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Pi Ds As A Hazmat Response Tool Unabridged 0207
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Pi Ds As A Hazmat Response Tool Unabridged 0207

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PID's as a Hazmat response tool.

PID's as a Hazmat response tool.

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  • 1.
    • PIDs as a HazMat Response Tool
    • Unabridged Version 7/02
  • 2.
    • Don’t LEL sensors measure VOCs?
    • How can we measure in ppm?
    • PID uses in HazMat
    • What is a PID?
    • The Power of Correction Factors
    • Setting PID alarms/interpreting PID output
    • Review of specific PID applications
    • Tips for Using and Maintaining PIDs
    Training Agenda:
  • 3.
    • Most HazMat Incidents are VOCs
  • 4.
    • Volatile Organic Compounds (VOCs)
    • Fuels (the majority of HazMats)
    • Degreasers, Heat Transfer Fluids
    • Paints, Solvents,
    • Plastics, Resins
    • The Chemical Compounds that keep Industry going!
    What is a VOC?
  • 5.
    • Refrigeration & Fertilizers: Ammonia (AP-201)
    • Plastics/Fiberglass: Styrene & Methylene Chloride
    • Petroleum: Hydrocarbons & Benzene
    • Automotive: Spray Booths (Paints) & Fuels
    • Aircraft: Wing Tank Entry, Solvents & Degreasers (AP-200)
    • Sausages: Carbon Disulfide
    Examples of Industrial PID Usage
  • 6.
    • Wool: Perchlorethylene (PERC)
    • Printing: MEK, Toluene, IPA
    • Environmental: Site assessments (AP-214)
    • Pulp & Paper: Turpentine (AP-204)
    • Heat Transfer Fluid: Therminol/DowTherm (AP-205)
    • Electronics: Solvents
    • Coke Oven gases
    Examples of Industrial PID Usage
  • 7.
    • Marine Chemists: Ship & Barge entry
    • Water & Wastewater: Spill investigators
    • Drug Enforcement: Clan Labs (AP-220)
    • College, Hospital, R&D Labs: Spills
    • Indoor Air Quality (IAQ) Consultants (AP-212)
    • Air Rifle Manufacturer
    • Waste Receiving Stations
    Examples of Industrial PID Usage
  • 8.
    • PID Sensitivity to VOCs make them an invaluable tool for HazMat Decisions:
    • Initial PPE Assessment
    • Leak Detection
    • Perimeter Establishment & Maintenance
    • Spill Delineation
    • Decontamination
    • Remediation
    PID Uses in HazMat
  • 9.
    • Many VOC’s are flammable and may be detected by the LEL (Lower Explosive Limit) or combustible gas sensors found in virtually every multigas monitor.
    • However, LEL sensors are not particularly useful in measuring toxicity because they do not have enough sensitivity.
    Doesn’t LEL measure VOCs?
  • 10. Wheatstone Bridge LEL Sensor
    • Measures change in resistance due to change in temperature of gas burning on detector
    Detector Compensator Output (+) 4.25 V (-) 1 k  1 k 
  • 11. Wheatstone Bridge is like a Stove
    • One element has a catalyst and one doesn’t
    • Both elements are turned on low
    • The element with the catalyst “burns” gas at a lower level and heats up
    • The hotter element has more resistance and the Wheatstone Bridge measures the difference in resistance between the two elements
  • 12. Is the LEL Sensor Sensitive Enough?
    • Two mechanisms can affect the performance of Wheatstone bridge LEL sensors:
    • Gases burn with different heat outputs at their LEL
    • “Heavier” hydrocarbon vapors have difficulty diffusing into the LEL sensor and reduce its output
  • 13. LEL Sensor Cut-Away Methane (CH 4 ) Heavier Hydrocarbons Heavier Hydrocarbons Rejected by the Flame Arrestor Active bead Compensating bead Flame arrestor
  • 14. LEL Sensor Relative Sensitivity Gas/Vapor LEL (%vol) Sensitivity (%) Acetone 2.2 45 Diesel 0.8 30 Gasoline 1.4 45 Methane 5.0 100 MEK 1.8 38 Propane 2.0 53 Toluene 1.2 40 LEL Sensor sensitivity varies with chemical
  • 15. LEL Sensor Cal Gases
    • Pentane and Propane are often used as LEL sensor calibration gases because their response is closer to most common flammable vapors
    • LEL sensors fail to “see” Methane first, so you could calibrate properly on Pentane or Propane yet not “see” Methane at all
    • The safest calibration is to calibrate with Methane gas and then set the scale to Pentane or Propane
    • Surrogate or simulant cal.
  • 16. Using PIDs for LEL
    • Multiply %volume by 10,000 to get ppm.
    • LEL Gasoline is 1.2% by volume or 12,000 ppm
    • 10% of LEL Gasoline is 1200 ppm
    • PIDs often are a better measurement tool for 10% of LEL for fuels and chemicals
  • 17. Using PIDs for 10% of LEL
  • 18. Wingtank LEL
    • Entrants can see and smell jet fuel but their LEL meters read nothing
    • LEL sensor just can’t see jet fuel
    • Aircraft maintenance exposes sensor to poisoning silicone compounds
    • PIDs are used to make LEL decision
  • 19. Wingtank LEL
    • Clues: wingtank containing jet fuel residue
    • LEL: little or no reading
    • PID: 800 ppm in jet fuel units is 10% of LEL
    Clues Tubes =800 ppm is 10% of LEL PID Toxic Sensors LEL
  • 20. Pulp & Paper Turpentine LEL
    • Operator using a properly calibrated monitor did not measure flammable levels of turpentine but was severely burned in a turpentine flash during hot work
    • LEL sensor just can’t see turpentine
    • Sulfur compounds in Pulp & Paper act as chronic poisons to LEL sensor that at its best can barely see turpentine
    • Monitors now have LEL and PID
  • 21. Pulp & Paper Turpentine LEL
    • Clues: turpentine recovery unit
    • Toxic Sensor: low reading on H 2 S sensor common in a pulp plant
    • LEL: no reading
    • PID: 800 ppm in turpentine units or 10% of LEL
    Clues Tubes =800 ppm is 10% of LEL PID Toxic Sensors LEL
  • 22. Using PIDs for 10% of LEL
    • 1000 ppm in Isobutylene units is a conservative measure of 10% of LEL for many common VOCs
  • 23.
    • LEL Measures EXPLOSIVITY not TOXICITY!
    • Many VOCs are toxic well below the sensitivity of an LEL sensor
      • Xylene = 100 ppm
    • Using LEL to measure for Toxicity is like using a yardstick to measure the thickness of a sheet of paper!
    • A PID can measure TOXICITY!
    Explosivity Vs Toxicity
  • 24. LEL Compared to PID
    • LEL gets you home tonight
    • PID lets you enjoy retirement!
    • LEL is more for Acute toxicity which will get you immediately (IDLH)
    • PID is more for Chronic Toxicity which will get you over a longer period of time (TWA)
    • Toxicity = Concentration x Exposure Period
  • 25.
    • We now need to measure in PPM!
  • 26. How can we measure in PPM?
    • Colorimetric Tubes
    • Metal Oxide Sensor (MOS)
    • Portable GC/MS
    • Flame Ionization Detectors (FID)
    • Photo Ionization Detector (PID)
  • 27. Colorimetric Tubes measure in PPM
    • Proven technology
    • “Snap Shots” like a “Polaroid” camera, non-continuous, no alarms
    • “Spot Checks” result in sampling error
    • Respond in minutes rather than seconds
    • 15-25% accuracy Piston/Bellows style
    • Readings subject to interpretation
    • Generate Glass splinters & chemical waste
    • Tubes expire & large stock is expensive
  • 28. MOS Sensors Measure in PPM
    • Faster response than tubes & continuous
    • Affordable (“Poor Man’s PID”)
    • Detection limits in 10s of ppm at best
    • Non-linear output limits accuracy (its like a rubber ruler)
    • Still slower to respond than PID or FID
    • Sensitive to Temperature and Humidity leading to false alarms
    • Can be poisoned & ruined by over-ranging
    • Non-specific
  • 29. Portable GC/MS measures in PPM
    • Very Accurate
    • Very Specific
    • “Snap Shots” like a “Polaroid” camera, non-continuous, no alarms
    • “Spot Checks” result in sampling error
    • Respond in minutes rather than seconds
    • Very complicated
    • Very heavy and bulky
    • Prohibitively expensive
  • 30. FIDs Measure in PPM
    • Fast response
    • Very Accurate
    • Complicated
    • Heavy and bulky
    • Expensive
    • Non-specific
    • The difference between FID and PID is like the difference between a meterstick and a yardstick!
  • 31. PIDs Measure in PPM
    • Fastest response
    • Very Accurate (the “heart of a GC”). Entry decisions can be made directly based on PPM with confidence.
    • Optical Technology not affected by contaminants
    • Non-specific
  • 32.
    • “ Traditional” PIDs Were Just One Step Away from the Lab!
    • High cost of purchase & maintenance
    • Lack of durability
    • Bulky size & heavy weight
    • Sensitivity to Humidity and RFI
    • Design breakthroughs solve these problems so that PIDs can be used for HazMat!
    Why aren’t PIDs More Common?
  • 33.
    • Initial PPE Assessment
    • Leak Detection
    • Perimeter Establishment & Maintenance
    • Spill Delineation
    • Decontamination
    • Remediation
    PID Uses in HazMat
  • 34.
    • Some “Incidents” may not be an “Incident” at all and many not require any PPE (Personal Protective Equipment)
    • Some non-incidents are really “INCIDENTS” and require substantial PPE
    • PIDs are an excellent AID in this decision making process
    Initial PPE Assessment with a PID
  • 35. Initial PPE Assessment with a PID
    • Pool of Liquid under Benzene Tank Car
    • Benzene (PEL = 1 ppm)
    • Ambient conditions: 95 o F (35 o C), 95% Humidity
    • How do you dress out?
  • 36. Initial PPE Assessment with a PID
    • PID is very sensitive to Benzene
    • Level A is unnecessary if no Benzene
    • Level A represents a Heat Stress Risk
    • Car contents at 65 o F (18 o C)
    • “ Leak” really condensation
  • 37. Leak Detection with a PID
    • “ See” the Concentration Gradient
    • PID allows you to “see” concentrations
    • As concentration increases you are closer to the source
    10,000 PPM P erchlorethylene (PERC) 0 PPM PERC
  • 38. Perimeter Monitoring with a PID
    • Set based upon conditions by experienced HazMat Techs
    • Physical Characteristics of Chemical
    • Toxicity of Gas or Vapor
    • Temperature
    • Wind Direction
    • Changes in Conditions are often Missed by Untrained Perimeter Workers
  • 39. Perimeter Monitoring with a PID Gasoline Tank Truck Rollover
    • 8:00 AM
    • 45 o F (7 o C)
    • No wind
    • TWA = 100 ppm
  • 40. Perimeter Monitoring with a PID Gasoline Tank Truck Rollover
    • 8:00 AM
    • 45 o F (7 o C)
    • No wind
    10,000 PPM Gas 50 PPM (1/2 of TWA)
    • Perimeter = 100 feet
  • 41. Perimeter Monitoring with a PID Gasoline Tank Truck Rollover
    • 11:00 AM
    • 75 o F (24 o C)
    • 10 mph wind
    10,000 PPM Gas 600 PPM
    • Perimeter now should be 300 feet
    • Perimeter worker overexposed
  • 42. Perimeter Monitoring with a PID
    • Datalogging as a Tool
    • Document Perimeter Worker Exposures
    • Provide Evidence to Justify Evacuations
  • 43. PIDs for Spill Delineation
    • Many Liquids can be present in a HazMat Incident
    • Water
    • Fuels
    • Engine Fluids
    • Foam
  • 44. PIDs for Spill Delineation
    • It’s Hard to tell pavement “wet” with water from pavement “wet” with diesel just by looking
  • 45. PIDs for Spill Delineation Limited Absorbent can be Efficiently used only on the Diesel Spill PIDs can help separate the “Water” from the “Oil”
  • 46. PIDs for Decon
    • Is Worker Contaminated?
    • Is Decon Complete?
    • Can we reuse suit?
    • Is my turn-out contaminated with Fuel Products?
    • This same sensitivity to hydrocarbons makes PIDs ideally suited for arson investigation
    • (Ref AP-207)
    PIDs can help answer these questions:
  • 47. Using a PID for Remediation
  • 48. Using a PID for Remediation
    • Hazardous Materials can evade the best attempts at containment:
    • Is Soil Contaminated enough to require further clean-up?
    • Is Water Contaminated enough to require further clean-up?
  • 49. Using a PID for Remediation
    • Put contaminated soil or water in a container
    • Cover the container and bring it up to room temperature (~15 min)
    • Put PID probe into container and sample
    • Generally <100 ppm is good
    • Ref AP-214
    How to do a Headspace Sample:
  • 50. What is a PID?
    • PID = Photo-Ionization Detector
    • Detects VOCs (volatile organic compounds) and Toxic gases from <10 ppb to as high as 10,000 ppm
    • Over 90% of HazMat incidents are fuel product related and are easily measured with a PID
    • A PID is a very sensitive broad spectrum monitor, like a “low-level LEL”
  • 51. How does a PID work? 100.0 ppm Gas enters the instrument It passes by the UV lamp It is now “ ionized” Charged gas ions flow to charged plates in the sensor and current is produced Current is measured and concentration is displayed on the meter. + - + - + - + - + - Gas “Reforms” and exits the instrument intact An optical system using Ultraviolet lamp to breakdown vapors and gases for measurement Photo Ionization Detector
  • 52.
    • Organics: Compounds Containing Carbon (C)
      • Aromatics - compounds containing a benzene ring
        • BETX: benzene, ethyl benzene, toluene, xylene
      • Ketones & Aldehydes - compounds with a C=O bond
        • acetone, MEK, acetaldehyde
      • Amines & Amides - Carbon compounds containing Nitrogen
        • diethyl amine
      • Chlorinated hydrocarbons - trichloroethylene (TCE)
      • Sulfur compounds – mercaptans, carbon disulfide
      • Unsaturated hydrocarbons - C=C & C C compounds
        • butadiene, isobutylene
      • Alcohol’s
        • ethanol
      • Saturated hydrocarbons
        • butane, octane
    • Inorganics: Compounds without Carbon
        • Ammonia
        • Semiconductor gases: Arsine
    What does a PID Measure?
  • 53. What PIDs Do Not Measure
    • Radiation
    • Air
      • N 2
      • O 2
      • CO 2
      • H 2 O
    • Toxics
      • CO
      • HCN
      • SO 2
    • Natural gas
      • Methane CH 4
      • Ethane C 2 H 6
    • Acids
      • HCl
      • HF
      • HNO 3
    • Others
      • Freons
      • Ozone O 3
  • 54.
    • Ionization Potential
    • IP determines if the PID can “see” the gas
    • If the IP of the gas is less than the eV output of the lamp the PID can “see” it
    • Ionization Potential (IP) does not correlate with the Correction Factor
    • Ionization Potentials are found in RAE handouts (TN-106), NIOSH Pocket Guide and many chemical texts.
    What does a PID Measure?
  • 55.
    • If the “wattage” of the gas or vapor is less than the “wattage” of the PID lamp then the PID can “see” the gas or vapor!
  • 56. What does a PID Measure? 8 9 10 11 12 13 14 15 8.4 9.24 9.54 9.99 10.1 10.5 10.66 11.32 11.47 12.1 14.01 Some Ionization Potentials (IPs) for Common Chemicals Benzene MEK Vinyl Chloride IPA Ethylene Acetic Acid Methylene chloride Carbon Tet. Carbon Monoxide Styrene Oxygen Ionization Potential (eV) 11.7 eV Lamp 10.6 eV Lamp Not Ionizable 9.8 eV Lamp
  • 57.
    • 9.8 & 10.6 provide more specificity
    • 10.6 lasts 24-36 months
    • 10.6 provides best resolution
    • 10.6 costs less ($195)
    • 11.7 is required for high energy compounds like Methylene Chloride
    • 11.7 crystal absorbs water and degrades
    • 11.7 lasts about 2-3 months
    • 11.7 costs more ($345 in ampule)
    Why not always use 11.7 eV Lamps?
  • 58. Selectivity Vs Sensitivity
    • PID is very sensitive and accurate
    • PID is not very selective
  • 59. Selectivity Vs Sensitivity
    • PID is very sensitive and accurate
    • PID is not very selective
    Ruler cannot differentiate between yellow and white paper
  • 60. Selectivity Vs Sensitivity
    • PID is very sensitive and accurate
    • PID is not very selective
    PID can’t differentiate between ammonia & xylene
  • 61. Selectivity Vs Sensitivity
    • Use your head for Selectivity and the PID for Sensitivity
    • PID is sensitive to chemicals not specific
    • Correction Factors set correct PID scale
    • PID should stay on Isobutylene (Calibration gas) until unknown is identified
    • A PID is a Gas Chromatograph where the column is between your ears!
  • 62. Selectivity Vs Sensitivity No Correction Factor is used until compound is identified Identify then Quantify!
  • 63.
    • Correction Factors are the key to unlocking the power of a PID for Assessing Varying Mixtures and Unknown Environments
    What is a Correction Factor?
  • 64.
    • Correction Factor (CF) is a measure of the sensitivity of the PID to a specific gas
    • CFs are scaling factors, they do not make a PID specific to a chemical, they only correct the scale to that chemical.
    • Correction Factors allow calibration on cheap, non-toxic “surrogate” gas.
    • Ref: RAE handout TN-106
    What is a Correction Factor?
  • 65.
    • Low CF = high PID sensitivity to a gas
    • If the chemical is bad for you then the PID needs to be sensitive to it
        • If Exposure limit is < 10 ppm, CF < 1
    • If the chemical isn’t too bad then the PID doesn’t need to be as sensitive to it
        • If Exposure limit is > 10 ppm, CF < 10
    • Use PIDs for gross leak detectors when CF > 10
    CF’s measure sensitivity
  • 66.
    • Toluene CF with 10.6eV lamp is 0.5 so PID is very sensitive to Toluene
    • If PID reads 100 ppm of isobutylene units in a Toluene atmosphere
    • Then the actual concentration is 50 ppm Toluene units
    • 0.5 CF x 100 ppm iso = 50 ppm toluene
    CF Example: Toluene
  • 67.
    • Ammonia CF with 10.6eV lamp is 9.7 so PID is less sensitive to Ammonia
    • If PID reads 100 ppm of isobutylene units in an Ammonia atmosphere
    • Then the actual concentration is 970 ppm Ammonia units
    • 9.7 CF x 100 ppm iso = 970 ppm ammonia
    CF Example: Ammonia
  • 68. Making a Decision with a PID
    • Two sensitivities must be understood to make a decision with a PID
    • Human Sensitivity: as defined by AGCIH, NIOSH, OSHA or corporate exposure limits
    • PID Sensitivity: as defined through testing by the manufacturer of your PID (RAE CF)
    • ONLY USE A CORRECTION FACTOR FROM THE MANUFACTURER OF YOUR PID!
  • 69. Making a Decision with a PID
    • PID sensitivity + Human Sensitivity = Decision
    • or
    • CF + Exposure Limit = Decision
    • Reference AP-221
  • 70. Making a Decision with a PID
    • Three scenarios on how to make a decision with a PID
    • Single Gas/Vapor
    • Gas/Vapor mixture with constant make-up
    • Gas/Vapor mixture with varying make-up
  • 71.
    • Single Chemicals are easy
    • Identify the chemical
    • Set the PID Correction Factor to that chemical
    • Find the Exposure Limit(s) for the chemical
    • Set the PID alarms according to the exposure limits
    • The “Real World” is rarely this easy. Most applications are a “Witches Brew” of VOCs
    PID Alarms: Single Chemical
  • 72.
    • Paint: 15% Styrene and 85% Xylene
    • EL mix = 1/(0.15/50 + 0.85/100) = 87 ppm
    • Where:
    • 0.15 is 15% styrene
    • 50 is the 50 ppm exposure limit for styrene
    • 0.85 is 85% xylene
    • 100 is the 100 ppm exposure limit for xylene
    • Ref: TN-106 & NIOSH Pocket guide, AP-211 & AP-221
    PID Alarms: Constant Mixtures
  • 73.
    • Paint: 15% Styrene and 85% Xylene
    • CF mix = 1/(0.15/0.4 + 0.85/.6) = 0.56
    • Where:
    • 0.15 is 15% styrene
    • 0.4 is the CF styrene
    • 0.85 is 85% xylene
    • 0.6 is the CF for xylene
    • Ref: TN-106, AP-211 & AP-221
    PID Alarms: Constant Mixtures
  • 74.
    • Paint: 15% Styrene and 85% Xylene
    • In the sealed up living room I got a reading of 120 iso on the PID in Isobutylene units
    • Multiplying it by the correction factor of 0.56 mix my real reading on the mixture was 67.2 mix ppm
    • This is under the calculated exposure limit of 87 mix ppm for the mixture
    PID Alarms: Constant Mixtures
  • 75.
    • Constant Mixture Shortcut #1
    • Paint: 15% Styrene and 85% Xylene
    • Lets consider it to be just Xylene
    • In the sealed up living room I got a reading of 120 on the PID in Isobutylene units
    • Multiplying it by Xylene CF of 0.59 my real reading as Xylene is 70.8 ppm
    • This is under the Xylene exposure of 100 ppm
    PID Alarms: Constant Mixtures
  • 76.
    • Constant Mixture Shortcut #2
    • Find the average make-up of the mixture
    • Determine the most toxic VOC
    • Base setpoints on the most toxic VOC
    • WARNING: Shortcuts only provide a quick guideline!
    PID Alarms: Constant Mixtures
  • 77.
    • Gasoline
    • “Gas” contains as much as 1% Benzene
    • Benzene is carcinogenic (PEL = 1 PPM)
    • 100 PPM of Gasoline contains as much as 1 PPM Benzene
    • Set High Alarm at 100 PPM Gas < 1.0 PPM Benzene
    • Set Low Alarm at 50 PPM Gas < 0.5 PPM Benzene
    PID Alarms: Constant Mixtures
  • 78.
    • The Controlling Compound
    • Every mixture has a compound that is the most toxic and “controls” the setpoint for the whole mixture
    • Determine that chemical and you can determine a conservative mixture setpoint
    • If we are safe for the “worst” chemical we will be safe for all chemicals
    PID Alarms: Varying Mixtures
  • 79. PID Alarms: Varying Mixtures
    • Ethanol “appears” to be the safest compound
    • Toluene “appears” to be the most toxic
    • This table only provides half of the decision making equation
    • Might as well compare 1000 apples to 100 oranges
  • 80. PID Alarms: Varying Mixtures
    • People are accustomed to making decisions solely on human sensitivity
    • Users of meters also need to take into account meter sensitivity
    • It is necessary to simultaneously interpret both human and meter sensitivity
  • 81. PID Alarms: Varying Mixtures
    • Set the PID for the compound with the lowest Exposure Limit (EL) in equivalent units and you are safe for all of the chemicals in the mixture
    • Divide the EL in chemical units by CF to get the EL in isobutylene
    • EL Isobutylene = EL chemical
    • CF chemical
  • 82. PID Alarms: Varying Mixtures
    • Now one can compare “Apples to Apples”
    • Its lower sensitivity on the PID makes Ethanol the “controlling compound” when the Exposure Limits are expressed in equivalent “Isobutylene Units”
  • 83. PID Alarms: Varying Mixtures
    • Setting the PID to 83 ppm alarm in Isobutylene units protects from all three chemicals no matter what their ratio
    • IMPORTANT: in the rest of this discussion, “Exposure Limit in Isobutylene” will be called or EL iso . EL iso is a calculation that involves a vendor specific Correction Factor (CF). Similar calculations can be done for any PID brand that has a published CF list.
  • 84. PID Alarms: EL iso & Unknowns
    • EL iso thresholds are a tool to help characterize unknown environments.
    • The lower the reading in isobutylene units on your PID the less risk.
    • If the reading on your PID is below the EL iso for a chemical there isn’t a threat.
  • 85. PID Alarms: Varying Mixtures
    • For example, if the PID reads 45 iso ppm in an area with Toluene (EL iso =400), Styrene (EL iso =250) and Cumene (EL iso =92) vapors we are safe because the EL iso for all three of these chemicals is well above 45 ppm.
  • 86. PID Alarms: EL iso & Unknowns
    • A RAE PID with a 10.6eV lamp set to the following alarms and not beeping provides protection from:
    • 44 chemicals at a 100 ppm alarm , includes solvents like Xylene, Toluene, MEK, Acetone
    • 65 chemicals at a 50 ppm alarm , from Cyclohexanone to Acetone.
    • 81 chemicals at a 25 ppm alarm , from Diethylamine to Acetone.
    • 105 chemicals at a 10 ppm alarm , from Toluidine to Acetone.
    • 140 chemicals at a 1 ppm alarm , from Diethylenetriamine to Acetone
  • 87. PID Alarms: EL iso & Unknowns
    • Setting an alarm to 1 ppm provides the highest protection, but it also causes the most alarms.
    • An alarm point of 1 ppm would be similar to always wearing a Level A suit!
    • A 50 ppm EL iso alarm is appropriate for going to respiratory protection in a fuel tanker roll-over because an EL iso alarm of 50 is very conservative for all hydrocarbon fuels.
  • 88. PID Alarms: the 50/50 Rule
    • Acetone
    • Cyclohexane
    • Diesel Fuel
    • Ethyl alcohol
    • Ethylbenzene
    • Gasoline
    • Heptane, n-
    • Hexane, n-
    • Stoddard Solvent
    • Styrene
    • Tetrahydrofuran
    • Toluene
    • Trichloroethylene
    • Xylene
    When Measuring in Isobutylene Units and set to 50 ppm RAE PIDs will protect from over 50 of the most common Chemicals:
    • IPA
    • Jet Fuel
    • MEK
    • MIBK
    • MPK
    • Nonane
    • Octane, n-
    • Pentane
  • 89. PID Alarms: EL iso & Unknowns
    • Of course, if there are known or suspected chemicals of higher risk a lower alarm might be called for .
    • In a potential terrorist chemical agent attack, a EL iso of 1.00 ppm might be more appropriate
  • 90. PID Alarms: EL iso & Unknowns
    • EL iso are only one gauge of the threat level in any circumstance.
    • The PID user must use all of the clues present to reach a decision.
  • 91. Integrating Gas Detection Techniques
    • PIDs can be an important part of any gaseous risk assessment and should be used with other clues present:
    • Response from other types of meters
    • Response from colorimetric tubes
    • Physical clues
    • Worker/Victim symptoms
  • 92. Integrating Gas Detection Techniques The Gas Monitoring Pyramid is a graphic depiction of how to integrate various gas monitoring techniques
  • 93. Integrating Gas Detection Techniques Tubes Single Gas: CO/O2/LEL Multigas CSE Broadband: MOS Selective: IMS Selective: GC/MS Selective: Tubes Broadband: PID/FID Gas Monitoring Pyramid Selectivity Increases as you move up the Pyramid The Answer
  • 94. Integrating Gas Detection Techniques Tubes Single Gas: CO/O2/LEL Multigas CSE Broadband: MOS Selective: IMS Selective: GC/MS Selective: Tubes Broadband: PID/FID PID + Tubes Approximates the selectivity of GC/MS w/o the cost Gas Monitoring Pyramid The Answer
  • 95. Integrating Gas Detection Techniques
    • Each circle represents the range of chemicals seen by a sensor
    • By overlaying multiple detection techniques we can zoom in on the solution
    • Use multiple techniques until you feel comfortable with the solution
    Clues LEL Tubes =The Real Answer PID Toxic Sensors
  • 96.
    • In food warehouse maintenance room had 80 ppm CO indicated
    • Assumed that they used propane forklifts (common source of CO) but found that they used battery powered forklifts
    • The maintenance room was located with in the battery charging area.
    • Lead acid batteries generate hydrogen (H 2 ) when charging
    Food Warehouse
  • 97. Food Warehouse
    • 80 ppm indicated CO translates to 200 ppm H 2 or about 0.5% of LEL H 2
    • No LEL reading, H 2 LEL is 4% (40,000 ppm), 1% of LEL H 2 is just 400 ppm
    • Checked with CO colorimetric tube and registered no CO reading
    • Concluded that CO reading on monitor was due to H 2 cross-sensitivity
  • 98. Food Warehouse: CO Cross-Sensitivity
    • Clues: Warehouse w/ battery powered forklifts
    • Toxic Sensor: 80 ppm reading on CO if H 2 it’s approximately 200 ppm
    • LEL: no reading on LEL
    • PID: no reading on PID
    • Tubes: no reading on CO tube
    Clues Tubes =Probably Hydrogen gas from forklift batteries PID Toxic Sensors LEL
  • 99.
    • CO sensor indicated 35-45 ppm in printed circuit board plant with styrene, xylene, acetone and other aromatics and ketones
    • Jumped to false conclusion that CO sensor was bad or responding to hydrocarbons
    • Fresh aired monitor outside plant and still had high CO in plant
    Printed Circuit Board Plant
  • 100.
    • Calibrated with CO gas and still had high CO in plant
    • Checked with CO colorimetric tube and registered 50 ppm CO reading
    • Investigated plant and found shrink-wrap machine pumping out 150 ppm CO in worker breathing zone
    Printed Circuit Board Plant
  • 101. Printed Circuit Board Plant
    • Clues: Printed circuit board plant
    • Toxic Sensor: 35-45 ppm reading on CO
    • LEL: no reading on LEL
    • PID: no reading on PID
    • Tubes: 50 ppm reading on CO tube
    Clues Tubes =CO from shrink wrap machine PID Toxic Sensors LEL
  • 102.
    • Portable CO monitor showed no CO
    • CO Colorimetric tube found no CO
    • PID read 100 ppm
    • Investigation revealed spray painting had taken place
    • Home CO detectors use less filtered CO sensors that can respond readily to hydrocarbons
    Home CO Detector
  • 103. Home CO Detector
    • Clues: Household CO call, smells like paint solvent
    • Toxic Sensor: 0 ppm reading on CO
    • LEL: no reading on LEL
    • PID: 100 ppm reading on PID
    • Tubes: no reading on CO tube
    Clues Tubes =spray paint set off home CO detector PID Toxic Sensors LEL
  • 104. Oil Refinery Remediation H 2 S
    • Datalogging meter showed H2S of straight 199 ppm indicating they had maxed out the H2S circuit on the meter (meter & sensor only rated to 100 ppm H2S)
    • This data is questionable but we certainly have more than 100 ppm and may have more than 200 ppm H2S
    • PID data from the same meter showed 240 ppm in Isobutylene units
    • No LEL reading and H2S is a LEL inhibitor
  • 105.
    • Using PID correction factor for H 2 S of 3.3, the concentration if it were just H 2 S is 792
    • PID measures total VOCs including H 2 S so part of the signal could be VOCs
    • We can be pretty sure that we had a lot of H 2 S and it could be 100-790 ppm (IDLH =100 ppm)
    • Further testing via sampling and lab testing was recommended
    • H 2 S colorimetric tubes could also be used
    Oil Refinery Remediation H 2 S
  • 106. Oil Refinery Remediation H 2 S
    • Clues: Refinery clean-up with strong H2S smell
    • Toxic Sensor: 199 ppm reading on H2S sensor
    • LEL: no reading (LEL = 4% or 40,000 ppm)
    • PID: 240 ppm in iso units or 792 in H2S units
    • Tubes: not used but would have been helpful
    Clues Tubes =a lot of H 2 S is present PID Toxic Sensors LEL
  • 107.
    • Homeowner “smells” natural gas after gas company work
    • Natural gas is methane and other short-chain saturated compounds
    • Natural gas doesn’t smell but Mercaptan odorant is added for safety purposes
    • Mercaptans are “sticky” and can remain on clothes and fabrics even after all work is done and the atmosphere is safe
    Home Natural Gas Leak
  • 108. Home Natural Gas Leak
    • Smell is most likely leftover from gas company work, but good idea to have gas company recheck their work
    • Olfactory threshold for Methyl Mercaptan is well below the detection capability of even the PID
  • 109. Home Natural Gas Leak
    • Clues: homeowner compliants
    • Toxic Sensor: no readings
    • LEL: no reading
    • PID: no reading
    • Tubes: no reading on mercaptans tube
    =odorants are very powerful and purvasive Clues Tubes PID Toxic Sensors LEL
  • 110. Review of Specific PID Applications
    • AP-201: Measuring Ammonia with PIDs
    • AP-207: PIDs as an Arson Tool
    • AP-212: PIDs for Indoor Air Quality (IAQ)
    • AP-216: Using PIDs for Terrorist Chemical Attacks
    • AP-219: Using PIDs for 10% of LEL Decisions
    • AP-220: Using PIDs in Clan Lab Investigations
  • 111. PIDs to Measure Ammonia
    • Decision to go from Respiratory protection to Level A is typically between 250-1500 ppm
    • Ammonia sensors “burn-out” at 200-300 ppm so responders go to Level A early
    • Ammonia sensors are for “nuisance” levels in range of 0-50 ppm
    • Use PIDs when you can “see” ammonia and levels are over 100 ppm
    • Ref. AP-201
  • 112. PIDs for Arson Investigation
    • Hydrocarbon liquids are common accelerants
    • The PID provides excellent sensitivity to hydrocarbons even after burn off
    • PIDs aren’t specific to accelerants
    • PIDs can help to confirm that a suspicious burn pattern is the best place to sample for the highest levels of accelerant
    • PIDs are less expensive than dogs
    • PIDs don’t suffer from olfactory fatigue and are not distractible
    • Ref. AP-207
  • 113. PIDs for IAQ
    • VOCs are one of the top IAQ Contaminants
    • Biological Agents (mold, dustmites, etc.)
    • Carbon Monoxide
    • Formaldehyde
    • Second Hand Smoke
    • VOCs
    • PIDs are one of the only direct measuring meters for IAQ
  • 114. PIDs for IAQ
    • PIDs Solve Paint Odor Problem
    • Normal IAQ is 100-500 PPB in isobutylene units
    • Above 500 ppb look for problems
    • Use PID like a “Geiger Counter” to find source
    • Chemical formulas on most paint and glue containers allow you to quickly identify the chemicals
  • 115. PIDs for IAQ
    • PIDs Solve Paint Odor Problem
    • NIOSH Pocket Guide helps you to quickly find the safe levels for chemicals
    • PID correction factors let you set the scale of the PID to the chemical of interest so that the reading is accurate
    • Using the PID scaled with the right correction factor you can quickly and accurately measure the level of the paint fumes
  • 116. PIDs for IAQ
    • PIDs Solve Paint Odor Problem
    • If fumes are at safe levels, the PID can help prove that it is safe for the occupants to stay in the building
    • It might be necessary to explain the difference between odor threshold and toxicity
    • For example, the odor threshold for toluene is 0.16-37 ppm while the 8 hour NIOSH TWA is 100 ppm.
  • 117. PIDs for IAQ
    • PIDs Solve Paint Odor Problem
    • In the politically charged situations posed by many IAQ complaints, a fast measurement tool like the PID is invaluable. It can save time, money and headaches
    • (Ref AP-212)
  • 118. Guidelines for Using PIDs for IAQ
    • In the politically charged situations posed by many IAQ complaints, a fast measurement tool like the PID is invaluable.
    • <100 ppb Isobutylene: normal outdoors
    • 100-400 ppb Isobutylene: normal indoors
    • 500-1000 ppb Isobutylene: threshold for potential IAQ complaints
    • It can save time, money and headaches
  • 119. PIDs for Terrorist Chemical Attacks
    • Initially WMD programs were focused on Chemical Warfare Agents (CWAs)
    • Terrorists don’t have to use military CWAs
    • There is better access to Toxic Industrial Chemicals (TICs) and there are many more TICs available
    • CWA Specific Detectors (IMS, SAW) can’t measure TICs and can be fooled by common chemicals
  • 120. PIDs for Terrorist Chemical Attacks
    • Just two words separate a Terrorist chemical attack from a HazMat Incident
    • If the “INTENT” is to create “FEAR”, then it’s terrorism
    • PIDs are one of the best broadband chemical detectors and they can be very useful in a risk based WMD response
    • Ref. AP-216
  • 121. PIDs for Terrorist Chemical Attacks
    • Each circle represents the range of chemicals seen by a sensor
    • By overlaying multiple detection techniques we can provide specificity to CWA
    • CWA specific sensors cannot measure TICs
    IMS SAW Tubes PID =CWA =TIC
  • 122.
    • Clan Labs typically are contaminated
    • Continuous measurement reduces responder risk
    • Wheatstone bridge sensors have difficulty in the clan lab environment
      • High Flashpoint chemicals
      • Common clan lab chemical poison LEL
    • Recommended Clan Lab alarms:
      • High: 250 ppm for 10% of LEL
      • Low: 5 ppm for respiratory
    • Ref: AP-220
    Using PIDs in Clan Lab Investigations
  • 123.
    • Tips for Using and Maintaining PIDs
  • 124.
    • Never Use Tygon tubing!
      • Absorbs chemicals like a “sponge”
      • Reduces ppm readout when chemicals exist
      • Causes “false positives” when chemicals don’t exist
    • Always use Teflon or similar non-reactive tubing
      • Will not absorb chemicals but might get coated
      • Clean with anhydrous methanol if it gets dirty
    PID: Tubing
  • 125. How Humidity Affects PIDs
    • The closer to the headlights the easier it is to see something through fog.
    • By reducing the distance the UV light travels in a PID the affects of humidity are drastically reduced
    Short Lightpath Long Lightpath
  • 126. PID: Maintenance
    • PID Drift is Due to Poor Sampling Technique
      • Aspirating liquids & vapors into sample probe
      • Aspirating dirt samples into sample probe
      • Hot liquids and vapors condensing in probe & sensor
      • Touching contaminated surfaces with probes
    • Clean PID Lamp & Sensor
      • When display creeps upwards after good zero
      • When PID responds to moisture
      • When movement of PID results in response on display
  • 127. PID: Maintenance
    • How to Clean PID Sensor
      • Always clean sample probe and replace or clean filters FIRST! If PID holds a stable zero after this step then further cleaning may not be necessary
      • Use anhydrous methanol (Lamp cleaning solution)
      • Clean lamp face with lens tissue
      • Clean sensor by immersion in cleaning solution (an ultrasonic cleaner will speed cleaning)
    • Drying the PID
      • Let air dry overnight
      • Warm air (not hot) will speed drying
  • 128. A PID is like a Magnifying Glass
    • A Magnifying glass lets a detective see fingerprints; a PID lets us “see” VOCs
    Identify then Quantify! Benzene Ammonia Carbon Disulfide Styrene Xylene Jet Fuel PERC
  • 129. Questions?
  • 130. RAE PID Products
  • 131. RAE PIDs: ToxiRAE
    • The ToxiRAE is a Personal Protection PID
    • Affordable personal monitor for
      • Initial PPE Assessment
      • Perimeter Establishment and Maintenance
    • Use 4 to for North, South, East and West Perimeter
  • 132.
    • PID & multigas monitor
    • For both Protection and Detection
    • Our most versatile monitor
    RAE PIDs: MultiRAE
      • Initial PPE Assessment
      • Leak Detection
      • Perimeter Establishment & Maintenance
      • Spill Delineation
      • Decontamination
      • Remediation
  • 133.
    • 0-10,000 PPM w/excellent linearity
    • Strong pump
    • Superior PID sensor resists moisture & dirt
    • Quick Lamp & Sensor Access w/o tools
    • Rugged rubber boot standard
    • NiMH Drop-in battery w/backup alkaline pack
    RAE PIDs: MiniRAE 2000
  • 134.
    • Continuous detection to 1 ppb!
    • 0-9999 PPB or 0-200 PPM
    • Can detect VOCs at or below the olfactory threshold for IAQ.
    • Measures highly toxic compounds with low vapor pressures like chemical agents and isocyanates (TDI & MDI)
    RAE PIDs: ppbRAE
  • 135.
    • Rugged, one-to-five sensor monitoring system
    • “ProRAE Remote” software simultaneously controls and displays readings for up to 16 remote units up to 2 miles downrange
    • Runs up to 36 hours on Li-Ion
    RAE PIDs: AreaRAE Local Area Monitoring ( ISM )