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Environmental Science and Pollution Research (2021) 28:59214–59232

https://doi.org/10.1007/s11356-020-09860-4

RECENT DEVELOPMENTS AND INNOVATIVE STRATEGIES IN ENVIRONMENTAL SCIENCES IN EUROPE

Investigation on air quality of specific indoor environments—spa


salons located in Gdynia, Poland
Klaudia Pytel 1 & Renata Marcinkowska 1 & Bożena Zabiegała 1

Received: 28 November 2019 / Accepted: 22 June 2020 / Published online: 13 July 2020
# The Author(s) 2020

Abstract
Due to excessive application of essential oils and scented products in spa salons during aromatherapy and massage sessions, the
elevated concentration of total volatile organic compounds (TVOCs), particularly terpenes, which are known as secondary
organic aerosol (SOA) precursors, is expected there. This study was aimed at determination of VOCs with a particular regard
to terpenes in air samples collected in selected spa salons located in Northern Poland. Active air sampling was conducted before
and after treatments. Samples were analyzed with the use of thermal desorption gas chromatography coupled with flame-
ionization detector (TD-GC-FID) and mass spectrometer (TD-GC-MS). Obtained results allowed to characterize chemical
composition of indoor air of spa salons and also to relate the dependence between applied essential oil and indoor air chemical
composition. It has been proved that (i) spa salons are characterized by TVOC concentrations exceeding recommended values of
300–400 μg m−3 in most of examined cases, reaching up to several thousand of micrograms per cubic meter, (ii) TVOC
concentration is strictly related to salon characteristics and carried out treatments, (iii) terpenes constitute a significant part of
TVOCs present in spa indoor air, from 22 up to 86%, (iv) most commonly investigated terpenes in the literature (D-limonene, α-
pinene, camphene, and linalool) were also determined at the highest concentration levels in this study and (v) VOC chemical
composition is strictly dependent on the type of applied essential oils. On the basis of obtained results, it may be stated that
extensive application of essential oils rich in terpenes can significantly alter indoor air chemistry of spa salons, thereby influenc-
ing health and well-being of employees working there.

Keywords Indoor air . Indoor air quality . Volatile organic compounds . Terpenes . Spa salons . Aromatherapy . Essential oils

Introduction referring already gained knowledge of atmospheric air to in-


door air may lead to inconsistencies, since mechanisms which
For several decades, indoor air quality has been a matter of govern indoor air chemistry are different from those charac-
interest of both scientists and politicians. This was triggered teristic to atmospheric air. Also, there are significant differ-
by the fact that people may spend up to even 90% of their time ences between these two environments in abundance of de-
indoors, and therefore, chemical and physical transformations fined components and direct sunlight, temperature, and hu-
which occur indoors (sometimes referred as “indoor chemis- midity fluctuations etc. (Weschler and Carslaw 2018; Abbatt
try”) appeared as greatly important to human health and well- and Chen 2020).
being (Samet 1993; Weschler and Carslaw 2018). Intensified Indoor air chemistry is greatly affected by primary emis-
interest in studying indoor air was triggered by proving that sion of volatile organic compounds (VOCs) from a wide range
of sources present indoors, i.e., furnishing, building materials,
Responsible Editor: Constantini Samara
everyday use products, human activities, and humans them-
selves (e.g., squalene, acetone) (Haghighat and De Bellis
* Renata Marcinkowska 1998; Klein et al. 2016; Lakey et al. 2017). Elevated VOC
renata.marcinkowska@pg.edu.pl concentrations in indoor air pose a threat to human health,
since a lot of VOCs (e.g., aldehydes, aromatics) (Liu et al.
1
Department of Analytical Chemistry, Faculty of Chemistry, Gdańsk
2019) are documented to cause adverse health effects such
University of Technology, G. Narutowicza 11/12 Str., as asthma and allergic reactions (Sofuoglu et al. 2011), as well
80-233 Gdańsk, Poland as damage of the liver, kidneys, and nervous system.
Environ Sci Pollut Res (2021) 28:59214–59232 59215

Moreover, some VOCs may exhibit a carcinogenic activity relaxation; therefore, more and more people are inclined to
resulting in lung, brain, liver, blood, and kidney cancer undergo it (Grand View Research 2019).
(Rumchev et al. 2007). Since terpenes are the main components of essential oils
Among VOCs, terpenes are a group of significant impor- (Bakkali et al. 2008), a significant quantities of them are ex-
tance, since terpene-rich essential oils are components of used pected to be emitted into indoor air of spa salons during aro-
indoor furnishing, cleaning, fragrance, cosmetic, and cooking matherapy sessions. Since customers of spa salons usually
products. In addition, terpenes may be emitted also from natural spent there ca. 1 h, it can be assumed that exposition to ele-
sources such as plants and citrus fruits; however, it is believed vated total volatile organic compounds (TVOCs) and terpene
that anthropogenic sources are those mostly responsible for oxidation product concentration would not strongly affect cli-
elevated concentration of terpenes indoors (Wolkoff et al. ents’ health and well-being. Therefore, visiting spa for relax-
2000; Nazaroff and Weschler 2004; Tsigonia et al. 2010). ation or taking physio- or aromatherapy session may actually
Terpenes with one or more double bonding in their structure be beneficial. However, employees of spa salons, by spending
are highly reactive; hence, they instantly and easily undergo whole working day—usually 8 h—in spa indoor air may be
oxidation processes in indoor air such as ozonolysis exposed to elevated TVOCs and terpene oxidation product
(Weschler 2000; Atkinson and Arey 2003). Terpene ozonolysis concentration, which may affect their health and well-being.
initiates a number of chemical transformations, which lead to Worldwide, studies in this research area are focused most
the formation of secondary organic aerosol (SOA) composition, commonly on the determination of the composition either of
especially in the first phase of rising, of nanosized (submicron) the essential oil or the volatile fraction emitted from essential
particles. These particles have been proved to pose a threat for oil (or scented candles) that are usually applied in aromather-
human health (Rösch et al. 2017) since they are able to enter apy. Such studies are typically carried out with the application
respiratory track and deposit along it by few mechanisms: dif- of a reaction chamber that mimics indoor air conditions, by
fusion, sedimentation, and impaction (Dockery et al. 1993; direct GC analysis of essential oil solutions or with the use of
Spengler et al. 1996; Yeh et al. 1996; Pope and Dockery SPME-based methodologies (Chiu et al. 2009; Huang et al.
2006). It has been proved that inhalation of SOA can cause 2011; Cheng and Lai 2014; Ahn et al. 2015; Nematollahi et al.
some serious health effects such as inflammatory response in 2018). The aim of this research was to expand the knowledge
body tissues (Anderson et al. 2013), changes in lung cells, and awareness related to temporary and permanent residence
breath frequency decrease (Clausen et al. 2001; Sunil et al. in indoor environments of specific types. Investigating indoor
2007; Wolkoff et al. 2008, 2012), eye-blink frequency increase air quality in spa salons, where traditional aromatherapy ses-
(Klenø and Wolkoff 2004; Nøjgaard et al. 2005), and even sion took place and, therefore, enhanced terpene evaporation
cancer (Pope and Dockery 2006). into indoor air is expected, delivers valuable data useful for
There is a wide range of research carried out to determine better understanding of indoor air chemistry. The main goal of
VOC concentration with emphasis on terpenes in various in- this study was to determine the concentration of terpenes de-
door environments, e.g., homes (Król et al. 2014; Mickaël tected in indoor air samples in spa salons and to correlate
et al. 2014; Schlink et al. 2016), offices (Su et al. 2007; carried out treatments and applied essential oils and cosmetic
Dudzinska et al. 2012; Katsoyiannis et al. 2014), and schools products with the chemical composition of indoor air. In the
(Larroque et al. 2006; Pegas et al. 2011; Markowicz and available literature, there are very few reported studies, in
Larsson 2015). However, there is a limited number of research which sampling was carried out in real spa indoor environ-
focusing on specific kind of indoor environments, where ments, e.g., located in Taiwan (Hsu et al. 2012; Huang et al.
terpinene concentration is expected to be elevated, such as 2012); however, a major emphasis has been put on SOA for-
wineries (Sanjuán-Herráez et al. 2014), treatment plants mation. To the best of our knowledge, this is the first study
(Gallego et al. 2012), elderly homes (Walgraeve et al. 2011), focused on VOC (with particular emphasis on terpenes) deter-
and beauty salons (Tsigonia et al. 2010). mination in such specific environments carried out in Poland.
Terpene-rich essential oils are widely applied as therapeu-
tic agents during aromatherapy sessions known as alternative
method of treatment. There are three main models of aroma- Materials and methods
therapy treatment: medical, where essential oils are most com-
monly delivered inside the body (oral, rectal, vaginal way); Sampling sites
subtle aromatherapy, where essential oils are most commonly
inhaled; and traditional aromatherapy, which is based on mas- Four spa salons located in Gdynia (Poland) City center were
sage with essential oils (Dunning 2013). Aromatherapy is an chosen as sampling sites. Sampling campaign lasted from
area of growing interest, which becomes popular for example January 2019 to April 2019, and the sum of 60 samples was
in psychiatry and oncology (da Silva Domingos and Braga collected during campaign. Forty-four of them were analyzed
2014). Aromatherapy massages are very willingly used for with an application of thermal desorption and gas
59216 Environ Sci Pollut Res (2021) 28:59214–59232

chromatography with flame-ionization detector (TD-GC-FID), and 14 samples were collected before and after treatment,
and 16 of them were analyzed by thermal desorption and gas respectively;
chromatography with mass spectrometry (TD-GC-MS). The & Spa salon 4—health and beauty studio which is special-
brief characteristics of sampling sites together with schematic ized in physiotherapy massages, which do not require ap-
representation of their space arrangement (see Fig. 1) are pre- plication of fragrance compounds. Relaxing massages
sented below. with essential oils are performed rarely. For sampling, 2
and 4 samples were collected before and after treatment,
& Spa salon 1—typical spa salon, in which main treatments respectively. Limited number of samples is due to salon
are aromatherapy massages with an application of large characteristics.
amounts of essential oils and body butters. Salons offers
also esthetic medicine treatments and manicure, but those
services are done in other rooms. Usually, clients are
served during all day, which results in over a dozen of Sampling
clients per day. For sampling, 4 and 13 samples were
collected before and after treatment, respectively; Air samples were collected before and after massage sessions
& Spa salon 2—massage center, in which relaxing aroma- (each session lasted 1 h). As sampling sorbent, Tenax TA®
therapy massages and physiotherapy massages are carried (Tenax TA 35/60®, 100 g, hydrophobic) was selected
out. This salon mostly serves regular customers, and visits (Arrhenius and Engelbrektsson 2016; Petr and Soukupová
are planned for whole day; therefore, over a dozen of 2017; Ramos et al. 2018; SIS 2019). Before sampling and
clients is served daily. For sampling, 2 and 16 samples after each analysis, sorbent tubes were conditioned for 6 h,
were collected before and after treatment, respectively; at temperature of 300 °C in inert gas atmosphere using thermal
& Spa salon 3—city spa which proposes few relaxing treat- desorption unit (Markes® Unity, Markes International, Great
ments: sensory deprivation, ganbanyouku, and ayurvedic Britain). Conditioning was followed by a blank gas chroma-
massages. Massage room is equipped with two heated tography run (Agilent 7820A, Agilent Technologies Inc.,
beds dedicated for ayurvedic massages. Spa 3 offers other USA with FID detector) to ensure no carry over effect. After
treatments than massages; therefore, amount of daily per- conditioning, sorbent tubes were sealed with two-piece brass
formed massages is not regular and hard to define. It is storage caps filled with one-piece PTFE ferrules (6 mm i.d.)
common that number of massage clients rises due to peri- and additionally closed in a screw cap glass vials for storage
odic circumstances, e.g., Valentine’s day. For sampling, 5 and transport. Samples were actively sampled via gas-tight

Fig. 1 Schematic representation


of room space arrangement of
each of chosen spa salon
Environ Sci Pollut Res (2021) 28:59214–59232 59217

syringe or automatic pump (constructed at Gdańsk University follows: 40 °C for 10 min, 10 °C/min to 125 °C, 15 °C/min to
of Technology especially for the purpose of this study with 240 °C held for 5 min. Detector temperature was 250 °C.
constant air flow of 120 ml min−1). During sampling, 1 l or 2 l For monoterpene concentration determination, five-point
of air (depending on the carried out treatment) was actively calibration curve was created using limonene ((R)-(+)-limo-
passed through the sorbent tubes. During each sampling, there nene standard, 97% purity, (Sigma-Aldrich, Poland) dissolved
was one blank sorbent tube, which was sealed and placed near in methanol (gradient grade for liquid chromatography 99.9%
the sampling spot. Blank tube was maintained and handled the purity, Merck) calibration solutions of following concentra-
same way as sorbent tubes used for sampling. After sampling, tions: 2.0; 4.0; 6.0; 8.0; and 10.0 ng μL−1. For each concen-
sorbent tubes were sealed in the same way as described above. tration 1 μl of calibration solution was introduced on previ-
All samples were stored in a temperature not exceeding 20 °C, ously conditioned sorbent tube, which was then flushed by a
hidden from the sunlight, and were analyzed during max. of stream of nitrogen (99.999% purity) for 4 min. Afterwards,
48 h since sampling. sorbent tube was sealed with two-piece brass storage caps,
closed in a screw cap glass vials and quickly (up to 1 min)
Analytes of interest analyzed by TD-GC-FID. Each calibration solution was ana-
lyzed by TD-GC-FID in at least 3 repetitions. In order to
The main goal of this work was to focus on determination of obtain the best possible match, first two points of calibration
terpenes present in spa indoor air at high concentration levels; curve were used to calculate LOD and LOQ values. For lim-
therefore, the main emphasis has been put on α-pinene, D- onene LOD = 0.7 ng, LOQ = 2 ng which after recounting per
limonene, camphene, and linalool. Other VOC characteristics 2-l air samples resulted in LOD = 0.35 μg m−3 (0.063 ppbv)
for each spa indoor environment, determined in this study and LOQ = 1 μg m−3 (0.18 ppbv). Percentage standard uncer-
qualitatively and quantitatively, are listed in Appendix tainty associated with application of determined calibration
Tables 2, 3, 4, 5, and 6. They represent such groups of chem- relationship was calculated using Formula (1), (2), and (3).
ical compounds as follows: alcohols, organic acids, esters, For limonene, percentage uncertainty is equal to 5.5%.
aldehydes, alkenes, alkanes, siloxanes, ketones, and terpene
oxides.  
  u xpr
u xpr %¼ ð1Þ
Chromatographic analysis and calibration xpr

where:
To carry out qualitative analysis, samples were subjected to
xpr—analyte content (half of calibration curve)
thermal desorption (Markes® Unity, Markes International,
u(xpr)—standard uncertainty
Great Britain) and further to gas chromatography (Agilent
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2ffi
6890, Agilent Technologies Inc., USA) coupled with mass u
u xpr −x
spectrometry (Agilent 5973 Mass Selective Detector,   S x;y t 1 1
u xpr ¼  þ þ ð2Þ
Agilent Technologies Inc., USA) (TD-GC-MS). Analytes b p n Qxx
were separated on DB-1 capillary column (Agilent
Technologies; 60 m × 0.25 mm × 1 μm; 100% polydimethyl- where:
siloxane). To carry out quantitative analysis, samples were Sx, y—standard deviation
subjected to thermal desorption (Markes® Unity 2, Markes b—slope
International, Great Britain) and further to gas chromatogra- p—number of repetitions
phy (Agilent 7820A, Agilent Technologies Inc., USA) n—number of repetitions for whole calibration curve
equipped with flame-ionization detector (TD-GC-FID). x —x mean value
Analytes were separated on DB-1 capillary column (Agilent  2
Technologies; 30 m × 0.32 mm × 5 μm; 100% polydimethyl- Qxx ¼ ∑ x−x ð3Þ
siloxane). In both cases, chromatographic analysis was pre-
ceded with 10-min thermal desorption under 290 °C which Concentration of other determined analytes (determined
was followed by transportation of desorbed analytes in the He separately and as TVOCs) was calculated as toluene equiva-
stream (45 mL min−1) to the microtrap cooled down to 0 °C lents. Toluene (CHROMASOLV Plus, for HPLC, 99.9% pu-
and subsequent heating of the microtrap to 300 °C for 5 min in rity, Honeywell) calibration solutions were prepared in the
order to release the analytes and direct them to chromato- same way like limonene standard solutions. The five-point
graphic column. Temperature program of the GC-MS analysis calibration curve was created using the following concentra-
was as follows: 50 °C, 10 °C/min to 280 °C. Temperature of tions of toluene standard solutions: 2.0; 4.0; 6.0; 8.0; and
ion source was 250 °C, while temperature of quadrupole was 10.0 ng/μl. All of the calculations were performed similarly
150 °C. Temperature program of the GC-FID analysis was as
59218 Environ Sci Pollut Res (2021) 28:59214–59232

as in the case of limonene calibration. Therefore, the following 500 μg m−3 (NHMRC 1993), Finland 200–600 μg m−3
values of metrological parameters were obtained: LOD = (FISIAQ et al. 1955). In Poland, there is no regulation for
1.9 ng, LOQ = 5.8 ng; for 2-l air samples MLOD = TVOC concentrations; there are several but only for some
0.95 μg m−3 (0.25 ppbv), MLOQ = 2.9 μg m−3 (0.77 ppbv). specific VOCs. However, taking into consideration the values
Percentage standard uncertainty was equal to 8.1%. from other countries, one may state that TVOC concentration
of 300–400 μg m−3 indicates that indoor air quality requires
deeper investigation. Moreover, in Report 19, released by the
Results and discussion ECA in 1997, it is mentioned that TVOC concentration above
25 mg m−3 increases the likelihood of sensory effects such as:
In 1992, ECA (European Collaborative Action) released Report dryness, sensory irritation, weak inflammatory irritation of
11 “Guidelines for Ventilation Requirements in Buildings,” eyes, nose, airways, and skin (ECA 1997).
according to which there are 4 comfort ranges of TVOCs in- The first step of this research was to determine, as recom-
doors, proposing 300 μg m−3 as target guideline concentration mended by the ECA (ECA 1997), as many volatile com-
for TVOCs indoors (European Collaborative Action 1992): pounds as possible in collected air samples, at least those
which are the most abundant. Qualitative analysis was done
& < 200 μg m−3—comfort range by TD-GC-MS. MS NIST 2.0 library was used to identify
& 200–3000 μg m−3—multifactorial exposure range detected VOCs. On this basis, the list of most commonly
& 3000–25,000 μg m−3—discomfort range occurring VOCs was created, which concerned compounds
& > 25,000 μg m−3—toxic range that were identified by NIST 2.0 library with probability
higher than 70% (see Appendix Table 6).
Unfortunately, only few countries have guidelines for in- TVOC concentration variations determined during all
door TVOC concentrations: Germany 300 μg m−3 (Seifert sampling days in all investigated spa salons are depicted
1990), the USA 200 μg m−3 (USA-EPA 1996), Australia in Fig. 2.

Fig. 2 Variations in TVOC concentrations determined during sampling campaign in all investigated spa salons
Environ Sci Pollut Res (2021) 28:59214–59232 59219

Determined instantaneous concentrations of TVOCs in all chimneys, there was lemongrass oil with wild rose and orange
spa salons exceeded proposed target concentration of oils, which made this massage exceptionally aromatic. Taking
300 μg m−3, even before the beginning of the massage. Most into consideration the sharp increase of TVOC concentration
commonly, TVOC concentrations determined before treatment after the massages with the application of essential oils, it may
were lower than concentrations determined after the treatment, be stated that increased temperature inside the massage room,
with two exceptions in spa 1 on the following sampling days: warm human skin and its large area contribute to intensified
30 January 2019 and 05 March 2019. High concentration of exposure of both workers and clients of spa salons to in-
TVOCs measured before the beginning of treatments was prob- creased concentration of TVOCs, including terpenes (espe-
ably related to high TVOC concentration in indoor air on the cially those of high volatility), in indoor air. This has been
previous day. Most of the results are within the multifactorial also proved by the results obtained by Huang et al. (2012)
exposure range. One exception is TVOC concentration mea- and Hsu et al. (2012) within their investigations on aromather-
sured in spa 4 after the massage—23,694 μg m−3, which was apy environments. In that studies, TVOC concentrations be-
almost in the toxic range. However, because measured concen- fore massages was in the range 400–600 μg m−3 and 250–
trations were instantaneous, it cannot be clearly stated whether 500 μg m−3 correspondingly, which is consistent with mea-
they pose a serious threat to human health, as the effect depends surement in this research’s “initial” concentrations in the
on how long the exposition to high concentrations lasts. This range 450–600 μg m−3. Huang et al. (2012) determined the
particular spa salon (spa 4) is not specialized in very scented highest TVOC concentration in 125–175 min of the measure-
and relaxing massages. Usually, physiotherapeutic massages ment (during first aromatherapy session), and it reached
are carried out there. Moreover, the number of carried out treat- 1200 μg/m3, while in Hsu et al. (2012) research, the highest
ments per day is not so high like in case of, e.g., spa 1, in which noted TVOC concentration was equal to 3250 μg m−3 (for the
all three massage rooms are simultaneously occupied for most details, see References). Determined in our study, TVOC con-
of the time. centration range of 600–1200 μg m−3 (with the exception of
Interesting fact is that in case of spa 2, concentration of measured in spa 4 exceptionally high value of TVOC concen-
TVOCs on 27 February 2019 was higher than on most of tration) is close to the discussed above cases.
the other days when sampling was carried out after treatment. To get closer to the main purpose of this research, a per-
This was probably due to the smoldering of Palo Santo branch centage share of terpene concentration in relation to all deter-
that day. According to the literature, Palo Santo (Bursera mined TVOCs was calculated and presented in Fig. 3.
graveolens) essential oil is mostly composed of terpenes. Applied during the treatment in spa 1, coconut and tea tree
Sotelo Mendez and co-workers (Sotelo Mendez et al. 2017) oils did not contribute significantly to percentage share of
investigated the chemical composition of Palo Santo essential terpene concentration in relation to determined TVOCs.
oil from Peru and determined that α-terpinene is a dominating Relatively low (22%) content of terpenes in collected air sam-
component. It has been proved that the country of origin plays ple was caused by the fact that coconut oil is not an essential
an important role in Palo Santo essential oil composition, oil and it is mainly composed of fatty acids (Marina et al.
since Fon-Fay et al. (2019) indicated that limonene constitutes 2009); hence, the only source of terpenes in this case was
34.9% of the composition of Bursera graveolens essential oil tea tree oil heated on the chimney. In spa 2, a massage with
from Ecuador, whereas according to the results obtained for an application of geranium and orchid oils resulted in elevated
essential oil from Peru (Sotelo Mendez et al. 2017), limonene terpene percentage share in comparison to spa 1, which can be
constituted only 0.19% of its composition. In spa 2 on 27 explained by the application of two essential oils during treat-
February 2019, Palo Santo began to smolder approximately ment. After the massage in spa 3, during which sesame and
an hour before the official opening of the salon and more than orange oils were applied, percentage content of terpenes in
one branch was used that day; therefore, it is highly probable collected sample was equal to 60%, probably due to the fact
that this activity was responsible for such high TVOC concen- that orange oil is mainly composed of limonene (77–95%)
tration measured, despite the fact that sampling was done be- (Verzera et al. 2004; Tao et al. 2009). Application of large
fore any massage started. amounts of different essential oils during treatment in spa 4
Generally observable trend was that TVOC concentration (orange, lilac petals, Scots pine, lemongrass, wild rose) result-
increased after each treatment in all spa salons. The greatest ed in very large percentage share of terpenes in air sample
impact of the carried out treatment on the indoor air chemical composition equal to 86%. These results indicate that terpene
composition was observable in the case of spa 4 on 08 content in spa indoor air depends on the type (chemical com-
March 2019. The TVOC concentration in sample collected position) and amount of applied oils and cosmetics during
after the massage was 55 times higher than that in the one aromatherapy.
collected before it started. During this treatment, a mixture According to the ECA, it is possible that specific VOCs
of the following essential oils was applied: orange, lilac petals, may influence indoor air quality and may be solely responsi-
Scots pine, and synthetic orange fragrance; whereas on the ble for or partially contribute to the development of health
59220 Environ Sci Pollut Res (2021) 28:59214–59232

Fig. 3 Percentage share of sum of


terpenes and other VOCs in
relation to TVOC content in air
samples collected in investigated
spa salons on exemplary
sampling days

effects in greater extent than other VOCs. If such circum- from 25 to 60 μg m−3, which is similar to limonene concen-
stances are suspected to occur, these specific VOCs (or one tration measured in studies on indoor air quality of shopping
specific VOC) should be listed and determined separately malls (Amodio et al. 2014) or homes (Villanueva et al. 2015).
(ECA 1997). Therefore, full list of 21 quantitatively deter- Concentrations of α-pinene, camphene, and linalool before
mined chemical compounds is available in Appendix treatments did not exceed 100 μg m−3. Concentrations of
Tables 2, 3, 4, and 5, whereas four terpene compounds that monoterpenes after massage treatment are visibly higher than
were determined at highest concentration levels (α-pinene, before treatment, which indicates the presence of strong emis-
limonene, camphene, and linalool) are discussed in detail be- sion sources. Extremely high increase of limonene concentra-
low. According to the literature, these compounds are com- tion up to 18,947 μg m−3 was probably caused by the use of
monly investigated in terms of indoor air quality because of complex essential oil mixture applied in huge amounts, which
high abundance of their emission sources indoors. α-Pinene resulted also in increased TVOC concentration. Hsu et al.
and limonene are the most commonly occurring terpenes in (2012) indicated in their research that limonene has very sim-
indoor environments. Camphene is also frequently deter- ilar increasing concentration trend as TVOCs and its concen-
mined terpene, but it is present in indoor air at concentrations tration in samples collected after massage was 16 to 60 times
lower than limonene and α-pinene (Tanaka-Kagawa et al. higher than in those collected before the treatment started. In
2005; de Gennaro et al. 2013). Linalool is not so frequently our study, this range was even greater, since limonene con-
determined in indoor air quality research as aforementioned centration in indoor air after massage was from 2.5 to almost
terpenes, but it was proved that the application of essential oils 740 times greater than before.
is responsible for high emission of this compound (Su et al. Since limonene is one of the most commonly occurring
2007). Concentration variations of these selected compounds, monoterpenes in indoor air and, as it was already men-
determined by TD-GC-FID before and after massage treat- tioned, it was the most abundant monoterpene in all stud-
ment, are presented in Fig. 4. To date, terpene emission ied salons, we investigated particularly limonene concen-
sources were the same as discussed above. tration variations along all sampling days. Results of this
According to the results presented in Fig. 4, limonene was investigation are presented in Table 1 as percentage share
the most abundant monoterpene in all investigated spa salons of limonene concentration in the sum of terpene concen-
and its background concentration (before treatment) varied trations. Such divergent results prove that each salon is a
Environ Sci Pollut Res (2021) 28:59214–59232 59221

Fig. 4 Variations of four


representative terpenes
determined before and after
massage treatments in all
investigated spa salons

specific and characteristic environment with dynamically (Régimbal and Collin 1994), orange oil mainly composed of
changing indoor air chemistry. All activities and applied limonene (77–95%) (Verzera et al. 2004; Tao et al. 2009),
cosmetic products have an influence on indoor environ- geranium oil rich in citronellol (37.5%) (Sharopov et al.
ment of each of the salons; therefore, chemistry of spa 2014), or sage oil rich in 8-cineole (71.6%) (Borek et al.
salons cannot be unified and has to be specified for each 2006), results in the dominant percentage share of terpenes
of the salon separately. in the investigated air samples. Geranium oil additionally con-
In order to better describe the air quality of investigated tains a large fraction of alcohols in its composition (50–60%)
salons, obtained qualitative results were combined to create (Babu and Kaul 2005), which also significantly influences
charts showing percentage content of specific groups of chem- collected air sample composition (see Fig. 5, spa 2 sampling
ical compounds in collected air samples. These results are day 07 March 2019). “Indian flower” is a commercial name of
presented in Fig. 5. mixture of essential oils, which is unfortunately unavailable to
On the basis of collected data presented in Fig. 5, it may be check; therefore, it is impossible to speculate on its
stated that the type of the oil applied during the session highly composition.
influences the chemical composition of air inside the room The high impact of the type (and composition) of essential
where it took place. The presence of compounds of other than oil during the treatment on the percentage content of limonene
monoterpene groups of chemicals is probably related to the among all chemical compounds determined in air samples
fact that commercially available essential oils (applied during may be indicated with the example of spa 3 indoor air sample
investigated aromatherapy sessions) are rarely composed of composition. Amounts of alcohols, organic acids, esters,
100% pure essential oil. It is very common that they contain ethers, aldehydes, alkenes, alkanes, siloxanes, ketones, and
additives such as alcohols, some other terpenes, and/or other other compounds are very alike between two sampling days.
fragrance compounds. However, the use of monoterpene-rich A significant difference concerns limonene content. Rose oil
essential oils or cosmetic products with such essential oils, applied on 26 March 2019 does not contain limonene; how-
e.g., fir needle oil mainly composed of β-pinene (35–48%) ever, it contains significant amounts of other terpenes and
59222 Environ Sci Pollut Res (2021) 28:59214–59232

2342.5 ± 128.8 (74.8)


93.1 ± 5.1 (29.7)
88.7 ± 4.9 (59.3)
81.2 ± 4.5 (29.4)
scented terpene derivatives (geraniol 22%, nerol 10%, and

Geometric mean
citronellol 35%) (Ulusoy et al. 2009). Mixture of essential oils
(ylang ylang, lavender, pink grapefruit oils) applied on 25
March 2019 changed limonene percentage share in sample
chemical composition significantly. Ylang ylang and lavender
oils contain trace amounts of limonene (Stashenko et al. 1996;
Baratta et al. 1998; Hui et al. 2010); however, this terpene is a

520.4 ± 28.6 (47.5)


90.6 ± 5.0 (59.8)

9620.2 ± 529.1 (76.6)


main component of pink grapefruit oil (88–91%) (Njoroge

84.0 ± 4.7 (36)


Arithmetic mean et al. 2005; Uysal et al. 2011); therefore, limonene was an
abundant component of air sample collected that day.
Concentration of limonene expressed as absolute value and percentage share in relation to a sum of terpene concentration measured within the research

Huang et al. (2012) and Hsu et al. (2012) in their studies


determined that aromatherapy treatment causes submicron (<
100 nm) SOA particles growth at a level from 10,000 to
100,000 particles/cm3, indicating that high terpene concentra-
108.5 ± 6.0 (73.9)
105.5 ± 5.8 (59.5)

18,950.8 ± 1042.3 (93.1)


tion in such environments, even at low-level ozone concentra-
1032.4 ± 56.8 (78)

tion, produces large amounts of nanosized SOA. Additionally,


terpene oxidation reactions in terpene-rich environments
caused formation of formaldehyde up to 0.025 ppm, while
background concentration was equal up to 0.005 ppm and I/
Max

O (indoor to outdoor ratio) indicated that formaldehyde emis-


sion sources were mainly indoors. Taking above into consid-
eration together with obtained results within this study, it may
72.6 ± 4.0 (50.6)

289.5 ± 15.9 (60.1)


62.4 ± 3.4 (4.3)
8.4 ± 0.5 (0.3)

be stated that indoor air quality in spa salons may pose a risk to
After treatment

human health and well-being.


Min

Summary and conclusions


74.4 ± 4.1 (56.2)
79.6 ± 4.4 (45.3)
30.2 ± 1.7 (17.3)
Geometric mean

This study, aimed at investigation of indoor air quality with


-

particular emphasis on terpene presence in specific kind of


environments such as spa salons, is, to the best of our knowl-
Concentration (ppbv) and percentage share (values in brackets [%])

edge, the first research of this type carried out in Poland.


Results obtained within this study allowed to characterize in-
Arithmetic mean

92.0 ± 5.1 (57.1)


93.1 ± 5.1 (45.8)
30.7 ± 1.7 (17.4)

door air quality and composition in selected spa salons. It has


been proved that spa salons are characterized by TVOC con-
-

centrations exceeding recommended values of 300–


400 μg m−3 and that TVOC concentration is strictly related
to salon characteristics and carried out treatments. The evalu-
ation of data gathered during this study indicates that terpenes
25.6 ± 1.4 (38.8)
146.1 ± 8.0 (71.1)
141.4 ± 7.8 (52.8)
35.9 ± 2.0 (20.9)

constitute a significant part of TVOCs present in spa indoor


air. Elevated terpene concentration is strongly related to the
application of essential oils during treatments; however, con-
Max

stant emission sources such as candle chimneys filled with


essential oils also contribute to increased terpene (and there-
fore TVOCs) concentration in indoor air. Indoor air quality in
Before treatment

37.9 ± 2.1 (46.8)


44.8 ± 2.5 (38.9)
25.5 ± 1.4 (14.8)

small spaces of spa salons can be easily altered by application


< LOD (-)

of even small amounts of essential oils or cosmetics contain-


ing terpenes. It is known now that even small indoor concen-
Min

tration of ozone may trigger the reaction of SOA formation, as


long as there is enough of second substrate—terpenes.
Table 1

Employees, by spending 8 h daily in such environment, may


Spa 1
Spa 2
Spa 3
Spa 4

be at the risk of high exposure to harmful VOCs and terpene


Environ Sci Pollut Res (2021) 28:59214–59232 59223

terpene oxide
spa 1 19.03.2019 2% spa 1 14.03.2019
aloe oil others fir needle oil
ketones green tea oil 8% orange oil
1% ketones
2% d-limonene
d-limonene 30%
others
alkanes 10%
siloxanes 19%
3%
15%
alkenes
2% siloxanes
26%
aldehydes terpenes terpenes
5% 15% 41%
ethers
4%
alcohols alkenes
esters 1% other terpenes
14%
21% other terpenes 11%
5% aldehydes
2% esters
6%
organic acids alcohols
1% organic acids
10%
2%

alcohols organic acids esters ethers aldehydes alkenes alkanes siloxanes ketones other terpenes others d-limonene

spa 2 07.03.2019
spa 2 19.03.2019
geranium oil
ketones others
geranium oil
others indian flower oil ketones
siloxanes
2% 10% 12% white sage oil
1%
siloxanes
12%
9%

alkenes alkanes other terpenes


3% 4% 31%
other terpenes
aldehydes 27% alkenes
6% 4%
terpenes aldehydes
33% terpenes
ethers 2% 36%
2% ethers
esters 1%
6%
d-limonene d-limonene
6% 5%
esters
20%

alcohols organic acids alcohols


26% 1% 10%

alcohols organic acids esters ethers aldehydes alkenes alkanes siloxanes ketones other terpenes others d-limonene

spa 3 25.03.2019
spa 3 26.03.2019 terpene oxide
1% ylang ylang oil
rose oil others
others
ketones
lavender oil
ketones 7% 8%
1% 1% pink grapefruit oil
siloxanes
siloxanes
10% sunflower oil
8% other terpenes d-limonene
42% 29%
alkanes alkanes
3% 2%
alkenes
alkenes 6%
6% terpenes terpenes
51% 46%
aldehydes aldehydes
5% 5%
other terpenes
ethers 17%
1% esters
5%
esters
d-limonene organic acids
8%
9% 3%
organic acids
1% alcohols
alcohols 13%
9%

alcohols organic acids esters ethers aldehydes alkenes alkanes siloxanes ketones other terpenes others d-limonene

Fig. 5 Percentage share of specific groups of compounds in air samples collected in spa salons with indication of applied essential oils during the
treatments

oxidation products, e.g., acetone, formaldehyde, and submi- Further research in this area supported by toxicological studies
cron SOA particles. would allow for obtaining results required for establishing and
Indoor air monitoring in spa salons would be highly advised, introducing of law regulations regarding maximum allowable
as well as checking ventilation/air exchange performance. concentrations of VOCs in these specific indoor environments.
Appendix 1
59224

Table 2 Determined concentrations of selected analytes in samples collected in SPA 1

SPA 1 date

29.01.2019 29.01.2019 30.01.2019 30.01.2019 05.02.2019 15.02.2019 19.02.2019 19.02.2019 26.02.2019 27.02.2019 05.03.2019 05.03.2019 06.03.2019
Before After Before After After After Before After After After Reception After After

Determined compounds Concentration (ppbv)


Isopropyl alcohol 20.64 n.d. n.d. 20.92 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Acetic acid 24.67 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Toluene n.d. 0.79 < LOQ 0.90 n.d. 0.87 < LOQ < LOQ 4.59 1.75 < LOQ < LOQ < LOQ
Cycli3siloxane 15.76 31.39 16.68 18.81 23.42 22.49 9.05 10.13 13.85 3.52 4.11 2.44 n.d.
2-Propanol 11.13 n.d. 16.30 8.17 23.60 32.09 n.d. 16.19 9.23 16.91 n.d. n.d. 10.39
α-Pinene < LOQ 3.79 1.95 1.05 3.06 4.48 1.68 3.62 2.81 2.55 2.38 < LOQ 1.74
Camphene 1.74 2.44 1.37 < LOQ 2.00 2.26 2.04 3.14 2.09 4.29 0.96 0.90 1.24
β-Pinene < LOQ 1.66 1.02 < LOQ 1.25 2.39 1.05 1.76 8.09 < LOD 0.90 0.93 1.13
α-Phellandrene 1.18 1.36 1.11 1.26 1.72 2.68 1.07 2.96 3.15 6.50 1.19 n.d. 2.79
3-Carene < LOQ < LOQ < LOQ 1.26 < LOQ < LOQ < LOQ 0.87 < LOD < LOQ n.d. 1.60 < LOQ
D-Limonene 11.02 28.37 7.11 3.91 11.89 13.06 26.28 34.75 30.16 < LOD 6.81 5.79 19.51
β-Phellandrene n.d. < LOQ < LOQ n.d. < LOQ 0.92 < LOQ < LOQ 2.18 < LOQ < LOQ 1.79 < LOQ
Eucalyptol 0.85 1.82 1.02 < LOQ 1.64 1.34 2.98 7.82 6.06 n.d. 1.42 < LOQ 2.16
Linalool 5.10 4.88 3.13 0.80 5.16 6.31 4.65 7.05 4.58 7.86 2.77 < LOQ 2.39
Undecan n.d. n.d. n.d. n.d. 3.76 19.34 4.53 n.d. 5.05 n.d. 3.58 n.d. 3.73
Borneol n.d. n.d. n.d. n.d. n.d. 8.13 n.d. 4.44 4.19 n.d. 2.28 n.d. 2.74
Cedrene/cryophyllene 3.52 4.96 2.44 n.d. n.d. n.d. 4.84 5.99 4.28 n.d. 2.30 n.d. n.d.
Geraniol < LOQ n.d. < LOQ n.d. 0.97 < LOQ < LOQ < LOQ n.d. n.d. < LOQ n.d. n.d.
Citronellal n.d. n.d. n.d. n.d. 2.46 2.70 2.31 5.71 8.08 1.82 2.27 n.d. 4.27
α-Amyl cinnamyl aldehyde n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2.99 n.d. n.d. n.d.
1,2-Dimethyl-3-nitrobenzene n.d. n.d. n.d. n.d. n.d. n.d. n.d. < LOQ n.d. n.d. n.d. < LOQ n.d.
Environ Sci Pollut Res (2021) 28:59214–59232
Appendix 2

Table 3 Determined concentrations of selected analytes in samples collected in SPA 2

SPA 2 date

05.02.2019 08.02.2019 08.02.2019 15.02.2019 19.02.2019 21.02.2019 26.02.2019 27.02.2019 05.03.2019 05.03.2019 06.03.2019 12.03.2019
After After After After After After After Before Before After After After

Determined compounds Concentration (ppbv)


Environ Sci Pollut Res (2021) 28:59214–59232

Isopropyl alcohol n.d. 29.26 21.26 28.44 7.36 60.90 56.81 n.d. n.d. n.d. n.d. n.d.
Acetic acid n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Toluene 2.05 0.49 1.05 1.07 1.27 2.18 < LOQ < LOQ 0.88 < LOQ < LOQ
Cycli3siloxane n.d. < LOQ < LOQ 0.80 0.89 0.78 n.d. 7.24 n.d. 0.95 < LOQ 1.56
2-Propanol n.d. n.d. n.d. n.d. n.d. 3.69 n.d. n.d. n.d. n.d. n.d. n.d.
α-Pinene 1.34 2.42 5.13 4.57 6.35 4.21 3.41 3.00 5.66 10.82 12.32 5.10
Camphene 1.34 1.62 3.18 1.69 2.48 0.87 2.17 2.52 1.59 6.87 2.48 3.48
β-Pinene 1.27 < LOQ 1.65 1.44 1.40 3.00 1.75 2.87 1.35 3.52 6.47 4.92
α-Phellandrene 0.80 0.99 1.59 1.25 0.96 2.75 < LOQ 3.34 1.35 1.28 2.17 < LOQ
3-Carene 6.26 1.70 1.97 1.96 2.09 3.84 < LOQ 1.67 2.72 2.58 3.50 7.01
D-Limonene 11.23 18.97 20.48 10.16 9.03 4.32 9.19 25.43 8.06 35.02 14.54 14.82
β-Phellandrene 237.98 6.21 3.92 5.47 2.74 7.21 n.d. 6.45 n.d. 10.74 31.88 9.63
Eucalyptol 1.07 2.42 7.55 2.10 5.16 < LOQ 2.16 3.44 5.21 5.40 4.53 12.92
Linalool 1.65 5.38 14.51 8.88 12.63 1.16 7.80 8.58 7.04 8.79 8.85 9.61
Undecan n.d. 3.38 7.35 4.47 2.41 3.73 6.82 9.52 8.37 n.d. 10.66
Borneol n.d. 1.51 4.49 1.59 3.66 n.d. 1.55 4.21 n.d. n.d. n.d. n.d.
Cedrene/cryophyllene n.d. n.d. 2.04 1.04 1.75 n.d. < LOQ 2.89 n.d. n.d. n.d. n.d.
Lilial n.d. n.d. n.d. n.d. 3.60 n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Geraniol n.d. 1.03 3.29 0.97 1.11 n.d. < LOQ < LOQ 1.49 1.49 < LOQ n.d.
1,2-Dimethyl-3-nitrobenzene < LOQ n.d. n.d. n.d. n.d. < LOQ n.d. n.d. n.d. n.d. n.d. n.d.
Citronellal n.d. n.d. 3.87 1.74 3.22 n.d. n.d. 6.77 n.d. n.d. n.d. n.d.
59225
59226 Environ Sci Pollut Res (2021) 28:59214–59232

Appendix 3

Table 4 Determined concentrations of selected analytes in samples collected in SPA 3

SPA 3 date

22.01.2019 22.01.2019 22.01.2019 01.02.2019 01.02.2019 04.02.2019 04.02.2019 16.02.2019


Reception Before After Before After Before After Before

Determined compounds Concentration (ppbv)


Isopropyl alcohol 2.56 31.43 8.00 21.47 23.94 35.15 28.93 21.61
Toluene 1.44 2.21 2.23 2.28 2.62 1.72 2.12 2.87
α-Pinene 13.19 20.34 18.90 17.55 24.70 17.97 23.51 12.40
Camphene 1.34 1.12 1.79 1.17 1.89 1.18 1.56 0.95
β-Pinene < LOQ < LOQ 0.78 0.84 0.93 1.07 1.39 2.97
α-Phellandrene < LOQ < LOQ 2.02 < LOQ < LOQ < LOQ 1.98 0.83
3-Carene 4.44 4.90 4.82 4.90 5.03 5.38 5.74 6.54
D-Limonene 4.02 4.59 25.23 6.45 36.43 5.80 14.48 4.40
β-Phellandrene < LOQ < LOQ n.d. n.d. n.d. n.d. n.d. < LOQ
Eucalyptol < LOQ < LOQ 0.94 < LOQ < LOQ < LOQ < LOQ < LOQ
Linalool 2.43 1.79 0.93 2.60 6.49 1.63 5.70 1.14
Undecan n.d. n.d. n.d. n.d. n.d. n.d. 2.28 2.01
4-Methoxy benzyl alcohol 1.77 < LOQ < LOQ 2.84 n.d. < LOQ n.d. n.d.
Geraniol n.d. n.d. n.d. n.d. n.d. n.d. n.d. < LOQ
Cireonellal n.d. n.d. n.d. n.d. n.d. n.d. n.d. < LOQ

SPA 3 date

16.02.2019 03.03.2019 25.03.2019 28.03.2019 29.03.2019 16.04.2019 18.04.2019


After After After After After After After

Determined compounds Concentration (ppbv)


Isopropyl alcohol n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Toluene 1.82 n.d. n.d. 5.67 n.d. n.d. 5.15
α-Pinene 0.96 24.34 87.96 74.65 120.36 26.56 29.87
Camphene < LOQ 7.20 15.51 10.52 46.55 9.86 5.85
β-Pinene < LOQ 24.30 5.20 5.07 299.46 3.02 2.18
α-Phellandrene 0.82 n.d. 6.99 3.54 n.d. 4.12 1.46
3-Carene 3.88 389.20 20.11 16.97 114.74 8.73 6.97
D-Limonene 4.81 1.51 327.11 288.41 305.04 185.69 91.99
β-Phellandrene 8.34 n.d. n.d. n.d. 71.55 n.d. n.d.
Eucalyptol n.d. < LOQ 6.18 n.d. n.d. < LOQ 1.43
Linalool 93.00 2.98 30.69 4.97 117.50 23.85 19.10
Undecan n.d. n.d. n.d. n.d. n.d. n.d. 13.27
4-Methoxy benzyl alcohol n.d. n.d. n.d. n.d. n.d. n.d. n.d.
Geraniol n.d. n.d. n.d. 24.74 n.d. n.d. n.d.
Cireonellal n.d. n.d. 1.2 n.d. 1.61 < LOD < LOD
Environ Sci Pollut Res (2021) 28:59214–59232 59227

Appendix 4

Table 5 Determined concentrations of selected analytes in samples collected in SPA 4

SPA 4 date

30.01.2019 30.01.2019 06.02.2019 08.03.2019


Determined compounds Before After Before After
Concentration (ppbv)

Isopropyl alcohol n.d. n.d. n.d. 3.25


Acetic acid n.d. n.d. n.d. n.d.
Toluene n.d. < LOD 0.82 n.d.
Cycli3siloxane n.d. n.d. n.d. 1.25
2-Propanol n.d. n.d. n.d. n.d.
α-Pinene n.d. 26.14 1.96 121.95
Camphene n.d. 2.71 < LOQ 89.17
β-Pinene n.d. 3.57 < LOQ 16.40
α-Phellandrene n.d. < LOQ < LOQ 4.32
3-Carene n.d. 2.16 < LOQ 17.84
D-Limonene n.d. 52.08 4.61 3408.67
β-Phellandrene n.d. n.d. n.d. n.d.
Eucalyptol n.d. 1.37 < LOQ 5.57
Linalool n.d. 3.72 1.49 10.73
Undecan n.d. 20.11 3.31 n.d.
Borneol n.d. n.d. n.d. 2.12
Cedrene/cryophyllene n.d. n.d. 5.30 2.36
Lilial n.d. n.d. n.d. n.d.
Geraniol n.d. n.d. < LOQ 2.68
α-Amyl cinnamyl aldehyde n.d. n.d. < LOQ n.d.
Appendix 5
59228

Table 6 VOCs identified by MS NIST 2.0 library with probability higher than 70%

SPA 1 SPA 2 SPA 3 SPA 4

Isopropyl alcohol Isopropyl alcohol Isopropyl alcohol 2-Methyl-1,3-butadiene


Acetic acid 1-Propanol Acetic acid Acetic acid
Ethyl acetate 1-Methoxy-2-propanol Ethyl acetate 2-Butanone
Pentanal Hexamethyl-cyclotrisiloxane 1-Butanol Ethyl acetate
2-Heptanol Hexanal Pentanal Toluene
Propylene glycol 4,5-Diethyl-octane 1,2-Dichloropropane Hexamethyl-cyclotrisiloxane
Toluene 2-Methyl-octane Propylene glycol α-Thujene
Hexamethyl-cyclotrisiloxane 3-Methyl-octane 1-Pentanol α-Pinene
Hexanal Ethylbenzene Toluene Camphene
Butyl ester acetic acid p-Xylene Hexamethyl-cyclotrisiloxane Cosmene
Ethyl ester 2-mehyl butanoic acid Nonane Hexanal β-Phellandrene
p-Xylene trans-1-Ethyl-4-methyl-cyclohexane Butyl ester acetic acid β-Pinene
Heptanal 2,4,6-Trimethyl-heptane Ethylbenzene 3-Carene
1-Butoxy-2-propanol 3,5-Dimethyl-octane p-Xylene Limonene
α-Pinene 1-Ethyl-2-methyl-cyclohexane Heptanal Terpinene
Benzaldehyde 2,6-Dimethyl-octane Bicyclo[4,2,0]octa-1,3,5-triene o-Isopropenyltoluene
β-Pinene 3-Ethyl-2-methyl-heptane Propanol Decamethyl-cyclopentasiloxane
Hexyl ester acetic acid Butyl-cyclopentane α-Pinene 1-Methyl-4-(1-methylethenyl)benzene
1,1″-oxybis-2-Propanol Propyl-cyclohexane Benzaldehyde ocimene
1-Methyl-4-(1-methylethyl)benzene α-Pinene β-Pinene (E,Z)-2,6-Dimethyl-2,4,6-octatriene
Limonene 4-Methyl-nonane 2-Pentylfuran Limonaketone
Benzyl alcohol 3-Ethyl-octane Octanal Naphthalene
Eucalyptol 1-Ethyl-3-methyl-benzene 1,2,4-Trimethylbenzene 1,7,7-Trimethyl-bicyclo[2,2,1]-hept-2-yl
acetic acid ester
(E)-2-Octenal 1-Ethyl-2-methyl-benzene p-Mentha-1,3,8- triene
2,6-Dimethyl-7-octen-2-ol 1,2,3-Trimethyl-benzene 3-Carene
Acetophenone decane 2-Ethyl-1-hexanol
Undecane cis-1,4-Dimethyl-cyclohexane 1-Methoxy-3-methylbenzene
Decamethyl-cyclopentasiloxane 4-Methyl-decane Limonene
3,7-Dimethyl-1,6-octadien-3-ol 1-Methyl-4-(1-methylethyl)-benzene β-Phellandrene
Phenylethyl alcohol Limonene Eucalyptol
Phenylmethyl ester acetic acid Eucalyptol (E)-2-Octenal
1,7,7-Trimethylbicyclo[2.2.1]heptan-2-one 2-Methyl-decane 2,6-Dimethyl-7-octen-2-ol
Dodecane 1-Methyl-3-propyl-benzene cis-Linaloloxide
Gardenol 1-Ethyl-2,3-dimethyl-benzene Acetophenone
4-Carene Undecane Decamethyl-cyclopentasiloxane
Naphthalene Decamethyl-cyclopentasiloxane (E,Z)-2,6-Dimethyl-2,4,6-octatriene
2-Phenoxy-ethanol 3,7-Dimethyl-1,6-octadien-3-ol Phenylethyl alcohol
Dodecamethyl-cyclohexasiloxane 3,7-Dimethyl-decane cis-Limonene oxide
(S)-2-Methyl-5-(1-methylethenyl)-2-cyclohexen-1-one Phenylethyl alcohol trans-Limonene oxide
2-(1,1-Dimethylethyl)-cyclohexanol 2-Methyl-undecane Phenylmethyl ester
Isobornyl acetate Tritetracontane 1,7,7-Trimethylbicyclo[2.2.1]heptan-2-one
2,2,4,4,6,8,8,-heptamethyl-nonane 1-Methyl-2-(1-methylethyl)-benzene Tetradecane
tetradecane 5-Methyl-2-(1-methylethyl)-cyclohexanone α-Methylbenzyl acetate
Environ Sci Pollut Res (2021) 28:59214–59232
Table 6 (continued)

SPA 1 SPA 2 SPA 3 SPA 4

Nopyl acetate 1,7,7-Trimethylbicyclo[2.2.1]heptan-2-one Cyclohexanol


4-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-3-penten-2-one p-allyl-Anisole p-Meth-1-en-8-ol
4-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-3-buten-2-one p-Menth-1-en-8-ol (Z)-3,7-Dimethyl-1,3,6-octatriene
Lilial (R)-3,7-Dimethyl-6-octen-1-ol Dodecamethyl-cyclohexasiloxane
Pentyl ester 2-hydroxy benzoic acid (Z)-3,7-Dimethyl-2,6-octadienal (E)-2-Decanal
Diethyl phthalate Dodecamethyl-cyclohexasiloxane (S)-2-Methyl-5-(1-methylethenyl)-2-cyclohexen-1-one
1,1″-Oxybis-octane 3-Methyl-6-(1-methylethyl)-2-cyclohexen-1-one Tridecane
Methyl ester 3-oxo-2-penthylmcyclopentaneacetic acid Tridecane 2-(1,2-Dimethylethyl)-cyclohexanol
Pentyl ester 2-hydroxy benzoic acid (1S-endo)-1,7,7-Trimethylbicyclo[2,2,1]heptan-2-ol Isobornyl acetate
Isopropyl myristate 2-(1,1-Dimethylethyl)-cyclohexanol 2,2,4,4,6,8,8,-Heptamethyl-nonane
1-Pentanol Isobornyl acetate tetradecamethyl-cycloheptasiloxane
Environ Sci Pollut Res (2021) 28:59214–59232

o-Xylene 4-tert-Bytulcyclohexyl acetate α-Cedrene


Camphene 3-Methyl-6-(1-methylidene)-cyclohexene Cedr-9-ene
Hexanoic acid Butyl ester butanoic acid Nopyl acetate
3-Carene Copaene Tricyclocaryophyllene
(E,Z)-2,6-Dimethyl-2,4,6-octatriene 4-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-3-buten-2-one Cedrene
cis-Limonene oxide Caryophyllene [4,2,1,1(2,5)]Dec-3-en-9-ol
trans-Limonene oxide Pentadecane Hexadecamethyl-cyclooctasiloxane
trans-5-mrthyl-2-(1-methylethyl)-Cyclohexanone 4-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-3-penten-2-one Hexadecane
Menthol 4-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-3-buten-2-one Ethane-1,1-diol dibutanoate
1-(4-Methylphenyl)-ethanone Lilial Cedrol
Terpineol Hexadecane Camphene
Tetradecamehtyl-hexasiloxane Diethyl phthalate Decane
n-Hexyl salicylate Methyl ester 3-oxo-2-pentyl-cyclopentane acetic acid 1,2,4-Trimethyl-benzene
n-Hexyl salicylate α-Phellandrene
Patchouli alcohol 1-Methyl-4-(1-methylehyl)benzene
Isopropyl myristate Benzene
Styrene Undecane
Camphene Linalool
β-Pinene Nonanal
4-Carene (2R-cis)-5-Mehtyl-2-(1-methylethyl)-cyclohexanone
Limonene p-Allyl-anisole
Eucalyptol Terpineol
2,6-Dimethyl-7-octen-2-ol 3,7-Dimethyl-1,6-octadien-1-ol
Nonanal 3,7-Dimethyl-2,6-octadienal
Camphor 4-tert-Butycyclohexyl acetate
(2R-cis)-5-Mehtyl-2-(1-methylethyl)-cyclohexanone
Borneol
Acetic acid
2-Butanone
Ethyl acetate
Benzene
Propylene glycol
2-Mehtylpropyl ester acetic acid
Toluene
3-Methyl-1-butanol acetate
2,3-Dimethyl-bicyclo[2,1,]-hept-2-ene
59229
59230 Environ Sci Pollut Res (2021) 28:59214–59232

Compliance with ethical standards

Conflict of interest The authors declare that they have no conflict of


interest.

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