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Recent Developments in Lead Migration Studies from Crystal Glassware

Explore findings on lead migration from crystal glassware in consumer use scenarios. Includes safe exposure levels and European legislation updates. Presented at XVI Technical Exchange Conference.

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Recent Developments in Lead Migration Studies from Crystal Glassware

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  1. RECENT DEVELOPMENTS IN LEAD MIGRATION Maryse FAVARD *, Sébastien DONZE# * IANESCO CHIMIE, Poitiers, FRANCE #ARC INTERNATIONAL - ICF Technical Committee International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004

  2. International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 INSTITUT D’ANALYSES ET D’ESSAIS EN CHIMIE DE L’OUEST - Poitiers - France • MATERIALS IN CONTACT WITH FOODSTUFFS • Overall migration – specific migration • Metals determination • Bacteriological tests • Sensory analysis Accredited by the COFRAC (French Committee of Accreditation) for the tests and analyses of materials and packaging in contact with foodstuffs. Laboratory recognized by the DGCCRF (French administration for protection of consumers) to issue certificates of analyses for materials in contact with foodstuffs. International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004

  3. Introduction Introduction of Lead Oxide in the batch composition   levels of exposure to lead Manufacturing process consumer exposure End of life (landfilling) - Environmental exposure - Occupational exposure (workers) Short-term contact : repetitive use of stemware and tumblers Medium and Long-term contact : storage in decanters International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 LEAD CRYSTAL GLASS = Noble material with specific and attractive properties Consumer Exposure

  4. Introduction 2003,ICF Technical Committee decision: update Risk Assessment performed in 1992 in the USA with an estimation of theEuropean Consumer Exposure to lead International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Is it safe to drink from lead crystal drinkware? An episode in the ever-lasting polemics since 1991, and despite the conclusions of the Safety Assessment in the USA (1992) : « Lead intakes through the use of lead crystal domestic ware are at most a small fraction of the safe limits recommended by the WHO and the US FDA » Since 1991, at the instigation of the International Crystal Federation  significant technical progresses within lead crystal industry : - improved product formulation - surface treatment techniques - process control techniques Today in Europe, an evolution of the European legislation on chemical products is discussed (the REACH procedure). Possible evolution of the legislation + VRAL procedure

  5. Introduction International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Lead migration from lead crystalware under conditions representative of a consumer use :  Short term contact with different beverages : stemware and tumblers Medium andLong term contact : storage of alcohol in decanters ICF TC approach in accordance with the guidelines of the Council of Europe on lead leaching from glass tableware intended to come into contact with foodstuffs Independant Laboratory : IANESCO CHIMIE, France  lead crystal glasses purchased on the open market : 5 European crystal glass producers : ARC INTERNATIONAL CALP INN CRYSTAL NACHTMANN WATERFORD  extraction procedure with different beverages  lead migration analysis

  6. Short-term contact : Test protocol International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Items : 50items from 5 companies : ARC INTERNATIONAL JG DURAND / Mikasa : Oenologue 28 cl and Oenologue 35 cl. INN CRYSTAL Lisa Mori-Chloe : wine glasses, and water glasses NACHTMANN Gourmet 2000 : wine glasses, water glasses, whisky glasses RCR CALP Opera : wine glasses, goblets, old fashioned tumblers. WATERFORD CRYSTAL Lismore claret glasses – Lismore 10.OZ goblets – Dolmen tumblers Beverages :- Whisky (40°, pH=4.4) - Red Wine (Bordeaux, AOC 12°, pH=3.7) - Mineral water (pH =7.2) - Carbonated drink (Perrier, pH=5.3)

  7. Short-term contact : Experimental procedure International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 • Extraction procedurerepresentative of normal repeated useTime of contact :45 minutes • Data on pattern of use in France • source CREDOC 1999, Enquêtes comportements alimentaires des Français • Lunch : 80% taken at home every day in week (5 days) • Dinner: 90% taken at home every day in week (5 days) • Average duration during week days = 33 minutes (only 13% less than 15 minutes) • Average duration during weekend = 43 minutes • Room temperature :22 °C  2°C • Before the 1st contact and between each contact : manual washing with a commercial detergent, rinsing with tap water, wiping with a tissue cloth Lead migration analysis[Pb] analysis in beverages after 1 - 5 - 10 - 15 - 20 contacts. Technique : -Atomic absorption spectrometry with graphite furnace : mineral water, carbonated drink, whisky and red wine (except 1st contact) - Flame atomic absorption spectrometry : 1st contact with red wine Method of quantification : -Direct determination in mineral water and carbonated drink -Standard addition in wine and whisky

  8. Short-term contact : IANESCO results  Rapid decrease of lead leaching, stabilization from the 10th contact LEAD MIGRATION DURING THE 10th CONTACT company A company B company C company D company E < 0,01 < 0,01 < 0,01 < 0,01 < 0,01 [Pb] mg/L AVERAGE VALUE : < 0,01 International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004  Lead migration in mineral water

  9. Short-term contact : IANESCO results LEAD MIGRATION DURING THE 10th CONTACT company A company B company C company D company E < 0,01 0,01 < 0,01 0,01 0,01 [Pb] mg/L AVERAGE VALUE : 0,01 International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004  Lead migration in carbonated drink

  10. Short-term contact : IANESCO results E. GUADAGNINO (S.S.V.) et al., 2000 Natural [Pb] in wine S.C. HIGHT(F.D.A.), 1996 LEAD MIGRATION DURING THE 10th CONTACT company A company B company C company D company E 0,02 0,03 < 0,02 0,02 < 0,02 [Pb] mg/L AVERAGE VALUE : 0,02 International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004  Lead migration in red wine 0,40 0,35 0,30 0,25 [Pb] mg/L 0,20 0,15 0,10 0,05 0,00 0 5 10 15 20 25 Number of contacts of 45 min.

  11. Short-term contact : IANESCO results LEAD MIGRATION DURING THE 10th CONTACT company A company B company C company D company E 0,01 0,02 0,02 0,01 0,02 [Pb] mg/L AVERAGE VALUE : 0,02 International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004  Lead migration in whisky

  12. Short-term contact : IANESCO results  rapid decrease of Pb leaching after the 1st contact Formation of a thin layer of glass depleted of diffusible lead  stabilization from the 10th contact International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 SUMMARY * similar behaviour for the 50 different items tested * results in accordance with the previous data from the literature

  13. Short-term contact : Consumer Risk Assessment International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Beverages consumption in Europe, year 2002 values expressed in liters/per capita/year WATER : 84.7 SODAS -TONICS : 67.1 WINE : 30.4 SPIRITS (40°) : 4.6 sources : World Drink Trends, 2004 2003 European Community, Eurostat

  14. Short-term contact : Consumer Risk Assessment 1st scenario : 2nd scenario : International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Estimation of Lead Intake based on : - average annual European consumption of beverages - lead migration results obtained for new glasses after 10 contacts - 2 different patterns of use of lead crystal items « Worst case »scenario 1- using lead crystal tableware at each meal 2- drinking the total amount of water, sodas, spirits and wine, using lead crystal glasses « more realistic » but still conservativescenario 1- using lead crystal glassesonce a week 2- drinking the total amount of spirits on these occasions 3- drinking half of the total amount of wine on these occasions

  15. Short-term contact : Consumer Risk Assessment International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 - 1st scenario:« worst case » scenario 1- using lead crystal tableware at each meal 2- drinking the total amount of water, sodas, spirits and wine, using lead crystal glasses Estimate of the Lead Weekly Intake For one beverage, Pb weekly intake = (1/52) average annual european consumption  lead migration Ex. : for water, Pb weekly intake = (1/52) 84.7 0.001 =0.016 mg/wk less than 3% of the PTWI Provisional Tolerable Weekly Intake (Joint FAO/WHO committee for Food additives, 1993) PTWI = 25 mg Pb/kg, ie 1500 mg Pb/week (adult, 60 kg)

  16. Short-term contact : Consumer Risk Assessment Source : Head Office of customs « Direction Générale des Douanes » International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004  Frequency of use of lead crystal tableware SYLAB-YPSIS study (2002) for ARC INTERNATIONAL 1182 people in Germany, France and USA having crystal tableware at home 86% : less than once a week Tendency of wine consumption in France

  17. Short-term contact : Consumer Risk Assessment International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 - 2ndscenario:« more realistic » but still conservative scenario 1- using lead crystal tablewareonly on occasional circumstances : once a week 2- drinkingthe total amount of spirits on these occasions 3- drinking half of the total amount of wine on these occasions Estimate of the Lead Weekly Intake less than 1% of the PTWI Provisional Tolerable Weekly Intake (Joint FAO/WHO committee for Food additives, 1993) PTWI = 25 mg Pb/kg, ie 1500 mg Pb/week (adult, 60 kg)

  18. Short-term contact : Conclusion International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 1Lead release from lead crystalware in use conditions is much lower than lead release in the standard testing method (more than 10 times lower) 2  For each beverage tested, lead extraction shows a very important decrease after the 1st contact. 3 Lead release from lead crystalware during short term contact is small compared to the natural lead content in wine itself (<0,02 mg/L vs 0,12 mg/L). 4  Using estimates based on statistics of : - beverage consumption in Europe - patterns of use of lead crystal tableware Lead ingestion from lead crystalware is negligible compared to the Provisional Tolerable Weekly Intake : < 3% PTWI for the WORST CASE SCENARIO

  19. Medium & Long-term contact - Storage in decanters Focus on medium-term storage in decanters International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 2 different patterns of use of decanters : 1- Refilling frequently the same decanter for storage of spirits  medium-term storage 2- Consumming spirits bottled in lead crystal decanters  long-term storage

  20. Medium-term contact : test protocol Items : 9decanters from 3 companies ARC INTERNATIONAL - 2 new « Bretagne » decanters - 1L. - 1 aged « Longchamp » decanter - 1L - aging procedure : 9 years in contact with whisky RCR CALP - 2 new whisky decanters – 0,75L. - 2 aged whisky decanters – 0,75L - aging procedure : 1st contact : 2 months 2nd contact : 2 months 3rd contact : 8 years WATERFORD CRYSTAL - 2 new decanters – 0,75L. with brandy International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Beverage : - Cognac : « Fine Cognac », 40°, pH=3,5

  21. Medium-term contact : test protocol International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Extraction procedure : Time of contact :1 month Room temperature :22 °C  2°C Preparation before extraction : - new decanters:Pre-washing procedure following ICF recommendations : Exposed to a mixture of vinegar and tap water (50/50) during 24 hours at room temperature. Then, rinsed with hot water and finally with distilled water. - aged decanters : Rinsed with distilled water before extraction Lead migration analysis [Pb] analysis in cognac after 1 month contact Technique : Atomic absorption spectrometry with graphite furnace Method of quantification : Standard addition method

  22. Medium-term contact : results Limit of quantification = 0,02 mg/L [Pb] in Cognac < limit of quantification International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004  relatively low Pb content in Cognac for new and aged decanters for 1 month contact (much lower than Pb content in red wine : 0,12 mg/L)

  23. Medium-term contact : discussion International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Aged decanters : very low level of Pb release  « passivated » layer  thin layer of glass that has been depleted of diffusible lead S.J. BARBEE and CONSTANTINE, 1994

  24. Medium-term contact : discussion International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 New decanters E. GUADAGNINO et al., 1998 FIRST USE OF DECANTER: Migration regulated by diffusion Lead Release = f(t1/2) Pb extracted after 28 days = 66% Pb extracted after 105 days  Much lower Pb release values  Pre-treatment with vinegar G. BOSCHI et al., ICF Technical Exchange Conference, 1996  Storage of spirits in used decanters, or new decanters after ICF recommended treatment, would result in very low lead release, <0.1 mg/L after 1 month

  25. Medium-term contact : consumer risk assessment Estimate of lead weekly Intake = (0,2  4.6)/52 < 0,018 mg/week < 1,2 % PTWI Provisional Tolerable Weekly Intake (Joint FAO/WHO committee for Food additives, 1993) PTWI = 25 mg Pb/kg, ie 1500 mg Pb/week (adult, 60 kg) International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Results : Average annual European consumption of spirits = 4,6 L/per capita Lead release from lead crystal decanters after 1 month contact < 0,1 mg/L Hypotheses :  Total amount of spirits is consumed using lead crystal decanter  Residence Time of spirit in the decanter < 2 months  According to our results and based on Guadagnino’s study, lead release from lead crystal decanters after 2 months contact < 0,2 mg/L

  26. General conclusions International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 New set of data of lead leaching from lead crystal tableware in conditions representative of a consumer use from an independant laboratory.  Results in accordance with previous studies from the literature Short-term contact :  For each beverage tested, lead extraction shows a very important decrease after the 1st contact. Lead release from lead crystalware during short term contact is small compared to lead content in wine itself (0,02 mg/L vs 0,12 mg/L). Medium-term contact :  Storage of spirits in used decanters, or new decanters after the ICF recommended treatment, would result in very low lead release, <0,1 mg/L after 1 month

  27. General conclusions For all types of leadcrystal drinkware, stemware or decanters, manufactured recently and used following ICF instructions, the consumer exposure to lead is much lower than 10% of the PTWI and the worst-case exposure levels are lower than current standards for lead in food and beverages NEGLIGIBLE CONSUMER EXPOSURE RISK IS ASSUMED International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 New approach of the consumer risk assessment using lead crystal tableware at an European level for -repeated short-term contacts (use of stemware) - medium-term contacts (use of decanters)

  28. General conclusions Lead Oxide in lead crystal glass composition - Long term alteration   levels of exposure to lead Manufacturing process Consumer exposure End of life (landfilling) VRAL procedure in progress Si-enriched layer Negligible Exposure - Environmental exposure - Occupational exposure (workers)  Stabilization of the glass A. BOUQUILLON ICF TEC, 2003  Complete the study on decanters - long-term storage : up to 6 months - study of the pre-washing effect International Crystal Federation - XVI Technical Exchange Conference Karlovy-Vary, Czech Republic - 9-11 October 2004 Consumer Exposure Direct food contact

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