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OH
Page 1 ofEnvironmental 26 ELECTROPHILICScience & Technology OH ROUTE
OH OH
OXIDATION & CONJUGATION
CH3
CH3 NO 2 OH OH
RADICAL Plus Environment ACS Paragon ROUTE
O 2N
CH3
Environmental Science & Technology
1
Nighttime aqueous-phase formation of
2
nitrocatechols in the atmospheric condensed
3
phase
Page 2 of 26
4 5
Kristijan Vidović,† Damjan Lašič Jurković,‡ Martin Šala,† Ana Kroflič,†* and Irena Grgić†*
6 †
7
Department of Analytical Chemistry, National Institute of Chemistry, SI-1000 Ljubljana,
8
Slovenia
9 ‡
10 11
Department of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia
12 13
*
Corresponding Authors
14
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Environmental Science & Technology
15
Abstract:
16
Yellow-colored methylnitrocatechols (MNC) contribute to the total organic aerosol mass and
17
significantly alter absorption properties of the atmosphere. To date, their formation
18
mechanisms are still not understood. In this work, the intriguing role of HNO2 (catalytic and
19
oxidative) in the dark transformation of 3-methylcatechol (3MC) under atmospherically
20
relevant aqueous-phase conditions is emphasized. Three possible pathways of dark 3-methyl-
21
5-nitrocatechol and 3-methyl-4-nitrocatechol formation, markedly dependent on reaction
22
conditions, were considered. In the dominant pathway, HNO2 is directly involved in the
23
transformation of 3MC via consecutive oxidation and conjugated addition reactions (non-
24
radical reaction mechanism). The two-step nitration dominates at pH around the pKa of
25
HNO2, which is typical for atmospheric aerosols, and is moderately dependent on
26
temperature. Under very acidic conditions, the other two nitration pathways, oxidative
27
aromatic nitration (electrophilic) and recombination of radical species, gain in importance.
28
The predicted atmospheric lifetime of 3MC according to the dominant mechanism at these
29
conditions (2.4 days at pH 4.5 and 25 °C) is more than 3-times shorter than via the other two
30
competitive pathways. Our results highlight the significance of catechol oxidation-conjugated
31
addition reaction in nighttime secondary nitroaromatic chromophore formation in the
32
atmosphere, especially in polluted environments with high NOx concentrations and relatively
33
acidic particles (pH around 3).
34
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35
Introduction
36
One of the most important properties of ambient volatile organic compounds (VOC) driving
37
the formation of secondary organic aerosol (SOA) is water solubility. Water-soluble organic
38
pollutants emitted into the troposphere in the gaseous form partition into the atmospheric
39
aqueous phase (clouds, fog, moist aerosols). There they can transform into low-volatility
40
products that remain in the particulate phase even after water evaporates and contribute
41
substantially to the atmospheric SOA mass. 1 Fundamentally, mechanisms of these reactions
42
are not always the same as of those in the gaseous phase. However, gas-phase reactions
43
predominantly proceed through molecular-type intermediates (e.g. activated complexes),
44
whereas aqueous-phase reactions often involve charged molecular forms and hydrated
45
species.2 Besides many short-lived radicals (OH•, NO3•, SO4•−),3 other non-radical oxidants
46
such as hydrogen peroxide (H2O2), organic hydroperoxides (ROOH), ozone (O3)4 and also
47
nitrous acid (HNO2) take an important part in aqueous-phase transformations. Although the
48
role of HNO2 in the atmospheric waters is not yet clear,5-9 its importance as a catalyst in
49
condensed-phase aromatic nitration has already been established.10-16 Furthermore, aromatic-
50
nitration products, particularly abundant methylnitrocatechols (MNC), are significant
51
contributors to atmospheric brown carbon (BrC),17 i.e., organic aerosol fraction that
52
efficiently absorbs solar and terrestrial radiation, and therefore ultimately producing climate
53
forcing.18 However, current understanding of their secondary formation in the atmosphere is
54
still incomplete.
55
The amount of HNO2/nitrite (NO2−) in the atmospheric aerosols strongly depends on
56
the level of local pollution, liquid water content, pH, etc. Because of its dissociation
57
equilibrium (pKa (HNO2) = 3.2)19 and modest water solubility (Henry's law constant, Hcc
58
(HNO2) = 1.2 x 103at 298 K),20 only very low HNO2 concentrations are found in acidic
59
droplets, normally in the range of 10−7–10−6 mol L−1.21, 22 As pH of atmospheric waters can 3 ACS Paragon Plus Environment
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range from 1.95 to 7.74 and considering that significant deviations from Henry's law have
61
been observed,9 total nitrite concentrations up to 10−4 mol L−1 have been measured in fog
62
water samples.21 Aromatic compounds, on the other hand, contribute significantly to the
63
budget of atmospheric pollutants.23 Nevertheless, because of the lack of appropriate kinetic
64
and mechanistic data, they are very seldom included into atmospheric models which deviate
65
substantially from field measurements.24 Of great importance are substituted aromatics;
66
catechol, hydroquinone and resorcinol are typical aromatic constituents of biomass-burning
67
emissions.25 According to Hoffmann et. al.26 aromatic compounds with a dimensionless
68
Henry’s law constant (Hcc) equal or greater than 103 are important for atmospheric multiphase
69
chemistry (Hcc (catechol) = 2.03 x 107, Hcc (resorcinol) = 2.5 x 108, Hcc (hydroquinone) = 6.4
70
x 108, Hcc (3-methylcatechol) = 3.3 x 108).26, 27
71
It has been speculated that dark nitration of substituted aromatics in the atmospheric
72
aqueous phase containing HNO2 can be an important source of nighttime BrC.6 The
73
importance of HNO2 in acidic aqueous solution of reactive aromatic compounds was first
74
recognized by Martinsen.28 He showed that nitration of activated aromatics such as phenol
75
was dependent on HNO2; in the presence of nitric acid (HNO3) only, phenol was not nitrated.
76
Already at that time, he concluded that HNO2 had a strong catalytic character. Veibel29 later
77
postulated a reaction mechanism where nitrosated intermediates formed from phenol and
78
HNO2. Bunton15 further proposed the existence of two reaction mechanisms of aromatic
79
nitration in HNO3 solution containing traces of HNO2. According to the first mechanism,
80
nitronium ion (NO2+ or its different carrier, e.g., H2NO3+, N2O5) was the main nitrating agent,
81
while HNO2 acted as a retardant. The second reaction mechanism assumed recombination of
82
aromatics with nitrosonium ion (NO+ or its different carrier, e.g., H2NO , N2O4 or HNO2
83
itself), which led to aromatic nitrosation followed by oxidation to yield nitrated products. In
84
this second case, HNO2 accelerated nitration of activated aromatic compounds. Recently,
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85
nitration of 2-methoxyphenol (guaiacol) in the presence of HNO2 under mild atmospheric
86
aqueous-phase conditions has been well described accounting for NO2+ and nitrogen dioxide
87
(NO2•) as nitrating species, and it was shown that the reaction pathways were competitive
88
under nighttime atmospheric conditions.30 In contrast, the majority of existing studies on the
89
atmospheric aqueous-phase nitration only refer to radical mechanisms, ignoring possible non-
90
radical reactions.4 Moreover, studies of non-radical reactions usually report only the identities
91
of formed products, providing very little mechanistic and kinetic information necessary for
92
the implementation in multiphase models.4
93
So far, there have been no aqueous-phase nitration studies performed on
94
methylcatechols being important precursors to yellow-colored MNC, which contribute to the
95
total organic aerosol mass and significantly alter absorption properties of atmospheric organic
96
aerosols.31-33 In this work, we emphasize the intriguing role of HNO2/NO2− in dark
97
transformation of 3-methylcatechol (3MC) under atmospherically relevant aqueous-phase
98
conditions. pH-dependent kinetic studies were performed in acidic solutions of sodium nitrite
99
(NaNO2/H2SO4), which allowed us to deduce the reactivity of 3MC towards HNO2/NO2−
100
with a great deal of confidence. We identify three possible routes of MNC formation under
101
atmospheric nighttime conditions, which are shown to depend markedly on reaction
102
conditions, specifically on pH and temperature.
103 104
Experimental section
105
Materials. Acetonitrile (Sigma-Aldrich, gradient grade, for HPLC >99.9%), formic acid
106
(Kemika), and high purity water (18.2 MΩ cm) supplied by a Milli-Q water purification
107
system were used for mobile phase preparation. Sulfuric acid 98% (H2SO4, EMSURE, p.a.
108
grade) and sodium nitrite (NaNO2, Sigma-Aldrich, ACS reagent, ≥97.0%) were used for
109
reaction mixture preparation. Standard substance 3-metylcatechol (3MC) (Sigma-Aldrich, 5 ACS Paragon Plus Environment
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98%) was used also as a reactant. Standards of reaction products 3-methyl-5-nitrocatechol
111
(3M5NC) and 3-metyl-4-nitrocatechol (3M4NC) were prepared in the laboratory by the
112
procedures adopted from Palumbo34 and Kitanovski.31 Griess reagent (modified) was used for
113
spectrophotometric determination of total nitrite.
114
Experimental Methods. Nitration of 3MC in acidic NaNO2 solution was investigated under
115
conditions relevant for the atmospheric aqueous phase. Initial concentrations of reactants in
116
the reaction mixture were 1×10−4 and 2×10−4 mol L−1 3MC, and 1×10−4, 2×10−4, 1×10−3 and
117
2×10−3 mol L−1 NaNO2. H2SO4 was used for pH adjustment. For details on experimental
118
conditions applied in each experiment see Table S1. Experiments were reproducible within
119
95%. Concentrations of 3MC and formed nitrated products during the reaction, 3M5NC and
120
3M4NC (500 µL sample was taken each time from 100 mL reaction mixture), were followed
121
by Agilent 1100 Series HPLC System equipped with a UV/vis diode-array detector (Atlantis
122
T3 column (3.0×150 mm, 3 µm particle size, Waters), isocratic elution by acetonitrile/0.1%
123
formic acid, 0.6 ml min–1, 10 µL injection, detection wavelengths: 275 nm for 3MC and 345
124
nm for MNCs). Total nitrite content was determined spectrophotometrically by use of Griess
125
reagent, for nitrite mass balance control.
126
Modeling. In order to elucidate the underlying mechanism of observed MNC formation, a
127
mathematical model was developed. The model explicitly considers three different pathways
128
of product formation presented in Figure 1. Overall, it includes 11 chemical species in 11
129
reactions (Table 1). As some of the reactions are reversible, 14 reaction constants describe
130
the experimental system. By writing down the mass balances of all species, a system of 11
131
ordinary differential equations is obtained, however some further simplifications were made.
132
It was assumed that due to a fast dissociation reaction, HNO2 and NO2− are always in the
133
equilibrium, pKa of 3.2 was used.35 Because of long reaction time-scales compared to oxygen
134
dissolution rate, the concentration of oxygen was assumed constant. We verified the latter 6 ACS Paragon Plus Environment
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135
assumption by performing an experiment with constant flushing of the reaction mixture with
136
oxygen (exp. 3 in Table S1) and no substantial deviation from the model was observed
137
(Figure S1a). In its final iteration, the system consists of 8 ordinary differential equations
138
describing 11 reactions altogether (with corresponding reaction rate constants), excluding
139
HNO2/NO2− equilibrium. From the model, time-dependent concentrations of all species were
140
obtained and compared with the experimental data.
141
The reaction system was solved in MATLAB® environment (MathWorks, Natick,
142
MA). Due to a high variance in rate constants (over several orders of magnitude), the system
143
of equations was rather stiff. “Ode15s” solver was utilized to solve it, which is a variable-
144
order backward-differentiation-formula based solver that uses a quasi-constant step size
145
allowing to solve stiff systems in a relatively short time-frame. To describe the experiments
146
in the best possible way, regression analysis was performed on all reaction constants
147
considering all experiments performed at 25 °C simultaneously, except k10 and k11 which
148
were taken from the literature and kept fixed during the regression analysis.36, 37 MATLAB’s
149
optimization scheme “fminsearch” utilizing the Nelder-Mead simplex algorithm was used for
150
this matter. The objective function that was minimized was the sum of squares of differences
151
between all experimental and model concentrations. In order to reduce the error of solver
152
getting stuck in local minima and to get the solution as close as possible to the global
153
minimum of the objective function, the regression was repeated numerous times with
154
different initial values. Overall, a very good agreement between the experimental data and the
155
model was achieved with the final set of rate constants values. The resulting set of best-fit
156
kinetic rate constants is gathered in Table 1.
157
Confidence intervals were calculated with the intent of quantifying the reliability of the
158
fitted rate constants. Herein the confidence interval is defined as a maximum allowed relative
159
change in the reaction constant that keeps the relative difference between model outputs with
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160
the original and modified sets of constants within 1%. The difference was defined as a sum of
161
relative differences in the concentrations of both products in the model outputs, and the
162
average value of all experiments was taken.
163
In order to investigate temperature-dependent behavior of the reaction system,
164
additional experiments were performed at 15 and 5 °C (experiments 17 and 18 in Table S1).
165
Although the collected experimental data are not sufficient for the exact analysis of
166
temperature dependence of the whole set of reaction rate constants, temperature dependence
167
of an apparent first-order reaction rate in regards to 3MC ( = [3MC]; kapp being the
168
apparent first-order rate constant) was studied by fitting the Arrhenius pre-exponential factor
169
(A) and activation energy (Ea); R and T are the gas constant and temperature, respectively
170
(Equation a).
171
=
(a)
172
Pseudo first-order kinetics was chosen because it was in-line with the proposed reaction
173
mechanism and very good matching was finally obtained (Figure S7).
174 175
Results and Discussion
176
Reaction mechanism. Figure 1 represents the proposed reaction scheme that resulted from
177
the extensive combined experimental and modeling investigation of dark 3MC nitration in
178
aqueous solution under acidic conditions relevant for the atmospheric aqueous phase. In the
179
presence of HNO2/NO2−, the dominant reaction mechanism is the conversion of 3MC to its
180
nitrated derivatives in two consecutive processes: oxidation and nitration by addition
181
(pathway I).7 HNO2 first oxidizes 3MC into the corresponding 3-methyl-o-quinone (4,
182
3MoQ) in two one-electron steps (k2 and k3). 3MoQ then undergoes a conjugate addition
183
reaction with NO2−, in which two isomeric nitro products form (k4 and k5). It should be
184
emphasized that this reaction pathway is strongly pH dependent; as both HNO2 and NO2− are 8 ACS Paragon Plus Environment
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185
the reactive species, nitration does not occur at pH far from the pKa of nitrous acid (i.e.,
186
3.2).19 At very low pH, the addition reaction is disfavored and at relatively high pH, HNO2 is
187
not present in its molecular form necessary for the oxidation of 3MC.
188 189
Figure 1. Proposed competitive reaction pathways of nighttime 3MC nitration in
190
NO2−/HNO2-containing atmospheric aqueous phase; 1 3-methylcatechol (3MC), 2 charge
191
transfer complex (CTC), 3 phenoxy radical (PhO•), 4 3-methyl-o-quinone (3MoQ), 5 3-
192
methyl-5-nitrocatechol (3M5NC), and 6 3-metyl-4-nitrocatechol (3M4NC). 5’, 6’ and 5’’, 6’’
193
are protonated forms of 3-methyl-o-quinones and sigma complexes (intermediates in Pathway
194
II) corresponding to 3-methyl-5-nitrocatechol and 3-methyl-4-nitrocatechol, respectively.
195
Pathway I summarizes the dominant reaction mechanism under the applied conditions.
196
Figure 2a shows that in the dark, 3MC can be well nitrated into two isomeric nitro
197
products, major 3M5NC and minor 3M4NC, even in the absence of any additional oxidant
198
(besides dissolved oxygen from the air). In slightly acidic aqueous solution of NaNO2 (pH
199
above 4.5) more than 97% 3MC is converted into the two identified products (see all product
200
yields in Table S1). However, we found that the ratio between the two products depended on
201
the total concentration of HNO2 in the reaction mixture (trace concentration or in excess to
202
3MC). This suggests that competitive routes to pathway I exist that prevail under distinct 9 ACS Paragon Plus Environment
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203
reaction conditions, which are presented in Figure 1. Specifically, NO+ in charge transfer
204
complex (CTC) with 3MC can also take part in an oxidative electrophilic nitration (pathway
205
II); besides another nitration mechanism is possible, involving combination of phenoxy
206
radical (PhO•) with NO2• (pathway III).30, 38, 39 Both competitive mechanisms are only active
207
if the solution is aerated and do not proceed in the absence of oxygen.
208 209
Figure 2. Experimental data (symbols) and calculated concentration profiles according to the
210
proposed reaction scheme (solid lines) of dark 3-methylcatechol (3MC) nitration in slightly
211
acidic NaNO2/H2SO4 solution at 25 °C: a) in the presence of O2 (exp. 2), b) in the absence of
212
O2 (exp. 4) and c) at trace HNO2 concentration (exp. 7). The following reaction products
213
were identified: 3-methyl-5-nitro-catechol (5, 3M5NC) and 3-methyl-4-nitro-catechol (6,
214
3M4NC).
215
Catalytic role of nitrous acid. Besides its direct role in the aromatic nitration (pathway II),
216
dissolved O2 is also capable of oxidizing the released NO• within 3MC oxidation by HNO2.40
217
This way, NO2• is produced in aerated reaction mixture, which after the recombination with
218
another NO• recovers HNO2.41
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219
2NO∙ + O 2NO∙
220
NO∙ + NO∙ + H O 2HNO
Page 12 of 26
(1)
(2)
221
The values for the rate constants k10 and k11 were taken from the literature36, 37 that seemed to
222
be the most relevant for the atmospheric aqueous phase. In order to reduce the number of
223
fitting parameters, these two constants were treated as non-adjustable. Note that even if k11
224
had been for two orders of magnitude higher (these values also appear in the literature) it
225
would not significantly change the modeling results. This is also evident from the confidence
226
interval determined for this constant (see Table 1).
227
The set of Reactions 1–2 nicely demonstrates that in 3MC nitration, the role of HNO2
228
is not only oxidative, but also catalytic, which is additionally supported by the experiments
229
performed in the absence of O2 (Figure 2b, Figure S1b).11, 15, 16, 42 Even if O2 is completely
230
expelled from the reaction mixture, 3MC nitration proceeds to a certain extent; until the
231
accumulated NO• in the reaction mixture moves the equilibria in pathway I towards the
232
reactants at the expense of PhO• and CTC. Note, to avoid NO loss, each solution (i.e., NaNO2
233
and 3MC stock solutions) was purged with N2 before mixing and the reaction mixture was
234
held under inert atmosphere during the experiment.
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235 236
Figure 3. Calculated concentration profiles of inorganic and organic reactive species in the
237
reaction mixture at pH 4.7 and 25 °C initially containing 1x10−3 mol L−1 NaNO2 and 1x10−4
238
mol L−1 3MC: a) and c) in the presence of O2 (exp. 2), b) and d) in the absence of O2 (exp. 4).
239
Calculated concentration profiles for NO•, NO2• and HNO2 (always in equilibrium with
240
NO2−) resulting from the proposed reaction scheme in the absence and presence of O2 are
241
shown in Figure 3a-b. In aerated solution (Figure 3a), NO• is scavenged by O2 yielding NO2•
242
in Reaction 1, which results in the lower NO• concentration in comparison to non-aerated
243
conditions. The concentration of NO2• is always lower than that of NO•, indicating its slower
244
formation and/or more numerous consumption routes (see below). PhO• and NO• compete for
245
NO2• in the solution. As the concentration of the former is always several orders of
246
magnitude lower (compare Figure 3a and c), the dominant sink of NO2• is the
247
disproportionation reaction with NO• to HNO2 (Reaction 2). The observed low PhO•
248
concentration in comparison to NO• results from the fast oxidation of PhO• by HNO2,
249
yielding 3MoQ and NO• (k3). However, if the concentration of HNO2 was too low to
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250
efficiently oxidize PhO• to 3MoQ, PhO• would become the dominant sink of NO2•. Similar
251
has been proposed for phenol.8, 43-46
252
Modeling results. Model function derived on the basis of the reaction scheme in Figure 1
253
describes the experimental data very well (see Figure 2 and Figures S1–S6). Parity plot
254
comparing experimental data with the calculated values is shown in Figure S8. Global fitting
255
to all experimental data at 25 °C at a time allowed us to determine kinetic parameters
256
describing the proposed reaction pathways gathered in Table 1 with a fair amount of
257
confidence. From the computed confidence intervals, it is however evident that even a
258
significant change in particular reaction rate constants has a negligible effect on product
259
formation. The least reliable constants are those denoting products formation by the
260
electrophilic and radical reaction pathways, which can be attributed to their minor roles in the
261
overall transformation of 3MC. Nevertheless, it can still be concluded that in pathways II and
262
III the formation of 3M4NC is favored in comparison to pathway I. With the most reliable
263
kinetic rate constants, the reaction of 3MC oxidation followed by the addition of NO2−
264
(pathway I) is recognized as the most significant pathway. Relative importance of
265
competitive nitration pathways depends on reaction conditions, which is elaborated in the
266
following sections.
267 268
Table 1. Best-fit kinetic rate constants (ki) with confidence intervals as defined above, valid
269
at 25 °C. k10 and k11 are taken from the literature and were kept fixed during the regression
270
analysis. Product
ri
2
k1[3MC][HNO2] – k−1[CTC]
3
k2[CTC] – k−2[PhO•][NO•]
4
k3[PhO•][HNO2] – k−3[3MoQ][NO•]
5
k4[3MoQ][NO2−]
Const.
ki
k1 k−1 k2 k−2 k3 k−3 k4
9.18·10−1 2.7·101 4.3·107 1.24·1010 1.90·108 1.46·106 1.25·100
Conf. int. [+/- %] 0.84 14.91 7.44 7.29 4.88 4.76 1.23
Units L mol−1 s−1 s−1 s−1 L mol−1 s−1 L mol−1 s−1 L mol−1 s−1 L mol−1 s−1
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6 5 6 5 6 NO2• NO2−
k5[3MoQ][NO2−] k6[CTC][O2] k7[CTC][O2] k8[PhO•][NO2•] k9[PhO•][NO2•] k10[O2][NO•]2 k11[NO2•][NO•]
k5 k6 k7 k8 k9 k10 k11
1.25·10−1 1.0·106 2.1·105 6.2·108 1.2·108 6.0·106 3.0·107
1.33 10.32 7.17 14.15 9.24 15.31 15.67
L mol−1 s−1 L mol−1 s−1 L mol−1 s−1 L mol−1 s−1 L mol−1 s−1 L2 mol−2 s−1 L mol−1 s−1
271 272
Experiments 17 and 18 (Table S1) were additionally used to quantify the temperature
273
dependence of the apparent first-order reaction rate with respect to 3MC. The best-fit values
274
of A and Ea obtained were 5.0 x 103 s−1 and 46.4 kJ mol−1, respectively. An observation was
275
made that the global pseudo first-order kapp considered for this purpose (kapp = 3.69 x 10-5 s−1
276
at 25 °C) is comparable to the reaction constant k1 multiplied with the initial HNO2
277
concentration yielding a pseudo first-order kinetic rate constant valid at the given conditions
278
(k1’ (exp. 2) = 3.83 x 10-5 s−1). This signifies the importance of this reaction step in
279
controlling the overall reaction rate under applied experimental conditions. Note also the
280
confidence interval of this reaction in Table 1 which is very narrow.
281
Pathway I: Initial oxidation step. As supported by our experimental-modeling study, the
282
mechanism of 3MC oxidation is likely to proceed via several reaction steps.11 When HNO2
283
approaches 3MC, HNO2 acts as an electron acceptor and 3MC as an electron donor and they
284
form a charge transfer complex also known as π-complex.42,
285
electrons from the aromatic system, it easily loses OH− (that is readily solvated in water) and
286
3MC-NO+ complex (2) remains in solution. In such CTC, 3MC is possibly subjected to a
287
one-electron oxidation process. The electron transfer between 3MC and NO+ yields an aryl
288
cation radical and nitrogen oxide (NO•), and after the loss of a proton from the phenolic
289
group (note the cation radical is a very strong acid, pKa = −1.9)51 it rapidly tautomerizes to a
290
more stable PhO• (3).12, 13, 16, 52 When HNO2 is in excess, PhO• is readily oxidized to 3MoQ
291
(4) through similar reaction steps as just described, leaving behind another NO•.12, 13
47-50
After HNO2 withdraws
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292
There are a few research papers investigating atmospheric processes where the
293
formation of quinone is reported.5, 6 However, it has always been considered as a side product
294
and little or no information is offered about the mechanism of its formation, particularly in
295
respect of its possible central role in the aqueous-phase nitration of aromatic pollutants.
296
HNO2 is not a strong oxidant; nevertheless, NO+ being liberated from HNO2 during its
297
interaction with the reactive aromatics can act as an oxidant as well. The redox potential of
298
NO+/NO• (E° = 1.325 V vs. Ag/AgCl)53 is substantially higher than the reversible oxidation
299
potential of 3MC/3MoQ at pH 4.5 (Eox = 0.3 V vs. Ag/AgCl), which means that an
300
exothermic electron transfer between them can occur.
301
Pathway I: Nitration of the corresponding quinone via conjugate addition reaction.
302
From 3MoQ, nitration proceeds by a unique conjugate addition reaction also known as 1,4
303
addition to diketone.54 Although the oxidative addition was discovered already two centuries
304
ago,55 its importance in the atmospheric processes has not been discussed before. To react
305
with NO2−, 3MoQ needs to be first activated towards the nucleophile, i.e., its protonation is
306
necessary. Depending on which carbonyl oxygen the protonation takes place, two different
307
isomeric nitro products can form. If C1-carbonyl oxygen is protonated (5’ in Figure
308
1),3M5NC forms upon the nucleophilic attack of NO2−. As this carbonyl oxygen is much less
309
sterically disturbed, more 3M5NC product forms in comparison to 3M4NC, which results
310
from the protonation of C2-carbonyl oxygen (6’ in Figure 1). This is in accordance with our
311
experimental observations.
312
For comparison, Khalafi and Rafiee7 investigated the nitration of 3MC under similar
313
conditions. They used different modeling approach and determined second-order rate
314
constants of consecutive oxidation (kox = 5.15 L mol−1 s−1) and nitration (knitr = 8.29 L mol−1
315
s−1) steps at 25 °C. Nematollahi56 calculated the homogenous second-order rate constant
316
(k = 7.3 L mol−1 s−1) for 1,4 addition reaction of electrochemically generated
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317
3MoQ with NO2− in aqueous phosphate buffer (pH 6.5, c = 0.15 mol L−1). These constants
318
are of the same order of magnitude as the rate limiting constants in pathway I determined in
319
our work (k1 = 0.918 L mol-1 s-1, k4 = 1.25 L mol−1 s−1).
320
Pathway II: oxidative aromatic nitration. Aromatic compounds can also be subjected to a
321
two-electron process, i.e., electrophilic aromatic substitution.30,
322
nitrosation products were found in the reaction mixture, which can be attributed to low
323
nitrosation rates resulting from significant energy barriers for N-protonated nitroso
324
derivatives formation from CTC.48,
325
autoxidized gaining nitrated products that are highly reminiscent of those from electrophilic
326
aromatic nitration.61 CTC oxidation (only possible in the presence of O2 or other oxidative
327
species) is believed to proceed through several rearrangement steps,60 each of them being
328
accompanied by a certain energy barier.59 Therefore, such oxidative nitration only happens if
329
the electron transfer in CTC is prohibited or highly reversible as proposed in our case.
330
Individual rearrangement steps, e.g., sigma complex formation (5’’ and 6’’ in Figure 1), are
331
not taken into account in our model study. To our knowledge, oxidative aromatic nitration
332
has never been considered in atmospheric processes, although some evidence has recently
333
been published by our group.30
50
57-60
Interestingly, no
However, in the presence of O2, CTC can be
334
If electron transfer in CTC is reversible, nitration mechanism through consecutive one-
335
electron processes (pathway I) cannot be easily distinguished from the more conventional
336
two-electron electrophilic nitration;62 especially if the aryl cation radical (or PhO•)
337
intermediate is not detectable.63 Usually, substituted aromatics exhibit higher degree of
338
charge transfer and the corresponding substituted CTC are more prone to electron transfer
339
resulting in the favorable nitration according to pathway I.62 Nevertheless, results of our
340
combined experimental and modeling approach show that in the case of 3MC, thermal
341
decomposition of CTC via one-electron transfer giving aryl cation radical and NO• competes
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342
with the electrophilic two-electron process following the autoxidation of 2 to 3MC-NO2+.
343
Once CTC is formed (its formation is considered rate limiting), it rather undergoes
344
thermolysis than oxidation with O2 (k2 >> k6, k7), supporting the domination of pathway I.
345
However, as 2 and 3 are both (trans)formed reversibly, their preferential reaction route
346
depends on applied conditions. When back-electron transfer (k−2[PhO•][NO•]) prevails over
347
the oxidation of phenoxy radical (k3[PhO•][HNO2]; i.e., at low HNO2 concentrations, Figure
348
2c), electrophilic substitution is preferred. Oxidative aromatic nitration of 3MC is thus
349
disfavored at high HNO2 concentrations (Figure 2a), but prohibited in the absence of O2
350
(Figure 2b and Figure S1b).
351
Pathway III: recombination of radical species. Following the existing literature64-68
352
another possible pathway was included in our model. 3MC can be nitrated via PhO•
353
combination with NO2• which could also result in the distinct ratio between 3MNC isomers.
354
As NO• is not present in the solution nor is expected to form during the studied reaction, O2 is
355
needed to oxidize NO• to NO2• and allow for this reaction pathway.
356
Product distributions. Numerical integration reveals (Figure 4) that the proposed
357
competitive pathways II and III to the dominant oxidation-addition mechanism contribute
358
more to the nitration in para position (i.e., 3M4NC formation), which actually allowed us to
359
distinguish between them and the dominant pathway in the model. As the formation of
360
reactive NO2+ occurs within the CTC (note NO2+ is 1014 times more reactive than NO+ in
361
electrophilic aromatic substitution reaction and reacts with all reactive aromatics at the same
362
rate),64,
363
observed as to particular MNC isomer. Similar explanation can be given for the radical
364
recombination. In contrast, the conventional pathway I yields for an order of magnitude more
365
3M5NC than 3M4NC. Compare the ratios k4/k5 with k6/k7 and k8/k9 in Table 1.
69, 70
3MC and NO2+ are encountered without diffusion and less preference is
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366 367
Figure 4: Product distributions (3-methyl-5-nitrocatechol (5, 3M5NC) with pattern and 3-
368
methyl-4-nitrocatechol (6, 3M4NC) without pattern) by mechanism (colors) at different
369
reaction conditions: with O2 (exp. 2) and without O2 (exp. 4) both at 1·10−3 mol L−1 HNO2,
370
and with O2 at 1·10-4 mol L−1 HNO2 (exp. 7, with O2).
371
Environmental Relevance. The presented investigation suggests that HNO2 is an important
372
mediator in dark aqueous-phase transformations of particular substituted aromatic pollutants
373
under mild environmental conditions. Its catalytic and oxidative roles in nitration of catechols
374
are emphasized. HNO2 is shown to be directly involved in the transformation of 3MC within
375
the non-radical reaction pathway including consecutive oxidation and conjugated addition
376
reactions, which can be a significant source of BrC and potential SOA compounds.
377
Considering atmospherically relevant aqueous-phase concentrations of 3MC (taken as an
378
upper limit of less water-soluble aqueous-phase atmospheric methoxyphenols)71 and total
379
HNO2/NO2− to be 10−5 and 10−4 mol L−1, respectively, we predicted the atmospheric lifetime
380
of 3MC according to this mechanism to be 2.4 days in the dark (at pH 4.5 and 25 °C;
381
compared with about 8 days for the other two competitive pathways, i.e., II and III, see Table
382
S2). Furthermore, 3MC nitration in the dark was found moderately dependent on
383
temperature.
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384
Dark two-step nitration pathway is expected to dominate at pH around the pKa of
385
HNO2, which is typical for atmospheric aerosols. Note that shorter atmospheric lifetimes of
386
3MC at lower pH values gathered in Table S2 do not result in faster production of nitrated
387
products; quinone and other intermediate products rather accumulate in the solution under
388
those reaction conditions (compare atmospheric lifetimes of 3MC and their nitrated products
389
formation equivalents in brackets). Because of the acid-base equilibrium, there is a lack of
390
NO2− under very acidic conditions, therefore the slower oxidative aromatic substitution and
391
radical nitration pathways gain in importance at low pH. Moreover, due to its rapid mass
392
transfer to the gaseous phase (because of relatively high HNO2 volatility and large surface-to-
393
volume ratio of small aerosol particles), the concentration of HNO2 in acidic aerosol water is
394
often very low, which would result in extremely long atmospheric lifetimes of 3MC
395
according to this transformation pathway; i.e., at pH 3.5 and 10−6 mol L−1 HNO2/NO2−
396
(constant concentration in the aerosol water shell is assumed in this case) only about 10% of
397
3MC would be consumed in 10 days. Long atmospheric lifetimes are also expected in cloud
398
water (higher pH and more diluted solutions), as the necessary initial oxidation step is
399
prohibited at those conditions. It is important to mention that benzene does not react at all
400
under these conditions,5 phenol barely gets nitrated (unpublished data), while guaiacol (2-
401
methoxy-phenol) has about 3-times longer expected lifetime.24
402
To support the conclusions made above, absorption properties of the reaction mixture
403
were also investigated (Figure 5). The two products formed, 3M5NC and 3M4NC, as well as
404
the reaction mixture all absorb in near-UV (300–400 nm) and Vis ranges (>400 nm,) and are
405
believed to contribute significantly to BrC and/or absorptive properties of the atmospheric
406
gas. MNC have been identified in PM1032 and PM2.517 samples and it is well known that they
407
are among the major components of HULIS,33 the most widespread chromophoric substance
408
in the atmosphere. Due to the global impacts of absorbing tropospheric aerosols, direct by
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409
absorbing solar irradiation and indirect by influencing the cloud formation, the mechanisms
410
of BrC formation are of utmost importance for the atmospheric science community. In this
411
regard we summarize our study and conclude that catechol two-step oxidation-conjugated
412
addition reaction mechanism can be an important pathway of dark secondary nitroaromatic
413
chromophore formation in the atmosphere, especially in polluted environments with high
414
NOx concentrations and relatively acidic particles (pH around 3).
415 416
Figure 5. Absorption spectra of 3-methylcatechol (3MC), 3-methyl-5-nitrocatechol
417
(3M5NC), 3-methyl-4-nitrocatechol (3M4NC) and the reaction mixture after 15h (exp. 2)
418
measured at pH 4.6.
419 420
Associated content
421
Supporting Information
422
Additional 2 tables and 8 figures. The supporting information is available free of charge via
423
the Internet on the ACS Publications website at http://pubs.acs.org.
424 425
Author information
426
Corresponding Authors
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427
*Phone: +386 (1) 4760 361 (IG) and +386 (1) 4760 384 (AK); fax: +386 (1) 4760 300; e-
428
mails:
[email protected] (IG) and
[email protected] (AK).
429
Notes
430
The authors declare no competing financial interest.
431 432
Acknowledgments
433
This work was supported by the Slovenian Research Agency (Contract Nos. P1-0034
434
and P2-0152), which is gratefully acknowledged.
435
436
References
437 438 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466
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