GMP-1 Project experience (Air Monitoring)
GMP-2 Project challenges and expectations
GMP -1 Project participant for Air Monitoring – Passive Sampling
______________________________________
Maria Yumiko Tominaga
__________________________
CETESB- Environmental Company of São Paulo State
Physical-Chemical Analysis Division
Montevideo, 1- 4th December 2015
Brazil – São Paulo State
BRAZIL : 190 MILLION PEOPLE
SAO PAULO STATE
AREA : 248,000 SQ. KM
POPULATION: 40 MILLION PEOPLE
SAO PAULO CITY:
20 MILLION PEOPLE
CETESB- Environmental
Company of São Paulo State
2
Pollution control
Environmental
Quality Monitoring
Air – Water - Soil
Technology
transfer
CETESB
Environmental company
of São Paulo State
Emergency actions
Risk analysis
International
cooperation
Contaminated
site management
Pollution prevention
Environmental analysis
3
CETESB Environmental Analysis laboratories
Taubaté
Monitoring network: Superficial water (freshwater)
Evolução dos pontos de amostragem
450
13
400
350
13
300
31
18
7
250
13
13
31
21
32
13
34
33
25
13
13
16
13
12
30
28
25
36
30
26
25
30
21
338
344
354
369
2009
2010
2011
2012
24
24
18
31
200
12
150
241
100
264
272
288
2004
2005
2006
323
333
2007
2008
196
50
47
0
1974
2002
2003
Rede Básica
Sedimento
Balneabilidade
Rede Automática
Laboratory tests
250.000 tests/year
Environmental Quality Monitoring
Water quality standards (regulation in Brazil):
Superficial water : Conama 357/2005 (OCPs/PCBs)
Wastewater: Conama 430/2011
Groundwater: Conama 396/2008 (OCPs/PCBs)
Drinking water: Portaria 2914/2011 (OCPs)
Sediment: Conama 454/2012 (OCPs/PCBs - dredged
material)
Soil quality standards (regulation in Brazil):
Soil: Conama 420/2009 (OCPs/PCBs)
Air Quality Monitoring
Manual Monitoring networks
SO2, FMC smog, PTS, PM2.5, PM10
Automatic monitoring network
SO2, NO, NO2, Nox, O3-Ozone, CO, PM10, PM2.5
www.cetesb.sp.gov.br
Analytical capacity - CETESB
Compounds Matrices
Sample preparation
Equipment
OCP
PCB
Water
Soil/Sedim.
Solid waste
Biota
Ext.: Líq/Líq, soxhlet,
microwave
Cleanup: GPC, silica,
florisil
GC-µECD
CG-MS/NCI
GC-MSMS
Dioxins ,
Furans,
dl-PCB
Soil/Sedim.
Solid waste
Biota
Air emission
Ext: Soxhlet,
microwave
Cleanup: multilayer
silica, alumina,
charcoal
GC-HRMS
OCP
PCB
Dioxins and
furans
Air ambient*
Ext.: Soxhlet
Cleanup: GPC, silica,
alumina..
GC-µECD
(MS-NCI)
GC-MSMS
GC-HRMS
* After GMP-1 - Built Capacity for POPs sampling/analysis in ambient air
Analytical capacity – New POPs
PFCs: need capacity building
LCMSMS dedicated for algae toxins analysis
LC-Q-TOF: purchasing process*
screening emerging compounds (including
PFCs)
PBDE: need capacity building
Project approved* to purchase new GCHRMS/prepare the lab site for installation
*State fund for Water resources
Analytical capacity – New POPs
Compounds not regulated (Quality Stantard – for
environment monitoring) in Brazil
Pentachlorobenzene
Chlordecone
GMP-1 Project Benefits
 Capacity built: OCP, PCB/dl-PCB, PCDD/F
sampling/analysis in ambient air
- training received: passive sampling/GC-HRMS
(CSIC and private lab in Germany)
 Passive sampling tecniques
- Initial idea: GMP – time trends
- Useful tool for CETESB´s monitoring activities
plans to extend for water sampling
ORGANOGRAMAGMP-1 Project
Ambient Air Results – 2010-2014
Dioxins/Furans + dl-PCBs (fg TEQ WHO2005/ m3)
(urban/vehicle traffic area)
ORGANOGRAMAGMP-1 Project
Ambient Air Results – Brasil (2010-2011)
Resolução RDC nº28 de 09 de Agosto de 2010
Art. 1º Determinar a retirada programada do ingrediente ativo endosulfan
do mercado brasileiro no prazo de 3 anos, a partir de 31 de Julho de 2010.
GMP-1 Project Problems
 Memorandum of understanding (MOU) signature:
bureaucracy took too much time
 CETESB received the project funding and
transferred to FIOCRUZ: bureaucracy took too
much time – not possible to transfer all part of the
funding
 Project time was too short (considering the delay
for MOU signature): no time for all results
discussion
Challenges and expectations for the GMP-2
project
 New POPs: there is no regulation in Brazil
(quality standards)
 CETESB: 2 projects – purchase new
equipments (LC-Q-TOF/ GCHRMS)
- Emerging compounds (including PFCs) in
superficial water
- POPs (including PBDEs) in an
urban/industrial area of São Paulo State
Challenges and expectations for the GMP-2
project
 Build analytical capacity for new POPs
1- PFCs and other emerging compounds: pharmaceiticals ,
pesticides, personal care products, etc
LC-Q-TOF for screening
2- PBDEs
GC-HRMS
 Evaluate the presence of PFCs/PBDE in the environment
 Capacity to use passive sampler for water quality
monitoring
Equipments – probably purchased in 1-1.5 year
STAFF to develop the work !!????
 alternatives: University, phD students?!
Gracias!!
Thank you!
Maria Yumiko Tominaga
[email protected]
Divisão de Análises Físico-Químicas
[email protected]
CETESB - CIA AMBIENTAL DO ESTADO DE SÃO PAULO
www.cetesb.sp.gov.br
ORGANOGRAMAGMP-1 Project
Ambient Air Results – 2010-2014
PCDD/F and dl-PCB contribution (%) for the total TEQ
(urban/vehicle traffic area)
ORGANOGRAMAGMP-1 Project
Ambient Air Results - Brasil
400
Endosulfan
350
300
250
200
150
100
50
0
Endos. I
Endos. II
Endos SO4
UNEP/GEF project 2009-2011
ORGANOGRAMA
Passive Air sampling
Pinheiros air monitoring station
Urban area – vehicle traffic
PUF disk samling:
D&F, OCP, PCBs and dl-PCBs
Sediment quality monitoring: 2002– 2010
Land occupation:
Industrial
In industrial development
Agriculture
Conservation
Tominaga et al. Organohalogen Compounds, 2011.
Equipamentos de análise - Guia UNEP
GC
ANALITOS
VANTAGENS/
DESVATAGENS
LIM. DET.
ECD
Pesticidas OC
PCBs orto
Sensível
Coeluição (erro)
DDT~ 1pg
HCB~ 0,5pg
MS
Pesticidas OC
PCBs
(-)Sensível(ECD)
Menor erro (ECD)
DDT ~1-10pg
HCB~ 1-10pg
MS/MS
Pesticidas OC
PCBs
(+)Sensível (MS)
Menor erro (ECD/MS)
DDT ~1pg
HCB ~1pg
HR/MS
Pesticidas OC
PCBs
Diox./Furanos
(+) Sensível(outros)
Identificação confiável
em baixas conc.
Alto custo
DDT ~0,05pg
HCB~0,05pg
Fonte: UNEP, 2004 (Guidance for a GMP for POPs).
23
GMP Project 2009-2011
ORGANOGRAMA
Ambient Air Results - Brasil
GAPs Network – Endosulfan I
Pozo,K. (Environ. Sci. Technol. 2006, 40, 4867-4873)
Harner, T (Montevideo, 2009)
25
GMP Project 2009-2011
Ambient Air Results - Brasil
São Paulo, Julho 2010 – Junho 2011
Recetox-Tocoen Report nº339, 2008 (www.pops.int)
GMP Project 2009-2011
ORGANOGRAMA
Ambient Air Results - Brasil
GMP Project 2009-2011
Ambient Air Results - Brasil
GMP Project 2009-2011 (Pinheiros)
Assunção et al., 2005 (F. Saúde Púb.)
28
GMP Project
ORGANOGRAMA
2009-2011
Ambient Air Results Brasil
Urban area:Gana,
Sudão, Tunísia, Brasil
Monitoramento PCBs em Peixes
Cancer slope factor (CSF): 2 per mg/kg-d (USEPA, 1997)9
Maximum acceptable cancer risk level (ARL): 1 in 100000 (10-5)
Reference dose for PCBs (RfD): 2 X 10-5 mg/kg-d (USEPA, 1996)10
Relative source contribution (RSC): 50% (Voorspoels et al., 2008)11
Parâmetros desconformes – 2011 e 2006-2010 (%)