GUIDE

Occupational Health and Safety of Hydrogen Sulphide (H2S)

2003-0004

The Canadian Association of Petroleum Producers (CAPP) represents 140 companies that explore for, develop and produce natural gas, natural gas liquids, crude oil, oil sands, and elemental sulphur throughout Canada. CAPP member companies produce over 97 per cent of Canadas natural gas and crude oil. CAPP also has 125 associate members that provide a wide range of services that support the upstream crude oil and natural gas industry. Together, these members and associate members are an important part of a $60-billion-a-year national industry that affects the livelihoods of more than half a million Canadians..

Review by July 2008

Disclaimer This publication was prepared for the Canadian Association of Petroleum Producers (CAPP) by CAPPs Industrial Hygiene and Safety Committee. While it is believed that the information contained herein is reliable under the conditions and subject to the limitations set out, CAPP does not guarantee its accuracy. The use of this report or any information contained will be at the users sole risk, regardless of any fault or negligence of CAPP.

2100, 350 7th Ave. S.W. Calgary, Alberta Canada T2P 3N9 Tel (403) 267-1100 Fax (403) 261-4622

230, 1801 Hollis Street Halifax, Nova Scotia Canada B3J 3N4 Tel (902) 420-9084 Fax (902) 491-2980

905, 235 Water Street St. Johns, Newfoundland Canada A1C 1B6 Tel (709) 724-4200 Fax (709) 724-4225

Email: communication@capp.ca

Website: www.capp.ca

Overview The Canadian Association of Petroleum Producers (CAPP) have developed this Hydrogen Sulphide (H2S) Guideline to assist member companies in the development of their Codes of Practice. It is specifically for upstream petroleum industry companies that do not have occupational health and safety expertise in their employ. This Guideline outlines the procedures for handling, monitoring, training, labeling and emergency response to petroleum products containing H2S. Its companion, Guideline: Occupational Health and Safety of Light Hydrocarbons, should be referenced and implemented where necessary (see CAPP Pub 1999-0002 and 1995-0011). It outlines the procedures for handling, monitoring, training, labeling and emergency response to methane, ethane, butane isomers and propane.

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Contents
Project Scope ..................................................................................................................... iii 1 Hazards of H2S ..................................................................................................... 1-1 1.1 1.2 1.3 2 3 4 Acute Health Hazards .............................................................................. 1-1 Long Term Health Hazards ...................................................................... 1-1 Physical Properties ................................................................................... 1-2

Occupational Exposure Limits............................................................................. 2-1 Hydrogen Sulphide Sources ................................................................................. 3-1 Detection .............................................................................................................. 4-1 4.1 4.2 Chemical Sensors ..................................................................................... 4-1 Detector Tubes ......................................................................................... 4-1

5 6 7 8

Monitoring ........................................................................................................... 5-1 Personal Protective Equipment ............................................................................ 6-1 Training ................................................................................................................ 7-1 Emergency Response ........................................................................................... 8-1 8.1 8.2 8.3 Pre-Job Planning ...................................................................................... 8-1 First Aid ................................................................................................... 8-1 Rescue ...................................................................................................... 8-1 Signage ..................................................................................................... 9-1 Product Labels ......................................................................................... 9-1 Hydrogen Sulphide in Residual Fuel Oil and Storage Tank Vapour Spacei

Signage and Product Labels ................................................................................. 9-1 9.1 9.2

Appendix A

Tables
Table 1-1: Health Effects from Inhaling H2S .......................................................................... 1-1 Table 2-1: Occupational Exposure Limits for H2S ................................................................. 2-1 Table 3-1: Examples of Critical H2S Tasks ............................................................................. 3-1 Table 9-1: WHMIS Supplier and Workspace Label Specifications...................................... 9-1

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Project Scope Hydrogen sulphide (H2S) is a common petroleum contaminant. It may be present as a gas or may be dissolved in produced water, crude oil or natural gas condensate. Hydrocarbons contaminated with H2S are called sour. For health and safety purposes, all facilities processing hydrocarbons contaminated with any concentration of H2S should be evaluated for the potential of worker overexposure. If the potential exists, then a Code of Practice should be implemented. In addition, implementing the Canadian Association of Petroleum Producers Light Hydrocarbon Code of Practice should be considered. The Light Hydrocarbon Code of Practice recommends handling and monitoring procedures for sweet methane, ethane, butane and propane.

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Hazards of H2S 1.1 Acute Health Hazards Hydrogen sulphide is extremely toxic at very low concentrations. More than 100 parts of H2S per million parts of air (100 ppm) is Immediately Dangerous to Life and Health (IDLH) for exposures of 30 minutes or more. Exposure to more than 10 ppm for eight hours, or more than 15 ppm for 15 minutes, may irritate the eyes, nose and throat. Hydrogen sulphide has a rotten egg odour. This odour cannot be used to detect H2S because people rapidly lose their sense of smell when H2S level sa re above 100 ppm. Table One summarizes the toxic effects that result from inhaling various concentrations of H2S. 1.2 Long Term Health Hazards Human studies have found no direct link between exposure to low H2S concentrations (less than 10 ppm) and long term health effects. Some research studies have suggested that low level health effects can be produced at hydrogen sulphide concentrations down to 1 ppm. However, these results have not been confirmed to date. One animal study has found some evidence of neurological symptoms such as memory loss after long term exposure to 50 ppm H2S but this finding has not been confirmed by other studies.

Table 1-1: Health Effects from Inhaling H2S

Effect
No known short term effects from 8 hr exposures. Eye, nose, throat and lung irritation. Marked eye, nose, throat and lung irritation. Severe eye, nose, throat and lung irritation. Loss of smell. Exposure duration of 8 hours or more may be fatal. Headaches, drowsiness. Prolonged exposures of several hours may cause the lungs to fill with fluids. May cause unconsciousness and death in 1 to 4 hours. Knockdown (may be fatal) with 1 hour exposure. Immediate knockdown (may be fatal).

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1.3

Physical Properties Pure hydrogen sulphide is slightly heavier than air and may collect in low spots under certain conditions. Hydrogen sulphide and hydrocarbon mixtures may act differently than pure H2S. When H2S is mixed with some light hydrocarbons such as methane, the mixture can be lighter than air. When mixed with heavier hydrocarbons, such as NGL, the mixture is much heavier than air. It is almost impossible to predict where H2S may concentrate in outdoor areas or buildings. It is important to monitor for H2S in all locations in outdoor areas or buildings. H2S is soluble in water and hydrocarbons. Any H2S gas that comes out of solution will collect in the head spaces of tanks, pipes and vessels containing sour liquids, liquid sulfur and solid sulfur. It is possible for H2S to collect in confined areas in concentrations far exceeding those found in the liquid. For example, the head space of a tank may exceed the Occupational Exposure Limit even though it may contain oil with as little as 0.5 ppm H2S. In some conditions, the H2S concentrations in the head space may exceed those immediately dangerous to life and health (IDLH). See Appendix A for more information on this potentially dangerous condition. Large spills or releases of sour liquids may also release hazardous concentrations of H2S. Pure hydrogen sulphide is flammable in air at 40,000 ppm (4 per cent) or higher.

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Occupational Exposure Limits Occupational Exposure Limits are set by provincial occupational health and safety agencies. Albertas Occupational Exposure Limits (OELs) are listed in the Chemical Hazards Regulation. British Columbia and Saskatchewan have developed their own exposure limits. Manitoba follows with exposure limits recommended by the American Conference of Governmental Industrial Hygienist (ACHIH). Table Two below summarizes the occupational exposure limits for H2S. Table 2-1: Occupational Exposure Limits for H2S
8 hour TWA1 (ppm)
Alberta British Columbia Saskatchewan ACGIH TLV
4

15 STEL2 (ppm)
15 -

Ceiling3 (ppm)
15 10 -

10 10 5

1 2

8 hour TWA Time Weighted Average. The average exposure based on an eight hour exposure period. 15 STEL Short Term Exposure Limit. The average exposure based on a 15 minute exposure period. No more than four STEL are permitted during an eight hour shift and the 8 hour TWA can not be exceeded. 3 Ceiling The maximum concentration to which a worker can be exposed to even instantaneously. 4 The American Conference of Governmental Industrial Hyienists recommends occupational exposure limits called Threshold Limit Values (TLVs). Although widely referenced, they are recommended values only except where formally adopted into legislation.

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Hydrogen Sulphide Sources The following table should be used as a guide to operations where high hydrogen sulphide exposures may be expected. However, it is not comprehensive. A risk assessment of the work operation should be performed, taking into account the following: H2S content of the process stream; previous exposure monitoring results; operation factors (e.g., purging, degassing, temperature/pressure of process stream), and; ventilation.

Table 3-1: Examples of Critical H2S Tasks

H2S Monitors Required

SCBA/SABA Required
no

yes yes

yes yes

yes

no

yes yes

yes yes

yes yes

yes yes

yes

no

yes no

yes no

yes yes

no no

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Task
General trucking sour fluids Uncoupling vent lines Uncoupling load lines Sulphur truck loading with degassing without degassing

H2S Monitors Required

SCBA/SABA Required
no yes no

yes yes

no yes

Sulphur rail car loading

yes

yes

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Detection H2S detection should be conducted using chemical sensing instruments or detector tubes. Operators should be aware of the potential limitations and interference associated with the use of the equipment. 4.1 Chemical Sensors Chemical sensors are the superior and recommended method of H2S monitoring. There are three types: personal, hand held and remote monitors. All provide accurate and reliable readings, only if properly calibrated and maintained. They should be calibrated at least once per month, or as recommended by the manufacturer. Calibration should be performed at the temperature at which the instruments will be used. Calibration at room temperature for use in cold conditions can cause inaccurate readings. Workers carry personal monitors. They provide continuous readings and sound an alarm if H2S levels exceed 10 ppm or any other predetermined concentration. Remote sensors are permanent fixed devices suitable for installations like gas plants or oil batteries. Remote sensors also continuously monitor H2S concentrations and sound an alarm at 10 ppm H2S. All chemical sensors have a response time from when the monitor is placed iin an H2S atmosphere to when the sensor reaches the actual reading. Some sensors may take up to one minute to respond to H2S concentrations of 10 ppm. However, in atmospheres exceeding 100 ppm, the response time to the alarm concentration (10 ppm) is almost instantaneous. Operation of sensors at temperatures below 20 degrees Centigrade may cause lengthened response times. Carbon monoxide and other gases may cause interference with H2S readings. The interference of the instrument being used should be known. 4.2 Detector Tubes Detector tubes detect and provide a rough measure of H2S concentrations. Detector tubes do not provide continuous monitoring or sound an alarm. Readings may take up to one minute. Respirators may not be required when detector tubes are used in low risk situations such as sampling process streams. Every situation should be evaluated to determine the possibility of exceeding the applicable occupational exposure limit.

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Monitoring All areas where H2S is present and may exceed 10 ppm must be checked to ensure H2S concentrations are below 10 ppm. Concentrations above 10 ppm require communication with other personnel to warn of an H2S hazard and to ensure that further testing is performed. Further testing shall be conducted while wearing pressure-demand self-contained breathing apparatus (SCBA) or supplied airbreathing apparatus (SABA). All personal and remote monitors shall be set to alarm at 10 ppm. Consideration should be given to wearing personal monitors in all areas where H2S may be encountered, except where remote sensing is present. Consideration should be given to supplement remote sensing with personal monitors if the hazard is deemed excessive (i.e., very high H2S). Personal monitors shall be maintained and calibrated by qualified personnel according to manufacturers recommendations as a minimum. Remote monitors shall be tested and calibrated according to manufacturers recommendations or at least quarterly.

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Personal Protective Equipment Respiratory protection is required when entering areas where: H2S concentrations are above 10 ppm; there is any indication of equipment failure or product leak; or entering a confined space containing sour liquids. a full face positive pressure self contained breathing apparatus (SCBA); or a full face positive pressure supplied air breathing apparatus (SABA) equipped with a 5 minute escape air bottle

The respiratory protection shall be:

Backup personnel are required when entering an IDLH atmosphere of greater than 100 ppm H2S. Backup personnel should be fully trained in rescue.

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Training All workers, prior to entering an area where H2S is present or may be encountered, shall: receive orientation on the site rules and procedures; receive rescue and evacuation procedures; and hold a current H2S Alive certificate or equivalent training.

At least one work crew member must hold a current First Aid certificate.

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Emergency Response 8.1 Pre-Job Planning Before starting a job, the following should be reviewed with personnel on the site: 1) 2) 3) 4) 5) 6) 7) 8.2 H2S hazards and where they may be found; backup personnel requirements; safety watch requirements; muster point location; respirator locations; alarms; and, communication procedures

First Aid First aid can only begin after the rescue personnel have left the H2S area, sounded the alarm, donned breathing apparatus, and brought the victim to a safe area. Mouth to mouth or rescue breathing is a quick and effective technique that should be used until qualified medical help arrives on the scene. Only qualified personnel may use mechanical resuscitators or oxygen.

8.3

Rescue There are seven steps to take during an H2S emergency. Step One: Evacuate immediately An H2S alarm indicates that there may be hazardous concentrations in the building or area. Get to a safe new area immediately by moving upwind or crosswind from the release. Move to higher ground in possible. Step Two: Sound the alarm Immediately notify someone that there is an H2S release, relay any information you may have and that you may require assistance. Step Three: Assess the situation Do a head count and consider other hazards. Step Four: Protect rescue personnel Put on SCBA/SABA to protect rescue personnel. If necessary, shut down the plant.

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Step Five: Rescue victim Start by ventilating the building with fans or by opening all doors. If safe, you may perform the rescue by yourself with backup or with assistance. Enter the area and remove the victim to fresh air (upwind if possible). Step Six: Revive victim Apply artificial respiration or CPR on the victim until the victim revives or until help arrives. Only qualified personnel may use mechanical resuscitators or oxygen. Step Seven: Get medical aid All H2S victims require medical attention. Even if they revive quickly, there is still a possibility that the lungs may collect fluid some hours after exposure. Arrange a transport of the victim to medical aid and provide the necessary information to Emergency Medical Services.

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Signage and Product Labels 9.1 Signage All facilities and sites where there is H2S present shall have suitable signs at the entrance warning of the presence of poisonous gas (ERCB Reg. Sec. 7.070). 9.2 Product Labels Table 9-1: WHMIS Supplier and Workspace Label Specifications
Product
Sour Natural Gas

WHMIS Classification
Class A: Compressed Gas Class B, Div. 1: Flammable Gas Class D, Div. 1, Sub-Div. A: Very toxic material. Immediate and Serious Effects.

PPE Symbols
SCBA/SABA
5

Sour Condensate

Class B, Div. 2: Flammable Liquids Class D, Div. 1, Sub-Div. A: Very toxic material. Immediate and Serious Effects.

SCBA/SABA Gloves Apron or skin protection SCBA/SABA Gloves Apron or skin protection

Sour Crude Oil

Class B, Div. 2: Flammable Liquids Class D, Div.1, Sub-Div. A: Very toxic material. Immediate and Serious Effects. Class D, Div. 2, Sub-Div A: Material cuasing other toxic effects. Very toxic material.

Sour Produced Water

Class D, Div. 1, Sub-Div. A: Very toxic material. Immediate and Serious Effects. If oil mix: Class B, Div. 2: Flammable Liquids

SCBA Gloves Apron or skin protection

SCBA/SABA: Self Contained Breathing Apparatus/Supplied Air Breathing Apparatus

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Appendix A

Hydrogen Sulphide in Residual Fuel Oil and Storage Tank Vapour Space

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