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F ACHBEREICH D SICHERHEITSTECHNIK ABWEHRENDEN BRANDSCHUTZ PROF . DR. ROLAND GOERTZ Ltd. Branddirektor a. D. Chemical and physical aspects of fire smoke

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FACHBEREICH D

SICHERHEITSTECHNIK

ABWEHRENDEN BRANDSCHUTZ

PROF. DR. ROLAND GOERTZLtd. Branddirektor a. D.

Chemical and physical aspects of fire

smoke

Sorting construction waste

Constructionwaste

Station

ca. 12.000 tonnes of construction waste

(plastic, small amount minerals and 3 % wood/textile)

Fire construction waste on Sunday 30.03.03, 5.30pm

Exploration with helicopter

Thoughts of the highest-in-charge- The process of leadership

Exploration/control

Dangersetting:

Kind and cause of damage

Damaged object and surroudings

Size of damagepeople, animalsenvironment and things

Thoughts of the highest-in-charge- The process of leadership

PlanningDecision/assessment

Decision:

Which dangers for people,animals, environment and things?

Which danger to combat first at which location?

Which possibilities exist withwhich advantages anddisadvantages?

What is the best possibility?

Thoughts of the highest-in-charge- The process of leadership

2,5 km

Fire smoke-

Determining the ingredients

?

Composition of fire smoke

Voice of press – opinion of people

Flames destroy

galvanizing

companyNo toxic compounds released

With ash it rained dioxines

on housesAfter plastic-fire 900 inhabitants evacuated

Fear the day after:

„Everything is contaminated now“School and kindergarten closed/ beddings closed

Dioxin-alarm after fire

on verandaPolice: Possibly no Seveso-toxics

released

Cloud of poison gas threatens SchwelmConflagration in storage/ chloride-fumes released

Poison gas-alarm: no

harvesting of fruitFear in Schwelm: inhabitants leave cities/ closures

Conflagration: Poison gas-

Alarm derailed HagenFire in galvanizing company/ No school for kids

Voice of press – opinion of people

General composition of fire smoke

NOx

HCN

NH3

SO2

H2S

Cl2

HClCOCl2

PH3CO

CO2

anorganische

Brandgase

organische Brand-

zersetzungsprodukte

Ruß

PC

DD

/F

NOx

HCN

NH3

SO2

H2S

Cl2

HClCOCl2

PH3CO

CO2

Inorganic

fire gasses

organische Brand-

zersetzungsprodukte

Ruß

PC

DD

/FGeneral composition of fire smoke

NOx

HCN

NH3

SO2

H2S

Cl2

HClCOCl2

PH3CO

CO2

Organic fire-

decompositionproducts

Ruß

PC

DD

/FGeneral composition of fire smoke

Inorganic

fire gasses

NOx

HCN

NH3

SO2

H2S

Cl2

HClCOCl2

PH3CO

CO2

Soot

PC

DD

/FGeneral composition of fire smoke

Organic fire-

decompositionproducts

Inorganic

fire gasses

NOx

HCN

NH3

SO2

H2S

Cl2

HClCOCl2

PH3CO

CO2

PC

DD

/FGeneral composition of fire smoke

Soot

Organic fire-

decompositionproducts

Inorganic

fire gasses

NOx

HCN

NH3

SO2

H2S

Cl2

HClCOCl2

PH3CO

CO2

organische Brand-

zersetzungsprodukte

Ruß

PC

DD

/FAnorganic fire gasses

Inorganic

fire gasses

Fire smoke in high concentrations is deadly!

11-12 important inorganic fire gasses

C

COCO2

N

NOx

HCNNH3

Cl

Cl2COCl2

HCl

S

SO2

H2S

P

PH3

Carbonmonoxide:

8.000 ppm Sudden death

3.000 ppm Dead after 30 min inhalation

1.500 ppm Dead after 1 hr inhalation

1.000 ppm Walking problems, dead after 1-2 hr

500 ppm Hallucinations after 30-120 min

200 ppm Headache after 2-3 hr

50 ppm MAK-value

F

HF

C

COCO2

N

NOx

HCNNH3

Cl

Cl2COCl2

HCl

S

SO2

H2S

P

PH3

F

HF

12 imporant organic fire gasses

Roland Goertz Abwehrender Brandschutz

Determination of danger

Which dangers exist

- for people

- animals

- environment

- things?

Measure-tactical (analytical) questions

Roland Goertz Abwehrender Brandschutz

Measure-tactics inorganic firegasses

1. Overview of source

2. Determination of

danger of emission

Roland Goertz Abwehrender Brandschutz

Measure-tactics inorganic firegasses

Roland Goertz Abwehrender Brandschutz

Organic fire-decompositionproducts

NOx

HCN

NH3

SO2

H2S

Cl2

HClCOCl2

PH3CO

CO2

anorganische

Brandgase

Soot

PC

DD

/F

Organic fire-

decomposionproducts

Roland Goertz Abwehrender Brandschutz

Dry wood destillation

Roland Goertz Abwehrender Brandschutz

Reaction zone

„After-burning“

of gasses

Fuel

Air inflowAir inflow

Thermic load

Fire-decompositionproducts

Combustionzones

Roland Goertz Abwehrender Brandschutz

Formation of aromaticcompounds and soot

SootAromatic

compounds

PAK

CH2

Radicals

en small

molecules

C2H2

+O2 +O2 +O2

CO2 + H2O

Carbon-

containing

fuel

„After-burning“

Roland Goertz Abwehrender Brandschutz

C CH H C C

H

HH

Acetylen

Vinylradikal

+ H.

+ C2H2 - H2

C C

H

H

C

C

H

H

H

1,3-Butadienradikal

+ C2H2

C

H

C

C

H

C

C

H

C

H

H

Phenylradikal

+ C2H2

- H2

C CH

Phenylacetylen

CCH

.H +

- H2

H

CCH

C C

H

+ C2H2

.

Naphthylradikal

+ C2H2

- H2.

..

Roet

Formation of aromatic compounds –

Reaction mechanisms

Ofen

Quarzwolle

Gasumlenkung

synth. Luft

Probeneinwurf

Probenhalter

Quarzrohr

Adsorptionsröhrchen

Quarzwolle

Quarzrohr

VCI-combustion-apparatus

Condensate (0), Quarzwolle (1) + int. Standard-Mix

+ 5ml Aceton

Collectionlayer (2), Control layer (3) + int. Standard (Hexadeuterobenzol) + 5ml Aceton

15 Minuten

Ultrasonic bath

Cleaning of extracts

"Clean-up"

Quarzwolle

Natriumsulfate

Quarzwolle

Cleaned

Extracts

(1) (2) (3) (0)

GC-MS-Analysis

Adsorptiontube

tube

Quarz-use for condensate

Sample preparation

Low-volatile PAKs

Volatile aromatic compounds

Airborne

Soot

Roland Goertz Abwehrender Brandschutz

CH3

CH2

Benzol Toluol Styrol Inden

CH3

Naphthalin Methylnaphthalin Biphenyl Acenaphthylen

Fluoren Phenanthren Anthracen Fluoranthen

Pyren Chrysen Benzpyren

Typical fire-smoke organic

fire-decompositionproducts

Roland Goertz Abwehrender Brandschutz

0

10

20

30

40

50

60

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29

Substanz-Nr.

A

n

z

a

h

l

0

100

200

300

400

500

1 2 3 4 6 7 8 9 10 13 16 17 20 21 23 27 28 35 38 39 40 43 44 48

Hauptklasse

A

n

z

a

h

l

Frequency of compounds - Evaluation

Roland Goertz Abwehrender Brandschutz

1 2 3 4 5 6 7 8 90

100000

200000

300000

400000

counts

/mg

BrandgutStyropor

PU-Schaum

Polycarbonat

Milchpulver

Zucker

Mehl

Kaffee

Trinkschokolade

Kakao

Part of medium-volatile compounds

(Benzol, Toluol, Styrol, Inden Naphthalin)

Roland Goertz Abwehrender Brandschutz

CNCH3

NH

CN

N

Benzonitril Methylindolin Naphthalincarbonitril Acridin

NNH

CN

Benz(A)acridin Carbazol Anthracencarbonitril

Typical organic fire-decomposition

products of PU-foam

Roland Goertz Abwehrender Brandschutz

O OCH3

CH3

Cl

Cl

2-Methoxyfuran 1-Chlorethylbenzol Chlornaphthalin

O

Dibenzofuran

Typical organic fire-decomposition

products of PVC

Roland Goertz Abwehrender Brandschutz

(81,0%)

(19,0%)

(81,0%)

(19,0%)

Share of nitrogen-containingdecompositionproducts whenburning polyurethane

Share of chloride-containingdecompositionproducts whenburning polyvinylchloride

Roland Goertz Abwehrender Brandschutz

Aldehyde

can cause damage

Oil/fat

- Low odor-theshhold

- Irritation of eyes and mucous membranes

- Large quantities detectable

Also: psychological damage of population

e.g.

Acrolene

Roland Goertz Abwehrender Brandschutz

Chloride-containing fuels

lead to hydrochloric acid

Cl

Cl2 COCl2

HClChloride-containing

organic compounds

Roland Goertz Abwehrender Brandschutz

PCDD/F

Low temperature

Large quantities of

chloride-containing fuel

Copper

Precursor substances

(e.g. PCB)

Favourable factors in forming

relevant quantities of PCDD/F

O

O ClxCly

O ClxCly

Relevant quantities

PCDD/F

Roland Goertz Abwehrender Brandschutz

inorganic gasses,

aromates and PAK

Dioxine/Furane

Chlooraromates

Emergency measures determined by:

- inorganic firegasses,

- aromatic compounds and

- PAKs

Roland Goertz Abwehrender Brandschutz

Summary:

Danger-determination fire smoke

2. Aromatic compounds (Benzol etc. and PAK) with

carcinogenic potential are always present

1. Inorganic firegasses determine instant toxicity!

3. Warm fires: from soot carcinogenic substances are

released in the air

breathingprotection

Inorganic firegasses

Organic fire-decompositionproducts

Roland Goertz Abwehrender Brandschutz

4. Soot contains low-volatile toxic compounds with

long-term effects

Avoid skincontact and adsorption

5. Chloride-containing organic compounds and PCDD/F

are only relevant under certain circumstances

Summary:

Danger-determination fire smoke

Roland Goertz Abwehrender Brandschutz

PREVIEW

Roland Goertz Abwehrender Brandschutz

PREVIEW

Univ.-Prof. Dr. Roland Goertz Lehrstuhl für Abwehrenden Brandschutz

Laboratory equipment

Roland Goertz Abwehrender Brandschutz

PREVIEW

Roland Goertz Abwehrender Brandschutz

PREVIEW