1. Product Control and Air Monitoring
Hazardous Materials
Product Control and Air Monitoring

2. Chapter 6: Overview Introduction Defensive operations
Air monitoring for first responders
Meter methodology
Oxygen monitors
Combustible gas indicators
Toxic gas monitors
Other detectors
Carbon monoxide incidents
Summary

3. Offensive Operations CONTAINMENT IS DEFINED AS:
Any Procedures Taken To Keep The Material In Its Original Container. Containment Activities Are Generally Undertaken By A Hazardous Material Technician Or Specialist And Require Many Hours Of Training And Practice. Your Imagination Is A Good Place To Begin To Develop Containment Methods.
Super Glue, Blocking, Wooden Taps, Tape, Secondary Containment And Fast Setting Materials For Casts Are Just Some Of The Simple Examples.

4. Defensive Operations
First responders should only use defensive methods to control releases of hazardous materials.
Entering the hot zone to take “hands on” action is not allowed.
You must have specific training to do other work.

5. Defensive Activities Absorption Dilution Diking Vapor dispersion
Damming
Diverting
Retention
Dilution
Vapor dispersion
Vapor suppression
Use of remote shutoffs

6. Absorption Material must be compatible.
There is a variety of absorbing media available.
Spilled material may still present risk (flammable).

7. Diking Must be sufficient size to collect material.
Minimum of three should be built.
Start away from the spill and work toward the spill.
Large spills require mechanical equipment.

8. Damming There are two types. At least three should be built.
Overflow
Underflow
At least three should be built.
Start away from spill and work toward spill.
Use mechanical equipment for large spills.

9. Damming

10. Damming

11. Damming

12. Damming

13. Damming

14. Diverting Commonly used to move a spill away from a risk area
Can use booms
Floating (absorbent)
Solid (harbor boom)

15. Retention Retention is creating a hole to retain the spilled material.
Large spills require mechanical equipment.
Line hole with plastic or compatible material.

16. Dilution Solution to pollution is not always dilution.
Non-soluble materials such as gasoline or fuels
Significant amounts of water are needed to neutralize corrosives.
May need several hundred thousand gallons for small spill

17. Vapor Dispersion Creates water runoff issues May not eliminate vapors
Just moves them
Requires large quantities of water

18. Vapor Suppression Foam usually used
Must be reapplied on a regular basis
Must be compatible with the material

19. Remote Shutoffs Tank trucks have emergency shutoffs.
Most tank facilities have remote shutoffs.
Responders should not endanger themselves to shut off valves.

20. Air Monitoring for the First Responder
Monitoring is essential to protect responders.
Fire risk
Toxic risk
Corrosive risk
Radiation risk

21. Regulations
It is OSHA’s intention that the worker (responder) be protected against workplace hazards.
Air monitors are the only way to identify potential airborne hazards.

22. Typical Configurations
Monitors usually have 3-5 functions.
LEL sensor
Oxygen sensor
Carbon monoxide
Hydrogen sulfide
Other toxic material

23. Basic Principles of Air Monitoring & Detection Devices
Air monitors
Primary protection
Can assist with determining the presence of risk materials
Help provide a possible identity of the material

24. Air Monitoring Strategies
Always use pH, LEL, O2, and PID as a minimum.
Expand the use of other monitors as more information is available.
The absence of readings does not mean that harmful materials are not present.
Biological threat agents

25. Determination of Risk Corrosive Oxygen Fire Toxic Radioactive pH paper
Oxygen sensor
Fire
LEL or flammable gas detector
Toxic
Photoionization detector (PID)
Radioactive
Rad pager and monitors

26. Meter Terminology Accuracy Precision Factors affecting precision
Ability to produce findings close to actual quantity of gas
Precision
Ability to reproduce the same results
Factors affecting precision
Sensor technology
Weather

27. Accuracy and Precision
Known Amount = 50 ppm
Reading A & P P A N

28. Bump Test
Exposing monitor to known gases and allowing it to go into alarm
Also known as a field test
If insufficient response, conduct calibration

29. Time and Monitors Lag time Reaction time
Monitors without a pump (diffusion) have a second lag time.
Monitors with a pump have a typical reaction time of 3-5 seconds.
Add 1-2 seconds of lag time for each foot of extension hose.

30. Response Times Photoionization = 1-2 seconds
LEL with pump = up to 7 seconds
LEL w/o pump = up to 30 seconds
CO and H2S sensors = >20 seconds
Ion mobility = up to 1 ½ minutes
Radiation monitors = up to 1 ½ minutes

31. Correction Factors (Relative Response)
A meter calibrated to methane is only accurate and precise for methane.
The meter will respond to any other flammable gas.
How well it responds is determined by the relative response.

32. Correction Factors for LEL Sensors
LEL sensors are typically calibrated for methane gas.
The LEL of methane is 5%.
When the meter reads 100% in a methane environment, there is 5% methane by volume in the room.

33. Example LEL Correction Factors
Propane = 1.82
Hexane = 2
Turpentine = 2.9
Acetone = 2.2
Ammonia = 0.8
Phosphine = 0.26
Instructor Notes:
THERE IS 1 MORE SLIDE ON CORRECTION FACTORS
Here are some example correction factors for the LEL sensor. The PID also has correction factors but they differ from the LEL sensors.
Translator Notes:
LEL = lower explosive limit
PID = photoionization detector

34. Correction Factors Gas Meter A Meter B Meter C Acetone 0.9 1 0.45
Hydrogen
Methane
Methanol
Propane
Meters calibrated with pentane to pentane

35. Correction Factors Meter C has a CF of 0.45 for acetone.
You enter an area and the meter reads 60% of the LEL.
Take the meter reading (60%) times the CF (0.45) and the actual meter reading is 27% of the LEL for acetone.

36. Correction Factors Meter A has a CF of 2.5 for the chemical EMUC.
The reading on the meter (calibrated to pentane) is 45% of the LEL.
The actual meter reading (AMR) is 112.5% and you are in the flammable range.

37. Correction Factors Acetone is being used in a process.
Correction factor for acetone is 2.2.
In the building, the meter reads 5% of the LEL.
Meter is calibrated to methane.
Multiply 5% times 2.2 = 11%.
The meter should be reading 11%.
Instructor Notes:
A bad guy is using acetone to make an explosive device. You are going to make an arrest, and enter his residence. There are possible acetone vapors present. When you enter the building the multi-RAE LEL sensor reads 5%. The LEL sensor in the multi-RAE is set to read methane accurately. It picked up the acetone vapors but the reading is not accurate. The correction factor for acetone is 2.2, which is provided by the owners manual for the multi-RAE. You multiply the correction factor times the meter reading. The formula is 5 x 2.2 = 11, which means the meter should be reading 11%, and would have alarmed if it had been set to acetone.
Correction factors are in the owners manual for the multi-RAE, and can also be set in the software.
Translator Notes:
LEL = lower explosive limit

38. pH Detection Used for corrosive materials
Should be one of the first items down range at a chemical release
Use of multi-range pH paper most common method

39. Oxygen Monitors Normal air contains 20.9% oxygen.
Less than 19.5% oxygen is considered oxygen deficient.
LEL readings are off.
Greater than 23.5% oxygen is oxygen enriched.

40. Oxygen Sensor Instructor Notes:
An example of an electrochemical sensor for the detection of oxygen. The oxygen flows into the senor and reacts with the electrolyte solution. The resulting chemical reaction generates energy which is read between the anode and the cathode, which can be read by a load resistor, hence the name electrochemical sensor.
Translator Notes:

41. Oxygen Sensor Limitations
Most oxygen sensors will only last 1-2 years.
Chemicals with additional oxygen in their molecular structure hurt the sensors.
Optimal temperature is between 32°-120°F.

42. Flammable Gas Indicators (FGIs)
Also referred to as combustible gas sensors or LEL sensors
Used to measure the lower explosive limit (LEL) of the calibration gas
Majority calibrated to methane (natural gas), using pentane gas as the calibration standard
When calibrated for methane, the sensor will read up to the LEL of methane.

43. Common Flammability Ranges
LEL UEL
Methane % %
Propane % %
Acetone % %
Ammonia % %
Carbon monoxide % %
Ethylene oxide % %
Hydrogen sulfide % %
Instructor Notes:
Some example flammable ranges. Note that it takes less propane to enter the flammable range than it does methane. Remind the students about another dangerous property of propane; it’ s vapor density, as it much heavier than air, and will stay low. Methane on the other hand is lighter than air, and will rise and go away.
Translator Notes:
LEL = lower explosive limit
UEL = upper explosive limit

44. Catalytic (Pellistor) Bead Structure
Instructor Note:
This is a close up of a catalytic bead, also known as a pellistor bead. It has a platinum coil wire in the middle of the coated bead providing the heat.
See the next slide
Translator Note:

45. LEL Sensor Types
The basic principle of LEL sensors is that a stream of sampled air passes through the sensor housing causing a heat increase and conversely creating an electric charge, causing a reading on the instrument.

46. LEL Sensor Types Catalytic bead Metal oxide sensor (MOS)
Round piece of heated metal strung between a wire
Quick reaction time and precise sensor
Metal oxide sensor (MOS)
A semiconductor in a sealed unit that has a Wheatstone bridge in it surrounded by coating of a metal oxide

47. Infrared Gas Detectors
Detectors use infrared light beams and a series of mirrors to detect flammable gases.
Each different type of gas blocks a specific amount of light.
Sensor does not require O2 to function.
It cannot be poisoned by overexposure.
Most units switch from % LEL to % by volume, when it reaches the LEL.

48. Flammable Gas Sensors

49. Toxic Gas Monitors Toxic sensors are available in a variety of gases.
Carbon monoxide
Hydrogen sulfide
Chlorine
Ammonia
Sulfur dioxide
Hydrogen chloride
Hydrogen cyanide
Nitrogen dioxide
Many others

50. Toxic Sensors
Most are electrochemical sensors with electrodes (two or more) and chemical mixture sealed in a sensor housing.
The gases pass over the sensor causing a chemical reaction within the sensor.
Electrical charge is created which causes a readout to be displayed.

51. Electrochemical Toxic Sensor
Instructor Notes:
The electrochemical toxic sensor is comprised of electrodes that measure electrical activity. The gas passes through the diffusion barrier, and if it is the right gas it will cause a chemical reaction in the sensor housing. This reaction causes a change in the electrical activity in the sensor which is read by the electrodes. The electrolyte is the chemical mixture.
Translator Notes:

52. Electrochemical Sensor Cross Sensitivity
Instructor Notes:
The CO and H2S sensor react to about 30 other gases in addition to CO and H2S. Some of the other gases are and the resulting readings are provided here. As an example CO at 100 ppm will read less than 10 ppm on a H2S sensor. H2S at a level of 100 ppm will read less than 10 ppm on a CO sensor. (See note)
Sulfur dioxide will indicate on both the CO and H2S sensor.
Note: The CO and H2S sensor are actually the same sensor, except the CO sensor is filtered to take out H2S, so that it only reads CO. The H2S sensor filters out CO.
Translator Notes:
CO = carbon monoxide
H2S = hydrogen sulfide
SO2 = sulfur dioxide
NO = nitrous oxide
NO2 =
Cl2 = chlorine
H2 = hydrogen
HCN = hydrogen cyanide
HCL = hydrochloric acid
NH3 = ammonia

53. Photoionization Detectors (PID)
Can detect a wide variety of gases in small amounts
Will not indicate what materials are present
Can identify potential areas of concern and possible leaks or contamination
Sensitivity from ,000 PPM
Part per billion unit available

54. PID Technology
Technology uses an ultraviolet (UV) lamp to ionize any contaminants in the air.
When contaminant particles become ionized, they carry an electrical charge which can be read.
Gas that is sampled must have ionization potential (IP).

55. What Does a PID Measure? Instructor Notes: Some example IP’s
Benzene 9.24
Methyl Ethyl Ketone (MEK) 9.54
Ethylene 10.5
Acetic acid 10.66
Methylene chloride 11.32
Oxygen 12.1
Those gases above 10.6 won’t be read by the PID lamp as they are higher than the lamp strength. The gases in the 11.7 lamp section can be slightly read by a 10.6 lamp, but the reading will not be accurate.
Translator Note:
MEK = methyl ethyl ketone
IPA = isopropyl alcohol
Carbon tet. = carbon tetrachloride
IP = ionization potential
eV = electron volt

56. What Does a PID Measure? Organics: Inorganics Sulfur compounds
Aromatics
Benzene
Ethyl benzene
Toluene
Xylene
Ketones & aldehydes
Acetone
MEK
Acetaldehyde
Amines & amides
Diethyl amine
Chlorinated hydrocarbons
Trichloroethylene (TCE)
Sulfur compounds
Mercaptans
Carbon disulfide
Unsaturated hydrocarbons
Butadiene
Isobutylene
Alcohols
Ethanol
Saturated hydrocarbons
Butane
Octane
Inorganics
Ammonia
Arsine
Instructor Notes:
This is not an exclusive list, it only provides some examples of the chemical families that can be detected by a PID. The original PID was designed to detect benzene vapors, as so detects the aromatics very well.
Organics are materials that have carbon in their molecular structure, and inorganics do not have any carbon in their molecular structure.
Translator Notes:
PID = photoionization detector

57. What PIDs Do Not Measure
Natural gas
Methane
Ethane
Acids
Hydrochloric acid
Hydrofluoric acid
Nitric acid
Others
Freons
Ozone
Radiation
Air
Nitrogen
Oxygen
Carbon monoxide
Water vapor
Toxics
Hydrogen cyanide
Sulfur dioxide
Instructor Notes:
This is what a PID will not detect.
High levels of water vapor will cause some readings in the PID, as the detection sensors actually short out, which cause a reading. In weather situations where there is a lot of fog in the air, the PID may provide a reading, which is a result of the airborne water vapor.
High levels of methane will suppress PID readings, these of course would be picked up by the LEL sensor.
Translator Notes:
PID = photoionization detector
LEL = lower explosive limit

58. Example PID Correction Factors
Benzene = 0.53
Toluene = 0.5
Acetone = 1.1
Nitrobenzene = 1.9
Diesel fuel = 0.7
Gasoline = ~1
Instructor Notes:
NEXT 2 SLIDES PROVIDE CORRECTION FACTOR EXAMPLES
Some example PID correction factors, which can be found in the owners manual for the Multi-RAE.
Translator Notes:
PID = photoionization detector

59. CF Example: Toluene Toluene CF with 10.6eV lamp is 0.5
If PID calibrated to isobutylene reads 100 ppm in a Toluene atmosphere, then the actual concentration is 50 ppm Toluene units.
0.5 x 100 ppm= 50 ppm
Instructor Notes:
The correction factor for toluene is 0.5 and the PID is calibrated to isobutylene, just as the multi-RAE is. The meter reads 100 when you enter a toluene contaminated atmosphere. Following the formula that takes the correction factor multiplied by the meter reading which provides the actual meter reading. The formula is
0.5 x 100 = 50 which provides that the meter should be reading 50 which can be called ppm.
Translator Notes:
PID = photoionization detector
CF = correction factor
Ppm = parts per million

60. Problems with PIDs
The lamps are affected by dirt and dust and require cleaning.
Higher levels of methane (natural gas, swamp gas, landfill gas) may suppress some readings.
Extreme humidity plays a role in the reading.

61. Colorimetric Sampling Types
Standard tubes
Multiple-test system
Chip measurement system
Instructor Notes:
The various type of Draeger test systems are shown. In the left side of the upper picture a chip measurement system (CMS) is shown. A chip box and a chip is shown in the middle of the upper photo. In the upper right the accuro pump and a single tube are shown. The bottom photos is a Civil Defense Simultest (CDS) kit with a tube set shown
Translator Notes:

62. Standard Colorimetric Systems
Glass tubes filled with a reagent material change color when exposed to the intended gas.
Air sample is drawn across the tube in a specific quantity.
The tube changes color in the presence of the contaminant the tube is intended to detect.
Instructor Notes:
Colorimetric testing implies a color change, and that is what happens when colorimetric tube sampling is done. The colorimetric tube has a chemical filler, usually a powder which is designed to react and change color in the presence of the target gas. The tubes are designed to have a known quantity of air/gas come across it to provide a reading. The tubes are calibrated devices, and the readings are based on a known quantity of gas moving through the tube.
If the target gas is present in levels that are above the minimum detection level of the tube, then the tube will have a color change which is indicated on the instruction sheet.
Translator Notes:

63. Standard Tubes Cover standard chemical families
Used to sample for identified and unidentified materials
Usually available in various sensitivities
Some bundled together in a manifold for simultaneous multiple sampling
Instructor Notes:
Colorimetric tubes are available from a number of manufacturers, and this program provide testing equipment manufactured by Draeger. The Dräeger colorimetric tube system has tubes that detect the standard chemical families, and can be used to sample for known and unidentified materials. The tubes can be purchased in a variety of sensitivities, some tubes may measure 1-5 ppm ammonia, while others may be ppm ammonia. Some tubes such as those provided with kits used in this program are bundled together to allow simultaneous sampling.
Translator Notes:
Ppm = parts per million

64. Colorimetric Sampling
Chip system involves the use of bar-coded sampling chips.
A sampling chip is inserted into a pump.
The pump recognizes the chip in use and provides the correct amount of sample through the reagent.
A reflective measurement provides an accurate reading of the gas that may be present.

65. Carbon Monoxide (CO) Colorless, odorless, and tasteless
Only detectable through the use of air monitors
Your nose is not effective at all at detecting CO, no matter what odor may be present.

66. CO Symptoms
Exposure can present flu-like symptoms, headache, nausea, dizziness, confusion, and irritability.
Exposure to high levels can cause vomiting, chest pain, shortness of breath, loss of consciousness, brain damage, and death.
Amounts in the 9 ppm range have killed unborn babies in the womb.

67. Exposure Levels
OSHA provides that less than an average of 50 ppm for an 8-hour period is acceptable.
NIOSH states 35 ppm for 10 hours.
ACGIH uses less than 25 ppm average for 8 hours.

68. Sources of CO Furnaces (oil and gas) Hot water heaters (oil and gas)
Fireplaces (wood, coal, and gas)
Kerosene heaters (or other fueled heaters)
Gasoline engines running inside (basements or garages)
Barbecue grills burning near the residence (garage or porch)
Faulty flues or exhaust pipes

69. Summary Defensive operations Air monitoring for first responders
Meter methodology
Oxygen monitors
Combustible gas indicators
Toxic gas monitors
Other detectors
Carbon monoxide incidents