Health Hazards of Air Pollutant (HAP) in Petrochemical Plants. From Scentroid TOXpro Webinar 2017. http://scentroid.com/webinar/

1. Free Online Webinar
Session #4
Health Hazards of Air Pollutant (HAP) in Petrochemical Plants
Vincent PERRET
CEO TOXpro SA
Toxicologist
Certified Industrial Hygienist
Webinar presented by :
1

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… a quick and short introduction
BSc chemical engineering
MSc chemistry
MAS occupational health
MAS applied human toxicology
Certified Industrial Hygienist
Founder of TOXpro SA, Geneva (Switzerland)
Occupational Hygiene & Industrial Toxicology services
Vincent PERRET

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… and my apologizes for this terrific accent

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What will we talk today ?
• Fundamental of toxicology
• Pollutant emission of pertrochemical plants
• Olfaction mechanisms
• Health impact on exposed populations Sampling,
exposure evaluation
• Exposure compliance

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Hazardous Air Pollutants
Hazardous substance :
Substance with an intrinsic capability to cause harm to health
Hazard classification of substances according to GHS (WHO).
(1) Signal Word
(2) GHS Symbols
(3) Manufacturer information
(4) Precautionary Statements / First Aid
(5) Hazard Statements
(6) Product Name or Identifiers

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Refulling may kill you … really ?
GASOLINE
H226: Flammable liquid and vapour.
H304: May be fatal if swallowed and enters airways.
H315: Causes skin irritation.
H336: May cause drowsiness or dizziness.
H340: May cause genetic defects.
H350: May cause cancer.
H361: Suspected of damaging fertility or the unborn child.
H411: Toxic to aquatic life with long lasting effects

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Risk vs Hazard
Risk :
Concept mixing gravity of an adverse event (illness, accident) and
the probability of occurance.
Risk = Hazard x Probability
In toxicology, probability is linked to the exposure dose
Dosis sola facit venenum
(the dose make the poison)
Paracelsius (1493-1541)

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Acute & Chronic Toxicity
All substances have two faces
Toxicities of substances
Acute toxicity
Short term effects after exposure (irritant, caustic, toxics)
Chronic toxicity
Delayed effects (sometimes years) after repeated sub-toxic
exposure (diseases, cancer, neuropathology, …)

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Saccharose :
(sugar)
Sodium chloride :
(salt)
Coffee :
(caffeine)
Cigarette :
(nicotine)
Compared toxicity of (commun) substances
Acute toxicity
(immediate death)
Chronic toxicity
(Lifetime illness prevention)
2 kg (rat 29.7 g/kg)
210 g (rat 3g/kg)
50-200 cups
(10 g caféine)
~50 (50 mg nicotine)
50 gr (daily allowed intake )
5 gr (daily allowed intake )
6 cups (daily allowed intake )
1 every 10 day
(1/100’000 whole life excess lung
cancer risk)

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So ? What are petrochemical plant emissions ?
OR

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Methane Ethane Propane
Isobutane 1-Butene n-Butane
Isopentane n-Pentane 2,2-Dimethylbutane
Cyclopentane 2,3-Dimethylbutane 2-Methylpentane
3-Methylpentane n-Hexane Methylcyclopentane
2,4-Dimethylpentane Benzene Cyclohexane
2-Methylhexane 2,3-Dimethylpentane 3-Methylhexane
n-Heptane Methylcyclohexane Toluene
2-Methylheptane 3-Methylheptane n-Octane
Ethylbenzene Xylenes Hydrogen Sulfide
Sulfur Oxides Methyl Mercaptan Ethyl Mercaptan
Dimethyl Sulfide Dimethyl Disulfide Formaldehyde
n-Nonane 1,2,3-Trimethylbenzene n-Undecane
Carbon Monoxide
Emissions from Oil and Gas Operations
From Shannon Ethridge, Texas Commission on Environmental Quality

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Methane Ethane Propane
Isobutane 1-Butene n-Butane
Isopentane n-Pentane 2,2-Dimethylbutane
Cyclopentane 2,3-Dimethylbutane 2-Methylpentane
3-Methylpentane n-Hexane Methylcyclopentane
2,4-Dimethylpentane Benzene Cyclohexane
2-Methylhexane 2,3-Dimethylpentane 3-Methylhexane
n-Heptane Methylcyclohexane Toluene
2-Methylheptane 3-Methylheptane n-Octane
Ethylbenzene Xylenes Hydrogen Sulfide
Sulfur Oxides Methyl Mercaptan Ethyl Mercaptan
Dimethyl Sulfide Dimethyl Disulfide Formaldehyde
n-Nonane 1,2,3-Trimethylbenzene n-Undecane
Carbon Monoxide
Emissions from Oil and Gas Operations
From Shannon Ethridge, Texas Commission on Environmental Quality
Non aromatic hydrocarbons
Gasoline odor
Low toxicity (except n-hexane)

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Methane Ethane Propane
Isobutane 1-Butene n-Butane
Isopentane n-Pentane 2,2-Dimethylbutane
Cyclopentane 2,3-Dimethylbutane 2-Methylpentane
3-Methylpentane n-Hexane Methylcyclopentane
2,4-Dimethylpentane Benzene Cyclohexane
2-Methylhexane 2,3-Dimethylpentane 3-Methylhexane
n-Heptane Methylcyclohexane Toluene
2-Methylheptane 3-Methylheptane n-Octane
Ethylbenzene Xylenes Hydrogen Sulfide
Sulfur Oxides Methyl Mercaptan Ethyl Mercaptan
Dimethyl Sulfide Dimethyl Disulfide Formaldehyde
n-Nonane 1,2,3-Trimethylbenzene n-Undecane
Carbon Monoxide
Emissions from Oil and Gas Operations
From Shannon Ethridge, Texas Commission on Environmental Quality
aromatic hydrocarbons
Sweet odour
Carcinogenic

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Methane Ethane Propane
Isobutane 1-Butene n-Butane
Isopentane n-Pentane 2,2-Dimethylbutane
Cyclopentane 2,3-Dimethylbutane 2-Methylpentane
3-Methylpentane n-Hexane Methylcyclopentane
2,4-Dimethylpentane Benzene Cyclohexane
2-Methylhexane 2,3-Dimethylpentane 3-Methylhexane
n-Heptane Methylcyclohexane Toluene
2-Methylheptane 3-Methylheptane n-Octane
Ethylbenzene Xylenes Hydrogen Sulfide
Sulfur Oxides Methyl Mercaptan Ethyl Mercaptan
Dimethyl Sulfide Dimethyl Disulfide Formaldehyde
n-Nonane 1,2,3-Trimethylbenzene n-Undecane
Carbon Monoxide
Emissions from Oil and Gas Operations
From Shannon Ethridge, Texas Commission on Environmental Quality
Sulfur compounds
Rotten egg odour
Irritants

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Sulfur and bad odors?

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© The McGraw-Hill Companies Inc.
The olfactive system
Mucus layer (water)
• Dissolution of
soluble molecules
• Olfactive transport
protein (OTP) for
hydrophobic
molecules

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(2-Hydroxypropyl)-β-
cyclodextrin
17
How to cheat the system
Hydrophobic cavity to trap
lipophilic molecules

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Yoshihito Niimura, Atsushi Matsui,
and Kazushige TouharaGenome
Research, July, 23, 201
5’000’000 OR
150’000’000 OR
Olfactive receptors

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Olfactive receptors
Odorant molecule dont
bind to a single specific
receptor.
Odorant molecule bind
to multiple receptors to
create a specific odor
map of activated
recepetors

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Ethanethiol
(ethyl mercaptan)
Ethanol
0.00076 ppm
10 ppm
13’000 X
Odor
threshold
The strong odour of sulfur compound

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Malodorous volatile thiols and amines
are protein degradation products found in
putrid food, so sensitive identification of
these compounds is crucial to avoiding
intoxication
Laska M, Bautista RM, Höfelmann D, Sterlemann V, Salazar LT.
Olfactory sensitivity for putrefaction-associated thiols and indols in
three species of non-human primate. J Exp Biol. 2007;210:4169–4178
The strong odour of sulfur compounds, due to
copper

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© 2017 Chemical Engineering
Can we rely on odour to evaluate toxicity ?
There’s no
correlation
between
odor and
toxicity

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HydrogenSulfideConcentrationinAir
(partsperbillion,ppb)
Short-TermExposureLong-TermExposure
Hydrogen
Sulfide
(lessthan14days)(monthstoyears)
10,000,000
HealthEffects
and
Regulatory
Levels
Chronichealtheffectsafter
repeatedexposurehave
1,000,000
100,000
Olfactorydamge-lossofabilitytosmell
Lossofconsciousnessanddeath
Eyeandrespiratorytractirritation
pp
notbeenestablished
OSHACeiling
10,000
1,000
NIOSH10-minuteCeiling
ACGIHTLVTWA
Impairedlungfunctioninasmthmatics
OlfactorydamgeinanimalsOSHACeiling
ACGIHTLVSTEL
100
10
TCEQ30-minutestandard(80ppb)
ATSDRacuteMRL(70ppb)
1
0.1
OdorThreshold(0.5ppb)
Page26
From Shannon Ethridge, Texas Commission on Environmental Quality
Odor Threshold (61 ppb)
Compared toxicity of Benzene and H2S

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Health impact on exposed populations
PUBLIC WORKERS
• Babies, young, eldery, sicks
• Permament exposure of diffuse ambiant
pollution (distance from the source)
• Selected robust people
• Daily exposure, proximity to pollutant sources

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Health impact on exposed populations
Public health
Acute issues Chronic issues

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Health impact on exposed populations
Public health
Acute issues Chronic issues
ARD : Acute respirtory diseases
Living close the plant, increase by a factor 2-3x
respiratory disease risk Top carcinogenic compounds
Leukemia
risk Lifetime
6.4 / 100’000

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Epidemiology, what is a 1/100’000 risk ?
Just to compare, below are some socially accepted 1/100’000 risks
• Lung cancer after smoking 15 cigarettes (whole life)
• 1 week as construction worker
• 2 days as timber
• 50 km moto race
• 0.5 day at 65 years old age
Source
Adapetd from« Risque de cancer dans les locaux floqués à
l'amiante »
E.Gubéran et al.
Médecine sociale et préventive, 1987; 32: 246-248

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Health impact on exposed populations
Occupational health
Compared to public exposure, Occupational
exposure is characterized by higher exposure
intensity (10 – 1000x) and substance diversity.
In petrochemistry, major identified chemical hazard
are :
- Benzene
- Hydrogene sulfide
- Formaldehyde
- Cristalline silica (drilling)
- Lubrification oil (drilling)
- Mercury (in gas)
- Asbestos (installations)
- Ionisation radiation (radon)

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Health impact on exposed populations
Occupational health
Even odd hazard issues (Ototoxicity)

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Health impact on exposed populations
Occupational health
Scenario 2B – Worker Exposure
Scenario 1 – Ambiant air in Refinery
Scenario 4 – Ambiant air outside the Refinery
Cancer lifetime risk : 170 / 100’000
Cancer lifetime risk : 4’400 / 100’000
Cancer lifteime risk : 11 / 100’000

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Health impact on exposed populations
Occupational health
smoke only
influence on sperm quality
smoke and exposure
influence on sperm quality

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How to measure exposure ?

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Is there a direct, cheap, specific and sensitive
method ?
Analytical chemistry
pick any 3 of following items
1. Direct
2. Cheap
3. Specific
4. Sensitive
Direct, cheap, sensitive
won’t be specific
Cheap, specific, sensitive
won’t be direct
Direct, cheap, specific
won’t be be sensitive
Direct, specific, sensitive
won’t be cheap
Portable GC-MS
Photoionisation
Colorimetric tubesAir sampling
Lab analysis

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Tedlar Bags® Canisters Canisters HDS ®
Whole air sampling (environmental)

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Low-flow constant pressure pump
(sampling 100-200 ml/min)
Activated charcoal
(hydrocarbons)
Silicagel DNPH
(aldehydes)
TENAX®
(hydrocarbons)
Active air sampling (ambiant, personal)
Silicagel silver nitrate
(hydrogen sulfide)

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Radiello© GABIE®
INRS
ORSA®
Dräger
UMEX®
SKC
3500®
3M ACS©
Passive air sampling (ambiant, personal)
Sorbents must be selected according to the target substances

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(+) very high specific surface
(-) sensitive to water
(-) low affinity for polar compounds
Carbon molecular sieve vs activated charcoal
(-) medium specific surface
(+) low sensitivity to water
(+) better affinity for polar compounds
Activated charcoal from coconut shell Carbon molecular Sieve

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Air Sorbent
Diffusion layer
Passive diffusion principle
Uptake flux depend on
diffusion Fick’s law
parameters of influence :
• Geometry of sampler
(surface, diffusion layer)
• Temperature
• Concentration gradient
• Molecular weight

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Analysis standards
Environmental EPA TO-15, TO-17 (volatile organic compounds)
GC-MS
Occupational NIOSH
OSHA
INRS
…
Benzene
method n.1501
method n.12
method n.237
H2S
method n.6013
method n.141
method n.184

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Multisite exposure assessment in chemical industry
1500 workers sampled (self assessment)screening of
200 substances (GC-MS)
Application exemple of massive passive personal
sampling
2012 Phase pilote
2013 EMEA phase 1
2014 LATAM + ASIA
2015 USA + EMEA II

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Samples Type Holder Activity Start
77007 COV Villamil Ramiro Emulsion 05.03.14 10:00
77005 COV Correa Rosario Flavorist creation lab 05.03.14 08:05
77009 COV Padilla Juan Sebastian Flavor compounding lab 05.03.14 08:00
77031 COV Sanchez A Maribel Flavor compounding lab 05.03.14 07:45
77032 COV Eccehomo Quintero David Flavor compounding lab 05.03.14 07:50
77036 COV Static Flavor creation lab 05.03.14 08:00
77040 COV Salinas Edwin Fragrance application lab 05.03.14 08:20
77041 COV Pineda Addy Fragrance application lab 05.03.14 08:20
77034 COV Belfan Teresa Fragrance compounding lab 05.03.14 08:10
77035 COV Martinez Carolina Fragrance compounding lab 05.03.14 08:10
77037 COV Cristina Cora Fragrance compounding lab 05.03.14 08:15
77038 COV Static Fragrance compounding lab 05.03.14 08:15
77039 COV Martinez Margarett Fragrance compounding lab 05.03.14 08:25
77025 COV Static Fragrance mixing room 04.03.14 07:45
77006 COV Diaz Gustavo Liquid 05.03.14 10:05
77033 COV Leon Helbert Maintenance electrical 04.03.14 08:05
77028 COV Amaya Anibal Maintenance mechanical 04.03.14 08:05
77013 COV Gaitan Isaias Oper manuf frag 04.03.14 07:00
77014 COV Diaz Gustavo Oper manuf frag 04.03.14 07:00
77015 COV Mejia Freddy Oper manuf frag 04.03.14 07:00
77016 COV Gonzalez Edwin Oper manuf frag 04.03.14 07:00
77017 COV Sandoval Julio E Oper manuf frag 04.03.14 07:35
77020 COV Beltran Carlos Oper manuf frag 04.03.14 07:25
77021 COV Carreno Carlos Oper manuf frag 04.03.14 07:30
77022 COV Gonzalez Julio C Oper manuf frag 04.03.14 07:20
77011 COV Static QC lab Instrumental 03.03.14 14:30
77008 COV Static QC lab Physico-chem 03.03.14 14:15
77012 COV Static QC lab sample prepa 03.03.14 14:20
77019 COV Hernandez Fabian Sampling Flavor 04.03.14 08:15
77026 COV Bustamante Ferney Sampling frag 04.03.14 07:40
77023 COV Arias Mauricio Spray dryer packaging 04.03.14 07:35
77018 COV Pinilla José Warehouse driver 04.03.14 08:00
77024 COV Nino Julian Warehouse driver 04.03.14 08:00
77027 COV Larrota Cesar Warehouse driver 04.03.14 08:00
77029 COV Figueroa Carlos Warehouse driver 04.03.14 08:00
77030 COV Camargo Juan Carlos Warehouse driver 04.03.14 08:00
EndDuration (min)
Acetone
Acetonitrile
AmylAcetate
AllylChloride
Anethole
Benzene
BenzylChloride
Bourgeonal
1,3-Butadiene
Butane
2-Butanone(MEK)
2-Butoxyethylacetate
ButylAcetate
Di-t-ButylPeroxyde
ButylCellosolve
1-ButylAlcohol
2-ButylAlcohol
Camphene
Camphor
Chlorobenzene
Chloroform
Cyclohexane
Cyclohexene
Cyclohexanol
m-Cymene
DiacetoneAlcohol
Diacetyl
1,2-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dimethylcyclopentane
Dimethylformamide
Dimethylsulfide
Dimethylsulfoxide
Dioxane
Estragole
EthylAcetate
EthylAlcohol
2-Ethyl-1-Hexanol
EthylBenzene
EthylButyrate
EthylEther
Ethylisobutyrate
EthylMethacrylate
4-EthylToluene
Eucalyptol
FurfurylAlcohol
Heptane
2-Heptanone
Hexane
Hexaneisomers
1-Hexanol
Hexone
Isoamylacetate
Isobutane
IsobutylAcetate
Isoprène
IsopropylAlcohol
D-Limonene
MethylAcetate
MethylAcrylate
2-Methylbutane
Methyleugenol
Methylparacresol
2-Methyl-1-Propanol
Methylcyclopentane
MethylChloroform
5-Methyl-2-Hexanone
MethylMethacrylate
Methyl-t-ButylEther
MethylStyrene
MethyleneChloride
Nonane
Octane(allisomers)
2,3-Pentadione
Pentane
PentaneIsomers
1-Pentanol
PentylAcetate
2-Pentanone
Perchloroethylene
Alpha-Pinene
2-Propoxyethanol
n-PropylAcetate
PropylBenzene
n-PropylBromide
Pyridine
ProypleneGlycolMethylEtherAcetate
PropyleneOxide
Styrene
Tetrahydrofuran
Toluene
Trichloroethylene
1,2,3-Trimethylbenzene
VinylAcetate
VinylChloride
Xylene
Terpeneexposuresum
Sumofpartialexposure
Numberofdetectedsubstances
450 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 131.9% 132.5% 7
625 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 2.1% 2.4% 4
440 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.2% 0.3% 3
495 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.3% 0.6% 4
496 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 1.7% 2.0% 4
453 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.4% 0.4% 2
618 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.5% 1.2% 6
625 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.8% 2.1% 7
590 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 1.1% 2.0% 6
550 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.5% 1.0% 5
545 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.9% 1.9% 9
451 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.3% 0.4% 2
582 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.4% 3.2% 7
450 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 3.3% 3.8% 6
445 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.3% 2.5% 6
1070 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 1.0% 13.3% 21
1100 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 1.8% 4.3% 18
630 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 5.3% 6.7% 8
630 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 11.5% 13.1% 7
630 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 5.3% 6.5% 8
630 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 7.9% 9.6% 6
590 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 12.6% 15.4% 8
600 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 4.0% 5.5% 8
600 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 10.9% 12.0% 7
610 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 4.3% 23.6% 14
2960 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.2% 5.1% 12
2975 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.3% 10.9% 13
2970 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 0.6% 13.5% 13
565 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 2.6% 3.0% 7
575 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 1.6% 3.0% 4
595 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 2.5% 3.0% 9
540 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 2.1% 2.4% 4
570 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 6.7% 7.0% 4
540 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 3.4% 3.6% 3
510 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 4.9% 5.1% 6
480 ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## ## 1.5% 2.0% 3
<"LOQ
<"1%"reference"value
>"1%"reference"value
>"10%"reference"value
>"100%"reference"value
Personal"samples"are"TWA"(8h)
Static"samples"are"mean"on"the"period
Workers
Detected substances
Results (color
codes vs % OEL)
< LOQ
< 1% reference value
> 1% reference value
> 10% reference value
> 100% reference value
Personal samples are TWA (8h)
Static samples are mean on the period
Global exposure index
Ethanol
Chloroform
D-Limonen
(terpene)
A-Pinene
(terpene)Ethyl
isobutyrate
41
Typical result (on production site)

42. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
0.0%
10.0%
20.0%
30.0%
40.0%
50.0%
60.0%
70.0%
80.0%
Acetone
Am
ylAcetate
Anethole
BenzylChloride
1,3-Butadiene
2-Butanone
(M
EK)
ButylAcetate
ButylCellosolve
2-ButylAlcohol
Cam
phor
Chloroform
Cyclohexene
m
-Cym
eneDiacetyl
1,4-Dichlorobenzene
Dim
ethylform
am
ide
Dim
ethylsulfoxideEstragole
EthylAlcohol
EthylBenzene
EthylEther
EthylM
ethacrylate
EucalyptolHeptaneHexane
1-Hexanol
Isoam
ylacetate
IsobutylAcetate
IsopropylAlcohol
M
ethylAcetate
2-M
ethylbutane
M
ethylparacresol
M
ethylcyclopentane
5-M
ethyl-2-Hexanone
M
ethyl-t-ButylEther
M
ethylene
Chloride
Octane
(allisom
ers)Pentane
1-Pentanol
2-Pentanone
Alpha-Pinene
n-PropylAcetate
n-PropylBrom
ide
Proyplene
GlycolM
ethylEtherAcetateStyreneToluene
1,2,3-Trim
ethylbenzene
VinylChloride
Referencevalue(%)
QC lab
Bad handling practices
General ventilation
weakness
42
Typical result (similar group of exposure)
Workers
(similar activity)

43. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
43
EMEA Global indicators
Total samples taken
measured
parameters
31620 12 4%
VOC scan
personal 309 81% Exceeding 10% reference value (action level) 89 29%
environmental 46 12%
Specific
personal 23 6%
environmental 2 1%
LABORATORIES SITES - Cumulative exposure evaluation
Name
23 2 77 18 5 0 6 0 8 4 6 0
0 0 2 0 0 0 0 0 0 0 0 0
Nb Prop Nb Prop Nb Prop Nb Prop Nb Prop Nb Prop
< LOQ 0 0% 0 0% 0 0% 0 0% 0 0% 0 0%
< 1% reference value 13 57% 40 52% 4 80% 5 83% 5 63% 4 67%
> 1% reference value 10 43% 29 38% 1 20% 1 17% 3 38% 2 33%
> 10% reference value 0 0% 8 10% 0 0% 0 0% 0 0% 0 0%
> 100% reference value 0 0% 0 0% 0 0% 0 0% 0 0% 0 0%
MANUFACTORING SITES - Cumulative exposure evaluation
Name
52 2 23 2 36 0 43 0 13 4 6 3
9 1 3 0 0 0 0 0 7 1 0 0
Nb Prop Nb Prop Nb Prop Nb Prop Nb Prop Nb Prop
< LOQ 0 0% 0 0% 0 0% 0 0% 0 0% 0 0%
< 1% reference value 1 2% 2 9% 0 0% 0 0% 8 62% 3 50%
> 1% reference value 10 19% 11 48% 20 56% 20 47% 2 15% 3 50%
> 10% reference value 32 62% 9 39% 16 44% 21 49% 3 23% 0 0%
> 100% reference value 9 17% 1 4% 0 0% 2 5% 0 0% 0 0%
Name
11 6 6 5
2 0 0 0 Global distribution of cumulative results for personal samples
Nb Prop Nb Prop
< LOQ 0 0% 0 0% Nb Prop
< 1% reference value 7 64% 5 83% < LOQ 0 0%
> 1% reference value 2 18% 26 433% < 1% reference value 92 30%
> 10% reference value 2 18% 5 83% > 1% reference value 114 37%
> 100% reference value 0 0% 1 17% > 10% reference value 91 29%
> 100% reference value 12 4%
Cumulative relative exposure
intensity distribution
Site G Site H
Cumulative relative exposure
intensity distribution
Lab 3 Lab 4Lab 1 Lab 2
Site A Site B Site C Site D
Lab 5 Lab 6
Specific personal / static
Formal reference personal value exceeding
Dust issues
Dust issues
Site E Site F
Cumulative relative exposure
intensity distribution
380
VOC personal / static
Specific personal / static
VOC personal / static
Specific personal / static
VOC personal / static
43
Typical result
multi-site benchmarking based
on occupational exposure

44. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
44
Dans le doute …
Exposure compliance, occupational exposure limits

45. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
45
Les Lettons
sont des
lopettes !
Occupational exposure limits, definition
Occupationa Exposure Limit (OEL) is usully defined as :
Acceptable mean exposure concentration to prevent occurrence of
adverse health effects (according to the actual best knowledge) on
the vast majority of healhy exposed workers.
OEL are usually defined for long term exposure (8h) and short term (STEL 15 min)

46. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
46
Les Lettons
sont des
lopettes !
… actual best knowledge
OEL (TWA 8h) for Benzene
through time
Source : ACGIH (USA)

47. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
47
Actual worldwide OEL
comparison for Toluene
Source : GESTIS database

48. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
48
Age specific morbidity ratio all
chronic conditions for all males. By
Employement Group
Sterling & Weinkam, 1985.
Employed
Seeking
employment
Not seeking
employement
Healthy worker effect

49. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
49
127’000’000
Number of organic
and inorganic
available substances
CAS registry 2017
1’700
Substances with an
OEL compilation of
all available national
values (GESTIS)
Une pointe
de l’iceberg
qui fait froid
dans le dos
700
Substances with an
OEL (Switzerland
2017)
Coverage of possible substances

50. Scentroid free webinar #4 – 15 February 2017 – HAP in petrochemical plants
50
For further informations