POLO DI SPECIALIZZAZIONE MICROINQUINANTI
DIPARTIMENTO PROVINCIALE DI TARANTO
Via Anfiteatro 8, 74100 Taranto
Tel +39 0999949764
Fax +39 0999946311
www.arpa.puglia.it
[email protected]
Levels of emerging and unregulated Persistent
Organic Pollutants (POPs) in urban ambient air
Esposito V,
V Maffei A, Varvaglione B, Bruno D, Ficocelli S, Rosito V,
Spartera M, Giua R, Blonda M, Assennato G
ARPA PUGLIA, Environment Agency of Apulia, Taranto ITALY
Ecomondo
Rimini 8 novembre 2013
Brominated flame-retardants
Brominated flame retardants are
chemicals used in many domestic
and industrial appliances with the
purpose to increase their
resistance to fire
Flame-resistant materials have a
large appeal on consumers
Picture taken at Doncaster Markets
(May 2004)
BFR consumption by
application
TVs
Computers
Cable insulation
Use of BFRs by application 2001
E&E
56%
(Source: BSEF)
Textile
7%
Clothing
Carpets
Upholstery
204 Mt
Transport
6%
Cars
Aircrafts
Subways
Building
31%
Materials
Paints
Adhesives
Molecular structures
HBCDD
= H, Br
PBDEs (209 congeners)
TBBPA
Relevance to the steel industry
PRODUCTION
USE
ELECTRONICS
TRANSPORT
FURNITURE
SOURCES
STEELMAKING (enters as scrap,
But also used in fireproofing,
ex. conveyor belts)
LANDFILL
BURNING
PBDEs properties
• Solids with low solubility (< 1ug/kg), high log Kow (>5)
• Lower congeners are more bioaccumulative, persistent
• Strong adsorption to soil/sediment/sludge
• No significant biodegradation in air/water
• Bioaccumulation - BCF > 5000
• Long Range Transport - Evidence of remote contamination
• Persistence: t 1/2 Atmospheric >2 days; Water >2 months; Soil,
sediment >6 months
PBDEs: Toxicity
• Adult mammalian
toxicity
– Hepatic enzyme induction
and toxicity
• decaBDE
hepatocarcinogen (high
dose)
– Endocrine disruptor
• Thyroid
• Estrogen/antiandrogen
• Developmental reproductive
toxicity
– BDE 99
– Delayed puberty, sex organ weight
changes, ovarian Tox, decreased
sperm counts
• Developmental neurotoxicity
– BDEs 47, 99, 203, 206, 209
– Deficits in sensory, motor, and
cognitive function
Molecular structures
pentaBDE 99
Thyroxine T4
PBDE levels in the environment
and people
Sample type
HUMAN
USA
UK
SWEDEN
blood
41.1
-
6.0
milk
29.2
-
1.8
AIR
indoor
-
1780.0
1400.0
(pg/m3)
outdoor
-
5.3
-
BIRDS
eggs
7510.0
1160.0
2140.0
FISH
other
7200.0
19.2
515.0
3.2
3.8
-
-
136.0
7190.0
farmed salmon*
SEDIMENT
river
Values are expressed in ng/g dry weight and represent the total concentration as sum
of congeners BDE 47, 99, 100, 153, 154, 209
Source:
R. A. Hites, Environ. Sci. Technol. 2004, 4.
*R. A. Hites et al, Environ. Sci. Technol. 2004, 38.
Human exposure pathways
Higher exposure occurs through diet
UK exposure assessment
Dietary intake (omnivorous, ng/day)
Inhalation intake (ng/day)
sum PBDEs
90.5
6.9
Omnivorous diet (pg/g dry weight)
195.5
Vegan diet (pg/g dry weight)
151.7
Sum PBDEs is the sum of concentrations for BDE 47, 99, 100, 153, and 154
Source:
S. Harrad et al, Environ. Sci. Technol. 2004, 38.
EU Legislation
Legal basis
Content
Deadline
BFR
WEEE Directive
Separation of BFR plastics from E&E
equipment prior to recovery and
Dec-06
recycling
All BFRs
RoHS Directive
Ban of use in new E&E applications
01-Jul-06
PentaBDE
OctaBDE
PBB
24th amendment to the
marketing and use
Directive 76/769/EEC
Ban of use in all applications for the
EU Market
15-Aug-04
PentaBDE
OctaBDE
EU Target
Cessation of emissions in the
Environment
2020
PentaBDE
Legislazione Italiana
MONITORAGGIO CORPI IDRICI SUPERDFICIALI (C.I.S.)
Tabella 1/A (acque superficiali interne) Allegato 1, Parte III, D.Lgs. N. 152/2006.
Numero CAS
Sostanza
SQA-MA (2)
Acque superficiali
interne
SQA-MA
Altre acque di
superficie
Difeniletere bromato (1)
0.0005 μg/L
0.0002 μg/L
...
32534-81-9
...
(1) Somma dei congeneri BDE 28, 47, 99, 100, 153 e 154
(2) Standard di qualità ambientale espresso come valore medio annuo (SQA-MA)
PBDE nei Corpi Idrici Superficiali - Puglia Anno 2012
Acque Marino-costiere, di transizione, fiumi, laghi, invasi
Somma BDE 28,47,99,100,153,154 microg/L
0,0025
0,002
0,0015
0,001
0,0005
0
Codice Stazione
6,7
1
5
2
3
4
8
9
The Taranto area (Southern Italy) hosts several
industrial facilities including thermal/combustion
processes with remarkably high raw materials and
high energy demand and known potential sources of
PCDD/Fs and PCBs release to air, land, and water.
These facilities include a large integrated steel plant
(1), a medium-sized oil refinery (2), a large cementworks (3), two power plants (4,5), and three waste
incinerators (6,7,8) as well as a large naval base with
military shipyards (9).
PM10 and Atmospheric depositions sampling network
QUARANTA farm (rural)
2
1
FORNARO farm (rural)
6
TAMBURI (industrial)
TAMBURI (industrial, SCHOOL!)
3
5
BORGO (urban, NO TRAFFIC)
Not active (as of june 2013)
4
Active (as of june 2013)
TALSANO (urban background, SCHOOL!)
Monthly PCDD/F + dl-PCB
ambient air (PM10) levels
POLO DI SPECIALIZZAZIONE MICROINQUINANTI
DIPARTIMENTO PROVINCIALE DI TARANTO
Via Anfiteatro 8, 74100 Taranto
Tel
+39 0997786806
Fax
+39 0997786802
www.arpa.puglia.it
[email protected]
(urban-industrial)
PCDD/F e PCB-DL nel PM10 Via Machiavelli (urbano-industriale)
PCDD/F
2008
100
90
80
70
fgTE/m3
60
50
40
30
20
10
0
2009
2010
PCB-DL
2011
2012
2013
Monthly ambient air (PM10) levels
(urban-background)
PCDD/F e PCB-DL nel PM10 Talsano (fondo urbano)
PCDD/F
2008
100
90
80
fgTE/m3
70
60
50
40
30
20
10
0
2009
2010
PCB-DL
2011
2012
2013
Profilo di congeneri PBDE nel PM10 (Machiavelli, ottobre 2012)
PBDE nel PM10 - Taranto 2012
Machiavelli (sito urbano-industriale)
Talsano (fondo urbano)
SOMMA BDE 28,47,99,100,153,154 fg/m3
2500
2000
1500
1000
500
0
Anno 2012
PBDE Media anno 2012
Machiavelli (sito urbano-industriale)
1221.3 fg/m3
Talsano (fondo urbano)
840,1 fg/m3
Mr Donato Bruno
Dr Annamaria Maffei
Dr Niki Varvaglione
Mr Luca Gigante