Safety Guidelines for Chlorine Applications

at Water Treatment Plants

October 2011
Emerency !esponse Centre Phone " #$1 %&''( 2)*$ 1+0
,-P- Pollution Control .oard/ P.0 " #$1 %&''( 2)*))2+12)**1$1
E2'/ Sector/ Parya3aran Parisar/ 4A0 " #$1 %&''( 2)*5 &)2
Arera Colony/ .hopal 6 )*2 01* E-mail " ercmppcb7nic-in
8ndia Web " 333-ercmp-nic-in
ERC/MPPCB/BPL - 1 -
INDEX
1. Introduction 03
2. Application of Disinfectant at Water Works 03
3. Characteristics of Chlorine 03
4. Eposure !outes 04
". Eposure #i$its 04
%. &ar$ful Effects of Chlorine 04
'. Causes of Concern for Chlorine Application 0"
(. !e)uire$ent of *afet+ *+ste$s at Water ,reat$ent -lant 0%
.. *tora/e and &andlin/ of Chlorine C+linders 0.
10. Chlorine Detection and Deconta$ination *+ste$ 0.
10.1 Detection *+ste$ 0.
10.2 Neutrali0ation -it 10
10.3 *cru11er *+ste$ 12
11. *pill 2 #eaka/e &andlin/ 13
12. -ersonal -rotecti3e 4ethods 14
13. 5irst Aid 1%
14. Appendices 14
i. A11re3iations used 1'

ERC/MPPCB/BPL - 2 -
1- 8ntroduction "
Chlorine is one of the most common chemicals used in diverse industrial fields
including pharmaceuticals, pulp paper industries, automo!ile components
manufacture, agrochemicals and in manufacturing products of domestic and
other use li"e cleaning !leaching agent, P#C etc$ Chlorine is %idel& used in
treatment of %ater as disinfectant and protection against %ater!orne micro!es$
Chlorine is ha'ardous and ma& pose potential ris" and a severe emergenc& ma&
suddenl& and une(pectedl& occur at chlorine storage and handling site$ )uch
eventualities should !e anticipated and proper s&stem must !e installed to tac"le
them effectivel&$
2- Application of 9isinfectants at Water Wor:s "
* %ide range of disinfectants are availa!le such as chlorination, o'oni'ation and
+# disinfection and all %ater %or"s use them for the suppl& of safe pota!le
%ater$ ,espite !eing to(ic, the chlorine is the most preferred disinfectant on
account of lo%er cost and eas& availa!ilit&$
5- Characteristics of Chlorine "
Chlorine gas is 2$-. times heavier than air and is greenish &ello% in colour %ith
disagreea!le, sharp, pungent and penetrating odor$ /t is non flamma!le !ut strong
o(idi'er and highl& corrosive, ver& to(ic to a0uatic organisms and !irds$ /t can
e(ists as a gas or as a li0uid$ 1he li0uid chlorine is am!er coloured and a!out
1$-- times heavier than %ater$ /t vapori'es at standard temperature and pressure
%ith 1 litre li0uid &ielding a!out -23 litres of gas$
Conversion 4 1 ppm 5 2$.6 mg/m
7
)olu!ilit& in %ater 4 3$89
:ree'ing Point 4 -123
o
:
#apor densit& 4 2$-. g/litre
#apor pressure 4 2$. !ar at 23
o
C
)p$ ;ravit& 4 1$-8 g/ml at 3
o
C
Critical 1emp$ 4 1--
o
C
Critical pressure 4 8<$1 atm =8811 "Pa>
#iscosit& 4 3$7-< centipoise at 3
o
C =li0>- 3$317- centipoise at 3
o
C =gas>
ERC/MPPCB/BPL - 7 -
)- E;posure !outes "
1he chlorine enters the !od& through )"in, E&es and /nhalation$
'- E;posure <imits "
?)@* PEL =1L#> - 1 PPM =2$.6 mg/m
7
>
/,L@ - 13 PPM
1A* limit - 1 PPM =:or s"in>
=. hours e(posure>
B/?)@-REL 3$2 PPM =1$-2 mg/m7>
=12 minutes e(posure>
*- =armful Effects of Chlorine"
Chlorine in high concentration acts as an asph&(iant !& causing cramps in the
muscles of the lar&n( =cho"ing>, s%elling of the mucous mem!ranes, nausea,
vomiting and an(iet&$ *cute respirator& distress including cough, hemopt&sis,
chest pain, d&spnea, and later tracheo!ronchitis, pulmonar& edema, and
pneumonia ma& supervene =see ta!le !elo%>$
To;ic Effects of Chlorine
Chlorine Concentration Effects
3$37 - 3$1 ppm Range of odour threshold
1 - 7 ppm Ma& cause mild irritation to e&es, nose, throat
7 - 2 ppm )tinging or !urning in e&es, nose, throat$ Ma& cause
headache, %atering e&es, snee'ing, coughing, !reathing
difficult&, !lood& nose and !lood-tinged sputum$
2 - 12 ppm )evere irritation of e&es, nose, throat and respirator&
tract
13 ppm /mmediatel& ,angerous to Life @ealth =/,L@>
73 - <3 ppm /mmediate !reathing difficult& resulting in pulmonar&
edema, possi!l& causing suffocation and death$
-73 ppm Lethal after 73 minutes$
1333 ppm or more :atal after a fe% !reathes
ERC/MPPCB/BPL - - -
Chlorine is corrosive to the e&es, s"in, and respirator& tract$ E&e contact can
cause permanent damage$ /nhalation of the gas can cause pulmonar& edema, a
medical emergenc& that can !e dela&ed for several hours$ 1his can cause death$
Rapid evaporation of the li0uid ma& cause frost!ite$ Repeated e(posure ma&
permanentl& damage the lungs or cause chronic !ronchitis$ Chlorine ma& affect
the teeth resulting in erosion, and cause s"in rash$ * single high e(posure ma&
cause similar health effects$
&- Causes of concern for Chlorine Applications"
1he use of chlorine for the disinfection of pota!le %ater supplies has !een of
great significance from a pu!lic health perspective !ut its application raises
serious concerns %hich need prime attention from safet& point of vie%$ 1he
causes of concern are as follo%s C
1$ Chlorine is a highl& to(ic su!stance that is transported !& truc"s/road
transport and can pose severe ha'ard in case of accident$
2$ Chlorine is highl& to(ic, corrosive and penetrating at am!ient temperature
%hich poses potential health ris" to staff at %ater treatment plant and
general pu!lic around, if released !& accident$
7$ )tringent provisions for containment and neutrali'ation needs to !e
maintained at chlorine storage and handling site at %ater %or"s$

Chlorination Mechanism Chlorine tonners C&linders
ERC/MPPCB/BPL - 2 -
+- !e>uirement of Safety Systems at Water Treatment Plant "
*ll such installations must have %ritten safe %or" procedures, !ut not limited to,
for the follo%ing C
C&linder change
Lea" detection control
+se of repair "it and container repair
Chec"ing protocol
Respiration protocol
)elf !reathing apparatus protocol
,isposal of damaged containers
Routine maintenance of e0uipment
*ll the %ater treatment plants that have chlorination s&stem and use chlorine for
disinfection should have follo%ing safet& arrangements in place to meet the
emergenc& situation C
1$ ?n-site Emergenc& Plan
2$ Breathing apparatus
7$ Emergenc& "it
-$ Lea" detectors
2$ Beutrali'ation tan"
<$ )cru!!er s&stem
8$ )iren s&stem$
.$ Communication s&stem$
6$ 1agging s&stem for e0uipments
13$ :irst aid including ta!lets and cough mi(tures
11$ E(haust fans
12$ :acilit& for testing of pressure vessels, chlorine lines etc$
17$ 1raining moc" drill
1-$ )afet& sho%ers E&e fountain
12$ Aater curtain around storage facilit&
1<$ Protecting hoods for ton-containers$
18$ :ire e(tinguishers$
1.$ Aind coc"
16$ Placards in local language for pu!lic cautioning, first aid and list of
different authorities %ith phone num!ers$
23$ Personal protective e0uipments, vi'$ protective glass, clothings, gloves,
shoes, helmet, goggles etc$
21$ Placards at strategic locations sho%ing Material )afet& ,ata )heet
=M),)>, /nternational Chemical )afet& Card =/C)C> etc$ of chlorine$
ERC/MPPCB/BPL - < -
$- Storae ? =andlin of Chlorine Cylinders "
1he chlorine has a great potential for creating ha'ard hence there is need to
o!serve certain precautions for the storage, use and handling of chlorine
c&linders at site$ )ome of the measures, that need to !e o!served in this regard,
are given as follo%s C
,o not store the c&linders in e(its or egress routes$
C&linder storage area should !e %ell ventilated$
C&linders should not !e stored in damp areas, near salt or corrosive
chemicals, fumes, heat or %here e(posed to the %eather$
C&linders should !e stored in an upright position$
*l%a&s use proper trunnians to place a c&linder on ground$

C&linders shall !e secured %ith a chain or appropriate !elt a!ove the
midpoint, !ut !elo% the shoulder$
1he& must !e stored in such a %a& that c&linders are used in the order in
%hich the& are received$
*void storing c&linder longer than one &ear %ithout use$
C&linders shall !e "ept at least 23 ft$ a%a& from all flamma!le, com!usti!le
or incompati!le su!stances$
ERC/MPPCB/BPL - 8 -
)torage areas that have a noncom!usti!le %all at least 2 ft$ in height and
%ith a fire resistance rating of at least 73 minutes ma& !e used to segregate
gases of different ha'ard classes in close pro(imit& to each other$

C&linders should not !e dragged, rolled or ph&sicall& carried$ * lifter, hand
truc", monorail etc$ should !e used to carr& or transport the c&linder in the
premises$
Magnets should not !e used for lifting c&linders$
1he c&linders should not !e painted !& users$
Close valves on gas c&linders %hen the s&stem is not in use$
ERC/MPPCB/BPL - . -
,o not open the c&linder if the valve is corroded$
Chec" e0uipment and lines fre0uentl& o%ing to the corrosive nature of
chlorine$
Bever attempt to modif&, alter or repair containers valves$ 1hese tas"s
should !e carried out !& the suppliers$
Remove regulator after use and flush %ith dr& air or nitrogen$
?nl& the %renches and tools provided !& the c&linder supplier should !e
used to handle the valve$ Pliers or other tools should never !e used instead$
Bever attempt to appl& P1:E tape or other sealing material to tight the seal$
1he tightening should !e achieved metal to metal else the valve or regulator
should !e replaced$
Bever use oil or grease on the regulator of a c&linder valve$
*n operator must !e given proper training to handle the c&linder$
*l%a&s follo% the chlorine suppliersD recommendations to dispose off
lea"ing or damaged c&linders$
10- Chlorine 9etection and 9econtamination System "
10-1 Detection System
Chlorine detection and neutrali'ation facilit& is essentiall& re0uired at %ater
treatment plants %here chlorine c&linders or tonners are used for disinfection
purpose$ 1his s&stem activates the emergenc& services and decontaminates the
spilled material to tac"le the chemical emergenc& situation$

1he chlorine detection e0uipment should !e installed at strategic locations in the
plant area, including at chlorine inEection area, c&linders storage area, c&linder
off-load site etc, so that it can sense the odor even at 3$1 ppm = 3$2.6 mg/m
7
> and
activate the siren to alert the people in and around$ 1he chlorine detection
s&stems should function in on-line as %ell as off-line mode, i$e$ in the event of
lea"age %hen the chlorination is in progress, i$e$ tonners in use, and also %hen
the chlorination process is off or tonners are "ept off line$
ERC/MPPCB/BPL - 6 -
/n addition to gas detection e0uipment, ammonia torch test should !e performed
periodicall& at strategic locations in the plant area to chec" the chlorine lea"age$
)ilver nitrate test can also !e tried to chec" the presence of chlorine, !ut the
former should !e preferred$ @and& electronic detectors can also !e used to chec"
the lea"age of chlorine$
*mmonia torch test Electronic detectors

Ammonia torch Test " * glass rod having cotton %rapper on one end, dipped in
li0uor ammonia, gives %hite smo"e of ammonium chloride %hen comes in
contact %ith chlorine$
Sil@er nitrate Test " Ahen a glass rod, dipped in silver nitrate solution, comes
in contact %ith chlorine, a %hite precipitate is formed at its tip$
10.2 Neutralization Pit
1he chlorine storage and handling area in a %ater treatment/purification plant
must have chlorine neutrali'ation facilit&, vi'$ neutrali'ation pit as %ell as
scru!!er s&stem$ 1he neutrali'ation pit should !e constructed close to
chlorination site and chlorine storage area$ 1here should !e sufficient slope
!et%een platform and neutrali'ation pit so that the lea"ed or defected chlorine
c&linder/tonner can !e rolled do%n easil& and s%iftl& into the neutrali'ation pit$
ERC/MPPCB/BPL - 13 -
1he surface area and the volume of pit should !e planned in such a manner that
chlorine container is immersed completel& in the al"ali solution$
1he caustic solution, sodium h&dro(ide, is preferred for the neutrali'ation
purpose o%ing to its faster and !etter a!sorption efficienc& as against lime %hich
cause pro!lem of sludge formation and cho"ing of treatment s&stem pipelines$ *
read& prepared caustic solution should !e used in the pit instead of pouring
sodium h&dro(ide pallets in the pit %ater as the a!sorption efficienc& in the later
case %ould !e less$ /deall& the 0uantit& of Ba?@ needed for the neutrali'ing one
tonner, i$e$ 633 "g, %ould !e 13<< "g$ 1he reaction !et%een Ba?@ and Cl
2
goes
as follo%s C
Cl
2
F 2Ba?@ Ba?Cl F BaCl F @
2
?
83$6 F .3 8-$2 F 2.$2 F 1.
Considering the stoichiometr& and mass !alance e0uation, 1 "g of Cl
2
and 1$7 "g
of Ba?@ %ill produce 1$32 "g sodium h&pochlorite, as evident from the a!ove
e0uation$

1he other chemicals that can also !e used for chlorine neutrali'ation are as
follo%s C
G Potassium h&dro(ide
G )odium car!onate
G Calcium h&dro(ide
G )odium sulphite
G )odium thiosulphite
G :errous chloride
G @&drogen pero(ide
1he 0uantit& of other chemicals re0uired for neutrali'ation of chlorine is given
on the follo%ing page C
ERC/MPPCB/BPL - 11 -
10.3 Scrubber Unit
/n addition to chlorine neutrali'ation pit, all the %ater treatment plants should
have an effective automated chlorine scru!!er s&stem %hich can activate
automaticall& immediatel& on sensing the chlorine presence in the am!ient
environment to a!sor! the lea"ed gas and neutrali'e it in the scru!!er$
1he Chlorine ;as Lea"age ,etection, *!sorption and Beutrali'ation )&stem
reduces the ris" of chlorine gas spreading into the atmosphere$ /t automaticall&
controls and a!sor!s heav& lea"s from 133 "g or from 633 "g ton containers to
a!sor! in caustic solution, thus forming h&po chlorite that can !e reused as a
cleaning agent$

ERC/MPPCB/BPL - 12 -
Caustic
)oda
Aater
#olume
)oda
*sh
Aater
#olume
@&drated
Lime
Aater
#olume
Chlorine
container
capacit& =Hg>
Aeight
=Hg>
Ltr Aeight
=Hg>
Ltr Aeight
=Hg>
Ltr
-2 2. 1.2 17< -23 2. 2<<
<. 63 283 223 <.3 .2 .12
633 11<3 7<.3 2823 6323 11<3 11723


1he scru!!er/neutrali'ation s&stem consists of a !lo%er, a!sorption to%er
pac"ed %ith rasching rings, an al"ali =Ba?@> tan", al"ali circulation pump,
piping valves and light %eight :RP and P#C duct$ 1he chlorine gas is suc"ed !&
!lo%er and is delivered to the a!sorption to%er %here it is a!sor!ed !& a!sor!ent
and the air is vented at the top of the to%er$ *s the e(tracted air, contaminated
%ith chlorine gas, is !lo%n up through the column the caustic soda reacts %ith it
to form sodium chloride and sodium h&pochlorite$ *s this a!sorption is
accompanied !& a chemical reaction, there is negligi!le chlorine in the air vent$
/t should !e ensured that a sufficient 0uantit& of a!sor!ent is continuousl&
circulated in the a!sorption to%er from the a!sor!ent tan" till the tonner gets
emptied$ 1he spent a!sor!ent, after completion of neutrali'ation of all chlorine,
%ill contain onl& sodium chloride or sodium h&pochlorite %hich are innocuous$
11- Spill 1 lea:ae handlin "
/n the event of spillage or lea"age of chlorine follo%ing measures ma& !e
o!served for speed& control and minimi'ing the e(tend of damageC
Contact Emergenc& Response Centre on phone no$ 3822-2-<61.3 =,irect>,
2-<--2., 2-<<161 =PBI> or :a( no$ 3822-2-<78-2 and other concerned
e(pert agencies for emergenc& support$
Evacuate danger area around the incident site$ Evacuate and restrict persons
not %earing protective e0uipment from area of spill or lea" until cleanup is
complete$
)top or reduce lea" if it is safe to do so and prevent chlorine from entering
se%ers, %ater%a&s or confined spaces$
)uppl& sufficient replacement air to ma"e up for air removed !& e(haust
s&stems$
1he person should %ear protective gloves, protective clothing, safet&
goggles, !reathing apparatus as specified in )ection 11$
/f the gas is lea"ed, stop the flo% of gas if it can !e done safel&$ /f the
source of the lea" is a c&linder and the lea" cannot !e stopped in place,
ERC/MPPCB/BPL - 17 -
remove the lea"ing c&linder to a safe place in the open air, and, repair the
lea", if possi!le, using a standard "it$
/f the lea" can !e stopped in place, !u!!le chlorine left in the service line
through a sodium sulfide and e(cess sodium !icar!onate solution %ith the
help of a trap in the line$
:ollo% the neutrali'ation process as stated in )ection 13$7$ /f the scru!!er
s&stem fails to operate, follo% the process as per )ection 13$2$
:or li0uid spills, ventilate area and %ash do%n spill %ith %ater$
12- Personal Protecti@e ,easures "
1here is al%a&s chance of lea"age or spillage of chlorine gas at %ater treatment
facilit& and there is li"elihood of e(cessive gas levels in case the lea"ed gas is
not controlled and this can adversel& affect the plant staff and people in the
vicinit& area$ /t is, therefore, strongl& recommended to have respirator&
protection in the form of full-face gas mas"s %ith proper canisters or supplied
air respirators =)*R> at site %hich can !e used !& the staff in times of
emergenc&$
1he s"in effects of chlorine can generall& !e controlled !& good personal
h&giene practices$ /f ver& high gas concentrations or li0uid chlorine is present,
full protective clothing, gloves, and e&e protection should !e used$ 1he
follo%ing are recommended in this regard C
But&l ru!!er, Beoprene, 1eflonJ, )arane( J, Barricade J, CP:7 J,
Responder J, #iton J, 1rellchem @P) J, 1&chem 13333 J =Resistance to
!rea"through longer than . hour> are among the recommended protective
materials$
Bitrile ru!!er, -@ J =Resistance to !rea"through longer than - hours> is also
recommended$
/t is not recommended to use ver& thin natural ru!!er, neoprene, nitrile and
P#C gloves of 3$7 mm or less$
Pol&eth&lene and pol&vin&l chloride are also not recommended$
ERC/MPPCB/BPL - 1- -
+se supplied air respirator =)*R> or chemical cartridge respirator %ith
cartridge to protect against Cl
2
up to 2 ppm$


Personal Protecti@e adets
+se )*R operated in a continuous flo% mode %ith cartridge / full face piece
chemical cartridge respirator %ith cartridge / gas mas" %ith canister / full face
ERC/MPPCB/BPL - 12 -
piece self-contained !reathing apparatus =)CB*> or full face piece )*R to
protect against chlorine up to 13 ppm$
15- 4irst Aid "
/n the event of an e(posure to chlorine, the follo%ing first aid measures can !e
adopted to minimi'e the damage to !od& s&stems C
1he aids that should !e made availa!le at chlorine storage and handling site for
immediate assistance include Compressed o(&gen, forced-o(&gen mas", soap,
%ater, normal saline, ,2A, RingerDs lactate, isoproterenol inhaler, sodium
!icar!onate etc$
,2A is 29 de(trose in %ater %hich consists of 28. mmol/L de(trose$ RingerDs
lactate is !asicall& cr&stalloids %hich include saline and de(trose$
/n case of s"in e(posure, remove the contaminated clothes immediatel&, rinse
s"in %ith plent& of %ater for at least 12 minutes and %ash the s"in %ith soap
and %ater$
/n case of e(posure to e&es, rinse the e&es %ith plent& of lu"e%arm %ater for at
least 12 minutes$ Contact doctors for medical aid$
,o not allo% the victim to drin" alcohol or smo"e$
;ive plent& of mil" to the victim, if he can drin"$
/n case of inhalation tr& to get fresh air or artificial respiration$ Chec"
respirator& rate and note an& trauma$ /n case if no pulse is detected, provide
cardiopulmonar& resuscitation =CPR>$ /f not !reathing, provide artificial
respiration$ /f !reathing is la!ored, administer o(&gen or respirator& support$
ERC/MPPCB/BPL - 1< -
A11re3iations 6sed
CPR - Cardiopulmonary Resuscitation
ERC - Emergency Response Centre
FRP - Fiber Reinforced Plastic
ICSC - International Chemical Safety Card
IDLH - Immediately Dangerous to Life Health
!SDS - !aterial Safety Data Sheet
mg"m
#
- !illigram per cubic meter
!mol"L - !illimole per liter
$I%SH - $ational Institute of %ccupational Safety Health
PP! - Parts Per !illion
PEL - Permissible E&posure Limit
P'FE - Polytetrafluoroethylene
REL - Recommended E&posure Limit
S(R - Supplied (ir Respirator
SC)( - Self Contained )reathing (pparatus
'L* - 'hreshold Limit *alue
'+( - 'ime +eightage (,erage
ERC/MPPCB/BPL - 18 -
P*C - Poly,inyl Chloride
ERC/MPPCB/BPL - 1. -