Antimony and acetaldehyde migration from Nigerian and British PET bottles into water and soft drinks under typical use conditions. Concentration of migrants and some trace elements in polyethylene terephthalate and in bottled contents.

Abstract

Polyethylene terephthalate (PET) is an excellent material for bottling water, beverages, edible oils and other liquids because it is light, tough and transparent. PET bottles are also extensively reused for storage of drinking water, beverages and other liquids and for solar disinfection of microbiologically unsafe drinking water in the tropics. In spite of the usefulness of PET bottles earlier works have reported leaching of antimony and acetaldehyde from the bottle matrix into the liquid contents. Both antimony trioxide and acetaldehyde belongs to Group 2B (possible carcinogens) in the International Agency for Research on Cancer (IARC) carcinogen classification. Additionally acetaldehyde associated with alcoholic beverages (derived from alcoholic beverage and formed endogenously) has recently been upgraded to IARC Group 1 carcinogen (carcinogenic to humans). The research aims to assess the pattern and extent of antimony and acetaldehyde migration from British and Nigerian polyethylene terephthalate bottles into bottle contents under typical use and reuse conditions. The research compares the assessed extents of migration with the current regulations to determine whether the maximum acceptable levels of antimony and acetaldehyde are being exceeded and whether current regulations might need to be reassessed. To achieve these goals the pattern and extent of PET bottle use and reuse in Britain and Nigeria were appraised through survey. The survey revealed that new bottles with contents are typically stored prior to use for periods ranging between one and 7 days, with Nigerians storing for longer periods than British respondents. However storage of up to one year was reported. The extent of bottle reuse was high and similar for the two countries. Nevertheless Nigerian respondents reuse bottles for longer periods than British respondents. The survey findings together with relevant literature were used to design laboratory experiments that assessed the extent of antimony and acetaldehyde migration from PET bottles into water/beverages. A total of 82 brands of bottled water and soft drinks in plastic and glass bottles and in cartons were collected. A few samples from Nigeria in plastic pouches were collected. Materials used in bottling including glass and plastic bottle materials, metal and plastic bottle cap materials and plastic cap lining materials were collected. All samples were collected in supermarkets and shops in Britain and Nigeria except drinking water from taps which was collected in Britain only. Some bottles were aged for the purpose of studying the impact of bottle aging on chemical migration. Other bottles were stored with their contents to study the impact of long term storage of bottle contents on chemical migration. Energy dispersive X-ray spectrometry (EDX) and Raman spectroscopy were used to characterise PET bottle material and other materials associated with water and soft drink bottling. Antimony and other trace metals in water and soft drinks were determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Antimony content of PET and other plastics was determined by microwave digestion and ICP-MS. Acetaldehyde content of water and soft drinks and PET were determined using headspace gas chromatography with flame ionisation detection (GC-FID). Accuracy and precision for determination of antimony and other trace elements in bottle materials and bottle contents were good as recoveries were around 100% and coefficients of variation were less than 15% for all analysis types. Accuracy and precision for determination of acetaldehyde in bottle materials and bottle contents were also good as recoveries were around 100% and coefficients of variation were less than 15% for all analysis types. Impact of long term storage, elevated temperatures, bottle thickness, carbonation, bottle aging and bottle size on migration of antimony and acetaldehyde were also assessed. All plastic bottle materials analysed were found to be PET. Bottle cap materials were either polyethylene or polypropylene. All plastic cap lining materials from Britain and some from Nigeria were found to be ethylene vinyl acetate/polypropylene copolymer. Plastic cap lining materials from some Nigerian soft drinks were identified as polyvinyl chloride. Glass bottle materials analysed were found to be soda-lime glass. Metal bottle caps were identified as tinplate, tin-free-steel coated with chromium or aluminium coated with chromium. The antimony concentration in 32 PET bottle materials from Britain and Nigeria were similar and ranged between 177 and 310 mg/kg with an average of 250±30 mg/kg. The concentration agrees well with the industry reported concentration of between 150 and 350 mg/kg. The concentration of residual acetaldehyde in 25 fresh PET bottle materials from Britain and Nigeria ranged between 0.95 and 12.52 µg/g. The average concentration in British and Nigerian soft drinks PET materials are 4.76 and 2.17µg/g respectively. Concentration of residual acetaldehyde was higher in soft drinks and still water PET materials than in sparkling water materials. The concentration of residual acetaldehyde decreases as the bottle wall material becomes older. Also the thinner the bottle walls the lower the concentration of residual acetaldehyde. Antimony concentration in 47 freshly purchased British bottled water and soft drinks ranged between 0.03 and 6.61µg/L with only one sample going above the EU acceptable limit. Concentrations of other trace elements measured were low except titanium which was detected at part per million levels in soft drinks. Lead content of a Nigerian soft drink in glass bottle stored for 2 months was above the EU acceptable limit for lead. At realistic temperatures of 40 and 60°C antimony concentration in the water remained below the EU acceptable limit even after 48 hours of exposure but the concentration exceeded the limit for most exposures at 80°C. Concentration of antimony in some Nigerian bottled water and soft drinks was above the EU limit after 11 months of storage at room temperature. Aged bottles leach lower amount of antimony than new bottles. Similarly larger bottles leach lower amount of antimony than smaller bottles. The average acetaldehyde concentrations found in British fruit juices, carbonated soft drinks, sparkling water and still water were 5113, 1458, 22 and 8 µg/L respectively. Acetaldehyde was not detected in water bottled in glass. The concentration of acetaldehyde in five fruit juice samples in PET bottles and carton was beyond the EU specific migration limit (SML) of 6mg/kg. Also the tolerable daily intake of acetaldehyde could be exceeded as a result of intake of some soft drinks and fruit juices. Acetaldehyde content in soft drinks increase with storage but the increase cannot be accounted for by the residual acetaldehyde in PET. Acetaldehyde was found to be outgassing from some bottles. It was also found to be capable of migrating from soft drinks into bottle wall. Without replenishment the concentration of acetaldehyde in solution decreases with time. The use of PVC cap lining in Nigeria as found in this study is a cause for concern as PVC is associated with health risk issues. The study recommends actions to ensure that antimony in fruit juices and other bottled products remain within the regulatory standard from bottling to consumption for the purpose of safeguarding the health of consumers. Glass used in bottling should be well scrutinized to ensure that it does not contain high levels of lead or other chemical substances that can cause harm to consumers through migration into contents. PET bottles can safely be used for solar water disinfection without the risk of antimony intake at concentrations above safe limits as water temperature achievable as the result of the technique doesn¿t go beyond 60°C. Also aged bottles are safer to use than new bottles because their chemical leaching was found to be lower than that of new bottles. This study recommends the reassessment of the absence of international guidelines for acetaldehyde in water and foods. The study also recommends that the amount of acetaldehyde that can be added to soft drinks as flavouring agent should be below the specific migration limit (SML) for migration of acetaldehyde from PET bottle into bottle contents. This is essential since the SML was designed to ensure that exposure to acetaldehyde, as a result of intake of bottled water and soft drinks in PET bottles, is below the tolerable daily intake (TDI) for acetaldehyde. As antimony was reported to go beyond the safe limits in some Nigerian bottled water and soft drinks after 11 months of storage this study discourages the use of bottle contents stored for a very long time.