Leaching from plastic bottles_bottle line operators in English Language

1. Leaching of chemicals in water
from plastic bottles
Aquasyn
Cyprus University of Technology

2. Module Overview
• Types of plastic bottles
• Presence of plasticizers in bottled water
• Chemical leaching from plastic bottles into water
• Chemical compounds found in bottled water
• Studies on the migration of chemicals into water
• Legislation on chemicals in drinking water
• Studies on health effects from compounds found
in bottled water
• Factors affecting chemical leaching
• Recommendations for minimizing chemical
leaching

3. Types of plastics
PET or PETE: Polyethylene
Terephthalate
HDPE: High-density
Polyethylene
Other (PC)
LDPE: Low-density
Polyethylene
PS: PolystyrenePP: Polypropylene
PVC: Polyvinyl Chloride
http://www.wrap.org.uk/content/types-plastic

4. PET
• The most widely used material
for bottling water1
• Resistance to chemicals
• Low gas and water vapour
permeability
• Strength and impact-
resistance
• Low weight
• Colourlessness and
transparency
• Easy recycling procedures
http://yoohuat1969.com/?portfolio=pet-bottles&lang=en

5. PC
• High transparency3
• High strength
• High heat resistance
• Good electrical insulation
properties
• Biologically inert
• Readily recyclable
• Easy to process
• Widely used in2
– infant feeding bottles
– tableware (plates, mugs, jugs, beakers)
– microwave ovenware
– storage containers
– returnable water and milk bottles
– refillable water containers
http://www.plastemart.com/upload/home/extrusion-3d-shuttle-blow-molding-machines-manufacturers.asp

6. Presence of plasticizers in bottled
water
• Can be attributed to4:
– Water contamination in the bottling plant
– Migration of plasticizers from the bottle material to
the water since quality may vary depending on the
raw material as well as the technology used in bottle
production
– Cross-contamination during analytical procedure due
to the wide use of plasticizers.

7. Chemical leaching from plastic bottles
• Broad functionality of polymers5
– Due to additives
• Additives
– Plasticizers, Coloring agents, Flow aids, Heat stabilizers
– Not chemically bound to the polymer chains
– Can migrate within the material and leach into water
– More prone to dissolve in the aqueous environment
– Contribute to the risk of exposure of humans

8. Leaching of EDCs in bottled water
• Endocrine-disrupting chemicals (EDCs)6
– Substances which interfere with the synthesis,
secretion, transport, binding, action or elimination of
natural hormones in the body that are responsible for
development, behaviour, fertility and maintenance of
homeostasis (normal cell metabolism)
– BPA, phthalates, perfluorinated compounds,
alkylphenols like 4-nonylphenol, adipates and perhaps
brominated flame retardants7

9. Chemical compounds found in bottled
waters
• Bisphenol A (BPA)4
– Monomer used in the production of polycarbonates and epoxy resins
– Demonstrates estrogenic activity
– Considered as important organic pollutant
• Nonylphenol (NP)
– Widely spread in the environment as a result of its use in industry as raw material, as additive in
epoxy resins to enhance properties of polymerization, drying, plasticity, etc
• Nonylphenol and octylphenol (OP)
– Present endocrine response
– Since January 2005, there has been a restriction in Europe on the sale and use of products that
contain more than 0.1% of 4-nonylphenol ethoxylates (NPEOs) or 4-nonylphenols (NPs)
• Phthalates (PEs)
– Ubiquitous pollutants in the environment due to their widespread use for around 50 years
– Used principally as plasticizers, to impact flexibility, workability and durability to polymers
– Also found in products such as paints, adhesives, inks and cosmetics
– Phthalates such as BBP, DBP and DIBP have been found to elicit estrogenic responses
– Possible that phthalates are a contributory factor to endocrine-mediated adverse effects observed
in wildlife and humans over the past few decades

10. Chemical compounds found in bottled
waters
• Acetaldehyde8
– Mainly used as an intermediate in the synthesis of other
chemicals
– Used in the production of perfumes, polyester resins and basic
dyes
– Ubiquitous in the environment
• Formaldehyde9
– Mainly used to produce resins and as an intermediate in the
synthesis of other chemicals
– Found in building materials furniture and some consumer
products
• Antimony (Sb)10
– Metal found at very low levels throughout the environment
– Antimony oxides are used as fire retardants for plastics, textiles,
rubber, adhesives, pigments and paper

11. Migration of compounds from bottles
into water
(a) PET bottles
• Acetaldehyde
– Aldehydes are formed due to thermal degradation of the polymer during the PET bottle
production11
– Acetaldehyde is held in the structure of bottle material and during the storage period,
passes from the wall into the water and into the air
– Trace amounts have been found in bottled water1,12-15
• Formaldehyde
– Variable amounts have been found in bottled water1,15,16,65
• Antimony17-21
– Antimony trioxide is the preferred catalyst for the fabrication of PET due to its adequate
catalytic activity, colour and cost23
• Esters of phthalic acid-Phthalates (?)
– Some studies suggest that phthalates are part of PET bottles for conferring flexibility1,17
– But there are claims that phthalates are not used in manufacturing PET24
– Known phthalates (DMP, DEP, DBP, and DEHP) have been detected in water contained in
PET bottles16, 25-27
– However, other sources of phthalate contamination cannot be ruled out4

12. (b) PC bottles
• BPA
– Unstable bond between BPA & PC28
– Migration of BPA into water29
(c) Tritan™ copolyester
– BPA-free plastic28
– Potential substitute of PC
– Low migration of BBP & DMIP (phthalate esters)
Migration of compounds from bottles
into water

13. • Dialkyl maleates & fumarates30
– Emerging chemicals found in bottled water
– Might represent a novel group of steroid receptor
antagonists
– So far, they have been disregarded by the scientific
and regulatory community
Migration of compounds from bottles
into water

14. Legislation on chemicals in drinking
water
• Directive 2008/105/EC, Annex II31
– DEHP, NP and OP are listed as priority substances in the field of water policy
– BPA: list of substances subject to review for identification as possible priority
substances in the field of water policy
• US EPA under the Safe Drinking Water Act32,33
– DEHP & DEHA under National Primary Drinking Water Regulations
– DEHP: maximum concentration limit of 0.006 mg/L
– Closely screening of phthalates in drinking water at concentrations above this
limit
– BBP, DBP, DEP, DINP, NP, NPEs, OP, OPEs and BPA are nominated in the third
contaminant candidate list for compounds that may require regulations under
the Safe Drinking Water Act
• Integrated Risk Information System (IRIS) of US EPA34
– Establishes reference dose for chronic oral exposure (RfD) based on chronic
health hazard assessment for non-carcinogenic effects
• RfD
– BPA: 5×10-2 mg/kg bw/day, DEP: 8×10-1, DBP: 1×10-1, BBP: 2×10-1, DEHP: 2×10-2

15. Legislation on chemicals in drinking
water
• European Food Safety Authority
– Tolerable daily intake (TDI) represents a safe level for daily exposure over a
lifetime
• TDI2,35,36
– BPA, DEHP: 0.050 mg/kg bw, DBP: 0.010 mg/kg bw
• European Commission37-39
– Specific Migration Limit (SML): set according to the Acceptable Daily Intake or
the Tolerable Daily Intake established by the Scientific Committee on Food
– Food-contact materials must not transfer their components into the foods in
unacceptable quantities (migration).
– The limit is set on the assumption that every day throughout lifetime, a person
weighing 60kg eats 1kg of food packed in plastics containing the substance in
the maximum permitted quantity.
– SML for BPA: 600 mg/kg food
– Ban the use of BPA for the manufacture of polycarbonate infant feeding bottles

16. Legislation on chemicals in drinking
water
• US National Toxicology Program (NTP) Center for the
Evaluation of Risks to Human Reproduction (CERHR)40
– Evaluation of BPA (2008)
– Based on approximately 500 studies reviewed
– ‘Minimal’ or ‘Negligible’ likelihood of human reproductive problems
– ‘Some Concern’ for neurological or behavioural effects in foetuses, infants, and
children
– ‘Minimal Concern’ that in utero exposure to BPA has a negative effect on the
prostate, produces birth defects and malformations and potentially causes
accelerations in puberty
– ‘Negligible Concern’ for adverse reproductive effects in the general population

17. Studies on health effects from
chemicals found in bottled water
• Acetaldehyde
– Genotoxic in many biological systems1
– Genotoxic: capable of altering DNA, thereby causing
cancer or mutation
– Possible human carcinogen (Group 2B, IARC)
• Formaldehyde
– Genotoxic & induces DNA & chromosomal damage in a
wide range of organisms1,41
– Human carcinogen (Group 1, IARC)

18. Studies on health effects from
chemicals found in bottled water
• BPA
– Its estrogenic activity and estrogen-independent activity are likely responsible
for its roles in promoting carcinogenesis of multiple cancers42
– Fetal exposure to BPA could lead to ‘‘long-lasting’’ effects on the carcinogenesis
of certain organs
– Found to induce breast carcinogenesis44
– May play a role in prostate carcinogenesis, in addition to promoting disease
progression43
– Association with several endocrine-related end points, such as reproductive
function studied in the setting of in vitro fertilization45,46, thyroid dysfunction
via fluctuations in up- or downregulation of thyroid hormones20, metabolic
syndrome, obesity, and type 2 diabetes mellitus47,48, hypertension49 and
cardiovascular conditions50
– In experimental animals exposed to low doses of BPA, potential adverse human
health effects observed, including an increase in prostate and breast cancer,
urogenital abnormalities in male babies, a decline in semen quality in men,
early onset of puberty in girls and neurobehavioral problems such as attention
deficit hyperactivity disorder51

19. Studies on health effects from
chemicals found in bottled water
• BPA Alternatives52
A) BPF & BPS
– Exhibit almost similar endocrine activity as BPA
– Substitution of BPA with these compounds should be
considered with caution
B) D-8 & Pergafast® 201
– Their in-vitro effects on steroidogenesis showed that
they may be good BPA alternatives
– Further research is needed to show that they do not
elicit adverse effects on the hormonal system

20. Studies on health effects from
chemicals found in bottled water
• Phthalates
– Environmental public health concern because of their demonstrated toxicity in animals53
Several phthalates produce testicular and liver injury, liver cancer and teratogenicity in
rodent studies
– Only limited human data on the relationship between exposure to phthalates & human
health54
– Significant association between the presence of urinary metabolites of phthalates and
some human health endpoints, particularly genital development in infants55
– In utero exposure to phthalates has been shown to be associated with a decreased
anogenital distance in male infants indicating undervirilization induced by
environmental levels of phthalates56
– Phthalate exposure to girls has claimed to be correlated with an earlier onset of
puberty57
(A) Di(2-ethylhexyl)phthalate (DEHP)
– Produces liver tumours in rats and mice by a non-DNA-reactive mechanism
– Classified as possible human carcinogenic (Group 2B, IARC)
– Characterized as probable human carcinogen (B2, IRIS list)
(B) Di-n-butyl phthalate (DBP)
– May adversely affect human reproduction or development
– DBP exposure levels that lead to adverse effects in rodents are far higher than those
experienced by people58,59

21. Factors affecting chemical leaching
• Generally
– The evidence suggests that PET bottles may yield
endocrine disruptors under conditions of common
use, particularly with prolonged storage and elevated
temperature61
– Classification of the studied factors according to their
contribution to chemical leaching from PET bottles:
Frequency of reuse > UV exposure duration >
Temperature62
– The most relevant parameters for degradation of PC
and thus migration of EDCs into water are
temperature and the food’s chemical properties like
pH and polymer age63

22. Factors affecting chemical leaching
• Formaldehyde & Acetaldehyde
– At 60 °C, the migration of these compounds was highly
accelerated64
– Carbon dioxide in bottled water contributed to the increase
of migration of both aldehydes
– Carbonation of water and high temperature enhance the
process of aldehyde migration or formation in water bottled
in PET13
– Higher concentration of acetaldehyde in bottled water stored
at 40 °C than at room temperature66
– Contrasting conclusions on the influence of sunlight have
been drawn. Nawrocki et al. (2002) observed an increase in
formaldehyde & acetaldehyde in carbonated water stored in
PET bottles exposed to sunlight over a period of time. In
contrast, Wegelin et al. (2001) observed the same level of
formaldehyde in unexposed bottled water in samples
subjected to the maximum irradiation rate.

23. Factors affecting chemical leaching
• Antimony
– The water’s natural composition may promote Sb migration64
– Antimony leaching in water was primarily enhanced with extending frequency
of reuse, but not to levels posing serious public health risk based upon existing
MCL value62
– Sb concentrations were found to have increased by 90% on average in 48
brands of bottled drinking water after a period of 6 months at room
temperature17
– Temperature, UV exposure promoted Sb leaching into finished water17,18,21,64
– PET exposure to sunlight appears to be less significant than other factors in Sb
migration21,67
– Sb dissolution rate into water is higher into sparkling water than into still water,
due to the lower pH of carbonated water21,67
– Contradictory conclusions have been reached regarding the effect of bottle
color on Sb migration. Whereas Westerhoff et al. (2008) detected an increase
in Sb concentration in clear PET compared to colored ones, Reimann et al.
(2010) concluded the opposite.
– It has been shown that higher bottle volumes release lower levels of Sb21,69
– Superior performance of PC, HDPE and PS over that of PET in minimizing
leaching of Sb from bottled water62

24. Factors affecting chemical leaching
• BPA
– The rate of BPA leaching increases when polycarbonate is scratched or
discolored59,70
– Water that is alkaline can degrade the PC plastic and lead to a release of BPA63
– Increased migration levels of BPA from PC baby bottles after dishwashing,
boiling and brushing. However, the TDI was not exceeded for infants. The
increased migration levels may be due to polymer degradation70. However, in
another study, it was shown that brushing of the bottle does not seem to raise
the release of BPA71
– Higher temperature and longer testing period resulted in higher BPA migration
from PC bottles73
– For PC reusable water bottles, filling with hot water or heating in the
microwave to high temperatures will increase the level of BPA migration72
– Temperature is the critical factor favouring BPA migration from PC bottles to
water74
– Heating by microwaving to 100°C for 9 min increased BPA migration levels71
– Filling PC bottles with boiling hot water (100°C) and leaving them to stand at
room temperature for up to 3 h resulted to increased mean BPA levels in a
time-dependent manner. However, none of the PC bottles released BPA at
levels that exceed the recently established SML of 600 ppb established by
European Union71

25. Factors affecting chemical leaching
• Phthalates
– The phthalate concentration of PET bottled mineral water may
vary with pH16, storage time26,77, storage temperature (30 °C–60
°C)27,79 and exposure to sunlight78,79
– Their occurrence depends strongly on the PET bottle material
(virgin vs. polymer containing recycled PET), pH (carbonated vs.
non-carbonated samples), packaging volume and temperature76
– Poor storage conditions (10 weeks outdoors at temperatures of up
30 °C) increases the concentrations of DBP, BBP and DEHP in
bottled water27
– Acidic pH stimulates the diffusion of phthalates75
– Phthalates migration in outdoor conditions is not substantial4,79
– Slight differences in DEHA amounts in PET bottled water have
been observed in association with high temperatures and in
samples from different countries79

26. Recommendations for minimization of
chemical leaching in bottled water
• Storage and transportation of bottled water should be
under room temperature conditions, without sunlight
exposure
• Contained water should be used in a short time after
bottle storage
• Reuse of plastic bottles should be minimized
• Boiling of water in plastic bottles should be minimized
• Filling hot water/tap water into plastic bottles should
be minimized
• Drying plastic bottle with hard water or residues of
alkaline detergent at a high temperature in a
dishwasher should be minimized

27. Quiz
Multiple Choice Questions
• Chemical compounds have be found in bottled
water. What is/are the source/s of these
compounds?
A. Migration of compounds from plastic bottles into water
B. Wide use of plasticizers which can cause cross-
contamination during analytical procedures
C. Contamination of water in the bottling facility
D. All of the above

28. • What were the results of the US National Toxicology
Program (NTP) Center for the Evaluation of Risks to
Human Reproduction (CERHR) on the evaluation of
BPA (2008)?
A. ‘Minimal Concern’ for neurological or behavioural
effects in foetuses, infants, and children
B. ‘Minimal’ or ‘Negligible’ likelihood of human
reproductive problems
C. ‘Negligible Concern’ that in utero exposure to BPA has a
negative effect on the prostate, produces birth defects and
malformations and potentially causes accelerations in
puberty
D. ‘Some Concern’ for adverse reproductive effects in the
general population

29. • What is known about the toxicity and carcinogenicity
of acetaldehyde?
A. Genotoxic and induces DNA & chromosomal damage in
many biological systems
B. Possible human carcinogen (Group 2B, IARC) and
genotoxic in many biological systems
C. Human carcinogen (Group 1, IARC) and genotoxic in
many biological systems
D. Not genotoxic and possible human carcinogen (Group
2B, IARC)

30. • What are some possible health effects of BPA
exposure?
A. It may promote carcinogenesis of multiple cancers and
it is associated with thyroid dysfunction, obesity and type
2 Diabetes Mellitus
B. Low exposure to BPA could lead to ‘‘long-lasting’’ effects
on the carcinogenesis of certain organs and it is associated
with thyroid dysfunction, obesity and metabolic syndrome
C. Cohort studies have shown that BPA exposure can cause
increase in prostate and breast cancer, urogenital
abnormalities in male babies, a decline in semen quality in
men, early onset of puberty in girls and neurobehavioral
problems such as attention deficit hyperactivity disorder
D. Genotoxic & induces DNA & chromosomal damage in a
wide range of organisms

31. • What are some of the factors promoting antimony
(Sb) leaching into the water?
A. Temperature, UV exposure, bottle color, extending
frequency of reuse and pH
B. Temperature, UV exposure, bottle reuse and color, bottle
type and volume and pH
C. Temperature, UV exposure, long-term storage, bottle
reuse and brushing
D. Temperature, UV exposure, long-term storage, bottle
reuse and pH

32. • Match the numbers from 1-7 with the appropriate
types of plastic
• What are the endocrine disrupting chemicals?
• Name 5 compounds that migrate from plastic
bottles into water
• What are some of the alternatives of PC bottles and
BPA and how safe are they?
• State 5 ways to minimize chemical leaching into
bottled water
Open Questions