Fluorinated Waste and Firefighting ActivitiesBiodegradation Of Halogenated Foams From Petrochemical Refinery Soil

Dr. Renato Nallin MontagnolliPostdoctoral research supervised

by Prof. Ederio Dino Bidoia

São Paulo State UniversityRio Claro – SP – Brazil

Petroleum

Coal

Hidroeletrical

Gas

Nuclear

Berkeley

Firefighting foam

AqueousFilmFormingFoam

Aqueous Film

Oxygen

Foam Blanket

Foam Blanket

Perfluorinated compounds (PFCs)

PFBSaAm

PFPeSaAmA

PFHxS

PFOSPFBA

PFHpA

PFNA

FtTAoS

FtSaAm

FtB

FtS

PFDS

PFOSaAm

PFUdA

PFHpS

PFBSaAmAPFBSaAm

PFPeSaAmA

PFHxSPFDS

PFHpS

PFHxS

PFOSPFBA

PFHpA

PFNA

FtTAoSFtB

FtS

PFBSaAm

PFPeSaAmA

PFHxS

PFHpS

PFOS

PFBA

PFHpA

PFNA

FtB

FtS

PFBSaAmA

PFBSaAm

PFHpS

PFBSaAm

PFPeSaAmA

PFHpS

Elet

roflu

orat

ion

Fluortelomeration

PFCs

PFASprecursoras

FtTAoSFTOH

PFOA e PFOS

ex.: PFHxS, PFBAPFCAsPFSAs

FtSsFtBs

Deg

rada

tion

Formulation

PersistenceBioacumulation

Ecotoxicity

Human HealthLow weight in

newborns (FEI et al., 2007)

Menopause ahead oftime (KNOX et al.,

2011)

Low fertility atdetected in young

men semen(JOENSEN et al.,

2009)

Tireoidal diseases athuman population in the US (MELZER et

al., 2010).

Lowered attention(HOFFMAN et al.,

2010)

Compromisedimmunoresponseafter vaccination

(GRANDJEAN et al., 2012).

Renal insuficiencynearby a PFAS

factory (BARRY et al., 2013).

Ecotoxicity

Hepatotoxicity (FUENTES et al., 2007, JOHANSSON et al., 2009)

Imunotoxicity (PEDEN -ADAMS et al., 2008 e THIBODEAUX et al., 2003, HUANG et al., 2010)

Neurotoxicity (HAGENAARS et al., 2008, ANKLEY et al., 2005).

Bioacumulation

General wildlife (BAO et al., 2009; HOUDE et al., 2011; LOOS et al., 2010). Swedish minks (PERSSON et al., 2013) Fish (OAKES et al., 2010) Canadian sea turtles (SOLLA et al.,

2012).

LawsA Norma ABNT NBR 12615, em vigor desde 25/03/92, supera os requisitos da norma Petrobrás N- 1886 (1983) e torna tais substancias aprovadas para a comercialização, sem a preocupação com contaminações ambientais subsequentes

BTEX AFFF

Petroleumindustrycontext

Micro-organisms

The objective of this research was to detect the effects of the

individual components of full AFFF formulations and

characterize shifts in aromaticsdegradation while measuring

byproducts.

- 50 mL BH media- 50 µL AFFF- 9 µL BTEX- 5 g soil

- Simulatedcontamination from a refinery sample

Aerobic

Anaerobic

GC-FID(BTEX)

present study

GC-MS(AFFF)

ongoing research

Biotransformation Monitoring

Incubation

(35oC / no shaking)

GC-FID

n-alcanes

BTEX

GC-FID

AFFF Ansulite FormulationComponent Structure Concentration Fncrion

Water 77~85% Solvent

Dietyleneglicol

butil eter (Butyl

carbitol - DGBE)

12% Co-solvent / anti-

freezing

Alkyl-sulfates 1~2% Foam formation

agente

Perfluoriunated

surfactants

(Lodyne)

1~6% Foam forming,

spreading, fuel

difusion limiting

agente

Tolyltriazole 0,05% Anti-corrosion

AFFF Ansulite FormulationWater

DGBE

PFCs

AFFF

GC-FID

� A (AFFF) – Average degradation� B (DGBE only) – Lowest removal� C (Lodyne only) – Highest removal

Chromatogram before biodegradation Benzene (peak A) and toluene (peak B) mixture

A

B

Chromatogram after biodegradation in C (Lodyne) assaysshowing possible cathecol (peak C) and styrene (peak D) byproducts

formation

A C

B D

The release of persistent compounds should be avoided.

The context of this release is that of emergency situations in which lives and properties are at risk.

Reasonable thinking is recommended for defining priorities, where environmental remediation must be

placed in the background, since human safety is compromised.

The goal is not to preserve the environment to the detriment of human lives. After all, for this reason we have

bioremediation techniques.

DISCLAIMER

Acknowledgements