H2S Awareness Hydrogen Sulfide in the Oil & Gas Industry Presented by Dan Klimek Sisk & Company

Why review H2S safety? Good safety practices require that all personnel working in an area where concentrations of Hydrogen Sulfide may exceed the 10 Parts Per Million (PPM) should be provided with training before beginning work assignments.

Training Requirements Safe practices and regulations require training Most operators require awareness level training for all personnel at facilities when potential for exposure exists Other OSHA standards come into play when potential for exposure above 10 parts-per-million (ppm) exists Your company policies

ANSI Z390.1 - 2006 This standard identifies accepted training practices for H2S training Much of what we cover is based on ANSI recommendations OSHA does not have specific rules, but uses recommendations from NIOSH, ANSI, API, etc. H2S quick card

H2S contingency plan required per API for Operators Appropriate instruction in the use of hydrogen sulfide safety equipment to all personnel present at all hydrogen sulfide hazard areas. Gas detection where hydrogen sulfide may exist. Appropriate respiratory protection for normal and emergency use. Respiratory Protection Standard, [29 CFR 1910.134] (H2S).

Objectives To Provide an Awareness of: Hydrogen sulfide properties & hazards Sources of H2S & Detection methods How H2S affects people - Exposure controls - Protective measures Work practices Emergency response considerations Regulations & guidelines

Hydrogen Sulfide Guidelines Applicability Most Operators have Hydrogen Sulfide Guidelines That apply to: All facilities owned / operated by operators All employees & contingent personnel Employer needs to provide awareness of the hazards you might experience

What should be covered in Operator’s Plan? Hydrogen Sulfide detection methods used on the site. Does operator have fixed system or do you use portable gas detectors? If using your portable detectors Calibration Where is the meter? Do you respond to alarms? What is your plan if there is an alarm?

What should be covered in Operator’s Plan? Confined space entry procedures Locations and use of safety equipment Locations of safe briefing areas Emergency response procedures, corrective action, & shutdown procedures Effects of Hydrogen Sulfide on the components of equipment on site

What should be covered in Operator’s Plan? Wind direction awareness & routes of egress Are wind socks on site? Rescue techniques & 1st aid procedures to be used in a Hydrogen Sulfide exposure. What does the operator expect and what “pre-planning” planning is done? If operator expects you to do this, what do you do? H2S concentration in tanks

Pre-job briefings Material we just covered should be included in your pre-job briefing No matter what is available on site, take responsibility to work safely, follow your procedures and use the equipment you have available

Physical & Chemical Properties Chemical Name Hydrogen Sulfide Synonyms Sulfereted hydrogen, hydrosulfuric acid, dihydrogen sulfide

Physical & Chemical Properties Hydrocarbons that contain hydrogen sulfide are often referred to as “Sour Oil” or “Sour Gas”.

Physical & Chemical Properties Chemical Formula: H2S Two hydrogen atoms attached to one sulfur atom Normal Physical State: Colorless, invisible gas, slightly heavier than air

Physical & Chemical Properties Concentrations expressed in parts-per-million (ppm) 1% vapor by volume in air equals 10,000 ppm

Physical & Chemical Properties Auto Ignition Temperature: 500o F Boiling Point: -76o F Melting Point: -117.2o F Flash Point: -116.32o F Vapor Density at 59o F & 1 atmosphere is 1.189 Flammable / Explosive Limits: 4.3% to 46% vapor by volume in air ***Forms an extremely explosive mixture with air *** Combustibility: Burns in air with a blue flame and produces Sulfur Dioxide ( SO2 ) Solubility: Easily dissolved in & released from liquids such as water and oil Corrosivity: Corrosive when dissolved in water Toxicity: Irritating at low concentrations, can cause death at high concentrations

Odor Has a distinctive “rotten eggs” smell at low concentrations ( 1 ppm + ) WARNING: At High Concentrations (100 ppm) over 2 to 15 minutes, Olfactory Nerve Paralysis - “loss of sense of smell” - occurs. The same thing can happen with long time exposure at low concentrations. DO NOT RELY ON ODOR OR “SMELL” AS A DETECTION METHOD

Toxicity & Health Hazards Concentrations Up to 10 ppm: Detectable “rotten egg” odor No recognized adverse health hazards Max Accepted level - 10 PPM STEL - 15 ppm averaged over 15 minutes, no more than 4 X per day - 60 minutes between successive exposures OSHA PEL - 20 PPM (ceiling level)

Toxicity & Health Hazards Concentrations of 10 – 100 ppm: Increasing irritation of the eyes and respiratory tract over time Coughing Irritation of mucous membranes Headaches Dizziness Nausea Intense odor with loss of sense of smell occurring at 100 ppm (NIOSH IDLH)

Toxicity & Health Hazards Concentrations of 100 – 500 ppm Loss of sense of smell Severe irritation of eyes and respiratory tract Drowsiness 100 ppm is considered as Immediately Dangerous to Life and Health(OSHA quick card)

Toxicity & Health Hazards Concentrations of 800 – 1000 ppm Nervous System Injury Respiratory Paralysis Loss of consciousness Coma Death

Toxicity & Health Hazards Concentrations of 1000 – 2000 ppm Unconsciousness or Death with One Breath

A couple of terms Acute exposure Chronic exposure

Variables affecting symptoms You - your size, physical condition, age, smoker, etc. Interaction with drugs or alcohol Medications Harder for the body to filter toxins

Low Concentration Signs & Symptoms Eye irritation Headaches Nausea Coughing Sore Throat Lungs Fill with Fluid Loss of Appetite Loss of Sleep

High Concentration Signs & Symptoms Loss of Sense of Smell Burning Eyes Coughing / Sneezing Headaches Nausea Diarrhea Lungs Fill with Fluid Breathing Stops Brain Damage Heart Stops Beating

Occupational Exposure Limits No OSHA Permissible Exposure Limit (8-hour/day limit) NIOSH Recommended Exposure Limit : 10 ppm (Time Weighted Average – 8-hour day) Short Term Exposure Limit – 15 minute period: 15 ppm OSHA Ceiling Concentration: 20 ppm Maximum Peak – 10 minutes at 50 ppm – if no other exposure occurs during the same 8-hour work period IDLH – 100 ppm

Occupational Exposure Limits 450 ppm: Lethal Dose (LD 50) 10 ppm is the General Industry Accepted Practice

Typical Exposure Practice Personnel without respiratory protection shall exit an area when H2S concentrations reach 10 ppm or higher When meter sounds alarm – leave quickly – go up wind Operator may require your company to have escape respirator.

Physical Hazards Highly flammable Hydrogen sulfide is highly flammable and can explode in concentrations of air under 5%. This level of flammability causes a high risk of fire and explosion

Physical Hazards Produces hazardous by-products By-products, such as sulfur dioxide, are produced when hydrogen sulfide is burned. These by-products add an additional risk of exposure.

Physical Hazards Corrosive Hydrogen sulfide is highly corrosive to some metals. This corrosion can cause structural damage to objects in the work area, such as tanks, pipes, valves and increases the risk of injury.

Hydrogen Sulfide Corrosion Metals can become brittle Contractors should take precautions when choosing equipment that can reasonably be expect to encounter H2S You need to look for corrosion concerns when working on equipment e.g. ladders failing, “stuff breaking” e.g. piping systems, valves failing

Physical Hazards Denser than air Hydrogen sulfide is heavier than air and can accumulate in low-lying areas, such as sewers, sumps, pits or wells where liquids collect, ditches and excavations. This accumulation can be deadly when working in confined spaces. Not only can you suffer from the health affects of this accumulation, but H2S may also displace available oxygen, making it even more dangerous.

Sources of H2S Component of Natural Gas & Crude Oil Caves, Mines, Volcanoes, Hot Springs Decaying organic matter: sewers, landfills, etc. Other industries likely to have H2S Breweries Tanneries Chemical Processes

Occurrence in Oil & Gas Industry Component of Crude Oil & Natural Gas Produced Water Condensate Tanks Pits Valve Vaults

Classification of sites by Operators All well-drilling sites should be classified according to areas of potential and/or actual exposure to H2S. The recommendations and employee instruction will vary depending on the type of area. No Hazard Condition API Condition I - Low Hazard API Condition II - Medium Hazard API Condition III - High Hazard

No Hazard Area Any well that will not penetrate / has not penetrated a known Hydrogen Sulfide formation would be categorized as a No Hazard Area. Special Hydrogen Sulfide equipment is not required.

API Condition I Low Hazard Work locations where atmospheric concentrations of H2S are less than 10ppm. Recommended for Area: Hydrogen Sulfide warning sign with green flag warning device present. Keep all safety equipment in adequate working order. Store the equipment in accessible locations.

API Condition II Medium Hazard Atmospheric concentrations of H2S are greater than 10ppm and less than 30ppm. Recommended for Area: Legible Hydrogen Sulfide warning sign with yellow flag warning device present. Keep a safe distance from dangerous locations if not working to decrease danger. Pay attention to audible and visual alarm systems.

API Condition II Medium Hazard – (continued) Follow the guidance of the operator representative. Keep all safety equipment in adequate working order. Store the equipment in accessible locations. An oxygen resuscitator. A properly calibrated, metered hydrogen sulfide detection instrument.

API Condition III High Hazard Work locations where atmospheric concentrations of H2S are greater than 30ppm. Recommended for Area: Post legible Hydrogen Sulfide warning sign with red flag warning device. Post signs 500 feet from the location on each road leading to the location, warning of the hydrogen sulfide hazard.

API Condition III High Hazard – (continued) Check all Hydrogen Sulfide safety equipment to ensure readiness before each tour change. Establish a means of communication or instruction for emergency procedures and maintain them on location, along with contact information of persons to be informed in case of emergencies. Ensure usability of two exits at each location.

API Condition III High Hazard – (continued) Do not permit employees on location without hydrogen Sulfide safety training. Pay attention to audible and visual alarm systems. Store the equipment in accessible locations.

API Condition III High Hazard – (continued) Recommended equipment Two Hydrogen Sulfide detectors should be present (meter and detector tubes) Oxygen resuscitator Three wind socks and streamers Two NIOSH/MSHA 30-minute, self-contained breathing apparatus for emergency escape from the contaminated area only

SCBA and Escape bottles are different. Respirators - OSHA highlight Respirator quick card

Detection Methods Air Monitoring Air monitoring is used to determine the amount of hydrogen sulfide present in the air or in a gas stream. The more hydrogen sulfide there is, the more frequently air monitoring must be done to make sure the levels stay safe. Gas Monitoring Basics

Detection Methods: Air Monitoring Air monitoring is performed with the Following devices and methods: Single gas or Multi-gas monitors Monitoring badges worn by employees Fixed monitors continuously measure the hydrogen sulfide present in the air Alarms that can be seen and heard when set points are exceeded Coated strips that change color when exposed to hydrogen sulfide Colorimetric detection tubes Wind socks located in various locations to monitor air direction in the event of a hydrogen sulfide release.

Additional air monitoring Additionally, air monitoring is performed when: There has been a change in a process that may result in new or additional exposures to hydrogen sulfide, or there is reason to suspect such a change. Spills, leaks, ruptures or other breakdowns occur. Monitoring is performed after clean-up or repair to ensure that exposures have returned to the previous level.

Protection & Controls Hydrogen sulfide occurs naturally so eliminating it completely is not always an option. If the presence of hydrogen sulfide is suspected or confirmed, the operator should provide and implement a written control plan that uses various engineering controls, work practice controls and PPE to control employee exposure

Protection & Controls Engineering controls The most effective engineering control for hydrogen sulfide is ventilation. Natural ventilation —natural air flow (e.g., working outdoors). Your company may put wind socks in the air so that you can see the direction the wind is blowing. In the event of an alarm indicating a hydrogen sulfide release, you can escape the danger by heading in the opposite direction from where you believe the hydrogen sulfide came. Mechanical ventilation — Fans and blowers are used to ventilate areas where hydrogen sulfide is suspected, such as in confined spaces.

Protection & Controls Work practices used to avoid possible hydrogen sulfide exposure include the use of: Signs that warn of the presence of H2S may be placed in hazardous areas. Job contingency planning Since hydrogen sulfide is often found in low-lying confined spaces, such as pits and tanks, most operators have developed confined space entry guidelines for these types of environments

Contingency plans Most operators have developed contingency plans for response in the event of a hydrogen sulfide release. Communication and emergency notification plans are developed to help protect employees, and the community. These plans include the evacuation response needed for worst-case scenarios. In creating the plan many variables are considered, such as: wind speed and direction weather conditions gas release rate and temperature gas concentration geographical environment

Personal Protective Equipment Protection & Controls Personal Protective Equipment PPE is the least preferred method of controlling exposure to hazardous substances Self-contained breathing apparatus (SCBA) is recommended to work in H2S atmosphere Must receive training if SCBA is used Other PPE, such as full protective body suits, may be required in certain conditions

Emergency Response In the event of a release or alarm, you should: Activate the facility Emergency Response Plan Evacuate through the nearest exit leading outdoors.  If already outdoors, move in a crosswind or upwind direction. Call or signal for help and tell the rescuers of the situation Do a head count and evaluate the site hazards Remember, you are not trained in rescue

If a person is exposed to H2S, do the following: First Aid If a person is exposed to H2S, do the following: Make sure YOU are adequately protected. Don’t risk being overcome by vapors and becoming an additional victim. Remember, just one breath is all it takes to affect you. Get the victim away from the high exposure area and to fresh air immediately. Remember to go upwind or crosswind to avoid the H2S gas. Give oxygen or artificial respiration if indicated. Seek immediate medical attention. Symptoms should disappear shortly after removal from the exposed area at moderate concentrations of H2S. However, you should ALWAYS seek medical attention if exposed to H2S.

H2S Awareness Review H2S may be present at all locations Know how to use your monitors Rescuers need to use SCBA and other PPE – You are not trained to do this Get to fresh air if alarm sounds – everyone!

Questions?