Chlorine Leak in Mumbai Port Trust (2010)

Chlorine leak in Mumbai Port Trust (2010)

Pratik Krishnan PhD student June 8th 2017 Steering Committee Meeting A little bit about me…

• Born in Mumbai, India

Dubai • Grew up in Dubai, UAE Mumbai • Bachelors degree in Chemical Engineering - Institute of Chemical Technology, Mumbai

Map data © 2017 Google, Mapa GISrael, ORION-ME Map of parts of South Asia and the Middle East [1] • MS in Chemical Engineering - Texas A&M University Some of my hobbies: Reading, swimming, traveling, watching TV shows, listening to music 2 Outline Background Incident Description Incident Analysis Response to the incident What went wrong? Chlorine properties and uses Consequence analysis Chlorine related incidents Regulations Recommendations 3

[2-5] Background

[2] Map of Maharashtra [3] Map of Mumbai

[4] Map of Haji Bunder Port

Haji Bunder Port, Mumbai Port Trust

Image of the Mumbai Port Trust [5] . Established in 1873 . Autonomous body owned by the Government of India . Built on a natural deep water harbor . Traffic carrying goods over 60 million tons annually 5 [6-15] Incident Description Location: Haji Bunder Port, Mumbai Date: 14th July 2010

Students at the LBS college of Maritime Studies [6]

• Sleeping students in a college dorm near the Mumbai Port Trust wake up vomiting • Some are awake, preparing for exams • An on site guard notices a gas leak and calls the 3 AM fire department 6

[6-15] Incident Description

First responders near the gas leak [15] Water being used on the chlorine leak [16] • By this time, the dorm is evacuated • Victims are taken to hospital • The Fire Department identifies it is a chlorine leak and sprays water but realize it is not enough • They ask for help from private companies 4 AM 7 [6-15] Incident Description

Safety officers from private companies help plug the leak [17] • Safety officers from nearby companies arrive • They manage to plug the leak • The National Disaster Response Force (NDRF) is 9 AM contacted 8 [6-15] Incident Description

The NDRF arrives with special breathing apparatus [17] • The NDRF arrives with self containing breathing apparatus • They don’t have proper equipment for neutralization 12:30 PM • They request help from a private company 9 NDRF- National Disaster Response Force [6-15] Incident Description

The NDRF tries to neutralize the tanks [17]

The NDRF gets the equipment and neutralizes the tanks

2:30 PM NDRF- National Disaster Response Force 10 [16-18] Incident analysis

2001

• Consignment of cylinders imported from Dubai • Abandoned by the importer • Reason - Customs department raised objections • Left exposed with no safeguards

2008

• Inspection team notifies that some cylinders contained residual gas • No action is taken

2010

• Chlorine leak occurs due to corrosion of one cylinder over time 11 [16-18] Incident analysis

5 have residual chlorine

141 cylinders

1 cylinder leaks after about 10 years due to corrosion

• More than 120 people hospitalized • Around 900 people evacuated • Luckily, there were no fatalities • Extensive damage to surrounding flora and fauna 12 [8,19-21] Response to the incident

• The NDRF is called to neutralize the chlorine in the tank

Federal • Ministry of Shipping sets up a committee to review guidelines

• The Maharashtra State Health State Department coordinates with those injured

• First responders arrive at the scene to mitigate the disaster • The BMC tries to ensure the leak Local Government is contained • The BMC, Police and MPT start a joint probe

NDRF- National Disaster Response Force BMC- Brihanmumbai Municipal Corporation (Municipal Corporation of Greater Mumbai) MPT – Mumbai Port Trust 13 [4,22] What went wrong? Contributing factors: • Improper storage of tanks • Extended storage of goods

350 m • Violation of safety guidelines (1150 feet) Port Aggravating factors: • Proximity of student dorms Dorm • Lack of mitigation systems Map data © 2017 Google Map of Haji Bunder Port [4] • Lack of emergency preparedness

[23-28] Chlorine properties and uses

• Greenish–yellow gas • Pungent odor Will not burn • Relative gas density – 2.5 Deadly • Soluble in water 3 • OSHA PEL (STEL) - 1 ppm / 3 mg/m Stable • NIOSH IDLH = 10 ppm • At low concentrations, Oxidizer – respiratory irritant, eye irritant • At high concentrations, – can cause loss of consciousness and death

PEL - Permissible Exposure Limits IDLH – Immediately Dangerous to Life or Health concentration 15 [23-28] Chlorine properties and uses 11.6 million tons produced in the US (2010) 65 million tons produced globally (2006) Uses Chlor-Alkali process

Others Salt + Water + Electricity 23% PVC 40% Basic organic chemicals 37% Chlorine + Sodium Hydroxide + Hydrogen

Others – Hydrochloric acid, Titanium oxide Also used in Water treatment, Pharmaceuticals 16 [4,29-32] Consequence analysis

• Britter-McQuaid model – Dense gas dispersion model • Dow’s CEI – Hazard Distance calculation

Concentration vs. Distance Distance vs Hole Diameter

Hole diameter

17 [4,29-32] Consequence analysis

Hole size = 1 mm

Distances given are radii of circles

19 Incidents in India [40-49]

Raisen Kolkata

Kheda Bhopal (1985) Jamshedpur (2008) Bhubaneshwar

Pune Berhampur (2010) Incidents before July, 2010 Incidents after July, 2010

Port Allegany

Atchison Proctor

Phoenix Elmo Graniteville, SC (2005) Addis

Macdona, TX (2004)

Regulations in India

Manufacture, Storage and Import of Hazardous Chemicals Rule,1989

Hazardous Wastes Rules, 2008

Chemical Accidents Rules, 1996

Public Liability Insurance Act, 1991

National Disaster Management Authority, 2007

22 [61-63] Regulations Regulations in the USA OSHA EPA

 Hazardous Waste Operations  Emergency Planning and Emergency Response [40 CFR Part 355] Standard [29 CFR 1910.120]

 Emergency Release Notification [40 CFR Part 355]  Process Safety Management Standard [29 CFR 1910]  Hazardous Chemical Reporting

[40 CFR Part 370]

 Hazard Communication  Toxic Chemicals Release [29 CFR 1910.1200] Inventory [40 CFR Part 372]

 Hazardous Substance Release Reporting [40 CFR Part 302]

23 Recommendations • Imported cylinders must be certified for how long they can be used[22] • Cylinders must only be accepted by the port authority once customs clearance is obtained • Conducting regular audits may be helpful – Internal safety checks help, frequency depends on size • If hazardous substances are imported, – proper storage is essential -- avoid storing it in the open, do not store beyond recommended date – proper mitigation systems must be in place[22] -- hoods, neutralization tank, high pressure water nozzles, foam • Have an emergency response plan 24

References

[1] Google Maps : India [2] Google Maps : Maharashtra [3] Google Maps : Mumbai [4] Google Maps : Haji Bunder Port [5] http://mumbaiport.gov.in/ [6] http://www.thehindu.com/todays-paper/tp-national/Gas-leak-in- Mumbai/article16196969.ece [7] http://www.dnaindia.com/mumbai/report-chlorine-leak-reveals-poor-state-of-disaster- management-in-mumbai-1409926 [8] http://www.dnaindia.com/mumbai/report-sewri-chlorine-leak-sends-123-to-hospital- 1409518 [9] http://www.manupatra.com/roundup/322/News.html [10] http://pib.nic.in/newsite/PrintRelease.aspx?relid=68675 [11] http://www.business-standard.com/article/economy-policy/gas-leak-4-mumbai-port- trust-officials-held-responsible-110121500085_1.html [12] http://www.hindustantimes.com/mumbai/police-seek-details-from-mpt-on-chlorine- leak/story-WOX6cghSBVCQuXIlnNhjbJ.html 25

References

[13] http://www.rediff.com/news/slide-show/slide-show-1-59-hospitalised-in-mumbai- gas-leak/20100714.htm [14] http://www.thehindubusinessline.com/economy/logistics/gas-leak-move-for-action- against-mumbai-port-officials-opposed/article1487147.ece [15] http://www.ndtv.com/photos/news/chlorine-gas-leak-in-mumbai-port-trust- 7732#photo-89062 [16] http://epaper.timesofindia.com/Repository/getFiles.asp?Style=OliveXLib:LowLevelEntity ToPrint_TOI&Type=text/html&Locale=english-skin- custom&Path=TOIM/2010/09/14&ID=Ar00400 [17] http://nidm.gov.in/PDF/Newsletter/25_jul_2010.pdf [18] http://www.dnaindia.com/mumbai/report-chlorine-leak-reveals-poor-state-of- disaster-management-in-mumbai-1409926 [19] http://timesofindia.indiatimes.com/city/mumbai/Chlorine-leak-in-Mumbai-port-area- sparks-panic/articleshow/6169587.cms [20] http://www.financialexpress.com/archive/panel-under-shipping-joint-secy-to-probe- chlorine-leak/661015/ [21] http://timesofindia.indiatimes.com/city/mumbai/103-ill-due-to-chlorine-gas-leak-in- Mumbai-probe-ordered/articleshow/6165579.cms 26

References

[22] Sharma, R. K., Chawla, R., & Kumar, S. (2010). Chlorine leak on Mumbai Port Trust’s Sewri yard: A case study. Journal of Pharmacy and Bioallied Sciences, 2(3), 161–165. http://doi.org/10.4103/0975-7406.68496 [23] http://www.praxair.com/-/media/documents/sds/chlorine-cl-2safety-data-sheet-sds- p4580.pdf [24] https://www.osha.gov/dts/chemicalsampling/data/CH_226500.html [25] http://www.es2inc.com/wp-content/uploads/2011/07/Chlorine-and-its-properties.pdf [26] https://chlorine.americanchemistry.com/Chlorine/ChlorineProduction/ [27] https://www.chlorineinstitute.org/stewardship/chlorine/chlorine-manufacture/ [28] https://www.americanchemistry.com/Jobs/EconomicStatistics/Chemistry-in- Economy/Chlorine-Chemistry-Industry-Fact-Sheet.pdf [29] http://www.academia.edu/30299801/Societal_Risk_Assessment_of_Chlorine_Release_ Scenario_A_case_study [30] http://www.hse.gov.uk/research/crr_pdf/1988/crr88017.pdf [31] https://www.wunderground.com/history/airport/VABB/2010/7/14/DailyHistory.html?req_ci ty=Mumbai&req_state=MH&req_statename=India&reqdb.zip=00000&reqdb.magic=170 &reqdb.wmo=43003 [32] http://www.safety- s2s.eu/modules/s2s_wp4/docs/S2S_CHEMICAL_EXPOSURE_INDEX.pdf

References

[33] http://www.ndtv.com/world-news/chlorine-gas-leak-poisons-kids-in-china-1395114 [34] http://gulftoday.ae/portal/a29cb17f-683d-4764-befe-bc3752ad74fa.aspx [35] http://www.irishtimes.com/news/health/chlorine-gas-leak-forces-staff-evacuation- at-st-vincent-s-1.2775884 [36] https://www.msdsonline.com/blog/health-safety/2015/02/27/fatal-accident-in-ca- even-small-quantities-of-chlorine-pose-danger [37] https://www.scientificamerican.com/article/chlorine-accidents-take-big-human-toll/ [38] https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2908650/ [39] http://nymag.com/daily/intelligencer/2014/12/chlorine-gas-attack-interupts-furry- convention.html [40] Google Maps - India [41]1985 –Union Carbide, Bhopal, Madhya Pradesh http://articles.latimes.com/1985-04-02/news/mn-19328_1_chlorine-gas [42] 2008 –Jamshedpur, Jharkhand http://www.idsa.in/idsastrategiccomments/TheChlorineGasLeakatJamshedpur_MJoshi _310508 [43] 2010 – Berhampur , Orissa http://www.ndtv.com/india-news/35-fall-ill-after-chlorine-gas-leak-in-orissa-421447

28 References

[44] 2011 – Bhubaneshwar, Orissa http://www.ndtv.com/bhubaneshwar-news/17-people-fall-ill-after-chlorine-gas-leak- 570242 [45] 2011 – Pondicherry http://www.ndtv.com/chennai-news/pondicherry-300-hospitalised-after-chlorine-gas- leak-446072 [46] 2011 – Pune, Maharashtra http://www.ndtv.com/pune-news/chlorine-gas-leak-in-pune-20-hospitalised-445337 [47] 2013 –Kolkata, West Bengal http://www.ndtv.com/kolkata-news/60-people-fall-sick-in-kolkata-after-gas-leak-516243 [48] 2014 –Raisen, Madhya Pradesh http://www.indiablooms.com/ibns_new/news-details/N/6300/mp-39-people-affected-in- gas-leak-at-chemical-plant-in-raisen-district.html [49] 2016 –Kheda, Gujarat http://www.hindustantimes.com/india-news/more-than-1-000-residents-evacuated-after- chlorine-leak-from-tanker/story-UUWoLqi38wutiPFLC9XKfI.html

29 References

[50] Google Maps – United States [51] Google Maps – Alaska [52] Google Maps - Hawaii [53] 2016 – Proctor, WV http://www.thenewscenter.tv/content/news/Axiall-releases-statement-Chlorine-leak- sends-two-people-to-hospital--391494151.html [54] 2016- Port Allegany, PA http://www.oleantimesherald.com/news/evacuations-follow-chlorine-gas-leak-in-port- allegany/article_96ffb5d6-a572-11e6-aa62-db5d312fbc97.html [55] 2017- Elmo, TX http://inforney.com/local-news/item/5137-valve-to-blame-for-chlorine-gas-leak-in-elmo- voluntary-evacuation-issued [56] 2016 – Hilo, HI http://hawaiitribune-herald.com/news/local-news/chlorine-gas-leak-probed-hilo-plant- incident-alarms-neighbors [57] 2016- Addis, LI https://www.rt.com/usa/369060-dow-chemical-release-lousiana/ 30

References

[58] 2016- Phoenix, AZ http://www.abc15.com/news/region-phoenix-metro/central-phoenix/officials-working- hazmat-situation-in-phoenix [59] 2016- Atchison, KN https://www.theweathernetwork.com/news/articles/chemical-spill-in-kansas-sends-over- 100-people-to-hospital/73629 [60] http://www.fireengineering.com/articles/print/volume-169/issue-11/features/the-jack- rabbit-tests-catastrophic-releases-of-compressed-liquefied-gases.html [61] http://www.business-standard.com/article/economy-policy/gas-leak-4-mumbai-port- trust-officials-held-responsible-110121500085_1.html [62] http://www.livemint.com/Politics/NtYcWmazGAis6CEpj4yAkP/Industrial-disasters- Is-India-better-prepared-than-it-was-i.html [63] https://www.epa.gov/sites/production/files/2013-11/documents/spalert.pdf

31 Question and Comments?

Thank You!

[email protected]

32 Backup slides

33 What happened? 2001- A consignment of cylinders is imported from Dubai. It is abandoned by the importer (Agro Gases Pvt. Ltd.) in April 2001. Customs department raised objections and did not give no objection certificates, therefore, it was never claimed and was left exposed with no safeguards. 2008-An inspection team notifies the MbPT (Mumbai Port Trust) authorities that some of the cylinders contained residual gas. No action is taken. 2010- The chlorine leak occurs due to corrosion of one cylinder over time. Out of the 141 cylinders, 136 were clean. 5 of them had residual chlorine. (Almost 1 ton) For over 6 hours, BMC, experts from private companies like RCF, Century Rayon tried to seal and clamp the cylinder Firefighters created a water curtain diluting the vapor cloud formed. They also tried to direct it towards the sea. An inventory check after the incident revealed that 77 consignments having chemicals like hydrogen sulfide and nitrous oxide apart from chlorine were unclaimed. There are reports of chlorine leaks in 2003 and 2007, but were kept under wraps. References: http://epaper.timesofindia.com/Repository/getFiles.asp?Style=OliveXLib:LowLevelEntityToPrint_TOI&Type=text/html&Locale=english-skin- custom&Path=TOIM/2010/09/14&ID=Ar00400 http://timesofindia.indiatimes.com/city/mumbai/Chlorine-leak-in-Mumbai-port-area-sparks-panic/articleshow/6169587.cms Sharma, R. K., Chawla, R., & Kumar, S. (2010). Chlorine leak on Mumbai Port Trust’s Sewri yard: A case study. Journal of Pharmacy and Bioallied Sciences, 2(3), 161–165. http://doi.org/10.4103/0975-7406.68496 34 http://www.news18.com/news/india/chlorine-344391.html

What went wrong?

Causes:

• No safety guidelines were observed nor were safety systems maintained at the facility. (Blatant disregard for safety norms) • Chlorine tanks were abandoned nearly a decade before the incident. • The cylinders were exposed to high temperatures outside.

Aggravating Factors:

• LBS college of advance maritime studies and research located very close by. (Student dorms were barely 100 m from the site of leak) • MPT did not have a chlorine neutralization tank. • Lime and caustic soda should have been readily available to handle chlorine leaks.

References: Sharma, R. K., Chawla, R., & Kumar, S. (2010). Chlorine leak on Mumbai Port Trust’s Sewri yard: A case study. Journal of Pharmacy and Bioallied Sciences, 2(3), 161–165. http://doi.org/10.4103/0975-7406.68496

35 Chlorine properties

Physical state – Gas Appearance – Greenish –yellow gas Odor – Pungent Relative gas density – 2.5 Actual density – 3.2 kg/m3 @0 oC Soluble in water Acute toxicity- Fatal if inhaled

LC50 (rat) – 146.5 ppm / 4 hrs OSHA PEL = 1 ppm or 3 mg/m3 NIOSH IDLH = 10 ppm Respiratory irritant, eye irritant Can cause nausea, vomiting, dizziness and headache. --- Acute exposure can result in acute respiratory distress syndrome – widespread inflammation in lungs, impaired gas exchange Can also cause loss of consciousness and death. References: http://www.praxair.com/-/media/documents/sds/chlorine-cl-2safety-data-sheet-sds-p4580.pdf https://www.osha.gov/dts/chemicalsampling/data/CH_226500.html http://www.ndtv.com/photos/news/chlorine-gas-leak-in-mumbai-port-trust-7732#photo-89066 http://www.es2inc.com/wp-content/uploads/2011/07/Chlorine-and-its-properties.pdf http://www.fireengineering.com/articles/print/volume-169/issue-11/features/the-jack-rabbit-tests-catastrophic- releases-of-compressed-liquefied-gases.html 36 https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3136961/ Chlorine production

Chlor-Alkali process

Chlorine can be manufactured by electrolysis of a sodium chloride solution (brine).

The production of chlorine results in the co-products caustic soda (sodium hydroxide, NaOH) and hydrogen gas (H2). These two products, as well as chlorine itself, are highly reactive.

Chlorine can also be produced by the electrolysis of a solution of potassium chloride, in which case the co-products are hydrogen and caustic potash (potassium hydroxide).

There are three industrial methods for the extraction of chlorine by electrolysis of chloride solutions, all proceeding according to the following equations:

+ − Cathode: 2 H (aq) + 2 e → H2 (g)

Anode: 2 Cl− (aq) → Cl (g) + 2 e− 2

Overall process: 2 NaCl (or KCl) + 2 H2O → Cl2 + H2 + 2 NaOH (or KOH)

Reference: https://en.wikipedia.org/wiki/Chlorine_production 37 Uses of chlorine

Organics Inorganics Lubricating oils Hair coloring and Etching and Printed circuit Adhesives care products engraving boards Aerosols Coatings Photography Dental cement Pharmaceuticals Inks Bactericides and Deodorants Polyurethane Refrigerants disinfectants Soap perfume varnishes, paints, Brush bristles Mirrors stabilizers foams Upholstery Pulp and paper Bleaches Nylon processing Crop protection

Direct use:

One of the most well known direct uses for chlorine is in water treatment to reduce bacteria content. This applies to domestic water supplies, but also to swimming pools and water used in industrial processes.

Reference: http://www.greener-industry.org.uk/pages/chlorine/1_chlorine_AP.htm 38 Consequence Analysis

Britter McQuaid model and Dow’s CEI based HD calculation Input variables:

3 Density of chlorine vapor (ρ0) = 3.2 kg/m

o Ambient temperature (Tambient) = 28 C

Ambient Pressure (Pambient) = 101.3 kPa Wind velocity (u) = 4 m/s at a 10 m elevation

Mass of chlorine in tank (mass) = 650 kg

Diameter of hole (d) = 1 mm

Pressure inside the tank (Ptank) = 912 kPa

Saturation Pressure of Chlorine (Psat) = 770 kPa Other necessary values: 3 Density of Liquid Chlorine (ρliquid) = 1468 kg/m

C0=1 (Assuming pure vapor at the source) Average heat capacity of the liquid (Cp) = 943.8 J/kg/K Acceleration due to gravity (g) = 9.8 m/s2 Heat of vaporization of the liquid (Hv) = 275030 J/kg

o Gas constant (R) = 8.314 J/K/mol Boiling point of chlorine (Tboiling) = -34 C

3 Diameter of tank (D) = 30 inches Density of air (ρambient)=Pambient*28.84/R/Tambient/1000 kg/m Length of tank (L) = 81.5 inches

Height of liquid in the tank (h) = 0.3645 m (calculate using http://www.handymath.com/cgi-bin/circlehei4.cgi) References: http://www.academia.edu/30299801/Societal_Risk_Assessment_of_Chlorine_Release_Scenario_A_case_study http://www.hse.gov.uk/research/crr_pdf/1988/crr88017.pdf https://www.wunderground.com/history/airport/VABB/2010/7/14/DailyHistory.html?req_city=Mumbai&req_state=MH&req_statename=India&reqdb.zip =00000&reqdb.magic=170&reqdb.wmo=43003 http://www.safety-s2s.eu/modules/s2s_wp4/docs/S2S_CHEMICAL_EXPOSURE_INDEX.pdf 39 Step 1: Identifying if the cloud formed is a dense cloud or not Step 2: Calculate maximum distance for cloud to be continuous g = g*(ρ -ρ )/ρ 0 0 ambient ambient Duration = Rd = mass/q0 = 19895 s On substituting the values, we get, Maximum distance = u* Rd /2.5 = 31832 m ~ 31.8 km 2 g0 = 16.8 m/s Step 3: Determine downward distances at different concentrations Liquid flow rate being released (q1)

2 5 1/5 alpha = log10 ((g0 *q0/u ) )= -0.5101 −7 2 Pg q = 9.44 ×10 d ρ 1000∗ +9.8∗h 1 liquid ρ Calculate beta for each concentration using the tables given in Crowl and Louvar. Where Pg= Ptank - Pambient Then estimate downward distance. On substituting the values, we get,

x=10beta*q /u0.5 q1= 0.0327 kg/s 0

Fraction flashed . x (m) C /C Cp m 0 Fv= T −T 2.891011 0.1 Hv tank boiling 4.784492 0.05

Fv= 0.21 7.310136 0.02 11.05403 0.01 Since F >0.2, Airborne Quantity = q = 0.0327 kg/s (No pool is v 1 15.94077 0.005 formed) 23.68822 0.002 3 Therefore, q0 = q1/ρ0 = 0.0102 m /s

0.5 Dc= (q0/u)

3 1/3 Criteria1 = (g0*q0/u /Dc) = 0.376 Reference: Crowl D.A. and Louvar J.F., “Chemical Process Safety: Fundamentals and Applications”, 3rd Edition 40 As criteria1>0.15, it is a dense cloud Dow’s CEI based Hazard Distance Now, plot concentration vs. time. ERPG or Emergence Response Planning Guidelines is published Fit using Power law on excel by the American Industrial Hygiene Association (AIHA) 0.12 Concentration vs time ERPG-2 for chlorine = 9 mg/m3

0.1 3 y = 0.8183x-1.863 ERPG-1 for chlorine = 3 mg/m R² = 0.995 0.08 q

Chemical Exposure Index CEI = 655.1 1

0 ERPG−2

/C 0.06 m

C CEI = 39.5

0.04

0.02 Hazard Distance calculation:

0 q HD=6551∗ 1 0 5 10 15 20 25 ERPG Downwind distance (m) We assume ERPG-1

Extrapolate the downwind distance to necessary concentrations HD=683.6 m (OSHA PEL, NIOSH IDLH)

41 Britter-McQuaid model – MATLAB code

1 2 C0=1; %m3 contaminant/m3 air %Pure vapor % Britter-McQuaid model --- Plumes at source % author of MATLAB code: Pratik Krishnan g=9.8;%m/s2 Pamb=101325;%Pa % Input variables TambK=Tamb+273.15;%K rho0=3.2;% kg/m3 density of material released R=8.314;%Gas constant initially rhoamb=Pamb*28.84/R/TambK/1000;%kg/m3 Tamb=25;%degC ambient temperature g0=g*(rho0-rhoamb)/rhoamb; u=4;%m/s wind speed at 10 m elevation Cd=0.61; mass=650;%kg of dense gas in tank q1=9.44e-7*d^2*rhol*sqrt(1000*(Ptank- d=2;%mm hole size 101.3)/rhol+9.8*dh); Ptank=912;%kPa Rd=mass/q1; Psat=770;%kPa q0=q1/rho0; rhol=1468;%kg/m3 Dc=(q0/u)^0.5; dh=0.3645;%m height of liquid in the tank criteria1=(g0*q0/u^3/Dc)^(1/3); %Dimensions of tank D=30 inches, if criteria1 < 0.15 Length=81.5 inches disp('Not a dense cloud') % calculate using end http://www.handymath.com/cgi- maximumx=u*Rd/2.5; %For cloud to be bin/circlehei4.cgi continuous

Britter-McQuaid model – MATLAB code

3 4 alpha=log10((g0^2*q0/u^5)^(1/5)); end if alpha > 1 i=3; disp('Error') concentration(i)=0.02; end if alpha <= -0.69 i=1; beta(i)=2.08; concentration(i)=0.1; elseif alpha <= -0.31 if alpha <= -0.55 beta(i)=0.45*alpha+2.39; beta(i)=1.75; elseif alpha <= -0.16 elseif alpha <= -0.14 beta(i)=2.25; beta(i)=0.24*alpha+1.88; else beta(i)=-0.54*alpha+2.16; else beta(i)=0.5*alpha+1.78; end end i=4; i=2; concentration(i)=0.01; concentration(i)=0.05; if alpha <= -0.70 if alpha <= -0.68 beta(i)=2.25; beta(i)=1.92; elseif alpha <= -0.29 elseif alpha <= -0.29 beta(i)=0.49*alpha+2.59; beta(i)=0.36*alpha+2.16; elseif alpha <= -0.20 elseif alpha <= -0.18 beta(i)=2.45; beta(i)=2.06; else beta(i)=-0.52*alpha+2.35; else beta(i)=-0.56*alpha+1.96; end 43

Britter-McQuaid model – MATLAB code

5 6 i=5; concentration(i)=0.005; for i=1:6 if alpha <= -0.67 x(i)=10^(beta(i))*(q0/u)^0.5; beta(i)=2.40; end elseif alpha <= -0.28 beta(i)=0.59*alpha+2.80; ERPG1=3;%mg/m3 elseif alpha <= -0.15 ERPG2=9;%mg/m3 beta(i)=2.63; CEI=655.1*sqrt(q1/ERPG2); else beta(i)=-0.49*alpha+2.56; HD=6551*sqrt(q1/ERPG1); end A=[x',concentration']; i=6; concentration(i)=0.002; if alpha <= -0.69 beta(i)=2.6; elseif alpha <= -0.25 beta(i)=0.39*alpha+2.87; elseif alpha <= -0.13 beta(i)=2.77; else beta(i)=-0.50*alpha+2.71; end

44 Chlorine incidents

Incident Location Year Injuries Fatalities Reason

Bhopal 1985 7 0 Chlorsulfonic acid spilled while being transferred on tank trucks Jamshedpur 2008 150-200 0 Leaking unused cylinder in water treatment plant Berhampur 2010 35 0 Cylinder of urban water treatment leak Bhubaneshwar 2011 17 0 Chlorine mixed into water tank Pondicherry 2011 300 0 Workers filling gas in cylinders Pune 2011 20 0 Chlorine leak from effluent treatment plant Kolkata 2013 60 0 Cylinder in warehouse leaks Raisen 2014 39 0 Kheda 2016 22 0 Chlorine gas leak from a tanker

Proctor 2016 2 0 Liquid chlorine leaked from a railcar Port Allegany 2016 0 0 Valve leak Elmo 2017 0 0 Valve leak Hilo 2016 0 (4 went to hospital) 0 Cylinder leak Addis 2016 0 (14 went to hospital) 0 Phoenix 2016 9 0 Crane punctures chlorine tank in scrapyard Atchison 2016 70 Mixing of sulfuric acid and sodium hypochlorite

Reference: [40-60] 45

Fatal incidents in the US

2004, Macdona, TX - 2 people died On June 28, 2004, a westbound Union Pacific Railroad (UPRR) freight train bound for Arizona was traveling on the same main line track as an eastbound Burlington Northern—Santa Fe Railway Company (BNSF) freight train. At 0503 hours, the UPRR train struck the midpoint of the 123-car BNSF train as the eastbound train was leaving the main line to enter a parallel siding in Macdona, Texas. Forty rail units derailed, including the four UPRR locomotives, that train’s first 19 cars, and 17 BNSF cars. As a result of the derailment and the subsequent pileup of railcars, a chlorine tank car was punctured. The car was a DOT-105 pressure container transporting 90 tons of liquefied chlorine at 37 pounds per square inch (psi) tank pressure; the tank car would ultimately release approximately 60 tons of chlorine. The escaping chlorine immediately vaporized into a chlorine vapor cloud that engulfed the accident area to a radius of at least 700 feet before drifting away from the site. The UPRR train’s conductor and two local residents died as a result of chlorine gas inhalation. Twenty-three civilians, six emergency responders, and the UPRR train engineer were also treated for respiratory distress or other injuries related to the collision and derailment

2005, Graniteville, SC - 8 people died On January 6, 2005, in Graniteville, South Carolina, at 0239 hours, northbound Norfolk Southern Railway Company (NS) Freight Train 192, traveling about 47 miles per hour, encountered an improperly aligned rail switch that diverted the train from the main line onto an adjoining industry track, where it struck an unoccupied parked train (P22). As a result, both locomotives and 16 of the 42 freight cars of Train 192, the P22 locomotive, and one additional car derailed. The derailed Train 192 cars included three chlorine tank cars, one of which was breached and ultimately released 60 tons of chlorine. The train engineer and eight civilians died as a result of chlorine gas inhalation. Also, approximately 5,400 people residing within a one-mile radius of the derailment site were evacuated. More than 500 civilians complaining of respiratory difficulties were taken to local hospitals, and 75 were admitted for treatment. Reference: http://www.fireengineering.com/articles/print/volume-169/issue-11/features/the-jack-rabbit-tests- catastrophic-releases-of-compressed-liquefied-gases.html 46 Regulations in India Manufacture, Storage and Import of Hazardous chemicals (MSIHC) rules, 1989 – detail and catalog chemicals deemed hazardous, port of entry and quantity

The Hazardous Wastes (Management, Handling and Transboundary Movement) Rules, 2008 – provide for means of safe storage, disposal and hazardous waste by working with the pollution control boards

Chemical Accidents (Emergency Planning, Preparedness, and Response) Rules, 1996- addresses gas leaks and similar events. It sets up a Central Crisis Committee with the secretary of the environment ministry as chairman and twenty other members “to deal with major chemical accidents and to provide expert guidance for handling major chemical accidents”. It has provisions for state-, district- and even local-level crisis groups.

Public Liability Insurance Act, 1991 - which was supposed to provide for immediate and interim relief to disaster victims till their claims of compensation were finally decided -Owners of industries dealing in hazardous substances are required to take out insurance policies under this Act.

National Disaster Management Authority, 2007 - management of chemical accidents, regulatory framework, preparedness, transportation of hazardous chemicals 47 Reference: http://www.livemint.com/Politics/NtYcWmazGAis6CEpj4yAkP/Industrial-disasters-Is-India-better-prepared-than-it-was-i.html Regulations in India

National disaster management authority gives guidelines to achieve zero tolerance in chemical safety (2007)

The NDMA along with the Ministry of Environment and Forests, Petroleum and Natural Gas Regulatory Board, Federation of Indian Chambers of Commerce and Industries conducted conferences across the country to deal with safety and security of provisions in handling chemical cargo. It also tested mock exercises of emergency plans. Its goals include awareness generation, education and training.

Its aim is to develop a community that is informed, resilient and prepared to face disasters.

Reference: Sharma, R. K., Chawla, R., & Kumar, S. (2010). Chlorine leak on Mumbai Port Trust’s Sewri yard: A case study. Journal of Pharmacy and Bioallied Sciences, 2(3), 161–165. http://doi.org/10.4103/0975-7406.68496 http://www.ndma.gov.in/images/guidelines/chemicaldisaster.pdf

48 Regulations in the US OSHA

Hazardous Waste Operations and Emergency Response Standard [29 CFR 1910.120]

Facilities must comply with worker protection requirements for emergency response operations for release of, or substantial threats of release of, hazardous substances.

Process Safety Management Standard [29 CFR 1910]

Facilities with highly hazardous substances in quantities at or above a threshold quantity are subject to a number of requirements for management of hazards, including performing a process hazards analysis and maintaining mechanical integrity of equipment.

Hazard Communication [29 CFR 1910.1200]

Facilities are required to evaluate the potential hazards of toxic and hazardous chemicals. Employers transmit this information to their employees.

Reference: https://www.epa.gov/sites/production/files/2013-11/documents/spalert.pdf 49 Regulations in the US EPA

Emergency Planning [40 CFR Part 355] Facilities that have listed substances above a specified threshold quantity must report to their LEPC and SERC and comply with certain requirements for emergency planning. Emergency Release Notification [40 CFR Part 355] Facilities that release listed chemicals over For More Information: reportable quantity must immediately report the release to the LEPC and the SERC. Hazardous Chemical Reporting [40 CFR Part 370] Facilities that have listed chemicals at or above threshold quantity must submit MSDSs to their LEPC, SERC, and local fire department and comply with the Tier I/ Tier II inventory reporting requirements. Toxic Chemicals Release Inventory [40 CFR Part 372] Manufacturing businesses with ten or more employees that manufacture, process, or otherwise use listed chemicals above an applicable threshold must file annually a Toxic Chemical Release form with EPA and the state. Hazardous Substance Release Reporting [40 CFR Part 302] Facilities must report to the National Response Center any environmental release which exceeds reportable quantities. A release may trigger a response by EPA, or by one or more Federal or state emergency response authorities.

Reference: https://www.epa.gov/sites/production/files/2013-11/documents/spalert.pdf 50 Recommendations

• The cylinders should have only been accepted for delivery when empty. • Cylinders containing chlorine should not have been stored in the open where there is a likelihood of temperature/pressure rise. • Area of storage should have suction pipelines/hoods connected to a neutralization tank. • Cylinders should be imported with certification on lifetime from the competent authority for the duration for which they can be used. • Use of high-pressure water nozzles to create a water blanket to minimize the effect of ambient temperature. • Spreading foam on leaked chlorine. • Ascertain wind speed and direction and use a public address system to communicate with community. • Safety data sheets must be available as well as emergency response plan.