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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 ______________________________________ Maria Yumiko Tominaga __________________________ CETESB- Environmental Company of São Paulo State Physical-Chemical Analysis Division Montevideo, 1- 4th December 2015

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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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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

CETESB

CETESB Environmental Analysis laboratories

Taubaté

Monitoring network: Superficial water (freshwater)

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196241 264 272 288

323 333 338 344 354 36912

1821 18

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25 26 25 21 2425

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3131 32

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3436 30 30

3028

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1313 13

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1313 13 13

1216

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400

450

1974 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Evolução dos pontos de amostragem

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

www.cetesb.sp.gov.br

Manual Monitoring networks SO2, FMC smog, PTS, PM2.5, PM10 Automatic monitoring network SO2, NO, NO2, Nox, O3-Ozone, CO, PM10, PM2.5

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

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

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

Chlordecone

Analytical capacity – New POPs

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

ORGANOGRAMA GMP-1 Project Ambient Air Results – 2010-2014

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

(urban/vehicle traffic area)

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 Ambient Air Results – Brasil (2010-2011)

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!

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

ORGANOGRAMA GMP-1 Project Ambient Air Results – 2010-2014

PCDD/F and dl-PCB contribution (%) for the total TEQ

(urban/vehicle traffic area)

ORGANOGRAMA GMP-1 Project Ambient Air Results - Brasil

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400 Endosulfan

Endos. I Endos. II Endos SO4

ORGANOGRAMA UNEP/GEF project 2009-2011

Pinheiros air monitoring station Urban area – vehicle traffic

Passive Air sampling

PUF disk samling: D&F, OCP, PCBs and dl-PCBs

Sediment quality monitoring: 2002– 2010

Tominaga et al. Organohalogen Compounds, 2011.

Land occupation:

Industrial

In industrial development Agriculture Conservation

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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

Fonte: UNEP, 2004 (Guidance for a GMP for POPs).

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)

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

São Paulo, Julho 2010 – Junho 2011

GMP Project 2009-2011 Ambient Air Results - Brasil

ORGANOGRAMA 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

ORGANOGRAMA

Urban area:Gana, Sudão, Tunísia, Brasil

GMP Project 2009-2011

Ambient Air Results - 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 (%)