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Cosmetic wastewater treatment by coagulation and

advanced oxidation processes
a a a a
Jeremi Naumczyk , Jan Bogacki , Piotr Marcinowski & Paweł Kowalik
a
Faculty of Environmental Engineering, Warsaw University of Technology, Nowowiejska 20,
00-653 Warsaw, Poland
Accepted author version posted online: 29 May 2013.Published online: 25 Jun 2013.

To cite this article: Jeremi Naumczyk, Jan Bogacki, Piotr Marcinowski & Paweł Kowalik (2014) Cosmetic wastewater
treatment by coagulation and advanced oxidation processes, Environmental Technology, 35:5, 541-548, DOI:
10.1080/09593330.2013.808245

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 Environmental Technology, 2014
Vol. 35, No. 5, 541–548, http://dx.doi.org/10.1080/09593330.2013.808245

Cosmetic wastewater treatment by coagulation and advanced oxidation processes

Jeremi Naumczyk∗ , Jan Bogacki, Piotr Marcinowski and Paweł Kowalik
Faculty of Environmental Engineering, Warsaw University of Technology, Nowowiejska 20, 00-653 Warsaw, Poland
(Received 23 January 2013; final version received 20 May 2013 )

In this study, the treatment process of three cosmetic wastewater types has been investigated. Coagulation allowed to achieve
chemical oxygen demand (COD) removal of 74.6%, 37.7% and 74.0% for samples A (Al2 (SO4 )3 ), B (Brentafloc F3) and C
(PAX 16), respectively. The Fenton process proved to be effective as well – COD removal was equal to 75.1%, 44.7% and
68.1%, respectively. Coagulation with FeCl3 and the subsequent photo-Fenton process resulted in the best values of final
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COD removal equal to 92.4%, 62.8% and 90.2%. In case of the Fenton process, after coagulation these values were equal to
74.9%, 50.1% and 84.8%, while in case of the H2 O2 /UV process, the obtained COD removal was 83.8%, 36.2% and 80.9%.
High value of COD removal in the Fenton process carried out for A and C wastewater samples was caused by a significant
contribution of the final neutralization/coagulation. Very small effect of the oxidation reaction in the Fenton process in case
of sample A resulting from the presence of antioxidants, ‘OH radical scavengers’ in the wastewater.
Keywords: chemical treatment; coagulation; cosmetic wastewaters; Fenton/photo-Fenton process; H2 O2 /UV process

1. Introduction equal to approximately 75%. The application of coagulation

Cosmetic wastewater is characterized by a significant
changeability of its composition and the concentration of
pollutants, which is caused by the changeable production
profile. Independent of the aforementioned variability, some
substances are always present in cosmetic wastewater. They
include synthetic musks, mainly polycyclic musks, as well
as ketone and xylene musks. Among them, galaxolide and
tonalide are used in the largest amount. These compounds
are not easily biochemically degradable and are partially
removed in a municipal wastewater treatment plant mainly
due to adsorption on activated sludge.[1] Other impor-
tant and not easily biodegradable compounds present in
cosmetic wastewater include UV filters. These are the com-
ponents of creams and their main responsibility is to absorb
UV radiation. UV filters include among others: benzophe-
none derivatives, p-aminobenzoic acid, benzoic acid esters,
ethylhexyl salicylate and heptan-2-one derivatives. These
compounds are called emerging pollutants and pose a real
threat to the water environment due to their toxicity.[2,3]
Literature concerning the application of chemical meth-
ods in cosmetic wastewater treatment is scarce. El-Gohary
et al. compared the effect achieved by means of the coagula-
tion combined with sedimentation and pressure flotation.[4]
The coagulants used in this study included Al2 (SO4 )3 ,
polymerized aluminium chloride, FeSO4 and FeCl3 . All
coagulants gave comparable results and their efficiency
depended on the type of investigated wastewater. The effi-
ciency of chemical oxygen demand (COD) removal was
combined with flotation did not improve the effect of COD
removal, compared with the effect of coagulation with sed-
imentation. However, the sludge volume decreased. The
effect of flotation process was improving with the increasing
contents of oils and fats. The results obtained for the elec-
trocoagulation and electro-Fenton processes, which were
carried out in parallel, gave slightly better results compared
with the results obtained for coagulation alone.[5] In both
cases, the COD removal was close to 80%. The Fenton
process for sewage pretreated by coagulation, with COD
4730 and 2660 mg/L and biochemical oxygen demand
(BOD)5 /COD ratio of 0.123 and 0.161, was also inves-
tigated by Bautista et al. [6] At optimal pH value 3,
Fe(II) dose was 300–500 mg/L, while H2 O2 /COD ratio
was 2.12, COD removal was equal to approximately 55%.
Cosmetic wastewater also underwent electrocoagulation
process and subsequent photocatalytic oxidation with TiO2 ,
which allowed for COD removal of 78–82%.[7] Bautista
et al.[8] also employed the catalytic oxidation process by
means of the H2 O2 and Fe/γ Al2 O3 catalyst. At 85◦ C, the
COD removal in the first cycle of the catalyst operation
was equal to 80%, while in the third cycle, it was 60%.
In this process, the improvement of organics biodegrad-
ability was observed.[8] Martins et al. applied catalytic
ozonation and Fenton-like processes to treat wastewater
from the detergent industry, which also contains many
substances present in cosmetic wastewater.[9] The best
treatment results and improvement of BOD5 /COD ratio

∗ Corresponding author. Email: jeremi.naumczyk@is.pw.edu.pl

© 2013 Taylor & Francis

 542 J. Naumczyk et al.
from 0.32 to 0.80 was achieved by applying the classic
Fenton process and ozonation catalysed by the mixture of
Ce and Mn oxides.
The removal of synthetic musks has also been stud-
ied. Carballa et al. employed the coagulation and pressure
flotation in order to remove tonalide and galaxolide from
municipal wastewater.[10] The best effect of tonalide (71%)
and galaxolide (63%) removal was achieved using PAX as a
coagulant. Slightly worse results were obtained when FeCl3
and Al2 (SO4 )3 were used. The presence of fats improved
the effect of flotation. Similar studies have been carried out
by Suarez et al. [11] As a result of coagulation employ-
ing FeCl3 , the obtained removal of tonalide, galaxolide and
celestoide was equal to 83.4%, 79.2% and 77.7%, respec-
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tively. In case of the coagulation/flotation process with
Al2 (SO4 )3, the effect was slightly worse – 75.8%, 64.8%
and 72.1%, respectively. Felis et al. removed polycyclic
musks from wastewater by means of the UV photolysis and
UV/H2 O2 processes, achieving the decrease in their content
by 93% and 99%, respectively.[12] Rosal et al. employed
ozonation to remove musks and UV filters from municipal
wastewater.[13] Galaxolide was removed in 72%, while
ketone musks only in 38%. Xylene musks and UV fil-
ters – 3-(4-benzylidene) camphor, octyl methoxycinnamate
and benzophenone-3 – turned out to be completely resis-
tant to ozonation. Triclosane was removed in 78%, while
octocrylene in 20%. High efficiency of ozonation of tonalide
and galaxolide has been also confirmed by Ternes et al.
[14] Li et al. investigated the removal of four UV fil-
ters – benzophenone-3, 4,4-methylbenzylidene camphor,
octyl methoxycinnamate and octocrylene – in the municipal
wastewater plant by means of subsequently applied pro-
cesses: coagulation with polyaluminium chloride, microfil-
tration and ozonation.[15] The removal of the investigated
substances in the three above-mentioned processes was
equal to 7.6–21%, 3.6–8.2% and 16–28%, respectively.
Many studies focused on the elimination of surfactants
from wastewater. Kaleta and Elektorowicz revealed that
coagulation with Al2 (SO4 )3 and FeCl3 yields poor effect
of anionic surfactant removal (24%).[16] Significantly bet-
ter effect of surfactants removal was achieved by means of
the Fenton process and H2 O2 /UV process – almost 100%
removal of six alcohol ethoxylates and four alkylphenol
ethoxylates.[17]
The aim of this study was to provide further infor-
mation and deepen the knowledge concerning cosmetic
wastewater treatment by means of coagulation and oxi-
dation processes for wastewater with different pollutants
composition and concentration. In the investigation of
coagulation, the range of coagulants employed has been
significantly extended. The results of coagulation have
been compared with the results of the Fenton process.
The effect of wastewater treatment in combined processes:
coagulation + advanced oxidation processes (AOPs) – has
also been investigated. Preliminary results of raw wastewa-
ter treatment by means of H2 O2 /UV and the photo-Fenton
processes were unsatisfactory due to high wastewater
turbidity. Therefore, these methods have been used only
for the treatment of wastewater which was preliminarily
coagulated.
2. Materials and methods
Wastewater samples were collected from the big cosmetic
factory in Poland, between October 2011 and February
2012. In this facility, a wide range of cosmetics, includ-
ing lipsticks, shampoo, serum, liquid soap and creams, was
manufactured. As main compounds galaxolide, tonalide
(synthetic musks), ethylhexyl salicylate (UV filter) and D5
(cosmetic base) were used. In raw wastewater, the follow-
ing parameters were determined according to EN or ISO
Standards: COD, CODdis (for sample filtered with 0.45 μm
filter) (ISO 6060), BOD5 (EN 1899), total suspended solids
(TSSs) (EN 872), pH (EN ISO 10523), turbidity (EN ISO
7027), specific conductivity (EN 27888), alkalinity (ISO
740), chlorides (ISO 9297), phosphates (EN 1189), ammo-
nia (ISO 5664), nitrates (V) (EN ISO 13395) and anionic
surfactants (EN 903). Petroleum ether extractable organics
(PEEOs) were gravimetrically determined by the extraction
of 500 mL sample with petroleum ether (50 + 50 mL). COD
of wastewater treated with AOP’s was determined without
the removal of unreacted H2 O2 . It was impossible to remove
residual H2 O2 by means of catalase, due to the inhibiting
effect of some pollutants present in the samples. Therefore,
H2 O2 was determined by means of the iodometric method
and the value of COD was corrected according to Kang’s
equation.[18]
In the studies of the coagulation of raw wastewater, the
following solutions have been used: FeCl3 and Al2 (SO4 )3
with the concentration of 100 mg/mL Fe3+ and 50 mg/mL
Al3+ , Brenntag Al: 1019, 3010, 3030, 3035 prehydrol-
ysed coagulants containing aluminium salts, FeCl3 -based
Brentafloc F3 and Kemipol PAX16 and PAX19 coagu-
lants containing aluminium salts. The correction of the pH
value after the addition of coagulant was done by means of
NaOH or H2 SO4 solutions. 5 min fast and 10 min slow stir-
ring times were employed. During 60 min of sedimentation
after coagulation, the changes in the sludge volume were
investigated.
Wastewater after coagulation with FeCl3 at pH 6.0
was treated using Fenton, photo-Fenton and H2 O2 /UV
processes. The application of the Fe salt was a result of
the application of Fe salt in the Fenton and photo-Fenton
processes. Consequently, it was necessary to assess the con-
tribution of the final coagulation in these processes. The
assumed value of pH 6.0 (not 9.0) resulted from the neces-
sity to reduce the amount of H2 SO4 used to decrease the pH
value in order to perform these processes. Also the amount
of NaOH solution needed for the adjustment to pH 9.0 is
significantly higher than the pH 6.0. The Fenton process
was carried out in a 2 L cylindrical reactor with a mag-
netic stirrer, at pH 3.0, by adding appropriate amounts of
 Environmental Technology 543

Table 1. The doses of reagents (mg/L) for AOP’s.

Fenton process for raw wastewater Fenton process Photo-Fenton process H2 O2 /UV process
Sample H2 O2 /Fe2+ H2 O2 /Fe2+ H2 O2 /Fe2+ H2 O2

A 1200–1700/150–250 400–500/50–80 400–500/40–55 1000–1500

B 600–800/80–100 500–700/60–80 500–700/50–70 1500–2000
C 1900–2300/200–360 550–700/80–120 600–750/55–70 1500–2000

acidic FeSO4 solution with the concentration of 50 mg/mL as in the Fenton process. The doses of reagents applied for
Fe2+ and 30% H2 O2 solution. After a specified time of 5, all AOPs and all samples are listed in Table 1.
15, 30 and 60 min, the process was stopped by increasing
the pH value to 9.0 and the reactor was left for 240 min in
order to allow for the sedimentation of the resulting sludge. 3. Results
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The Photo-Fenton process was carried out in a glass cylin-
drical 1 L Heraeus Nobelight photoreactor with a water
cooling blanket and TQ (150 W) medium pressure mer-
cury lamp. The lamp radiation includes the range from 200
to 580 nm with several sharp emission peaks at 365 (the
strongest peak), 545, 580, 430, 320, 250, 265 and 300 nm.
The conditions of the process were the same as in the case
of the Fenton process with the only difference being that
Fe2+ /H2 O2 weight ratios were lower. The process dura-
tion time and the operation after finishing the process were
the same as in case of the Fenton process. The H2 O2 /UV
process was carried out in a glass cylindrical 1 L Heraeus
Nobelight photoreactor equipped with a low-pressure mer-
cury lamp (15 W). The lamp emits a sharp radiation of the
wavelength of approximately 254 nm. Since, during the pro-
cess, the pH value slightly decreased, its initial value was
increased to 8.0. The process duration time was the same
3.1. Wastewater characteristics
The characteristic of the investigated wastewater is
presented in Table 2. The investigated samples were diver-
sified as far as both quality and pollutant concentration is
concerned. The highest COD value was observed for sam-
ple C (2124 mg/L), while the lowest value was obtained for
sample B (758 mg/L). The majority of the pollutants hav-
ing contributed to the COD value was dissolved (CODdis ).
Wastewater was not susceptible to biological treatment,
which is proved by the BOD5 /COD ratio – 0.06–0.10. Oil
content was not at a high level and the highest contribu-
tion of oils to the total organics (PEEO/COD) was detected
in sample B. Sample A was characterized by the highest
TSS content, but at the same time, the highest value of
CODdis /COD ratio (0.78) implies that there is a significant
contribution of mineral TSS. The lowest level of TSS in
relation to content of organic substances was detected in

Table 2. Characteristics of raw wastewaters.

Parameter Conductivity COD CODdis BOD5 BOD5 / PEEO TSS

(unit) pH (−) (μS/cm) (mg/L) (mg/L) (mg/L) COD (−) (mg/L) (mg/L)

Sample A 7.9 1265 1507 1179 150 0.1 58 811

Sample B 9.1 1042 758 527 48 0.06 137 129
Sample C 7.4 2640 2124 1402 168 0.08 258 584

Parameter Turbidity Chlorides Ammonia Nitrates Phosphates Alkalinity Surfactants

(unit) (NTU) (mg/L) (mg/L) (mg/L) (mg/L) (mval/L) (mg/L)

Sample A 150 122 12.5 2.5 2 7.6 20

Sample B 70 82 2 2 4 5.3 15
Sample C 800 742 2.5 3 5 3.2 20

Table 3. Coagulation results for wastewater A.

Coagulant FeCl3 FeCl3 F3 Al2 (SO4 )3 3010 1019 3030 3035 PAX16 PAX19
pH 6.0 9.0 6.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0
COD (mg/L) 435 392 400 383 409 383 387 418 400 400
Optimal dose (mg/L or mL/L) 100 100 1.5 125 1.0 1.0 1.0 0.5 1.25 0.75
Sludge volume (mL/L) 150 95 230 230 280 430 450 320 200 170
 544 J. Naumczyk et al.

sample C. Very high turbidity of wastewater C implies that

the suspension was very fine. Content of anionic surfactants
was low for all samples.

3.2. Wastewater treatment

3.2.1. Wastewater A
Table 3 shows the results of the studies of the coagula-
tion process for wastewater A. The differences between
COD removal values obtained using different coagulants
are small – the values ranged from 71% (FeCl3 at pH 6.0) to
74.6% (Al2 (SO4 )3 and Brenntag Al 1019). FeCl3 at pH 9.0
was regarded as the best Fe-based coagulant. The obtained
value of COD removal (74.0%) corresponded to the small-
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est volume and hydration of the resulting sludge – 95 ml/L

after 60 min of sedimentation. The Fenton process proved
to be efficient as well (Figure 1). For optimal doses of
H2 O2 /Fe(II) equal to 1500/190 mg/L and after 60 min of
the process, the obtained COD removal was 75.1% (down to
375 mg/L). The process was very fast during the first 5 min
(36.6% COD removal) and after 30 min slowed down sig-
nificantly (74.6% COD removal). The Fenton process using
the doses of H2 O2 /Fe(II) of 435/55 mg/L carried out after
coagulation with FeCl3 at pH 6.0 and dose of 100 mg/L
(Figure 2(a)), resulted in COD removal of only 12.9%
(from 435 to 379 mg/L) – in total 74.9%. Significantly
better results of the treatment of the same sample were
achieved by means of the H2 O2 /UV process (Figure 2(a))
– after 60 min of the process and with the H2 O2 dose of
1300 mg/L, the COD removal value was equal to 43.9%,
while the total result for COD removal: coagulation and
H2 O2 process was equal to 83.8% (down to 244 mg/L).
The best effect of wastewater treatment for sample A after
coagulation was achieved by means of the photo-Fenton
process with H2 O2 /Fe(II) doses of 435/45 mg/L. After Figure 2. COD vs. reaction time: AOP’s for samples after
60 min (Figure 2(a)), the obtained COD removal was equal coagulation: sample A (a), sample B (b) and sample C (c).
to 73.1% (down to 117 mg/L) and the total effect was equal
to 92.4%. 3.2.2. Wastewater B
The effect of coagulation (Table 4) achieved for sample
B was significantly lower than in the case of sample A
(Table 3). The highest effect of COD removal (37.7%) was
obtained by means of F3 at pH 6.0 and also by means of
FeCl3 at pH 9.0–32.2%. Additionally, in the latter case, the
lowest sludge volume (45 mL/L) was obtained, in contrary
to the coagulation with F3, when the volume was 80 mL/L.
The lowest efficiency in COD removal was observed for
the coagulation with FeCl3 at pH 6.0 (20.1%), but the
sludge volume was one of the lowest (80 mL/L). The
Fenton process after 60 min proved to be more effective
compared with coagulation (Figure 1 vs. Table 4). The
value of COD removal at the optimal H2 O2 /Fe(II) dose
of 760/90 mg/L and after 60 min of the process was 44.7%
(down to 419 mg/L). The instant drop in the COD value
Figure 1. COD vs. reaction time: Fenton process for raw in the initial stage of the process has not been observed.
wastewater. The Fenton process of wastewater B after coagulation and
 Environmental Technology 545

Table 4. Coagulation results for wastewater B.

Coagulant FeCl3 FeCl3 F3 Al2 (SO4 )3 3010 1019 3030 3035 PAX16 PAX19
pH 6.0 9.0 6.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0
COD (mg/L) 606 514 472 589 573 589 589 573 539 570
Optimal dose (mg/L or mL/L) 75 75 0.75 100 0.5 0.5 0.75 0.5 1.0 1.0
Sludge volume (mL/L) 80 45 80 110 130 150 170 90 130 130

Table 5. Coagulation results for wastewater C.

Coagulant FeCl3 FeCl3 F3 Al2 (SO4 )3 3010 1019 3030 3035 PAX16 PAX19
pH 6.0 9.0 6.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0
COD (mg/L) 637 680 595 680 595 595 658 595 552 595
Optimal dose (mg/L or mL/L) 100 100 1.0 125 0.5 0.5 0.75 0.75 1.25 1.0
Sludge volume (mL/L) 65 55 80 200 120 120 120 110 180 120
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at the optimal doses of reagents equal to 600/75 mg/L
(Figure 2(b)) allowed for 37.6% COD removal (down to
378 mg/L) and total COD removal at the level of 50.1%.
The H2 O2 /UV process (Figure 2(b)) was less effective –
after 60 min of the process at the H2 O2 dose of 1800 mg/L,
20.1% of COD removal (down to 484 mg/L) was achieved,
while the total effect was equal to 36.2%. The photo-Fenton
process proved to be the most effective of all processes
investigated (Figure 2(b)). At the optimal H2 O2 /Fe(II) dose
of 600/60 mg/L, the values of COD removal and total COD
removal after 60 min of the process were 53.5% (down to
282 mg/L) and 62.8%, respectively.
3.2.3. Wastewater C
The best effect of COD removal (Table 5) was achieved
for PAX 16–74.0% of COD removal. However, the sludge
volume was one of the highest – 180 mL/L. The effect
obtained by means of the F3 coagulant can be regarded
as optimal – 72.0% COD removal and sludge volume of
80 mL/L. The worst effect was achieved using FeCl3 at pH
9.0–68.0% COD removal but the sludge volume was the
lowest (55 mL/L). The process was carried out using FeCl3
at pH 6.0 that produced the COD removal at the 70.0% level
(down to 637 mg/L) and the sludge volume of 65 mL/L.
The Fenton process on raw wastewater (Figure 1)
resulted in 68.1% COD removal (down to 680 mg/L) when
using optimal H2 O2 /Fe(II) doses of 2125/265 mg/L. A rel-
atively high value of COD removal (39.3%) was already
obtained after 5 min of the process. In the case of wastewater
after coagulation with FeCl3 at pH 6.0, the Fenton pro-
cess produced 52.4% COD removal (down to 324 mg/L)
when using optimal H2 O2 /Fe(II) doses of 640/105 mg/L
(Figure 2(c)) and a total COD removal of 84.8%. In case
of this type of wastewater, the relatively high value of
COD removal was also observed after 5 min (33.8%). The
H2 O2 /UV process (Figure 2(c)) turned out to be less effec-
tive, since COD removal after 60 min of the process and
with the H2 O2 dose of 1900 mg/L was only 36.4% (down to
405 mg/L). The total COD removal was 80.9%. The photo-
Fenton process proved to be the most effective (Figure 2(c)).
With the H2 O2 /Fe(II) dose of 640/65 mg/L, the COD
removal value, achieved after 60 min of the process, was
equal to 67.5%. Total COD removal value was 90.2%. Sim-
ilarly, the raw wastewater and in the case of the Fenton
process, a relatively high decrease in COD (54.0%) was
observed within the first 5 min.
4. Discussion
Diversity of the chemical composition and the total organic
content in three investigated samples of wastewater induce
the differences in their susceptibility to chemical treatment.
Samples A and C exhibit a high susceptibility to coagula-
tion for all coagulation tests. The obtained high value of
COD removal (>70%) is suspected, since both the samples
of wastewater are characterized by a high content of sus-
pended solids. In the case of sample C, its contribution to
COD [(COD – CODdis )/COD] was equal to 34%, while in
the case of sample A its contribution was much lower and
high efficiency of the process might have been affected by
the presence of fine, easily coagulating mineral SS, acting
as a load for organic suspension. The presence of a high
amount of synthetic musks might have been another reason
for high efficiency of coagulation of sample A. Polycyclic
musks are characterized by high lipophilicity, especially
galaxolide and tonalide (log Kow 5–6), which are used in
large amounts.[14,19] Musk xylene and musk ketone are
only slightly less lipophilic. Studies on the coagulation
of those types of musks in hospital wastewater revealed
that they are removed in 70–84%, and the effect achieved
by means of FeCl3 is better than the ones obtained using
Al2 (SO4 )3 .[11] These compounds are removed mostly as a
result of their adsorption on the resulting sludge. The best
effect for wastewater A achieved using FeCl3 at pH 9 means
that in the case of dissolved organic removal, the sorption
process plays a crucial role. At pH 9, the Fe(OH)3 species
are present in the solution, while at lower pH Fe(OH)+ 2,
 546 J. Naumczyk et al.
Fe(OH)2+ and Fe3+ ions are detected.[4] A poor coagu-
lation effect is observed for sample B that resulted from a
relatively lower TSS content and from a relatively high con-
tent of substances much more polar than synthetic musks,
which have nonionic composition and can be extracted from
petroleum ether. Those substances mostly include UV fil-
ters (produced in the periods preceding sample collection),
which according to the results of studies carried out by
Li et al. were removed in 7.1–21% by means of coagu-
lation with polyaluminium chloride.[15] The best results
of COD removal by means of F3 at pH 6 proves that in
cases of these types of wastewater, the mechanism of pol-
lutant removal was mixed. In the case of sample C, high
values of COD removal achieved for all coagulants studied
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proves the mixed mechanism of pollutant removal. The best
results obtained using (prehydrolized) PAX 16 coagulant
and good results obtained using other prehydrolized polya-
luminium salts are consistent with the results reported by
Carballa et al. [10] The polymeric structure leads to the
agglomeration properties of these coagulants and stronger
destabilization of negative colloids.
The results of the studies on the efficiency of the Fenton
process for wastewater A proved the dominant contribu-
tion of the final neutralization/coagulation to the final value
of COD removal. This contribution is characterized by a
high value of COD removal in the first stage of the process
(5 min).[20] In the Fenton process carried out after the coag-
ulation of wastewater A, general COD removal was only
3.8% higher than the one obtained by means of coagulation
alone, which proves the conclusions presented above. Sub-
stances remaining in the wastewater after coagulation are
characterized by relatively low susceptibility to oxidation
by HO radicals, which is confirmed by the value of COD
removal equal to only 12.9%. Those substances mostly
included the ketone and xylene musk. As it was shown by
Rosal et al. [13] and Li et al. [15], they are poorly (that is to
significantly lower extent than polycyclic musks) removed
not only in the coagulation process, but also in the ozona-
tion process. Poorly removable UV filters were present in
the wastewater at low concentration. A much better effect
in the H2 O2 /UV process was achieved for the wastewa-
ter after coagulation and even better results were obtained
by the photo-Fenton process, which may be explained by
the excitation of UV filters and other compound molecules
by means of UV radiation. In the case of the photo-Fenton
process, the emission spectrum was broader and this phe-
nomenon was much stronger. The reason for low efficiency
of the Fenton process after coagulation for sample A and a
small contribution of the oxidation reaction in the Fenton
process for raw wastewater might have been the presence
of antioxidants (i.e. hyaluronic acid), which are HO rad-
ical scavengers.[21] Those substances were used in the
production of cosmetics just before sample A collection.
Those substances undergo photolysis, which explains the
good results of H2 O2 /UV and photo-Fenton processes.[21]
Similarly to sample A, in the Fenton process carried out
for sample C, the final neutralization/coagulation plays a
significant role. However, a high value of COD removal
achieved after 5 min of the process may result from the
presence of a certain amount of substances quickly react-
ing with HO radicals. This is confirmed by high value of
COD removal after 5 min in cases of all AOPs carried out
for wastewater after coagulation, which is most evident in
the case of the photo-Fenton process. Lower values of COD
removal in H2 O2 /UV process compared with the value of
COD removal in the Fenton process results probably from a
significant contribution from coagulation in the Fenton pro-
cess, which is absent in the H2 O2 /UV process. In the case
of sample B, the effect of neutralization/coagulation in the
total effect of the Fenton process is significantly lower. It
results from the weak effect of coagulation itself. However,
this effect exists and most probably consists in the adsorp-
tion of pollutants. It is confirmed by the fact that the Fenton
process carried out after coagulation in conditions produc-
ing the worst effect (FeCl3 , pH 6) gave better results of COD
removal than the effect of H2 O2 /UV process. Definitely the
best, but worse than in the case of sample A, the effect of the
photo-Fenton process may be explained by the contribution
of neutralization/coagulation, by the stronger excitation of
molecules of UV filters by the UV lamp irradiation and by
Fe2+ ions reproduction according to reaction (1).[20]
Fe(OH)2+ + hν → Fe2+ + HO• . (1)
In all Fenton and photo-Fenton processes, the optimal
dose of H2 O2 was similar to the COD value, while Fe(II)
dose was eight times smaller. Increasing the doses did not
improve the effect of the process.
In order to estimate the efficiency of the Fenton process,
a parameter referred to as ‘efficiency of hydrogen peroxide’
was recommended by Kang and Hwang.[22]
COD × 100
η(%) = , (2)
0.476[H2 O2 ]
where  COD, COD removed (mg/L); [H2 O2 ], dose of
H2 O2 (mg/L); 0.476, factor COD theoretically removed
(mg) by 1 mg of H2 O2 .
The value of this parameter for the Fenton process and
sample A was high – 160.0. Such high values of H2 O2 effi-
ciency are caused not only by the oxidation process, but
also by the final coagulation. This is proved by a very low
value (27.4%) of this parameter for the same wastewater
sample, but after the coagulation process. For wastewater
B, for which the effect of the Fenton process is smaller, the
value of η parameter is also lower, namely 94.7%. The con-
tribution of the final coagulation to this parameter is less
significant. For wastewater B after coagulation, this value
is slightly lower (80.7%). In the case of wastewater C, for
which the effect of the Fenton process is intermediate (closer
to the effect for wastewater A), the value of η parameter
(144.7%) is close to the value obtained for wastewater A.
The contribution of the final coagulation to this parameter
 Environmental Technology
Table 6. H2 O2 efficiency (%) in AOP’s for samples A, B and C and process time 60 min.
Fenton process for Coagulation + Fenton
raw wastewater process
A B C A B C
160.0 94.7 144.7 27.4 80.7 112.3
is low, which is proved by the value of η parameter for
the wastewater after coagulation (112.3%). This value is
only slightly lower than without the coagulation process.
The value of η parameter for the photo-Fenton process
and wastewater after coagulation is high for all investi-
gated wastewater samples and is equal to 155.3%, 114.8%
Downloaded by [The University of British Columbia] at 04:12 24 November 2014
and 142.8%, respectively. The values of η for all processes
and wastewater, and 60 min reaction time, are presented in
Table 6. Since the contribution of the final coagulation to
the value of η parameter cannot be significant, the high
value of the parameter is caused by the presence of oxygen
in the aerated sample and the presence of organic radicals
formed in the reactions mentioned below.[23]
HO• + RH → R • + H2 O, (3)
•
R + O2 → RO•2 . (4)
Very low values of η parameter for the H2 O2 /UV process
for wastewater after coagulation, which are equal to 31.3%,
14.4% and 26.0%, respectively, result not only from the low
efficiency of this process. It was achieved using relatively
a high (optimal) H2 O2 /COD ratio.
Presented results of the studies may be compared only
with the results of the studies published by El-Gohary et al.
[4] The results obtained by those authors were slightly
higher (up to 77.5% COD removal) and similar to the studies
presented in this paper, the differences between the coagu-
lants were small. The investigated samples of wastewater
were characterized by COD values similar to the value for
sample C. However, they contained much more biodegrad-
able substances – i.e. vitamins and sorbitol. The results of
the studies on the Fenton process may be compared with
the results presented by Bautista et al. [6] The authors
treated the pre-coagulated wastewater with a COD value
of 2720 mg/L and with a higher susceptibility to biologi-
cal treatment. The obtained results of COD removal were
slightly lower than those reported in the present study. Addi-
tionally, they were achieved using almost twofold higher
values of H2 O2 /COD ratio.
5. Conclusions
Composition and concentration of pollutants in cosmetic
wastewater generated by a big cosmetic factory signifi-
cantly changes in time and according to the changes in
the production profile. This type of wastewater is resistant
to biological treatment and the pollutant concentration is
usually high.
547
Coagulation + photo- Coagulation+H2 O2 /UV
Fenton process process
A B C A B C
155.3 114.8 142.8 31.3 14.4 26.0
Cosmetic wastewater is generally characterized by high
but diversified (37.7–74.6% COD removal) susceptibility to
coagulation, which depends on the wastewater composition.
The effect of the Fenton process is slightly higher than
the coagulation effect (44.7–75.1% COD removal). Con-
tribution of the final neutralization/coagulation to the final
effect is significant.
Antioxidants present in wastewater lead to the decrease
in the effect of the Fenton process.
In the case of wastewater after coagulation, the photo-
Fenton process proved to be the most effective of all
oxidation processes investigated. In case of wastewater A,
the total effect of COD removal was equal to 92.4%.
Acknowledgements
The authors gratefully acknowledged the financial support pro-
vided by the National Science Centre (grant no. 7385/B/
T02/2011/40 ‘Chemical pretreatment of effluents from cosmetic
industry’).
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