NEHA November 2022 Journal of Environmental Health

JOURNAL OF f i f t e e n d o l l a r s Environmental Health Published by the National Environmental Health Association Dedicated to the advancement of the environmental health professional Volume 85, No. 4 November 2022

November 2022 • Journal of Environmental Health 3 ADVANCEMENT OF THE SCIENCE A Rapid Screening Method for Detecting Hazardous Chemicals in Consumer Products, Food Contact Materials, and Thermal Paper Receipts Using ATR-FTIR Spectroscopy .............. 8 Risks and Understanding of Carbon Monoxide Poisoning in an Ice Fishing Community ....... 16 ADVANCEMENT OF THE PRACTICE Bystander Chemical Exposures and Injuries Associated With Nearby Plastic Sewer Pipe Manufacture: Public Health Practice and Lessons .................................................. 22 Feature Story: American Indian/Alaska Native Environmental Health Programs and Strategies ............................................................................................................................. 32 Building Capacity: Building Capacity Through Communities of Practice .................................... 38 Direct From ATSDR: Public Health Assessment Site Tool and Aliated Applications: A Key Resource for Evaluating the Health Impact of Community Exposure to Hazardous Chemicals............................................................................................... 40 Direct From CDC/Environmental Health Services: Leveraging Informatics to Improve Environmental Health Practice and Innovation ........................................................... 44 ADVANCEMENT OF THE PRACTITIONER Environmental Health Calendar ............................................................................................... 48 Resource Corner........................................................................................................................ 49 YOUR ASSOCIATION President’s Message: “To Infinity and Beyond!” .......................................................................................6 U.S. Postal Service Statement of Ownership .............................................................................. 47 Special Listing ........................................................................................................................... 50 Special Report From NEHA: Our New Brand ........................................................................... 52 A Tribute to Our 25-Year Members ........................................................................................... 54 NEHA News .............................................................................................................................. 58 NEHA 2023 AEC....................................................................................................................... 60 DirecTalk: Organization of Consequence ..................................................................................... 62 JOURNAL OF Environmental Health Dedicated to the advancement of the environmental health professional Volume 85, No. 4 November 2022 A B O U T T H E C O V E R The National Environmental Health Association (NEHA) is pleased to unveil our new brand within the pages of the November 2022 Journal of Environmental Health! The cover shines a spotlight on the new NEHA logo—the cornerstone of our new brand. You will find components of our new brand throughout this issue via new colors and redesigned promotions for our products and services. You can learn about the rebranding process and what it means for our association and the professionals we represent through columns by our leadership on pages 6 and 62. We have also included a special report on page 52 that highlights our new brand and explains what the new logo represents, as well as provides a history of our past logos. Cover image © iStockphoto: phochi A D V E R T I S E R S I N D E X Custom Data Processing....................................... 21 HS GovTech (Formerly HealthSpace) .................. 64 Industrial Test Systems, Inc. ................................... 5 Inspect2GO Environmental Health Software ......... 2 NEHA-FDA Retail Flexible Funding Model Grant Program .......................................... 63 Ozark River Manufacturing Co. ........................... 21

4 Volume 85 • Number 4 in the next Journal of Environmental Health don’t miss Of f i c i a l Pub l i ca t i on Journal of Environmental Health (ISSN 0022-0892) Kristen Ruby-Cisneros, Managing Editor Ellen Kuwana, MS, Copy Editor Hughes design|communications, Design/Production Cognition Studio, Cover Artwork Soni Fink, Advertising For advertising call (303) 802-2139 Technical Editors William A. Adler, MPH, RS Retired (Minnesota Department of Health), Rochester, MN Gary Erbeck, MPH Retired (County of San Diego Department of Environmental Health), San Diego, CA Thomas H. Hatfield, DrPH, REHS, DAAS California State University, Northridge, CA Dhitinut Ratnapradipa, PhD, MCHES Creighton University, Omaha, NE Published monthly (except bimonthly in January/February and July/ August) by the National Environmental Health Association, 720 S. Colorado Blvd., Suite 105A, Denver, CO 80246-1910. Phone: (303) 7569090; Fax: (303) 691-9490; Internet: E-mail: kruby@ Volume 85, Number 4. Yearly subscription rates in U.S.: $150 (electronic), $160 (print), and $185 (electronic and print). Yearly international subscription rates: $150 (electronic), $200 (print), and $225 (electronic and print). Single copies: $15, if available. Reprint and advertising rates available at CPM Sales Agreement Number 40045946. Claims must be filed within 30 days domestic, 90 days foreign, © Copyright 2022, National Environmental Health Association (no refunds). All rights reserved. Contents may be reproduced only with permission of the managing editor. Opinions and conclusions expressed in articles, columns, and other contributions are those of the authors only and do not reflect the policies or views of NEHA. NEHA and the Journal of Environmental Health are not liable or responsible for the accuracy of, or actions taken on the basis of, any information stated herein. NEHA and the Journal of Environmental Health reserve the right to reject any advertising copy. Advertisers and their agencies will assume liability for the content of all advertisements printed and also assume responsibility for any claims arising therefrom against the publisher. Full text of this journal is available from ProQuest Information and Learning, (800) 521-0600, ext. 3781; (734) 973-7007; or www.proquest. com. The Journal of Environmental Health is indexed by Current Awareness in Biological Sciences, EBSCO, and Applied Science & Technology Index. It is abstracted by Wilson Applied Science & Technology Abstracts and EMBASE/Excerpta Medica. All technical manuscripts submitted for publication are subject to peer review. Contact the managing editor for Instructions for Authors, or visit To submit a manuscript, visit Direct all questions to Kristen Ruby-Cisneros, managing editor, Periodicals postage paid at Denver, Colorado, and additional mailing offices. POSTMASTER: Send address changes to Journal of Environmental Health, 720 S. Colorado Blvd., Suite 105A, Denver, CO 80246-1910. Printed on recycled paper. Join our environmental health community. It is the only community of people who truly understand what it means to do what you do every day to protect the health of our communities. Join us today. Your people are waiting. Find Your People. Find Your Training. Find Your Resources.  Biological Factors That Impact Variability of Lead Absorption and Blood Lead Level Estimation in Children  Brown elds in Romania and the United States: A Visual Tour  Microbial Source Tracking in the Sasco Brook, Lower Farm River, and Goodwives River Watersheds of Long Island Sound

November 2022 • Journal of Environmental Health 5 WATER TESTING NEEDS? eXact® Photometers SenSafe® Test Strips Drinking and Wastewater WATER QUALITY eXact® Photometers Pool Check Test Strips Screening and Compliance POOL & SPA eXact® Photometers WaterWorks™ Test Strips Process Water FOOD SAFETY WaterWorks™ Childcare Kits Sanitizing and Disinfecting CHILDCARE LEARN ABOUT OUR WATER QUALITY PRODUCTS; THE FIRST CHOICE OF HEALTH INSPECTORS. Certified to NSF/ANSI Standard 50 (800) 861-9712 SENSAFE.COM SENSAFE ITSSENSAFE SENSAFE_ITS R0222

6 Volume 85 • Number 4 YOUR ASSOCIATION D. Gary Brown, DrPH, CIH, RS, DAAS “To Infinity and Beyond!”  PRES I DENT ’ S MESSAGE As Buzz Lightyear says, “To infinity and beyond!” These new heights are where we at the National Environmental Health Association (NEHA), with your partnership, plan to take the profession to with our new mission and vision statements and updated logo. Just as modes of transportation have evolved—from horseback to air travel and in the future, space travel—our messaging has also evolved, embracing our history while leading us into the future. Like a fine wine, this rebranding process has been in the works for several years. NEHA sta„ led the e„ort, involving stakeholders along with marketing professionals. We also formed several committees that assisted with the development of the new mission and vision statements along with the logo. As with travel, advertising has developed over the years from printed ads and billboards to radio and TV and now to web-based ads. We are evolving to make an impact in the digital age. The rebranding process began by reexamining our history. As George Santayana stated, “Those who cannot remember the past are condemned to repeat it.” To keep ourselves centered and maintain our sense of mission, we returned to our original charter to reflect on the wisdom of our professional forebearers. The National Association of Sanitarians was formed at a meeting in Long Beach, California, on June 25, 1937. Over the next several decades, the association had major input into the development and implementation of the nation’s environmental health programs and succeeded in demonstrating the significant role that environmental health professionals should play on the public health stage. In 1970, the name of the association was changed to the National Environmental Health Association. The statement of purpose from the original charter created in 1937 included the following goals: • Promote welfare of workers in public health inspection. • Promote high standards of qualifications. • Standardize methods of law enforcement. • Cultivate social intercourse among members. • Establish a central point of union for members. The original slogan was, “Sanitation—the Beacon Light of Public Health,” with the most recent mission being, “To advance the environmental health and protection professional for the purpose of providing a healthful environment for all.” Our new mission—To build, sustain, and empower an e ective environmental health workforce—is anchored in the past and future, looking beyond the horizon like Ferdinand Magellan did when most Europeans thought the world was flat. The environmental health profession includes a rich and diverse array of professionals with expertise in air quality, body art, climate change, drinking water, food safety, healthy homes, informatics, industrial hygiene, preparedness and response, safety, sanitation, tracking, vectors, and wastewater. We work in a variety of sectors including local, tribal, state, territorial and federal government; nonprofits; the uniformed services; private entities; and academia. Environmental health science is a fabric made up of interwoven professional threads representing a mosaic of the most critical and essential services in society. When NEHA sta„, board members, and affiliate leaders come to work, we ask: “What is in the best interest of our members?” The change to the mission emphasizes the importance of supporting your educational needs, filling knowledge gaps, providing policy leadership, and advocating for funding to enable our members to e„ectively do their jobs. We define advancement in terms of both education and motivation. Our activities are grounded in our belief that the environmental health professional who is educated and motivated is the professional who will make This new logo will lead NEHA into the next 85 years of building, empowering, and sustaining the environmental health profession.

November 2022 • Journal of Environmental Health 7 the greatest contribution to the healthful environmental goals that we all seek. Accordingly, through each of our programs, great emphasis is placed on providing both educational as well as motivational opportunities. Similar to what Staples has popularized in their advertising, we wants you to know that we are the “easy button” for environmental health professionals. The future outlook of environmental health is bright and the mid-1980s song by Timbuk 3, “The Future’s So Bright, I Gotta Wear Shades,” comes to mind. Our new vision reflects a new era: Healthy environments. Protected communities. Empowered professionals. This change reflects our ultimate goal of healthy and safe environments for all communities and a valued and empowered environmental health workforce. To reach that vision we will continue to provide training, webinars, presentations, and study materials to bring the latest practices and research to the workforce. The final piece of the rebranding puzzle is the NEHA logo. The original logo was introduced in 1937 and was a shield with a beacon in the center. That logo was updated in 1965 to include the phrase, “Environmental Health Around the World,” around the shield. Since 1975, the NEHA logo has been the map of the U.S. with the name of the association around it. See page 53 for a history of our logos. The new NEHA logo and brand reflect the development of both NEHA and the profession. The bursting petals signify a new era and excitement for what is possible for NEHA and the profession, particularly after the COVID-19 pandemic. The position of the petals over the “eh” letters represent the shelter NEHA provides to the workforce through advocacy, education, and community. Finally, the range of blue-colored petals acknowledge the importance of including diverse perspectives and experiences to address the environmental health challenges of today and beyond. This new logo will lead NEHA into the next 85 years of building, empowering, and sustaining the environmental health profession. The cherry on top of the sundae is the launch of a new website, which includes an online community platform. Our online Community aims to create a virtual community for environmental health professionals to network, engage, and provide best practices and mentorship. We have become a worldwide leader in environmental health through the hard work of our sta—, board, and members. We have become the organization many people around the world look to for best practices or guidance—a wonderful achievement. We will continue to work to ensure healthy environments, protected communities, and empowered professionals for this “big old goofy world” as singer-songwriter John Prine sang. Members are extremely important to NEHA and our mission. Our membership structure includes five di erent membership categories—Professional, Emerging Professional, Retired Professional, International, and Life. Membership with us provides connection, education, and advancement for environmental health professionals at any career stage. Our nationally recognized credentials, extensive learning opportunities, and community of dedicated leaders position our members for greater professional success. We believe that the success of our members elevates the environmental health profession as a whole. Learn more at Did You Know? Stand out in the crowd. Show the world you are the environmental health expert you know you are with a credential. You might even earn more or get promoted.

8 Volume 85 • Number 4 A D VANC EME N T O F T H E SCIENCE Introduction The Ecology Center of Ann Arbor, Michigan, tests consumer products, publishes reports, and uses the data to engage with product manufacturers, brands, and retailers to eliminate chemical hazards and replace them with alternatives. This work has led to documented reductions in hazardous chemical content of products sold in the U.S. in several sectors, such as child car seats and vinyl flooring (Ecology Center, 2019; Miller et al., 2019). We use attenuated total ref lectance– Fourier-transform infrared (ATR-FTIR) spectroscopy to probe a range of chemicals including flame retardants, plasticizers, and bisphenols. For samples that require it, we have developed a simple passive extraction method using very low volumes of nonhalogenated solvents only. We refer to the latter technique as extraction-infrared spectroscopy (extraction-IR). We have demonstrated that ATR-FTIR of intact and extracted samples can be a rapid, inexpensive method to identify chemicals of concern in products, particularly at levels arising from intentional use. Companies that make consumer products have an interest in monitoring their products and supply chains for hazardous chemicals, as do nongovernmental organizations (NGOs) and health or environmental agencies that aim to minimize exposure to substances that increase disease risk (Doherty et al., 2019; Goodwin Robbins et al., 2020; Maffini et al., 2021; Zota et al., 2017). Governmental restrictions on plastic additives across the world include specific ortho-phthalate esters (phthalates), flame retardant chemicals, and bisphenol A (BPA). Most companies maintain restricted substance lists, whose scope can go beyond legal restrictions to include unregulated chemicals of concern. In addition, NGO pressure—the pressure exerted by advocacy groups on brands and retailers to eliminate hazardous chemicals— has prompted many companies to phase out known hazards and to strengthen their corporate chemical policies and communications with suppliers (Ecology Center, 2019; Toxic-Free Future, 2021). Therefore, a rapid and inexpensive analysis tool to test for chemicals in products can be useful for product makers, retailers, NGOs, and government agencies. Commercial laboratories will test plastic items for specific chemicals using gas or liquid chromatography coupled with mass spectrometry (GC/MS and LC/MS, respectively), and for modest numbers of samples this approach might be feasible. When testing for intentional additives, however, FTIR can substantially reduce cost and time, particularly when large numbers of samples or on-site analyses are desired. Vibrational spectroscopies have been used previously to detect phthalates and other plasAbs t r ac t We investigated the performance of attenuated total reflectance–Fourier-transform infrared (ATR-FTIR) spectroscopy to rapidly identify intentional additives in a variety of items commonly handled by consumers and workers. We investigated ortho-phthalate esters, specific alternative plasticizers, and flame retardants in food contact materials and consumer products. We also investigated bisphenol A (BPA) and bisphenol S (BPS) developers in thermal paper purchase receipts. Applications include regulatory compliance screening and product deformulation. We compared FTIR results with mass spectrometry measurements. Samples were analyzed either intact or after a simple liquid-phase extraction using small amounts of nonhalogenated solvents. These methods greatly reduced the time and expense of identifying intentionally added phthalates and other plasticizers compared with more sensitive methods. Similarly, BPA and BPS were readily identified in receipts and organophosphorus flame retardants were identified in child car seats. In some samples, FTIR detected novel or unexpected additives not detected by conventional targeted methods. These approaches are useful for screening diverse product samples for intentional additives with a relatively portable instrument while generating very low volumes of spent solvent. A Rapid Screening Method for Detecting Hazardous Chemicals in Consumer Products, Food Contact Materials, and Thermal Paper Receipts Using ATR-FTIR Spectroscopy Gillian Zaharias Miller, PhD Jeff Gearhart, MS Ecology Center

November 2022 • Journal of Environmental Health 9 ticizers in polyvinyl chloride (PVC) items. The infrared and Raman spectra of phthalates in particular are well-characterized (Nørbygaard & Berg, 2004; Socrates, 2004). In this article, we assess the feasibility of using ATR-FTIR along with simple sample preparation to screen for three categories of hazardous chemicals found variably in consumer products, food-contact materials, and receipt papers: 1) phthalates and nonphthalate plasticizers, 2) organophosphate flame retardants, and 3) BPA and bisphenol S (BPS) in thermal paper. The screened samples consisted of 114 consumer products and food contact materials purchased between 2014 and 2020, and >200 receipts collected from retail businesses in 2017. We also tested PVC standards containing known levels of phthalates to assess detection limits and to compare with real-world products. We discuss e’ects of co-additives and fillers on spectral identification. Finally, we highlight cases in which our FTIR approach revealed novel or unexpected chemical additives in consumer products. Methods We used a Nicolet iS5 FTIR spectrometer with a single-bounce diamond ATR accessory. Absorbance spectra were collected from 4,000–500 cm-1 with 4 cm-1 resolution averaging 12–16 scans using Omnic software. No smoothing or processing was applied to the spectra. We used a combination of visual inspection of the spectral data and match searching within FTIR libraries both purchased (i.e., Thermo Fisher Scientific in 2008) and obtained in-house. Omnic Specta software was used to help identify some multicomponent samples. Regardless of the software, to determine a positive match we required visually apparent alignment of key peaks in the experimental spectrum with a known spectrum. Chemicals purchased as FTIR standards were: 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH; Toronto Research); decabromodiphenyl ethane (DBDPE; TCI); tris(2-butoxyethyl) phosphate (TBOEP; Wellington Laboratories); triethyl phosphate and triphenyl phosphate (TEP and TPHP, respectively; Cambridge Isotope Laboratories); and bis(2-ethylhexyl) phthalate, diisononyl phthalate, and diisodecyl phthalate (DEHP, DINP, and DIDP, respectively; Sigma Aldrich). We used two certified reference materials from SPEX CertiPrep that contained PVC with 0.8% and 7.8% total phthalates. The 7.8% certified reference material contained 30,000 mg/kg each of DINP and DIDP and 3,000 mg/kg each of DEHP, benzyl butyl phthalate (BBP), dibutyl phthalate (DBP), di-n-octyl phthalate, diethyl phthalate, and dimethyl phthalate. The 0.8% certified reference contained 1,000 mg/kg each of DEHP, BBP, DBP, di-n-hexyl phthalate, diamyl phthalate, dicyclohexyl phthalate, diisobutyl phthalate (DIBP), and DINP. Additional reference standards with phthalate levels ranging from 0.1–1.0% were prepared in our laboratory by mixing PVC powder from Millipore Sigma with the certified reference materials in appropriate mass proportions. These powders were clamped directly on the ATR stage. Other chemicals reported in our results were identified based on matches within the purchased libraries. For extraction-IR, we used isopropanolcleaned scissors or a scraping tool to remove pieces of sample to be analyzed. After placing cut pieces into a glass vial, a few drops of isopropanol or ethanol (both from Fisher Scientific) were added to cover the sample. Vial lids contained either a Teflon or polypropylene gasket that were una’ected by the solvent. After at least 10 min, a metal dipstick was used to remove a drop of solution from the vial and place it on the ATR stage. The solvent was left to evaporate; then a spectrum was collected. A method blank was prepared by placing a few drops of isopropanol or ethanol in an empty vial and analyzing it in the same way. For plasticizers and bisphenols analyzed externally, GC/MS was carried out by two laboratories, Eurofins and TUV Rheinland. Both used organic solvent extraction and GC/MS based on CPSC-CH-C1001-09.3 or CPSC-CH-C1001-09.4. For flame retardants in child car seat samples, LC/MS/MS was carried out at Indiana University as described in Wu et al. (2019). Results and Discussion Phthalates and Alternative Plasticizers We used FTIR to identify phthalates as a class, not as specific congeners (e.g., diethylhexyl phthalate), because the di’erences in their FTIR spectra are too subtle. With few exceptions, phthalate congeners used in plastic products di’er only in length and branching of the alkyl chains R and R’ (Figure 1). Most phthalates we have identified in products have R and R’ of 8–10 carbons as determined by GC/MS. Thus, their FTIR spectra are extremely similar, di’ering only slightly in CH2 and CH3 stretching (near 2,900 cm-1) and bending (near 1,400 cm-1). Distinguishing these di’erent phthalates is further complicated because a given product could include more than one phthalate congener and/or di’ering isomers. Figure 2 shows ATR-FTIR spectra of PVC powders containing di’erent levels of total phthalates. We identified six key peaks that are useful for identifying phthalate presence and distinguishing phthalates from alternative plasticizers. The six key peaks are labeled in Figure 2: “twin peaks” 1,600 and 1,580 (orthophenyl stretching); 1,124 (symmetric COC stretch) appearing as a doublet with 1,073; and 1,040; and 743 cm-1 (out-of-plane CH deformation) (Socrates, 2004). By comparing FTIR with GC/MS results, we observed that when all six key peaks are apparent in the characteristic pattern in a spectrum, phthalate presence is unequivocal. When the twin peaks are unclear but the other peaks are apparent, phthalate presence is highly likely. When only a small number of phthalate peaks are visible, such as just 1,040 and 743 cm-1, phthalate presence is suspected and can be further investigated by extraction-IR. Figure 2 suggests that the limit of detection (LOD) for phthalates in PVC by visual observation with this method is 0.3–0.4% by mass. Two of the peaks, 1,124 and 1,073 cm-1, are still weakly apparent at 0.3% and even slightly at 0.2%. Extraction-IR allows clearer detection below 0.3%. We caution, however, that this LOD is based on high-purity PVC containing only phthalates. Real-world products, discussed shortly, typically have a higher LOD due to the obscuring e’ects of fillers, additional plasticizers, and other additives. An advanced data processing technique might detect phthalates at lower levels. Such an approach has been used, for example, with food adulterants (Özen & Tokatli, 2012), but might require too much development time to be practical. Interestingly, Omnic Specta multicomponent searching did not correctly identify the

10 Volume 85 • Number 4 A D VANC EME N T O F T H E SCIENCE phthalate-spiked PVC powders at levels below 0.5%. This finding suggests visual identification based on the six key peaks is at least as reliable in detecting lower-level phthalates as are purely software-based searches. Figure 3 shows total phthalate levels measured in 90 of 114 consumer products tested by FTIR and GC/MS. The 24 samples not shown had no phthalate detection by either technique. Product types are summarized in Table 1. Most samples had a PVC matrix; five samples were other polymers (see Supplemental Table 1 at mental). A log scale is used in Figure 2 to ensure subpercent levels are visible. GC/MS phthalate levels ranging from 1.36% to 50% (solid circles) were correctly identified by FTIR as containing phthalates. Phthalate levels of ≤0.45% (open circles) were not detectable by visual inspection or software searching. Thus, the e•ective LOD for product samples was approximately 1%. As expected, this LOD is higher than for the higher-purity reference materials. Some samples (Supplemental Table 1) required extraction-IR for confident plasticizer identification. Figure 4 illustrates how passive extraction removes the matrix and fillers from the spectrum. In Figure 4A, a cowmilking inflation liner spectrum (“intact” in figure) indicates synthetic rubber of polystyrene and polybutadiene with a curved baseline typical of samples containing carbon black. The baseline distortion is caused by similar infrared absorptivities of carbon black and the diamond ATR crystal (Thermo Scientific, 2013). The presence of phthalate (Figure 4A) became clear after extraction. Several nonphthalate plasticizers were identified by FTIR (Table 1). Di(ethylhexyl) terephthalate (DEHT) was the most commonly detected. DEHT, DINCH, acetyltributylcitrate (ATBC), and di(ethylhexyl)adipate (DEHA) were confirmed by GC/MS. GC/MS typically was carried out nonquantitatively due to cost constraints; thus, e•ective LODs could not be determined. Five plasticizers Structure of Ortho-Phthalate Note. R and R’ are alkyl groups. For example, R and R’ in diisononyl phthalate (DINP) are both isononyl groups with nine carbons each. FIGURE 1 Attenuated Total Reflectance–Fourier-Transform Infrared (ATR-FTIR) Spectra of Polyvinyl Chloride (PVC) Powder With Differing Levels of Total Phthalates Note. The six key peaks useful for identifying phthalates in PVC are labeled and marked with dotted lines. Peaks from PVC are not labeled; the most prominent of these is the C-Cl stretch at 610 cm-1. 1,600 1,580 1,124 1,073 1,040 743 Phthalate Level: 7.8% 1.0% 0.8% 0.5% 0.4% 0.3% 0.2% 0.1% 0% Absorbance Wavenumber (cm-1) 1,700 1,500 1,300 1,100 900 700 500 FIGURE 2 Total Phthalates Measured by Gas Chromatography/Mass Spectrometry (GC/MS) in 90 Consumer Product Samples Note. Fourier-transform infrared (FTIR) spectroscopy correctly identified the presence of phthalates in samples represented by solid circles. FTIR did not detect phthalates in samples represented by open circles, all of which had <1% total phthalate. Data were taken from Supplemental Table 1. 0.001 0.01 0.1 1 10 100 Total Phthalates (% by Mass, GC/MS) Consumer Product Samples Tested for Total Phthalates by GC/MS and FTIR FTIR Positive Detection FTIR No Detection FIGURE 3

November 2022 • Journal of Environmental Health 11 were identified by library matching but not confirmed by GC/MS: phenyl esters of alkyl sulfonic acids (ASEs; trade name Mesamoll), dibenzoate esters (trade name Benzoflex), epoxidized soybean oil (ESBO), glycerin triacetate, and tris(2-ethylhexyl)trimellitate. Extraction-IR was needed to clearly identify phthalates and alternatives in some samples such as vinyl floor tiles. Spectra from floor tiles (not shown) frequently were dominated by calcium carbonate such that the plasticizer peaks were not discernible. Upon extraction, the plasticizer could be clearly identified. FTIR did not produce false positives for phthalates. For DEHT, however, there were two apparent false positives out of 96 GC/MS results under the LOD for reason unknown. There were none for DINCH, ATBC, and DEHA. Four cases of apparent false negatives for DEHT were samples that had either high levels of phthalates or, for the two wire insulation samples, a trimellitate, suggesting DEHT was a minor plasticizer that was obscured (Supplemental Table 1). Our testing of hundreds of products has revealed potential pitfalls in identifying phthalates. Dibenzoate esters have a pair of twin peaks close to phthalates. DEHT has a weak peak in the same region. Trimellitates have a pair of peaks at 1,114 and 1,068 cm-1, which is close to two key phthalate peaks. If phthalates initially are suspected due to any of these features, their exact peak positions should be verified and other key phthalate regions should be examined. DINCH, ATBC, and DEHA lack sharp, well-separated peaks and can be confused with one another in a multicomponent sample. FTIR sometimes failed to identify a plasticizer in a sample containing more than one. Performance was least consistent for DEHA. It is likely that the adipate was obscured by higher level co-plasticizers. Phosphate esters, which are used as plasticizers or as flame retardants, are also detectable by FTIR in various matrices. We identified triphenyl phosphate, for example, in nail polishes that we dried and subjected to passive extraction with isopropanol. Omnic Specta software was used to assist in the multicomponent nail polish extracts. Selected Flame Retardants Flame retardants can be added to polymers at relatively low levels (e.g., a few tenths of a perSummary of Plasticizers and Flame Retardant Chemicals Detected by Fourier-Transform Infrared (FTIR) Spectroscopy in Consumer Product Samples Collected Between 2014 and 2020 Additive Detected by FTIR Confirmed by Gas Chromatography/ Mass Spectrometry (GC/MS) Product Types Plasticizers Ortho-phthalates Yes (see Supplemental Table 1 for details) Cap gaskets from bottled beverages, vinyl gloves, floor tiles, dance floors, tub mats, flipflop straps, wire insulation, floor runners, pencil pouches, garden hoses, shelf liners, headbands, shower curtain liners, wall decals, wallpaper, window shades, tub appliques Adipate Yes (DEHA) Wall decals, milking inflation liner ATBC or TBC Yes (ATBC) Doll heads, rubber ducks, flip-flop straps DEHT Yes Cap gaskets from bottled beverages, vinyl gloves, floor tiles, dance floors, tub mats, shelf liners, jelly shoes, doll heads, placemats, window shades, wall decals, window clings, crib mattress covers, garden hoses, pencil pouches, paddleballs, bath toys DINCH Yes Doll heads, window clings, crib mattress covers, bath toys ASEs Not tested Crib mattress covers Benzoate ester (dibenzoate esters of dipropylene or ethylene glycols) Not tested Floor tiles ESBO Not tested Cap gaskets from bottled beverages Glycerin triacetate Not tested Dairy tubing Tris(2-ethylhexyl) trimellitate Not tested Wire insulation Flame retardants PMMMPs Yes Child car seat fabrics and foams TBOEP Yes Child car seat fabrics and foams TEP Yes (two samples); no (two samples) Child car seat fabrics and foams DBDPE Yes Child car seat fabrics and foams Triaryl or diaryl phosphates Yes (TPHP and RDP) Child car seat fabrics and foams TDCPP Not tested Child headphone foams TCPP Not tested Child headphone foams Note. GC/MS data for the individual samples can be viewed in Supplemental Tables 1 and 2. ASEs = alkyl sulfonic acid phenyl esters; ATBC = acetyltributylcitrate; DBDPE = decabromodiphenyl ethane; DEHA = di(2-ethylhexyl) adipate; DEHT = di(2-ethylhexyl) terephthalate; DINCH = 1,2-cyclohexane dicarboxylic acid diisononyl ester; ESBO = epoxidized soybean oil; PMMMPs = 5-ethyl-2-methyl-2-oxido-1,3,2-dioxaphosphinan-5-yl)methyl methyl methylphosphonate and bis[(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)methyl] methyl phosphonate p,p’-dioxide); RDP = resorcinol bis(diphenyl phosphate); TBC = tributyl citrate; TBOEP = tris(2-butoxyethyl)phosphate; TCPP = tris(1-chloro-2-propyl) phosphate; TDCPP = tris(1,3-dichloro-2-propyl)phosphate; TEP = triethyl phosphate; TPHP = triphenyl phosphate. TABLE 1

12 Volume 85 • Number 4 A D VANC EME N T O F T H E SCIENCE cent), and thus we found that flame retardant bands were not consistently distinguishable by ATR-FTIR of intact consumer products. Therefore, we routinely used extraction-IR to screen for flame retardants. We identified phosphorus-based f lame retardants in 36 samples taken from 18 child car seats. Samples included fabrics, polyurethane foams, and fabric–foam composites. An overview of these findings is presented in Table 1 with details in Supplemental Table 2. FTIR allowed discovery of a little-known flame retardant chemical that is a mixture of two cyclic phosphonates: 5-ethyl2-methyl-2-oxido-1,3,2-dioxaphosphinan5-yl)methyl methyl methylphosphonate and bis[(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)methyl] methyl phosphonate p,p’-dioxide (PMMMPs). FTIR spectra of extracts from several car seat samples closely matched a spectrum in the HR Polymer Additives and Plasticizers Library called “phosphonate ester (cyclic)” or “Antiblaze 1045.” A literature search led to a CAS number and structure, revealing the mixture to be PMMMPs (Wu et al., 2019). To validate the finding, LC/MS/MS was carried out as described in Wu et al. (2019). An authentic standard for PMMMPs was not available, but a technical mixture (Hans TEX-3) was obtained from a supplier. Using this mixture as a standard, LC/MS/MS testing confirmed the presence of PMMMPs in the car seat fabrics, which was the first report of PMMMPs in consumer products in North America. This flame retardant had previously been reported in window curtains purchased in Japan (Miyake et al., 2018). Figure 4B shows spectra from car seat fabric and its isopropanol extract revealing PMMMPs. The intact fabric has a characteristic polyethylene terephthalate spectrum (“polyester”) with indications of an additive, but the matrix bands and subpercent level of the flame retardant make further identification di¢cult. Performing a multicomponent search using Omnic Specta software did not correctly identify PMMMPs in the mixture. Obtaining a drop of extract, however, led to the correct identification. Data in Supplemental Table 2 show we correctly identified PMMMPs with simple extraction-IR down to a concentration of slightly >400 mg/kg or 0.04%. The method did not produce false positives. PMMMPs were visible in the intact FTIR spectra for many samples, although extraction made the bands clearer. Phosphate esters—used as flame retardants in fabrics, polyurethane foams, and PVC articles—were also assessed. Supplemental Table 2 shows detection of TBOEP, TEP, and a small number of other flame retardants by extraction-IR compared with LC/MS/MS. Car seat samples with TBOEP ranging from 356 to 3,461 mg/kg were correctly identified by extraction-IR. The method did not detect TBOEP at 206 mg/kg. The method did not produce false positives. Extraction-IR performed poorly for TEP detection, failing in samples that concurrently contained higher levels of PMMMPs, presumably due to PMMMPs bands obscuring TEP. A total of four samples showed apparent false positives; the reason is unknown but could be due to nonhomoAttenuated Total Reflectance–Fourier-Transform Infrared (ATR-FTIR) Spectra Illustrating How Extraction-IR Reveals Additives Note. A: Cow-milking inflation liner intact sample and evaporated ethanol extract. Labeled peaks are consistent with styrene-butadiene rubber (intact) and with ortho-phthalates (extract). The six key phthalate peaks are labeled in bold. B: Child car seat fabric intact sample and evaporated isopropanol extract. Labeled peaks are characteristic of poly(ethylene terephthalate) (intact) and PMMMPs (extract). PMMMPs = 5-ethyl-2-methyl-2-oxido-1,3,2-dioxaphosphinan-5-yl)methyl methyl methylphosphonate and bis[(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)methyl] methyl phosphonate p, p’-dioxide). 500 700 900 1,300 1,500 1,700 Absorbance 1,100 1,728 1,712 1,408 1,463 1,315 1,242 1,075 1,062 1,027 1,339 1,240 1,094 1,016 1,464 1,380 1,286 1,435 1,069 1,600 1,580 1,124 1,073 743 961 739 908 697 Intact Extract 500 700 900 1,300 1,100 1,500 1,700 Absorbance Wavenumber (cm-1) Wavenumber (cm-1) 969 827 909 871 722 846 Intact Extract A B FIGURE 4

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

14 Volume 85 • Number 4 cium carbonate bands, BPS or BPA characteristic peaks are apparent. The decline of BPA use due to toxicity concerns and the rise of BPS as its common replacement in thermal paper is an example of an ill-informed substitution. The biological activity of BPS and its adverse eects on organisms have become better understood in recent years (Catanese & Vandenberg, 2017; Gorini et al., 2020; Kinch et al., 2015), with implications particularly for workers at stores and restaurants who are disproportionately exposed to developer chemicals from receipts (Ehrlich et al., 2014; Hehn, 2016; Hormann et al., 2014). Other analytical methods can be used to identify developers on thermal paper (Eckardt et al., 2020; Kinch et al., 2015), but the comparative ease of using FTIR to rapidly screen papers presents an opportunity for NGOs and regulatory agencies to better address the unnecessary and widespread human exposure to these chemicals. Untargeted Phthalates We highlight three cases in which nonspecific detection of phthalates by FTIR proved key to determining composition. In the first case, FTIR identified phthalates in a vinyl garden hose in which GC/MS initially found just 0.15% DINP, which is below the FTIR LOD. When a second GC/MS analysis was carried out with an expanded target list, an uncommon phthalate was found: 1.3% 1-nonyl 2-undecyl 1,2-benzenedicarboxylate or dinonylundecyl phthalate (DNUP). In the next two cases, FTIR identified the presence of phthalates in vinyl disposable gloves that was not initially detected by targeted GC/MS. GC/MS was carried out a second time with an expanded target list, resulting in determination of 22.7% and 24.9% dipropylheptyl phthalate (DPHP) in the gloves. DPHP is an isomer of DIDP that is also used as a plasticizer. Thus, FTIR prevented unexpected or novel phthalate congeners from being overlooked. This nonspecificity can be a downside when speciation is desired. Conclusion This article aims to inform public and environmental health professionals how to use a relatively inexpensive, rapid technique to test consumer products, food contact materials, and receipt paper for common hazardous chemicals. To evaluate the utility of this approach, we aggregated FTIR data from product research carried out between 2014 and 2020. We tested over 100 diverse products for added plasticizers, 18 children’s car seats for flame retardants, and >200 receipts for BPS and BPA. We carried out ATR-FTIR directly on product samples and—when a clearer spectrum was desired—after passive extraction using very low volumes of isopropanol or ethanol. The extraction proved useful for products with complex matrices, removing matrix and filler bands from the spectrum to reveal additive chemicals. In fabric and polyurethane foam, extraction-IR allowed detection of both chlorinated and nonhalogenated organophosphate flame retardants, but not most brominated flame retardants. Extraction was not needed to determine BPA or BPS presence in receipts. Comparison with certified test methods at contract laboratories showed FTIR and extraction-IR reliably detected phthalates and nonphthalate plasticizers in PVC and other polymers, several organophosphorus flame retardants in fabrics and foams, and BPA and BPS in receipts. Interestingly, for low phthalate levels close to LOD, visual identification of phthalate peaks was more reliable than the software’s multicomponent search. LOD for total phthalates in PVC was found to be approximately 0.3% for “ideal” samples and closer to 1.0% for real-world products. The method revealed phthalate presence in products appearing phthalate-free by targeted mass spectrometry. Similarly, the method identified an unexpected phosphonate flame retardant in car seats. Acknowledgements: This work was funded by grants from the Environmental Defense Fund and the John Merck Fund as well as the Cedar Tree Foundation, Marisla Foundation, and Cornell Douglas Foundation. Corresponding Author: Gillian Zaharias Miller, Ecology Center, 339 East Liberty Street, Suite 300, Ann Arbor, MI 48103. Email: A D VANC EME N T O F T H E SCIENCE Attenuated Total Reflectance–Fourier-Transform Infrared (ATR-FTIR) Spectra From the Printed Sides of Purchase Receipts Containing Bisphenol S (BPS) as the Developer (Top) and Bisphenol A (BPA) as the Developer (Bottom) Note. Peaks that are characteristic of BPS (top) and BPA (bottom) that are useful for distinguishing the two chemicals are labeled. Asterisks (*) indicate calcium carbonate. 500 700 900 1,300 1,100 1,500 1,700 Absorbance 872* 713* 552 827 564 722 1,601 1,586 1,409* 1,139 1,103 1,073 1,084 1,103 1,177 549 557 692 BPS Receipt BPA Receipt Wavenumber (cm-1) FIGURE 6

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