Journal of Environmental Chemical Engineering 4 (2016) 1102–1109

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Removal of emerging micropollutants from wastewater by activated

carbon adsorption: Experimental study of different activated carbons
and factors influencing the adsorption of micropollutants in
wastewater
R. Maillera,* ,1, J. Gasperia,* , Y. Coquetb , C. Deromea , A. Buletéc , E. Vullietc , A. Bressyd,
G. Varraulta , G. Chebbod, V. Rochere
a
LEESU (UMR MA 102, Université Paris-Est, AgroParisTech), Université Paris-Est Créteil, 61 avenue du Général de Gaulle, 94010 Créteil Cedex, France
b
SAUR, Direction de la Recherche et du Développement, 1 rue Antoine Lavoisier, 78064 Guyancourt, France
c
Université de Lyon, Institut des Sciences Analytiques, UMR5280 CNRS, Université Lyon 1, ENS-Lyon, 5 rue de la Doua, Villeurbanne 69100, France
d
LEESU (UMR MA 102, Université Paris-Est, AgroParisTech), École des Ponts ParisTech, 6-8 avenue Blaise Pascal, Champs-sur-Marne, 77455 Marne-la-Vallée
Cedex 2, France
e
SIAAP, Direction du Développement et de la Prospective, 82 avenue Kléber, 92700 Colombes, France

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

Article history: Activated carbon processes, initially designed for drinking water production, are tested for wastewater
Received 21 September 2015 application in order to characterize their efficiency to remove micropollutants from wastewater treatment
Received in revised form 26 November 2015 plants (WWTPs) discharges. In that purpose, a pilot was studied by the Paris sanitation service (SIAAP) and
Accepted 14 January 2016
the water environment and urban systems laboratory (LEESU). The in-situ study raised several additional
Available online 16 January 2016
questions related to the structural and morphological properties of activated carbons, in order to select the
proper material, the influence of operational parameters such as the activated carbon dose and the contact
Keywords:
time, the role of organic matter concentration and composition, the presence of a residual concentration of
Adsorption
Organic matter
methanol or the impact of ferric chloride addition. Thus, various complementary experiments were carried
Pharmaceuticals out at laboratory scale to improve the understanding of the micropollutants adsorption process on
Activated carbon activated carbon, in particular on powdered activated carbon (PAC).
Wastewater The results have highlighted a strong link between the efficiency of PACs and their specific surface (BET),
which can be easily estimated by their bulk density. The study of the sorption process has also confirmed the
strong influence of the PAC dose and the rapidity of the sorption kinetic. From an operational point of view,
the ferric chloride injection seems to slightly improve most of the detected compounds adsorption, probably
thanks to the coagulation of the dissolved organic matter colloidal fraction. In contrary, the presence in the
water of a residual concentration of methanol seems to have no impact on the micropollutant fate. The
influence of the wastewater matrix is strong, with notably lower adsorption in water from primary settling
compared to various WWTP discharges. However, the dissolved organic carbon concentration is not always
sufficient to explain sorption competitions in wastewater, and the nature of the organic matter should be
considered too. In particular, the carbon removal from biological treatments is the step that clearly modifies
both the quantity and the composition of the organic matter. It has been observed that discharges from
WWTPs operating with different biological processes (activated sludge, membrane bioreactor or
biofiltration) have similar organic matter concentrations and compositions, and allows comparable
removals of organic matter and micropollutants by adsorption. The lower performances on micropollutants
observed in the settled water can be explained by the higher quantity of protein-like molecules
(fluorophores Id and Ig), which compose the most competitive organic matter fraction for adsorption on
activated carbon, compared to the other waters.
ã 2016 Elsevier Ltd. All rights reserved.

* Corresponding authors.
E-mail addresses: [email protected] (R. Mailler), [email protected] (J. Gasperi).
1
Present address: SIAAP, Direction du Développement et de la Prospective, 82 avenue Kléber, 92700 Colombes, France.

http://dx.doi.org/10.1016/j.jece.2016.01.018
2213-3437/ ã 2016 Elsevier Ltd. All rights reserved.
 R. Mailler et al. / Journal of Environmental Chemical Engineering 4 (2016) 1102–1109 1103

1. Introduction are assessed. Then, the influence of the dose of carbon, the contact
time, the organic matter quantity and composition, the presence of
The presence of a large range of emerging micropollutants, a residual concentration of methanol and the presence of FeCl3
particularly pharmaceuticals and hormones, personal care prod- were studied.
ucts or pesticides, have been highlighted in wastewater treatment
plant (WWTP) discharges [1–4]. Even if several hydrophobic, 2. Materials and methods
volatile or biodegradable compounds are strongly removed by
conventional wastewater treatments [5,6], most of micropollu- 2.1. Activated carbon characterization
tants are poorly removed. Thus, various strategies of contamina-
tion reduction, such as source reduction, WWTP optimization or 11 adsorbents, including micro and mesoporous PACs and
tertiary treatment implementation, are assessed by the scientific mGAC, have been selected based on their technical datasheets
community and water treatment engineers. Among them, the provided by the producers. Among them, 3 are commercialized by
implementation of tertiary treatments dedicated to micropollu- DaCarb1 (PB 1701, PB 170-4001 and PC 10001 —France), 3 by
tants elimination represents a relevant solution. In particular, Chemviron1 (WP 2351, Carbsorb 281 and Cyclecarb 3051—
adsorption on activated carbon appears to be efficient, adapted to Belgium), 2 by Norit1 (W 351 and SA Super1—Netherlands) and 3
any types of WWTP and relatively cheap [7], together with not by Jacobi1 (LP 391, MP 251 and Hydro XP 171—Sweden). These
producing oxidation by-products. activated carbons are recognized for their high affinity for organic
In this context, the Parisian public sanitation service (SIAAP) and pollutants, but their use in wastewater was poorly studied in the
the water environment and urban systems laboratory (LEESU) study literature.
the CarboPlus1 process, in collaboration with SAUR teams. This Several structural properties such as the specific BET surface
process is based on a fluidized bed of activated carbon (powder – PAC (m2/g), the porous volume (mL/g), the pore size distribution and
- or micro-grain – mGAC) to remove micropollutants by adsorption. A the bulk density (g/cm3) have been measured on the 11 activated
large-scale pilot based on this technology was set up at the Seine carbons. In addition, the particle size distribution and the
Centre (SEC) WWTP (240,000 m3/day) to characterize the efficiency micropollutant elimination have been determined for 4 of them:
of activated carbon to remove a wide range of pollutants from WWTP PB 1701, WP 2351, W 351 and PC 10001.
discharges. The in-situ results are presented in Mailler et al. for PAC The specific BET surface and the pore size distribution were
and Mailler et al. for mGAC [4,8]. measured with an ASAP 2010 Micromeritics analyzer equipped
In parallel to the in situ study, complementary laboratory scale with a degasing station and a gas isotherm adsorption analyses
experiments were conducted to (i) improve the understanding of station (nitrogen), according to the conventional methods used to
the micropollutant adsorption mechanisms in wastewater appli- determine these parameters. Fresh activated carbon samples
cation, in particular with PAC, and (ii) better understand the (100 mg) were degased at least 12 h before analysis. Results
relationships between activated carbon properties and the correspond to the specific surface in m2/g obtained with the BET
adsorption processes in wastewater. method. The pore size distribution is determined with the BJH
Activated carbon is characterized by different structural and (Barrett, Joyner and Halenda) method, using the desorption curve
morphological properties that can affect adsorption [9–12]. The of the same gas on the same analyzer. This method allows also
understanding of the links between activated carbon properties calculating the micro and mesoporous volumes.
and pollutant adsorption is still incomplete. Thus, the first axis The bulk density was measured by weighting, with a high
consists in studying the relationships between activated carbon precision balance (0.01 mg), 50 to 100 mL of activated carbon,
properties and their efficiency to remove micropollutants. In measured with a 100 mL graduated cylinder. The activated carbon
particular, a focus is performed on the specific BET (Brunauer, is introduced by doses (10 mg) and is compacted by patting gently
Emmett and Teller) surface and the bulk density. the cylinder several times every 10 mL to minimize the vacuum
The second axis consists in studying the adsorption mechanism between particles.
in wastewater representing a complex matrix. Indeed, the The particles size distribution of the 4 PACs was measured with
literature highlighted that the matrix where the adsorption is a Mastersizer 2000 Malvern laser particle sizer. Every analysis
performed plays a crucial role in the fate of molecules [13–17], corresponds to 15,000 light diffraction measures. 3 scans were
particularly the organic matter which competes with pollutants for performed at least per sample.
adsorption through direct sites competition or pore blocking. The
adsorption interactions were already deeply studied in the 2.2. Pollutants and analytical procedures
literature, but most of the studies were conducted for drinking
water production or in surface waters, and these mechanisms were Samples were filtered on 0.7 mm glass fibers filters (GF/F) before
poorly assessed in wastewater [18,19]. In this context, the influence all analyses. For every sample, several parameters were measured
of both the quantity and the composition of the organic matter on in the dissolved phase: UV absorbance (Secomam1 UV Light) at
micropollutant adsorption in wastewater was assessed using 3D 254 nm (UV-254), dissolved organic carbon (DOC) and concen-
spectrofluorometry. The study of such interactions between trations of 17 pharmaceuticals and 2 pesticides (list and limit of
activated carbon, emerging micropollutants and organic matter quantification – LQ – in Supporting material—Table S1). Analytical
in wastewater using this innovative technique and adopting field protocols are validated and given in [4].
conditions (limited contact time with PAC) is novel. The novelty of 3D fluorescence spectrometry analyses were also performed
this study is also the assessment of different types (settled, carbon after filtration. This method is used to characterize the dissolved
treatment effluent, various WWTP effluents) and quality of organic matter (DOM) present in the sample. It gives information
wastewater, as well as the effects of (i) the FeCl3 injection and about the nature and origin of the DOM through an excitation
(ii) the presence of a residual methanol concentration in the emission matrix (EEM) containing all excitation and emission
effluents on the adsorption of emerging micropollutants. Such spectra obtained for the DOM. Indeed, the different fractions of the
influences were not or poorly documented in the literature [20]. DOM fluoresce in different zones of the spectrum. The detailed
This article summarizes the results from the laboratory scale description of 3D fluorescence spectrometry is given in [21].
experiments conducted within this project. First, the relationships Analyses have been performed with a Jasco FP-8300 spectrofluo-
between micropollutant removals and activated carbon properties rometer equipped with a 1 cm quartz cell. The ranges of
1104 R. Mailler et al. / Journal of Environmental Chemical Engineering 4 (2016) 1102–1109

wavelengths were 240–450 nm in excitation (intervals of 2 nm) contacting individually 10 mg/L of each PAC with 1 L of SEC WWTP
and 300–600 nm in emission (intervals of 5 nm). discharges during 45 min under strong mixing. 45 min is repre-
The EEM obtained was treated following the fluorophores defined sentative of the contact time in PAC tertiary processes [4]. To
in Parlanti et al. [22], as indicated for SEC settled water and evaluate PACs, UV-254, DOC and micropollutants were measured
discharges in Supporting material—Fig. S1. Ia and Ia’ correspond to both before and after PAC contact.
humic-like substances, Ib results from a recent autochthone
material production, Ig and Id respectively represents tyrosine-like
2.3.2. PAC dose and adsorption kinetic
and tryptophan-like proteins. Then, Ia/Ia’, Ib/Ia’, Id/Ia’ and Ig/Ia’
Regarding its performances on micropollutant removals
indexes were calculated to evaluate the distribution of DOM. Finally,
(results presented after), PB 1701 was selected to characterize
the humification index (HIX) and the biological activity index (BIX)
the relationship between PAC dose, contact time and micro-
were also evaluated [22,23]. HIX is the ratio H/L of two spectral areas
pollutant removal. First, 10 mg/L of this PAC were contacted with
(H = maximum between 300 and 345 nm; L = maximum between
1 L of SEC discharges under strong mixing during different contact
435 and 480 nm) from the emission spectrum scanned at an
times (5–10–30–45–60 min). Then, 3 PAC doses (5–10–20 mg/L)
excitation wavelength of 254 nm. BIX is the ratio of the intensity at
were tested with 1 L of SEC discharges and during 45 min. UV-254,
an emission wavelength of 380 nm and the intensity at 430 nm,
DOC and micropollutants were measured both before and after PAC
scanned at an excitation wavelength of 310 nm.
contact.
2.3. Laboratory experiments protocols
2.3.3. DOM and adsorption
The laboratory experiments have been performed in the SEC To determine the role of both the quantity and the quality of the
WWTP (Colombes, France) between April 2013 and May 2015. This DOM in the adsorption process, 7 types of wastewater featuring by
water is characterized by a relatively low content of dissolved different levels of organic matter have been contacted under strong
organic matter, with an average DOC value of 5.6  0.9 mgC/L [4]. mixing with PAC (10 mg/L of PB 1701 during—45 min). These
Wastewater was punctually sampled from the WWTP discharges wastewaters have similar concentrations concerning the studied
with 10 L glass bottles, properly rinsed and grilled, and used the micropollutants since these WWTPs receive water from the same
same day for experiments (2 h after sampling maximum). In the catchment (Paris conurbation). Among the tested waters, 4 were
different experiments, the water was contacted with PAC under WWTP discharges, from SEC, Seine Aval (SAV), Seine Morée (SEM)
strong mixing in rinsed and grilled (500  C) 2 L batches covered and Seine Amont (SAM) WWTPs. The WWTPs layouts are given in
with aluminum paper. Then, samples were filtered on 0.7 mm GF/F Supporting material—Fig. S2. The 3 other tested waters were outlet
filters after experiments and conditioned before analyses. UV- waters from a physico-chemical lamellar settling unit (SEC settled
254 was measured directly after filtration, while DOC was analyzed water), a carbon biofiltration unit (SEC carbon biofiltration stage),
within 24 h and micropollutants were analyzed within 48 h and the SEC settled water diluted with ultra-pure water to reach a
(storage at 4  C). DOC level comparable to the WWTP discharges. The layouts of the
different studied WWTPs are given in Supporting material—
2.3.1. Efficiency comparison of 4 PACs Table S1, as well as the sampling points (red circles). UV-254, DOC
The efficiency of 4 PACs (PB 1701, WP 2351, W 351 and PC and 3D fluorescence spectrometry have been measured both
10001—Table 1) to remove micropollutants was assessed, by before and after PAC contact for the 7 wastewaters, while the

Table 1
Characterization and performances of the 4 PACs studied.

PB 1701 WP 2351 W 351 PC 10001

Producer DaCarb Chemviron Norit DaCarb

Raw material Wood Coal Peat Coconut
Bulk density (g/cm3) 0.30 0.38 0.33 0.54
Specific BET surface (m2/g) 957  28 909  30 768  19 458  14
Pore size distribution (%) 54%–35%–11% 53%–31%–16% 45%–45%–10% 59%–29%–12%
(micro, meso, macroporous)a
Pore volume (micro + meso) (mL/g) 0.5066 0.4841 0.4876 0.2435
Particle size distribution (mm) 3.4–16.2–58.9 3.4–18.0–58.0 3.2–19.4–86.2 3.7–31.7–129.4
d10–d50–d90
Concentration in SEC WWTP discharges (ng/L) Micropollutant removal (%) with 10 mg/L of PAC during 45 min of contact
Atenolol 435 54 44 41 21
Atrazine 6 40 35 37 12
Carbamazepine 267 63 44 48 16
Ciprofloxacin 425 77 63 62 49
Diclofenac 303 32 22 28 5
Diuron 57 75 66 60 24
Erythromycin 585 26 17 22 5
Ketoprofen 61 17 22 31 10
Metronidazole 33 16 13 10 0
Norfloxacin 197 79 69 62 58
Ofloxacin 1632 79 71 68 46
Propranolol 206 81 76 70 46
Roxithromycin 68 43 38 40 21
Sulfamethoxazole 186 51 60 57 60
Trimethoprim 355 46 36 33 10
Average removal of investigated pollutants 52 45 45 26
a
Pore size distribution (%): micro < 2 nm, meso 2–50 nm and macropores > 50 nm. Bezafibrate, lorazepam, naproxen and oxazepam were not detected during this
experiment.
 R. Mailler et al. / Journal of Environmental Chemical Engineering 4 (2016) 1102–1109 1105

micropollutants have been assessed only with SEC settled water, investigated micropollutants is 52%, 45%, 45% and 26% respectively
SEC carbon biofiltration effluent, SEC and SAV discharges. for PB 1701, WP 2351, W 351 and PC 10001.
The micropollutant removal is well correlated with the specific
2.3.4. Influence of the residual methanol concentration in the WWTP BET surface (Fig. 1): the higher the specific BET surface, the higher
discharges the micropollutant removal. This correlation is significant (p-value
A residual methanol concentration is present in both SEC and SAV <0.05; tests Shapiro-Wilk and Pearson) for atenolol (p-value =
discharges (20% of DOC, SIAAP source) because of the post- 0.029), metronidazole (p-value = 0.005), of loxacin (p-value =
denitrification stage. Indeed, denitrifying microorganisms needs a 0.015), propranolol (p-value = 0.005), trimethoprim (p-value =
carbon source and the carbon content is too low as denitrification is 0.020), diuron (p-value = 0.010) and the average removal of
performed in post-denitrification configuration in both SEC and SAV detected pollutants (p-value = 0.029). Correlation parameters are
[24]. Methanol is then added during this stage as carbon source, but given for all detected pollutants in Supporting material—Table S2.
its consumption by the microorganisms is not complete. Operation- The specific BET surface is also significantly correlated (rpearson =
ally speaking, it is interesting to study the impact of this residual 0.742; p-value = 0.009) to the bulk density of the PAC, a low bulk
concentration on the micropollutant adsorption by activated carbon. density corresponding to a high BET surface. This relationship has
Thus, the performances obtained with the SEC discharges have been been verified with 7 other PACs differing by their nature (Fig. 1), as
compared to performances obtained with the same water spiked the bulk density is very easy to measure and could therefore be a
with methanol (6 and 12 mgC/L; methanol analytical grade Merck1). proxy of the BET surface. Thus, the bulk density could be used as an
The previously cited micropollutants, as well as UV-254 and DOC, indicator to select activated carbons and estimate their BET surface
were measured before and after contact with PAC (45 min). The and efficiency for micropollutants removal from wastewater.
adsorbability of methanol has also been studied by following DOC The link between the efficiency of activated carbons and their
and preliminary tests demonstrated that no adsorption of methanol specific BET surface (600–1500 m2/g) has already been observed in
occurs when contacting 12 mgC/L of methanol in ultra-pure water the literature [24], but the distribution of this surface between the
with 10 mgPAC/L. different categories of pores (micro <2 nm, meso 2–50 nm and
macropores >50 nm) has also to be considered. This is particularly
2.3.5. Influence of the ferric chloride important in presence of organic matter because it competes with
The CarboPlus1 process operating in PAC configuration requires micropollutants for adsorption, directly or by pore blocking [11,27].
the injection of FeCl3 to stabilize the PAC bed and prevent any Thus, a mesoporous structure with a large pore size distribution
leakage. This substance is known to destabilize particles by should limit the competition with the DOM [13].
neutralization of the surface charges [25], which could impact the
adsorption of micropollutants. To evaluate the impact of FeCl3, 1 L 3.2. Adsorption of micropollutants on PAC in presence of organic
of SEC discharges have been contacted with PAC alone (10 mg/L of matter
PB 1701), FeCl3 alone (2.5 gFeCl3/m3) and both PAC (10 mg/L of PB
1701) and FeCl3 (2.5 gFeCl3/m3) under strong mixing during 3.2.1. Influence of fresh PAC dose and adsorption kinetic
45 min. The previously cited micropollutants, as well as UV- The Fig. 2 displays the influence of the contact time and the PAC
254 and DOC, were measured before and after contact with PAC. dose on the removal of micropollutants from SEC discharges
The FeCl3 product (commercial solution, 40% FeCl3–Quaron SA1)
and dose were the same as in the pilot.

3. Results and discussion

3.1. Influence of PAC characteristics on its efficiency

Structural and morphological properties of the 4 tested PACs are

given in Table 1. The removals of the micropollutants with a PAC
dose of 10 mg/L during 45 min are also provided, as well as their
concentrations in SEC WWTP discharges.
Among the 4 PACs, the PB 1701 and WP 2351 have a similar
mesoporous structure with close pore size distribution and specific
BETsurface (900–1000 m2/g), while W 351 and to a greater extent PC
10001 have different pore surface distributions and lower specific
BET surfaces (Table 1; Supporting material—Fig. S3). W 351 is
strongly mesoporous with 45% of the BET surface resulting from
mesopores, while PC 10001 is microporous with 59% of the surface
resulting from micropores. 3 of the tested PACs have similar bulk
densities (0.30–0.40 g/cm3) while PC 10001 is heavier (0.54 g/cm3).
Regarding the particle size distribution, PB 1701 and WP 2351 are
comparable while the two other PACs have a larger particle size
distribution and a higher median diameter. This is particularly
notable for the PC 10001 which is characterized by median and
d90 values twice higher than those of the PB 1701 and WP 2351.
Even if only 1 punctual experiment was performed, a clear
trend can be observed with most of the compounds. For individual
compounds, the PB 1701 allows the highest removals for 15 of the
19 micropollutants and the PC 10001 is always the worst efficient.
The WP 2351 and W 351 seem to have similar performances, Fig. 1. Correlations between the specific BET surface and the micropollutant
slightly weaker than PB 1701. Overall, the average removal of the removals obtained with a PAC, and link with its bulk density.
1106 R. Mailler et al. / Journal of Environmental Chemical Engineering 4 (2016) 1102–1109

(DOC = 5.6  0.9 mgC/L [4]) by PAC. The average removal of all most pollutants with the 3 other waters, which have undergone an
pollutants detected in this experiment has also been calculated. intense biological carbon treatment. In particular, both WWTP
A higher dose of PAC logically results in higher micropollutant discharges have comparable removals. For instance, the carba-
removals (Fig. 2), i.e., carbamazepine (32–54–80%; removals at 5– mazepine is removed at 18% in SEC settled water, against 38–42% in
10–20 mgPAC/L), diclofenac (22–36–60%), propranolol (56–81– the other matrixes. Similarly, the trimethoprim removal increases
95%) or sulfamethoxazole (51–61–80%). The relationship is from 5% in settled water to 39–50% in the other waters.
logarithmic resulting in the reaching of a plateau when increasing These results indicate that DOC value has a negative impact on
the dose, as displayed in Supporting material—Fig. S4. Thus, the micropollutant adsorption, as the removals observed in the SEC
PAC dose in wastewater has a great influence on the removal, as settled water, featuring the highest DOC concentration (27 mgC/L),
already observed in the literature [3,25,26] or at large scale with are the lowest compared to the other waters. The negative influence of
the CarboPlus1 pilot [4]. Considering the individual results of the DOC on micropollutant adsorption from wastewater was also
micropollutants, this positive influence of the dose is statistically observed in the literature [3,16,29]. However, complementary
significant (test of Shapiro-Wilk, Fischer and Student—p-value experiments should be performed to determine if this reduction of
<0.05) between 5 and 10 mgPAC/L (p-value = 0.016) and between micropollutant adsorption is due to adsorption competition or to
10 and 20 mgPAC/L (p-value = 0.0005). interactions of micropollutants with non adsorbable DOM maintain-
Furthermore, the removals notably increase with the contact ing them in solution. In contrary, DOC value seems to have a limited
time (Fig. 2), i.e., ciprofloxacin (29–40–62–66–71%; removals at 5– impact on propranolol behavior. This compound is positively charged
10–30–45–60 min contact times) or diclofenac (19–23–32–36– at pH 7–8 and it has been observed that positive compounds have a
39%). However, the PAC is very fine (<50 mm), resulting in a high affinity for activated carbon adsorption in wastewater [3,4].
relatively fast adsorption kinetic. As a consequence, although the According to what is previously stated, micropollutant remov-
equilibrium is not reached after 60 min, differences of removal als should be lower in SAV discharges compared to those in the SEC
between 30, 45 and 60 min contact time for a same PAC dose are carbon biofiltration effluent and discharges, regarding the differ-
limited (< 10%). Thus, the short contact times (30–60 min) ences of DOC (11 vs. 6.6–6.8 mgC/L). This is observed for
employed in PAC tertiary treatments are suitable for an efficient bezafibrate, lorazepam and metronidazole. However, removals
adsorption of micropollutants. For several compounds (8/15), such are similar for the other compounds, in spite of slightly higher
as atrazine (26–46%; removals after 5 and 60 min), norfloxacin influent concentrations in the SAV discharges. Besides, considering
(38–71%), ofloxacin (39–64%) or sulfamethoxazole (40–55%), the the individual removals of compounds from Fig. 3, the removals
removal achieved after 5 min represents more than half of the from SEC and SAV discharges are significantly similar (p-value =
removal after 60 min, confirming the very fast kinetic. In contrary, 0.175). The organic matter of SAV discharges should then be less
erythromycin (7–39%) or roxithromycin (3–38%) seem to have competitive than organic matter from other discharges, what
slower kinetics, probably because of their high molecular weight counterbalances the higher DOC.
(respectively 734 and 837 g/mol). These compounds will then be This result indicates that the sole DOC level is not sufficient to
more sensitive to changes of contact time in adsorption processes. explain the variations of removals from water to water, both the
organic matter composition and nature have also to be considered.
3.2.2. Influence of the matrix Considering that, a deeper analysis of the DOM nature and
adsorption was performed before and after contact with PAC for
3.2.2.1. Influence of dissolved organic carbon on the micropollutant these 4 waters, as well as 3 additional wastewater matrixes.
removals. The Fig. 3 displays the removals of micropollutants
observed with different types of wastewater, sorted from the 3.2.2.2. Composition and adsorption of the organic matter
highest to the lowest DOC value. The average removal of all 3.2.2.2.1. Composition of the organic matter. Fig. 4 displays the
pollutants detected in this experiment has also been calculated. indexes from 3D fluorescence analysis of the organic matter from
Removals observed with the SEC settled water are overall lower 7 wastewater matrixes, as well as the organic matter removal by
than those from the three other wastewaters. In particular, they are PAC adsorption (10 mgPAC/L—45 min). The different fluorophores,
significantly lower (p-value = 0.001) than in the SEC discharges HIX and BIX are given in Supporting material—Table S3 for the
(water from the same WWTP), considering all the compounds 7 tested wastewaters.
displayed on Fig. 3. Comparable removals are overall achieved for First of all, the 4 WWTP discharges (SEC, SAM, SEM and SAV)
and the SEC carbon biofiltration effluent have a similar distribution

Fig. 2. Micropollutant adsorption kinetic in the SEC discharges and influence of the Fig. 3. Pharmaceutical removals by PAC adsorption from different types of
PAC dose on removals. wastewater.
 R. Mailler et al. / Journal of Environmental Chemical Engineering 4 (2016) 1102–1109 1107

of DOM with a large fraction of humic-like (peaks Ia and Ia’; index water compared to the other ones. This suggests that in this water,
Ia/Ia’) and recent autochthone DOM (Ib; index Ib/Ia’), and a less sites will be available for micropollutants as more DOM is
smaller fraction of protein-like DOM resulting from bacterial sorbed, what is consistent with micropollutant results (Fig. 3). For
activity (Ig and Id; Ig/Ia’ and Id/Ia’), as shown on Fig. 4 and in the other wastewaters, the DOM removal is rather comparable (10–
Supporting material—Table S3. In contrary, the DOM distribution is 25% for UV-254 and 5–10% for DOC).
different in the SEC settled water with a larger fraction of protein- In addition, fluorophore removals are rather similar in all
like DOM, compared to the other fractions. This indicates that wastewaters except in the SEC settled water. In the WWTP
carbon biological treatments significantly remove DOC and discharges, all the fluorophores are removed between 10 and 30%.
fluorophores Id and Ig (see SEC settled water and carbon In contrary, in SEC settled water, fluorophores d and g are
biofiltration effluent in Supporting material—Table S3), resulting predominant (Ig/Ia’ and Id/Ia’) and are better removed (35–50%)
in a significant modification of the DOM nature and quantity than the other fluorophores. They are also better removed than in
(Fig. 4). Together with this difference of DOM composition, the SEC the other water. In consequence, these fluorophores will have the
settled water has a higher DOC (27 mgC/L), highlighting a higher highest impact on the competition with micropollutants for
quantity of DOM. adsorption. Moreover, the fluorophores removal pattern is the
In addition, the HIX increases along the different steps of same in SEC diluted settled water, confirming that the quality of
wastewater treatment, as shown by the low HIX in the SEC settled DOM is as important as the DOC value in the adsorption process.
water (1.0) and the higher HIX after the biological treatments (>3). In this context, and considering that the carbon biological
This confirms that protein-like DOM (Id and Ig) is more degraded treatment significantly reduces the DOC and the quantity of
than humic-like DOM (Ia and Ia’) during biological treatments. fluorophores Id and Ig (the most competing DOM), the lower
The HIX from SAM and SEC discharges, as well as SEC carbon removals of micropollutants by PAC in the SEC settled water (Fig. 3)
biofiltration effluent, are similar (3.2–3.6), while those from SAV compared to the other waters are then consistent. Indeed, the
and SEM discharges are higher (5.0–6.4). competition is stronger in this water resulting from (i) a higher
quantity of DOM (DOC and UV-254) and ii a different DOM nature,
3.2.2.2.2. Adsorption of organic matter on activated with more protein-like substances and less humic-like substances.
carbon. Regarding the removal of DOM by activated carbon, In addition, Ig/Ia’ and Id/Ia’ are lower in the SAV discharges than in
DOC and UV-254 removals are notably higher in the SEC settled SEC carbon biofiltration effluent and discharges, together with a

Fig. 4. DOM adsorption and distribution using the defined indexes for the different studied wastewaters.
1108 R. Mailler et al. / Journal of Environmental Chemical Engineering 4 (2016) 1102–1109

higher HIX. This means that this water has less very competitive
DOM what counterbalances the higher DOC, resulting in similar
micropollutant removals.

3.2.2.3. Influence of the methanol residual concentration on

micropollutant and DOM removals. The micropollutant and
organic matter (DOC and UV-254) removals obtained in
presence of a residual concentration of methanol are presented
in Fig. 5. The average removal of all the detected pollutants in this
experiment has also been calculated.
The comparison of removals obtained in the carbon biofiltration
effluent and in the SEC discharges allows assessing the impact of
the methanol presence in the wastewater on the PAC adsorption
(Fig. 5). Its presence does not decrease the performances as the
removals observed in the SEC discharges are similar or higher than
those in the carbon biofiltration effluent. The better removals in
Fig. 6. Influence of the presence of FeCl3 on the pharmaceuticals removals by PAC
the SEC discharges could be explained (i) by the methanol itself, adsorption.
and (ii) by the carbon and nitrogen treatment achieved in the
second and third biofiltration stages, but further experiments are seems to be the only one with a lower removal ( 30%) in presence
needed to bring an answer. of ferric chloride.
Moreover, no clear trend is observed between the increase of The limited effect of coagulation on micropollutants adsorption
the residual concentration of methanol and the micropollutant by activated carbon is confirmed in the literature [20,31]. However,
removals, except for sulfamethoxazole and naproxen for which the the mechanism at the origin of this improvement is not identified.
removal decrease and increase respectively. However, the results Supplementary tests are required to determine if coagulation,
indicate that the increase of the methanol concentration does not complexation or direct decrease of the competition with organic
lead to a significant degradation of the PAC performances for most matter are involved.
compounds.
Thus, results have shown that the residual concentration of 4. Conclusions
methanol does not affect negatively the removal of micro-
pollutants by activated carbon (Fig. 5). In contrary, its presence The Parisian public sanitation service (SIAAP) and the water
in biological treatment effluents could favor a biological activity in environment and urban systems laboratory (LEESU) study a
the tertiary treatments by activated carbon. tertiary treatment by PAC called CarboPlus1 at large scale, in
collaboration with the SAUR teams. In parallel to the study of the
3.2.3. Influence of the injection of FeCl3 large scale pilot, complementary laboratory scale experiments
The ferric chloride influence on the fate of micropollutants in were carried out to improve the understanding of the micro-
presence of PAC is illustrated on Fig. 6. The average removal of all pollutants adsorption on activated carbon, in particular PAC.
pollutants detected in this experiment has also been calculated. These experiments allowed displaying the links between
Three types of behaviors are observed for micropollutants. For structural properties of activated carbons and their efficiency to
most compounds, such as carbamazepine, beta blockers or remove micropollutants. In particular, it has been shown that the
diclofenac, and for DOM (DOC and UV-254), a slightly higher PAC performances are closely related to the specific BET surface,
removal (+5–15%) is obtained by coupling PAC and ferric chloride, which can easily be estimated through the bulk density measure.
probably by coagulation of the colloidal fraction. These differences The strong influence of the PAC dose has also been confirmed, as
are not significant and limited taking uncertainties into account, well as the suitability of the adsorption kinetic (less than one hour)
but 10 compounds in 13, as well as DOC and UV-254, have a greater for WWTP application (operational requirements). In an opera-
removal in presence of FeCl3. In contrary, no clear influence is tional point of view, the injection of FeCl3 does not disrupt the
observed for lorazepam and bezafibrate. Finally, sulfamethoxazole adsorption process. A slight improvement is even observed for
most compounds (+10–15%), except for sulfamethoxazole, proba-
bly through coagulation of the colloidal fraction of the DOM. In
contrary, the residual concentration of methanol present in the
WWTP discharges due to the post denitrification process seems to
have no impact on the fate of most micropollutants.
Then, this study highlighted the differences of micropollutants
adsorption in the various wastewater matrixes. The DOC concen-
tration is important considering the competition of adsorption but
it is not always sufficient to explain the performances reductions
from water to water. It has been shown that the distribution of the
different molecular components of the DOM should be considered
in addition to the quantity of DOM. Indeed, protein-like
fluorophores have been identified as the most problematic for
adsorption competition in wastewater, while a high HIX is
favorable to micropollutants adsorption. Then, the reduction of
protein-like substances in wastewater would be a way to maximize
the adsorption of micropollutants by activated carbon.
This study provides particularly interesting results both for
Fig. 5. Impact of a residual concentration of methanol in the WWTP discharges on scientists and WWTP managers, especially the data about the
the adsorption of pharmaceuticals by PAC.
 R. Mailler et al. / Journal of Environmental Chemical Engineering 4 (2016) 1102–1109 1109

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