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

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1 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, 1-4 th December 2015

2 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

3 Pollution control Environmental Quality Monitoring Air Water - Soil CETESB Environmental company of São Paulo State Technology transfer International cooperation Contaminated site management Emergency actions Risk analysis Environmental analysis Pollution prevention 3

4 CETESB Environmental Analysis laboratories Taubaté

5 Monitoring network: Superficial water (freshwater) Evolução dos pontos de amostragem Rede Básica Sedimento Balneabilidade Rede Automática

6 Laboratory tests tests/year

7 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)

8 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

9 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

10 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

11 Analytical capacity New POPs Compounds not regulated (Quality Stantard for environment monitoring) in Brazil Pentachlorobenzene Chlordecone

12 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

13 ORGANOGRAMA GMP-1 Project Ambient Air Results Dioxins/Furans + dl-pcbs (fg TEQ WHO 2005 / m 3 ) (urban/vehicle traffic area)

14 ORGANOGRAMA GMP-1 Project Ambient Air Results Brasil ( ) 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.

15 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

16 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

17 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 year STAFF to develop the work!!???? alternatives: University, phd students?!

18 Gracias!! Thank you! Maria Yumiko Tominaga Divisão de Análises Físico-Químicas CETESB - CIA AMBIENTAL DO ESTADO DE SÃO PAULO

19 ORGANOGRAMA GMP-1 Project Ambient Air Results PCDD/F and dl-pcb contribution (%) for the total TEQ (urban/vehicle traffic area)

20 ORGANOGRAMA GMP-1 Project Ambient Air Results - Brasil 400 Endosulfan Endos. I Endos. II Endos SO4

21 ORGANOGRAMA UNEP/GEF project Passive Air sampling Pinheiros air monitoring station Urban area vehicle traffic PUF disk samling: D&F, OCP, PCBs and dl-pcbs

22 Sediment quality monitoring: Land occupation: Industrial In industrial development Agriculture Conservation Tominaga et al. Organohalogen Compounds, 2011.

23 Equipamentos de análise - Guia UNEP GC ANALITOS VANTAGENS/ DESVATAGENS LIM. DET. ECD Pesticidas OC Sensível DDT~ 1pg PCBs orto Coeluição (erro) HCB~ 0,5pg MS Pesticidas OC (-)Sensível(ECD) DDT ~1-10pg PCBs Menor erro (ECD) HCB~ 1-10pg MS/MS Pesticidas OC (+)Sensível (MS) DDT ~1pg PCBs Menor erro (ECD/MS) HCB ~1pg HR/MS Pesticidas OC (+) Sensível(outros) DDT ~0,05pg PCBs Diox./Furanos Identificação confiável em baixas conc. Alto custo HCB~0,05pg Fonte: UNEP, 2004 (Guidance for a GMP for POPs). 23

24 ORGANOGRAMA GMP Project Ambient Air Results - Brasil

25 GAPs Network Endosulfan I Pozo,K. (Environ. Sci. Technol. 2006, 40, ) Harner, T (Montevideo, 2009) 25

26 GMP Project Ambient Air Results - Brasil São Paulo, Julho 2010 Junho 2011 Recetox-Tocoen Report nº339, 2008 (

27 ORGANOGRAMA GMP Project Ambient Air Results - Brasil

28 GMP Project (Pinheiros) GMP Project Ambient Air Results - Brasil Assunção et al., 2005 (F. Saúde Púb.) 28

29 GMP Project Ambient Air Results - Brasil ORGANOGRAMA Urban area:gana, Sudão, Tunísia, Brasil

30 Monitoramento PCBs em Peixes Cancer slope factor (CSF): 2 per mg/kg-d (USEPA, 1997) 9 Maximum acceptable cancer risk level (ARL): 1 in (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

31 Parâmetros desconformes 2011 e (%)

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