Development and Modification of Water Treatment Technologies

for Removal of Trihalomethanes from Drinking Water

0.1 Need for the project

The water treatment plants and processes play an important role in making water safe and
drinkable. The initial steps remove suspended non-settable particles, whereas the
disinfection finally fulfills two essential purposes – i) killing or deactivating pathogenic
microorganisms ii) maintaining the residual disinfectants in treated water to prevent the
regrowth of microorganisms in the distribution network (Gupta et al., 2015). Disinfection
By-Products (DBPs) are formed when water containing chemical disinfectant reacts with the
DBP precursor, such as natural organic matter (NOM). The reactions between natural
organic matter, anthropogenic contaminants, ions, and disinfectants lead to the formation of
Disinfection-by-products (DBPs) such as Trihalomethanes (THMs) in drinking water.  The
formation of THMs is strongly related to the chlorination of water. DBPs are formed when
water containing chemical disinfectant reacts with the DBP precursor, such as natural
organic matter. There are almost 600 types of DBPs discovered, and it is estimated that
more new DBPs are yet to be found because of the changing water quality and treatment
processes. The trihalomethanes consist of four DBPs subspecies: Chloroform, Bromoform,
Dibromochloromethane, and Bromodichloromethane. The THMs are also known as
brominated and chlorinated methane, but the formation of THM is not due to the reaction
between methane and chlorine. Instead, it is by-product of the reaction between the natural
organic matter (NOM) and dissolved organic carbon (DOC) with chlorinated water, forming
THM as shown in equation 1.

Chorine + Bromide +NOM THMs ……………… eq 1.

There are several different methods to reduce or remove THMs from the water 1) reduce the
disinfection dosage and residual 2) Improve the distribution network 3) alternative
disinfecting methods 4) reduce NOM concentration 5) remove pre-formed THMs. But the
cost effective and potential method to reduce THM is yet to be come. Hence this experiment
will help to achieve the goal by following this objectives:

Following objective of the reducing THMs in drinking water includes

 Evaluation of existing post disinfection water treatment technologies (chlorination)

and their effect on THM formation potential in the lab to improve the existing system.

 Identification of potential post-disinfection method (sequential disinfection) and

outline preventive and control strategies for minimizing adverse impacts of THM on
the human body.

 Establishing the baseline data for developing a cost-effective lab-scale advanced

water treatment model based on the evaluation and experiments.

The efficiency to removal low molecular weight NOM in conventional water treatment
technologies is very less and mostly use chlorine as a primary or secondary disinfectant.
Which act as a catalyst to increase the THM concentration in drinking water. But thinking in
a new direction to have effective NOM removal technique and disinfection method which
will not only reduce the THMs concentration but will also maintain the quality of water is a
new challenge. As more surface water is used for drinking water purposes, treatment
strategies for controlling and minimizing THMs become more essential.
02 Research gap

After determining THMs in chlorinated water numerous study’s experiments has carried out
to investigate the mechanism of THM formation, health risk assessment associated with
THMs and factors affecting the formation of THMs. Most of the study’s about THM
forming mechanism has been carried out in European countries. However, to date, there has
been no significant study on effective water treatment and disinfection technology to reduce
THMs concentration. There is lack of experimental data and literature on possible effects of
sequential disinfection on THM formation and water quality. An integrated approach in
treatment plants is needed to reduce THM concentration such that shortcoming of one
treatment method can be overcome by another technology. Hence a pilot-scale treatment
plant is need to be design based on the literature review and understanding to establish the
baseline data on THM reducing technology. The plant uses alternative technologies at three
stage of water treatment: effective coagulation, maintaining pH of water and post-
disinfection. The technology supports low usage of chlorine to reduce the formation of
THMs. The formation of THM majorly depends on the concentration of NOM, pH of water,
and the chlorination of water. Hence the experiment will focus on these three focuses areas:

2.1 Effective coagulation

Presences of NOM in water does not cause any harm to human being in primary pollutant,
but this NOMs when started reacting with disinfectant present in water tends to form
carcinogenic compound like THMs as a secondary pollutant. In general, a high NOM level
in the water will raise the chlorine demand, leading to further increases in THM formation.
Using appropriate coagulants to oxidize these NOMs will enhance the THM reduction in
water. The optimal pH for effective coagulation process ranged in between 5-7 with rapid
mixing of water.

There are two major types of coagulant use in WTP that are Alum and PAC. Hear in this
experiment PAC will be use as a coagulant this is because PAC is more effective in
removing NOM than Alum. As PAC work well with all turbidity levels and has wide pH
level from 7 to 8. PAC also causes minimum pH drop in water which can minimize the use
of lime for pH adjustment in water also, NOM removal efficiency of PAC is 80% higher
than of Alum (Jiva, 2018).

2.2 pH adjustment

The pH is the most influencing factor in THM formation (Basu et al., 2011), the
concentration of THM increases as the pH of water rises above 8. The reactivity of chlorine
in water depends on the pH of water; hence, the demand for chlorine in acidic water is more
than alkaline water. The rate of organic matter oxidation varies with the increase in pH
above 7. Hence maintaining pH ranged in between 6-7 for effective coagulation process to
remove NOM is most essential method to reduce THMs formation in water.

2.3 Sequential disinfection process

Chlorination of water with high contact time can lead to the formation of high THM in
water. Disinfection of water is the crucial part on which the quality of water depends.
Whereas the concentration of THM increases with increase in the contact time between the
chlorine and precursor. Thus, conventional post-disinfection technique can be replaced by
sequential disinfection. In the sequential disinfection process, more than one disinfectant is
used sequentially. The effect of combined action of disinfectant promotes the inactivation of
microorganisms than the same disinfectant applied separately (USEPA, 1999). This
treatment supports the sequential disinfection by alternative disinfectant followed by
chlorination. Generally, after chlorine dosing a 30 min contact time is maintained. But, in
sequential disinfection, the contact time of chlorine is reduced to 15 min and a dose of
alternative disinfectant is given. Hear in this experiment this three combinations of
sequential disinfection will be evaluated that are: chloramine + chlorine, sonication +
chlorine, chlorine dioxide + chlorine. The reason for selecting this disinfectant is, according
to the research, free chlorine generates more THM while chloramines barely yield halogen-
THMs and give the same residual effect as chlorine. Sonication helps in breaking the
clusters of bacteria to make them more readily available for further treatment processes and
 effective coagulation. Sonication also increases the pre-disinfection effectiveness and can
reduce THM formation.

The process of sequential chlorination disinfection could control THMs more effectively
due to keeping a short contact time of free chlorine and water. As THMs in drinking water
have raised public health issues and can cause health risks like bladder cancer, liver, kidney
damage, reproductive system disorders, carcinogenic and mutagenic problems (Bavcon et
al., 2003). Many epidemiologic studies have established the viable hypothesis that exposure
to chlorinated water is connected with the increased health risk, mainly for bladder cancer
(International Agency For Research On Cancer, 1995). This emerging water treatment
technology’s will be helpful to reduce the health causing various life-threatening diseases
like cancer and reproductive disorders. Also, this alternative THM minimization strategies
will be accessible, scalable, and cost-effective for large water treatment plant.

03 Scope

3.1 Analysis of THM in water

Identification and determination of THMs compounds in water can be performed by using

the by liquid-liquid extraction and gas chromatography with MS. The analysis of the
collected experimental sample will be carried out by using Gas Chromatography-Mass
Spectrometry (GC-MS). The operational parameters of GC-MS for THM determination is
shown in the Table. 3.1 The Colum use for analysis is fused-silica column. A 50 ml sample
can be extracted by using 3 ml of methyl tert-butyl ether (MTBE), 50 µ/L
decaflurobyphynil ether and 20 gm of Na 2Cl in a separating funnel. The sample is shake
vigorously for four minutes and 2 minutes it is keep in rest position for layers’ separation.
The sample is extracted by using separating funnel and collected in GC amber vial (2ml),
which is further used for analysis of THMs by using GC-MS.
3.2 Factors affecting THM formation

The formation of THM is not only affected by the use of chlorine, raw water quality,
location, or the method of water treatment used. But pH of raw water, the concentration of
NOM, and their types also affect the THM formation (Zhang et al., 2020). In addition to
that, the conditions under which the disinfection of water is carried out like chlorine dose,
contact time, the concentration of free chlorine, point of adding, also affect the THM
formations (Wang et al., 2015).

3.1 Concentration of natural organic matter in water

The characterization of NOM is based on the hydrophobicity of the compound. The

hydrophobic subdivision is dominated by humic species (fulvic acids, humic acids)
generally having a large molecular weight and accounts for half of the total dissolved
organic carbon (DOC) (Sillanpää et al., 2015). This hydrophobic compound is considering
to be the major precursor for THM formation in drinking water.

3.2. Chlorine dose and residual chlorine in the water

In the various countries studied, chlorine doses in drinking water treatment plants are
ranged from 0. 2 mg/L to 5 mg/L (Poleneni, 2020). They have concluded that an increase in
chlorine dosage increases the THM concentration, especially Cl-THMs in water (Ma et al.,
2015). Interestingly, an increase in Cl dosage increases the concentration of Br-THM.

3.3. Time of interaction between disinfectant and NOM

The generation of THM is the continuous chemical reaction between chlorine and organic
matter. As THMs are the specific hydrolysis end product, thus reaction time will affect the
yield of THMs formation. The THM precursor and disinfectant's reaction may last for days
unless and until either the disinfectant or precursor is exhausted completely (Kumari et al.,
2015). Hence the concentration of THM increases as the contact time increases.
 3.4 pH of the water
The pH is the most influencing factor in THM formation (Basu et al., 2011), the
concentration of THM increases as the pH of water rises above 8. The reactivity of chlorine
in water depends on the pH of water; hence, the demand for chlorine in acidic water is
more than alkaline water.

04 Approach to minimize THM concentration

The study aims to examine the effectiveness of the alternative water treatment technology
as a THMs controlling strategies by using the Multiple-Liner Model. In this model the
evaluation of most cost-effective and potential water treatment method as shown in the
Figure 4.1 will be carried out in high, medium, low dosages and conditions of water with
respect to this parameter (pH and chemical dosages). All the experiments will be carried
out in the laboratory by using either raw lake water source Ambazari lake or Kanhan river
as the river is the source of raw water for the water treatment plant across the Nagpur city.

4.1 Detailed experimental procedure

The two replicate run will be carried out of the water source to study the effectiveness
of the advanced water treatment technology’s on THMs controlling. For the
experiment 10 litters of water will be collected in the plastic drum or bag from the
Ambazari lake or Kanhan river. The container will be rinsed and clean before
collecting the raw water sample to reduce the contamination. Further the collected
sample will be taken to the NEERI laboratory and store inside a 4◦C refrigerator until
analysis is performed. For every experiment each run will conduct one control
experiment for quantifying the effect of the different method used to control THMs
formation. Followed by the three variation of dosage that are dosage 1, dosage 2 and
dosage 3.
The experiment will be conducted in a jar test; this jar test will mimic as a water
treatment plant to simulate this conventional water treatment plant for this study. The
experiment will have the following sequence:

4.1.1 Pre-Experimental Preparation

Take out water from the refrigerator and allowed it to come at room temperature, and
rinse the jar with distill water and then with sample water. Next add 2 L of water into
the jar according to the number of sets and labeled it accordingly. The physio-
chemical water quality data of each experiment will be reported for raw water and
treated water. At each sample point the water quality parameters that will be monitor
are listed in Table.4.2. Before starting the analysis take out 500 ml of water in to the
sampling bottle for raw water quality testing and store it in refrigerator.

4.1.2 Adjusting pH of the water

For effective coagulation process and removal of NOM the optimal pH of the water
throughout the experiment will be maintained in between 6-7. To maintain the pH of
water phosphate buffer 7 will be used. For each of control, dosage 1, dosage 2 and
dosage 3 give the buffer dosage to maintain the pH 7 throughout the experiment.

4.1.3 Coagulation, flocculation, sedimentation

The coagulant used in each of the experiment is PAC whose dosage for control
experiment will be 5 mg/L for 2 min rapid mixing on 150 RPM at pH 6, followed by
three variation of coagulation dosage that are:

i. Dosage 1: 10 mg/L for 2 min rapid mixing on 150 RPM at pH 6-7

ii. Dosage 2: 15 mg/L for 2 min rapid mixing on 150 RPM at pH 6-7

iii. Dosage 3: 20 mg/L for 2 min rapid mixing on 150 RPM at pH 6-7

Flocculation will be carried out for 20 mins slow mixing on 75 RPM, followed by
sedimentation for 45 mins at zero RMP for all the three dosage. After sedimentation
process 50 ml sample will be collected from each of the experimental run in 50 ml
glass bottle for the analysis of NOM concentration in water.

4.1.4 Filtration

After sedimentation process the pre-treated water will be filtered of for control, dosage
1 dosage 2 and dosage 3 experiment by using 0.1 um membrane filter. Transfer the
filtered water carefully in the amber bottle and cover it with cap for avoiding
contamination and labeled the bottle accordingly.

4.1.5 Disinfection

Now for each sequential disinfection method give the disinfectant dosage as shown in
Table: 4.3 while adding the disinfection dosage keep the jar on magnetic stare and
stare the water sample for 2 minutes while adding the disinfectant. Once the
disinfection process is carried out the sample will be keep for incubation in the
incubator at 25 C and the THMs formation potential will be check at different holding
time in this following sequence: 00hr, 03hr, 06hr, 9hr, 12hr, 15hr, 18hr, 21hr, 24hr. To
check THM formation potential in water for each of the holding time 50 ml water
sample will be collected in separate 50 ml amber glass bottle. Further the THM
formation potential will be check on GC-MS. After giving the disinfection dosage the
residual chlorine and free chlorine of each sequential disinfection method will be
check by using Chlorine Test Kit at different holding time mentioned above.

4.1.5 Post-experiment analysis

After giving the disinfection dosages take out 500 ml of water in separate container for
the post water quality analysis. To check the portability of the sample water before and
after of each running experiment the qualitative and quantitative analysis of microbial
test will be carried out for each water sample. A separate 100 ml water will be
collected to analyze the presences of total coliform and fecal coliform in water by
 using Membrane Filtration Technique. Here the water will be drawn through the
porous membrane to trap the microorganism having size larger than 0.45um, afterward
the filter will be applied to the Mendo and MFC agar plate. Further this plats of total
and fecal coliform will be keep in incubator for overnight at 37 C and 44 C
respectively. The total coliform plate will give metallic shin red colony’s whereas, the
fecal coliform will give blue colour colony’s. By using counter, the colony forming
unit (CFU) per 100 ml will estimated to estimate the microbial water quality of treated
water.

5. Expected out come

The expected outcome of this study will be the identification of THM formation
potential in the water with respect to different water disinfection technologies, and the
areas for improvement in WTP. The second major outcome of the study will be
pragmatic advances and cost-effective water disinfection techniques for preventing and
controlling THM formation in water without compromising the water quality.

Table 3.1: GC–ECD parameters for THM determination

Parameter Value
GC parameter
1. Injector temperature 200 C
2. ECD Temperature 280 C
3. Interface 250 C
4. Carrier gas Helium
5. Headspace pressure of the carrier gas (kPa)
Oven program temperature
Initial temperature C 40
Temperature raising 10 (◦Cmin−1) 160
 Constant temperature 20 (◦Cmin−1) 250
Head space analysis
Volume of the sample required (ml) 50 ml
Volume of NaCl 20 gm
Volume of the MTBE required 3 ml
Volume of the Decaflurobyphenil required 50 µ/L
Volume of the flask 50 ml
Time 4 min
Temperature 30 ◦C

Table: 4.2 Water Quality Monitoring Parameters

Sr. No Parameters Instrument

01 pH pH meter
02 Turbidity Turbidity meter
03 EC EC meter
04 Colour Spectrophotometer
05 Residual chlorine Chlorine test kit
06 THMs GC-MS
Control
Run 1
07 Chloramine + and
Anions Cations
chlorine
08 Total and fecal Coliform MFT
Dosage 1
09 TOC
Run 2 TOC analyzer
Raw water Sonication +chlorine
10 NOM Spectrophotometer
Dosage 2

Run 3
Chlorine dioxide Dosage 3
+chlorine
Figure 4.1: Sematic representation of the experiment
Sequential Run Oxidation Coagulation Flocculation Sedimentation Ultra- Disinfection
disinfection RPM CT Dosage RP CT RP CT filtration
M M

Chlorine Chlorination
Control Cl dosage: 0.5 mg/L 150 2 min 5 mg/L 75 20 0 45 min 0.1 um Cl dosage: 1 mg/L
CT: 5 min min CT: 30 min

Chloramine Chloramines
Cl dosage: 0.5mg/L NH2Cl dosage: 0.5 mg/L CT: 15 min
Dosage 1 CT: 15min 150 2 min 10 75 20 0 45 min 0.1 um Chlorination
mg/L min Cl dosage: 0.75 mg/L CT: 30 min
Chloramine
+ Chlorine
Chloramine Chloramines
Cl dosage: 0.75 mg/L NH2Cl dosage: 0.75 mg/L CT: 15 min
Dosage 2 CT: 15 min 150 2 min 15 75 20 0 45 min 0.1 um Chlorination
mg/L min Cl dosage: 1 mg/L CT: 30 min

Chloramine Chloramines
Cl dosage: 1 mg/L NH2Cl dosage: 1 mg/L CT: 15 min
Dosage 3 CT: 15 min 150 2 min 20 75 20 0 45 min 0.1 um Chlorination
mg/L min Cl dosage: 1.5 mg/L CT: 30 min

Chlorine Chlorination
Cl dosage: 0.5 mg/L Cl dosage: 1 mg/L
Control CT: 5 min 150 2 min 5 mg/L 75 20 0 45 min 0.1 um CT: 30 min
min
 Sonication Sonication
Dosage 1 Frequency: 20 kHz Frequency: 20 kHz
Squeeze film 150 2 min 10 75 20 45 min Squeeze film thickness: 2 mm, CT: 1 min
thickness: 2 mm mg/L min 0 0.1 um Chlorination
CT: 1 min Cl dosage: 0.5 mg/L CT: 15 min

Sonication Sonication
Sonication Dosage 12 Frequency: 40 kHz Frequency: 20 kHz
+ Chlorine Squeeze film 150 2 min 15 75 20 0 45 min Squeeze film thickness: 2 mm, CT: 2 min
thickness: 2 mm mg/L min 0.1 um Chlorination
CT: 1 min Cl dosage: 0.75 mg/L CT: 15 min

Sonication Sonication
Dosage 3 Frequency: kHz 150 2 min 20 75 20 0 45 min 0.1 um Frequency: 20 kHz
Squeeze film mg/L min Squeeze film thickness: 2 mm, CT: 5 min
thickness: 2 mm Chlorination
CT: 1 min Cl dosage: 1 mg/L CT: 15 min

Chlorination
Control Chlorine 2 min Cl dosage: 1 mg/L
Cl dosage: 0.5 mg/L 150 5 mg/L 75 20 0 45 min 0.1 um CT: 30 min
CT: 5 min min

Dosage 1 Chlorine dioxide Chlorine dioxide

Chlorine Cl dosage: 0.5mg/L NH2Cl dosage: 0.5 mg/L CT: 15 min
dioxide + CT: 15 min 150 2 min 10 75 20 0 45 min 0.1 um Chlorination
Chlorine mg/L min Cl dosage: 0.75 mg/L CT: 30 min

Dosage 2 Chloramine Chlorine dioxide

Cl dosage: 0.75 mg/L NH2Cl dosage: 0.75 mg/L CT: 15 min
CT: 15 min 150 2 min 15 75 20 0 45 min 0.1 um Chlorination
mg/L min Cl dosage: 1 mg/L CT: 30 min

Dosage 3 Chloramine Chlorine dioxide

Cl dosage: 1 mg/L NH2Cl dosage: 1 mg/L CT: 15 min
CT: 15 min 0.1 um Chlorination
150 2 min 20 75 20 0 45 min Cl dosage: 1.5 mg/L CT: 30 min
mg/L min