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Evaluation of Trihalomethane Formation Risk Analysis in Swimming Pools in Eskisehir, Turkey

Authors:
  • Eskisehir Technical University
  • Eskisehir Technical University
  • Eskişehir Teknik Üniversitesi

Abstract

Swimming pools are popular entertainment and sport areas that people often use. For this reason, it is crucial to determine the physicochemical properties and Trihalomethanes (THMs) concentrations of swimming pools and the effect of THMs on swimmer health. This study focuses on the physicochemical parameters and THM concentrations of six swimming pools in Eskisehir and the impacts of THMs on human health. Within the study context, physicochemical parameters were examined and swimming pool water standards of various countries and organizations were evaluated. The alkalinity, pH, temperature, hardness, and free chlorine values of the swimming pools were determined to compare with the current standards. Concentrations of chloroform (TCM), bromodichloromethane (BDCM), and dibromochloromethane (DBCM) were also determined in the collected samples. Concentrations were found to be in the range of 11.6-100.1 µg/l for BDCM, 151.5-366.4 µg/l for TCM, ND-6.95 µg/l for DBCM, and 172.1-380.7 µg/l for TTHM. From the results, it was determined that TTHM concentrations were above the limit values defined by WHO, while chloroform (except P1 and P5 pools), BDCM (except P3 pool), and DBCM concentrations were significantly below the limit values. TTHMs and chloroform concentrations were high in tap water using sodium hypochlorite as a disinfectant. BDCM and DBCM concentrations were high in pools where groundwater was used. Health risks of THMs in pools through ingestion and dermal absorption were also estimated for both women and men. In the interpretation of the result, it was also found that high concentrations of TTHMs increased the risk, and women’s ingestion-based risk values are slightly higher than men’s ingestion-based risk values. Fingerprints of THM formation in pool water are precursor parameters and it is of great importance to constantly control and take precautions. It has been observed that the use of groundwater as a water source and NaCl as a disinfectant significantly reduces THM formation in swimming pools. However, in order to reduce the BDCM and DBCM concentrations in the use of groundwater, it is recommended to measure the precursor bromide and establish the relevant limit values. The use of hypochlorite disinfectants in pools where tap water is used as a water source increases THM formation. For this reason, it is necessary to determine the amount of organic carbon as a precursor for pools using tap water as a water source and add it to the limit values. In addition, the use of calcium hypochlorite disinfectant instead of sodium hypochlorite reduces THM formation. • Highlight • Physicochemical properties and THMs concentrations of swimming pools and effects of trihalomethanes (THMs) on the health of swimmers. • Physicochemical parameters and THM concentrations of six swimming pools were determined, and the effects of THMs’ on human health. • Physicochemical parameters (alkalinity, pH, temperature, and hardness), chloroform (TCM), bromodichloromethane (BDCM), and dibromochloromethane (DBCM) were studied. • As a result of the study, total THMs and TCM concentrations were high in pools where tap water, and sodium hypochlorite were used. BDCM and DBCM concentrations were high in pools where groundwater was used. • High THM concentrations increase the risk, and at the same time, women’s ingestion-based risk values are slightly higher than men’s ingestion-based risk values.
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Environmental Forensics
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Evaluation of Trihalomethane Formation Risk
Analysis in Swimming Pools in Eskisehir, Turkey
Zehra Yigit Avdan, Serdar Goncu & Ece Tuğba Mızık
To cite this article: Zehra Yigit Avdan, Serdar Goncu & Ece Tuğba Mızık (2022): Evaluation of
Trihalomethane Formation Risk Analysis in Swimming Pools in Eskisehir, Turkey, Environmental
Forensics, DOI: 10.1080/15275922.2022.2047829
To link to this article: https://doi.org/10.1080/15275922.2022.2047829
Published online: 01 Apr 2022.
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Evaluation of Trihalomethane Formation Risk Analysis in Swimming Pools in
Eskisehir, Turkey
Zehra Yigit Avdan, Serdar Goncu, and Ece Tu
gba Mızık
Eskisehir Technical University, Engineering Faculty, Environmental Engineering Department, Eskisehir, Turkey
ABSTRACT
Swimming pools are popular entertainment and sport areas that people often use. For this
reason, it is crucial to determine the physicochemical properties and Trihalomethanes
(THMs) concentrations of swimming pools and the effect of THMs on swimmer health. This
study focuses on the physicochemical parameters and THM concentrations of six swimming
pools in Eskisehir and the impacts of THMs on human health. Within the study context,
physicochemical parameters were examined and swimming pool water standards of various
countries and organizations were evaluated. The alkalinity, pH, temperature, hardness, and
free chlorine values of the swimming pools were determined to compare with the current
standards. Concentrations of chloroform (TCM), bromodichloromethane (BDCM), and dibro-
mochloromethane (DBCM) were also determined in the collected samples. Concentrations
were found to be in the range of 11.6-100.1 mg/l for BDCM, 151.5-366.4 mg/l for TCM, ND-
6.95 mg/l for DBCM, and 172.1-380.7mg/l for TTHM. From the results, it was determined that
TTHM concentrations were above the limit values defined by WHO, while chloroform
(except P1 and P5 pools), BDCM (except P3 pool), and DBCM concentrations were signifi-
cantly below the limit values. TTHMs and chloroform concentrations were high in tap water
using sodium hypochlorite as a disinfectant. BDCM and DBCM concentrations were high in
pools where groundwater was used. Health risks of THMs in pools through ingestion and
dermal absorption were also estimated for both women and men. In the interpretation of
the result, it was also found that high concentrations of TTHMs increased the risk, and wom-
ens ingestion-based risk values are slightly higher than mens ingestion-based risk values.
Fingerprints of THM formation in pool water are precursor parameters and it is of great
importance to constantly control and take precautions. It has been observed that the use of
groundwater as a water source and NaCl as a disinfectant significantly reduces THM forma-
tion in swimming pools. However, in order to reduce the BDCM and DBCM concentrations
in the use of groundwater, it is recommended to measure the precursor bromide and estab-
lish the relevant limit values. The use of hypochlorite disinfectants in pools where tap water
is used as a water source increases THM formation. For this reason, it is necessary to deter-
mine the amount of organic carbon as a precursor for pools using tap water as a water
source and add it to the limit values. In addition, the use of calcium hypochlorite disinfect-
ant instead of sodium hypochlorite reduces THM formation.
HIGHLIGHT
Physicochemical properties and THMs concentrations of swimming pools and effects of
trihalomethanes (THMs) on the health of swimmers.
Physicochemical parameters and THM concentrations of six swimming pools were deter-
mined, and the effects of THMson human health.
Physicochemical parameters (alkalinity, pH, temperature, and hardness), chloroform
(TCM), bromodichloromethane (BDCM), and dibromochloromethane (DBCM)
were studied.
As a result of the study, total THMs and TCM concentrations were high in pools where
tap water, and sodium hypochlorite were used. BDCM and DBCM concentrations were
high in pools where groundwater was used.
High THM concentrations increase the risk, and at the same time, womens ingestion-
based risk values are slightly higher than mens ingestion-based risk values.
KEYWORDS
swimming pool; risk
analysis; public health;
trihalomethanes; ingestion;
dermal absorption
CONTACT Zehra Yi
git Avdan zyigit@eskisehir.edu.tr Eskisehir Technical University, Engineering Faculty, Environmental Engineering Department,
Eskisehir, Turkey
Supplemental data for this article is available online at https://doi.org/10.1080/15275922.2022.2047829
ß2022 Informa UK Limited, trading as Taylor & Francis Group
ENVIRONMENTAL FORENSICS
https://doi.org/10.1080/15275922.2022.2047829
GRAPHICAL ABSTRACT
Introduction
Swimming, one of the most recommended aerobic
physical activities, is a well-known exercise method
for good health and prevention of diseases (World
Health Organization 2006b; Valeriani et al. 2017).
Therefore, swimming pools in public areas, hotels,
gyms, or private areas should comply with the guide-
lines to protect human health and safety. During
swimming activities, human substances (hair, skin
particles, urine, feces, sweat, etc.) and personal care
products (sunscreen, body cream, shampoo, etc.) with
organic and inorganic content may contaminate
swimming pool waters (Barbot and Moulin 2008;
Bessonneau et al. 2011; L. Yang, Yang, et al. 2018).
Besides, pollution from plants in the vicinity of out-
door pools, dust, and rainwater also cause pollution of
swimming pools (Wyczarska-Kokot, Lempart, and
Marciniak 2019). This tends to support the growth of
pathogenic microorganisms, which can lead to out-
breaks of infectious diseases in waters. Therefore, dis-
infection of swimming pools is vital in preserving the
microbiological quality of swimming pools and pre-
venting infections (Akinnola et al. 2020; Karimi
et al. 2019).
Chlorine derivatives and ozone have been widely
used for the disinfection of swimming pools. Sodium
hypochlorite (liquid bleach), calcium chloride, or
chlorine gases from such chlorines are used in indoor
swimming pools. In contrast, stabilized chlorine prod-
ucts (stabilized chlorine granules, chlorinated isocya-
nurates, chlorine tablets, etc.) are used in outdoor
swimming pools (Chowdhury, Alhooshani, and
Karanfil 2014). Chlorine disinfection is a process that
removes harmful pathogens from water. However,
during this process, several organic halogenated com-
pounds, known as disinfection byproducts (DBPs), are
formed, which are not only unwanted microorganisms
but also very harmful to human health (Chu and
Nieuwenhuijsen 2002; Teo, Coleman, and Khan 2015;
Weaver et al. 2009). Researchers encountered DBPs in
1970 and identified more than 600 types of DBPs in
drinking water over the past 40 years (Richardson
et al. 2007). Investigation of the formation of DBPs
formed as a result of chlorination of pool waters dates
back to the 1980s. Since 1980, studies have been con-
ducted on the formation and effects of DBPs in many
pools. The first report on DBPs found in the water of
swimming pools was published in the early 1980s, and
trihalomethanes (THMs) in pool water were studied
(Beech et al. 1980; Weil, Jandik, and Eichelsdorfer
1980). More than 100 types of DBP have been identi-
fied in swimming pool and spa waters in recent stud-
ies, and it has been observed that these waters are
more mutagenic than tap waters (Jmaiff Blackstock
et al. 2017). In addition, since chlorinated compounds
such as TCM, which are frequently caused by indus-
trial processes in todays studies, are the leading cause
of groundwater contamination in urban areas, it is
crucial to monitor and determine the source of this
pollution (Colombo et al. 2020). The formation of
DPBs in swimming pool waters is usually caused by
the reaction of disinfection products with contami-
nants such as natural organic matters (NOMs), urine,
sweat, body cells (hair, skin fragments), cosmetics,
and personal care products from swimmers (Jmaiff
Blackstock et al. 2017; Kanan and Karanfil 2011;
Zheng et al. 2017). Tsamba et al. (2020) investigated
the effects of the body fluids on the formation of
DBPs in swimming pool water and air with kinetic
studies (Tsamba et al. 2020).
The concentration of DBPs in swimming pools
depends on many factors such as the type and amount
of disinfectant, the quality of filling water, and the
number, age, breed, and hygiene of swimmers using
2 Z. YIGIT AVDAN ET AL.
the pool (Harman et al. 2017). Organic pollution
resulting from frequent use of swimming pools by
swimmers, microbial mass, and long-term conversion
of water in the pool can lead to the formation of
waterborne diseases, therefore, the pool water should
be disinfected regularly with chlorine (Fantuzzi et al.
2001). Although the chlorination process contributes
to protecting human health by removing pathogenic
microorganisms and organic pollutants in water,
DBPs formed from the chlorination process adversely
affect human health (Cardador and Gallego 2011). For
instance, DBP varieties cause asthma, endocrine sys-
tem problems, severe irritation of the skin, mucous
membranes, and respiratory tract (Zhang et al. 2015).
Besides, they can have cytotoxic (Carter et al. 2019),
teratogenic (Mayer and Ryan 2017), carcinogenic
(Abbasnia et al. 2019), and mutagenic (Richardson
et al. 2007) properties (Hang et al. 2016). In addition
to the adverse effects of DBPs on water quality during
the chlorination process, the air quality in indoor
pools is also affected due to the volatile nature of
DBPs. In this context, it is imperative to create a
healthier and safer environment by evaluating the
indoor air quality of indoor pools (Gabriel et al.
2019). DBPs in indoor pools are essential for the
health of swimmers who exhibit high respiration dur-
ing regular and long-term training. Trainers and other
pool workers are also affected during the training of
the swimmers (Gouveia et al. 2019).
Having a complex structure, DBPs have many
classes, including haloacetic acids (HAAs), trihalome-
thanes (THMs), haloacetonitriles (HANs), haloacetal-
dehydes (HALs), haloketones (HKs), etc. (Manasfi,
Coulomb, and Boudenne 2017;Ulyanovskii et al.
2020). THMs are common in swimming pool waters
and drinking water; there is a lot of work on this issue
(F. Yang, Yang, et al. 2018). THMs are very important
compounds because of their potential carcinogenic
properties, effects on reproductive functions, develop-
mental outcomes in children, and causing asphyxia
(Aggazzotti et al. 2004; Hamidin, Yu, and Connell
2008; Imo et al. 2007; Villanueva et al. 2007). The use
of different disinfection methods is important to man-
age and prevent THM formation. THMs generally
consist of chloroform (TCM) (CHCl
3
), bromodi-
chloromethane (BDCM) (CHCl
2
Br), chlorodibromo-
methane (CDBM) (CHClBr
2
), and bromoform
(CHBr
3
) (Catto et al. 2012; Padhi et al. 2019). All of
these compounds are called total trihalomethanes
(TTHM). The most common THM in the swimming
pool and drinking water is chloroform (Chu and
Nieuwenhuijsen 2002). Chloroforms are defined as
group B2 possibly carcinogens to humans by the
International Cancer Research Agency (IARC) (EPA
and U. S 2021; Righi et al. 2014).
This study investigated the physico-chemical prop-
erties of six swimming pools in Eskisehir, Turkey, and
the THM (TCM, BDCM, and DBCM) formation after
disinfection using sodium hypochlorite, sodium chlor-
ide, and calcium hypochlorite and their effects on the
human health.
Methodology
Study cases
The study was carried out in 6 public indoor swim-
ming pools in Eskisehir, Turkey. The structural char-
acteristics of the swimming poolsand disinfection
methods of pool water are collected and summarized
in Table 1.
Sampling strategy
The swimming pool water samples were collected at
three different points based on the pool hydraulics
and structural characteristics at a depth of 20 cm and
at a distance of 50 cm from the coign of the pool
(Figure 1). The three pool water samples were col-
lected at the same point in time. Pool water samples
were taken early in the morning to ensure that the
pools have the same characteristics during the hours
when the pools are open to swimmers. It was kept at
þ4C and brought to the department laboratory, and
stored under appropriate conditions.
Table 1. Information on swimming pools.
Pool Code Water source Disinfection chemicals
P1 Tap water Sodium hypochlorite (NaClO)
P2 Groundwater Sodium hypochlorite (NaClO)
P3 Groundwater Sodium chloride (NaCl)
P4 Tap water Calcium hypochlorite (Ca(ClO)
2
)
P5 Tap water Sodium hypochlorite (NaClO)
P6 Tap water Sodium hypochlorite (NaClO)
Figure 1. Swimming pool sampling point.
ENVIRONMENTAL FORENSICS 3
Analytical methods
The water quality parameters, together with analysis
methods and instruments used are shown in Table 2.
First, all samples were filtered through a 0.45 mm
membrane filter to remove turbidity, then placed into
a 10 mm path length quartz cell, and then measure-
ments were taken at wavelengths of 254 nm. Dissolved
organic carbon measurements were performed with
non-purgeable organic carbon using a Shimadzu
TOC-5000 with an autosampler. The sample was fil-
tered using a 0.45 lm membrane filter, and then DOC
was measured. Water samples for the determination
of THMs were collected in screw-capped glass vials
(40 cm
3
) with Teflon-faced septa. 5 mg of sodium
thiosulfate was added to the vials to quench the
remaining chlorine reactions. Liquid-liquid extraction
was used to measure THMFP following modified EPA
Method 551.1 (Munch and Hautman 1995; Akcay,
Avdan, and Inan 2016; Inan, Avdan, and Akcay
2017). First, 35 ml of the sample was poured into a
60-ml glass vial with a polypropylene screw cap and
TFE-faced septum. Then, 8 gr Na
2
SO
4
and 3 ml n-
pentane were added, and liquid-liquid extraction was
performed. TTHMs composed of TCM, bromodi-
chloromethane, and dibromochloromethane are
expressed as mgL
1
, the sum of the three species. The
GC operating conditions for THM measurements
were as follows: injector temperature: 250 C, detector
temperature: 300 C, injection volume: 1 mL, tempera-
ture program: 40 C for 5 min, 5 C min
1
ramp to
80 C, 20 C min
1
ramp to 150 C.
Statistical analysis
The IBM SPSS Statistics 22 software was used to
evaluate the relationship between THMs and water
quality parameters of swimming pool samples.
Pearson correlation analysis was performed using nor-
mally distributed data (Shapiro-Wilk, theoretical
distribution).
Results and discussion
Examination of physicochemical parameters
The water quality of swimming pools is of critical
importance in terms of human health. Accordingly,
water samples taken from swimming pools are eval-
uated and managed by various standards. Swimming
pool regulations of different countries and organiza-
tions are shown in Table 3 (APSPA 2009; DHM 2015;
DIN 19643 2012; Official Journal 2011; World Health
Organization 2006a).
Table 4 shows the analysis results of water samples
taken from 6 different swimming pools. When the
results of the analysis are examined, it is seen that the
alkalinity value complies with the standards of the
USA, Turkey, and WHO. Dissolved oxygen content is
affected by the source of water, water temperature,
and in-Pool processes used in distribution. There is
no standard for dissolved oxygen value in swimming
pools. Free chlorine values in Table 4 are significantly
higher than the standards of WHO, Poland, and
Germany. However, when the standards in Turkey are
examined, it is seen that the free chlorine values of
the P1 and P2 coded swimming pools comply with
the indoor pool standard. Regarding the other param-
eters shown in Table 4, it was determined that the pH
value of the pools was in compliance with the relevant
standards, but the pH value of the P5 coded pool was
slightly higher than the standards. When pool temper-
atures are examined, it is seen that the temperature
values correspond to others than WHO standards (P1,
P2, and P5 coded pools are not in compliance with
the standard). Finally, the hardness values in samples
Table 2. Parameters, analysis instruments, and methods.
Parameter Analysis Instrument Analysis Methods
Water temperature (C) Hach HQ40D Multimeter USEPA Electrode Method 8156
pH Hach HQ40D Multimeter USEPA Electrode Method 8156
Dissolved oxygen (mg/L) Hach HQ40D Multimeter USEPA LDO Probe Method 10360
Electrical conductivity (mS cm
-1
) Hach HQ40D Multimeter USEPA Direct Measurement Method 8160
Alkalinity (mgCaCO
3
/L) EPA Standard Methods 2320-B
Hardness ((mgCaCO
3
/L) EPA Standard Methods 2040-C
Turbidity (NTU) WTW TURB 355 IR ISO 7027/DIN EN 27027
Nitrite (mgNO
3-
/L) Dionex ICS 3000 Ion Chromatograph EPA Method 300.1
Orthophosphate (mg/L) Dionex ICS 3000 Ion Chromatograph EPA Method 300.1
Sulfate (mg/L) Dionex ICS 3000 Ion Chromatograph EPA Method 300.1
Chlorate (mg/L) Dionex ICS 3000 Ion Chromatograph EPA Method 300.1
Chlorite (mg/L) Dionex ICS 3000 Ion Chromatograph EPA Method 300.1
Free and Total Chlorine (mg/L) PC Compact - Aqualytic Spectrophotometer DPD/KI Method/ EN ISO 7393-2:2000
UV
254
(cm
-1
) Hach-Lange DR5000 Spectrophotometer USEPA Direct Reading Method 100054
DOC (mg/L) Shimadzu TOC-5000 EPA Method 415.3
THMs (mg/L) Gas Chromatography-ECD EPA Method 551.1
4 Z. YIGIT AVDAN ET AL.
taken from all pools comply with the standards of the
USA and WHO.
During the chlorination process, DBPs are formed
as a result of a reaction with the organic substances in
the pool water. For prevention, Total Organic Carbon
(TOC) is measured, and values are evaluated with
standards. In many studies, total organic carbon, dis-
solved organic carbon, UV
254
, and/or Specific UV
absorbance (SUVA) measurements are performed to
determine the organic precursors that are effective in
the formation of DBPs (Keuten et al. 2012;Łaskawiec,
Dudziak, and Wyczarska-Kokot 2018; Peng et al.
2016). In the Chowdhury (2016) study, the DOC val-
ues in the pool feed water, pool water before swim-
ming, and pool water after swimming, respectively,
were 1,79-2,27-2,52 in mg/L, and UV
254
values of
0,025-0,04-0,05, respectively, were reported as cm
1
(Chowdhury, Alhooshani, and Karanfil 2014).
According to this study, DOC and UV
254
values in
other pools, except for the P4 coded pool, have
high values.
The carbonaceous and nitrogenous organic com-
pounds formed by swimmers play an essential role in
forming DBPs. When the nitrate concentration was
examined, it was found that nitrate concentrations of
P1, P5, and P6 were consistent with the literature,
while P2, P3, and P4 pools contained high levels of
nitrate (Lee et al. 2010). When examined together
with other studies, nitrite and nitrate concentrations
were consistent with the literature; even the nitrite
concentration is relatively low (Uysal et al. 2017,
Onifade, Olowe, and Obasanmi 2019). In summary,
Table 3. Regulations applied by different countries and organizations on the parameters of swimming pools.
Parameters
American National
Standard for Water
Quality in Public Pools
and Spa (APSPA 2009)
Regulation on the
health principles and
conditions of
swimming pools
(Turkey) (Official
Journal 2011)
World Health
Organization (WHO)
(World Health
Organization 2006a)
Decree of the health
minister on the
requirements for water
in swimming pools
(Poland) (DHM 2015)
DIN 19643-2012:
Treatment of water of
swimming pools and
baths (German) (DIN
19643 2012)
Disinfectant used Free chlorine
Chlorinated
isocyanates
Free chlorine Free chlorine
Combination of free
chlorine and
other methods
Free chlorine
Combination of free
chlorine and
other methods
Free chlorine
Combination of free
chlorine and
other methods
pH 7.2-7.8 6.5-7.8 7.2-7.8 6.5-7.6 6.5-7.2
Temperature (C) 26-30 26-28 (indoor) 26-
38 (outdoor)
26-28 28-32 28-32
Turbidity (NTU) 0.5 0.5 0.3 0.5
Nitrates (mgNO
3-
/L) 50 20 20
Total alkalinity
(mgCaCO
3
/L)
60-180 30-180 60-180 ––
Hardness (mgCaCO
3
/L) 150-1000 150-1000 ––
Oxidation-reduction
potential
(ORP) (mV)
–––>750 >750
Free chlorine (mgCl
2
/L) 1-3 (Indoor) <1.2 0.3-0.6(07-1.0)
b
0.2-0.6(07-1.0)
b
b
In pools with hydromassage devices, aerosol-producing devices or pools with temperatures above 30 C.
Table 4. Physicochemical parameters of swimming pool water samples.
Parameters
Pool Code
P1 P2 P3 P4 P5 P6
Alkalinity (mg/L CaCO
3
) 62 ± 0.2 108 ± 0.7 128± 0.04 78 ± 0.02 104 ± 0.44 32 ± 0.26
Dissolved Oxygen (mg/L O
2
) 7.13 ± 0.02 7.55 ± 0.01 7.84 ± 0.07 7.13 ± 0.02 7.23 ± 0.03 7.34 ± 0.04
DOC (mg/L) 8.26 ± 0.02 3.04 ± 0.03 1.91 ± 0.02 6.85 ± 0.10 13.92 ± 0.42 8.56± 0.02
Electrical Conductivity (mS cm
-1
) 1.07 ± 0.02 1.73 ± 0.01 14.89 ± 0.02 4.53 ± 0.01 4.2 ± 0.02 2.56 ± 0.02
Free Chlorine (mgCl
2
/L) 1.40 ± 0.02 1.22 ± 0.02 1.83 ± 0.02 1.54 ± 0.02 2.90 ± 0.02 3.06 ± 0.03
Hardness (mg/L CaCO
3
) 243.6 ± 0.26 613.3 ± 0.10 439.1 ± 0.44 478.9 ± 0.10 225.3 ± 0.10 580.6 ± 0.10
Nitrate (mg/L) 8.64 ± 0.01 34.99 ± 0.30 32.55 ± 0.06 27.90 ± 0.36 16.61 ± 0.08 7.09 ± 0.02
Nitrite (mg/L) 0.015 0.013 0.003 0.021 0.028 0.016
Orthophosphate (mg/L) 1.16 ± 0.04 1.43 ± 0.03 1.61 ± 0.02 0.78 ± 0.04 1.67 ± 0.02 0.74 ± 0.03
pH 7.41 ± 0.02 7.37 ± 0.02 7.61 ± 0.06 7.41 ± 0.03 7.88 ± 0.07 7.04 ± 0.06
SO
42-
(mg/L) 26.12 ± 0.59 39.93 ± 0.76 27.79 ± 0.24 19.76 ± 0.08 83.91 ± 0.23 51.37 ± 0.45
SUVA (L/mg.m) 0.96 ± 0.01 2.73 ± 0.11 0.73 ± 0.02 0.83 ± 0.01 0.7 ± 0.01 1.47 ± 0.01
Temperature (C) 29.2 ± 0.30 29.7 ± 0.10 29.2 ± 0.10 27.8 ± 0.10 29.3 ± 0.10 27.3 ± 0.10
Total Chlorine (mg/L) 2.38 ± 0.01 2.09 ± 0.02 2.12 ± 0.02 2.40 ± 0.02 3.29 ± 0.02 3.80 ± 0.02
Turbidity (NTU) 0.13 ± 0.02 0.07 ± 0.01 0.13 ± 0.01 0.16 ± 0.02 0.09 ± 0.03 0.12 ± 0.01
UV
254
(cm
-1
) 0.079 0.083 0.014 0.057 0.103 0.126
Notes. DOC: dissolved organic carbon; SUVA: Specific Ultraviolet Absorption.
ENVIRONMENTAL FORENSICS 5
the turbidity values were lower than the literature,
and the temperature, pH, nitrate, and EC values were
higher than the literature.
DBPs in swimming Pool water samples
After the disinfection process, it is imperative to ana-
lyze the organic residues caused by swimmers and the
DBP concentrations that cause various health prob-
lems caused by the reaction of disinfection chemicals.
Figure 2 shows the concentrations of trihalomethanes
(THMs), chloroform, bromodichloromethane
(BDCM), and dibromochloromethane (DBCM) in the
sampled pools.
In Figure 2, the DBPs shown for each pool were
evaluated according to the disinfection chemicals used
and water sources. THM concentrations were found
to be high in pools using tap water as a water source
and sodium hypochlorite as a disinfectant. THM for-
mation was above average, calcium hypochlorite disin-
fectant was used instead of sodium hypochlorite.
Concentrations of THM in each pool using tap water
and sodium hypochlorite are affected by various fac-
tors, such as the amount of pool use and the users
profile. In addition, when the sodium chloride and
sodium hypochlorite disinfectants used in pools where
the water source is groundwater were examined, it
was determined that less THMs are formed in the
pool where sodium chloride was used (P2).
When chloroform concentrations are examined, it
is seen that the amount of chloroform in the pools
where tap water and sodium hypochlorite are used is
higher than the other pools; and the P1 pool contains
the highest level of chloroform. It was determined
that the level of chloroform found in the P4 pool
where calcium hypochlorite is used as a disinfectant
and tap water as a water source was average. Also,
when the pools where groundwater is used as a water
source were examined, it was determined that they
contained about the same amount of chloroform by
using tap water, although various disinfectants
were used.
When BDCM concentrations were examined, it
was determined that the highest BDCM concentration
was measured in pool P3. This suggested that the
groundwater in pool P3 contained bromide. This has
shown that the P2 pool, another pool where ground-
water is used, also has a higher amount of BDCM
than the other pools. Finally, when DBCM concentra-
tions were examined, it was determined that the high-
est concentration was in pool P6, where tap water and
sodium hypochlorite disinfection were used. When
DBCM concentrations in other pools were examined,
it was determined that the values were quite close to
each other. In previous studies, it has been
Figure 2. DBP concentrations in swimming pools; (a) P1 pool, (b) P2 pool, (c) P3 pool, (d) P4 pool, (e) P5 pool, and (f) P6 pool.
6 Z. YIGIT AVDAN ET AL.
determined that brominated DBPs are formed in high
concentrations in swimming pools where seawater
and/or bromide-based disinfectants are used
(Chowdhury, Alhooshani, and Karanfil 2014; Parinet
et al. 2012; Richardson et al. 2010).
Table 5 shows the DBP types, carcinogenic effects,
and limits determined for the 6 pools within the scope
of the study. Based on the analysis results, it is seen
that the average value of TTHM is well above the lim-
its set by the World Health Organization. Also, the
mean of TTHM is substantially higher than the value
shown in many studies based on the determination of
DBPs in pool water samples (Chu and
Nieuwenhuijsen 2002; Gabriel et al. 2019; L. Yang
et al. 2016). However, in some studies, TTHM con-
centrations in swimming pool waters were above the
desired standards (Chambon et al. 1983; Lahl et al.
1981). The high concentration of TTHM shows that
people who use the swimming pool use cosmetic
products, body fluids, and other organic materials to
form disinfection byproducts effectively. To prevent
this, cosmetic products must be controlled and
reduced before entering the pool.
Among the TTHMs, the most common and car-
cinogenic disinfection byproduct in swimming pool
waters and drinking water is chloroform. Average
chloroform concentrations in the 6 pools are shown
in Table 5. These values are in line with WHO regula-
tions on recreational water and drinking water quality
standards, except for pool P1. In 2018, Bahmani
and Ghahramani reported that chloroform concentra-
tions in public and private swimming pools were
123.4 mg/L and 147.7 mg/l, respectively (Bahmani and
Ghahramani 2018). Compared to this study, the con-
centrations of chloroform measured in the 6 swim-
ming pools in the study were relatively high.
Chloroform accounts for 85.3% of the mean TTHM
concentration.
Other important disinfection byproducts in swim-
ming pools and drinking water are bromodichlorome-
thane (BDCM) and dibromochloromethane (DBCM).
BDCM concentrations in the 6 swimming pool sam-
ples are shown in Table 5. BDCM concentrations for
all pools except pool P3 were determined to be com-
patible with WHO standards. When DBCM concen-
trations were examined, it was determined that the
values of all pools were significantly lower than
WHO standards.
Relationship between DBPs and
physicochemical parameters
Studying the relationship between DBP concentrations
and physico-chemical parameters, which are essential
for human health, is very important for obtaining
information about formation processes. Figure 3
shows the relationship between the temperature par-
ameter and DBP concentrations which are important
for the chlorine disinfection process. There is a high
linear relationship (r ¼0.609) between the temperature
data and the THM concentrations, while there is a
moderate positive linear relationship between the
BDCM (r ¼0.344) and TCM concentrations
(r ¼0.428). When DBCM concentrations were exam-
ined, it was determined that they had a high negative
relationship (r ¼0.671) with temperature values.
Lara et al. (2020) determined that the water tempera-
ture in swimming pools was very influential on the
concentrations of DBP (THM and HAA concentra-
tions) (Lara et al. 2020).
Table 5. DBPs parameters of swimming pool water samples.
Pool Code Cancerogenic
Group US EPA,
IRIS (EPA and
U. S 2021)
WHO (mg/L)
(World Health
Organization
2011)P1 P2 P3 P4 P5 P6
BDCM (mg/L) 11.6 ± 0.8 48.1 ± 6.4 100.1 ± 5.7 30.3 ± 3.7 15.8 ± 0.1 13.6 ± 0.85 B2 60
TCM (mg/L) 366.4 ± 22 183.3 ± 14.5 182.1 ± 9.1 198.9 ± 24 278.9 ± 1.6 151.5 ± 14 B2 300
DBCM (mg/L) 2.7 ± 0.2 1.90 0 1.96 ± 0.1 2.7 ± 0.1 6.97 ± 0.22 C 100
TTHM (mg/L) 380.7 ± 0.3 233.3 ± 0.6 282.2 ± 0.1 238.1 ± 0.4 297.4 ± 0.1 172.1 ± 0.3 100
Notes. BDCM: bromodichloromethane; TCM: Chloroform; DBCM: dibromochloromethane; TTHM: total trihalomethane.
Figure 3. Relationship between DBP concentrations and
temperature.
ENVIRONMENTAL FORENSICS 7
Figure 4 shows the relationship between DBP con-
centrations of free chlorine concentration. There is a
moderately negative relationship among free chlorine
concentration, THMs (r ¼ 0.373), and BDCM
(r ¼ 0.334) concentrations in pools. In addition,
free chlorine concentration was determined to have a
high positive relationship (r ¼0.648) with DBCM
concentration.
It is also essential to evaluate the effects of dis-
solved organic carbon (DOC) concentration, which is
another crucial factor in forming DPB concentrations.
Figure 5 shows the relationship between THM con-
centrations in pools and DOC concentrations. DOC
concentration was determined to have a moderately
positive relationship with chloroform (r ¼0.472), and
DBCM (r ¼0.475) concentrations, while it had a high
negative relationship (r ¼ 0.787) with BDCM
concentration.
Cancer risk analysis
At this stage of the study, the health risks of DPBs
formed in swimming pools for swimmers were
evaluated. In this context, the method applied in the
literature and applied by the EPA was used (EPA and
U. S 2011; Gan et al. 2013; Wang, Deng, and Lin
2007). Risk analysis was conducted for chloroform,
bromodichloromethane (BDCM), and dibromochloro-
methane (DBCM) of THM types formed in 6 swim-
ming pools. Since all the necessary data about the
constants used in the analysis process are not avail-
able, they were obtained from various sources.
Analysis of ingestion risk of DBPs
Ingestion risks were calculated for mean chloroform,
BDCM, and DBCM concentrations based on reference
values used in literature studies for women and men
(Avsar, Avsar, and Hayta 2020; EPA and U. S 2011;
Gan et al. 2013; Wang, Deng, and Lin 2007). The risk
of ingestion was calculated for women and men refer-
ence values and mean DBP concentrations given in
studies conducted by Avsar, Avsar, and Hayta (2020).
Details of the calculations are shown in the supporting
information file. When the risks posed by chloroform
for women and men in Tables 6 and 7are examined,
it was determined that the highest risk occured in
pool P1, and the lowest risk in pool P6. When BDCM
ingestion-based risks were discussed, it was deter-
mined that the highest risk was in pool P3, and the
lowest risk was in pool P1. When DBCM ingestion-
based risks were examined, it was determined that the
highest risk was in pool P6, and the lowest risk was in
pool P2. Also, there is risk as there is no DBCM con-
centration in the pool P3 for both women and men.
Women ingestion-based risk values were slightly
higher than men ingestion-based risk values in Tables
6and 7. Chowdhury (2016) determined cancer risk
through ingestion of THM concentrations and found
it to be in the range of 4.8610
8
and 3.4110
7
.In
this context, the cancer risks in our study are approxi-
mately in this range. When ingestion risks for men
and women were examined, it was determined that
the risk values were below the negligible risk limit
accepted by USEPA (10
6
) (USEPA 1999; Gouveia
et al. 2019; Peng et al. 2020). However, the risk of
ingestion caused by BDCM concentrations in the P3
pool was determined to be 1.36 times the negligible
risk limit. This indicates that DBP concentrations in
pools should be considered. In Turkey, there is no
limit to the risks caused by ingestion in swimming
pools. However, compared to current studies con-
ducted for our country, it seems that the risks associ-
ated with ingestion are similar to the values in the
literature (Genisoglu, Ergi-Kaytmaz, and Sofuoglu
2019; Avsar, Avsar, and Hayta 2020).
Figure 4. Relationship between DBP concentrations and free
chlorine concentrations.
Figure 5. Relationship between DBP concentrations and DOC
concentrations.
8 Z. YIGIT AVDAN ET AL.
Analysis of dermal risk of DBPs
Another risk faced by swimmers, the dermal risk,
caused by dermal absorption, was similarly calculated
using the sources in the literature (Avsar, Avsar, and
Hayta 2020; EPA and U. S 2011; Gan et al. 2013;
Wang, Deng, and Lin 2007). Detailed information
about the calculation of dermal risk is also indicated
in the supporting information file. Dermal exposure
risk values calculated for women are shown in Table
8, and values calculated for men are shown in Table
9. When the risks associated with dermal absorption
were evaluated for both women and men, the highest
risk from chloroform was in pool P1, and the lowest
risk in pool P6. When dermal-based risks of BDCM
were examined, the highest risk was in pool P3, and
the lowest risk in pool P1. When the dermal-based
risk of DBCM was reviewed, the highest risk was in
pool P6, and the lowest risk in pool P2. In addition,
there was no risk in the P3 pool that does not contain
DBCM concentration. Similar to ingestion-based risk
values, the skin-based risk was slightly higher in
women. When the dermal risk values determined for
men and women were examined, it was determined
that they were significantly lower than the negligible
risk limit determined by USEPA (USEPA 1999;
Gouveia et al. 2019; Peng et al. 2020). In this context,
the dermal risk of DBPs is very low for both women
and men in swimming pools. When the current risk
assessment studies (swimming pool and tap water) in
Turkey were examined, it was seen that dermal risk
values were among the values in the literature
(Genisoglu, Ergi-Kaytmaz, and Sofuoglu 2019; Avsar,
Avsar, and Hayta 2020).
Conclusion
This study is based on the physicochemical quality of
swimming pools and the determination of THMs con-
centrations formed after the disinfection process and
the effects of THMs on health. In this context, the
water quality and THM concentrations of 6 swimming
pools frequently used in Eskisehir, a student city of
Turkey, were determined.
DOC concentration, which has a vital role in the
formation of THMs, was relatively high in the P4
swimming pool. Consequently, the P4 pool has a high
chloroform concentration.
Table 8. Dermal-based cancer risk values of THM species for women.
Swimming Pool Code
P1 P2 P3 P4 P5 P6
Chloroform 7.8810
-10
3.9410
-10
3.9210
-10
4.2810
-10
610
-10
3.2610
-10
BDCM 1.6510
-10
6.8510
-10
1.4310
-9
4.3210
-10
2.2510
-10
1.9410
-10
DBCM 3.510
-11
2.4710
-11
0 2.5410
-11
3.510
-11
9.0410
-11
Table 9. Dermal-based cancer risk calculated values of THM species for men.
Swimming Pool Code
P1 P2 P3 P4 P5 P6
Chloroform 7.3810
-10
3.6910
-10
3.8710
-10
4.0310
-10
5.6210
-10
3.0510
-10
BDCM 1.5510
-10
6.4210
-10
1.3410
-9
4.0410
-10
2.1110
-10
1.8110
-10
DBCM 3.2810
-11
2.3110
-11
0 2.3810
-11
3.2810
-11
8.4710
-11
Table 6. Ingestion-based cancer risk values of THM species for women.
Swimming Pool Code
P1 P2 P3 P4 P5 P6
Chloroform 4.8910
-7
2.4510
-7
2.4310
-7
2.6610
-7
3.7210
-7
2.0210
-7
BDCM 1.5710
-7
6.5310
-7
1.3610
-6
4.1110
-7
2.1410
-7
1.8510
-7
DBCM 4.9610
-8
3.4910
-8
0 3.6010
-8
4.9610
-8
1.2810
-7
Table 7. Ingestion-based cancer risk values of THM species for men.
Swimming Pool Code
P1 P2 P3 P4 P5 P6
Chloroform 4.0510
-7
2.0210
-7
2.0110
-7
2.2010
-7
3.0810
-7
1.6710
-7
BDCM 1.3010
-7
5.4010
-7
1.1210
-6
3.4010
-7
1.7710
-7
1.5310
-7
DBCM 4.1110
-8
2.8910
-8
0 2.9810
-8
4.1110
-8
1.0610
-7
ENVIRONMENTAL FORENSICS 9
When the quality of pool water was examined, it
was determined that the nitrate concentrations of the
P2, P3, and P4 pools were higher than the values in
the literature. When examining pools P2 and P3, the
water source is groundwater and has higher nitrate
concentrations. In addition, when the pool coded as
P4 where tap water was used as a source is reviewed;
it can be considered that the concentration of nitrate
is caused by swimmers. According to studies in the
literature, the temperature data, which is effective in
the formation of THM concentrations in pools, is
high. In this context, it was determined that the tem-
perature of the pool waters should be kept under con-
trol. It was determined that THM concentrations were
high in pools where tap water was used as a water
source, and sodium hypochlorite was used as a disin-
fectant. In this context, it would be appropriate to use
various disinfectants or to use different disinfection
methods. In addition, limit values for precursors such
as organic carbon and bromide need to be added to
THM control standards. Pearson correlation analysis
was performed to evaluate the relationship between
DBPs in pools and the temperature, free chlorine, and
DOC concentrations. The analysis of results shows
that temperature has a positive correlation with THM
(r ¼0,609), BDCM (r ¼0,344), and TCM (r ¼0.428)
concentrations in pools and a high negative relation-
ship with DBCM (r ¼0.671). Free chlorine concen-
tration has a negative correlation with THM
(r ¼0.373), BDCM (r ¼0.373), and TCM
(r ¼0.195) concentrations, while it has a high posi-
tive correlation with DBCM (r ¼0.648). DOC concen-
tration has a positive relationship with THM
(r ¼0.173), TCM (r ¼0.472), and DBCM (r ¼0.475)
concentrations and a high negative relationship with
BDCM (r ¼0.787) concentration. To control DBCM
concentrations in pools, temperature and free chlorine
concentration must be closely monitored. In addition,
the temperature, free chlorine, and DOC concentra-
tions in the pools should be continuously monitored,
even if they are within the thresholds set by the stand-
ards. In addition, continuous monitoring and mini-
mization of DBP concentrations is essential for water
administration managers and legislators, and water
epidemiologists. Since water epidemiologists consider
the spatial-seasonal variations of DBPs in drinking
water, it is important to consider the variations of
DBPs in pool as well (Graves, Matanoski, and Tardiff
2001; Uyak et al. 2014).
The health risks associated with ingestion and der-
mal absorption, which were analyzed for men and
women, found that the risks in women are slightly
higher than in men. In this context, it was determined
that THMs concentrations in pools are more critical
factors than the gender factor in the analysis of
health risks. When the health risks posed by THMs
were examined, it was determined that swimmers
were at constant risk during the time they used the
pools. In this context, the physico-chemical parame-
ters and THM concentrations of the relevant pools
should be continuously monitored. Continuous mon-
itoring of these parameters in pool water can may
contribute to obtaining information about future
health problems. Also In addition, to reduce THMs in
pools, necessary training should be provided to the
pool managers.
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ENVIRONMENTAL FORENSICS 13
... It carried its DBPs studies to a different point and carried out DBPs concentration measurement in swimming pools for the first time in Canakkale [30]. This study on swimming pools may have inspired the swimming pool studies completed in Bitlis [31] and Eskisehir [32]. The cities where DBPs studies are carried out in our country are shown in Figure 1. ...
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In this study, water quality parameters and disinfection by products (DBPs) were monitored and correlations between them were statistically investigated in a swimming pool in the province of Bitlis in Turkey. Risk assessment was then performed for trihalomethanes (THMs) and haloacetic acids (HAAs) in the context of public health. According to results, the carbonaceous organics (maximum total organic carbon (TOC): 3.89 mg/L) and nitrogenous (maximum total nitrogen (TN): 6.84 mg/L) substances came from swimmers as the precursor compounds for the formation of DBPs. Pool water free chlorine concentration varied depending on the manual dosage (between 0 to 2.2 mg/L) and sometimes exceeded the Turkish limits (1-1.5 mg/L). This situation increased DBPs formation. Bromide concentration detected in pool water can reach up to 15-fold the value in groundwater. This provides the basis for formation of brominated DBPs which are more carcinogenic than chlorinated species. The THM4 (mean: 85.4 µg/L) and bromoform (mean: 70.2 µg/L) concentrations were higher than those obtained in most countries. Low nitrogenous compounds limited the haloacetonitrile (HAN) production (mean: 3.52 µg/L). Significant differences were detected between HAA5 and HAA9 concentrations (mean: 181 and 219 µg/L respectively) and this difference came from high amounts of brominated HAA species. Other DBPs that cannot be detected on species basis varied and constituted mean 53.5% of adsorbable organic halogens (AOX). This situation creates uncertainty in terms of health hazards. According to Pearson correlations, there were significant correlations between AOX formation and TOC, TN, conductivity, total chlorine, nitrate and temperature. This indicates that DBPs formation was mainly influenced by the precursors in the water and the physical conditions in the pool. Therefore these parameters are the fingerprint of DBP formation in the studied pool water and negative or positive changes in these parameters directly affect DBP generation. It is very important to keep them under constant control in pool water. According to the risk assessment results, HAA concentration in the pool was found to have the potential to pose a risk to public health. The study provides fingerprinting information for DBP formation under uncontrolled pool conditions.
Article
The maintenance of public swimming pools requires numerous technological steps. One of the most important issues involves microbiological safety. Benzalkonium chloride (BAC) encompasses homologous alkylbenzyldimethylammonium chlorides with various alkyl chains, in particular C12 and C14, and is known as a popular algaecide for keeping water clean. In addition to BAC, NaOCl and UV-irradiation are also used to treat pool water as additional technological steps. Therefore, BAC itself can become a precursor of disinfection byproducts (DBPs). High-performance liquid chromatography – tandem mass spectrometry (HPLC-MS/MS), with accurate mass measurements, has allowed the discovery of several groups of DBPs that are related to BAC in public pool water in Arkhangelsk (Russia). These DBPs include numerous isomeric monochlorinated derivatives ([C21H37ClN]+ and [C23H41ClN]+), hydroxyl derivatives ([C21H38NO]+ and [C23H42NO]), carbonyl ([C21H36NO]+ and [C23H40NO]+), and dicarbonyl derivatives ([C21H34NO2]+ and [C23H38NO2]+). In addition, chlorinated alcohols, ketones and ketoalcohols of BAC were also detected, including [C21H35ClNO]+, [C21H37ClNO]+ and [C21H35ClNO2]+ for BAC-12; and [C23H39ClNO]+, [C23H41ClNO]+ and [C23H39ClNO2]+ for BAC-14. MS/MS allowed reliable elucidation of the structures of novel DBPs, proving that chlorination starts via radical substitution in the long aliphatic chains of BAC. UV-irradiation dramatically accelerates the reaction completely destroying the original compounds in less than an hour, while the array of the intermediate products remains the same as in the dark. The formation of other DBPs proceeds due to further reactions of these primary products. The concentrations of novel DBPs in pool water reach μg L−1 levels. These conclusions were proved by conducting model reactions of BAC with NaOCl.
Article
Disinfection by-products (DBP) such as trihalomethanes (THM) are formed when chlorine and bromine interact with natural organic materials in chlorine-treated swimming pools. Epidemiological evidence demonstrated an association between exposure to swimming pool environment and adverse health effects. Therefore, this study aimed to assess carcinogenic and non-carcinogenic risk of long-term exposure of elite swimmers and their coaches. In an Olympic-size indoor chlorinated swimming pool, THM levels were determined in water (21–69 µg/L), in the boundary layer above the water surface (59–397 µg/m³), and in the air surrounding the pool (28–390 µg/m³). These values were used to predict multi-pathway chronic daily intake (CDI), cancer risk (CR) and hazard index (HI). Oral and dermal CDI for swimmers were 2.4 × 10⁻⁶ and 2.0 × 10⁻⁸, respectively. The swimmers’ inhalation CDI (1.9 × 10⁻³ mg/kg/day) was estimated to be sixfold higher than levels obtained for coaches (3.3 × 10⁻⁴ mg/kg/day). According to guidelines, the HI was acceptable, but CR exceeded the recommended limit for both, coaches (CR: 5.5 × 10⁻⁷–8.5 × 10⁻⁵; HI: 6.5 × 10⁻⁴–1 × 10⁻¹) and swimmers (CR: 1.4 × 10⁻⁵–3.6 × 10⁻⁴ HI: 1.6 × 10⁻²–4.3 × 10⁻¹). Our findings provide further support to the need to develop comprehensive guidelines to safeguard the health of individuals involved in elite swimming.
Article
Disinfection by-products (DBPs) are formed in swimming pools by the reactions of bather inputs with the disinfectant. Although a wide range of molecules has been identified within DBPs, only few kinetic rates have been reported. This study investigates the kinetics of chlorine consumption, chloroform formation and dichloroacetonitrile formation caused by human releases. Since the flux and main components of human inputs have been determined and formalized through Body Fluid Analogs (BFAs), it is possible to model the DBPs formation kinetics by studying a limited number of precursor molecules. For each parameter the individual contributions of BFA components have been quantified and kinetic rates have been determined, based on reaction mechanisms proposed in the literature. With a molar consumption of 4 mol Cl2/mol, urea is confirmed as the major chlorine consumer in the BFA because of its high concentration in human releases. The higher reactivity of ammonia is however highlighted. Citric acid is responsible for most of the chloroform produced during BFA chlorination. Chloroform formation is relatively slow with a limiting rate constant determined at 5.50 × 10-3 L/mol/sec. L-histidine is the only precursor for dichloroacetonitrile in the BFA. This DBP is rapidly formed and its degradation by hydrolysis and by reaction with hypochlorite shortens its lifetime in the basin. Reaction rates of dichloroacetonitrile formation by L-histidine chlorination have been established based on the latest chlorination mechanisms proposed. Moreover, this study shows that the reactivity toward chlorine differs whether L-histidine is isolated or mixed with BFA components.