RESUMO
Ethylene oxide (EtO) is a hazardous air pollutant that can be emitted from a variety of difficult to measure industrial sources, such as fugitive leaks, wastewater handling, and episodic releases. Emerging next generation emission measurement (NGEM) approaches capable of time-resolved, low parts per billion by volume (ppbv) method detection limits (MDLs) can help facilities understand and reduce EtO and other air pollutant emissions from these sources yielding a range of environmental and public health benefits. In October 2021, a first of its kind 4-day observational study was conducted at an EtO chemical facility in the midwestern United States. The study had dual objectives to both improve understanding of EtO emission sources within the facility and advance NGEM methods. Using cavity ring-down spectroscopy (CRDS) instruments, a combination of mobile surveys and stationary multipoint process unit monitoring assessed EtO concentrations in and near facility operations, while testing and comparing measurement methods. The study concluded that four main areas of EtO source emissions existed within the facility, each possessing unique emission characteristics. Episodic EtO emissions from supply railcar switchovers and batch reactor washouts, lasting seconds to minutes in duration, produced EtO concentrations exceeding 500 ppbv inside the process unit in some cases. In one instance, EtO at ~30 ppbv was briefly observed hundreds of meters from the process unit. Lower level but more sustained EtO concentrations were observed near an EtO transfer pump and wastewater tank outfall and drain system. Overall, 4.6% of mobile survey data were above the 1.2 ppbv mobile test MDL while the nine stationary sampling locations ranged from 17.7% to 82.8% of data above the 1.0 ppbv multipoint test MDL. This paper describes the EtO emissions observed in and near the four defined source areas within the facility and provides details of the NGEM method development advances accomplished as part of the study.
RESUMO
Fused filament fabrication is a 3D printing technique that has gained widespread use from homes to schools to workplaces. Thermoplastic filaments, such as acrylonitrile-butadiene-styrene (ABS) and polylactic acid (PLA), are extruded at temperatures near their respective glass transition temperature or melting point, respectively. Little has been reported on the inorganic elemental composition and concentrations present in these materials or the methods available for extracting that information. Because inorganic constituents may be included in the aerosolized particulates emitted during the printing process, identifying elements that could be present and at what specific concentrations is critical. The objective of the current research is to determine the range of metals present in thermoplastic filaments along with their relative abundance and chemical speciation as a function of polymer type, manufacturer, and color. A variety of filaments from select manufacturers were digested using a range of techniques to determine the optimal conditions for metal extraction from ABS and PLA polymers. The extraction potential for each method was quantified using by ICP-MS analysis. When possible, further characterization of the chemical composition of the filaments was investigated using X-ray Absorption spectroscopy to determine chemical speciation of the metal. Optimal digestion conditions were established using a high temperature, high pressure microwave-assisted acid digestion method to produce the most complete and repeatable extraction results. The composition and abundance of metals in the filaments varied greatly as a function of polymer, manufacturer, and color. Potential elements of concern present in the filaments at elevated concentration included that could pose a respiratory risk included Si, Al, Ti, Cu, Zn, and Sn. XAS analysis revealed a mixture of metal oxides, mineral, and organometallic compounds were present in the filaments that were being used to increase opaqueness impart color (dyes), polymeric catalysts, and flame retardants. This work shows that a variety of metals are present in the starting materials used for 3D printing and depending on their partitioning into 3D printed products and byproducts as well as the exposure route, may pose a health risk which merits further investigation.
