Leaching from plastic bottles bottle line operators 1

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

Transcript of Leaching from plastic bottles bottle line operators 1

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Leaching of chemicals in water from plastic bottles

Aquasyn Cyprus University of Technology

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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

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Types of plastics

PET or PETE: Polyethylene Terephthalate

HDPE: High-density Polyethylene

Other (PC) LDPE: Low-density Polyethylene

PS: Polystyrene PP: Polypropylene

PVC: Polyvinyl Chloride

http://www.wrap.org.uk/content/types-plastic

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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

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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

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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.

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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

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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

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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

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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

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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

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(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

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• 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

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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

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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

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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

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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)

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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

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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

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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

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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

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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.

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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

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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

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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

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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

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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

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• 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

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• 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)

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• 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

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• 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

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• 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