DOI: 10.3303/CET24112009 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Paper Received: 8 March 2024; Revised: 17 April 2024; Accepted: 13 June 2024 
Please cite this article as: Bouguerra M.D.E., Witkowski B., Gierczak T., Barczak R.J., 2024, Methodology of Key Odorants Selection from 
Wastewater Treatment Plants Based on Their Kinetics with Selected Atmospheric Oxidants, Chemical Engineering Transactions, 112, 49-54  
DOI:10.3303/CET24112009 
  

 CHEMICAL ENGINEERING TRANSACTIONS  
 

VOL. 112, 2024 

A publication of 

 

The Italian Association 
of Chemical Engineering 
Online at www.cetjournal.it 

Guest Editors: Selena Sironi, Laura Capelli 

Copyright © 2024, AIDIC Servizi S.r.l. 
ISBN 979-12-81206-13-7; ISSN 2283-9216 

Methodology of Key Odorants Selection from Wastewater 

Treatment Plants Based on their Kinetics with Selected 

Atmospheric Oxidants 

Marouane Dhia Eddine Bouguerra, Bartłomiej Witkowski, Tomasz Gierczak, 

Radosław J. Barczak* 

Faculty of Chemistry, University of Warsaw, 1 Pasteura Street, 02-093, Warsaw, Poland 

rbarczak@chem.uw.edu.pl 

Nowadays, wastewater treatment plants (WWTPs) are considered significant contributors to odour emissions, 

which can have a sensorineural impact on surrounding communities. In this study, calculations of the half-lives 

of selected odorants commonly found in wastewater treatment plants were carried out, considering varying 

concentrations of atmospheric oxidants that exhibit diurnal and geographical fluctuations. Odorants displaying 

quick reactivity and brief half-lives, which were deemed less significant contributors to odour nuisances, reacted 

with nitrate radicals (NO3•) during nighttime and chlorine atoms (Cl*) with T½ ranging from 1.23 to 2.77×105 

minutes and from 6.57×10-4 to 3.14x103 minutes, respectively. On the other hand, extended half-lives were 

observed during reactions with ozone (O3), ranging between 1.81×103 and 1.61x1011 minutes, suggesting a 

potentially smaller role in the degradability of odorants in the atmosphere. These insights into odorant-oxidant 

kinetics may aid in predicting atmospheric lifetimes and their contribution to secondary aerosol formation, thus 

informing regulatory and mitigation strategies to improve air quality. 

1. Introduction 

The nuisance caused by unpleasant odours is a significant concern from both a societal and industrial standpoint 

(Chaignaud et al., 2014). Nuisance due to odour generation by WWTPs, and animal production operations is 

one of the major sources of complaints of people living near these facilities. It also has triggered increased 

emphasis on controlling the impact of atmospheric pollutants on neighbouring areas (Rincón et al., 2019). 

Undesirable odours can elicit a range of emotional and adverse responses in individuals, spanning from irritation 

to documented health effects, ultimately resulting in a diminished quality of life (Blanes-Vidal, 2015). The odours 

from WWTPs emissions form an intricate mixture containing a diverse range of odorants derived from various 

chemical groups, including sulphur and nitrogen compounds, aldehydes, acids, alcohols, aromatics, ketones, 

terpenes, indole, and skatole (Barczak et al., 2021; Byliński et al., 2019). Only certain malodorous compounds 

are detected in significant concentrations. 

The atmosphere possesses oxidizing capabilities, with key atmospheric daytime oxidant hydroxyl radical (OH). 

Additionally, oxidation processes can be initiated by NO3, O3, and Cl or Br atoms, and organic peroxyl radicals 

(RO2). These oxidants have the ability to transform initial air contaminants like carbon monoxide (CO), 

hydrocarbons (HCs), other organic compounds, nitrogen oxides (NOx), and sulphur dioxide (SO2) into carbon 

dioxide and some other products, rendering them more readily removable from the atmosphere (Chapleski et 

al., 2016). The understanding of odorant molecules kinetics in the presence of atmospheric oxidants is crucial 

for elucidating their fate and impact on air quality.  

In the lower atmosphere known as the troposphere, hydroxyl radicals play a crucial role as the main oxidizer for 

both naturally occurring and man-made compounds, which contributes to the formation of ozone. Within the 

troposphere, hydroxyl radicals are generated when oxygen atoms resulting from the breakdown of ozone 

photolysis (< 282 nm), interact with water vapor (Avallone, 2003). Therefore, OH radicals are formed, and active 

as an oxidant only during the daytime.  

49



The aim of this paper is to assess the role of different oxidants active mainly in the time when OH concentration 

is very low. Ozone undergoes gas-phase reactions with alkenes, or it reacts heterogeneously with building 

materials or surface-sorbed alkenes like squalene or monoterpenes. Ozone is active as an oxidant during the 

day as well as night. Ozone also serves as the initiator and primary driver of indoor chemistry, predominantly 

entering indoor environments through outdoor-to-indoor transport. Indoor ozone concentrations commonly 

range from 20% to 70% of ambient values.  

Nitrate radicals are generated through O3 reacting with nitrogen dioxide (NO2) to produce NO3 and O2 (Nazaroff 

& Cass, 1986). Following its formation, the oxidation facilitated by NO3 is primarily notable during nighttime and 

plays a role in the initiation of the oxidation of many trace gases at night, especially in the boundary layer. Also, 

NO3 has a rapid photolysis, characterized by a brief lifetime of approximately 5 seconds during the day. Due to 

the instability of NO3 in daylight and the rapid reaction between NO3 and NO, both N2O5 and NO3 are commonly 

depleted during the day and increase during the night (Wang & Ruiz, 2017). In contrast, this lifetime is notably 

curtailed in the presence of NO, especially in a photochemical steady state with NO2, during daytime conditions. 

Nevertheless, studies have demonstrated that NO3 can assume a pivotal role as a daytime oxidant within the 

canopy of forested environments.  

The chlorine atoms are the exceptionally reactive radicals that could have a notable impact on the oxidative 

chemistry of the troposphere, especially over oceanic and coastal regions abundant in available chloride. The 

photochemical cycling of reactive chlorine species is a process through which their interactions and 

transformations occur. The chlorine atoms can be formed in marine air through multiphase photochemical 

mechanisms. The oxidation of chloride in marine aerosols by various species leads to the production of gas-

phase species such as Cl2 and ClNO2. These compounds undergo photolysis during the daytime, releasing Cl 

atoms. In heavily polluted air, the generation of reactive chlorine is initiated by the reaction of N2O5 with aerosol 

chloride, as demonstrated in both laboratory and field observations. When gaseous N2O5 reacts 

heterogeneously with particulate chloride, it produces nitrile chloride (ClNO2). In urban sites, Cl atoms are 

derived from particle-phase chloride in the presence of both NO2 and ozone (O3). This trend encourages the 

accumulation of ClNO2 during nighttime. Following sunrise, ClNO2 undergoes photolysis, leading to the 

liberation of chlorine. 

Globally, oxidant concentrations vary depending on the surrounding environment, whether it be marine, urban, 

rural, and/or mountainous areas. Usually, ozone concentration is less in marine environment, medium in urban 

areas, and high in mountains, whereas chlorine is completely opposite. While for nitrate radicals are high in 

marine and mountains and less in urban areas as reported for oxidants in Table 2. 

In the present era, there is a gap in knowledge about the kinetics of some odorants with atmospheric oxidants. 

The study focuses on calculating the half-lives of odorants commonly found in WWTPs, considering varying 

atmospheric oxidants. The understanding of odorant molecules' kinetic in the presence of atmospheric oxidants 

is important because odorants with extended half-lives suggest a potentially heightened role in causing odour 

nuisances, while those with quick reactivity and brief half-lives in the presence of air oxidants are deemed less 

significant contributors to odour nuisances. 

 

Figure 1: The schematic illustrates how the odour can be emitted from WWTPs and its effect on surrounding 

residential communities. 

2. Methodology 

2.1 Selection of Odorants 

Targeted odorants listed in Table 1 have been identified in a previous work done by Barczak et al. (2022). Thus, 

based on the NIST Chemical Kinetics Database, these odorants have been assessed reaction rates and 

mechanisms of, spanning volatile organic compounds to sulfur-containing compounds, with atmospheric 

oxidants like ozone, nitrate radicals, and chloride atoms. In addition, depending on the reaction rate coefficients, 

(k), which have been extracted from the NIST Chemical Kinetics Database, and the oxidants concentration as 

50



well as the odorants concentrations taken from the literature, it will allow to choose potentially important odorants 

by calculating their half-lives. 

2.2 Sites description 

In this study, we employed ongoing measurements of oxidants, expanding upon insights gleaned from prior 

research endeavors. To comprehensively assess oxidant concentrations, our data primarily originated from 

monitoring activities conducted at three specific locations: marine, urban, and areas characterized by 

mountainous or rural landscapes. This approach aimed to capture a diverse range of environmental conditions 

and contribute to a more nuanced understanding of oxidant dynamics for odorants across varied settings. Table 

2 describes the different concentrations of the mentioned oxidants. 

2.3 Half-Lives Calculations 

This section utilizes the reaction information presented in Table 1 to construct models that explore the kinetics 

and reactions of the selected oxidants O3, NO3•, and Cl* atoms with the odorants. Based on the reactions of 

these odorants, which are Ammonia (NH3), Trimethylamine (TMA), Carbonyl sulfide (COS), Methanethiol (MT), 

Carbonyl disulfide (CS2), Ethanethiol (ET), Dimethyl sulfide (DMS), Dimethyl disulfide (DMDS), α-pinene 

(C10H16), Hydrogen sulfide (H2S), p-Xylene (C8H10), Toluene (C6H5CH3), 1,3,5-Trimethylbenzene (C9H12), 

Butanol (C4H9OH), with each oxidant, and using the previously determined reaction rate coefficients, at 298K. 

Consequently, the half-lives of the odorants computed by considering the concentrations of the oxidants [A] are 

constant and vary depending on diurnal and geographical fluctuations as shown in Table 2. The observed 

equation as reported by Atkins and De Paula (2006) is used for the targeted calculations (3). We obtain the 

equation for the half-life of a second-order reaction from the equation (1) as follows: 

(
[𝐵]0[𝐴]𝑡
[𝐵]𝑡[𝐴]0

) = 𝑘𝑡([𝐴]0 − [𝐵]0) (1) 

When the concentration of the odorant [B] is half of its initial:  

[𝐵]𝑡 =
[𝐵]0
2

 
(2) 

Substituting this into the equation, we get: 

T 
1

2
=

1

𝑘([𝐴]0−[𝐵]0)
𝑙𝑛 (

[𝐴]0[𝐵]0

[𝐴]𝑡.
[𝐵]0
2

) 

(3) 

Table 1 Selected odorants to be applied for kinetics determination. 

Reactant Reaction k298 /cm3 molecule-1 s-1 

 F* F* 

 Ammonia NH3 + NO3 → HNO3 + ·NH2 5.99 X10-16 

 NH3 + ·Cl → HCl + ·NH2 1.05 X10-13 

 (CH3)3N + O3 → Products 7.84 X10-18 

Trimethylamine F* F* 

 (CH3)3N + ·Cl → HCl + CH2N(CH3)2 4.83 X10-10 

 F* F* 

Carbonyl sulfide COS + NO3 → Products 1.00 X10-16 

 COS + ·Cl → CO + SCl 1.00 X10-16 

 F* F* 

Methanethiol CH3SH + NO3 → Products 9.20 X10-13 

 CH3SH + ·Cl → HCl + ·CH2SH 4.30 X10-12 

 F* F* 

Carbonyl disulfide CS2 + NO3 → Products 4.00 X10-16 

 CS2 + ·Cl → Products 4.00 X10-15 

 (CH3)2S + O3 → Products 1.00 X10-18 

Ethanethiol (CH3)2S + NO3 → HNO3 + CH3SCH2 1.10 X10-12 

 (CH3)2S + ·Cl → Products 3.30 X10-10 

 (CH3)2S + O3 → Products 1.00 X10-18 

Dimethyl sulfide (CH3)2S + NO3 → HNO3 + CH3SCH2 1.09 X10-12 

 (CH3)2S + ·Cl → Products 4.30 X10-10 

51



 ((CH3)2S + O3 → Products F* 

Dimethyl disulfide (CH3)2S + NO3 → Products 7.00 X10-13 

 (CH3)2S + ·Cl → CH3SCl + CH3S· 2.02 X10-10 

 alpha-pinene + O3 → Products 9.60 X10-17 

Alpha pinene alpha-pinene + NO3 → Products 6.16 X10-12 

 alpha-pinene + ·Cl → Products 4.70 X10-10 

 H2S + O3 → SO2 + H2O 3.99 X10-16 

Hydrogen sulfide H2S + NO3 → Products 1.00 X10-15 

 H2S + ·Cl → HCl + SH 7.44 X10-11 

 1,4-Dimethylbenzene + O3 → Products 5.00 X10-21 

p-xylene 1,4-Dimethylbenzene + NO3 → Products 4.53 X10-16 

 1,4-Dimethylbenzene + ·Cl → Products 1.40 X10-10 

 Toluene + O3 → Products 3.90 X10-22 

Toluene Toluene + NO3 → Products 6.79 X10-17 

 Toluene + ·Cl → Other Products + HCl 5.81 X10-11 

 1,3,5-Trimethylbenzene + O3 → Products F* 

1,3,5-trimethylbenzene 1,3,5-Trimethylbenzene + NO3 → Products 8.00 X10-16 

 1,3,5-Trimethylbenzene + ·Cl → Products Not- found 

 F* F* 

Butanol sec-C4H9OH + NO3 → Products 2.34 X10-15 

 sec-C4H9OH + ·Cl → CH3CH2C·(OH)CH3 + HCl 2.57 X10-9 

F* refers to that no data has been published in the NIST database. 

Table 2 Observed oxidant concentrations in different tropospheric environments. 

Oxidant Marine environment 

(molecules/cm3) 

Urban environment 

(molecules/cm3) 

Mountain environment 

(molecules/cm3) 

Ozone 
5.93×1011 

(Ding et al., 2020) 
10.6×1011 

(Haslett et al., 2023) 
1.31×1012 

(Chevalier et al., 2007) 

Nitrate Radicals 
24.3×1012 

(Li et al., 2022) 
2.16×1012 

(Haslett et al., 2023) 
0.00044×1012 

(Yun et al., 2024) 

Chlorine Atoms 

31.7×103 
(Lawler et al., 2011) 

14.5×103 
(Priestley et al., 2018) - 

3. Results and discussion 

In this section, we present the findings from assessing how various odorants emitted from wastewater treatment 

plants interact with air oxidants (such as ozone, nitrate radicals, and chlorine atoms). The assessment considers 

differences in oxidant concentrations across the areas where measurements were taken. However, certain 

odorants were excluded from analysis due to the lack of their reaction rate coefficients (k298) in the NIST 

database. As a result, it was not feasible to calculate their half-lives or estimate their persistence in the air as 

confirmed by (Ng et al., 2017). The excluded odorants due to lack of data published on the NIST database, 

which showed no reaction with O3, include ammonia, carbonyl sulfide, methanethiol, carbonyl disulfide, 1,3,5-

trimethylbenzene, and butanol. Additionally, two other odorants were not shown any reaction with nitrate radicals 

and chlorine atoms, which are trimethylamine and 1,3,5-Trimethylbenzene, respectively. Furthermore, to align 

with the primary objective of our study, we focused on identifying odorants that potentially play a significant role 

in causing odor nuisances with a high half-life duration. The nitrate radicals during the night showed a fast 

decrease in odorants concentration (brief half-lives) compared to those reacted with ozone, while chlorine atoms 

were fluctuating depending on the geographical environment. Table 3 shows all odorants achieved the 

maximum range of half-lives calculations. 

 

 

 

 

52



Table 3 List of odorants that achieved the maximum range of half-lives values. 

Reactant Environment T ½ O3 (min) T ½ NO3• (min) T ½ Cl* (min) 

 Marine site N* 1.51 1.63 

 Methanethiol Urban site N* 5.43×101 1.52 

 Mountain site N* 1.42×101 N* 

 Marine site 6.13×107 1.23 3.20×10-2 

Ethanethiol Urban site 2.14×109 2.38×101 2.97×10-2 

 Mountain site 1.09×108 1.79×101 N* 

 Marine site 1.04×105 N* 6.57×10-4 

Trimethylamine Urban site 1.07×105 N* 6.11×10-4 

 Mountain site 1.09×105 N* N* 

 Marine site N* 1.86×101 3.70×10-2 

Ammonia Urban site N* 1.71×101 3.44×10-2 

 Mountain site N* 1.21×101 N* 

 Marine site N* 2.89×104 3.14×103 

Carbonyl sulfide Urban site N* 8.81×103 2.92×103 

 Mountain site N* 5.85×103 N* 

 Marine site N* 3.86×103 7.13×102 

Carbonyl disulfide Urban site N* 4.24×104 6.73×102 

 Mountain site N* 1.33×104 N* 

 Marine site 1.77×107 1.31 1.19×10-2 

Dimethyl sulfide Urban site 2.58×107 1.85×104 1.11×10-2 

 Mountain site 2.34×107 8.74 N* 

 Marine site N* 1.93 5.39×10-2 

Dimethyl disulfide Urban site N* 3.63×101 5.00×10-2 

 Mountain site N* 2.90×101 N* 

 Marine site 1.01×106 2.18×10-1 2.67×10-2 

Alpha pinene Urban site 1.64×106 3.69 2.49×10-2 

 Mountain site 6.92×105 3.80 N* 

 Marine site 1.81×103 2.13×103 3.80×10-3 

Hydrogen sulfide Urban site 1.87×103 7.87×102 3.53×10-3 

 Mountain site 1.90×103 5.26×102 N* 

 Marine site 1.30×1010 2.88×103 4.80×10-1 

p-xylene Urban site 6.34×109 3.22×104 4.46×10-1 

 Mountain site 4.99×109 2.77×105 N* 

 Marine site 6.08×1010 2.06×104 1.08×10-1 

Toluene Urban site 1.03×1011 1.08×106 1.00×10-1 

 Mountain site 1.61×1011 1.72×105 N* 

 Marine site N* 1.66×103 N* 

1,3,5-trimethylbenzene Urban site N* 2.19×104 N* 

 Mountain site N* 5.14×104 N* 

 Marine site N* 5.57×102 3.12×10-2 

Butanol Urban site N* 6.15×103 2.89×10-2 

 Mountain site N* 6.39×104 N* 

N* refers to that no available data published for certain oxidants concentrations. 

4. Conclusion 

The evaluation indicates that the chosen odorants and VOCs emitted from the WWTPs exhibit prolonged 

persistence, lasting billions of seconds when exposed to air oxidants as reported in this study. Given the intricate 

nature of odor mixtures and perception, further in-depth studies are required to comprehensively understand 

the kinetics of these odorants. Understanding the kinetics of odorant-oxidant interactions is essential for 

predicting atmospheric lifetimes and their role in secondary aerosol formation, thereby guiding regulatory and 

mitigation efforts aimed at enhancing air quality. 

Acknowledgment 

This work was supported by an OPUS-21 no UMO-2021/41/B/ST8/03440 from National Science Centre, Poland. 

 

53



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	Methodology of Key Odorants Selection from Wastewater Treatment Plants Based on their Kinetics with Selected Atmospheric Oxidants