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Benzothiazole, benzotriazole, and their derivates in clothing textiles—a potential source of environmental pollutants and human exposure

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Textiles play an important role in our daily life, and textile production is one of the oldest industries. In the manufacturing chain from natural and/or synthetic fibers to the final clothing products, the use of many different chemicals is ubiquitous. A lot of research has focused on chemicals in textile wastewater, but the knowledge of the actual content of harmful chemicals in clothes sold on the retail market is limited. In this paper, we have focused on eight benzothiazole and benzotriazole derivatives, compounds rated as high production volume chemicals. Twenty-six clothing samples of various textile materials and colors manufactured in 14 different countries were analyzed in textile clothing using liquid chromatography tandem mass spectrometry. Among the investigated textile products, 11 clothes were for babies, toddlers, and children. Eight of the 11 compounds included in the investigation were detected in the textiles. Benzothiazole was present in 23 of 26 investigated garments in concentrations ranging from 0.45 to 51 μg/g textile. The garment with the highest concentration of benzothiazole contained a total amount of 8.3 mg of the chemical. The third highest concentration of benzothiazole (22 μg/g) was detected in a baby body made from "organic cotton" equipped with the "Nordic Ecolabel" ("Svanenmärkt"). It was also found that concentrations of benzothiazoles in general were much higher than those for benzotriazoles. This study implicates that clothing textiles can be a possible route for human exposure to harmful chemicals by skin contact, as well as being a potential source of environmental pollutants via laundering and release to household wastewater.
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RESEARCH ARTICLE
Benzothiazole, benzotriazole, and their derivates in clothing
textilesa potential source of environmental pollutants
and human exposure
Rozanna Avagyan &Giovanna Luongo &Gunnar Thorsén &
Conny Östman
Received: 19 August 2014 /Accepted: 2 October 2014 / Published online: 25 October 2014
#Springer-Verlag Berlin Heidelberg 2014
Abstract Textiles play an important role in our daily life, and
textile production is one of the oldest industries. In the
manufacturing chain from natural and/or synthetic fibers to
the final clothing products, the use of many different
chemicals is ubiquitous. A lot of research has focused on
chemicals in textile wastewater, but the knowledge of the
actual content of harmful chemicals in clothes sold on the
retail market is limited. In this paper, we have focused on eight
benzothiazole and benzotriazole derivatives, compounds rated
as high production volume chemicals. Twenty-six clothing
samples of various textile materials and colors manufactured
in 14 different countries were analyzed in textile clothing
using liquid chromatography tandem mass spectrometry.
Among the investigated textile products, 11 clothes were for
babies, toddlers, and children. Eight of the 11 compounds
included in the investigation were detected in the textiles.
Benzothiazole was present in 23 of 26 investigated garments
in concentrations ranging from 0.45 to 51 μg/g textile. The
garment with the highest concentration of benzothiazole
contained a total amount of 8.3 mg of the chemical. The third
highest concentration of benzothiazole (22 μg/g) was detected
in a baby body made from organic cottonequipped with the
Nordic Ecolabel(Svanenmärkt). It was also found that
concentrations of benzothiazoles in general were much higher
than those for benzotriazoles. This study implicates that cloth-
ing textiles can be a possible route for human exposure to
harmful chemicals by skin contact, as well as being a potential
source of environmental pollutants via laundering and release
to household wastewater.
Keywords HPLC-MS/MS .Benzothiazoles .
Benzotriazoles .Clothing .Textiles .Garments
Introduction
Textiles play an important role in our dai ly life. The
manufacturing chain from natural or synthetic fibers to the
final clothing products is a process that includes many stages
in different factories around the world and with a frequent use
of various types of chemicals (Fransson and Molander 2012).
Pesticides, biocides, and fungicides are involved when culti-
vating raw materials for natural fibers, as well as in the
production of synthetic fibers, and more chemicals are intro-
duced during the different textile manufacturing stages (Swed-
ish Chemical 2013). While gaining benefits from the use of
these substances, they also come with potential harmful ef-
fects. The use of toxic chemicals in textile products is a
growing problem for both public health and the environment
(Rydberg 2009).
Benzothiazoles (BTs) and benzotriazoles (BTris) are high
production volume chemicals that have a wide range of appli-
cations (Kloepfer et al. 2004; Weiss and Reemtsma 2005).
BTs are most commonly used not only as vulcanization ac-
celerators in rubber production (Ni et al. 2008) but also as
biocides and fungicides, as well as in antifreeze as corrosion
inhibitors (Kloepfer et al. 2004). BTri and methylated
tolyltriazoles (TTri) are also commonly used corrosion inhib-
itors in deicing fluids for aircrafts, automotive antifreeze for-
mulations, and industrial cooling systems (Weiss and
Re emt sma 2 005 ). 2-H ydr oxy phe nyl d eri vati ves o f
Responsible editor: Leif Kronberg
Electronic supplementary material The online version of this article
(doi:10.1007/s11356-014-3691-0) contains supplementary material,
which is available to authorized users.
R. Avagyan :G. Luongo :G. Thorsén :C. Östman (*)
Department of Analytical Chemistry, Arrhenius Laboratory,
Stockholm University, 10691 Stockholm, Sweden
e-mail: conny.ostman@anchem.su.se
Environ Sci Pollut Res (2015) 22:58425849
DOI 10.1007/s11356-014-3691-0
benzotriazole, benzotriazole UV stabilizers (BUVs), are used
as stabilizers, to prevent yellowing and degradation, in textiles
(Kim et al. 2011), plastics, building materials, automobile
components, paint, and sports equipment (Nakata et al. 2009).
Both BTs and BTris are frequent pollutants in wastewater
in populated areas (Reemtsma et al. 2006) and have been
detected in wastewater, surface water, and groundwater
(Weiss and Reemtsma 2005). BTs have also been detected in
household wastewater not affected by road surface runoff, and
the authors suggested that the presence of these compounds
was not only a result of the release from aged products
containing BTs but that certain consumer products used in
the households may be responsible (Kloepfer et al. 2005).
BUVs have been found in fish (Kim et al. 2011), clams,
oysters, and gastropods (Nakata et al. 2009), in concen-
trations of several hundreds of nanograms per gram in
lipid weight.
Several of these compounds have been shown to exhibit
biological effects. BT, 2-mercapto benzothiazole (MBT), and
2-methylthio benzothiazole (MTBT) have shown acute aquat-
ic toxicity in various test systems (Reemtsma et al. 1995). BT
has been found to cause eye, skin, and respiratory irritation
and skin sensitization (Fishbein 1991), and it has also shown
to be a gill toxicant in sheepshead minnow (Evans et al. 2000).
2,2-Dithiobisbenzothiazole (MBTS) has been identified as an
allergen (Jung et al. 1988), and BTri has demonstrated both
mutagenicity and estrogenic potential in aquatic organisms
(Tangtian et al. 2012). On the other hand, the acute toxicity
of 5-methyl-benzotriazole (5-TTri) to aquatic organisms is
low (Cancilla et al. 2003). Information on toxicity and
ecotoxicity of BUVs is limited. However, it has been reported
that both 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol
(UV-328) and 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)
phenol (UV-327) can accumulate in birds, fish, and inverte-
brates (Nakata et al. 2009). This has lead the European
Chemicals Agency (ECHA) to propose that both these
chemicals shall be included in the candidate list as substances
of very high concern (SVHCs) (European Chemical 2013).
A lot of research work has focused on chemicals in textile
production wastewater, and there are regulations regarding the
use of several kinds of chemicals during the textile production
process (Bisschops and Spanjers 2003; Correia et al. 1994).
However, the knowledge of the actual content of harmful
chemicals in clothes distributed and retailed on the common
market is highly insufficient. This is due to difficulties to
obtain information on what substances that actually have been
used and especially the lack of analytical data of chemicals
present in clothing textiles (Zhong et al. 2006). Thus, investi-
gating the levels of different chemicals present in clothes is of
great importance, as clothing textiles can be a possible route
for human exposure to these compounds by skin contact, as
well as being a potential source of environmental pollutants
via laundering.
In an initial screening study, using untargeted analysis with
gas chromatography/mass spectrometry (GC/MS), we found
indications of BTs being present in almost all the investigated
clothing textiles. For that reason, the present study was
laun ched in o rder to i nvest igate t he occu rrenc e of
benzothiazole and benzotriazole derivatives in common cloth-
ing textiles on the Swedish retail market, using a previously
developed high-performance liquid chromatography tandem
mass spectrometry (LC-MS/MS) method for analysis of tex-
tiles with respect to these compounds (Avagyan et al. 2013).
Most of the retailers and brands investigated in this study are
available on the retail markets worldwide.
Materials and methods
Chemicals and solvents
Benzothiazole (96 %), 1-H-benzotriazole (99 %), and 2-
methyl benzothiazole (MeBT; 99 %) were purchased from
Sigma-Aldrich (China). 2,2-Di-thio-(bis)benzothiazole
(99 %), 2-methylthio benzothiazole (97 %), and 5,6-
dimethylbenzotriazole (99 %) were purchased from Sigma-
A l d r i c h ( G e r m a n y ) . N- c y c l o h e x y l - 2 -
be nzo thi azo les ulfe nam ide , 2-( ben zot ria zol - 2-y l)- 4-
methylphenol (97 %), 2-(2H-benzotriazol-2-yl)-4,6-di-tert-
pentylphenol (98 %), and 2-(2H-benzotriazol-2-yl)-4,6-bis
(1-methyl-1-phenylethyl)phenol (powder) were purchased
from Sigma-Aldrich (USA). 5-Methyl-benzotriazole (98 %)
and 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol
(98 %) were from Sigma-Aldrich, Japan and Sigma-Aldrich,
India, respectively. More details on the analytes are presented
in Table 1. Methanol, acetone, acetonitrile (ACN), dichloro-
methane (DCM) were of HPLC grade and purchased from
Rathburn Chemicals Ltd. (UK). Formic acid was purchased
from Fluka Analytical (Germany). Water was purified using a
Millipore Synergy 185 (Millipore Corp., Billerica, MA, USA)
water purification system equipped with a Millipak 0.22-μm
membrane filter (Millipore Corp.).
Clothing textile samples
The samples included in this study are presented in Table 2. A
total of 26 clothing samples diverse in material, color, and
price were purchased between September 2011 and April
2012 from a number of commonclothing stores in Stockholm,
Sweden. The samples covered 14 of the most common brands
occurring on the Swedish retail market and represented a wide
selection of clothes, from T-shirts to jeans, manufactured in 14
different countries. Most of the retailers and brands are avail-
able on the retail markets in many countries, e.g., two of the
retailers have 3,300 and 2,000 stores and are located across 54
and 88 countries, respectively. Eight of the 14 brands
Environ Sci Pollut Res (2015) 22:58425849 5843
investigated were common sport brands with distributors
worldwide. Among the samples, 11 were clothes for babies,
toddlers, and children, and four of the clothes were marked
organic cottonof which three were labeled with European
Union or Nordic Ecolabels. The investigation was focused on
the textile material, meaning that print and accessories on the
clothes were excluded. The samples were stored separate from
each other in aluminum foil, at room temperature. Prior to
extraction, the textile was cut into 5×5-mm pieces.
Analytical method
The analytical method is described in detail elsewhere
(Avagyan et al. 2013). Briefly, portions of 1.52 g cut textile
were placed in 15-mL test tubes with Teflon-lined screw caps,
and the internal standard MeBT was added. Ten milliliters of
20 % acetone in DCM was then added, and the samples were
ultrasonicated for 20 min. The extracts were filtered by
0.2-μm Nylon filters into new test tubes, and the extraction
was repeated once again with fresh solvent. Prior to evapora-
tion, 0.2 mL purified water was added to the pooled extract,
and the solvent volume was reduced to 0.2 mL under a gentle
stream of nitrogen. Methanol (0.3 mL) was added, and the
extracts were filtered once again prior to analysis. Each sam-
ple was analyzed in triplicate.
LC-MS/MS analysis
The LC-MS/MS system consisted of an HPLC system from
PerkinElmer (Waltham, USA) equipped with a Series 200
membrane degasser, two Series 200 micro pumps, and a
Series 200 autosampler. The chromatographic separation
was p erformed on a C 8 microbore col umn (ACE 3,
2.1 mm×50 mm, 5 μm particle size, Advanced Chromatog-
raphy Technologies, Aberdeen, Scotland). A guard column,
C8 Guard-PAKHPLC precolumn (Waters, Millipore Corp.,
Milford, MA, USA), was used prior the analytical column.
Mobile phase A was purified water with 0.10 % (v/v) formic
acid, and mobile phase B was acetonitrile with 0.10 % (v/v)
formic acid. A 5-μL injection loop volume was used, and the
Table 1 Investigated analytes,
CAS no., abbreviations, and mo-
lecular weight (Mw) [g/mol]
Analytes Abbreviation CAS no. Mw
Benzothiazole BT 95-16-9 135.19
2-Methylthio benzothiazole MTBT 615-22-5 181.28
2,2-Dithiobisbenzothiazole MBTS 120-78-5 332.49
N-cyclohexyl-2-benzothiazolesulfenamide CBS 95-31-8 264.42
1-H-benzotriazole BTri 95-14-7 119.12
5,6-Dimethylbenzotriazole XTri 4184-79-6 147.18
5-Methyl-benzotriazole 5-TTri 136-85-6 133.15
2-(Benzotriazol-2-yl)-4-methylphenol UV-P 2440-22-4 225.25
2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol UV-328 25973-55-1 351.49
2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol UV-234 70321-86-7 447.58
2,4-Di-tert-butyl-6-(5-chlorobenzotriazol-2-yl) phenol UV-327 3864-99-1 357.88
Table 2 Material, color, model, and origin of the investigated clothing
samples. The samples table is ordered according to textile material in the
garments
No. Material Color Model Origin
2 100 % PE Blue Male Philippines
11 100 % PE Blue Female Indonesia
12 100 % PE Blue Female Indonesia
20 100 % PE Blue Kid Switzerland
22 100 % PE Black Female India
23 100 % PE Red Male Georgia
24 100 % PE Pink Kid China
25 100 % PE Yellow Kid Cambodia
26 100 % PE White Male Egypt
17 85 % PE, 15 % EL Blue Female Cambodia
1 100 % CT Black Male Bangladesh
4 100 % CT Red Male Georgia
5 100 % CT Orange Kid Portugal
6 100 % CT Rose Baby China
10 100 % CT Pink Baby India
14 100 % CT Blue Male Bangladesh
16 100 % CT Blue Female India
18 100 % CT Blue Male China
13 99 % CT, 1 % EL Blue Female Bangladesh
3 95 % CT, 5 % EL White Female Bangladesh
15 75 % CT, 20 % PA, 5 % EL Blue Male Turkey
19 78 % CT, 20 % PE, 2 % EL Blue Kid Turkey
7 100 % OCT
e
, EU Ecolabel Blue Baby Bulgaria
8 100 % OCT, Nordic Ecolabel White Baby Latvia
9 100 % OCT, Nordic Ecolabel Red Baby Lithuania
21 100 % OCT Blue Kid India
PE polyester, CT cotton, EL elastan/lycra, PA polyamide, OCT organic
cotton
5844 Environ Sci Pollut Res (2015) 22:58425849
mobile phase flow rate was set to 120 μL/min. The HPLC
gradient program was as follows: 0 min., 5 % B; 5 min., 50 %
B; 10 min., 95 % B; 23 min., 95 % B; 23.1 min., 5 % B; and
28.1 min., 5 % B using linear ramps. The system was equili-
brated for 5 min. with 5 % B before each run.
An API 2000
TM
triple quadrupole mass spectrometer (PE
Sciex , To r o nto, O N , C a n a d a ) e q u ipped w i t h a
TurboIonSpray® electro spray interface was used in positive
ion mode. The MS parameters were set as follows: curtain gas
(N
2
), 20 psi; collision gas (N
2
), 6 psi; ion spray voltage, +
4,200 V; ion source gas (N
2
), 20 psi; and source temperature,
120 °C. The dwell time for each selected reaction monitoring
(SRM) transition was set to 0.25 s. The optimal instrumental
parameters for each analyte were obtained by tuning using
direct infusion. Quantitative analyses were performed in MS/
MS mode. Identification of the analytes was based on two
SRM transitionsand the chromatographic retention times. The
specific parameters for each of the analytes are presented in
Table S1 in the Electronic Supplementary Material (ESM).
Data was acquired and processed with Analyst software (Ver.
1.4.2.; AB Sciex, Concord, ON, Canada).
Quality assurance/quality control (QA/QC)
Extraction solvent was used as procedural blank, and the
targeted compounds could not be detected above the limits
of detection (LOD). A methanol blank injection was made
after every sample as a check for carryover of the analytes.
Detailed information on method validation is described else-
where (Avagyan et al. 2013). Briefly, it can be mentioned that
LOD and method quantification limit (MQL) ranged from 1.7
to 56 pg injected and 18 to 140 pg/g, respectively, and the
coefficients of determination (R
2
) of all calibration curves
were 0.99. Recoveries of the analytes from spiked textile
matrices ranged from 69 to 102 %, and the relative standard
deviations (RSDs) of repeated experiments ranged from 4 to
18 %. R
2
, LOD, MQL, as well as recovery and repeatability
are shown in Table S2 in ESM.
Results and discussion
Benzothiazole derivatives in clothing textiles
Twenty-six clothes from common brands and retail stores in
Sto ck holm were investi ga ted. Benzothi az oles and/or
benzotriazoles were detected in 24 (92 %) of these garments.
These results strongly indicate that these two groups of com-
pounds may be frequent chemical residues in common textile
materials used in clothes. The concentrations of eight of the
analytes are presented in Table 3. CBS, XTri, and UV-327
have been excluded from the table since they were below
MDL in all investigated garments.
The most abundantcompound was BT. It was present in 23
(88 %) of the analyzed textiles with a concentration ranging
up to 51 μg/g garment. The highest BT concentration was
found in a pair of white soccer shorts made from 100 %
polyester (sample 26). These shorts contained a total of
8.3 mg BT yielding a potential skin exposure of 1.3 μg BT/
cm
2
garment. These shorts also contained two BUV com-
pounds, the UV protection additives UV-234 and UV-P, with
concentrations of 4.0 and 2.0 ng/g garment, respectively. The
second highest BT concentration, 29 μg/g, was detected in a
blue-colored blouse made from a 100 % polyester garment
(sample 17). These two polyester garments were intended for
adult males and females, respectively, and had no kind of
environmental friendlylabel. However, the third highest
BT concentration was detected in the garment of a red baby
body made from organic cottonand marked with Nordic
Ecolabel(sample 9). This garment contained 22 μg BT/gram
and a total amount of 0.7 mg in the entire baby body garment,
yielding a potential skin exposure of 447 ng/cm
2
. An indica-
tion of the significance of the amounts of BT found in these
garments is to compare to skin patch tests performed on
humans. In a study of allergic skin reactions, it was shown
that 25 mg BT placed on a 2-cm
2
area of the flexor surface of
the wrist was sufficient to elicit an acute local dermatitis in 17
of 43 human subjects (Bogert and Husted 1931). The amount
detected in sample 26 was one third of this amount. That BT is
detected in most of the garments, and in some cases in com-
parably high amounts, raise the question if these textiles are
able to induce allergic reactions. The amounts are lower than
in the quoted study, but clothes are on the other hand wornon
a lifelong daily basis. However, there is lack of toxicological
information, and no recent studies on allergy-inducing prop-
erties of BT are available in the published literature. Thus,
textile-to-skin migration studies have to be made in order to
draw any further conclusions regarding exposure scenarios.
While sufficiently high exposure to BT is required for acute
toxicity, chronic exposure, as in the case of wearing clothes,
may cause skin sensitization and allergic reactions.
MTBT was the second most frequently detected compound
in the sampled garments. It was present in 14 of the 26
samples in a concentration ranging from 0.15 to 1.7 μg/g.
Sample 17 showed the highest concentration yielding a total
amount of 0.17 mg MTBTin the whole garment. The highest
average MTBT concentrations were observed in samples
made of 100 % polyester. However, in these garments, the
detection frequency was 50 % and sample 17 gave a large
contribution to the average value. In both organic cotton and
modified cotton garments, MTBT was detected in three of
four samples in concentration levels of 0.50.8 and 0.3
1.0 μg/g textile, respectively. MBTS was present only in
two samples in concentrations of 58.8 and 366 ng/g, in a
Environ Sci Pollut Res (2015) 22:58425849 5845
100 % cotton and a mixed cotton sample, with total amounts
of 2 and 154 mg, respectively, in the whole garments. In a
study, 3,448 patients suffering from occupational dermatitis
were tested because of suspected glove allergy, and 3 % of
these patients were sensitized to mercaptobenzothiazole and/
or its derivatives, while 1 % was sensitized to MBTS only
(Geier et al. 2012). Although the amount of MBTS is lower in
the clothes compared to the gloves, gloves are only used in
occupational purposes and the total exposure arising from
everyday clothing may be far greater.
Benzotriazole derivatives in clothing textiles
Both the amount as well as the frequency of occurrence in the
garments were generally lower for BTris compared to BTs.
UV-234 was the benzotriazole present in more than half of the
samples (54 %), with a concentration ranging from 2.70 to
2,750 ng/g textile, followed by UV-P detected in 31 % of the
samples with a concentration range of 1.9711.45 ng/g. The
highest amount of UV-234 was present in a mixed cotton
sample. UV protection agent UV-328 was present in two
samples in concentrations of 8.05 and 106 ng/g. This com-
pound is however of special concern since it has shown
bioaccumulative properties and proposed to be included on
the candidate list of ECHA (European Chemical 2013). Both
samples containing this compound were made of 100 % cot-
ton, one of which was an eco-labeledso-called organic
cotton. The knowledge of toxicological and ecotoxicological
effects of BUVs is limited. It has however been stated that
BUVs have low acute mammalian toxicity and moderate
chronic toxicity and are probably more of environmental
concern, due to their widespread occurrence, high lipophilic-
ity, and persistence (Fent et al. 2014). According to the liter-
ature, the two remaining analyzed benzotriazole derivatives,
BTri and 5-Ttri, are mainly used as corrosion inhibitors. Still,
5-TTri was detected in one sample and BTri in two samples.
The latter compounds were detected in concentrations com-
parable to BT, yielding total amounts of 0.5 and 1.3 mg,
respectively, in these two garments. As in the case of BUVs,
there is a lack of adequate toxicological data for BTri and 5-
TTri for proper risk assessment, although they have been
reported to have low acute toxicity (Cancilla et al. 2003).
Table 3 Determined concentrations (ng/g) of benzothiazole andbenzotriazole derivatives in clothing textile samples(n= 3). Samples14 and 22 are not
included in the table since none of the analytes were detected in these two samples
BT mean
(SD
a
)
MTBT Mean
(SD)
MBTS Mean
(SD)
UV-234 Mean
(SD)
UV-328 Mean
(SD)
UV-P Mean
(SD)
BTri Mean
(SD)
5-Ttri Mean
(SD)
2 1,710 (174) 179 (52.9) n.d. 3.55 (0.41) n.d. n.d. n.d. n.d.
11 3,230 (318) 147 (16.1) n.d. 109 (9.92) n.d. 4.38 (0.03) n.d. n.d.
12 2,120 (525) n.d. n.d. n.d. n.d. n.d. n.d. n.d.
20 8,640 (429) 738 (103) n.d. 27.7 (0.26) n.d. 4.05 (0.01) n.d. 17.1 (1.88)
23 3,130 (416) n.d. n.d. n.d n.d. n.d. n.d. n.d.
24 10,700 (748) 284 (20.1) n.d. 1.91 (0.08) n.d. 1.44 (0.01) n.d. n.d.
25 3,660 (124) n.d. n.d. 2.70 (0.09) n.d. n.d. n.d. n.d.
26 50,900 (188) n.d. n.d. 3.97 (0.02) n.d. 1.97 (0.07) n.d. n.d.
17 28,700 (92.7) 1,700 (92.7) n.d. n.d. n.d. n.d. n.d. n.d.
1 455 (90.3) n.d. n.d. 5.27 (0.06) n.d. n.d. n.d. n.d.
4 819 (59.9) 183 (16.8) n.d. n.d. n.d. n.d. n.d. n.d.
5 1,502 (182) 236 (50.3) n.d. 4.03 (0.0 2) n.d. n.d. n.d. n.d.
6 2,410 (821) n.d. 58.8 (2.98) n.d. n.d. n.d. n.d. n.d.
10 1,320 (194) n.d. n.d. n.d. n.d. n.d. n.d. n.d.
16 672 (171) 252 (34.2) n.d. 6.97 (0.02) 106 (1.30) 2.58 (0.01) n.d. n.d.
18 425 (85.8) n.d. n.d. 4.82 (0.06) n.d. 11.45 (0.14) n.d. n.d.
13 12,200 (395) 966 (189) 366 (17.9) 43.7 (2.02) n.d. n.d. 3,120 (69.9) n.d.
3 1,390 (301) n.d. n.d. n.d. n.d. n.d. n.d. n.d.
15 2,690 (94.4) 331 (21.6) n.d. 2,750 (58.2) n.d. n.d. n.d. n.d.
19 5,480 (262) 387 (9.3) n.d. 18.1 (2.70) n.d. n.d. 2,960 (53.6) n.d.
7 n.d. n.d. n.d. n.d 8.05 (0.043) n.d. n.d. n.d.
8 8,180 (809) 505 (68.6) n.d. n.d. n.d. 6.2 (0.01) n.d. n.d.
9 22,400 (679) 774 (32.7) n.d. 8.50 (0.02) n.d. 6.71 (0.02) n.d. n.d.
21 5,150 (617) 752 (151) n.d. n.d. n.d. n.d. n.d. n.d.
SD standard deviation, n.d. not detected
5846 Environ Sci Pollut Res (2015) 22:58425849
Thus, there is a need of further investigations of their chronic
impact on human health and environment.
Correlations and indications
The samples with the largest number of detected compounds,
five compounds each, were samples 13, 16, and 20, made
from 99 % cotton/1 % Lycra, 100 % polyester, and 100 %
cotton, respectively. Sample 13 also exhibited the highest
amount/area for three of the compounds, MTBT, MBTS,
and BTri, with 41, 16, and 133 ng/cm
2
, respectively.
Statistical correlations between analyte content and color or
manufacturing country gave no significant results. To increase
the statistical power of the generated data, the textiles were
divided into four groups: 100 % polyester, 100 % cotton,
modified cotton, and 100 % organic cotton (Fig. 1). The
highest amount of the investigated compounds was observed
in 100 % polyester (13 μg/g, n=10), followed by modified
cotton (10 μg/g, n=4), 100 % organic cotton (9.6 μg/g, n=4),
and 100 % cotton (1.5 μg/g, n=8). BT was the most abundant
compound in all types of textile materials followed by MTBT.
One hundred percent organic cotton and 100 % polyester had
similar chemicalprofiles, with high amounts of BTs and lower
amounts of BTri derivatives. One can therefore assume that
BTs are added to a greater extent to polyester materials rather
than cotton textiles, in the investigated garments. One hundred
percent organic cotton is an exception, probably due to that the
target compounds are not used in the manufacturing process
of this textile material but are present as contaminations from
the transportation of the garments. Similarly, when comparing
textile materials, the highest average BT concentration was
observed in the garment samples made of 100 % polyester
(11 μg/g, n=10), followed by 100 % organic cotton garments
(8.9 μg/g, n=4) and cotton mix (5.4 μg/g, n=4), while the
average concentration for garments made of 100 % cotton was
0.95 μg/g (n=8). However, significant differences in the
average concentrations of BT were found between polyester
garments and garments made of 100 % cotton (p=0.08), using
ttest for unequal variances. The average and median concen-
trations of BT in the different textile materials are shown in
Fig. 2. An interesting observation is that three of four gar-
ments marked 100 % organic cottonand branded with eco
Fig. 1 Average concentrations of
benzothiazole and benzotriazole
derivatives in the investigated
textile materials (concentrations
given in μg/g textile)
Fig. 2 Average (blue) and
median (red) concentrations of
benzothiazole in the investigated
textile materials (concentrations
given in μg/g textile)
Environ Sci Pollut Res (2015) 22:58425849 5847
labelscontained BT, as well as MTBT. In the case of BT,
these concentrations were 7 to 30 times higher than the medi-
an concentration of the ordinary100 % cotton garments. A
conclusion is that this kind of eco labelingis no guarantee
that textiles are free from harmful chemicals. In a study by
Blum et al. in 1978, it was shown that during a nights sleep,
tris(2,3-dibromopropyl) phosphate present in the textile mate-
rial of childrens sleepwear migratedfrom the garment into the
children, and a metabolite excreted with the morning urine
could be measured (Blum et al. 1978). BT, which we in this
study have shown to be common in clothing textiles, has also
been detected in solvent extracts from human skin experi-
ments performed in another study (Gallagher et al. 2008).
These observations indicate that wearing clothes could be a
source of human exposure to chemicals, such as BT.
As stated above, pesticides, biocides, and fungicides are
used when growing cotton and also in transportation of the
textiles, and some of the BTs detected are probably used as
fungicides in these processes. However, the high amounts of
BTs in polyester show that BTs are likely to be used in other
processes as well or are contaminants from other additives
used. That BUVs were detected in the analyzed textiles may
not be surprising since BUVs are used as UV stabilizers in
textiles. However, the presence of UV-328 in only two sam-
ples in low concentrations suggests that it may occur in
textiles as a contaminant from, e.g., plastic products. The
presence of BTri and 5-Ttri in some samples is also unexpect-
ed since they are mainly used as corrosion inhibitors. This
demonstrates that the knowledge of the actual content of
chemicals in textiles distributed on the retail market is highly
insufficient, and further investigations on chemicals used and
present in textiles are needed.
Conclusions
This study demonstrates the presence of BTs and BTris in
clothing, implying that they are commonly occurring in gar-
ments and that clothes could be a possible route to human
exposure to these groups of compounds. It can be assumed
that human health risks such as allergic reactions are mostly
associated with BTs, while BTri derivatives are more of envi-
ronmental concern. Laundering of clothes may be a source of
BTs and BTris which earlier have been detected in household
wastewater by other authors (Kloepfer et al. 2005). That these
compounds are common pollutants in municipal wastewater
has earlier been shown in several other studies (Kloepfer et al.
2004,2005; Weiss and Reemtsma 2005), but few studies have
investigated the possible sources of these compounds in the
aquatic environment. Thus, this study can provide some base-
line data for future investigations and risk assessment of
clothing textiles as a source of BTs and BTris. Since most of
the retailers and brands analyzed in this study are available on
the retail markets worldwide, it can be assumed that BTs and
BTris are not only present in clothing textiles on the Swedish
market, emphasizing the global significanceof this study. This
point out the importance to further investigate the occurrence
of BTs and BTris in clothing textiles in other brands, gar-
ments, and retail markets, as well as the potential human
exposure and emissions to the environment.
Acknowledgments Meng Hu is acknowledged for the initial GC/MS
screening work on the present study. This study has been funded by
Stockholm University.
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