Supporting Information (SI)

New mechanistic insights into the transformation of reactive

oxidizing species in UV/sulfite system under aerobic

conditions: Modeling and the impact of Mn(II)

Dandan Rao,† Hongyu Dong,† Lushi Lian,‡ Yuankui Sun,†,‡ Xin Zhang,§ Lei Dong,§

Gongming Zhou,†,‡ XiaohongGuan*,†,‡

†State Key Laboratory of Pollution Control and Resources Reuse, College of

Environmental Science and Engineering, Tongji University, Shanghai 200092, P.R.

China
‡Department of Environmental Science, School of Ecological and Environmental

Sciences, East China Normal University, Shanghai 200241, China.

§Shanghai Municipal Engineering Design Institute (Group) Co., LTD., Shanghai,

200092, P.R. China

*Author to whom correspondence should be addressed

Xiaohong Guan, Email: guanxh@tongji.edu.cn; Phone: +86(21)65983869

 Content
Text S1. Chemicals and Reagents.

Text S2. Determination of average fluence rate and the effective path of radiation of

the experimental photochemical setup.

Text S3. Analytical methods.

Text S4. Simulation analysis of the influence of dissolved oxygen (DO) concentration

on both UV/S(IV) and UV/Mn(II)/S(VI) system.

Text S5. Calculation of model accuracy and sensitivity analysis.

Text S6. Identifying the violations of the principle of detailed balancing with software

DETBAL.

Text S7. Impact of ethanol and tert-butanol on the transformation kinetics of S(IV) and

IBU in the UV/S(IV) system.

Text S8. Calculation of ΦHSO5― and ΦSO25 ― in the UV/PMS system.

Text S9. Calculation of the time-dependent contributions of various reaction routes to

IBU degradation, S(IV) consumption, SO4•− consumption, and SO5•−

transformation in the UV/S(IV) system.

Figure S1. Illustration of the photochemical experiment setup.

Figure S2. (a) Generation of I3− under UV irradiation in KI/KIO3 system; (b)

Photodecomposition of dilute H2O2 under UV irradiation.

Figure S3. Decay kinetics of IBU and S(IV) in various systems.

Figure S4. Influence of (a-c) S(IV) dosage and (d-f) solution pH on the transformation

kinetics of IBU and S(IV) in the UV/Mn(II)/S(IV) and the UV/S(IV) systems.

Figure S5. Influence of tert-butanol and ethanol on the transformation of IBU and S(IV)

in the UV/S(IV) system.

Figure S6. Experimental vs modeled decomposition kinetics of PMS and IBU

decomposition in the UV/PMS system under different conditions.

Figure S7. Experimental vs modeled amounts of PMS generated after S(IV) depletion

in the UV/Mn(II)/S(IV) system at different pH levels in the UV/S(IV) system.

Figure S8. Experimental vs modeled transformation of S(IV) and IBU in the UV/S(IV)

system at various S(IV) dosages (panels a, b, e, f) and at various pH levels (panels

c, d, g, h).

Figure S9. Influences of (a–d) S(IV) dosage and (e–h) solution pH on the

transformation of IBU, S(IV), SO5•−, and SO4•− in the UV/S(IV) system.

Figure S10. Transformation kinetics of SO3•−, SO5•−, SO4•−, and HO• in the UV/S(IV)

at various (a–d) S(IV) dosages and (e–h) pH levels.

Figure S11. Modeled transformation kinetics of (a) S(IV) and (b) IBU in the UV/S(IV)

system.

Figure S12. The experimentally determined vs modeled transformation kinetics of

S(IV), IBU, and PMS in the UV/Mn(II)/S(IV) system at different initial Mn(II)

dosages.

Figure S13. Experimental vs modeled transformation kinetics of IBU, S(IV), and PMS

in the UV/Mn(II)/S(IV) system at different solution pH.

Figure S14. (a) UV-vis spectra evolution in the UV/Mn(II)/S(IV) system at pH 9.0; (b)

after the depletion of S(IV) in the UV/Mn(II)/S(IV) system at pH 9.0 appropriate

amount of PP was added and reacted for 20 min, and then the UV-vis absorption

spectrum of the resulting solution was recorded and shown in panel b, along with

the standard spectrum of 20 M Mn(III)-PP.

Table S1. Supplementary reactions involved in the UV/S(IV) process (Reactions in this

table have nonsignificant influence on the decay kinetics of S(IV) or IBU in the

UV/S(IV) system over the pH range of 6.0–9.0).

Table S2. Initial concentrations, absorption coefficients, and quantum yields of

concerned species used for the simulation.

Table S3. Reported rate constants of reaction between SO5•− and S(IV).

Table S4. Calculated SD values in the UV/PMS system as a function of ΦHSO5― and
 ΦSO25 ― (number of data for experiments performed at pH 7.0 and 9.0 are 36 and

34, respectively).

Table S5. Calculated overall SD values in the UV/S(IV) system (corresponding to

Figure 2 in main text) and the UV/Mn(II)/S(IV) system (corresponding to Figure

S14) under various experimental conditions.

Table S6. Calculated sensitivity measure S for SO32−, HSO3−, IBU, HSO5−, SO52−,

SO4•−, SO5•−, SO3•−, HO• and the summation of these 9 species as overall S in the

UV/S(IV) system at pH 7.0.

Table S7. Calculated SD values under the UV/Mn(II)/S(IV) system as a function of

kR33, kR34 and kR35 at pH 6.0–9.0.

Text S1. Chemicals and Reagents.

All chemicals were used as received from commercial sources, and all solutions

were prepared in ultrapure Milli-Q water (18.2 MΩ·cm, Millipore). Sodium sulfite

(Na2SO3, S(IV)) (98.0%), manganese (II) perchlorate (Mn(ClO4)2‧6H2O), ibuprofen

(IBU) (99.0%), peroxymonosulphate (2KHSO5·KHSO4·K2SO4) (4.5% active oxygen),

peroxydisulfate (PDS) (99.99%), hydrogen peroxide (H2O2) of 30 wt.% in H2O, ethanol

( ≥ 95%), tert-butanol ( ≥ 98.0%), 5,5-dithiobis(2-nitrobenzonic acid) (DTNB)

(99.0%), boric acid (H3BO3) ( ≥ 99.8%), sodium tetraborate (Na2B4O7) ( ≥ 99.5%),

sodium phosphate dibasic (Na2HPO4) ( ≥ 99.0%), sodium phosphate monobasic

dihydrate (NaH2PO4·2H2O) ( ≥ 99.0%), and sodium pyrophosphate tetrabasic

decahydrate (Na4P2O7·10H2O, PP) (≥99.0%) were obtained from Aladdin Industrial

Corporation.

The stock solution of S(IV) was freshly prepared at a concentration of 250 mM

every 2 hours to minimize its deterioration. The stock solution of 10 mM Mn(II)

(Mn(ClO4)2‧6H2O) was prepared every month.

Text S2. Determination of the photon flux and the effective path of radiation of

the photochemical setup.

The photon flux (I0) entering the working solution and the effective path of

radiation (L) should be accurately determined in order to guarantee the kinetic modeling

results. Based on Lambert-beers law, the disappearance rate of an actinometer

substance is defined as follows:

dCa I0
― dt = Φa 𝑉 (1 ― e ―2.303LεaCa) (S1)

where a, a, and Ca are the quantum yield, extinction coefficient, and

concentration of the actinometer, respectively. Eq. S1 can be simplified in two cases

according to the value of the exponential term1 as indicated below:

dCa I0
If 2.303LaCa > 2, ― dt = Φa 𝑉 (S2)
dCa I0
If 2.303LaCa < 0.2, ― dt = 2.303LΦa 𝑉 εaCa (S3)

When a is known, Eq. S2 allows the determination of I0, and then Eq. S3 can be

applied to determine L.

(a) Determination of I02

A solution containing 0.50 M iodide (KI), 0.10 M iodate (KIO3), and 0.01 M borate

buffer (pH 9.25) was used as a chemical actinometer to measure the I0. The KI/KIO3

chemical actinometer on exposure to UV forms triiodide (I3−), and the proposed

reaction has the following stoichiometry:

8KI + KIO3 + 3H2O + hv → 3I3− + 6OH− + 9K+ (S4)

The temperature- and concentration-corrected quantum yield for the KI/KIO3

system was determined to be 0.74 according to Eq. S5.3

a = 0.75×(1+0.23×(C-0.577))×(1+0.02×(T–20.7)) (S5)

Where C is the initial concentration of I− and T is the temperature. The absorbance

at 353 nm is used to calculate the concentration of I3− ((353 nm, I3−) = 2.64×104

M−1‧cm−1).

Before irradiation, the spectrum of the KI/KIO3 mixture is optically opaque at 254
nm and meet the condition of 2.303LaCa > 2. Therefore, the number of photons
d𝐼3― I0
absorbed by the sample, i.e., I0, can be calculated using dt = Φ 𝑉 . The solution

volume-averaged fluence rate (Is) was estimated to be 3.13 ×10−6 einstein‧s−1‧L−1, and

I0 was calculated to be 2.35×10−6 einstein‧s−1 (Eq. S2, Figure S2a).

(b) Determination of L4

The average light path length (L) of the radiation through the reactor was

determined using H2O2 (150 M) as the chemical actinometer. In this case, Eq. S3 was
used, and Is = 3.13×10−6 einstein‧s−1‧L−1, εH2O2 = 19 M -1‧cm -1, ΦH2O2

(total quantum yield) = 1.0 mol‧einstein ―1. Eq. S3 indicates a first-order decay

kinetics for H2O2, so a linear plot of ln(C/C0) vs time can be obtained (Figure S2b) and
the slope of this plot should be equal to 2.303LΦ𝐻2𝑂2Isε𝐻2𝑂2. Consequently, L was

calculated to be 2.9 cm. It has to be noted, the residual H2O2 in the UV/H2O2 process

was monitored using the ABTS colorimetric method at pH 2.0 as reported in a previous

study.4
Text S3. Analytical methods.

To track the removal of organic contaminants, 2.0 mL aliquots were periodically

collected during oxidation processes, quenched by 10 μL of 1.0 M hydroxylamine

hydrochloride (NH2OH•HCl), and filtered with 0.22-μm membranes before analyses.

The sample collected at 0 min was subject to the identical pretreatment and analysis

process. The concentrations of IBU were determined using an UPLC system (UPLC,

Waters ACQUITY UPLC H-Class, Waters Co.). Chromatographic separations were

performed using a BEH C18 column (2.1 × 100 mm, 1.7 μm; Waters Co.) in an isocratic

mode of elution at 35 ± 1 °C. The injection volume of samples was 10 L. The detailed

operation parameters of the UPLC method to detect IBU were listed in Table SA1.

Table SA1. UPLC parameters for target compounds analysis.

Mobile phase constitution (v%)
Column flow Detection
A Retention time
Organics B rate wavelength
(0.1% formic acid (min)
(acetonitrile) (mL‧min−1) (nm)
solution)
IBU 33 67 0.25 224 2.1

Solution pH was monitored with a Shanghai Leici pH meter. The concentration of

S(IV) was monitored using the modified 5,5'-dithiobis(2-nitrobenzoic acid)

colorimetric method.4 The concentrations of PMS in solution were determined with a

modified 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) method developed in our

previous study.4All the UV-vis spectra in this study were collected with an Agilent Cary

60 UV-vis spectrometer. The concentration of dissolved oxygen (DO) was measured

online with a JPB-607A portable meter (Leici, Shanghai, China).

Text S4. Simulation analysis of the influence of dissolved oxygen (DO)

concentration on both UV/S(IV) and UV/Mn(II)/S(VI) systems.

Considering the continuous aeration during the reaction processes, DO

concentration was set as a constant value of 8.0 mg‧L−1 (0.25 mM) in both Model 1 and

Model 2. In practical, however, the DO concentration would temporarily decrease from

8.2 mg‧L−1 to 6.6 mg‧L−1 in the UV/S(IV) process and to 4.0 mg‧L−1 in the

UV/Mn(II)/S(IV) process in the first 30 s of reaction (Figure S15). Taking advantage

of the constructed kinetic models (Model 1 and Model 2), we found the simulated

transformation kinetics of S(IV), SO4•−, and PMS was independent of the DO

concentration once it was ≥ 0.5 mg‧L−1 (Figure S16). Therefore, the temporary

decrease in DO concentration would not influence the transformation kinetics of the

concerned species in both UV/S(IV) and UV/Mn(II)/S(IV) systems.

During the S(IV) chain transformation process, the two major reactions consuming

O2, i.e., quenching eaq− (R3) and combining with SO3•− to form SO5•− (R2), proceeded

extremely fast (k ≥ 1.10×109 M−1‧s−1) and thus a low level of DO was enough to

maintain the fast S(IV) chain transformation process. However, a further decrease in

DO concentration to 0 mg‧L−1 would completely inhibit the generation of SO4•− and

facilitate the massive accumulation of eaq− (Figure SA2), turning the UV/S(IV) system

into a reductive system. Therefore, it is essential to guarantee the supply of oxygen in

actual application of S(IV)-based AOPs.

 2D Graph 1

DO (mg/L)
6
UV/S(IV)
UV/Mn(II)/S(IV)
4

0
0 50 100 150 200 250 300

Time (s)

Figure SA1. Time evolution of DO concentration in UV/S(IV) and UV/Mn(II)/S(IV)

systems. Conditions: [S(IV)]ini = 250 M, [Mn(II)]ini = 36 M (if any), [IBU]ini = 2.0

M, pH 7.0.

8 5
(a) (b) (c) 600 (d)
1.0
500
(M)

4 (M)
0.8 6 30
PMS (M)
S(IV) C/C0

8.0 mg/L
12

3
× 10

14

0.6 4.0 mg/L

eaq × 10

0.5 mg/L 4 20
0.4 0 mg/L 2
· -

-
SO4

2 1 10
0.2

0.0 0 0 0
0 100 200 300 400 500 0 100 200 300 400 500 0 100 200 300 400 500 0 100 200 300 400 500

Time (s) Time (s) Time (s) Time (s)

100
1.0 (e) 15 (f) (g) 600 (h)
(M)

500
80
(M)

0.8
S(IV) C/C0

30
PMS (M)
12

14
× 10

0.6 10 60
eaq × 10

20
0.4 40
· -

5
-
SO4

0.2 20 10

0.0 0
0 0
0 100 200 300 400 500 0 100 200 300 400 500 0 100 200 300 400 500 0 100 200 300 400 500
Time (s) Time (s) Time (s) Time (s)

Figure SA2. Simulated transformation kinetics of S(IV), SO4•−, PMS, and eaq− in the

UV/S(IV) (Model 1) (a–d) and UV/Mn(II)/S(IV) (Model 2) (e–h) systems at various

DO concentrations. Conditions: [S(IV)]ini = 250 M, [Mn(II)]ini = 36 M, [IBU]ini =

2.0 M, pH = 7.0.

Text S5. Calculation of model accuracy and sensitivity analysis.

To quantify the deviations between model prediction and experimental

observation, the overall sample deviation (SD) was calculated using Eq. S6.
1 N
overall 𝑆𝐷 = ∑
N ― 1 𝑖 = 1[(Cexp,𝑖 ― Ccal,𝑖)/Cexp,𝑖]2 (S6)

where N is the number of total data points; Cexp,i and Ccal,i are the experimental and

calculated concentrations of major species (i.e., HSO3−, SO32−, HSO5−, SO52−, and IBU),

respectively; and the index i refers to the set of concerned species and times for which

experimental data are available.

For all the rate constants listed in Table 1 (R1–R32) and S1, sensitivity analysis

was conducted to evaluate the importance of each reaction rate constant to the simulated

evolution of major species, i.e., S(IV), IBU, PMS, SO4•−, SO5•−, and SO3•−. In short,

the absolute sensitivity coefficient (Si,j) of a reaction (i) for a concerned species (j) was

measured by changing the reaction rate constant by a small amount from its input value.

The overall sensitivity coefficient (overall Si) of this reaction (i) was then calculated by

summing Si,j for all major species. In specific, Kintecus can generate normalized

sensitivity coefficients (NSC) at any times during a simulation run. The NSC is

typically defined by Eq. S7, in which the partial derivatives of the output (Ci) with

respect to each input (kj) is normalized by multiplying by kj/Ci.

∂[𝐶𝑖]
[𝐶𝑖] ∂[𝐶𝑖] 𝑘𝑗
𝑁𝑆𝐶 = ( ∂𝑘𝑗 ) = ( ∂𝑘𝑖 [𝐶𝑗]) (S7)
𝑡
𝑘𝑗
𝑡

For each time point, NSC is a matrix with signed numbers, which indicates the

influence of the reactions on certain species. To measure the impact of one specific

reaction rate constant, kj, on the evolution of one major species i, we calculated absolute
∂[𝐶𝑖] 𝑘𝑗
values of Si for the major species by summing | ∂𝑘𝑖 [𝐶𝑗] | 𝑡
over various time points

spanning over the system (For sensitivity analysis in Table S7, 16 timepoints were

selected over the 600-s reaction time) (Eq. S8).

∂[𝐶𝑖] 𝑘𝑗
𝑆𝑖 = ∑ 𝑡 | ∂𝑘𝑖 [𝐶𝑗] | 𝑡
(S8)
 The overall sensitivity coefficient (overall S) was also calculated by summing Si

for all major species (Eq. S9) to evaluate the significance of one reaction rate constant

(j) in influencing the overall simulation results.

∂[𝐶𝑖] 𝑘𝑗
𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑆 = ∑i∑𝑡 | ∂𝑘𝑖 [𝐶𝑗] | 𝑡
(S9)
Text S6. Identifying the violations of the principle of detailed balancing with

software DETBAL.

Large kinetic models containing a large quantity of individual reactions might

violate the principle of detailed balancing, and these violations can lead to erroneous

simulations.7 To exclude the possibility that the models built in this study violate the

principle of detailed balancing, we performed a detailed balancing analysis for Model

2, which containing all reactions involved in Model 1. DETBAL is a commonly used

software to identify the reversible and illegal reaction loops in kinetics models. A listing

of the code and instructions for its use are provided in the reference. 8

The first step of the analysis is to ensure that all reactions in the model correspond

to balanced chemical equations. Therefore, those species in brackets in Table 1 and

Table S1 (R1–R90) were taken into account for detailed balancing analysis. Secondly,

the corrected reactions were input into DETBAL, and then the software identified a

total of 9 reversible steps that were represented as separate forward and reverse steps

in the original model. Those reactions are summarized below.

HO2• ⇌ H+ + O2•− (S10)

HSO3− ⇌ SO32− + H+ (S11)

HSO5− ⇌ H+ + SO52− (S12)

HO• + OH− ⇌ •O− + H2O (S13)

SO3•− + SO52− ⇌ SO5•− + SO32− (S14)

SO3•− + HSO5− ⇌ SO5•− + HSO3− (S15)

H• + OH− ⇌ eaq− + H2O (S16)

H+ + OH− ⇌ H2O (S17)

H+ + SO42− ⇌ HSO4− (S18)

Then, DETBAL reports 46 reaction loops, most of which are legal but one is illegal.
This illegal loop is composed of the following steps:

H• + OH− ⇌ eaq− + H2O (S16)

H+ + OH− ⇌ H2O (S17)

eaq− + H+ → H• (R50)

Equation S16 + S17 = R50. Since this loop contains a single irreversible step, it is

illegal. It can be made legal by making reaction R50 reversible. The value for the kS50b

value can be calculated from the equation KS16×KS17 = KR50, from which it can be

derived that kR50b = (KS16×kR50f)/KS17 = 1.87×102 M−1s−1. It turns out that incorporating

the counterreaction of R50 as R91 in Model 1 and Model 2 has no influence on the

simulated transformation kinetics of IBU and S(IV).

Text S7. Impact of ethanol and tert-butanol on the transformation kinetics of S(IV)

and IBU in the UV/S(IV) system.

The generation of SO4•− and HO• has been well documented in other S(IV)-

relevant AOPs,9 and here their contributions to IBU removal in the UV/S(IV) system

were identified using alcohol scavenging experiments. For the UV/S(IV) system, tert-

butanol (10 mM), a more efficient scavenger for HO• than for SO4•− (kHO•,TBA = 6.0 ×

108 M−1·s−1 ， kSO•4 - ,TBA = (4.0−9.1) × 105 M−1·s−1),[121] slowed down the removal rate

of IBU by 66%, while 10 mM ethanol, a highly efficient scavenger for both HO• and

SO4•− (kHO•,EtOH = 1.9 × 109 M−1·s−1 ， kSO•4 - ,EtOH = (1.6−7.7) × 107 M−1·s−1),[112]

suppressed the removal of IBU to the same level as that by UV photolysis alone (Figure

S6a–b). The above results indicated that SO4•− and HO• are primary oxidants

responsible for IBU removal in both the UV/S(IV) and the UV/Mn(II)/S(IV) systems.

During the S(IV) chain transformation process, SO4•− could be generated from the

reaction between SO5•− and S(IV) (R4 and R6 in Table 1), and HO• would be generated

through reactions between SO4•− and H2O/OH− (R15 and R16 in Table 1). Moreover,

the photolysis of PMS would also contribute to the production of SO4•− and HO• (R21

and R22 in Table 1). The generation of HO•, to some extent, increased the

decontamination efficiency due to the non-selective nature of HO•.

It has been documented that both SO5•− and SO3•− are fairly inert toward alcohols

(e.g., ethanol and tert-butanol), with k ≤ 103 M−1‧s−1,8, 9 let alone more recalcitrant

organic contaminant like IBU. Assuming that the rate constants of IBU by both SO5•−

and SO3•− were 103 M−1‧s−1, these two reactions were added to Model 1. It turns out

imperceptible changes were observed for the transformation kinetics of IBU, SO3•−, and
SO5•− after adding these two reactions at pH 6.0–9.0 in UV/S(IV) system. Moreover,

the enhanced removal of IBU arising from S(IV) addition in UV/S(IV) system was

completely inhibited by dosing excess ethanol, implying the negligible contributions of

SO5•− and SO3•− to IBU degradation. Taken together, the oxidizing role of SO3•− and

SO5•− for IBU degradation were excluded.

Text S8. Calculation of 𝚽𝐇𝐒𝐎𝟓― and 𝚽𝐒𝐎𝟐𝟓 ― in the UV/PMS system.

UV photolysis of PMS leads to the formation of SO4•− and HO•. The primary

quantum yield of PMS in the UV/PMS system was reported to be 0.12±0.02 at  = 248
nm but the solution pH was not specified.12 A more recent study found that PMS was
decomposed by UV faster at elevated pH due to the larger molar absorption coefficient
of SO52− (149.5 M−1‧s−1) than HSO5− (13.8 M−1‧s−1), but only an overall quantum yield

of SO4•− was reported to be 0.52±0.01 at pH 7.0.13

The rection set applied for simulating ΦHSO5― and ΦSO25 ― in the UV/PMS system

was all incorporated into the reaction set used for modeling of the UV/S(IV) system in
Table 1 (R1–R32) and Table S1. So, the same reaction set as that applied for modeling
the UV/S(IV) process was used when simulating the transformation kinetics of PMS
and IBU in the UV/PMS system by setting [HSO3−]ini = [SO32−]ini = 0 mM, [HSO5−]ini
(pH - pKa2)
1 2−] 10
= (pH–pKa2) [PMS], [SO5 ini = (pH - pKa2) [PMS], [IBU]ini = 2.0×10−6 M, [O2]constant
10 +1 10 +1

= 2.5×10−4 M, [H+]constant = 10-pH, and [OH−]constant = 10−(14−pH), where square brackets

denote concentrations of various species [S], the subscript ‘ini’ denotes the initial
concentration of S, and the subscript ‘constant’ denotes that the concentration of S was
set as a constant value during the modeling process.

UV photolysis of PMS leads to the formation of SO4•− and HO•, and

ΦPMS = ΦSO•4 - = ΦHO•. The ΦHSO5― was firstly evaluated at pH 7.0, where PMS

existed in the form of HSO5−, and the UV photolysis of SO52− was thus negligible. By

fitting to experimental data of PMS decay and IBU degradation, ΦHSO5― was

calculated to be 0.135±0.005 mol einstein−1 (Figure S7a, b). Subsequently, ΦSO25 ―

(0.174±0.12 mol‧einstein−1) was calculated and optimized with the minimum sum of
SD at pH 9.0 (Figure S7c, d), where SO52− constitute 28.5% of the total PMS. Moreover,

good model fitting was observed at pH 8.0 using the calculated ΦHSO5― and ΦSO25 ―
values (Figure S7e, f), which verified the reliability of the modeling results.
Text S9. Calculation of the time-dependent contribution of various reaction routes

to IBU degradation, S(IV) consumption, SO4•− consumption, and SO5•−

transformation in the UV/S(IV) system.

According to the reduced reaction scheme of R1–R32 (see Section Sensitivity

Analysis for Reactions in the UV/S(IV) system), the transformation kinetics of S(IV),

IBU, SO4•−, and SO5•− were listed as follows:

d[S(IV)]
dt = ―ΦSO23 ― 𝑓SO23 ― I0(1 ― e ―2.303LΣϵiCi) ― 𝑘R4[SO•5 ― ]—𝑘R5[SO•5 ― ][SO23 ― ] ―—

[HSO3― ] ―𝑘R7[SO•5 ― ]— ― 𝑘R13[SO•4 ― ][S—] ― 𝑘R14[SO•4 ― ]—[HO•][SO23 ― ] ― 𝑘R23—

― 𝑘R24[HSO5― ][SO23 ― ] —

(9)
—[SO•4 ― ][IBU] ― 𝑘28[HO•][IBU] ― ΦIBU𝑓IBUI0(1 ― e ―2.303A) (10)
d[SO•4 ― ]
dt = 𝑘R4[SO•5 ― ][SO23 ― ] +

𝑘R6[SO•5 ― ][HSO3― ] + 𝑘R8[SO•5 ― ][SO•5 ― ] ―𝑘R13[SO•4 ― ][SO23 ― ] ― 𝑘R14[SO•4 ― ][HSO3― ] ― 𝑘R15[SO•4 ― ][H

[HSO5― ] ― 𝑘R27[SO•4 ― ][IBU] (11)

d[S—]
dt = 𝑘2[SO•3 ― ][O2] ― 𝑘4— ― 𝑘5[SO•5 ― ][SO23 ― ] ― 𝑘6[SO•5 ― ][HSO3― ] ―𝑘7[SO•5 ― ]

[HSO3― ] ― 𝑘R8[SO•5 ― ][S—] ― 𝑘R9[SO•5 ― ]— ― 𝑘R10[SO•5 ― ][HO•2] - —[SO•5 ― ][O•2 - ]

— (12)

Where  is the quantum yield (in mol‧einstein−1); f is the fraction of light absorbed

by individual species; I0 is the volume-averaged UV fluence rate (in einstein L−1s−1) ;

A is the total absorbance of the solution; and kRi is the reaction rate constants (in M−1‧s−1)

of the corresponding reaction Ri in Table 1. With all reactions and their rate constants

listed in Table 1 (R1–R32) and Table S1, the concentration time profiles of various

intermediates could be output via Kintecus V6.80 modeling software. Then, the time-

dependent contribution of various reaction routes to IBU degradation, S(IV)

consumption, SO4•− consumption, and SO5•− transformation processes could be

integrated according to equations S9–S12 using the function Integrate in software

Origin. The integrated transformation kinetics of S(IV), IBU, and PMS were compared

with that simulated using Model 1, and negligible difference was observed between

them, which further confirmed the reliability of the integration process.

Figure S1. Illustration of photochemical experiment setup. LP: low pressure.
 1.6
(a) (b)
2000
1.2

ln(C0/C)
I3 (M)

0.8
1000
-

-1
0.0004 s
2.35× 10
-6
mol/s 0.4

0 0.0

0 200 400 600 800 0 1000 2000 3000

Time (s) Time (s)

Figure S2. (a) Generation of I3− under UV irradiation in KI/KIO3 system; (b)

Photodecomposition of dilute H2O2 under UV irradiation. Conditions: (a) [I−]ini = 0.503

M, [IO3−]ini = 0.100 M, pH 9.25; (b) [H2O2]ini = 150 M.

 1.00 (a) 1.00 (b)
-1 -1
0.75 0.0006 s 0.75 0.0005 s

S(IV) C/C0
IBU C/C0

0.50 0.50
-1
0.0017 s
0.25 0.25 UV/Mn(II)
S(IV) alone
Mn(II)/S(IV)
0.00 0.00
0 200 400 600 800 0 200 400 600 800 1000
Time (s) Time (s)

Figure S3. Decay kinetics of IBU and S(IV) in various systems. Conditions: [S(IV)]ini

= 250 M, [Mn(II)]ini = 36 M, [IBU]ini = 2.0 M. The solid lines represent the fitting

curves with pseudo-first-order rate law.

 1.00 (a) 125 M 1.00 (c) 180 M 1.00 (b) 250 M
IBU S(IV)
UV/Mn(II)/S(IV)
0.75 0.75 0.75
UV/S(IV)

C/C0
C/C0

C/C0
0.50 0.50 0.50

0.25 0.25 0.25

0.00 0.00 0.00

0 250 500 750 1000 0 250 500 750 1000 0 150 300 450 600
Time (s) Time (s) Time (s)
1.00 (a) pH 6.0 1.00 (b) pH 8.0 1.00 (c) pH 9.0

0.75 0.75 0.75

C/C0
C/C0

0.50 C/C0 0.50 0.50

0.25 0.25 0.25

0.00 0.00 0.00

0 250 500 750 1000 0 250 500 750 1000 0 1000 2000 3000
Time (s) Time (s) Time (s)

Figure S4. Influence of (a-c) S(IV) dosage and (d-f) solution pH on the transformation

kinetics of IBU and S(IV) in the UV/Mn(II)/S(IV) and UV/S(IV) systems. The removal

kinetics was fitted using the pseudo first-order rate law and the obtained rate constants

are summarized in Figure 1(d–i). Conditions: [Mn(II)]ini = 36 M, [IBU]ini = 2.0 M;

(a–c) pH = 7.0; (d–e) [S(IV)]ini = 250 M.

 1.00 (a) IBU 1.00 (b) S(IV)
-1 -1
(0.0006 s ) (0.0005 s )
0.75 0.75
Blank control
C/C0

C/C0
TBA = 10.0 mM
0.50 0.50 EtOH = 10.0 mM
-1
(0.0014 s )
-1
0.25 0.25 (0.0035 s )

-1 -1
(0.0041 s ) (0.0087 s )
0.00 0.00
0 200 400 600 0 200 400 600
Time (s) Time (s)

Figure S5. Influence of tert-butanol and ethanol on the transformation kinetics of (a)

IBU and (b) S(IV) in the UV/S(IV) system. Conditions: [S(IV)]ini = 250 M, [Mn(II)]ini

= 36 M, [IBU]ini = 2.0 M, pH 7.0. The solid lines represent the fitting curves with

pseudo first-order assumption and the colored numbers indicate the derived pseudo

first-order rate constants.

 200 (a) (c) (e)
200 100

150 150 75
PMS (M)

100 100 50

50 50 25

0
0 0
0 1000 2000 3000 4000 0 1000 2000 3000 4000 0 1000 2000 3000 4000
2.0 2.0 (d) 2.0
(b) (f)
[PMS]ini = 100 M [PMS]ini = 100 M
1.5 1.5 1.5
[PMS]ini = 200 M [PMS]ini = 200 M
IBU (M)

1.0 1.0 1.0

0.5 0.5 0.5

0.0 0.0 0.0

0 50 100 150 200 0 50 100 150 200 0 50 100 150 200
Time (s) Time (s)
Time (s)

Figure S6. Experimental vs modeled kinetics of PMS decomposition and IBU

degradation in the UV/PMS system under different conditions: (a–b) pH 7.0, (c–d) pH

9.0, (e–f) pH 8.0. In (a–b), solid/dashed/dotted lines represent the model predictions

with 𝚽𝑺𝑶𝟐𝟓 ― = 0 mol‧einstein−1 and 𝚽𝑯𝑺𝑶𝟓― = 0.135/0.130/0.140 mol‧einstein−1,

respectively. In (c–d), solid/dashed/dotted lines represent the model predictions with

𝚽𝑯𝑺𝑶𝟓― = 0.135 mol‧einstein−1 and 𝚽𝑺𝑶𝟐𝟓 ― = 0.174/0.162/0.188 mol‧einstein−1,

respectively. In (e-f), solid lines represent the model predictions with 𝚽𝑺𝑶𝟐𝟓 ― = 0.174

mol‧einstein−1 and 𝚽𝑯𝑺𝑶𝟓― = 0.135 mol‧einstein−1. Conditions: [PMS]ini = 100 or 200

M, [IBU]ini = 2.0 M.

 3 8
(a) (b)
Exp.
Simul. 6
2
PMS (M)

PMS (M)
4

1
2

0 0
125 180 250 6.0 8.0 9.0
[S(IV)]ini (M) pH

Figure S7. Experimental vs modeled amounts of PMS accumulated after S(IV)

depletion in the UV/S(IV) system (a) at different S(IV) dosages and (b) at various pH

levels. Conditions: [IBU]ini = 2.0 M, sampling time = 1000 s, pH = 7.0 in panel a, and

[S(IV)]ini = 250 M in panel b.

 Exp. Simul.
Exp. Simul.
pH 6.0
125 M pH 7.0
180 M pH 8.0
250 M pH 9.0

(a) (b) 1.0 (c) 1.0 (d)

1.0 1.0

0.8 0.8 0.8 0.8

S(IV) C/C0

S(IV) C/C0
IBU C/C0

IBU C/C0
0.6 0.6 0.6 0.6

0.4 0.4 0.4 0.4

0.2 0.2 0.2 0.2

0.0 0.0 0.0 0.0

0 500 1000 0 500 1000 0 500 1000 0 500 1000
Time (s) Time (s) Time (s) Time (s)
(e) (f) 1.0 (g) 1.0 (h)
1.0 1.0

0.8 0.8 0.8 0.8

S(IV) C/C0

S(IV) C/C0
IBU C/C0

IBU C/C0
0.6 0.6 0.6 0.6

0.4 0.4 0.4 0.4

0.2 0.2 0.2 0.2

0.0 0.0 0.0 0.0

0 500 1000 0 500 1000 0 500 1000 0 500 1000
Time (s) Time (s) Time (s) Time (s)

Figure S8. Experimental (symbols) vs modeled (lines) transformation kinetics of S(IV)

and IBU in the UV/S(IV) system at (a, b, e, f) various S(IV) dosages and (c, d, g, h) pH

levels. Dashed lines in panels (a–d) represent the model predictions with kR4 =

(1.4±0.8)×105 M−1s−1, kR5 = (3.6±0.8)×105 M−1s−1, kR6 = (3.4±0.4)×102 M−1s−1, and kR7

= (8.3±1.0)×103 M−1s−1;14 while dashed lines in panels (e–h) represent the model

predictions with kR4 = 7.4×104 M−1s−1, kR5 = 2.5×104 M−1s−1, kR6 = 3×105 M−1s−1, and

kR7 = 3×105 M−1s−1.15 Conditions: [IBU]ini = 2.0 M, pH = 7.0 for panels a, b, e, and f,

while [S(IV)]ini = 250 M for panels c, d, g and h.

 100 100 100 100
(a) IBU removed (b) S(IV) consumed (c) SO5· - transformed (d) SO4· -
consumed
Contribution (%) 80 80 80 80
125 M
60 180 M 60 60 60
250 M
40 40 40 40

20 20 20 20

0 0 0 0
- - · - · - · - 2-
MS hv
· · · - · -
by SO4· -
O O8 MS V) U
OH
by hv by HO· SO 5 y SO 4by P by by H by O 2 O4
to S to S
O3
to S 2 to P S(I by IB O/ O 2
by b by H 2 by
by
100 100 100 100
(e) IBU removed (f) S(IV) consumed (g) SO5· - transformed (h) SO4· -
consumed
80 80 80 80
Contribution (%)

pH 6.0
60 pH 7.0 60 60 60
pH 8.0
40 pH 9.0 40 40 40

20 20 20 20

0 0 0 0
- - · - · - · - 2-
MS hv
· · ·
· -
by SO4· MS V)
-
by hv by HO· O O4 O3 O8 U
SO 5 y SO 4by P by by H by O 2 to S to S to S 2 to P S(I by IB O 2
by b by by

Figure S9. Influence of (a–d) S(IV) dosage and (e–h) solution pH on the transformation

of IBU, S(IV), SO5•−, and SO4•− in the UV/S(IV) system. Conditions: [S(IV)]ini = 250

M, [IBU]ini = 2.0 M.

 0.8 5.0 2.0 8.0
(M) (a) (b) (c) (d)

(M)

(M)

(M)
4.0
0.6 125 M 1.5 6.0
11

11

11
180 M

14
3.0
[SO3 ] x 10

[SO5 ] x 10

[SO4 ] x 10

[HO ] x 10
250 M
0.4 1.0 4.0
2.0
· -

· -

· -

·
0.2 0.5 2.0
1.0

0.0 0.0 0.0 0.0

0 200 400 600 800 0 200 400 600 800 0 200 400 600 800 0 200 400 600 800
Time (s) Time (s) Time (s) Time (s)
2.0 5.0 2.0 8.0
(e) (f) (g) (h)
(M)

(M)

(M)

(M)
4.0
1.5 1.5 6.0
pH 6.0
11

11

11

14
3.0
[SO3 ] x 10

[SO5 ] x 10

[SO4 ] x 10
pH 7.0

[HO ] x 10
1.0 pH 8.0 1.0 4.0
pH 9.0 2.0
· -

· -

· -

·
0.5 0.5 2.0
1.0

0.0 0.0 0.0 0.0

0 200 400 600 800 0 200 400 600 800 0 200 400 600 800 0 200 400 600 800
Time (s) Time (s) Time (s) Time (s)

Figure S10. Transformation kinetics of SO3•−, SO5•−, SO4•−, and HO• in the UV/S(IV)

system at various (a–d) S(IV) dosages and (e–h) pH levels simulated using Model 1.

Conditions: [IBU]ini = 2.0 M; pH = 7.0 for panels (a–d); [S(IV)]ini = 250 M for panels

(e–h).
 1.0 (c) 1.0 (d)
0.8 pH 6.0 0.8

S(IV) C/C0
pH 7.0

IBU C/C0
0.6 pH 8.0 0.6
pH 9.0
0.4 0.4

0.2 0.2

0.0 0.0
0 500 1000 1500 0 500 1000 1500
Time (s) Time (s)

Figure S11. Modeled transformation kinetics of (a) S(IV) and (b) IBU in the UV/S(IV)

system. Solid lines represent the model prediction by considering reactions in both

Table 1 (R1–R32) and Table S1; hollow points represent the model prediction by only

considering the reactions in Table 1 (R1–R32). Conditions: [S(IV)]ini = 250 M,

[IBU]ini = 2.0 M, pH = 6.0–9.0.

 1.0 (a) 1.0 (b) Exp. Simul. (c)
Exp. Simul. Exp. Simul.
100
18 M
0.8 S(IV) 0.8 S(IV)
9 M

PMS (M)
IBU IBU 75
0.6 0.6
C/C0

C/C0
0.4 0.4 50

0.2 0.2 25

0.0 0.0
0
0 100 200 300 400 500 0 100 200 300 400 500 0 500 1000 1500 2000

Time (s) Time (s) Time (s)

Figure S12. Experimental vs modeled kinetics of S(IV), IBU, and PMS transformation

in the UV/Mn(II)/S(IV) system at different initial Mn(II) dosages. Solid lines in figures

(a–c) represent the model predictions with 𝒌𝐑𝟑𝟑 = 2.30 × 109 M−1‧s−1 and 𝒌𝐑𝟑𝟒 = 1.0

× 108 M−1‧s−1, and 𝒌𝐑𝟑𝟓 = 1.0 × 106 M−1‧s−1. Conditions: [S(IV)]ini = 250 M, [IBU]ini

= 2.0 M, pH 7.0.

 1.0 (a) 1.0 (b) 150 (c)
pH 6.0
pH 8.0 125
0.8 0.8

S(IV) C/C0

PMS (M)
pH 9.0
IBU C/C0

100
0.6 0.6
75
0.4 0.4
50
0.2 0.2
25
0.0 0.0
0
0 500 1000 1500 2000 0 500 1000 1500 2000 0 500 1000 1500 2000

Time (s) Time (s) Time (s)

Figure S13. Experimental vs modeled kinetics of IBU, S(IV), and PMS transformation

in the UV/Mn(II)/S(IV) system at different pH levels. Solid lines in figures (a–c)

represent the model predictions with 𝒌𝐑𝟑𝟑 = 2.30 × 109 M−1‧s−1 and 𝒌𝐑𝟑𝟒 = 5.00 ×

107 M−1‧s−1, and 𝒌𝐑𝟑𝟓 = 106 M−1‧s−1 at pH 6.0, 𝒌𝐑𝟑𝟑 = 2.30 × 109 M−1‧s−1 and 𝒌𝐑𝟑𝟒

= 6.00 × 104 M−1‧s−1, and 𝒌𝐑𝟑𝟓 = 1.40 × 106 M−1‧s−1 at pH 8.0; and 𝒌𝐑𝟑𝟑 = 2.30 × 109

M−1‧s−1 and 𝒌𝐑𝟑𝟒 = 6.70 × 103 M−1‧s−1, and 𝒌𝐑𝟑𝟓 = 5.20 × 107 M−1‧s−1 at pH 9.0.

Conditions: [S(IV)]ini = 250 M, [Mn(II)]ini = 2.0 M, [IBU] = 2.0 M.
 0.6 0.20
5.0 mM PP was added and
0.5 then stand for 20 min
0.15 Standard spectrum of
0.4 20 M Mn(III)-PP
Abs

Abs
0.3 0.10

0.2
t = 0-40 min (every 2.0 min) 0.05
0.1
(a) (b)
0.00
0.0
200 300 400 500 600 300 400 500 600 700

 (nm)  (nm)

Figure S14. (a) UV-vis spectra evolution in the UV/Mn(II)/S(IV) system at pH 9.0; (b)

After the depletion of S(IV) in the UV/Mn(II)/S(IV) system at pH 9.0, appropriate

amount of PP (final concentration is 5.0 mM) was added and reacted for 20 min, and

then the UV-vis absorption spectrum of the resulting solution was recorded and shown

in panel b (solid line), along with the standard spectrum of 20 M Mn(III)-PP (doted

line). Note that in panel b, UV lamp was turned off after the depletion of S(IV) in the

UV/Mn(II)/S(IV) system and then PP was added to induce the generation of Mn(III)-

PP via the reaction MnO2 + Mn(II) → Mn(III)-PP. Conditions: [S(IV)]ini = 250 M,

[Mn(II)]ini = 36 M, [IBU] = 0 M.

Table S1. Supplementary reactions involved in the UV/S(IV) process (Reactions below

have insignificant influence on the decay kinetics of S(IV) or IBU in the UV/S(IV)

system over the pH range of 6.0–9.0)a.

No. Reactions Rate constants (listed in M−1‧s−1 Ref.

unless otherwise specified)
I0
R43 S O 2− ℎ𝑣
2SO4•− 𝑟S2O28 ― = ΦSO•4 ― 𝑓S2O28 ― V (1 ― e2.303LΣϵiCi)
12, 16
2 8
AbsS2O28 ―
fS2O28 ― =
Abstotal
ΦS2O8 = 0.7 mol‧einstein−1
2 ―

I0
R44 H O ℎ𝑣
2HO• 𝑟H2O2 = ΦSO•4 ― 𝑓H2O2 V (1 ― e2.303LΣϵiCi)
17
2 2
AbsH2O2
fH2O2 =
Abstotal
ΦHO• = 1.0 mol‧einstein−1

R45 SO4•− + HO2• → SO42− + H+ + O2 3.50×109 16

R46 •O− + O2 → O3•− 2.00×109 16, 18

R47 O3•− + H2O → HO3• + OH− 8.50×109 s−1 16

R48 O2•− + SO32− (+ 2H+) → SO3•− + H2O2 82.00 19

R49 eaq− + eaq− (+ 2H2O) → 2OH− + H2 5.05×109 16, 18

R50 eaq− + H+ → H• 2.30×1010 16, 18

R51 eaq− + •O− (+ H2O) → 2OH− 2.20×1010 18

R52 eaq− + O2•− → O22− 1.30×1010 18

R53 eaq− + H2O → H• + OH− 27.0 20

R54 H• + H2O → H2 + HO• 10.0 18

R55 H• + OH− → eaq− + H2O 2.20×107 18

R56 H• + H• → H2 5.00×109 16

R57 H• + O2 → HO2• 1.20×1010 16

R58 H• + HO2• → H2O2 2.00×1010 16

R59 H• + S2O82− → HSO4− + SO4•− 1.40×107 16

R60 H• + HSO5− → SO4•− + H2O 8.00×107 16

R61 eaq− + H• (+ H2O) → OH− + H2 2.50×1010 16

R62 eaq− + S2O82− → SO4•− + SO42− 1.20×1010 16

R63 eaq− + HSO5− → HO• + SO42− 8.40×109 16

R64 eaq− + HSO5− → OH− + SO4•− 2.10×109 16

R65 eaq− + H2O2 → OH− + HO• 1.30×1010 16

R66 HO2• + HO2• → H2O2 + O2 8.30×105 21

R67 H2O2 + HSO3− → H+ + SO42− + H2O 1.00×103 21

R68 SO4•− + HO• → HSO5− 1.00×1010 16

R69 SO4•− + SO4•− → S2O82− 7.00×108 16

R70 SO4•− + SO52− → SO5•− + SO42− 1.00×108 16

R71 SO4•− + HSO5− → SO42− + SO5•− + H+ 1.00×106 16

R72 SO4•− + S2O82− → SO42− + S2O8•− 6.30×105 16

R73 SO4•− + H2O2 → HO2• + SO42− + H+ 1.20×107 16

R74 HO• + HSO3− → SO3•− + H2O 4.50×109 16

R75 HO• + S2O82− → OH−+ S2O8•− 1.20×107 16

R76 SO3•− + SO3•− → S2O62− 2.40×108 16

R77 SO3•− + SO3•− → SO32− + SO3 3.20×108 16

R78 SO3•− + SO52− → SO5•− + SO32− 4.30×106 16

R79 SO3•− + HSO5− → SO5•− + HSO3− 1.30×104 16

R80 SO5•− + S2O62− → SO4•− + S2O72− 1.00×107 16

R81 HO• + HO• → H2O2 5.50×109 16

R82 HO• + H2O2 → HO2• + H2O 2.70×107 16

R83 HO• + H• → H2O 7.00×109 16

R84 HO• + eaq− → OH− 3.30×1010 16

R85 H+ + OH− ⇌ H2O kf = 1.00×1011 M−1‧s−1

kb = 1.00×10−3 s−1
pKa = 14
R86 H+ + SO42− ⇌ HSO4− kf = 8.32×1012 M−1‧s−1 22
kb = 1.00×1011 s−1
pKa = 1.92
R87 O2•− + HO• → OH− + O2 1.10×1010 16, 18

R88 HO2• + HO• → H2O + O2 1.00×1010 16

R89 O2•− + •O− (+ H2O) → 2OH− + O2 6.00×108 18

R90 HO2• + SO32− (+ H+) → SO3•− + H2O2 82.00 19

R91 H• → eaq− + H+ 1.87×102 This
study
b

a. Species in brackets were written to keep equations balanced but were not taken into
account in the kinetic models.
b. Detailed calculation method was shown in Text S6
Table S2. Initial concentrations, absorption coefficients, and quantum yields of

concerned species used for the simulation.

Initial concentration 254 nm 
Species Ref.
(M) (M−1‧cm−1)
(pK - pH)
10 a2
[S(IV)],
HSO3− (pK - pH)
10 a2 +1   20

S(IV) = 125–250 M
1
2− (pKa2 - pH) [S(IV)], 20
SO3 10 +1 17.6 0.39
S(IV) = 125–250 M
IBU 2.0 350 0.1259 This study
HSO5− 0 13.52 0.135±0.005 This study
SO52− 0 149.5 0.174±0.12 This study
S2O82− 0 27.5 0.174±0.12 This study
Table S3. Reported rate constants of the reactions between SO5•− and S(IV).

No. Reactions Reference = rate constant (M−1‧s−1)

R4 16 = 5.60 × 108 (pH 9.5–11.5); 14 = (1.4±0.8) × 105

SO5•− + SO32− → SO42− +
(pH 9.0); 15 = 7.4 × 104 (pH 8.7);
SO4 •−

R5 16 = 1.00×108 (pH 9.5–11.5); 14 = (3.6±0.8) × 105

SO5•− + SO32− → SO52− +
(pH 9.0); 15 = 2.5 × 104 (pH 8.7);
SO3•−

R6 16 = 6.00 × 107 (pH 4–4.5); 14 = (3.4±0.4) × 102 (pH

SO5•− + HSO3− → SO4•−
4.0); 15 < 3 × 105 (pH 4.9);
+ H+ + SO42−
21 = 2.8 × 108 (pH ≈ 4);
R7 16 = 3.00 × 107 (pH 4–4.5); 14 = (8.3±1.0) × 103 (pH
SO5•− + HSO3− → HSO5−
4.0); 15 < 3 × 105 (pH 4.9); 21 = 8.5 × 103 (pH ≈ 4);
+ SO3 •−
Table S4. Calculated SD values in the UV/PMS system as a function of 𝚽𝐇𝐒𝐎𝟓― and

𝚽𝐒𝐎𝟐𝟓 ― (The quantity of data obtained from experiments performed at pH 7.0 and 9.0

are 36 and 34, respectively).

Parameter SD (HSO5−) SD (SO52−) SD (IBU) SD (overall)

𝚽𝑯𝐒𝐎𝟓―
(mol‧einstein−1)
0.125 0.0071 0.0071 0.0817 0.0221
0.127 0.0073 0.0073 0.0759 0.0211
0.129 0.0075 0.0075 0.0722 0.0202
0.130 0.0078 0.0078 0.0683 0.0199
0.133 0.0084 0.0084 0.0621 0.0192
0.135 0.0088 0.0088 0.0607 0.0189
0.136 0.0091 0.0091 0.0602 0.0190
0.137 0.0094 0.0094 0.0602 0.0196
0.139 0.0100 0.0100 0.0612 0.0202
0.140 0.0103 0.0103 0.0623 0.0207
0.142 0.0110 0.0110 0.0651 0.0218
0.146 0.0127 0.0127 0.0736 0.0248
𝚽𝐒𝐎𝟐𝟓 ―
(mol‧einstein−1
)
0.160 0.0745 0.0744 0.0897 0.0754
0.162 0.0732 0.0731 0.0831 0.0728
0.165 0.0719 0.0719 0.0739 0.0695
0.168 0.0716 0.0716 0.0668 0.0674
0.170 0.0718 0.0718 0.0629 0.0665
0.172 0.0724 0.0724 0.0591 0.0659
0.174 0.0733 0.0733 0.0562 0.0657
0.176 0.0743 0.0743 0.0540 0.0659
0.178 0.0758 0.0758 0.0520 0.0664
0.180 0.0773 0.0774 0.0506 0.0671
0.185 0.0824 0.0824 0.0491 0.0702
0.188 0.0858 0.0859 0.0493 0.0727
0.190 0.0887 0.0887 0.0500 0.0748
0.195 0.0959 0.0959 0.0530 0.0806
Table S5. Calculated overall SD values in the UV/S(IV) system (corresponding to

Figure 2 in main text) and the UV/Mn(II)/S(IV) system (corresponding to Figure S14)

under various experimental conditions.

System Quantity of
experiment Initial S(IV) dosages (M) pH conditions
al data
UV/S(IV) 236 125 180 250 6.0 8.0 9.0
0.058 0.123 0.049
0.0103 0.1825 0.0598
7 5 0
Initial Mn(II) dosages
(M)
UV/Mn(II)/S(IV) 98 18 9
0.3135 0.1308
Table S6. Calculated sensitivity measure S for SO32−, HSO3−, IBU, HSO5−, SO52−, SO4•−, SO5•−, SO3•−, and HO• and the summation of these 9

species as overall S in the UV/S(IV) system at pH 7.0.

Elementary reactions SO32− HSO3− IBU HSO5− SO52− SO4•− SO5•− SO3•− HO• overall S

R1 SO32− → SO3•− + eaq− 19.650 19.650 11.556 10.460 10.451 7.230 8.127 14.750 26.784 128.658

R27 IBU + SO4•− → Products + SO42− 5.639 5.639 20.177 5.932 5.928 8.744 8.586 8.140 11.827 80.612

R31a HSO3− → SO32− + H+ 5.774 19.084 5.978 4.348 3.000 2.986 10.366 4.356 15.004 70.895

R31 SO32− + H+ → HSO3− 5.770 19.027 5.964 4.349 2.993 2.986 10.348 4.357 15.026 70.820

R24 HSO5− + SO32− → 2SO42− + H+ 7.696 7.696 5.472 8.321 8.326 3.375 3.193 10.710 3.189 57.978

R29 ℎ𝑣
57.505
IBU Products 10.354 10.354 9.794 1.588 1.588 2.106 2.163 10.690 8.868

R26 HO• + HSO5− → SO5•− + H2O 9.111 9.111 6.398 2.010 2.011 2.664 2.438 11.371 5.501 50.615

R4 SO5•− + SO32− → SO42− + SO4•− 2.021 2.021 2.139 12.088 12.087 1.920 11.913 1.790 1.329 47.308

R12 O2•− + HO2• → H2O2 + O2 7.102 7.102 5.198 3.359 3.359 4.074 3.882 10.767 2.415 47.258

R14 SO4•− + HSO3− → SO42− + SO3•− 3.414 3.414 8.994 2.524 2.522 9.035 3.663 4.872 6.075 44.513

R13 SO4•− + SO32− → SO42− + SO3•− 3.268 3.268 8.530 2.566 2.563 9.047 3.693 5.461 5.641 44.037

R23 HSO5− + HSO3− → 2SO42− + 2H+ 1.533 1.533 0.954 10.895 10.888 1.323 1.370 0.296 3.801 32.593

R17 SO4•− + O2•− → SO42− + O2 4.851 4.851 2.997 2.571 2.569 2.229 2.322 2.948 6.999 32.337
R5 SO5•− + SO32− → SO42− + SO3•− 2.138 2.138 1.364 9.812 9.825 1.277 1.142 1.741 1.820 31.257

R30 H+ + O2•− → HO2• 2.552 2.552 1.585 1.376 1.298 1.353 1.411 1.375 3.814 17.314

R30a HO2• →H+ + O2•− 2.549 2.549 1.584 1.375 1.297 1.353 1.410 1.375 3.815 17.308

R32 SO52− + H+ → HSO5− 0.079 0.079 0.050 0.053 0.072 0.075 0.009 16.085 0.199 16.700

R32a HSO5− →SO52− + H+ 0.078 0.078 0.050 0.053 0.072 0.074 0.009 16.001 0.198 16.614

R21 ℎ𝑣
16.605
HSO5− SO4•− + HO• 1.995 1.995 1.278 1.142 1.142 1.833 1.890 0.211 5.119

R2 SO3•− + O2 → SO5•− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 16.040 0.000 16.04

R7 SO5•− + HSO3− → HSO5− + SO3•− 1.016 1.016 0.649 4.665 4.651 0.607 0.543 0.828 0.865 14.84

R15 SO4•− + H2O → H+ + SO42− + HO• 0.016 0.016 0.010 0.011 0.011 0.370 0.029 0.030 14.047 14.54

R74 HO• + HSO3− → SO3•− + H+ + H2O 0.100 0.100 0.076 0.062 0.062 0.100 0.109 0.014 8.638 9.261

R6 SO5•− + HSO3− → SO4•− + H+ + SO42− 0.967 0.967 0.684 0.138 0.139 0.337 0.149 1.112 4.409 8.902

R63 eaq− + HSO5− → HO• + SO42− 0.343 0.343 0.363 2.050 2.050 0.326 2.020 0.303 0.225 8.023

R20 HO•+ SO32− → SO3•− + OH− 1.365 1.365 0.965 0.213 0.213 0.296 0.247 1.588 0.960 7.212

R45 SO4•− + HO2• → SO42− + H+ + O2 0.076 0.076 0.058 0.047 0.047 0.075 0.083 0.011 6.538 7.011

R66 HO2• + HO2• → H2O2 + O2 1.303 1.303 0.928 0.226 0.226 0.303 0.256 1.550 0.783 6.878

R65 eaq− + H2O2 → OH− + HO• 1.288 1.288 0.916 0.212 0.213 0.289 0.243 1.527 0.780 6.756
R51 eaq− + •O− → 2OH− 1.259 1.259 0.896 0.209 0.209 0.284 0.239 1.493 0.762 6.61

R3 eaq− + O2 → O2•− 1.178 1.178 0.837 0.194 0.194 0.264 0.222 1.395 0.712 6.174

R43 ℎ𝑣
5.658
S2O82− 2SO4•− 1.077 1.077 0.760 0.156 0.156 0.219 0.179 1.223 0.811

R57 H• + O2 → HO2• 0.997 0.997 0.713 0.142 0.142 0.198 0.157 1.151 0.620 5.117

R68 SO4•− + HO• → HSO5− 0.977 0.977 0.697 0.150 0.150 0.207 0.169 1.144 0.598 5.069

R56 H• + H• → H2 0.961 0.961 0.685 0.148 0.148 0.203 0.167 1.125 0.588 4.986

R50 eaq− + H+ → H• 0.961 0.961 0.685 0.148 0.148 0.203 0.167 1.125 0.588 4.986

R11 SO5•− + O2•− → SO52− + O2 0.958 0.958 0.683 0.147 0.147 0.203 0.166 1.121 0.586 4.969

R48 O2•− + SO32− → SO3•− + OH− + H2O2 0.761 0.761 0.465 0.341 0.341 0.348 0.385 0.459 1.088 4.949

R71 SO4•− + HSO5− → SO42− + SO5•− + H+ 0.593 0.593 0.350 0.246 0.246 0.133 0.140 0.538 0.712 3.551

R28 IBU + HO• → Products + OH- 0.373 0.373 0.269 0.038 0.038 0.048 0.028 0.400 0.250 1.817

R22 ℎ𝑣
1.234
SO52− SO4•− + HO• 0.105 0.105 0.181 0.064 0.064 0.070 0.083 0.030 0.532

R18 HO• + OH− → •O− + H2O 0.077 0.077 0.049 0.044 0.044 0.071 0.073 0.008 0.198 0.641

R19 •O − + H2O → OH− + HO• 0.045 0.045 0.030 0.029 0.029 0.078 0.081 0.036 0.199 0.572

R46 •O − + O2 → O3•− 0.031 0.031 0.020 0.020 0.020 0.052 0.053 0.023 0.133 0.383

R87 O2•− + HO• → OH− + O2 0.031 0.031 0.020 0.020 0.020 0.051 0.053 0.023 0.133 0.382
R12 SO5•− + HO2• → HSO5− + O2 0.026 0.026 0.016 0.016 0.016 0.026 0.028 0.002 0.097 0.253

R73 SO4•− + H2O2 → HO2• + SO42− + H+ + H2O 0.032 0.032 0.020 0.014 0.014 0.015 0.016 0.019 0.046 0.208

R63 eaq− + HSO5− → HO• + SO42− 0.016 0.016 0.010 0.010 0.010 0.014 0.014 0.003 0.029 0.122

R67 H2O2 + HSO3− → H+ + SO42− + H2O 0.018 0.018 0.011 0.007 0.007 0.006 0.006 0.014 0.023 0.11

R16 SO4•− + OH− → SO42− + HO• 0.012 0.012 0.006 0.007 0.007 0.013 0.013 0.002 0.022 0.094

R90 HO2• + SO32− → SO3•− + OH− + H2O2 0.000 0.000 0.000 0.000 0.000 0.003 0.000 0.000 0.084 0.087

R52 eaq− + O2•− → O22− 0.000 0.000 0.000 0.000 0.000 0.002 0.000 0.000 0.072 0.074

R70 SO4•− + SO52− → SO5•− + SO42− 0.004 0.004 0.002 0.002 0.002 0.001 0.001 0.003 0.004 0.023

R25 HO• + SO52− → SO5•− + OH− 0.001 0.001 0.001 0.000 0.000 0.000 0.000 0.001 0.001 0.005

R82 HO• + H2O2 → HO2• + H2O 0.000 0.000 0.000 0.001 0.001 0.000 0.000 0.000 0.001 0.003

R9b SO5•− + SO5•− → S2O82− + O2 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.002 0.002

R88 HO2• + HO• → H2O + O2 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.001

R69 SO4•− + SO4•− → S2O82− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R53 eaq− + H2O → H• + OH− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.001

R8 SO5•− + SO5•− → 2SO4•− + O2 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R77 SO3•− + SO3•− → SO32− + SO42− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0
R76 SO3•− + SO3•− → S2O62− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R54 H• + H2O → H2 + HO• 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R78 SO3•− + SO52− → SO5•− + SO32− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R79 SO3•− + HSO5− → SO5•− + HSO3− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R89 O2•− + •O− → 2OH− + O2 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R83 HO• + H• → H2O 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R80 HO• + HO• → H2O2 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R60 H• + HSO5− → SO4•− + H2O 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R72 SO4•− + S2O82− → SO42− + S2O8•− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R62 eaq− + S2O82− → SO4•− + SO42− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R49 eaq− + eaq− → 2OH− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R84 HO• + eaq− → OH− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R59 H• + S2O82− → HSO4− + SO4•− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R58 H• + HO2• → H2O2 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R61 eaq− + H• → OH− + H2 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R75 HO• + S2O82− → OH−+ S2O8•− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0
R80 SO5•− + S2O62− → SO4•− + S2O72− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R55 H• + OH− → eaq− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

R47 O3•− + H2O → HO3• + OH− 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0

Note: a. These reactions are deprotonation processes, and are the complementary process of the corresponding protonation reaction.
Table S7. Calculated SD values in the UV/Mn(II)/S(IV) system as functions of kR33,

kR34 and kR35 at pH 6.0–9.0.

pH 7.0; Number of experimental data is 151

Parameter SD (HSO3−) SD (SO32−) SD (IBU) SD (HSO5−) SD (overall)

kR33
2.10 × 109 0.3664 0.3774 0.4591 0.0062 0.3366
2.15 × 109 0.3278 0.3301 0.4424 0.0061 0.3127
2.20 × 109 0.3117 0.3074 0.4270 0.0063 0.2988
2.30 × 109 0.3258 0.3142 0.3993 0.0075 0.2918
2.40 × 109 0.3596 0.3476 0.3740 0.0096 0.2952
2.45 × 109 0.3732 0.3630 0.3633 0.0110 0.2969
2.50 × 109 0.3871 0.3821 0.3570 0.0125 0.3011
2.55 × 109 0.3947 0.3894 0.3422 0.0144 0.2983
2.60 × 109 0.4024 0.3991 0.3326 0.0164 0.2982
3.00 × 109 0.4510 0.4531 0.2732 0.0383 0.2983
kR34
1.00 × 106 1.8509 2.0133 2.8567 0.0388 1.9428
1.00 × 107 0.3120 0.3113 0.5113 0.0061 0.3340
1.26 × 107 0.3050 0.3017 0.4867 0.0063 0.3206
1.58 × 107 0.3021 0.2968 0.4662 0.0065 0.3108
3.16 × 107 0.3045 0.2954 0.4293 0.0069 0.2960
3.60 × 107 0.3064 0.2970 0.4235 0.0070 0.2943
3.80 × 107 0.3074 0.2977 0.4216 0.0070 0.2939
5.00 × 107 0.3119 0.3015 0.4144 0.0072 0.2926
1.00 × 108 0.3258 0.3142 0.3993 0.0075 0.2918
3.16 × 108 0.3469 0.3344 0.3872 0.0077 0.2951
5.00 × 108 0.3531 0.3405 0.3848 0.0078 0.2966
6.31 × 108 0.3556 0.3429 0.3837 0.0078 0.2971
1.00 × 109 0.3594 0.3466 0.3822 0.0078 0.2980
1.00 × 1010 0.3621 0.3492 0.3787 0.0079 0.2977
kR35
0 0.3263 0.3146 0.3995 0.0078 0.2921
1.00 × 101 0.3263 0.3146 0.3995 0.0078 0.2921
1.00 × 102 0.3263 0.3146 0.3995 0.0077 0.2921
1.00 × 103 0.3263 0.3146 0.3995 0.0076 0.2921
1.00 × 104 0.3263 0.3146 0.3996 0.0075 0.2921
1.00 × 105 0.3263 0.3146 0.3999 0.0075 0.2922
1.00 × 106 0.3258 0.3142 0.3993 0.0075 0.2918
1.20 × 106 0.3258 0.3142 0.3993 0.0075 0.2918
1.00 × 107 0.3226 0.3111 0.4016 0.0074 0.2918
1.00 × 108 0.3048 0.2949 0.4296 0.0070 0.2960
 3.00 × 108 0.2957 0.2891 0.4775 0.0064 0.3126
5.00 × 108 0.2946 0.2910 0.5202 0.0061 0.3301
1.0 × 109 0.3080 0.3114 0.6152 0.0060 0.3757
pH 6.0; Number of experimental data is 54
Parameter
SD (HSO3−) SD (SO32−) SD (IBU) SD (HSO5−) SD (overall)
kR34
1.00 × 106 0.5185 0.5185 0.7464 0.1896 0.5072
2.00 × 10 6 0.3946 0.3946 0.5143 0.0454 0.3545
3.00 × 10 6 0.3946 0.3946 0.5127 0.0458 0.3537
4.00 × 106 0.3918 0.3918 0.5072 0.0483 0.3503
5.00 × 106 0.3819 0.3819 0.5019 0.0505 0.3454
1.00 × 10 7 0.3583 0.3583 0.4985 0.054 0.3385
2.00 × 10 7 0.3328 0.3328 0.4941 0.0566 0.3308
3.00 × 10 7 0.2263 0.2263 0.4439 0.122 0.2868
5.00 × 10 7 0.1502 0.1502 0.4372 0.0985 0.2712
1.00 × 10 8 0.1538 0.1538 0.4464 0.0867 0.2762
1.00 × 10 9 0.1773 0.1773 0.4547 0.0794 0.2835
1.00 × 10 10 0.267 0.267 0.479 0.0645 0.3103
kR35
0 0.1553 0.1553 0.4526 0.0849 0.2799
101 0.1553 0.1553 0.4526 0.0849 0.2799
10 2 0.1553 0.1553 0.4526 0.0849 0.2799
10 3 0.1553 0.1553 0.4525 0.0849 0.2798
10 4 0.1551 0.1551 0.4519 0.0850 0.2794
10 5 0.1532 0.1532 0.4495 0.0863 0.2779
10 6 0.1502 0.1502 0.4372 0.0985 0.2712
3.00 × 10 6 0.1920 0.1920 0.4465 0.1214 0.2831
4.00 × 10 6 0.2191 0.2191 0.4663 0.1312 0.2986
5.00 × 10 6 0.2461 0.2461 0.4930 0.1402 0.3180
1.00 × 107 0.3645 0.3645 0.6803 0.1770 0.4419
1.00 × 108 1.1175 1.1175 5.7261 0.4210 3.4432
pH 8.0; Number of experimental data is 56
Parameter
SD (HSO3−) SD (SO32−) SD (IBU) SD (HSO5−) SD (overall)
kR34
1.00 × 104 1.8219 1.9299 0.1630 0.9195 1.3759
4.00 × 10 4 0.5360 0.5086 0.0595 0.8238 0.4515
4.30× 10 4 0.5086 0.4704 0.0570 0.8171 0.4311
4.50× 10 4 0.4947 0.4500 0.0558 0.8126 0.4205
5.00 × 10 4 0.4730 0.4145 0.0540 0.8010 0.4023
6.00 × 104 0.4679 0.3941 0.0543 0.7749 0.3910
7.00 × 104 0.4899 0.4133 0.0581 0.7426 0.3975
8.00 × 10 4 0.5219 0.4484 0.0639 0.7017 0.4111
9.00 × 10 4 0.5560 0.4874 0.0713 0.6502 0.4265
1.00 × 10 5 0.5888 0.5254 0.0813 0.5871 0.4480
 1.00 × 106 0.9219 0.9116 0.6092 6.4021 2.0668
kR35
1.00 × 105 0.7675 0.7334 0.2234 0.7909 0.6025
3.00 × 105 0.6470 0.5926 0.1005 0.4009 0.4658
5.00 × 105 0.5753 0.5094 0.0751 0.6015 0.4333
7.00 × 105 0.5298 0.4572 0.0650 0.6848 0.4137
1.00 × 106 0.4899 0.4134 0.0580 0.7409 0.3973
1.40 × 106 0.4679 0.3941 0.0543 0.7749 0.3910
2.00 × 106 0.4703 0.4093 0.0537 0.7992 0.3998
3.00 × 106 0.5137 0.4772 0.0573 0.8186 0.4348
4.00 × 106 0.5715 0.5546 0.0623 0.8294 0.4768
pH 9.0; Number of experimental data is 42
Parameter
SD (HSO3−) SD (SO32−) SD (IBU) SD (HSO5−) SD (overall)
kR34
5.00 × 103 0.0904 0.0530 0.1087 0.0847
5.30 × 103 0.0815 0.0449 0.1094 0.0805
5.40 × 103 0.0787 0.0425 0.1096 0.0793
5.50 × 103 0.0759 0.0403 0.1099 0.0782
6.00 × 103 0.0640 0.0330 0.1110 0.0742
6.40 × 103 0.0570 0.0330 0.1120 0.0728
6.70 × 103 0.0536 0.0362 0.1127 0.0729
7.00 × 103 0.0520 0.0414 0.1134 0.0737
7.40 × 103 0.0527 0.0501 0.1144 0.0760
7.60 × 103 0.0542 0.0549 0.1149 0.0776
7.80 × 103 0.0562 0.0598 0.1153 0.0794
7.90 × 103 0.0575 0.0624 0.1156 0.0804
8.00 × 103 0.0589 0.0649 0.1158 0.0814
9.00 × 103 0.0771 0.0905 0.1182 0.0940
1.00 × 104 0.0991 0.1155 0.1206 0.1088
5.00 × 104 0.0904 0.0530 0.1087 0.0847
kR35
1.00 × 107 0.1565 0.1724 0.1120 0.1449
3.00 × 107 0.0657 0.0672 0.1102 0.0812
3.10 × 107 0.0643 0.0649 0.1103 0.0803
4.00 × 107 0.0563 0.0485 0.1112 0.0750
5.20 × 107 0.0536 0.0362 0.1127 0.0728
6.00 × 107 0.0541 0.0320 0.1137 0.0728
7.00 × 107 0.0555 0.0299 0.1149 0.0735
1.00 × 108 0.0608 0.0329 0.1183 0.0768
1.30 × 108 0.0651 0.0390 0.1212 0.0801
2.00 × 108 0.0712 0.0503 0.1266 0.0861
5.00 × 108 0.0805 0.0727 0.1398 0.0992
1.00 × 109 0.0877 0.0886 0.1503 0.1095
Note that the SD (HSO5−) and SD (SO52−) values were absent for experiments
performed at pH 9.0 because only little (~2.0 M) PMS was generated after S(IV)
depletion at pH 9.0 and thus the consumption kinetics of PMS was not determined.
Moreover, PMS exists in the form of HSO5− at pH 6.0–8.0, and thus only SD (HSO5−)
was calculated for data derived from experiments performed at pH 6.0–8.0.
References
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polynuclear aromatic hydrocarbons in water. 2. UV radiation and
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(5), 1607-1615.
(2) Rahn, R. O.; Stefan, M. I.; Bolton, J. R.; Goren, E.; Shaw, P.-S.; Lykke,
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