Using real-time portable atmospheric monitors
Transcript of Using real-time portable atmospheric monitors
AIHCe 2012 – PDC 411 Page 1 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 1
Bob Henderson, BS, MBA
GFG Instrumentation Inc.
Ann Arbor, MI
Using real-time portable
atmospheric monitors
(Electron States)
August, 2012 Using real-time portable atmospheric monitors Slide 2
Requirements for use of portable
real-time gas detectors
• Common uses for real-time portable gas detectors:
• Hazard assessment
• Exposure assessment
• Indoor-air quality
• General atmospheric monitoring
• Non-permit spaces
• Permit spaces which have been reclassified as non-
permit spaces
• Permit-required confined spaces (per 29CFR 1910.146)
AIHCe 2012 – PDC 411 Page 2 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 3
Many technologies are available for use in
portable real-time instruments
• The most
commonly used
technologies are
highlighted in red
• Each type of
detection has
capabilities and
limitations which
must be
understood for
safe use
• Oxygen deficiency and enrichment:
• Fuel cell oxygen sensors
• Solid polymer (“oxygen pump”) sensors
• Combustible gases and vapors:
• Catalytic % LEL (“Wheatstone bridge”)
sensors
• Non-dispersive infrared (NDIR) % LEL and
% volume sensors
• Thermal conductivity (TC) sensors
• Toxic gases and vapors:
• Electrochemical sensors
• Photoionization detectors
• Non-dispersive infrared (NDIR)
• Flame ionization (FID)
• Ion Mobility Spectroscopy (IMS)
August, 2012 Using real-time portable atmospheric monitors Slide 4
Common Atmospheric Hazards
• Oxygen Deficiency
• Oxygen Enrichment
• Presence of Toxic
Gases
• Presence of
Combustible Gases
AIHCe 2012 – PDC 411 Page 3 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 5
Composition of fresh air
• 78.1 % Nitrogen
• 20.9 % Oxygen
• 0.9 % Argon
• 0.1 % All other gases
• Water vapor
• CO2
• Other trace gases
August, 2012 Using real-time portable atmospheric monitors Slide 6
Oxygen Deficiency
• Any area that has an oxygen
level of less then 19.5% by
volume is considered to be
oxygen deficient
AIHCe 2012 – PDC 411 Page 4 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 7
Causes of Oxygen Deficiency
• Combustion
• Welding and cutting torches
• Internal combustion engines
• Decomposing of organic matter
• Rotting foods, plant life and fermentation
• Oxidation of metals
• Rusting
• Inerting
• Displacement
• Absorption
August, 2012 Using real-time portable atmospheric monitors Slide 8
Oxygen displacement in an
open topped confined space
Argon
• Open-topped pits and spaces
potentially very dangerous from
standpoint of trapping or containing
dangerous atmospheres
AIHCe 2012 – PDC 411 Page 5 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 9
Deliberate displacement of oxygen
(inertion) in a fully enclosed vessel
O 2
O 2 O
2
O 2
O 2
O 2
N 2
N 2 N
2
N 2
N 2
N 2
N 2
N 2
N 2
N 2
N 2
N 2
O 2
N 2
Methane
O2 & N2
N 2
N 2
N 2
CH 4
N 2
N 2
N 2
N 2
N 2
CH 4
N 2
N 2
N 2
N 2
CH 4
N 2
N 2
N 2
CH
N
4
2
• For every 5% total volume displaced, O2 concentration
drops by about 1%
• If 5% of the fresh air in a closed vessel is displaced by
methane, the O2 concentration would be about 19.9%
• The atmosphere would be fully explosive while the O2
concentration would still be above the normal alarm setting!
August, 2012 Using real-time portable atmospheric monitors Slide 10
Oxygen Enrichment
• Proportionally increases rate of many chemical reactions
• Can cause ordinary combustible materials to become flammable or explosive
• Any area with
an O2 level of more than 23.0% is dangerously enriched
AIHCe 2012 – PDC 411 Page 6 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 11
Effects of oxygen at
various concentrations
Concentration Effect
> 23% Oxygen enrichment
20.90% Normal air concentration
19.50% Minimum “safe level”
16% First sign of anoxia appears
16 – 12% Breathing and pulse rate increase, muscular
co-ordination is slightly impaired
14 – 10%
Behavioral changes, impaired mental ability,
abnormal fatigue upon exertion, disturbed
respiration
10 – 6% Nausea and vomiting, inability to move freely
and loss of consciousness may occur
< 6% Convulsive movements and gasping occurs,
respiration stops
August, 2012 Using real-time portable atmospheric monitors Slide 12
Measuring Oxygen
(Deficiency and Enrichment)
AIHCe 2012 – PDC 411 Page 7 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 13
Fuel Cell Oxygen Sensors
Sensor generates electrical current proportional to the O2 concentration
Sensor used up over time (one to three years)
Oxygen reduced to hydroxyl ions at cathode:
O2 + 2H2O + 4e- 4OH -
Hydroxyl ions oxidize lead (anode):
2Pb + 4OH - 2PbO + 2H2O + 4e-
Overall cell reaction:
2Pb + O2 2PbO
August, 2012 Using real-time portable atmospheric monitors Slide 14
Oxygen Sensor
Major
Components
of an Oxygen
Sensor
AIHCe 2012 – PDC 411 Page 8 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 15
Partial Pressure O2 vs. % Vol at
Varying Altitudes
Height
Atm.
Pressure
PO2
Con.
feet
meters
mmHg
mmHg
kPa
% Vol
16,000
4,810
421.8
88.4
11.8
20.9
10,000
3,050
529.7
111.0
14.8
20.9
5,000
1,525
636.1
133.3
17.8
20.9
3,000
915
683.3
143.3
19.1
20.9
1,000
305
733.6
153.7
20.5
20.9
0
0
760.0
159.2
21.2
20.9
19.5% O2 at sea level = 18 kPa
August, 2012 Using real-time portable atmospheric monitors Slide 16
Most O2 sensors have a “capillary pore” used to
allow sensor to self-stabilize at new pressure
• O2 sensors with capillary pore are
true percent by volume
measurement devices
• Are able to self stabilize to changes
in pressure due to:
• Barometric pressure
• Pressurized buildings
• Altitude
• Stabilization at new pressure is not
instantaneous, may take 30 seconds
or longer
Capillary pore (located
under external moisture
barrier filter)
AIHCe 2012 – PDC 411 Page 9 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 17
O2 sensor output
is affected by
temperature
Temperature
Ou
tpu
t %
re
lati
ve
to
ou
tpu
t a
t 2
0°
C
• Increasing temperature increases rate of detection reaction
• Readings automatically corrected by instrument
• Correction may not be fully linear outside manufacturer’s stated operating temperature range
• Stabilization at new temperature is not instantaneous, may take 30 seconds or longer
August, 2012 Using real-time portable atmospheric monitors Slide 18
Actual readings of instrument cycled from
+20°C to –20°C then back to +20°C
• While temperature
dropping O2 readings
slightly high
• Once stabilized at –20°,
readings return to 20.9%
• As chamber returned to
room temperature O2
readings slightly
depressed
• Once stabilized at room
temperature, O2 readings
return to 20.9%
• Other sensor readings
(LEL, CO, H2S) unaffected
by temperature
AIHCe 2012 – PDC 411 Page 10 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 19
O2 sensor response to 100% N2
• Instruments used to
measure very low O2
concentrations should
be calibrated at “Zero
Percent” O2 as well as
20.9% “Fresh Air”
concentration
• O2 sensors can take
two minutes or longer
to stabilize completely
in very low oxygen
• Make sure to wait until
sensor completely
stabilized before
noting reading!
“Two point” O2 sensor
calibration evaluates
performance both at 20.9%
and 0% oxygen
August, 2012 Using real-time portable atmospheric monitors Slide 20
O2 sensor response to 25% CO2 and 75% N2
AIHCe 2012 – PDC 411 Page 11 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 21
O2 sensor response to 18% O2, 4% CO2 and 78% N2
August, 2012 Using real-time portable atmospheric monitors Slide 22
O2 sensor response to 5% O2, 77% CO2 and 18% N2
AIHCe 2012 – PDC 411 Page 12 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 23
O2 sensor response to 6% O2 in CO2
August, 2012 Using real-time portable atmospheric monitors Slide 24
O2 Sensor Failure Mechanisms
Lower current output:
All available surface of Pb anode converted to PbO2
Electrolyte poisoned by exposure to contaminants
Electrolyte leakage
Desiccation
Blockage of capillary pore
Higher current output:
Short-term upward “ramping” readings due to cracks, tears or leaks
allowing O2 direct access to anode
Contraction of “bubbles” in electrolyte due to rapid temp change
Readings do not change:
Loss (reduction) in platinum content in current collector and / or sensing
electrode
Partial occlusion of capillary pore
Test sensor before each day’s use!
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August, 2012 Using real-time portable atmospheric monitors Slide 25
Oxygen Pump
(Lead Free) O2 Sensors
• European Union (EU) “Reduction of Hazardous
Substances” (ROHS) directive restricts use of
certain substances in new electronic equipment
• Pb, Cd, Hg, hexavalent chromium,
polybrominated biphenyls (PBB's), and
polybrominated diphenyl ethers (PBDE's)
• Lead containing “fuel cell” sensors specifically
excluded (for the time being)
• “Oxygen pump” sensors are lead-free alternative
to fuel cell sensors
August, 2012 Using real-time portable atmospheric monitors Slide 26
Oxygen Pump
Detection Principle
• Oxygen passively diffuses into polymer (catalyst)
substrate
• Power from instrument battery used to “pump” the
oxygen back out
• Reactions: Oxidation / Reduction of target gas by
catalyst
Sensing: O2 + 4H+ + 4e- 2 H2O
Counter: 2 H2O O2 + 4H+ + 4e-
• Oxygen generated on counter electrode
• Amount electricity required to remove reaction
product and return sensor to ground state (by
generating O2 at counter electrode) proportional to
concentration of oxygen present
AIHCe 2012 – PDC 411 Page 14 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 27
Oxygen Pump Sensor
Advantages and disadvantages
• Advantages:
• Non-consuming detection technique (sensor
does not lose sensitivity or consume itself
over time)
• Disadvantages / concerns:
• Detection reaction may be influenced by
shifts in humidity
• Sensor is net consumer of electricity (drain
on power supply)
• Important to ensure that reaction product
(H2O) is removed from sensor
August, 2012 Using real-time portable atmospheric monitors Slide 28
Explosive or Flammable
Atmospheres
AIHCe 2012 – PDC 411 Page 15 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 29
Fire Tetrahedron
Oxygen
Chain reaction
Fuel
Source of ignition
August, 2012 Using real-time portable atmospheric monitors Slide 30
Explosive limits
• Lower Explosive Limit (LEL):
• Minimum concentration of a
combustible gas or vapor in air
which will ignite if a source of
ignition is present
• Upper Explosive Limit (UEL):
• Most but not all combustible gases
have an upper explosive limit
• Maximum concentration in air
which will support combustion
• Concentrations which are above
the UEL are too “rich” to burn
Above UEL
mixture too rich
to burn
Below LEL
mixture too lean
to burn
Flammable
range
AIHCe 2012 – PDC 411 Page 16 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 31
Flammability Range
• The range between the LEL and the UEL of
a combustible gas or vapor
• Concentrations within the flammable
range will burn or explode if a source of
ignition is present
LEL
Gas Concentration
Flammability
Range
UEL
August, 2012 Using real-time portable atmospheric monitors Slide 32
Fuel Gas LEL (%VOL) UEL (%VOL)
Acetylene 2.2 85
Ammonia 15 28
Benzene 1.3 7.1
Butane 1.8 8.4
Carbon Monoxide 12 75
Ethylene 2.7 36
Ethylene oxide 3.0 100
Ethyl Alcohol 3.3 19
Fuel Oil #1 (Diesel) 0.7 5
Hydrogen 4 75
Isobutylene 1.8 9
Isopropyl Alcohol 2 12
Gasoline 1.4 7.6
Kerosine 0.7 5
Methane 5 15
MEK 1.8 10
Hexane 1.1 7.5
Pentane 1.5 7.8
Propane 2.1 10.1
Toluene 1.2 7.1
p-Xylene 1.1 7.0
Different gases have
different flammability
ranges
Gas Concentration
LEL UEL
Flammability
Range
AIHCe 2012 – PDC 411 Page 17 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 33
Explosive Limits
Lower Explosive
Limit
Flammable range
2.2 – 9.0%
Upper Explosive
Limit
Propane
• Propane (C3H8)
1
4
0
August, 2012 Using real-time portable atmospheric monitors Slide 34
Explosive Limits
Lower Explosive
Limit
Flammable range
5.0 – 15.0%
Upper Explosive
Limit
Methane
• Methane (CH4)
1
4
0
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August, 2012 Using real-time portable atmospheric monitors Slide 35
Explosive Limits
Lower Explosive
Limit
Flammable range
2.3 – 100.0%
Acetylene
• Acetylene (C2H4) has no
Upper Explosion Limit!
1
4
0
August, 2012 Using real-time portable atmospheric monitors Slide 36
Vapor density
• Measure of a vapor’s weight compared to air
• Gases lighter than air tend to rise; gases
heavier than air tend to sink
Lighter than air
Propane Hydrogen sulfide Carbon dioxide Gasoline
Heavier than air
Carbon monoxide
Hydrogen
Ammonia
Methane
AIHCe 2012 – PDC 411 Page 19 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 37
Stratification
• Atmospheric hazards in confined
spaces form layers
• Depending on their weights gases
could be at the bottom, middle or top
of a given space
• The only safe way to test the
atmosphere of a vessel is to sample
all levels at 4 foot intervals with
properly calibrated instruments
August, 2012 Using real-time portable atmospheric monitors Slide 38
Catalytic “Hot Bead” Combustible Sensor
• Detects
combustible gas
by catalytic
oxidation
• When exposed to
gas oxidation
reaction causes
the active
(detector) bead to
heat
• Requires oxygen
to detect gas!
D.C. voltage supply
Output - +
+
-
Compensator
Detector
Signal
Trimming resistor
R1
R2
VR1
+VS
-VS
AIHCe 2012 – PDC 411 Page 20 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 39
Combustible Gas Sensor
• The catalyst in the LEL sensor bead can be harmed if it is exposed to certain substances
• LEL sensor poisons permanently reduce or destroy the sensor’s response to gas
• The most common LEL sensor poisons are silicon containing vapors (like the silicones used in Armour All)
• Sensors which may have been exposed to a poison must be tested before further use
Platinum
wire coil
Porous
refractory
bead with
catalyst
0.1 mm
August, 2012 Using real-time portable atmospheric monitors Slide 40
Stainless steel
housing
Flame arrestor
(sinter)
Traditional LEL sensors are
“Flame proof” devices
• Flame proof sensors depend on
physical barriers such as stainless
steel housings and flame arrestors to
limit the amount of energy that can
ever be released by the sensor
• The flame arrestor can slow, reduce,
or even prevent larger molecules from
entering the sensor
• The larger the molecule, the slower it
diffuses through the flame arrestor
into the sensor
AIHCe 2012 – PDC 411 Page 21 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 41
Catalytic Sensor Structure
August, 2012 Using real-time portable atmospheric monitors Slide 42
Typical carbon number distribution
in No. 2 Diesel Fuel (liquid)
Less than 2% of
total diesel
molecules small
enough to be
measured by
means of standard
LEL sensor
AIHCe 2012 – PDC 411 Page 22 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 43
Vaporization is a
function of temperature
• Vapors are the gaseous state of
substances that are either
liquids or solids at room
temperatures
• Gasoline evaporates
• Dry ice (solid carbon
dioxide) sublimates
• Increasing the temperature of
the combustible liquid
increases the amount of vapor
produced
August, 2012 Using real-time portable atmospheric monitors Slide 44
Flashpoint Temperature
Temperature at which a combustible liquid gives off enough vapor to form an ignitable mixture
38 - 88 °C 100 - 190 °F Diesel oil
17 °C 62 °F Ethanol (96 %)
- 4 °C 24 °F Methyl ethyl ketone
- 18 °C 0 °F Acetone
- 45 °C (approx.) - 50 °F (approx.) Gasoline
(aviation grade)
Degrees C Degrees F
AIHCe 2012 – PDC 411 Page 23 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 45
Flammable and combustible liquid
classifications (OSHA 29 CFR 1910.106)
Flash Point
Temp °F
Boiling
Point °F
Examples
Class IA flammable
liquid
Below 73 °F
Below
100 °F
Methyl ethyl ether
Pentane
Petroleum ether
Class IB flammable
liquid
Below 73 °F
Above
100 °F
Acetone
Ethanol
Gasoline
Methanol
Class IC flammable
liquid
At or above
73 °F
Below
100 °F
Styrene
Turpentine
Xylene
Class II combustible
liquid
At or above
100 °F
Below
140 °F
Fuel oil no. 44 (Diesel)
Mineral spirits
Kerosene
Class IIIA
combustible liquid
At or above
140 °F
Below
200 °F
Aniline
Carbolic acid
Phenol
Naphthalenes
Pine oil
Class IIIB
combustible liquid
At or above
200 °F
August, 2012 Using real-time portable atmospheric monitors Slide 46
Typical catalytic LEL sensor
relative responses
Relative responses of 4P-75 catalytic LEL sensor
Combustible gas / vapor
Relative response when sensor calibrated on pentane
Relative response when sensor calibrated on propane
Relative response when sensor calibrated on methane
Hydrogen 2.2 1.7 1.1
Methane 2.0 1.5 1.0 Propane 1.3 1.0 0.7 n-Butane 1.2 0.9 0.6 n-Pentane 1.0 0.8 0.5 n-Hexane 0.9 0.7 0.5 n-Octane 0.8 0.6 0.4 Methanol 2.3 1.8 1.2 Ethanol 1.6 1.2 0.8 Isopropanol 1.4 1.1 0.7 Acetone 1.4 1.1 0.7 Ammonia 2.6 2.0 1.3 Toluene 0.7 0.5 0.4 Gasoline (unleaded) 1.2 0.9 0.6
AIHCe 2012 – PDC 411 Page 24 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 47
Catalytic pellistor combustible gas response curves
Reading % LEL
True LEL Concentration
August, 2012 Using real-time portable atmospheric monitors Slide 48
Correction Factors
Correction factor is the reciprocal of the relative response
The relative response of 4P-75 LEL sensor (methane
scale) to ethanol is 0.8
Multiplying the instrument reading by the correction factor
for ethanol provides the true concentration
Given a correction factor for ethanol of 1.25, and an
instrument reading of 40 per cent LEL, the true
concentration would be calculated as:
40 % LEL X 1.25 = 50 % LEL
Instrument Correction True
Reading Factor Concentration
AIHCe 2012 – PDC 411 Page 25 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 49
Catalytic combustible LEL
sensor correction factors
Correction factors for 4P-75 catalytic LEL sensor
Combustible gas / vapor Relative response when sensor calibrated on pentane
Relative response when sensor calibrated on propane
Relative response when sensor calibrated on methane
Hydrogen 0.45 0.59 0.91
Methane 0.50 0.67 1.00
Propane 0.77 1.00 1.54
n-Butane 0.83 1.11 1.67
n-Pentane 1.00 1.33 2.00
n-Hexane 1.11 1.43 2.22
n-Octane 1.25 1.67 2.50
Methanol 0.43 0.57 0.87
Ethanol 0.63 0.83 1.25
Isopropanol 0.71 0.95 1.43
Acetone 0.71 0.95 1.43
Ammonia 0.38 0.50 0.77
Toluene 1.43 2.00 2.86
Gasoline (unleaded) 0.83 1.11 1.67
August, 2012 Using real-time portable atmospheric monitors Slide 50
According to Preamble to
OSHA 1910.146
• A combustible hazard exists whenever the
combustible gas concentration exceeds 10% LEL
• This is the general hazardous condition threshold,
NOT the concentration that should always be used for
the LEL alarm set-point
• According to the original preamble to 1910.146, if
Alternate Entry Procedures are used, the hazard
condition threshold is 5% LEL
• In some cases it may be necessary to use an even
lower alarm setting to allow workers adequate time to
escape
AIHCe 2012 – PDC 411 Page 26 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 51
Using a lower alarm setting minimizes effect of relative response on readings
CH4 response
new sensor
Response to nonane
Propane
response
True LEL Concentration
50% LEL
Instrument
Reading
20% LEL
10% LEL
5% LEL
August, 2012 Using real-time portable atmospheric monitors Slide 52
Typical catalytic percent LEL sensor response to
50% LEL methane (2.5% vol. CH4)
AIHCe 2012 – PDC 411 Page 27 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 53
Typical catalytic percent LEL sensor response
to 50% LEL pentane (0.7% vol. C5H12)
August, 2012 Using real-time portable atmospheric monitors Slide 54
Catalytic combustible sensor
exposed to various gases
AIHCe 2012 – PDC 411 Page 28 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 55
CC Combustible Sensor t90 Response Versus
Molecular Weight (g/mol-1) of Various Target Gases
August, 2012 Using real-time portable atmospheric monitors Slide 56
Catalytic combustible sensor relative response
inversely proportional to molecular weight of target gas
AIHCe 2012 – PDC 411 Page 29 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 57
Response to methane over life of sensor
• Relative response to
methane may change
substantially over life
of sensor
CH4 response
new sensor
CH4 response partially
poisoned sensor
Propane
response
August, 2012 Using real-time portable atmospheric monitors Slide 58
Combustible Gas /
Vapor
Relative response
when sensor is
calibrated to 2.5%
(50% LEL) methane
Concentration of
methane used for
equivalent 50% LEL
response
Hydrogen
1.1
2.75% CH4
Methane
1.0
2.5% Vol CH4
Ethanol
0.8
2.0% Vol CH4
Acetone
0.7
1.75% Vol CH4
Propane
0.65
1.62% Vol CH4
n-Pentane
0.5
1.25% Vol CH4
n-Hexane
0.45
1.12% Vol CH4
n-Octane
0.4
1.0% Vol CH4
Toluene
0.35
0.88% Vol CH4
Methane based equivalent
calibration gas mixtures
AIHCe 2012 – PDC 411 Page 30 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 59
CC LEL sensor response to 50% LEL methane ( 2.5% vol. CH4), 50% LEL pentane
(7.0% vol. C5H12) and 50% LEL "pentane equivalent" (1.25% vol. CH4)
August, 2012 Using real-time portable atmospheric monitors Slide 60
Combustible sensor limitations
Contaminant
LEL (Vol %)
Flashpoint
Temp (ºF)
OSHA PEL
NIOSH REL
TLV
5% LEL in
PPM
Acetone
2.5%
-4ºF
(-20 ºC)
1,000 PPM
TWA
250 PPM
TWA
500 PPM
TWA;
750 PPM
STEL
1250 PPM
Diesel (No.2)
vapor
0.6%
125ºF
(51.7ºC)
None Listed
None Listed
15 PPM
300 PPM
Ethanol
3.3%
55ºF
(12.8 ºC)
1,000 PPM
TWA
1000 PPM
TWA
1000 PPM
TWA
1,650 PPM
Gasoline
1.3%
-50ºF
(-45.6ºC)
None Listed
None Listed
300 PPM
TWA; 500
PPM STEL
650 PPM
n-Hexane
1.1%
-7ºF
(-21.7 ºC)
500 PPM TWA
50 PPM
TWA
50 PPM TWA
550 PPM
Isopropyl
alcohol
2.0%
53ºF
(11.7ºC)
400 PPM
TWA
400 PPM
TWA; 500
PPM STEL
200 PPM
TWA; 400
PPM STEL
1000 PPM
Kerosene/
Jet Fuels
0.7%
100 – 162ºF
(37.8 – 72.3ºC )
None Listed
100 mg/M3
TWA (approx.
14.4 PPM)
200 mg/M3
TWA (approx.
29 PPM)
350 PPM
MEK
1.4%
16ºF
(-8.9ºC)
200 PPM
TWA
200 PPM
TWA; 300
PPM STEL
200 PPM
TWA; 300
PPM STEL
700 PPM
Turpentine
0.8
95ºF
(35ºC)
100 PPM
TWA
100 PPM
TWA
20 PPM TWA
400 PPM
Xylenes (o, m
& p isomers)
0.9 – 1.1%
81 – 90ºF
(27.3 – 32.3 ºC)
100 PPM
TWA
100 PPM
TWA; 150
PPM STEL
100 PPM
TWA; 150
STEL
450 – 550
PPM
AIHCe 2012 – PDC 411 Page 31 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 61
C1 – C4 Aliphatic
Hydrocarbon Gases
• TLV® officially adopted in 2004
• Specifies toxic exposure limit
(8 hour TWA) for methane,
ethane, propane and butane of
1,000 ppm
• Has the force of law in many
jurisdictions in the United
States and Canada
August, 2012 Using real-time portable atmospheric monitors Slide 62
C1 – C4 Monitoring Strategy
• Choosing a pentane level of sensitivity and 4% LEL alarm setting
ensures C1 – C4 TLV concentration is never exceeded
• For methane the alarm is activated at exactly at the 1,000 PPM limit
• For ethane, propane and butane the alarm is activated before the
concentration reaches the 1,000 ppm limit
• The 4% alarm activated by:
• Approximately 1,000 ppm methane
• Approximately 816 ppm ethane
• Approximately 667 ppm propane
• Approximately 635 ppm butane
• An added bonus: At 4% the alarm is also activated at the TLV for
pentane (600 ppm)
AIHCe 2012 – PDC 411 Page 32 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 63
Effects of O2 concentration
on combustible gas readings
• Look at O2 readings first!
• LEL readings may be affected if
levels of O2 are higher or lower
than fresh air
• Catalytic LEL sensors require a
minimum level of 10% oxygen to
read LEL
• If the O2 concentration is too low
the LEL reading should be
replaced with question marks
Readings in
fresh air
Readings when O2 too
low for LEL sensor
Readings in O2
deficient air
August, 2012 Using real-time portable atmospheric monitors Slide 64
Effects of high concentrations
of gas on LEL sensor
• When doing atmospheric
testing we are only concerned
with the LEL. Why is that?
• Work is not permitted in areas where the concentration of gas exceeds safety limits!
• If the explosive gas concentration is too high there may not be enough oxygen for the LEL sensor to detect properly
• Concentrations above 100% LEL can damage the LEL sensor
Readings in
fresh air
High (“Alarm 2”)
at 20% LEL
Initial alarm at
10% LEL
High (“Alarm 3”)
at 50% LEL
Over-limit alarm
(arrows) at
100% LEL
AIHCe 2012 – PDC 411 Page 33 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 65
Response of electrochemical and LEL
sensor to 20,000 ppm hydrogen in nitrogen
August, 2012 Using real-time portable atmospheric monitors Slide 66
Combustible
sensor poisons
• Combustible sensor poisons:
• Silicones (by far the most virulent poison)
• Hydrogen sulfide
Note: The LEL sensor includes an internal filter that is more than
sufficient to remove the H2S in calibration gas. It takes very high
levels of H2S to overcome the filter and harm the LEL sensor
• Other sulfur containing compounds
• Phosphates and phosphorus containing substances
• Lead containing compounds (especially tetraethyl lead)
• High concentrations of flammable gas!
• Combustible sensor inhibitors:
• Halogenated hydrocarbons (Freons, trichloroethylene, methylene
chloride, etc.)
AIHCe 2012 – PDC 411 Page 34 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 67
Effects of H2S on
combustible gas sensors
H2S affects sensor as inhibitor AND as poison
Some byproducts of oxidation of H2S left as deposit on
active bead that depresses gas readings while inhibitor
is present
Sensor generally recovers most of original response
once it is returned to fresh air
H2S functions as inhibitor BUT byproducts of catalytic
oxidation become very corrosive if they build up on active
bead in sensor
Corrosive effect can rapidly (and permanently) damage
bead if not “cooked off” fast enough
How efficiently bead “cooks off” contaminants is
function of:
Temperature at which bead is operated
Size of the bead
Whether bead under continuous power versus
pulsing the power rapidly on and off to save
operating energy
4
4 0
August, 2012 Using real-time portable atmospheric monitors Slide 68
“Silicone resistant” vs. “standard”
pellistor type LEL sensors
"Silicone resistant" combustible
sensors have an external silicone
filter capable of removing most
silicone vapor before it can diffuse
into the sensor
Silicone vapor is the most virulent
of all combustible sensor poisons
Filter also slows or slightly
reduces response to heavier
hydrocarbons such as hexane,
benzene, toluene, xylene, cumene,
etc.
The heavier the compound, the
greater the effect on response
(should not be used on C8 – C9
hydrocarbons)
AIHCe 2012 – PDC 411 Page 35 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 69
Effects of hexamethyldisiloxane
(HMDS) on pellistor sensor
August, 2012 Using real-time portable atmospheric monitors Slide 70
Low-power pellistor issues
• Volume of pellistor bead (a sphere): V = 4/3 π r3
• Since most catalyst sites are within the bead (not on the surface of the bead), when you decease the radius of the bead by “x”, you reduce the volume of the bead (and number of catalyst sites) by “x” to the third power ( x3 )
• So, smaller low power LEL sensors are much easier to poison.
AIHCe 2012 – PDC 411 Page 36 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 71
• Allow enough time for full stabilization prior to
performing fresh air zero
– DO NOT PERFORM AUTO ZERO AS PART
OF AUTOMATIC START-UP SEQUENCE
• Perform functional test before each day’s use!
• Use methane based test gas mixture OR if you
use a different gas (e.g. propane or pentane)
challenge the sensor with methane periodically
to verify whether the sensor has
disproportionately lost sensitivity to methane
Low-power pellistor advice
August, 2012 Using real-time portable atmospheric monitors Slide 72
Non-dispersive infrared
(NDIR) sensors
• Many gases absorb infrared
light at a unique wavelength
(color)
• In NDIR sensors the amount of
IR light absorbed is
proportional to the amount of
target gas present
• The longer the optical path
through the sensor the better
the resolution
AIHCe 2012 – PDC 411 Page 37 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 73
Infrared Detectors
• When infra-red radiation passes through a sensing
chamber containing a specific contaminant, only those
frequencies that match one of the vibration modes are
absorbed
• The rest of the light is transmitted through the chamber
without hindrance
• The presence of a particular chemical group within a
molecule thus gives rise to characteristic absorption
bands
August, 2012 Using real-time portable atmospheric monitors Slide 74
2000 2500 3000 3500 4000 4500
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
1,1
1,2
Wellenlänge [nm]
Tra
nsm
issio
n
2000 2500 3000 3500 4000 4500
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
1,1
Wellenlänge [nm]
Tra
nsm
issio
n
2000 2500 3000 3500 4000 4500
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
1,1
Wellenlänge [nm]
Tra
nsm
issio
n
Gas absorption
spectra
Methane CH4
T
l [nm]
Propane C3H8
Water H2O
Carbon dioxide CO2
Infrared absorption spectra
for several gases
AIHCe 2012 – PDC 411 Page 38 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 75
Infrared Detectors
• NDIR sensors measure absorbance at
specific wavelength to determine
concentration of target gas
• NDIR sensor consists of:
• Infrared emitter
• Optical filters that limit IR source
to specific infrared wavelength
range
• Optical chamber
• Pyroelectric detectors (active and
reference)
August, 2012 Using real-time portable atmospheric monitors Slide 76
• Optical path can be longer than it looks from the outside of sensor
• Optimal pathlength may be different for different gases
Light path through
NDIR sensor
AIHCe 2012 – PDC 411 Page 39 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 77
• LEL: 3.3 μm
• CO2: 4.3μm
• Ref: 4.0μm
2000 2500 3000 3500 4000 4500
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
1,1
Wellenlänge [nm]
Tra
nsm
issio
n
T
l [nm]
3.3μm 4.0 μm 4.3 μm
Wavelengths
typically used for
NDIR
measurement
August, 2012 Using real-time portable atmospheric monitors Slide 78
Requirements for IR
Absorption
• CO2 and CH4 as well as most other combustible
gases absorb IR
• Hydrogen gas ( H2 ) DOES NOT absorb IR
• While acetylene absorbs IR, it is also effectively
undetectable at 3.3 μm
• Also IR-transparent:
• N2
• O2
• F2
• Cl2
• Hg2
• Ar
AIHCe 2012 – PDC 411 Page 40 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 79
Nonlinear Molecules
Linear molecules: SO
S O
Symmetric Asymmetric Bend
Stretch Stretch
Must have a COVALENT CHEMICAL BOND
Energy Absorbed by “Bond
Stretching” and “Bending” Vibration
August, 2012 Using real-time portable atmospheric monitors Slide 80
Infrared Spectroscopy
• Geometry of molecule and absorbance of light by specific
bonds gives rise to a characteristic IR absorbance
“fingerprint” of molecule
AIHCe 2012 – PDC 411 Page 41 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 81
Relative response of pellistor and
infrared sensors to n-Hexane
• Both sensors were
calibrated to 50%
LEL methane
• Uncorrected
readings for the
pellistor LEL
sensor much
lower than the true
concentration
• Uncorrected
readings for the IR
sensor more than
twice as high as
the true
concentration
50% LEL n-Hexane
August, 2012 Using real-time portable atmospheric monitors Slide 82
Response of calibrated pellistor and IR
sensors to 50% LEL n-Hexane
• Both sensors were
calibrated to 50% LEL
n-Hexane
• Readings for both
sensors are now very
close to the true 50%
LEL concentration
• Initial response of IR
sensor is slightly
quicker than the
pellistor sensor
• However, the time to
the final stable
response (T100) is
virtually identical for
both sensors, (about
150 seconds)
50% LEL n-Hexane
AIHCe 2012 – PDC 411 Page 42 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 83
Linearized NDIR combustible
gas response curves
August, 2012 Using real-time portable atmospheric monitors Slide 84
• Shape of raw NDIR
CH4 curve (at 3.33 μm)
is less linear than
other detectable
gases
• CH4 curve can be
mathematically
corrected
(normalized) against
the response curves
of other gases of
interest
Response of NDIR LEL sensor (3.33 μm, 44
mm path) to various target gases
AIHCe 2012 – PDC 411 Page 43 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 85
• When CH4 is present, direct calibration to
methane is the most conservative approach
• Calibration to CH4 generally overestimates
uncorrected readings for other aliphatic
hydrocarbons; the higher the concentration
the greater the overestimation
• Calibration to other aliphatic hydrocarbons
(such as propane or hexane)
underestimates uncorrected readings for
methane;
• However, readings can be automatically
corrected by choosing response curve from
on-board library
• When other aliphatics are present,
calibration to propane provides the most
accurate response
0
10
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100D
isp
lay [
%L
EL
C3H
8 ]
Concentration [%UEG]
MK231-5 C3H8-Range and CH4-Response
Cal-gas C3H8Testgas CH4
0
20
40
60
80
100
0 10 20 30 40 50 60 70 80 90 100
Dis
pla
y [
%L
EL
CH
4 ]
Concentration [%LEL]
MK231-5 CH4-Range and C3H8-Response
Cal-Gas CH4Testgas…
NDIR sensor
performance
August, 2012 Using real-time portable atmospheric monitors Slide 86
Toxic Gases and Vapors
AIHCe 2012 – PDC 411 Page 44 of 98
PDC 411: Exposure Assessment Chemical Detection in Real Time Slide 87
Common causes
of toxic gases
• Materials or chemicals
stored in the work area or
space
• Compounds absorbed or
present in structures or
soils of work area or space
• Contents being disturbed
upon entry
• Work being performed
• Decomposing materials
• Adjacent areas
August, 2012 Using real-time portable atmospheric monitors Slide 88
Toxic Exposure
Limits
• Toxic exposure limits are
defined by means of:
• 8-hour TWA
• 15-minute STEL
• Ceiling
• The exposure limit for
a particular contaminant
may include more than
one part
AIHCe 2012 – PDC 411 Page 45 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 89
Meaning of parts-per-million (ppm)
• 100% by volume = 1,000,000 ppm
• 1% by volume = 10,000 ppm
• 1.0 ppm the same as:
• One centimeter in 10
kilometers
• One minute in two years
• One cent in $10,000
August, 2012 Using real-time portable atmospheric monitors Slide 90
USA Permissible
Exposure Limit (PEL)
• Determined by the United States
Occupational Safety and Health
Administration (OSHA)
• Sets limits for legal unprotected
worker exposure to a listed toxic
substance
• Force of law in USA!
• Individual states free to enact stricter,
but never less conservative limits
• Given in “Parts-per-Million” (ppm)
concentrations
• 1 % = 10,000 ppm
AIHCe 2012 – PDC 411 Page 46 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 91
• Determined by USA National
Institute of Occupational Safety
and Health (NIOSH)
• Guidelines for control of
potential health hazards
• Usually more conservative than
Federal OSHA exposure limits
• Intended as recommendation but
incorporated by adoption in
many states with OSHA
approved safety and health
plans
• Force of law in these states
NIOSH Recommended
Exposure Limit (REL)
August, 2012 Using real-time portable atmospheric monitors Slide 92
TLV® Toxic Exposure Limits
• Threshold Limit Values (TLVs®) are
published by the American Conference of
Governmental Industrial Hygienists (ACGIH)
• TLVs® are the maximum concentrations to
which workers may be repeatedly exposed,
day after day, over a working lifetime,
without adverse health effects
• TLVs® are usually more conservative than
USA OSHA Permissible Exposure Limits
(PELs) or NIOSH Recommended Exposure
Limits (RELs)
AIHCe 2012 – PDC 411 Page 47 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 93
Toxic Exposure Limit
Terms: TWA
• TWA: The Time Weighted
Average (TWA) is the
exposure averaged over a full
8-hour shift
• When the monitoring session
is less than eight hours, the
TWA is projected for the full
8-hour shift
• When monitoring session
more than 8 hours, the TWA
limit is calculated on an
“equivalent” 8-hour shift
basis
August, 2012 Using real-time portable atmospheric monitors Slide 94
TWA is
Projected Value
According to OSHA cumulative TWA exposures for an eight
hour work shift are calculated as follows:
E = (Ca Ta + CbTb + .... CnTn ) / 8
Where:
• E is the equivalent exposure for the eight hour
working shift
• C is the concentration during any period of time
T where the concentration remains constant
• T is the duration in hours of the exposure at
concentration C
AIHCe 2012 – PDC 411 Page 48 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 95
Toxic Exposure
Limit Terms: STEL
• Some gases and
vapors (like CO and
H2S) have an
allowable maximum
Short Term Exposure
Limit (STEL) which is
higher than the 8-hour
TWA
• The STEL is the
maximum average
concentration to
which an unprotected
worker may be
exposed during any
15-minute interval
The average concentration may never
exceed the STEL during any 15-minute
interval
Any 15-minute interval where the average
concentration is higher than the TWA (but
less than the STEL) must be separated by
at least 1-hour from the next, with a
maximum of 4 times a shift
August, 2012 Using real-time portable atmospheric monitors Slide 96
Ceiling Limit
• Ceiling is the maximum
concentration to which an
unprotected worker may be
exposed
• Ceiling concentration should
never be exceeded even for
an instant
• The “Low Peak” and “High
Peak” alarms in most portable
instruments are activated
whenever the concentration
exceeds the alarm setting for
even a moment
AIHCe 2012 – PDC 411 Page 49 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 97
Immediately Dangerous to Life and Health
• IDLH is not part of PEL
• IDLH is maximum concentration from which it is
possible for an unprotected worker to escape
without suffering injury or irreversible health
effects during a maximum 30-minute exposure
• Primarily used to define the level and type of
respiratory protection required
• Unprotected workers may NEVER be deliberately
exposed to IDLH or ANY concentrations which
exceed the PEL
August, 2012 Using real-time portable atmospheric monitors Slide 98
Exposure limits
for ammonia
Federal
USA OSHA
PEL
8-Hr
TWA
STEL
Ceiling
50
NA
NA
State OSHA
(1989) PEL
(NIOSH REL)
25
ppm
35
ppm
NA
TLV
25
ppm
35
ppm
NA
AIHCe 2012 – PDC 411 Page 50 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 99
How are these calculations affected
by the choice of datalogging interval?
• They’re not!
• PEL calculations are continuously updated
by the instrument
• The datalogging interval simply specifies
how often the instrument stores a “snap
shot” of the current readings for the
purposes of generating a printed report or
database file of test results
August, 2012 Using real-time portable atmospheric monitors Slide 100
Substance-specific
electrochemical (EC) sensors
• More types of
sensors available
every year, both for
individual toxic
gases as well as
sensors designed to
detect a range of
toxic or combustible
gases
AIHCe 2012 – PDC 411 Page 51 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 101
Substance-specific electrochemical sensors
• Gas diffusing into sensor reacts at surface of the sensing electrode
• Sensing electrode made to catalyze a specific reaction
• Use of selective external filters further limits cross sensitivity
August, 2012 Using real-time portable atmospheric monitors Slide 102
Typical Electrochemical
Detection Mechanism
H2S Sensor:
Hydrogen sulfide is oxidized at the sensing electrode:
H2S + 4H2O H2 SO4 + 8H+ + 8e-
The counter electrode acts to balance out the reaction at the sensing electrode by reducing oxygen present in the air to water:
2O2 + 8H+ + 8e- 4H2O
And the overall reaction is: H2S + 2O2 H2 SO4
4HS Signal Output: 0.7 A / ppm H2S
AIHCe 2012 – PDC 411 Page 52 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 103
Electrochemical Sensor Performance
August, 2012 Using real-time portable atmospheric monitors Slide 104
Effects of
humidity on
EC sensors
• Sudden changes in
humidity can cause
"transientys" in
readings
• Sensor generally
stabilizes rapidly
• Avoid breathing into
sensor or touching
with sweaty hand
AIHCe 2012 – PDC 411 Page 53 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 105
Major Components
of Electrochemical
H2S Sensor
August, 2012 Using real-time portable atmospheric monitors Slide 106
Cross sensitivities of Sensoric HCN 2E
30 F hydrogen cyanide sensor at 20°C
Relative responses of Sensoric HCN 2E-30F hydrogen cyanide (HCN) sensor at 20°C
Gas Concentration Reading (ppm)
Alcohols 1000 ppm 0 Ammonia 100 ppm 0 Arsine 0.2 ppm 1 Carbon dioxide 5000 ppm 0 Carbon monoxide 100 ppm 1 Chlorine 1.0 ppm 0 Diborane 0.25 ppm 0.4 Hydrocarbons 1000 ppm 0 Hydrochloric acid 5 ppm 0 Hydrogen 10000 ppm 0 Hydrogen sulfide 10 ppm 0¹ Nitric oxide 100 ppm 0 Nitrogen 100% 0 Nitrogen dioxide 10 ppm -19 Ozone 0.25 ppm 0 Sulfur dioxide 20 ppm 0.04 1) Short gas exposure in minute range; after filter saturation: ca. 40 ppm reading.
AIHCe 2012 – PDC 411 Page 54 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 107
PID, CC LEL, IR LEL and CO sensors exposed
to 50% LEL acetylene (1.25% volume)
August, 2012 Using real-time portable atmospheric monitors Slide 108
CO and LEL sensor response to 500 ppm
(2.0% LEL) acetylene in air
Co
ncen
trati
on
(%
LE
L)
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
Important notes:
1. 500 ppm acetylene = 2.0% LEL
2. Sensitivity of LEL sensor set to
hexane scale
AIHCe 2012 – PDC 411 Page 55 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 109
Response of PID and CO channel of COSH
sensor to 100 ppm isobutylene (C4H8)
August, 2012 Using real-time portable atmospheric monitors Slide 110
Effects of hydrogen on
CO sensor readings
AIHCe 2012 – PDC 411 Page 56 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 111
Effects of hydrogen on
CO sensor readings
August, 2012 Using real-time portable atmospheric monitors Slide 112
Characteristics of
Hydrogen Sulfide
• Colorless
• Smells like “rotten eggs”
(at low concentrations)
• Heavier than air
• Corrosive
• Flammable (LEL is 4.3%)
• Soluble in water
• High concentrations kill
sense of smell
• Extremely toxic!
4
4 0
AIHCe 2012 – PDC 411 Page 57 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 113
Hydrogen Sulfide
• Produced by anaerobic
sulfate-reducing bacteria
• Especially associated with:
• Raw sewage
• Crude oil
• Marine sediments
• Tanneries
• Pulp and paper industry
August, 2012 Using real-time portable atmospheric monitors Slide 114
Toxic effects of H2S
Toxic effects of H2S
Concentration Symptoms
0.13 ppm Minimal detectable odor
4.6 ppm Easily detectable, moderate odour
10.0 ppm Beginning eye irritation.
27 ppm Strong unpleasant odor but not intolerable
100 ppm Coughing, eye irritation, loss of smell after 2-5 min
200 – 300 ppm Marked eye inflammation, rapid loss of smell, respiratory tract irritation, unconsciousness with prolonged exposure
500 – 700 ppm Loss of consciousness and possible death in 30 to 60 min
700 – 1,000 ppm Rapid unconsciousness, stopping or pausing of respiration and death
1,000 – 2,000 ppm
Immediate unconsciousness, death in a few minutes. Death may occur even if person is moved to fresh air
AIHCe 2012 – PDC 411 Page 58 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 115
Exposure limits for H2S
Federal USA OSHA PEL
8-Hour
TWA
STEL
Acceptable
Ceiling
Concentration
Acceptable Max Peak Above Ceiling
for an 8-Hour Shift
Concentration
Maximum Duration
NA
NA
20 ppm
50 ppm
10-minutes once only
if no other
measurable exposure
occurs during shift
REL
10 ppm
15 ppm
NA
TLV
(2010)
1.0 ppm 5.0 ppm
NA
NA
NA
NA
NA
DFG
MAK
10 ppm
20 ppm peak in any 10-min period,
(as momentary ceiling value),
maximum 4 per shift
NA
UK OEL
10 ppm
15 ppm
NA
NA
NA
FR VL
5 ppm
10 ppm
NA
NA
NA
August, 2012 Using real-time portable atmospheric monitors Slide 116
Are H2S sensors capable of
measuring at the new TLV limits?
• The answer is “Yes” BUT with
qualifications…..
• Some H2S sensors easily capable of providing
readings with 0.1 or 0.2 ppm resolution
• Instrument programming (firmware) must
permit setting the alarms at the desired
concentration
• May be necessary to update firmware or
replace older instrument with a newer model
• Dual channel COSH sensors used to measure
both CO and H2S have a smaller measurement
signal
• Depends on the manufacturer whether or not
the instrument can be used with alarms set to
the new TLV
4
4 0
AIHCe 2012 – PDC 411 Page 59 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 117
Exposure limits for H2S
4
4 0
• Old TLV:
• TWA = 10 ppm
• STEL = 15 ppm
• New TLV:
• TWA = 1.0 ppm
• STEL = 5.0 ppm
• Many instruments now
provide readings in 0.1
or 0.2 ppm increments
• Often possible to
update firmware in
existing instruments to
increase resolution
August, 2012 Using real-time portable atmospheric monitors Slide 118
Toxic effects H2S
AIHCe 2012 – PDC 411 Page 60 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 119
Where should practitioners who care
about the TLV set the alarms?
• TLV only includes STEL and TWA limits; does not
include a Ceiling or “Peak” limit
• GfG instruments have 4 user settable alarms
(Low, High, STEL and TWA)
• Many practitioners use the following approach:
• Low: 5.0 ppm
• High: 10.0 ppm
• STEL: 5.0 ppm
• TWA: 1.0 ppm
August, 2012 Using real-time portable atmospheric monitors Slide 120
Characteristics of
Carbon Monoxide
• Colorless
• Odorless
• Slightly lighter
than air
• By-product of
combustion
• Flammable (LEL
is 12.5%)
• Toxic!
2
4 0
AIHCe 2012 – PDC 411 Page 61 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 121
Carbon Monoxide
• Bonds to hemoglobin in red
blood cells
• Contaminated cells can’t
transport O2
• Chronic exposure at even
low levels harmful
August, 2012 Using real-time portable atmospheric monitors Slide 122
Toxic Effects CO
• Concentration of only
1,600 ppm fatal within
hours
• Even lower level
exposures can result in
death if there are
underlying medical
conditions, or when
there are additional
factors (such as heat
stress)
2
4 0
AIHCe 2012 – PDC 411 Page 62 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 123
Toxic effects of CO
Toxic effects of carbon monoxide
25 ppm TLV exposure limit for 8 hours (TWA)
200 ppm Possible mild frontal headaches in 2-3 hours
400 ppm Frontal headaches and nausea after 1-2 hours.
800 ppm Headache, dizziness and nausea in 45 min. Collapse and possibly death in 2 hours
1,600 ppm Headache and dizziness in 20 min. Unconsciousness and danger of death in 2 hours
3,200 ppm Headache and dizziness in 5-10 min. Unconsciousness and danger of death 30 min.
6,400 ppm Headache and dizziness in 1-2 min. Unconsciousness and danger of death 10-15 min
12,800 ppm Unconsciousness immediately, danger of death in 1-3 min.
August, 2012 Using real-time portable atmospheric monitors Slide 124
Exposure Limits for
Carbon Monoxide
• OSHA PEL:
• 50 ppm 8-hr. TWA
• NIOSH REL:
• 35 ppm 8-hr. TWA
• 200 ppm Ceiling
• TLV:
• 25 ppm 8-Hr. TWA
2
4 0
AIHCe 2012 – PDC 411 Page 63 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 125
Characteristics of SO2
• Colorless gas
• Irritating, pungent odor
• Heavier than air
• Reacts with H2O to
form sulfurous acid
• Respiratory irritant
• Toxic!
0
3 0
August, 2012 Using real-time portable atmospheric monitors Slide 126
Exposure limits for SO2
• OSHA PEL:
• TWA = 5.0 ppm
• NIOSH REL:
• TWA = 2.0 ppm
• STEL = 5.0 ppm
• Old TLV :
• TWA = 2 ppm
• STEL = 5 ppm
• New (2009) TLV:
• STEL = 0.25 ppm
0
3 0
AIHCe 2012 – PDC 411 Page 64 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 127
Exposure limits for SO2
• Suggested alarms:
• Low: 2.0 ppm
• High: 5.0 ppm
• STEL: 0.25
• TWA: 0.25 ppm 0
3 0
August, 2012 Using real-time portable atmospheric monitors Slide 128
Exposure limits for NO2
• Old TLV:
8 hr. TWA = 3 ppm
5 min. STEL = 5 ppm
• New 2012 TLV
8 hr. TWA = 0.2 ppm
• US OSHA PEL:
Ceiling = 5 ppm
• US NIOSH REL:
15 min. STEL = 1 ppm
0
3 0
OX
AIHCe 2012 – PDC 411 Page 65 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 129
Suggested alarm settings for NO2
• Suggested GfG alarms:
• Low: 3.0 ppm
• High: 5.0 ppm
• STEL: 1.0 ppm
• TWA: 0.2 ppm 0
3 0
OX
August, 2012 Using real-time portable atmospheric monitors Slide 130
Exposure limits for HCN
• US OSHA PEL:
TWA = 10 ppm
• US NIOSH REL:
15 min. STEL = 4.7 ppm
• TLV:
Ceiling = 4.7 ppm
4
4 1
AIHCe 2012 – PDC 411 Page 66 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 131
Exposure limits for NH3
• US OSHA PEL:
• TWA = 50 ppm
• US NIOSH REL:
• 8 hr. TWA = 25 ppm
• 15 min. STEL = 35
ppm
• TLV:
• 8 hr. TWA = 25 ppm
• 15 min. STEL = 35
ppm
1
3 0
August, 2012 Using real-time portable atmospheric monitors Slide 132
Characteristics of
Chlorine Dioxide (ClO2)
• Yellow to reddish gas
• Strong oxidizer
• Odor similar to chlorine
• Heavier than air
• Used in water treatment
and as bleaching agent
(pulp and paper)
• Extremely toxic!
0
3 4
OX
AIHCe 2012 – PDC 411 Page 67 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 133
Exposure limits for
Chlorine Dioxide (ClO2)
• OSHA PEL:
• 0.1 ppm (8-hr. TWA)
• NIOSH REL:
• 0.1 ppm (8-hr. TWA)
• 0.3 ppm STEL
• TLV:
• 0.1 ppm (8-hr. TWA)
• 0.3 ppm STEL
0
3 4
OX Remember: it only
takes 0.000001% by
volume to exceed
the exposure limit !!!
August, 2012 Using real-time portable atmospheric monitors Slide 134
Photoionization Detectors
• Used for measuring
solvent, fuel and VOC
vapors in the workplace
environment
AIHCe 2012 – PDC 411 Page 68 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 135
PID - Operating Principle
PIDs use ultraviolet light as source of energy to remove an
electron from neutrally charged target molecules creating
electrically charged fragments (ions)
This produces a flow of electrical current proportional to the
concentration of contaminant
The amount of energy needed to remove an electron from a
particular molecule is the ionization energy (or IE)
The energy must be greater than the IE in order for an
ionization detector to be able to detect a particular substance
August, 2012 Using real-time portable atmospheric monitors Slide 136
LEL vs. PID Sensors
Catalytic LEL and photoionization detectors
are complementary detection techniques
Catalytic LEL sensors excellent for
measurement of methane, propane, and other
common combustible gases NOT detectable
by PID
PIDs detect large VOC and hydrocarbon
molecules that are undetectable by catalytic
sensors
Best approach to VOC measurement is to use
multi-sensor instrument capable of measuring
all atmospheric hazards that may be
potentially present
AIHCe 2012 – PDC 411 Page 69 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 137
Detection sequence:
1. Neutrally charged
molecule diffuses
into glow zone
Operation of PID lamp, sensing
and counter electrodes
Reading
Counter
electrode
Sensing
electrode
Benzene
molecule
(neutrally
charged)
August, 2012 Using real-time portable atmospheric monitors Slide 138
Detection sequence:
2. Molecule is ionized
Operation of PID lamp, sensing
and counter electrodes
Reading
Counter
electrode
Sensing
electrode
Benzene
molecule is
ionized +
e-
AIHCe 2012 – PDC 411 Page 70 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 139
Detection sequence:
3. Free electron is
electrostatically
accelerated to
positively charged
sensing electrode
where it is counted
Operation of PID lamp, sensing
and counter electrodes
Reading
Counter
electrode
Sensing
electrode
Electron counted
at sensing
electrode +
e-
August, 2012 Using real-time portable atmospheric monitors Slide 140
Operation of PID lamp, sensing
and counter electrodes
Detection sequence:
4. Positively charged
fragment (ion) is
electrostatically
accelerated to
counter electrode,
where it picks up a
replacement
electron and
regains neutral
charge
Reading
Counter
electrode
Sensing
electrode
Neutrally charged
molecule diffuses
out of detector
e-
AIHCe 2012 – PDC 411 Page 71 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 141
How does a PID work?
August, 2012 Using real-time portable atmospheric monitors Slide 142
IE determines if the PID can detect the gas
If the IE of the gas is less than the eV output of the lamp the
PID can detectthe gas
Ionization Energy (IE) measures the bond strength of a gas
and does not correlate with the Correction Factor
Ionization Energies are found in the NIOSH Pocket Guide
and many chemical texts
Ionization Energy
AIHCe 2012 – PDC 411 Page 72 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 143
Ionization Energy Values
Ionization energy values
Gas / vapor Ionization energy (eV)
Carbon monoxide 14.01
Carbon dioxide 13.77
Methane 12.98
Water 12.59
Oxygen 12.08
Chlorine 11.48
Hydrogen sulfide 10.46
n-Hexane 10.18
Ammonia 10.16
hexane (mixed isomers) 10.13
acetone 9.69
benzene 9.25
butadiene 9.07
toluene 8.82
August, 2012 Using real-time portable atmospheric monitors Slide 144
PID Components
• Detector assembly
• Electrodes: sensing, counter and (in some designs) fence
• Lamp: most commonly 10.6EV, 11.7eV or 9.8 eV
AIHCe 2012 – PDC 411 Page 73 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 145
PID lamp characteristics
Window material and the filler gas
determine output characteristics as well as
operational life of lamp
PID lamp characteristics
Nominal lamp photon energies
Primary gas in lamp
Major emission lines
Relative intensity
Window crystal
Crystal transmittance λ range (nm)
eV λ (nm)
11.7 eV
Argon
11.83 104.8 1000 Lithium fluoride (LiF)
105 - 5000
11.62 106.7 500
10.6 eV
Krypton
10.64 116.5 200 Magnesium fluoride (MgF2)
115 - 7000
10.03 123.6 650
9.8 eV Krypton 10.03 123.6 650 Calcium fluoride (CaF2)
125 - 8000
August, 2012 Using real-time portable atmospheric monitors Slide 146
Critical PID Performance Issues:
Effects of Humidity and Contamination
• Condensation and contamination on lamp window
and sensor surfaces can create surface conduction
paths between sensing and counter electrodes
• Buildup of contamination provides nucleation
points for condensation, leading to surface
currents
• If present, surface currents cause false readings
and / or add significant noise that masks intended
measurement (sometimes called “moisture
leakage”)
• PID designs MAY require periodic cleaning of the
lamp and detector to minimize the effects of
contaminants and humidity condensation on PID
readings
AIHCe 2012 – PDC 411 Page 74 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 147
PID instruments are nonspecific
Cannot distinguish between different contaminants they are
able to detect
Provide single total reading for all detectable substances
present
PID readings always relative to gas used to calibrate
detector
August, 2012 Using real-time portable atmospheric monitors Slide 148
Correction factors are APPROXIMATE values
Correction Factor (CF) is measure of sensitivity of PID to
specific gas
CFs do not make PID specific to a chemical, only correct
the measurement scale to that chemical
CFs allow calibration on inexpensive, non-toxic
“surrogate” gas (like isobutylene)
Most manufacturers furnish tables, or built-in library of
CFs to correct or normalize readings when contaminant is
known
Instrument able to express readings in parts per million
equivalent concentrations for the contaminant measured
PID Correction Factors
AIHCe 2012 – PDC 411 Page 75 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 149
Low CF = high PID sensitivity to a gas
More toxic the gas, more desirable to have low correction factor:
If Exposure limit is < 10 ppm, CF should be < 1
If chemical less toxic, higher CF may be acceptable
If Exposure limit is > 10 ppm, CF < 10
When CF > 10 use PIDs as gross leak detectors only
High correction factor magnifies effects of humidity
effects, zero drift, and interfering gases and vapors
CF measures sensitivity
August, 2012 Using real-time portable atmospheric monitors Slide 150
Decision making 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
ONLY USE A CORRECTION FACTOR FROM THE MANUFACTURER
OF YOUR PID!
AIHCe 2012 – PDC 411 Page 76 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 151
Correction Factors (10.6 eV Lamp)
Examples of manufacturer PID correction factors (10.6 eV lamp) Gas / vapor RAE BW Ion GfG IE (eV)
Acetaldehyde 5.50 4.60 4.90 5.40 10.21
Acetone 1.10 0.90 0.70 1.20 9.69
Ammonia 9.70 10.60 8.50 9.40 10.20
Benzene 0.50 0.55 0.50 0.53 9.25
Butadiene 1.00 0.90 0.85 0.69 9.07
Diesel fuel 0.80 0.93 0.75 0.90 n/a
Ethanol 12.00 13.20 8.70 10.00 10.48
Ethylene 10.00 11.00 8.00 10.10 10.52
Gasoline 0.90 0.73 1.10 1.10 n/a
n-Hexane 4.30 4.00 3.30 4.50 10.18
Jet fuel (JP-8) 0.60 0.51 0.70 0.48 n/a
Kerosene n/a 1.11 0.80 n/a 9.53
Methyl-ethyl-ketone (MEK) 0.90 0.78 0.77 0.90 9.53
Naptha (iso-octane) 1.20 1.20 1.10 1.30 9.82
Styrene 0.40 0.45 0.45 0.40 8.47
Toluene 0.50 0.53 0.51 0.53 8.82
Turpentine 0.40 0.45 0.45 0.45 n/a
Vinyl chloride 2.00 2.19 2.20 1.80 10.00
Xylene (mixed isomers) 0.40 0.50 0.43 0.50 8.50
August, 2012 Using real-time portable atmospheric monitors Slide 152
Actual response of 10.6 eV equipped PID isobutylene
(C4H8)scale to 1000 ppm toluene (C7H8)
AIHCe 2012 – PDC 411 Page 77 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 153
• The Controlling Compound
• Every mixture of gases and vapors 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
August, 2012 Using real-time portable atmospheric monitors Slide 154
Ethanol “appears” to be the safest compound
Turpentine “appears” to be the most toxic
This table only provides half of the decision making equation
PID Alarms:
Varying Mixtures
Chemical
Name
10.6eV CF NIOSH REL
Exposure Limit
(8-hr. TWA)
Ethanol 10.0 1000
Turpentine 0.45 100
Acetone 1.2 250
AIHCe 2012 – PDC 411 Page 78 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 155
• 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
ELchemical
CFchemical
PID Alarms:
Varying Mixtures
ELIsobutylene =
August, 2012 Using real-time portable atmospheric monitors Slide 156
• IF you are following the NIOSH REL then ethanol is the “controlling
compound” when the exposure limits are expressed in equivalent
“Isobutylene Units”
• The equivalent ELiso is a calculation that involves a manufacturer
specific Correction Factor (CF)
• Similar calculations can be done for any PID brand that has a
published CF list
• BE CAREFUL: If you are following the TLV the controlling chemical
would be turpentine!
PID Alarms:
Varying Mixtures
Chemical name CFiso
(10.6eV)
NIOSH REL
(8 hr. TWA)
ELISO (PEL) TLV®
(8hr. TWA)
ELISO (TLV)
Ethanol 10.0 1000 100.0 1000 100.0
Turpentine 0.45 100 222.3 20 44.5
Acetone 1.2 250 208.4 500 416.7
AIHCe 2012 – PDC 411 Page 79 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 157
Choosing the best sensor
configuration
• Multi-sensor instruments can
include up to seven channels
of real-time measurement
• Available sensors for
combustible gas and VOC
measurement::
• CC %LEL
• IR %LEL
• IR %Vol
• Thermal Conductivity %Vol
• Electrochemical toxic
• PID
August, 2012 Using real-time portable atmospheric monitors Slide 158
PID, CC LEL, IR LEL and CO sensors exposed
to 50% LEL isobutylene (9,000 ppm)
The maximum full-range
reading for the PID was 3,000
ppm (= 17.5% LEL
Isobutylene). Readings at or
above this concentration are
logged at the maximum value
AIHCe 2012 – PDC 411 Page 80 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 159
Response of IR LEL, CC LEL, PID and CO sensors
to 15% LEL turpentine vapor
August, 2012 Using real-time portable atmospheric monitors Slide 160
Test run# 1: PID, CC LEL, IR LEL and CO
sensors exposed to diesel vapor
AIHCe 2012 – PDC 411 Page 81 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 161
Test run# 4: PID, CC LEL, IR LEL and CO
sensors exposed to diesel vapor
August, 2012 Using real-time portable atmospheric monitors Slide 162
Selection matrix for Sensors for
measurement of combustible gas and VOCs
AIHCe 2012 – PDC 411 Page 82 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 163
Examples of possible sensor configurations
optimized for specific applications*
* Note that the listed sensor configurations represent possible solutions for
specific applications. The presence of additional conditions or requirements
may change the optimal sensor configuration.
August, 2012 Using real-time portable atmospheric monitors Slide 164
Case Study
Fuel barge
explosion
and cleanup
On February 21, 2003, a fuel barge loaded with gasoline
exploded at a fuel loading dock on Staten Island, New York
Two workers were killed and another critically burned
The explosion was the result of an accident, not terrorism or
sabotage
The barge had unloaded about half its cargo of 4 million
gallons of unleaded gasoline when the explosion occurred
USCG photo by PA3 Mike Hvozda
AIHCe 2012 – PDC 411 Page 83 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 165
Case Study
Gasoline was released from the damaged berth area where a section of the aboveground piping ruptured
USCG photos by PA3 Mike Hvozda
August, 2012 Using real-time portable atmospheric monitors Slide 166
As the blaze was at its height, officials used tugs to push a nearby barge loaded with 8 million gallons of gasoline to the other side of the waterway, where they covered it with water and foam to ensure that it did not explode.
Case Study
AIHCe 2012 – PDC 411 Page 84 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 167
Once the fire was
extinguished and the barges
cooled, Marine Chemist and
Coast Guard personnel
conducted structural
inspections
Exposure to toxic VOCs was
a primary concern
Chemicals of concern
included the remaining
gasoline, benzene,
total BTEX (benzene,
toluene, ethylbenzene, and
xylenes) and total polycyclic
aromatic
hydrocarbons (such as
naphthalene)
USCG photo by PA3 Mike Hvozda
Case Study
August, 2012 Using real-time portable atmospheric monitors Slide 168
What about benzene?
Benzene is almost never present all by its by itself
Benzene is usually minor fraction of total VOC
present
Test for total hydrocarbons (TVOC), especially if the
combustible liquid has an established PEL or TLV
Diesel 15 ppm
Kerosene 30 ppm
Jet Fuel (JP-8) 30 ppm
Gasoline 300 ppm
AIHCe 2012 – PDC 411 Page 85 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 169
Actual toxicity testing results
from gasoline fuel barge #1
Previous Loadings: Cat Feedstock/Crude Oil/Cat Feedstock
SPACE % LEL PPM TVOC
(iso)
PPM
Benzene
%TVOC from
benzene
No (1) Port Cargo Tank 0 32.8 0.8 2.44 %
No (2) Port Cargo Tank 0 38.2 0.4 1.05%
No (3) Port Cargo Tank 0 45.5 0.4 0.88%
No (4) Port Cargo Tank 0 75.8 0.3 0.4%
No (5) Port Cargo Tank 0 64.3 0.3 0.47%
No (1) Stbd Cargo Tank 0 34.8 0.6 1.72%
No (2) Stbd Cargo Tank 0 44.6 0.3 0.67 %
No (3) Stbd Cargo Tank 0 39.6 0.2 0.51 %
No (4) Stbd Cargo Tank 0 58.4 0.4 0.68 %
No (5) StbdCargoTank 0 64.8 0.5 0.77%
August, 2012 Using real-time portable atmospheric monitors Slide 170
TVOC alarm setting based on fractional
concentration benzene for Barge #1
Worst case (No 1 Port Cargo Tank)
TVOC hazardous condition threshold alarm of 172 ppm
isobutylene would prevent exceeding the PEL for
benzene of 1.0 PPM
41 x .0244 = 1.0004 ppm
TVOC Hazardous Condition Threshold Alarm for compliance
with:
Benzene Exposure
Limit
1.0 PPM 0.5 PPM 0.1 PPM
TVOC alarm setting 41 PPM 20.5 PPM 4.1 PPM
AIHCe 2012 – PDC 411 Page 86 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 171
Actual toxicity testing results
from gasoline fuel barge #2
Previous Loadings: Natural Gasoline (3X)
SPACE % LEL PPM TVOC
(iso)
PPM
Benzene
%TVOC from
benzene
No (1) Port Cargo Tank 0 37.3 0.0 0 %
No (2) Port Cargo Tank 0 44.1 0.1 0.23%
No (3) Port Cargo Tank 0 53.8 0.2 0.37 %
No (4) Port Cargo Tank 0 48.2 0.1 0.21%
No (5) Port Cargo Tank 0 68.5 0.4 0.58 %
No (1) Stbd Cargo Tank 0 13.2 0.0 0 %
No (2) Stbd Cargo Tank 0 29.0 0.0 0 %
No (3) Stbd Cargo Tank 0 58.1 0.1 0.17%
No (4) Stbd Cargo Tank 0 48.7 0.2 0.41 %
No (5) StbdCargoTank 0 63.3 0.3 0.44%
August, 2012 Using real-time portable atmospheric monitors Slide 172
TVOC alarm setting based on fractional
concentration benzene for Barge #2
Worst case (No 5 Port Cargo Tank)
TVOC hazardous condition threshold alarm of 172 ppm
isobutylene would prevent exceeding the PEL for
benzene of 1.0 PPM
172 x .0058 = 0.9976 ppm
TVOC Hazardous Condition Threshold Alarm for compliance
with:
Benzene Exposure
Limit
1.0 PPM 0.5 PPM 0.1 PPM
TVOC alarm setting 172 PPM 86 PPM 17.2 PPM
AIHCe 2012 – PDC 411 Page 87 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 173
Ways of using gas
detectors
• Diffusion mode: Passively measures contaminants or
conditions in atmosphere immediately surrounding the
instrument
• Simple, convenient, continuous
• Remote sampling: uses motorized pump or hand-aspirator
(squeeze bulb) to draw sample through hose and probe
assembly back to instrument
• “Pick-hole” sampling:
• Pre-ventilation
• Sampling during initial (purge) ventilation
• Final pre-entry
• Whatever the sampling method, monitor continuously while
the work or entry underway!
August, 2012 Using real-time portable atmospheric monitors Slide 174
Sample-Draw vs. Diffusion
• Drawbacks of diffusion operation:
• Instrument only able to monitor the
atmosphere in the immediate vicinity of
sensors
• Only way to obtain readings from remote
location is to lower the instrument by rope or
lanyard into the confined space
• Not possible to use monitor for “pick hole”
sampling (requires additional hand aspirator
sample draw kit or motorized pump)
AIHCe 2012 – PDC 411 Page 88 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 175
Hand-aspirated
sample-draw kit
• Available for almost all models
of diffusion type multi-gas
instruments
• Make sure to squeeze the bulb
the required number of times
for sample to reach the sensors
• Continue to squeeze bulb until
readings are stable
• Make sure to test the system
for leakage prior to use:
• Block end of the sample tubing
or probe with finger
• Squeeze the aspirator bulb
• Bulb should stay deflated until
blockage is removed
August, 2012 Using real-time portable atmospheric monitors Slide 176
Sample-Draw vs. Diffusion
• Drawbacks of sample-draw operation:
• Sample lag time: instrument cannot detect contaminants until they
reach the sensors
• Always wait long enough for sample to reach sensors PLUS time it
takes for sensors to respond fully
• Potential for leakage in the system: critical to test system for leakage
prior to use
• Potential for pump malfunction: instruments with internal motorized
pump only operable as long as pump functions
• Potential for absorbance: some types of tubing, filters and materials in
the squeeze-bulb or pump can absorb or limit some gases and vapors
from reaching sensors
• Make sure type of tubing used (e.g. Tygon, butyl, PTFE, etc.) is
compatible or appropriate for type of vapor being measured
• Potential for vapor condensation in tubing: keep length of sample
tubing as short as possible
AIHCe 2012 – PDC 411 Page 89 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 177
Using motorized sample pump
equipped instruments
• Sampling Rules
• Do not exceed the manufacturer’s maximum sampling distance
• Allow 2 seconds per foot of tubing for sample to reach the sensors (minimum requirement)
• Allow at least 2 minutes AFTER sample reaches sensors before noting respons
• Confined Space sampling:
• Top, Middle, Bottom (at a minimum, sample at every 4 ft. interval
August, 2012 Using real-time portable atmospheric monitors Slide 178
Performing a
Gas Test
• Perform proper instrument start up
• Make sure instrument has been properly
bump-tested before use
• Perform proper pump start up
(if applicable)
• Make sure sample probe assembly
is used whenever using the motorized
sampling pump
• Make sure sample probe assembly is
equipped with hydrophobic barrier and
particulate filters – replace if discolored or
dirty, or if the flow is being blocked
• Test all areas as required
AIHCe 2012 – PDC 411 Page 90 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 179
Time required for
proper testing
• Wait until the sensor readings have completely stabilized!
• Remember that when you use an instrument in diffusion mode you may need up to 2-minutes – or even longer – for the sensors to finish stabilizing
• If tubing or a wand is used as well you have to add an additional 2-sec per foot for the gas to reach the sensors
• So if you are testing a vessel that is 10 feet deep and tubing is used, how long would it take to test the entire vessel (entry level, mid level and bottom):
((120 seconds) + (2 sec. x 10 feet)) x 3 = 420 seconds = 7 minutes
The time it takes for the
sensors to finish stabilizing
after the gas begins to reach
the sensors
The time it takes for the
pump to pull the
sample through a 10
foot length of tubing
The number of
tests required
August, 2012 Using real-time portable atmospheric monitors Slide 180
Mandatory to use a "calibrated"
instrument maintained according to
"manufacturer requirements"
• 1910.146(c)(5)(ii)(C):
• Before an employee enters the space,
the internal atmosphere shall be
tested, with a calibrated direct-
reading instrument
• What does OSHA accept as a
"calibrated" direct reading
instrument?
• A testing instrument maintained
and calibrated in accordance with
the manufacturer's
recommendations
• The best way for an employer to
verify calibration is through
documentation
AIHCe 2012 – PDC 411 Page 91 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 181
Why do instruments need to be
tested and / or calibrated?
• The response of gas detecting sensors
can change over the life of the sensor
• The changes may be sudden, or can be
gradual
• Substances or conditions present in the
atmosphere can have an adverse effect
on the sensors
• Different types of sensors have
different constraints and conditions
which can lead to loss of sensitivity or
failure
• Important to know how sensors detect
gas to understand conditions that can
lead to inaccurate readings
August, 2012 Using real-time portable atmospheric monitors Slide 182
Make sure the instrument
has been calibrated!
• Follow manufacturer
recommendations
• Allow instrument to stabilize after
turning on
• Make sure readings in fresh air are
correct
• Perform fresh air calibration if needed
• Verify Accuracy Daily!
• Perform functional “bump” test before
each day’s use
• Perform “span” calibration if
necessary
AIHCe 2012 – PDC 411 Page 92 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 183
Loss of sensitivity
can be due to:
• Aging or desiccation of the sensors,
• Mechanical damage due to dropping or
immersion
• Exposure to sensor poisons present in
the atmosphere being monitored
• Loss of sensitivity due to other causes
August, 2012 Using real-time portable atmospheric monitors Slide 184
Regulatory
Requirements
• OSHA 1910.146 requires use of a
“calibrated” instrument
• This means (per OSHA CPL 2.100) that
the instrument must be maintained and
calibrated according to manufacturer
guidelines
AIHCe 2012 – PDC 411 Page 93 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 185
Calibration Frequency
• The safest course of action is to
expose the sensors to known
concentration test gas before
each day’s use!
• This test is very simple and
takes only a few seconds to
accomplish
August, 2012 Using real-time portable atmospheric monitors Slide 186
Functional “Bump”
Test vs. Calibration
• Functional “bump” test only
provides verification of sensor
performance
• Calibration includes adjustment
• Only necessary to adjust
sensor sensitivity if readings
are off
• Most manufacturers
recommend adjustment if
readings are off by more than
10% of expected values
AIHCe 2012 – PDC 411 Page 94 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 187
Retest instrument
if necessary
• Any conditions, incidents, or
exposure to contaminants
which might have an adverse
effect on the sensors should
trigger immediate re-
verification before further use
• Any changes in the custody or
ownership of the instrument
should trigger immediate re-
verification before further use
• If there is any doubt at any time
as to the accuracy of the
sensors, verify the calibration
of the sensors by exposing
them to known concentration
test gas before further use!
August, 2012 Using real-time portable atmospheric monitors Slide 188
Don’t be afraid of calibration!
• Modern designs make calibration
easy and automatic
• Keep the Calibration Materials
With the Instrument!
• All-In-One Calibration
Mixtures Make Functional
Testing Easy!
AIHCe 2012 – PDC 411 Page 95 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 189
Record
Keeping
• Documentation is critical!
• Without good records you
cannot defend or explain
your procedures
• If you don’t have the
records to prove it was
being done right -- it wasn’t!
August, 2012 Using real-time portable atmospheric monitors Slide 190
Atmospheric hazards are frequently
invisible to human senses
• You don’t know whether it’s safe until it’s been tested!
AIHCe 2012 – PDC 411 Page 96 of 98
August, 2012 Using real-time portable atmospheric monitors Slide 191
Questions?