Ecotoxicology and Environmental Safety 190 (2020) 110140

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Ecotoxicology and Environmental Safety

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D151 resin preloaded with Fe3+ as a salt resistant adsorbent for glyphosate T
from water in the presence 16% NaCl
Guqing Xiao∗, Qiudong Meng
College of Materials and Chemical Engineering, Hunan City University, Yiyang, 413000, PR China

ARTICLE INFO ABSTRACT

Keywords: D151 resin preloaded with Fe3+ [denoted as R–Fe3+] was to investigate R–Fe3+ as an adsorbent for glyphosate
D151 resin preloaded with Fe3+ from water in the presence high concentration of salt. The adsorption mechanism revealed the coordination of
Salt resistance Fe3+ inside R–Fe3+ with O atoms of P–O and N atoms in glyphosate molecule. The adsorption capacity of
Glyphosate glyphosate by R–Fe3+ was much larger than that of D151 resin preloaded with Ni2+, Cu2+, Na+ and H+. Even
Coordination
in glyphosate solutions containing 16% NaCl, R–Fe3+ showed the constant adsorption capacity of glyphosate.
Adsorption
The result provided the first evidence of R–Fe3+ as a salt resistant adsorbent for glyphosate. The adsorption
capacity of glyphosate was the maximum at pH 3.35. The adsorption thermodynamics showed that the ad-
sorption of glyphosate by R–Fe3+ was the ligand exchange of glyphosate and water. The maximum coordination
ratio of glyphosate to Fe3+ inside R–Fe3+ was 1:1. The maximum adsorption capacity of glyphosate by R–Fe3+
was up to 481.85 mg/g, which is much higher than that of other reported adsorbents in the presence 16% NaCl.
2 mol/L NaOH, 2 mol/L H2SO4 and 2 mol/L Fe2(SO4)3 could all be used to achieve over 97% regeneration of
R–Fe3+.

1. Introduction
Glyphosate, as a non-selective herbicide, is the most commonly used
herbicide in the world (Skeff et al., 2018) [1]. About 82.6 × 104 tons of
glyphosate have been used only in 2014 (Zhang et al., 2018). Glypho-
sate can be detected in surface water and soil because of its widespread
use (Zhou et al., 2017; Arroyave et al., 2016). The US Environmental
Protection Agency (US EPA) has set the maximum concentration of
glyphosate in water at 0.28 mg/L (Lan et al., 2016). Once glyphosate
enters the human body through the food chain and water, it can in-
terfere with the function of the nervous and endocrine systems (Zavareh
et al., 2018). Glyphosate can also cause genetic mutation (Jiang et al.,
2018) and cancer (Yamaguchi et al., 2016). There are two methods to
produce glyphosate in the industry. The mother liquor used to produce
glyphosate with glycine contains about 1.5% glyphosate and 13–15％
NaCl (Liu et al., 2013; Shen et al., 2013), while the mother liquor of
glyphosate by IDA method contains about 2.0% glyphosate and 4.5％
NaCl (Shen et al., 2013). Direct discharge of the two mother liquors can
cause severe environmental pollution and the loss of glyphosate (Hu
et al., 2011). Obviously, the recovery of glyphosate from the two mo-
ther liquors has important environmental and economic benefits.
One way to treat glyphosate mother liquor is to neutralize it, then
evaporate and concentrate to produce glyphosate pesticide reagent
containing 10% glyphosate for sale. The disadvantage of the method is
that the glyphosate reagent contains a large amount of salt, which can
easily lead to soil salinization. Of course, the method has been banned
in China (Shen et al., 2013). The evaporation solvent is another tradi-
tional method to recover glyphosate from the two mother liquors in
China (Shen et al., 2013), which consumes a great deal of energy. There
are other methods such as electrochemical oxidation (Rubí-Juárez
et al., 2016), biodegradation (Wang et al., 2016) and visible light cat-
alytic degradation (Huo et al., 2017), these treatments result in the
waste of glyphosate. Ore adsorption is not suitable for large scale gly-
phosate wastewater due to its defects of low efficiency (Yang et al.,
2018). The recovery of glyphosate in the presence high concentration of
salt has been a scientific problem for many years.
-NH- groups exhibit alkalinity, while the groups [-COOH and (HO)2-
PO-] exhibit acidity. So glyphosate is an amphoteric substance.
Glyphosate can exhibit four levels of ionization constants (Fiorilli et al.,
2017). Glyphosate, as a weak electrolyte, is mainly in the first ioniza-
tion equilibrium without adding acid and base. The first ionization
equation of glyphosate (pKa1) is described in Scheme 1. Glyphosate
exhibits a high solubility in water and a small solubility in organic
solvents (Mata et al., 2014; Divisekara et al., 2018). Therefore, it is
difficult to adsorb glyphosate from aqueous solution by polystyrene
because of the weak hydrophobic action as the adsorption driving force.

∗
Corresponding author.
E-mail address: xiaoguqing2005@163.com (G. Xiao).

https://doi.org/10.1016/j.ecoenv.2019.110140
Received 12 November 2019; Received in revised form 25 December 2019; Accepted 26 December 2019
Available online 03 January 2020
0147-6513/ © 2019 Elsevier Inc. All rights reserved.
G. Xiao and Q. Meng
Scheme 1. Resin transformation and the adsorption mechanism of glyphosate by R–Fe3+.
–NH– groups of glyphosate turns into NH2+ in the first ionization
equilibrium. The force of the weak acid groups on NH2+ is weak.
Hence the weak acid resin exhibits very small adsorption capacity for
glyphosate.
Our team is inspired by the modification of zeolite 4A as an ad-
sorbent for glyphosate (reported in the literature of Ecotoxicol. Environ.
Saf. 2018, 155, 1–8). D151 resin preloaded with Fe3+ [denoted as
R–Fe3+] as a new adsorbent for glyphosate from water in the presence
16% NaCl is carried out in the work. It's a surprise that the maximum
adsorption capacity of glyphosate by R–Fe3+ is much higher than that
of other reported adsorbents in the presence 16% NaCl.
2. Experimental
2.1. Material and chemicals
D301 resin, D151 resin and 330 resin were supplied by Anhui
Sanxing resin technology co., Ltd (Anhui Province, China). KBr, NaNO2,
FeCl3, CuCl2 and NiCl2 were analytical reagents. Ultra-pure water was
used to prepare various solutions in the work. The standard glyphosate
was purchased from SigmaeAldrich (Steinheim, Germany).
2.2. D151 resin preloaded with Fe3+
As the resin transformation is described in Scheme 1, 30 g of D151
resin were rinsed with 2 mol/L HCl, then rinsed with deionized water to
the neutral and D151-COOH resin [denoted as R–H+] was obtained.
R–H+ was rinsed with 2 mol/L NaOH. The resin was rinsed with
deionized water to neutral further and D151-COONa resin [denoted as
R–Na+] was obtained. R–Na+ was rinsed with 2 mol/L FeCl3. The resin
was rinsed with deionized water to no outflow of Cl−. D151 resin
preloaded with Fe3+ [denoted as R–Fe3+] was obtained. Fe3+ was
represented with Ni2+ and Cu2+ as the same operation by turns,
R–Ni2+ and R–Cu2+ were obtained accordingly. The method is simple
to operate, low cost and beneficial to industrial production.
2.3. Static adsorption of glyphosate
About 0.200 g (W g) of resin were weighed out and placed into the
flasks containing 25 mL of glyphosate solution. Its initial concentrations
(Ci mg/mL) of glyphosate ranged from 0.5 to 1.1 mg/mL pH value and
the content of salt in glyphosate solution were regulated. Adsorption
equilibrium was reached in a shaker at 150 rpm. The equilibrium
2
Ecotoxicology and Environmental Safety 190 (2020) 110140
concentrations (Ce mg/mL) of glyphosate in the aqueous phase were
determined with UV-3010 spectrophotometer at 242 nm. According to
Chinese national standard GB12686-2004, glyphosate reacted with
sodium nitrite to turn into glyphosate nitroso derivatives under the
acidic condition (Song et al., 2013). Glyphosate nitroso derivatives had
the maximum absorption peak at the wavelength of 242 nm (Song
et al., 2013). The adsorption capacity of glyphosate q(mg/g) was cal-
culated according to (1).
q = 25(Ci-Ce)/W (1)
3. Results and discussion
3.1. Characterization of the resins
1.0 g of R–Fe3+ are added into a cone-shaped flask with 25 mL of
2.0 mol/L H2SO4, then the flask is continuously shaken for 48 h at
298 K so that R–Fe3+ is converted into R–H+ to release of Fe3+ com-
pletely. In the transformation of the two resins, the color of the two
resins changes from brown to white. Fe3+ in desorption solution is
determined at 478 nm by KSCN coloring. Fe3+ inside R–Fe3+ is de-
termined to be 2.85 mmol/g. Zero charge point of the resin (denoted as
pHPZC) is pH value at which the net charge on the resin surface is equal
to zero. Zero charge point of resin is determined by inert electrolyte
titration (Lazarević et al., 2007). pH values of glyphosate solution be-
fore and after adsorption are denoted as pHi and pHf respectively. The
difference of pHi and pHf is denoted as ΔpH. ΔpH against pHi is plotted
as shown in Fig. S1. Zero point of ΔpH corresponds to the zero charge
point of the resin. Zero charge points of R–Na+, R–Fe3+ and R–H+ are
8.26, 3.35 and 2.05, respectively. Zero charge points of R–Na+, R–Fe3+
and R–H+ decrease gradually, which proves that the acidity of the resin
surface increases (Lazarević et al., 2007). Total exchange capacities of
the resins are determined by acid-base neutralization titration (Xiao
and Wen, 2016). The main characteristic parameters of the resins are
listed in Table S1.
3.2. Spectral analysis of the adsorption mechanism of glyphosate by R–Fe3+
3.2.1. FTIR analyses
As shown in Fig. S2, Fourier transform infrared spectra of R–H+,
R–Na+ and R–Fe3+ were measured by ATR method. 2930 cm−1 and
1700 cm−1 can be assigned to C–H stretching and C]O stretching of
R–H+, respectively. 1450 cm−1 and 1160 cm−1 are related to –COO–
G. Xiao and Q. Meng Ecotoxicology and Environmental Safety 190 (2020) 110140

asymmetric stretching and C–O stretching of R–H+. After H+ of R–H+

is replaced by Na+, C]O and C–O of COONa are homogenized into two
coupling equal carbon oxygen bonds, which brings the result that
strong anti-symmetric stretching and symmetric stretching appear at
1550 cm−1 and 1400 cm−1. The characteristic absorption peak of Fe–O
in R–Fe3+ appears at 648 cm−1. The stretching vibration peaks of C–H
(2933 cm−1) and C]O (1704 cm−1) in R–Fe3+ show “red shift”
compared with the infrared spectra of R–H+. Compared with the in-
frared spectrum of R–Na+, the symmetrical stretching vibration peak of
COO− (1415 cm−1) appears “red shift”, while its anti-symmetric
stretching vibration peak (1548 cm−1) exhibits “blue shift”, indicating
that Fe3+ is partially coordinated with COO−. Due to the coordination
of Fe3+ with COO−, Fe3+ inside R–Fe3+ is fixed by the coordination
bond and are not to fall off from R–Fe3+ into aqueous solution.
As for the infrared spectra of R–Fe3+ adsorbed glyphosate [denoted
as R–Fe3+/glyphosate], symmetrical stretching vibration peak of
COO− shows “red shift” from 1415 cm−1 to 1420 cm−1. The anti-
symmetric vibration peak (1548 cm−1) of R–Fe3+ and in-plane bending
vibration peak of N–H (1558 cm−1) of glyphosate exhibit “red shift”, Fig. 1. The comparative adsorption of glyphosate by the five resins
and merge into the broad absorption peak (1590 cm−1) of R–Fe3+/ (m = 0.200 g, V = 25 mL, Ci = 0.5–1.1 mg/mL, T = 298 K, t = 24 h).
glyphosate. The vibration peak of P]O (1155 cm−1), P–OH
(908 cm−1) and the asymmetric stretching vibration of P–O
usually 6 (Ramezanpour et al., 2014). Compared with Ni2+ and Cu2+,
(1070 cm−1) of glyphosate all merge into the broad absorption peak
the vacant orbitals of Fe3+ are partially coordinated by lone pair
(1060 cm−1) of R–Fe3+/glyphosate. All the spectral changes indicate
electrons of COO− in R–Fe3+, and more remaining vacant orbitals can
that R–Fe3+ and glyphosate have been coordinated and integrated into
form coordination bonds with glyphosate. Therefore, adsorption capa-
R–Fe3+/glyphosate after the adsorption of glyphosate.
city of glyphosate by R–Fe3+ is much greater than that of R–Ni2+ and
R–Cu2+. R–Fe3+ exhibits the eximious adsorption performance of
3.2.2. XPS analyses
glyphosate.
XPS analyses before and after adsorption have been carried to elu-
cidate the adsorption mechanism of glyphosate by R–Fe3+ further. As
shown in Fig. S3. (a), N1s and P2p emerge in the spectrum of R–Fe3+/ 3.4. Excellent salt resistance of R–Fe3+
glyphosate, indicating glyphosate molecules are connected on the sur-
face of R–Fe3+ after the adsorption of glyphosate. XPS spectrum of N1s Industrial wastewater used to produce glyphosate contains a lot of
of glyphosate is presented in Fig. S3. (b). The high binding energy (BE) NaCl, and the maximum content of NaCl is 13–15% (Liu et al., 2013;
at 401.9 eV ascribes to NH2+, and the low BE at 399.9 eV assigns to Shen et al., 2013). Therefore, NaCl is selected to investigate the salt
NH (Sheals et al., 2007). N1s of R–Fe3+/glyphosate (Fig. S3. (c)) is resistance of R–Fe3+ for the adsorption of glyphosate, and the max-
divided into three peaks at 401.9, 400.6, and 399.9 eV, which are at- imum content of NaCl is controlled 16%. The experimental results are
tributed to NH2+, Fe–N, and NH, respectively (Fiorilli et al., 2017). shown in Fig. 2. Large adsorption capacities of glyphosate by 330 resin
Fe–N peak provides the direct evidence that Fe3+ inside R–Fe3+ has and D301 resin can be observed in the absence of NaCl. The adsorption
been coordinated with N of glyphosate. P2p BE of glyphosate (Fig. S3. capacities of glyphosate by 330 resin and D301 resin are very small at
(d)) occurs at 133.9 eV (P]O) and 132.9 eV (P–O), and that of R–Fe3+/ 0.3% NaCl and at 2% NaCl respectively. Adsorption of glyphosate by
glyphosate (Fig. S3. (e)) adds a new BE peak at 133.4 eV (P–O–Fe) 330 resin and D301 resin is based on the mechanism of anion exchange.
indicating that Fe3+ inside R–Fe3+ has been coordinated with O of P–O Cl− of NaCl will compete with glyphosate anion for the anion exchange
(Xie et al., 2017). O1s of R–Fe3+ (Fig. S3. (f)) has three chemical states, sites of 330 resin and D301 resin, resulting in significantly lessened
and their corresponding binding energies are 530.1 eV (Fe–O), 531.6 eV adsorption capacity of glyphosate by the two resins. According to Fig. 2,
(C–O) and 533.0 eV (C]O), respectively (Li et al., 2018). The char- NaCl exhibits no significant effect on the adsorption of glyphosate by
acteristic peak of O1s of R–Fe3+/glyphosate (Fig. S3. (g)) occurs at R–Fe3+. Adsorption of glyphosate by R–Fe3+ is not anion exchange
531.3 ev assigning to Fe–O–P and P]O after the adsorption of gly- mechanism, but that Fe3+ inside the resin can form coordination bonds
phosate (Xie et al., 2017). As described adsorption mechanism of gly- with glyphosate. Even if the content of NaCl in glyphosate solution is as
phosate by R–Fe3+ in Scheme 1, XPS spectra reveal the coordination of high as 16%, the salt shows no significant effect on the adsorption of
Fe3+ inside R–Fe3+ with O atoms of P–O and N atoms in glyphosate glyphosate by R–Fe3+. The paper provide the first evidence of Fe3+
molecule. inside D151 resin as an excellent salt resistant adsorbent for glyphosate
from water in the presence 16% NaCl.
3.3. Comparative adsorption of glyphosate
3.5. Effect of pH on the adsorption of glyphosate by R–Fe3+
3+ 2+ 2+
Comparative adsorption of glyphosate by R–Fe , R–Ni , R–Cu ,
R–Na+ and R–H+ is shown in Fig. 1. The adsorption capacity of gly- As shown in Fig. 3, pH exerts a significant effect on the adsorption of
phosate by R–Fe3+ is much larger than that of R–Ni2+, R–Cu2+, R–Na+ glyphosate by R–Fe3+. At pH 3.35, which is the zero charge point of
and R–H+. pKa1 of glyphosate is 0.78 (Fiorilli et al., 2017). Phosphate R–Fe3+, R–Fe3+ shows the net charge of zero and the maximum ad-
group of glyphosate ionizes H+, and H+ binds to amino group of gly- sorption capacity of glyphosate. At pH < 3.35, H+ increases with the
phosate. As there is no added acid or base, glyphosate exits mainly in decrease of pH values of glyphosate solution, and R–Fe3+ gradually
the form of HO–PO2–CH2–NH2+-CH2-COOH. The interaction force turns into R–H+. Fe3+ is desorbed from R–Fe3+, and the adsorption
between the functional groups of glyphosate and Na+ or H+ is small, so capacity of glyphosate decreases. At pH > 3.35, many negative
R–Na+ or R–H+ can hardly adsorb glyphosate. The central ion co- charges exist on the surface of R–Fe3+. The negative charge of R–Fe3+
ordination numbers of Ni2+ and Cu2+ are 4 (Takjoo et al., 2014; Jóvári increase with pH values of glyphosate solution. According to pKa and
et al., 2014), while the central ion coordination number of Fe3+ is the ionization equation of glyphosate, the ionization degree of

3
G. Xiao and Q. Meng
Fig. 2. The salt resistance of the resins (m = 0.200 g, V = 25 mL, Ci = 0.5–1.4 mg/mL, T = 298 K, t = 24 h).
Fig. 3. Effect of pH on the adsorption of glyphosate by R–Fe3+ (m = 0.200 g,
V = 25 mL, Ci = 1.1 mg/mL, T = 298 K, t = 24 h).
glyphosate increases with pH values of glyphosate solution, and the
negative charge of glyphosate anion increase. The repulsive force of the
negative charges between R–Fe3+ and glyphosate anion increase, re-
sulting in the adsorption capacity of glyphosate by R–Fe3+ decreases.
3.6. Adsorption thermodynamics of glyphosate by R–Fe3+
Fig. 4 describes the adsorption isotherms of glyphosate by R–Fe3+.
The greater adsorption capacity of glyphosate by R–Fe3+ is observed
with the higher temperature, indicating an endothermic process in-
volving a chemical reaction. Fe3+ inside D151 resin can form the co-
ordination bonds with glyphosate, and the increasing temperature is
conducive to the formation of the ligand between Fe3+ and glyphosate.
Freundlich equation q = KF Ce n
1
1 1 1
Langmuir equation = +
q qm qm KL Ce
Freundlich equation and Langmuir equation are used for the ad-
sorption isotherms of glyphosate by R–Fe3+. KF and n are the para-
meters of Freundlich equation to reflect the adsorption capacity (Peng
et al., 2019), while qm and KL are the parameters of Langmuir equation
to reflect the adsorption capacity (Wang et al., 2019). The fitting results
of the adsorption of glyphosate by R–Fe3+ are listed in Table S2. The
correlation coefficients (R2 > 0.99) indicate that the adsorption of
Ecotoxicology and Environmental Safety 190 (2020) 110140
Fig. 4. The adsorption isotherms of glyphosate by R–Fe3+ (m = 0.200 g,
V = 25 mL, Ci = 0.5–1.1 mg/mL, t = 24 h, 16%NaCl).
glyphosate by R–Fe3+ is accordance with Freundlich equation, and the
adsorption of glyphosate by R–Fe3+ is heterogeneous (Xiao et al.,
2017). n > 2 indicates that the adsorption of glyphosate by R–Fe3+ is
favorable (Xiao and Wen, 2016). The higher values of KF and n are
observed at the higher temperature for the adsorption of glyphosate by
R–Fe3+, which is consistent with the trend that the adsorption capa-
cities of glyphosate increase with the increase of temperature.
The adsorption thermodynamic parameters such as adsorption en-
thalpy ΔH (kJ/mol), adsorption entropy ΔS (J/(mol K)), and adsorption
free energy ΔG (kJ/mol) can be calculated based on the following
equations (Zhang and Huang, 2017; Yamaguchi et al., 2016; Xiao et al.,
2016):
d ln Ce H
=
(2) dT RT 2 (4)
ΔG = -RTlnKd (5)
(3)
ΔS=(ΔH-ΔG)/T (6)
where qe and Ce are equilibrium adsorption capacity and equilibrium
concentration, respectively. Kd stands the equilibrium solid-liquid dis-
tribution coefficient, and which can be obtained from the intercept of
the ordinate by plotting ln(qe/Ce) versus qe (Yamaguchi et al., 2016). T
(K) stands the temperature, and R (8.314 J/mol K) is the ideal gas
constant. ΔH can be calculated by plotting ln Ce versus 1/T based on Eq.
4
G. Xiao and Q. Meng Ecotoxicology and Environmental Safety 190 (2020) 110140

Fig. 5. The coordination ratio of glyphosate to Fe3+ inside R–Fe3+ (the mole
ratio of glyphosate to Fe3+ inside R–Fe3+ = 0.12:1, 0.24:1, 0.36:1, 0.48:1,
0.72:1, 0.96:1, 1.2:1, 2.4:1, 3.6:1, 4.8:1, 6.0:1, 12:1, T = 298 K, t = 24 h).
the results are shown in Fig. 5. With the increase of the mole ratio of
glyphosate to Fe3+ inside R–Fe3+, the coordinated glyphosate in-
creases. As the mole ratio of glyphosate to Fe3+ inside R–Fe3+ increases
to 2.4: 1, even if glyphosate is added, the coordinated glyphosate re-
mains unchanged. The maximum coordination ratio of glyphosate to
Fe3+ inside R–Fe3+ is 1:1. The maximum coordination ratio is also
described in the adsorption mechanism in Scheme 1. Fe3+ inside
R–Fe3+ is 2.85 mmol/g, and the maximum adsorption capacity (qmax)
of glyphosate by R–Fe3+ is calculated to be 481.85 mg/g.
As compared qmax of glyphosate by R–Fe3+ with the adsorbents in
the literature (Zhou et al., 2017; Zavareh et al., 2018; Jiang et al., 2018;
Yamaguchi et al., 2016; Hu et al., 2011; Xiao and Wen, 2016; Herath
et al., 2016; Yang et al., 2017; Khenifi et al., 2010; Vasiljević et al.,
2019; Shen et al., 2006; Zhou et al., 2014; Milojević -Rakić et al., 2013;
Mayakaduwa et al., 2016) (Table 1), the adsorption capacity of gly-
phosate by R–Fe3+ is much higher than that of the other adsorbents,
except for UiO-67/GO (Yang et al., 2017) and alkalescent fiber FFA-1
(Zhou et al., 2014). However, it is exciting that the adsorption capacity
of glyphosate by R–Fe3+ in the presence 16% NaCl is much higher than
that of the other reported adsorbents. R–Fe3+ is proven to be a pro-
mising salt resistant adsorbent for the efficient recovery of glyphosate
in the high concentration of salt solution.

(4) (Zhang and Huang, 2017). ΔG and ΔS can be calculated according to

Eq. (5) and Eq. (6) (Xiao et al., 2016), respectively. ΔH, ΔG and ΔS are
3.8. Desorption agents of glyphosate
presented in Table S3. The values of ΔH are all positive, illustrating that
the adsorption of glyphosate by R–Fe3+ is endothermic further (Zhang
25 mL of H2O, 2 mol/L NaOH, 2 mol/L H2SO4 and 2 mol/L
and Huang, 2017). In particular, the values of ΔH increase with the
Fe2(SO4)3 are used as desorption agents respectively, and the results are
increase of adsorption capacity. The values of ΔG are negative, con-
shown in Table S4. The desorption rate of glyphosate is only 5.35% as
firming that the adsorption of glyphosate by R–Fe3+ is spontaneous
water is used as the desorption agent. The coordination between gly-
(Lou et al., 2012). Moreover, the absolute values of ΔG increase with
phosate and Fe3+ is stronger than that of water, so the desorption rate
the increasing temperature, implying it is the more spontaneous ad-
of glyphosate by water is small. 2 mol/L NaOH can be used to re-
sorption of glyphosate for the higher temperature. The result is in
generate R–Fe3+. Fe3+ inside R–Fe3+ is easy to bind with OH−, so that
agreement with their capacities of glyphosate by R–Fe3+. The positive
Fe3+ no longer coordinates with glyphosate. 2 mol/L Fe2(SO4)3 is used
values of ΔS can be explained by the release of H2O molecules around
as the desorption agent, and the regeneration ratio of glyphosate is up
Fe3+ after the adsorption of glyphosate. This is the reason that gly-
to 98.92%. More Fe3+ in desorption agent Fe2(SO4)3 will compete with
phosate, as a stronger ligand than H2O molecule, coordinates with
Fe3+ inside R–Fe3+ for glyphosate. Glyphosate adsorbed by R–Fe3+
Fe3+. The positive values of ΔS show that the adsorption of glyphosate
will coordinate with Fe3+ of Fe2(SO4)3, and glyphosate can be desorbed
by R–Fe3+ is the ligand exchange of glyphosate and water.
from R–Fe3+. The desorption rate of glyphosate is up to 99.97% using
2 mol/L H2SO4 as the desorption agent. Under the strong acidic con-
3.7. Coordination ratio of glyphosate to Fe3+ inside R–Fe3+ dition of 2 mol/L H2SO4, R–Fe3+ is converted to R–H+, releasing of
Fe3+ and its ligand of glyphosate. 2 mol/L NaOH, 2 mol/L H2SO4 and
The mole ratio of glyphosate to Fe3+ inside R–Fe3+ (0.12:1, 0.24:1, 2 mol/L Fe2(SO4)3 can all be used for the desorption agent to achieve
0.36:1, 0.48:1, 0.72:1, 0.96:1, 1.2:1, 2.4:1, 3.6:1, 4.8:1, 6.0:1, 12:1) is over 97% regeneration of R–Fe3+ and the recovery of glyphosate.
adopted. The adsorption reaches equilibrium at 298 K, and the co-
ordination ratio of glyphosate to Fe3+ inside R–Fe3+ is calculated, and

Table 1
Comparison of qmax of glyphosate adsorbed by R–Fe3+ with the adsorbents in the literature.
NO Adsorbents qmax/(mg/g) Salt References

1 D201Cu 113.7 18% NaCl Zhou et al. (2017)

2 Cu-zeolite 4A 112.7 No Zavareh et al. (2018)
3 Biochar supported nano-zero-valent iron 80 No Jiang et al. (2018)
4 MnFe2O4-G 39 No Yamaguchi et al., 2016
5 Alum sludge in dewatered form 85.9 No Hu et al. (2011)
6 Alum sludge in liquid form 113.6 No Hu et al. (2011)
7 GQ-08 resin 66.44 16% NaCl Xiao and Wen (2016)
8 Steam activated RHBC 123.03 No Herath et al. (2016)
9 UiO-67/GO 482.69 No Yang et al. (2017)
10 Ni2AlNO3 layered double hydroxide 172.4 No Khenifi et al. (2010)
11 Potassium tungstophosphate on BEA zeolite 92.2 No Vasiljević et al. (2019)
12 Active carbon 58.4 No Shen et al. (2006)
13 Alkalescent fiber FFA-1 565.19 No Zhou et al. (2014)
14 PANI/ZSM-5 61.9 No Milojević -Rakić et al., 2013
15 PANI 59.9 No Milojević -Rakić et al., 2013
16 Woody biochar 44 No Mayakaduwa et al. (2016)
17 (D151-COO)3Fe 481.85 16% NaCl This work

5
G. Xiao and Q. Meng
4. Conclusions
D151 resin preloaded with Fe3+ is simple to operate, low cost and
beneficial to industrial production. XPS spectra reveals the coordination
of Fe3+ inside R–Fe3+ with O atoms of P–O and N atoms in glyphosate
molecule. Fe3+ inside D151 resin exhibits the eximious adsorption
performance of glyphosate and excellent salt resistance in the presence
16% NaCl. The maximum coordination ratio of glyphosate to Fe3+ in-
side D151 resin is 1:1. The coordination adsorption of glyphosate by
R–Fe3+ not only solves the serious environmental problems of gly-
phosate, but also has important economic benefits through the efficient
recovery of glyphosate.
CRediT authorship contribution statement
Guqing Xiao: Methodology, Data curation, Writing - original draft.
Qiudong Meng: Writing - review & editing.
Acknowledgments
We gratefully acknowledge generous support provided by the
National Natural Science Foundation of China (Grant No. 51678225).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ecoenv.2019.110140.
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