Determination of melamine and its derivatives in textiles and infant clothing purchased in the United States

Journal Pre-proof Determination of melamine and its derivatives in textiles and infant clothing purchased in the United States

Hongkai Zhu, Kurunthachalam Kannan PII:

S0048-9697(19)36392-2

DOI:

https://doi.org/10.1016/j.scitotenv.2019.136396

Reference:

STOTEN 136396

To appear in:

Science of the Total Environment

Received date:

6 November 2019

Revised date:

26 December 2019

Accepted date:

27 December 2019

Please cite this article as: H. Zhu and K. Kannan, Determination of melamine and its derivatives in textiles and infant clothing purchased in the United States, Science of the Total Environment (2018), https://doi.org/10.1016/j.scitotenv.2019.136396

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

© 2018 Published by Elsevier.

Journal Pre-proof Determination of melamine and its derivatives in textiles and infant clothing purchased in the United States Hongkai Zhu† and Kurunthachalam Kannan*,†,‡,‖

†

Wadsworth Center, New York State Department of Health, Empire State Plaza, P.O. Box 509,

Department of Pediatrics, New York University School of Medicine, New York, New York,

ro

‖

of

Albany, New York 12201-0509, United States

Biochemistry Department, Faculty of Science and Experimental Biochemistry Unit, King Fahd

re

‡

-p

United States

na

lP

Medical Research Center, King Abdulaziz University, Jeddah 22254, Saudi Arabia

*Corresponding author at: Wadsworth Center, Empire State Plaza, P.O. Box 509, Albany, New

Jo

Fax: +1 518 473 2895

ur

York 12201-0509, United States

e-mail: [email protected] (K. Kannan)

Submitted to: Science of the Total Environment

1

Journal Pre-proof HIGHLIGHTS

Melamine and cyanuric acid are present in textiles.



Cotton fabrics contain notable levels of melamine derivatives.



Laundering can remove melamine derivatives from textiles.



Dermal exposure risk of melamine and cyanuric acid from textiles is minimal.

ro

of



Jo

ur

na

lP

re

-p

Graphic Abstract

2

Journal Pre-proof ABSTRACT Melamine-based resins are used extensively in fabrics to impart fire and heat resistance as well as wrinkle-free properties. Little is known, however, regarding the occurrence of melamine and its derivatives in textiles. In this study, concentrations of melamine, ammeline, ammelide, and cyanuric acid were determined in 77 textile samples and infant clothing purchased from Albany, New York, USA. All textile samples contained one or more target analytes, at concentration

of

ranges of 1.19–81800, 3.21–17800, <1.20–25700, and <0.50–550 ng/g for melamine, cyanuric

ro

acid, ammeline, and ammelide, respectively. Melamine was the predominant compound,

-p

accounting for 52% of the total concentrations of four analytes (i.e., ∑melamines). Significant positive correlations were found between the concentrations of melamine and its three

re

derivatives (0.347 < r < 0.862, p < 0.01). The concentrations of ∑melamines were significantly

lP

higher in cotton fabrics (mean: 10500 ng/g) and cotton clothes (10200 ng/g) than in synthetic

na

fabrics (1380 ng/g) and socks (40.0 ng/g) (p < 0.01). Simulated laundry experiments suggested that even a single round of washing with water removed 76–90% of melamine derivatives from

ur

clothing. The calculated dermal exposure doses of melamine and cyanuric acid were three to four

Jo

orders of magnitude below the reference value. This study provides the first evidence of the occurrence of melamine derivatives in textiles and clothing purchased in the United States.

Keywords: Melamine; Cyanuric acid; Textiles; Infant clothing; Dermal exposure

Capsule: Melamine and cyanuric acid are widely distributed in textiles and infant clothing collected from the United States.

3

Journal Pre-proof 1. Introduction Melamine is a nitrogen-rich (approximately 66% by mass) heterocyclic triazine compound that has received considerable attention over the past 10 years due to a series of food scandals (Ingelfinger, 2008). Apart from its deliberate addition in food products, melamine has been used legally in many consumer products. Melamine formaldehyde resins (MFRs; fire resistant and heat tolerant) have been widely used in decorative laminates (e.g., countertops, laminate

of

flooring), wood products (e.g., oriented strand board), and molding compounds (e.g.,

ro

kitchenware, tableware) as flame retardants and as modifiers in coatings, textiles, and paper since

-p

the 1950s (Merline et al., 2013; Rovina and Siddiquee, 2015). Ammeline, ammelide, and

re

cyanuric acid are present as impurities in melamine mixtures and are formed as intermediates during the hydrolytic breakdown of melamine (Braekevelt et al., 2011). Cyanuric acid also is

lP

used as a stabilizer in the production of disinfectants, sanitizers, and bleaches (Dorne et al.,

na

2013). More than 2 million tons of melamine and cyanuric acid are used globally each year (European Food Safety Authority, 2010).

ur

Melamine and its derivatives (i.e., ammeline, ammelide, and cyanuric acid) have been

Jo

reported to occur in indoor dust, sediment, sludge, soil, and water (Zhu and Kannan, 2018b; Zhu et al., 2019a, 2019c, 2019d, 2019e). Owing to their nephrotoxicity, neurotoxicity, and reproductive toxicity, as reported in several in vitro and in vivo animal studies (An et al., 2011; Bolden et al., 2017; Chang et al., 2014; Dalal and Goldfarb, 2011; Yang et al., 2012; Yin et al., 2013), melamine and cyanuric acid have been recognized as emerging contaminants since 2010 (Richardson, 2010). Our previous studies showed that foodstuffs, especially dairy, cereal, and meat products, are the major sources of melamine and cyanuric acid exposure in U.S. adults (Zhu and Kannan, 2018c, 2019a). For infants, formula feeding contributed to higher melamine

4

Journal Pre-proof exposure than did breastfeeding (Zhu and Kannan, 2018a, 2019b). Other sources of human exposures are still not fully understood. Textiles contain a variety of endocrine-disrupting chemicals (EDCs) and are a source of human exposure to several synthetic chemicals. Li and Kannan (2018) reported 23 EDCs in pantyhose collected from six countries, with sum concentrations as high as a few percent. Bisphenol A (BPA) and parabens were found in infants’ and children’s socks collected in Spain

of

(Freire et al., 2019). Dermal absorption of phthalates from cotton clothing was identified as an

ro

important route for infant exposure to this class of chemicals (Li et al., 2019). Textiles, from raw

-p

fibers to finished fabric, undergo a long series of chemical treatments (i.e., preparation and

re

pretreatment, dyeing, printing, and refinement of fabrics) (Papaspyrides et al., 2009). Melamine is one of the chemicals added during the production of textiles (IHS Markit, 2019). Textiles are

lP

treated with MFRs to improve wrinkle resistance and to add flame-retardant properties. Thus,

melamine and its derivatives.

na

textiles used for clothing and bedding can be a significant source of human exposure to

ur

In this study, several types of textiles, including raw fabric, infant clothing, and diapers, were

Jo

collected from local stores in Albany, New York, USA, to (1) determine the concentrations and profiles of melamine and its derivatives, (2) assess removal of these chemicals from textiles during laundering, and (3) estimate dermal exposure doses of these chemicals from wearing clothes. To our knowledge, this is the first study to determine the occurrence of melamine and its derivatives in textile samples.

2. Materials and methods 2.1. Chemicals and reagents

5

Journal Pre-proof Information regarding the standards and reagents used in this study is provided in the Supporting Information (SI; Text S1). 2.2. Sample collection and preparation In total, 77 textile samples were purchased from local stores in Albany, New York, USA, in April 2016. Further details of the samples have been reported earlier (Liu et al., 2017; Xue et al., 2017). The textiles varied in use, color, fabric types, and country of origin. On the basis of usage,

of

textiles were categorized as raw textiles (n = 19), infant clothing (n = 52; e.g., socks, bodysuits,

ro

pants, trousers, skirts, shirts) and others (n = 6; e.g., cloth diapers, blankets). On the basis of

-p

composition, textiles were grouped as cotton (n = 51) and synthetic fabrics (n = 26; e.g.,

re

polyester, nylon, blended). The textile samples originated from China (n = 47), India (n = 11), Cambodia (n = 8), Ecuador (n = 3), Bangladesh (n = 2), Sri Lanka (n = 2), Vietnam (n = 2), and

lP

El Salvador (n = 2). Details of the textiles analyzed in this study are provided in the SI (Table

na

S1). The textile samples were sealed in polyethylene bags and stored at 4 °C in the dark. For analysis, five square pieces of cloth (2 ×2 cm2) were randomly cut from the textile

ur

sample and further cut into small pieces, using stainless-steel scissors. Approximately 0.05 g of

Jo

the garment was weighed into a 15 mL polypropylene (PP) tube and spiked with 10 ng each of isotope-labeled internal standard mixture of all four target chemicals. Textiles were extracted with 5 mL of methanol by shaking in an orbital shaker at 180 strokes per min for 2 h. The mixture was centrifuged at 3500 g for 10 min (Eppendorf Centrifuge 5804, Hamburg, Germany), and the supernatant was transferred into a new PP tube. Residuals were extracted twice, and the extracts were combined. After concentration to near-dryness under a gentle nitrogen stream, 0.5 mL of 90% acetonitrile/5 mM ammonium formate buffer (pH = 4.0) (v/v) was added and filtered

6

Journal Pre-proof through a 0.2 μm nylon filter (Spin-X, Costar, Corning, NY, USA) prior to high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis. Chromatographic separation was achieved, using a Shimadzu LC-30 AD Series HPLC system (Shimadzu Corporation, Kyoto, Japan) connected to a Kinetex hydrophilic interaction liquid chromatography column (100 mm × 2.1 mm, 2.6 μm; Phenomenex, Torrance, CA, USA). Identification and quantification of target analytes were performed with an Applied Biosystems

of

API 5500 electrospray triple quadrupole-mass spectrometer (ESI-MS/MS) (Applied Biosystems,

ro

Foster City, CA, USA). Detailed information about instrumental analysis and compound specific

-p

analytical parameters are provided in the SI (Text S2, Table S2, and Figure S1).

re

2.3. Simulated laundry experiments

Simulated laundry experiments were conducted with all 77 textile samples to evaluate the

lP

removal rates of melamine derivatives from textiles during laundering. In the first experiment,

na

five square pieces of textile (2 ×2 cm2) were cut from each sample and placed in a 15 mL PP tube, and 5 mL of HPLC-grade water was added (hereafter referred to as water washing). The

ur

mixture was shaken in an orbital shaker at 180 strokes per min for 45 min, dewatered by

Jo

extrusion, and drip-dried at room temperature. The second set of experiments involved the use of a detergent for laundering (hereafter referred to as detergent washing). Newly purchased textile pieces were shaken in 5 mL of HPLC-grade water and 50 µL of detergent (97% plant-based ingredients, found to be free of melamine derivatives) for 45 min and then dewatered. The dewatered textile was cut into small pieces, extracted in methanol, and analyzed by HPLCMS/MS, as described above. 2.4. Quality assurance (QA)/quality control (QC)

7

Journal Pre-proof A 12-point standard calibration curve, with concentrations that ranged from 0.02 to 200 ng/mL, with regression coefficients of >0.995, was used for the quantification of target analytes by an isotope-dilution method. Textile samples with concentrations beyond the calibration range were diluted and reanalyzed. A midpoint calibration standard was injected after every 20 samples for checking instrumental drift in response factors. Sample-to-sample carryover of target analytes was monitored by the injection of a pure solvent (acetonitrile) after every 10 samples. Procedural

of

blanks were analyzed with each batch of 20 samples to determine contamination that arises from

ro

sample preparation and analytical steps. No background levels, except for melamine (<0.2

-p

ng/mL), were found in procedural blanks. Melamine concentrations in textile samples were

re

subtracted from blank values. This method was validated for accuracy and precision by replicate analysis of two fortified levels of analytes (i.e., 10 and 1000 ng) onto three select textile samples

lP

(n = 3 × 2 × 3). The average recoveries of analytes ranged from 85% (for ammeline) to 112%

na

(for melamine) with the relative standard deviation of <20%. The method quantification limits

Jo

ng/g for cyanuric acid.

ur

(MQLs) were 0.80 ng/g for melamine, 1.2 ng/g for ammeline, 0.50 ng/g for ammelide, and 1.5

3. Results and discussion

3.1. Melamine and its derivatives in textiles The rank order of detection frequency (df) of target analytes in textile was melamine (100%) = cyanuric acid (100%) > ammelide (83%) > ammeline (70%) (Table S3). The median concentrations of melamine, cyanuric acid, ammeline, and ammelide in the 77 textile samples were 53.0, 43.5, 3.42, and 4.04 ng/g, respectively (Table 1). Melamine was the abundant compound found in textiles and was detected at concentrations as high as 81,800 ng/g.

8

Journal Pre-proof Ammeline (maximum: 25,700 ng/g) and cyanuric acid (17,800 ng/g) also were found at elevated concentrations in select textile samples, whereas the highest concentration determined for ammelide was 550 ng/g (Table S3). In general, 13 out of 77 samples (17%) had Σmelamines (sum of four melamine derivatives) concentrations above 10,000 ng/g, and approximately onethird of the samples had concentrations above 1,000 ng/g. In comparison to previously reported concentrations of other emerging chemicals in textiles, the median concentrations of Σmelamines

of

(146 ng/g) were 3- to 140-fold higher than those reported for bisphenols, benzophenones,

ro

parabens, and benzothiazoles (1.02–51.1 ng/g) in raw textiles and infant clothing (Freire et al.,

-p

2019; Liu et al., 2017; Wang et al., 2019; Xue et al., 2017) but 1–2 orders of magnitude lower

re

than those reported for bisphenols in pantyhose (13,400 ng/g) (Li and Kannan, 2018) and phthalates in infant clothing (4,150 ng/g) (Li et al., 2019) (Table 1). Our results suggest that

lP

melamine contamination is ubiquitous in textiles. Melamine is widely used in the production of

na

water-soluble resins for application in wrinkle-free textiles (Schramm and Amann, 2019) and as flame retardants for the production of flame-resistant textiles (Kilinc, 2013).

ur

The contribution of each target compound (based on mean concentrations) to the sum

Jo

concentrations of all four derivatives measured in the textile samples is shown in Figure 1A. Melamine and cyanuric acid collectively accounted for 89% of the total concentrations, with melamine as contributing 52% and cyanuric acid, 37% of the total concentrations. In general, our results are in agreement with previous reports of melamine derivatives in sewage sludge, indoor dust, soil, and sediment (Zhu and Kannan, 2018b; Zhu et al., 2019a, 2019c, 2019d), in which melamine and cyanuric acid were the predominant compounds. Our earlier studies showed that melamine concentrations were significantly correlated with ammeline and ammelide concentrations in urine, infant formula, breast milk, dairy products, and

9

Journal Pre-proof foodstuffs but not with cyanuric acid (Zhu and Kannan, 2018a, 2018c, 2019a, 2019b; Zhu et al., 2019b). In this study, however, significant positive correlations were observed among melamine derivatives, including cyanuric acid, in textile samples (0.347< r < 0.862, p < 0.01; Figure 1B). This suggests that ammeline, ammelide, and cyanuric acid are present as impurities in melamine mixtures used in textiles or are formed during textile processing. 3.2. Removal rate of melamine derivatives during simulated laundering

of

Simulated laundry experiments were conducted to examine the removal rates of melamine

ro

derivatives from textiles. Median Σmelamines concentrations in textiles significantly decreased

-p

from 146 ng/g to 32.2 ng/g (p < 0.041) after water washing. Detergent washing decreased the

re

median concentrations of melamine, ammeline, ammelide, and cyanuric acid in textiles by 82–90% of the original concentrations (Table S3). There was no significant difference in melamine

lP

derivatives’ concentrations between water washing and detergent washing (p > 0.298; Figure 2).

na

In general, a single wash removed 76–90% of melamine derivatives from the original textile material (Figure 3). The removal efficiencies were not affected by fabric types or textile colors.

ur

High removal efficiencies may be attributed to high water solubilities (1.99–1,000 g/L at 25 °C)

Jo

of melamine derivatives. This also suggests that washing machine drains can be a significant source of melamine derivatives in the aquatic environment. It should be noted that melamine is used mainly as a resin that is cross-linked with formaldehyde in the textile industry (Merline et al., 2013). Our extraction method depicts only freely available melamine in textiles, and, therefore, our results may be an underestimate of actual amounts of melamine present in textiles. Further studies are needed to assess bound and polymeric forms of melamine and their toxicological significance. 3.3 Textile properties and melamine derivatives

10

Journal Pre-proof The measured concentrations of ∑melamines (ng/g) were compared between different categories of textiles, i.e., (A) raw textiles vs. infant clothing; (B) cotton vs. synthetic fabrics; (C) colored vs. white; and (D) socks vs. bodysuits (Figure 4). We found no significant differences in ∑melamines concentrations between raw textiles (mean: 7380 ng/g) and infant clothing (7420 ng/g) (p = 0.695; Figure 4), indicating that MRF is used during the production of fabric. Colored textiles (mean: 7670 ng/g) contained similar concentrations of melamine derivatives as those of

of

white ones (6000 ng/g; p > 0.789). In contrast, Xue et al. (2017) found higher BPA

ro

concentrations in colored clothes than in white clothes. Li and Kannan (2018) found higher

-p

concentrations of bisphenols in black pantyhose than in tan or khaki. Significantly higher

re

∑melamines concentrations were found in cotton textiles (mean: 10480 ng/g) than in synthetic textiles (1380 ng/g; p < 0.008). Because cotton fabrics are more likely to produce creases

lP

compared to synthetic textiles (Schramm and Amann, 2019), melamine-based resins may be

na

added to impart crease-resistant properties. Conversely, BPA concentrations were up to 72-fold higher in synthetic fibers than in cotton clothing (Freire et al., 2019; Xue et al., 2017). BPA is

ur

utilized for improving the elasticity and strength of synthetic fibers. The mean concentration of

Jo

∑melamines in infant clothing (10230 ng/g) was ~250 times greater than that found in socks (40.0 ng/g). In general, contamination profiles of melamine derivatives in textiles are different from those found for other EDCs in textiles. 3.4. Dermal exposure assessment for infants The dermal exposure dose to melamine and cyanuric acid, the two most important derivatives found in textiles, was calculated by using eq. 1 for infants at 0−<1, 1−<3, 3−<6, and 6−<12 months: EXPderm

𝐶×𝐷×𝑆𝐴×𝐹mig ×𝐹contact ×𝐹pen ×𝑇×𝑁 𝐵𝑊

11

(1)

Journal Pre-proof where EXPderm is the dermal absorption dose (ng/kg bw/day); C is the concentration of melamine and cyanuric acid measured in textiles (ng/g). The mean concentrations of target chemicals measured in the original and detergent-washed textile samples were used separately for the exposure assessment; D is the density of the textile (mg/cm2; estimated to be 22.4 mg/cm2) (Xue et al., 2017); SA is the skin surface area contacted by textiles, which was assumed to be the total body surface area of the infants for each of the four age groups, i.e., 2040, 2310, 2660, and 3160

of

cm2, respectively (U.S. Environmental Protection Agency [EPA], 2011); Fmig is the daily

ro

migration rate of chemicals to the skin (assumed to be 0.005 1/day) (Federal Institute for Risk

-p

Assessment [BfR], 2012); Fcontact is the fraction of skin contact area (assumed to be 1, unitless)

re

(BfR, 2012); Fpen is the penetration factor of chemicals into the body (assumed to be 0.01, unitless) (BfR, 2012); T is the contact time between the skin and textiles (assumed to be 1 day)

lP

(Rovira et al., 2015); N is the average number of events daily (assumed to be 1, 1/day) (Rovira et

na

al., 2015); and BW is the average body weight for infants, which were 4.8, 5.9, 7.4, and 9.2 kg for the above four categories, respectively (U.S. EPA, 2011).

ur

The calculated dermal exposure doses to melamine and cyanuric acid for infants are shown in

Jo

Table 2. Dermal melamine exposure doses from original textiles ranged from 1.89 ng/kg bw/day for 6−12-month-old infants to 2.34 ng/kg bw/day for newborns. Cyanuric acid exposure doses ranged from 0.175 to 0.217 ng/kg bw/day. Melamine and cyanuric acid exposure doses through textiles were approximately 10- to 30-fold and 500- to 2,000-fold lower than those reported for infants’ exposure via breast milk and formula consumption, respectively (Table 2) (Zhu and Kannan, 2018a, 2019b). Dermal exposure doses to melamine and cyanuric acid in infants decreased to less than 0.300 and 0.010 ng/kg bw/day, following a single laundering. Choi et al. (2010) recommended tolerable daily intakes (TDI) of 3,150 ng/kg bw/day for melamine and

12

Journal Pre-proof 2,500 ng/kg bw/day for cyanuric acid. Our calculated EXPderm values were at least 3–4 orders of magnitude lower than the recommended TDI values.

4. Conclusions We found that raw textiles and infant clothing contain measurable levels of melamine and cyanuric acid. The sum concentrations of four melamine derivatives in original textiles are on the

of

order of several tens to tens of thousands of nanograms per gram. Washing clothes removes

ro

melamine and its derivatives considerably, and, therefore, newly purchased clothing should be

-p

washed prior to use to avoid exposure to these potentially toxic chemicals. However, this may

re

not imply that the wrinkle-free properties are lost after the first laundry because melamine may be added to textiles in its polymeric form to impart wrinkle free or fire-resistant properties. In

lP

this regard, it is worth to state that our method extracted only freely available form of melamine

na

from textiles. Therefore, our results may be an underestimate of actual amounts of melamine present in textiles. The mean daily dermal exposure dose of melamine and cyanuric acid in

ur

infants from clothing was in the range of few nanograms per kilogram body weight. Compared to

Jo

other exposure routes (e.g., indoor dust ingestion, consumption of breast milk and infant formula), textiles are minor contributors to infant exposure to melamine and cyanuric acid. Nevertheless, high concentrations of melamine derivatives present in textiles suggest extensive use of this chemical in textile products and potential environmental release through laundering. This is the first evidence of the ubiquitous occurrence of melamine derivatives in textile samples in the United States. Supporting Information

13

Journal Pre-proof The SI contains additional information regarding chemicals and reagents (Text S1), instrument analysis (Text S2), and data analysis (Text S3) and detailed information on textile samples (Table S1), compound specific tandem mass spectrometric parameters for target analytes (Table S2), measured concentrations (ng/g) of melamine derivatives in textiles before and after laundering (Table S3), and typical chromatograms of standard and real textile samples (Figure S1).

of

Corresponding Author

ro

Kurunthachalam Kannan

re

E-mail: [email protected]

-p

Tel.: +1 518 474 0015. Fax: +1 518 473 2895.

Notes

na

lP

The authors declare no competing financial interest.

REFERENCES

ur

An, L., Li, Z.Y., Yang, Z., Zhang, T., 2011. Cognitive deficits induced by melamine in rats.

Jo

Toxicol. Lett. 206, 276-280.

Bolden, A.L., Rochester, J.R., Kwiatkowski, C.F., 2017. Melamine, beyond the kidney: A ubiquitous endocrine disruptor and neurotoxicant? Toxicol. Lett. 280, 181-189. Braekevelt, E., Lau, B.P.Y., Feng, S., Menard, C., Tittlemier, S.A., 2011. Determination of melamine, ammeline, ammelide and cyanuric acid in infant formula purchased in canada by liquid chromatography-tandem mass spectrometry. Food Addit. Contam. Part A Chem. Anal. Control Expo. Risk Assess. 28, 698-704. Chang, L.L., She, R.P., Ma, L.H., You, H., Hu, F.J., Wang, T.T., 2014. Acute testicular toxicity induced by melamine alone or a mixture of melamine and cyanuric acid in mice. Reprod. Toxicol. 46, 1-11.

14

Journal Pre-proof Choi, L., Kwak, M.Y., Kwak, E.H., Kim, D.H., Han, E.Y., Roh, T., 2010. Comparative nephrotoxicitiy induced by melamine, cyanuric acid, or a mixture of both chemicals in either sprague-dawley rats or renal cell lines. J. Toxicol. Env. Heal. A 73, 1407-1419. Dalal, R.P., Goldfarb, D.S., 2011. Melamine-related kidney stones and renal toxicity. Nat. Rev. Nephrol. 7, 267-274. Dorne, J.L., Doerge, D.R., Vandenbroeck, M., Fink-Gremmels, J., Mennes, W., Knutsen, H.K., 2013. Recent advances in the risk assessment of melamine and cyanuric acid in animal feed. Toxicol. Appl. Pharmacol. 270, 218-229.

of

European Food Safety Authority (EFSA), 2010. Scientific opinion on melamine in food and feed.

ro

EFSA J. 8, 1573-1717.

Federal Institute for Risk Assessment (BfR), 2012. Introduction to the problems surrounding textiles,

updated

BfR

opinion

No.

041/2012,

July

2012;

-p

garment

textiles.pdf (accessed Oct 23, 2019).

re

https://www.bfr.bund.de/cm/349/introduction-to-the-problems-surrounding-garment-

lP

Freire, C., Molina-Molina, J.M., Iribarne-Duran, L.M., Jimenez-Diaz, I., Vela-Soria, F., Mustieles, V., 2019. Concentrations of bisphenol a and parabens in socks for infants and

IHS

Markit,

2019.

na

young children in spain and their hormone-like activities. Environ. Int. 127, 592-600. Textile

chemicals:

Specialty

chemicals

update

program.

https://ihsmarkit.com/products/chemical-textile-scup.html/(accessed Oct 23, 2019).

ur

Ingelfinger, J.R.. 20018. Melamine and the global implications of food contamination. N. Engl. J.

Jo

Med. 359, 2745-2748.

Kilinc, F.S., 2013. Handbook of fire resistant textiles chapter 7: Flame resistant cotton. Woodhead Publishing, Cambridge. Li, A.J., Kannan, K., 2018. Elevated concentrations of bisphenols, benzophenones, and antimicrobials in pantyhose collected from six countries. Environ. Sci. Technol. 52, 1081210819. Li, H.L., Ma, W.L., Liu, L.Y., Zhang, Z., Sverko, E., Zhang, Z.F., 2019. Phthalates in infant cotton clothing: Occurrence and implications for human exposure. Sci. Total Environ. 683, 109-115. Liu, W.B., Xue, J.C., Kannan, K., 2017. Occurrence of and exposure to benzothiazoles and benzotriazoles from textiles and infant clothing. Sci. Total Environ. 592, 91-96. 15

Journal Pre-proof Merline, D.J., Vukusic, S., Abdala, A.A., 2013. Melamine formaldehyde: Curing studies and reaction mechanism. Polym. J. 45, 413-419. Papaspyrides, C.D., Pavlidou, S., Vouyiouka, S.N, 2009. Development of advanced textile materials: Natural fibre composites, anti-microbial, and flame-retardant fabrics. Proc. Inst. Mech. Eng. Pt. L J. Mater. 223, 91-92. Richardson, S.D., 2010. Environmental mass spectrometry: Emerging contaminants and current issues. Anal. Chem. 82, 4742-4774. Rovina, K., Siddiquee, S., 2015. A review of recent advances in melamine detection techniques.

of

J. Food Compos. Anal. 43, 25-38.

ro

Rovira, J., Nadal, M., Schuhmacher, M., Domingo, J.L., 2015. Human exposure to trace elements through the skin by direct contact with clothing: Risk assessment. Environ. Res.

-p

140, 308-316.

Schramm, C., Amann, A., 2019. Formaldehyde-free, crease-resistant functionalization of material

modified

by

a

hydrolyzed

re

cellulosic

dicarboxylic

acid

based

lP

alkoxysilane/melamine finishing system. Cellulose 26, 4641-4654. United States Environmental Protection Agency (US EPA), 2011. Exposure factors handbook.

na

EPA/600/R-09/052F; US Environmental Protection Agency: Washington, DC. Wang, L., Zhang, Y.L., Liu, Y.B., Gong, X.Y., Zhang, T., Sun, H.W., 2019. Widespread occurrence of bisphenol a in daily clothes and its high exposure risk in humans. Environ.

ur

Sci. Technol. 53, 7095-7102.

Jo

Xue, J.C., Liu, W.B., Kannan, K. Bisphenols, benzophenones, and bisphenol a diglycidyl ethers in textiles and infant clothing. Environ. Sci. Technol. 51, 5279-5286. Yang, Y., Xiong, G.J., Yu, D.F., Cao, J., Wang, L.P., Xu, L., 2012. Acute low-dose melamine affects hippocampal synaptic plasticity and behavior in rats. Toxicol. Lett. 214, 63-68. Yin, R.H., Wang, X.Z., Bai, W.L., Wu, C.D., Yin, R.L., Li, C., 2013. The reproductive toxicity of melamine in the absence and presence of cyanuric acid in male mice. Res. Vet. Sci. 94, 618-627. Zhu, H.K., Kannan, K., 2019a. Melamine and cyanuric acid in foodstuffs from the united states and

their

implications

for

human

https://doi.org/10.1016/j.envint.2019.104950.

16

exposure.

Environ.

Int.

DOI:

Journal Pre-proof Zhu, H.K., Lee S., Moon, H.B., Kannan, K., 2019a. Spatial and temporal trends of melamine and its derivatives in sediment from lake shihwa, south korea. J. Hazard. Mater. 373, 671-677. Zhu, H.K., Loganathan, B.G., Kannan, K., 2019b. Occurrence and profiles of melamine and cyanuric acid in bovine feed and urine from China, India, and the United States. Environ. Sci. Technol. 53, 7029-7035. Zhu, H.K., Halden, R.U., Kannan, K., 2019c. A nationwide survey of the occurrence of melamine and its derivatives in archived sewage sludge from the united states. Environ. Pollut. 245, 994-999.

of

Zhu, H.K., Kannan, K., 2018a. Continuing occurrence of melamine and its derivatives in infant

ro

formula and dairy products from the united states: Implications for environmental sources. Environ. Sci. Technol. Lett. 5, 641-648.

-p

Zhu, H.K., Kannan, K., 2018b. Distribution profiles of melamine and its derivatives in indoor dust from twelve countries and the implications for human exposure. Environ. Sci. Technol.

re

52, 12801-12808.

lP

Zhu, H.K., Kannan, K., 2018c. Inter-day and inter-individual variability in urinary concentrations of melamine and cyanuric acid. Environ. Int. 123, 375-381.

na

Zhu, H.K., Kannan, K., 2019b. Occurrence of melamine and its derivatives in breast milk from the united states and its implications for exposure in infants. Environ. Sci. Technol. 53, 7859-7865.

ur

Zhu, H.K., Wang, Y., Sun, H., Kannan, K., 2019d. Fertilizers as a source of melamine and

Jo

cyanuric acid in soils: A nationwide survey in china. Environ. Sci. Technol. Lett. 6, 55-61. Zhu, H.K., Kannan, K., 2019e. Occurrence and distribution of melamine and its derivatives in surface water, drinking water, precipitation, wastewater, and swimming pool water. Environ. Pollut. DOI: https://doi.org/10.1016/j.envpol.2019.113743.

17

Journal Pre-proof Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:

Jo

ur

na

lP

re

-p

ro

of

No known competing financial interests

18

Journal Pre-proof TABLE AND FIGURE LEGENDS

Tables: Table 1. Concentrations of melamine derivatives found in textile samples (this study) compared with other emerging chemicals reported in previous studies. Table 2. Mean dermal exposure dose (ng/kg bw/day) to melamine and cyanuric acid from textiles (this

of

study) in comparison with exposure doses (ng/kg bw/day) calculated through breastfeeding and formula

-p

ro

feeding for the U.S. infants reported in previous studies.

re

Figures:

lP

Figure 1. Composition profiles (A) and Spearman’s rank correlations (B) of melamine and its derivates in

na

textile samples collected from Albany, New York, USA.

Figure 2. Concentrations (ng/g) of melamine (A), ammeline (B), ammelide (C), and cyanuric acid (D) in

ur

original and water- or detergent-washed textiles

Jo

Figure 3. Removal rates (%) of melamine derivatives during water- and detergent-laundering Figure 4. Concentrations of ∑melamines (ng/g) in different categories of textiles: (A) raw textiles vs. infant clothing; (B) cotton vs. synthetic fabric; (C) colored vs. white; (D) socks vs. bodysuits

19

Journal Pre-proof Table 1. Concentrations of melamine derivatives found in textile samples (this study) compared with other emerging chemicals reported in previous studies.

U.S.

77

New and used clothing

China , Japan, Korea , Portu China gal,

24

Chile, Spain U.S. U.S.

ammelide

47.4

4.04

cyanuric acid

460

43.5

bisphenol A

366

10.7

bisphenol S

15.0

1.02

benzophenone-3

11.3

5.94

bisphenol F diglycidyl bisphenolether A

13.6

2.44

72.1

26.9

bisphenol S

44.0

7.38

∑7bisphenols

225000

13400

∑5benzophenones

62200

20.5

∑9parabens

2950

145

di-(2-ethylhexyl) phthalate dibutyl phthalate

-

2740

-

1510

di-iso-butyl phthalate bisphenol A

-

690

-

20.5

ethyl-paraben

-

3.09

benzothiazoles

117

51.1

Jo

ur

79

3.42

na

clothing

Raw textiles and infant clothing

1990

lP

Infant cotton

32

ammeline

China

74

Socks for infants and children

median (ng/g) 53.0

U.S.

93

Pantyhose

melamine

mean (ng/g) 4900

of

77

Target analytes

ro

Raw textiles and infant clothing

Count ry

-p

Raw textiles and infant clothing

Sample size

re

Sample type

20

reference

This study

(Xue et al., 2017)

(Wang et al., 2019) (Li and Kannan, 2018)

(Li et al., 2019)

(Freire et al., 2019) (Liu et al., 2017)

Journal Pre-proof

Table 2. Mean dermal exposure dose (ng/kg bw/day) to melamine and cyanuric acid from textiles (this study) in comparison with exposure doses (ng/kg bw/day) calculated through breastfeeding and formula feeding for the U.S. infants reported in previous studies.

Jo

ur

na

lP

re

-p

ro

of

Melamine Cyanuric acid Melamine Cyanuric acid Detergent Detergent a b Age group Original Original Breast Formula Breast Formula laundered laundered textile textile feeding feeding feeding feeding textile textile newborns (<1 month) 2.34 0.291 0.217 0.009 30.6 60.8 161 473 1 to <3 months 2.15 0.267 0.200 0.008 28.6 67.3 150 523 3 to <6 months 1.98 0.246 0.184 0.007 22.4 52.5 118 409 6 to 12 months 1.89 0.235 0.175 0.007 16.9 28.2 88.8 219 a,b : previously reported daily intakes (ng/kg bw/day) of melamine and cyanuric acid through breastfeeding and formula feeding for the U.S. Infants, respectively (Zhu and Kannan, 2018a, 2019b).

21

Figure 1

Figure 2

Figure 3

Figure 4