INTERNATIONAL JOURNAL OF PHYTOREMEDIATION

2017, VOL. 19, NO. 8, 782–788

https://doi.org/10.1080/15226514.2017.1284756

Baffled duckweed pond system for treatment of agricultural drainage water

containing pharmaceuticals
Doaa Bassuney and Ahmed Tawfik
Department of Environmental Engineering, Egypt-Japan University of Science and Technology (E-Just), Alexandria, Egypt

ABSTRACT KEYWORDS
The aim of the study is to assess the efficiency of a novel bioremediation system namely baffled duckweed agricultural drainage water;
pond (BDWP) system for the treatment of agricultural drainage water containing pharmaceuticals at pharmaceuticals; baffled
different hydraulic retention times (HRTs). The removal efficiencies of acetaminophen (ACT), amoxicillin duckweed pond system; HRT;
(AMX), and ampicillin (AMP) increased from 69.3 § 8.6 to 87.3 § 3.5%, from 52.9 § 9.4 to 82.9 § 5.2%, and carrier sponge
from 55.3 § 7.9 to 90.6 § 2.8% at increasing the HRT from 6 to 8 days, respectively. However, ACT, AMX,
and AMP removal efficiencies were slightly improved at increasing the HRT from 8 to 12 days. Diclofenac
(DFC) removal efficiencies amounted to 56.6 § 11.6, 55.7 § 11.9, and 28.3 § 12.9% at an HRTs of 12, 8, and
6 days, respectively. The results showed no relationship between the uptake/absorption of
pharmaceuticals fractions and BOD5/chemical oxygen demand (COD) ratio except ACT where R2 was 0.84.
The effect of COD/N ratio on the removal efficiency of pharmaceuticals fractions was slight. Additional
removal of pharmaceuticals fractions and nitrification occurred in carrier sponge media situated in the last
compartment of the BDWP.

Introduction
At present about 40% of the agricultural drainage water
(ADW) in Egypt is directly reused in irrigation via controlled
mixing with Nile water (Allam et al. 2016a; Fleifle et al.
2014). The remaining portions of ADW (60%) is mainly
heavily polluted and dumped directly into Mediterranean
Sea which continuously causes serious environmental prob-
lems for the biodiversity (Allam et al. 2015, 2016b). Nowa-
days, treatment and reutilization of ADW is a major concern
in the country, especially after the construction of Ethiopian
Dams which will affect negatively on the allocated water
quota. Indeed, ADW is considered as a strategic reserve to
cope with the ever-increasing demand for fresh water (Allam
et al. 2016c). However, the composition of ADW manifests
the presence of a wide spectrum of pollutants including, but
not limited to, agricultural chemicals, heavy metals, pharma-
ceuticals, and microbial contaminants. Our previous results
(Allam et al. 2016a) showed that chemical oxygen demand
(COD) concentration of the ADW varied from 50–
250 mg L¡1 which is not complying for reuse in irrigation
purposes based on Egyptian standards (COD D 16% for sulfate and 14% for total dissolved solids (TDS)
60 mg L¡1). Treatment of ADW via low cost technologies
and producing a water quality complying for reuse in agri-
cultural purposes is urgently required. However, the presence
of bio-recalcitrant and micro-pollutants pollutants in the
drainage water needs more attention for reuse. So far, signifi-
cant attention has been focused on the removal of emerging
organic pollutants including pharmaceuticals via classical
duckweed system (Reinhold et al. 2010). In earlier research
Tront and Reinhold (2007) indicated that duckweed rapidly
and actively uptakes 21 of 24 of halogenated phenols com-
pounds with aqueous depletion half-lives of 0.62–3.5 days.
Richard et al. (2004) found that duckweed is effective for the
removal of pharmaceuticals where the plants transformed
micro-pollutants into nonparent compounds, adsorbed/
absorbed, stored/assimilated into plant tissue, and/or tran-
spired and volatilized into the atmosphere. The growth of
Lemna gibba and Lemna minor in the presence of wastewater
with circulation were extensively investigated by Dilek and
Hatice (2011). They found that prolonged application of
high circulation level improved the removal efficiency
of BOD5 (85.3–88.2%) and COD (59.6–66.8%). The potential
of water lettuce (Pistia stratiotes L.) and duckweed (L. minor
L.) for the removal of chlorpyrifos was assessed by Pichamon
and Naiyanan (2011). The maximum removal efficiency of
chlorpyrifos at an initial culture concentration of 0.5 mg L¡1
ranged from 82 to 87%. The results of Priyanka et al. (2014)
showed that, duckweed effectively removed 30% for chloride,
from steel waste water.
Pharmaceuticals originally derived from manufacturing
processes and human consumption severely contaminate
ADW. To what extent the fate of pharmaceuticals contami-
nation in aquatic systems is not well known. The pathway
of degradation/uptake of four pharmaceuticals (acetamino-
phen, diclofenac, amoxicillin, and ampicillin) in duckweed

CONTACT Ahmed Tawfik Ahmed.tawfik@ejust.edu.eg; tawfik8@hotmail.com; Environmental Engineering Department, Egypt-Japan University of Science and
Technology (E-Just), P.O. Box 179, New Borg El Arab City, 21934 Alexandria, Egypt.
Color versions of one or more of the figures in this article can be found online at www.tandfonline.com/bijp.
© 2017 Taylor & Francis Group, LLC
 INTERNATIONAL JOURNAL OF PHYTOREMEDIATION 783

Table 1. Physciochemical characteristics of agricultural drainage water (ADW) con- promote and implement practical, environmentally friendly,
taining pharmaceuticals. and cost-efficient technology for treatment of ADW con-
Parameters Units Average values § STDEV taining pharmaceuticals to reduce emerging micro-pollu-
tants discharge into the environment, and thus reduce
pH-value — 7.13 § 0.3
Macro-pollutants serious alterations of the aquatic ecosystem. The emphasis
COD mgl¡1 277.3 § 41 is afforded for studying the effect of HRT, COD/N and
BOD5 mgl¡1 185.3 § 25.9 BOD5/COD ratio on the removal efficiency of pharmaceuti-
TSS mgl¡1 127 § 32
TKj-N mgl¡1 16.8 § 4.1 cals using a novel technology namely BDWP system. More-
NH4-N mgl¡1 11.9 § 2.5 over, the effect of addition a carrier sponge material in the
TP mgl¡1 2.5 § 1.2 last compartment of the system on the overall removal effi-
Pharmaceuticals (micro-pollutants)
Acetaminophen (ACT) mgl¡1 190.5 § 42.5 ciency was assessed.
Diclofenac (DFC) mgl¡1 111.1 § 32.8
Amoxicillin (AMX) mgl¡1 303.0 § 74.7
Ampicillin (AMP) mgl¡1 277.5 § 59.1 Materials and methods
Agricultural drainage water characteristics

pond system was extensively investigated in this study.
Moreover, much less, attention has been given to the design
of a novel baffled duckweed system which separates the
removal of macro- and micro-pollutants from ADW. The
effect of temperature, light intensity, nitrogen, and phospho-
rus concentrations on the efficiency of duckweed plants
were investigated by Zhao et al. (2014).However, adequate
understanding of the factors affecting on the performance
of the duckweed system treating ADW containing pharma-
ceuticals such as dissolved oxygen (DO), HRT, COD/N, and
BOD5/COD ratio was not earlier investigated. Therefore,
integrated system consists of baffled L. gibba (aquatic mac-
rophytes) and carrier sponge material for the treatment of
ADW containing pharmaceuticals is extensively investigated
in this study. Presumably, the removal of organics and
pharmaceuticals will occur in the first and last compart-
ments of baffled duckweed pond (BDWP) system (L. gibba)
respectively. Therefore, the objective of the study is to
ADW containing pharmaceuticals were collected from Gharbia
drainage canal, Egypt. The drainage canal receives several sour-
ces of domestic and industrial wastewater including pharma-
ceuticals. The characteristics of ADW are presented in Table 1.
Baffled duckweed-based treatment system (BDBS)
Schematic diagram of a continuous flow baffled duckweed-
based treatment system (BDBS) treating ADW containing
pharmaceuticals are presented in Figure 1. Three duckweed
units connected in series were designed and fabricated from
Perspex as described earlier by Allam et al. (2016a). Each duck-
weed unit has the following dimensions (L D 50 cm, W D
30 cm, and D D 23.5 cm) with a capacity of 35.25 l. The walls
of the units were covered by light impervious sheets in order to
reduce the unwanted algal growth. The units were continuously
fed with ADW containing pharmaceuticals using a peristaltic
pump (MasterflexÒ L/S).Two experiments were conducted 1.

Figure 1. Baffled duckweed-based treatment system treating agricultural drainage water containing pharmaceuticals.
784 D. BASSUNEY AND A. TAWFIK

Assessing the efficiency of BDBS for treatment of ADW con- Results and discussion
taining pharmaceuticals at different HRTs [Equations (1) and
Performance of baffled duckweed based treatment system
(2)]. Studying the effect of the addition of carrier sponge mate-
rial for further reduction of pollutants. All experiments were Organics and coarse suspended solids removal
carried out for a period of 290 days at local ambient tempera- The results presented in Figure 2a–c show the efficiency of
ture of 17–35
C. BDBS for the removal of COD, BOD5, and TSS at different
HRTs. The data displayed high fluctuations of the COD,
BOD5, and TSS concentrations in the influent. The COD,
HRT .d/ D V =Q (1) BOD5, and TSS largely varied from 200 to 367 mg L¡1, from
143 to 267 mg L¡1, and from 78 to 183 mg L¡1, respectively.
This is mainly due to seasonal variation of drainage water dis-
Where HRT is the hydraulic retention time, V is the reactor charge, and dumping of sewage and industrial wastewater into
volume (l), and Q is the flow rate (L d¡1). receiving canals. The effluent quality in terms of COD, BOD5,
The duckweed species was harvested from open water and TSS remained unaffected as the system was in steady state
streams and inoculated to the reactor. The plants were initially operating conditions. However, the removal efficiency of
washed vigorously with tap water for 10 minutes. to remove organics and coarse suspended solids is HRT dependent. The
debris, and they were acclimatized for one month with agricul- COD, BOD5, and TSS removal efficiency increased from
ture drainage water. Potassium silicate and fungicide (Ridomil 72.6 § 5.6 to 83.1 § 2.5%, from 74.3 § 5.9 to 87.5 § 2.4%,
Gold EC) (0.3 mL L¡1) were added once in the feed to overcome and from 69.8 § 7.6 to 79 § 7% at increasing the HRT from
the chlorosis /necrosis of the species. The cultivated duckweed 6 to 8 days, respectively. Nevertheless, the removal of COD,
stocking density (SD) was 50 mg cm¡2 (wet weight) to prevent
the duckweed overcrowding and to provide sufficient cover of
the water surface to prevent unwanted algal growth. Samples of
5 cm2 were periodically harvested every 10 days for the deter-
mination of biomass production. The plants were rinsed thor-
oughly with deionized water, drained through a sieve, and
blotted on paper towels for 5 minutes. The duckweed was
weighed before drying at a temperature of 105
C for 24 hours.
The protein content was determined and calculated based on:
protein (g g¡1) D organic N (g g¡1)£6.25 (Patel et al. 2010).
The production rate of biomass was estimated according the
following Equation (2),

.
Duckweed Production rate D ðDf ¡ Di Þ (2)
t0

where, Df: final fresh duckweeds density (g m¡2), Di: initial

fresh duckweed density (g m¡2), and to: harvesting cycle (days).

Samples collection and analytical methods

Composite samples of the influent and treated effluents were
collected three times/week for analysis. Dissolved oxygen (DO),
temperature, and pH were regularly measured using Thermo
Scientific Orion Star(TM) A111 Meters. The total suspended sol-
ids (TSS), COD, biochemical oxygen demand (BOD5), total
Kjeldahl nitrogen (TKj-N), ammonia (NH4-N), nitrate (NO3-
N), and total phosphorous (TP) were determined according to
APHA (2005). The concentrations of pharmaceuticals in terms
of ACT, DFC, AMX, and AMP were measured by Shimadzu
high-performance liquid chromatography (HPLC) equipped
with C-18 phenomenex reverse phase column, degasser
(20A5), pump (LC-20AT), and prominences Diode Array
Detector (SPD-M20A). The samples were initially filtered by
micro syringe filters (0.2 mm). The mobile phase was (60:40)
0.025 M KH2PO4 buffer solution in ultrapure water and aceto-
nitrile. The flow rate was 0.5 mL minutes¡1 and the tempera- Figure 2. (a) COD removal at different HRTs, (b) BOD5 removal at different HRTs,
ture was 60
C. and (c) TSS removal at different HRTs.

Figure 3. (a) Nitrification and denitrification efficiency, (b) TKj-N removal at differ-
ent HRTs, and (c) pH values and dissolved oxygen in the treated effluent.
BOD5, and TSS was slightly affected at increasing the HRT
from 8 to 12 days, as shown in Figure 2a–c. This indicates
that most of the biodegradable organics was utilized at an
HRT not exceeding 8 days, and the system was operated
under substrate limiting conditions (HRT D 12 days). The
removal of suspended solids and particulate organics were
mainly removed by settling process in duckweed chambers.
The COD and BOD5 were mainly oxidized into carbon diox-
ide by heterotrophic bacteria situated on the roots of the
plants. These results are similar to those obtained by Sims
et al. (2013) where the duckweed pond system removed 79 §
3% for COD from storm water at a HRT of 10 days. Iatrou
et al. (2015) found that cultivating duckweed L. minor in
urine and treated domestic wastewater achieved a removal
efficiency of 80% for COD. Likely, the use of duckweed system
for post-treatment of anaerobically pretreated sewage achieved
removal values of 93, 96, and 91% for COD, BOD5, and TSS,
respectively (El-Shafai et al. 2007). A continuous flow of the
duckweed plant L. gibba L. treating primary treated sewage
achieved residual values of 13.1 § 9.7 mg L¡1 for TSS and
INTERNATIONAL JOURNAL OF PHYTOREMEDIATION 785
40.3 § 11.9 mg L¡1 for BOD5 at an HRT of 4.26 § 0.61 days,
(Ran et al. 2004). Duckweed has the potential to reduce TSS
in wastewater (Zirschky and Reed 1988), primarily by shading
the water column below to prevent algae growth.
Nitrogen removal
Figure 3a shows the nitrification efficiency and nitrogen
removal in BDWP system at different HRTs. The results
revealed that the nitrification process was positively affected at
increasing the HRT and reducing the organic loading rate
(OLR). The ammonia removal efficiency substantially
increased from 32.9 § 17 to 61.9 § 9.9% at increasing the
HRT from 6 to 8 days. However, ammonia oxidation effi-
ciency was slightly increased by a value of 2.7% at increasing
the HRT from 8 to 12 days. Only 17 § 5.1, 15.1 § 2.8, and
12.4 § 3.3% of ammonia was removed through the nitrifica-
tion process resulting 1.8 § 0.4, 1.9 § 0.3, and 1.4 § 0.4
mgNOxL¡1 in the treated effluent at HRTs of 12,8 and
6.0 days, respectively. This is mainly because a major portion
of ammonium was up-taken by the plants and little additional
removal was carried out by autotrophic bacteria resulting only
4.9 § 1.6 mgNH4-N L¡1 in the final effluent. El-Shafai et al.
(2007) found that N removal from anaerobic effluent via
duckweed pond system was mainly due to 80% for plant
uptake, 5% for sedimentation, 15% unaccounted; and the
residual values of ammonia was only 0.41 mg N L¡1 in the
treated effluent. Ammonia volatilization showed a minor
mechanism removal (1.1%) in duckweed pond system treating
diluted domestic wastewater at an HRT of 7.0 days, and N
uptake represented 30% as earlier reported by Zimmo et al.
(2004). Apparently, the duckweed acts as a physical barrier
for volatilization of ammonia. Duckweed (L. gibba L.) was
responsible for 30–47% of the total N-loss by the uptake of
ammonium (K€orner and Vermaat 1998). The indirect contri-
bution of duckweed to the total nitrogen removal was due to
nitrification/denitrification by bacteria attached to the duck-
weed, walls of reactor, and the sediment; and by algae. Like-
wise, van der Steen et al. (1998) found that ammonium
removal was due to the uptake by duckweed plants (18%),
nitrification (3%), sedimentation (8%), and combined volatili-
zation of NH3 and denitrification (73%). The results in
Figure 3b show the efficiency of duckweed system for removal
of TKj-N at different HRTs. 42.3 § 12, 41.7 § 10.8 and
31.2 § 8.6% of TKj-N was removed at an HRTs of 12, 8, and
6 days, respectively. This corresponded to nitrogen removal of
37.7 § 11, 36.9 § 24 and 51.3 § 22.5 respectively. These
results are lower than those reported by van der Steen et al.
(1998) where the contribution of denitrification process for
nitrogen removal was 73% and similar to Bal Krishna and
Polprasert (2008) and Iatrou et al. (2015) who achieved 58
and 50% of nitrogen removal, respectively, using duckweed
system treating domestic wastewater and mixed wastewater at
an HRT of 10 days. Some of nitrogen removal was presumed
to have occurred in the lower portions of the duckweed units
where the dissolved oxygen level is quite low and the sediment
could be utilized as a carbon source for denitrifiers. The
increased pH in the treated effluent was mainly due to algal
growth and consumption of CO2, bicarbonate, and carbonate
alkalinity (Figure 3c).
786 D. BASSUNEY AND A. TAWFIK
Pharmaceuticals fractions removal
Figure 4a–d show the performance of BDWP system for the
removal of acetaminophen (ACT), diclofenac (DFC), amoxicil-
lin (AMX), and ampicillin (AMP) at different HRTs. The sys-
tem was efficient for the removal of pharmaceuticals. However,
the residual values of pharmaceuticals were deteriorated in the
treated effluent at decreasing the HRT from 12 to 6 days. The
residual values of ACT, AMX, AMP, and DFC were 21.9 § 7.2,
54.1 § 15.5, 20.2 § 5.2, and 23.4 § 5.3 mg L¡1, respectively, in
the treated effluent at an HRT of 12 days. The elimination of
pharmaceuticals using duckweed system was mainly due to
photodegradation, biodegradation, and plant uptake. Iatrou
et al. (2015) found that ciprofloxacin and sulfamethoxazole
Figure 4. (a) Removal of ACT at different HRT, (b) removal of DFC at different HRT,
(c) removal of AMX at different HRT, and (d) removal of AMP at different HRT.
were effectively removed (80%) using cultivating duckweed L.
minor in urine and treated domestic wastewater. The main
removal mechanism for ciprofloxacin was photodegradation,
while plant uptake and biodegradation seem to be of significant
importance for the latter. Microbial degradation of ibuprofen,
uptake of fluoxetine, metabolite products of triclosan, and 2,4-
dichlorophenoxyacetic acid has occurred in duckweed pond
system (Reinhold et al. 2010). Sorption contributed to the aque-
ous depletion of fluoxetine and triclosan. Lagesson et al. (2016)
found that diphenhydramine, oxazepam, trimethoprim, diclo-
fenac, and hydroxyzine were mainly up-taken in situ in a semi-
natural large-scale pond system. However, light conditions and
eutrophication are affected on the elimination of emerging pol-
lutants polychlorinated biphenyls (PCB) and pesticides (Guiliz-
zoni 1991). Likely, the presence of copper (Cu) in the water
containing veterinary antibiotic tetracyclines (TCs) would
effect on the plant growth, uptake, and accumulation process
(Lu et al. 2014). Influence of only Cu or TCs on plant growth
was not significant, except for TCs at 15 mg L¡1 which pro-
duced a negative effect on plant biomass. The presence of low-
Cu and high-TCs acted synergistically to promote the negative
effect of TCs on plant biomass, but increasing Cu concentration
Figure 5. (a) Effect of DO on the removal of pharmaceuticals, (b) effect of BOD5/
COD ratio on the removal of pharmaceuticals, and (c) effect of COD/N ratio on the
removal of pharmaceuticals.
 INTERNATIONAL JOURNAL OF PHYTOREMEDIATION 787

partially alleviated the adverse effect. The environmental fate

(pathways) of the tricyclic antipsychotic drug chlorpromazine
in an aerobic and anaerobic biodegradation as well as abiotic
photolytic degradation by sunlight was investigated by Traut-
wein et al. (2012). Photodegradation showed almost complete
elimination of chlorpromazine after 4 h of irradiation. Duck-
weed plants removed 99% of acetaminophen mainly by plant
uptake; 98% progesterone primarily by absorption to plant tis-
sue, 90% fluoxetine by adsorption with some biological removal
attributed to plants, and sulfamethoxazole removal varied from
25 to 90%. However, carbamazepine did not react with duck-
weed plants (Farrell 2012). pH is an important driver for phar-
maceuticals’ fate because it affects their ionization which affects
their solubility in water and their tendency to adsorb or absorb
in duckweed (Tront and Saunders 2006). Pharmaceuticals
removed by duckweed plants may be transformed into nonpar-
ent compounds, adsorbed/absorbed, stored/assimilated into
plant tissue, and/or transpired and volatilized into the
atmosphere.
Figure 5a shows the effect of dissolved oxygen (DO) on the
removal of pharmaceuticals fractions. The results showed that
the removal of ACT, DFC, AMX, and AMP increased at
increasing the DO concentration in the bulk liquid. This indi-
cates that the aerobic biodegradation of pharmaceuticals has
occurred to some extent. Hijosa-Valsero et al. (2010) found
that high and low positive redox potentials (i.e., aerobic and
micro-aerophillic conditions) impacted on the degradation of
some pharmaceutical compounds.
The results in Figure 5b show no relationship between the
uptake/absorption of pharmaceuticals fractions and BOD5/
COD ratio except ACT where R2 was 0.84. Similar trends were
Figure 6. (a) Effect of addition carrier sponge on the COD, BOD5 and TSS removal,
observed at different COD/N ratio as shown in Figure 5c where (b) effect of addition carrier sponge on the nitrification efficiency, and (c) effect of
the removal of pharmaceuticals fractions was slight at values addition carrier sponge on the removal efficiency of pharmaceuticals fractions.
ranging from 12 to 23.3.

efficiency of TN and NH4C-N by 19.97 and 15.02%, respec-

Effect of addition of carrier sponge material in last
compartment on the performance of the baffled
duckweed pond system
The results presented in Figure 6a–c show the COD, BOD5, and
TSS removal efficiencies were improved by the addition of car-
rier sponge media. The residual values of COD, BOD5, and TSS
were 29.2 § 6.96, 13.4 § 3.4, and 12.7 § 3.2 mg L¡1, respec-
tively, which comply for reuse in agricultural purposes. The
removal of organic matter could be attributed to the entrap-
ment capacity of particulate matter by porous polyurethane
foam (sponge) occupying the chamber and the presence of the
biofilm improved the biosorption of organic matter and conse-
quently biodegradation process. These results are comparable
to those obtained by Mahmoud et al. (2011) and lower than
those found by Tawfik et al. (2012) who used moving bed bio-
film reactor (MBBR) based on polyurethane carrier material
for posttreatment of anaerobically pretreated sewage. The
MBBR achieved a substantial reduction of COD resulting in an
average effluent concentration of 63 § 27 mg L¡1, respectively.
Likely the system was efficient for additional removal of phar-
maceuticals fractions and nitrification efficiency as shown in
Figure 6b and c. Zhao et al. (2015) found that the addition of
the carrier to the duckweed pond system improved the removal
tively. Moreover, the carrier biofilm had the highest bacterial
diversity and relative abundance of nitrifying bacteria (3%) and
denitrifying bacteria (24% of Rhodocyclaceae), which improved
nitrogen removal of the system.
Conclusions
BDWP system is very efficient for the removal of organics,
nitrogen, and pharmaceutical fractions from ADW. However
the efficiency of the system is mainly affected by several param-
eters such as HRT and DO. The maximum removal efficiencies
of pharmaceuticals fraction were achieved at an HRT of
12 days. The effect of changing of COD/N and BOD5/COD
ratio on uptake and absorption of pharmaceuticals fraction was
negligible. The use of dissolved oxygen in the treated effluent of
BDWP system was efficiently used for further reduction of
pharmaceuticals fraction, nitrification, and organics removal in
subsequent carrier sponge chamber.
Acknowledgments
The first author thanks the Ministry of Higher Education (MOHE) for giv-
ing her Ph-D scholarship at EJUST.
788 D. BASSUNEY AND A. TAWFIK
Funding
The authors are very grateful for science technology development fund
(STDF), project no. 3665 for financing this research.
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