GMP-1 Project experience (Air Monitoring) GMP-2 Project challenges and expectations

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GMP-1 Project experience (Air Monitoring) GMP-2 Project challenges and expectations

GMP -1 Project participant for Air Monitoring – Passive Sampling

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Maria Yumiko Tominaga

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CETESB- Environmental Company of São Paulo State Physical-Chemical Analysis Division

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2

Brazil – São Paulo State

SAO PAULO CITY: 20 MILLION PEOPLE

BRAZIL : 190 MILLION PEOPLE SAO PAULO STATE

AREA : 248,000 SQ. KM

POPULATION: 40 MILLION PEOPLE

CETESB- Environmental Company of São Paulo State

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3 Technology transfer International cooperation Contaminated site management Environmental Quality Monitoring Air – Water - Soil

Pollution control Environmental analysis Pollution prevention Emergency actions Risk analysis Environmental company of São Paulo State

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CETESB Environmental Analysis laboratories

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Monitoring network: Superficial water (freshwater) 47 196 241 264 272 288 323 333 338 344 354 369 12 18 21 18 24 25 26 25 21 24 25 31 31 31 32 33 34 36 30 30 30 28 7 13 13 13 13 13 13 13 13 12 16 0 50 100 150 200 250 300 350 400 450 1974 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Evolução dos pontos de amostragem

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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):

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Air Quality Monitoring

www.cetesb.sp.gov.br

Manual Monitoring networks

SO2, FMC smog, PTS, PM2.5, PM10 Automatic monitoring network

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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

Analytical capacity - CETESB

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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 GC-HRMS/prepare the lab site for installation *State fund for Water resources

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Compounds not regulated (Quality Stantard – for environment monitoring) in Brazil

Pentachlorobenzene Chlordecone

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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

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ORGANOGRAMA GMP-1 Project

Ambient Air Results – 2010-2014

Dioxins/Furans + dl-PCBs (fg TEQ WHO₂₀₀₅/ m3₎

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ORGANOGRAMA

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

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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

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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

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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 !!????

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Gracias!!

Thank you!

CETESB - CIA AMBIENTAL DO ESTADO DE SÃO PAULO www.cetesb.sp.gov.br

Maria Yumiko Tominaga mytominaga@sp.gov.br

Divisão de Análises Físico-Químicas ela_cetesb@sp.gov.br

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Ambient Air Results – 2010-2014

PCDD/F and dl-PCB contribution (%) for the total TEQ (urban/vehicle traffic area)

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Ambient Air Results - Brasil

0 50 100 150 200 250 300 350 400 Endosulfan

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ORGANOGRAMA UNEP/GEF project 2009-2011

Pinheiros air monitoring station

Urban area – vehicle traffic

Passive Air sampling

PUF disk samling:

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Sediment quality monitoring: 2002– 2010

Tominaga et al. Organohalogen Compounds, 2011.

Land occupation:

Industrial

In industrial development Agriculture

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23 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

Equipamentos de análise - Guia UNEP

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ORGANOGRAMA GMP Project 2009-2011 Ambient Air Results - Brasil

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GAPs Network – Endosulfan I

Harner, T (Montevideo, 2009) Pozo,K. (Environ. Sci. Technol. 2006, 40, 4867-4873)

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Recetox-Tocoen Report nº339, 2008 (www.pops.int)

São Paulo, Julho 2010 – Junho 2011

GMP Project 2009-2011 Ambient Air Results - Brasil

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GMP Project 2009-2011 (Pinheiros)

Assunção et al., 2005 (F. Saúde Púb.)

GMP Project 2009-2011 Ambient Air Results - Brasil

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ORGANOGRAMA

Urban area:Gana,

Sudão, Tunísia, Brasil

GMP Project 2009-2011

Ambient Air Results - Brasil

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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

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