Environmental Research 218 (2023) 114908

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

Equilibria of semi-volatile isothiazolinones between air and glass surfaces

measured by gas chromatography and Raman spectroscopy
Seungwoon Sohn a, 1, Vu Thi Huong b, 1, Phuong-Dong Nguyen b, Nguyễn Hoàng Ly c,
Soonmin Jang d, Hyewon Lee e, Cheolmin Lee e, Jung Il Lee f, Yasser Vasseghian b, g, h, i, *,
Sang-Woo Joo b, ***, Kyung-Duk Zoh a, **
a
Department of Environmental Health Sciences, School of Public Health, Seoul National University, Seoul 08826, Republic of Korea
b
Department of Chemistry, Soongsil University, Seoul, 06978, Republic of Korea
c
Department of Chemistry, Gachon University, Seongnam, 13120, Republic of Korea
d
Department of Chemistry, Sejong University, Seoul, 143-747, Republic of Korea
e
Department of Chemical & Biological Engineering, Seokyeong University, Seoul, 02713, Republic of Korea
f
Korea Testing & Research Institute, Gwacheon, 13810, Republic of Korea
g
School of Engineering, Lebanese American University, Byblos, Lebanon
h
University Centre for Research & Development, Department of Mechanical Engineering, Chandigarh University, Gharuan, Mohali, Punjab, 140413, India
i
Department of Sustainable Engineering, Saveetha School of Engineering, SIMATS, Chennai, 602105, India

A R T I C L E I N F O A B S T R A C T

Keywords: Trace amounts of semi-volatile organic compounds (SVOCs) of the two isothiazolinones of 2-methylisothiazol-3
Silver nanocubes (2H)-one (MIT) and 2-octyl-4-isothiazolin-3-one (OIT) were detected both in the air and on glass surfaces.
Isothiazolinone Equilibria of SVOCs between air and glass were examined by solid phase microextraction-gas chromatography/
Surface-enhanced Raman scattering
mass spectrometry (SPME-GC/MS). Surface to air distribution ratios of Ksa for MIT and OIT were determined to
Surface-air equilibria
be 5.10 m and 281.74 m, respectively, suggesting more abundant MIT in the gas phase by a factor of ~55. In
addition, a facile method of silver nanocube (AgNC)-assisted surface-enhanced Raman scattering (SERS) has been
developed for the rapid and sensitive detection of MIT and OIT on glass surfaces. According to MIT and OIT
concentration-correlated SERS intensities of Raman peaks at ~1585 cm− 1 and ~1125 cm− 1, respectively. Their
calibration curves have been obtained in the concentration ranges between 10− 3 to 10− 10 M and 10− 3 to 10− 11 M
with their linearity of 0.9986 and 0.9989 for MIT and OIT, respectively. The limits of detection (LODs) of the two
isothiazolinones were estimated at 10− 10 M, and 10− 11 M for MIT and OIT, respectively. Our results indicate that
AgNC-assisted SERS spectra are a rapid and high-ultrasensitive method for the quantification of MIT and OIT in
practical applications. The development of analytical methods and determination of the Ksa value obtained in
this study can be applied to the prediction of the exposure to MIT and OIT from various chemical products and
dynamic behaviors to assess human health risks in indoor environments.

including for cosmetics and household products (Alvarez-Rivera et al.,

1. Introduction
Isothiazolinones including 2-methylisothiazol-3(2H)-one (MIT), and
2-octyl-4-isothiazolin-3-one (OIT) are organic compounds, composed of
a five-membered heterocyclic ring, as well as the simplest formula
(CH)2SN(H)CO of endo-cyclic atoms of both sulfur and nitrogen atoms.
Isothiazolinones have been used as antimicrobials in many fields,
2012), consumer cleaning products, sunscreens (Novick et al., 2013),
and paint (Schwensen et al., 2015). Such products are popular, but
disinfectant preservatives can accumulate in indoor environments or
even in the human body and thus have a toxic impact on human health.
High doses of isothiazolinone can cause skin sensitization risk (Basketter
et al., 1999).
MIT is widely used in the paper industry, cosmetics, shampoo, and

* Corresponding author. Department of Chemistry, Soongsil University, Seoul, 06978, Republic of Korea.
** Corresponding author.
*** Corresponding author.
E-mail addresses: vasseghian@ssu.ac.kr (Y. Vasseghian), sjoo@ssu.ac.kr (S.-W. Joo), zohkd@snu.ac.kr (K.-D. Zoh).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.envres.2022.114908
Received 27 May 2022; Received in revised form 16 October 2022; Accepted 21 November 2022
Available online 26 November 2022
0013-9351/© 2022 Elsevier Inc. All rights reserved.
S. Sohn et al.
Abbreviations
SVOC semi-volatile organic compound
SPME solid phase microextraction
Cg the concentration of OIT (or BIT) in the air
Csat the saturated concentration OIT (or BIT) in the air
Cair the concentration OIT (or BIT) in the air
Csurface the concentration OIT (or BIT) on the surface
Psat the saturated vapor pressure of OIT (or BIT)
Ksa surface-air partition coefficient
Da diffusion coefficient
LC50 lethal concentration 50%
NOEL no observed effect level
NOAEC no observed adverse effect concentration
skincare products that are used in households, and OIT is primarily used
in industry for the protection of materials or surfaces and can be found in
paints and varnishes (Emmett et al., 1989; Fewings and Menné, 1999).
In an acute inhalation toxicity experiment on rats, US EPA reported the
LC50 value of MIT at 0.33 mg/L (EPA, 1998). In a subchronic inhalation
toxicity study, the exposure of rats to MIT at dose levels of 0.34 mg/m3
was observed as the non-observed effect level (NOEL) via inhalation for
90 days (EPA, 1998). Acute inhalation toxicity of OIT known as LC50 is
more than 200 mg/kg (EPA, 2007). For short- and intermediate-term
inhalation exposures of OIT, a NOAEL of 0.64 mg/m3 was reported in
a 90-day inhalation study on rats (EPA, 2007).
Several methods, including gas chromatography (GC), liquid chro­
matography (LC), high-performance liquid chromatography (HPLC),
mass spectroscopy (MS), GC-MS, and LC-MS/MS are often used in the
identification of isothiazolinones (Alvarez-Rivera et al., 2012; Varga
et al., 2020). These analytical methods require expensive equipment and
are time-consuming, with a lot preparation and complicated procedures.
However, a significant disadvantage of these technologies is that they
are not able to effectively monitor isothiazolinone compounds in
real-time in the production lines of industrial factories.
In recent years, SERS has emerged as an attractive analytical tool
that comes with a variety of advantages of rapid, simple, and non-
destructive sample preparation (Langer et al., 2020; Pilot et al., 2019).
Relying on the enhanced Raman vibrational modes of the analytic mo­
lecular, the SERS method offers several potential applications in many
fields of environment (Lê et al., 2021; Song et al., 2021; C. C. Tian et al.,
2021), food (Hussain et al., 2020; Ko et al., 2015), and biology (Chen
et al., 2020; Ly and Joo, 2020).
The SERS-based method has been developed to attract many re­
searchers investigating the development of novel and efficient SERS
substrates. Because the key factor of the SERS may be enhanced Raman
vibrational spectrum of analytic molecules on surface plasmon reso­
nance of nanomaterials, there are many reports on the synthesis of
several novel nanostructured materials that create hot spots at the sur­
face. Recently, a number of studies have improved SERS sensors based
on the development of a novel nanostructured platform, aimed at
detecting dangerous materials such as urchin-like gold-silver nano­
crystals (Zhou et al., 2019), gold nanorods (Kim et al., 2021; Zhao et al.,
2020), silver nanorods (Qu et al., 2019), gold nanowires (Y. Y. Tian
et al., 2021), gold nanostars (Nguyen et al., 2019), and silver nanoplates
(Liu et al., 2013; Zhu et al., 2012). In addition, a theoretical computation
method – density functional theory (DFT) – has been used to investigate
adsorption (Sun et al., 2021; Yu et al., 2021), roles of noble metals in
preventing oxidation (Lee et al., 2021), and vibrational fingerprint
bands in Raman spectroscopy of 4-mercaptophenylboronic acid in Hg2+
detection (Zhao et al., 2020). In many studies, ultra-sensitive detection
of analytes has been carried out using Raman spectra based on the
development of an efficient-reliable-single SERS substrate. Therefore,
2
Environmental Research 218 (2023) 114908
SERS studies on the development of various novel SERS substrates are
still crucial for real-life applications.
AgNC-based SERS substrates are currently the potential spectro­
scopic platforms for highly sensitive detection of thiram (Bhavya et al.,
2020), proteins (Matteini et al., 2017), explosives (Ben-Jaber et al.,
2017), chemical vapor (Kodiyath et al., 2013), and arsenic (Mulvihill
et al., 2008). Numerous studies have indicated that AgNCs are an effi­
cient plasmonic nanostructure that can be utilized for various moni­
toring applications. To the best of the authors’ knowledge, no study has
used the AgNC-based SERS combined DFT calculation method for the
identification of isothiazolinones. In the present study, 45 nm AgNCs
were used as efficient substrates for the detection of isothiazolinones via
SERS technology. AgNCs raised a high enhancement of the Raman signal
of analytes and exhibited a highly sensitive detection. This work has
found that the LOD values for isothiazolinones is much lower than their
maximum residual limit, which can have serious health effects on peo­
ple’s health. SERS substrates were developed by assemblies of 45 nm
AgNCs on glass surfaces. Next, SERS spectra of unknown isothiazolinone
concentrations were performed and the isothiazolinone concentration in
unknown samples was estimated through calibration curves. Therefore,
the proposed method can be considered as a feasible SERS detection for
demonstrating a suitable approach to monitoring isothiazolinones in
many products, based on the intensified electromagnetic field as well as
on hot spots concentrated on the corners of an individual AgNC (Fig. S1).
Isothiazolone-based biocides are widely used as cosmetics, cleaners,
bathroom products, and various preservatives in our day-to-day lives,
However, there is a lack of objective data on exposure and behavior,
particularly in relation to surfaces and the air. In South Korea, the iso­
thiazolinones have been the causative agents of humidifier disinfectants
and thus have recently been studied in various exposure pathways (i.e.,
exposure to the human body by inhalation due to vaporization or
spraying from the humidifier) (Lee et al., 2019; Park et al., 2020; Ryu
et al., 2019).
In this study, we investigated the mechanism for exposure and
behavior to routes of exposure on surfaces for the products other than
humidifier disinfectants. When MIT and OIT are exposed to glass-like
inert surfaces in a particular space (e.g., closed system) in an industry
or a household, the amount of physical property associated with surface-
air concentration, equilibrium time, and distribution coefficient can be
identified. In addition, exposure information and policy proposals
related to products containing biocidal substances were discussed in
relation to the prediction of spatial behavior according to the charac­
teristics of each isothiazolinone substance.
2. Materials and methods
2.1. Materials
Silver trifluoroacetate (CF3COOAg, ≥99.99%), polyvinylpyrrolidone
(PVP, Mw ≈ 55000), sodium sulfide nonahydrate (Na2S • 9H2O,
≥98.0%), and (3-aminopropyl)triethoxysilane (APTES, 99%) were all
provided by Sigma-Aldrich Co., Ltd (Korea). 2-Methylisothiazol-3(2H)-
one (MIT) and 2-octyl-4-isothiazolin-3-one (OIT) were purchased from
Tokyo Kasei (Tokyo, Japan). The standard solution of isothiazolinone
was prepared by dissolving neat MIT and OIT in acetone. Ethylene glycol
(EG, 99.5%) was obtained from Daejung, Korea. Ethanol (C2H5OH,
99.9%) was procured from Samchun, Korea. 1 N-hydrochloric acid was
purchased from Yakuri chemical. De-ionized water (DI, resistivity: 18
MΩ cm, Millipore Direct-Q 5 system) was used throughout the
experiment.
2.2. Preparation of AgNCs
The synthesis of AgNCs was performed according to previous works
with a slight modification. All materials were dissolved in EG and be
prepared at least for 1 h before the reaction. In the standard synthesis, a
S. Sohn et al.
25 mL flask containing 5 mL EG was heated up to 150 ◦ C for 1 h in
stirring mantles. Firstly, 0.06 mL of Na2S solution of 3 mM was intro­
duced. After 2 min, 0.5 mL of HCl of 3 mM was added, followed by 1.25
mL of PVP of 282 mM. 0.4 mL of CF3COOAg of 282 mM was added after
another 2 min. Subsequently, the synthesis was quenched in ice water
bath to terminate the reaction. The products were washed several times
with acetone and DI waster and were collected by centrifugation.
Finally, AgNCs were redispersed in 6 mL DI, which was stored in
refrigerator at 4 ◦ C. The AgNC samples were obtained at about ~45 nm
in diameter according to the measurements by a zeta-potential analyzer
(ELZ-2, Otsuka) and high-resolution transmission electron microscope
(TEM) (JEM-3100, JEOL) (Fig. S1). Thermal Schottky type field emis­
sion gun was used at 200 kV with a magnification of x20 to x2.0 M.
Lattice distances of 0.10 nm could be resolved with a sample tilting of -
X/Y: ±35◦ /± 35◦ (Tomography ± 70◦ ). CCD camera of an OneView
camera was used with 25 fps at full 4 k x 4 k resolution.
2.3. Preparation of AgNC-based SERS substrates
The synthesis of AgNC-based SERS substrate was performed ac­
cording to previous works with a slight modification. Microscope glass
slides were cut into 0.5 × 0.5 cm pieces and cleaned following several
washing steps using 0.5% NaOH, DI water, ethanol and acetone,
respectively, before AgNC-staining of an amino-capped glass substrate.
Firstly, reactive hydroxyl groups (-OH) was generated through utilizing
oxygen plasma machine (Vita, Femto Science Inc., Korea) for 2 min.
Then, the amine-modified sample was prepared via immersing the wafer
in a 3% APTES solution in ethanol at RT for 2 h. The wafers were washed
twice with ethanol and dried in an oven at 80 ◦ C for 1 h. After silani­
zation, the APTES-modified glass was immersed into AgNC solution at
RT for 24 h in order to form silver-coated substrates (SERS substrates).
Also, the SERS substrates were checked via a field-emission TEM (JEM-
F200, JEOL) and a field emission-scanning electron microscope (FE-
SEM) (JSM 7500 F, JEOL).
2.4. Raman spectral measurements
20 μL of isothiazolinone was dissolved in DI water and dropped onto
the SERS substrates for Raman detection. Raman spectra were obtained
utilizing an inVia confocal Raman microscope (Reflex, Renishaw) with
an excitation laser wavelength of 633 nm with a ×20 objective lens. A
silicon wafer (520 cm− 1) was used to calibrate the Raman spectral po­
sitions. Raman spectra were compiled with laser power of 5 mW with the
acquisition time of 10 s per spectrum with a range of 200–3200 cm− 1.
2.5. SPME-GC/MS detection
Experiments to determine the distribution of isothiazolinones be­
tween air and surfaces were performed in 10 mL glass vials. Two ex­
periments were performed to determine the behavior of isothiazolinone
compounds between air and glass surfaces. First, we examined the time
of reaching equilibrium by injecting high concentrations of iso­
thiazolinone into the glass surface. Then, we determined the fraction of
isothiazolinone distributed in the air by injecting different amount onto
the surface.
For these experiments, either 100 μL of MIT 2000 mg/L or OIT 1500
mg/L solutions were injected into 10 mL vials, and 20, 50, 200, 500, and
750 mg/L of MIT standard solution were added to each glass surface to
confirm air distribution when different amounts of isothiazolinone were
injected. The acetone solvent was then evaporated and sealed at room
temperature for 15 min. To block the light, the reactors were sealed with
aluminum foils, and incubated at 25 ◦ C for 2 days (48 h) for MIT and 8
days (192 h) for OIT until the equilibrium reached in the air, which
remained unchanged throughout the kinetic experiment. In consider­
ation of the distributed mass in the air from the surface and the quan­
titative limitations of SPME-GC/MS analysis, each isothiazolinone was
3
Environmental Research 218 (2023) 114908
injected in different amounts onto the glass surfaces (Table S1; Fig. S2).
The equilibrium experiments were duplicated and the gradient experi­
ments were triplicated.
2.6. Gas chromatographic determination of MIT and OIT
Analysis of isothiazolinones was carried out with an Agilent 6890 A
gas chromatograph (GC) with 5973 N mass spectrometry detector (MSD)
(Agilent Technologies, USA). A fused silica capillary column DB 5-MS UI
(30 m × 0.25 mm, 0.25 μm) was used for GC separation of the analytes.
Solid phase micro-extraction (SPME)-GC/MS was used for the analysis of
SVOCs in air to reduce the experimental time (Cao et al., 2017). After the
equilibrium was reached, a 100 μm polydimethylsiloxane (PDMS) SPME
fiber (Merck Supelco Analytic, Cat. No. 57300-U) was fixed to the vial,
and each isothiazolinone compound was exposed to headspace for 15
min. After the extraction, a PDMS fiber placed in the GC injector for 15
min at 250 ◦ C for MIT and 270 ◦ C for OIT. The SPME fiber was thermally
desorbed at splitless mode, and the temperature of the transfer line was
280 ◦ C. The carrier gas flow and oven temperature program were set for
MIT and OIT respectively.
For the MIT analysis, helium with a purity of 99.9990% was used as a
carrier gas with a flow rate of 1 mL/min and the oven temperature was
programmed to increase from 60 ◦ C (held for 1 min) to 150 ◦ C (held for
4 min) at 10 ◦ C/min and then to increase to 280 ◦ C (held for 2 min) at
60◦ C/min. In the case of OIT, Helium was used as the carrier gas at a
constant flow rate of 1.2 mL/min and the oven temperature was started
at 50 ◦ C (held for 2 min), set at 20 ◦ C/min to 80 ◦ C (held for 6 min), set at
15 ◦ C/min to 280 ◦ C and held isothermally at 280 ◦ C for 10 min.
Quadrupole temperature at 150 ◦ C, and source temperature at 230 ◦ C.
The MSD was operated in the electron ionization (EI) mode (70 eV). The
selected ion mode was used for detection and quantification. The
selected mass-charge ratios (m/z) were 61, 87, 115 for MIT and 101,
102, 114, 115 were selected for OIT (Fig. S3).
The calibration curve (0.02–0.8 μg of MIT and OIT) was obtained by
injecting 2 μL of 10–400 mg/L standard solutions of MIT and OIT. The R2
values of the calibration curve were greater than 0.995 for the iso­
thiazolinones. The quality assurance and quality control (QA/QC) for
the measurement of the isothiazolinones selected using SPME-GC/MS
were provided in Table S2. The equilibrium in the air of iso­
thiazolinones was confirmed by measuring a constant detection amount.
The sampling time of SPME fiber for accurate determination of gas-
phase concentration was obtained according to the method described
in the literature (Cao et al., 2017).
2.7. Calculation of air concentration and Ksa
To calculate the concentration (Cg) of isothiazolinone in the air, the
mass (M) adsorbed to the SPME fiber, the diffusion coefficient (Da), and
the SPME sampling time (t) of isothiazolinone were substituted into Eq.
(1) (Cao et al., 2017).
M = D a S Cg t (1)
According to Cao (Cao et al., 2017), when the mass adsorbed on the
SPME fiber was found at equilibrium, the mass of SVOCs on SPME fibers
was linearly increased in proportion to the SPME sampling time (t) and
air concentration (Cg). During sampling, the SPME fiber adsorption was
performed by the diffusion of isothiazolinones in the air by the fiber
fixed inside the vial, and the diffusion coefficient (Da) of iso­
thiazolinones in the air at 25 ◦ C was estimated using empirical corre­
lations (Schwarzenbach et al., 2005). The shape coefficient (S) was
0.0125 m, calculated by Eq. (2) using the SPME fiber diameter (D) of
310 μm and the SPME fiber length (L) of 1 cm (Cao et al., 2017).
/ [ √̅̅̅̅̅̅̅̅̅̅̅̅̅]
√̅̅̅̅̅̅̅̅̅̅̅̅̅ 1 + 1 − γ2
S = 4π L 1 − γ 2 ln √̅̅̅̅̅̅̅̅̅̅̅̅̅ , γ = D / L (2)
1− 1 − γ2
S. Sohn et al. Environmental Research 218 (2023) 114908

The mass of isothiazolinone was divided by the glass surface area could be obtained as shown in Eq. (3).
(1.77 × 10− 4 m2) to obtain the surface concentration. Then the iso­ ( )
Mass adsorbed per unit surface area Csurface
thiazolinones concentration in the air previously calculated, was intro­ Ksa = (3)
duced and the surface-air partitioning coefficient (Ksa) with the unit (m) Concentration in the air (Cair )

Fig. 1. Detection scheme of SVOC isothiazolinones.

4
S. Sohn et al. Environmental Research 218 (2023) 114908

10− 4 to 0.8 mmHg for MIT and 3.7 × 10− 5 to 2.0 × 10− 4 mmHg for OIT,
3. Results and discussion
respectively, the theoretical saturation concentration (Csat) range was
calculated using equation (4) as MIT 3.84–495.9 mg/m3 and OIT
3.1. Estimation of equilibrium time and surface - air distribution
0.422–209.2 mg/m3.
According to the gas phase saturation concentration values calcu­
We performed the experiments to estimate the concentrations of MIT
lated from the vapor pressure in the literatures, the best approximations
and OIT evaporating into the air according to the scheme depicted in
were 123.98 mg/m3 for MIT and 0.422 mg/m3 for OIT. Fig. 2(c) and 2
Fig. 1. Time-dependent trends were obtained by measuring MIT and OIT
(d) shows the stick diagrams of Cair at MIT and OIT. Overall, the air
concentrations in the headspace of the vials using GC-MS. Fig. 2 shows
concentration appears to be proportional to the amount of MIT and OIT
the kinetic results at the glass surfaces using higher concentrations of
initially added to the reactor. From the glass surface addition amount,
isothiazolinone, 200 μg MIT and 150 μg OIT, respectively.
the air concentration of MIT was found to be 8.876–53.210 mg/m3, and
After incubation for 24 h for MIT and 192 h for OIT, we observed that
after a sufficient time to reach equilibrium, the air concentration of OIT
MIT and OIT nearly reached a dynamic equilibrium between the air and
was 0.237–0.849 mg/m3 (48 h for MIT, 192 h for OIT). This result in­
glass surfaces. Each equilibrium concentration was expected to reach
dicates that the air concentration of MIT was higher than that of OIT
60.36 mg/m3 for MIT and 1.032 mg/m3 for OIT (Fig. 2(a) and 2(b)).
when the same amounts were injected on the surface. In addition, the
Since the concentration-dependent kinetic experiments to determine the
result implies that high molecular weight biocides such as OITs tend to
surface/air partition coefficient (Ksa) were performed at much lower
settle on the surface of objects rather than volatilize into the air in the
levels below 100 μg, the 48 h reaction time of MIT, and 192 h of OIT to
gaseous state.
reach complete equilibrium could be sufficient. In a closed system, when
an excessive amount of the SVOC material falls on the glass surface, it
would not evaporate above its saturation concentration (Csat) as a gas.
3.2. Determination of Ksa
The saturation concentration (Csat) of a gas could be theoretically
calculated from the vapor pressure (Psat) (Dutour et al., 2004) as Eq. (4).
Previous studies have investigated how isothiazolinone compounds
m Psat × MW are distributed between water surfaces (e.g., polymer surfaces or organic
Csat = = (4)
V RT components) after being applied to the surface of an object in the form of
a paint or coating agent (Bollmann et al., 2015; Urbanczyk et al., 2016).
We investigated the range of vapor pressure (Psat) in the literatures
However, there are no studies on the surface-to-air distribution of iso­
(Burnett et al., 2010; Ducup de Saint Paul et al., 2021; ECHA, 2021; EPA,
thiazolinone compounds.
1998) and the two common softwares - Estimation Programs Interface
Comparing the physicochemical properties of MIT and OIT, it can be
(EPI) Suite™ software and the Advanced Chemistry Development
seen that MIT has a lower boiling point, higher vapor pressure, and
(ACD/Labs) software from the Percepta Platform (PhysChem Module).
lower octanol-air partition coefficient (Koa) than those of OIT (Table 1).
Since the values of the investigated vapor pressure range were 6.2 ×
It can be seen that the boiling point, vapor pressure, and log Koa values

Fig. 2. Estimation of equilibrium time from (a) MIT and (b) OIT. Determination of air concentrations dependent on added amounts of (c) MIT and (d) OIT.

5
S. Sohn et al. Environmental Research 218 (2023) 114908

Table 1 show similar trends for the surface-air partition coefficient (Ksa).
Physicochemical properties of selected isothiazolinones. At the glass surface, the Ksa values were estimated to be 5.10 m for
Molecules 2-methylisothiazol-3 2-octyl-4-isothiazolin-3-one (OIT) MIT and 281.74 m for OIT, respectively. This result indicates that MIT is
(2H)-one (MIT) expected to be more distributed in the air than on the surface in com­
Chemical C4H5NOS C11H19NOS parison with the case of OIT. On the other hand, OIT has a lower vapor
formula pressure and a higher molecular weight than those of MIT. OIT tends to
CAS number 2682-20-4 26530-20-1 be less distributed in the air than MIT, and instead, it can exist in a larger
Molecular 115.2 213.3 amount on the surface. When an amount of OIT equal to that of MIT is
weight (g/
mol)
exposed on a surface, a smaller concentration is expected to be distrib­
Boiling point 130 342 uted in the air.
(◦ C) This is consistent with the physicochemical properties of MIT, which
− 2 5
Vapor pressure 2 × 10 3.68 × 10− is smaller in molecular weight and more volatile than OIT. The human
(mmHg, 25
body is more likely to inhale MIT, when the biocidal substances are
◦
C)
Density (g/ 1.35 1.04 exposed on a surface. Like a previous study on the surface-air partition
cm3) coefficients of phthalates (Kim et al., 2022), for SVOC compounds of MIT
Log Kow − 0.49 2.45 and OIT to which people are commonly exposed in indoor environ­
Log Koa 4.863 8.522 ments, the Ksa values are correlated with the vapor pressure and log Koa
Structure
values. In the case of OIT with a lower vapor pressure than that of MIT,
the Ksa value did not change relatively significantly.
The Ksa of MIT on the glass surface was smaller than that of DBP
(5.10 m < 5.54 × 101 m), whereas the Ksa of OIT was larger than DBP
and smaller than that of BBP (5.54 × 101 m < 2.82 × 102 m < 2.05 ×
104 m). Considering the correlation with the size of the Ksa value, it
seems that the boiling point was the property that followed the clearest
trend among different substances (Boiling point: MIT (130 ◦ C) <DBP
(340 ◦ C) <OIT (342 ◦ C) <BBP (370 ◦ C) <DEHP (385 ◦ C)).

Fig. 3. (a) Baseline-corrected experimental SERS and normal Raman spectra of MIT compared with the calculations. (b) Raman mapping of a MIT film on a glass
surface at 1585 cm− 1. (c) Concentration-dependent Raman spectra of MIT on the AgNC-based SERS substrate. (d) The corresponding calibration curve of Raman
signal centered at 1585 cm− 1 as a function of MIT concentration with a range from 10− 3 to 10− 10 M in distilled water. Error bars indicate the standard deviations of
three measurements.

6
S. Sohn et al. Environmental Research 218 (2023) 114908

3.3. Raman spectral analysis of MIT and OIT on surfaces Table 2

Vibrational assignments of MIT on the basis of density functional theory
The average sizes of AgNCs were measured to be ~45 nm according calculations.
to the TEM measurements (Fig. S1). AgNCs were coated on glass sur­ Exp. Exp. normal Cal. SERS Assignment
faces, creating a novel SERS substrate, which not only provided fairly SERS Raman on Ag6
uniform hot spots but also illustrated high reproducibility and high – 525 511 Bending of -N-C– –C (ring), and -C-N-S-
sensitivity. AgNC-assisted SERS spectroscopy was used to analyze MIT (ring)
and OIT adsorbed on glass surfaces. Figs. 3(a) and 4(a) compare the – 633 605 Bending of –C– –C–C= (ring), and ring
deformation
experimental SERS, normal Raman, and calculated SERS spectra of MIT
697 690 654 Stretching of -S-N-, -S-C-, and ring
and OIT, respectively. The geometries of MIT and OIT have been opti­ deformation
mized, subsequently, their spectroscopy has been computed by DFT – 798 781 Bending of {-S-C––C, –C– –C–C-} (ring),
calculations. As a result, MIT and OIT had a solid phase compared with a and ring deformation
gas-phased MIT and OIT, inducing slightly different Raman peaks in the – 906 880 Stretching of -N-C = , -N-S- (ring), and
bending out of plane of H–C–H (-CH3
experimental SERS than their computed spectra (Tables 2 and 3). As group)
shown in Figs. 3(a) and 4(a), the measured and simulated SERS spectra – 1035 – Twisting of H–C– –C- (ring)
of MIT and OIT matched well in a consistent manner. The measured – 1104 1127
spectra showed the strong bands at 1585 and 1125 cm− 1 in the SERS – 1264 – Bending of -N-C-H
1313 1313 1313 Stretching of { = C–N-, =C–C-} (ring), and
spectra of MIT and OIT, respectively. Herein, the authors illustrated a
bending of -N-C-H
novel AgNC-assisted SERS platform exhibiting not only homogeneous – – 1440 Wagging of H–C–H (-CH3 group)
size ~45 nm but also a high density of hot spots. The SERS substrate is 1478 1489 1492 Bending out of plane of H–C–H (-CH3
composed of self-assembled arrays of AgNCs on glass surfaces, which group)
have sharp corners and edges that AgNCs can lead to the formation of 1585 1589 1559 Stretching of –C––C- (ring)
1631 1621 1625 Stretching of –C––O (ring)
numerous nanogaps between the high density of nanocubes.
Note: Exp., experimental wavenumbers (cm− 1); Cal., calculated wavenumbers
(cm− 1).

Fig. 4. (a) Baseline-corrected experimental SERS and normal Raman spectra of OIT compared with the calculations. (b) Raman mapping of a OIT film on a glass
surface at 1125 cm− 1. (c) Concentration-dependent Raman spectra of OIT on the AgNC-based SERS substrate. (d) The corresponding calibration curve of Raman
signal centered at 1125 cm− 1 as a function of OIT concentration with a range from 10− 3 to 10− 11 M in distilled water. Error bars indicate the standard deviations of
three measurements.

7
S. Sohn et al. Environmental Research 218 (2023) 114908

Table 3 in living spaces. Although it is impossible to confirm an exposure to

Vibrational assignments of OIT on the basis of density functional theory inhalation pathways due to volatilization of substances, it is our belief
calculations. that further studies on surface-air behavior is needed in relation to other
Exp. Exp. normal Cal. SERS Assignments isothiazolinone-based materials that may be used in the indoor
SERS Raman on Ag6 environments.
577 569 550 Bending of -N-C-C, and ring
deformation Credit author statement
– 645 629 Asymmetric stretching of -N-S-, -S-C = ,
and ring deformation
710 693 689 Symmetric stretching of -N-S-, -S-C = , Seungwoon Sohn: Data curation, Conceptualization, Formal anal­
and ring deformation ysis, Software, Methodology, Validation, Writing - original draft,
898 – 902 Bending out of plane of H–C–H (-CH3 Writing - review & editing. Vu Thi Huong: Data curation, Conceptual­
group) ization, Formal analysis, Software, Methodology, Validation, Writing -
1084 1058 1087 Stretching of -C-C- (-CH2- group)
original draft, Writing - review & editing. Phuong-Dong Nguyen:
1125 1114 1141
1309 1309 1312 Rocking of –C––C–H (ring) Conceptualization, Formal analysis, Software, Methodology, Validation.
1438 1435 – Wagging of H–C–H (-CH2- group) Nguyễễn Hoàng Ly: Conceptualization, Formal analysis, Software,
1513 1506 1504 Bending out of plane of H–C–H (-CH2-, Methodology, Validation, Writing - original draft, Writing - review &
–CH3 group)
editing. Soonmin Jang: Conceptualization, Formal analysis, Software,
– – 1565 –C- (ring)
Stretching of –C–
– 1618 1631 –O (ring)
Stretching of –C– Methodology, Validation, Writing - original draft, Writing - review &
editing. Hyewon Lee: Conceptualization, Formal analysis, Software,
Note: Exp., experimental wavenumbers (cm− 1); Cal., calculated wavenumbers
Methodology, Validation. Cheolmin Lee: Conceptualization, Formal
(cm− 1).
analysis, Software, Methodology, Validation, Writing - original draft,
Writing - review & editing. Jung Il Lee: Conceptualization, Formal
3.4. MIT and OIT detection using AgNC-based SERS substrates analysis, Software, Methodology, Validation, Writing - original draft,
Writing - review & editing. Yasser Vasseghian: Project administration,
Figs. 3(c) and 4(c) showed the concentration-dependent SERS Conceptualization, Formal analysis, Software, Methodology, Validation,
spectra of MIT and OIT respectively. The calibration curves have been Writing – original draft, Writing - review & editing. Sang-Woo Joo:
obtained in ranges from 10− 3 to 10− 10 M, and 10− 3 to 10− 11 M. Their Project administration, Conceptualization, Formal analysis, Software,
linearity has been determined to be 0.9986, and 0.9989 for MIT and OIT, Methodology, Validation, Writing – original draft, Writing - review &
respectively. The LOD values of the two isothiazolinones were estimated editing. Kyung-Duk Zoh: Project administration, Conceptualization,
at 10− 10 M, and 10− 11 M for MIT and OIT, respectively. Our SERS result Formal analysis, Software, Methodology, Validation, Writing – original
was consistent with the GC-MS data that MIT evaporated more signifi­ draft, Writing - review & editing.
cantly than OIT, resulting in the surface detection of OIT with better
sensitivity than MIT. During the measurement, the adsorption on the
surface of OIT was found to be denser than that of MIT through the Declaration of competing interest
microscopic images of the Raman equipment. The adsorption of the
substance on the surface of the material affects the sensitivity of SERS. The authors declare that they have no known competing financial
Briefly, the detection limit of SERS increases when the analyte is interests or personal relationships that could have appeared to influence
strongly adsorbed onto the precious metal nanostructure. the work reported in this paper.

4. Conclusions Data availability

A new AgNC-based SERS substrate was developed to aim for highly
sensitive detection of MIT and OIT. The AgNC-coated on the glass sur­
face, which led to an increase in the electromagnetic field around the
surface of the nanomaterial, was introduced as an efficient SERS plat­
form. The LOD values were determined to be 10− 10 M and 10− 11 M for
MIT and OIT, respectively, without the need for sample pretreatments in
a fast detection time of a few min. Our results suggest that AgNC-based
SERS substrate is an effective novel sensing platform for trace analysis of
MIT and OIT.
The NOAEC values of MIT and OIT are 0.34 mg/m3 (Burnett et al.,
2021) and 0.64 mg/m3 (EPA, 2007), respectively. According to the
surface-air partitioning coefficient of this study, an exposure to higher
than 3.47 mg of MIT and 360.63 mg of OIT per surface area of 1 m2
volatilized to a concentration in the air of a 8 m3 enclosed room can
cause adverse health effects. In terms of a risk assessment and man­
agement of domestic household chemical products, in the case of MIT,
when exposed to the surface, a large amount is converted to concen­
tration in the air within a shorter time than that of OIT.
Although the use of spray-type products is currently prohibited in
South Korea after the humidifier disinfectant incident, all non-spray
products such as cleaners, fabric softeners, and coatings, however, are
allowed to contain MIT. OIT is permitted to contain both spray and non-
spray products. In the case of MIT, when exposed to surfaces, a large
amount of exposure is converted to air concentration in a shorter time
than OIT, so its air distribution can lead to harmful amounts of exposure
All data has been reported in the article.
Acknowledgements
We acknowledge the financial support from the Korea Environment
Industry & Technology Institute (KEITI) through Technology Develop­
ment Project for Safety Management of Household Chemical Product
Program, funded by Korea Ministry of Environment (MOE)
(2020002970006, 1485018531 and 2020002970005, 1485018696).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.envres.2022.114908.
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