Conclusions: The present data analysis showed that the sensitization spectrum and spectrum of cross-reactivity are largely unchanged as compared with the 1990s. It can be concluded that test recommendations are still valid and useful, except for the methacrylate DUDMA, which could be omitted.
Article
This article presents a comprehensive review of scientific literature concerning the blooming of additives on the surface of polymers, a phenomenon that depends on the solubility of an additive in a polymer and occurs in a time that depends on the diffusion coefficient of the additive in the polymer. Blooming is an important phenomenon as its occurrence can modify the material properties and lower its resistance to degradation. We report the parameters that influence the occurrence of blooming such as temperature, polymer morphology, additive shape and size. We also highlight the main fields in which the blooming was studied, the consequences of blooming on the material properties and the various characterization methods that are able to analyze the blooming phenomenon in situ. We focused next on the biomedical field, as blooming of additives on the surface of medical devices, especially those that are implanted or in contact with body fluids, can impact the device biocompatibility and represent a risk for the patient.
Article
Background: Acrylic monomers (acrylates), methacrylates and cyanoacrylates all cause asthma by respiratory sensitization. Occupational inhalation exposures occur across a variety of industries including health care and dental work, beauty, laboratory science, assembly and plastic moulding. Aims: To examine notifications of occupational asthma caused by acrylic compounds from a UK-based regional surveillance scheme, in order to highlight prevalent exposures and trends in presentation. Methods: Retrospective review of all cases reported to the SHIELD surveillance scheme for occupational asthma, West Midlands, UK between 1989 and 2014. Patient data were gathered on demographics, employment, asthma symptoms and diagnostic investigations including serum immunological testing, serial peak flow analysis and specific inhalation challenge tests. Descriptive statistics were used to illustrate worker characteristics and evidence for sensitization to acrylic compounds. Results: There were 20 affected patients out of 1790 total cases of occupational asthma (1%); all cases were confirmed by OASYS (Occupational Asthma SYStem) analysis of serial peak flow measurements, with three additional positive specific inhalation challenge tests. Three out of 20 (15%) patients were current smokers and 11/20 (55%) were atopic. A variety of exposures and industries were implicated including: manufacturing, health care, beauty and printing and a novel presentation seen in teachers exposed to floor adhesives. Conclusions: This is the largest reported series of occupational asthma caused by acrylic compounds, which remain an important aetiological factor in this disease. Exposure occurs in a variety of industries, particularly in manufacturing and is seen with other, perhaps better recognized sensitizing agents such as isocyanates and epoxy resins.
Article
Objectives: Additive manufacturing, which is more colloquially referred to as 3D printing, is quickly approaching mainstream adoption as a highly flexible processing technique that can be applied to plastic, metal, ceramic, concrete and other building materials. However, taking advantage of the tremendous versatility associated with in situ photopolymerization as well as the ability to select from a variety of preformed processible polymers, 3D printing predominantly targets the production of polymeric parts and models. The goal of this review is to connect the various additive manufacturing techniques with the monomeric and polymeric materials they use while highlighting emerging material-based developments. Methods: Modern additive manufacturing technology was introduced approximately three decades ago but this review compiles recent peer-reviewed literature reports to demonstrate the evolution underway with respect to the various building techniques that differ significantly in approach as well as the new variations in polymer-based materials being employed. Results: Recent growth of 3D printing has been dramatic and the ability of the various platform technologies to expand from rapid production prototypic models to the greater volume of readily customizable production of working parts is critical for continued high growth rates. This transition to working part production is highly dependent on adapting materials that deliver not only the requisite design accuracy but also the physical and mechanical properties necessary for the application. Significance: With the weighty distinction of being called the next industrial revolution, 3D printing technologies is already altering many industrial and academic operations including changing models for future healthcare delivery in medicine and dentistry.
Article
As an indicator of general indoor air quality in industrial facilities, the concentrations of total volatile organic compounds (TVOC) were determined in the workplaces of 37 industry sectors during the years of 2006–2011. For comparison, the TVOC levels in office-type workplaces were also determined. Based on the results, the TVOC target and guideline values are proposed for industrial workplaces. The geometric mean and median concentrations in the industrial workplaces were 778 and 845 µg/m3, respectively, while the 90th, 25th percentiles were, respectively, 6616 and 270 µg/m3. In the office-type environments, the geometric mean and median concentrations were 55 and 50 µg/m3, and the 90th and 25th percentiles were 230 and 27 µg/m3. Based on the measured TVOC distributions and the target values previously set, we propose a TVOC target value of 300 µg/m3 and guideline value of 3000 µg/m3 for the general indoor air in industrial workplaces. The concentration of 3000 µg/m3 could be achieved with reasonable measures by most industry sectors, but does not guarantee that the inhalation exposure to volatile organic compounds in the occupational environments is free from health concerns or perceived discomfort. Therefore, when reasonably achievable, a TVOC concentration close to or below the target value is recommended. This would make the TVOC levels in industrial facilities similar to those in the non-occupational indoor environments.
Article
This is a cross-sectional review of biomarkers used in air pollution research from January 2009 through December 2012. After an initial keyword search in PubMed retrieving 426 articles, a comprehensive abstract review identified 54 articles of experimental design that used biomarkers of exposure or effect in human studies in the area of air pollution research during this specified time period. A thorough bibliographic search of the included articles retrieved an additional 65 articles meeting the inclusion criteria. This review presents these 119 studies and the 234 biomarkers employed in these air pollution research investigations. Data presented are 70 biomarkers of exposure with 54% relating to polycyclic aromatic hydrocarbons, 36% volatile organic carbons, and 10% classified as other. Of the 164 biomarkers of effect, 91 and 130 were used in investigating effects of short-term and chronic exposure, respectively. Results of biomarkers used in short-term exposure describe different lag times and pollutant components such as primary and secondary pollutants, and particle number associated with corresponding physiological mechanisms including airway inflammation, neuroinflammation, ocular, metabolic, early endothelial dysfunction, coagulation, atherosclerosis, autonomic nervous system, oxidative stress, and DNA damage. The review presents three different exposure scenarios of chronic, occupational, and extreme exposure scenarios (indoor cooking) with associated biomarker findings presented in three broad categories of (1) immune profile, (2) oxidative stress, and (3) DNA damage. This review offers a representation of the scope of data being explored by air pollution researchers through the use of biomarkers and has deliberately been restricted to this particular subject rather than an extensive or in-depth review. This article provides a contextualization of air pollution studies conducted with biomarkers in human subjects in given areas while also integrating this complex body of information to offer a useful review for investigators in this field of study.
Article
Volatile organic compounds (VOCs) may be emitted from surfaces indoors leading to compromised air quality. This study scrutinized the influence of relative humidity (RH) on VOC concentrations in a building that had been subjected to water damage. While air samplings in a damp room at low RH (21-22 %) only revealed minor amounts of 2-ethylhexanol (3 μg/m(3)) and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB, 8 μg/m(3)), measurements performed after a rapid increase of RH (to 58-75 %) revealed an increase in VOC concentrations which was 3-fold for 2-ethylhexanol and 2-fold for TXIB. Similar VOC emission patterns were found in laboratory analyses of moisture-affected and laboratory-contaminated building materials. This study demonstrates the importance of monitoring RH when sampling indoor air for VOCs in order to avoid misleading conclusions from the analytical results.
Article
Objectives: Thermoplastics may contain a wide range of additives and free monomers, which themselves may be hazardous substances. Laboratory studies have shown that the thermal decomposition products of common plastics can include a number of carcinogens and respiratory sensitizers, but very little information exists on the airborne contaminants generated during actual industrial processing. The aim of this work was to identify airborne emissions during thermal processing of plastics in real-life, practical applications. Methods: Static air sampling was conducted at 10 industrial premises carrying out compounding or a range of processes such as extrusion, blown film manufacture, vacuum thermoforming, injection moulding, blow moulding, and hot wire cutting. Plastics being processed included polyvinyl chloride, polythene, polypropylene, polyethylene terephthalate, and acrylonitrile-butadiene-styrene. At each site, static sampling for a wide range of contaminants was carried out at locations immediately adjacent to the prominent fume-generating processes. Results: The monitoring data indicated the presence of few carcinogens at extremely low concentrations, all less than 1% of their respective WEL (Workplace Exposure Limit). No respiratory sensitizers were detected at any sites. Conclusions: The low levels of process-related fume detected show that the control strategies, which employed mainly forced mechanical general ventilation and good process temperature control, were adequate to control the risks associated with exposure to process-related fume. This substantiates the advice given in the Health and Safety Executive's information sheet No 13, 'Controlling Fume During Plastics Processing', and its broad applicability in plastics processing in general.