Petra Fišerová
Modern Methods for Analyses of Organic Pollutants
May 2017
recetox logo.jpg logo muni.jpg

}whether or why is it important
}phthalates
}utilization, measuring/monitoring
}instrumental analyses
}phthalate surrogates
}conclusion
2

}ubiquitous, high-volume production
}plasticizers, non-odour solutions
}pseudopersistent compounds
}considered high priority pollutants
}reprotoxicity, cardiotoxicity, hepatotoxicity
}indoor pollutants – 95% of time actually indoor
}
}
}              à It IS important to solve
3

}ortho-phthalic acid esthers
}lipophilic with ability to bioaccumulate, semivolatile (DMP* – volatile) }since 20. of 20.
century, industrially 80 years ago
}about 40 million tuns per year made
}not directly bonded to plastic, easily enter environment }can constitute up to 40% of total mass
in PVC
DEHP.png
DEHP – diethyl hexyl phthalate
4
*DMP – dimethyl phthalate

}ubiquitous in environment, possible migration
}metabolism – phase I – hydrolysis – transformation from dialkyl-form to monoalkyl-form }
– phase II – conjugation – excretion in glucuronidated form in urine
}
5
Source
Matrix
Phthalates [ng/mL]
Ustun et al., 2014
Bottled mineral water
85,0-312,0
Del Carlo et al., 2008
Wine
138,0-385,0
Mortensen et al., 2005
Comercially available milk
0,6-9,1
Frederiksen et al., 2007
Human amniotic fluid
2,8-264,0
Černá et al., 2015
Human urine
3,3-98,4
Mortensen et al., 2005
Human milk
72,0-10 900,0

Phthalate
Peňalver et al., 1999
Valton et al., 2014
DMP
<LOD
0.04
DEP
0.26-0.62
0.53
DBP
0.12-0.16
0.12
BzBP
<LOD
0.06
DEHP
0.70-2.12
0.98
LOD
0.0007-0.17
-
Method
SPE-GC-MS
GC-MS
Sampling site
Ebro, Spain
Orge, France
6
Ø comparison of concentration of phthalates in river water from years 1999 and 2014 [ng/mL]
DMP – dimethyl phthalate, DEP – diethyl phthalate, DBP – dibutylphthalate, BzBP- benzylbutyl
phthalate, DEHP – diethylhexyl phthalate, LOD – limit of detection

}Used as:
}Already measured in:
}
}plasticizers
}solutions in cosmetics (personal care products - PCPs): deodorants, perfumes, hair sprays, nail
polish }industrial products – paints, glues, building materials, house stuff, clothes
}
}
}
}air
}water
}soils, sediments
}dust
}food packaging materials, food itself
}human blood/serum, milk, urine
}bottled drinks, beer, wine
}PCPs, wet wipes, diapers,…
}
}
7

Plasticizer
REACH
Endocrine Disruptor
Toxicity
TDI [mg/kg of body weigh]
Banned in
DEHP
X
Cat. 1
Reproductive, causes alergies, asthma
0,05
Toys, products for children, cosmetics
DBP
X
Cat. 1
Reproductive, developmental
0,01
Toys, products for children, cosmetics
DIDP
Cat. 2
Hepatotoxicity
0,15
Toys for „chewing“
BzBP
X
Cat. 1
Reproductive, developmental
0,50
Toys, products for children, cosmetics
DINP
Cat. 2
Hepatotoxicity, causes alergies, asthma
0,15
Toys for „chewing“
DIBP
X
Cat. 2
Reproductive, developmental
Unknown
-
DNOP
-
Hepatotoxicity
-
Toys, products for children
DPP (dipentyl phthalate)
X
-
Reproductive, developmental
-
-
8

}highest exposure – children (toys, playing on the foor in dust, eating everything, cosmetics,
mainly private parts - diapers, wet wipes), breast milk
}women – higher exposure to phthalates used in PCPs than men (MEP, MBP, MiBP)
}interesting – high concentration of MEP in pregnant women (3rd trimester)
}phthalates in plastic products  - not gender specific (MMP, MBzP, MEHHP)
}
}
9
MEP – monoethyl phthalate, MBP – monobutylphthalate, MiBP – monoisobutyl phthalate, MMP –
monomethyl phthalate, MBzP- monobenzyl phthalate, MEHHP – monoethylhexyl hexyl phthalate

}plenty of data, but not in highest quality
}measurements in huge amount of matrices
}„standard“ environmental – air, water, soils, sediments
}human matrices – blood/serum, urine, milk
}beverages – non-alcoholic and alcoholic
}food wrapping materials, food itself
}PCPs, diapers, wet wipes, …
}toys
}mural paintings, fishing baits, pharmaceutic wrapping, glues, building materials, …
10

}
ØGC-ECD
ØGC-MS, GC-MS/MS
ØLC-UV/VIS
ØLC-APCI-MS, LC-APCI-MS/MS
ØLC-ESI-MS, LC-ESI-MS/MS
11

12
}create high quality instrumental method respecting metabolism, monitor in urine
}measurement possible in many matrices, difficult to estimate exposure or main source
}some phthalates characterised well (toxicity), desirable to complete these information to all
phthalates
}

}1999/815/ED – DEHP, DBP a BzBP in toys
}e.d. 1223/2009 – DEHP and BzBP in cosmetics
}decree. No. 38/2001 Coll., + 271/2008 Coll.,  - DEHP and DBP in food wrapping materials
}2009/48/ED – DINP in toys (czech legislation – government regulation 86/2011 Coll.) }decree. No.
284/2006 Coll. – DIDP and DNOP in toys and in children care products }decree. No. 38/2001 Coll., +
54/2004 Coll. – DIDP in food wrapping materials
}usage of surrogates
13
DINP – diisononyl phthalate, DIDP – diisodecyl phtthalate, DNOP – di-n-octyl pthalate

}DEHP banned, substituted by DINP and DIDP, banned in 2005 }2002 – DINCH introduced to the market
(1,2-cyclohexane carboxylic acid) aka Hexamoll (instead of DINP) }does not have influence on
fertility up to 1000 mg/kg body weigh per day
}1999, 2003 – DINCH not detected
}since 2006 concentration of DINCH increase
14
DINCH
2006
2009
2012
Increase in samples
(from 2003)
7%
43%
98%

}in 80. of the last century – DEHT introduced, aka Kodaflex DOTP
}50 thousand tuns per year
}no information about toxicity
}NOAEL (reproductive toxicity) = 800-1000 mg/kg body weigh per day }NOEL (carcinogenity) = 666
mg/kg body weigh per day
15
DEHT – diethylhexyl terephthalate

}Comparison of boiling point (DINP, DINCH):
}Comparison of boiling point (DEHP, DEHT):
DINP
DINCH
244-252 °C
240-250 °C
16
DEHP
DEHT
385 °C
400 °C

}toxicological information is not complete
}hard to quantitate exposure routes
}difficult to find surrogates with simmilar properties without creating the same problem }not
possible to ban phthalates and surrogates – necessary to plastic production }(possible to reduce
plastic products – e.g.using glass)
17

}Until now
}plenty of data
}huge amount of matrices }some toxicological information available } few phthalates forbidden
}Future plan
}higher quality of data
}more precise instrumental methods
}monitoring in urine (pregnant women, +children)
}combination with personal questionares
}being focused on surrogates now
18