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Removal of dexamethasone from aqueous solution and hospital wastewater by electrocoagulation


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This study is concerned with the removal of the anti-inflammatory dexamethasone from aqueous solution and hospital wastewater by electrocoagulation. The variation of the toxicity during the electrocoagulation was also studied through experiments that were designed and optimized by means of response surface methodology. The coagulation efficiency was evaluated by measuring the dexamethasone concentration by high performance liquid chromatography coupled to a diode array detector. In addition, variation was evaluated through a Vibrio fischeri test. The results showed an increase in the removal of dexamethasone (up to 38.1%) with a rise of the current applied and a decrease of the inter-electrode distance, in aqueous solutions. The application to hospital effluent showed similar results for the removal of dexamethasone. The main effect of the electrocoagulation was that it removed colloids and reduced the organic load of the hospital wastewater. Regarding the current applied, the calculated energy efficiency was 100%. Without pH adjustment of the aqueous solution or hospital wastewater, the residual aluminum concentration always remained lower than 10mgL(-1), and, with adjustment (to pH6.5), lower than 0.30mgL(-1), at the final stage. No toxicity variation was observed during the electrocoagulation process in aqueous solution, either in the presence or absence of dexamethasone.
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Removal of dexamethasone from aqueous solution and hospital wastewater
by electrocoagulation
Daniel R. Arsand
, Klaus Kümmerer
, Ayrton F. Martins
Chemistry Department, Federal University of Santa Maria, RS, Brazil
Institute for Environmental Chemistry, Leuphana University Lüneburg, Germany
Removal of DEX and organic load from aqueous solution and hospital wastewater by EC
Evaluation of the toxicity during the removal of DEX by EC
Suggestion of the EC process as a pretreatment for subsequent processes
abstractarticle info
Article history:
Received 25 August 2012
Received in revised form 23 October 2012
Accepted 30 October 2012
Available online 30 November 2012
Hospital efuent
Vibrio scheri test
Residual aluminum
This study is concerned with the removal of the anti-inammatory dexamethasone from aqueous solution
and hospital wastewater by electrocoagulation. The variation of the toxicity during the electrocoagulation
was also studied through experiments that were designed and optimized by means of response surface
methodology. The coagulation efciency was evaluated by measuring the dexamethasone concentration
by high performance liquid chromatography coupled to a diode array detector. In addition, variation was
evaluated through a Vibrio scheri test. The results showed an increase in the removal of dexamethasone
(up to 38.1%) with a rise of the current applied and a decrease of the inter-electrode distance, in aqueous
solutions. The application to hospital efuent showed similar results for the removal of dexamethasone.
The main effect of the electrocoagulation was that it removed colloids and reduced the organic load of
the hospital wastewater. Regarding the current applied, the calculated energy efciency was 100%. Without
pH adjustment of the aqueous solution or hospital wastewater, the residual aluminum concentration al-
ways remained lower than 10 mg L
, and, with adjustment (to pH 6.5), lower than 0.30 mg L
nal stage. No toxicity variation was observed during the electrocoagulation process in aqueous solution,
either in the presence or absence of dexamethasone.
© 2012 Elsevier B.V. All rights reserved.
1. Introduction
In the last two decades, there has been evidence worldwide attribut-
able to the discharge of wastewater containing pharmaceutical residues
(Daughton, 2008; Halling-Sørensen et al., 1998; Santos et al., 2010). A
number of studies have pointed to the presence of endocrinedisruptors
in efuents discharged in streams, e.g. as a cause of sexual disturbance
in sh (Kümmerer, 2008; Woodling et al., 2006,) and mutagenicity for
living organisms (Bagatini et al., 2009).
After administration and excretion, the pharmaceuticals can reach
the sewage system and, then supercial waters. Investigations have
shown that conventional municipal sewage treatment plants are not al-
ways effective in dealing with efuents containing pharmaceuticals
(Cha et al., 2006; Jelic et al., 2011; Schuster et al., 2008; Sim et al.,
2010; Sui et al., 2010). Moreover, active substances, such as ciprooxa-
cin, have been found in hospital efuents after local treatment (Brenner
et al., 2011; Martins et al., 2008a, 2011; Vasconcelos et al., 2009).
Several processes for treating wastewater containing pharmaceuticals
have been studied including the following: an improvement of conven-
tional processes employing anaerobic reactors (Chelliapan et al., 2011)
and membrane bioreactors (Wen et al., 2004), and an evaluation of ad-
vanced oxidation processes, as well as combinations of these techniques
(Arslon-Alaton and Dogruel, 2004; Arslan-Alaton et al., 2004; Andreozzi
et al., 2005; Borràs et al., 2011; Martins et al., 2009; Sui et al., 2010;
Vasconcelos et al., 2009). Other processes, such as electrocoagulation
Science of the Total Environment 443 (2013) 351357
Abbreviations: CC, chemical coagulation; DEX, dexamethasone; EC, electrocoagulation;
GC, glucocorticoid; HUSM, University HospitaloftheFederalUniversityofSantaMaria;
HPLCDAD, high performance liquid chromatography coupled to diode array detector;
RSM, response surface methodology.
Corresponding author at: Departamento de Química, Universidade Federal de
Santa Maria, Campus Camobi, CEP 97105-900 Santa Maria, RSBrasil. Tel.: +55
55 3220 8664; fax: +55 55 3220 8031.
E-mail addresses: (D.R. Arsand), (K. Kümmerer),, (A.F. Martins).
0048-9697/$ see front matter © 2012 Elsevier B.V. All rights reserved.
Contents lists available at SciVerse ScienceDirect
Science of the Total Environment
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(EC) have been investigated for the treatment of hospital efuent
(Gürses et al., 2002; Ryan et al., 2008; Tir and Moulai-Mostefa, 2008).
A study comparing EC and chemical coagulation (CC) showed that the
CC needs 20 times more mass of reagent to treat the same volume of
wastewater, to achieve the same degree of efciency (Ryan et al., 2008).
Chen et al. (2002) has carried out extensive study about the EC reactions.
There are a number of advantages in EC such as low-cost, easy
handling, and high efciency in the removal of organic matter. On
the other hand, the sludge generation rate, the use of sacricial elec-
trodes, and electrical energy consumption can be cited as drawbacks
(Mollah et al., 2001).
Anti-inammatories constitute an important pharmaceutical class
and include glucocorticoids (GC) that are widely used in human and vet-
erinary medicine, but carry the risk of side effects (Reid, 2000; Schäcke
et al., 2002). The most potent GC cortisone derivate used in hospitals
and clinics is dexamethasone (DEX) and relatively high levels of DEX
have been detected in sewage efuent (Herrero et al., 2012). Fig. 1
shows the main structure of DEX.
This study forms part of a major project which is attempting to
deal with the problem of pharmaceuticals in the environment and
the main objective here is to investigate the features of EC and its ef-
fectiveness in the removal of DEX from water solution and hospital
wastewater. Experiment design and response surface methodology
(RSM) were employed to optimize the EC operational conditions for
DEX removal. In addition, the chemical oxygen demand (COD) and re-
sidual aluminum concentration were evaluated and the variation of
the toxicity was monitored throughout the evaluation, with the aid of
the Vibrio scheri test. An analysis of the advantages of the V. scheri
test was undertaken by Parvez et al. (2006).
As far as we are aware, this is the rst study of how electrocoagulation
can be a means of removing dexamethasone from hospital wastewater.
2. Material and methods
2.1. Reagents
The DEX base (Sigma-Aldrich, Munich, Germany) standard solu-
tions were prepared shortly before the experiments. NaCl 99.5%
(Sigma-Aldrich, Munich, Germany) was used as electrolyte. Aceto-
nitrile HPLC grade (JT Baker, Mexico City, Mexico) and analytical
grade sodium formate (Sigma-Aldrich, Munich, Germany) were
used to prepare the mobile phase. All the solutions were prepared
with chemicals of at least analytical grade, by using ultrapure water
(Millipore, Molsheim, France).
2.2. Sampling of hospital wastewater
The studied wastewater samples were collected end-of-pipe from
the University Hospital (HUSM) of the Federal University of Santa
Maria after leaving the sewage treatment system. A composite sample
was formed by collecting samples, every 2 h, from 8:00 to 16:00 h.
The wastewater samples were collected, kept in the dark, at 4C
and, at end of the day, ltered (cellulose lter, 7 μm) and submitted
to the EC experiments. The physico-chemical characteristics of the
HUSM efuent are shown in Table 1 (different samples, different
2.3. Aliquot collection for the analytical measurements
Samples were taken in 0, 5, 15, 30 and 45 min of the EC experiments
conducted. The standard solutions and the hospital wastewater samples
treated, were passed through cellulose lter (7 μm), and afterwards,
through PTFE Millipore lter (0.45 μm),andthen,storedat4C,in
the dark, until the analytical measurement.
2.4. Analytical methods
The residual aluminum was measured by means of a 1-02
Nanocolor test (Macherey-Nagel, Düren, Germany) and UVvis
Shimadzu Multispec-1501 spectrophotometer (Schimadzu GmbH,
Duisburg, Germany).
A WTW LF 196 microprocessor conductivity meter was employed
for measuring conductivity and temperature; pH and dissolved oxygen
(DO) were measured by using WTW pH/Oxi 340i equipment (WTW
GmbH, Weilheim, Germany).
The DEX concentration was determined with the aid of a Shimadzu
high performance liquid chromatography coupled to a diode array de-
tector, and equipped with a LC-20AT pump (Shimadzu, Duisburg,
Germany). The mobile phase used was acetonitrile:formate buffer
[33:67] (0.0209 mol L
sodium formate, pH 3.6); the column employed
was a Nucleodur CC 70/3 C18 ec equipped with a pre-column containing
thesamematerial;theow rate was set to 0.5 mL min
and the injec-
tion volume to 50 μL; the measurement was at 254 nm. The retention
time of DEX was 3.5 min under these conditions. The deconvolution
method based on UV absorbance (Martins et al., 2008b) was used to esti-
mate the organic load of the hospital wastewater.
2.5. Electrocoagulation
The electrocoagulation was carried out by using commercial alumi-
num electrodes (61 cm
effective area) immersed vertically and, in par-
allel, monopole conguration. NaCl was added as the electrolyte; an EC
Apparatus Corporation EC570 (Milford, MA, USA) power supply and a
VC-840 digital multimeter (Volcraft, Meggen, Switzerland) were used.
The experimental conditions were dened by factorial design.
A glass reactor (d
=105 mm) was used for the treatment of 1 L of
sample. The optimization step was performed using standard solution
of 100 μgL
DEX, which is also used for the fortication of the hos-
pital wastewater samples. For the measurement of the initial conduc-
tivity, (3.3 mS cm
), 2.0 g L
NaCl as electrolyte was added to the
samples of wastewater, which had been previously ltered through a
cellulose lter (7 μm). All the experiments were performed at room
temperature (2025 °C). The EC experiments were conducted under
Fig. 1. Dexamethasone structures.
352 D.R. Arsand et al. / Science of the Total Environment 443 (2013) 351357
gentle magnetic stirring (120150 rpm) and the system used can be
seen in Fig. 2.
2.6. Design of the experiments
Optimization of the experiments was conducted by employing an
experimental design. The xed parameters were: applied current
(100500 mA); inter-electrode distance (630 mm); electrolyte
concentration (NaCl, 2501250 mg L
) and 5 levels of signicance
(2, 1, 0, +1 and +2). The matrix that is formed comprises a
group of 17 experiments: 8 factorial, 3 central and 6 axial. These ex-
periments were performed at random to ensure the reliability of the
results. The parameter used to evaluate the efciency of the process
was the lowering of the DEX concentration.
2.7. The efciency of the procedure
The efciency of the EC was calculated by means of Eq. (1) in opti-
mized conditions. The electrode mass loss during the process was mea-
sured by means of material balance in a time interval of 045 min.
100 ð1Þ
where φis the current efciency (%), ΔM
is the experimental mass
variation and ΔM
is the theoretical mass variation of the electrodes
during the EC experiments. The theoretical mass loss can be calculated
according to Eq. (2).
ΔΜtheor ¼ItM
zF ð2Þ
where I is the current (A), t is the time (s), M is the molar mass of the
predominant element of the electrode, z is the number of electrons in-
volved in the oxidation of the electrode (3 e
) and F is the Faraday con-
stant (C mol
). Eq. (3) was used to evaluate the cost of the process,
where EE is the electric energy consumption (kWh), I is the current ap-
plied (A), U is the tension (V), and t, the time of treatment (h).
EEtheor ¼IUt
1000 ð3Þ
2.8. Toxicity test
The toxicity variation was monitored by using the V. scheri test in ac-
cordance with ISO 11348-1 (1998), under optimized conditions; four
groups of experiments were carried out in aqueous solution: 1) without
DEX (blank), to evaluate the toxicity of the residual aluminum; 2) to
measure the toxicity of the DEX solution without EC treatment; 3) sub-
mitting DEX solution to EC with an inter-electrode distance of 6 mm,
or 4) with an inter-electrode distance of 30 mm. The different times of
exposure in the V. scheri test were assumed to be those for acute and
chronic toxicity: 30 min and 24 h, respectively (Blaschke et al., 2010).
3. Results and discussion
3.1. Removal of dexamethasone Pareto chart
The Pareto chart from the factorial design of experiments indicates
that the current is the most important variable for DEX removal, followed
by the electrolyte concentration (with 0.05 reliability; mean square pure
rent is dominant. The regression coefcient (R
) was 0.943 and the ad-
justed R-square (R
) was 0.870 for the DEX removal.
3.2. Surface response curves for removal of dexamethasone by
Astronginuence of the applied current was observed in the removal
of DEX from aqueous solutions: the DEX removal increased along with
the current, even when there were greater electrode distances. As well
as the no signicant effect of the inter-electrode distance, a compensa-
tion effect was detected: when the electrolyte concentration decreased,
a reduction of the inter-electrode distance restored the level of conduc-
tivity. The best results for DEX removal (up to 38%) were obtained in
two situations: by a small inter-electrode distance combined with low
electrolyte concentration, and by high electrolyte concentration com-
bined with a large inter-electrode distance. The results can be seen in
Fig. 3.
These were expected results because EC depends on the anode
reactionaluminum oxidation (Dalvand et al., 2011; Gürses et al.,
2002). However, account should be taken of the mass transfer and
polarization close to the electrodes, and the occurrence of concomi-
tants, that may change the optimum conditions for the removal of a
specicsubstance(Gómez and Callao, 2008).
Table 1
Physico-chemical characteristics of the HUSM efuent.
Parameter Value
Chloride (mg L
) 132.0
(mg O
) 303.7
COD (mg O
) 420.0
Phosphate (mg L
) 7.5
Nitrate (μgL
) 680.0
Ammoniacal nitrogen (mg L
) 52.0
Total nitrogen (mg L
) 59.1
pH 7
Potassium (mg L
) 21.9
Sodium (mg L
) 150.5
Total suspended solids (mg L
) 57.0
Total solids (mg L
) 484.0
Sulfate (mg L
) 4.0
Temperature (°C) 22.0
Fig. 2. EC assembly used for the treatment of the aqueous solutions and hospital
wastewater samples containing DEX, where: (a) oxymeter and (a) oxymeter elec-
trode; (b) conductivity meter and (b) conductivity electrode; (c) 1 L glass reactor
and magnetic stirrer; (d) aluminum electrodes; (e) power supply and (f) multimeter.
353D.R. Arsand et al. / Science of the Total Environment 443 (2013) 351357
3.3. Dissolved oxygen (DO) variation during the electrocoagulation
The DO variation was measured during the EC: an exponential de-
cline rate was observed when the applied current was increased. A
lower variation was observed when there was a higher electrolyte
concentration and a greater inter-electrode distance. This phenome-
non can be attributed to the lower gas solubility in a saline solution
and to the warming effect close to the electrodes, as well as to the for-
mation of gas during the process. When the inter-electrode distance
is greater, the electric current is deprived of power; as a result, the
electrolysis of water increases, and this leads to a higher rate of H
gas formation and, thus, a reduction of DO.
The higher the current applied, the higher the DO variation, the nal
DO value reached 0.5 mg L
. After EC, the DO of an aqueous medi-
um is not high enough for a subsequent aerobic biological treatment, or
for any other direct use where a higher DO concentration is required,
e.g., for sh farming (Becker et al., 2009; Kempton et al., 2002).
Nilsson et al. (2007) found that sh could not tolerate DO levels
below 0.78 mg L
. In these cases, an oxygenation step will be
needed. Moreover, EC can be regarded as a useful pre-treatment
stage for anaerobic processes, where an absence of oxygen is need-
ed, e.g. by Anammox (Yang et al., 2010). The same can be said for
photocatalytic mechanisms where a transparent solution is highly
3.4. Loss of mass of the electrodes
During the EC, aluminum electrodes are decomposed by the electro-
chemical oxidation. The real metal loss was determined by weighing
the electrodes before and after each experiment and carried out under
optimized conditions. The correlation coefcient for the mass loss of
aluminum and the current applied was 0.998 by p-levelb0.0001,
which suggests that the electrical energy applied was almost entirely
used for the electrode oxidation in the EC process. This is a matter of in-
terest with regard to the economic balance, as no signicant waste of
energy occurred in an undesired heating process. Essadki et al. (2008)
recommend conducting the experiments by applying a current density
lower than 30 mA cm
in order to avoid unnecessary aluminum oxi-
dation and thus achieve more economical results.
3.5. Physicalchemical parameters
The results of all the EC experiments showed that there was no
signicant temperature increase (+1.8 ±0.94 °C) and the pH varia-
tion was only +2.0±0.15 units. This behavior can be attributed to
the high conductivity and the low electrical current applied: the elec-
trolysis of water was not enough to modify the pH signicantly and
the variation of the conductivity was only + 8.0 ± 2.8 μScm
. The
experiments using 400 and 500 mA showed a temperature variation
of +3 °C, and when 100 mA was applied, only +0.3 °C. Similar re-
sults were obtained for the pH variation.
Aluminum ion is a byproduct in the EC process when Al-electrodes
are used. The residual aluminum was7.0± 1.5 mg L
without pH cor-
rection, below the general threshold limit for aluminum concentration
in wastewater.
3.6. Optimized conditions
The experiments were carried out under optimized conditions,
and a higher current (1000 mA) and higher electrolyte concentra-
tion (2000 mg L
) were applied. These higher values were employed
by inter-electrode distance 6 and 30 mm, because the distance was clas-
sied as no signicant by the Pareto chart for the experimental design.
Fig. 3. Surface response curves for dexamethasone removal by electrocoagulation: (a) inter-electrode distance and the applied current; (b) applied current and the electrolyte con-
centration; and (c) electrode distance and the electrolyte concentration as variables mean square pure error 8.40.
354 D.R. Arsand et al. / Science of the Total Environment 443 (2013) 351357
Fig. 4 shows the DEX variation during the experiments: the DEX removal
was similar when both inter-electrode distances were used, after 45 min
of treatment.
The variables of the EC process were monitored during the exper-
iments (at 0, 5, 15, 30 and 45 min) with the exception of the temper-
ature and the pH. It is well known, that slight temperature variations
do not constitute a problem for the EC processes. As pH adjustment
was used to control the residual aluminum, pH variations were not
taken into account. The residual aluminum concentration was 4.0 ±
1.40 mg L
without pH adjustment (actual pH 8.5) and 0.25±
0.03 mg L
with pH adjustment (to pH 6.5). The DEX concentration
was 68.2 ± 1.5% by pH 8.5 and 67.2± 2.9% by pH 6.5. These results
show that the pH adjustment to 6.5 does not inuence the DEX re-
moval; however, it is a very efcient means of reducing the residual
aluminum. This pH range (6.58.5) is very important for the practical
application of EC. Emamjomeh and Sivakumar (2006) also found that
the pH interval 68 was the best pH work zone for the removal of
uoride from waters by means of the EC process.
The prole of the DO decay curve during the EC process is almost
the same, regardless of the inter-electrode distance (see Fig. 5).
3.7. Process efciency and energy consumption
The absolute value of the process efciency (φ) of the experiments
carried out under optimized conditions was calculated as 117.9% and
113.7%, by using 6 and 30 mm inter-electrode distances, respectively.
The values higher than 100% can be attributed to the addition of the
electrochemical to the chemical oxidation process of the electrodes.
Moreover, this high process efciency remains in accordance with what
is shown in Section 2.8. The electric tension of the system was 20 V in
both cases and the cost of the EC treatment under these conditions was
15 kWh m
. The total aluminum consumption was 405.4 g m
and 412.5 g m
using 6 and 30 mm inter-electrode distance, respec-
tively, with no perceptible conductivity variations, during the 45 min
of treatment.
The cost of the process depends on energy consumption: Asselin
et al. (2008), e.g. studied the EC process under optimal conditions
and the cost of treatment reached 0.46 US$ m
3.8. Hospital wastewater treatment by electrocoagulation
Fortied hospital wastewater with DEX (100 μgL
) was treated by
EC under optimized conditions. The DEX removal showed similar char-
acteristics to the effects of the aqueous solution treatment. However,
the removal of DEX only starts after 15 min of treatment (Fig. 6). This
behavior can be attributed to the competition between DEX and other
concomitants in the wastewater.
The absorbance prole was monitored (see Fig. 7) during the process:
the absorbance decays in accordance with the removal of colloids and
reduction of the organic load of the hospital wastewater. In general,
organic molecules absorb ultraviolet light as a result of double bonds
and aromatic groups; thus, UV absorbance measurements can provide
a quick means of estimating the level of the organic carbon content
(Martins et al., 2008b). At the end of the EC process, the treated hospital
wastewater was almost claried but the DEX concentration only par-
tially removed.
Most of the colloidal particles in wastewater have a negative charge,
depending on the related Zeta Potential (Harif et al., 2012). In EC, the
hydrolyzed species destabilize the suspended particles and react to
the dissolved organic material, and are thus able to determine the oc
growth kinetics. The particles can be effectively destabilized by neutral-
ization of the surface charge, which leads to precipitation. In general, or-
ganic molecules are large and contain many functional groups, such as
DEX, which means that different destabilization mechanisms can
occur (Harif et al., 2012). As the DEX base shows low hydrosolubility,
its removal mechanism can be attributed to repression of the double
layer and entrapment of colloidal particles by a sweeping oc.
As mentioned in Section 3.3, EC may be used as a pre-treatment
for advanced oxidation processes, as well as in anaerobic degradation
treatments. Since it can achieve a high rate of removal for the inter-
fering organic substances, EC may also be employed in cleaning up
the sample solutions before the analytical determinations.
Fig. 4. DEX concentration variation during the EC treatment in optimized conditions
using inter-electrode distances 6 mm () and 30 mm ().
Fig. 5. DO variation during the experiments using 6 () and 30 mm () inter-electrode
Fig. 6. Hospital efuent treatment containing 100 μgL
DEX in optimized conditions.
355D.R. Arsand et al. / Science of the Total Environment 443 (2013) 351357
3.9. Variation of toxicity during the electrocoagulation process
The toxicity variation during the DEX removal by the EC process
was evaluated by carrying out experiments using pH adjustment
(pH 6.5), and obtaining a maximum residual aluminum concentra-
tion of 0.30 mg L
. Acute and chronic toxicity were evaluated in a
blank sample (without DEX spike); in a standard solution of DEX
without EC treatment (100 μgL
); in the standard DEX solution
after 45 min treatment using 6 mm inter-electrode distance; and in
the DEX standard solution after 45 min treatment using 30 mm
inter-electrode distance. The results obtained from tests usingV. scheri
assay, demonstrate that the residual aluminum concentrations in the
nal solutions from the EC process are not toxic. The experiments
with DEX aqueous solutions, whether submitted to electrocoagulation
or not, showed similar average values for acute and chronic toxicity.
However, in view of possible undetectable problems arising from the
DEX response to the V. scheri test, the application of another toxicity
test is recommended. In this particular case, the toxicity test may lead
to a false response because allegedly, the V. scheri bacterium has no
glicocorticoid receptor.
4. Conclusions
This study shows that the process of removing DEX increased
when higher EC current and electrolyte concentration were applied
to aqueous solutions of DEX. The EC process under optimized condi-
tions only showed a DEX removal rate of up to ~38%. Apart from
the different curve proles of the decay, almost the same result was
achieved after 45 min of EC treatment of the hospital wastewater.
There was a signicant removal of colloidal material and reduction
of the organic load by the EC treatment of the hospital wastewater in
the rst 15 min of the process; however, most of the DEX remained in
solution. This means that most of the analyte that occurred was not
adsorbed on the organic matter.
The nal DO concentration, which was close to 0.5 mg L
suggests that the EC process as a pretreatment for subsequent pro-
cesses, where reduced DO is needed.
The residual aluminum concentration in all the experiments
was lower than 10.0 mg L
without pH adjustment, and below
0.30 mg L
by adjustment to pH 6.5. Given the environmental
concerns related to free aluminum ions, an adjustment of the pH
by the EC treatment is advisable.
When the values of acute and chronic toxicity that were measured
by V. scheri tests, both before and after the EC treatment of aqueous
solutions of DEX were compared, no noticeable toxicity variation was
found, even when by the process was carried out with or without
DEX, i.e., no toxic byproducts were formed.
Finally, it is hoped that this study can make a signicant contribu-
tion to knowledge of the environmental occurrence of DEX, since as
far we know, no similar work dealing with this subject can be found
in the literature.
The authors are grateful to Capes Foundation (Brazilian Ministry
of Education) and the German Academic Exchange Service (DAAD),
for providing grants for this study, and to the Brazilian National Coun-
cil for Scientic and Technological Development (CNPq), for its nan-
cial support.
The authors have declared no conict of interests.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://
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... Degradation of DXM was studied earlier using AOPs including UV-C/H2O2, UV-C/S2O8 2− [25] and UV/iodide [26] combinations, photocatalysis [27,28], sono-nanocatalysis [29], gamma irradiation [30] and electrocoagulation [31]. The authors failed to find earlier reports related to DXM degradation by electric discharge treatment, although attempts to apply ozonation were undertaken [32,33]. ...
... Degradation of DXM was studied earlier using AOPs including UV-C/H 2 O 2 , UV-C/S 2 O 8 2− [25] and UV/iodide [26] combinations, photocatalysis [27,28], sono-nanocatalysis [29], gamma irradiation [30] and electrocoagulation [31]. The authors failed to find earlier reports related to DXM degradation by electric discharge treatment, although attempts to apply ozonation were undertaken [32,33]. ...
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The most widely used anti-inflammatory corticosteroid dexamethasone (DXM), frequently detected in waterbodies due to its massive consumption and incomplete removal in wastewater treatment processes, was experimentally studied for oxidation with gas-phase pulsed corona discharge (PCD) varied in pulse repetition frequency, pH, DXM initial concentration and additions of surfactant sodium dodecyl sulphate (SDS) and tert-butyl alcohol (TBA). The experimental study also included ozonation as compared to PCD in energy efficiency. The advantageous energy efficiency of PCD was observed in wide spans of pH and DXM initial concentrations surpassing ozonation by about 2.4 times. Identified transformation by- and end-products (fluoride and acetate), as well as the impact of radical scavengers, point to the prevalent radical oxidation of DXM. Somewhat increased toxicity observed on the course of PCD-treatment of high DXM concentrations presents a subject for further studies.
... Laboratory scale: hospital wastewater. In their study, Arsand et al. (2013) were able to eliminate 38% of the Dexamethasone present in fortified hospital wastewater until attaining an initial concentration of 100 μg L −1 of the drug. The electrocoagulation process was developed at laboratory scale for 45 min. ...
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During the COVID-19 pandemic, high consumption of antivirals, antibiotics, antiparasitics, antiprotozoals, and glucocorticoids used in the treatment of this virus has been reported. Conventional treatment systems fail to efficiently remove these contaminants from water, becoming an emerging concern from the environmental field. Therefore, the objective of the present work is to address the current state of the literature on the presence and removal processes of these drugs from water bodies. It was found that the concentration of most of the drugs used in the treatment of COVID-19 increased during the pandemic in water bodies. Before the pandemic, Azithromycin concentrations in surface waters were reported to be in the order of 4.3 ng L−1, and during the pandemic, they increased up to 935 ng L−1. Laboratory scale studies conclude that adsorption and advanced oxidation processes (AOPs) can be effective in the removal of these drugs. Up to more than 80% removal of Azithromycin, Chloroquine, Ivermectin, and Dexamethasone in aqueous solutions have been reported using these processes. Pilot-scale tests achieved 100% removal of Azithromycin from hospital wastewater by adsorption with powdered activated carbon. At full scale, treatment plants supplemented with ozonation and artificial wetlands removed all Favipiravir and Azithromycin, respectively. It should be noted that hybrid technologies can improve removal rates, process kinetics, and treatment cost. Consequently, the development of new materials that can act synergistically in technically and economically sustainable treatments is required.
The oxidation of anti-inflammatory dexamethasone (DXM) in water was experimentally studied using a gas-phase pulsed corona discharge (PCD) with the addition of extrinsic oxidants: peroxydisulfate (PDS), peroxymonosulfate (PMS), and hydrogen peroxide (H2O2), aiming the increased energy and overall treatment efficiency. The effects of pH, the dose of supplementary oxidant, and the composition of real water matrix on the efficiency of DXM oxidation were established. For PCD and the PCD/oxidant combinations, a faster and more complete degradation of DXM was observed in acidic media. In neutral media, the PCD/PDS process showed the highest TOC removal and energy efficiency of DXM oxidation. Overall, the carefully optimized dose of extrinsic oxidant resulted in a perceptible improvement of oxidation efficiency in PCD/PDS and PCD/H2O2 combinations compared to PCD under similar treatment conditions. In the groundwater matrix, the use of PCD/PDS and PCD/H2O2 combinations demonstrated considerably faster DXM degradation and mineralization at higher efficiency. The results of this study contribute to the possible application of combined PCD/oxidant processes for efficient removal of DXM from polluted water matrices.
In this work, high removal of contaminants in hospital wastewater has been achieved using an integration of electrocoagulation (EC) with ultrafiltration (UF) and reverse osmosis (RO). In EC system, Al electrodes were arranged in a monopolar-parallel and bipolar configuration. There are two parameters studied in the EC system, i.e., the configuration of electrodes (2A-2C-2B and 4A-2C-2B) and current densities. The EC-UF system with a configuration of 4A-2C-2B and a current density of 88.5 A.m⁻² resulted in high removal of TSS, TDS, BOD, and COD by 95.12%, 97.53%, 95.18%, and 97.88%, respectively. The effluent quality of the EC-UF was improved by substituting UF with RO membrane. The TSS, TDS, BOD, and COD removal were enhanced to 97.64%, 99.85%, 97.88%, and 98.38%, respectively. The permeate flux decline in UF membrane system was 47.83% during 60 minutes of filtration time due to cake layer fouling on the membrane surface, while in the RO membrane system was 29.49%. Since the EC-UF and EC-RO showed high efficiency in contaminants removal, these configurations could be used as clean technology to produce clean water for water reuse purposes. At a wastewater capacity of 5 m³.day⁻¹, the operating cost for the EC-UF system was 3.92 US$.m⁻³, while the EC-RO system was 4.02 US$.m⁻³. The increase of wastewater capacity to 50 m³.day⁻¹ reduced the operating cost to 0.89 US$.m⁻³ for the EC-UF system and 0.93 US$.m⁻³ for the EC-RO system.
This study assessed different regression models to estimate the concentration that inhibits 50% of Allium cepa root growth after exposure to different concentrations (5 to 100%v/v) of hospital wastewater for 72 h. In addition, the mitotic index was also calculated. The results indicate alterations in the normal development of A. cepa owing to the possible presence of toxic substances, identifying a maximum root inhibition of 61.01% and a minimum mitotic index of 2.15%. The Gompertz model was better than other models for its adequate adjustment and low error with a half maximal inhibitory concentration of 57.5% (moderately toxic waters) and a difference of 23% with traditional models such as Probit (80%) or Log-Logistic (80%). Toxicity tests with bioluminescent bacteria (Vibrio fischeri) confirmed the results obtained from A. cepa bioassays.
Electrocoagulation (EC) has been attracting increasing amounts of attention due to its ability to remove the pollutants in widespread wastewater. Chloride ions (Cl⁻) are the most commonly used electrolyte in the EC process. However, the role of the reactive chlorine species (RCS) generated near the electrode is often being underemphasised. In this study, the experiments focused on the generation of RCS and its contribution to the removal of metronidazole (MNZ) during EC. The present findings demonstrated the presence of Cl and ClO near the anode in solution, which dominated the degradation of MNZ. The MNZ decomposition pathways was proposed based on the generation of intermediate products. The toxicity of MNZ and its main degradation products was evaluated by Toxicity Estimation Software Tool (TEST) model and most of intermediates were less toxic than MNZ. Furthermore, the flocs could adsorb part of MNZ by characterizing the flocs using SEM-EDS, FT-IR, XRD and XPS. The contribution ratio of the flocs adsorption and the RCS oxidation for removing MNZ were 57.30% and 41.70%, respectively. Response surface methodology (RSM) was applied to optimize the operation parameters. The present work reveals a new mechanism of EC and manifest good potential for removing antibiotics from chloride-containing wastewater.
A [email protected]/TiO2 flower composite photocatalyst (CDs: carbon dots, HQCA: 8-hydroxyquinoline-5-carboxylic acid) was constructed by exploiting the synergy of complex-sensitization, TiO2-morphology control, and carbon dot-surface modification. The photocatalytic degradation of phenol, norfloxacin, tetrabromobisphenol A and Cr (VI) by Cu-HQCA/TiO2 particle, tube, diamond and flower-like show that the Cu-HQCA complex effectively extends the visible light absorption range of composite photocatalysts, and the flower morphology of TiO2 not only improves the adsorption of pollutants but also enhances the photoelectric response of the composite photocatalyst. In this manner, a [email protected]/TiO2 flower catalyst that demonstrates excellent performance for the removal of dexamethasone, which does not degrade well naturally, was prepared, which delivered a rate of degradation of 99.4% and a degree of mineralization of 77.4% for dexamethasone. Possible degradation sites and dexamethasone degradation products were studied by combining computational chemistry with high-resolution mass spectrometry, and a possible mechanism for photogenerated carrier transmission and separation in the [email protected]/TiO2 flowers is proposed.
Leachate is a complex solution of contaminants produced from municipal waste compacting stations, being primarily comprised of household waste. In this research, leachate was treated in an electrochemical batch process with a dissolved air floatation system using aluminium as the anode with cathode electrodes. Conditions such as pH, current density (i), contact time, and air flowrate were varied and tested to determine their effects on the removal efficiency in terms of Chemical Oxygen Demand (COD), Oil, and Turbidity (Turb.). Under the best conditions, the removal efficiencies for oil, COD, and turbidity were 78.7%, 77.5%, and 98.6%, respectively, suggesting that this method can be considered an efficient and effctive treatment for leachate.
Dexamethasone (DEX) belongs to a class of steroid hormones that can potentially be harmful due to their endocrine disrupting properties. The efficient elimination of DEX during the treatment of drinking water is needed to ensure that the health of both human and aquatic species are protected. Thus different oxidative processes were investigated in order to assess the effect of these procedures and conditions on DEX. Aqueous solutions of DEX were treated by conventional chlorination ([NaClO]=10 mg.L⁻¹) and advanced oxidative processes (ozonation – [O3]=8 mg.L⁻¹; photocatalysis – [TiO2]=120 mg.L⁻¹ and UV-C; photolysis – UV-C). The most and least efficient processes for DEX removal were ozonation (95%) and chlorination (54%), respectively. In total, 16 degradation products were identified and characterized by high-resolution mass spectrometry and only two have been proposed in previous reports. Chemical structures of the degradation products were proposed and alcohol oxidation, ozonolysis and decarboxylation were the main chemical transformations observed. The toxicities of DEX and its derivatives were evaluated by following methods: MTT assay (HepG2 cell), ECOSAR (acute and chronic toxicity) and molecular docking (AutoDock). MTT assay results demonstrated that only a mixture DEX and the chlorinated derivative were toxic at high concentrations. ECOSAR analysis showed that products formed from dehydration and fluoride elimination were more toxic than intact DEX, mainly for fish and Daphnid and to a lesser extent for green algae. The docking study revealed that these degradation products were not capable of making hydrogen bonds with residual amino acids GLN570, GLN642 and CYS736, but were stable at the glucocorticoid receptor indicating the possibility of being toxic to humans.
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In this work, an analytical methodological study was carried out to determine the antimicrobials sulfamethoxazole and trimethoprim, as well as their metabolites, in hospital effluent. The determinations were conducted by liquid chromatography tandem mass spectrometry using a hybrid triple quadrupole-linear ion trap mass spectrometer (LC-QqLIT-MS). The data acquisition was made in selected reaction monitoring (SRM) mode, in which two SRM transitions were monitored to ensure that the target compounds were accurately identified by the information dependent acquisition (IDA) function. The limits of detection (LOD) and quantification (LOQ) were 0.25 and 0.80 µg L−1 for sulfamethoxazole and 0.15 and 0.50 µg L−1 for trimethoprim. The linear range for the SMX was 0.8–100.0 µg L−1 and TMP was 0.5–100.0 µg L−1 on the basis of six-point calibration curves generated by means of linear regression analysis. The coefficients of the correlation were higher than 0.999, which ensured the linearity of the method. The average concentration of sulfamethoxazole and trimethoprim found in hospital effluent was 27.8 and 6.65 µg L−1, respectively. The analytical methodology employed allowed two metabolites to be identified, N4-acetyl-sulfamethoxazole and α-hydroxy-trimethoprim. Fragmentation pathways were proposed.
When the first green wave appeared in the mid and late 1960s, it was considered a fea­ sible task to solve pollution problems. The visible problems were mostly limited to point sources, and a comprehensive "end of the pipe technology" (= environmental technology) was available. It was even seriously discussed in the US that what was called "zero dis­ charge" could be attained by 1985. It became clear in the early 1970S that zero discharge would be too expensive, and that we should also rely on the self purification ability of ecosystems. That called for the development of environmental and ecological models to assess the self purifica­ tion capacity of ecosystems and to set up emission standards, considering the rela­ tionship between impacts and effects in the ecosystems. This idea is illustrated in Fig. 0.1. A model is used to relate an emission to its effect on the ecosystem and its components. The relationship is applied to select a good solution to environmental problems by application of environmental technology.
Pharmaceutical active ingredients continually enter the environment as trace pollutants largely resulting from their intended use in human and veterinary medical practices, agriculture, and personal care. The primary route is their unintentional and largely unavoidable release via excretion and bathing. A secondary route is purposeful disposal to sewerage and trash of leftover, unwanted medications which also poses acute poisoning risks due to intentional or accidental diversion of unused drugs to others. Humans can be inadventently and chronically exposed to trace residues of pharmaceuticals from the environment by consuming contaminated drinking water (or plant and animal tissues), or from dermal or pulmonary exposure during bathing. These exposure risks (and supporting data), as well as possible approaches for reducing exposure, are discussed.
An unique up-flow anaerobic stage reactor (UASR) treating pharmaceutical wastewater at various organic loading rate (OLR) was investigated and showed efficient substrate removal at low OLRs (0.43–1.86kg CODm−3d−1) by promoting efficient chemical oxygen demand (COD) reduction (70–75%). However, increasing the OLRs to 3.73kg CODm−3d−1 by reducing the hydraulic retention time (HRT) (4–2d) reduced the COD removal efficiency (45%). Fluorescent in situ hybridisation (FISH) analysis showed that the microbial community of the reactor stages was dominated by methanogenic archaea (56–79% of 4′, 6 diamidino-2-phenylindole (DAPI)-stained cells in all stages) when the reactor was fed at OLR 0.86–2.98kgCODm−3d−1 but decreased in Stage 1 (30% of DAPI-stained cells) when the OLR was at 3.73kgCODm−3d−1. The two methanogenic genera detected were Methanosarcina and Methanosaeta. Generally, Methanosaeta dominated the reactor stages when the OLR was 0.86–1.86kgCODm−3d−1, while Methanosarcina dominated during the period of high OLR (2.98–3.73kgCODm−3d−1). Based on the number of Desulfovibrio cells detected (8–36% of the total eubacteria) in all stages during the entire operation of the reactor, it appears that sulfidogenic bacteria contributed to the overall degradation of organic substances in the pharmaceutical wastewater.
Effluents arising from molasses fermentation are highly coloured and carry a large organic load. Existing anaerobic/aerobic biological treatments effectively reduce the biological oxygen demand (BOD), but are unable to decolourise or remove the colour associated chemical oxygen demand (COD) from the wastewaters. This study investigated the remediation efficacy of chemical flocculation and electrocoagulation, the process whereby sacrificial anodes corrode to release active coagulant precursors into solution. The chemical flocculants used Als(SO4)2 and FeCl3 have an optimum dosage concentrations, above and below which they are less effective. Both removed almost 90% of the colour and up to 80% of the COD, although this was dependant on effluent quality. Altering the pH alone was also shown to cause colour removal. Electrocoagulation using sacrificial iron or aluminium anodes was as effective as chemical flocculation in reducing colour and COD. The bubbles of hydrogen from the cathode floated almost all the coagulated material to the surface of the reactor, facilitating separation. Particle size distributions of the treated wastewater were measured by laser diffraction. The volume-based frequency distribution made it clear that both chemical flocculation and electrocoagulation resulted in considerable aggregation. A linear relationship between colour and COD removal was demonstrated.
The relation between electrolysis voltage and the other variables of an electrocoagulation process was analyzed. Theoretical models describing such a relation were established. Experiments were conducted to confirm the theoretical analysis and to determine the constants in the models. Both the theoretical analysis and experiments demonstrated that water pH and flow rate had little effects on the electrolysis voltage within a large range. The electrolysis voltage depends primarily on the inter-electrode distance, conductivity, current density and the electrode surface state. The models obtained can be used to calculate the total required electrolysis voltage for an electrocoagulation process.
Performance of a submerged hollow fiber membrane bioreactor (MBR) for treatment of hospital wastewater was investigated. The removal efficiency for COD, NH4+-N, and turbidity was 80, 93 and 83% respectively with the average effluent quality of COD <25 mg/l, NH4+-N < 1.5 mg/l and turbidity <3 NTU. Escherichia coli removal was over 98%. The effluent had no colour and no odour. The transmembrane pressure increased slowly during 6 months operation. No membrane cleaning operation was used and no sludge was discharged during the 6-month operation period.
Fish kills are not uncommon within estuaries in many regions of the world. In seasonally open systems, which are common in temperate areas, they are often associated with mouth openings. Such a kill occurred in July 2005 in the Surrey Estuary following a closed mouth period of seven months resulting in the loss of many thousands of fish. At the time the fish community within the estuary was under investigation which provided comprehensive data of this population prior to the kill. Monthly water quality monitoring was also being conducted prior to the kill and also carried out on a daily basis following the mouth opening. The Surrey was stratified during the closed mouth phase, isolated waters below the halocline had stagnated and become anoxic. As a result only waters above the halocline contained oxygen concentrations capable of sustaining most fish. It appears that if a mouth opening happens under low flow conditions, a shearing effect occurs within the water column where surface waters flow out to sea leaving deeper waters behind. This resulted in only anoxic waters being present for in excess of six days and was responsible for the fish kill. Fish sampling of the Surrey Estuary was conducted three and six months following the kill and those data were compared to that collected in the 12 months prior to the event. Three months after the kill few fish were collected within the estuary and included marine opportunists near the mouth and estuarine resident species in the far upper reaches of the system. However six months following the kill large numbers of estuarine resident species were collected throughout the Surrey Estuary. As many species were euryhaline, it is believed that some individuals migrated into freshwater reaches of the Surrey to escape the anoxic conditions within the estuary. As conditions improved they recolonised the Surrey Estuary. The high fecundity and rapid growth of these small, short lived species probably aided in their re-establishing populations within the estuary. It is clear from this research that artificial openings of estuaries should be avoided during low flow periods when oxygen concentrations are low. It also appears that many of the small estuarine resident species common in seasonally open estuaries are capable of recolonising estuaries following fish kills. The effects on larger, longer lived resident species are not known but likely to be more detrimental due to longer time required for them to reach sexual maturity.