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Article
Article
31P
P NMR
NMR Investigations
Investigations on
on Roundup
Roundup Degradation
Degradation by
31
by
AOP
AOP Procedures
Procedures
Marcin H. Kudzin 1,1,*, Renata Żyłła 11, Zdzisława Mrozińska 1 and Paweł Urbaniak 2
Marcin H. Kudzin *, Renata Żyłła , Zdzisława Mrozińska 1 and Paweł Urbaniak 2
11 Textile
TextileResearch
ResearchInstitute,
Institute,Brzezinska
Brzezinska5/15,
5/15, Lodz
Lodz92-103, Poland;
92-103, Poland;zylla@iw.lodz.pl
zylla@iw.lodz.pl(R.Ż.);
(R.Ż.);
zmrozinska@iw.lodz.pl (Z.M.)
zmrozinska@iw.lodz.pl (Z.M.)
22 Faculty
FacultyofofChemistry,
Chemistry,University
UniversityofofLodz,
Lodz,Tamka
Tamka12,
12,Lodz
Lodz90-136,
90-136,Poland;
Poland;pawelurb@chemia.uni.lodz.pl
pawelurb@chemia.uni.lodz.pl
Correspondence:kudzin@iw.lodz.pl;
* Correspondence: kudzin@iw.lodz.pl;Tel.:
Tel.:+48-42-6163-100
+48-42-6163-100
Abstract:
Abstract: The
The reactions
reactions of
of (N-(PhosphonoMethyl)Glycine)
(N-(PhosphonoMethyl)Glycine) PMG PMG with
with HH2O 2 in homogenous systems
2 O2 in homogenous systems
were investigated using 31P NMR (Nuclear Magnetic Resonance). These reactions were carried out
31
were investigated using P NMR (Nuclear Magnetic Resonance). These reactions were carried out in
in
twotwo reaction
reaction modes:
modes: without
without UV UV radiation
radiation and and
underunder UV radiation.
UV radiation. The reactions
The reactions of PMG of PMG
with Hwith
2 O2
H 2O2 without UV radiation were carried out in two modes: the degradations of PMG (0.1 mmol) by
without UV radiation were carried out in two modes: the degradations of PMG (0.1 mmol) by means
means
of 5–10of 5–10 excess
molar molar excess of hydrogen
of hydrogen dioxidedioxide
(PMG-H (PMG-H 2O2 = 1:5 and 1:10) and the degradation of
2 O2 = 1:5 and 1:10) and the degradation of PMG
PMG (0.1 mmol)
(0.1 mmol) in homogenous
in homogenous Fenton reactions
Fenton reactions (PMG-H2(PMG-H
O2 -Fe2+ 2=O1:10:0.05
2-Fe2+ = 1:10:0.05 and 1:10:0.1). All
and 1:10:0.1). All reactions
reactions were carried out at ambient temperature, at pH 3.5, for
were carried out at ambient temperature, at pH 3.5, for 48 h. The reactions 48 h. The ofreactions
PMG (in ofRoundup
PMG (in
Roundup herbicide composition, 12 mmol) with H 2O2 under UV radiation (254 nm) were carried
herbicide composition, 12 mmol) with H2 O2 under UV radiation (254 nm) were carried out using
out
5 ×using
molar5 excess
× molarofexcess
H2 O2 of H2mmol),
(60 O2 (60 mmol), in the
in the pH pH of
range range
2 ≤ofpH 2 ≤≤pH12,≤ for
12, 6for
h.6 In
h. this
In this mode
mode of
of PMG oxidation, the splitting of C-P was observed in the ratios dependent on
PMG oxidation, the splitting of C-P was observed in the ratios dependent on the applied pH of thethe applied pH of
the reaction
reaction mixture.
mixture.
Keywords:
Keywords: glyphosate;
glyphosate; oxidation
oxidation stability;
stability; oxidative
oxidative dephosphonylation;
dephosphonylation; Fenton
Fenton reaction
reaction
1.
1. Introduction
Introduction
Glyphosate
Glyphosate (N-(PhosphonoMethyl)Glycine)
(N-(PhosphonoMethyl)Glycine) (PMG)
(PMG) isis aa broad-spectrum
broad-spectrum systemic
systemic herbicide,
herbicide,
invented
invented by Franz and brought to market in 1974 by Monsanto under the trade name Roundup [1,2].
by Franz and brought to market in 1974 by Monsanto under the trade name Roundup [1,2].
O O
H
C N P(OH)2
HO C C
H2 H2
PMG
Glyphosate, absorbed
Glyphosate, absorbed mainly mainly
throughthrough foliage,a plant
foliage, inhibits inhibits a plant enzyme —5-
enzyme—5-enolpyruvylshikimate-
enolpyruvylshikimate-3-phosphate
3-phosphate (EPSP) synthetase (EC (EPSP) synthetase (EC
2.5.1.19)—involved in 2.5.1.19)—involved
the bio-synthesis ofin the bio-synthesis
aromatic amino acids of
aromatic amino acids (AAA) substrates in a
(AAA) substrates in a build-up of plant lignins [3–5]. build-up of plant lignins [3–5].
A
A significant
significant fraction
fraction of
of glyphosate
glyphosate sprayed
sprayed onon crops
crops returns
returns toto the
the soil,
soil, and
and inin spite
spite of
of strong
strong
adsorption to soil solids [6], is able to contaminate surface water (runoff and erosion)
adsorption to soil solids [6], is able to contaminate surface water (runoff and erosion) [7–9]. [7–9].
Animal
Animal andand epidemiological
epidemiological studies
studies published
published inin recent
recent decades
decades point
point to
to aa potential
potential glyphosate
glyphosate
toxicity [10–12]. Further,
toxicity [10–12]. Further,the
the World
World Health
Health Organization’s
Organization’s International
International AgencyAgency for Research
for Research on Canceron
Cancer concluded that glyphosate is “probably carcinogenic to humans” [13]
concluded that glyphosate is “probably carcinogenic to humans” [13] and Anifandis et al. [14,15] and Anifandis et al.
[14,15] demonstrated that glyphosate/PMG induce
demonstrated that glyphosate/PMG induce DNA fragmentation. DNA fragmentation.
Therefore,
Therefore, various
various treatment
treatment processes
processes have
have been
been investigated
investigated to to reduce
reduce thethe pesticide
pesticide
concentration
concentration in water and to minimize the potential health risks associated with exposure to
in water and to minimize the potential health risks associated with exposure to these
these
Water2019, 11, x; doi: FOR PEER REVIEW www.mdpi.com/journal/water
Water 2019, 11, 331; doi:10.3390/w11020331 www.mdpi.com/journal/water
Water 2019, 11, 331 2 of 16
chemicals by the
Water 2019, 11, x consumption of contaminated water [16–26]. Advanced oxidation processes
FOR PEER REVIEW 2 of(AOPs)
16
are a key technology to solve pesticide contamination problems during both water and wastewater
chemicals
treatment (Tableby 1).
the consumption of contaminated water [16–26]. Advanced oxidation processes (AOPs)
are a key technology to solve pesticide contamination problems during both water and wastewater
treatment
Table (Table 1).
1. Representative applications of advanced oxidation process (AOP) technology in the chemical
degradation of N-(PhosphonoMethyl)Glycine (PMG) and aminomethylphosphonic acid (GlyP ).
Table 1. Representative applications of advanced oxidation process (AOP) technology in the chemical
degradation of N-(PhosphonoMethyl)Glycine (PMG) and aminomethylphosphonic
Phosphorus acid (GlyP)
No P-Herbicide AOP Systems Analysis Reference
Degradation Products
Phosphorus
and GlyP
1 No PMGP-Herbicide Birnessite AOP (Mn 4+ and Mn3+ )
Systems H3 PO4
Degradation VIS (P-Mo Blue)Reference
Analysis [20]
2 PMG (III) m −
Fe (C2 O4 )n /UV (365 nm) Products
H3 PO4 VIS (P-Mo Blue) [21]
3 1 PMG and GlyP Birnessite (Mn(312
4+ and Mn3+) H3PO 4 VIS (P-Mo Blue) [20] [22]
PMG TiO2 /UV nm) H3 PO4 HPLC-UV
2 PMG Fe(III)(C2O4)nm−/UV (365 nm) H3PO4 VIS (P-Mo Blue) [21]
4 PMG O2 /TiO2 /SiO2 /UV (365 nm) H3 PO4 TOC, HPLC [23]
3 PMG TiO2/UV (312 nm) H3PO4 HPLC-UV [22]
4 PMG O
O2/TiO (pH = 6.5 and
3 2/SiO2/UV (365 nm) 10) H3POH PO
34 4 TOC,
TOC, HPLC HPLC-FD [23]
5 PMG and GlyP Photolysis
O3 (pH = 6.5 (292
andnm)
10) H3POH3 PO
4 4 TOC,TOC, HPLC-FD
HPLC-FD [24]
TiO2 /O2 (292 nm) H3 PO4 TOC, HPLC-FD
5 PMG and Gly P Photolysis (292 nm) H3PO4 TOC, HPLC-FD [24]
6 PMG HTiO
2 O2 2/UV (254nm)
/O2 (292 nm) H3POH3 PO
4 4 HPLC-FD
TOC, HPLC-FD [25]
7 6 PMGPMG H O /UV
Birnessite (Mn and Mn )
2 2 4+
(254 nm) 3+ H PO
H3 PO4 + Gly + C-P
3 4 P x 31
HPLC-FD P NMR [25] [26]
7 PMG Birnessite
4+ (Mn
3+ 4+ and Mn3+)
Birnessite (Na Ca K )(Mn , Mn ) O × 1.5 H O. Fe (C O ) H 3PO
(III) 4 +GlyP +mC-P
− x 31P NMR
−
− Fe(C O ) and Fe(C O ) . P [26]
3 −
0.3 0.1 0.1 2 4 2 2 4 n 2 4 2 2 4 3 i
Birnessitedetermination
(Na0.3Ca0.1K0.1using
)(Mn4+, Mn 3+)2O4 × 1.5 H2O. Fe(III)(C2O4)nm− − Fe(C2O4)2− and Fe(Cx2O4)33−. Pi
colorimetrical the phospho-molybdate blue reaction. TOC—total carbon. C-P —unidentified
compound.
colorimetrical determination using the phospho-molybdate blue reaction. TOC—total carbon. C-Px—
unidentified compound.
The various mechanisms of PMG degradation using AOP technology, according to the literature,
The various mechanisms of PMG degradation using AOP technology, according to the literature,
were presented by Manassero [25]. These not always coherent results (Figure 1) led us to investigate
were presented by Manassero [25]. These not always coherent results (Figure 1) led us to investigate
thesethese
process by using 31 P NMR monitoring of the PMG degradation processes. This 31 P NMR
process by using 31P NMR monitoring of the PMG degradation processes. This 31P NMR
technique has has
technique been applied
been forfor
applied the
theanalysis
analysisof
of PMG metabolitesand
PMG metabolites and degradation
degradation products
products in only
in only a a
few earlier research works [26–33].
few earlier research works [26–33].
.
O
HO
H3PO4 + H2N C P(OH)2 + H3C N C CO2H + H3C CO2H
H2 H H2
[21]
GlyP Me-Gly
O
HO./O2.(-)
O H2N C CO2H + H3C P(OH)2
[22] H2
P(OH)2 MeP
Gly
HN O
C
O
OH HO./O2.(-)
-
PMG H3PO4 + H2N C P(OH)2 + H3C N C CO2H + CO2 + NO3
[23] H2 H H2
Me-Gly
GlyP
O O
Mn3+&Mn4+
H3PO4 + H2N C P(OH)2 + R P(OH)2
[26] H2
GlyP RP
deionized water.
(10 mL).
• Solution •of 2Solution
M H2 SO of 0.02 M Fe(II): a sample of FeSO4 × 7H2O [278] (56 mg) was dissolved in water
4 (in 20% D2 O): samples of 2.5 M H2 SO4 (20 mL) were diluted to 25 ml with
(10 mL).
D2 O (5 mL).
• Catalase solution: a sample of 10 mg of catalase was dissolved in 50 mL of distilled or
deionized water.
2.3. Instruments
• Solution of 2 M H2SO4 (in 20% D2O): samples of 2.5 M H2SO4 (20 mL) were diluted to 25 ml
31 P with D2O (5 mL).
NMR spectra were recorded on a Bruker AC 200 spectrometer operating at 81.01 MHz and on
a Bruker Avance III 600 spectrometer operating at 242.9 MHz. 1 H NMR spectra were recorded on a
2.3. Instruments
Bruker Avance 31
31P III
NMR 600 spectrometer
spectra were recordedoperating at AC
on a Bruker 600200Hz. Positive chemical
spectrometer operating atshift
81.01 values
MHz andof P were
reported for
on acompounds
Bruker Avanceabsorbed at loweroperating
III 600 spectrometer fields than H3MHz.
at 242.9 PO4 .1H NMR spectra were recorded on
a Bruker Avance III 600 spectrometer operating at 600
The pH measurements were performed using a CX-505 multifunction Hz. Positive chemical shift values of 31P
laboratory were (Elmetron,
meter
reported for compounds absorbed at lower fields than H3PO4.
Zabrze, Poland) equipped with a combination pH electrode EPP-1 (Elmetron, Zabrze, Poland).
The pH measurements were performed using a CX-505 multifunction laboratory meter
The chemical degradation
(Elmetron, of aqueous
Zabrze, Poland) solutions
equipped of the Roundup
with a combination herbicide
pH electrode EPP-1 formulation in PMG-H2 O2
(Elmetron, Zabrze,
and PMG-H 2 O2 -UV
Poland). systems
The chemical was carried
degradation out. Experiments
of aqueous were performed
solutions of the Roundup in the reactor
herbicide formulation in shown
in Figure PMG-H
2. 2O2 and PMG-H2O2-UV systems was carried out. Experiments were performed in the reactor
shown in Figure 2.
5
B
1 2
(a) (b)
Figure 2.Figure 2. Reactor used for Roundup degradation by means of AOP technology. (a) Figure of a
Reactor used for Roundup degradation by means of AOP technology. (a) Figure of a
photoreactor with UV lamp used for the oxidation of PMG by means of UV/H2O2. (b) Schematic
photoreactor with UV lamp used for the oxidation of PMG by means of UV/H2 O2 . (b)
diagram: 1—glass reactor; 2—quartz tube with UV lamp (254 nm; 22 W); 3—peristaltic pump; 4—
Schematic
diagram: reactor
1—glass reactor;
connector; 5—UV 2—quartz tube with
power supply; UV lampdetector;
6—temperature (254 nm; A, 22 W); 3—peristaltic
B—samples. Applied pump;
4—reactor connector;
conditions: PMG 5—UV
(12 mmol),power supply;
H2O2 (60 mol) in 6—temperature detector;
an aq. solution (3.7 L) at differentA,initial
B—samples.
pH values Applied
applied:
conditions: PMG 2 ≤(12
pHsmmol),
≤ 12. Irradiation
H2 O2 time
(60 was
mol)upin
to an
360 aq.
min. solution
Temperature was
(3.7 L)25at°C.different initial pH values
applied: 2 ≤ pHs ≤ 12. Irradiation time was up to 360 min. Temperature was 25 ◦ C.
Water 2019, 11, 331 5 of 16
Table 3. Preparation of the reaction mixtures for PMG-H2 O2 and PMG-H2 O2 -Fe2+ systems.
PMG 10 M H2 O2 FeSO4
Exp. H2 O
0.1 mmol 0.5 mmol 1 mmol 0.01 M 0.02 M
1 17 mg 0.55 mL 0.05 mL − − −
2 17 mg 0.5 mL − 0.1 mL − −
0.5 mL
3 17 mg − − 0.1 mL −
(0.005 mmol)
0.5 mL
4 17 mg − − 0.1 mL −
(0.01 mmol)
Table 4. Preparation of the reaction mixtures for AOP degradations of PMG in Roundup herbicide.
Table
Water 2019, 11, x FOR PEER 5. Representative works on pKa determination of PMG.
REVIEW 6 of 16
pK
Table 5. Representative works on pKa determination of PMG.
No. Method Reference
pK1 pK2 pK3 pK4
pK
No. Method Reference
1 2.0 pK1 2.6pK2 pK5.6
3 pK4 10.6 pH metric titration [40]
2 1 2.0 2.322.6 5.6
5.86 10.6 10.86 pH metric
pHtitration [40]
metric titration [41]
2 2.32 5.86 10.86 pH metric titration
1 H and 31 P NMR [41]
3 <1 2.0 5.5 10.5 1 [42]
3 <1 2.0 5.5 10.5 H and 31P NMR [42]
4 0.34 2.32.3 5.6 1 and 31 P NMR
0.3 5.6 10.6 10.6 1H and 31H P NMR [43] [43]
5 5 2.092.09 5.52
5.52 10.28 10.28 pH metric titration
pH metric titration [44] [44]
logβ 9.66 logβ 14.86 log β 16.44
6 logβ 9.66 logβ 14.86 pH metric titration
log β 16.44 [45]
6 (1.58) (5.20) (9.66) pH metric titration [45]
(1.58) (5.20) (9.66)
O H O O H O -H+ O H O
+
-H+ + + -
C C N C P OH C C N C P OH C C N C P O
H2 H2 H2 H2 - +H+ - H2 H2
HO H OH +H+ HO H O O H OH
pKa1 pKa2
H4L+ H3L H2L-
O H O O H O O O
-H+ + -
-H+
+ - -
C C N C P O C C N C P O C C N C P O
- H2 H2 +H+ - H2 H2 -
+H+ H2- H2 -
O H OH O H O O H O
pKa3 pKa4
H2L- HL2- L3-
-H+
-H+
+H+ +H+
(pKa3) O O (pKa4)
-
C C N C P O
- H2 H2
O H OH
[HL2-]*
Figure
Figure 3. 3.Dissociation/protonation
Dissociation/protonation equilibria
equilibria ofof glyphosate
glyphosate(lower
(lowerbranch
branch(arrows
(arrowsininmagenta)
magenta)
considering the reports of Peixoto et al., 2015 [45] and Liu et al., 2016 [46].)
considering the reports of Peixoto et al., 2015 [45] and Liu et al., 2016 [46]).
Despite
Despite thethelarge
largeamount
amountofofresearch
research data,
data, there
there is
is conflicting
conflicting information
informationininthetheliterature
literature
concerning the first protonation step of glyphosate, namely whether the first dissociable
concerning the first protonation step of glyphosate, namely whether the first dissociable proton proton in
the HL 2− formations is attached to the nitrogen atom of the amino group or to the oxide atom of the
2 −
in the HL formations is attached to the nitrogen atom of the amino group or to the oxide atom
phosphonate function. As a matter of fact, only two recent reports consider that the first protonation
of the phosphonate function. As a matter of fact, only two recent reports consider that the first
step occurs on the one of the oxygen atoms in the phosphonate group (Figure 4, magenta arrows)
protonation step occurs on the one of the oxygen atoms in the phosphonate group (Figure 4, magenta
[45,46].
arrows) [45,46].
On the basis of this analysis of the speciation graph (Figure 4), we assumed that in aqueous
On the basis of this analysis of the speciation graph (Figure 4), we assumed that in aqueous
solutions PMG exists in the following forms: at pH = 0—mainly as H4L++form; at pH = 1.5—mainly as
solutions PMG exists in the following forms: at pH = 0—mainly as H L form; at pH = 1.5—mainly as
H3L form; at pH = 3.5–4—mainly as H2L−; at pH = 8—mainly as HL2−4; and at pH ≥ 12—mainly as L3−
L form; at pH = 3.5–4—mainly as H2 L− ; at pH = 8—mainly as HL2− ; and at pH ≥ 12—mainly as
H3 form.
L3− form.
Water
Water2019,
2019,11,
11,xxFOR
FORPEER
PEERREVIEW
REVIEW 77of
of16
16
Figure
Figure4.4.Figure
Diagram
Diagram
Diagram of
ofPMG
4. DiagramPMG ofspecies
PMG
species distribution
species
distribution calculated
distribution using
calculated
calculated the
using
using pK
the
the pKpKa values
valuesof
values
a avalues ofAppleton
of Appleton
Appletonet etetal.
al. [42]
[42]
al. [42]
(pK a1 <<
(pKa1 1; pK
(pK
1;pK
a1 < 1;
<= 2.0;
1; pK
pKa2a2= =2.0;
a2
a1 pK =
2.0;pK
a2 pKa3 =
2.0; 5.5;
pK pK
=
= 5.5;
a3
= 5.5;
a3a3
5.5;
pKpK
a4 =
a4 =
10.5),
pK = and
10.5),
= 10.5),
a4
a410.5),
the
and
andand HySS
the
thethe program
HySS
HySS
HySS program
program
program (Alderighi
(Alderighi
(Alderighi
(Alderighi et
etal.,
al.,
et al., 1999)
1999)
et al.,
1999)[47].
[47].
1999) [47].
[47].
Figure
Figure 5.
5. Dissociation/protonation
Dissociation/protonation
Dissociation/protonation equilibria
dioxideof
equilibria
dihydrogen
equilibria ofdihydrogen
dihydrogendioxide.
speciation
of dihydrogen dioxide.
dioxide.
100
dihydrogen
dihydrogen dioxide
dioxide speciation
speciation
100
100
80
% formation relative to A
80
80
toAA
60
HO-OH HO-O-
relativeto
formationrelative
60
60 40 HO -
HO--OH
OH HO
HO--O
O-
%formation
40
40 20
HO-O+H2
%
20 0
20
-2 2 6 10 14
pH
HO +
HO--O O+HH22
Figure 6. Diagram of0dihydrogen dioxide distribution: percent species formation calculated with the
0
HySS program (Alderighi-2
-2 2
et al., 1999)
2
[47] for a 6 10
10 millimolar
6 10 14
solution of
14
H2O2 (pKa1 = −3.1, pKa2 =
11.7). pH pH
Figure
Figure6.6.
Figure Diagram
6. Diagram ofdihydrogen
Diagramof dihydrogendioxide
dioxidedistribution:
distribution:percent
percentspecies
percent speciesformation
species formationcalculated
formation calculatedwith
calculated withthe
with the
the
HySS
HySS program
program (Alderighi
(Alderighi et
et al.,
al., 1999)
1999) [47]
[47] for for
a 10a 10 millimolar
millimolar solution
solution of H 2 of
O 2 H 2Oa1
(pK 2 (pK
= − =
3.1,
a1
HySS program (Alderighi et al., 1999) [47] for a 10 millimolar solution of H2O2 (pKa1 = −3.1, pKa2 = −3.1,
pK a2 pK
= a2 =
11.7).
11.7).
11.7).
Water
Water 2019,
2019, 11,
11, x331
FOR PEER REVIEW 88of
of16
16
Water 2019, 11, x FOR PEER REVIEW 8 of 16
3.2. Reaction of PMG and H2O2
3.2. Reaction
3.2. Reaction of of PMG
PMG and
and H22OO22
It is generally knownHthat the oxidation potential of H2O2 greatly increases during UV irradiation
It is
(Mierzwa
It isgenerally
generally known
et al., 2018, that the
the oxidation
and references
known that oxidation potential
cited therein) [50]of
potential Hwell
asH 22OO22greatly
greatly
as increases
in theincreases during
presenceduring UV
of metal
UV irradiation
ions (Figure
irradiation
(Mierzwa
7) [50–55]. et al., 2018, and references cited therein) [50] as well as in the presence
(Mierzwa et al., 2018, and references cited therein) [50] as well as in the presence of metal ions (Figure of metal ions
(Figure
7) [50–55]. 7) [50–55].
hν .
H2O2 +
-.
hν HO H O O2 + H + HOH
. 2 2 -. +
HO O2 + H + HOH
HO-OH
2+
HO-OH Fe
2+ 3+ . -
Fe Fe + HO + HO
3+ . -
Fe + HO + HO
Figure 7. Activation of dihydrogen peroxide via the generation of radicals.
Figure 7.
Figure Activationof
7. Activation ofdihydrogen
dihydrogen peroxide
peroxide via
via the
the generation
generation of
of radicals.
radicals.
Therefore, we assumed that the reaction between PMG and dihydrogen peroxide consumed
Therefore,
eitherTherefore, we
we assumed
the molecular form ofthat
assumed H 2O
thatthe inreaction
2 thethe between
absence
reaction PMG and and
of irradiation,
between PMG dihydrogen
or hydroxide peroxide
dihydrogen and consumed
peroxide
peroxide either
radicals
consumed
the molecular
during
either the form ofform
UVmolecular
irradiation H2in
or Oof in
2the the absence
H2presence
O2 in theof of irradiation,
Fenton
absence or The
ofreagents. hydroxide
irradiation, results
or and peroxide
of PMG
hydroxide radicalsradicals
degradation
and peroxide during
in both
UV
modesirradiation
during are or
UVillustratedin the presence
irradiationinorFigure
in the 8. of Fenton reagents. The results of PMG degradation in both
presence of Fenton reagents. The results of PMG degradation in both modes
are illustrated
modes in Figure
are illustrated 8.
in Figure 8.
[%] 100
[%] 100
80
80
60
60
40
40
20
20
0
0 0 10 20 30 40 50
0 10 20 30 40 [h]
50
PMG-H2O2 (a) PMG-H2O2 (b) PMG-H2O2-Fe+2 (c) PMG-H2O2-Fe+2
[h] (d)
PMG-H2O2 (a) PMG-H2O2 (b) PMG-H2O2-Fe+2 (c) PMG-H2O2-Fe+2 (d)
Figure 8. The profiles of PMG consumption in reaction with H2 O2 in PMG-H2 O2 and PMG- H2 O2 -Fe2+
Figure 8. at
ThepHprofiles of PMG2 O consumption in reaction 2+ 2+=
systems = 3.5: PMG:H 2 = 1:5 (PMG-H 2 O2 (a)) with H2O(PMG-H
and 1:10 2 in PMG-H2 O22O 2 and
(b)); PMG-2H
PMG:H O22O 2-Fe
:Fe
systems 2+ (c)); 2+ (d))
Figure 8.at(PMG-H
1:10:0.05 ThepHprofiles
=3.5:
2 O2PMG:H
-FePMG
of 2O = 1:51:10:0.1
2 and (PMG-H
consumption 2O2 (a))
in(PMG-H
reaction 2Oand
2 -Fe1:10
with H 2O2(PMG-H 2O22O
in(residual
PMG-H (b));
PMG
2 and PMG:H
(%) vs. 2H
PMG- O :Fe 2+ =
exposure
22O 2-Fe2+
1:10:0.05
time (h)).(PMG-H
systems 2O2-Fe
at pH =3.5: 2+
PMG:H (c));2O
and
2 = 1:10:0.1 (PMG-H
1:5 (PMG-H O2-Fe
2O2 2(a)) and(d))
2+ (residual
1:10 (PMG-H PMG (%) vs.
2O2 (b)); exposure
PMG:H 2O2:Fe time
2+ =
(h)).
1:10:0.05 (PMG-H2O2-Fe2+ (c)); and 1:10:0.1 (PMG-H2O2-Fe2+ (d)) (residual PMG (%) vs. exposure time
The reaction of PMG with H2 O2 , both with H2 O2 and H2 O2 -Fe3+ , did not occur at the applied
(h)).
pH =The 3.5,reaction
at whichofPMGPMGexists
with mainly
H2O2, both in the H2 LH−2O
with protonated
2 and H2O2on -Fenitrogen
3+, did not form
occur(Figures
at the 3applied
and 4) and
pH
hydrogen
= 3.5,The peroxide
at which
reaction PMG mainly in
existswith
of PMG H
mainly L forms
2H2Oin (Figures
the H
2, both 5 and
2L protonated
with − 6).
H2O2 and Hon Therefore,
nitrogen
2O2-Fe 3+ we assumed
, did form that
(Figures
not occur the protonation
at the3 applied
and 4) and pH
=of3.5,
theat
hydrogen amino function
peroxide
which in PMG
PMG mainly
exists inefficiently
mainly H2Linforms the reduces
H2(Figuresthe interaction
5 andon6).
L− protonated of PMGform
Therefore,
nitrogen andwe H2 O 2 (no
assumed
(Figures 3 trace
and of and
that
4) P-C
the
bond splitting
protonation
hydrogen of was
peroxide observed
the amino
mainly in
in aH
function 48-h
2in period)
L PMG
forms (Figure 8).
efficiently
(Figures However,
reduces
5 and during thewe
the Therefore,
6). interaction irradiation
of PMG
assumedandofHthat
aqueous
2O2 (no
the
solutions
trace of PMG
of P-C bond
protonation (in the
of thesplitting form of the
was observed
amino function herbicide
in PMG Roundup)
in aefficiently
48-h period) and
(Figure
reduces H O
the8). (1:5),
However,
2 interaction
2 for a pH
during
of range
PMGthe and H22O≤2 (no
of pH
irradiation
≤ aqueous
of
trace12,ofthe
P-Csplitting
solutions ofof
the
bond splitting P-C
PMGwas(inbondtheof
observed PMG
form a was
inof observed,
the herbicide
48-h to an 8).
Roundup)
period) (Figure extent anddependent
However, (1:5),on
H2O2during the
for
the pH range
of the
airradiation
pH
applied
of ≤ pHsolution
2aqueous ≤ 12, the (Figures
splitting 9 and
of the 10).
P-C Is
bondworth
of noting
PMG wasthat the
observed,irradiation
to an of
extent
solutions of PMG (in the form of the herbicide Roundup) and H2O2 (1:5), for a pH range aqueous
dependent PMG on solution
the pH
without
of 2the
≤ pH H≤212,
O2 the
applied during
solution a 48-hofperiod
(Figures
splitting 9 and
the P-C did not
bond exhibit
10).ofIsPMG any
worthwas sign
noting ofthat
observed,PMG the
to decomposition
anirradiation of(100%
extent dependent aqueous of PMG).
on PMG
the pH
solution withoutsolution
of the applied H2O2 during
(Figuresa 48-h
9 andperiod10).did
Is not exhibit
worth notinganythat
signthe of PMG decomposition
irradiation of aqueous (100%
PMG of
PMG).
solution without H2O2 during a 48-h period did not exhibit any sign of PMG decomposition (100% of
PMG).
Water 2019, 11, x FOR PEER REVIEW 9 of 16
Water 2019, 11, 331 9 of 16
Water 2019, 11, x FOR PEER REVIEW 9 of 16
[%]100
[%]100
80
80
60
60
40
40
20
20
0
0 1 2 3 4 5 6
0 [h]
0 pH2 1 pH4 2 pH6 3 pH8 4 pH10 5 pH12 6
[h]
pH2 pH4 pH6 pH8 pH10 pH12
Figure 9. The profile of PMG consumption in reactions with H2O2 in PMG-H2O2-(UV) systems (with
UV irradiation)
Figure carried
9. The profile of out
PMG at consumption
a pH range ofin
2 ≤reactions
pH ≤ 12 with
and aHtemperature
O in PMG-Hof 25
2 O°C (residual
2 -(UV) PMG
systems
Figure 9. The profile of PMG consumption in reactions with H2O22 in2 PMG-H2O2-(UV) systems (with
(with UVexposure
(%) vs. irradiation) (h)). out at a pH range of 2 ≤ pH ≤ 12 and a temperature of 25 ◦ C (residual
carried
time
UV irradiation) carried out at a pH range of 2 ≤ pH ≤ 12 and a temperature of 25 °C (residual PMG
PMG (%) vs. exposure time (h)).
(%) vs. exposure time (h)).
[%] 100
[%] 100
80
80
60
60
40
40
20
20
0
0 1 2 3 4 5 6
0
[h]
0 1 2 3 4 5 6
13.6 10.6 -0.071 [h]
Figure
Figure10. 10.The
Theprofile ofof
profile PMG reaction
PMG reaction
13.6
with H2H
with O22Oin 10.6 2 O2 -(UV)
PMG-H
2 in PMG-H
systems (UV; 25 ◦ C) carried out
-0.071
2O2-(UV) systems (UV; 25 °C) carried out
atatpH = =1212(relative P-compounds contribution (Gly P :−
pH (relative P-compounds contribution (Gly: P13.6
: 13.6ppm,
ppm,PMG:
PMG: 10.6 ppm;
10.6 Pi P
ppm; 0.071 ppm) (%)
i: −0.071 ppm) (%)
Figure 10.
vs.vs.exposition The profile of PMG reaction with H 2O2 in PMG-H2O2-(UV) systems (UV; 25 °C) carried out
expositiontimetime(h)).
(h)).
at pH = 12 (relative P-compounds contribution (GlyP: 13.6 ppm, PMG: 10.6 ppm; Pi: −0.071 ppm) (%)
vs. exposition
The residual PMG quantities were calculated from the corresponding 31 P NMR spectra using
time (h)).
The residual PMG quantities were calculated from the corresponding 31P NMR spectra using
Equation (1):
Equation (1):
The residual PMG quantities were calculated S(PMG)from the corresponding 31P NMR spectra using
PMG = × 100%, (1)
Equation (1): S +SS((R−P)) + S(Pi)
PMG = (PMG) × 100%, (1)
S( 31 ) +S(S( ) ) + S( )
where S(PMG) , S(R−P) , and S(Pi) PMG are
= the P signals corresponding × 100%,to PMG, phosphonic acids, (1)
where
and S(PMG), phosphate,
inorganic S(R−P), and S(Pi) S(
are the 31P signals
respectively. + S( ) + S( to) PMG, phosphonic acids, and inorganic
) corresponding
TheS31
phosphate, respectively.
P NMR spectra of the degradation mixtures of PMG-H2 O2phosphonic -(UV) (UV; 25 ◦ C) recorded for
where (PMG), S(R−P), and S(Pi) are the 31P signals corresponding to PMG, acids, and inorganic
The
reactions 31P NMR
carried out
phosphate, respectively. spectra
at pH of
= 2,the
8, degradation
10, and 12 aremixtures of
presented PMG-H
in Figure 2O 2-(UV)
11. For (UV;
the 25 °C) recorded
identification of thefor
reactions
reaction carried
products out
of at
PMG-HpH =
O 2, 8,
-(UV)10, and 12
mixtures, are presented
we recorded in
the 31 P NMR
Figure 11. For the
spectra identification
of PMG of
potentialthe
The 31P NMR spectra of 2 the
2 degradation mixtures of PMG-H2O2-(UV) (UV; 25 °C) recorded for
reaction products of PMG-H 2O2-(UV)
31 P))we
mixtures, recorded in the
degradation products. The chemical shifts (δ( of these compounds 31P NMR
areForspectra
listed of PMG6. potential
reactions carried out at pH = 2, 8, 10, and 12 are presented Figure 11. theinidentification
Table of the
degradation
reaction products.
products The chemical
of PMG-H shifts (δ( P)) of these compounds are listed in Table 6.
31
2O2-(UV) mixtures, we recorded the 31P NMR spectra of PMG potential
degradation products. The chemical shifts (δ(31P)) of these compounds are listed in Table 6.
Water 2019, 11, 331 10 of 16
Water 2019, 11, x FOR PEER REVIEW 10 of 16
(a)
(b)
(c)
(d)
(e)
(f)
Figure11.
Figure Representative 31
11.Representative 31P NMR spectra of the degradation mixtures of PMG-H2O2-(UV) carried
NMR spectra of the degradation mixtures of PMG-H2 O2 -(UV) carried
outatatpH
out pH== 2–12
2–12 (UV; ◦
(UV; 25 °C),
C), recorded after
after aagiven
givenreaction
reactiontime.
time.(a)(a)3131
PP NMR
NMR spectrum
spectrum ofof
thethereaction
reaction
mixturerecorded
mixture recordedbefore
beforeradiation
radiation (dissolved
(dissolved in in 22 M SO44/D
MHH22SO /D2SO
2 SO4/);/);
4 (b)(b)
reaction
reactionmixture
mixture after UV
after UV
radiationat
radiation atpH
pH== 2 (reaction time 360
360 min);
min); (c)(c)reaction
reactionmixture
mixtureafter
afterUVUVradiation
radiationatatpH
pH= =
8 (reaction
8 (reaction
time360
time 360min);
min); (d)
(d) reaction
reaction mixture after UVUV radiation
radiationat atpH
pH==10 10(reaction
(reactiontime
time360
360min); (e)(e)
min); reaction
reaction
mixture after UV radiation at pH = 12 (reaction time 30 min); (f) reaction mixture after
mixture after UV radiation at pH = 12 (reaction time 30 min); (f) reaction mixture after UV radiation atUV radiation
at pH
pH = 12= (reaction
12 (reaction time
time 360360 min).
min).
Water 2019, 11, 331 12 of 16
Water 2019,6.11,31xPFOR
Table PEER REVIEW
Chemical shifts (δ(ppm)) of PMG and its potential degradation products in acidic 12
andof 16
basic solutions.
Table 6. 31P Chemical shifts (δ(ppm)) of PMG and its potential degradation products in acidic and
basic solutions. 2 M HCl
Comp. PMG GlyP Me-GlyP 2 M
MeHCl
2 -Gly
P Me-PO3 H2 H3 PO4 H3 PO3
δ (31Comp.
P) PMG Gly P Me-Gly P Me2-Gly P Me-PO3H2 H3PO4 H3PO3
δ (31P)
10.6 13.9 11.4 9.4 30.7 −0.47 5.15
(ppm)
10.6 13.9 11.4 9.4 30.7 −0.47 5.15
(ppm)
2 M KOH
2 M KOH
Comp. P P -GlyPP
Comp. PMG PMG Gly GlyP Me-GlyP
Me-Gly Me
Me22-Gly Me-PO
Me-PO 3H
3H
H3 PO
2 2 H3PO
H PO3
4 4 H3PO33
31
δ ( P)δ ( P)
31
16.3
16.3 19.3
19.3 16.0
16.0 15.0
15.0 20.5
20.5 5.45.4 3.2 3.2
(ppm) (ppm)
P δ(ppm):
31 P31δ(ppm): in 2inM 2HCl
M solutions
HCl solutions (protonated
(protonated forms offorms of in
P-acids); P-acids);
2 M KOH in solutions
2 M KOH solutions
(deionized (deionized
forms of P-acids).
forms of P-acids).
The results of 3131P NMR investigations on PMG degradation with H2 O2 are shown graphically
The results of P NMR investigations on PMG degradation with H2O2 are shown graphically in
in Figure
Figure12.
12.
O
2 < pH < 10
HO P(OH)2 + PMG
O O
pH = 12
HO P(OH)2 + H2N P(OH)2 + PMG
C
H2
GlyP
O O O O
H H2O2 H
C N P(OH)2 N P(OH)2 or H3C P(OH)2
HO C C H3C C
H2 H2 UV H2
Me-GlyP -
O O
PMG
+
HO2C N P(OH)2
C
O OH O H2
H
C N P(OH)2
HO C C O-PMG
H2 H2
-
HO-PMG
O
+
HO2C N H
C
H2
P(OH)2
O
Figure 12.Possible
Figure12. Possible degradation pathsof
degradation paths ofPMG
PMG(reaction
(reactiontime:
time:4848
h).h).
4. 4.
Conclusions
Conclusions
The data
The presented
data presentedsuggest the PMG
suggest the PMG inertness towardtoward
inertness H2 O2 inH2the
O2 modes
in the without UV irradiation,
modes without UV
both with (PMG-H O -Fe 2+ ) as well as without Fe 2+ catalyst (PMG-H
irradiation, both with2 2 (PMG-H2O2-Fe ) as well as without Fe catalyst
2+ 2+ 2 2(PMG-H2O2). considering
O ). The data The data
theconsidering
reaction modes of PMG
the reaction modeswithofHPMG2 O2 under
with HUV irradiation
2O2 under (PMG- H(PMG-
UV irradiation 2 O2 -(UV))H2O2exhibit the slow
-(UV)) exhibit
degradation of PMG atof
the slow degradation ≤ pHat≤210,
2 PMG ≤ pHwhich
≤ 10,becomes faster at
which becomes pH at
faster = 12.
pH The
= 12.analysis
The analysis of 31
of the P NMR
the 31P
spectra of PMG-H2 O2 reaction mixtures obtained for reactions carried out at 2 ≤ pH ≤ 10 indicate the
NMR spectra of PMG-H 2 O 2 reaction mixtures obtained for reactions carried out at 2 ≤ pH ≤ 10 indicate
the presence
presence of PMG
of initial initialand
PMG H3 POand4 , H 3PO
and the4, and the of
mixture mixture P , andGly
of PMG,
PMG, Gly P, and H3PO43/H
H3 PO −xxPO 3−x for
4 /Hx PO4 for 4reactions
reactions
carried carried
out at pH =out 12. at
The pH = 12. The
results results
suggest thesuggest the slowof
slow formation formation of an intermediate
an intermediate PMG × H2PMG O2 phase×
H O phase in the first stage of degradation which decomposes very fast
in the first stage of degradation which decomposes very fast (no intermediates were observed in the
2 2 (no intermediates were
observed
31 P in the 31by
NMR spectra) P NMR spectra)of
the scission bythe
theP-Cscission
bondofof the P-C and
PMG bondtheof PMG and therelease
subsequent subsequent release
of phosphoric
of phosphoric
acid/phosphate ion. acid/phosphate ion.
Recapitulating, in the experiments carried out without UV radiation we observed:
Water 2019, 11, 331 13 of 16
Author Contributions: M.H.K. designed the research study and contributed to the data interpretation and to
the manuscript drafting and revisions and was involved in the concept of the research study, analyzed the data,
and contributed to writing the manuscript. R.Ż. participated in the publication preparation. Z.M. performed
experiments. P.U. recorded N.M.R. spectra and analyzed the experimental data.
Funding: This research was funded by the Polish Ministry of Science and Higher Education within statutory
research work carried out in 2018 at the Textile Research Institute, Łódź, Poland.
Conflicts of Interest: The authors declare no conflict of interest.
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