Chemosphere 93 (2013) 857–869

Contents lists available at SciVerse ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

Fate and transport of fragrance materials in principal

environmental sinks
Xiaolei Zhang a, Satinder Kaur Brar a,⇑, Song Yan a, Rajeshwar Dayal Tyagi a, Rao Y. Surampalli b
a
INRS Eau, Terre et Environnement, 490, rue de la Couronne, Québec G1K 9A9, Canada
b
U.S. Environmental Protection Agency, P.O. Box 17-2141, Kansas City, KS 66117, United States

h i g h l i g h t s

 How fragrance materials could impact human health is addressed.

 A complete frame of where fragrances enter and end up in environment is provided.
 Fate of fragrances in water, wastewater, wastewater sludge, and soil is discussed.

a r t i c l e i n f o a b s t r a c t

Article history: Fragrance materials are widely present in the environment, such as air, water, and soil. Concerns have
Received 31 January 2013 been raised due to the increasing utilization and suspected impact on human health. The bioaccumulat-
Received in revised form 22 May 2013 ing property is considered as one of the causes of the toxicity to human beings. The removal of fragrance
Accepted 23 May 2013
materials from environmental sinks has not been paid enough attention due to the lack of regulation and
Available online 17 June 2013
research on their toxicity. This paper provides systematic information on how fragrance materials are
transferred to the environment, how do they affect human lives, and what is their fate in water, waste-
Keywords:
water, wastewater sludge, and soil.
Fragrance
Wastewater
Ó 2013 Elsevier Ltd. All rights reserved.
Soil
Water
Wastewater sludge

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 858
2. Sources and toxicity of fragrance materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 858
3. Fragrance materials in water, wastewater and wastewater sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 860
3.1. How they enter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 860
3.2. Technologies of fragrance materials removal from water, wastewater and wastewater sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 860
3.2.1. Physical treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 860
3.2.2. Chemical treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 862
3.2.3. Biological treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 863
3.3. Fate of fragrance materials in drinking water treatment plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
3.4. Fate of fragrance materials in conventional wastewater treatment plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 864
4. Fragrance materials in soil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 866
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 866
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867

⇑ Corresponding author. Tel.: +1 418 654 3116.

E-mail address: satinder.brar@ete.inrs.ca (S.K. Brar).

0045-6535/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2013.05.055
858 X. Zhang et al. / Chemosphere 93 (2013) 857–869

1. Introduction
Fragrance materials (FMs) are generally semi-volatile organic
compounds (SOCs) that are used to deliver preferred odor in con-
sumer products including cosmetics, detergents, fabric softeners,
household cleaning products, fine fragrances, and air fresheners.
They are complex combination of natural and synthetic sub-
stances. Fragrances have been utilized for thousands of years,
and hundreds of the same are created every year, in countries all
over the world. FMs are added in more and more products due to
their attractive scent to customers. According to the survey of
1995–1996, FMs used with less than 1% in volume had global
industry volumes of around 4000 metric tons per year, while over
the decade, it dramatically grew at a rate of 3–5% per year (Simo-
nich et al., 2000; Simonich, 2005). North America and Europe alone
account for almost two-thirds of global consumption (Global Fla-
vor & Fragrance Market Report, 2011). The large amount of FMs
consumed ultimately enters into environment through disposal
of consumer products, and has grabbed huge attention. Although
FMs industries have addressed the fact that FMs are safer to skin
of the product users, still they leave many blind points, such as ef-
fect on indoor air quality, health, and environment. It has been re-
ported that FMs can trigger or cause allergic, asthma, non-allergic
rhinitis, chronic respiratory disease, and central nervous system
disorders (http://www.anapsid.org/cnd/mcs/bridges.html). More-
over, the awareness has become a particular concern that FMs
are persistent in the environment and bioaccumulate in the fatty
tissue of aquatic organisms. Hence, the management of FMs has
become very important.
The physical and chemical properties of FMs determine their
management strategy. Volatilization, biodegradation, sorption,
and/or oxidation are frequently applied methods of FMs removal
(DiFrancesco et al., 2003; Joss et al., 2005; Janzen et al., 2011). As
FMs are normally semi-volatile organic compounds, volatilization
occurs during the treatments as there is the contact between air
and water.
Tonalide 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphtha-
lene (AHTN) and galaxolide 7-acetyl-1,1,3,4,4,6-hexahydro-
4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyrane (HHCB) are
two of the most often used low-cost FMs present in wastewater
with a large concentration range from 1 to 25 lg L1 (Artola-Gari-
cano et al., 2003; Santiago-Morales et al., 2012). It was found that
their removal is significantly associated with the degradation abil-
ity which is the primary mechanisms of the removal from waste-
water (Simonich et al., 2002; Artola-Garicano et al., 2003). It
leads to the preference of the utilization of macrocyclic musk
which has high biodegradability, over nitro- musk and polycyclic
musk. Macrocyclic, nitro-, and polycyclic musk are artificially syn-
thesized aromachemicals with musk-like smells. Macrocyclic musk
consists of a single ring normally with around 10–15 carbons such
as habanolide and muscone. Nitro-musk is a group of nitrated ben-
zenes. Musk xylene, musk ketone and musk ambrette are three
most popular nitro-musk. Polycyclic musk has multiple rings in
the structures such as celestolide, tonalide, and galaxolide. Some
of the commonly used FMs are listed in Table 1 with acronyms,
commercial trade names, and chemical names.
Hydrophobic FMs are easily removed by sorption. It was re-
ported that activated sludge and activated carbon showed higher
efficiency in FMs removal which was up to 90% (Serrano et al.,
2010). FMs widely exist in water, wastewater, wastewater sludge,
and soil, while there are only very few studies on the fate and effect
of FMs in principal environmental sink.
This review discusses the sources and toxicity of FMs, and pro-
vides the insight on the mode of entry of FMs, their transport, and
removal mechanisms in the relative environment.
2. Sources and toxicity of fragrance materials
FMs have become a key factor of the products sold in market as
they deliver pleasant smell to the users. Consumer research reveals
that FMs is leading the people’s preference for the products, which
indicates that the use of FMs would increase rather than decrease
in the future. Fragrances are identified as natural and synthetic
semi-volatile substances. The former are made from essential oils
extracted from plants or animals, and the latter are man-made
substances mostly referring to petroleum-based chemicals. In the
early period of the utilization of fragrances, natural ones were
dominating, while synthetic ones took over due to increased

Table 1
Commonly used fragrances in surface water and wastewater.

Commercial trade name Chemical name Acronyms Conc. in Conc. in Ref.

surface water wastewater
Cashmeran 1,2,3,5,6,7-Hexahydro-1,1,2,3,3-pentamethyl-4H- DPMI NA <1.6 lg L1 (Zeng et al. (2007))
inden-4-one
Celestolide 1-[6-(1,1-Dimethylethyl)-2,3-dihydro-1, 1- ADBI <50 ng L1 <30 lg L1 Zeng et al. (2007), Clara et al. (2011), Villa
dimethyl-1H-inden-4-yl]-ethanone et al. (2012)
1 1
Galaxolide 7-Acetyl-1,1,3,4,4,6-hexahydro-4,6,6,7,8,8- HHCB <300 ng L <25 lg L Bester (2005), Lee et al. (2010), Rosal et al.
hexamethylcyclopenta(g)-2-benzopyrane (2010))
Habanolide (12E)-1-oxacyclohexadec-12-en-2-one – NA <1.6 lg L1 (Vallecillos et al., 2012)
Methyl dihydrojasmonate Methyl 2-(3-oxo-2-pentylcyclopentyl)acetate MDJ NA <5.4 lg L1 Simonich et al. (2000)
Muscone (R)-3-methylcyclopentadecanone - NA NA Posada-Ureta et al. (2012)
Musk ambrette 4-tert-Butyl-2,6-dinitro-3-methoxytoluene MA ND ND Yang and Metcalfe (2006)
Musk ketone 1-(4-Tert-butyl-2,6-dimethyl-3,5- MK <30 ng L1 <420 ng L1 Sumner et al. (2010), Gómez et al. (2012)
dinitrophenyl)ethanone
Musk moskene 1,1,3,3,5-Pentamethyl- 4,6-dinitroindane MM ND ND Yang and Metcalfe (2006)
Musk tibetene 1-Tert-butyl-2,6-dinitro-3,4,5-trimethylbenzene MT ND ND Yang and Metcalfe (2006)
Musk xylene 1-Tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene MX <7 ng L1 <260 ng L1 Sumner et al. (2010), Gómez et al. (2012)
Patchouli ethanone 1-(2,3,8,8-Tetramethyl-1,3,4,5,6,7- OTNE <30 ng L1 <1.9 lg L1 Bester (2005), Lee et al. (2010), Rosal et al.
hexahydronaphthalen-2-yl)ethanone (2010), Sumner et al. (2010)
Phantolide 6-Acetyl-1,1,2,3,3,5-hexamethylindane AHMI <5.5 ng L1 <50 ng L1 Clara et al. (2005), Zeng et al. (2007),
Pedrouzo et al. (2011)
Tonalide 7-Acetyl-1,1,3,4,4,6- AHTN <60 ng L1 <1.9 lg L1 Rosal et al. (2010)
hexamethyltetrahydronaphthalene
Traseolide 5-Acetyl-3-isopropyl-1,1,2,6-tetramethylindane ATII <2.5 ng L1 <32 ng L1 Zeng et al. (2007), Clara et al. (2011)

NA: not available; ND: not detected.

 X. Zhang et al. / Chemosphere 93 (2013) 857–869 859

Table 2 the cause of allergy, sensitization, asthma, and irritation (Elberling

Concentration of fragrances in the products. et al., 2009). A fragrance mixture with 1% of evernia prunastri, iso-
Products Fragrance fraction (% v/v) eugenol, eugenol, cinnamal, cinnamic alcohol, alpha-amyl cinn-
Perfume extract 15–40 amal, geraniol, and hydroxycitronellal, respectively, was tested
Esprit de Parfum 15–30 on 14,104 females and 9742 males with different age (>0 year)
Eau de parfum 10–20 for 15 years (Buckley et al., 2003). It was observed that females
Eau de toilette 5–15 were more sensitive to the FMs than males (8.4% females and
Eau de cologne 3–8
Perfume mist 3–8
6.4% males allergic to the FMs) and higher aged persons
Splash and aftershave 1–3 (>60 year-old) showed higher frequency of fragrance allergy
Candle (g g1) 4–6 (14.4% of those aged tested persons). Two irritations have been
Shower gel 0.5–1 found among 33 tests after 2 d of the application of cinnamyl alco-
Soaps (g g1) 0.5–3
hol (0.3 mL aliquot of 10% cinnamyl alcohol in petrolatum) on hu-
Detergent 0.03–0.15
Maintenance and cleaning products 0.07–0.1 man skin (RIFM, 1977a). A study of application of 0.5 mL aliquot of
Hair-care products Less than 1 8% cinnamaldehyde in petrolatum on 5 males showed that the five
Shampoos Less than 1 subjects got severe irritation after 48 h (RIFM, 1973).
Bodywash Less than 1 The modern fragrances have been suspected to lead to neuro-
Nail polish Less than 0.1
toxicants. In addition, it is reported that fragrances derived from
Makeup Less than 0.1
Cosmetics Less than 0.1 petroleum could even cause cancer, birth defects, skin disease
Air fresher 0.5–1 (rashes, hives, dermatitis, or eczema), and central nervous system
Deodorants Less than 0.5 disorders, and in fact, around 95% of the fragrances currently used
Body lotions Less than 0.1
are derived from petroleum (Furic, 2010). It is found that benzyl
Dishwash 0.1–0.5
salicylate, benzyl benzoate and butylphenylmethylpropional (lili-
The data are from the product fact sheet of each of the products. al) at concentration range from 5  105 to 5  104 M were able
to increase the growth of human breast cancer cells (Charles and
Darbre, 2009). Impact of some of the frequently used fragrances
on human health is summarized in Table 3.
demand and variety as well as the cost concerns. The development Four fragrances, tonalide, galaxolide, musk ketone and musk xy-
of fragrances is a complex mixture of chemistry and art which indi- lene were used to study toxicity by exposing them to rats in a dos-
cates that fragrances, in fact, are chemical compounds. It is esti- age of 5, 50, 150, 200 mg kg1 d1, respectively, and the dosages
mated that there are more than 3000 chemicals used in used were greater than multiples of the estimated maximal daily
fragrance manufacture. Even a single fragrance may contain 10 to human dermal exposure (Christian et al., 1999). The results
several hundred chemicals. A detailed list of fragrance chemicals showed that the exposure caused reduction in weight gain and
included more than 1500 types (Briges, 1997). Octadienes, hexyl- feed consumption. In order to have longer life on fabrics and skin
oxyacetonitriles, cyclopentane derivatives, a-oxo (oxo) sulfides, to provide long-term pleasant odor, FMs which have high log (oct-
aliphatic dibasic acid diesters, 3-(10-undecenyloxy) propionitrile, anol–water partition coefficients) are widely used in the products.
tricyclodecane-methylol derivatives, 2-methyl-2-alkyl-alkanoic The log (octanol–water partition coefficients) normally is de-
esters, trimethylcyclonexylethyl ethers, cyanoethylidene-bicyclo- scribed as log Kow and the indictor of hydrophobicity of materials.
heptenes, crotonyl-trimethyl cyclohexanes, nonanols, nonenols, However, higher log Kow would lead to bioaccumulation in organ-
a-oxo (oxo) mercaptanes, safranic acid esters, and maltyl-2-methyl isms. Animal toxicity studies have proved that fragrances are haz-
alkenoates are typically used FMs in the products. ardous, mainly due to their persistence and accumulation in living
Personal and household products are the major utilization of beings (Dietrich and Hitzfield, 2004).
fragrances. The typical source of fragrances in the environment is Due to the bioaccumulation of FMs, the effect of fragrances on
perfume, cologne, eau de toilette, body wash, detergent, cosmetics, health is normally not acute poisoning but it is chronic. Skin and
shampoos, hair-care products, air freshener, candles, and deodor- nervous system are the most concerned to be easily impacted by
ants. The general concentration of fragrances in the products is FMs. FMs effect on skin: When personal-care products are applied
listed in Table 2. It can be seen that humans are widely and con- to the healthy skin, the irritation or inflammation may not be ob-
stantly adsorbing an unknown number of fragrance chemicals in served right away. However, it doesn’t mean that the product has
thousands of products by direct application, contact with fragrance no effect on the skin. In fact, it could cause the breakdown of col-
items, and exposure to the air containing fragrances. However, lagen below the skin surface, and then result in the loss of the abil-
there is minimal government regulation and monitoring of their ity to self-heal when there is damage in the skin (Tanida et al.,
safety. A study from Stanford University published by the National 2008; Schnuch et al., 2010). Moreover, it would also reduce the
Institutes of Health (Banihani et al., 2009) revealed that some per- skin ability to decrease the wrinkles. The application of personal-
sonal care products in water can harm humans even at low con- care products on the skin with rosacea or acne problem can cause
centration (60.3 ppm) as it can block the ability of human cells serious irritation and inflammation. Some FMs causing irritation
to fight toxic substances (http://leas.ca/Synthetic-Fragrances.htm). are listed in Table 3. FMs effect on nervous system: FMs go into hu-
Fragrances are called indoor pollutants as many chemicals in man body through absorption, inhalation, or ingestion, and there-
fragrances are the same as in cigarette smoke. The fragrances can after, will be transferred to brain through blood stream. FMs
enter the body through the nose by inhalation, the mouth by inges- modify brain blood flow and alter blood pressure which is the ma-
tion or the skin by absorption, and then go into our bloodstream. A jor cause of central nervous system disorders, expressed as head-
report studied the transportation of an artificial fragrance on hu- aches, anxiety, phobia, panic attacks, depression, obsessive
man body (RIFM, 1987). About 10 mg of phenethyl alcohol was ap- compulsive disorder, and hormone disruption (Tanida et al.,
plied on a 100 cm2 area of human chest with occlusion of 6 h d1 2008). Ethylhexanol 2-ethyl-1-hexanol was found to cause central
for 5 d. It was observed that its maximum concentration in the ur- nervous system depression when the accepted amount was up to
ine was 7.6% of the dose after 48 h application, and around 90% of 3 g kg1 body weight in rat (Scala and Burtis, 1973). Similar clinic
the dose was evaporated. Therefore, nearly 2.4% of the dose accu- sign was observed while using methyl jasmonate (5 g kg1 body
mulated in the body. The most apparent toxicity of FMs embodies weight in rat) (RIFM, 1980). Obviously, FMs can slowly take down
860 X. Zhang et al. / Chemosphere 93 (2013) 857–869

Table 3
Fragrances effect on human health.

Fragrances Dose Application method Exposure Results References

time
Cinnamaldehyde 10 lL of 100% the fragrance in every Applied on human skin 3 d Leading to allergy Smith et al.
day (2000)
Cinnamic alcohol 10 lL of 100% the fragrance in every Applied on human skin 3 d Leading to allergy Smith et al.
day (2000)
Ethylene brassylate 50 lL of 10% the fragrance in ethanol/ Applied on human skin 3 weeks 10 irritation out of 36 subjects RIFM (1989)
diethylphthalate (1:1, v:v) in every
other day
Ethylene dodecanedioate 20% the fragrance in petrolatum in 3 d a Applied on human skin 3 weeks 2 irritation out of 25 subjects RIFM (1978)
week
Juniperus occidentalis 25 lL of 50% the fragrance in Applied on rat skin 3d 5 irritation out of 5 subjects Craig et al.
petrolatum in every day (2004)
Chamaecyparis lawsoniana 25 lL of 100% the fragrance in every Applied on rat skin 3d 5 irritation out of 5 subjects Craig et al.
day (2004)
Lyral 10 lM the fragrance in agar plates Applied on human non- 24 h 85 cells death out of 100 Usta et al.
tumoral keratinocyte (2013)
cells
Lilial 10 lM the fragrance in agar plates Applied on human non- 24 h 65 cells death out of 100 Usta et al.
tumoral keratinocyte (2013)
cells
Methyl dihydrojasmonate 1000 mg the fragrance kg body Fed to Rat 7–20 d Dehydration RIFM (2007)
weight1 d1
Methyl dihydrojasmonate 120 mg the fragrance kg body Fed to rat 7–20 d Found tan areas in the liver and Politano et al.
weight1 d1 a pale spleen of 2 subjects out of (2008)
25
Methyl jasmonate 3 g kg body weight1 d1 Fed to rat 7d Central nervous system Scala and
depression Burtis (1973)
Oxotridecyl alcohol (Isotridecan-1-ol) 4.75 g kg body weight1 d1 Fed to rat 7d Central nervous system Scala and
depression Burtis (1973)
Cervolide (12-oxahexadecanolide) 0.025 ml 3% the fragrance Guinea pig Once 10 irritations out of 10 subjects RIFM (1977)
Octyl alcohol (2-ethyl-1-hexanol) 5 g kg body weight1 d1 Fed to rat 7–20 d Central nervous system RIFM (1980)
depression
Rose ester (2-phenoxyethanol) 1 g kg body weight1 d1 Fed to rat 15 d Central nervous system Scognamiglio
depression et al. (2012)
Rose ester 2 g kg body weight d1 Fed to rat 15 d Death Scognamiglio
et al. (2012)

the defence system of skin and nervous system and eventually
harm them. Therefore, caution should be taken in the use of FMs
in the products. Moreover, FMs finally enter the environment after
utilization. Therefore, their transportation and fate in environment
should be well understood.
3. Fragrance materials in water, wastewater and wastewater
sludge
3.1. How they enter
The root of FMs to surface water, ground water, wastewater,
and wastewater sludge is down-the-drain disposal of the products
containing FMs such as detergent and shampoo and the discharge
of the wastewater of the industry fabricating FMs products (Fig. 1).
In municipal and industrial wastewater treatment, these materials
cannot be completely eliminated and will go with the effluent of
wastewater treatment to the receiving water body, such as rivers
and oceans. It is found that galaxolide, tonalide, and patchouli eth-
anone (1-(2,3,8,8-tetramethyl-1,3,4,5,6,7-hexahydronaphthalen-2-
yl)ethanone (OTNE)) are three major compounds in rivers, and
their concentrations are around 30–300 ng L1 (Bester et al.,
2008a; Carballa et al., 2008). Others, such as celestolide, phanto-
lide, musk xylene, and musk ketone were also found (Sumner
et al., 2010). The concentrations of the FMs in surface water and
wastewater are inhibited in Table 1.
The FMs would also enter groundwater due to exchange with
surface water. In addition, FMs (semi-volatile) in the air can be
caught by the dusts and after settling to the ground, they might
be sent to surface water by wind or they would directly settle on
the surface water. Similarly, the FMs would be transferred to
groundwater due to water exchange between surface water and
groundwater. Moreover, it is known that the FMs which are not re-
moved during wastewater sludge treatment (digestion, composting,
or incineration) can remain in the sludge or compost or ash. Landfill-
ing or land application would carry the FMs to the land and go into
soil, and may be released to groundwater due to leaching (rainfall).
The water exchange between groundwater and surface water would
lead to presence of FMs in the surface water. FMs would also be
transferred to groundwater or surface water due to the disposal of
expired or the leftover detergents or shampoos from homes to mu-
nicipal solid waste which would go to landfill.
3.2. Technologies of fragrance materials removal from water,
wastewater and wastewater sludge
The fact that there are no standards on FMs in drinking water
and the effluent of wastewater treatment leads to less attention
to be paid to treat these materials in drinking water and wastewa-
ter treatment by designing the processes aiming to remove FMs.
However, the awareness of FMs toxicity to human being brings
up more and more concern on FMs removal. Physical (sorption, fil-
tration, and volatilization), chemical (hydrolysis and oxidation),
and biological (biodegradation) removal are normally considered
the technologies of FMs elimination from water, wastewater, and
wastewater sludge (Simonich et al., 2002; Joss et al., 2005; Cirja
et al., 2008; Janzen et al., 2011).
3.2.1. Physical treatment
Physical treatment is the process that relates to the removal of
FMs due to the physical characteristics, such as surface charge,
lipophilicity, volatility, and molecule size.
 X. Zhang et al. / Chemosphere 93 (2013) 857–869
Fig. 1. FMs transportation in environment.
Sorption is one of the most important reasons for FMs removal
from drinking water and wastewater. Hydrophobicity and electro-
static interaction are the major mechanisms of FMs removal by
sorption. The sorption amount is associated with sorption constant
of the FMs, the concentration of suspended solids and the concen-
tration of FMs in the water (Siegrist et al., 2004).
In wastewater treatment, FMs can be removed in both primary
(coagulation–flocculation/flotation followed by sedimentation)
and secondary (such as, activated sludge followed by settling)
treatment as there is the presence of suspended solids. The hydro-
phobic FMs would be adsorbed on the surface of the suspended
solids, and after settling, they would go into the sludge. The FMs
adsorbed in lipophilic phase would be removed by flotation.
Charge attraction is another removal mechanism of FMs from
wastewater. The FMs with positive surface charges would be en-
trapped by the suspended solids with negative surface charge
(such as, microorganisms) and then removed from wastewater
with eventual transfer to sludge by settling. Thus, sorption of
FMs onto sludge is another reason of FMs removal from wastewa-
ter in biological treatment processes. The removal of two fra-
grances, AHTN and HHCB which comprise about 95% of the EU
market and 90% of the USA market for all polycyclic musk, cosmet-
ics, and detergents (HERA, 2004) was investigated in conventional
activated sludge, membrane bioreactor, and fixed-bed reactor (Joss
861
et al., 2005). The results showed that around 50% of the FMs were
removed and it was predicted that sorption of FMs on sludge was
the major removal mechanism as no significant relationship was
observed between BOD5 removal and FMs. The similar phenome-
non of 50% removal of patchouli ethanone and cashmeran
(1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one
(DPMI)) attributed to the sorption onto sludge was observed by
Zeng et al. (2007) and Bester et al. (2008b). It is obvious that FMs
removal by sorption is in fact not a solution of the problem but
is the transfer of the problem as FMs are not really removed rather
transferred to a more complex stream i.e. sludge. In sludge treat-
ment, the fate of FMs is dependent on the treatment selection. In
aerobic/anaerobic sludge digestion and composting treatment,
the sorbed FMs would remain in the system unless they are biode-
gradable. For other treatments, such as sludge incineration, the
FMs would volatilize to air or they are converted to carbon dioxide
due to oxidation.
In drinking water treatment, addition of adsorbents is utilized
to remove the color and small particles. Activated carbon and car-
bonaceous nanoparticles have been used in the removal of organic
matter from surface water or groundwater (Tomaszewska et al.,
2004; Gorham et al., 2007; Wang et al., 2010). FMs with higher
affinity to the carbonaceous surface would be sorbed and removed
from water. Powdered activated carbon (PAC) is one of the most
862 X. Zhang et al. / Chemosphere 93 (2013) 857–869
applied adsorbents, and it was reported that over 70% organic
materials can be removed with half an hour hydraulic retention
time by PAC (Tansakul et al., 2011). PAC with a dosage of 5 mg L1
could remove more than 90% of 17beta-estradiol (initial concentra-
tion 27 ng L1) regardless contact time (Yoon et al., 2005) and 81%
musk ketone (regardless the initial concentration) with 4 h contact
time (Westerhoff et al., 2005). It was found that removal efficiency
of PAC for many endocrine-disrupting compounds and pharmaceu-
ticals and personal care products was proportional to log Kow of the
compounds (Westerhoff et al., 2005). Granular activated carbon
has also been employed for organic materials removal and the re-
moval efficiency of organic materials with hydrophobic character-
istics had reached above 60%. It was also predicted that
biofiltration was one of the removal mechanisms besides adsorp-
tion (Gur-Reznik et al., 2008). Generally, in order to enhance the re-
moval, combination of coagulation and adsorption is conducted.
The researchers found that the removal of water color (organic
matter) was complete by using PAX XL-69 polyaluminum chloride
as coagulant and PAC as adsorbent (Tomaszewska et al., 2004). In
another report, carbonaceous nanoparticles and alum were used
as adsorbent and coagulant, respectively. Similar trend was ob-
served with the combination of coagulation and adsorption, which
significantly enhanced the removal of organic material from water
(Wang et al., 2010). pH is an important parameter when coagula-
tion is involved as coagulation changes surface charge properties
or polarity of the materials (Tomaszewska et al., 2004; Wang
et al., 2010). Flocculation has also been used for organic material
removal by combining adsorption and enhancement of the re-
moval. However, this process seemed more efficient for the re-
moval of hydrophilic materials than the hydrophobic materials
such as AHTN and HHCB, the two most employed FMs (Shon
et al., 2004, 2005).
Apart from sorption, filtration could also result in FMs removal
from drinking water wastewater. Filtration including ultrafiltra-
tion, nanofiltration, and reverse osmosis are used for the removal
of small particles. Normally, the membranes are not barriers of
FMs, while flocculation, coagulation, and adsorption followed by
filtration are applied for FMs removal (Tansakul et al., 2011). This
is due to the fact that small particles sorbing FMs are not settled
and can be eliminated by filtration. A report showed that compar-
ing with conventional activated sludge (CAS) process, membrane
bioreactor (MB) (ultrafiltration membrane) has shown higher re-
moval of HHCB (87% and 92% in CAS and MB, respectively) and
AHTN (83% and 91% in CAS and MB, respectively) (Clara et al.,
2005), which could be due to the filtration contribution in mem-
brane bioreactor system.
Electrodialysis (ED) is also a membrane process which removes
contaminants by migration-diffusion, charge interaction, solute–
solute interaction, and membrane deposition/sorption. ED has a
long history in water treatment, and it has been used for desalina-
tion of surface water and groundwater since 1951 (Allison, 1995).
The main principle of ED is to use the electrical potential difference
across the membrane that is used to separate the two solutions. It
can be easily understood that the FMs with charge can be removed
by ED, and the diluted solution would be the treated water with
the removal of FMs. It is reported that around 90% of estrogenic
compounds was removed by ED (Pronk et al., 2007). ED also pos-
sessed the potential for the removal of trace organic contaminants,
such as hormone and endosulfan from water (Banasiak, 2009).
Due to the high cost requirements, no report has been released
on FMs removal with filtration process itself even in tertiary treat-
ment. Volatilization could occur when turbulence is present byaer-
ation, agitation, stripping, spraying, in the processes such as
flotation and activated sludge in which air is introduced to help
the flotation of suspended solids or enhance mass transfer in the
system. The removal of FMs by volatilization depends on vapor
pressure and octanol–water coefficient (Kow). A higher H value sug-
gests that the resistance of FMs to air (volatilization) is from water,
while a lower H value would imply the resistance of FMs to air
(volatilization). Normally, the resistance from gas transfer is negli-
gible in an open or aerated surface system because of the infinite
dilution. It indicates that volatilization of FMs with lower H is eas-
ier than that of FMs with higher H. It is observed that the removal
is higher when Henry’s constant (H) is between 102 and 103
(Stenstrom et al., 1989). It is known that log octanol–water coeffi-
cient is the indicator of lipophilicity of the substances; therefore,
high log Kow would lead to the higher tendency of FMs to escape
from water which may cause FMs to enter air. In addition, it is pre-
dicted that the compounds are easily removed from the system by
volatilization at higher Kow (Rogers, 1996; Galassi et al., 1997). As
mentioned earlier, turbulence enhances volatilization; thus gas
flow rate and agitation speed are critical factors for FMs removal
by volatilization. In fact, volatilization is normally not considered
in FMs removal from drinking water, wastewater or sludge due
to their low concentrations and large energy requirements (to cre-
ate turbulence). It is predicated that the removal of synthetic musk
compounds, such as galaxolide and tonalide through volatilization
during wastewater treatment was less than 1% (EPA, 2009), how-
ever, it was found that the removal of galaxolide in aeration tank
was up to 14% (Upadhyay et al., 2011). It suggests that volatiliza-
tion also contributes to FMs removal when aeration is employed
in the treatment because the other important factor, the contacting
surface area of water and air, is increased. The high contacting sur-
face area between water and air would lead to enhanced volatiliza-
tion which can be understood by two-film theory. Thus, forced
aeration can enhance the volatilization removal mode for the FMs.
3.2.2. Chemical treatment
Chemical treatment is the process by which FMs are converted
to other substances due to the chemical reaction mainly consisting
of hydrolysis and oxidation. Hydrolysis is the most popular method
of conversion of complex compounds to simple substance. The
addition of acid or base under natural or thermal condition would
break down the large molecules to substances which are simple
and more susceptible to uptake. It is reported that alkaline hydro-
lysis provided the release of simple substances (alcohol) from 2-
formyl- and 2-acetyl-benzoates (Enggist et al., 2001), which indi-
cates that hydrolysis can transform FMs to other substances. Final-
ly, these FMs would be removed from wastewater or wastewater
sludge. The technology is normally applied in FMs removal from
sludge. Hydrolysis will take place prior to sludge biological treat-
ment (digestion) in order to increase the bioavailability of FMs to
microorganisms. However, it should be noted that the pH should
be readjusted before entering the digestion tanks due to the con-
cern of pH inhibition on microbial activities. When the purpose
is to remove FMs from sludge, the hydrolysis step can be placed
after sludge digestion and before final disposal to landfill or agri-
cultural land. Generally, this mode is not preferred due to the fact
that the concentration of FMs in the sludge is normally small (in
lg kg1 or ng kg1).
Oxidation converts one compound into another compound
which is less harmful or easy to be removed by addition of chem-
icals or light. Most of the chemical treatments are advanced oxida-
tion processes (AOPs) as normally there is relative radical
generation, such as hydroxyl radical and superoxide. Ozonation,
O3–H2O2, O3–UV, H2O2–UV, and TiO2/UV treatments grabs huge
attention due to the higher removal efficiency of synthetic organic
compounds (Zhou and Smith, 2002). The radical generation from
AOPs is summarized in the following equations (Eqs. (1)–(11)):
Ozonation:
O3 þ e !  O2 ð1Þ
 X. Zhang et al. / Chemosphere 93 (2013) 857–869 863

Ozonation at high pH:
OH
O3 þ H2 O ! H2 O2 þ O2
Ozone – hydrogen peroxide:
H2 O2 þ H2 O ! HO2 þ H3 Oþ

HO2 þ O3 !  OH þ O2 þ O2
Ozone – ultraviolet radiation:

O3 þ hv ! O2 þ O
O þ H2 O ! 2 OH
Hydrogen peroxide – ultraviolet:
H2 O2 þ hv ! 2 OH
Heterogeneous photocatalytic processes:
þ
TiO2 þ hv ! h þ e
þ  þ The FMs with biodegradability, such as benzyl acetate, methyl
h þ H2 O ! OH þ H
þ isobornyl acetate, hexyl salicylate can be readily removed during
h þ OH !  OH
e þ O2 !  O2
Radicals are oxidizing species which can accelerate the oxida-
tion of the contaminants. It has been reported that AOPs have
shown the ability of FMs removal from water, and some examples
are summarized in Table 4. In fact, the removal efficiency is not
only related to resistance of FMs to oxides but also to the reaction
time, the dosage of the oxides, and the presence of other contam-
inants. So far, very limited research has been reported on FMs re-
moval by AOPs, in fact more serious efforts need to be made in
this direction.
Ozonation alone or coupled with UV or H2O2 are the most stud-
ied technologies of FMs removal from wastewater or sludge. It is
observed that aromatic structures are readily oxidized by ozone
(Nakada et al., 2007). By applying 10–15 mg L1 of ozone, galaxo-
lide and tonalide (0.1–0.73 lg L1) in municipal wastewater were
completely removed after 18 min contact time (Ternes et al.,
2003a). Similar results were reported in another study (Janzen
et al., 2011). The removal of musk xylene, musk ketone, and patch-
ouli ethanone from municipal wastewater treatment plant were
also investigated by Janzen et al. (2011). It was found that the re-
moval of patchouli ethanone could be 99.9% but the other two
musk xylene and musk ketonemolecules showed no removal dur-
ing ozonation treatment which implies that musk xylene and musk
ketone have higher resistance to ozone. The combination of ozone
with UV or H2O2 should be attempted for the complete removal.
Even though ozonation has shown higher potential for the removal
of FMs, there are negative aspects due to the potential formation of
by-products which have higher toxicity than the original FMs and
are mostly produced due to the partial oxidation. Galaxolide con-
ð2Þ centration was reduced while galaxolide-lactone was detected
after ozonation in water (Janzen et al., 2011). In addition, it was
shown that sludge dewaterability was decreased after ozonation
ð3Þ treatment (Ternes et al., 2003a; Carballa et al., 2007).
Photolysis is another type of oxidation which takes place in the
ð4Þ presence of solar irradiation (Doll and Frimmel, 2003; Bouillon and
Miller, 2005). Photo-oxidation of patchouli ethanone in sludge and
wastewater under artificial sunlight irradiation has been studied,
ð5Þ and the results displayed that the oxidation was associated with
light penetration and the oxidation of patchouli ethanone in-
ð6Þ creased with higher irradiation intensity (Ozaki et al., 2011). In
fact, the functional part of solar irradiation is the UV-light. UV irra-
diation alone requires higher cost in FMs removal from wastewater
ð7Þ and sludge due to higher suspended solids concentration. Never-
theless, it could be used in the removal of FMs from drinking water.
ð8Þ
3.2.3. Biological treatment
ð9Þ
salicylate, methyl dihydrojasmonate, terpineol, isobornyl acetate,
ð10Þ
biological treatment (Simonich, 2005). Biodegradation is the pro-
cess whereby microorganisms take up organic matter for growth
ð11Þ
when in contact with wastewater. Biodegradation of FMs by micro-
organisms is determined by the accessibility of the FMs to micro-
organisms which is also the distribution of the FMs from
wastewater to microorganism, and the uptake ability of the com-
pounds into the internal cell compartment in the biological treat-
ment. Generally, the distribution can be achieved in treatment
system by aeration or agitation, while the uptake is a limitation
step of biodegradation of FMs. Several parameters including water
solubility, lipophilicity, affinity of microbial enzymes to FMs, and
antimicrobial effect govern the uptake step. The higher solubility
would enhance the chance of contact of FMs to microorganisms
in aqueous medium as the microorganisms are surrounded by
wastewater. Microbial cell membrane (the lipophilic characteris-
tics) can readily absorb FMs with higher lipophilicity which results
in the enhancement of the uptake of FMs by microorganisms (Cav-
ret and Feidt, 2005; Ehlers and Loibner, 2006). Among all the
parameters, the affinity of microbial enzymes to FMs is the deter-
mining step of the biodegradation. If the FMs adsorbed cannot be
transformed or decomposed, the FMs have to be released to the
aqueous system, once the mass is saturated in the cells. The anti-
microbial effect of FMs is significantly important in biological
treatment as it would harm microorganisms and reduce their abil-
ity to decompose organic materials. In general, nitro- musk, macro-
cyclic musk, and polycyclic musk are three major FMs used in the
products. Among all, macrocyclic musks have been tested for use
instead of nitro-musk and polycyclic musk due to its biodegrad-
ability and potentially lower toxicity to the microorganisms. The

Table 4
Fragrances removal by advanced oxidation processes.

Processes Fragrances Degradation efficiency (%) Reference

O3 Galaxolide and Tonalide 100 Ternes et al. (2003a)
O3 Galaxolide 90 (Rodríguez et al., 2011)
O3 Tonalide 80–90 (Rodríguez et al., 2011)
O3 Musk xylene 60–95 (Rodríguez et al., 2011)
UV Galaxolide and Tonalide 99 (Felis et al., 2008)
UV/O3 D-limonene 46–75 (Yu et al., 2010)
UV/H2O2 Galaxolide and Tonalide 99 (Felis et al., 2008)
TiO2/SiO2/Fe3O4/UV Benzoic acid 50 (Su et al., 2012)
TiO2/UV D-limonene 49–99 (Yu et al., 2010)
TiO2/UV/O3 D-limonene 62–99 (Yu et al., 2010)
864 X. Zhang et al. / Chemosphere 93 (2013) 857–869
study showed that benzylalcohol, cinnamic aldehyde, cinnamyl
alcohol, citral, coumarin, eugenol, hydroxycitronellal, and isoeuge-
nol was biodegraded by over 95% (MITI, 1992). Biological treat-
ment (conventional activated sludge, membrane bioreactor,
biofilm, aerobic or anaerobic sludge digestion) could be efficient
to remove these compounds from wastewater or sludge. The anal-
ysis on transformation product such as galaxolide-lactone from
galaxolide in effluent of biological treatment could be used to
determine the occurrence of biodegradation of FMs (Bester, 2004).
3.3. Fate of fragrance materials in drinking water treatment plant
As mentioned, there is no regulation on FMs in drinking water
in most of the countries which is mainly due to the fact that con-
centrations were rather small and difficult to detect in the past.
As the usage amount of FMs increased, some of the fragrances,
such as limonene and nitro-musk have been found in groundwater
and river water which are the main source of drinking water (San-
tiago et al., 2012). Concentrations are less than 1 lg L1 which is
considered unlikely causing acute toxicity to humans. Moreover,
FMs can bioaccumulate in numerous animals and human breast
milk (Reiner et al., 2007). Therefore, the major concern is the im-
pact on humans under long-term exposure of the lower concentra-
tions of FMs.
Drinking water treatment processes vary with water source and
quality. In many rural areas, groundwater is directly supplied as
drinking water without any treatment because normally the
groundwater can satisfy the US federal requirements. When sur-
face water is used as drinking water source, treatment is de-
manded due to the direct exposure of surface water to
atmosphere which would result in easy contamination. The most
commonly applied treatment includes aeration, flocculation, sedi-
mentation, filtration, adsorption, and disinfection.
Aeration is usually the first process to liberate the trapped gases
and to allow water to absorb oxygen by introducing air to the
water in order to remove the odor and obtain a better taste (Burns,
1998; Mostefa and Ahmed, 2012). In the process, FMs can be re-
moved by volatilization and the higher retention time and aeration
intensity would lead to higher removal of the FMs.
The materials and particles, such as clay, organic materials, me-
tal, and microorganisms in surface water are often too small to set-
tle without assistance. In order to promote the settling, coagulants,
such as alum, iron salts, and polymers are added (McCurdy et al.,
2004; Guida et al., 2007). During flocculation, the smaller particles
will stick on the coagulants and grow into flocs and then will settle
in sedimentation step. The FMs sorbed on the small particles or
caught by the flocs will be removed from the water and go into
sludge, and then finally be transported to landfill which will go
back to groundwater or air due to leaching or volatilization. In
addition, the FMs which have greater affinity for the coagulants
can also be removed.
Filtration with sand or charcoal beds will trap and remove the
particles which still remain in water (Sävenhed et al., 1987; Meffe
et al., 2010). FMs which are sorbed on the particles will be removed
along with the particle removal by filtration. After filtration, there
could still be some contaminants, such as organic and color/taste/
odor causing compounds in the water. Activated carbon (GAC or
PAC) which are capable of removing these materials are typically
used in adsorption step. Hydrophobic FMs will adsorb onto the
adsorbents and can be removed from water (Hernández-Leal
et al., 2011; Nguyen et al., 2012).
Disinfection is the last step of the treatment but is also the most
important step as it ensures the mortality of potentially dangerous
microbes, such as disease-causing pathogens. Chlorination and
AOPs can achieve efficient disinfection. It is also known that AOPs
are efficient to destroy the microbes in the disinfection tank but are
not efficient to control the biological contaminant in the distribu-
tion pipes. Therefore, chlorination is the most applied technology
for disinfection in drinking water treatment plants (Camel and Ber-
mond, 1998; Molnar et al., 2012). Some of the FMs could be re-
moved when they are oxidized by chlorine, chloramines, or
chlorine dioxide. However, no report has been published on this
aspect as yet. When the aim of the treatment is to remove FMs
from drinking water, the combination of AOPs and chlorination
can be considered as some of FMs can be removed by AOPs (Ta-
ble 4) and chlorination will ensure efficient disinfection of drinking
water during distribution.
Other than the disinfection step, FMs removal from drinking
water treatment processes is just a mere transfer as the problem
(FMs contamination) is transferred from one (water) to another
(air or land) compartment. Moreover, the disinfection could re-
move the FMs but the impact of the by-products on human health
is not understood as yet. Related research should be performed and
accordingly the process should be properly designed when the tar-
get is FMs removal from drinking water.
3.4. Fate of fragrance materials in conventional wastewater treatment
plants
The traditional wastewater treatment plant consists of screen-
ing, primary sedimentation, bioreactor, secondary sedimentation,
tertiary treatment (disinfection), and sludge treatment.
In screening and gritting processes, the coarse materials, such
as paper, wood, plastic bags, and sands are screened from the
wastewater and hence the hydrophobic FMs which are sorbed onto
the materials would be simultaneously removed from wastewater.
The amount to be removed in these processes depends on the
quantity of FMs retained by the coarse materials.
The primary sedimentation process is aimed to remove sus-
pended solids and generally around 50–65% of suspended solids
would be reduced. As discussed above, sorption of FMs is propor-
tional to suspended solids concentration; therefore, the reduction
of SS from wastewater would lead to the removal of FMs which
are sorbed onto SS due to hydrophobicity and electrostatic interac-
tion (Joss et al., 2005). However, it should be realized that the FMs
are transferred into sludge.
In bioreactor, due to the presence of microorganisms, the biode-
graded FMs would be assimilated and converted to energy for
microbial growth (Deegan et al., 2011). The removal of FMs is
determined by their biodegradability and the hydraulic retention
time (HRT). In addition, biomass concentration has significant ef-
fect on their removal. The longer HRT and high biomass concentra-
tion would enhance FMs removal from bioreactor.
Secondary sedimentation allows the solids (biomass and sus-
pended solids which are not biodegraded) to settle and dis-
charge the excess sludge to maintain balance between
microorganisms and organic materials. As mentioned, the FMs
can be sorbed by suspended solids (hydrophobicity) as well
as microorganisms (electrostatic interaction). Therefore, the
fraction of FMs would go into sludge due to the settling and
discharged to sludge treatment along with the excess sludge
(non-recycled part).
Tertiary treatment disinfects the effluent in order to meet the
requirements of further application such as irrigation. AOPs are of-
ten used (Oller et al., 2011) and some of FMs would be destroyed
and removed from the wastewater (Ternes et al., 2003a; Broséus
et al., 2009).
The sludge produced from primary and secondary treatment
would go to sludge treatment before final disposal. Aerobic and
anaerobic digestion, composting, and incineration are the common
methods of sludge treatment. FMs removal in aerobic and anaero-
bic digestion and composting is mainly due to biodegradation as in
 X. Zhang et al. / Chemosphere 93 (2013) 857–869 865

Table 5
Fragrances removal in wastewater treatment.

Fragrances Treatments Removal Removal efficiency References

mechanism (%)
AHTN Ozonation disinfection (5 mg O3 L1 for 18 min) Oxidation 100 Ternes et al. (2003b)
HHCB Ozonation disinfection (5 mg O3 L1 for 18 min) Oxidation 90.41 Ternes et al. (2003b)
AHTN Conventional activated sludge process Biodegradation 63 Bester (2004)
(SRT = 10 d) Sorption on sludge
HHCB Conventional activated sludge process Biodegradation 64 Bester (2004)
(SRT = 10 d) Sorption on sludge
Oxidation
AHTN Sequencing batch reactor Biodegradation 92.1 Berset et al. (2004)
Sorption on sludge
HHCB Sequencing batch reactor Biodegradation 87.5 Berset et al. (2004)
Sorption on sludge
Oxidation
AHTN Membrane bioreactor (SRT = 27 d) Biodegradation 90.7 Clara et al. (2005)
Filtration
Sorption on sludge
AHTN Conventional activated sludge process Biodegradation 82.81 Clara et al. (2005)
(SRT = 237 d) Sorption on sludge
HHCB Membrane bioreactor (SRT = 27 d) Biodegradation 91.6 Clara et al. (2005)
Filtration
Sorption on sludge
HHCB Conventional activated sludge process Biodegradation 86.5 Clara et al. (2005)
(SRT = 237 d) Sorption on sludge
AHTN Conventional activated sludge process Biodegradation 54.5 Kupper et al. (2006)
(SRT = 16 d) (43%)
Sorption on sludge
HHCB Conventional activated sludge process Biodegradation 87 Kupper et al. (2006)
(SRT = 16 d) (20%)
Sorption on sludge
ADBI Conventional activated sludge process Biodegradation 90.9 Kupper et al. (2006)
(SRT = 16 d) Sorption on sludge
AHMI Conventional activated sludge process Biodegradation 88.75 Kupper et al. (2006)
(SRT = 16 d) Sorption on sludge
ATII Conventional activated sludge process Biodegradation 87.78 Kupper et al. (2006)
(SRT = 16 d) Sorption on sludge
DPMI Conventional activated sludge process Biodegradation 88.24 Kupper et al. (2006)
(SRT = 16 d) Sorption on sludge
DPMI Primary settling Sorption on sludge 50 Zeng et al. (2007)
DPMI Conventional activated sludge process Biodegradation 36–47 Zeng et al. (2007)
Sorption on sludge
OTNE Primary settling Sorption on sludge 56–64 Bester et al. (2008)
HHCB Aeration Volatilization 14 Upadhyay et al.
(2011)
AHTN Ozonation (2 mg O3 L1 for 15 min) Oxidation 22 Janzen et al. (2011)
HHCB Ozonation (2 mg O3 L1 for 15 min) Oxidation 80 Janzen et al. (2011)
MX Ozonation (2 mg O3 L1 for 15 min) Oxidation 0 Janzen et al. (2011)
MK Ozonation (2 mg O3 L1 for 15 min) Oxidation 0 Janzen et al. (2011)
OTNE Ozonation (2 mg O3 L1 for 15 min) Oxidation 91 Janzen et al. (2011)
Polybrominated diphenyl ethers Aeration Volatilization Around 5 Weinberg et al.
(2011)
Poly- and perfluorinated compounds Aeration Volatilization Around 6 Weinberg et al.
(2011)
Musk MC4 (ethylenedodecanedioate) Addition of silica adsorbent (contact Sorption 66.7–83.3 Vallecillos et al.
time = 8.82 min) (2012)
Muscone Addition of silica adsorbent (contact Sorption 50–98 Vallecillos et al.
time = 7.91 min) (2012)
Musk-NN (ethylenetridecanedioate) Addition of silica adsorbent (contact Sorption 90–100 Vallecillos et al.
time = 9.98 min) (2012)
Habanolide Addition of silica adsorbent (contact Sorption 60–100 Vallecillos et al.
time = 7.91 min) (2012)
Exaltolide(Oxacyclohexadecan-2-one) Addition of silica adsorbent (contact Sorption 50–100 Vallecillos et al.
time = 7.87 min) (2012)
Ambrettolide (Oxacycloheptadec-8-en-2- Addition of silica adsorbent (contact Sorption 68.2–90.9 Vallecillos et al.
one) time = 8.58 min) (2012)
Civetone (9-Cycloheptadecen-1-one) Addition of silica adsorbent (contact Sorption 50–97.7 Vallecillos et al.
time = 9.12 min) (2012)
Exaltone (Cyclopentadecanone) Addition of silica adsorbent (contact Sorption 44–50 Vallecillos et al.
time = 7.84 min) (2012)

bioreactor. Removal during incineration is due to the oxidation Artola-Garicano et al. (2003) investigated the fate of AHTN and
(converted into carbon oxide and other as gases) and volatilization HHCB in traditional wastewater treatment plant with concentra-
(as temperature is higher in incineration and FMs are semi-volatile, tions of 0.21–0.57 and 0.79–2.0 lg L1 in the influent were, respec-
the FMs will return to air). tively. They proved that the removal of FMs were due to the
866 X. Zhang et al. / Chemosphere 93 (2013) 857–869
FMs
Volatilization
organisms
Biodegradation FMs
microorganisms
Seepage
Groundwater flow
Fig. 2. The fate of FMs in soil.
volatilization, biodegradation, and sorption. It is easy to under-
stand that only FMs removed by biodegradation and oxidation
are considered as permanent and efficient removal. Therefore,
the FMs removed by biodegradation in bioreactor and sludge
digestion/composting, and oxidation by chemicals/UV addition
and incineration are most efficient. The rest of the FMs either go
out with the effluent which may discharged into ocean/revers/
lakes, or go into soil or groundwater by sludge disposal (landfilling
or land application), or remain in the ash of incineration, or volatil-
ize to air. The common fragrances removal in wastewater treat-
ment is shown in Table 5.
4. Fragrance materials in soil
The FMs which are not degraded by chemical or biological treat-
ment will flow out with the effluent of wastewater treatment or go
into wastewater sludge. Application/disposal of the effluent and
the sludge determine the fate of FMs in the environment (Fig. 1).
Wastewater effluent is either discharged into receiving water body,
such as rivers and oceans. Study has revealed that solid–water dis-
tribution coefficient of FMs, such as AHTN (5300 L kg1) and HHCB
(4900 L kg1) is rather high (Ternes et al., 2004), which would
cause the FMs distribute to soil from water. Wastewater effluent
is often used for irrigation of the plants and irrigation is one of
the pathways of FMs entering the soil (Ternes et al., 2007; Chase
et al., 2012). The soil irrigated using wastewater effluent showed
higher AHTN (6.24 ng g1 with irrigation and 0.4 ng g1 without
irrigation) and HHCB (1.98 ng g1 with irrigation and 0.71 ng g1
without irrigation) concentration than the one without irrigation
(Chase et al., 2012). FMs can also be transferred into soil due to
the landfilling or wastewater sludge land application. Apart from
these, the disposal of product containers containing FMs in muni-
cipal solid waste will be transported to landfill and it is another
way of the FMs entering soil. In addition, the FMs volatizing in
the air may be sorbed onto the dust and thus settle in the soil.
The removal of FMs in the soil is determined by the physical
and chemical characteristics as well as the soil condition. Vola-
tilization of hydrophilic FMs would occur when the moisture
Big plants
Small plants
Mass transfer
of the soil is low and the process can also possibly take place
for the hydrophobic FMs when the ambient temperature is high
(summer or warm regions). Photodegradation could also contrib-
ute to FMs removal from soil. Fragrance OTNE has been studied
to investigate its photodegradation ability (Ozaki et al., 2011). It
was observed that the half-life of OTNE (initial concentration
1 lg g1) was 7 d under light irradiation (27 W m2), while the
removal occurred only on the surface layer due to shading effect
of light in the deeper layer. Biodegradation is another mecha-
nism of FMs removal from soil (Chase et al., 2012). In the soil,
the microorganisms may uptake FMs and decompose them. It
is possible that the FMs which are not biodegraded during bio-
logical wastewater or sludge treatment will be degraded in the
soil. It is due to the fact that some of the FMs require long per-
iod time to be biodegraded but retention time of FMs in biolog-
ical wastewater or sludge treatment is limited due to the
consideration of the cost for operating or building large volume
of tanks. However, the time would not be a problem for their
degradation in soil. The FMs can also be transferred to the plants
which are growing on the soil under the driving force of their
concentration difference between soil and plants (Pellmyr
et al., 1987; Rimkus, 1999). Transportation of the FMs from soil
to groundwater could also occur due to rainfall. The fate of FMs
in soil is demonstrated in Fig. 2.
5. Conclusions
The fate of FMs in the environment (air, water, and soil) has sig-
nificant impact on health as humans are daily exposed through
contact. As the atmosphere is infinite, therefore, FMs in the air
can be possibly neglected due to the huge dilution rate. However,
chances of interaction with other contaminants and formation of
other toxic by-products is an issue. FMs in the water including
wastewater, surface water, and groundwater could be partially re-
moved by hydrolysis, oxidation, chlorination, sorption, filtration,
volatilization, and biodegradation (for wastewater) during waste-
water or drinking water treatment. Among these processes, only
chemical and biological processes including hydrolysis, oxidation,
 X. Zhang et al. / Chemosphere 93 (2013) 857–869
chlorination, and biodegradation can be considered as the solution
of the problem as they convert FMs into other products, but phys-
ical processes including sorption, volatilization, and filtration are
just the transfer of the problem from one compartment to the
other (water M air M soil M water). The FMs which are not re-
moved during wastewater and drinking water treatment will go
to the receiving water body and humans by wastewater treatment
effluent discharge and tap water utilization, respectively. In waste-
water sludge, there is also the presence of FMs which are sorbed on
the sludge or bioaccumulated on microorganisms generated during
the processes. The release of FMs in sludge is determined by the
sludge treatment, disposal, and applications. Sludge digestion
could degrade some of the FMs as types of microorganisms during
sludge digestion and biological wastewater treatment are normally
different. Hence, the FMs that are not biodegraded in wastewater
treatment might be decomposed during sludge digestion. Simi-
larly, sludge composting could also remove some of the FMs. Incin-
eration is also a popular sludge treatment process. In the process,
FMs can be volatilized to air or transmitted to other products
due to high temperature and the presence of oxygen. Landfilling
and agricultural land applications are the most often employed
ways of sludge disposal. FMs remaining in the sludge would go
to soil or groundwater due to leaching by rainfalls. FMs in the soil
can be removed by the inhabiting organisms (including microor-
ganisms) by biodegradation, which could go into air or groundwa-
ter by volatilization or soil seepage, and could be further
transferred to plants as well.
Even though scientists have pointed out that FMs affect health,
but there are still very limited studies on FMs removal due to the
lack of regulations. To control the entry of FMs into the environ-
ment, human beings should put efforts, thus introduce control at
source level. For example, users can choose FMs free or containing
less FMs, or containing biodegraded FMs products. In addition, reg-
ulations on FMs in wastewater effluent or drinking water should be
made to encourage research on development of advanced waste-
water and drinking water treatment processes.
Acknowledgements
Sincere thanks are due to the Natural Sciences and Engineering
Research Council of Canada (Grant A 4984, Canada Research Chair,
Discovery grant) for their financial support. The views and opinions
expressed in this paper are those of the authors.
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