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TECHNOLOGY OF TRIHALOMETHANES

(THMs) REMOVAL FROM WATER AND


WASTEWATER
.

HASSIMI ABU HASAN, PhD

Department Of Chemical and Process Engineering


Faculty Of Engineering and Built Environment
Universiti Kebangsaan Malaysia

Presentation Outline
o Introduction
o Level of thrihalomethanes (THMs) in

water and wastewater


o Physical-chemical treatment
technology
o Biological treatment technology
o Conclusion

Introduction What is THMs?


THMs is categorised as volatile compounds (Zhang et

al. 2015).
THMs are among the most abundant and thoroughly
studied disinfection by-products (DBPs) (Burch et al.
2015).
THMs is measured as total THMs (< 0.08 mg/L) (USEPA
2012) which consist of:
Chloroform (CHCl3), Dibromochloromethane (CHBr2Cl),

Bromodichloromethane (CHBrCl2), Bromoform (CHBr3)

THMs have the highest occurrence levels in the

disinfected drinking waters and are currently regulated


in a number of countries (Wang et al. 2014),
United States, Florida, Canada, Australia, European Union (UE),

Japan, Netherlands, New Zealand, South Africa, Sweden, United


Kingdom and Malaysia

How DBPs formed?

particulate organic matter


(POM)
dissolved organic matter
(DOC).

(haloacetic acids)
(haloacetonitriles)

Effect of THMs on Human Health


Human exposure to THMs not only on direct

ingestion of drinking water, but also occurs due to


volatilization of DBPs during:
Showering, bathing and cooking (Rivera-Nunez et
al. 2012)
These compounds were identified as genotoxic
mutagen which is able to lead to the risk of toxicity
to human and aquatic life (Zhang et al. 2013).
THMs exposure has been associated with adverse
reproductive outcomes, as well as cancers of the
digestive and genitourinary systems (Grellier et al.
2010)
THMs compound should be identified and removed
from drinking water and wastewater whether by

How to measure THMs?


Pretreatment
Filtration
using
Puradisc
25 nylon
syringe
filter with
0.45m
pore size
SS and
particle

LiquidLiquid
Extractio
Solvent:
n n-pentane
Mixed and
vigorously
shaked
with
water
sample (1
min)
Upper
phase
collection
THMs
analysis

GCECD
DB-5

capillary
column (60
m L x 0.32
mm Di
Carrier gas:
helium (10
mL min-1).
Initially:
temperatur
e kept
constant 40C (4
min)
Temperatur
e

Levels of THMs in Industrial


Wastewater

TTHMs = 2008.4
g/L
TTHMs = 1519.6 g/L
TTHMs = 2589.2
g/L

TTHMs = 1565.0
g/L

Levels of THMs in Tap Wastewater


1563.52 g/L

1551.77 g/L
1529.81 g/L

1522.55 g/L

1502.60 g/L

Regulation of THMs in water


Country

Organis
ati-on

Australia
Europea
n Union
Germany
Japan
Netherla
nds
New
Zealand
UK:
England/
Wales
UK:
Northern
Ireland
UK:
Scotland
USA

NHMRC

Malaysia

CHCl3
TTHM
CHBrCl CHBr2Cl CHBr3
Date
s
(g/L
Set
(g/L) (g/L)
2 (g/L)
(g/L)
)
2004
250

EC

1998

100

FHM
MHLW

2001
2004

60

30

100

90

50
100

VROM

2000

25

MH

2005

200

60

150

100

DWI

2000

100

DWI

2007

100

DWR

2001

100

EPA

2006

80

80

80

80

80

MH

2010

200

60

100

100

Refere
nce

(Jackson
et al.
2008)

(DWQSP
2010)

Abbreviations
DWI
Drinking Water Inspectorate
EC
European Commission
EPA
Environmental Protection Agency
DWAF
Department of Water Affair and
Forestry
DWR
Department of Water Resources
DWQSP Drinking Water Quality Surveillance
Programme
FHM
Federal Health Ministry
HC
Health Canada
MH
Ministry of Health
MHLW
Ministry of Health, Labour and Welfare
NFA
National Food Administration
NHMRC National Health & Medical Research :
Council
VROM
Minidtry of Housing, Spatial lanning
and the Environment

Prevent the THMs formation and its


removal technology
Treatme
nt
technolo
gy
Chemical
-Physical
treatmen
t
Granular
activate
d carbon
(GAC)

Membra
ne
filtration

Advance
d
Oxidatio
n
Process
(AOP)

Biologica
l
treatmen
t
Biologica
l
Activate
d Carbon
(BAC)

Combine
treatmen
t
Ozonatio
n + BAC

Ozonatio
n/Ultravi
olet-BAC

Physical-Chemical Technology

Granular Activated Carbon


Forms and Conditions:
Powder Activated Carbon

(PAC)
Granular Activated
Carbon (GAC)
Beads Activated Carbon
(BAC),
Polymer-coated carbon
and etc.
Eliminate THM formation
potential (THMFP), taste
and odor
Percent removal of THMFP and TOC
by granular activated carbon
Get rid of synthetic organic
contact at 2, 4, and 6 gallon per
minute flow rates (Karen 1980)
chemicals (SOCs) and

Chlorine Dioxide
Effective as a

disinfectant
Does not react with
organic materials that
exist in nature to form
THMs
Low capital cost
Operating system is
almost the same as
chlorination system

1. For disinfection
2. Pre-oxidation to control
taste and odour
3. Regulated
Chlorine
dioxidethe
used as
concentration of iron and
pre-treatment
manganese in water

4. Controlling the amount of


hydrogen sulfide and
phenolic compound
5. Oxidized the precursor of
THMs

Advanced Oxidation Process (AOP) - Ozonation

Oxidation is defined as the transfer of one or more electron

from an electron donor (reductant) to an electron acceptor


(oxidant)
Decrease the formation of THMs upon subsequent
chlorination.
Available oxidizing agent, most active and easily decomposed
into oxygen.
THMs oxidize by ozone.
More complex technology compare to chlorination

27-30% reduction

Micro & Ultrafiltration


Microfiltration (MF)
Membrane with a pore
size of 0.1-10 m
Remove all bacteria
but only part of the
viral contaminated is
caught in the process
Able to remove 5.56.6 % of THMFP from
surface waters
(Mohamed Siddiqui et
al. 2000)

Ultrafiltration (UF)
Membrane with pore
size of 0.001-0.1 m
Effective in reducing
turbidity, particulates,
suspended solid and
total coliforms as well
as bacteria
Able to remove 42-48
% of THMFP from
surface waters
(Mohamed Siddiqui et
al. 2000)

Nanofiltration & Revere


Osmosis
Nanofiltration (NF)
Effectively remove
NOM
Competitive with
other NOM removal
technologies
Simplicity of
operation
High flux memrane
Low fouling
potential
Lower membrane
cost
Able to remove 90-

Reverse Osmosis
(RO)
Remove almost all type

of pollutant
Bio fouling of membrane
easily occurred

Coagulation
Able to remove natural

organic matter (NOM),


at low pH or higher
coagulant dosage
Alum is a widely used
coagulant - Al2(SO4)3,
AlCl3, FeCl3,
Polyaluminum chloride
Used as pre-treatment
and can improved
membrane
performance
By removing fraction of
dissolved organic

Enhanced coagulation of the


different raw water sources (Garcia.
2005).

Biological Technology

Biological Activated Carbon


(BAC)
Lower cost and higher

performance than
normal activated carbon
adsorption treatment
Suitable to apply to
reduce THMs content in
drinking water
Removal of DBPs
precursor correlates
with the removal of DOC
Able to remove 85-90 %
of THMFP in water
sample

Variation of THMFP, HAA and Nnitrosodimethylamine (NDMA) formation


potential before and after treatment
(Pramanik et al. 2015)

Combine Technology

Ozonation and Filtration

Able to reduce up to 50 % of dissolved organic carbon


Limited research in this area show that ceramic
membranes combine with ozonation achieved a high
permeate flux without membrane damage

Ozonation
Produce by-products as they
are easily biodegradable
Ozonation prior to
membrane filtration reduces
membranes fouling and
enhances permeate flux

Filtration
An effective method to remove
particles, microorganism and
organic matter
Ozonation by-product can easily
removed by biofiltration

Advanced Oxidation Process (AOP)


Reduce the TOC concentration and the THMFP of raw water
Proven more effective in removing organic pollutants than
treatment of each alone

O3/UV
Effectively destroy
organic
contaminants largely
Able to remove 83-88
% of THMFP.

UV/ H2O2
Applied in
commercial drinking
water application for
removal of various
organic pollutants
Able to remove 8085 % of THMFP.

Advanced Oxidation Process (AOP)


H2O2/O3
H2O2 in excess leads to
a decrease in the
effectiveness of the
oxidation process
because OH formed
react with H2O2
Able to remove 70-80
% of THMFP

THMs for raw and oxidized water


As a result O3/UV and UV/H2O2 are viable options for maximum
reduction of NOM
UV/ H2O2 like other AOPs, typically cost much more than conventional
treatment were it could be best applied to address a seriously
concerning contaminant or multiple contaminants due to the
economical and practical aspects

Ozonation & BAC


This process is one of

the promising
processes to remove
some of NOM
compounds that
soluble, hardly
biodegradable and
irremovable
This technology leads
to biologically stable
water
Although the ozone can
slightly remove the

Performance of integrated
O3/BGAC compared with GAC for
the Yellow River
Water in DOC removal (Yan et
al.2010)

Ozonation/Ultraviolet-BAC
To avoid the formation of DBPs
Promising treatment for the reduction of DOC, harmful DBPs as

well as their precursors


THM removal of O3/UV, BAC alone and combination of O3/UVBAC were 33, 31 and 71 % respectively.
THMFP removals of O3/UV, BAC alone and O3/UV-BAC process
were 16, 25 and 40% respectively.

(a) Changes in concentration of THM species, (b) THM and THMFP


at each treatment process

Conclusion
The removal of THM and THMFP by AOP combine technology.
O3/UV 83-88%
UV/H2O2 80-85%
H2O2/O3 70-80%
NF reduce the largest amount of THM and THMFP (90-95%)

compared with MF and UF.


O3-filtration remove 50-70% of THM and THMFP.
Coagulation remove 85-90% of THM and THMFP in wastewater.
O3/UV-BAC remove 71% of THM in water source.
BAC conduct 85-90% of THM and THMFP removal.
Biological technology is more convincing in term of cost and
more effective in removal of THMs and THMFP.
Chemical technology give high percentage in THMs and THMFP
removal but it is not environmental friendly and higher cost

THANK YOU