Determination of the Migration of Lactide in PLA Food Contact Materials by Gas Chromatography Mass Spectrometry
-
摘要: 建立气相色谱质谱联用法（GC-MS）测定聚乳酸食品接触材料中丙交酯迁移量的方法。橄榄油模拟物经过乙腈提取，离心分层与过滤后，使用GC-MS测试分析；异辛烷模拟物过滤后直接使用GC-MS测试分析。该法实现了聚乳酸食品接触材料中丙交酯迁移量的测定，检出限为0.01 mg/kg，加标回收率为80.0%~120.0%，相对标准偏差为2.6%~6.6%（n=6）。运用该方法对7款聚乳酸（PLA）食品接触材料的实际样品进行测定，丙交酯的整体检出率为85.7%，迁移量的检出范围为0.033~1.1 mg/kg。该方法灵敏度、回收率和准确度高，检测限能够满足法规判定要求，可用于PLA食品接触材料中丙交酯迁移量的实际检验工作。实际样品检测结果表明，PLA样品中的丙交酯迁移量检出率较高，需引起安全关注。相对于替代溶剂异辛烷，由于橄榄油迁移温度较高，样品的橄榄油迁移量比替代条件下异辛烷的迁移量高。Abstract: The method for the determination of migration of lactide in polylactic acid (PLA) food contact material by gas chromatography-mass spectrometry (GC-MS) was established. Olive oil simulants were extracted by acetonitrile, centrifuged and filtered, and then analyzed by GC-MS. Isooctane simulants were directly filtered and analyzed by GC-MS. The method could achieve the determination of lactide migration in PLA. The limit of detection was 0.01 mg/kg and the recoveries at spiked levels were 80.0%~120.0%. The relative standard deviations were 2.6%~6.6% (n=6). Seven PLA samples were analyzed by the method. The detection rate was 85.7% and the range of concentration were 0.033~1.1 mg/kg. The method had the advantages of high sensitivity, high recovery and accuracy. The detection limit can meet the requirements of regulations. The method was suitable for migration of lactide in PLA food contact materials. The results showed that the detection rate of migration of lactide in PLA samples was high and migration of lactide should be paid attention to. Compared with isooctane, the migration of olive oil in the sample was higher than that of isooctane under the substitution condition due to the higher migration temperature of olive oil.
-
Key words:
- lactide /
- migration /
- PLA food contact material /
- oily simulant /
- gas chromatography mass spectrometry
-
图 1 丙交酯的选择离子色谱图
注：a：聚乙二醇毛细管色谱柱；b：5%苯基-甲基聚硅氧烷毛细管色谱柱。
Figure 1. The selected iron chromatograms of lactide
表 1 模拟物的回归方程、线性范围及决定系数
Table 1. Regression equations, linear ranges and determination coefficient of simulant
模拟物 回归方程 R2 线性范围（mg/kg或mg/L） 异辛烷 y=23093.182503x+37.768905 0.9977 0.020~0.20 橄榄油 y=64490.193284x+1413.581534 0.9959 
下载: 导出CSV
表 2 不同模拟物中丙交酯的回收率及相对标准偏差
Table 2. Recoveries and relative standard deviations of lactide in different simulants
模拟物 加标量（mg/kg） 回收率（%） 相对标准偏差（%） 异辛烷 0.02 85.0~95.0 5.5 0.10 81.0~90.0 4.7 0.15 80.0~86.7 4.2 橄榄油 0.02 100.0~120.0 6.6 0.10 96.0~114.0 6.4 0.15 100.0~107.0 2.6
下载: 导出CSV
表 3 实际样品检测结果
Table 3. Test result of actual samples
编号 测试结果 橄榄油迁移量
（mg/kg）异辛烷迁移量
（mg/kg）样品丙交酯残留量
（%）1# 1.1±0.10 0.068±0.003 0.27±0.02 2# 0.39±0.03 0.042±0.003 0.23±0.02 3# 0.42±0.02 0.039±0.003 0.19±0.02 4# 0.33±0.03 0.033±0.003 0.086±0.004 5# 0.76±0.05 0.12±0.010 0.17±0.01 6# 0.19±0.01 <0.01 0.16±0.01 7# <0.01 <0.01 0.023±0.003
下载: 导出CSV
-
[1] FILICIOTTO L, ROTHENBERG G. Biodegradable plastics: Standards, policies, and impacts[J]. Chem Sus Chem,2021,14:56−72. doi: 10.1002/cssc.202002044 [2] SONG J H, MURPHY R J, NARAYAN R, et al. Biodegradable and compostable alternatives to conventional plastics[J]. Philosophical Transactions of the Royal Society of London Series B, Biological Sciences,2009,364(1526):2127−2139. doi: 10.1098/rstb.2008.0289 [3] MOY C H, TAN L S, SHOPARWE N F, et al. Comparative study of a life cycle. Assessment for bio-plastic straws and paper straws: Malaysia’s perspective[J]. Processes,2021,9:1007. doi: 10.3390/pr9061007 [4] TAYLPR P, AHMED J, VARSHNEY S K. Polylactides-Chemistry, properties and green packaging technology: A review[J]. Int J Food Prop,2010,14:37−58. [5] ALFONSO J, PELTZER M, RUSECHAITE R. Poly (lactic acid) science and technology. Processing, properties, additives and applications[M]. UK: Royal Society of Chemistry, 2014. [6] ZAABA N F, JAAFAR M. A review on degradation mechanisms of polylactic acid: Hydrolytic, photodegradative, microbial, and enzymatic degradation[J]. Polymer Engineering and Science,2020,60(9):2061−2075. doi: 10.1002/pen.25511 [7] LAGARON J M. Multifunctional and nanoreinforced polymers for food packaging[M]. Sawston: Woodhead Publishing, 2011. [8] AURAS R, HARTE B, SELKE S. An overview of polylactides as packaging materials[J]. Macromolecular Bioscience,2004,4(9):835. doi: 10.1002/mabi.200400043 [9] SANGRONIZ A, SANGRONIZ L, HAMZEHIOU S, et al. Lactide-valerolactone copolymers for packaging applications[J]. Polymers, 2022, 14: 52. [10] BODBODAK S, SHAHABI N, MOHAMMAID M, et al. Development of a novel antimicrobial electrospun nanofiber based on polylactic acid/hydroxypropyl methylcellulose containing pomegranate peel extract for active food packaging[J]. Food and Bioprocess Technology,2021,14:2260−2272. doi: 10.1007/s11947-021-02722-y [11] IGLESIAS-MONTES M L, LUZI F, DOMINICI F, et al. Migration and degradation in composting environment of active polylactic acid bilayer nanocomposites films: Combined role of umbelliferone, lignin and cellulose nanostructures[J]. Polymers,2021,13(2):282. doi: 10.3390/polym13020282 [12] ZHONG Y, YAO Q M, CAO C Y, et al. Improvement of β-cyclodextrin/cardanol inclusion complex for the thermal-oxidative stability and environmental-response antioxidation releasing property of polylactic acid[J]. Polymers for Advanced Technologies,2022,33(2):492−504. doi: 10.1002/pat.5531 [13] OLIVEIRA W, AZEREDO H, NERI-NUMA I A, et al. Food packaging wastes amid the COVID-19 pandemic: Trends and challenges[J]. Trends in Food Science & Technology,2021,16:1195−1199. [14] HAVELT T, BRETTSCHNEIDER S, SCHMITZ, M. Evaluation of practical applicability and synergistic effects of bio-based food packaging materials combined with plant-based stabilisers[J]. Processes,2021,9:1838. doi: 10.3390/pr9101838 [15] WRONA M, NERIN C. Analytical approaches for analysis of safety of modern food packaging: A review[J]. Molecules,2020,25(3):752. doi: 10.3390/molecules25030752 [16] MUTSUGA M, KAWAMURA Y, TANAMOTO K. Migration of lactic acid, lactide and oligomers from polylactide food-contact materials[J]. Food Additives and Contaminants Part A-Chemistry Analysis Control Exposure & Risk Assessment,2008,25(10):1283−1290. [17] CONN R E, KOLSTAD J J, BORZELLECA D S, et al. Safety assessment of polylactide (PLA) for use as a food-contact polymer[J]. Food and Chemical Toxicology,1995,33(4):273−283. doi: 10.1016/0278-6915(94)00145-E [18] UBEDA S, AZNAR M, NERIN C, et al. Fabric phase sorptive extraction for specific migration analysis of oligomers from biopolymers[J]. Talanta,2021,233:122603. doi: 10.1016/j.talanta.2021.122603 [19] UBEDA S, AZNAR M, NERÍN C. Determination of volatile compounds and their sensory impact in a biopolymer based on polylactic acid (PLA) and polyester[J]. Food Chemistry,2019,294:171−178. doi: 10.1016/j.foodchem.2019.05.069 [20] ZIMMERMANN L, DOMBROWSKI A, VOLKER C, et al. Are bioplastics and plantbased materials safer than conventional plastics? In vitro toxicity and chemical composition[J]. Environment International,2020,154:106066. [21] MUNCKE J, ANDERSSON A M, BACKHAUS T, et al. Impacts of food contact chemicals on human health: A consensus statement[J]. Environmental Health,2020,19(1):25. doi: 10.1186/s12940-020-0572-5 [22] MSDS.Safety data sheet[EB/OL]. Thermo Fisher Scientific, 2012, www. alfa. com/en/content/msds/USA/L09031. pdf. [23] HEBERT C D, GILES H D, HEATH J E, et al. Toxicity of lactide in dog after 2 and 13 weeks of daily oral dosing[J]. Food Chem Toxicol,1999,37(4):335−342. doi: 10.1016/S0278-6915(99)00014-9 [24] 中华人民共和国卫生部. GB 9685-2016 食品安全国家标准 食品接触材料及制品用添加剂使用标准[S]. 北京: 中国标准出版社, 2016Ministry of Health of the People’s Republic of China. GB 9685-2016 National food safety standard. Standard for use of additives in food contact materials and articles[S]. Beijing: China Standards Press, 2016 [25] 中华人民共和国国家卫生和计划生育委员会. GB 4806.6-2016 食品安全国家标准 食品接触用塑料树脂[S]. 北京: 中国标准出版社, 2016National Health and Family Planning Commission of the People’s Republic of China, National Medical Products Administration. GB 4806.6-2016 National food safety standard. Food contact plastic resin[S]. Beijing: China Standards Press, 2016. [26] The European Commission. (EU) 10/2011. Plastic food contact materials and articles[S]. European: the European Food Safety Authority, 2011. [27] FENG L, CHEN X S, SUN B, et al. Water-catalyzed racemisation of lactide[J]. Polymer Degradation & Stability,2011(96):1745−1750. [28] BOR Y, ALIN J, HAKKARAINEN M. Electrospray ionization-mass spectrometry analysis reveals migration of cyclic lactide oligomers from polylactide packaging in contact with ethanolic food simulant[J]. Packaging Technology and Science,2012,25(7):427−433. doi: 10.1002/pts.990 [29] ROCCA-SMITH J R, CHAU N, CHAMPION D, et al. Effect of the state of water and relative humidity on ageing of PLA films[J]. Food Chemistry,2017,236:109−119. doi: 10.1016/j.foodchem.2017.02.113 [30] NIM B, OPAPRAKASIT P. Quantitative analyses of products from chemical recycling of polylactide (PLA) by alcoholysis with various alcohols and their applications as healable lactide-based polyurethanes[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2021,255:119684. doi: 10.1016/j.saa.2021.119684 [31] 中华人民共和国卫生部. GB 31604.1-2015 食品安全国家标准 食品接触材料及制品迁移试验通则[S]. 北京: 中国标准出版社, 2015Ministry of Health of the People’s Republic of China. GB 31604.1-2015 National food safety standard. General rules for migration test of food contact materials and products[S]. Beijing: China Standards Press, 2015. [32] 中华人民共和国卫生部. GB 5009.156-2016 食品安全国家标准 食品接触材料及制品迁移试验通则[S]. 北京: 中国标准出版社, 2016Ministry of Health of the People’s Republic of China. GB 5009.156-2016 National food safety standard. Food contact materials and products migration test pretreatment method[S]. Beijing: China Standards Press, 2016. [33] 刘智慧, 尹霞, 王燕清, 等. 气相色谱法测定药用辅料聚乳酸中丙交酯残留量[J]. 海峡药学,2020,32(6):50−51. [LIU Z H, YIN X, WANG Y Q, et al. Determination of residue of lactide in polylactides pharmaceutic adjuvant by gas chromatography[J]. Strait Pharmaceutical Journal,2020,32(6):50−51. doi: 10.3969/j.issn.1006-3765.2020.06.017 [34] GORRASI G, PANTANI R. Hydrolysis and biodegradation of poly (lactic acid). In: DI LORENZO M, ANDROSCH R (eds) Synthesis, structure and properties of poly (lactic acid)[J]. Advances in Polymer Science,2017,279:119−152. [35] JEFFREY J, KOLSTAD, ERWIN T H, et al. Assessment of anaerobic degradation of Ingeo™ polylactides under accelerated landfill conditions[J]. Polymer Degradation and Stability,2012,97(7):1131−1141. doi: 10.1016/j.polymdegradstab.2012.04.003 [36] KARUNATHILAKA S R, FAIDIN-KIA A R, ROBERTS D, et al. Determination of moisture in olive oil: Rapid FT-NIR spectroscopic procedure based on the Karl-Fischer reference method[J]. Journal of Oleo Science,2020,69(11):1373−1380. doi: 10.5650/jos.ess20078 [37] FAIDIN-KIA A R, KARUNATHILAKA S R, YAKES B J, et al. A rapid, univariate FT-NIR procedure to determine moisture concentration in olive oil[J]. Journal of Oleo Science,2019,68(11):1105−1112. doi: 10.5650/jos.ess19118 [38] BOR Y, ALIN J, HAKKARAINEN M. Polylactide stereocomplexation leads to reduced migration during microwave heating in contact with food simulants[J]. Journal of Food Engineering,2014,134:1−4. doi: 10.1016/j.jfoodeng.2014.02.017 [39] 朱蕾, 张俭波. 食品接触材料及制品迁移试验标准实施指南[M]. 北京: 国家食品安全风险评估中心, 2018ZHU L, ZHANG J B. Food contact materials and products migration test standards implementation guidelines[M]. Beijing: National Center for Food Safety Risk Assessment, 2018. -
下载:
点击查看大图
图(2) / 表(3)
计量
- 文章访问数: 15
- HTML全文浏览量: 9
- PDF下载量: 0
- 被引次数: 0
京公网安备 11010502036328号 京ICP备17033152号