Research Article Qualitative Analysis of Air Freshener Spray

Fatima Ibrahim ALshaer, Dalal Fuad ALBaharna, Haﬁz Omer Ahmed , Mohammed Ghiyath Anas, and Jasem Mohammed ALJassmi

Department of Environmental Health, College of Health Sciences, University of Sharjah, Sharjah, UAE

Correspondence should be addressed to Haﬁz Omer Ahmed; haﬁ[email protected]

Received 10 April 2019; Revised 5 September 2019; Accepted 19 September 2019; Published 5 November 2019

Academic Editor: Giuseppe La Torre

Copyright © 2019 Fatima Ibrahim ALshaer et al. -is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Air fresheners contain various chemicals that may or may not be harmful to human health and the environment. -ese products are widely used in different settings such as homes, schools, offices, and hospitals with ignorance of their real ingredients and their relative health effects. -us, this preliminary study was carried out to identify the presence of different compounds in spray air fresheners that were not disclosed on the product’s label. Four different brands of spray air fresheners were selected randomly from a local store, in which two were of mid-to-high cost and the remaining two of low cost. -e samples were analyzed using gas chromatography/mass spectrometry headspace, in which single components of the samples were identified by the mass spectrometry detector. -e results were shown as a chromatogram of several peaks, each representing different compounds. -e chemicals found in the samples include; lilial, galaxolide, benzenemethanol, musk ketone, butylated hydroxytoluene, and linalool. -ese chemicals may cause irritation and other health problems. However, none of them were revealed on the product’s label. -e study concludes that air fresheners need to be free of any toxic or harmful chemicals and include natural ingredients instead.

1. Introduction acetaldehyde, acetone, benzaldehyde, and limonene that were not listed on the product label. Air fresheners are chemical products that have been used in Numerous studies have been carried out by different the field of environmental sanitation for decades [1]. -ese researchers on the composition of air fresheners and their products are used in different settings, including dwellings, relative health effects. For instance, Fleming indicated that hospitals, offices, schools, hotels, restrooms etc. -ey are some compounds in such products including benzene de- available in various forms such as incense, scented candles, rivatives, pinene and limonene, aldehydes, phenol, and oils, disks, aerosol sprays, electric diffusers, and gels. cresol may pose serious health effects when reacting with According to Jung et al. [2], air fresheners are indiscrim- other indoor pollutants. Other common chemicals that inately used to mask the effects of the deodorizing and could be found in air fresheners include VOCs such as fragrant components in indoor environments. benzyl alcohol, toluene, myrcene, phthalates, artificial -e main purpose of using air fresheners is to get rid of musks, lilial, and linalool [6, 7]. disturbing odours that may result from different activities or Air fresheners have been recognized as a primary source processes within an area. -ey may consist of several in- of volatile organic compounds throughout buildings from gredients that have the ability to provide a pleasant ambi- an indoor air-quality perspective. However, air fresheners ence. Nevertheless, drawbacks may also result due to their have been related with adverse effects such as asthma attack, excessive usage. -ey consist of many chemicals that are not mucosal symptoms, infant illness, breathing difficulties, and revealed on the product label as manufacturers are not migraine headaches from a health perspective [6]. In the required to disclose all ingredients [3]. -ese chemicals previous two national surveys of the US population, could be allergens, irritants, or even toxic [4]. Steinemann breathing difficulties, headaches, and other health problems et al. [5] found numerous chemicals in air fresheners, such as were reported by 19 percent population when exposed to 2 Journal of Environmental and Public Health

Table 1: Brief description of each chemicals used in the sample freshener. Sample Cost Packaging Usage Quantity CAS Galaxolide AED 105 Glass bottle Aroma/fragrance preparations 30 ml (1 ﬂuid ounce) 1222-05-5 Lilial AED 274 Glass bottle Aroma/fragrance preparations 50 ml 80-54-6 Benzenemethanol AED 124 — — 16 oz 202-859-9 Musk ketone AED 76.80 Drum Perfumery compound 5.25 kgs — Butylated hydroxytoluene AED 12.80 Customized Perfumery compound 2 kg — Linalool AED 69.15 Customized Perfumery compound 5 g 78-70-6

Mcounts dr-hafez-s1-1[3-20-2017]sms 50:650 filtered 50.650 2.25

2.00

1.75

2 1.50

1.25

1.00

0.75

23.325 23.350 23.375 23.400 23.425 23.450 minutes Seg2, SCAN, Time: 2.00-34.57, EI-auto-full, 50-650 m/z Scans 2806 2809 2812 2815 2819 2822 Figure 1: Chromatogram of galaxolide in air freshener sample 1. deodorizers and air fresheners. 10.9 percent population life products comprising or emitting formaldehyde and reported health problems from the scent of laundry products examine quantity-related human exposure by either direct vented outdoors [7, 8]. or indirect sources [11]. -e contribution of a range of risk factors has been Information lacks concerning the gaseous emissions of assessed by the World Health Organization to the stress of fragrance products in spite of the extensive indoor exposure disease and indicated indoor pollution as the 8th most and widespread use of fragrances to them [12]. In addition, important risk factor and accountable for 2.7 percent of the 95 percent of the chemicals are synthetic compounds in burden of disease, globally. Every year, indoor air pollution fragrances that are derived from petroleum [13]. Humans is accountable for the death of 20 individuals [9]. Con- have been exposed to specific compounds for assessing the centrations of a number of volatile organic compounds are safety of those compounds inhaled when examining the consistently higher indoors as compared to outdoors. hazard of fragrance compounds [14]. Volatile organic compounds are comprised within house- It is important to carry out this study to increase hold products, such as wood preservatives, aerosol sprays, awareness and understanding of their hidden ingredients cleansers, disinfectants, paints, paint strippers, moth re- becasue of the extensive use of air fresheners with the ig- pellents, air fresheners, hobby supplies, dry-cleaned cloth- norance of their actual contents and their relative effects on ing, stored fuels and automated products, and other solvents humans and the environment. -erefore, the present study [10]. aims to identify the presence of different compounds in A National Environment Health Action Plan (NEHAP) spray air fresheners that are not disclosed on the product’s has been launched by the French government in June 2004, label. for improving indoor air quality. -e Ministries of Health, Labour, and Environment for evaluating health risks related 2. Material and Methods with formaldehyde and other volatile organic ompounds indoors have been mandated by the French Agency for 2.1. Study Design and Sample Collection. A qualitative, cross- Environmental and Occupational Health Safety (AFSSET). sectional study was conducted to determine the presence of In this regard, the role of AFSSET was to recognize everyday toxic chemicals in the air fresheners. Four different brands of Journal of Environmental and Public Health 3

BP: 243.3 (270451 = 100%), 23.368min, Scan: 2810, 50:650, Ion: 76us, RIC: 2.057e + 6 243.3 100 270451

91.3 143634 (%) 50

257.2 83271 25

(a) Galaxolide 1 BP 243.0 (999 = 100%) 182058 in MAINLIB C18H26O, MW258 243.0 100 999

(%) 50

0 100 200 300 400 500 600 Maximum range m/2 (b)

Figure 2: Mass spectrum of galaxolide in air freshener sample 1. (a) Air freshener analysis. (b) Main library of NIST11. spray air fresheners were selected randomly from a local of 1 μL sample was injected into the column, where the store, in which two were of mid-to-high cost and the separation of the chemical compounds in the air fresheners remaining two of low cost. was performed using an HP VF-5 ms, (30 m × 0.32 mm, 0.25 μm). Helium was used as the carrier gas at a ﬂow rate of 1.0 mL/min, and the injector temperature was at 230°C. -e 2.2. Sample Analysis. Gas chromatography/mass spec- temperature program of the column oven was started at trometry (GC/MS) headspace has been used to analyse the 50°C, was held for 1 min, ramped at 7°C/min to 250°C, and samples obtained from the air fresheners in environmental held for 5 mins. and analytical chemistry laboratories for the segregation and -e conditions for the ion trap mass spectrometer were analysis of readily volatile compounds. -e GC 3900/Saturn as follows: 2100T GC/MS (ion trap) system was controlled using a Varian GC/MS workstation version 5.52 software. A volume (i) Ionization mode; EI (70 ev) 4 Journal of Environmental and Public Health

Mcounts Dr-Hafez-S1-1[3-20-2017] SMS 50:650 fltered 50.650

7.5

5.0

2.5

0.0

17.00 17.25 17.50 17.75 18.00 18.25 18.50 18.75 minutes Seg 2, SCAN, Time: 2.00-34.57, EI-auto-full, 50-650 m/z Scans 2013 2044 2076 2107 2138 2169 2201 2233 Figure 3: Chromatogram of lilial in air freshener sample 1.

BP: 189.2 (211719 = 100%), 17.750min, Scan: 2107, 50:650, Ion: 289us, RIC: 972846 100 189.2 211719 75

(%) 50 131.3 52885 25

(a)

Lilial BP 189.0 (999 = 100%) 155329 in MAINLIB CAS No. 80-54-6, C14H20O, MW 204 100 189.0 999 75

(%) 147.0 50 412 91.0 253 25

0 0 100 200 300 400 500 600 Maximum range m/z (b)

Figure 4: Mass spectrum of lilial in air freshener sample 1. (a) Air freshener analysis. (b) Main library of NIST11. Journal of Environmental and Public Health 5

Mcounts dr-hafez-s1-1[3-27-2017], sms 50:650 filtered 50.650

1.75

1.50

1.25

1 1.00

0.75

0.50 22.3 22.4 22.5 22.6 22.7 22.8 22.9 minutes Seg 2, SCAN, Time: 1.00-34.57, EI-auto-full, 50-650 m/z

Scans 2825 2838 2850 2863 2875 2888 2901 Figure 5: Chromatogram of galaxolide in air freshener sample 2.

BP: 243.3 (142330 = 100%), 22.734min, Scan: 2880, 50:650, Ion: 352 us, RIC: 834967 100 243.3 142330 75

(%) 50 213.5 35386 25

(a) Galaxolide 2 BP 243.0 (999 = 100%) 182059 in MAINLIB C18H26O, MW 258 100 243.0 999

75 (%) 50

0 0 100 200 300 400 500 600 Maximum range m/z (b)

Figure 6: Mass spectrum of galaxolide in air freshener sample 2. (a) Air freshener analysis. (b) Main library of NIST11. 6 Journal of Environmental and Public Health

Mcounts dr-hafez-s2-1[3-27-2017] sms 50:650 filtered 50.650 1A

1.50

1.25

1.00

0.75

0.50

0.25

10.9 11.0 11.1 11.2 11.3 11.4 11.5 minutes Seg 2, SCAN, Time: 1.00-34.57, EI-auto-full, 50-650 m/z Scans 1378 1391 1403 1416 1429 1441 1454 Figure 7: Chromatogram of benzenemethanol in air freshener sample 2.

BP: 121.9 (235209 = 100%), 11.137min, Scan: 1408, 50:650, Ion: 181us, RIC: 1.137e + 6 100 121.9 235209 75 104.1 (%) 113407 50

(a)

Benzenemethanol, .alpha, -methyl-, acetate BP 122.0 (999 = 100%) 18109 in REPLIB CAS No. 93-92-5, C10H12O2, MW 164 100 122.0 999 75 (%) 107.0 164.0 50 43.0 382 365 261 25

0 0 100 200 300 400 500 600 Maximum range m/z (b)

Figure 8: Mass spectrum of benzenemethanol in air freshener sample 2. (a) Air freshener analysis. (b) Main library of NIST11. Journal of Environmental and Public Health 7

Mcounts dr-hafez-s3-1[3-27-2017] sms 50:650 filtered 50.650

7.5 1A

1 5.0

2.5

0.0

17 18 19 20 21 minutes Seg 2, SCAN, Time: 1.00-34.57, EI-auto-full, 50-650 m/z

Scans 2096 2224 2353 2482 2613 Figure 9: Chromatogram of benzenemethanol in air freshener sample 3.

BP: 107.0 (315625 = 100%), 18.000min, Scan: 2224, 50:650, Ion: 221us, RIC: 1.202e + 6 100 107.0 315625 75

(%) 50 148.9 93262 25

(a) Benzenemethanol, .alpha, -(trichloromethyl)-, acetate BP 107.0 (999 = 100%) 75216 in MAINLIB CAS No. 90-17-5, C10H9Cl3O2, MW 266 100 107.0 999 43.0 75 650 (%) 50 149.0 291 25

0 0 100 200 300 400 500 600 Maximum range m/z (b)

Figure 10: Mass spectrum of benzenemethanol in air freshener sample 3. (a) Air freshener analysis. (b) Main library of NIST11. 8 Journal of Environmental and Public Health

Mcounts dr-hafez-s3-1[3-27-2017] sms 50:650 filtered 1A 2.5 50.650

2.0

1.5 1

1.0

0.5

23 24 25 26 minutes Seg 2, SCAN, Time: 1.00-34.57, EI-auto-full, 50-650 m/z Scans 2871 3000 3128 3257 Figure 11: Chromatogram of musk ketone in air freshener sample 3.

BP: 279.1 (118990 = 100%), 24.591min, Scan: 3076, 50:650, Ion: 450us, RIC: 717919 100 279.1 118990 75

(%) 50

(a) Musk ketone BP 43.0 (999 = 100%) 3258 in REPLIB CAS No. 81-14-1, C14H18N2O5, MW 894 100 43.0 999 75 279.0 (%) 473 50

0 0 100 200 300 400 500 600 Maximum range m/z

(b)

Figure 12: Mass spectrum of musk ketone in air freshener sample 3. (a) Air freshener analysis. (b) Main library of NIST11. Journal of Environmental and Public Health 9

Mcounts 50.650 dr-hafez-s4-1[4-27-2017] sms 50:650 filtered

1A 4

1 3

16 17 18 19 20 minutes Seg 2, SCAN, Time: 1.00-34.57, EI-auto-full, 50-650 m/z Scans 1972 2099 2227 2354 2482 Figure 13: Chromatogram of butylated hydroxytoluene in air freshener sample 4.

BP: 205.3 (81153 = 100%), 17.216min, Scan: 2127, 50:650, Ion: 879us, RIC: 365327 100 205.3 81153 75

(%) 50

(a) Butylated Hydroxytoluene BP 205.0 (999 = 100%) 165050 in MAINLIB CAS No. 128-37-0, C15H24O, MW 220 100 205.0 999 75 (%) 50 57.0 284 25

0 0 100 200 300 400 500 600 Maximum range m/z

(b)

Figure 14: Mass spectrum of butylated hydroxytoluene in air freshener sample 4. (a) Air freshener analysis. (b) Main library of NIST11. 10 Journal of Environmental and Public Health

Mcounts dr-hafez-s4-1[4-2-2017] sms 50:650 filtered 50.650

15 16 17 18 19 minutes Seg 2, SCAN, Time: 1.00-34.57, EI-auto-full, 50-650 m/z

Scans 1644 1972 2099 2227 2354 Figure 15: Chromatogram of lilial in air freshener sample 4.

BP: 189.3 (155083 = 100%), 17.481min, Scan: 2161, 50:650, Ion: 442us, RIC:702203 100 189.3 155083 75

(%) 50 131.3 45746 25

(a) Lilial BP 189.0 (999 = 100%) 155329 in MAINLIB CAS No. 80-54-6, C14H20O, MW 204 100 189.0 999 75 (%) 147.0 50 412 91.0 253 25

0 0 100 200 300 400 500 600 Maximum range m/z

(b)

Figure 16: Mass spectrum of lilial in air freshener sample 4. (a) Air freshener analysis. (b) Main library of NIST11. Journal of Environmental and Public Health 11

Mcounts dr-hafez-s4-1[4-2-2017] sms 50:650 filtered 50.650

1A 5

1 3

12 13 14 15 minutes Seg 2, SCAN, Time: 1.00-34.57, EI-auto-full, 50-650 m/z Scans 1452 1587 1716 1844 Figure 17: Chromatogram of linalool in air freshener sample 4.

BP: 81.1 (484679 = 100%), 12.471min, Scan: 1521, 50:650, Ion: 153us, RIC: 1.395e + 6 100 81.1 484679

(%) 50 137.0 148689 25

(a)

Linalool BP 81.0 (999 = 100%) 18015 in nist_msms CAS No. 78-70-6, C10H18O, MW 154 100 81.0 999 75 137.0 (%) 478 50

0 0 100 200 300 400 500 600 Maximum range m/z (b)

Figure 18: Mass spectrum of linalool in air freshener sample 4. (a) Air freshener analysis. (b) Main library of NIST11. 12 Journal of Environmental and Public Health

(ii) Target 5000 Table 2: Labeling chemicals present in the four samples of air (iii) Prescan ionization time 1500 μs fresheners. Air Freshener Sample 1 (iv) Scan time 0.66 s Aqua Labeled (v) Scan mode (50–650 M/z) Isopropyl alcohol Labeled (vi) Ion trap temperature was at 200°C PEG 40 hydrogenated castor oil Labeled Parfum Labeled ° (vii) Transfer line temperature 220 C Lilial Not labeled (viii) Manifold temperature at 45°C. Galaxolide Not labeled Air Freshener Sample 2 Finally, the National Institute of Standards and Tech- Aqua Labeled nology 05 (NIST) mass spectral library was used for the Alcohol surfactant Labeled identification of the obtained peaks. Table 1 shows brief Fragrance Labeled description of each chemicals used in sample freshener. Preservative Labeled Malodour counteracting (MOC) ingredient Labeled 3. Results Antifoam Labeled Galaxolide Not labeled -e chemicals found after the analysis of the four spray air Benzenemethanol Not labeled fresheners include galaxolide, lilial, benzenemethanol, musk Air Freshener Sample 3 ketone, butylated hydroxytoluene (BHT), and linalool. -e Butane Labeled chromatograms with peaks representing each component SD alcohol 40-B Labeled found in the samples, along with their boiling points and Propane Labeled molecular weights have been illustrated in Figures 1–18. Fragrance Labeled Water Labeled Table 2 presents the product labels that were labeled Butylene glycol Labeled and not labeled on the air fresheners. Some chemicals Camellia sinensis leaf extract Labeled after analysis turned out to be noted as skin allergens or Musk ketone Not labeled irritants and even chemicals that may interfere with bodily Benzenemethanol Not labeled functions. Some other chemicals found were safe to use in Air Freshener Sample 4 fragrance and household products and did not pose any Butane Labeled health risk. Propane Labeled Isobutane Labeled 4. Discussion Alcohol Labeled Parfum Labeled -e frequent use of air fresheners containing such synthetic Lilial Not labeled chemicals may cause health effects on the long run; although Linalool Not labeled exact concentrations of the chemicals present are not Butylated hydroxytoluene (BHT) Not labeled known. -e present study has not included any laboratory tests or assessment regarding the potential health effects of Cosmetics along with -e Environmental Working Group air fresheners, as the main emphasis was on the identifi- found that BHT and musk ketone were present in fragrance cation of the chemical compounds found in the products. products [19, 20]. Both of these chemicals are associated with Lilial is found among two of the four samples analyzed that estrogenic effects. BHT and musk ketone were found to be can sometimes act as an allergen and cause contact der- present only in the low-cost air fresheners. Finally, linalool is matitis in susceptible individuals [15]. -e Campaign for considered to be safe unless found in the oxidized form and Safe Cosmetics and -e Environmental Working Group causes skin reactions [20]. In the present study, this chemical confirmed that Lilial is found in fragrance products, such as was found in the low-cost air freshener only. A previous perfumes, colognes, and body sprays [16]. Galaxolide was study by Steinemann [6] confirmed that linalool, a terpe- found in two of the medium-to-high cost air fresheners. -is noid, is emitted by air fresheners. chemical may interfere with hormones and other chemical Previous studies have used other prevalent volatile signals in the body resulting in developmental, reproductive, organic compounds (VOC) such as acetaldehyde, ethanol, metabolic, brain, and behavioural problems. Women’s Voice beta-myrcene, acetone, beta-pinene, limonene, and alpha- for the Earth (WVE) revealed the presence of this chemical pinene in at least 40% of the products. Similarly, ethanol, in cleaning products, including air fresheners [17]. acetaldehyde, alpha pinene, phenoxyethanol, limonene, Benzenemethanol, also known as benzyl alcohol, was and ethyl butyrate were the six most prevalent VOC’s in found in both the low-cost and medium-to-high cost air building materials detected by GC/MS [21, 22]. -ese fresheners. It is a known irritant when used in cosmetics and compounds, however, were not discussed and monitored causes many problems and abnormalities. -e Danish En- in the present study. Furthermore, in air sampling, VOC’s vironmental Protection Agency confirmed the presence of were not detected, which were obtained once daily from benzyl alcohol in specific fragrance ingredients used in air one site outside the hospital. Aromatic hydrocarbons such fresheners and other fragrance liberating products [18]. A as ethylbenzene, toluene, and xylenes, esters (butyl acetate previous study undertaken by -e Campaign for Safe and ethyl acetate), and aliphatic hydrocarbons (n-hexane) Journal of Environmental and Public Health 13 were monitored and detected with TVOC concentrations Acknowledgments surpassing the suggested maximum concentration (400 μg/m3) before occupying the building [23]. However, -e authors would like to express their gratitude to Mr. the study missed these chemicals or compounds to be Muaath Khairi Mousa, the Laboratory officer at Research monitored and detected, and thus failed to detect them in Institute of Science and Engineering (RISE) at the University air fresheners sprays. of Sharjah, UAE, who provided expertise and help in the analysis of samples. 5. Conclusion References -e present study has identified the presence of different compounds in spray air fresheners that were not disclosed [1] M. Telpner, %e Unfreshening Ingredients in Toxic Air Fresh- eners, 2016, https://www.meghantelpner.com/blog/ingredients- on the product’s label. -e results depicted common in-toxic-air-fresheners/. compounds in both low- and high-cost air fresheners. [2] Y.-R. Jung, H.-H. Park, Y.-H. Oh et al., “Emission charac- Chemicals found in this study were not revealed on the teristics of volatile organic compounds from air fresher using product label as manufacturers are not required to list all small emission chamber,” Journal of Korean Society of En- ingredients. -ese chemicals usually tend to be listed on the vironmental Engineers, vol. 33, no. 3, pp. 183–190, 2011. product label as “parfum” or “fragrance”. -ere should be a [3] A. Cohen, S. Janssen, and G. 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Fund CaEWG, Washington, DC, USA, 2010, http://www.ewg. org/sites/default/ﬁles/report/SafeCosmetics_FragranceRpt.pdf. [17] Galaxolide: A Long-Lasting Fragrance Contaminating the Great Lakes, January 2019, http://www.womensvoices.org/fragrance- ingredients/galaxolide-a-long-lasting-fragrance-contaminating- the-great-lakes/. [18] J. Pors and R. Fuhlendorﬀ, “Mapping of chemical substances in air fresheners and other fragrance liberating products. Survey on chemical substances in consumer products,” Survey, vol. 30, 2003. [19] J. L. Reiner, C. M. Wong, K. F. Arcaro, and K. Kannan, “Synthetic musk fragrances in human milk from the United States,” Environmental Science & Technology, vol. 41, no. 11, pp. 3815–3820, 2007. [20] Linalool, 2016, http://www.tech-faq.com/linalool.html. [21] H. Kataoka, Y. Ohashi, T. Mamiya et al., “Indoor air moni- toring of volatile organic compounds and evaluation of their emission from various building materials and common products by gas chromatography-mass spectrometry,” Ad- vanced Gas Chromatography - Progress in Agricultural, Bio- medical and Industrial Applications, InTechOpen, London, UK, 2012. [22] N. Nematollahi, A. Doronila, P. J. Mornane, A. Duan, S. D. Kolev, and A. Steinemann, “Volatile chemical emissions from fragranced baby products,” Air Quality, Atmosphere & Health, vol. 11, no. 7, pp. 785–790, 2018. [23] Y. Huang, S. S. H. Ho, K. F. Ho et al., “Characterization of biogenic volatile organic compounds (BVOCs) in cleaning reagents and air fresheners in Hong Kong,” Atmospheric Environment, vol. 45, no. 34, pp. 6191–6196, 2011.