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International Journal of Phytoremediation

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/bijp20

Sorption of cadmium, chromium, lead, and


vanadium from artificial wetlands using Lemna
aequinoctialis

Abraham O. Ekperusi, Francis D. Sikoki & Eunice O. Nwachukwu

To cite this article: Abraham O. Ekperusi, Francis D. Sikoki & Eunice O. Nwachukwu
(28 Oct 2023): Sorption of cadmium, chromium, lead, and vanadium from artificial
wetlands using Lemna aequinoctialis, International Journal of Phytoremediation, DOI:
10.1080/15226514.2023.2272766

To link to this article: https://doi.org/10.1080/15226514.2023.2272766

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Published online: 28 Oct 2023.

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INTERNATIONAL JOURNAL OF PHYTOREMEDIATION
https://doi.org/10.1080/15226514.2023.2272766

Sorption of cadmium, chromium, lead, and vanadium from artificial wetlands


using Lemna aequinoctialis
Abraham O. Ekperusia�, Francis D. Sikokib, and Eunice O. Nwachukwuc
a
Africa Centre of Excellence in Oilfield Chemicals Research, University of Port Harcourt, Port Harcourt, Nigeria; bDepartment of Animal and
Environmental Biology, University of Port Harcourt, Port Harcourt, Nigeria; cDepartment of Plant Science and Biotechnology, University of
Port Harcourt, Port Harcourt, Nigeria

ABSTRACT KEYWORDS
The efficacy of the lesser duckweed, Lemna aequinoctialis (Welw.), to remediate varying concentra­ Constructed wetlands;
tions of cadmium, chromium, lead, and vanadium from an organo-metallic contaminated media was metal uptake;
tested in artificial surface wetland mesocosm experiment. A 100 g of fresh-weight duckweed was phytoextraction; phytoreme­
diation; pollutants
introduced into each of the mesocosm, except for the control setup and monitored for 120 days remediation
while the metals removal rate was quantified using an atomic absorption spectrometer. A time-
dependent and partial sorption of metals was observed with the highest removal rate recorded for
cadmium (71.96%), followed by lead (69.23%), vanadium (55.22%), and chromium (41.64%). The
uptake and bioaccumulation of metals were reflected in the increased plant biomass (p < 0.05,
F ¼ 97.12) and relative growth rate (p < 0.05, F ¼ 1214.35) in duckweed. A coefficient (r2) of 0.951,
0.919, 0.970, and 0.967 was recorded for cadmium, chromium, lead, and vanadium respectively, indi­
cating that the remediation of metals followed the first-order kinetic rate model. This study highlights
the efficacy of the lesser duckweed to preferentially remediate metals in an organo-metallic complex
medium for potential wastewater treatment in the petrochemical industry.

NOVELTY STATEMENT
Appling ecological or nature-based solutions for the treatment of complex wastewater from the
petrochemical industry in Africa remains a challenge due to the paucity of evidence-based science
to support the implementation that is acceptable to regulators and the industry. Although labora­
tory and field-based demonstration of phytoremediation studies has shown the potential of mac­
rophytes for the treatment of organic and inorganic pollutants, studies on the application of
duckweed for complex organo-metallic wastewater treatment for heavy metals are few. This study
demonstrates the efficacy of the lesser duckweed, Lemna aequinoctialis in the sorption of cad­
mium, chromium, lead, and vanadium from an organo-metallic complex with potential application
in the petrochemical industry.

GRAPHICAL ABSTRACT

HIGHLIGHTS
� Oil spill releases hydrocarbons and associated metals into the environment.
� Hydrocarbons are degraded, but heavy metals remain in the environment.
� Lemna aequinoctialis demonstrated the partial sorption of metals in artificial wetlands.
� The phytoremediation of metal was time-dependent.
� The sorption rate fits into the first-order kinetic rate equation.

CONTACT Abraham O. Ekperusi ekperusiab@gmail.com Africa Centre of Excellence in Oilfield Chemicals Research, University of Port Harcourt, Port
Harcourt, P.M.B. 5323, Rivers State, Nigeria.
�Present Address: Department of Environmental Management and Pollution, Nigeria Maritime University, Okerenkoko, Delta State, Nigeria.
Supplemental data for this article can be accessed online at publisher’s website.
� 2023 Taylor & Francis Group, LLC
2 A. O. EKPERUSI ET AL.

Introduction withstand and thrive in polluted environment and bio­


accumulate pollutants from surface waters (Miretzky et al.
Petroleum remains a crucial energy source to the global
2004; Shuvaeva et al. 2013; Ekperusi et al. 2019; Zhou et al.
economy, despite significant investment in alternative energy
2023).
sources. Many developing economies particularly in the glo­
Several species within the five genera have been applied
bal south rely on petrochemicals to meet their energy
for the uptake and removal of organic and inorganic pollu­
demand and economic investment (Ekperusi et al. 2017).
tants in constructed wetlands (Sukumaran 2013; Muradov
During oil spills, petroleum hydrocarbons and several
et al. 2014; Preetha and Kaladevi 2014; Ekperusi et al. 2019,
impurities like heavy metals associated with oil are released
2020; Baek et al. 2021; Ort� uzar et al. 2022; Zhou et al.
into the environment (Ahmad et al. 2010; Ekperusi et al.
2023), but there is a paucity of literature on the use of
2017). After the spill, volatile hydrocarbons evaporate from
Lemna aequinoctialis for the remediation of heavy metals
soil and water, while larger carbon chains are naturally
associated with petroleum in artificial wetlands. This study
degraded by microbial action leaving heavy metals in the
aimed to assess the efficacy of L. aequinoctialis in removing
environment due to their non-biodegradable nature
(Adesiyan et al. 2018). Many of the non-essential metals are metals from contaminated media with the objectives to (i)
toxic and are classified as possible human carcinogens understand the plant growth condition under organo-metal
(Nguyen et al. 2005; Tchounwou et al. 2012). Exposure to contamination, (ii) determine plant growth characteristics in
elevated levels of non-essential metals results in degenerative contaminated media, and (iii) assess the metal removal rate
bone disease, central nervous system damage, endocrine dis­ by duckweed in artificial wetlands.
ruption, congenital disorders, liver, and kidney problems
(Nguyen et al. 2005; Adesiyan et al. 2018). Materials and method
Several species of terrestrial and aquatic plants have been
tested for their ability to remove various contaminants from Duckweed collection and preparation
the environment (Van Epps 2006; Ekperusi et al. 2019). The Duckweed colonies for the study were collected with poly­
efficacy of plants to bioaccumulate significant levels of met­ propylene containers from natural wetlands in Effurun,
als is a characteristic present in several plant species and Delta State after permission was granted for sample collec­
approximately 0.2% of all angiosperms (Sarma 2011;
tion by landowners. At the lab, the collected duckweeds
Ekperusi et al. 2019; Baek et al. 2021; Ahmad et al. 2023;
were rinsed thoroughly with tap water to remove debris and
Zhou et al. 2023). Aquatic macrophytes are applied in nat­
transferred into culture containers with distilled water for
ural or artificial wetlands for the removal of a wide range of
growth and acclimation before use. Duckweeds were cul­
pollutants from aquatic ecosystems. Artificial wetlands are
tured (see Figure S1) in nutrient solution under prevailing
designed to mimic natural wetlands to treat contaminants in
environmental conditions; temperature (27–34 � C), photo­
surface waters, waste streams, runoff, municipal and indus­
period (12 h), and relative humidity (63–67%). Voucher
trial wastewater, sewage effluents, aquaculture discharge,
specimens (NG/UP/191022) of duckweed were prepared and
mine drainage, and petroleum wastes (ITRC 2003; Ekperusi
deposited at the herbarium at the Department of Plant
et al. 2019; Zhou et al. 2023). Duckweeds are a group of
Science and Biotechnology. Identification of duckweed was
aquatic floating macrophytes with global distribution
carried out using historical references with the aid of appro­
(Hillman and Culley 1978; Landolt 1980). The duckweed
(Lemnaceae) group is represented by 37 species sorted into priate taxonomic keys (Datko et al. 1980; Landolt 1980,
five genera (Landoltia, Lemna, Spirodela, Wolffia, and 1986; Mbagwu and Adeniji 1988). Prior to use, samples of
Wolffiella), based on their morphology (Liu et al. 2021; duckweed were analyzed for heavy metals contamination
Zhou et al. 2021). Unlike other angiosperms, members of and were found negligible for the metals applied in this
the group have their leaves and stems fused into a simple study.
structure known as fronds, which is supported by a fragile
root system (Zhou et al. 2023). Due to their simplified struc­ Experimental setup
ture, invasive nature, sporadic reproduction, and high meta­
bolic activities, duckweeds play an essential role in the The experimental design and setup followed a previously
ecology of reservoirs including nutrient recycling and regu­ described method (Ekperusi et al. 2020). An artificial sur­
lating oxygen balance worldwide (Zhou et al. 2021, 2023). face-constructed wetland (ASCW) was created using polyvi­
Their simplified nature has also increased attention to duck­ nyl tanks. Two sets of experimental tanks were added 8 L of
weed research and potential application in various sectors distilled water and contaminated with 10 mL of crude oil
(Ekperusi et al. 2019; Zhou et al. 2023). (API of 33.51 and specific gravity of 0.85) with metals in the
Duckweed is consumed as protein for animal and human following concentrations; 3.21, 11.4, 0.39, and 3.64 mg L−1,
food as a substitute for meat with the potential to reduce respectively, for cadmium, chromium, lead, and vanadium
greenhouse gas emissions (Ekperusi et al. 2019; Baek et al. to simulate a spill environment. A 5 mL of a nutrient solu­
2021; Zhou et al. 2023). Duckweed has also been explored tion containing NPK was added to each ASCW and allowed
for its use in pharmaceuticals, biofuels, space exploration, to stand for 7 days. After 7 days, 100 g of acclimated duck­
bioplastics, and remediation of contaminants (Baek et al. weed was added to one set of the contaminated ASCW,
2021; Ort� uzar et al. 2022; Zhou et al. 2023). Duckweed can while the second set was without duckweed (control setup).
INTERNATIONAL JOURNAL OF PHYTOREMEDIATION 3

Figure 1. Experimental setup (a) wetland with contaminants, (b) contaminants and duckweed, (c) duckweed only.

A third set of the ASCW tanks was added with duckweed, Plant biomass and relative growth rate
distilled water, and nutrients without contaminants. The
Plant biomass (fresh weight) was determined following the
setup was repeated in triplicates (Figure 1). The ASCW was
method described by Vollenweider (1974). Plants were har­
monitored daily for 120 days. Distilled water was regularly
vested from the wetlands, washed with tap water several
added to replace water loss due to evapotranspiration.
times, and sorted into beakers. The plants were allowed to
air dry and weighed (Denver Instruments, Model APX-200)
Laboratory analysis for the measurement of biomass. The relative growth rate
(RGR) was calculated following methods described by
Samples for laboratory analysis were collected with appro­ Tkalec et al. (1998)
priate sampling bottles and transported to the lab for chem­
ical analysis. In situ measurements and all samples for number of fronds at day n − number of fronds at day 0
laboratory analyses were collected bi-monthly (0, 15, 30, 45, RGR ¼
number of fronds at day 0
60, 75, 90, 105, and 120 days) throughout the study. The pH (1)
in wetlands was determined with a digital pH meter
(Hanna, HI9813) after calibration with a buffer solution.
where RGR, plant relative growth rate (grams/grams/day); n,
Conductivity was measured with the aid of a conductivity
number of fronds at n (120) days; 0, number of fronds at
meter (Hanna, HI9812) after calibration using a KCl solu­
the start day of the experiment.
tion. Determination of cadmium, chromium, lead, and van­
adium in wetlands was done following methods described
earlier (ASTM. 2017) using Solaar Thermo Elemental Contaminant removal efficiency
Atomic Absorption Spectrometer (AAS – Model SG 71906).
The removal rate for metals in the wetlands was calculated
About 100 mL of the sample was drawn into a 150 mL bea­
using methods described by Megateli et al. (2013)
ker with the addition of 5.0 mL of concentrated nitric acid
(HNO3). The solution was evaporated to near dryness using Co − Ct
an oven set at 60 � C. After cooling down, another 5.0 mL of Rð%Þ ¼ � 100 (2)
Co
HNO3 was added to the beaker and covered with a watch
glass. The beaker was returned to the oven and the heating
R (%), removal rate of the contaminant in wetlands; Co,
was continued until complete digestion of the sample was
initial contaminant level at the start of the experiment
achieved. Another 2 mL of HNO3 was further added to the
(mg L−1 ); Ct, final contaminant level at the end of the
residue and washed with distilled water. The solution was
experiment (mg L−1).
filtered into a 100 mL volumetric flask to remove silicate
and other insoluble materials and the volume made up to
the mark. The filtrate was aspirated into the air-acetylene Bioconcentration factor (BCF)
flame (fast sequential) of the spectrometer to determine the
The BCF was calculated as the concentration of metals in
concentration of heavy metals present in the sample.
the tissue of duckweed over the concentration in wetlands
Standards were treated with 10 mL of sample filtrate and
as described by Rahmani and Sternberg (1999)
5 mL of diphenylcarbazide before analysis. At the termin­
ation of the experiment, samples of duckweed were col­ �
lected, air-dried, and digested with HNO3. The digested HMP mgkg−1
BCF ¼ � (3)
sample was filtered using Whatman 42 filter paper and HMS mgL−1
made to volume with distilled water. The filtrate was ana­
lyzed with AAS to determine the concentration of heavy BCFheavy metals, bioconcentration factor for heavy metals;
metals present in duckweed. All chemical reagents and HMP, heavy metal concentration in plant (mg kg−1); HMS,
blanks used were of analytical grades. heavy metal concentration in wetlands (mg L−1).
4 A. O. EKPERUSI ET AL.

First-order kinetic rate equation nutrient content, or contaminant level in plant tissues
(Roberts et al. 1985).
Experimental data were inputted into the first-order kinetic
Plant biomass initially decreased in wetlands by 2.16% in
rate equation described by Benefield and Randall (1980) to
the first 15 days. This decrease may be connected to the ini­
model the contaminant removal rate tial stress of duckweed exposed to an environmental con­
InCt ¼ InC0 –kt (4) taminant in the wetland. Sun et al. (2013) reported a
−1 significant decreased in plant biomass by 31.2%, 38.5%, and
Ct, concentration of parameter at time, t (mg L ); Co, initial
39.5%, respectively with Acorus calamus, Iris pseudacorus,
concentration of parameter at time, t (mg L−1); k, first-order
and Typha orientalis exposed to heavy metals in effluents. In
rate constant (day−1); t time (day).
our study, after 15 days, plant biomass did not only recov­
ered, but it increased significantly (p < 0.05, F ¼ 97.121)
Data analysis throughout the study, reaching 83.50% compared to the
control which was 34.57% (Figure S2). Significant increases
Data were analyzed using Statistical Package for Social in plant biomass have been reported with macrophytes on
Sciences (SPSS) version 21. Descriptive statistics such as various effluents with metal accumulation (Mohedano et al.
means, standard errors, and percentages were summarized, 2012; Sun et al. 2013; Bokhari et al. 2019). In a recent study,
while one-way analysis of variance (ANOVA) was applied increased plant biomass was also reported for manganese
for the level of significance at p < 0.05 probability level, fol­ and nitrate medium (Kishchenko et al. 2023), while no
lowed by a post-hoc test (Duncan) where necessary. Graphs change in plant biomass was reported in a boron-contami­
were created using Microsoft Excel v.2020. nated media with L. gibba (Zhou et al. 2023).
Plant RGR with L. aequinoctialis increased significantly
Results and discussion (p < 0.05, F ¼ 1214.345) from 0.012 to 0.952 g/g/day com­
pared to the control (from 0.041 to 0.678 g/g/day). Similar
Plant growth condition RGR was observed in the phytoremediation of metals using
L. gibba and L. minor (Sobrino et al. 2010; Uç€ € unc€u et al.
Plant growth characteristic is essential in determining the
2013). Sobrino et al. (2010) reported the highest RGR in the
general health condition of a plant. In this study, the colony
first 3 days, while in our study the highest RGR was
of L. aequinoctialis remains healthy throughout the study
observed at day 120 (Figure S3). The application of a con­
with no obvious inhibition or chlorosis in the contaminated
stant concentration of metals for the study period could be
wetlands. A similar observation was reported with duckweed
responsible for the time-dependent increase in RGR
species (L. aequinoctialis, Lemna punctata, Lemna turioni­
observed in our study. The reverse is the case for studies
fera, Spirodela polyrhiza, and Lemna minuta) exposed to
where metals or contaminant concentrations were increased
manganese, chromium, and phenol (Paisio et al. 2018; Zhou with an increase in time.
et al. 2019).
The introduction of a nitrogenous fertilizer as a source of
nutrients may have aided the growth condition of duckweed. Physicochemical condition of wetlands
Zhou et al. (2021) also observed no signs of chlorosis for six
The mean pH of wetlands after contamination was 6.42. It
species of duckweed (L. punctata, L. aequinoctialis, Lemna
increased significantly (p < 0.05, F ¼ 6.071) after the intro­
minor, L. turionifera, S. polyrhiza, and Wolffia globosa) with
duction of L. aequinoctialis by 2.34% (6.57) but decreased by
a nitrate medium. In contrast, Kishchenko et al. (2023)
15.42% (5.43) in the control setup (Figure 2a). The increased
reported severe chlorosis and death of S. polyrhiza in a man­
pH in the presence of duckweed could be attributed to the
ganese setup with nitrate, while mild chlorosis with ammo­ decreasing metal concentration associated with duckweed
nia as the nitrogen source. Other studies reported oxidative activities in the wetland. A significant improvement was
stress and impairment with L. minor and Lemna gibba observed in the physicochemical parameters including pH
exposed to cadmium, copper and chromium (Megateli et al. (from 6.74 to 7.5) for the phytoremediation of iron, copper,
€ unc€
2009; Uç€ u et al. 2013). The level of inhibition reported zinc, lead and cadmium with L. minor and Pistia stratiotes
in these studies may have resulted from the high concentra­ (Br�ahaița et al. 2015). A corresponding increase in pH (from
tion of metals (ranging from 1 to 100 mg L−1) compared to 7.2 to 7.5) was reported for the decrease in arsenic from 6
our study. Exposing macrophytes to concentrations of met­ to 0.1 mg L−1 (Jasrotia et al. 2017). Furthermore, Zhou et al.
als beyond their tolerable threshold could result in physio­ (2021) and Kishchenko et al. (2023) reported increased pH
logical stress, chlorosis, and death. in media with nitrate while the reverse was the case with
ammonia, reflecting a limiting potential of the latter as a
Plant biomass and relative growth rate nitrogen source for duckweed.
The conductivity of contaminated wetlands was
Plant biomass and RGR are two parameters that express the 22.33 ± 1.33 lS/cm. It increased significantly (p < 0.05,
general growth condition of a plant exposed to stressors in F ¼ 10.203) with the application of duckweed by 44.78%
the environment. Plant biomass measured in fresh or dry (32.33 ± 2.63), while it decreased by 2.24% (22.83 ± 0.73) in
weight could be assessed for the determination of protein, the control setup (Figure 2b). A similar increasing
INTERNATIONAL JOURNAL OF PHYTOREMEDIATION 5

conductivity trend was also observed for the phytoremedia­


tion of metals with L. minor and P. stratiotes (Br�ahaița et al.
2015).

Heavy metals removal from wetlands


There was a decreasing trend observed in the concentration of
metals from cadmium (3.21–0.90 mg L−1), chromium (11.48–
6.70 mg L−1), lead (0.39–0.12 mg L−1), and vanadium (3.64–
1.63 mg L−1), respectively, in wetlands with duckweeds. The
decrease in metal concentration highlights the efficacy of L.
aequinoctialis for the sorption of metals from contaminated
media. The initial concentration of manganese decreased sig­
nificantly from 4.12 to 0.097 mg L−1 with the application of L.
aequinoctialis (Zhou et al. 2019), while the powdery form of L.
aequinoctialis was effective in the removal of lead as high as
20 mg L−1 from wetlands (Chen et al. 2013).
For each metal profile, cadmium decreased significantly
(p < 0.05, F ¼ 12.335) by 4.36%, 11.21%, 19.94%, 32.40%,
41.75%, 57.32%, 64.80%, and 71.96% after 15, 30, 45, 60, 75,
90, 105, and 120 days, respectively. A similar decreasing
trend was also observed for chromium (7.06%, 13.15%,
16.9%, 13.76%, 22.74%, 37.81%, 39.72%, and 41.64%), lead
(17.95%, 20.51%, 30.77%, 41.03%, 53.85%, 51.28%, 58.97%,
and 69.23%), and vanadium (2.47%, 4.12%, 15.66%, 26.37%,
Figure 2. Physicochemical parameters (mean ± SE) for (a) pH and (b) conductiv­ 32.97%, 40.11%, 46.98%, and 55.22%), respectively
ity in artificial wetlands with L. aequinoctialis.
(Figure 3). In general, no significant variation was observed
in the removal rate of chromium (p > 0.05, F ¼ 1.999), lead

Figure 3. Removal rate for heavy metals (mean ± SE) with time (from day 0 to 120 days) for (a) cadmium, (b) chromium, (c) lead, and (d) vanadium in contaminated
artificial wetlands with L. aequinoctialis and control setup.
6 A. O. EKPERUSI ET AL.

(p > 0.05, F ¼ 0.650), and vanadium (p > 0.05, F ¼ 2.212) in concentration of lead from 10 to 40 mg L−1 resulted in a
the study. The potential route for metal removal from artifi­ decrease in the remediation potentials of L. aequinoctialis
cial wetlands was the sorption and methylation or chelation (Tang et al. 2017). Shuvaeva et al. (2013) also indicated that
via enzymatic action in the tissues of duckweed (Pilon-Smits metal uptake increases at the inception of the study but
2005; Mkandawire and Dudel 2007). decreases with time. In this regard, metal removal from wet­
Aquatic macrophytes including duckweed can detoxify lands could be more favorably disposed toward using a con­
organic compounds like hydrocarbons and industrial dyes stant concentration compared to increasing concentration
via biosorption and cellular metabolism (Ekperusi et al. with increased in time.
2020; Zhou et al. 2023), but for non-biodegradable inor­
ganics like heavy metals, sorption is through chelation,
Bioconcentration factor (BCF)
sequestration, and compartmentalization in intracellular tis­
sues. This is aided by antioxidant enzyme activities to In this study, the BCF was calculated as the concentration of
reduce metal stress and toxicity (Baek et al. 2021; Zhou metals in duckweed over the concentration in the wetlands.
et al. 2023). The BCF for metals in wetlands with L. aequinoctialis were
An aquatic ecosystem with a pH less than 6.5 as observed 2.54, 0.74, 3.25, and 1.24 for cadmium, chromium, lead, and
at the beginning of the study could leach metal ions into the vanadium, respectively (Figure S4). A BCF value greater
media thereby increasing their mobility. Not only were met­ than 1 is a good indication of a plant with high potency for
als bioavailable for uptake, but duckweed was also effective metal uptake (Landis et al. 2011). The BCF values reported
in the sorption of metals from the contaminated wetland. in our study were greater than 1, except for chromium
The highest percentage removal rate among the heavy met­ which makes L. aequinoctialis an effective phytoremediation
als in this study was recorded with cadmium (71.96%), fol­ agent for metal sorption in artificial wetlands. A similar
lowed by lead (69.23%), vanadium (55.22%), and chromium trend was reported with aquatic plants for chromium, cop­
(41.64%) in the following decreasing order; Cd > Pb > V > per, lead, aluminum, cadmium, iron, and zinc (Galal and
Cr. The factor responsible for the sorption trend observed Farahat 2015; Galal et al. 2017). Chaudhary and Sharma
in this study may be connected with the speciation and (2019) reported higher BCF for cadmium and chromium
mobility of the metals present in light crude oil as applied with L. gibba thereby demonstrating hyper-accumulation
in this study. Previous studies on duckweed reported similar potentials compared to L. aequinoctialis.
or higher removal rates compared to this study. Tang et al.
(2017) reported increased efficiency of lead removal with L.
Relationship between physicochemical parameters and
aequinoctialis (97.81%), L. punctata (98.10%), and S. poly­
heavy metals
rhiza (98.04%). Metals such as aluminum, cadmium, chro­
mium, copper, nickel, lead, and zinc were remediated with The relationship between the pH, conductivity, and metals
percentages ranging from 49% to 93% in artificial wetlands was assessed using Pearson’s correlation. The pH of wet­
treating domestic effluents in Flanders (Lesage et al. 2007), lands had a significant (0.01, 2-tailed) positive correlation
while an 84% removal rate was reported with L. minor for with conductivity (0.549) and a significant negative correl­
cadmium, copper, lead, and nickel in a municipal and ation with cadmium (0.470), vanadium (0.347), and chro­
industrial effluent (Bokhari et al. 2016). The variation mium (0.296). No significant correlation was observed
reported in previous studies compared to our study could be between pH and lead (Table S1). On the other hand, con­
associated with the metal concentration, study duration, and ductivity had a strong positive correlation with pH and a
nutrients solution applied. Aside from the behavior of met­ strong negative correlation with cadmium (0.728), chro­
als in contaminated media, the preferential accumulation of mium (0.563), lead (0.472), and vanadium (0.406). A signifi­
contaminants in multi-contaminated media could provide a cant correlation was reported for copper, zinc, manganese,
better understanding of contaminant removal rates by duck­ nickel, lead, chromium, and aluminum in wetlands with L.
weeds. In a previous study, Zhou et al. (2021) reported that € unc€
minor (Uç€ u et al. 2013; Tunca et al. 2016) and between
all six species of duckweed (L. punctata, L. aequinoctialis, L. iron, zinc, copper, chromium, and cadmium with P. strat­
minor, L. turionifera, S. polyrhiza, and W. globose) demon­ iotes, S. polyrhiza, and Eichhornia crassipes (Mishra and
strated an apparent preference for ammonia over nitrate. Tripathi 2008). A strong positive correlation was found in
Similarly, L. minor preferentially favored the uptake of cal­ metals removal with submerged macrophytes (Xing et al.
cium sulfate over magnesium (Walsh et al. 2020). So, the 2013) and for the removal of arsenic with Vallisneria natans
traits or intracellular factors in L. aequinoctialis that favored (Chen et al. 2017). No correlation was observed with copper
the preferential removal of cadmium over lead, vanadium, in the phytoremediation of metals with duckweed (U瀀 unc€ u
and chromium given their initial concentration remains et al. 2013).
unclear. Future studies on intracellular activities could pro­
vide more insight in this regard.
First-order kinetic rate model
In this study, metal sorption from the media was time-
dependent. This is similar to the removal of cadmium, cop­ Certain chemical and biological degradation processes follow
per, lead, and nickel from industrial and municipal effluents linearly the first-order kinetic rate model, which is charac­
(Bokhari et al. 2016). In contrast, increasing the initial terized by a single exponential rate constant. The data
INTERNATIONAL JOURNAL OF PHYTOREMEDIATION 7

Table 1. First-order kinetic rate modeling for heavy metals removal in wetlands.
Metals (mg L−1) Treatments 1st order model 1st order rate constant (k) t1/2 (days) r2
Cadmium Setup y ¼ −0.011(t) þ 1.3257 0.011 63.0 0.9509
Control y ¼ 1 � 10−5(t) þ 1.1648 0.00001 69310.0 0.008
Chromium Setup y ¼ −0.0047(t) þ 2.4618 0.0047 147.5 0.9186
Control y ¼ −0.0006(t) þ 2.4626 0.0006 1155.2 0.6997
Lead Setup y ¼ −0.009(t) − 0.941 0.009 77.0 0.9696
Control y ¼ 0.0009(t) − 0.9709 0.0009 770.1 0.4876
Vanadium Setup y ¼ −0.0069(t) þ 1.385 0.0069 100.4 0.9672
Control y ¼ −0.0002(t) þ 1.2844 0.0002 3465.5 0.3036

generated from this study were subjected to a first-order Data availability


kinetic rate model to predict the remediation rate of metals
All data generated or analyzed during this study are included in this
in wetlands with duckweed. A best line of fit was drawn for published article (and its Supplementary Information file).
metals and r2 was found with a coefficient of 0.951, 0.919,
0.970, and 0.967 for cadmium, chromium, lead, and van­
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