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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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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
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
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
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
, 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
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
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
), 20 psi; collision gas (N
), 6 psi; ion spray voltage, +
4,200 V; ion source gas (N
), 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
) 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
, 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/
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
. 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
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
UV-234 Mean
UV-328 Mean
UV-P Mean
BTri Mean
5-Ttri Mean
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
, 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.
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.
Avagyan R, Sadiktsis I, Thorsén G, Östman C, Westerholm R (2013)
Determination of benzothiazole and benzotriazole derivates in tire
and clothing textile samples by high performance liquid chromatog-
raphyelectro spra y ionization ta ndem mass spectrome try. J
Chromatogr A 1307:119125
Bisschops I, Spanjers H (2003) Literature review on textile wastewater
characterisation. Environ Technol 24:13991411
Blum A, Gold MD, Ames BN, Jones FR, Hett EA, Dougherty RC,
Horning EC, Dzidic I, Carroll DI, Stillwell RN, Thenot J-P (1978)
Children absorb tris-BP flame retardant from sleepwear: urine con-
tains the mutagenic metabolite, 2,3-dibromopropanol. Science 201:
Bogert MT, Husted H (1931) Contribution to the pharmacology of the
benzothiazoles. J Pharmacol Exp Ther 45:189207
Cancilla DA, Baird JC, Geis SW, Corsi SR (2003) Studies of the envi-
ronmental fate and effect of aircraft deicing fluids: detection of 5-
methyl-1H-benzotriazole in the fathead minnow (Pimephales
promelas). Environ Toxicol Chem 22:134140
Correia VM, Stephenson T, Judd SJ (1994) Characterisation of textile
wastewatersa review. Environ Technol 15:917929
European Chemical Agency (2013)New public consultation launched on
10 potential SVHCs.
Evans JJ, Shoemaker CA, Klesius PH (2000)In vivo and in vitro effects
of benzothiazole on sheepshead minnow (Cyprinodon variegatus).
Mar Environ Res 50:257261
Fent K, Chew G, Li J, Gomez E (2014) Benzotriazole UV-stabilizers and
benzotriazole: antiandrogenic activity in vitro and activation of aryl
hydrocarbon receptor pathway in zebrafish eleuthero-embryos. Sci
Total Environ 482:125136
FishbeinL (1991) Municipaland industrial hazardouswaste management
an overview. Toxicol Ind Health 7:209220
Fransson K, Molander S (2012) Handling chemical risk information in
internationaltextile supply chains.J Environ PlanManag 56:345361
Gallagher M, Wysocki CJ, Leyden JJ, Spielman AI, Sun X, Preti G
(2008) Analyses of volatile organic compounds from human skin.
Brit J Dermatol 159:780791
Geier J, Lessmann H, Mahler V, Pohrt U, Uter W, Schnuch A (2012)
Occupational contact allergy caused by rubber glovesnothing has
changed. Contact Dermatitis 67:149156
Jung JH, McLaughlin JL, Stannard J, Guin JD (1988) Isolation, via
activity-directed fractionation, of mercaptobenzothiazole and
dibenzothiazyl disulfide as 2 allergens responsible for tennis shoe
dermatitis. Contact Dermatitis 19:254259
Kim J-W, Ramaswamy BR, Chang K-H, Isobe T, Tanabe S (2011)
Mul ti re sidue analy ti ca l me thod for th e de te rm inati on o f
5848 Environ Sci Pollut Res (2015) 22:58425849
antimicrobials, preservatives, benzotriazole UV stabilizers, flame
retardantsand plasticizers in fish usingultra high performance liquid
chromatography coupled with tandem mass spect rome try. J
Chromatogr A 1218:35113520
Kloep fe r A, J ek el M, Reemtsm a T (2 00 4) D etermin at io n of
benzothiazoles from complex aqueous samples by liquid chroma-
tographymass spectrometry following solid-phase extraction. J
Chromatogr A 1058:8188
Kloepfer A, Jekel M, Reemtsma T (2005) Occurrence, sources, and fate
of benzothiazoles in municipalwastewater treatmentplants. Environ
Sci Technol 39:37923798
Nakata H, Murata S, Filatreau J (2009) Occurrence andconcentrations of
benzotriazole UV stabilizers in marine organisms and sediments
from the Ariake Sea, Japan. Environ Sci Technol 43:69206926
Ni HG, Lu FH, Luo XL, Tian HY, Zeng EY (2008) Occurrence,
phase distrib ution , and mass loadings of benzothiazoles in
riverine runoff of the pearl river delta, China. Environ Sci
Technol 42:18921897
Reemtsma T, Fiehn O, Kalnowski G, Jekel M (1995) Microbial transfor-
mations and biological effects of fungicide-derived benzothiazoles
determined in industrial wastewater. EnvironSci Technol 29:478485
Reemtsma T, Weiss S, Mueller J, Petrovic M, Gonzalez S, Barcelo D,
Ventura F, Knepper TP (2006) Polar pollutants entry into the water
cycle by municipal wastewater:a European perspective.Environ Sci
Technol 40:54515458
Rydberg K (2009) Contact allergy to textile dyes clinical and chemical
studies on disperse dyes. Ph.D. Dissertation, Faculty of Medicine,
Lund University
Swedish Chemical Agency (2013) Hazardous chemicals in textiles
report of a government assignment 2013.
Tangtian H, Bo L, Wenhua L, Shin PKS, Wu RSS (2012) Estrogenic
potential of benzotriazole on marine medaka (Oryzias melastigma).
Ecotox Environ Safety 80:327332
Weiss S, Reemtsma T (2005) Determination of benzotriazole corrosion
inhibi tor s fro m aqueous en vir onm ental samples b y liq uid
chromatography-electrospray ionization-tandemmass spectrometry.
Anal Chem 77:74157420
Zhong W, Malcolm M, Xing Q, Pan N, Maibach HI (2006) Textile and
human skin, microclimate, cutaneous reactions: an overview. Cutan
Ocul Toxicol 25:2339
Environ Sci Pollut Res (2015) 22:58425849 5849
... In particular, X-Static textiles, silver-coatedyarn-threaded fabrics, are currently used in sports clothing for odor control, hygiene, and social comfort, which can thereby enhance product performance. Overall, there has been an increased demand for the antibacterial effects of metal ions, such as silver in the textiles industry (16)(17)(18)(19). ...
Full-text available
With growing awareness that what we put in and on our bodies affects our health and wellbeing, little is still known about the impact of textiles on the human skin. Athletic wear often uses silver threading to improve hygiene, but little is known about its effect on the body's largest organ. In this study, we investigated the impact of such clothing on the skin's chemistry and microbiome. Samples were collected from different body sites of a dozen volunteers over the course of 12 weeks. The changes induced by the antibacterial clothing were specific for individuals, but more so defined by gender and body site. Unexpectedly, the microbial biomass on skin increased in the majority of the volunteers when wearing silver-threaded T-shirts. Although the most abundant taxa remained unaffected, silver caused an increase in diversity and richness of low-abundant bacteria and a decrease in chemical diversity. Both effects were mainly observed for women. The hallmark of the induced changes was an increase in the abundance of various monounsaturated fatty acids (MUFAs), especially in the upper back. Several microbe-metabolite associations were uncovered, including Cutibacterium, detected in the upper back area, which was correlated with the distribution of MUFAs, and Anaerococcus spp. found in the underarms, which were associated with a series of different bile acids. Overall, these findings point to a notable impact of the silver-threaded material on the skin microbiome and chemistry. We observed that relatively subtle changes in the microbiome result in pronounced shifts in molecular composition. IMPORTANCE The impact of silver-threaded material on human skin chemistry and microbiome is largely unknown. Although the most abundant taxa remained unaffected, silver caused an increase in diversity and richness of low-abundant bacteria and a decrease in chemical diversity. The major change was an increase in the abundance of various monounsaturated fatty acids that were also correlated with Cutibacterium. Additionally, Anaerococcus spp., found in the underarms, were associated with different bile acids in the armpit samples. Overall, the impact of the silver-threaded clothing was gender and body site specific.
... BTRs, BTHs, and BUVs have been detected at ppb or ppt concentrations in surface waters, wastewater, sewage sludge, sediments, indoor dust, and textiles by pretreatment methods such as solid-phase extraction (SPE), stir bar sorption extraction (SBSE), microwave-assisted extraction (MAE), and accelerated solvent extraction (ASE) (Hu et al. 2021;Maceira et al. 2019;Montesdeoca-Esponda et al. 2013a;Speltini et al. 2016). The main analytical tools used for detecting these compounds are LC-MS (Avagyan et al. 2015;Carpinteiro et al. 2012;Mizukawa et al. 2017) or GC-MS (Cantwell et al. 2015;Xu et al. 2015;Zhao et al. 2017). GC-MS method for determining these compounds in environmental samples has better isomers separation, lower matrix effect, and better selectivity (Chafi and Ballesteros 2022;Johnson et al. 2021). ...
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Benzotriazoles (BTRs), benzothiazoles (BTHs), and benzotriazole ultraviolet absorbers (BUVs) are common products in plastic rubber and personal care products. Due to their toxicity and bioaccumulation, they have been identified as emerging contaminants (ECs) in the environment. Solid-phase microextraction (SPME) and solid-phase extraction (SPE) combined with gas chromatography-mass spectrometry (GC–MS) were used for the enrichment and detection of the contaminants in seawater and sediment, respectively. The conditions of SPE and SPME were optimized in terms of material, temperature, time, pH, ionic strength, extraction solvent, and elution solvent. Although SPME requires a small sample volume, it is not reliable for the extraction efficiency and reproducibility of BTHs, BTRs, and BUVs in seawater. However, the precision of SPE-GC–MS for the determination of BTHs, BTRs, and BUVs was around 10%, with recoveries of 67.40–102.3% and 77.35–101.8% in seawater and sediment, respectively. The limits of detection of 14 contaminants in seawater and sediment were 0.03–0.47 ng/L and 0.01–0.58 ng/g, respectively. Secondly, BTHs, BTRs, and BUVs were detected with low ecological risk when SPE-GC–MS was applied to the analysis of seawater and sediment samples from the Yangtze estuary and its adjacent areas. The SPE-GC–MS was highly precise with lower detection limits relative to previous studies and thus was able to meet the requirements for the detection of BTHs, BTRs, and BUVs in seawater and sediments.
... Microplastics from synthetic clothing and running shoes vary in polymer and additive chemistry, which may leach a complex mixture of monomers, additives, and manufacturing and degradation by-products into the surrounding environment (e.g. benzothiazole, benzotriazole derivatives, benzophenones, bisphenols, dichloromethane and p-xylene) (Avagyan et al., 2015;Kim et al., 2022;Sait et al., 2021). Trail running clothing and footwear exposed to UV light, heat and mechanical stressors during laundering and active use will degrade. ...
Clothing and footwear designed for trail running shed microplastics (MPs) during use. Trail running events may therefore present a significant source of MP pollution in conservation and wilderness areas. Microplastics may present long-term risks to biodiversity and endemic plant and animal species in such areas. In this study, we used a before-after-control-impact approach to quantify and characterise MP emissions from clothing and shoe outsoles during trail running events. Microplastic deposition on trail surfaces was assessed using both a controlled study and during two public trail running events in New South Wales, Australia (the Duval Dam Buster and the Washpool World Heritage Trail Race). Microplastics were present on trails after all events and included fibres and rubber fragments. Microplastic counts varied considerably depending on trail surface hardness and gradient, and clothing and footwear properties. The controlled study showed running tights (leggings) and shoes with soft rubber outsoles produced more MPs than shirts and hard rubbers. In the trail running events, abrasive wear to shoe outsoles produced an average of 0.3 ± 0.1 to 0.9 ± 0.2 MPs/linear metre/runner, and clothing produced 0.7 ± 0.3 to 2.0 ± 0.3 fibres/linear metre/runner, with fibres accounting for 63-69% of MPs. Microplastic deposition from both footwear and clothing was higher on sloped and rock trail surfaces than flat and soil surfaces. Laser Direct Infrared (LDIR) Imaging indicated the main types of MPs present on trails were polyurethane, polyethylene terephthalate and polyamide. Trail running is increasing in popularity and large-scale events may cause a rapid and significant input of MPs in protected areas. Land managers, event coordinators and outdoor apparel manufacturers could mitigate MP impacts however, by diverting foot traffic around ecologically sensitive areas, capping participant numbers, and developing abrasion resistant clothing and footwear.
... Moreover, those chemicals can be lost during use and wear or even during washing . They may be transferred to high trophic levels via the food chain having the ability to harm the ecosystem , even some of them have been reported as lethal and/or carcinogenic substances (Avagyan et al., 2015). ...
This is the first report of anthropogenic particles (APs), including microplastics and synthetic, semi-synthetic and anthropogenically-altered natural fibers, in water and sediment of the Chubut River estuary. This river is the main source of freshwater in Chubut Province (Patagonia, Argentina), where wastes and pollutants are poured and finally end in the Atlantic Ocean. The average concentration in surface and bottom water samples was 5.5 items/L, while in sediment was 175.4 items/kg dw. Raman's analysis identified particles dominated by polyethylene terephthalate (PET) (35.5 %), dye signature only (18.5) and anthropogenic cellulose (10 %). Fibers were the prevalent shape (83 %), and the chemical identification evidenced a textile origin. The highest APs concentration was found in sediments from the site with the finest grain size and the greatest amount of organic matter. Present results will provide a baseline for future studies and raise public and governmental awareness.
Benzotriazoles, benzothiazoles, and p-phenylenediamines discharged from wastewater treatment plants (WWTPs) are of concern because they pose risks to aquatic organisms. South/Southeast Asian countries are heavily populated and face challenges in providing clean water. Here, the chemical fates in five WWTPs in Malaysia and Sri Lanka were investigated and their environmental risks were assessed. Benzotriazoles and benzothiazoles were dominant (at concentrations of 3.4–21000 and 7.0–2500 ng/L, respectively). The p-phenylenediamine concentrations were much lower (not detected─60 ng/L). The WWTP removal efficiencies varied widely, from negative to 100%, lower than in developed countries, indicating the WWTP elimination capacities were limited and secondary releases of the chemicals from particles could occur. The highest total consumptions (72–5000 mg/(d·1000 inhabitants)) were for a hospital WWTP in Malaysia, mainly contributed by benzotriazoles (81%). The daily total chemical mass loadings in effluents from WWTPs in Malaysia and Sri Lanka were 0.04–48 and 0.27–9.4 g/d, respectively. Benzothiazoles and N-(1,3-dimethylbutyl)-N′-phenyl-1,4-phenylenediamine-quinone pose medium–strong risks to aquatic organisms and should be prioritized for wastewater management. The results improve our understanding of emerging contaminant fates and effects in WWTPs and how management systems could be modified to ensure clean water.
Benzotriazoles (BTRs) and benzothiazoles (BTHs) are emerging benzo-heterocyclic compounds that may induce neurotoxicity. However, the effect of prenatal exposure to BTs (BTRs and BTHs) on child neurodevelopment has not been elucidated. We aimed to explore the associations between maternal urinary concentrations of BTs in single or in mixture with child neurodevelopment at the age of two. This study recruited 513 mother-child pairs based on a birth cohort from 2014 to 2015 in Wuhan. Maternal urinary concentrations of eight BTs (four BTRs and four BTHs) in the first, second, and third trimesters were measured. The mental development index (MDI) and psychomotor development index (PDI) of children, as two indexes of neurodevelopment, were assessed at two years old by the Bayley Scales. In the analyses of single BTs, prenatal average tolyltriazole (TTR) exposure level was associated with decreased boys' MDI scores (β = -2.84, 95 % CI: -5.11, -0.57) and prenatal average 1-H-benzotriazole (1-H-BTR) exposure level was associated with decreased boys' PDI scores (β = -1.44, 95 % CI: -2.70, -0.17), respectively. Maternal urinary concentrations of benzothiazole (BTH) in the 1st trimester (β = -1.79, 95 % CI: -2.78, -0.80), 2nd trimester (β = -1.14, 95 % CI: -2.19, -0.09), and the prenatal average exposure (β = -2.15, 95 % CI: -3.69, -0.61) were also negatively associated with boys' PDI scores. However, no significantly negative association was observed among girls. In the further mixture analysis, the quantile g-computation model found a significant negative association between prenatal average concentrations of BTs in mixture and boys' PDI scores [β = -4.80 (95 % CI: -9.08, -0.52)], and BTH weighted the highest in the negative association. As far as we know, this is the first research to estimate the effect of prenatal exposure to BTs on child neurodevelopment. The findings showed that prenatal exposure to BTs was negatively associated with neurodevelopment among boys, suggesting that the associations may be modified by infant sex.
The production of face towels is growing at an annual rate of about 4% in China, reaching 1.13 million tons by 2021. Phthalates (PAEs) are widely used in textiles, and face towels, as an important household textile, may expose people to PAEs via the skin, further leading to health risks. We collected new face towels and analyzed the distribution characterization of PAEs in them. The changes of PAEs were explored in a face towel use experiment and a simulated laundry experiment. Based on the use of face towels by 24 volunteers, we calculated the estimated daily intake (EDI) and comprehensively assessed the hazard quotient (HQ), hazard index (HI), and dermal cancer risk (DCR) of PAEs exposure in the population. PAEs were present in new face towels at total concentrations of <MDL–2388 ng/g, with a median of 173.2 ng/g, which was a lower contamination level compared with other textiles. PAE contents in used face towels were significantly higher than in new face towels. The concentrations of PAEs in coral velvet were significantly higher than those in cotton. Water washing removed some PAEs, while detergent washing increased the PAE content on face towels. Gender, weight, use time, and material were the main factors affecting EDI. The HQ and HI were less than 1, which proved PAEs had no significant non-carcinogenic health risks. Among the five target PAEs studied, DEHP was the only carcinogenic PAE and may cause potential health risks after long-term exposure. Therefore, we should pay more attention to DEHP.
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Industrial discharges pose global ecological risks. This study investigates Algeria’s GL1K (gas liquification complex of Skikda) plant’s hazardous effluents. The impact assessment evaluates the environmental repercussions of the researched facilities, including the effects on populations and their way of life. Thus, it is possible to stress suggestions to improve facility design to remove or restrict negative effects and to minimize or compensate for the current facility’s unfavorable repercussions. This technique is consistent with establishing and monitoring the industrial plant’s environmental management system. The method utilized to determine impacts in this EIA can be used to evaluate the EMS’s significant aspects and effects and provide improvement options. An evaluation matrix can rate impacts, the grid and criteria are based not regulation but on “good practices” for this type of assessment, and results obtained from modelling the effects using PHAST software. Therefore, they can be modified to fit the facility’s activity. Based on examining activities and identifying elements likely to interact with the environment, environmental aspects are identified using the proposed grid and criteria. This study describes a section-by-section approach. Each determined environmental impact can be graded based on environmental factor criteria.
In 2019, 368 mln tonnes of plastics were produced worldwide. Likewise, the textiles and apparel industry, with an annual revenue of 1.3 trillion USD in 2016, is one of the largest fast-growing industries. Sustainable use of resources forces the development of new plastic and textile recycling methods and implementation of the circular economy (reduce, reuse and recycle) concept. However, circular use of plastics and textiles could lead to the accumulation of a variety of contaminants in the recycled product. This paper first reviewed the origin and nature of potential hazards that arise from recycling processes of plastics and textiles. Next, we reviewed current analytical methods and safety assessment frameworks that could be adapted to detect and identify these contaminants. Various contaminants can end up in recycled plastic. Phthalates are formed during waste collection while flame retardants and heavy metals are introduced during the recycling process. Contaminants linked to textile recycling include; detergents, resistant coatings, flame retardants, plastics coatings, antibacterial and anti-mould agents, pesticides, dyes, volatile organic compounds and nanomaterials. However, information is limited and further research is required. Various techniques are available that have detected various compounds, However, standards have to be developed in order to identify these compounds. Furthermore, the techniques mentioned in this review cover a wide range of organic chemicals, but studies covering potential inorganic contamination in recycled materials are still missing. Finally, approaches like TTC and CoMSAS for risk assessment should be used for recycled plastic and textile materials.
Forty-seven compounds among synthetic phenolic and amino antioxidants and ultraviolet filters, three suites of widely used chemical additives, were measured in eighteen popular children's car seats (fabric, foam, and laminated composites of both layers) marketed in the United States in 2018. Significantly higher levels of target compounds were found in foam and composite samples than in fabric samples. Median total concentrations of phenolic antioxidants and their transformation products ranged from 8.11 μg/g in fabric to 213 μg/g in foam In general, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (AO-1135) and 2,4-di-tert-butylphenol (24-DBP) were the most abundant among all target compounds with maximum levels of526 μg/g in composite and 13.7 μg/g, respectively. The total concentrations of amino antioxidants and their transformation products and of ultraviolet filters were at least one order of magnitude lower than those of phenolic antioxidants, with medians of 0.15–37.1 μg/g and 0.29–1.81 μg/g, respectively, in which the predominant congeners were 4-tert-butyl diphenylamine (BDPA), 4,4′-di-tert-butyl diphenylamine (DBDPA), 4-tert-octyl diphenylamine (ODPA), 2,4-dihydroxybenzophenone (BP-1), 2-hydroxy-4-methoxybenzophenone (BP-3), and 2-(2-benzotriazol-2-yl)-4-methylphenol (UV-P). Large variabilities in usage of these chemicals resulted in different compositional patterns among the car seats. These results suggest that these compounds are major polymeric additives in children's car seats as they are present at greater levels than previously measured groups of chemicals like brominated flame retardants and per- and polyfluoroalkyl substances. Given the documented toxic potentials of synthetic antioxidants and ultraviolet filters, their abundances in children products are a cause for concern.
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Human skin emits a variety of volatile metabolites, many of them odorous. Much previous work has focused upon chemical structure and biogenesis of metabolites produced in the axillae (underarms), which are a primary source of human body odour. Nonaxillary skin also harbours volatile metabolites, possibly with different biological origins than axillary odorants. To take inventory of the volatile organic compounds (VOCs) from the upper back and forearm skin, and assess their relative quantitative variation across 25 healthy subjects. Two complementary sampling techniques were used to obtain comprehensive VOC profiles, viz., solid-phase microextraction and solvent extraction. Analyses were performed using both gas chromatography/mass spectrometry and gas chromatography with flame photometric detection. Nearly 100 compounds were identified, some of which varied with age. The VOC profiles of the upper back and forearm within a subject were, for the most part, similar, although there were notable differences. The natural variation in nonaxillary skin odorants described in this study provides a baseline of compounds we have identified from both endogenous and exogenous sources. Although complex, the profiles of volatile constituents suggest that the two body locations share a considerable number of compounds, but both quantitative and qualitative differences are present. In addition, quantitative changes due to ageing are also present. These data may provide future investigators of skin VOCs with a baseline against which any abnormalities can be viewed in searching for biomarkers of skin diseases.
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In the textile industry, a large number of potentially harmful chemicals are used during production. This raises the importance of communication about chemical risks between different actors in the supply chain and therefore this study aims at describing the flows of chemical risk information up- and downstream in an international textile supply chain. The outcomes show that the main communication between retailers and suppliers is through a list of restricted substances. Information most often only reaches the next tier up- or downstream in the supply chain. However, different approaches exist, of which one is described in further detail.
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The characteristics of wastewater from textile processing operations are comprehensively reviewed. The categorisation of wastewaters proceeds through a consideration of the nature of the various industrial processes employed by the industry and the chemicals associated with these operations. Chemical pollutants arise both from the raw material itself and a broad range of additives used to produce the finished product. The industrial categories considered include sizing and desizing, weaving, scouring, bleaching, mercerizing, carbonizing, fulling, dyeing and finishing. Pollutants of concern range from non‐biodegradable highly‐coloured organic dyes to pesticides from special finishes such as insect‐proofing. It is evident that the textile wastewater chemical composition is subject to considerable change due to both the diversity in the textile processes employed and the range of chemicals employed within each industrial category.
Benzotriazole UV-stabilizers (BUVs) are applied in materials for protection against UV-irradiation. They are widely used, bioaccumulate and share structural similarities to benzotriazole. Benzotriazole (1HBT) finds application as corrosion inhibitor in dishwashing detergents, antifreeze (vehicles) and aircraft de-icing agent. BUVs and 1HBT are persistent and ubiquitous in the aquatic environment, but there is little understanding of the ecotoxicological implications. Here, we comparatively analyze the hormonal activity in vitro and effects in zebrafish eleuthero-embryos in vivo. 2-(2-Hydroxy-5-methylphenyl)benzotriazole (UV-P), 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole (UV-326), UV-327, UV-328, UV-329 and UV-320 showed no estrogenicity (YES assay) and androgenicity (YAS assay). However, UV-P and 1HBT showed significant antiandrogenic activity.
A high performance liquid chromatography-tandem mass spectrometry method utilizing electrospray ionization in positive and negative mode has been developed for the separation and detection of benzothiazole and benzotriazole derivates. Ultra-sonication assisted solvent extraction of these compounds has also been developed and the overall method demonstrated on a selected clothing textile and an automobile tire sample. Matrix effects and extraction recoveries, as well as linearity and limits of detection have been evaluated. The calibration curves spanned over more than two orders of magnitude with coefficients of correlation R(2)>0.99 and the limits of detection and the limits of quantification were in the range 1.7-58pg injected and 18-140pg/g, respectively. The extraction recoveries ranged between 69% and 102% and the matrix effects between 75% and 101%. Benzothiazole and benzotriazole derivates were determined in the textile sample and benzothiazole derivatives determined in the tire sample with good analytical performance.
Allergic contact dermatitis caused by rubber gloves is not infrequent, and has almost exclusively been attributed to contact sensitization to accelerators. Thiurams have been the most frequent allergens, followed by dithiocarbamates. To describe the current allergen pattern in patients with occupational allergic contact dermatitis caused by rubber gloves. This study was a retrospective analysis of data from the Information Network of Departments of Dermatology (IVDK), 2002-2010. Of 93 615 patients patch tested in the IVDK, 3448 both suffered from occupational dermatitis and were tested because of suspected glove allergy. Among these, healthcare workers were the largest group (n = 1058). Of all occupational dermatitis patients, 13% were sensitized to thiurams, 3.5% to dithiocarbamates, 3% to mercaptobenzothiazole and/or its derivatives, and 0.4% to thioureas. Positive test reactions to 1,3-diphenylguanidine were seen in 3.0%. Reaction frequencies varied with the years, but showed no uniform time trend. As compared with a former IVDK data analysis (1995-2001), there was no change in sensitization pattern and no decline in sensitization frequencies. This is in line with data from the literature. Particularly in healthcare, there is a need for (i) allergen declaration on the glove package, and (ii) gloves with reduced accelerator content.
This study, for the first time, assessed the reproductive effects of benzotriazoles, widely used industrial chemicals, on marine fish. Marine medakas (Oryzias melastigma) were exposed to 0.01, 0.1, and 1mg/L benzotriazole for periods of four and 35 days. The results that are obtained showed that the expression levels of CYP1A1 were down-regulated in the liver, gills and intestines of both males and females. Vitellogenin (VTG) was highly induced in the liver, gills and intestine of both male and female marine medaka, and CYP19a was up-regulated in the ovaries especially after being exposed for 35 days. Most importantly, the results of the present study suggest that even at environmentally relevant concentrations detected in the aquatic environment, 0.01 mg/L, benzotriazole also caused notable changes in expression levels of VTG, CYP1A1 and CYP19a. More concerns about the toxicity of benzotriazoles on marine animals should be raised.
Benzothiazole (BT), 2-mercaptobenzothiazole (MBT), and 2-(methylthio)benzothiazole (MTBT) were determined as degradation products of the fungicide 2-(thiocyanomethylthio)benzothiazole (TCMTB) in tannery wastewater and are shown to be incompletely removed (75%) in an anaerobic and aerobic wastewater treatment pilot plant. Average total concentration of these benzothiazoles is 5.7 mu mol L(-1) in the untreated wastewater and 1.4 mu mol L(-1) after aerobic treatment. Aerobic batch degradation tests revealed that TCMTB is transformed to MBT. MBT is primarily methylated to MTBT, which was not further degradable. BT was aerobically degraded along unknown pathways. Potential effects of benzothiazoles entering the aquatic environment are illustrated by luminescence inhibition of Vibrio fischeri (= Photobacterium phosphoreum; EC(50) between 0.03 mu mol L(-1) for TCMTB and 32 mu mol L(-1) for BT) and growth inhibition of the same organism with TCMTB and MBT. MBT, BT, and MTBT at concentrations of 0.1- 0.2 mu mol L(-1) inhibit nitrification on sediment columns and mixed culture respiration determined as BOD (0.6-11 mu mol L(-1)). It is concluded that 2-substituted benzothiazoles employed in industrial processes are not completely removable by biological wastewater treatment and are of concern for aquatic environment due to their limited biodegradability and potential toxicity.
A multiresidue analytical method for the determination of emerging pollutants belonging to personal care products (PCPs) (antimicrobials, preservatives), benzotriazole UV stabilizers (BUVSs) and organophosphorus compounds (OPCs) in fish has been developed using high speed solvent extraction (HSSE) followed by silica gel clean up and ultra fast liquid chromatography coupled with tandem mass spectrometry (UFLC-MS/MS) analysis. Developed extraction and clean up method yielded good recovery (> 70%) for all the four groups of emerging pollutants, i.e. antimicrobials (78.5-85.6%), preservatives (85.0-89.4%), BUVSs (70.9-112%) and OPCs (81.6-114%; except for TEP - 68.9% and TPeP - 58.1%) with RSDs ranging from 0.7 to 15.4%. Intra- and inter-day repeatabilities were less than 19.8% and 19.0%, respectively at three spiked levels. The concentrations were given in lipid weight (lw) basis, and the method detection limits were achieved in the lowest range of 0.001-0.006 ng g⁻¹ for two antimicrobials, 0.001-0.015 ng g⁻¹ for four preservatives, 0.0002-0.009 ng g⁻¹ for eight BUVSs and 0.001-0.014 ng g⁻¹ for nine OPCs. Finally, the method was successfully validated as a simple and fast extraction method for the determination of 23 compounds belonging to PCPs, BUVSs and OPCs and applied to the analysis of three species of fish from Manila Bay, the Philippines. Concentrations ranged from 27 to 278 ng g⁻¹ for antimicrobials, 6.61 to 1580 ng g⁻¹ for paraben preservatives, <MDL (method detection limit) to 179 ng g⁻¹ for BUVSs and ND (not detected) to 266 ng g⁻¹ for OPCs suggesting the ubiquitous contamination by these emerging pollutants in Manila Bay. This is the first method developed for the determination of triclocarban, four paraben preservatives and four BUVSs, in fish.