PAPER IN FOREFRONT

Quinolines in clothing textiles—a source of human exposureand wastewater pollution?

Giovanna Luongo & Gunnar Thorsén & Conny Östman

Received: 29 November 2013 /Revised: 28 January 2014 /Accepted: 10 February 2014 /Published online: 7 March 2014# Springer-Verlag Berlin Heidelberg 2014

Abstract A production process in which the use of var-ious types of chemicals seems to be ubiquitous makesthe textile industry a growing problem regarding bothpublic health as well as the environment. Among severalsubstances used at each stage, the present study focuseson the quinolines, a class of compounds involved in themanufacture of dyes, some of which are skin irritantsand/or classified as probable human carcinogens. Amethod was developed for the determination of quinolinederivatives in textile materials comprising ultrasound-assisted solvent extraction, solid phase extraction clean-up, and final analysis by gas chromatography/mass spec-trometry. Quinoline and ten quinoline derivatives weredetermined in 31 textile samples. The clothing samples,diverse in color, material, brand, country of manufacture,and price, and intended for a broad market, were pur-chased from different shops in Stockholm, Sweden.Quinoline, a possible human carcinogen, was found tobe the most abundant compound present in almost all ofthe samples investigated, reaching a level of 1.9 mg in asingle garment, and it was found that quinoline and itsderivatives were mainly correlated to polyester material.This study points out the importance of screening textileswith nontarget analysis to investigate the presence ofchemicals in an unbiased manner. Focus should be pri-marily on clothing worn close to the body.

Keywords Quinoline . Clothing . Textiles . Garment . Gaschromatography/mass spectrometry

Introduction

Textile production is a long, multistep process involving theuse of many chemical compounds, not all harmless, in order toprovide goods of different characteristics and functionalities.Although most manufacturing chemicals added during theprocess of converting fabrics into textiles are rinsed out,residual levels may remain in the finished products and mayeventually be released during use by consumers. Controlmeasures for many hazardous compounds exist in theEuropean Union (EU), but the continuing relocation of textileproduction to countries outside Europe with fewer restrictionsregarding environmental and work environment standards, aswell as complex raw material supply chains and the largenumbers of operators involved in the different productionsteps, makes control very difficult. Rapid changes in fashiontrends also lead to fluctuation in the types of prints and dyes,i.e. in the types of chemicals, used during the productionprocess. It is therefore difficult to find information on whichtoxic substances are handled during the production processand to estimate possible health effects [1].

Textiles are present in almost every indoor location andsome goods, such as clothing, are worn in direct contact withthe skin. This is the largest organ of the human body, account-ing for approximately 12–15 % of body weight. It exposes alarge area to the environment, it is permeable to molecules withspecific size and polarity, and thus provides a potential route forhuman exposure to chemicals [2–5]. An in vivo experimentperformed by Blum et al. [6] in 1978 demonstrated the migra-tion and dermal absorption of tris (2,3‐dibromopropyl) phos-phate from a clothing textile. Several studies have also corre-lated chemicals present in textiles with the risk of contactallergy [7–9]. A few studies of textile materials have beendirected toward pigments such as azo dyes [10] and somecommon environmental pollutants, such as polyfluorinatedand perfluorinated compounds, organophosphorus pesticides,

G. Luongo :G. Thorsén : C. Östman (*)Department of Analytical Chemistry, Arrhenius Laboratory,Stockholm University, 106 91 Stockholm, Swedene-mail: conny.ostman@anchem.su.se

Anal Bioanal Chem (2014) 406:2747–2756DOI 10.1007/s00216-014-7688-9

polycyclic aromatic hydrocarbons, and dioxins [11–17], andoccupational exposure has also been studied [9]. Despite thelarge number of chemicals involved in the production of textile-based clothes, only a few (e.g., nonylphenol ethoxylate andphthalates) have recently been shown to be present in consumergarments [18].

This study focuses on the presence of quinoline and itsmonomethyl and dimethyl derivatives, organic bases belong-ing to the group of polycyclic aromatic nitrogen compounds.These compounds occur naturally in petroleum and coal tar,but have also been detected in tobacco smoke, air particulatematter, groundwater, as well as lake and marine sediments[19–22]. Quinoline derivatives are constituents of pharmaceu-ticals with several medicinal purposes [23–25], but also wide-ly used in chemical treatment of wood and as additives infoods and cosmetics [26]. Their industrial application relatedto textiles is the manufacture of dyes [27], and their presencein wastewater from the production of dyes and intermediateindustry products has been reported [28, 29].

Bioassay studies have provided evidence that quinolineand some of its methylated isomers induce hepatocellularcarcinosarcoma in mice and rats when administered orally[30, 31]. When administered topically, quinoline, 4-methylquinoline, and 8-methylquinoline have exhibitedtumor-initiating activity on SENCAR mouse skin [32].Along with several monomethyl derivates, quinoline has beenshown to be mutagenic toward Salmonella typhimurium aftermetabolic activation [33, 34]. Dimethylquinolines have beenfound to be moderately toxic in the aquatic environmentaccording to both Microtox and rainbow trout assays [35].Quinoline can also be absorbed through skin and can causeskin and eye irritation, have effects on the liver and retina, andcause lethargy and respiratory depression, and it is classifiedas a possible human carcinogen [36].

On the basis of available information, it is concluded thatquinoline is a potential hazard to human health as well as theenvironment. In the present study, quinoline, isoquinoline,s e v e n me t h y l q u i n o l i n e d e r i v a t i v e s , a n d twodimethylquinoline derivatives, which are present as impuritiesin commercial quinoline products, were investigated in 31samples of clothing textiles purchased on the Swedish con-sumer market. They were manufactured in at least 17 differentcountries, were intended for a broad market, and were diversein color, material, and brand.

Materials and methods

Materials

The solvents used in this study, n-hexane, acetone, and di-chloromethane, were all of pesticide residue grade, with apurity greater than 99.8 %, and were purchased from Fisher

Scientific (Gothenburg, Sweden), Merck Millipore(Darmstadt, Germany), and Fluka/Sigma-Aldrich (St. Louis,MO, USA) respectively. The quinoline compounds acquiredare listed in Table 1. The Isolute® C18(EC) 200 mg/3 ml end-capped C18 solid phase extraction (SPE) cartridge was obtain-ed from Biotage (Uppsala, Sweden), and the Chromabond®C18ec 200 mg end-capped C18 SPE cartridge was purchasedfrom Macherey-Nagel (Düren, Germany).

Clothing textile samples

The investigation included 31 clothing textile itemsrepresenting a variety of colors, materials, countries of origin,brands, and prices. They were purchased between September2011 and October 2012 from several authorized retailers inStockholm. These garments included a number of differenttypes of clothes, from T-shirts and jeans to dresses, designatedfor a broad market. They were manufactured in at least 17different countries for 17 global fashion brands, although fortwo of them the country of manufacture could not be identi-fied. Among the textiles were 17 blue clothes made of differ-ent materials, 11 clothes for babies, toddlers, and children, andten clothes made of material containing more than 85 %polyester. Three of the samples were made of organic cottonand labeled with EU or Nordic Ecolables. All of the garmentswere stored in the original packaging from the shops untilanalysis. Information on the samples is given in Table 2.

Table 1 Names, Chemical Abstracts Service (CAS) numbers, molecularweights, and suppliers of the target analytes

Compound CAS no. Molecularweight

Supplier

Q 91-22-5 129 Merck, Germany

Iso-Q 119-65-3 129 Aldrich, Beerse Belgium

2-MQ 91-63-4 143 Aldrich, China

3-MQ 612-58-8 143 Aldrich, USA

4-MQ 491-35-0 143 SAFC, USA

6-MQ 91-62-3 143 Fluka, Sweden

7-MQ 612-60-2 143 Fluka, Sweden

8-MQ 611-32-5 143 Aldrich, Japan

1-iso-MQ 1721-93-3 143 Aldrich, USA

2,6-DMQ 877-43-0 157 ICN·K&K, USA

2,4-DMQ 1198-37-4 157 ICN·K&K, USA

Quinoline-d7 (IS) 34071-94-8 136 Fluka, Sweden

1-Indanone (VS) 83-33-0 132 Fluka, Sweden

Q quinoline, iso‐Q isoquinoline, 2‐MQ 2‐methylquinoline, 4‐MQ 4‐methylquinoline, 1‐isoMQ 1‐methylisoquinoline, 6‐MQ 6‐methylquinoline, 3‐MQ 3‐methylquinoline, 7‐MQ 7‐methylquinoline, 8‐MQ 8‐methylquinoline, 2,4‐DMQ 2,4‐dimethylquinoline, 2,6‐DMQ 2,6‐dimethylquinoline, IS internal standard, VS volumetric standard

2748 G. Luongo et al.

Extraction and cleanup

About 1 g of each garment was cut into 5mm×5mmpieces andweighed for the extraction. Print and accessories on the clotheswere excluded. Fully deuterium substituted quinoline (quino-line-d7) was used as an internal standard and was added to thesample before extraction. Each sample was extracted twice with5 ml dichloromethane for 10 min at 25ºC using ultrasound-assisted solvent extraction in a Sonorex Digital 10 P ultrasonicbath (Bandelin Electronic, Berlin, Germany). The two extractswere combined and the volume was reduced to about 1.0 ml bya gentle stream of nitrogen at room temperature.

The raw extracts had high contents of fibers and particu-lates, which had to be removed prior to analysis. A number ofsyringe filters were tested for removal of this material, but theyall gave rise to contamination in the subsequent analysis bygas chromatography (GC)/mass spectrometry (MS). Instead, a

Chromabond® C18ec 200 mg SPE cartridge was selected forthe filtration step. This phase has weak retention for slightlypolar compounds such as the quinolines when dichlorometh-ane is used. Each cartridge was washedwith 10ml hexane and5 ml dichloromethane in order to remove impurities and wetthe cartridge sorbent. The cartridge was kept wet and thesample extract was loaded. Elution volumes were tested forthe SPE, and 10ml dichloromethane was sufficient to elute theextract. The volume of the eluate was reduced to about 1.0 mlby a gentle stream of nitrogen at room temperature, spikedwith 1-indanone as a volumetric standard, and 1 μl wasinjected into the GC/MS system.

Gas chromatography/mass spectrometry

The GC/MS system consisted of a 6890N gas chromatograph(Agilent Technologies, Palo Alto, CA, USA) connected to a

Table 2 Number, color, material,type, and country of manufactureof the samples

a EU Ecolabelb Nordic Ecolabel

No. Color Material Type Country

1 Black 100 % cotton T‐shirt Bangladesh

2 Blue 100 % polyester Sports T‐shirt Philippines

3 White 95 % cotton, 5 % elastane T‐shirt Bangladesh

4 Red 100 % cotton Sports T‐shirt Georgia

5 Orange 100 % cotton T‐shirt Portugal

6 Rose 100 % cotton Baby body China

7 Blue 100 % organic cottona Baby body Bulgaria

8 White 100 % organic cottonb Baby body Latvia

9 Red 100 % organic cottonb Baby body Lithuania

10 Pink 100 % cotton Sports T‐shirt India

11 Blue 100 % polyester T‐shirt Indonesia

12 Blue 100 % polyester T‐shirt Indonesia

13 Blue 99 % cotton, 1 % elastane Jeans Bangladesh

14 Blue 100 % cotton Jeans Bangladesh

15 Blue 75 % cotton, 20 % polyamide, 5 % elastane Shirt Turkey

16 Blue 100 % cotton T‐shirt India

17 Blue 85 % polyester, 15 % elastane Dress Cambodia

18 Blue 100 % cotton T‐shirt China

19 Blue 78 % cotton, 20 % polyester, 2 % elastane Jeans Turkey

20 Blue 100 % polyester Sports T‐shirt Switzerland

21 Blue 100 % organic cotton T‐shirt India

22 Black 100 % polyester Dress India

23 Red 100 % polyester Sports T‐shirt Georgia

24 Pink 100 % polyester Sports T‐shirt China

25 Yellow 100 % polyester Sports T‐shirt Cambodia

26 White 100 % polyester Soccer shorts Egypt

27 Blue 100 % cotton Jeans Unknown

28 Blue 98 % cotton 2 % elastane Jeans Italy

29 Blue 100 % cotton Jeans Unknown

30 Pink 98 % cotton 2 % elastane Jeans Pakistan

31 Blue 86 % cotton, 12 % polyester, 2 % elastane Jeans Poland

Quinolines in clothing textiles—a source of human exposure 2749

5975C mass spectrometer (Agilent Technologies). The gaschromatograph was equipped with a programmable tempera-ture vaporizer injector and a model 7683 autosampler (bothfrom Agilent Technologies). The temperature program for theprogrammable temperature vaporizer was 70 °C for 0.5 minfollowed by a ramp of 700 °C/min to 310 °C, which wasmaintained for 8 min. The GC column oven temperatureprogram was 50 °C for 1 min followed by two ramps,9 °C/min to 170 °C and 20 °C/min to a final temperature of300 °C, which was kept for 3 min. The gas chromatographwas equippedwith a J&WHP5-MS capillary column (AgilentTechnologies; length 30 m, inner diameter 0.25 mm, filmthickness 0.25 μm), and helium was used as the carrier gasat a linear flow rate of 45 cm/s in constant-flow mode. The ionsource temperature was set to 300 °C, and the quadrupoletemperature was set to 150 °C. Ionization of the moleculeswas done using electron ionization at 70 eV, and the analysiswas performed in selected ionmonitoringmode. Two ions, themolecular ion and a second, qualifier ion with high intensity,were selected for all the analytes and for the internal standard.A total ion chromatogram of a standard mixture at a concen-tration around 1 ng/μl is shown in Fig. 1. Ions 129 and 102 Thwere chosen for quinoline and isoquinoline, ions 143 and115 Th were chosen for the methylquinoline isomers, ions157 and 115 Th were chosen for the dimethylquinoline iso-mers, and ions 136 and 108 Th were chosen for the internalstandard, quinoline-d7.

Results and discussion

SPE selectivity

Two end-capped C18 phases [Isolute® C18(EC) 200 mg andChromabond® C18ec 200 mg] were tested for use in thecleanup step. A textile sample in which the compounds ofinterest could not be detected was used as a blank sampleduring the SPE selectivity test and the method validationprocedure. Extraction recoveries from the two SPE phaseswere tested in triplicate using a blank sample extract spikedwith each analyte at concentrations of around 1 ng/μl. TheChromabond® C18ec phase exhibited good recoveries for allthe analytes, with yields higher than 85 % when 10 ml dichlo-romethane was used for the elution. Similar recoveries werealso found using the Isolute® C18(EC) phase for most ofthe compounds. However, there were two exceptions:1-methylisoquinoline and 2,4-dimethylquinoline. These com-pounds exhibited recoveries of 48 % and 60 %, respectively, asignificant difference from the rest of the quinoline deriva-tives. Even though both the SPE phases consisted of end-capped octadecylsilica, they showed this large difference inyield of these two specific compounds. A probable explana-tion for this is that both 1-methylisoquinoline and 2,4-dimethylquinoline have methyl groups instead of hydrogenatoms at the position next to the nitrogen atom in the ringsystem, and 2,4‐dimethylquinoline has one more methyl

Fig. 1 Gas chromatography/mass spectrometry selected ion monitoring (SIM) chromatogram of the quinoline derivative standard mixture. Abbrevi-ations as in Table 1

2750 G. Luongo et al.

group attached to the same ring. This will partly shield the freeelectron pair of the nitrogen from interacting with the sur-roundings, making these molecules less polar than the otherquinoline derivatives. The stronger retention of these com-pounds on the Isolute® C18(EC) phase indicates that thisphase has a more efficient deactivation from the end-cappingcompared with the Chromabond® C18ec phase.

Method validation

The extraction efficiency was evaluated by exhaustive extrac-tion of several textile samples, using three organic solventswith different polarity: hexane, dichloromethane, and acetone.It was shown that two extractions with dichloromethane weresufficient to obtain more than 99 % yield for a number oftarget analytes.

Calibration curves were obtained using dichloromethanesolutions containing a mixture of all the quinolines investigat-ed. A set of solutions with different concentrations of theanalytes and a constant concentration of the deuterated inter-nal standard were used for the calibration. The area of eachanalyte normalized to the area of the internal standard wasplotted against their concentrations.

Two calibration curves at different concentrations wereused. Each curve consisted of six calibration points, analyzedin duplicate, covering the range from 0.001 to 0.10 ng/μl forthe low-range calibration curve and from 0.01 to 1 ng/μl forthe high-range calibration curve. Both calibration curves hadcoefficients of determination, R2, greater than 0.992 for thelinear regression (Table 3).

Extracts of samples free from quinolines were fortified withthe analytes at two concentrations, and were included in eachanalysis batch as quality-control samples.

Since quinolines have the possibility to be ubiquitous pol-lutants, blanks were run before and alongside each set ofsamples to assess that no contamination was present. Whenrunning samples of polyester extracts with a high content ofquinolines, the number of blanks were increased to eliminatethe risk of carry over effects.

The recoveries of quinoline and quinoline derivatives fromtextiles were determined by analyzing a fortified blank sampleat two concentrations, 20 pg and 1 ng. The recoveries were inthe range from 82 to 106 % (n=3).

The limit of detection (LOD) was determined from fiveblank analysis and replicate injections of 1 pg of the individualquinoline derivatives. The detection limit was calculated asthe mean value of the blank plus three times the standarddeviation from the measurements at 1 pg, and the limit ofquantification (LOQ) was determined in the same way usingten times the standard deviation. The detection limit rangedfrom 0.4 to 3.4 pg (n=5), and the corresponding quantificationlimit ranged from 1.3 to 11 pg injected for the differentanalytes. When 1 g of garment samples was used and the finalsample extract was dissolved in 1.0 ml, this detection limitcorresponded to a method detection limit (MDL) of 0.4–3.4ng/g garment, which was found to be satisfactory (Table 3).

Precision and accuracy were evaluated in terms of therelative standard deviation (RSD) and relative errors whendetermining the concentrations in spiked blank samples con-taining each analyte at two concentrations: 20 pg/g and 1 ng/g(n=3). The RSD for all the compounds investigated was in therange from 1 to 8 % at the 1-ng level, and was between 2 and4 % at the 20-pg level. The relative error, measured as thedeviation from the spiking concentration of the blank sample,was 10% or less for all analytes at both concentrations, exceptfor both dimethylquinolines at the 1-ng level, where theydemonstrated a relative error of 14 and 15 %, respectively.

Table 3 Method detection limit(MDL), relative standard devia-tion (RSD), and relative error ofthe analysis at low and highlevels, and coefficients of deter-mination (R2) for the calibrationcurves at low and highconcentrations

MDL (ng/g) 20 pg injected 1 ng injected Low High

RSD (%) Error (%) RSD (%) Error (%) R2 R2

Q 0.8 2 6 1 3 0.998 0.998

Iso-Q 3.4 2 2 2 6 0.993 0.999

2-MQ 1.2 2 10 2 2 0.996 0.998

4-MQ 0.4 2 10 2 1 0.996 0.998

1-iso-MQ 2.1 1 10 4 4 0.992 0.999

6-MQ 0.7 2 8 4 <1 0.998 0.998

3-MQ 1.1 2 <1 4 1 0.998 0.998

7-MQ 1.3 2 2 5 1 0.996 0.997

8-MQ 1.0 2 2 6 2 0.997 0.997

2,6-DMQ 1.2 4 6 7 14 0.993 0.997

2,4-DMQ 1.7 4 10 8 15 0.993 0.998

Quinolines in clothing textiles—a source of human exposure 2751

The larger errors in these two cases are most probably due tothe 1-ng spiking concentration being at the high end of thecalibration curve, where fragmentation was less reproducible.The relative error, RSD, and coefficients of determination forthe calibration curves for the compounds are summarized inTable 3.

Quinolines in clothing textiles

The sampled garments were analyzed for the content of quin-oline and ten of its derivatives (Table 4). Quinolines weredetected in 29 of the 31 samples, with quinoline being thedominating compound, constituting up to around 50 % of thetotal amount of quinolines. In five samples the concentrationof quinoline was below the LOQ but above the LOD. Sevenof the samples had quantifiable levels for all the quinolinecompounds, with the exception of 1-isomethylquinoline.On average, isoquinoline accounted for 13 % of the totalamount, followed by 2‐methylquinoline with 7 %, and1‐methylisoquinoline (less than 1 %) was the least abundantof the detected compounds. The highest amount of quinolinedetected in a garment was 35,600 ng/g, corresponding to atotal amount of 4.1 mg in the entire piece of clothing. Thequinolines showed similar concentration profiles in the differ-ent samples (Fig. 2). This similarity in the concentrationprofiles indicates that quinolines are not added to the textilesas single compounds, but are added as a low-purity industrialchemical being a mixture of isomers.

Quinoline was detected in all garments made from 100 %polyester, and the highest levels were found in these samples.The concentrations in these garments ranged from 26 to16,700 ng/g, with a mean concentration of 4,700 ng/g. Thismean concentration was more than 100 times higher than theaverage quinoline concentration in blended cotton garmentsand around 600 times higher than in the 100 % cotton gar-ments. The highest concentration of quinoline was detected ina short-sleeved men’s sports T-shirt. This blue, 100 % poly-ester garment weighed 115 g, giving a total amount of 1.2 mgin the T-shirt. The second most abundant compound wasisoquinoline, reaching concentrations up to 4,400 ng/g, corre-sponding to a total amount of 0.5 mg in the entire garment.Among the polyester garments, a blue blouse made inIndonesia showed the highest total concentration of quinolinederivatives, 35,600 ng/g, corresponding to a total amount of4.1 mg in the garment and a skin exposure of 249 ng quino-lines per square centimeter of garment. Sample 2, a light-blueT-shirt manufactured in the Philippines, had the secondhighest concentration, with a total quinoline derivatives con-tent of 27,900 ng/g, corresponding to an area concentration of320 ng/cm2 for the quinoline derivatives and 187 ng/cm2

solely for quinoline. High levels were also found in a pinkT-shirt for children made in China, with a total quinolinecontent of 7,260 ng/g (70 ng/cm2).

In the clothes made of 100 % cotton, quinoline reached aconcentration of 33 ng/g, with an average of 8 ng/g. In sixof these 14 cotton clothes, the concentration of quinolinewas below the detection limit. Sample 9, a red baby bodymade in Lithuania having the Nordic Ecolabel, had thehighest quinoline concentration (33±2)ng/g of all the cot-ton garments. A pair of blue jeans, sample 27, sold as awell-known brand but with unknown origin had the secondhighest quinoline concentration, (25±2)ng/g. The otherquinoline derivatives were below the quantification limitor detection limit in the cotton samples, with the exceptionof sample 9.

Blended-material garments showed a higher mean con-centration of quinolines compared with the samples made ofpure cotton. The highest concentration of quinoline itselfwas 180 ng/g, which was found in a pair of blue women’sjeans made of 99% cotton and 1% elastin (sample 13).Sample 17, a blue blouse made from a mix of artificial fibers(85% polyester and 15 % elastin) and manufactured inCambodia, showed the second highest level for all the quin-oline derivatives.

To search for pattern differences, the obtained data werenormalized to the quinoline concentration, and principal com-ponent analysis (PCA) was performed. Samples for which noquinoline derivatives were found, mainly cotton garmentswith the exception of sample 9, had no relevance in theanalysis and were excluded. For the others, no pattern differ-ence was observed.

Possible correlations between the content of quinolines andcharacteristics of the clothes such as color, material, brand, andcountry of origin were explored by conducting PCA withoutdata pretreatment. No correlations to color, country of manu-facture, or brand were found. However, PCA indicated acorrelation with the material in the clothes. Samples made of100 % polyester were clearly distinguished from the others byPCA. The loadings plot showed that quinoline had the stron-gest influence on clustering, with an explained variance of99 %. Furthermore, quinoline derivative concentrations weredependent on the amount of quinoline and strongly correlatedwith each other (Fig. 3). Two samples, samples 2 and 12, had astrong influence on the PCA model. When these extremesamples were removed and the data were recalculated, cottongarments were still clustered compared with the polyester ones,which were more spread out. This suggests that the content oftarget compounds in the clothes depends on the material used.A t-test for unequal variances showed that the average con-centration of the polyester garments was significantly differentfrom that of the garments made of 100 % cotton (p=0.056),modified cotton (p=0.057), and organic cotton (p=0.056). Apossible explanation is that the most common dye sensitizersbelong to the disperse dyes, many based on quinoline, whichare used to color synthetic textile materials based on polyester,acrylic, acetate, and polyamide fibers [37].

2752 G. Luongo et al.

Table4

Concentratio

n(ng/g)

ofquinolineandtenquinolinederivativ

esin

clothing

textile

samples

(n=3)

Sample

QIso-Q

2-MQ

4-MQ

1-iso-MQ

6-MQ

3-MQ

7-MQ

8-MQ

2,6-DMQ

2,4-DMQ

17.6(±0.2)

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

216,300

(±200)

3,200(±300)

2,400(±260)

1,110(±10)

190(±60)

920(±40)

580(±60)

1,100(±70)

640(±20)

400(±10)

940(±60)

35.5(±0.4)

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

414

(±1)

ND

Det

ND

ND

ND

ND

ND

ND

ND

ND

5Det

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

6Det

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

7ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

8Det

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

933

(±2)

Det

9(±1)

Det

ND

12(±4)

Det

5(±1)

Det

ND

Det

103.1(±0.2)

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

119,000(±700)

2,200(±170)

1,600(±130)

1,000(±70)

120(±10)

830(±50)

590(±30)

1,000(±40)

460(±30)

260(±6)

510(±20)

1216,700

(±300)

4,400(±700)

2,600(±400)

1,900(±300)

230(±30)

2,100(±300)

1,600(±200)

2,600(±400)

1,200(±200)

690(±100)

1,600(±300)

13180(±7)

23(±2)

22(±1)

2.3(±0.2)

ND

8(±1)

10(±2)

9(±1)

8.7(±0.4)

Det

7.7(±0.6)

1411

(±1)

ND

Det

ND

ND

ND

ND

ND

ND

ND

ND

1510

(±1)

ND

Det

ND

ND

Det

ND

ND

ND

ND

ND

16Det

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

17160(±20)

24(±1)

17(±1)

3.1(±0.4)

ND

6.6(±0.7)

Det

3.9(±0.5)

Det

5.7(±0.2)

11(±2)

188.1(±0.1)

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

1938

(±2)

Det

7(±2)

Det

ND

8(±2)

5(±1)

4(±1)

Det

ND

ND

20133(±2)

47(±5)

20(±1)

7.2(±0.3)

Det

24(±1)

15(±1)

28(±1)

16(±1)

17(±1)

20(±2)

21ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

22127(±2)

58(±3)

24(±1)

11(±1)

Det

32(±5)

13(±2)

40(±4)

23(±1)

9(±1)

36(±1)

2326

(±2)

Det

Det

ND

ND

ND

Det

ND

ND

ND

ND

243,300(±300)

980(±100)

680(±60)

370(±20)

56(±8)

390(±40)

260(±20)

440(±50)

240(±25)

200(±20)

290(±50)

251,500(±80)

250(±50)

110(±7)

60(±6)

Det

66(±10)

47(±8)

67(±20)

33(±10)

15(±5)

29(±8)

2655

(±5)

14(±3)

5.5(±0.3)

ND

ND

3.8(±0.5)

Det

Det

ND

Det

Det

2725

(±2)

ND

Det

ND

ND

Det

ND

ND

ND

ND

ND

289(±1)

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

293.9(±0.4)

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

30Det

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

317.9(±0.3)

ND

ND

ND

ND

ND

ND

ND

ND

ND

ND

Detdeterm

ined,N

Dnotd

etermined

Quinolines in clothing textiles—a source of human exposure 2753

Conclusions

Quinoline and ten quinoline derivatives were determined in31 clothes. Quinoline was found to be present in 25 samples

at levels up to 1.9 mg in a single garment, and up to 4.1 mgwhen all the quinoline derivatives determined were includ-ed. The presence of quinoline derivatives was correlated tothe use of polyester fibers in the garments, and substantial

Fig. 3 a Principal componentanalysis (PCA) scores plot ofquinolines in samples made ofpolyester (PE), blended material(Mix), and cotton (CT). b PCAloadings plot of quinolines insamples made of polyester (PE),blended material (Mix), andcotton (CT). Abbreviations as inTable 1

Fig. 2 Concentration profiles ofthe quinoline derivativesnormalized to quinoline.Abbreviations as in Table 1

2754 G. Luongo et al.

differences were found between garments made from poly-ester and garments made from pure cotton as well as cottonblended with synthetic materials. An interesting observa-tion is that sample 9, a baby body made of “organic cotton”and marked with the Nordic Ecolabel, showed the highestquinoline concentration among the garments made exclu-sively from cotton.

This study suggests that clothing textiles are a possibleroute of human exposure to quinolines as well as release ofthese compounds into the environment. In a person wearinggarments containing quinoline and its derivatives, the skinis exposed to a large surface area of clothing containing acompound that can possibly be absorbed through the skin.Quinoline can cause skin irritation and is classified by theUS Environmental Protection Agency as a group 2B com-pound, a probable human carcinogen [36]. In a report from2013, the Swedish Chemicals Agency [38] surveyed anal-yses of textiles during the years 2005–2012. There had beenfew studies of chemicals in clothing, and these were onlyfocused on a couple of specific, regulated chemicals. Theresults for quinolines presented in this article, as well as in astudy on benzothiazoles and benzotriazoles to be publishedseparately, demonstrate the importance of screening textileswith nontarget analysis to investigate in an unbiased man-ner the presence of potentially harmful chemicals. Focusshould be on clothing worn close to the body and oncompounds present in textiles which have the potential forhuman exposure to be able to estimate their conceivablehealth effects. The clothes investigated originated from atleast 17 countries, and many were of brands with world-wide distribution and retail, pointing out that thesechemicals are of worldwide concern. Another matter toinvestigate is the possible washout of these compounds intohousehold wastewater.

Acknowledgement Meng Hu is acknowledged for the initial work onthe present study.

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Giovanna Luongo is a graduatestudent in the Department of An-alytical Chemistry, StockholmUniversity. Her research interestis method development for theidentification and quantificationof hazardous compounds in tex-tile materials and wastewatersamples.

Gunnar Thorsén is a researchscientist in the Department of An-alytical Chemistry, StockholmUniversity. He is active in re-search concerning glycan analysisof serum proteins and therapeuticb iopha rmaceu t i ca l s us ingmicrofluidic techniques in combi-nation with mass spectrometry.Another research interest is theidentification and determinationof organic compounds in variousmatrices, such as textiles or envi-ronmental samples. He has previ-ously worked with development

of centrifugal microfluidic systems and trace-level analysis of smallbioactive compounds using capillary electrophoresis.

Conny Östman is an associateprofessor, researcher, and seniorlecturer in the Department of An-alytical Chemistry, ArrheniusLaboratories of Natural Sciences,Stockholm University. He hasbeen working for several years inthe field of the analytical chemis-try of polycyclic aromatic com-pounds, plasticizers, and organo-phosphates in work environmentsand indoor air. At present, hiswork is focused on breath analy-sis, chemicals in clothes, and thechemistry of phototherapy for oral

bacteria. His is an expert in air sampling, sample preparation, gas chro-matography, high-performance liquid chromatography, gas chromatogra-phy–mass spectrometry, liquid chromatography–mass spectrometry, liq-uid chromatography–gas chromatography, and liquid chromatography–gas chromatography–mass spectrometry.

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