NEHA November 2022 Journal of Environmental Health

November 2022 • Journal of Environmental Health 13 geneous TEP distribution in polyurethane foams. All TEP detections were in polyurethane foams, not fabrics. One seat fabric was determined by extraction-IR to contain diaryl and/or triaryl phosphates, which was corroborated by LC/MS/ MS measurement of triphenyl phosphate at 409 mg/kg and resorcinol bis(diphenyl phosphate) (RDP) at 5,018 mg/kg (Wu et al., 2019). LC/MS/MS measured RDP and tris(2-ethylhexyl) phosphate (TEHP) at 111 and 140 mg/kg in two samples, but they were not detected by extraction-IR, which suggests that these levels were below LOD. Detecting halogenated flame retardants without using halogenated solvents or a more intensive extraction method has presented a challenge. On the one hand, we found chlorinated organophosphate flame retardants such as tris(1,3-dichloro-2-propyl)phosphate (TDCPP) and tris(1-chloro-2-propyl)phosphate (TCPP) were readily extracted from polyurethane foam by ethanol and detectable by ATR-FTIR. Figure 5 shows spectra of these two “chlorinated tris” flame retardants extracted from foam in child headphones purchased in 2020. On the other hand, brominated flame retardants were poorly extracted in this manner, even when toluene or acetone was used in place of or in addition to ethanol or methanol. Decabromodiphenyl ethane (DBDPE), however, was correctly identified by ATRFTIR in two intact car seat fabrics. LC/MS/ MS measured slightly >100 mg/kg DBDPE in these samples. We conclude that using alcohols, acetone, or toluene for extraction-IR is of limited use in identifying brominated flame retardants in polymeric matrices but is useful for chlorinated and nonchlorinated organophosphates and phosphonates. Bisphenol S and Bisphenol A on Thermal Paper Most purchase receipts are printed on thermal paper that is coated with a layer containing a dye, a sensitizer, and a developer. In 2017, using ATR-FTIR of intact samples, we tested >200 cash register receipts from retail stores and restaurants for BPS, BPA, and other developer chemicals (Ecology Center, 2018). We found that 75% of the receipts were coated with BPS and 18% with BPA. Additionally, we tested three receipt samples using GC/MS; the receipts were collected as convenience samples from consumers (Table 2). FTIR had previously identified BPS in receipt #1 and BPA in receipt #2. GC/MS concurred, measuring 71,000 mg/kg BPS and 14,500 mg/kg BPA, respectively. Receipt #3, which was uncoated paper, showed far lower levels of BPS (27 mg/kg) and BPA (3 mg/kg). Those levels are too low to indicate intentional use of BPA or BPS developer and are also too low for detection by our FTIR method. The finding of low levels on uncoated paper likely reflects the ease with which unbound BPS and BPA are transferred from one surface to another (Liao & Kannan, 2011). Furthermore, some level of BPA and BPS might also come from recycled paper used to manufacture the thermal paper (Liao & Kannan, 2011). Figure 6 shows typical spectra from thermal paper receipts. Superimposed on the calFourier-Transform Infrared (FTIR) Spectroscopy and Gas Chromatography/Mass Spectrometry (GC/MS) Results for Thermal Paper Cash Register Receipts Name FTIR Result GC/MS Measurement * BPA (mg/kg) BPS (mg/kg) Receipt #1 Bisphenol S (BPS) 95 71,000 Receipt #2 Bisphenol A (BPA) 14,500 not tested Receipt #3 Uncoated paper 3 27 * Method detection limit = 1 mg/kg. TABLE 2 Attenuated Total Reflectance–Fourier-Transform Infrared (ATR-FTIR) Spectra From Evaporated Ethanol Extracts of Polyurethane Foam in Two Different Child Headphones Note. The top spectrum is consistent with TDCPP and the bottom spectrum with TCPP. Bands that are characteristic of the two flame retardant chemicals are labeled. CO2 = carbon dioxide; TCPP = tris(1-chloro-2-propyl)phosphate; TDCPP = tris(1,3-dichloro-2-propyl)phosphate. 500 700 900 1,300 1,100 1,500 1,700 Absorbance Wavenumber (cm-1) 993 919 1,385 1,280 1,213 1,189 1,266 1,137 1,011 1,034 875 701 763 800 (Background CO2) FIGURE 5

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